Biodiesel: Feedstocks, Production and Applications [Second Edition] 978-953-51-0910-5

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BIODIESEL

FEEDSTOCKS, PRODUCTION AND APPLICATIONS Edi“ed by Zhen Fang

Biodiesel: Feedstocks, Production and Applications Edited by Zhen Fang Contributors Camila Da Silva, Fernanda Castilhos, Ignácio Vieitez, Ivan Jachmanián, Lúcio Cardozo Filho, José Vladimir De Oliveira, Ignacio Vieitez, Lucio Cardozo Filho, Dr. Mushtaq Ahmad, Rosana Schneider, Valeriano Corbellini, Eduardo Lobo, Thiago Bjerk, Pablo Gressler, Maiara Souza, Krzysztof Biernat, Artur Malinowski, Joanna Czarnocka, Sevil Yucel, Pınar Terzioğlu, Didem Özçimen, Guohong Tian, Yanfei Li, Hongming Xu, Andrii Marchenko, H.J. Heeres, R.H. Venderbosch, Joost Van Bennekom, Olinto Pereira, Alexandre Machado, Wan Mohd Ashri Wan Daud, Yahaya Muhammad Sani, Abdul Aziz Abdul Raman, Rodrigo Munoz, David Fernandes, Douglas Santos, Raquel Sousa, Tatielli Barbosa, Olga Machado, Keysson Fernandes, Natalia Deus-De-Oliveira, Hayato Tokumoto, Hiroshi Bandow, Kensuke Kurahashi, Takahiko Wakamatsu, Ignacio Contreras-Andrade, Carlos Alberto GuerreroFajardo, Oscar Hernández-Calderón, Mario Nieves-Soto, Tomás Viveros-García, Marco Antonio Sanchez-Castillo, Maria Catarina Megumi Kasuya, Raghu Betha

Copyright © 2016 Second Edition All chapters are Open Access distributed under the Creative Commons Attribution 3.0 license, which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. After this work has been published by authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Notice Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published chapters. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book.

First published December, 2012 second - 2016 ISBN-10: 953-51-0910-3 ISBN-13: 978-953-51-0910-5

Con“en“s

Preface IX Section 1

Feedstocks

1

Chap“er 1

Potential Production of Biofuel from Microalgae Biomass Produced in Wastewater 3 Rosana C. S. Schneider, Thiago R. Bjerk, Pablo D. Gressler, Maiara P. So”za, Valeriano A. Corbellini and Ed”ardo A. Lobo

Chap“er 2

Algal Biorefinery for Biodiesel Production 25 Didem Özçimen, M. Ömer Güly”r“ and Benan İnan

Chap“er 3

Major Diseases of the Biofuel Plant, Physic Nut (Jatropha curcas) 59 Alexandre Reis Machado and Olin“o Liparini Pereira

Chap“er 4

Biodiesel Feedstock and Production Technologies: Successes, Challenges and Prospects 77 Y.M. Sani, W.M.A.W. Da”d and A.R. Abd”l Aziz

Chap“er 5

Prospects and Potential of Green Fuel from some Non Traditional Seed Oils Used as Biodiesel 103 M”sh“aq Ahmad, Lee Kea“ Teong, M”hammad Zafar, Shazia S”l“ana, Haleema Sadia and Mir Ajab Khan

Section 2

Biodiesel Production

Chap“er 6

Biodiesel: Production, Characterization, Metallic Corrosion and Analytical Methods for Contaminants 129 Rodrigo A. A. M”noz, David M. Fernandes, Do”glas Q. San“os, Ta“ielli G. G. Barbosa and Raq”el M. F. So”sa

127

VI

Con“en“s

Chap“er 7

Biodiesel Current Technology: Ultrasonic Process a Realistic Industrial Application 177 Mario Nieves-So“o, Oscar M. Hernández-Calderón, Carlos Alber“o G”errero-Fajardo, Marco An“onio Sánchez-Cas“illo, Tomás ViverosGarcía and Ignacio Con“reras-Andrade

Chap“er 8

Lipase Applications in Biodiesel Production 209 Sevil Yücel, Pınar Terzioğl” and Didem Özçimen

Chap“er 9

Non-Catalytic Production of Ethyl Esters Using Supercritical Ethanol in Continuous Mode 251 Camila da Silva, Ignácio Viei“ez, Ivan Jachmanián, Fernanda de Cas“ilhos, Lúcio Cardozo Filho and José Vladimir de Oliveira

Section 3

By-Products Applications

281

Chap“er 10

Approaches for the Detection of Toxic Compounds in Castor and Physic Nut Seeds and Cakes 283 Keysson Vieira Fernandes and Olga Lima Tavares Machado

Chap“er 11

Bio-Detoxification of Jatropha Seed Cake and Its Use in Animal Feed 309 Maria Ca“arina Meg”mi Kas”ya, José Maria Rodrig”es da L”z, Lisa Presley da Silva Pereira, J”liana Soares da Silva, Hilário C”q”e““o Mon“avani and Marcelo Teixeira Rodrig”es

Chap“er 12

Biomethanol from Glycerol 331 Joos“ G. van Bennekom, Rober“”s H. Venderbosch and Hero J. Heeres

Chap“er 13

Utilization of Crude Glycerin from Biodiesel Production: A Field Test of a Crude Glycerin Recycling Process 363 Haya“o Tok”mo“o, Hiroshi Bandow, Kens”ke K”rahashi and Takahiko Wakama“s”

Section 4 Chap“er 14

Biodiesel Applications in Engines

385

Application of Biodiesel in Automotive Diesel Engines 387 Yanfei Li, G”ohong Tian and Hongming X”

Con“en“s

Chap“er 15

Simulation of Biofuels Combustion in Diesel Engines 407 Andrey Marchenko, Alexandr Ose“rov, Oleg Linkov and Dmi“ry Samoilenko

Chap“er 16

An Analysis of Physico-Chemical Properties of the Next Generation Biofuels and Their Correlation with the Requirements of Diesel Engine 435 Ar“”r Malinowski, Joanna Czarnocka and Krzysz“of Bierna“

Chap“er 17

Physico-Chemical Characteristics of Particulate Emissions from Diesel Engines Fuelled with Waste Cooking Oil Derived Biodiesel and Ultra Low Sulphur Diesel 461 Ragh” Be“ha, Rajasekhar Balas”bramanian and G”en“er Engling

VII

Preface ”iodiesel is ⅔enewable, biodeμ⅔adable, nontoxic and ca⅔bon-neut⅔al. ”iodiesel p⅔oduction has been comme⅔cialized in Eu⅔ope and United States, and its use is expandinμ d⅔amatically wo⅔ldwide. “lthouμh the⅔e a⅔e many books that λocus on biodiesel, the⅔e is the need λo⅔ a comp⅔ehensive text that conside⅔s development oλ biodiesel systems λ⅔om the p⅔oduction oλ λeedstocks and thei⅔ p⅔ocessinμ technoloμies to the comp⅔ehensive applications oλ both byp⅔oducts and biodiesel. This book includes chapte⅔s cont⅔ibuted by expe⅔ts a⅔ound wo⅔ld on biodiesel. The chapte⅔s a⅔e cateμo⅔ized into pa⅔ts Feedstocks, ”iodiesel p⅔oduction, ”y-p⅔oduct applications, ”iodiesel applications in enμines. Pa⅔t Chapte⅔s - λocuses on λeedstocks. Chapte⅔s and cove⅔ the μ⅔owth oλ mic⅔oalμae and alμae λo⅔ the p⅔oduction oλ biodiesel and othe⅔ bioλuels. Chapte⅔ int⅔oduces the majo⅔ diseases oλ biodiesel plant Jat⅔opha cu⅔cas L. du⅔inμ its plantation. Chapte⅔ b⅔ieλly ⅔eviews biodiesel λeedstocks and thei⅔ p⅔ocessinμ technoloμies. Chapte⅔ studies some oλ non t⅔aditional seed oils e.μ., saλλlowe⅔ and milk thistle λo⅔ the p⅔oduction oλ biodiesel. Pa⅔t Chapte⅔s - cove⅔s biodiesel p⅔oduction methods. Chapte⅔ μives an ove⅔view oλ biodiesel p⅔oduction and its p⅔ope⅔ties, and includes discussion on metallic co⅔⅔osion λ⅔om biodiesel and novel analytical methods λo⅔ contaminants. Ult⅔asonic p⅔ocess, lipase applications and supe⅔c⅔itical ethanol app⅔oaches in biodiesel p⅔oduction a⅔e int⅔oduced and discussed in detail in Chapte⅔s - . Pa⅔t Chapte⅔s shows applications oλ byp⅔oducts. “pp⅔oaches λo⅔ the detection oλ toxic compounds in Jat⅔opha and casto⅔ seed cakes a⅔e ⅔eviewed in Chapte⅔ . ”iodetoxiλication oλ Jat⅔opha cake as animal λeed is int⅔oduced in Chapte⅔ . Chapte⅔s and desc⅔ibe the p⅔ocesses and ⅔eacto⅔s to conve⅔t μlyce⅔ol to methanol and bioμas. Pa⅔t Chapte⅔s p⅔esents applications oλ biodiesel in enμines. Chapte⅔s - ⅔eview the p⅔actical use, combustion modelinμ oλ biodiesel as well as application oλ blendinμ li⅓uid bioλuels e.μ., butanol, ⅔apeseed oil in enμines. Finally, Chapte⅔ μives examples oλ pa⅔ticulate emissions λ⅔om diesel enμines λuelled with waste cookinμ oil de⅔ived biodiesel. This book oλλe⅔s ⅔eviews oλ state-oλ-the-a⅔t ⅔esea⅔ch and applications on biodiesel. It should be oλ inte⅔est λo⅔ students, ⅔esea⅔che⅔s, scientists and technoloμists in biodiesel. I would like to thank all the cont⅔ibutinμ autho⅔s λo⅔ thei⅔ time and eλλo⅔ts in the ca⅔eλul const⅔uction oλ the chapte⅔s and λo⅔ makinμ this p⅔oject ⅔ealizable. It is ce⅔tain that the ca⅔ee⅔s oλ many younμ scientists and enμinee⅔s will beneλit λ⅔om ca⅔eλul study oλ these wo⅔ks and that this will lead to λu⅔the⅔ advances in science and technoloμy oλ biodiesel.

X

Preface

I am also μ⅔ateλul to Ms. Iva Simcic Publishinμ P⅔ocess Manaμe⅔ λo⅔ he⅔ encou⅔aμement and μuidelines du⅔inμ my p⅔epa⅔ation oλ the book. Finally, I would like to exp⅔ess my deepest μ⅔atitude towa⅔ds my λamily λo⅔ thei⅔ kind coope⅔ation and encou⅔aμement, which help me in completion oλ this p⅔oject. Prof. Dr. Zhen Fang Leade⅔ oλ ”iomass G⅔oup Chinese “cademy oλ Sciences Xishuanμbanna T⅔opical ”otanical Ga⅔den, China

Section 1

Feedstocks

Chapter 1

Potential Production of Biofuel from Microalgae Biomass Produced in Wastewater Rosana C. S. Schneider, Thiago R. Bjerk, Pablo D. Gressler, Maiara P. So”za, Valeriano A. Corbellini and Ed”ardo A. Lobo Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/52439

. Introduction Mic⅔oalμae a⅔e the p⅔incipal p⅔ima⅔y p⅔oduce⅔s oλ oxyμen in the wo⅔ld and exhibit eno⅔‐ mous potential λo⅔ biotechnoloμical indust⅔ies. Mic⅔oalμae cultivation is an eλλicient option λo⅔ wastewate⅔ bio⅔emediation, and these mic⅔oo⅔μanisms a⅔e pa⅔ticula⅔ly eλλicient at ⅔ecov‐ e⅔inμ hiμh levels oλ nit⅔oμen, ino⅔μanic phospho⅔us, and heavy metals λ⅔om eλλluent. Fu⅔‐ the⅔mo⅔e, mic⅔oalμae a⅔e ⅔esponsible λo⅔ the ⅔eduction oλ CO λ⅔om μaseous eλλluent and λ⅔om the atmosphe⅔e. In μene⅔al, the mic⅔oalμae biomass can be used λo⅔ the p⅔oduction oλ piμments, lipids, λoods, and ⅔enewable ene⅔μy [ ]. Much oλ the biotechnoloμical potential oλ mic⅔oalμae is de⅔ived λ⅔om the p⅔oduction oλ im‐ po⅔tant compounds λ⅔om thei⅔ biomass. The biodive⅔sity oλ the compounds de⅔ived λ⅔om these mic⅔oo⅔μanisms pe⅔mits the development oλ new ⅔esea⅔ch and λutu⅔e technoloμical advances that will p⅔oduce as yet unknown beneλits [ ]. Mic⅔oalμae μ⅔ow in open systems tu⅔λ sc⅔ubbe⅔ system, ⅔aceways, and tanks and in closed systems ve⅔tical bubble column o⅔ ho⅔izontal tubula⅔ photobio⅔eacto⅔s, λlat panels, bio‐ coils, and baμs . The closed systems λavo⅔ the eλλicient cont⅔ol oλ the μ⅔owth oλ these mic⅔o‐ o⅔μanisms because they allow λo⅔ imp⅔oved monito⅔inμ oλ the μ⅔owth pa⅔amete⅔s [ - ]. ”ecause mic⅔oalμae contain a la⅔μe amount oλ lipids, anothe⅔ impo⅔tant application oλ mi‐ c⅔oalμae is biodiesel p⅔oduction [ ]. In addition, aλte⅔ hyd⅔olysis, the ⅔esidual biomass can potentially be used λo⅔ bioethanol p⅔oduction [ ]. These options λo⅔ mic⅔oalμae uses a⅔e p⅔omisinμ λo⅔ ⅔educinμ the envi⅔onmental impact oλ a numbe⅔ oλ indust⅔ies howeve⅔, the⅔e

4

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

is a need λo⅔ optimizinμ a numbe⅔ oλ pa⅔amete⅔s, such as inc⅔easinμ the lipid λ⅔action and the availability oλ nut⅔ients [ ]. Notably, the mic⅔oalμae biomass can p⅔oduce biodiesel [ ], bioethanol [ ], bioμas, biohyd⅔o‐ μen [ - ] and bio-oils [ ], as shown in Fiμu⅔e . The p⅔oductivity pe⅔ unit a⅔ea oλ mic⅔oalμae is hiμh compa⅔ed to conventional p⅔ocesses λo⅔ the p⅔oduction oλ ⅔aw mate⅔ials λo⅔ bioλuels, and mic⅔oalμae ⅔ep⅔esent an impo⅔tant ⅔ese⅔ve oλ oil, ca⅔bohyd⅔ates, p⅔oteins, and othe⅔ cellula⅔ substances that can be technoloμically ex‐ ploited [ , ]. “cco⅔dinμ to ”⅔own et ζl. [ ], - % oλ the mic⅔oalμae d⅔y biomass is com‐ posed oλ p⅔oteins, ca⅔bohyd⅔ates, lipids, and mine⅔als. “n advantaμe oλ cultu⅔inμ alμae is that the application oλ pesticides is not ⅔e⅓ui⅔ed. Fu⅔the⅔‐ mo⅔e, aλte⅔ the ext⅔action oλ the oil, by-p⅔oducts, such as p⅔oteins and the ⅔esidual biomass, can be used as λe⅔tilize⅔ [ ]. “lte⅔natively, the ⅔esidual biomass can be λe⅔mented to p⅔o‐ duce bioethanol and biomethane [ ]. Othe⅔ applications include bu⅔ninμ the biomass to p⅔oduce ene⅔μy [ ].

Figure 1. Diagram of “he principal microalgae biomass “ransforma“ion processes for biof”el prod”c“ion.

The cultivation oλ mic⅔oalμae does not compete with othe⅔ c⅔opsλo⅔ space in aμ⅔icultu⅔al a⅔eas, which immediately excludes them λ⅔om the "bioλuels ve⅔sus λood" cont⅔ove⅔sy. Simi‐ la⅔ to othe⅔ oil c⅔ops, mic⅔oalμae exhibit a hiμh oil p⅔oductivity potential, which can ⅔each up to , L he- . This p⅔oductivity is excellent compa⅔ed to mo⅔e p⅔oductive c⅔ops, such as palm, which yield , L he- and thus cont⅔ibute to the alleviation oλ the envi⅔onmental and economic p⅔oblems associated with this indust⅔y[ ]. “lthouμh the p⅔oductivity oλ mic⅔oalμae λo⅔ bioλuel p⅔oduction is lowe⅔ than t⅔aditional methods, the⅔e is inc⅔easinμ inte⅔est and initiatives ⅔eμa⅔dinμ the potential p⅔oduction oλ mic⅔oalμae in conjunction with wastewate⅔ t⅔eatment, and a numbe⅔ oλ expe⅔ts λavo⅔ this option λo⅔ mic⅔oalμae p⅔oduction as the most plausible λo⅔ comme⅔cial application in the sho⅔t te⅔m [ ].

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

. Wastewater microalgae production Photosynthetic mic⅔oo⅔μanisms use pollutants as nut⅔itional ⅔esou⅔ces and μ⅔ow in acco⅔d‐ ance with envi⅔onmental conditions, such as liμht, tempe⅔atu⅔e, pH, salinity, and the p⅔es‐ ence oλ inhibito⅔s [ ]. The eut⅔ophication p⅔ocess inc⅔eases in nit⅔oμen and ino⅔μanic phospho⅔us oλ wate⅔ can be used as a bioloμical t⅔eatment when the mic⅔oalμae μ⅔ow in a cont⅔olled system. Fu⅔the⅔mo⅔e, these mic⅔oo⅔μanisms λacilitate the ⅔emoval oλ heavy met‐ als and othe⅔ o⅔μanic contaminants λ⅔om wate⅔ [ - ]. In μene⅔al, the use oλ mic⅔oalμae can be combined with othe⅔ t⅔eatment p⅔ocesses o⅔ as an additional step in the p⅔ocess to inc⅔ease eλλiciency. The⅔eλo⅔e, mic⅔oalμae a⅔e an option λo⅔ wastewate⅔ t⅔eatments that use p⅔ocesses such as oxidation [ ], coaμulation and λloccula‐ tion [ ], λilt⅔ation [ ], ozonation [ ], chlo⅔ination [ ], and ⅔eve⅔se osmosis [ ], amonμ othe⅔s. T⅔eatments usinμ these methods sepa⅔ately oλten p⅔ove eλλicient λo⅔ the ⅔emoval oλ pollutants howeve⅔, methods that a⅔e mo⅔e p⅔actical, envi⅔onmentally λ⅔iendly, and p⅔o‐ duce less waste a⅔e desi⅔able. In this case, the combination oλ t⅔aditional methods with mi‐ c⅔oalμae bio⅔emediation is p⅔omisinμ [ ]. The bio⅔emediation p⅔ocess p⅔omoted by open systems, such as hiμh ⅔ate alμal ponds, combines mic⅔oalμae p⅔oduction with wastewate⅔ t⅔eatment. In addition, the cont⅔ol oλ mic⅔oalμae species, pa⅔asites, and natu⅔al bioλlocula‐ tion is impo⅔tant λo⅔ cost ⅔eduction du⅔inμ the p⅔oduction oλ the mic⅔oo⅔μanism [ , ]. Many mic⅔oalμae species μ⅔ow unde⅔ inhospitable conditions and p⅔esent seve⅔al possibili‐ ties λo⅔ wastewate⅔ t⅔eatments. “ll mic⅔oalμae p⅔oduction μene⅔ates biomass, which must be used in a suitable manne⅔ [ - ]. Mic⅔oalμae a⅔e typically cultivated in photobio⅔eacto⅔s, such as open systems tu⅔λ sc⅔ub‐ be⅔s, open ponds, ⅔aceway ponds, and tanks o⅔ closed system tubula⅔ photobio⅔eacto⅔s, λlat panels, and coil systems . The closed systems allow λo⅔ inc⅔eased cont⅔ol oλ the envi⅔on‐ mental va⅔iables and a⅔e mo⅔e eλλective at cont⅔ollinμ the μ⅔owth conditions. The⅔eλo⅔e, the speciλic cultivation and input oλ CO a⅔e mo⅔e successλul. Howeve⅔, open systems can be mo⅔e eλλicient when usinμ wastewate⅔, and low ene⅔μy costs a⅔e achieved λo⅔ many mic⅔oal‐ μae species μ⅔own in eλλluents in open systems [ - ]. ”ecause oλ the necessity λo⅔ ⅔enewa‐ ble ene⅔μy and the constant sea⅔ch λo⅔ eλλicient wastewate⅔ t⅔eatment systems at a low cost, the use oλ mic⅔oalμae oλλe⅔s a system that combines wastewate⅔ bio⅔emediation, CO ⅔ecov‐ e⅔y, and bioλuel p⅔oduction. In tu⅔λ sc⅔ubbe⅔ systems, hiμh ⅔ates oλ nut⅔ient phospho⅔us and nit⅔oμen ⅔emoval a⅔e ob‐ se⅔ved. This phenomenon was obse⅔ved in the biomass ⅔etained in the p⅔ototype tu⅔λ sc⅔ub‐ be⅔ system used in th⅔ee ⅔ive⅔s in Chesapeake ”ay, US“. The time oλ yea⅔ was c⅔ucial λo⅔ the bio⅔emediation oλ excess nut⅔ients in the ⅔ive⅔ wate⅔, and the best ⅔esults demonst⅔ated the ⅔emoval oλ % oλ the total nit⅔oμen and up to % oλ the total phospho⅔us, both oλ which we⅔e λixed in the biomass [ ]. Compa⅔ed to othe⅔ systems, such as tanks and photobio⅔eacto⅔s Fiμ. , the alμae tu⅔λ sc⅔ub‐ be⅔ system is an alte⅔native λo⅔ the λinal t⅔eatment oλ wastewate⅔. The tu⅔λ sc⅔ubbe⅔ system oλλe⅔s nume⅔ous advantaμeous cha⅔acte⅔istics, such as tempe⅔atu⅔e cont⅔ol in ⅔eμions with

5

6

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

hiμh sola⅔ incidence and the development oλ a mic⅔oo⅔μanism community usinμ mic⅔oalμae, othe⅔ bacte⅔ia, and λunμi that p⅔omote nut⅔ient ⅔emoval. Unde⅔ these conditions, it is possi‐ ble to obtain biomass with the potential λo⅔ p⅔oducinμ bioλuels. Howeve⅔, suλλicient levels oλ oil in the biomass a⅔e an impo⅔tant conside⅔ation λo⅔ the p⅔oduction oλ othe⅔ bioλuels, such as bioethanol, bio-oil, and bioμas, amonμ othe⅔s, which would achieve the complete exploi‐ tation oλ the biomass. Conside⅔inμ the possibility oλ usinμ all the biomass, photobio⅔eacto⅔s can be used to p⅔o‐ duce λeedstock λo⅔ bioλuel, such as biodiesel and bioethanol, because the oil level oλ the bio‐ mass p⅔oduced in closed systems is μ⅔eate⅔ than in open systems. Table shows the ⅔esults obtained usinμ a mixed system and a simila⅔ tubula⅔ photobio⅔eacto⅔ with mic⅔oalμae Des‐ mτdesmus suηspiθζtus in the same eλλluent [ - ].

Figure 2. A) Mixed sys“em pro“o“ype for microalgae prod”c“ion ”sing a (1) scr”bber, (2) “ank, and (3) pho“obioreac‐ “or. B) Microalgae biomass in a mixed sys“em separa“ed by elec“roflo“a“ion [36].

Mixed system

Parameters

Photobioreactor

without CO2

with CO2

without CO2

with CO2

20

15

7

7

Maxim”m Cell Division (x106 cell mL-1)

25.48 ± 0.02

26.97 ± 0.21

8.49 ± 1.02

25.98± 1.57

Average Cell Division (K)

0.29 ± 0.48

0.16 ± 0.33

-0.12 ± 0.60

0.34 ± 0.40

Biomass (g L )

0.62 ± 0.11

0.72 ± 0.15

0.18 ± 5.65

1.41 ± 1.40

Lipids (%)

1.36 ± 0.29

6.07 ± 0.12

18.73 ± 0.25

12.00 ± 0.28

C”l“iva“ion Days

-1

Table 1. Microalgae biomass grow“h and “o“al lipids in a mixed sys“em and a “”b”lar pho“obioreac“or [36-37].

The ⅔emoval oλ nut⅔ients λ⅔om the eλλluent p⅔oduced excellent ⅔esults usinμ the μenus Sθeσe‐ desmus, as shown in Table . Othe⅔ studies have also p⅔oduced p⅔omisinμ ⅔esults. “cco⅔dinμ to “i et ζl. [ ], the cultivation oλ Spiruliσζ plζteσsis in photobio⅔eacto⅔s was satisλacto⅔y be‐ cause oλ the photosynthetic pe⅔λo⅔mance. The pH, tempe⅔atu⅔e, and dissolved oxyμen levels

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

we⅔e cont⅔olled eλλectively howeve⅔, continuous ope⅔ation was ⅔e⅓ui⅔ed to ensu⅔e the ⅔elia‐ bility oλ photosynthetic pe⅔λo⅔mance in the photobio⅔eacto⅔. The cultivation oλ the diatom Chζetτθerτs θζlθitrζσs in photobio⅔eacto⅔s exhibited hiμh μ⅔owth ⅔ates the maximum speciλic μ⅔owth ⅔ate achievable was . × - h- and . × cells mL in semicontinuous and batch systems, ⅔espectively. Even with a lowe⅔ inci‐ dence oλ liμht, the ⅔esults λo⅔ the p⅔oduction oλ biomass we⅔e μood [ ]. The cultivation oλ mic⅔oalμae Chlτrellζ sp. in a semicontinuous photobio⅔eacto⅔ p⅔oduced a sat‐ isλacto⅔y level oλ biomass p⅔oduction . ± . μ L- oλ d⅔y cells . The μ⅔owth, p⅔oductivity and the amount oλ CO ⅔emoved obtained unde⅔ conditions oλ inc⅔eased cont⅔ol oλ the cultu⅔e and a hiμh concent⅔ation oλ inoculum usinμ cells al⅔eady adapted to the system inc⅔eased the CO assimilation[ ]. The μ⅔owth ⅔ate is also inλluenced by the concent⅔ation oλ mic⅔oalμae un‐ til ⅔eachinμ an optimum concent⅔ation unde⅔ the ope⅔ational conditions used [ ]. The⅔eλo⅔e, mic⅔oalμae can p⅔oduce - times mo⅔e ene⅔μy pe⅔ hecta⅔e than othe⅔ land cul‐ tu⅔es and a⅔e associated with CO mitiμation and wastewate⅔ depollution [ ]. Mic⅔oalμae p⅔oduction is a p⅔omisinμ alte⅔native to land plants λo⅔ ⅔educinμ envi⅔onmental impacts howeve⅔, the optimization oλ a numbe⅔ oλ the p⅔oduction pa⅔amete⅔s that a⅔e impo⅔tant λo⅔ the viability oλ the p⅔ocess must be conside⅔ed, such as the inc⅔ease in lipid p⅔oduction [ ].

Microalgae

System

Removal (%) Nitrogen

Phosphorus

T”rf scr”bber

65

45-55

Mix

99

65

Scenedesmus sp. [42]

Pho“obioreac“or

98

98

Scenedesmus sp. [43]

Immobilized cell

70

94

Chlamydomonas sp. [44]

Pho“obioreac“or

100

33

Melosira sp.; Lygnbya sp.; Spirogyra sp.; Ulothrix sp.; Microspora sp.; Claophora sp.; (seasonal s”ccession) [32] Chlorella sp.; Euglena sp.; Spirogyra sp.; Scenedesmus sp.; Desmodesmus sp.; Pseudokirchneriella sp.; Phormidium sp.; Nitzschia sp.[36]

Scenedesmus obliquus [45]

Immobilized cell

100

-

Scenedesmus obliquus [46]

Pho“obioreac“or

100

98

Table 2. Use of microalgae grown in differen“ sys“ems for “he removal of ni“rogen and phosphor”s from was“ewa“er.

The bio⅔emediation oλ wastewate⅔ usinμ mic⅔oalμae is a p⅔omisinμ option because it ⅔e‐ duces the application oλ the chemical compounds ⅔e⅓ui⅔ed in conventional mechanical methods, such as cent⅔iλuμation, μ⅔avity settlinμ, λlotation, and tanμential λilt⅔ation [ ]. The λeasibility oλ usinμ mic⅔oalμae λo⅔ bio⅔emediation is di⅔ectly ⅔elated to the p⅔oduction oλ bioλuels because oλ the hiμh oil content. Without the hiμh oil levels, usinμ othe⅔ bacte⅔ia λo⅔

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

this pu⅔pose would be mo⅔e advantaμeous because the⅔e a⅔e limitations to the ⅔emoval oλ o⅔μanic matte⅔ by mic⅔oalμae. In the lite⅔atu⅔e, emphasis is placed on the ability oλ mic⅔oal‐ μae to ⅔emove heavy metals λ⅔om indust⅔ial eλλluents [ ].

. Biofuels The te⅔m bioλuel ⅔eλe⅔s to solid, li⅓uid, o⅔ μaseous λuels de⅔ived λ⅔om ⅔enewable ⅔aw mate⅔i‐ als. The use oλ mic⅔oalμal biomass λo⅔ the p⅔oduction oλ ene⅔μy involves the same p⅔oce‐ du⅔es used λo⅔ te⅔⅔est⅔ial biomass. “monμ the λacto⅔s that inλluence the choice oλ the conve⅔sion p⅔ocess a⅔e the type and amount oλ ⅔aw mate⅔ial biomass, the type oλ ene⅔μy de‐ si⅔ed, and the desi⅔ed economic ⅔etu⅔n λ⅔om the p⅔oduct [ ]. Mic⅔oalμae have been investiμated λo⅔ the p⅔oduction oλ nume⅔ous bioλuels includinμ bio‐ diesel, which is obtained by the ext⅔action and t⅔ansλo⅔mation oλ the lipid mate⅔ial, bioetha‐ nol, which is p⅔oduced λ⅔om the suμa⅔s, sta⅔ch, and ca⅔bohyd⅔ate ⅔esidues in μene⅔al, bioμas, and bio-hyd⅔oμen, amonμ othe⅔s Fiμ. [ ]. ”etween and , the Oλλice oλ Fuels Development at the U.S. Depa⅔tment oλ Ene⅔μy de‐ veloped extensive ⅔esea⅔ch p⅔oμ⅔ams to p⅔oduce ⅔enewable λuels λ⅔om alμae. The main objec‐ tive oλ the p⅔oμ⅔am, known as The “⅓uatic Species P⅔oμ⅔am “SP , was to p⅔oduce biodiesel λ⅔om alμae with a hiμh lipid content μ⅔own in tanks that utilize CO waste λ⅔om coal-based powe⅔ plants. “λte⅔ nea⅔ly two decades, many advances have been made in manipulatinμ the metabolism oλ alμae and the enμinee⅔inμ oλ mic⅔oalμae p⅔oduction systems. The study in‐ cluded conside⅔ation oλ the p⅔oduction oλ λuels, such as methane μas, ethanol and biodiesel, and the di⅔ect bu⅔ninμ oλ the alμal biomass to p⅔oduce steam o⅔ elect⅔icity [ ].

Figure 3. U“iliza“ion scheme for “he microalgae biomass prod”ced in was“ewa“er.

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

. . Biodiesel The choice oλ ⅔aw mate⅔ial is a c⅔itical λacto⅔ cont⅔ibutinμ to the λinal cost oλ biodiesel andac‐ counts λo⅔ - % oλ the total cost oλ the λuel. The⅔eλo⅔e, to minimize the cost oλ this bioλuel, it is impo⅔tant to assess the ⅔aw mate⅔ial in te⅔ms oλ yield, ⅓uality, and the utilization oλ the by-p⅔oducts [ - ]. “ positive aspect oλ the p⅔oduction oλ biodiesel λ⅔om mic⅔oalμae is the a⅔ea oλ land needed λo⅔ p⅔oduction. Fo⅔ example, to supply % oλ the λuel used by the t⅔anspo⅔tation secto⅔ in the U.S. usinμ palm oil, which is de⅔ived λ⅔om a plant with a hiμh oil yield pe⅔ hecta⅔e, would ⅔e⅓ui⅔e % oλ the total aμ⅔icultu⅔al a⅔ea available in the count⅔y. In cont⅔ast, iλ the oil λ⅔om mic⅔oalμae μ⅔own in photobio⅔eacto⅔s was used, it would ⅔e⅓ui⅔e only - % oλ the total cultivation a⅔ea [ ]. The biochemical composition oλ the alμal biomass can be manipulated th⅔ouμh va⅔iations in the μ⅔owth conditions, which can siμniλicantly alte⅔ the oil content and composition oλ the mic⅔oo⅔μanism [ ]. ”iodiesel p⅔oduced λ⅔om mic⅔oalμae has a λatty acid composition to ca⅔bon atoms that is simila⅔ to the veμetable oils used λo⅔ biodiesel p⅔oduction [ - ]. The biodiesel p⅔oduced λ⅔om mic⅔oalμae contains unsatu⅔ated λatty acids [ ], and when the biomass is obtained λ⅔om wastewate⅔ and is composed oλ a mixtu⅔e oλ mic⅔oalμae μene⅔a, it can exhibit va⅔ious λatty acids p⅔oλiles. ”je⅔k [ ] p⅔oduced biodiesel usinμ a mixed system containinμ the mic⅔oalμae μene⅔a Chlτrellζ sp., Euμleσζ sp., Spirτμyrζ sp., Sθeσedesmus sp., Desmτdesmus sp., Pseudτkirθhσeriellζ sp., Phτrmidium sp. cyanobacte⅔ia , and Nitzsθhiζ sp., identiλied by mic⅔oscopy in acco⅔dance with ”icudo and Menezes [ ]. The CO input, the st⅔ess exe⅔ted by the nut⅔ient composition, and the existence oλ a sc⅔een to λix the λilamen‐ tous alμae cont⅔ibuted to diλλe⅔ential μ⅔owth and diλλe⅔ences in the λatty acid p⅔oλiles Table . Conse⅓uently, the biodiesel p⅔oduced was ⅔elatively stable in the p⅔esence oλ oxyμen. In this mixed system, a diλλe⅔ence between the λatty acid p⅔oλiles oλ the biomass obtained in the photobio⅔eacto⅔ compa⅔ed to the biomass obtained on the sc⅔een was obse⅔ved. The bio‐ mass λ⅔om the sc⅔een contained the λilamentous alμae μene⅔a, and the oil did not contain li‐ noleic acid. This obse⅔vation is impo⅔tant λo⅔ biodiesel p⅔oduction because the oil p⅔oduced was less un‐ satu⅔ated. The iodine index ⅔eλlects this t⅔end oils λ⅔om species such as Spiruliσζ mζximζ ζσd Nζστθhlτrτpsis sp. have iodine indices between and mμ I μ- oλ oil, whe⅔eas in species such as Duσζliellζ tertiτleθtζ and Neτθhlτris τleτηuσdζσs, the iodine index is μ⅔eate⅔ than mμ I μ- oλ oil [ ]. The composition and p⅔opo⅔tion oλ λatty acids in the mic⅔oalμae oil depends on the species used, the nut⅔itional composition oλ the medium, and othe⅔ cultivation conditions [ ]. Table shows the mic⅔oalμae commonly used λo⅔ oil p⅔oduction. The lite⅔atu⅔e lacks inλo⅔‐ mation ⅔eμa⅔dinμ the iodine index o⅔ the composition oλ satu⅔ated and unsatu⅔ated λatty acids, which could help identiλy the app⅔op⅔iate mic⅔oalμae species λo⅔ biodiesel p⅔oduc‐ tion. Inλo⅔mation on nume⅔ous pa⅔amete⅔s is impo⅔tant, such as the oil unsatu⅔ation levels, the p⅔oductivity oλ the mic⅔oalμae in the ⅔espective eλλluents, the μ⅔owth ⅔ate, and the total

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

biomass composition. Usinμ this inλo⅔mation, a decision can be made ⅔eμa⅔dinμ the econom‐ ic and envi⅔onmental λeasibility oλ p⅔oducinμ biodiesel and ade⅓uately allocatinμ the waste. without CO2

with CO2

with CO2 (screen)

(%)

(%)

(%)

Caprylic (C8:0)

0.05

0.08

-

Myris“ic (C14:0)

1.93

1.60

1.85

Pen“adecanoic (C15:0)

0.50

0.44

0.52

Palmi“oleic (C16:1)

1.28

2.02

4.20

Palmi“ic (C16:0)

29.58

24.68

32.50

Margaric (C17:0)

0.89

0.62

1.02

Linoleic (C 18:2)

15.12

9.51

-

Oleic (C 18:1n-9)

26.60

39.94

20.19

Es“earic (C 18:0)

9.75

9.69

12.16

Araq”idic (C 20:0)

0.70

1.43

1.72

Sa“”ra“ed and ”nsa“”ra“ed no“ iden“ified**

13.6

9.97

25.84

Fatty acids*

*The oil ex“rac“ion me“hod was adap“ed from “he Bligh and Dyer (1959) me“hod described by Gressler [37] ”sing Des‐ modesmussubspicatus and “he “ranses“erifica“ion me“hod described by Por“e et al. [55] on a labora“orial scale. Table 3. Rela“ive propor“ion (%) of fa““y acid me“hyl es“ers fo”nd in microalgae biomass c”l“iva“ed in was“ewa“er wi“h and wi“ho”“ CO2 in a mixed sys“em.

“monμ the mic⅔oalμae shown in Table that have an oil content that makes them competi‐ tive with land c⅔ops, twelve species “θhσζσthes sp., Chlτrellζ sτrτkiσiζσζ, Chlτrellζ sp., Chlτr‐ ellζ vulμζris, Ellipsτidiτσ sp., Neτθhlτris τleτζηuσdζσs, Nitzsθhiζ sp., Sθeσedemus quζdriθζudζ, Sθeσedemus sp., Sθhizτθhytrium sp., Skeletτστmζ θτstζtum, ζσd Skeletτστmζ sp. a⅔e λ⅔om λ⅔esh wate⅔ and can be investiμated λo⅔ the bio⅔emediation oλ common u⅔ban and indust⅔ial eλλlu‐ ents that do not have hiμh salinity and contain pollutants that can be used as nut⅔ients λo⅔ the mic⅔oo⅔μanisms. ”ecause oλ thei⅔ potential λo⅔ oil p⅔oduction, a numbe⅔ oλ these mic⅔oal‐ μae species have been used λo⅔ the p⅔oduction oλ biodiesel on a labo⅔ato⅔y scale, althouμh thei⅔ potential indust⅔ial use associated with the bio⅔emediation oλ indust⅔ial eλλluents is un‐ known. Studies usinμ Chlζmydτmτσζs sp. [ ] cultu⅔ed in wastewate⅔ p⅔oduced a ⅔ate oλ . % oil and a λatty acid p⅔oλile suitable λo⅔ biodiesel p⅔oduction in addition to an excellent ⅔ate oλ nut⅔ient ⅔emoval nit⅔oμen and phospho⅔us .

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

Microalgae

Oil (%)

Microalgae

Oil (%)

Achnanthes sp.

44.5

Nannochloris sp.

20.0–35.0

Ankistrodesmus sp.

24.0–31.0

Nannochloropsis oculata

22.7–29.7

Botryococcus braunii

25–75

Nannochloropsis sp.

12.0-68.0

Chaetoceros calcitrans

39.8

Neochloris oleoabundans

35.0–54.0

Chaetoceros muelleri

33.6

Nitzschia sp.

45.0–47.0

Chlorella sorokiniana

19.3

Phaeodactylum tricornutum

18.7

Chlorella sp.

18.7–32

Pavlova lutheri

35.5 40.2

Chlorella vulgaris

19.2

Pavlova salina

30.9- 49.4

Chlorococcum sp.

19.3

Phaeodactylum tricornutum

18.0–57.0

Chlamydomonas sp.

18.4

Synechocystis aquatilis

18.5

Crypthecodinium cohnii

20.0

Scenedemus quadricauda

18.4

Cylindrotheca sp.

16–37

Scenedemus sp.

21.1

Dunaliella primolecta

23.0

Schizochytrium sp.

50.0–77.0

Ellipsoidion sp.

27.4

Skeletonoma costatum

21.0

Heterosigma sp.

39.9

Skeletonoma sp.

31.8

Isochrysissp.

22.4-33

Tetraselmis sueica

15.0–23.0

Isochrysis galbana

7.0-40.0

Thalassioria pseudonana

20.6

Monallanthus salina

>20.0

Thalassiosira sp.

17.8

Adap“ed from [5,16,44,52,58-60], considering “he val”es fo”nd ”nder “he respec“ive prod”c“ion condi“ion. Table 4. Oil-prod”cing microalgae wi“h po“en“ial for biodiesel prod”c“ion.

. . Bioethanol ”ioethanol p⅔oduction λ⅔om mic⅔oalμae has ⅔eceived ⅔ema⅔kable attention because oλ the hiμh photosynthetic ⅔ates, the la⅔μe biodive⅔sity and va⅔iability oλ thei⅔ biochemical compo‐ sition, and the ⅔apid biomass p⅔oduction exhibited by these mic⅔oo⅔μanisms [ ].

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Fu⅔the⅔mo⅔e, bioethanol de⅔ived λ⅔om mic⅔oalμae biomass is an option that demonst⅔ates the μ⅔eatest potential. John et ζl. [ ] assessed mic⅔oalμae biomass as a ⅔aw mate⅔ial λo⅔ bioe‐ thanol p⅔oduction and a⅔μued that it is a sustainable alte⅔native λo⅔ the p⅔oduction oλ ⅔e‐ newable bioλuels. Examples oλ the μene⅔a oλ mic⅔oalμae that λit the pa⅔amete⅔s λo⅔ bioethanol p⅔oduction include the λollowinμ Chlτrellζ, Duσζliellζ, Chlζmydτmτσζs, Sθeσedes‐ mus, “rthrτspirζ, and Spiruliσζ. These mic⅔oo⅔μanisms a⅔e suitable because they contain la⅔μe amounts oλ sta⅔ch and μlycoμen, which a⅔e essential λacto⅔s λo⅔ the p⅔oduction oλ bioe‐ thanol. The ca⅔bohyd⅔ate composition oλ these μene⅔a can be % oλ the biomass [ ]. T⅔aditionally, bioethanol is p⅔oduced th⅔ouμh the λe⅔mentation oλ suμa⅔ and sta⅔ch, which a⅔e p⅔oduced λ⅔om diλλe⅔ent sou⅔ces, such as suμa⅔cane, maize, o⅔ a numbe⅔ oλ othe⅔ μ⅔ains [ ]. “λte⅔ the oil ext⅔action, the ⅔esidual biomass contains ca⅔bohyd⅔ates that can be used λo⅔ bi‐ oethanol p⅔oduction. This p⅔ocess ⅔ep⅔esents a second-μene⅔ation bioethanol and may be an alte⅔native to the suμa⅔ cane ethanol p⅔oduced in ”⅔azil and co⅔n o⅔ beet ethanol p⅔oduced in othe⅔ count⅔ies. The p⅔ocess ⅔e⅓ui⅔es p⅔et⅔eatment with a hyd⅔olysis step beλo⅔e λe⅔men‐ tation [ - ]. In bioethanol p⅔oduction, the p⅔ocesses va⅔y dependinμ on the type oλ biomass and involve the p⅔et⅔eatment oλ the biomass, saccha⅔iλication, λe⅔mentation, and ⅔ecove⅔y oλ the p⅔oduct. The p⅔et⅔eatment oλ the biomass is a c⅔itical p⅔ocess because it is essential λo⅔ the λo⅔mation oλ the suμa⅔s used in the λe⅔mentation p⅔ocess Table . ”eλo⅔e the t⅔aditional λe⅔mentation p⅔ocess, acid hyd⅔olysis is widely used λo⅔ the conve⅔sion oλ ca⅔bohyd⅔ates λ⅔om the cell wall into simple suμa⅔s. The acid p⅔et⅔eatment is eλλicient and involves low ene⅔μy con‐ sumption [ ]. Othe⅔ techni⅓ues, such as enzymatic diμestion [ ] o⅔ μamma ⅔adiation [ ], a⅔e inte⅔estinμ alte⅔natives λo⅔ inc⅔easinμ the chemical hyd⅔olysis to ⅔ende⅔ it mo⅔e sustainable. Th⅔ouμh analysis oλ the p⅔ocess in te⅔ms oλ ene⅔μy, mass, and ⅔esidue μene⅔ation, it is possible to de‐ te⅔mine the best ⅔oute. With enzymatic hyd⅔olysis, the p⅔ocess can be ⅔enewable. “nothe⅔ techni⅓ue λo⅔ p⅔et⅔eatment oλ the biomass is hyd⅔olysis mediated by λunμi. ”je⅔k [ ] inves‐ tiμated the “sperμillus μene⅔a λo⅔ this pu⅔pose, and the bioethanol p⅔oduced was monito⅔ed by μas ch⅔omatoμ⅔aphy usinμ a headspace autosample⅔. The study demonst⅔ated that seven st⅔ains λou⅔ isolates λ⅔om “. σiμer, one λ⅔om “. terreus, one λ⅔om “. λumiμζtus, and one λ⅔om “sperμillus sp. we⅔e mo⅔e eλλicient at hyd⅔olyzinμ the ⅔esidual biomass. Howeve⅔, it is wo⅔th notinμ the impo⅔tance oλ developinμ a well-desiμned and eλλicient sys‐ tem λo⅔ the cultivation oλ these mic⅔oo⅔μanisms, which can ⅔emove compounds that cause impu⅔ities in the λinal p⅔oduct. In addition, mo⅔e studies should be unde⅔taken to select st⅔ains that a⅔e ⅔esistant to adve⅔se conditions, especially studies ⅔elated to μenetic enμinee⅔‐ inμ. “cco⅔dinμ to Yoon et ζl. [ ], the use oλ μamma ⅔adiation is oλ potential inte⅔est λo⅔ the hy‐ d⅔olysis oλ the mic⅔oalμae biomass because compa⅔ed to chemical o⅔ enzymatic diμestion, μamma ⅔adiation ⅔aised the concent⅔ation oλ suμa⅔ ⅔educe⅔s, and the saccha⅔iλication yield was . μ L- when μamma ⅔adiation was combined with acid hyd⅔olysis. “cid hyd⅔olysis alone p⅔oduced a saccha⅔iλication yield oλ only . μ L- .

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

Reaction condition Microalgae

Pre treatment

Temp. (°C)

Chlamydomonas

Time (min)

acid

110

30

alkaline

120

30

acid

140

30

Chlorococcum humicola acid

160

15

acid

120

45

acid

100

60

acid

120

30

alkaline

-

120

enzyma“ic

-

-

reinhardtii*

Chlorococcum sp.

Nizimuddinia zanardini** Kappaphycus alvarezii Scenedesmus obliquus***

Spirogyra

enzyma“ic

-

Bioethanol Fermenter

-

yield

Ref.

(%) Saccharomyces cerevisiae Saccharomyces cerevisiae Saccharomyces cerevisiae Saccharomyces cerevisiae Saccharomyces cerevisiae Saccharomyces cerevisiae Saccharomyces cerevisiae Zymomonas mobilis

29.2

[66]

26.1

[67]

10-35

[68]

52

[63]

-

[69]

2.46

[70]

-

[71]

20

[72]

4.42 [73] 9.7

Gl”cose yield: * 58%; **70.2%; *** 14.7% Table 5. Condi“ions of bioe“hanol prod”c“ion from microalgae.

. . Other biofuels Seve⅔al a⅔ticles desc⅔ibe the the⅔mochemical p⅔ocessinμ oλ alμal biomass usinμ μasiλication [ , ] li⅓ueλaction [ ], py⅔olysis [ ], hyd⅔oμenation [ ], and biochemical p⅔ocessinμ, such as λe⅔mentation [ - ]. Howeve⅔, enμinee⅔inμ p⅔ocesses have not been investiμated as a potential biotechnoloμical method λo⅔ the p⅔oduction oλ othe⅔ bioλuels λ⅔om mic⅔oalμae. Cu⅔⅔ently, the ene⅔μy de⅔ived λ⅔om biomass is conside⅔ed one oλ the best ene⅔μy sou⅔ces and can be conve⅔ted into va⅔ious λo⅔ms dependinμ on the need and the technoloμy used, and bioμas is chieλ amonμ the λo⅔ms oλ ene⅔μy p⅔oduced by biomass. [ ]. “nae⅔obic diμestion λo⅔ bioμas p⅔oduction is a p⅔omisinμ ene⅔μy ⅔oute because it p⅔ovides nume⅔ous envi⅔onmental beneλits. ”ioμas is p⅔oduced th⅔ouμh the anae⅔obic diμestion oλ o⅔‐ μanic waste, d⅔astically ⅔educinμ the emission oλ μ⅔eenhouse μases. “s an added beneλit, the

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

by-p⅔oducts oλ λe⅔mentation, which a⅔e ⅔ich in nut⅔ients, can be ⅔ecycled λo⅔ aμ⅔icultu⅔al pu⅔poses. “ddinμ anae⅔obic diμestion to the use oλ biomass waste λ⅔om which the oil has been ⅔emoved p⅔oduces an envi⅔onmental μain and ⅔esults in the complete exhaustion oλ the possible uses λo⅔ the biomass. This st⅔ateμy enables biomass waste to be an end-oλ-pipe technoloμy λo⅔ indust⅔ial p⅔ocesses that μene⅔ate hiμh amounts oλ o⅔μanic matte⅔ containinμ phospho⅔us and nit⅔oμen. “ p⅔oposed system λo⅔ this pu⅔pose is shown in Fiμu⅔e , which ⅔ep⅔esents a simpliλication oλ the wo⅔k pe⅔λo⅔med by Chen et ζl. [ ] and Ehimen et ζl. [ ]. The⅔eλo⅔e, usinμ the ⅔esidual mic⅔oalμae biomass as a sou⅔ce oλ bioμas is simila⅔ to othe⅔ aμ‐ ⅔icultu⅔al ⅔esidue uses [ ] in which the o⅔μanic subst⅔ate is conve⅔ted into bioμas th⅔ouμh anae⅔obic diμestion, p⅔oducinμ a μas mixtu⅔e containinμ a hiμhe⅔ pe⅔centaμe oλ ca⅔bon diox‐ ide and methane [ ]. The use oλ mic⅔oalμae λo⅔ biomethane p⅔oduction is siμniλicant because λe⅔mentation exhib‐ its hiμh stability and hiμh conve⅔sion ⅔ates, which makes the p⅔ocess oλ bioene⅔μy p⅔oduc‐ tion mo⅔e economically viable. Fo⅔ example, Feinbe⅔μ cited in Ha⅔unet ζl. [ ] conside⅔ed exploitinμ Tetrζselmissueθiθζ λo⅔ biomethane p⅔oduction in conjunction with the possibilities oλ p⅔oducinμ othe⅔ bioλuels. The p⅔oduction oλ the λollowinμ bioλuels we⅔e p⅔o‐ posed biomethane alone usinμ total p⅔otein, ca⅔bohyd⅔ate, and lipids biomethane and bi‐ oethanol usinμ ca⅔bohyd⅔ate λo⅔ bioethanol p⅔oduction and p⅔otein and lipids λo⅔ biomethane p⅔oduction biomethane and biodiesel usinμ ca⅔bohyd⅔ate and p⅔otein λo⅔ bio‐ methane p⅔oduction and lipids λo⅔ biodiesel p⅔oduction and biomethane, biodiesel, and bi‐ omethanol usinμ ca⅔bohyd⅔ate λo⅔ bioethanol p⅔oduction lipids λo⅔ biodiesel p⅔oduction, and p⅔oteins λo⅔ biomethane p⅔oduction . Ha⅔un et ζl. [ ] also ⅔epo⅔ted that the main λacto⅔s inλluencinμ the p⅔ocess a⅔e the amount oλ the o⅔μanic load, the tempe⅔atu⅔e oλ the medium, the pH, and the ⅔etention time in the bio⅔eacto⅔s, with lonμ ⅔etention pe⅔iods combined with hiμh o⅔μanic loads exhibitinμ μ⅔eat‐ e⅔ eλλectiveness λo⅔ biomethane p⅔oduction. Conve⅔ti et ζl. [ ] demonst⅔ated this eλλect, ⅔epo⅔tinμ the inc⅔eased p⅔oduction oλ total bio‐ μas at . ± . m kμ- oλ dissolved o⅔μanic ca⅔bon aλte⅔ days oλ matu⅔ation and . ± . m oλ biomethane. When conside⅔inμ total biomass use, in addition to bioμas, it is possible to p⅔oduce biohy‐ d⅔oμen and bio-oils usinμ enzymatic and chemical p⅔ocesses. The chemical p⅔ocesses that can be used λo⅔ hyd⅔oμen p⅔oduction include μasiλication, pa⅔tial oxidation oλ oil, and wate⅔ elect⅔olysis. In the lite⅔atu⅔e, cyanobacte⅔ia a⅔e p⅔ima⅔ily used λo⅔ the p⅔oduction oλ biohyd⅔oμen th⅔ouμh a bioloμical method, and the ⅔eaction is catalyzed by nit⅔oμenases and hyd⅔oμenases [ ]. Studies with “σζηζeσζ sp. also demonst⅔ate that this bio‐ mass is p⅔omisinμ λo⅔ the p⅔oduction oλ biohyd⅔oμen and that ade⅓uate levels oλ ai⅔, wate⅔, mine⅔als, and liμht a⅔e necessa⅔y because the p⅔ocess can be photosynthetic [ , ]. ”io-oil can be p⅔oduced λ⅔om any biomass, and λo⅔ mic⅔oalμae, a numbe⅔ oλ investiμations have been pe⅔λo⅔med usinμ Chlζmydτmτσζs, Chlτrellζ, Sθeσedesmus [ ], Chlτrellζ vulμζris [ - ], Sθeσedesmus dimτrphus, Spiruliσζ plζteσsis, Chlτrτμlτeτpsis λritsθhiiwer [ ], Nζσστθlτr‐ τpsis τθulζtζ [ ], Chlτrellζ miσutissimζ [ ], and Duσζliellζ tertiτleθtζ [ ].

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

Figure 4. Anaerobic diges“ion of biomass was“e in a ”ni“ of bioenergy prod”c“ion associa“ed wi“h an effl”en“ “rea“‐ men“ plan“.

These initiatives hiμhliμht the potential use oλ hyd⅔othe⅔mal li⅓ueλaction, which is a p⅔ocess that conve⅔ts the biomass into bio-oil at a tempe⅔atu⅔e ⅔anμe oλ °C and p⅔essu⅔es oλ - MPa. “cco⅔dinμ to ”ille⅔ et al. [ ], yields oλ - % a⅔e possible, takinμ into account that mic⅔oalμae can be p⅔oduced usinμ ⅔ecycled nut⅔ients, p⅔ovidinμ μ⅔eate⅔ sustainability to the system. “ diλλe⅔ent bio-oil can be p⅔oduced usinμ py⅔olysis in which the oil composition λeatu⅔es compounds exhibitinμ boilinμ points lowe⅔ than the hyd⅔othe⅔mal li⅓ueλaction p⅔oduct [ ]. In py⅔olysis, the nit⅔oμen content oλ the mic⅔oalμae is conve⅔ted into NOx du⅔inμ combus‐ tion. NOx is an undesi⅔able emission that inc⅔eases dependinμ on the mic⅔oalμae and thei⅔ p⅔otein content howeve⅔, NOx emissions can be ⅔educed by % usinμ a hyd⅔othe⅔mal p⅔et⅔eatment p⅔ocess. In te⅔ms oλ waste ⅔ecove⅔y, the use oλ Duσζliellζ tertiτleθtζ cake unde⅔ va⅔ious catalyst dos‐ aμe conditions, tempe⅔atu⅔es, and times we⅔e used in hyd⅔othe⅔mal li⅓ueλaction, and the yield was . % usinμ % sodium ca⅔bonate as catalyst at °C [ ]. The⅔eλo⅔e, in addition to p⅔oducinμ mic⅔oalμae in u⅔ban o⅔ indust⅔ial eλλluents, it is possible that aλte⅔ the ext⅔action oλ the oil λo⅔ biodiesel p⅔oduction and the p⅔oduction oλ bioethanol λ⅔om ca⅔bohyd⅔ates, bioμas o⅔ bio-oil can be p⅔oduced λ⅔om the waste mate⅔ial.

. Conclusions This chapte⅔ ⅔eviews the initiatives λo⅔ bioλuel p⅔oduction λ⅔om mic⅔oalμae cultivated in wastewate⅔s. The exploitation oλ the total mic⅔oalμae biomass was conside⅔ed, and the po‐ tential λo⅔ biodiesel and bioethanol p⅔oduction was explo⅔ed. The va⅔ious systems λo⅔ mic⅔oalμae p⅔oduction usinμ wastewate⅔ and the conse⅓uences λo⅔ biodiesel and bioethanol p⅔oduction we⅔e discussed in detail.

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Mic⅔oalμae have been used to p⅔oduce biodiesel and bioethanol with excellent ⅔esults how‐ eve⅔, the use oλ mic⅔oalμae must be expanded to include bio⅔emediation combined with bio‐ λuel p⅔oduction. The comme⅔cial initiatives λo⅔ this pu⅔pose will depend on the composition and volume oλ the eλλluent, on the selected mic⅔oalμae species, and on the tempe⅔atu⅔e and liμht conditions oλ the ⅔eμion. The initiatives will also depend on the pa⅔ticula⅔ bioλuel oλ inte⅔est to the ⅔eμion o⅔ that ⅔e⅓ui⅔ed λo⅔ local consumption. The⅔eλo⅔e, each situation must be analyzed on an individual basis, and the⅔e is no sinμle model howeve⅔, because oλ the wide biodive⅔sity oλ mic⅔oalμae and the extensive onμoinμ ⅔esea⅔ch capacity oλ many coun‐ t⅔ies, it is likely that a conditions λo⅔ viable mic⅔oalμae p⅔oduction can be achieved any‐ whe⅔e. Finally, it should be noted that mic⅔oalμae that a⅔e adapted to the envi⅔onment could p⅔o‐ duce biomass that, dependinμ on the composition oλ cells, can be used as the ⅔aw mate⅔ial λo⅔ the p⅔oduction oλ one o⅔ mo⅔e bioλuels. The ⅔esea⅔ch and development oλ mic⅔oalμae p⅔oduction in u⅔ban o⅔ indust⅔ial eλλluents in‐ volve p⅔inciples oλ sustainable development, clean technoloμy, and the ecoloμy oλ the p⅔o‐ ductive secto⅔s, p⅔io⅔itizinμ p⅔eventive and ⅔emediation steps with the dec⅔eased use oλ ene⅔μy and inputs. The⅔eλo⅔e, the⅔e is an emphasis on the methods oλ t⅔eatment, the t⅔ans‐ λo⅔mation p⅔ocesses, and the biotechnoloμical p⅔oducts bioλuels , p⅔io⅔itizinμ the use oλ wastewate⅔ λo⅔ biomass and bioene⅔μy p⅔oduction. These developments will dec⅔ease the impact on activities oλ anth⅔opoμenic o⅔iμin λ⅔om the indust⅔ial, comme⅔cial and se⅔vice sec‐ to⅔s, amonμ othe⅔s.

Acknowledgements The National Council oλ Technoloμical and Scientiλic Development Conselho Nacional de Desenvolvimento Cientíλico e Tecnolóμico, CNP⅓ , the National Council λo⅔ the Imp⅔ove‐ ment oλ Hiμhe⅔ Education Coo⅔denação de “pe⅔λeiçoamento de Pessoal de Nível Supe⅔io⅔, C“PES and the Unive⅔sity oλ Santa C⅔uz do Sul Resea⅔ch Foundation Fundo de “poio à Pes⅓uisa da Unive⅔sidade de Santa C⅔uz do Sul, F“P/UNISC

Author details Rosana C. S. Schneide⅔, Thiaμo R. ”je⅔k, Pablo D. G⅔essle⅔, Maia⅔a P. Souza, Vale⅔iano “. Co⅔bellini and Edua⅔do “. Lobo Envi⅔onmental Technoloμy Post-G⅔aduation P⅔oμ⅔am, Unive⅔sity oλ Santa C⅔uz do Sul, UNISC, ”⅔azil

Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

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Po“en“ial Prod”c“ion of Biof”el from Microalgae Biomass Prod”ced in Was“ewa“er h““p://dx.doi.org/10.5772/52439

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] Jena U., Vaidyanathan N., Chinnasamy S., Das K.C., Evaluation oλ mic⅔oalμae culti‐ vation usinμ ⅔ecove⅔ed a⅓ueous co-p⅔oduct λ⅔om the⅔mochemical li⅓ueλaction oλ al‐ μal biomass, ”io⅔esou⅔ce Technoloμy . doi . /j.bio⅔tech. . .

Chapter 2

Algal Biorefinery for Biodiesel Production Didem Özçimen, M. Ömer Güly”r“ and Benan İnan Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10. 5772/52679

. Introduction In ⅔ecent yea⅔s, the ⅔apid depletion oλ λossil λuels, inc⅔ease in ene⅔μy demand, μlobal wa⅔m‐ inμ, inc⅔ease in p⅔ice oλ λossil λuels depends on economic and political behavio⅔s inc⅔eased o⅔ientation to alte⅔native ene⅔μy sou⅔ces. In this context, biodiesel that is one oλ the ⅔enewa‐ ble alte⅔native ene⅔μy sou⅔ces d⅔aws attention because oλ its useλul λeatu⅔es such as easily biodeμ⅔adable and envi⅔onmentally λ⅔iendly. Howeve⅔, biodiesel p⅔oduction λ⅔om oil c⅔ops does not meet the ⅔e⅓ui⅔ed demand oλ vehicle λuel, and ⅔ecently it is not economic and λeasi‐ ble. It needs to be imp⅔oved to p⅔oduce mo⅔e economically to be able to compete with diesel in the ma⅔ket. Veμetable oils and c⅔ops which biodiesel p⅔oduced λ⅔om a⅔e a kind oλ human λood sou⅔ces and the sho⅔taμe on λood sou⅔ce cause to μo up p⅔ices and make the biodiesel hiμh-p⅔iced. To meet the ⅔e⅓ui⅔ements, the inte⅔est on alμae is inc⅔eased day by day since this technoloμy has potential to meet μlobal demand [ ]. Mic⅔oalμae have hiμhe⅔ p⅔oductivi‐ ty pe⅔ a⅔ea and no need λo⅔ λa⅔m λield to μ⅔ow as opposed to oil c⅔ops and animal λat. Mic⅔o‐ alμae use sunliμht to ⅔educe CO to bioλuels, λoods, λe⅔tilize⅔s, and valuable p⅔oducts. Fu⅔the⅔mo⅔e, mic⅔oalμae can be used to μet diλλe⅔ent types oλ bioλuels. Usinμ mic⅔oalμae as λuel sou⅔ce is not a novel idea but ⅔ecently the p⅔ices oλ diesel and μlobal wa⅔minμ hit this solution to the top [ ]. Mic⅔oalμae have lots oλ advantaμes λo⅔ biodiesel p⅔oduction ove⅔ othe⅔ ⅔aw mate⅔ials such as c⅔ops, waste cookinμ oils, and so on. Mic⅔oalμae have sho⅔t doublinμ time which is a⅔ound - h since they have a simple st⅔uctu⅔e and capable to hiμh photosynthetic eλλi‐ ciency and they contain much mo⅔e amount oλ oil than othe⅔ oil c⅔ops that can be used as oil sou⅔ce λo⅔ biodiesel p⅔oduction. Compa⅔ed with the oil yields λ⅔om va⅔ious oil c⅔ops such as co⅔n L/ha , soybean L/ha , canola L/ha , jat⅔opha L/ha , coconut L/ha and oil palm L/ha , oil yield λ⅔om mic⅔oalμae is ve⅔y hiμh as L/ha and L/ha λo⅔ % oil in biomass and % oil in biomass, ⅔espectively [ - ].

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

The othe⅔ siμniλicant λeatu⅔e is that alμae can μ⅔ow eve⅔ywhe⅔e and eve⅔y season in a yea⅔ since the⅔e a⅔e thousands oλ alμae species that have diλλe⅔ent adaptations and diλλe⅔ent p⅔op‐ e⅔ties. They can μ⅔ow in saltwate⅔, λ⅔eshwate⅔, lakes, dese⅔ts, ma⅔μinal lands, etc. In addition to biodiesel p⅔oduction, alμae can be also used as λeedstock to p⅔oduce diλλe⅔ent valuable p⅔oducts such as λe⅔tilize⅔, ene⅔μy, neut⅔aceuticals, p⅔otein, animal λeed etc. The othe⅔ siμniλi‐ cant p⅔ope⅔ty is that mic⅔oalμae can ⅔emove some heavy metals, phospho⅔ous, and nit⅔oμen λ⅔om wate⅔ du⅔inμ its μ⅔owth. “lμae also clean up the wate⅔. Mo⅔eove⅔, mic⅔oalμae se⅓ueste⅔ lots oλ ca⅔bon by photosynthesis. Utilization oλ ca⅔bon dioxide by alμae is siμniλicantly lowe⅔‐ inμ the ⅔isk λo⅔ μ⅔eenhouse μas eλλects. Lastly, usaμe oλ mic⅔oalμae λo⅔ biodiesel almost can‐ cels out the ca⅔bon dioxide and sulλu⅔ ⅔elease to atmosphe⅔e [ ]. These ⅔easons mentioned above a⅔e enouμh to believe that mic⅔oalμae can take the place oλ λossil λuels completely. The⅔e a⅔e many oλ mic⅔oalμae studies λo⅔ biodiesel p⅔oduction. ”ecause the most oλ the sci‐ entists believe that mic⅔oalμae will take the place oλ the pet⅔oleum diesel, howeve⅔, alμal bi‐ odiesel p⅔oduction is not λeasible yet since the⅔e is no much comme⅔cial o⅔ la⅔μe scale p⅔oduction oλ mic⅔oalμae λo⅔ biodiesel. That is why most oλ the wo⅔ks a⅔e λocused on de‐ c⅔easinμ the cost oλ biodiesel p⅔oduction o⅔ make it competitive ve⅔sus pet⅔oleum diesel. Su⅔ely, until these imp⅔ovements a⅔e achieved, alμal biodiesel can not be an accu⅔ate alte⅔‐ native. The cu⅔⅔ent p⅔oblems makinμ biodiesel expensive can be imp⅔oved with some inno‐ vations. The λi⅔st oλ all is about the alμae st⅔ain which is also λi⅔st step oλ alμal biodiesel p⅔oduction. The alμae st⅔ain should be bette⅔ than ⅔ecent ones. The⅔e a⅔e natu⅔al many kinds oλ alμae st⅔ains and isolation oλ new natu⅔al alμae st⅔ain may help p⅔ocedu⅔e to be cost eλλec‐ tive. The alμae st⅔ain has to have hiμh lipid p⅔oductivity and adaptability to new envi⅔on‐ ments. These λeatu⅔es let it p⅔oduce mo⅔e and obtain mo⅔e oil content [ , ]. “s an example, iλ the λlue μas is used as ca⅔bon dioxide sou⅔ce, mic⅔oalμae have to be adapted λo⅔ this situa‐ tion so that it can tole⅔ate the hiμh concent⅔ation oλ SOx, NOx, and othe⅔ μases [ ]. That will ⅔educe the cost and inc⅔ease the biomass μ⅔owth ⅔ate. The othe⅔ impo⅔tant innovation should λocus on cultivation oλ alμae. The la⅔μe-scale p⅔oduction is one oλ the most cost-in‐ tense pa⅔ts. The innovative thinkinμ should show a tendency to lowe⅔ the cost oλ ope⅔ation and capital λo⅔ cultivation systems. “s it is explained below, open ponds a⅔e the cheapest way but the eλλiciency oλ them has to be wo⅔ked on. Mo⅔eove⅔, the closed photobio⅔eacto⅔s P”R a⅔e also beinμ imp⅔oved λo⅔ a cheape⅔ way to cont⅔ol and liμhten the system. Fu⅔the⅔‐ mo⅔e, mic⅔oalμae can be λixed in a cultivation system with an immobilization techni⅓ue to μet hiμhe⅔ biomass. The last way to lowe⅔ the cost is to p⅔oduce sub-p⅔oducts λ⅔om mic⅔oal‐ μae beyond biodiesel. The⅔e a⅔e lots oλ hiμh value p⅔oducts and sub-p⅔oducts p⅔oduced λ⅔om mic⅔oalμae such as bioμas [ , ], biobutanol, acetone [ ], Omeμa oil [ ], eicosapen‐ taenoic acid [ ], livestock λeed [ ], pha⅔maceuticals and cosmetics [ , ]. Especially subp⅔oducts can be p⅔eλe⅔⅔ed λo⅔ economic suppo⅔t oλ main p⅔ocess. Fo⅔ example, ⅔ecove⅔y oλ methane λ⅔om mic⅔oalμae pulp aλte⅔ biodiesel p⅔oduction develops ⅔enewability oλ conve⅔sion oλ mic⅔oalμae biomass to biodiesel p⅔ocess as much as it makes the cost oλ p⅔ocess and envi⅔onmental eλλects less. The mic⅔oalμae pulps aλte⅔ oil ⅔emoved contain siμniλicant amounts oλ p⅔otein and ca⅔bohyd⅔ate that can conve⅔t to bioμas by anae‐ ⅔obic λe⅔mentation. Conve⅔sion oλ alμal waste to bioμas by anae⅔obic λe⅔mentation will play a dual ⅔ole λo⅔ ⅔enewable ene⅔μy p⅔oduction and also sustainable development oλ mic⅔oalμal biodiesel indust⅔y [ , ].

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

“lμae can be also used in bioethanol p⅔oduction. “lμae a⅔e mo⅔e uniλo⅔m and continuous than te⅔⅔est⅔ial plant, due to lack oλ λunctional pa⅔ts such as ⅔oot and leaλ composition. Thei⅔ cell walls made oλ polysaccha⅔ides that can hyd⅔olyze to the suμa⅔. Fo⅔ this ⅔eason, mic⅔oal‐ μae can be used as ca⅔bon sou⅔ce in λe⅔mentation p⅔ocess. Ethanol p⅔oduced by λe⅔menta‐ tion can be pu⅔iλied λo⅔ usinμ as a λuel, CO as a nut⅔ient may also be ⅔ecycled to alμae cultu⅔e to μ⅔ow mic⅔oalμae [ , ]. In this chapte⅔, alμae p⅔oduction methods that cove⅔ the alμae st⅔ain and location selection, alμae cultivation, ha⅔vestinμ, oil ext⅔action, and alμal biodiesel p⅔oduction p⅔ocesses a⅔e p⅔esented in detail with alte⅔natives. New p⅔oμ⅔esses in this a⅔ea a⅔e also explained.

. Algae strains and properties “lμae a⅔e simple o⅔μanisms includinμ chlo⅔ophyll. They can be λound in seas, soils and lakes whe⅔eve⅔ they can use the liμht λo⅔ thei⅔ photosynthesis. The⅔e a⅔e two types oλ main alμae μ⅔oups. The λi⅔st μ⅔oup is mac⅔o alμae, which includes μ⅔een, b⅔own and ⅔ed alμae. The second μ⅔oup is mic⅔oalμae as phytoplankton in the coasts, lakes and oceans, which in‐ cludes diatoms, dynoλlaμellates, μ⅔een and b⅔ownish λlaμellate, and blue-μ⅔een alμae [ ]. The classiλication oλ alμae can be done in many ways since the⅔e is a millions oλ kind. “lso the⅔e is no standa⅔d on classiλication so you can see diλλe⅔ent types oλ classiλication. The taxonomic μ⅔oup oλ alμae can be μiven as λollow “rθhζeplζstidζ, Chlτrτphytζ μ⅔een alμae , Rhτdτphytζ ⅔ed alμae , Glζuθτphytζ, Chlτrζrζθhσiτphytes, Euμleσids, Heterτkτσts, ”ζθillζriτphy‐ θeζe diatoms , “xτdiσe, ”τlidτmτσζs, Eustiμmζtτphyθeζe, Phζeτphyθeζe b⅔own alμae , Chrysτ‐ phyθeζe μolden alμae , Rζphidτphyθeζe, Syσurτphyθeζe, Xζσthτphyθeζe yellow-μ⅔een alμae , Cryptτphytζ, Diστλlζμellζtes, Hζptτphytζ[ ]. “lμae a⅔e the most common wide photosynthetic bacte⅔ia ecoloμically. To μ⅔ow alμae some pa⅔amete⅔s such as amount and ⅓uality oλ inμ⅔edients, liμht, pH, tu⅔bulence, salini‐ ty, and tempe⅔atu⅔e become p⅔ominent. Mac⅔o nit⅔ate, phosphate, silicate and mic⅔o some metals, ” , ” and biotin vitamins elements a⅔e ⅔e⅓ui⅔ed in the μ⅔owth oλ alμae. Liμht intensity has also an impo⅔tant ⅔ole, the liμht demand chanμes up to mic⅔oalμae density and type oλ mic⅔oalμae. The othe⅔ pa⅔amete⅔ pH is mostly between and λo⅔ most oλ alμae st⅔ains and mostly the optimum ⅔anμe is . - . . The last pa⅔amete⅔ salini‐ ty should be between - ppt. Mo⅔eove⅔, nit⅔oμen also aλλects the μ⅔owth oλ some alμae st⅔ains as such as μ⅔een alμae [ - ]. . . Macroalgae Mac⅔oalμae a⅔e adapted to liλe in ocean and it is a plant mostly seen on the costal st⅔ips. The⅔e a⅔e plenty oλ mac⅔o alμae types. “lμae can be classiλied as b⅔own, ⅔ed, and μ⅔een based on type oλ piμments. Recently, seve⅔al b⅔own alμae types have been used in the indus‐ t⅔y and ene⅔μy p⅔oduction as an alte⅔native sou⅔ce to λossil λuels, and μ⅔een alμae is also studied to p⅔oduce biodiesel [ ].

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

”⅔own alμae have xanthophyll piμments and λucoxanthin, which ⅔esults the colou⅔ oλ b⅔own alμae. These substances mask the othe⅔ piμments [ ]. Polysaccha⅔ides and hiμhe⅔ alcohols a⅔e nut⅔ition ⅔ese⅔ves oλ b⅔own alμae but the main ca⅔bohyd⅔ate ⅔ese⅔ve is lamina⅔in. The cell walls oλ b⅔own alμae a⅔e made oλ cellulose and alμinic acid. ”⅔own alμae have a lot oλ λeatu⅔es such as Cytotoxic and antitumo⅔ activity, “ntiλunμal activity, “nti-inλlammato⅔y activity, “ntivi⅔al activity, P⅔otection aμainst he⅔bivo⅔ous animals λish, sea u⅔chins , “nti‐ oxidant activity [ , , ]. Composition oλ b⅔own alμae can va⅔y acco⅔dinμ to species, thei⅔ location, salinity and season. “cco⅔dinμ to analysis, b⅔own alμae contain about % hiμh moistu⅔e and % hiμh sodium ca⅔bonate [ ]. G⅔een alμae contain chlo⅔ophyll a and b. P⅔esence oλ these piμments makes μ⅔een colo⅔ oλ the μ⅔een alμae. The⅔e a⅔e a λew ⅔epo⅔ts about second metabolites oλ μ⅔een alμae. [ ]. Mois‐ tu⅔e content oλ μ⅔een alμae is hiμhe⅔ than b⅔own alμae but they have simila⅔ sodium ca⅔bo‐ nate content. G⅔een alμae species can access hiμhe⅔ suμa⅔ levels and this makes them useλul ene⅔μy sou⅔ces. They also have hiμh cellulose content [ ]. G⅔een alμae have a lot oλ λeatu⅔es such as “nti-inλlammato⅔y substances, Cytotoxic and immunosupp⅔essive activities, “nti‐ bacte⅔ial activity, “ntivi⅔al activity, “ntiλunμal activity [ ]. Red “lμae have phycoe⅔yth⅔in and phycothcyanin piμments that make ⅔ed colo⅔ oλ these al‐ μae. These piμments mask the othe⅔ piμments. The cell walls oλ ⅔ed alμae made oλ cellulose, aμa⅔ and ca⅔⅔aμeenan [ ]. The⅔e a⅔e app⅔oximately ⅔ed alμae species. In compa⅔ison oλ the othe⅔ alμae species, ⅔ed alμae a⅔e conside⅔ed as the most impo⅔tant active metabolite ⅔e‐ sou⅔ce. They have a lot oλ λeatu⅔es such as Cytotoxic activities, “ntivi⅔al activity, “nti-in‐ λlammato⅔y activity, “ntimic⅔obial activity, F⅔ee ⅔adical scavenμe⅔ activity [ , ]. . . Microalgae The⅔e a⅔e at least mic⅔oalμae species in the wo⅔ld. Mic⅔oalμae a⅔e mostly deλined as unicellula⅔ photosynthetic cells but some complex associations c⅔eate la⅔μe⅔ colonies. This is a hete⅔oμenic μ⅔oup, which contains p⅔oka⅔yotic o⅔μanisms simila⅔ to bacte⅔ia and euka⅔y‐ otic cells [ , ]. Mic⅔oalμae p⅔oduction is concent⅔ated on pa⅔ticula⅔ species, which have special tole⅔ance λo⅔ ext⅔eme conditions in thei⅔ μ⅔owth. This situation enables the p⅔oduc‐ tion in open ponds and canals. In λutu⅔e, mic⅔oalμae p⅔oduction will λocus on mo⅔e ad‐ vanced species λo⅔ the demand oλ ene⅔μy and pu⅔e monocultu⅔es which have speciλic capabilities like p⅔oduction oλ ca⅔bohyd⅔ate, lipid o⅔ hyd⅔oμen will be cultivated [ ]. “c‐ co⅔dinμ to use oλ alμae, biomass oλ mic⅔oalμae has va⅔iable chemical composition. They can be ⅔ich o⅔ balanced composition oλ p⅔otein, lipid and suμa⅔. Mic⅔oalμae selection should be made acco⅔dinμ to desi⅔ed bioλuels. Mic⅔oalμae have impo⅔tant lipid content even in the ex‐ t⅔eme conditions they ⅔each hiμhe⅔ lipid content [ ]. G⅔een alμae o⅔ diatoms a⅔e the most used mic⅔oalμae species λo⅔ p⅔oduction oλ alte⅔native ene⅔μy de⅔ives. Just a handλul oλ these species has comme⅔cial impo⅔tance. This μ⅔oup con‐ tains Chlτrellζ, Spiruliσζ, Duσζliellζ and Hζemζtτθτθθus. Only Duσζliellζ is a dominant sea spe‐ cies. These a⅔e usually cultivated λo⅔ ext⅔action oλ hiμh value component like piμments o⅔ p⅔oteins [ ].

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

”lue-μ⅔een alμae cyanobacte⅔ia have a lot oλ common st⅔uctu⅔al λeatu⅔es with bacte⅔ia. They a⅔e classiλied as alμae because they contain chlo⅔ophyll and othe⅔ components. They have also nit⅔oμenic components because all oλ the p⅔oka⅔yote species conve⅔t atmosphe⅔ic nit⅔oμen to ammonium [ , ]. Mo⅔pholoμically blue μ⅔een alμae can have λilamentous, conical o⅔ unicellula⅔ shape. They have a lot oλ λeatu⅔es such as anticance⅔ and cytotoxic ac‐ tivities, antibacte⅔ial activity, antiλunμal activity, immunosupp⅔essive activity [ , , ]. Pyrrhτphytζ Diστλlζμellζtes a⅔e unicellula⅔ o⅔μanisms, which a⅔e classiλied as p⅔imitive al‐ μae. La⅔μe amount concent⅔ations oλ these o⅔μanisms exist in ocean su⅔λace and they cause λish deaths. “lso because oλ thei⅔ piμments, dinoλlaμellates μive the wate⅔ b⅔own to ⅔ed colo‐ ⅔ation in the sea [ , ]. Pa⅔ticula⅔ dinoλlaμellate species p⅔oduce toxin in case oλ consumed by species such as shellλish. Consumption oλ contaminated shellλish by humans can cause a lot oλ health p⅔oblems includinμ death [ ]. ”ζθillζriτphyθeζe Diatoms a⅔e the most ve⅔satile and λ⅔e⅓uent λamily. They a⅔e mo⅔e λeasible λo⅔ la⅔μe-scale p⅔oductions due to sho⅔t doublinμ time and easy to μ⅔ow. Unlike Diστλlζμel‐ lζtes they c⅔eate less second metabolites [ ]. Mic⅔oalμae a⅔e investiμated as biodiesel λeedstock because oλ thei⅔ hiμh photosynthetic eλλi‐ ciency, thei⅔ ability to p⅔oduce lipids. Mac⅔oalμae usually don t contain lipids too much and they a⅔e taken into conside⅔ation λo⅔ the natu⅔al suμa⅔s and othe⅔ ca⅔bohyd⅔ates that they contain. These contents can be λe⅔mented to p⅔oduce alcohol-based λuels o⅔ bioμas. . . Lipid content of microalgae species “s the st⅔uctu⅔e oλ many mic⅔oalμae species can accumulate siμniλicant amounts oλ lipid and p⅔ovide hiμh oil yield. Thei⅔ ave⅔aμe lipid contents can be ⅔eached to % oλ d⅔y bio‐ mass unde⅔ some ce⅔tain conditions [ ]. Table shows lipid content oλ some mic⅔oalμae species. Microalgae

Oil content (dry weight %)

Botryococcus braunii

25-75

Chlorella protothecoides

14-57

Crypthecodinium cohnii

20-51

Dunaliella tertiolecta

16-71

Nannochloris sp.

20-56

Neochloris oleoabundans

29-65

Phaeodactylum tricornutum

18-57

Schizochytrium sp.

50-77

Skeletonema coastatum

13-51

Table 1. Lipid con“en“ of some microalgae species [15, 39, 40-45].

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“lso hiμh p⅔oductivity is ve⅔y impo⅔tant beside hiμh oil content. “s shown in table , mic⅔oalμal lipid content can ⅔each % by weiμht oλ d⅔y biomass but it is obse⅔ved that the⅔e can be low p⅔oductivity oλ ”τtryτθτθθusηrζuσii, howeve⅔, Chlτrellζ appea⅔s to be a μood choice in biodiesel p⅔oduction, since it has hiμh p⅔oductivity thouμh lowe⅔ oil content [ ]. Lipid content can be aλλected by seve⅔al pa⅔amete⅔s such as nut⅔ition, envi⅔onment, cultiva‐ tion phases and conditions μ⅔owth can aλλect λatty acid composition [ ], Fatty acid compo‐ sition is impo⅔tant in mic⅔oalμae selection because it has a siμniλicant eλλect on biodiesel p⅔ope⅔ties. Fo⅔ example, iλ unsatu⅔ated λatty acid content is hiμh in alμal oils and thei⅔ p⅔es‐ ence ⅔educes the eλλiciency oλ este⅔iλication to p⅔oduce biodiesel [ ]. Value chain staμes oλ biodiesel p⅔oduction λ⅔om mic⅔oalμae can be μiven as alμae and site selection, alμae cultivation, ha⅔vestinμ, λilt⅔ation, dewate⅔inμ, oil ext⅔action and biodiesel p⅔oduction [ ].

. Biodiesel production from microalgae The selection oλ species depends on some λacto⅔s like ability to usaμe oλ nut⅔ition o⅔ μ⅔ow unde⅔ speciλic envi⅔onment conditions. “ll these pa⅔amete⅔s should be evaluated λo⅔ biodie‐ sel p⅔oduction. . . Selection of algae strain and location To make alμal biodiesel cost eλλective lots oλ ⅔esea⅔che⅔s keep μoinμ on alμae cultu⅔inμ. The c⅔ite⅔ia to select location and sou⅔ces a⅔e mentioned below [ ] • Wate⅔ sou⅔ces and demand, salinity, content • The ⅔eμion inλo⅔mation such as topoμ⅔aphy, μeoloμy • Weathe⅔ conditions, isolation, evapo⅔ation • “vailability oλ ca⅔bon and λood ⅔esou⅔ces The next decision should be on the alμae cultu⅔inμ p⅔ocess type. It can be eithe⅔ batch o⅔ continuous p⅔ocess. Dependinμ on mic⅔oalμae st⅔ain, envi⅔onmental conditions, availability oλ nut⅔ition and mo⅔eove⅔ indust⅔ial pollutions the p⅔ocess type has to be selected. The devi‐ ces and appa⅔atuses also have to be adjusted λo⅔ these conditions and nut⅔ients [ ]. “lμae st⅔ains have diλλe⅔ent contents, diλλe⅔ent doublinμ time the total biomass pe⅔ time and volume and ⅔esistance to chanμe in envi⅔onmental conditions. ”iodiesel p⅔oduction di‐ ⅔ectly depends on the oil content oλ mic⅔oalμae and its eλλiciency. So that, even the p⅔ocess and cultu⅔inμ systems a⅔e selected pe⅔λectly, time and othe⅔ ⅔elated λacto⅔s plays an impo⅔‐ tant ⅔ole [ ].

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

. . Methods used for algae growth Not only the mic⅔oalμae st⅔ain is impo⅔tant λo⅔ eλλiciency oλ oil but also μ⅔owinμ conditions a⅔e impo⅔tant. The⅔e a⅔e diλλe⅔ent ways to μ⅔ow alμae. Each type oλ mic⅔oalμae has a diλλe⅔‐ ent mechanism which let them to ⅔espond diλλe⅔ent weathe⅔ and envi⅔onmental conditions [ , ]. Diλλe⅔ent μ⅔owinμ conditions aλλect the mic⅔oalμae doublinμ time. The⅔e a⅔e μ⅔ow‐ inμ type basically photot⅔ophic, hete⅔ot⅔ophic, mixot⅔ophic, and photo hete⅔ot⅔ophic. “ll oλ them will be explained in detail. . . . Phτtτtrτphiθ μrτwth Mic⅔oalμae a⅔e mostly thouμht to be photot⅔ophic since it ⅔e⅓ui⅔es liμht [ ]. Photot⅔ophic μ⅔owinμ method is based on usinμ liμht and ca⅔bon dioxide to p⅔oduce chemical ene⅔μy du⅔inμ photosynthesis. This is the most common way used to μ⅔ow mic⅔oalμae. The best ad‐ vantaμe oλ the p⅔ocess is usinμ ca⅔bon dioxide as a ca⅔bon sou⅔ce to μ⅔ow o⅔ p⅔oduce λatty acid. Since ca⅔bon dioxide is only the ca⅔bon sou⅔ce, locations close to λab⅔ics and companies could be selected to p⅔ocu⅔e ca⅔bon dioxide. Iλ it is compa⅔ed to othe⅔ μ⅔owinμ types, photo‐ t⅔ophic method has the lowest contamination ⅔isk [ ]. . . . Heterτtτtrτphiθ μrτwth Some mic⅔oalμae a⅔e not able to μ⅔ow photot⅔ophic conditions but they can μ⅔ow in da⅔k usinμ o⅔μanic ca⅔bon as a ca⅔bon sou⅔ce like bacte⅔ia. Iλ mic⅔oalμae is usinμ o⅔μanic ca⅔bon these mic⅔oalμae a⅔e hete⅔ot⅔ophic μ⅔owinμ alμae. Hete⅔ot⅔ophic μ⅔owth has advantaμes ove⅔ photot⅔ophic μ⅔owth because liμht is not ⅔e⅓ui⅔ed. The biμμest p⅔oblem with the pho‐ tot⅔ophic is the liμht penet⅔ation when the density oλ the cultu⅔e μets hiμhe⅔. In that way one oλ the biμμest p⅔oblems is solved with hete⅔ot⅔ophic μ⅔owth. Hete⅔ot⅔ophic μ⅔owth will be mo⅔e cost eλλective compa⅔ed to photot⅔ophic μ⅔owth [ ]. “nd this method is said the most p⅔actical and p⅔omisinμ way to inc⅔ease the p⅔oductivity [ - ]. “lso hiμhe⅔ oil ⅔ates and eλλiciency can be obtained when the alμae μ⅔ow hete⅔ot⅔ophic, but the contamination ⅔isk is much hiμhe⅔ compa⅔ed to photot⅔ophic [ ]. Mic⅔oalμae uses diλλe⅔ent o⅔μanic ca⅔bon sou⅔ces such as μlucose, acetate, μlyce⅔ol, λ⅔uctose, suc⅔ose, lactose, μalactose, and mannose, especially μ⅔owth with suμa⅔ is mo⅔e eλλicient [ ]. Mostly the o⅔μanism μ⅔owinμ hete⅔ot⅔ophic should have adaptation p⅔ope⅔ty to new habitat as soon as possible since when cultu⅔inμ to new media the laμ phase should be too sho⅔t, and du⅔ability du⅔inμ p⅔ocessinμ in λe⅔mente⅔s and othe⅔ machines [ ]. . . . Mixτtrτphiθ μrτwth Mixot⅔ophic μ⅔owth is a combination oλ photot⅔ophic and hete⅔ot⅔ophic μ⅔owth. Mixot⅔o‐ phic μ⅔owth is usinμ o⅔μanic and ino⅔μanic ca⅔bon and the p⅔ocess ⅔e⅓ui⅔es liμht because oλ photosynthesis. Thus the mic⅔oalμae have ability to live in both conditions. Mic⅔oalμae uses o⅔μanic compounds and ca⅔bon dioxide as a ca⅔bon sou⅔ce and the ⅔eleased ca⅔bon dioxide a⅔e also captu⅔ed with the photosynthesis. “lthouμh mixot⅔ophic-μ⅔owinμ meth‐

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od mostly is not p⅔eλe⅔⅔ed compa⅔ed to hete⅔ot⅔ophic and photot⅔ophic μ⅔owth [ ], be‐ cause oλ othe⅔ advantaμes even so mixot⅔ophic method is applied in some studies. Fo⅔ example Pa⅔k et ζl. λound that biomass and lipid p⅔oductivities we⅔e boosted by mixot⅔o‐ phic cultivation [ ]. ”hatnaμa⅔ et al. λound the mixot⅔ophic μ⅔owth oλ some mic⅔oalμae st⅔ains ⅔esulted in times mo⅔e biomass p⅔oduction compa⅔ed to that obtained unde⅔ photot⅔ophic μ⅔owth conditions [ ]. . . . Phτtτheterτtτtrτphiθ μrτwth When mic⅔oalμae use o⅔μanic compounds as ca⅔bon sou⅔ces, sometimes it ⅔e⅓ui⅔es liμht. The main diλλe⅔ence between mixoth⅔ophic and photohete⅔ot⅔ophic is that mixot⅔ophic μ⅔owth usinμ o⅔μanic compounds as ene⅔μy sou⅔ces, as photohete⅔ot⅔ophic μ⅔owth ⅔e⅓ui⅔es liμht as ene⅔μy sou⅔ce. This method is mostly used λo⅔ p⅔oduction oλ some beneλicial metab‐ olites howeve⅔, it is ⅔a⅔ely used λo⅔ biodiesel p⅔oduction [ ]. Metabolisms can split into μ⅔oups due to pH chanμes. Chlτrellζ vulμζris, Hζemζtτθτθθus pluviζlis, “rthrτspirζ Spiruliσζ platensis st⅔ains a⅔e the examples λo⅔ the μ⅔owth by mixoth⅔ophic, photot⅔ophic and hete⅔o‐ t⅔ophic methods. Seleσζstrum θζpriθτrσutum and Sθeσedesmus ζθutus a⅔e able to μ⅔ow in pho‐ tot⅔ophic, hete⅔ot⅔ophic, photohete⅔ot⅔ophic conditions [ ]. “lμae ⅔e⅓ui⅔e mo⅔e than o⅔μanic ca⅔bon, suμa⅔, p⅔otein, oil o⅔ any ca⅔bon sou⅔ces. “lμae cannot μ⅔ow without vitamins, salts, o⅔ some othe⅔ nut⅔ients nit⅔oμen and phospho⅔ . Mo⅔eove⅔, the⅔e a⅔e lots oλ pa⅔amete⅔s has to be cont⅔olled du⅔inμ alμae μ⅔owth to maxi‐ mize and stabilize the p⅔oduction. Some oλ these pa⅔amete⅔s a⅔e oxyμen ⅔ate, ca⅔bon diox‐ ide ⅔ate, pH, heat, liμht intensity and so on. When app⅔op⅔iate weathe⅔ conditions and enouμh nut⅔ients a⅔e p⅔ovided mic⅔oalμae μ⅔ow λaste⅔. Mostly doublinμ time is between . h and h [ ]. “s a ⅔esult, iλ we compa⅔e diλλe⅔ent methods mentioned above λo⅔ mic⅔oalμae μ⅔owth Hete⅔‐ ot⅔ophic μ⅔owth is much bette⅔ than the othe⅔s λo⅔ the application oλ biodiesel. These meth‐ ods can p⅔oduce mo⅔e oil than othe⅔ μ⅔owinμ types. Howeve⅔, hete⅔ot⅔ophic cultu⅔es may contaminate especially in open pond systems and ⅔esult in biμ p⅔oblems in la⅔μe-scale p⅔o‐ duction. Mo⅔eove⅔, o⅔μanic ca⅔bon as a ca⅔bon sou⅔ce is an expensive ⅔aw mate⅔ial and makes the p⅔ocess cost hiμhe⅔. Photot⅔ophic μ⅔owth is an easily scalable and mostly uses the ca⅔bon dioxide λ⅔om exhaust μas λo⅔ the p⅔oduction oλ oil. Howeve⅔, the eλλiciency oλ the oil is lowe⅔ than hete⅔ot⅔ophic μ⅔owth because the biomass doublinμ time is hiμhe⅔ and total biomass ⅔ate is lowe⅔ at the end. Photot⅔ophic method mostly p⅔eλe⅔⅔ed to set a cost eλλective system [ ]. . . . Cτσditiτσs λτr μrτwth τλ ζlμζe . . . . Liμht The mic⅔oalμae μ⅔owinμ photosynthetically needs liμht and the liμht intensity is the most siμniλicant limitinμ λacto⅔. “lμae cultu⅔e systems mostly use both sun and lamp liμht. Mostly lamp-liμhtened alμae cultu⅔e systems uses wide⅔ sc⅔eens to be able to abso⅔b mo⅔e liμht

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

λ⅔om the system. Fo⅔ photosynthetic p⅔oduction, at least % oλ the volume oλ P”R has to μet enouμh liμht [ ]. Open ⅔aceway ponds, plate, plate P”R, Ve⅔tical-column P”Rs, Inte⅔‐ nally-illuminated P”Rs, inclined tubula⅔ type, ho⅔izontal/continuous type, bubble column and ai⅔-liλt P”Rs a⅔e the systems used λo⅔ photosynthetic alμae μ⅔owth. Plate photo bio⅔eac‐ to⅔ is mo⅔e eλλicient than tubula⅔ photo bio⅔eacto⅔ because the liμht can penet⅔ate to bottom mo⅔e in plate desiμn. Recent wo⅔ks a⅔e on closed system photobio⅔eacto⅔s to imp⅔ove the capacity. Some wo⅔ks a⅔e done to inc⅔ease the capacity howeve⅔ the liμht penet⅔ation be‐ comes a majo⅔ p⅔oblem. Liμht sou⅔ce λo⅔ open ponds is only Sun. That is why the alte⅔ation is not possible λo⅔ ⅔aceway ponds. The depth oλ the pond that the only thinμ can be chanμed. Thus mostly ⅔esea⅔ches a⅔e μoinμ on closed systems to optimize liμht emission. Mostly pho‐ tobio⅔eacto⅔s in lab scale a⅔e liμhtened by λluo⅔escence liμhts λ⅔om inside and outside [ ]. The liμht wavelenμth should be between nm to maximize the photosynthesis. Liμht intensity depends on mic⅔oalμae density. Hiμhe⅔ alμae density ⅔e⅓ui⅔es hiμhe⅔ liμht intensi‐ ty. Liμht also aλλects the lipid content. Yeesanμ and Chei⅔silp ⅔epo⅔ted that the lipid contents in all st⅔ains inc⅔eased with inc⅔easinμ liμht intensity in thei⅔ study [ ]. Chanμes in liμht intensity and ⅓uality can alte⅔ bioλuel ⅓uality [ ]. Each type oλ mic⅔oalμae has its own optimal liμht abso⅔binμ point. Iλ this point exceeds the optimum point, mic⅔oal‐ μae liμht abso⅔ption ⅔atio dec⅔eases. “λte⅔ a speciλic point, liμht dec⅔eases the biomass p⅔o‐ duction and this is called photoinhibition. Photoinhibition p⅔ocesses depend on time and aλte⅔ st⅔ess oλ liμht λo⅔ a λew minute biomass loss sta⅔ts. - min late⅔ mo⅔e than % damaμe can be seen. Chei⅔silp and To⅔pee investiμated the eλλect oλ liμht intensity on μ⅔owth and lipid content oλ ma⅔ine Chlτrellζ sp. and Nζσστθhlτrτpsis sp. The μ⅔owth oλ ma‐ ⅔ine Chlτrellζ sp. inc⅔eased when the liμht intensity was inc⅔eased λ⅔om to lux. ”ut up to lux its μ⅔owth dec⅔eased. They ⅔epo⅔ted that this could be some extent oλ eλλect λ⅔om photoinhibition. The μ⅔owth oλ Nζσστθhlτrτpsis sp. continuously inc⅔eased up to the maximum level when inc⅔easinμ liμht intensity up to a maximum liμht intensity oλ lux. [ ]. Hiμh liμht intensity limited alμal μ⅔owth, but μave the beneλit oλ hiμhe⅔ lipid con‐ tent and yield. It can be seen in Ruanμsomboon s study whose cultu⅔es exposed to low liμht intensity showed a hiμhe⅔ biomass compa⅔ed to othe⅔s [ ]. To inc⅔ease the mic⅔oalμae p⅔oduction, photoinhibition should be cut oλλ o⅔ exceed to hiμh liμht intense. In addition, photo⅔espi⅔ation dec⅔eases the photosynthetic eλλiciency. The⅔e‐ λo⅔e the p⅔ocess has to avoid photo⅔espi⅔ation. Photo⅔espi⅔ation occu⅔s when the oxyμen concent⅔ation inc⅔eases dependinμ on ca⅔bon dioxide [ ]. Sa⅔a et al. investiμated the liμht eλλects on mic⅔oalμae. The ⅔esea⅔ch was done by usinμ ⅔ed and blue lase⅔s as liμht sou⅔ce λo⅔ photosynthetic μ⅔owth oλ μ⅔een alμae. The ⅔esults showed that the both blue and ⅔ed lase⅔s inc⅔eased the alμae cell count [ ]. “llen and “⅔non tested the eλλect oλ liμht on μ⅔een alμae μ⅔owth. The liμht intensity was a⅔ound lux. The⅔e we⅔e two samples. One oλ the samples was analyzed unde⅔ h da⅔kness and h liμht. The othe⅔ sample was analyzed unde⅔ liμht λo⅔ h and the ⅔esults showed that the μ⅔owth ⅔ate was same. Howeve⅔ aλte⅔ days the μ⅔owth ⅔ate λo⅔ the sample with h liμht was declined [ ].

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The eλλects oλ liμht on Pζrietτθhlτris iσθisζ was analyzed by Solovchenko et al. The ⅔esults showed that best μ⅔owth was seen on hiμh liμht mol photons m− s− . With hiμh liμht condition, total λatty acid and a⅔achidonic amount was inc⅔eased due to inc⅔ease in biomass [ ]. “nothe⅔ study Yeh et al. was λocused on eλλects oλ diλλe⅔ent liμht sou⅔ces on mic⅔oalμae C. vulμζris μ⅔owth. In the sutdy, th⅔ee diλλe⅔ent liμht sou⅔ces was used which a⅔e tunμsten lamp, λluo⅔escent lamp TL , λluo⅔escent lamp helix lamp . The ⅔esults showed that λluo⅔escence lamps we⅔e much bette⅔ λo⅔ alμae μ⅔owth. In an othe⅔ study by Flo⅔eto et al., it was mentioned that hiμh liμht intensity inc⅔eased the palmitic acid and most λatty acids ⅔atio [ ]. . . . . Cζrητσ diτxide Ca⅔bon dioxide is the natu⅔al ca⅔bon sou⅔ce oλ the mic⅔oalμae cultu⅔e. Oxyμen is ⅔eleasinμ dependinμ on dec⅔easinμ ca⅔bon amount and it is delive⅔ed to the medium. Ca⅔bon dioxide is an μene⅔al ca⅔bon sou⅔ce λo⅔ photosynthetic mic⅔oalμae. When the ca⅔bon amounts μet low, oxyμen is p⅔oduced by photolysis oλ wate⅔ and ⅔eleased to media. Since alμae lives in hiμh ca⅔bon dioxide concent⅔ation, μ⅔eenhouse μases, nit⅔oμen dioxide and atmosphe⅔ic pollutants came λ⅔om diλλe⅔ent sou⅔ces became a λood λo⅔ alμae. The exhausted μases can λeed alμae p⅔oduction λacilities λ⅔om λossil λuels and also its eλλiciency would be inc⅔eased. Wo⅔ks on usaμe oλ stack μases as ca⅔bon sou⅔ce we⅔e done but the toxicity oλ the stack μas components couldn't be documented well. The amount oλ ca⅔bon dioxide ⅔e⅓ui⅔ed λo⅔ the μ⅔owth ⅔elates to type oλ mic⅔oalμae and photo bio⅔eacto⅔. Some types oλ alμae st⅔ains a⅔e able to keep μ⅔owinμ in hiμh ca⅔bon dioxide conditions, in cont⅔ast λo⅔ λaste⅔ μ⅔owth lowe⅔ ca⅔bon dioxide concent⅔ation is ⅔e⅓ui⅔ed [ ]. Widjaja studied the eλλect oλ CO on μ⅔owth and it was seen that this eλλect co⅔⅔elates di⅔ectly to the lipid p⅔oductivity since μ⅔owth was enhanced t⅔emendously by inc⅔easinμ the CO concent⅔ation [ ]. CO ⅔e⅓ui⅔ement can chanμe up to st⅔ains. Vi⅔thie”hola et al. ⅔epo⅔ted in thei⅔ studies that at % CO concent⅔a‐ tion the⅔e is a -λold decline in biomass yield when compa⅔ed to the yield p⅔oduced at a % CO concent⅔ation. This suμμests that the st⅔ain unde⅔ study could not endu⅔e CO concen‐ t⅔ations μ⅔eate⅔ than % [ ]. “lso Eb⅔ahimzadeh et al. ⅔epo⅔ted that inc⅔easinμ CO injec‐ tion had a siμniλicant eλλect on mic⅔oalμae μ⅔owth [ ]. CO input is also impo⅔tant. Sonnekus ⅔epo⅔ted that the CO should make up . - % oλ the total μas λlow and beinμ ca⅔eλul about the CO input does not lowe⅔ the pH oλ the cultu⅔e [ ]. . . . . Heζt “lμal μ⅔owth is also dependent on tempe⅔atu⅔e. Fo⅔ maximum μ⅔owth the⅔e is a need to know the optimal tempe⅔atu⅔e. The tempe⅔atu⅔e chanμes also lipid p⅔oduction and composition [ ]. The deμ⅔ee oλ unsatu⅔ation oλ alμal memb⅔ane lipids inc⅔eases iλ cultu⅔es a⅔e maintained at tempe⅔atu⅔es below thei⅔ optimum [ ]. Othe⅔ than this tempe⅔atu⅔e is siμniλicant λo⅔ dissolu‐ bility oλ ca⅔bon pa⅔ticles, which helps ca⅔bon to be used λo⅔ photosynthesis. Heat eλλects ⅔espi‐ ⅔ation and photo⅔espi⅔ation mo⅔e than photosynthesis. Howeve⅔, iλ ca⅔bon dioxide and liμht a⅔e the limitinμ λacto⅔, the eλλect oλ heat is not siμniλicant anymo⅔e. Optimal tempe⅔atu⅔e λo⅔ mi‐ c⅔oalμae cultu⅔es is between - °C. This can be diλλe⅔ent acco⅔dinμ to media composition,

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

type oλ cultu⅔e and st⅔ain. The most μene⅔al cultu⅔ed mic⅔oalμae can tole⅔ate the tempe⅔atu⅔e between °C. The tempe⅔atu⅔es lowe⅔ than °C will inc⅔ease the duplication time and hiμhe⅔ than °C will have a λatal eλλect on alμae [ ]. Howeve⅔, these ⅔anμes can be chanμed by envi⅔onmental λacto⅔s such as salinity, pH, ca⅔bon dioxide etc. In the study oλ Flo⅔eta etal., the λacto⅔s aλλectinμ alμae μ⅔owth we⅔e dete⅔mined. Tempe⅔a‐ tu⅔e eλλect was dete⅔mined with salinity simultaneously. The ⅔esults showed that low tem‐ pe⅔atu⅔e °C with hiμh salinity is the best choice. Low tempe⅔atu⅔e inc⅔eases the level oλ oleic and linoleic λatty acids. Mo⅔eove⅔, hiμh salinity inc⅔eases the amount oλ C and C poly-unsatu⅔ated λatty acids [ ]. . . . . pH Mic⅔oalμae ⅔e⅓ui⅔e diλλe⅔ent pH values acco⅔dinμ to the media. Du⅔inμ hiμh pH concent⅔a‐ tion, the ca⅔bon dioxide miμht be limitinμ λacto⅔ λo⅔ μ⅔owth and photosynthesis. The most used pH ⅔anμe λo⅔ alμal μ⅔owth is a⅔ound - . The optimal pH λo⅔ alμae is between . - . . ”ut it can chanμe with diλλe⅔ent st⅔ains. Fo⅔ example, Weissel and Stadle⅔ studied with Cryp‐ tτmτσζs sp. which showed positive population μ⅔owth ⅔ates ove⅔ a wide pH ⅔anμe, λ⅔om . to . [ ]. “pp⅔op⅔iate pH can be adjusted by ventilation o⅔ μassinμ. The⅔e is a complex ⅔elationship between CO concent⅔ation and pH in mic⅔oalμal bio⅔eacto⅔ systems, owinμ to the unde⅔lyinμ chemical e⅓uilib⅔ium amonμ such chemical species as CO , H CO , HCO and CO . Inc⅔easinμ CO concent⅔ations can inc⅔ease biomass p⅔oductivity, but will also de‐ c⅔ease pH and this causes impo⅔tant eλλect upon mic⅔oalμal physioloμy [ ]. Wate⅔ contami‐ nated with a hiμh pH has neμative eλλects on alμal abundance [ ]. Iλ the⅔e is not enouμh CO μas supply, alμae will utilize ca⅔bonate to maintain its μ⅔owth [ ]. “lthouμh hiμh concent⅔ation oλ ca⅔bon dioxide p⅔ovides hiμh biomass eλλiciency, on the oth‐ e⅔ side hiμhe⅔ contamination ⅔isk and eλλect oλ low pH on mic⅔oalμae physioloμy occu⅔s [ ]. Except the pa⅔amete⅔s mentioned above the⅔e a⅔e also some pa⅔amete⅔s which aλλect on al‐ μal μ⅔owth o⅔ lipid accumulation. Nit⅔oμen, phospho⅔us and salinity can be examples λo⅔ these pa⅔amete⅔s [ ]. Widjaja et al. studied about nit⅔oμen sta⅔vation eλλect on lipid accu‐ mulation. They ⅔epo⅔ted that lonμe⅔ time oλ nit⅔oμen sta⅔vation obviously ⅔esulted in hiμhe⅔ accumulation oλ lipid inside the cells. Unde⅔ all CO concent⅔ations, the lipid content tend to inc⅔ease when the alμae was exposed to nit⅔oμen sta⅔vation condition that total lipid content was hiμhe⅔ than lipid obtained du⅔inμ no⅔mal nut⅔ition [ ]. Ruanμsomboon λound the hiμhest biomass concent⅔ation was λound unde⅔ the hiμhest phospho⅔us concent⅔ation [ ]. Li Xinet all. have ⅔epo⅔ted in thei⅔ study that lipid p⅔oductivity was not at its hiμhest when the lipid content was hiμhest unde⅔ nit⅔oμen o⅔ phospho⅔us limitation [ ]. Yeesanμ and Chei⅔silp also studied about nit⅔oμen and salinity eλλect. They λound an inc⅔ease in alμal bio‐ mass unde⅔ nit⅔oμen-⅔ich condition λo⅔ all st⅔ains and in the absence oλ a nit⅔oμen sou⅔ce, no μ⅔owth was obse⅔ved. They ⅔epo⅔ted that althouμh some loss in alμal biomass was λound, the lipid contents oλ λou⅔ st⅔ains inc⅔eased. They also noticed that μ⅔owth and lipid accumu‐ lation by these mic⅔oalμae could be aλλected by salinity. Unde⅔ nit⅔oμen-⅔ich condition, all st⅔ains su⅔vived at hiμh salinity but μ⅔owth oλ some st⅔ains dec⅔eased [ , ].

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. . Microalgae cultivation systems Cultivatinμ mic⅔oalμae can be achieved in open systems like lakes and ponds and in hiμh cont⅔olled closed systems called photobio⅔eacto⅔. “ bio⅔eacto⅔ is deλined as a system, which ca⅔⅔ies out bioloμical conve⅔sion. Photobio⅔eacto⅔s a⅔e ⅔eacto⅔s, which used λo⅔ p⅔otot⅔oph to μ⅔ow inside o⅔ photo bioloμical ⅔eactions to occu⅔ [ ]. . . . Opeσ pτσds Gene⅔ally open ponds a⅔e used in mic⅔oalμae cultivation. Open ponds have va⅔ious shapes and λo⅔ms and ce⅔tain advantaμes and disadvantaμes. In the scientiλic investiμations and in‐ dust⅔ial applications, ⅔aceway ponds, shallow biμ ponds, ci⅔cula⅔ ponds tanks and closed ponds a⅔e used [ ]. “⅔ea whe⅔e pool exist is c⅔itical λacto⅔ λo⅔ selection oλ pond type. Ponds become local climate λunction due to lack oλ cont⅔ol in open ponds [ , ]. The⅔eλo⅔e, a⅔ea cont⅔ibutes to the success. Open ponds a⅔e limited by key μ⅔owth pa⅔amete⅔s, which include liμht intensity, tempe⅔atu⅔e, pH and dissolved O concent⅔ation. “nothe⅔ p⅔oblem seen in open ponds is contamination. It limits cultivation system oλ alμae, which can μ⅔ow unde⅔ ce⅔tain conditions [ ]. Cost oλ cultivation systems is an impo⅔tant λacto⅔ λo⅔ compa⅔ison oλ open and closed sys‐ tems. Const⅔uction, ope⅔ation and maintaininμ costs a⅔e less than photobio⅔eacto⅔s in ponds and these systems a⅔e simple⅔ than the othe⅔s [ , ]. . . . Phτtτηiτreζθtτrs Nowadays ⅔esea⅔ches a⅔e made λo⅔ desiμninμ photobio⅔eacto⅔s due to cultivatinμ mic⅔oal‐ μae. Photobio⅔eacto⅔s oλλe⅔ bette⅔ cont⅔ol than open systems [ ]. Thei⅔ cont⅔olled envi⅔on‐ ment allows hiμh yield λo⅔ cultivatinμ. P⅔oductivity is the most impo⅔tant indicato⅔ λo⅔ bio⅔eacto⅔ technoloμy. It is ve⅔y diλλicult to compa⅔e p⅔oductivity oλ bio⅔eacto⅔s due to va⅔ious st⅔ains and scale oλ mic⅔oalμae [ ]. Photobio⅔eacto⅔s basically can be tubula⅔ and λlat type. When it is compa⅔ed with the othe⅔ bio⅔eacto⅔s, tubula⅔ ⅔eacto⅔s conside⅔ed as mo⅔e suitable λo⅔ open cultivatinμ. La⅔μe illumi‐ nation su⅔λace oλ ⅔eacto⅔, which made oλ t⅔anspa⅔ent tubes, is the main λacto⅔ to beinμ suita‐ ble λo⅔ cultivation. Tubes can be adjusted in va⅔ious types, adjustments convenience is depend to the speciλication oλ system. “ μene⅔al conλiμu⅔ation includes st⅔aiμht line and coilinμ tubes [ ]. Reacto⅔ μeomet⅔y is also impo⅔tant, tubula⅔ ⅔eacto⅔s can be ve⅔tical, ho⅔izontal o⅔ inclined shape. The⅔e a⅔e im‐ po⅔tant diλλe⅔ences between conλiμu⅔ations oλ ve⅔tical and ho⅔izontal. Ve⅔tical desiμns p⅔o‐ vide mo⅔e mass t⅔ansλe⅔ and ⅔educe ene⅔μy consumption ho⅔izontal desiμns can be scaled but needs mo⅔e space. The⅔e a⅔e mo⅔e studies about tubula⅔ photobio⅔eacto⅔s but usually λlat type photobio⅔eacto⅔s is p⅔eλe⅔⅔ed because it can oλλe⅔ hiμh cell density [ ]. In addi‐ tion, this type oλ ⅔eacto⅔s is advantaμeous due to low ene⅔μy consumption and hiμh mass t⅔ansλe⅔ capacity, ⅔eduction oλ oxyμen inc⅔eases, hiμh photosynthetic eλλiciency, no da⅔k volumes when compa⅔ed with the othe⅔ photobio⅔eacto⅔s. Suitable ⅔eacto⅔ desiμn should

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

be p⅔ovided with maximum cell mass. Va⅔ious λlat-plate photobio⅔eacto⅔ desiμns a⅔e made oλ μlass, thick t⅔anspa⅔ent PVC mate⅔ials and V-shape and inclined. “lthouμh the othe⅔ desiμns a⅔e cheap and easy to const⅔uct, μlass and PVC is mo⅔e t⅔anspa⅔ent λo⅔ maximum liμht penet⅔ation [ , - ]. . . . . Flζt-plζte phτtτηiτreζθtτrs These systems have la⅔μe illuminated su⅔λaces. Gene⅔ally these photobio⅔eacto⅔s a⅔e made oλ t⅔anspa⅔ent mate⅔ials to utilize the sola⅔ liμht with maximum deμ⅔ee. Dissolved oxyμen concent⅔ation is low compa⅔ed to the ho⅔izontal tubula⅔ photobio⅔eacto⅔s. In this system hiμh photosynthetic activity can achieve. “lthouμh it is ve⅔y suitable λo⅔ cultu⅔inμ alμae but it has some limitations [ ]. . . . . Tuηulζr phτtτηiτreζθtτrs Most oλ tubula⅔ photobio⅔eacto⅔s a⅔e made oλ μlass o⅔ plastic tubes. They can be ho⅔izontal, se⅔pentine, ve⅔tical, nea⅔ ho⅔izontal, conical and inclined photobio⅔eacto⅔s. Ventilation and mixinμ is μene⅔ally pe⅔λo⅔med by pump o⅔ ventilation systems. Tubula⅔ photobio⅔eacto⅔ is suitable with thei⅔ illuminated su⅔λaces. ”ut one oλ the impo⅔tant limitations oλ this system is poo⅔ mass t⅔ansλe⅔. It is a p⅔oblem when photobio⅔eacto⅔ is scaled. “lso photoinhibition is seen in photobio⅔eacto⅔s [ , ]. Iλ the⅔e is not suλλicient mixinμ system cells don t have enouμh liμht λo⅔ thei⅔ μ⅔owth. Devel‐ opinμ mixinμ systems can p⅔ovide eλλective liμht dist⅔ibution. “lso cont⅔ollinμ cultu⅔e tempe⅔atu⅔e is ve⅔y diλλicult in these systems. The⅔mostat can be used but it is expensive and ha⅔d to cont⅔ol. “lso cells can attach the walls oλ tubes. Lonμ tubula⅔ photobio⅔eacto⅔s a⅔e cha⅔acte⅔ized with t⅔ansλe⅔ oλ oxyμen and CO [ , ]. Ve⅔tical column photobio⅔eacto⅔s a⅔e low cost, easily const⅔ucted and compact systems. They a⅔e p⅔omisinμ λo⅔ la⅔μe scale oλ alμae p⅔oduction. ”ubble column and ai⅔liλt photobio⅔‐ eacto⅔s can ⅔each speciλic μ⅔owth ⅔ate [ ]. . . . . Iσterσζlly illumiσζted phτtτηiτreζθtτrs Flo⅔escent lamps can illuminate some photobio⅔eacto⅔s inte⅔nally. Photobio⅔eacto⅔ is e⅓uip‐ ped with wheels λo⅔ mixinμ alμal cultu⅔es. Sp⅔aye⅔ p⅔ovides ai⅔ and CO to cultu⅔e. This type oλ photobio⅔eacto⅔s can utilize sola⅔ liμht and a⅔tiλicial liμht [ ]. When sola⅔ liμht in‐ tensity is low niμht o⅔ cloudy day a⅔tiλicial liμht is used. “lso in some ⅔esea⅔ches, it is told that sola⅔ liμht can be collected and dist⅔ibuted with optic λibe⅔s in cylind⅔ical photobio⅔eac‐ to⅔s [ ]. “nothe⅔ advantaμes oλ this system a⅔e can be ste⅔ilized with heat unde⅔ p⅔essu⅔e and minimizinμ the contamination [ , ]. . . . . Pyrζmid phτtτηiτreζθtτr The Py⅔amid photobio⅔eacto⅔ is usinμ λully cont⅔olled and automatic system that inc⅔eas‐ es the p⅔oduction ⅔ate. With this system, it is easy to μ⅔ow any mic⅔oalμae at any climate

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conditions. The desiμn is in py⅔amid shape to abso⅔b liμht mo⅔e eλλectively. “s men‐ tioned above, liμht is one oλ the siμniλicant pa⅔amete⅔s aλλectinμ alμae μ⅔owth ⅔ate and with this ⅔ecent system alμae can be supplied with optimal liμht intensity. That is why the shape oλ the system is the last innovation λo⅔ p⅔oduction step. So, havinμ optimal liμht in‐ tensity du⅔inμ hiμh mic⅔oalμae p⅔oduction dec⅔eases the ene⅔μy consumption. The body desiμn is anμled to ⅔educe to pump costs by usinμ ai⅔-liλtinμ method and dec⅔ease the de‐ λo⅔mation on cell walls. The⅔mo-isolated and hiμh technoloμic mate⅔ials a⅔e used to avoid ene⅔μy lost and ove⅔ heatinμ [ ]. . . Biocoil microalgae production system ”iocoil is a holozoic tubula⅔ photobio⅔eacto⅔ which made oλ plastic tubes with small diame‐ te⅔ between . - cm , cent⅔iλuμes, diaph⅔aμm pumps o⅔ pe⅔istaltic pumpinμ a⅔e utilized in this system. ”iocoil desiμn p⅔ovides e⅓ual mixinμ and ⅔educes the attachment oλ alμae to the walls. It automates the p⅔oduction p⅔ocess. It is not suitable λo⅔ all alμae species. Some oλ alμae species damaμes by ci⅔culation system and some oλ them attach to the inte⅔nal su⅔λace oλ tubes and aλλects alμae p⅔oduction neμative. In this system, when the level oλ alμae in‐ c⅔eases maximum deμ⅔ee, because oλ the liμht limitation photosynthesis can slow. ”iocoil systems with utilizinμ sola⅔ liμht in o⅔ outsides can executable. Liμht is μiven with an anμle so alμal cell can utilize bette⅔ and photosynthesis occu⅔s easily [ , , ]. . . . Desiμσ τλ θulture μrτwth systems Depends oλ local conditions and suitable mate⅔ials va⅔ious cultu⅔e systems can be desiμned by va⅔ious sizes, shapes oλ const⅔uction mate⅔ial, slope and mixinμ type. These λacto⅔s aλλect pe⅔λo⅔mance, cost and ⅔esistance. To const⅔uct suitable photobio⅔eacto⅔ mate⅔ial has main impo⅔tance. Mate⅔ials like plastic o⅔ μlass ⅔elax and ⅔iμid shouldn t be toxic, they should have mechanical powe⅔, ⅔esistance, chemical stability and low cost. Tubula⅔ photobio⅔eac‐ to⅔s a⅔e the most suitable ones λo⅔ open cultu⅔e systems. They have biμ illumination su⅔λace, μood biomass p⅔oductivity and they a⅔en t expensive because they a⅔e made oλ μlass o⅔ plastic tubes. Flat-type photobio⅔eacto⅔s a⅔e made oλ t⅔anspa⅔ent mate⅔ials to utilize sola⅔ liμht ene⅔μy in maximum deμ⅔ee. This type oλ photobio⅔eacto⅔s allows μood immobilization oλ alμae and they a⅔e cleaned easily [ ]. Pond walls and deep side can made oλ simple sand, clay, b⅔ick o⅔ cement even PVC, μlass λibe⅔ o⅔ polyu⅔ethane. Fo⅔ coatinμ mostly lonμ lastinμ plastic memb⅔ane is used. e. μ., - mm thick, UV-⅔esistant, PVC o⅔ polyethylene sheets sometimes to lowe⅔ the cost uncoatinμ ponds a⅔e used but that time some p⅔oblems occu⅔ like contamination, a laye⅔ oλ mud and sand [ ]. . . . Mixiσμ Mixinμ is a p⅔ocess λo⅔ inc⅔easinμ the p⅔oductivity oλ biomass in photobio⅔eacto⅔s. Mixinμ p⅔ovides dist⅔ibution oλ liμht intensity, suλλicient CO t⅔ansλe⅔ and maintains uniλo⅔m pH. Mixinμ is necessa⅔y λo⅔ p⅔eventinμ alμae sedimentation and avoidinμ cell attachment to the ⅔eacto⅔ wall. Mixinμ is also p⅔ovides e⅓ual liμht and nut⅔ients to all cells and inc⅔eases the μas t⅔ansλe⅔ between cultu⅔e medium and ai⅔ [ ]. The second oλ p⅔io⅔ity measu⅔es is ca⅔bon

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

supply λo⅔ usinμ in photosynthesis. In ve⅔y dense cultu⅔es, CO λ⅔om ai⅔ includes . % oλ CO and bubbles du⅔inμ the cultu⅔e can be limited λo⅔ alμal μ⅔owth. CO addition c⅔eates a buλλe⅔ λo⅔ the ⅔esult oλ chanμinμ pH in the wate⅔ [ ]. Poo⅔ mixinμ allows cells to clumpinμ like diλλe⅔ent size oλ aμμ⅔eμates the⅔eλo⅔e it leads phase solid-li⅓uid-μas system in ⅔eacto⅔. This situation tends to ⅔educe the mass t⅔ansλe⅔. ”ut all alμae cannot tole⅔ate aμitation. ”ecause they a⅔e sensitive to hyd⅔odynamic st⅔ess. Hiμh mixinμ ⅔ate can cause the damaμinμ oλ cells. Mixinμ in bubble column and ai⅔ liλt ⅔eac‐ to⅔s can cha⅔acte⅔ize with axial dispe⅔sion coeλλicient, mixinμ time, ci⅔culation time and ”odenstein numbe⅔ [ ]. “nalysis oλ mixinμ in bubble column shows it has sho⅔te⅔ time than ai⅔liλt ⅔eacto⅔s. ”ubbles beyond the suction pipe p⅔ovide less blu⅔⅔y a⅔ea and causes bette⅔ exposu⅔e to the liμht. In addition, existence oλ suction pipe in ai⅔liλt ⅔eacto⅔s causes mo⅔e eλλective mixinμ because inte⅔nal loop p⅔ovides a ci⅔culation. “i⅔liλt ⅔eacto⅔ μives in‐ λo⅔mation about λluid λlow and hiμh μas-li⅓uid mass t⅔ansλe⅔ ⅔ate. ”ubble column causes un‐ balance cell density and these causes to death oλ alμae [ , ]. . . . Liμht peσetrζtiτσ “nothe⅔ key oλ successλully scale up is liμht penet⅔ation. IIumination in the photobio⅔eacto⅔ aλλects biomass composition, μ⅔owth ⅔ate and p⅔oducts. Mic⅔oalμae need liμht λo⅔ thei⅔ pho‐ tosynthesis [ ]. Photosynthetic active ⅔adiation wave chanμes about nm and this is e⅓ual to the visible liμht [ ]. In intense cultu⅔es, liμht μ⅔adient chanμes ove⅔ the photobio⅔‐ eacto⅔ ⅔adius due to the weakeninμ oλ the liμht. Reduction oλ liμht intensity ⅔elated to wave lenμth, cell concent⅔ation, photobio⅔eacto⅔ μeomet⅔y and distance oλ the liμht t⅔ansmittance. Liμht intensity in photobio⅔eacto⅔ ⅔elated to liμht way, cell concent⅔ation and liμht which emits by mic⅔oalμae [ ]. . . . Gζs iσjeθtiτσ Supplement oλ CO by bubbles is an impo⅔tant λacto⅔ to be conside⅔ed in desiμns. Injection oλ CO bases on μivinμ CO to photobio⅔eacto⅔ a⅔tiλicially. Resea⅔ches show that ⅔ich ventila‐ tion oλ CO p⅔ovides CO to alμae, suppo⅔ts deooxyμenation oλ suspension, to imp⅔ove cy‐ clinμ p⅔ovides mixinμ and limits the liμht inhibition [ ]. ”ut hiμh ventilation ⅔ate leads to hiμhe⅔ cost that is why in la⅔μe scale oλ mic⅔oalμae p⅔oduction it is not ⅔ecommended. These ⅔esea⅔ches ⅔esults λo⅔ mic⅔oalμae p⅔oduction necessa⅔y optimum ae⅔ation ⅔ate oλ CO μas. Includes about % o⅔ % oλ CO v/v , ⅔ate oλ . - vvm [ ]. Volume oλ ai⅔/medium/ time is λound cost eλλective λo⅔ ai⅔ mass cultu⅔e [ ]. . . . Cτmpζrisτσ τλ τpeσ ζσd θlτsed θulture systems Open and closed cultu⅔e systems have advantaμes and disadvantaμes. Const⅔uction and op‐ e⅔ation oλ open cultu⅔e systems a⅔e cheape⅔ and they a⅔e mo⅔e ⅔esistant than closed ⅔eacto⅔s and have la⅔μe p⅔oduction capacity [ ]. Ponds use mo⅔e ene⅔μy to homoμenize to nu‐ t⅔ients and to utilize the sola⅔ ene⅔μy λo⅔ μ⅔owth thei⅔ wate⅔ level cannot be less than cm [ ]. Ponds a⅔e exposinμ to ai⅔ conditions because wate⅔ tempe⅔atu⅔e evapo⅔ation and illu‐

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mination cannot be cont⅔olled. They p⅔oduce la⅔μe amounts oλ mic⅔oalμae but they need la⅔μe⅔ a⅔eas than closed systems and they a⅔e open to othe⅔ contaminations λ⅔om the othe⅔ mic⅔oalμae and bacte⅔ia. “lso when atmosphe⅔e has only . - . % oλ CO , mass t⅔ansλe⅔ limitation slows the μ⅔owth oλ mic⅔oalμae cell. Photobio⅔eacto⅔s a⅔e λlexible systems, which can ope⅔ate λo⅔ bioloμical and physioloμical cha⅔acte⅔istics oλ cultu⅔ed mic⅔oalμae. It can be possible to p⅔oduce mic⅔oalμae, which cannot p⅔oduce in ponds. Exchanμe oλ μas and contaminants between atmosphe⅔e and cultu⅔ed cells in photobio⅔eacto⅔ is limited o⅔ blocked by ⅔eacto⅔ walls [ ]. Depends on the shape and desiμn, photobio⅔eacto⅔s have mo⅔e advantaμes than open ponds. Cultu⅔e conditions and μ⅔owth pa⅔amete⅔s can be cont⅔olled bette⅔, it p⅔events evapo⅔ation, ⅔e‐ duces loss oλ CO , p⅔ovides hiμh mic⅔oalμae density o⅔ cell concent⅔ation, hiμh yield, c⅔e‐ ates mo⅔e saλe and p⅔ese⅔ved envi⅔onment, p⅔events contamination. Despite the advantaμes, photobio⅔eacto⅔s have p⅔oblems to be solved. Ove⅔ heatinμ, bioloμical pollu‐ tion, accumulation oλ oxyμen, diλλiculty oλ scale-up, hiμh cost oλ const⅔uction and ope⅔a‐ tion and cell damaμe because oλ shea⅔ st⅔ess and deμ⅔adation oλ mate⅔ial in photo phase a⅔e main p⅔oblems in photobio⅔eacto⅔s [ ]. Compa⅔inμ photobio⅔eacto⅔s and open ponds is not easy because μ⅔owth oλ alμae ⅔elated to al lot oλ diλλe⅔ent λacto⅔s. Th⅔ee pa⅔amete⅔s a⅔e conside⅔ed in alμae p⅔oduction units λo⅔ yield [ ] • Volumet⅔ic p⅔oductivity VP p⅔oductivity pe⅔ unit ⅔eacto⅔ volume exp⅔essed as μ/L. d . • “⅔eal p⅔oductivity “P p⅔oductivity pe⅔ unit oλ μ⅔ound a⅔ea occupied by the ⅔eacto⅔ ex‐ p⅔essed as μ/m d . • Illuminated su⅔λace p⅔oductivity ISP p⅔oductivity pe⅔ unit oλ ⅔eacto⅔ illuminated su⅔‐ λace a⅔ea exp⅔essed as μ/m d . “cco⅔dinμ to ⅔esea⅔ches closed systems don t p⅔ovide advantaμe λo⅔ a⅔eal p⅔oductivity but p⅔ovide volumet⅔ic p⅔oductivity times and cell concent⅔ation times mo⅔e than open ponds [ , ]. . . . Cτmpζrisτσ τλ ηζtθh ζσd θτσtiσuτus prτθess Photobio⅔eacto⅔s can be ope⅔ated in batch o⅔ continuous p⅔ocess. The⅔e a⅔e a lot oλ advan‐ taμes λo⅔ usinμ continuous bio⅔eacto⅔s than batch bio⅔eacto⅔s. Continuous bio⅔eacto⅔s p⅔o‐ vide mo⅔e cont⅔ol than batch bio⅔eacto⅔s. G⅔owth ⅔ates can be ⅔eμulatinμ in lonμ time pe⅔iods, can be saved and with va⅔iable dilution ⅔ates biomass concent⅔ation can be cont⅔ol‐ led. With steady state continuous bio⅔eacto⅔s ⅔esults is mo⅔e dependable, p⅔oducts can be easily p⅔oduced and can be ⅔eached desi⅔ed p⅔oduct ⅓uality. Continuous ⅔eactions oλλe⅔ many oppo⅔tunities λo⅔ system ⅔esea⅔ch and analysis [ ]. ”ut some type oλ bio⅔eacto⅔s is not suitable λo⅔ continuous p⅔ocess. Fo⅔ some p⅔oductions, cell aμμ⅔eμation and wall μ⅔owth can inhibit the steady state μ⅔owth. “nothe⅔ p⅔oblem is loss oλ o⅔iμinal p⅔oduct st⅔ain in time. Mixtu⅔es viscosity and hete⅔oμenic natu⅔e make diλλi‐

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

cult λo⅔ maintaininμ λilamentous o⅔μanisms. Lonμ μ⅔owth pe⅔iods inc⅔ease the contamina‐ tion ⅔isks [ ]. . . Harvesting alternatives The⅔e a⅔e seve⅔al ways to ha⅔vest mic⅔oalμae and d⅔y them. Some main ha⅔vestinμ methods a⅔e sedimentation, λlocculation and λilt⅔ation. Sedimeσtζtiτσ When a pa⅔ticle moves continuously in a phase, the velocity is aλλected by two λacto⅔s. Fi⅔st oλ them is inc⅔easinμ the velocity because the density μ⅔adient between pa⅔ticle and λluid c⅔eate buoyant λo⅔ce. “t the end, buoyant λo⅔ce μets e⅓ual to d⅔aμμinμ λo⅔ce and pa⅔ticle sta⅔ts movinμ with a constant velocity. The same idea is applied to collect mic⅔oal‐ μae λ⅔om the ponds. G⅔avity λo⅔ce is used λo⅔ settlinμ oλ suspended pa⅔ticles in λluid. This method is cheap and easy. Howeve⅔, the pa⅔ticles suspended in the λluid have to be incom‐ p⅔essible. The p⅔oblem with the Sθeσedesmus sp. and Chlτrellζ sp. is that they a⅔e comp⅔essi‐ ble. That is why sedimentation cannot be used λo⅔ these types [ ]. Fo⅔ low value p⅔oducts, sedimentation miμht be used iλ it is imp⅔oved with λlocculation [ ]. Flτθθulζtiτσ: is also used λo⅔ ha⅔vestinμ mic⅔oalμae. The μene⅔al idea is mic⅔oalμae ca⅔⅔ies neμative cha⅔μe on it and iλ the λlocculants disappea⅔ the neμative cha⅔μe, alμae sta⅔ts coaμu‐ lation. Some used λlocculants a⅔e “l SO , FeCl , Fe SO [ ]. Filtrζtiτσ: This is one oλ the most competitive methods λo⅔ the collection oλ alμae. The⅔e a⅔e diλλe⅔ent types oλ λilt⅔ations, λo⅔ example, dead end, mic⅔oλilt⅔ation, ult⅔aλilt⅔ation, p⅔essu⅔e λilte⅔ and vacuum λilte⅔. Mostly λilt⅔ations ⅔e⅓ui⅔e the li⅓uid media with alμae to come th⅔ouμh λilt⅔ation. Filte⅔ can be λed until a thick laye⅔ oλ mic⅔oalμae is collected on the sc⅔een. This method is ve⅔y expensive λo⅔ especially mic⅔oalμae. The po⅔e sizes oλ the λilte⅔s a⅔e the most impo⅔tant pa⅔t. Iλ the po⅔e size is biμμe⅔ than alμae you cannot collect it. In con‐ t⅔ast, iλ the po⅔e size is too small it miμht ⅔esult in dec⅔ease oλ the λlow ⅔ate and block the po⅔es [ ]. . . Extraction of lipid from microalgae The⅔e a⅔e a lot oλ methods λo⅔ ext⅔action oλ lipid λ⅔om mic⅔oalμae but the most common techni⅓ues a⅔e oil p⅔esses, li⅓uid-li⅓uid ext⅔action solvent ext⅔action , supe⅔c⅔itical λluid ex‐ t⅔action SFE and ult⅔asonic techni⅓ues. Oil p⅔esses a⅔e usually used λo⅔ ext⅔actinμ oλ lipids λ⅔om nuts and seeds. The same p⅔ocess and devices can be used λo⅔ lipid ext⅔action λ⅔om mi‐ c⅔oalμae. Fo⅔ the pu⅔pose oλ this p⅔ocess to be eλλective, λi⅔stly mic⅔oalμae must be d⅔ied. P⅔esses use p⅔essu⅔e λo⅔ b⅔eakinμ cells and ⅔emovinμ oil [ ]. This method can ext⅔act % oλ oil but in lonμe⅔ ext⅔action times it is less eλλective [ ]. Solvent ext⅔action is mo⅔e successλul λo⅔ ext⅔actinμ lipids λ⅔om mic⅔oalμae. In this method o⅔μanic solvents such as hexane, acetone, and chlo⅔oλo⅔m a⅔e added in the alμae paste. Solu‐ bility oλ oil is hiμhe⅔ in o⅔μanic solvents than wate⅔. The⅔eλo⅔e solvent b⅔eaks the cell wall and ext⅔acts oil easily. Solvent ext⅔action continues with distillation p⅔ocess λo⅔ sepa⅔atinμ oil λ⅔om the solvent [ ]. Hexane is cheap and has hiμh ext⅔action capacity. Fo⅔ this ⅔eason it is ⅔epo⅔ted to be the most eλλective solvent in ext⅔actions.

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In addition to this studies, staμe p⅔ocess usinμ ethanol imp⅔oves lipid ext⅔action. The yield oλ ⅔ecove⅔y oλ oil ⅔eaches about %. ”utanol is also eλλective in ext⅔action oλ lysophospholi‐ pids. ”ut evapo⅔ation oλ butanol is diλλicult and the⅔e a⅔e some impu⅔ities because oλ its hiμh pola⅔ity [ ]. Supe⅔c⅔itical ext⅔action uses hiμh p⅔essu⅔e and tempe⅔atu⅔e λo⅔ b⅔eakinμ cells. This method is widely used and eλλicient λo⅔ ext⅔action time. Studies ⅔epo⅔ted that tempe⅔atu⅔e and p⅔es‐ su⅔e don t aλλect the yield oλ components but it aλλects ext⅔action ⅔ate. Simila⅔ eλλects a⅔e seen in SFE system and solvent ext⅔action [ ]. “nothe⅔ method is usinμ ult⅔asonic techni⅓ues. In this method mic⅔oalμae is exposed to hiμh intensity ult⅔asonic waves and these waves c⅔eates bubbles a⅔ound the cell. Shock waves a⅔e emitted by collapsinμ bubbles. It b⅔eaks cell wall and desi⅔ed components ⅔elease to the solution. This method is also imp⅔oves the ext⅔action ⅔ate with the same way. This techni⅓ue is widely used in labo⅔ato⅔y scale but in comme⅔cially scale the⅔e is not enouμh inλo⅔mation about cost and applicability [ , ]. . . Biodiesel Production from Oil “λte⅔ ext⅔action the⅔e a⅔e main methods λo⅔ p⅔oducinμ biodiesel di⅔ect used and mixinμ with ⅔aw oils mic⅔oemulsion py⅔olysis and t⅔anseste⅔iλication. . . . Dilutiτσ This is a dilution method that ce⅔tain p⅔opo⅔tion oλ veμetable and waste oils blended with diesel λuel and anothe⅔ solvent. The most used oils λo⅔ p⅔oducinμ biodiesel with this way a⅔e waste oils and veμetable oils like sunλlowe⅔ and ⅔apeseed. Di⅔ect use o⅔ blendinμ μene⅔ally conside⅔ed beinμ unsatisλacto⅔y and imp⅔actical λo⅔ both di⅔ect and indi⅔ect diesel enμines. The⅔e a⅔e speciλic p⅔oblems such as hiμh viscosity, acid composition, λ⅔ee λatty-acid content, μum λo⅔mation because oλ oxidation, polyme⅔ization du⅔inμ sto⅔aμe and combustion, ca⅔bon deposits and also lub⅔icatinμ-oil thickeninμ [ ]. Dilution oλ veμetable oils with solvents lowe⅔s the viscosity. The viscosity oλ oil can be low‐ e⅔ed by blendinμ with pu⅔e ethanol [ ]. The low viscosity is μood λo⅔ bette⅔ pe⅔λo⅔mance oλ enμine, which dec⅔eases with inc⅔easinμ the pe⅔centaμe oλ diesel [ ]. In this method the⅔e is no chemical p⅔ocess and viscosity can be lowe⅔ but the⅔e a⅔e also ca⅔bon deposits and lube pollution p⅔oblems to be solved. To solve p⅔oblems caused by hiμh viscosity, mi‐ c⅔o-emulsion, py⅔olysis and t⅔anseste⅔iλication methods a⅔e used [ ]. . . . Miθrτ-emulsiτσ It is deλined that the size oλ nm, the two immiscible li⅓uid o⅔μanic mixtu⅔es with ionic o⅔ non-ionic, selλ-λo⅔med stable colloidal dist⅔ibution. With this method it is possible to λo⅔m alte⅔native diesel λuels except pet⅔oleum [ ]. In this method veμetable oils with an este⅔ and dispe⅔sant co-solvent , o⅔ oλ veμetable oils, an alcohol and a su⅔λactant, with o⅔ without diesel λuels can be used to make a mic⅔oemulsion. Due to thei⅔ alcohol contents, mic⅔oemul‐

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

sions have lowe⅔ volumet⅔ic heatinμ values than diesel λuels. ”ut these alcohols have hiμh latent heats oλ vapo⅔ization and also tend to cool the combustion chambe⅔, which cause a ⅔eduction oλ nozzle cokinμ. “ mic⅔oemulsion made oλ methanol and veμetable oils can pe⅔‐ λo⅔m like diesel λuels [ ]. To solve the p⅔oblem oλ the hiμh viscosity oλ veμetable oils, mi‐ c⅔oemulsions with solvents and immiscible li⅓uids, such as methanol, ethanol, -butanol and ionic o⅔ non-ionic amphiphiles have been studied [ ]. . . . Pyrτlysis Py⅔olysis is the conve⅔sion oλ o⅔μanic substance into anothe⅔ by means oλ heat o⅔ by heat in the p⅔esence oλ a catalyst. Veμetable oil, animal λat, alμae oil, natu⅔al λatty acids o⅔ methyl este⅔s oλ λatty acids can be py⅔olyzed [ ]. “lthouμh this method is not ve⅔y cheap, howev‐ e⅔, λuel can be p⅔oduced without ext⅔action oλ lipids o⅔ hyd⅔oca⅔bons. Mo⅔e uniλo⅔m p⅔od‐ uct can be obtained and ideally inc⅔eases yields ove⅔ t⅔anseste⅔iλication with this method [ ]. P⅔oducts a⅔e chemically simila⅔ de⅔ived λ⅔om pet⅔oleum p⅔oducts, which a⅔e to μaso‐ line and diesel λuel de⅔ived [ ]. “lso with py⅔olysis some low value mate⅔ials and some‐ times mo⅔e μasoline than diesel λuel a⅔e p⅔oduced [ ]. In compa⅔ison between py⅔olysis and the othe⅔ c⅔ackinμ p⅔ocesses, py⅔olysis is seen mo⅔e simple, pollution λ⅔ee and eλλective [ ]. Sha⅔ma et al. ⅔epo⅔ted that py⅔olysis oλ the veμetable oil can p⅔oduce a p⅔oduct which has hiμh cetane numbe⅔, low viscosity, acceptable amounts oλ sulλu⅔, wate⅔ and sediments contents, acceptable coppe⅔ co⅔⅔osion values [ ]. .

. Trζσsesteriλiθζtiτσ

T⅔anseste⅔iλication oλ the oil is the most p⅔omisinμ solution to the hiμh viscosity p⅔oblem [ ]. In this p⅔ocess, t⅔iμlyce⅔ides a⅔e conve⅔ted to diμlyce⅔ides, then the diμlyce⅔ides a⅔e conve⅔ted to monoμlyce⅔ides, and the monoμlyce⅔ides a⅔e conve⅔ted to este⅔s biodiesel and μlyce⅔ol by-p⅔oducts [ ]. The⅔e a⅔e th⅔ee common kinds oλ catalysts used in t⅔anses‐ te⅔iλication p⅔ocess such as lipase catalysts, acid catalysts and alkali catalysts. Each catalyst has advantaμes and disadvantaμes [ ]. In the acid-catalytic t⅔anseste⅔iλication, the ⅔eaction can be catalyzed by sulλu⅔ic, phospho⅔ic, hyd⅔ochlo⅔ic and o⅔μanic sulλonic acids. Ve⅔y hiμh yields can be obtained by usinμ this cata‐ lyst. These ⅔eactions need the use oλ hiμh alcohol-to-oil mola⅔ ⅔atios in o⅔de⅔ to obtain μood p⅔oduct yields in p⅔actical ⅔eaction times. ”ut este⅔ yields do not p⅔opo⅔tionally inc⅔ease with mola⅔ ⅔atio and the ⅔eaction time is ve⅔y lonμ h [ , , ]. Xu et al. studied the acidic t⅔anseste⅔iλication oλ mic⅔oalμae Hete⅔ot⅔ophic C. P⅔otothecoides oil. They used methanol λo⅔ alcohol and they achieved % oλ F“ME yield [ ]. Johnson made a study on Sθhizτθhytrium limζθiσum mic⅔oalμae species. He conve⅔ted this alμal oil to biodiesel with acidic t⅔anseste⅔iλication and he achieved . % oλ biodiesel yield [ ]. In the alkali-catalytic t⅔anseste⅔iλication, the ⅔eaction can be catalyzed by alkaline metal alk‐ oxides, and hyd⅔oxides, as well as sodium o⅔ potassium ca⅔bonates. Sodium methoxide is the most widely used biodiesel catalyst. This ⅔eaction is λaste⅔ than acid-catalytic t⅔anseste⅔i‐ λication and ⅔eactions can occu⅔ in low tempe⅔atu⅔es with a small amount λo⅔ catalyst and

43

44

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

with little o⅔ no da⅔keninμ oλ colou⅔ oλ the oil [ ]. Hiμh ⅓uality can be obtained howeve⅔ this p⅔ocess is ve⅔y sensitive to the p⅔esence oλ wate⅔ and λ⅔ee λatty acids and needs lots oλ methanol. Iλ the ⅔aw mate⅔ials have a hiμh pe⅔centaμe oλ λ⅔ee λatty acids o⅔ wate⅔, the alkali catalyst ⅔eacts with the λ⅔ee λatty acids to λo⅔m soaps [ ]. The⅔e a⅔e some studies on mic⅔o‐ alμae oil to p⅔oduce biodiesel by usinμ alkali t⅔anseste⅔iλication. Velas⅓uez-O⅔ta et al. stud‐ ied on biodiesel p⅔oduction λ⅔om Chlτrellζ vulμζris. In that study, alkali t⅔anseste⅔iλication was used λo⅔ conve⅔sion and they achieved % oλ F“ME yield [ ]. Fe⅔⅔entino et al. stud‐ ied on biodiesel p⅔oduction λ⅔om mic⅔oalμae too. They used Chlo⅔ella sp. oil and thei⅔ p⅔o‐ duction method was alkali t⅔anseste⅔iλication. They have obtained hiμh yield λ⅔om thei⅔ expe⅔iment [ ]. In anothe⅔ study, Ca⅔valho et al. used alkali t⅔anseste⅔iλication λo⅔ biodie‐ sel p⅔oduction λ⅔om alμae oil. In thei⅔ study, they used Chlτrellζ emersτσii oil and they have obtained % conve⅔sion yield [ ]. It can be seen that the⅔e a⅔e some p⅔oblems such as ⅔ecove⅔y oλ μlyce⅔ol o⅔ ⅔emovinμ cata‐ lysts λ⅔om p⅔oduct and need oλ wastewate⅔ t⅔eatment in acid o⅔ alkali-catalytic t⅔anseste⅔iλi‐ cation. Enzymatic catalysts like lipases a⅔e able to catalyze the t⅔anseste⅔iλication oλ t⅔iμlyce⅔ides eλλectively. With this p⅔ocess μlyce⅔ol can be easily ⅔ecove⅔ed howeve⅔ enzy‐ matic catalysts a⅔e oλten mo⅔e expensive than chemical catalysts. The hiμh cost oλ enzyme p⅔oduction is the main obstacle to the comme⅔cialization oλ enzyme-catalyzed p⅔ocesses. ”ut usinμ solvent-tole⅔ant lipases and immobilized lipases can be a solution λo⅔ this. Lipasecatalyzed t⅔anseste⅔iλication is conside⅔ed to be one oλ the most eλλective ⅔eactions λo⅔ p⅔o‐ duction oλ biodiesel [ ]. In anothe⅔ study T⅔an et al. used mic⅔oalμae oil Chlτrellζ vulμζris ESPλo⅔ p⅔oducinμ biodiesel. Thei⅔ method was enzyme-catalyzed t⅔anseste⅔iλication and they used lipase in this p⅔ocess. In the ⅔esult, they ⅔epo⅔ted that they achieved . % oλ F“ME yield [ ]. Table p⅔esents the t⅔anseste⅔iλication studies λo⅔ biodiesel p⅔oduction λ⅔om mic⅔oalμae oil. Supe⅔c⅔itical p⅔ocess, mic⅔owave-assisted method and ult⅔asonic-assisted p⅔ocess a⅔e novel methods used in biodiesel p⅔oduction a⅔ea. Since these methods a⅔e novel methods and also alμae a⅔e new mate⅔ials λo⅔ bioλuel a⅔ea, the⅔e is a λew studies biodiesel p⅔oduction λ⅔om al‐ μae oil with these novel methods, these studies we⅔e ⅔eviewed and p⅔esented below. With superθritiθζl prτθess biodiesel p⅔oduction can be easily achieved without catalysts. Su‐ pe⅔c⅔itical λluid is a substance whose tempe⅔atu⅔e and p⅔essu⅔e is above the c⅔itical point. These λluids a⅔e envi⅔onmentally λ⅔iendly and economic. Usually wate⅔, ca⅔bon dioxide and alcohol is used λo⅔ supe⅔c⅔itical λluid. In biodiesel p⅔oduction μene⅔ally supe⅔c⅔itical metha‐ nol and supe⅔c⅔itical ethanol is used. “dvantaμes oλ this p⅔ocess a⅔e beinμ easie⅔ λo⅔ pu⅔iλi‐ cation, sho⅔te⅔ the ⅔eaction time and mo⅔e eλλective ⅔eaction [ ]. In the study oλ Patil et al., usinμ supe⅔c⅔itical methanol p⅔oduced biodiesel. The wet alμae we⅔e used and the ⅔atio oλ alcohol/ oil was chosen as . The tempe⅔atu⅔e oλ the ⅔eaction occu⅔⅔ed at and psi and ⅔esulted in % oλ F“ME yield [ ]. Miθrτwζves activate diλλe⅔ences in small deμ⅔ees oλ pola⅔ molecules and ions, because the molecula⅔ λ⅔iction and chemical ⅔eactions sta⅔t. Molecules have not the enouμh time to ⅔elax and heat μene⅔ation occu⅔s in a sho⅔t time because ene⅔μy inte⅔acts with molecules ve⅔y ⅓uickly. T⅔anseste⅔iλication ⅔eaction is ca⅔⅔ied out with mic⅔owave in a sho⅔t time and mi‐

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

c⅔owave ⅔esults in an eλλicient manne⅔. “s a ⅔esult in a sho⅔t time sepa⅔ation and pu⅔e p⅔od‐ ucts with hiμh yield is obtained. Thus, p⅔oduction costs and the λo⅔mation oλ by-p⅔oduct a⅔e ⅔educed [ ]. Patil et al., made a study on biodiesel p⅔oduction λ⅔om d⅔y mic⅔oalμae by us‐ inμ mic⅔owave-assisted p⅔ocess. KOH was used as catalyst in the study and mic⅔owave con‐ dition is set to W. The pe⅔λo⅔mance oλ the study is a⅔ound % [ ]. The othe⅔ study with mac⅔oalμae λo⅔ mic⅔owave-assisted alμal biodiesel was showed that methanol to mac‐ ⅔oalμae ⅔atio oλ was the best condition. In the study, sodium hyd⅔oxide concent⅔ation was wt % and ⅔eaction time oλ min λo⅔ the best condition [ ]. Kobe⅔μ et al. was ⅔epo⅔t‐ ed the study used Nζσστθhlτrτpsis λo⅔ alμal biodiesel p⅔oduction with mic⅔owave-assisted method. The hiμhe⅔ biodiesel yield was obse⅔ved which was a⅔ound . % with mic⅔owave techni⅓ue. The same conditions λo⅔ sonication techni⅓ue ⅔esulted in lowe⅔ yield [ ]. Algae strain

Method

Alcohol

Alcohol / Temp.

Time

Results

Ref.

4h

80% (FAME

[121]

oil molar ratio Heterotrophic C.

Acidic “rases“erifica“ion

Me“hanol

56:1

30 °C

Yield

Protothecoides (microalga) Chlorella vulgaris

Enzyma“ic

ESP-31 (microalga)

“ranses“erifica“ion (Lipase)

Chlorella vulgaris

in si“” alkaline

(microalga)

“ranses“erifica“ion

Nannochloropsis

he“erogeneo”s

oculata (microalga)

“ranses“erifica“ion

Chlorella (microalga) In-si“” acidic

Me“hanol

98.81

25-40 °C

48 h

94.78% (FAME Yield)

[126]

Me“hanol

600:1

60 °C

75 min

71% (FAME Yield)

[123]

Me“hanol

30:1

50 °C

4h

97.5% (FAME Yield)

[127]

Me“hanol

315:1

23 and 30 15 min-2 h

70-92% (FAME Yield)

[17]

90 (Fl”orome“ric

[124]

“ranses“erifica“ion Chlorella sp.

°C

Alkali Transes“erifica“ion Me“hanol

-

100 °C

25 h

(microalga) Schizochytrium

Reading) Acidic Transes“erifica“ion Me“hanol

-

90 °C

40 min.

82.6% (biodiesel Yield) [122]

Chlorella emersonii

Alkali “rases“erifica“ion

Me“hanol

5:1

60 °C

2h

93% conversion

[125]

Fucus spiralis

Alkali Transes“erifica“ion Me“hanol

6:1

60 °C

4h

1.6-11.5% (Process

[128]

limacinum (microalga)

(macroalga)

Yield)

Commercially refined McGyan macroalga (Kelp)

Me“hanol

32:1

360 °C

30 s

process

Table 2. The “ranses“erifica“ion s“”dies for biodiesel prod”c“ion from microalgae oil

94.7% (FAME Yield)

[129]

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46

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Recent yea⅔s, ultrζsτσiθ-ζssisted prτθess is widely used in biodiesel p⅔oduction. Mixinμ is ve⅔y impo⅔tant λacto⅔ λo⅔ biodiesel yield in t⅔anseste⅔iλication ⅔eactions. It is an eλλective mixinμ method in li⅓uid-li⅓uid mass t⅔ansλe⅔ to p⅔ovide bette⅔ mixinμ. Powe⅔λul mixinμ c⅔eates smalle⅔ d⅔oplets than the conventional mixinμ and inc⅔eases the contact a⅔eas between the oil phases. “lso it p⅔ovides the activation ene⅔μy, which needs λo⅔ initiatinμ t⅔anseste⅔iλica‐ tion ⅔eactions [ ]. In the study oλ Eihaze et al., they a⅔e λocused on the in situ t⅔anseste⅔iλi‐ cation oλ mic⅔oalμae by ult⅔asound techni⅓ue. The ⅔eaction takes h with the use oλ methanol/oil ⅔atio to . The ⅔esult was . ± . μ biodiesel/μ d⅔y Chlτrellζ which shows that this is hiμhe⅔ than mechanically sti⅔⅔ed in situ techni⅓ue [ ]. . . Design of algae and biodiesel production In this section oλ study, alμae p⅔oduction staμes that cove⅔ the alμae st⅔ain and location se‐ lection, alμae cultivation, ha⅔vestinμ, oil ext⅔action, and biodiesel p⅔oduction p⅔ocess λ⅔om mic⅔oalμae a⅔e p⅔esented by usinμ ChemCad desiμn p⅔oμ⅔am. “ll staμes a⅔e μiven in this p⅔ocess λlow diaμ⅔am pλd and e⅓uipment table in detail. “s it is seen in a p⅔ocess λlow dia‐ μ⅔am pλd , the st⅔eams between - a⅔e the a⅔ea oλ the p⅔ocess whe⅔e alμae μ⅔owth occu⅔s. The alμae bodies contain a lipid, which can be ext⅔acted and conve⅔ted into a type oλ bioλuel. The a⅔ea whe⅔e between st⅔eam - has seve⅔al la⅔μe ponds to μ⅔ow alμae containinμ la⅔μe amounts oλ lipid in p⅔epa⅔ation λo⅔ lipid ext⅔action. Once a pond is ha⅔vested, it is ⅔e-inocu‐ lated λo⅔ anothe⅔ c⅔op oλ alμae st⅔eam - . Once the alμae ⅔each matu⅔ity in the μ⅔owth ponds and have the desi⅔ed lipid content, the cells a⅔e ha⅔vested in the a⅔ea whe⅔e st⅔eam - . This a⅔ea at a concent⅔ation oλ μ-alμae/L wate⅔. The alμae collected will be dewate⅔ed, and the usable lipid is ext⅔acted λo⅔ the ⅔eaction p⅔ocess whe⅔e st⅔eam , , - . The ⅔e‐ maininμ alμal biomass will be sent to alμal pulp tank, it may be evaluated λo⅔ bioμas p⅔oduc‐ tion in diμeste⅔s. Lipids, catalysts and alcohol a⅔e sent λo⅔ λuel conve⅔sion to heat-jacketed t⅔anseste⅔iλication ⅔eacto⅔. Once the lipid is ha⅔vested λ⅔om the alμae cells, the usable t⅔iμly‐ ce⅔ides a⅔e conve⅔ted to bioλuel in st⅔eams - . Then p⅔oducts sent to the sepa⅔ato⅔ to sep‐ a⅔ate biodiesel and byp⅔oduct μlyce⅔ol in st⅔eam - . The byp⅔oduct oλ this ⅔eaction is μlyce⅔ol, which is ⅔emoved and t⅔eated as waste. The bioλuel is then ⅔eady to be used in mode⅔n λa⅔m e⅓uipment, o⅔ as a λuel supplement λo⅔ diesel. “ll the e⅓uipments, tanks and ponds a⅔e labeled in the Fiμu⅔e .

. Conclusion Nowadays, demands on ene⅔μy a⅔e caused to ⅔eduction oλ sou⅔ces and envi⅔onmental p⅔ob‐ lems let the wo⅔ld to use alte⅔native λuels. Mic⅔oalμae have impo⅔tant potential as an alte⅔‐ native ene⅔μy sou⅔ce. “ lot oλ valuable p⅔oducts can be p⅔oduced λ⅔om mic⅔oalμae such as biodiesel, bioμas, bioethanol, medicines and nut⅔aceuticals. ”iodiesel is one oλ the most im‐ po⅔tant alte⅔native λuels. Mic⅔oalμal biodiesel p⅔oduction is ve⅔y new technoloμy. In this study, mic⅔oalμae and thei⅔ classiλications, impo⅔tant steps oλ biodiesel p⅔oduction λ⅔om mi‐ c⅔oalμae have been mentioned. In p⅔oduction sections, steps a⅔e explained b⅔ieλly and easily unde⅔standable. “lso advantaμes and disadvantaμes in the p⅔oduction a⅔e mainly dis‐

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

Figure 1. The process flow diagram of biodiesel prod”c“ion process from microalgae by ChemCAD.

47

48

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

cussed. “t the end oλ this chapte⅔, a biodiesel p⅔oduction λ⅔om mic⅔oalμae is desiμned by ChemCadp⅔oμ⅔am, which shows a simple p⅔ocess λlow diaμ⅔am λo⅔ who desi⅔es to p⅔oduce biodiesel λ⅔om mic⅔oalμae. Recently, mic⅔oalμae a⅔e not economically viable. The main p⅔ob‐ lems a⅔e the cost oλ capital cost. The ⅔ate oλ ⅔etu⅔n is not sho⅔t as it is expected. The ope⅔a‐ tion cost is also aλλectinμ the total cost siμniλicantly. The main pa⅔t, which makes the p⅔ocess expensive due to ope⅔ation and capital costs, a⅔e alμae μ⅔owth, ha⅔vestinμ, dewate⅔inμ, and λuel conve⅔sion. ”eyond these, oil ext⅔action step siμniλicantly inc⅔eases the cost. Iλ the oil could be ext⅔acted easily and at hiμhe⅔ ⅔ates, the cost would be much lowe⅔. Howeve⅔, the⅔e a⅔e needs to innovate new ways to make the p⅔ocess economically λeasible. Reμa⅔dless, mi‐ c⅔oalμae a⅔e seen as impo⅔tant ⅔esou⅔ces λo⅔ the λutu⅔e and the⅔e will be a lot oλ imp⅔ove‐ ments on ⅔ecent technoloμy.

Author details Didem 5zçimen, M. 5me⅔ G(lyu⅔t and ”enan İnan *“dd⅔ess all co⅔⅔espondence to [email protected]⅔ YıldızTechnical Unive⅔sity, Faculty oλ Chemical and Metallu⅔μical Enμinee⅔inμ, ”ioenμin‐ ee⅔inμ Depa⅔tment, Istanbul, Tu⅔key

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] Hi⅔ayama S, Ueda R, Oμushi Y, Hi⅔ano “, Samejima Y, Hon-Nami K, Kunito S. Etha‐ nol p⅔oduction λ⅔om ca⅔bon dioxide by λe⅔mentative mic⅔oalμae. Studies in Su⅔λace Science and Catalysis .

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] ”ush R“, Hall KM. P⅔ocess λo⅔ the p⅔oduction oλ ethanol λ⅔om alμae. U. S. Patent , , .

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] Raλi⅓ul IM, Jalal KC“, “lam MZ. Envi⅔onmental λacto⅔s λo⅔ optimisation oλ Spiruliσζ biomass in labo⅔ato⅔y cultu⅔e. ”iotechnoloμy - .

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] ”⅔uton T, Lyons H, Le⅔at Y, Stanley M. “ Review oλ the Potential oλ Ma⅔ine “lμae as a Sou⅔ce oλ ”ioλuel in I⅔eland. Sustainable Ene⅔μy I⅔eland - .

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] Gua⅔dia SD, Valls R, Mesμuiche V, ”⅔unei JM, Gulioli G. Enantioselective synthesis oλ - -biλu⅔acadiol a natu⅔al antitumo⅔ ma⅔ine p⅔oduct. Tet⅔ahed⅔on Lette⅔s .

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] ”ennama⅔a “, “bou⅔⅔ichi “, ”e⅔⅔ada M, Cha⅔⅔ouλ M, Chaib N, ”oudouma M, Ga⅔‐ neau XF. Methoxybiλu⅔-ca⅔enone an antiλunμal and antibacte⅔ial me⅔odite⅔penoid λ⅔om the b⅔own alμa Cystτseirζ tζmζrisθiλτliζ. Phytochemist⅔y .

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] Choi JS, Pa⅔k HJ, Junμ H“, Chunμ HY, Junμ JH, Choi WC. “ cyclohexanonyl b⅔omo‐ phenol λ⅔om the ⅔ed alμa Symphyτθlζdiζ lζtiusθulζ. Jou⅔nal oλ Natu⅔al P⅔oducts .

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] Sheehan J, Dunahay T, ”enemann J, Roessle⅔ P. “ Look ”ack at the U. S. Depa⅔tment oλ Ene⅔μy s “⅓uatic Species P⅔oμ⅔am ”iodiesel λ⅔om “lμae .

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] Sinμh SP and Sinμh D. ”iodiesel p⅔oduction th⅔ouμh the use oλ diλλe⅔ent sou⅔ces and cha⅔acte⅔ization oλ oils and thei⅔ este⅔s as the substitute oλ diesel “ ⅔eview. Renewa‐ ble and Sustainable Ene⅔μy Reviews .

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] Ge⅔wick WH, Robe⅔ts M“, P⅔oteau PJ, Chen JL. Sc⅔eeninμ cultu⅔ed ma⅔ine mic⅔oal‐ μae λo⅔ anticance⅔-type activity. Jou⅔nal oλ “pplied. Phycoloμy .

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] Li Y, Ho⅔sman M, Wu N, Lan CQ, Dubois-Cale⅔o N. ”ioλuels λ⅔om mic⅔oalμae. ”io‐ technoloμy P⅔oμ⅔ess .

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] Rodol L, Zittelli GC, ”assi N, Padovani G, ”iondi N, ”onini G, et al. Mic⅔oalμae λo⅔ oil st⅔ain selection, induction oλ lipid synthesis and outdoo⅔ mass cultivation in a low-cost photobio⅔eacto⅔. ”iotechnoloμy and ”ioenμinee⅔inμ .

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] Zhu CJ, Lee YK. Dete⅔mination oλ biomass d⅔y weiμht oλ ma⅔ine mic⅔oalμae. Jou⅔nal oλ “pplied Phycoloμy .

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] Pa⅔k KC., Whitney C, McNichol, JC, Dickinson KE, MacQua⅔⅔ie S, Sk⅔upski ”P. Zou, J. Wilson, K. E. O Lea⅔y, S. J. ”. McGinn, P. J. Mixot⅔ophic and Photoautot⅔ophic cultivation oλ mic⅔oalμae isolates λ⅔om Saskatchewan, Canada Potential applica‐

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] Conve⅔ti “, Casazza ““, O⅔tiz EY, Pe⅔eμo P, Del ”o⅔μhi M. Eλλect oλ tempe⅔atu⅔e and nit⅔oμen concent⅔ation on the μ⅔owth and lipid content oλ Nζσστθhlτrτpsis τθulζtζ and Chlτrellζ vulμζris λo⅔ biodiesel p⅔oduction. Chemical Enμinee⅔inμ and P⅔ocessinμ P⅔ocess Intensiλication .

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] Molina G⅔ima E, ”ela⅔bi E, “cie ´n Fe⅔na ´ndez F, Robles Medina “, Chisti Y. Recov‐ e⅔y oλ mic⅔oalμal biomass and metabolites p⅔ocess options and economics. ”iotech‐ noloμy “dvances .

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] Dan⅓uah M, “nμ L, Uduman N, Moheimani N, Fo⅔de G. Dewate⅔inμ oλ mic⅔oalμal cultu⅔e λo⅔ biodiesel p⅔oduction explo⅔inμ polyme⅔ occulation and tanμential ow lt⅔ation. Jou⅔nal oλ Chemical Technoloμy and ”iotechnoloμy .

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] Popoola TOS, Yanμomodou OD. Ext⅔action, p⅔ope⅔ties and utilization potentials oλ cassava seed oil. ”iotechnoloμy .

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] Macias-Sanchez MD, Mantell C, Rod⅔iμuez M, Ma⅔tinez De La Ossa E, Lubian LM, Monte⅔o O. Supe⅔c⅔itical uid ext⅔action oλ ca⅔otenoids and chlo⅔ophyll a λ⅔om Nζσ‐ στθhlτrτpsis μζditζσζ. Jou⅔nal oλ Food Enμinee⅔inμ .

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] Wiltshi⅔e KH, ”oe⅔sma M, Molle⅔ “, ”uhtz H. Ext⅔action oλ piμments and λatty acids λ⅔om the μ⅔een alμa Sθeσedesmus τηliquus Chlτrτphyθeζe . “⅓uatic Ecoloμy .

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] Yusuλ N, Kama⅔udin SK, Yaakub Z. Ove⅔view on the cu⅔⅔ent t⅔ends in biodiesel p⅔o‐ duction. Ene⅔μy Conve⅔sion and Manaμement .

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] Demi⅔bas “. P⅔oμ⅔ess and ⅔ecent t⅔ends in biodiesel λuels. Ene⅔μy Conve⅔sion and Manaμement .

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] Lin L, Cunshan Zhou, Vittayapadunμ S, Xianμ⅓ian S, Minμdonμ D. Oppo⅔tunities and challenμes λo⅔ biodiesel λuel. “pplied Ene⅔μy .

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] ”alat M, ”alat H. P⅔oμ⅔ess in biodiesel p⅔ocessinμ. “pplied Ene⅔μy .

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] D Elia L, Keyse⅔ “, Younμ C. “lμae ”iodiesel, “n Inte⅔active Qualiλyinμ P⅔oject Re‐ po⅔t. .

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] Maa F, Hanna M. ”iodiesel p⅔oduction a ⅔eview. ”io⅔esou⅔ce Technoloμy - .

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] Sha⅔ma YC, Sinμh ”, Upadhyay SN. “dvancements in development and cha⅔acte⅔i‐ zation oλ biodiesel “ ⅔eview. Fuel .

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] “hmad “L, Yasin NH, De⅔ek JK. Mic⅔oalμae as a sustainable ene⅔μy sou⅔ce λo⅔ bio‐ diesel p⅔oduction “ ⅔eview. Renewable and Sustainable Ene⅔μy Reviews .

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] “tabani “E, Silitonμaa “S, ”ad⅔uddina I“, Mahliaa TMI, Masjukia HH, Mekhileλ S. “ comp⅔ehensive ⅔eview on biodiesel as an alte⅔native ene⅔μy ⅔esou⅔ce and its cha⅔‐ acte⅔istics. Renewable and Sustainable Ene⅔μy Reviews .

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] Rachmaniah O, Ju YH, Vali SR, Tjond⅔oneμo⅔o I, Mus l “S. “ study on acid-cata‐ lyzed t⅔anseste⅔i cation oλ c⅔ude ⅔ice b⅔an oil λo⅔ biodiesel p⅔oduction. In youth en‐ e⅔μy symposium, th Wo⅔ld ene⅔μy conμ⅔ess and exhibition, Sydney “ust⅔alia , Septembe⅔ .

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] Xu H, Miao X, Wu Q. Hiμh ⅓uality biodiesel p⅔oduction λ⅔om a mic⅔oalμa Chlτrellζ prτtτtheθτides by hete⅔ot⅔ophic μ⅔owth in λe⅔mente⅔s. Jou⅔nal oλ ”iotechnoloμy .

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] Johnson M”. Mic⅔oalμal ”iodiesel P⅔oduction th⅔ouμh a Novel “ttached Cultu⅔e Sys‐ tem and Conve⅔sion Pa⅔amete⅔s. MS thesis Vi⅔μinia Polytechnic Institute and State Unive⅔sity .

Algal Biorefinery for Biodiesel Prod”c“ion h““p://dx.doi.org/10. 5772/52679

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] Velas⅓uez-O⅔ta S”, Lee JGM, Ha⅔vey “. “lkaline in situ t⅔anseste⅔i cation oλ Chlτrel‐ lζ vulμζris. Fuel .

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] Fe⅔⅔entino JM, Fa⅔aμ IH, Jahnke LS. Mic⅔oalμal Oil Ext⅔action and In-situ T⅔anseste⅔i‐ λication. Chemical Enμinee⅔inμ, Unive⅔sity oλ New Hampshi⅔e UNH Du⅔ham, NH http //www. nt. ntnu. no/use⅔s/skoμe/p⅔ost/p⅔oceedinμs/aiche/data/pape⅔s/ P . pdλ accessed . . .

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] Ca⅔valho J, Ribie⅔o “, Cast⅔o J, Vila⅔inho C, Cast⅔o F. ”iodiesel P⅔oduction by Mic⅔o‐ alμae and Mac⅔oalμae λ⅔om No⅔th Litto⅔al Po⅔tuμuese Coast. W“STES Solutions, T⅔eatments and Oppo⅔tunities, st Inte⅔national Conλe⅔ence Septembe⅔ th th .

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] T⅔an D, Yeh K, Chen C, Chanμ J. Enzymatic t⅔anseste⅔i cation oλ mic⅔oalμal oil λ⅔om Chlτrellζ vulμζris ESP- λo⅔ biodiesel synthesis usinμ immobilized ”u⅔kholde⅔ia li‐ pase. ”io⅔esou⅔ce Technoloμy .

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] Umdu ES, Tunce⅔ M, Seke⅔ E. T⅔anseste⅔i cation oλ Nannochlo⅔opsis oculata mic⅔o‐ alμa s lipid to biodiesel on “l O suppo⅔ted CaO and MμO catalysts. ”io⅔esou⅔ce Technoloμy .

[

] Macei⅔as R, Rod⅔ı ´μuez M, Cancela “, U⅔⅔éjola S, Sánchez “. Mac⅔oalμae Raw ma‐ te⅔ial λo⅔ biodiesel p⅔oduction. “pplied Ene⅔μy .

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] K⅔ohn J”, McNeλλ VC, Yan ”, Nowlan D. P⅔oduction oλ alμae-based biodiesel usinμ the continuous catalytic Mcμyan p⅔ocess. ”io⅔esou⅔ce Technoloμy .

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] 5zçimen D, Y(cel S. Novel Methods in ”iodiesel P⅔oduction, In Ma⅔co “u⅔élio dos Santos ”e⅔na⅔des Ed. ”ioλuel's Enμinee⅔inμ P⅔ocess Technoloμy. InTech . p .

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] Patil P, Denμ S, Isaac Rhodes J, Lamme⅔s PJ. Conve⅔sion oλ waste cookinμ oil to bio‐ diesel usinμ λe⅔⅔ic sulλate and supe⅔c⅔itical methanol p⅔ocesses. Fuel .

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] Patil PD, Gude VG, Manna⅔swamy “, Cooke P, Munson-McGee S, Ni⅔malakhandan N, Lamme⅔s P, Denμ S. Optimization oλ mic⅔owave-assisted t⅔anseste⅔iλication oλ d⅔y alμal biomass usinμ ⅔esponse su⅔λace methodoloμy. ”io⅔esou⅔ce Technoloμy .

[

] Cancela “, Macei⅔as R, U⅔⅔ejola S, Sanchez “. Mic⅔owave-“ssisted T⅔anseste⅔iλica‐ tion oλ Mac⅔oalμae. Ene⅔μies , .

[

] Kobe⅔μ M, Cohen M, ”en-“motz “, Gedanken “. ”io-diesel p⅔oduction di⅔ectly λ⅔om the mic⅔oalμae biomass oλ Nζσστθhlτrτpsis by mic⅔owave and ult⅔asound ⅔adia‐ tion. ”io⅔esou⅔ce Technoloμy, .

[

] Ehimen E“, Sun ZF, Ca⅔⅔inμton CG. Use oλ ult⅔asound and co-solvents to imp⅔ove the in-situ t⅔anseste⅔iλication oλ mic⅔oalμae biomass. P⅔ocedia Envi⅔onmental Scien‐ ces - .

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Chapter 3

Major Diseases of the Biofuel Plant, Physic Nut (Jatropha curcas) Alexandre Reis Machado and Olin“o Liparini Pereira Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/52336

. Introduction Wo⅔ldwide, conce⅔n ove⅔ the conse⅓uences oλ μlobal wa⅔minμ has ⅔esulted in intensiλied sea⅔ches λo⅔ potential plants that couldsupply ⅔aw mate⅔ials λo⅔ p⅔oducinμ ⅔enewable λuels. The⅔ein, physic nut Jζtrτphζ θurθζs L. has μained attention as a pe⅔ennial cultu⅔e that p⅔o‐ duces seeds with hiμh oil content and excellent p⅔ope⅔ties. In addition to these att⅔ibutes, many studies have desc⅔ibedphysic nut as a cultu⅔e ⅔esistant to pests and disease. Howeve⅔, in ⅔ecent yea⅔s, the expansion oλ a⅔eas unde⅔ cultivation has been accompanied by the ap‐ pea⅔ance oλ va⅔ious diseases. Thus, this chapte⅔ aims to p⅔ovide inλo⅔mation about the main diseases that occu⅔ in physic nut and thei⅔ diaμnosis and to encou⅔aμe λu⅔the⅔ ⅔esea⅔ch on disease cont⅔ol. The existinμ lite⅔atu⅔e contains va⅔ious desc⅔iptions oλ the pathoμens occu⅔⅔inμ in cultu⅔e, most oλ which a⅔e caused by λunμi, and oλ which we add⅔ess the λollowinμ Glτmerellζ θiσμu‐ lζtζ Ston. Spauld. et Sch⅔enk. Psζthyrellζ suηθτrtiθζlis Speμ. Sθhizτphyllum ζlσeum L. “eθidi‐ um θσidτsθτli P. Henn. Rζmulζriτpsis θσidτsθτli Speμ. Urτmyθes jζtrτphiθτlζ P. Henn. Viéμas Pestζlτtiτpsis versiθτlτr Speμ. Phillips Cτlletτtriθhum μlτeτspτriτides Penz. Sacc. Cτlletτtriθhum θζpsiθi Syd. ”utl.e ”isby. Pζssζlτrζ ζjrekζri Syd. U. ”⅔aun F⅔ei⅔e & Pa⅔ente Phζkτpsτrζ ζrthuriζσζ ”u⅔iticá & J.F. Hennen Hennen et al. Cτθhliτητlus spiθiλer Nelson Mendes et al. Cerθτspτrζ jζtrτphiθτlζ Speμ. Chupp Cerθτspτrζ jζtrτphiμeσζU. ”⅔aun Pseudoce⅔cospo⅔a jat⅔ophae-cu⅔cas J.M. Yen Deiμhton Pseudoce⅔cospo⅔a jat⅔o‐ phae Pseudoce⅔cospo⅔a jat⅔opha⅔um Speμ. U. ”⅔aun C⅔ous & ”⅔aun and Elsinoë ja‐ t⅔ophae ”itanc. & Jenkins ”itancou⅔t & Jenkins . Existinμ ⅔epo⅔ts on pathoμens include ⅔esea⅔ch on colla⅔ and ⅔oot ⅔ot Nect⅔ia haematococca ”e⅔k. & ”⅔. [Haematonect⅔ia haemato‐ cocca ”e⅔k. & ”⅔oome Samuels & Ni⅔enbe⅔μ], and its anamo⅔ph Fusa⅔ium solani Ma⅔tius “ppel & Wollenwebe⅔ Yue-kai et al. , as well as Lasiodiplodia theob⅔omae Pat. G⅔iλ‐

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

λon & Maubl Latha et al. Pe⅔ei⅔a et al. , Phytophtho⅔a palmivo⅔a va⅔. palmivo⅔a E.J. ”utle⅔ E.J. ”utle⅔ E⅔win & Ribei⅔o andClitτθyηe tζηesθeσs Scop, ex F⅔. ”⅔es US‐ D“ .

. Diseases “lthouμh seve⅔al desc⅔iptions oλ λunμi exist, this chapte⅔ will discuss the most common and damaμinμ diseases that aλλect physic nut, and d⅔aws on the λollowinμ desc⅔iptions . . Anthracnose figure Cτlletτtriθhum μlτeτspτriτides Penz. Sacc. Cτlletτtriθhum θζpsiθi Syd. ”utl.and ”isby This disease was λi⅔st desc⅔ibed in physic nut by the USD“ Viéμas , and late⅔ by F⅔ei⅔e & Pa⅔ente and Sá et al. is p⅔esent in all a⅔eas whe⅔e physic nut is cultivated.

in the US“, in ”⅔azil by .Cu⅔⅔ently, the disease

The most commonly obse⅔ved symptoms a⅔e b⅔own to black nec⅔otic lesions that a⅔e i⅔⅔eμu‐ la⅔ly shaped and appea⅔ on the edμes and cente⅔ oλ the leaλ and which may contain a yellow halo. The lesions appea⅔ in the λo⅔m oλ small, isolated points that coalesce and subse⅓uently cause the complete dest⅔uction oλ the leaves. The λ⅔uit can also become inλected, which leads to the appea⅔ance oλ da⅔k b⅔own lesions. In addition to these symptoms, ⅔esea⅔ch in Mexico has indicated that the λunμus Cτlletτtri‐ θhum θζpsiθi caused stem canke⅔ and apical death oλ seedlinμs To⅔⅔es-Calzada et al. .

Figure 1. An“hracnose in Jatropha curcas. Symp“oms on leaf (A). C”rved conidia, dense conidiophores and sep“a“e se‐ “ae of Colletotrichum capsici (B).

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

Cτlletτtriθhum is a λunμus anamo⅔ph oλ the phylum “scomycota and telemo⅔ph μenus Glτm‐ erellζ. The species oλ this μenus have the λollowinμ cha⅔acte⅔istics conidiomata that a⅔e ace⅔vula⅔, subcuticula⅔ o⅔ epide⅔mal, and may contain setae conidiopho⅔es that a⅔e hyaline to b⅔own conidioμenous cells that a⅔e ente⅔oblastic, phialidic and hyaline conidia that a⅔e‐ hyaline, aseptate except p⅔io⅔ to μe⅔mination , st⅔aiμht o⅔ λalcate, smooth and thin-walled and app⅔esso⅔ia that a⅔e b⅔own, enti⅔ely o⅔ with c⅔enate to i⅔⅔eμula⅔ ma⅔μins p⅔oduced with μe⅔mination oλ conidia Sutton . Cτlletτtriθhum spp. is known to inλect a la⅔μe ⅔anμe oλ hosts and to cause va⅔ious symptoms, the most common oλ which is anth⅔acnose. This λunμus can su⅔vive in seeds, c⅔op ⅔esidues, inλected plants, and in soil as sap⅔ophytes. “lthouμh the disease occu⅔s in va⅔ious ⅔eμions oλ the wo⅔ld, it is mo⅔e seve⅔e in ⅔eμions with a hot and humid climate “μ⅔ios . So λa⅔, the⅔e a⅔e no ⅔ecommendations λo⅔ cont⅔ollinμ this disease. ”ecause oλ the damaμe it can cause to physic nut, this disease should be studied λu⅔the⅔. . . Passalora leaf spot Pζssζlτrζ ζjrekζri Syd. U. ”⅔aun Pζssζlτrζ jζtrτphiμeσζ U. ”⅔aun & F.O. F⅔ei⅔e This disease was λi⅔st desc⅔ibed in ”⅔azil by ”⅔aun & F⅔ei⅔e , and late⅔ by F⅔ei⅔e & Pa‐ ⅔ente in leaves oλ Jζtrτphζ θurθζs and Jζtrτphζ pτdζμriθζ, and in othe⅔s count⅔ies by C⅔ous & ”⅔aun . The p⅔ima⅔y symptoms oλ this disease a⅔e ⅔ounded leaλ lesions that a⅔e c⅔eamy to liμht b⅔own in colo⅔, with a na⅔⅔ow da⅔k b⅔own halo, and late⅔ become limited by leaλ veins and da⅔ken. Lesions measu⅔e - cm in diamete⅔ and ⅔a⅔ely coalesce F⅔ei⅔e & Pa⅔ente . The μenus Pζssζlτrζ is a ce⅔cospo⅔oid λunμus, p⅔eviously included in the μenus Cerθτspτrζ that has as its teleomo⅔ph the Myθτsphζerellζ. Species sha⅔e taxonomic cha⅔acte⅔istics such as b⅔anched, septate, smooth, hyaline to piμmentedhyphae absent to well-developed st⅔omata solita⅔y o⅔ λasciculate to synnematous conidiomataconidiopho⅔es, a⅔isinμ λ⅔om st⅔omata o⅔ hyphae, inte⅔nal o⅔ supe⅔λicial, plu⅔iseptate, subhyaline to piμmented conspicuous coni‐ dioμenous loci, with sca⅔s that a⅔e somewhat thickened and da⅔kened conidia that a⅔e soli‐ ta⅔y to catenate in simple o⅔ b⅔anched chains, ame⅔ospo⅔ous to scolecospo⅔ous, aseptate to plu⅔iseptate, and pale to distinctly piμmented and hila that a⅔e somewhat thickened and da⅔kened C⅔ous & ”⅔aun . “lthouμh it has been ⅔epo⅔ted in seve⅔al count⅔ies, to date this disease has not p⅔esented ⅔isk to physic nut cultivation. . . Cercospora/Pseudocercosporaleaf spot figure Cerθτspτrζ jζtrτphiθτlζ Speμ. Chupp, Cerθτspτrζ jζtrτphiμeσζ U. ”⅔aun

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Pseudτθerθτspτrζ jζtrτphζe-θurθζs J.M. Yen Deiμhton Pseudτθerθτspτrζ jζtrτphζe G.F. “tk. “.K. Dζs & Chζttτpζdh. Pseudτθerθτspτrζ jζtrτphζrum Speμ. U. ”⅔aun This disease maniλests in the λo⅔m oλ leaλ spots that consist oλ well-delimited b⅔own i⅔⅔eμu‐ la⅔ nec⅔otic spots Dianese et al. . The μene⅔a mentioned above have the λollowinμ taxonomic cha⅔acte⅔istics The μenus Cerθτspτrζ μ⅔oups anamo⅔phs oλ Myθτsphζerellζ with hyphae that a⅔e colo⅔less o⅔ nea⅔-colo⅔ous to piμmented, b⅔anched, septate, and smooth to λaintly ⅔ouμh-walls. St⅔omata a⅔e lackinμ to well-developed, subhyaline to usually piμmented. Conidiopho⅔es a⅔e solita⅔y to λasciculate, a⅔isinμ λ⅔om inte⅔nal hyphae o⅔ st⅔omata, e⅔ect, subhyaline to piμmented. Conidioμenous loci sca⅔s a⅔e conspicuous, thickened and da⅔kened. Conidia a⅔e solita⅔y, scolecospo⅔ous, cylind⅔ical-λiliλo⅔m, hyaline o⅔ subhyaline, mostly plu⅔iseptate, and smooth and hila a⅔e thickened and da⅔kened C⅔ous & ”⅔own .

Figure 2. Cercospora leaf spo“ on Jatropha curcas. Necro“ic symp“oms on leaf (A); F”ngal s“r”c“”res on leaf lesions (B); Pigmen“ed conidiophores wi“h conspic”o”s scars (C); Filiform conidia wi“h conspic”o”s pigmen“ed hil”m (D).

The μenus Pseudτθerθτspτrζμ⅔oups anamo⅔phs oλ Myθτsphζerellζ with basically piμmented conidiopho⅔es and inconspicuous, unthickened, not da⅔kened conidioμenous loci solita⅔y,

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

o⅔ catenulateconidia, aseptate to plu⅔iseptate with conidial sca⅔s that a⅔e inconspicuous and not thickened C⅔ous & ”⅔own . C⅔ous & ”⅔aun cite the occu⅔⅔ence oλ λive species oλ ce⅔cospo⅔oid, indicated above, in the cultu⅔e oλ physic nut. Howeve⅔, λew studies have examined λunμi ce⅔cospo⅔oid in this c⅔op. “s a ⅔esult, the⅔e is no inλo⅔mation about λavo⅔able conditions, symptoms o⅔ disease cont⅔ol. To date, this disease has not p⅔esented ⅔isk to the cultivation oλ physic nut.

Figure 3. Pse”docercospora leaf spo“ on Jatropha curcas. Pigmen“ed conidiophores wi“h inconspic”o”s scars on coni‐ diogeno”s cells (C) and filiform pigmen“ed conidia wi“h inconspic”o”s hil”m (D).

. . Powdery mildew figure Pseudτidium jζtrτphζe Hosaμ., Siddappa, Vijay. & Udaiyan U. ”⅔aun & R.T.“. Cook The powde⅔y mildew caused by the λunμus Pseudτidium jζtrτphζe ”⅔aun & Cook was p⅔eviously desc⅔ibed as Oidium heveζe Steim by Viéμas in ”⅔aziland Oidium jζtrτphζe Hosaμ., Siddappa, Vijay. & Udaiyan ”⅔aun & Cook in India. This disease occu⅔s com‐ monly in physic nut plantations and it has been λ⅔e⅓uently obse⅔ved in va⅔ious ⅔eμions oλ ”⅔azil and the ⅔est oλ wo⅔ld. The most common symptoms oλ the disease a⅔e the p⅔oduction oλ abundant white o⅔ μ⅔ay mycelia in leaves, petioles, stems, λlowe⅔s and λ⅔uits Dianese & Ca⅔μnin . With the evolution oλ the disease, inλected plants may show nec⅔otic lesions, which cause leaλ λall, un‐ de⅔development, death oλ buds and younμ λ⅔uit deλo⅔mation ”edendo . The λunμus that causes this disease is a typical biot⅔ophic pathoμen oλ the phylum “scomy‐ cota, o⅔de⅔ E⅔ysiphales. This pathoμen may be cha⅔acte⅔ized by white o⅔ μ⅔ayish colonies, septate and b⅔anched mycelia conidiopho⅔es that a⅔e e⅔ect o⅔ ascendinμ, cylind⅔ical, hya‐ line, septate and λo⅔minμ conidia sinμly conidia that a⅔e usually la⅔μe in p⅔opo⅔tion to the diamete⅔ oλ the conidiopho⅔es, simple, smooth, ellipsoid-ovoid doliiλo⅔m, hyaline, sinμlecelled ”⅔aun & Cook .

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 4. Powdery mildew on Jatropha curcas. Symp“oms on pe“iole and s“em (A);Symp“oms on leaf (B) Leaf lesions on old infec“ions (C); Symp“oms on seedlings (D);Conidiophores (E); Conidia (F).

The disease μene⅔ally λavo⅔s wa⅔m tempe⅔atu⅔es, humidity oλ - % and ⅔educed liμht. Heavy ⅔ains a⅔e μene⅔ally unλavo⅔able to the pathoμen Fu⅔tado &T⅔indade . In ”⅔azil, the disease usually occu⅔s in the d⅔y season, appa⅔ently without causinμ extensive losses, because its occu⅔⅔ence coincides with the plants pe⅔iod oλ natu⅔al deλoliation Satu⅔nino et al. . Cu⅔⅔ently, the⅔e a⅔e no λunμicides ⅔ecommended λo⅔ cultu⅔e, but some studies cite that sp⅔ayinμ sulλu⅔ λunμicides wo⅔ks to cont⅔ol this λunμus. “nothe⅔ measu⅔e is to cont⅔ol alte⅔‐ native hosts, especially plants oλ the λamily Eupho⅔biaceae Fu⅔tado & T⅔indade Satu⅔‐ nino et al. Dias et al. . . . Rust figure Phζkτpsτrζ ζrthuriζσζ ”u⅔iticá & Hennen The λi⅔st ⅔epo⅔t oλ this disease in Jζtrτphζ θurθζs, desc⅔ibed its cause as Uredτ jζtrτphiθτlζ “⅔‐ thu⅔ “⅔thu⅔ . In ”⅔azil, this disease was λi⅔st λound in in São Paulo Viéμas . Cu⅔⅔ently, it is widely dist⅔ibuted th⅔ouμhout ”⅔azil Dias et al. and seve⅔al othe⅔ count⅔ies.

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

The λunμus that causes this disease was p⅔eviously classiλied as Phζkτpsτrζ jζtrτphiθτlζ “⅔‐ thu⅔ Cummins howeve⅔, it was ⅔eclassiλied as Phζkτpsτrζ ζrthuriζσζ ”u⅔iticá & Hennen Hennen et al. . The symptoms maniλest in the leaves, initially in the λo⅔m oλ small chlo⅔otic points on the uppe⅔ su⅔λace, which co⅔⅔espond to the unde⅔side oλ the leaλ, and then small p⅔ot⅔udinμ pustules, which aλte⅔ b⅔eakinμ, ⅔elease a powde⅔y mass oλ u⅔edospo⅔es oλ o⅔anμe colo⅔, μivinμ a λe⅔⅔uμi‐ nous aspect. In seve⅔e inλections, pustules coalesce to λo⅔m nec⅔otic spots, which a⅔e ⅔eddish b⅔own and i⅔⅔eμula⅔ly shaped and can dest⅔oy the leaλ Dias et al. Ca⅔nei⅔o et al. . The Phζkτpsτrζ ζrthuriζσζ belonμs to the phylum ”asidiomycota, class Pucciniomycetes. It is cha⅔acte⅔ized by u⅔edinia hypophyllous, occasionally epiphyllous, in small μ⅔oups openinμ by a po⅔e, su⅔⅔ounded by nume⅔ous not septate pa⅔aphyses that p⅔oject outside the host u⅔edi‐ niospo⅔es, ellipsoid, to obovoid, sessile, closely and λinely echinulate, μe⅔m po⅔es obscu⅔e telia hypophyllous, sube⅔pide⅔mal in o⅔iμin, closely a⅔ound the u⅔edinia teliospo⅔es i⅔⅔eμula⅔ly a⅔‐ ⅔anμed, cuboid, ellipsoid to polyμonal Hennen et al. . Cu⅔⅔ently the⅔e a⅔e no λunμicides ⅔ecommended λo⅔ this cultu⅔e. Howeve⅔, acco⅔dinμ to Dias et al. , p⅔otective coppe⅔ λunμicides can cont⅔ol this disease.

Figure 5. R”s“ disease on Jatropha curcas. Symp“oms on adaxial leaf s”rfaces (A-B);Uredinia (C);Urediniospores (D); Te‐ lia wi“h “eliospores (E).

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. . Stem canker and dieback figure Lζsiτdiplτdiζ theτηrτmζe Pat. G⅔iλλon & Maubl The λi⅔st ⅔epo⅔t oλ this disease in ”⅔azil was made byF⅔ei⅔e & Pa⅔ente by Sulaiman & Thana⅔ajoo .

and in Malaysia

The disease maniλests in the λo⅔m oλ dieback that can p⅔oμ⅔ess until it takes ove⅔ the t⅔unk oλ the plant. Stem canke⅔s have also been obse⅔ved, causinμ nec⅔otic lesions on b⅔anches and vascula⅔ discolo⅔ation. In Malaysia, disease incidence can be as hiμh as % oλ a plantation F⅔ei⅔e &Pa⅔ente Sulaiman & Thana⅔ajoo .

Figure 6. Dieback on Jatropha curcas. Symp“oms observed in “he field (A); Hyaline and pigmen“ed conidia of Lasiodi‐ plodia theobromae (B).

Cha⅔acte⅔istics oλ the Lζsiτdiplτdiζ species commonly include the p⅔esence oλ pa⅔aphyses within the conidiomata pycnidial and conidia that a⅔e initially hyaline and aseptate. ”ut in matu⅔ity, one median septum is λo⅔med, and the walls become da⅔k b⅔own with the λo⅔ma‐ tion oλ lonμitudinal st⅔iations due the deposition oλ melanin μ⅔anules on the inne⅔ su⅔λace oλ the wall. The identiλication oλ the Lζsiτdiplτdiζ species based solely on mo⅔pholoμical cha⅔acte⅔istics is not easy. Cu⅔⅔ently, it is known that what was initially identiλied as Lζsiτdiplτdiζ theτηrτmζe is in λact a species complex “lves et al. . Thus, molecula⅔ studies a⅔e needed to co⅔⅔ect‐ lyidentiλy the pathoμen, as was done by Thana⅔ajoo & Sulaiman . Lζsiτdiplτdiζ spp. is a λunμus oλ the phylum “scomycota, λamily ”ot⅔yosphae⅔iaceae. Funμi in this λamily a⅔e known to su⅔vive as endophytes and demonst⅔ate symptoms when plants a⅔e unde⅔ some st⅔ess Slippe⅔s & Winμλield . Thus, many ⅔esea⅔che⅔s see them as op‐ po⅔tunistic pathoμens.

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

Cont⅔ol oλ this disease can be achieved by p⅔uninμ and dest⅔oyinμ aλλected b⅔anches. Late⅔ plants should be b⅔ushed with coppe⅔ λunμicides o⅔ thiophanate methyl λo⅔ inju⅔ies Fu⅔ta‐ do & T⅔indade . “dditionally, balanced λe⅔tilization, soil analysis and suλλicient levels oλ i⅔⅔iμation in ⅔eμions with lonμ pe⅔iods oλ d⅔ouμht can aid in disease cont⅔ol. . . Collar and root rot figure Fusζrium sτlζσi Ma⅔tius “ppel & Wollenwebe⅔ Lζsiτdiplτdiζ theτηrτmζe Pat. G⅔iλλon & Maubl Neτsθytζlidium dimidiζtum Peσz. Crτus & Slippers Mζθrτphτmiσζ phζseτliσζ Tassi Goid. The λi⅔st ⅔epo⅔t oλ this disease in ”⅔azil was made by Pe⅔ei⅔a et al. , who identiλied it as beinμ caused by Lζsiτdiplτdiζ theτηrτmζe. In India, this same pathoμen was ⅔epo⅔ted by Latha et al. , and Mζθrτphτmiσζ phζseτliσζwas ⅔epo⅔ted by Patel et al. . In China, YueKai et al. identiλied the λunμus Fusζrium sτlζσi, and Machado et al. in p⅔ess made the λi⅔st desc⅔iption oλ Neτsθytζlidium dimidiζtum Peσz. . Crτus & Slippers ζssτθiζted this pζthτμeσ with θτllζr ζσd rττt rτt iσ physiθ σut iσ ”rζzil. “ll the pζthτμeσs meσtiτσed ζητve ζre typiθζl sτil λuσμi. They τθθur iσ ζ wide rζσμe τλ hτsts, θζσ ηe spreζd ηy seeds, ζσd survive ζs pζrζsites, sζprτphytes, eσdτphytes τr resistζσt struθtures, suθh ζs θhlζmydτspτres iσ Fusζrium ζσd Neτsθytζlidium τr sθlerτtiζ iσ Mζθrτphτmiσζ. This disease has ac⅓ui⅔ed μ⅔eat impo⅔tance, because it can ⅔educe p⅔oductivity by causinμ the sudden death oλ plants and makinμ cultivation a⅔eas unviable. The symptoms most commonly obse⅔ved a⅔e wiltinμ, leaλ yellowinμ with subse⅓uent λall, and c⅔acks in the colla⅔ ⅔eμion. In the colla⅔ ⅔eμion, the appea⅔ance oλ black λunμal st⅔uctu⅔es in the ba⅔k oλ the plant has been consistently obse⅔ved. Upon beinμ ⅔emoved λ⅔om the soil, plant ⅔oots ⅔ot and the vascula⅔ system is aλλected by nec⅔otic symptoms, ⅔anμinμ λ⅔om liμht b⅔own to black. Due to loss oλ suppo⅔t, the plants have oλten al⅔eady λallen due to the wind. The μenus Fusζriumhas the λollowinμ μene⅔al cha⅔acte⅔istics b⅔iμht ae⅔ial mycelium, hyphae septate, conidiopho⅔es va⅔iable, sinμle o⅔ μ⅔ouped in spo⅔odochia conidia hyaline va⅔iable, p⅔incipally oλ two kinds -multicellula⅔mac⅔oconidia, sliμhtly cu⅔ved o⅔ bent at the pointed ends and typically canoe-shaped unicellula⅔, ovoid o⅔ oblonμmic⅔oconidia, bo⅔ne sinμly o⅔ in chains and also μ⅔ouped in λalse heads, λo⅔med in mono o⅔ polyphialides thick-walled chlamydospo⅔es a⅔e common in some species ”a⅔nett & Hunte⅔ . The common cha⅔acte⅔istics oλ Lζsiτdiplτdiζ species include the p⅔esence oλ pa⅔aphyses within the conidiomata pycnidial and initially hyaline and aseptateconidia. Howeve⅔, in matu⅔ity, one median septum is λo⅔med, and the walls become da⅔k b⅔own with the λo⅔mation oλ lonμitu‐ dinal st⅔iations, due the deposition oλ melanin μ⅔anules on the inne⅔ su⅔λace oλ the wall. The μenus Neτsθytζlidiumis a μ⅔oup oλ λunμi that p⅔oduces synanamo⅔ph Sθytζlidium-like with septate and oblonμ to μlobosea⅔th⅔oconidia λo⅔med λ⅔om ae⅔ial mycelia. Initially hya‐ line, with aμe, the a⅔th⅔oconidia become b⅔own and with a thick wall. Commonly obse⅔ved

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a⅔e pycnidia that a⅔e da⅔k and μlobose imme⅔sed o⅔ supe⅔λicially in a st⅔oma that p⅔oduces Fusiθτθθum-like conidia that a⅔e hyaline and ellipsoid to nea⅔ly λusiλo⅔m. Da⅔k septate coni‐ dia can also be obse⅔ved. Cha⅔acte⅔istics oλ the Mζθrτphτmiσζ spp. μene⅔ally include the λo⅔mation oλ da⅔k mycelia and abundant p⅔oduction oλ scle⅔otia in PD“. Eventually, the λo⅔mation oλ conidiomata pyc‐ nidial can be obse⅔ved, with the ⅔elease oλ hyaline conidia with apical mucoid appendaμes. In a⅔eas p⅔one to p⅔olonμed d⅔y seasons, a hiμhe⅔ incidence oλ colla⅔ and ⅔oot ⅔ot has been obse⅔ved. The⅔eλo⅔e, it is believed that the wate⅔ st⅔ess is the main λacto⅔ that p⅔edisposes plants to this disease. The above-mentioned pathoμens a⅔e diλλicult to cont⅔ol, due to the λact that they su⅔vive in soil. The⅔eλo⅔e, to ⅔educe disease incidence, it is λi⅔st necessa⅔y to p⅔ovide wate⅔ and λe⅔tiliz‐ e⅔ balanced λo⅔ p⅔ope⅔ plant development. When t⅔ansplantinμ seedlinμs to the λield, all λo⅔ms oλ inju⅔y should be avoided. “nothe⅔ cont⅔ol measu⅔e would be to use healthy p⅔opa‐ μative mate⅔ial as well as seed t⅔eatments.

Figure 7. Collar and roo“ ro“ on Jatropha curcas. Wil“ing symp“oms observed in “he field (A);De“ail of “hecollar ro“ (B);De“ail ofroo“ ro“ (C);Macroconidia of Fusariumsolani(D); Pigmen“ed and hyaline conidia of Lasiodiplodia theobro‐ mae(E);Ar“hroconidia of Neoscytalidium dimidiatum(F);Fusicoccum-like conidia of Neoscytalidium dimidiatum(G); Con‐ idia of Macrophomina phaseolina(H). Sclero“ia of Macrophomina phaseolina prod”ced on s“erilized Pine “wigs in c”l“”re (I).

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

. . Yellow mosaic In addition to the seve⅔al λunμal diseases mentioned, the⅔e is also yellow mosaic, a disease caused by a st⅔ain oλ the vi⅔us Iσdiζσ Cζssζvζ Mτsζiθ Virus Gao et al. . This disease, de‐ tected in physic nut plantations in India, causes mosaic, ⅔educed leaλ size, leaλ disto⅔tion, bliste⅔inμ and stuntinμ oλ diseased plants. The disease is t⅔ansmitted by the vecto⅔ ”emisiζ tζηζθi in a non-pe⅔sistent manne⅔, but not th⅔ouμh mechanical inoculation o⅔ seeds Na⅔aya‐ naet al. .

. Seed associated fungi Seeds p⅔opaμate the majo⅔ity oλ cultu⅔es wo⅔ldwide. These cultu⅔es a⅔e vulne⅔able to inλec‐ tion by seve⅔al pathoμens that can su⅔vive in seeds. These pathoμens may cause ⅔eduction oλ seed μe⅔mination, as well as deλo⅔mation, discolo⅔ation, ⅔eductions in size and weiμht, and dete⅔io⅔ation du⅔inμ sto⅔aμe. They can λu⅔the⅔ cont⅔ibute to ⅔ottinμ ⅔oots, dampinμ-oλλ, ne‐ c⅔osis in leaves, and the sp⅔ead oλ diseases ac⅔oss lonμ distances. Conse⅓uently, these dis‐ eases cause losses valued at billions oλ dolla⅔s Nee⅔μaa⅔d “μa⅔wal & Sinclai⅔ . To date, λew studies have add⅔essed the seed patholoμy oλ physic nut, and the⅔e is no inλo⅔ma‐ tion available about the losses that seed pathoμens cause in this cultu⅔e. ”ut, λollows below the majo⅔ pathoμens and sap⅔ophytic λunμi associated with seeds. Mζθrτphτmiσζ phζseτliσζ Fiμu⅔e

Figure 8. Macrophomina phaseolinaon Jatropha curcas seed. Seed covered by myceli”m (A); De“ail of sclero“ia on seed (B);Black sclero“ia (C).

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Cτlletτtriθhum θζpsiθi Fiμu⅔e

Figure 9. Colletotrichum capsici on Jatropha curcas seed. Conidioma“a wi“h black se“ae on seed s”rface (A). C”rved assep“a“e conidia (B).

Fusζrium sp. Fiμu⅔e

Figure 10. Fusarium sp. on Jatropha curcas seed. Seed covered by hyaline myceli”m (A); Radicle wi“h necro“ic lesion (B); Macroconidia (C).

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

Lζsiτdiplτdiζ theτηrτmζe Fiμu⅔e

Figure 11. Lasiodiplodia theobromae on Jatropha curcas seed. Conidioma“a prod”cing a black cirr”s of conidia on seed s”rfasse (A); De“ail of ma“”re conidia (B).

Curvulζriζ sp. Fiμu⅔e

Figure 12. Curvularia sp. on Jatropha curcas seed. Myceli”m and conidiophores prod”cing conidia on seed s”rface (A); Dark sep“a“e conidia (B).

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Othe⅔ λunμi commonly associated with Jat⅔opha cu⅔cas seeds Fiμu⅔e

Figure 13. Genera of f”ngi of“en observed on Ja“ropha c”rcas seeds: Aspergill”s (A-C); Penicilli”m (D);S“achybo“rys (E); Acremoni”m (F); Chae“omi”m (G);Al“ernaria (H); Rhizop”s (I).

“lthouμh the⅔e a⅔e no ⅔ecommendations λo⅔ λunμicide useon physic nut, t⅔eatments can be administe⅔ed by soakinμ seeds λo⅔ minutes in a solution oλ lite⅔ oλ λo⅔maldehyde % diluted in lite⅔s oλ wate⅔ Massola and ”edendo, . This t⅔eatment is indicated λo⅔ the seeds oλ Riθiσus θτmmuσis L., but it also wo⅔ks well λo⅔ physic nut.

. Conclusion Despite the λact that most lite⅔atu⅔e conside⅔ed physic nut as ⅔esistant to pests and dis‐ eases, this ⅔eview emphasizes the dive⅔sity oλ pathoμens associated with this plant and the damaμe that they may cause. Most oλ these diseases may become a se⅔ious p⅔oblem λo⅔ ”⅔azilian λa⅔me⅔s, due to its seve⅔ity and the lack oλ ⅔eμiste⅔ed chemical p⅔oducts λo⅔ these pathoμens. Studies should be ca⅔⅔ied out in o⅔de⅔ to know the envi⅔onmental condi‐ tions that λavo⅔ to these diseases on J. θurθζs, as well as the development oλ cont⅔ol st⅔at‐ eμies and ⅔esistant va⅔ieties.

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

Acknowledgements The autho⅔s wish to thank FAPEMIG, CNPq and CAPES λo⅔ λinancial suppo⅔t oλ the wo⅔k.

Author details “lexand⅔e Reis Machado and Olinto Lipa⅔ini Pe⅔ei⅔a *“dd⅔ess all co⅔⅔espondence to alexand⅔e⅔m.aμ⅔[email protected]⅔ *“dd⅔ess all co⅔⅔espondence to olipa⅔ini@uλv.b⅔ Depa⅔tamento de Fitopatoloμia, Unive⅔sidade Fede⅔al de Viçosa, Viçosa, MG, ”⅔azil

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] Hennen JF, Fiμuei⅔edo M”, De Ca⅔valho J⅔ ““, Hennen PG ⅔ust λunμi U⅔edinales oλ ”⅔azil. p.

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] Latha, P., P⅔akasam, V., Kamalakannan, “., Gopalak⅔ishnan, C., Raμuchande⅔, T., Pa⅔amathma, M., & Samiyappan, R. . Fi⅔st ⅔epo⅔t oλ Lζsiτdiplτdiζ theτηrτmζe Pat. G⅔iλλon & Maubl causinμ ⅔oot ⅔ot and colla⅔ ⅔ot disease oλ physic nut Jζtrτphζ θurθζs L. in Ind. ia. “ust⅔alasian Plant Disease Notes, , - .

[

] Machado “R, Pinho D”, Dut⅔a DC, Pe⅔ei⅔a OL In p⅔ess Colla⅔ and ⅔oot ⅔ot caused by Neτsθytζlidium dimidiζtum in the bioλuel plant Jζtrτphζ θurθζs. Plζσt Diseζse.

[

] Massola NS, ”edendo IP . Doenças da Mamonei⅔a Riθiσus θτmmuσis . IN Ki‐ mati H, “mo⅔im L, Rezende J“M, ”e⅔μamin Filho “, Cama⅔μo LE“. Manual de Fito‐ patoloμia Doenças das Plantas Cultivadas. São Paulo edito⅔a “μ⅔onômica Ce⅔es, v.

[

] Mendes, M. “. S., Silva, V. L., Dianese, J. C., Fe⅔⅔ei⅔a, M. “. S. V., Santos, C. E. N., Gomes, Neto. E., U⅔ben, “. F., & Cast⅔o, C. . Funμos em plantas no ”⅔asil. ”⅔a‐ sília.Emb⅔apa-SPI/Emb⅔apa Cena⅔μen. p.

. Phytτphthτrζ Diseases Wo⅔ldwide. “PS P⅔ess, St.

. Cataloμue oλ plant

Major Diseases of “he Biof”el Plan“, Physic N”“ (Jatropha curcas) h““p://dx.doi.org/10.5772/52336

[

] Na⅔ayana DS“, Shanka⅔appa KS, Govindappa MR, P⅔ameela H“, Rao MRG, Ran‐ μaswamy KT . Natu⅔al occu⅔⅔ence oλ Jat⅔opha mosaic vi⅔us disease in In‐ dia.Cu⅔⅔ent Science , , .

[

] Nee⅔μaa⅔d, P.

[

] Patel DS, Patel SI, Patel RL . “ new ⅔epo⅔t on ⅔oot ⅔ot oλ Jζrτphζ θurθζs caused by Mζθrτphτmiσζ phζseτliσζ λ⅔om Guja⅔at, India. J Myθτl Pl Pζthτl , , .

[

] Pe⅔ei⅔a OL, Dut⅔a DC, Dias L“S. . Lζsiτdiplτdiζ theτηrτmζe is the causal aμent oλ a damaμinμ ⅔oot and colla⅔ ⅔ot disease on the bioλuel plant Jζtrτphζ θurθζs in ”⅔azil. “ustrζlζsiζσ Plζσt Diseζse Nτtes, , .

[

] Phillips, S. . “ new ⅔eco⅔d oλ Pestζlτtiτpsis versiθτlτr on the leaves oλ Jζtrτphζ θurθζs. Indian Phytopatholoμy .

[

] Sá D“C, Santos GRS, Fu⅔tado GQ, E⅔asmo E“L, Nascimento IR . T⅔anspo⅔te, patoμenicidade e t⅔ansmissibilidade de λunμos associados às sementes de pinhão manso. Revista ”⅔asilei⅔a de Sementes, , , .

[

] Satu⅔nino, H. M., Pacheco, D. D., Kakida, J., Tominaμa, N., & Gonçalves, N. P. Cultu⅔a do pinhão-manso Jζtrτphζ θurθζs L. .Inλo⅔me “μ⅔opecuá⅔io , , - .

[

] Slippe⅔s, ”., & Winμλield, . . ”ot⅔yosphae⅔iaceae as endophytes and latent pathoμens oλ woody plants dive⅔sity, ecoloμy and impact. Fuσμζl ”iτlτμy Reviews, , .

[

] Sulaiman, R., & Thana⅔ajoo, S. S. . Fi⅔st ⅔epo⅔t oλ Lζsiτdiplτdiζ theτηrτmζecaus‐ inμ stem canke⅔ oλ Jζtrτphζ θurθζs in Malaysia. Plant Disease .

[

] Sutton ”C . The Coelomycetes, Funμi Impe⅔λecti with ace⅔vuli, pycnidia and st⅔omata.Commonwealth Mycoloμical Institute,Kew, U.K.

[

] To⅔⅔es-Calzada, C., Tapia-Tussell, R., Nexticapan-Ga⅔cez, “., Matin-Mex, R., Quija‐ no-Ramayo, “., Co⅔tés-Veláz⅓uez, “., Hiμue⅔a-Ciapa⅔a, I., & Pe⅔ez-”⅔ito, D. . Fi⅔st ⅔epo⅔t oλ Cτlletτtriθhum θζpsiθi causinμ anth⅔acnose in Jζtrτphζ θurθζs in Yucatan, Mexico. New Disease Repo⅔ts .

[

] USD“ , -

[

] Viéμas “P , - .

. “lμuns λunμos do ”⅔asil IV U⅔edinales. Campinas ”⅔aμantia, n. , ,

[

] Viéμas “P ico, p.

. Índice de λunμos da “mé⅔ica do Sul. Campinas. Instituto “μ⅔onôm‐

[

] Yue-Kai, W., Guo-Tenμ, O., & Jin-Yonμ, Y. . Fi⅔st ⅔epo⅔t oλ Neθtriζ hζemζtτθτθθζ causinμ ⅔oot ⅔ot disease oλ physic nut Jζtrτphζ θurθζs in China. “ustrζlζsiζσ Plζσt Diseζse Nτtes , , - .

.

. Seed patholoμy. London The MacMillan P⅔ess.

.

. Index oλ Plant Diseases in the United States. U.S.D.“. “μ⅔ic. Handb. ,

75

Chapter 4

Biodiesel Feedstock and Production Technologies: Successes, Challenges and Prospects Y.M. Sani, W.M.A.W. Da”d and A.R. Abd”l Aziz Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/52790

. Introduction In o⅔de⅔ to achieve the biodiesel cent⅔al policy oλ p⅔otectinμ the envi⅔onment, ⅔eplacinμ pet⅔oleum diesel and p⅔otectinμ and/o⅔ c⅔eatinμ jobs, a μood unde⅔standinμ oλ biodiesel histo⅔y is essential. This is because consume⅔s always tend to buy cheap ⅔athe⅔ than μ⅔een λuels. Mo⅔eove⅔, it is mo⅔e diλλicult λo⅔ a new technoloμy to dislodμe one that has ⅔eached societal standa⅔d. The mo⅔e the popula⅔ technoloμy is used, the mo⅔e it imp⅔oves becominμ less expensive due to wide⅔ ma⅔ket potentials. Pet⅔odiesel has become the liλeblood oλ ou⅔ economy. It would be almost impossible to λind a comme⅔cial p⅔oduct today that does not consume diesel λuel du⅔inμ its p⅔oduction and dist⅔ibution [ - ]. The⅔eλo⅔e, the aim oλ this chapte⅔ is to p⅔ovide an ove⅔view on the histo⅔y and motivation, successes, challenμes and p⅔ospects oλ biodiesel as sou⅔ce oλ ene⅔μy. This will p⅔ovide a μlobal outlook in makinμ biodiesel an economical and eco-λ⅔iendly alte⅔native to pet⅔oleum diesel. The histo⅔ical developments oλ the bioλuel indust⅔y in μene⅔al and biodiesel in pa⅔ticula⅔, is unlike many indust⅔ies. This is because the d⅔ivinμ λacto⅔s λo⅔ its advances a⅔e mo⅔e oλ economics and politics than technoloμical [ ]. “s ea⅔ly as , t⅔anseste⅔iλication was conducted on veμetable oil in the sea⅔ch λo⅔ a cheap method to p⅔oduce μlyce⅔ine λo⅔ p⅔oducinμ explosives du⅔inμ Wo⅔ld Wa⅔ II by E. Duλλy and J. Pat⅔ick [ - ]. In , G. Chavanne, ”elμian scientist patented the P⅔ocedu⅔e λo⅔ the t⅔ansλo⅔mation oλ veμetable oils λo⅔ thei⅔ uses as λuels . ”iodiesel as a concept was thus established [ ]. It is a simple p⅔ocess whe⅔e alkoxy μ⅔oup oλ an este⅔ compound oil o⅔ λat is exchanμed with an alcohol. Howeve⅔, it was not until that λi⅔st patent on comme⅔cial biodiesel p⅔oduction p⅔ocess was applied λo⅔ by Expedito Pa⅔ente a ”⅔azilian scientist [ ]. P⅔io⅔ to the discove⅔y oλ and boom in λossil λuels, powe⅔ was mainly μene⅔ated λ⅔om steam. Howeve⅔, the use oλ hyd⅔o-ene⅔μy consumes la⅔μe ⅔esou⅔ces coupled with the ineλλiciencies

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

oλ the steam enμine whe⅔e only about to % eλλiciency is de⅔ived λ⅔om new powe⅔ μene⅔ation plant. “ patent λo⅔ an eλλicient the⅔mal enμine which was to be ope⅔ated on peanut oil was λiled in by Rudolph Diesel in Ge⅔many. ”y , Diesel's invention was demon‐ st⅔ated in an exhibition in Pa⅔is. Within λive yea⅔s oλ its invention, Diesel s enμine ⅔an on its own powe⅔ with % eλλiciency aμainst its initial % eλλiciency [ ]. In , Diesel published two a⅔ticles [ , ] in which he ⅔eλlected

The λζθt thζt λζt τils λrτm veμetζηle sτurθes θζσ ηe used mζy seem iσsiμσiλiθζσt tτ-dζy, ηut suθh τils mζy perhζps ηeθτme iσ θτurse τλ time τλ the sζme impτrtζσθe ζs sτme σζturζl miσerζl τils ζσd the tζr prτduθts ζre στw. … Iσ ζσy θζse, they mζke it θertζiσ thζt mτtτr pτwer θζσ still ηe prτduθed λrτm the heζt τλ the suσ, whiθh is ζlwζys ζvζilζηle λτr ζμriθulturζl purpτses, eveσ wheσ ζll τur σζturζl stτres τλ sτlid ζσd liquid λuels ζre exhζusted.

The demand λo⅔ bioλuels beμan to inc⅔ease in “me⅔ica λ⅔om the 's to 's. These we⅔e att⅔ibuted to the pionee⅔inμ eλλo⅔ts on the diesel enμine by “dolphus ”usch and Clessie L. Cummins alonμ with othe⅔ enμine manuλactu⅔e⅔s. Howeve⅔, the bioλuel indust⅔y was λaced with a majo⅔ challenμe oλ cheap and ⅔eadily available λeedstock. Unλo⅔tunately λo⅔ the bioλuel indust⅔y, at this same pe⅔iod, the pet⅔oleum indust⅔ies λound out mo⅔e advanced technoloμies λo⅔ imp⅔ovinμ the p⅔ope⅔ties oλ the black μold . The discove⅔ies oλ la⅔μe ⅔ese⅔voi⅔s and developments c⅔eated new ma⅔kets λo⅔ this black μold . The⅔eλo⅔e, by , diesel enμines we⅔e alte⅔ed to enable them use pet⅔oleum-based λuels which have lowe⅔ viscosities. The⅔e‐ aλte⅔, the sales oλ biodiesel we⅔e weakened and the p⅔oduction st⅔uctu⅔e was pushed to the backμ⅔ound. The⅔eλo⅔e, no siμniλicant eλλo⅔ts we⅔e made to inc⅔ease the public awa⅔eness on its potentials. This pe⅔iod witnessed inc⅔eased demands λo⅔ automobiles which we⅔e p⅔opelled by pet⅔oleum λuels. The availability oλ public λunds, and new t⅔anspo⅔tation inλ⅔ast⅔uctu⅔e such as inte⅔state and hiμhway systems helped in this ⅔eμa⅔d [ ]. The ea⅔ly post-WWII λossil λuel demand and supply was inλluenced by the commencement oλ oλλsho⅔e oil and μas p⅔oduction in at the Gulλ oλ Mexico and the invention oλ jet ai⅔c⅔aλt [ ]. Howeve⅔ in the s, speculations ⅔eμa⅔dinμ the λinite natu⅔e oλ the λossil oil ⅔ese⅔ves became an issue wo⅔th ponde⅔inμ ove⅔. In and , OPEC ⅔educed oil supplies and inc⅔eased the p⅔ices to meet with the sho⅔taμes oλ the pet⅔oleum c⅔isis oλ that time. This ma⅔ked the ⅔eeme⅔μence oλ the potentials oλ bioλuels in the public consciousness. Thus in , South “λ⅔ica sta⅔ted the comme⅔cial development oλ biodiesel. Sunλlowe⅔ oil was t⅔anseste⅔iλied and ⅔eλined to a standa⅔d simila⅔ to pet⅔oleum diesel λuel [ ]. The outcome was the discove⅔y oλ seve⅔al sou⅔ces and technoloμies that imp⅔oved enμine pe⅔λo⅔mance with ⅔educed envi⅔on‐ mental impacts. Expe⅔iences λ⅔om past we⅔e used in achievinμ imp⅔oved eλλiciencies, while ⅔educinμ costs by developinμ the ⅔enewable ene⅔μy ma⅔ketinμ advantaμe. The p⅔ocedu⅔e λo⅔ the p⅔oduction, ⅓uality and enμine-testinμ λo⅔ biodiesel was λinalized and published inte⅔nationally in . The South “λ⅔ican technoloμy was obtained by Gaskoks an “ust⅔ian company. Gaskos established the λi⅔st pilot plant λo⅔ biodiesel p⅔oduction in .

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

”y “p⅔il oλ , the λi⅔m set up the λi⅔st comme⅔cial-scale plant p⅔oducinμ million μallon pe⅔ yea⅔ MGPY . Howeve⅔ du⅔inμ this pe⅔iod, biodiesel was only beinμ p⅔oduced on a noncomme⅔cial scale in the United States. The μ⅔owth in p⅔oducinμ biodiesel in Eu⅔ope beμan in because oλ the need to ⅔educe envi⅔onmental impacts λ⅔om emissions oλ μ⅔eenhouse μases GHG . Th⅔ee yea⅔s late⅔, the λi⅔st comme⅔cial biodiesel p⅔oduction was sta⅔ted in “me⅔ica. ”y , the Commodity C⅔edit Co⅔po⅔ation sta⅔ted subsidizinμ value-added aμ⅔icultu⅔e towa⅔ds biodiesel p⅔oduction. The past decade to witnessed an unp⅔ecedented p⅔oduction oλ biodiesel. Incentives λ⅔om policy make⅔s such as tax exemptions, tax c⅔edits and ⅔enewable λuel standa⅔ds aided the biodiesel μ⅔owth. Howeve⅔, some p⅔ope⅔‐ ties oλ biodiesel also cont⅔ibuted to the unp⅔ecedented μ⅔owth we a⅔e witnessinμ in the biodiesel indust⅔y [ - ]. The inc⅔easinμ inte⅔ests on biodiesel is λueled by the need to λind a sustainable diesel λuel alte⅔native. This is mainly because oλ envi⅔onmental issues, app⅔ehensions ove⅔ ene⅔μy independence and sky⅔ocketinμ p⅔ices. Seve⅔al p⅔ocessinμ options a⅔e available λo⅔ the biodiesel p⅔oduction. The va⅔ious λeedstocks and p⅔ocessinμ conditions p⅔ovide seve⅔al p⅔ocessinμ technoloμies. The choice oλ a pa⅔ticula⅔ technoloμy is dependent on catalyst and the sou⅔ce, type and ⅓uality oλ λeedstock. Othe⅔s include postp⅔oduction steps such as p⅔oduct sepa⅔ation and pu⅔iλication and catalyst and alcohol ⅔ecove⅔y. The dominant λacto⅔ in the p⅔oduction p⅔ocess is the cost oλ λeedstock while capital costs cont⅔ibute only about %. It is the⅔eλo⅔e essential to utilize cheap λeedstock to ⅔educe the ove⅔all p⅔oduction costs. In the same ⅔eμa⅔ds, some technoloμies a⅔e desiμned to handle va⅔iety oλ λeedstocks.

. Past achievments Non-λossil λuel alte⅔natives a⅔e λavo⅔ed because oλ thei⅔ common availability, ⅔enewability, sustainability, biodeμ⅔ablability, job c⅔eation, ⅔eμional development and ⅔educed envi⅔on‐ mental impacts. Table summa⅔izes some oλ the majo⅔ successes oλ biodiesel. . . Feedstocks Nume⅔ous λeedstocks have been expe⅔imented in biodiesel p⅔oduction. “dvancements λ⅔om such expe⅔imentations led to establishment oλ waste-to-wealth biodiesel p⅔oduction. Cheap and ⅔eadily available ⅔aw mate⅔ials such as used cookinμ oil and yellow μ⅔ease a⅔e used λo⅔ p⅔oducinμ biodiesel. These eλλo⅔ts helped in ⅔educinμ the envi⅔onmental impacts associated with dumpinμ in landλills as well as saves the cost oλ payinμ λo⅔ such dumpinμ. “nothe⅔ notable success is the use oλ Jat⅔opha o⅔ the mi⅔acle plant in many developinμ count⅔ies. The λact that it can be cultivated almost anywhe⅔e with minimal i⅔⅔iμation and less intensive ca⅔e, made it suitable λo⅔ peasant λa⅔me⅔s. Sustained hiμh yields we⅔e obtained th⅔ouμhout its ave⅔aμe liλe cycle oλ yea⅔s. Casto⅔ plantation a⅔e also inte⅔c⅔opped with jat⅔opha to imp⅔ove the econmic viability oλ jat⅔opha within the λi⅔st to yea⅔s [ ]. “nothe⅔ oil c⅔op that is used to imp⅔ove soil ⅓uality is the nit⅔oμen-λixinμ Pτσμζmiζ piσσζtζ. It p⅔oduces seeds with siμniλicant oil contents.

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. . Technologies ”iodiesel is one oλ the most tho⅔ouμhly tested alte⅔native λuel in the ma⅔ket today. Studies by many ⅔esea⅔che⅔s have conλi⅔med simila⅔ enμine pe⅔λo⅔mance oλ biodiesel to pet⅔oleum diesel. T⅔anseste⅔iλication p⅔oduce oil with simila⅔ b⅔ake powe⅔ as obtained with diesel λuel. Minimal ca⅔bon deposits we⅔e noticed inside the enμine except the intake valve deposits which we⅔e sliμhtly hiμhe⅔. The level oλ injecto⅔ cokinμ was also ⅔educed siμniλicantly lowe⅔ than that obse⅔ved with D λuel [ , ]. “n impo⅔tant b⅔eakth⅔ouμh in t⅔anseste⅔iλication is the Mcμyan P⅔ocess®, which can utilize va⅔ious inexpensive, non-λood-μ⅔ade and λ⅔ee λatty acids FF“s containinμ λeedstocks Fiμu⅔e . The p⅔ocess can be small in physical size and it utilizes hete⅔oμeneous catalysts to p⅔oduce biodiesel within s [ , ]. The easy λatty acid ⅔emoval o⅔ EF“R system ensu⅔es that no wastes a⅔e p⅔oduced λ⅔om the p⅔ocess. It eliminates post p⅔oduction costs such as the washinμ and neut⅔alization steps. To achieve % conve⅔sion, it ⅔ecycles all un⅔eacted λeedstock and excess alcohol back into the ⅔eacto⅔. Ene⅔μy eλλiciency is also achieved th⅔ouμh heat t⅔ansλe⅔ mechanism in-cominμ cold ⅔eactants a⅔e p⅔eheated by the out-μoinμ hot p⅔oducts [ , ].

Figure 1. Process flow diafram of a biodiesel plan“ based on “he Mcgyan proces[21].

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

Economic & social impact

Environment impact

Energy security

S”s“ainabili“y; made from agric”l“”ral or was“e

Red”ced 78% GHG

Red”ced dependence on fossil

reso”rces

emissions

f”els

F”el diversi“y & improved f”el efficiency &

Red”ced air poll”“ion

Domes“ic “arge“s

Improved r”ral economy

Biodegradabili“y

S”pply reliabili“y

Increased income “ax & “rade balances

Improved land & wa“er ”se

Readily available

In“erna“ional compe“i“iveness

Carbon seq”es“ra“ion

Renewabili“y

Increased inves“men“s on feeds“ocks &

Lower s”lf”r con“en“

Domes“ic dis“rib”“ion

Technological developmen“s (R & D)

Lower aroma“ic con“en“

Improved f”el economy

Higher ce“ane n”mber (52 vs. 48), l”brici“y &

Lesser “oxici“y

Comparable energy con“en“

economy

eq”ipmen“

flash poin“ Knowledge developmen“ & diff”sion

(92.19%) Safer handling & s“orage

S“ric“ q”ali“y req”iremen“s are me“

S“rong grow“h in demand & marke“ forma“ion

Viscosi“y 1.3 “o 1.6 “imes “ha“ of D2 f”el

Improved engine performance

Good energy balance (3.24:1 vs. 0.88:1)

Red”ces “he need for main“enance & prolongs engine life Compa“ible wi“h all conven“ional diesel engines Offers “he same engine d”rabili“y & performance Has “he po“en“ial of displacing pe“role”m diesel f”el Comparable s“ar“-”p, “orq”e range & ha”lage ra“es Table 1. Major achievemen“s of biodiesel [16,23-27]

. . Environmental impacts and health effects “ % ⅔eduction in GHG emission was ⅔epo⅔ted by the U.S. Depa⅔tments oλ “μ⅔icultu⅔e and Ene⅔μy with biodiesel usaμe. Essentially, biodiesel is non-a⅔omatic and sulphu⅔-λ⅔ee as compa⅔ed with pet⅔odiesel which contains to wt.% a⅔omatic compounds and ppm

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

SO [ ]. The potential oλ pu⅔e biodiesel to λo⅔m ozone smoμ λ⅔om hyd⅔oca⅔bons is % less. “lso, sulλates and oxides oλ sulλu⅔ majo⅔ constituents oλ acid ⅔ain a⅔e essentially eliminated λ⅔om the exhaust emissions compa⅔ed to pet⅔odiesel. These help in cu⅔binμ the inc⅔easinμ μlobal wa⅔minμ p⅔oblems. “ve⅔aμe dec⅔ease oλ . % λo⅔ smoke density, . % λo⅔ CO and % λo⅔ CO have been ⅔epo⅔ted when biodiesel was used [ ]. Human liλe expectancy is the⅔eby enhanced because oλ imp⅔oved ai⅔ ⅓uality. . . . Eσerμy iσdepeσdeσθe ”iodiesel ⅔educes the excessive ⅔eliance on λossil λuels. This enhances the μlobal ene⅔μy secu⅔ity [ ]. It also has the potential to ⅔eplace oil impo⅔tation since it is p⅔oduced domestically, the⅔eby p⅔ovidinμ additional ma⅔ket λo⅔ aμ⅔icultu⅔al p⅔oducts. It suppo⅔ts the ⅔u⅔al commun‐ ities whe⅔e it is cultivated by p⅔otectinμ and μene⅔atinμ jobs. P⅔oducinμ bioλuels e⅓uivalent to % oλ automobile λuel consumption in the EU p⅔otected and/o⅔ c⅔eated app⅔oximately , jobs [ ]. “pp⅔oximately, λo⅔ eve⅔y unit oλ λossil ene⅔μy used in biodiesel p⅔oduction, . units oλ ene⅔μy is μained. Mo⅔eove⅔, lesse⅔ ene⅔μy is ⅔e⅓ui⅔ed λo⅔ biodiesel p⅔oduction than the ene⅔μy de⅔ived λ⅔om the λinal p⅔oduct [ ].

. Different feedstocks used in the production of biodiesel Mo⅔e than oil-bea⅔inμ c⅔ops have been identiλied as potential sou⅔ces λo⅔ p⅔oducinμ biodiesel. Howeve⅔, only palm, jat⅔opha, ⅔apeseed, soybean, sunλlowe⅔, cottonseed, saλλlowe⅔, and peanut oils a⅔e conside⅔ed as viable λeedstocks λo⅔ comme⅔cial p⅔oduction [ ]. . . Edible feedstocks Dependinμ on availability, diλλe⅔ent edible oils a⅔e utilized as λeedstocks λo⅔ biodiesel p⅔o‐ duction by diλλe⅔ent count⅔ies. Palm oil and coconut oil a⅔e commonly used in Malaysia and Indonesia. Soybean oil is majo⅔ly used in U.S. [ ]. . . Non-edible feedstocks In o⅔de⅔ to ⅔educe p⅔oduction costs and to avoid the λττd-λτr-λuel conλlict, inedible oils a⅔e used as the majo⅔ sou⅔ces λo⅔ biodiesel p⅔oduction. Compa⅔ed to edible oils, inedible oils a⅔e aλλo⅔dable and ⅔eadily available. They a⅔e obtained λ⅔om Jζtrτphζ θurθζs jat⅔opha o⅔ ⅔atanjyote o⅔ seemaikattamankku , Pτσμζmiζ piσσζtζ ka⅔anja o⅔ honμe , Cζlτphyllum iστphyllum naμ‐ champa , Hevθζ ηrζsilieσsis ⅔ubbe⅔ seed t⅔ee , “zζdirζθhtζ iσdiθζ neem , Mζdhuθζ iσdiθζ ζσd Mζdhuθζ lτσμiλτliζ mahua , Ceiηζ peσtζσdrζ silk cotton t⅔ee , Simmτσdsiζ θhiσeσsis jojoba , Euphτrηiζ tiruθζlli, babassu t⅔ee, mic⅔oalμae, etθ. [ ]. “monμ the plant species which have mo⅔e than % oil in thei⅔ seed/ke⅔nel palm, Jζtrτphζ θurθζs, and Pτσμζmiζ piσσζtζ Ka⅔anja we⅔e λound to be the most suitable λo⅔ biodiesel p⅔oduction [ ]. Many Eu⅔opean count⅔ies utilize ⅔apeseed [ ]. Du⅔inμ Wo⅔ld Wa⅔ II, oil λ⅔om Jζtrτphζ seeds was used as blends with and substituted λo⅔ diesel [ , ]. It has been ⅔epo⅔ted that biodiesel p⅔oduced λ⅔om palm and

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

Jat⅔opha have physical p⅔ope⅔ties in the ⅔iμht balance conλe⅔⅔inμ it with ade⅓uate oxidation stability and cold pe⅔λo⅔mance [ ]. Most oλ the st⅔ict ⅔e⅓ui⅔ements set by the “me⅔ican and Eu⅔opean biodiesel standa⅔ds λo⅔ biodiesel have been achieved [ ]. The majo⅔ oils used λo⅔ p⅔oducinμ biodiesel a⅔e p⅔esented in Table .

Group Major oils

Source of oil Cocon”“ (copra), corn (maize), co““onseed, canola (a varie“y of rapeseed), olive, pean”“ (gro”ndn”“), safflower, sesame, soybean, and s”nflower.

N”“ oils

Almond, cashew, hazeln”“, macadamia, pecan, pis“achio and waln”“.

O“her edible

Amaran“h, aprico“, argan, ar“ichoke, avocado, babass”, bay la”rel, beech n”“, ben, Borneo “allow

oils

n”“, carob pod (algaroba), coh”ne, coriander seed, false flax, grape seed, hemp, kapok seed, lalleman“ia, lemon seed, maca”ba fr”i“ (Acrocomia sclerocarpa), meadowfoam seed, m”s“ard, okra seed (hibisc”s seed), perilla seed, peq”i, (Caryocar brasiliensis seed), pine n”“, poppy seed, pr”ne kernel, q”inoa, ram“il (G”izo“ia abyssinica seed or Niger pea), rice bran, “allow, “ea (camellia), “his“le (Silyb”m marian”m seed), and whea“ germ.

Inedible oils

Algae, babass” “ree, copaiba, honge, ja“ropha or ra“anjyo“e, jojoba, karanja or honge, mah”a, milk b”sh, nagchampa, neem, pe“role”m n”“, r”bber seed “ree, silk co““on “ree, and “all.

O“her oils

Cas“or, radish, and “”ng.

Table 2. Major oil species for biodiesel prod”c“ion [37]

. . . “lμζe τil Cu⅔⅔ently, alμae-based biodiesel is the λocus oλ many ⅔esea⅔ch inte⅔ests because they have the potential to p⅔ovide suλλicient oil λo⅔ μlobal consumption. It has the potential to p⅔oduce biodiesel yields > times those attainable pe⅔ hecta⅔e λ⅔om plant λeedstock Table . ”esides thei⅔ hiμh lipid contents and λast μ⅔owth ⅔ate, mic⅔oalμae have the potential to mitiμate the competitions λo⅔ land-use and λood-λo⅔-λuel conλlicts. They a⅔e also able to ⅔educe the GHG eλλect via CO se⅓uest⅔ation [ ]. Mic⅔oalμae can be cultivated in habitats which a⅔e not λavo⅔able λo⅔ ene⅔μy c⅔ops. Compa⅔ed with oilseeds, the ha⅔vestinμ and t⅔anspo⅔tation costs oλ mic⅔oalμae a⅔e ⅔elatively low. Nζσστθhlτrτpsis, membe⅔s oλ the ma⅔ine μ⅔een alμae a⅔e conside⅔ed the most suitable candidates λo⅔ biodiesel p⅔oduction. These st⅔ains have shown hiμh lipid content and biomass p⅔oductivity. Howeve⅔, ⅔esea⅔ch in this a⅔ea especially alμal oil ext⅔action is still limited and in ea⅔ly staμes. . . . Other λeedstτθks Used veμetable oils UCO , yellow μ⅔ease - wt% FF“ , b⅔own μ⅔ease > wt% FF“ , and soapstock by-p⅔oduct oλ ⅔eλininμ veμetable oils a⅔e potential λeedstocks λo⅔ biodiesel p⅔oduction. Thei⅔ low costs and availability make them suitable λo⅔ ⅔educinμ the p⅔oduction

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costs oλ biodiesel. To achieve this howeve⅔, the p⅔oblems associated with hiμh FF“ which a⅔e common to these λeedstocks, pa⅔ticula⅔ly when alkaline catalysts a⅔e employed need attention. Solid acid catalysts a⅔e cu⅔⅔ently ⅔eceivinμ μ⅔eat attention because they a⅔e suitable λo⅔ λeedstocks containinμ FF“s [ - ]. “nothe⅔ p⅔ocess that has the potential oλ p⅔ocessinμ these λeedstocks is supe⅔c⅔itical t⅔anseste⅔iλication. The p⅔et⅔eatment step, soap and catalyst ⅔emoval common to alkaline catalysis a⅔e eliminated since the p⅔ocess ⅔e⅓ui⅔es no catalyst [ , ]. The p⅔ocess has λast ⅔eaction ⅔ate which siμniλicantly ⅔educes the ⅔eaction time [ ]. The p⅔ocess is insensitive to wate⅔ and FF“s [ , ]. Howeve⅔, this method is not economical because it ⅔e⅓ui⅔es hiμh ⅔eaction tempe⅔atu⅔e, p⅔essu⅔e and hiμhe⅔ mola⅔ ⅔atio oλ alcohol to λeedstock [ , , ]. “nothe⅔ inte⅔estinμ λeedstock is Sζliθτrσiζ ηiμelτvii Halophytessuch . It can p⅔oduce e⅓ual biodiesel yields obtained λ⅔om soybeans and othe⅔ oilseeds. They μ⅔ow in saltwate⅔ oλ coastal a⅔eas unsuitable λo⅔ ene⅔μy c⅔ops.

Microalgae/Plant

Oil yield

Oil content

Required

Biodiesel productivity

(L/ha/year)

(% wt in

land

(kg biodiesel/ha/

biomass)

(M ha -1a )

year)

Microalgaeb (high oil con“en“)

136 900

70

2

121 104

Microalgaec (low “o low oil

58 700 “o 97

30 “o 50

4.5

51 927-85 515

con“en“)

800

Oil palm (Elaeis guineensis)

5 950

30 “o 60

45

4747

Jatropha (Jatropha curcas L.)

1 892

Kernel: 50 “o 60

140

656

Seed: 35 “o 40 Canola/Rapeseed (Brassica napus

1 190

38 “o 46

223

862

Soybean (Glycine max L.)

446

15 “o 20

594

562

Corn/Maize (Germ) (Zea mays L.)

172

44 “o 48

1540

152

L.)

Table 3. Es“ima“ed oil con“en“, yields and land req”iremen“ for vario”s biodiesel feeds“ocks.[36,47,48]

. Methods of oil extraction The th⅔ee common methods used in ext⅔actinμ oil a⅔e i Mechanical ext⅔action, ii solvent ext⅔action and iii enzymatic ext⅔action.

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

. . Mechanical extraction method This method is used by smalle⅔ p⅔oduction λi⅔ms λo⅔ p⅔ocessinμ less than , kμ/day. Usually, an enμine d⅔iven sc⅔ew p⅔ess o⅔ a manual ⅔am p⅔ess is used to ext⅔act % o⅔ % oλ the available oil ⅔espectively. P⅔et⅔eatment such as dehullinμ and cookinμ inc⅔ease oil yields to % and % aλte⅔ sinμle and dual pass ⅔espectively [ , ]. Howeve⅔, most oλ the mechanical p⅔esses a⅔e desiμned λo⅔ pa⅔ticula⅔ seeds which aλλect yields with othe⅔ seeds. “lso, ext⅔a t⅔eatments such as deμumminμ and λilt⅔ation a⅔e ⅔e⅓ui⅔ed λo⅔ oil ext⅔acted by this techni⅓ue. . . Chemical solvent extraction method The commonly used chemical methods a⅔e soxhlet ext⅔action, Ult⅔asonication techni⅓ue and hot wate⅔ ext⅔action [ , ]. Solvent ext⅔action o⅔ leachinμ is typically used λo⅔ p⅔ocessinμ mo⅔e than , kμ/day [ ]. Yields a⅔e aλλected by pa⅔ticle size, solvent type and concent⅔ation, tempe⅔atu⅔e and aμitation. To inc⅔ease the exposu⅔e oλ the oil to the solvent, the oilseeds a⅔e usually λlaked. “λte⅔ ext⅔action, the oil-solvent mixtu⅔e o⅔ misθellζ, is λilte⅔ed while heat is used to vapo⅔ize the solvent λ⅔om the miscella. Steam is injected to ⅔emove any solvent ⅔emaininμ λ⅔om the oil. The immiscibility oλ the solvent and steam vapo⅔s is used to sepa⅔ate them in a settlinμ tank aλte⅔ condensation. The hiμhest oil yields a⅔e obtained with nhexane. Howeve⅔, the p⅔ocess ⅔e⅓ui⅔es hiμhe⅔ ene⅔μy and lonμe⅔ time compa⅔ed to othe⅔ methods. Fu⅔the⅔mo⅔e, the human health and envi⅔onmental impacts associated with toxic solvents, waste wate⅔ μene⅔ation and emissions oλ volatile o⅔μanic compounds a⅔e challenμes λacinμ this method. . . Enzymatic extraction method Oilseeds a⅔e ⅔educed to small pa⅔ticles and the oil is ext⅔acted by suitable enzymes. Volatile o⅔μanic compounds a⅔e not p⅔oduced by this method which makes it envi⅔onmentally λ⅔iendly when compa⅔ed to the othe⅔ methods. Howeve⅔, it has the disadvantaμe oλ lonμ p⅔ocessinμ time and hiμh cost oλ pu⅔chasinμ enzymes [ ].

. Technologies used in biodiesel production Seve⅔al ⅔esea⅔ches we⅔e ca⅔⅔ied out to ove⅔come o⅔ minimize the p⅔oblems associated with p⅔oducinμ biodiesel. The methods that have been used λo⅔ minimizinμ the viscosity oλ veμetable oils λo⅔ p⅔actical application in inte⅔nal combustion enμines include py⅔olysis, mic⅔oemulsiλication, blendinμ dilutinμ and t⅔anseste⅔iλication. Dilution and mic⅔oemulsiλi‐ cation a⅔e not p⅔oduction p⅔ocesses and a⅔e the⅔eλo⅔e not discussed in this chapte⅔. “ summa⅔y oλ veμetable oils and animal λats and the majo⅔ biodiesel p⅔oduction technoloμies a⅔e p⅔esented in Table .

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . Pyrolysis or catalytic cracking Py⅔olysis is the heatinμ oλ o⅔μanic matte⅔ in the absence oλ ai⅔ to p⅔oduce μas, a li⅓uid and a solid [ ]. Heat o⅔ a combination oλ heat and catalyst is used to b⅔eak veμetable oils o⅔ animal λats into smalle⅔ constituents. Oleλins and pa⅔aλλins a⅔e thus obtained with simila⅔ p⅔ope⅔ties to pet⅔odiesel whe⅔e such p⅔oducts de⅔ived the name diesel-like-λuel [ ]. Studies on eλλects oλ ⅔apeseed pa⅔ticle size showed that the p⅔oduct yield is independent oλ the oilseed pa⅔ticle size [ ]. The maximum tempe⅔atu⅔e ⅔anμe λo⅔ conve⅔sion oλ bio-oil is °C to °C [ ]. Rapid devolatilization oλ cellulose and hemicellulose occu⅔ at this tempe⅔atu⅔e. Heatinμ ⅔ate and tempe⅔atu⅔e have siμniλicant eλλects on bio-oil yields, cha⅔ and μas ⅔eleased λ⅔om olive [ ]. The viscosity, λlash and pou⅔ points and e⅓uivalent calo⅔iλic values oλ the oil a⅔e lowe⅔ than diesel λuel. Thouμh the py⅔olyzate has inc⅔eased cetane numbe⅔, it is howeve⅔ lowe⅔ than that oλ diesel oil. “pa⅔t λ⅔om ⅔educinμ the viscosity oλ the veμetable oil, py⅔olysis enables decouplinμ oλ the unit ope⅔ation e⅓uipment in sho⅔te⅔ time, place and scale. It p⅔oduces clean li⅓uids which needs no additional washinμ, d⅔yinμ o⅔ λilte⅔inμ. P⅔oduct oλ py⅔olysis consists oλ hete⅔oμeneous molecules such as wate⅔, pa⅔ticulate matte⅔, sulλu⅔, alkanes, alkenes and ca⅔boxylic acids [ , ]. Conse⅓uently, it is diλλicult to cha⅔acte⅔ize λuel obtained λ⅔om py⅔olysis [ ]. This p⅔ocess is ene⅔μy consuminμ and needs expensive distillation unit. Mo⅔eove⅔, the sulλu⅔ and ash contents make it less eco-λ⅔iendly [ ]. . . Transesterification alcoholysis T⅔anseste⅔iλication is the most widely employed p⅔ocess λo⅔ comme⅔cial p⅔oduction oλ biodiesel. It involves heatinμ the oil to a desiμnated tempe⅔atu⅔e with alcohol and a catalyst, the⅔eby ⅔est⅔uctu⅔inμ its chemical st⅔uctu⅔e. This conve⅔sion ⅔educes the hiμh viscosity oλ the oils and λats. Fo⅔ the t⅔anseste⅔iλication oλ t⅔iμlyce⅔ide TG molecule, th⅔ee consecutive ⅔eactions a⅔e needed. In these ⅔eactions, FF“ is neut⅔alized by the TG λ⅔om the alcohol. One mole oλ μlyce⅔ol and th⅔ee moles oλ alkyl este⅔s a⅔e p⅔oduced λo⅔ each mole oλ TG conve⅔ted at the completion oλ the net ⅔eaction. These sepa⅔ate into th⅔ee laye⅔s, with μlyce⅔ol at the bottom, a middle laye⅔ oλ soapy substance, and biodiesel on top [ ]. T⅔anseste⅔iλication is a ⅔eve⅔sible ⅔eaction. To obtain ⅔easonable conve⅔sion ⅔ates the⅔eλo⅔e, it ⅔e⅓ui⅔es a catalyst. The ⅔eaction conditions, λeedstock compositional limits and post-sepa⅔ation ⅔e⅓ui⅔ements a⅔e p⅔edete⅔mined by the natu⅔e oλ the catalyst. Table p⅔esents a μena⅔al ove⅔view oλ the seve⅔al t⅔anseste⅔iλication techni⅓ues λo⅔ biodiesel p⅔oduction. . . . Hτmτμeσeτus ζlkζli-θζtζlyzed trζσsesteriλiθζtiτσ “lkali catalysts such as NaOH and KOH we⅔e p⅔eλe⅔⅔ed ove⅔ othe⅔ catalysts because oλ thei⅔ ability to enhance λaste⅔ ⅔eaction ⅔ates [ ]. This is because they a⅔e ⅔eadily available at aλλo⅔dable p⅔ices and enable λast ⅔eaction ⅔ates [ ]. Detailed ⅔eview on base-catalyzed t⅔anseste⅔iλication oλ veμetable oils can be λound in ⅔eλ [ ]. Howeve⅔, homoμeneous catalysis has been λaced with the been λaced with the p⅔oblems saponiλication, hiμhly sensitive to FF“s, expensive sepa⅔ation ⅔e⅓ui⅔ement, waste wate⅔ μene⅔ation and hiμh ene⅔μy consumption.

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

. . . Hτmτμeσeτus ζθid-θζtζlyzed trζσsesteriλiθζtiτσ Thouμh the pe⅔λo⅔mance oλ this method is not st⅔onμly aλλected by FF“s in the λeedstock, the p⅔ocess is not as popula⅔ as the base-catalyzed p⅔ocess. This is because the use oλ st⅔onμ acids such as H SO [ , ], HCl, ”F , H PO , and o⅔μanic sulλonic acids [ ], is associated with hiμhe⅔ costs and envi⅔onmental impacts. Mo⅔eove⅔, the techni⅓ue is about times slowe⅔ than the homoμeneous base-catalyzed ⅔eaction. The mechanism oλ the acid-catalyzed t⅔anseste⅔iλica‐ tion can be λound in ⅔eλ [ ]. . . . Heterτμeσeτus ζθid ζσd ηζse-θζtζlyzed trζσsesteriλiθζtiτσ Solid acid can simultaneously catalyze the este⅔iλication and t⅔anseste⅔iλication without the need λo⅔ p⅔et⅔eatinμ λeedstocks with hiμh FF“s. Thus, this techni⅓ue has the potential oλ ⅔educinμ the hiμh cost oλ biodiesel p⅔oduction by di⅔ectly p⅔oducinμ biodiesel λ⅔om ⅔eadily available and low-cost λeedstocks [ ]. Solid basic catalysts also have the potential oλ ⅔educinμ the cost oλ biodiesel p⅔oduction be‐ cause oλ lesse⅔ catalyst consumption, ⅔euse and ⅔eμene⅔ation. Howeve⅔, these catalysts have some disadvantaμes which hinde⅔ thei⅔ wide acceptability. These include mass t⅔ansλe⅔ diλ‐ λusion p⅔oblem which ⅔educes the ⅔ate oλ ⅔eaction as a ⅔esult oλ the λo⅔mation oλ th⅔ee phas‐ es with alcohol and oil. Othe⅔ p⅔oblems associated with base catalyzed t⅔anseste⅔iλication a⅔e loss oλ catalyst activity in the p⅔esence oλ wate⅔ and post-p⅔oduction costs such as p⅔od‐ uct sepa⅔ation, pu⅔iλication and polishinμ. . . . Eσzymζtiθ trζσsesteriλiθζtiτσ Some oλ the p⅔oblems associated with homoμeneous catalysts such as expensive p⅔oduct sepa⅔ation, wastewate⅔ μene⅔ation, and the p⅔esence oλ side ⅔eactions a⅔e avoided with enzymatic t⅔anseste⅔iλication [ ]. Enzyme immobilization is usually done to enhance the p⅔oduct ⅓uality, inc⅔ease the numbe⅔ oλ times the catalyst is ⅔eused and to ⅔educe cost [ , ]. Howeve⅔, seve⅔al technical diλλiculties such as hiμh cost oλ pu⅔chasinμ enzymes, p⅔oduct contamination, and ⅔esidual enzymatic activity a⅔e limitinμ the applicability oλ this techni⅓ue. . . . Superθritiθζl ζlθτhτl trζσsesteriλiθζtiτσ Unlike the conventional t⅔anseste⅔iλication oλ two hete⅔oμeneous li⅓uid phases involvinμ alcohol pola⅔ molecule and non-pola⅔ molecules TGs , supe⅔c⅔itical t⅔anseste⅔iλication is done in sinμle homoμeneous phase. Subjectinμ solvents containinμ hyd⅔oxyl μ⅔oups such as wate⅔ and alcohol to conditions in excess oλ thei⅔ c⅔itical points make them to act as supe⅔acids. Unde⅔ supe⅔c⅔itical conditions, alcohol se⅔ves a dual pu⅔pose oλ acid catalyst and a ⅔eactant [ , ]. The absence oλ inte⅔phase solves the mass t⅔ansλe⅔ limitations which μives the possibility oλ completinμ the ⅔eaction in minutes ⅔athe⅔ than seve⅔al hou⅔s. In λact, the Mcμyan P⅔ocess® was used to p⅔oduce biodiesel unde⅔ s [ , ]. Howeve⅔, this p⅔ocess is not economical especially λo⅔ comme⅔cial p⅔oduction as it ⅔e⅓ui⅔es expensive ⅔eactinμ e⅓uipment due to hiμh tempe⅔atu⅔e and p⅔essu⅔e [ ]. Studies a⅔e cu⅔⅔ently beinμ unde⅔taken in o⅔de⅔ to ⅔educe these hiμh ⅔eactinμ conditions.

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Direct use

Advantages

Dilution with

Microemulsion

Pyrolysis and catalytic

vegetable oils

of oils

cracking

Advantages

Simple process Simple process

Advantages

Advantages

Simple process

Simple process & non-

and non-

and non-

poll”“ing

poll”“ing

poll”“ing

no addi“ional washing,

Transesterification of oils and fats

Catalytic

Non-catalytic

drying or fil“ering req”ired Disadvan“ages Disadvan“ages

Disadvan“ages

Disadvan“ages

Acid-ca“alyzed

BIOX cosolven“ process

Highly visco”s Highly visco”s

Highly

Incomple“e

Con“ains he“erogeneo”s

comb”s“ion

molec”les

Highly ”ns“able Injec“or needle

”ns“able

Low p”ri“y

s“icking

Alkali ca“aly“ic

S”percri“ical alcohol

Enzyme-

Microwave and

ca“alyzed

”l“raso”nd assis“ed

Low vola“ili“y

Low vola“ili“y

Carbon deposi“s

No“ s”i“able

No“ s”i“able for No“ s”i“able for

for commercial commercial

commercial

prod”c“ion

prod”c“ion

prod”c“ion

Req”ires high “empera“”re Ca“aly“ic s”percri“ical alcohol Req”ires expensive

See Table 5 for advan“ages and

eq”ipmen“

disadvan“ages

Table 4. Use of vege“able oils and animal fa“s and major biodiesel prod”c“ion processes.

. . Technologies . . . Miθrτwζve ζssisted trζσsesteriλiθζtiτσ The mic⅔owave i⅔⅔adiation as ene⅔μy stimulant has been att⅔actinμ the attention oλ many ⅔esea⅔che⅔s. This is because the ⅔eaction p⅔ocess λast within minutes , it employs a lowe⅔ alcohol-oil ⅔atio and it ⅔educes by-p⅔oducts ⅓uantities. It uses a continuously chanμinμ elect⅔ical and maμnetic λields to activate the smallest deμ⅔ee oλ va⅔iance oλ the ⅔eactinμ molecules. These ⅔apidly ⅔otatinμ cha⅔μed ions inte⅔act easily with minimal diλλusion limita‐ tion [ ]. Howeve⅔, this p⅔ocess also has comme⅔cial scale-up p⅔oblem because oλ hiμh ope⅔atinμ conditions and saλety aspects [ ]. “n even mo⅔e dauntinμ challenμe is in inc⅔easinμ the i⅔⅔adiation penet⅔ation depth beyond a λew centimete⅔s into the ⅔eactinμ molecules. . . . Ultrζsτuσd ζssisted trζσsesteriλiθζtiτσ This p⅔ocess utilizes sound ene⅔μy at a λ⅔e⅓uency beyond human hea⅔inμ. It st⅔etches and comp⅔esses the ⅔eactinμ molecules in an alte⅔natinμ manne⅔. “pplication oλ hiμh neμative

Biodiesel Feeds“ock and Prod”c“ion Technologies: S”ccesses, Challenges and Prospec“s h““p://dx.doi.org/10.5772/52790

p⅔essu⅔e μ⅔adient beyond the c⅔itical molecula⅔ distance λo⅔ms cavitation bubbles. Some oλ the bubbles expand suddenly to unstable sizes and collapse violently. This causes emulsiλication and λast ⅔eaction ⅔ates with hiμh yields since the phase bounda⅔y has been dis⅔upted [

Chemical catalysed

Chemical catalysed (Modified)

-

].

Biochemical Noncatalysed catalysed

Homogene‐ Homogeneous ous acid

Heterogeneous

Heterogene‐

Microwave ir‐

Ultrasound

Oscillatory

acid

ous base

radiation

(sonication)

flow reactor

base

Merits

Merits

Employs feeds“ocks

Merits

Merits

Supercritical methanol

Merits

Merits

Reac“ion is 4000 High possibili“y of High possibili“y Speeds ”p ra“e

Increases

Increases mix‐ Opera“es a“

“imes fas“er

re”sing and re‐

of re”sing and

of reac“ion

FAME prod”c‐ ing of reac‐

milder reac‐

“ranses“erifica‐

wi“h high

“han homoge‐

genera“ing ca“a‐

regenera“ing

(from ho”rs “o

“ion from

“ion condi‐

“ion of TGs and

FFAs

neo”s acid ca“a‐ lys“ many “imes

ca“alys“ many

min”“es)

seedcakes

“ions

es“erifica“ion

("/>2 w“ %)

lysed reac“ions

“imes

No pre“rea“‐

Opera“es a“

Sim”l“aneo”s

Improves ca“a‐

In situ ex“rac‐

Efficien“ hea“

Cleaner bio‐

High biodiesel

men“ re‐

mild “empera‐

“ranses“erifica“ion p”rchasing ca“‐ lys“ ac“ivi“y and “ion “ranses‐

and mass

diesel and

yield

q”ired

“”re (50 “o 80

of TGs and es“eri‐

“ransfer

glycerol are

Saves cos“ of

alys“

Merits

Enzyme

“an“s

Merits

Merits Sim”l“aneo”s

of FA

selec“ivi“y

“erifica“ion

°C)

fica“ion of FA

Lower alcohol-

Simpler and less

Simpler and less Minimizes ener‐ High FAME

Higher yield in Energy con‐

Sim”l“aneo”s

“o-oil (5:1) mo‐

energy in“ensive

energy in“en‐

gy cons”mp‐

shor“er “ime

s”mp“ion is

“ranses“erifica‐

sive

“ion

compared “o

minimized

“ion of TGs and

lar ra“io

prod”ced

yields

ba“ch-“ype

es“erifica“ion

Red”ces reac‐ Was“e gen‐

Req”ires no

of FA High biodiesel

Does no“ req”ire

Easy separa“ion

Elimina“es of

yield

feeds“ock pre‐

of prod”c“s

saponifica“ion “or leng“h-“o- era“ion is

“rea“men“ Ca“alys“s are

Mild reac“ion con‐ Mild reac“ion

cheap and read‐ di“ions & less ily available

ca“alys“

diame“er ra“io minimized

condi“ions

Low reac“ion

Red”ces cos“s

Rela“ively fas“

“ime

reac“ion ra“e

Was“e genera“ion

Mild reac“ion

Shor“ reac“ion

is minimized

condi“ions

“ime

Rela“ively fas“ re‐

Enhances mass

ac“ion ra“es

“ransfer

prone “o leaching

(51

FAME con“en“ (%)

>99

0

-

> 96.5

0

93

>101

≤ 0.5

≤ 0.5

2 -1

S”lf”r (ppm) Flash poin“ (ºC) Acid n”mber (mgKOHg-1)

Depend of process

Table 3. USA and E”rope in“erna“ional s“andards for biodiesel [23].

Figure 7. Prod”c“ive chain for non-“oxic JC research projec“ in Norwes“ Mexico [23].

189

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . Materials and methods . . . Physiθζl θhemiθζl JC τil θhζrζθterizζtiτσ The study used JC λ⅔om selected elite μe⅔moplsms and cultivated in th⅔ee zones oλ Sinaloa, Mexico. The app⅔oach used to obtain Jζtrτphζ θurθζs oil JCO was the well-established cold p⅔essinμ λollowed by solvent oil ext⅔action. The JCO physicochemical p⅔ope⅔ties studied in this wo⅔k included λatty acid p⅔oλile, acid index “I , saponiλication index SI , pe⅔oxide in‐ dex PI , and iodine index II , which we⅔e obtained λollowinμ the methodoloμies suμμested by the “ssociation oλ “nalytical Communities, “O“C. The ⅓uality c⅔ite⅔ia λo⅔ the p⅔oduction oλ biodiesel a⅔e speciλied in EN . In pa⅔ticula⅔, method EN speciλies the F“ME content, which is used to p⅔oλile the veμetable o⅔ ani‐ mal oil λeedstock used in biodiesel p⅔oduction. EN ⅔e⅓ui⅔es calib⅔ation oλ all F“ME components by ⅔elative ⅔esponse to a sinμle compound, methyl heptadecanoate. This ⅔e‐ ⅓ui⅔es the measu⅔ement oλ accu⅔ate weiμhts λo⅔ each sample and the addition oλ an inte⅔nal standa⅔d. The F“ME ⅔anμe λo⅔ which the method is intended lies between C and C . “ modiλied EN ch⅔omatoμ⅔aphic method was used. In this method, F“ME analysis was ca⅔⅔ied out in a N “μilent Gas Ch⅔omatoμ⅔aph GC , e⅓uipped with a capilla⅔y split/splitless injecto⅔ and a selective “μilent mass spect⅔omete⅔ detecto⅔. “ L split injection split ⅔atio was made to a Supelco omeμa wax column bonded polyethylene μlycol , usinμ mlmin- oλ helium into the column as ca⅔⅔ie⅔. Samples we⅔e injected via an auto sample⅔ se⅔ies also λ⅔om “μilent technoloμies. “ μood ⅔esolution and peak shape was obtained when usinμ the λollowinμ oven tempe⅔atu⅔e p⅔oμ⅔am The initial tempe⅔atu⅔e, °C was kept λo⅔ min then a heatinμ ⅔ate oλ °C min- was used to inc⅔ease the tempe⅔‐ atu⅔e to °C and, λinally, this tempe⅔atu⅔e was kept λo⅔ min. Fo⅔ identiλication and cali‐ b⅔ation oλ the individual F“ME, the Supelco standa⅔d Component F“ME Mix was used. The ⅔esponse and ⅔etention time oλ each component was expe⅔imentally dete⅔mined. Then, the calib⅔ation was ve⅔iλied by both, the analysis oλ a calib⅔ation-check standa⅔d and the database oλ mass spect⅔um ⅔epo⅔ted by the National Institute oλ Standa⅔ds and Technol‐ oμy NIST . Results oλ analyses we⅔e then compa⅔ed with the ce⅔tiλicate oλ analysis, ve⅔iλy‐ inμ the ⅓uality oλ the calib⅔ation. The standa⅔d p⅔epa⅔ation λo⅔ this techni⅓ue consisted oλ the dilution oλ the F“ME standa⅔d into mL oλ n-heptane. The sample p⅔epa⅔ation was also ⅓uite simple with L oλ biodiesel λeedstock into mL oλ n-heptane. Finally, concent⅔a‐ tion ⅔epo⅔ts we⅔e based on the a⅔ea pe⅔centaμe ⅔athe⅔ than a mass pe⅔centaμe, to simpliλy the calculations. On the othe⅔ hand, ⅓uantitative dete⅔mination oλ λ⅔ee and total μlyce⅔in in biodiesel ” was also ca⅔⅔ied out by μas ch⅔omatoμ⅔aphy, λollowed by a modiλied methodoloμy p⅔o‐ posed by the “STM D - a .The same “μilent GC system was also used λo⅔ this analy‐ sis, the only diλλe⅔ence beinμ the use oλ a MS detecto⅔. “D”- ms column λ⅔om “μilent Technoloμies was used λo⅔ λ⅔ee and total μlyce⅔in analysis, which is e⅓uivalent in ch⅔omato‐ μ⅔aphic eλλiciency and selectivity to that oλ the MET-”iodiesel capilla⅔y column oλ Siμma “l‐ d⅔ich.

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

. . . Trζσsesteriλiθζtiτσ prτθedure . . . . Cτσveσtiτσζl prτθess Conventional alkaline t⅔anseste⅔iλication was conducted in a -necked μlass ⅔eacto⅔ mL, “ld⅔ich . “ homoμeneous ⅔eaction mixtu⅔e was obtained by usinμ plate sti⅔⅔e⅔s, and a con‐ stant ⅔eaction tempe⅔atu⅔e was kept by usinμ isolated bath vessels e⅓uipped with a stainless steel coils. The ⅔eaction tempe⅔atu⅔e was λixed by usinμ oλ a heate⅔/coole⅔ ⅔eci⅔culation iso‐ the⅔mal bath Fishe⅔ Scientiλic . Fiμu⅔e shows that each ⅔eacto⅔ was connected to‐ cooled st⅔aiμht μlass condense⅔ to avoid alcohol leaks wate⅔ at ºC λ⅔om anothe⅔ isothe⅔mal bath Fishe⅔ Scientiλic was used as coolinμ λluid.

Figure 8. Transes“erifica“ion reac“ion sys“em for “he conven“ional process

“nhyd⅔ous methanol Siμma-“ld⅔ich, . %, and KOH ⅔eaμent μ⅔ade Siμma-“ld⅔ich, % we⅔e used λo⅔ all expe⅔iment oλ this study. The sti⅔⅔e⅔ was λixed at ⅔pm, and the tempe⅔atu⅔e at , , o⅔ C , a methanol JCO mola⅔ ⅔atio was o⅔ . P⅔evious‐ ly to each ⅔eaction, methanol and KOH solutions we⅔e p⅔epa⅔ed acco⅔dinμ to the p⅔o‐ posed mola⅔ ⅔atio. Then, the ⅔eaction volume was λixed to mL oλ JCO. “λte⅔ the desi⅔ed ⅔eaction tempe⅔atu⅔e was ⅔eached, a p⅔eheated methanol-catalyst solution was added to sta⅔t the ⅔eaction. Reaction mixtu⅔e was sampled aλte⅔ , , , , and min. These samples we⅔e ⅓uenched by a sudden imme⅔sion oλ the sample to a plastic containe⅔ at C, λo⅔ min. Then, ⅔eaction p⅔oducts we⅔e pu⅔iλied acco⅔dinμ to the methodoloμy suμμest‐ ed by Ce⅔vantes [ ] Fiμu⅔e , and the biodiesel yield was dete⅔mined by means oλ the λollowinμ e⅓uation Yield =

wt ” wt τil

x

191

192

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . . . Heterτμeσeτus prτθess “s ⅔epo⅔ted elsewhe⅔e [ ], JCO t⅔anseste⅔iλication was also conducted by usinμ ZnO, “l O and ZnO-“l O mixed oxide powde⅔s as catalysts. The objective was to compa⅔e the hete⅔o‐ μeneous catalytic conve⅔sion oλ the same JCO. In this case, the catalytic activity was meas‐ u⅔ed in a Pa⅔⅔ sti⅔⅔ed tank ⅔eacto⅔, ope⅔ated at ⅔pm, ºC, P= . atm. “ methanol JCO mola⅔ ⅔atio oλ and a wt% oλ catalysts based on JCO weiμht we⅔e used. P⅔eviously to the ⅔eaction, the ⅔eacto⅔ was uploaded with the ml oλ JCO, the ⅔e⅓ui⅔ed methanol to achieve the mola⅔ ⅔atio, and . μ oλ catalyst. Then, the ⅔eacto⅔ was pu⅔μed with nit⅔oμen P⅔axai⅔, ⅔eaμent μ⅔ade λo⅔ min to avoid JCO bu⅔ninμ. The ⅔eaction time was h and then the ⅔eacto⅔ mixtu⅔e was suddenly cooled to ⅔oom tempe⅔atu⅔e. The p⅔od‐ uct sepa⅔ation included the λollowinμ steps. .

Catalysts ⅔emoval by means oλ vacuum λilt⅔ation.

.

Methanol ⅔ecove⅔y by usinμ a ⅔ota⅔y evapo⅔ato⅔ at the same condition indicated in Fiμ‐ u⅔e .

.

Glyce⅔ol and biodiesel sepa⅔ation by cent⅔iλuμation, usinμ the same condition indicated in Fiμu⅔e .

“t the end, the biodiesel yield was calculated by usinμ e⅓uation

Figure 9. Biodiesel p”rifica“ion process for a conven“ional alkaline “ranses“erifica“ion process.

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

. . . . Superθritiθζl methζστl prτθess Non-catalytic t⅔anseste⅔iλication p⅔ocess was evaluated by means oλ the supe⅔c⅔itical metha‐ nol ⅔eaction. This p⅔ocess was also ca⅔⅔ied out usinμ the Pa⅔⅔ sti⅔⅔ed tank ⅔eacto⅔. The eλλect oλ both, methanol JOC mola⅔ ⅔atio and and tempe⅔atu⅔e , , and ºC was evaluated usinμ nit⅔oμen as co-solvent. Once the ⅔e⅓ui⅔ed ⅔eaμents amounts we⅔e cha⅔μed to the ⅔eacto⅔, the ai⅔ was vented with nit⅔oμen and the sti⅔⅔e⅔ was λixed at ⅔pm. Next, the tempe⅔atu⅔e was inc⅔eased until the desi⅔ed set point in this p⅔ocess the p⅔essu⅔e inc⅔eased but not enouμh to ⅔each the methanol supe⅔c⅔itical point. The⅔eλo⅔e, ad‐ ditional nit⅔oμen was loaded to ensu⅔e MPa. “s an alte⅔native to dec⅔ease the d⅔astic op‐ e⅔ation conditions N was used as co-solvent. The ⅔eaction took place ove⅔ min, samplinμ the mixtu⅔e eve⅔y min th⅔ouμh the li⅓uid ⅔eacto⅔ valve. “λte⅔ the ⅔eaction was λinished, the ⅔eacto⅔ was suddenly cooled to ⅔oom tempe⅔atu⅔e. The p⅔oduct sepa⅔ation included the λollowinμ steps. .

Methanol ⅔ecove⅔y by usinμ a ⅔ota⅔y evapo⅔ato⅔ at the same condition indicated in Fiμ‐ u⅔e .

.

Glyce⅔ol and biodiesel sepa⅔ation by decantation.

“t the end, the biodiesel yield was calculated by usinμ e⅓uation .

. . . . Ultrζsτσiθ prτθess The sonot⅔anseste⅔iλication oλ JCO was conducted by usinμ a hiμhly eλλicient Hielsche⅔ Ul‐ t⅔asonic p⅔ocesso⅔, model UP HS. This e⅓uipment was used to μene⅔ate mechanical vi‐ b⅔ations by means oλ the ⅔eve⅔sed piezoelect⅔ic eλλect elect⅔ic excitation , with λ⅔e⅓uency oλ kHz, and a cont⅔ol ⅔anμe oλ kHz. The vib⅔ations we⅔e ampliλied by the S sonot⅔ode λitted to the ho⅔n and λo⅔med as a

vib⅔ato⅔s, and t⅔ansλe⅔⅔ed via its end λace to the JCO.

To optimize the sonot⅔anseste⅔iλication ⅔eaction, the eλλect acoustic powe⅔ density N , soni‐ cation time o⅔ ⅔eaction time , and methanol JCOmola⅔ ⅔atio MR we⅔e evaluated at ⅔oom tempe⅔atu⅔e ºC and ambient p⅔essu⅔e atm . Reaction tempe⅔atu⅔e was cont⅔olled by usinμ an isothe⅔mal bath Fishe⅔ Scientiλic . The continuous sonication oλ the ⅔eaction mixtu⅔e was conducted usinμ N= Wcm- and a mola⅔ ⅔atio oλ , λollowinμ the app⅔oach desc⅔ibed in Fiμu⅔e . Reaction time was λixed at , , , , , , , , o⅔ min. Next, the methanol JCO mola⅔ ⅔atio was evaluated va⅔ied to , and . Fo⅔ the smalle⅔ ⅔eac‐ tion time and mola⅔ ⅔atio, the acoustic powe⅔ density eλλect was evaluated at , , . , , . , and Wcm- . When the best set oλ pa⅔amete⅔s was λound, an expe⅔iment was con‐ ducted aμain to dete⅔mine the biodiesel ⅓uality.

193

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . Results and discussions . . . Physiθζl θhemiθζl JC τil θhζrζθterizζtiτσ The Jζtrτphζ θurθζs oil obtained λ⅔om non-toxic, ha⅔vested seed in No⅔thwest Mexico, seems to be an excellent candidate λo⅔ biodiesel p⅔oduction due to its hiμh ⅓uality. Table includes the basic JCO physicochemical cha⅔acte⅔istics that back up this ⅓uality. The iodine index is a measu⅔ement oλ the oils unsatu⅔ation deμ⅔ee a hiμhe⅔ iodine index co⅔⅔esponds to hiμhe⅔ deμ⅔ee oλ unsatu⅔ation [ ], and p⅔obably leads to oxidation and viscosity p⅔oblems. The JCO iodine index was . cμ I μ- , which is well below the maximum speciλied value cμ I μ- λo⅔ biodiesel as indicated in the EN speciλication. The limitation oλ unsatu⅔at‐ ed λatty acids is convenient because heatinμ hiμhe⅔ unsatu⅔ated λatty acids ⅔esults in poly‐ me⅔ization oλ μlyce⅔ides, leadinμ to the λo⅔mation oλ deposits o⅔ to dete⅔io⅔ation oλ the lub⅔icant [ ]. Fuels with this cha⅔acte⅔istic e.μ Sunλlowe⅔, soybean and saλλlowe⅔ oil a⅔e also likely candidates to p⅔oduce thick sludμe s in the sump oλ the enμine, when λuel seeps down the sides oλ the cylinde⅔ into c⅔ankcase [ ]. The JCO iodine index could was caused by the hiμh content oλ unsatu⅔ation λatty acid such as oleic and linoleic acid Table . Test

Parameter1

Appearance

Yellowish “ransparen“

Free fa““y acid (%)

1.51 ± 0.10

Densi“y a“ 15ºC (gml )

0.92 ± 0.01

-1

Acid index (mg KOH g-1)

3.07 ± 0.12

Saponifica“ion index (mg KOH g )

180.92 ± 2

Iodine index (cg I2 g )

28.75 ± 0.1

-1

-1

Peroxide index (meq O2 Kg ) -1

18.5 ± 0.7

Table 4. Physical chemical proper“ies of Jatropha curcas Oil. 1 S“andard desvia“ion meas”red from “riplica“e de“ermina“ions.

In on anothe⅔ hand, JCO pe⅔oxide index was . me⅓μ- , that is hiμhe⅔ than the index ⅔ecently ⅔epo⅔ted in the lite⅔atu⅔e λo⅔ c⅔ude seed Jat⅔opha oil, . me⅓μ- [ ] and . me⅓μ- [ ]. Despite this hiμh pe⅔oxides index, JCO upholds the μood ⅓uality oλ biodie‐ sel pu⅔poses. The JCO saponiλication index was mμ KOH μ- , which suμμested that JCO was mostly no⅔mal t⅔iμlyce⅔ides, and ve⅔y useλul in biodiesel p⅔oduction due to its low FF“ content . wt% . The content oλ FF“ was assessed λ⅔om the acid index “I measu⅔ement, takinμ into account the composition showed in Table . The acid index oλ . mμ KOH μ- ⅔epo⅔ted in Table was lowe⅔ than the values ⅔epo⅔ted by othe⅔ au‐ tho⅔s mμ KOH μ- λo⅔ c⅔ude JCO [ , ] this could be att⅔ibuted to the chanμe oλ local envi⅔onmental conditions whe⅔e by the Jζtrτphζ θurθζs plant was μ⅔own. The⅔e‐ λo⅔e, acid index becomes a ve⅔y impo⅔tant pa⅔amete⅔ to dete⅔mine the most convenient

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

p⅔ocessinμ ⅔oute oλ a μiven F“ME this means that oils can unde⅔μo a p⅔et⅔eatment o⅔ di⅔ect t⅔anseste⅔iλication as a λunction oλ FF“ amount. Compound

Estructure

wt %

Palmi“ic

16:00

23.992

S“earic

18:00

7.224

Oleic

18:01

41.368

Linoleic

18:02

27.186

Table 5. Fa“y acid composi“ion de Jatropha curcas Oil de“ermine by MS-CG.

The p⅔ope⅔ties oλ t⅔iμlyce⅔ide and biodiesel a⅔e dete⅔mined by the amounts oλ each λatty acid p⅔esent in the molecules. Chain lenμth and numbe⅔ oλ double bonds dete⅔mine the physical cha⅔acte⅔istics oλ both λatty acids and t⅔iμlyce⅔ides [ ]. Neve⅔theless, t⅔anseste⅔iλica‐ tion does not alte⅔ the λatty acid composition oλ the λeedstocks, and this composition plays an impo⅔tant ⅔ole in some c⅔itical pa⅔amete⅔s oλ the biodiesel, as cetane numbe⅔ and cold λlow p⅔ope⅔ties. The⅔eλo⅔e, measu⅔inμ λatty acid p⅔oλile oλ JCO was anothe⅔ impo⅔tant ta⅔μet oλ this study. These ⅔esults a⅔e shown in Table .

Figure 10. Type of fa““y acids in Jatropha curcas oil from “he Norwes“ of México

The⅔e a⅔e th⅔ee main types oλ λatty acids that can be p⅔esent in a t⅔iμlyce⅔ide which is satu‐ ⅔ated Cn , monounsatu⅔ated Cn and polyunsatu⅔ated with two o⅔ th⅔ee double bonds Cn , . Ideally, the veμetable oil should have low satu⅔ation and low polyunsatu⅔ation,

195

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

that is, be hiμh in monounsatu⅔ated λatty acids, as shown in Fiμu⅔e . Veμetable oils ⅔ich in polyunsatu⅔ated linoleic and linolenic acids, such as soybean and sunλlowe⅔ oils [ ], usu‐ ally p⅔oduce methyl este⅔ λuels with poo⅔ oxidation stability. In the othe⅔ hand, veμetable oils with hiμh deμ⅔ee oλ unsatu⅔ation Cn , lead to a p⅔oduct with hiμh λ⅔eezinμ point, poo⅔ λlow cha⅔acte⅔istics and may become solid e.μ palm oil at low tempe⅔atu⅔es, althouμh they may pe⅔λo⅔m satisλacto⅔ily in hot climates. The main λatty acids in the JCO used in this study we⅔e the oleic, linoleic, palmitic and the stea⅔ic λatty acids. The p⅔edominant acids we⅔e monounsatu⅔ated . % , polyunsatu⅔ated . % and satu⅔ated λatty acid . % Fiμu⅔e . This ⅔esult was in aμ⅔eement with the ⅔epo⅔ted by “kba⅔ [ ], althouμh it was sliμhtly diλλe⅔ent in te⅔ms oλ satu⅔ated and polyunsatu⅔ated compounds λo⅔ the JCO λ⅔om Malaysia. Thus, JCO can be classiλied as oleic linoleic oil. Compa⅔ed to othe⅔s veμeta‐ ble oil JCO had hiμhest oleic acid contain than palm oil, palm ke⅔nel, sunλlowe⅔, coconut, and soybean oil. . . . Jζtrτphζ θurθζs τil trζσsesteriλiθζtiτσ Th⅔ee cu⅔⅔ent biodiesel technoloμies we⅔e evaluated and compa⅔ed with the conventional homoμeneous t⅔anseste⅔iλication, usinμ the JCO cha⅔acte⅔ized above. The main objective was to evaluate the potential advantaμes oλ sonot⅔anseste⅔iλication in te⅔ms oλ ope⅔atinμ conditions, t⅔anseste⅔iλication ⅔ate and p⅔ocessinμ steps and costs. Cτσveσtiτσζl ζlkζliσe trζσsesteriλiθζtiτσ “cco⅔dinμ to the ove⅔all t⅔anseste⅔iλication pathway shown in Fiμu⅔e , stoichiomet⅔ically, JCO methanolysis ⅔e⅓ui⅔es th⅔ee moles oλ methanol λo⅔ each mole oλ oil. Since the t⅔anseste⅔‐ iλication oλ t⅔iμlyce⅔ides is a ⅔eve⅔sible ⅔eaction, excess methanol shiλts the e⅓uilib⅔ium to‐ wa⅔ds the di⅔ection oλ este⅔ λo⅔mation. “s it is evident λ⅔om Fiμu⅔e , the maximum yield λo⅔ the conventional alkaline t⅔anseste⅔iλication p⅔ocess % was ⅔eached aλte⅔ min ⅔eac‐ tion time aλte⅔wa⅔ds no siμniλication va⅔iations we⅔e obse⅔ved. In addition, when the meth‐ anol JCO mola⅔ ⅔atio was inc⅔eased λ⅔om to , no majo⅔ diλλe⅔ences we⅔e λound within the λi⅔st min howeve⅔, a hiμhe⅔ biodiesel yield was obse⅔ved in the expe⅔iment with a mola⅔ ⅔atio towa⅔d the end oλ the ⅔eaction. On the othe⅔ hand, ⅔esults shown in table indi‐ cate that tempe⅔atu⅔e eλλect is not impo⅔tant. These ⅔esults co⅔⅔espond to the biodiesel yield evaluated aλte⅔ min. Thus, the hiμhe⅔ biodiesel yield was λound at °C, and then it de‐ c⅔eased to a⅔ound % λo⅔ tempe⅔atu⅔es between and °C. Cu⅔⅔ent ⅔esults oλ the conventional p⅔ocess disclosed in Fiμu⅔e and Table suμμested a siμniλicant imp⅔ove to the conventional alkaline t⅔anseste⅔iλication p⅔ocess, because the ⅔eac‐ tion yield was enhanced at a sho⅔te⅔ ⅔eaction time min as compa⅔ed min and tempe⅔‐ atu⅔e °C as compa⅔ed to ºC λo⅔ indust⅔ial application [ ]. “ sho⅔te⅔ ⅔eaction time can be t⅔anslated to a continuous p⅔ocess with a sho⅔te⅔ ⅔esident time and then, the possibility to ⅔educe costs at the ⅔eaction staμe. Howeve⅔, a hiμhe⅔ JCO conve⅔sion is needed to ensu⅔e a sustainable p⅔ocess. Mo⅔eove⅔, the biodiesel pu⅔iλication p⅔ocess is still a p⅔oblem because it implies lonμ times and it is ene⅔μy demandinμ.

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

Figure 11. Progress of “rans“erifica“ion reac“ion as f”nc“ion of me“hanol:JCO ra“io a“ 40ºC

Yield, %

Temperature, ºC

(At 15 min of reaction time)

40

84.0

60

73.06

70

73.60

90

75.30

Table 6. The effec“ of “empera“”re on “he performance of alkaline “ranses“erifica“ion of JCO by conven“ional process.

Superθritiθζl methζστl prτθess Thus, as an alte⅔native oλ the p⅔oblems indicated above, the supe⅔c⅔itical methanol p⅔ocess SMP , usinμ nit⅔oμen as co-solvent, was conducted. Fiμu⅔e

shows that the best set oλ op‐

e⅔atinμ conditions λo⅔ this non-catalytic p⅔ocess we⅔e methanol JCO mol ⅔atio oλ ºC. Unde⅔ these conditions, a biodiesel yield θζ. be obse⅔ved that aλte⅔

% was obtained. F⅔om Fiμu⅔e

and , it can

min the e⅓uilib⅔ium was ⅔eached λo⅔ the t⅔anseste⅔iλication ⅔eaction

λo⅔ both mola⅔ ⅔atios studied

and

. This is a ve⅔y p⅔omisinμ ⅔esult iλ it is compa⅔ed

with ⅔epo⅔ted λo⅔ palm [ ] and soybean oils [ ], whe⅔e biodiesel yields up to obtained unde⅔ ve⅔y hiμh p⅔essu⅔e,

and

Mpa, ⅔espectively.

% we⅔e

197

198

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 12. Effec“ of “empera“”re and me“hanol: JCO molar ra“io on “he yield of Biodiesel ob“ained by s”percri“ical me“hanol process a“ 14Mpa and 30 min.

Figure 13. Progress of “rans“erifica“ion reac“ion as f”nc“ion of me“hanol: JCO ra“io a“ T= 350ºC for s”percri“ical me“h‐ anol process

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

Impo⅔tantly, supe⅔c⅔itical methanolysis did not ⅔e⅓ui⅔e any kind oλ catalyst, and no p⅔e‐ t⅔eatment to ⅔emove wate⅔ o⅔ FF“ was used in this wo⅔k. “ ve⅔y simple sepa⅔ation p⅔ocess‐ es evapo⅔ation and laye⅔ sepa⅔ation we⅔e used λo⅔ biodiesel pu⅔iλication. Ou⅔ λindinμs aμ⅔ee with the lite⅔atu⅔e that supe⅔c⅔itical p⅔ocess is simple⅔ and λaste⅔ than conventional al‐ kaline t⅔anseste⅔iλication λo⅔ biodiesel p⅔oduction. In addition, since wastewate⅔ was not in‐ t⅔oduced by p⅔et⅔eatment o⅔ washinμ p⅔ocesses, the supe⅔c⅔itical p⅔ocess is envi⅔onmental λ⅔iendly. Howeve⅔, to date, hiμh investment and ene⅔μy cost a⅔e still ⅔e⅓ui⅔ed due to hiμh tempe⅔atu⅔e and p⅔essu⅔e oλ the supe⅔c⅔itical state. “nothe⅔ issue with economic implica‐ tions is the la⅔μe methanol needed to enhance the λo⅔wa⅔d ⅔eaction without catalyst. It could expected that these costs a⅔e compa⅔able to those oλ the p⅔et⅔eatment and sepa⅔ation p⅔ocess oλ the conventional alkaline t⅔anseste⅔iλication p⅔ocess. Clea⅔ly, as the methanol demand be dec⅔eased, and the ope⅔atinμ conditions be mo⅔e mode⅔ate, the economic λeasibility oλ su‐ pe⅔c⅔itical methanol p⅔ocess would be possible. Heterτμeσeτus prτθess “s indicated in the p⅔evious section, th⅔ee hete⅔oμeneous powde⅔ catalysts, ZnO, “l O and ZnO- “l O mixed oxides suppo⅔ted on S”“- we⅔e evaluated λo⅔ t⅔anseste⅔iλication ⅔eac‐ tion. Fiμu⅔e shows ou⅔ best ⅔esults to date, when expe⅔iments we⅔e conducted with a methanol JCO mola⅔ ⅔atio oλ , ºC, and wt % oλ catalyst. Results we⅔e collected aλte⅔ h oλ ⅔eaction time. Unde⅔ these conditions, the e⅓uilib⅔ium biodiesel yield % was ⅔eached λo⅔ the suppo⅔ted “l O catalysts. Impo⅔tantly, no catalysts deactivation was ob‐ se⅔ved λo⅔ at least ⅔uns without ⅔eμene⅔ation t⅔eatment . It is notewo⅔thy that “l O is t⅔a‐ ditionally used as suppo⅔t instead oλ active phase due to its poo⅔ catalytic activity λo⅔ t⅔anseste⅔iλication [ ]. In λact, in ou⅔ expe⅔iments “l O itselλ showed no mo⅔e than % oλ F“ME yield, but the it showed a totally diλλe⅔ent catalytic pe⅔λo⅔mance when it was well dispe⅔sed on S”“- . On the othe⅔ hand, seve⅔al suppo⅔ted basic catalysts have also been ⅔epo⅔ted in the lite⅔atu⅔e -sodium [ ] o⅔ potassium [ ] loaded on a suppo⅔t no⅔mally alu‐ mina , usinμ seve⅔al p⅔ecu⅔so⅔s and t⅔eated at hiμh calcination tempe⅔atu⅔es ºC . The catalysts showed μood activities - % biodiesel yield at low tempe⅔atu⅔es - ºC , but no data we⅔e ⅔epo⅔ted about thei⅔ stability. K CO suppo⅔ted on both MμO and “l O p⅔ovided μood ⅔esults λo⅔ ⅔apeseed oil t⅔anseste⅔iλication with methanol at ºC, but K CO leached into the solution. Meantime, pu⅔e ZnO and ZnO suppo⅔ted on “l O have also been ⅔epo⅔ted as μood t⅔anses‐ te⅔iλication catalyst. In expe⅔iments pe⅔λo⅔med in a packed-bed ⅔eacto⅔ at ºC, . % and . % oλ F“ME yields we⅔e obtained, λo⅔ and h, ⅔espectively [ ] in this case, no Zn leachinμ was p⅔actically obse⅔ved ppm . In addition, no data about catalysts has been ⅔e‐ po⅔ted. In ou⅔ case, expe⅔iments conducted with ZnO and ZnO/“l O showed biodiesel yields below %. The most p⅔omisinμ ⅔esults λound λo⅔ the “l O /S”“ have to be stud‐ ied in detail to optimize the catalyst λo⅔mulation.

199

200

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 14. Yield of biodiesel of “ranses“erifica“ion of JCO wi“h MR=6, and 250ºC, 1 h and 3 w“.% of each he“erogene‐ o”s ca“alys“.

Sτστtrζσsesteriλiθζtiτσ Expe⅔imental ⅔esults oλ JCO sonot⅔anseste⅔iλication a⅔e shown in Fiμu⅔e

. The λi⅔st issue

that became evident was that sonot⅔anseste⅔iλication was much λaste⅔ than the conventional alkaline t⅔anseste⅔iλication. Thus, in just yield θζ. oλ u⅔e λ⅔om

minute oλ ⅔eaction time the maximum F“ME

% was ⅔eached λo⅔ the expe⅔iment conducted with a methanol JCO mola⅔ ⅔atio

, an acoustic powe⅔ density N oλ shows that λo⅔ to

Wcm- and tempe⅔atu⅔e oλ

ºC. Mo⅔eove⅔, Fiμ‐

min oλ ⅔eaction time, a ⅔eduction oλ the methanol JCO mola⅔ ⅔atio

inc⅔eased the biodiesel yield. Unde⅔ these conditions, a

% biodiesel yield

was obtained. Noto⅔iously, the late⅔ mola⅔ ⅔atio is close⅔ to the stoichiomet⅔ic one, thus help‐ inμ to dec⅔ease the excess oλ alcohol ⅔e⅓ui⅔ed by the othe⅔ biodiesel technoloμies unde⅔ com‐ pa⅔ison in this study. These ⅔esults clea⅔ly showed the λollowinμ advantaμes λo⅔ the sonot⅔anseste⅔iλication p⅔ocess a sho⅔te⅔ p⅔ocessinμ time is ⅔e⅓ui⅔ed, a lowe⅔ amount oλ al‐ cohol is ⅔e⅓ui⅔ed almost the stoichiomet⅔ic amount , and the expe⅔iment is conducted at ⅔oom tempe⅔atu⅔e and atmosphe⅔ic p⅔essu⅔e.

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

Figure 15. Effec“ of “he sonica“ion “ime on “he yield of biodiesel by sono“rans“erifica“ion reac“ion wi“h MR of 6:1, room “empera“”re, and aco”s“ic power densi“y of 105 Wcm-2.

Figure 16. Effec“ of “he me“hanol:JCO molar ra“io on “he yield of biodiesel by sono“rans“erifica“ion reac“ion a“ room “empera“”re,1 min of reac“ion “ime, and aco”s“ic power densi“y of 105 Wcm-2.

201

202

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Despite oλ the impo⅔tant advantaμes initially λound λo⅔ the sono t⅔anseste⅔iλication p⅔ocess in this wo⅔k, the biodiesel yield had to be inc⅔eased to make it at⅔active λ⅔om the indust⅔ial point oλ view. To this ⅔espect, a mo⅔e detail study oλ the acoustic powe⅔ eλλect was conduct‐ ed. Fiμu⅔e N oλ

shows that acoustic sonocation powe⅔ had a siμniλicant eλλect on yield. Fo⅔ an

Wcm- , coupled with the best set oλ pa⅔amete⅔s used in p⅔evious expe⅔iments, a

F“ME yield up to

% was ⅔eached at ⅔oom tempe⅔atu⅔e. The ⅔eason why a hiμhe⅔ t⅔anses‐

te⅔iλication ⅔ate was obtained with the ult⅔asonic p⅔ocess was al⅔eady outlined in the p⅔evi‐ ous sections. ”⅔ieλly, the huμe local tempe⅔atu⅔e μene⅔ated in the hot spot λo⅔med du⅔inμ the cavitation phenomenon λavo⅔s the λo⅔mation oλ hiμhly ⅔eactive species and p⅔omotes mass t⅔ansλe⅔. These issues a⅔e the key to imp⅔ove the t⅔anseste⅔iλication ⅔eaction ⅔ate be‐ cause unde⅔ the expe⅔imental ult⅔asonic conditions the p⅔ocess is not aλλected by mass t⅔ans‐ λe⅔ o⅔ by kinetic limitations, but ⅔athe⅔ by the e⅓uilib⅔ium condition.

Figure 17. Effec“ of “he aco”s“ic power densi“y on “he yield of biodiesel by sono“rans“erifica“ion reac“ion wi“h MR of 4:1, room “empera“”re, and one min”“e of reac“ion “ime.

In this scena⅔io, sono t⅔anseste⅔iλication becomes a ve⅔y att⅔active p⅔ocess to be implement‐ ed in a continuous indust⅔ial p⅔ocess. Thus, ⅔esults λound in Fiμu⅔e

we⅔e used to con‐

λiμu⅔e a continuous US p⅔ocess with a tubula⅔ sono⅔⅔eacto⅔, usinμ a ⅔esident time oλ min. In this case, a constant yield oλ

% was ⅔eached. Impo⅔tantly, the ⅓uality oλ the

biodiesel obtained in this expe⅔iment, ove⅔came the ⅓uality oλ biodiesel with inte⅔nation‐ al standa⅔ds Table

.

Biodiesel C”rren“ Technology: Ul“rasonic Process a Realis“ic Ind”s“rial Applica“ion h““p://dx.doi.org/10.5772/ 52384

Parameter FAME con“en“a (%)

Value 98

Densi“y a“ 15ºC (gml-1)

0.84

Acid index (mgKOHg-1)

0.5

To“al glycerin (w“. %)

90

[48]

“riolein Pse”domonas fl”orescens

Polypropylene powder

Soybean

(conversion) Me“hanol

and Pse”domonas cepacia

58

[49]

37 ( yield)

Penicillium expansum

Resin D4020

Was“e

Me“hanol

92.8 (yield)

Rhizomucor miehei

Hydrophilic resins

Olive h”sk

E“hanol

-

[50] [51]

Rhizomucor miehei

Silica

Was“e cooking

Me“hanol

91.08 (yield)

[52]

Rhizopus oryzae

Macroporo”s resin HPD-400Pis“acia chinensis Me“hanol

94 (yield)

[53]

bge seed Saccharomyces cerevisiae

Mg–Al hydro“alci“e

Rape

Me“hanol

96 (conversion)

[5454]

Thermomyces lanuginosus

Hydro“alci“e

Was“e cooking

Me“hanol

95 (yield)

[55]

(Lipozyme TL IM)

Table 3. Comparison of biodiesel prod”c“ion performance ”sing immobilized lipase via adsorp“ion me“hod

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

Lipase Source

Carrier

Acid/Oil Source Alcohol

Maxim”m

Reference

Performance (%) Burkholderia cepacia

Niobi”m Oxide (Nb2O5) Babass”

E“hanol

74.13

[60]

(yield) Burkholderia cepacia

Polysiloxane–Polyvinyl Babass” Alcohol (SiO2–Pva)

E“hanol

Beef Tallow

100

[60]

89.7 (yield)

Candida rugosa

Chi“osan Microspheres Soybean

Me“hanol

87

[58]

(conversion) Candida rugosa

Chi“osan Powder

Rapeseed

Me“hanol

Soaps“ock Enterobacter aerogenesSilica

Ja“ropha

95

[61]

(conversion) Me“hanol

94

[62]

(yield) Porcine pancreatic

Chi“osan Beads

Salicornia

Me“hanol

55

[63]

(conversion) Pseudomonas

Toyopearl Af-

fluorescens

Amino-650m Resin

Babass”

E“hanol

Rhizopus oryzae

Resin Amberli“e Ira-93 Pis“acia Chinensis Me“hanol Polys“yrene

[64]

(yield) Bge Seed

Rhizopus oryzae

94.9

Soybean

92

[63]

(yield) Me“hanol

Polymer(Amberli“e

90.05

[65]

(yield)

Ira-93) Rhizopus Orizae

Silica

-

Me“hanol

+Candida rugosa Rhizop”s orizae

[66]

(conversion) Silica

Cr”de Canola

Me“hanol

+Candida r”gosa Thermomyces

"/>98 88.9

[59]

(conversion) Olive Pomace

Pomace

Me“hanol

lanuginosus

93

[67]

(yield)

Thermomyces

Polygl”“araldehyde

lanuginosus

Ac“iva“ed S“yrene-

Canola

Me“hanol

97

[68]

(yield)

Divinylbenzene Copolymer Thermomyces

Toyopearl Af-

lanuginosus

Amino-650m Resin

Thermomyces

Poly”re“hane Foam

Palm

E“hanol

[64]

(yield) Canola

Me“hanol

lanuginosus Thermomyces

100 90

[69]

(yield) Aldehyde-Lewa“i“

Soybean

E“hanol

lanuginosus

100

[70]

(conversion)

Thermomyces

Magne“ic Fe3O4 Nano- Soybean

lanuginosus

Par“icles

Me“hanol

90

[71]

(conversion)

Table 4. Comparison of biodiesel prod”c“ion performance ”sing immobilized lipase via covalen“ binding me“hod

215

216

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . . Eσtrζpmeσt teθhσique Ent⅔apment method is based on captu⅔inμ oλ the lipase within a polyme⅔ netwo⅔k that ⅔etains the enzyme but allows the subst⅔ate and p⅔oducts to pass th⅔ouμh [ ]. This method can be simply deλined as mixinμ an enzyme with a polyme⅔ solution and then c⅔osslinkinμ the poly‐ me⅔ to λo⅔m a lattice st⅔uctu⅔e that captu⅔es the enzyme [ ]. Ent⅔apment is oλten used λo⅔ in‐ dust⅔ial applications because the method is λast, cheap and can be ca⅔⅔ied out unde⅔ mild conditions [ ]. Ent⅔apment can be divided into th⅔ee cateμo⅔ies such as μel o⅔ λibe⅔ ent⅔ap‐ pinμ and mic⅔oencapsulation [ ]. “ numbe⅔ oλ suppo⅔ts have been investiμated such as alμi‐ nate, celite, ca⅔⅔aμeenan, ⅔esins, ac⅔ylic polyme⅔s etc. Some ca⅔⅔ie⅔s used λo⅔ ent⅔apment and the biodiesel p⅔oduction yields obtained by these enzymes a⅔e displayed in Table . “ disad‐ vantaμe oλ ent⅔apment method is the mass t⅔ansλe⅔ p⅔oblem due to the act oλ suppo⅔t as a ba⅔‐ ⅔ie⅔, so the lipase became eλλective only λo⅔ low molecula⅔ weiμht subst⅔ates [ , ]. Lipase Source

Carrier

Acid/Oil Source Alcohol

Maximum

Reference

Performance (%) B”rkholderia cepacia

K-Carrageenan

Palm

Me“hanol

100

[76]

(conversion) B”rkholderia cepacia B”rkholderia cepacia

Phyllosilica“e

Tallow and

Sol–Gel

Grease

M“ms-Based Silica

Ja“ropha

E“hanol

94

[77]

(yield) Me“hanol

Monoli“h Coa“ed

95

[78]

(yield)

Wi“h B”“yl-S”bs“i“”“ed Silica“es Candida antarctica

Celi“e®

Triolein

Me“hanol

60

[79]

(conversion) Candida rugosa

Calci”m Algina“e Ma“rixPalm

E“hanol

83

[80]

(yield) Candida rugosa

Ac“iva“ed Carbon

Palm

E“hanol

85

[81]

(conversion) Pse”domonas cepacia

Hydrophobic Sol–Gel

Soybean

Me“hanol

67

[82]

(conversion) Pseudomonas fluorescens Algina“e

Ja“ropha

Me“hanol

M“cc 103

72

[83]

(yield)

Via Encaps”la“ion Me“hod B”rkholderia cepacia

Silica Aerogels

S”nflower Seed -

56

[84]

(conversion) B”rkholderia cepacia

K-Carrageenan

Palm

Me“hanol

100

[85]

(conversion) Candida an“ar“ica

Silica Aerogels

S”nflower Seed Me“hanol

90

[86]

(conversion) Table 5. Comparison of biodiesel prod”c“ion performance ”sing immobilized lipase via en“rapmen“ me“hod

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

. . . Crτss liσkiσμ teθhσique C⅔oss-linkinμ is anothe⅔ method λo⅔ immobilization that can be deλined as the inte⅔action oλ a th⅔ee dimensional netwo⅔k within enzyme, couplinμ ⅔eaμent, and ca⅔⅔ie⅔ [ ]. The advant‐ aμe oλ c⅔oss-linkinμ is obtaininμ stable lipases due to the st⅔onμ inte⅔action between the li‐ pase and the ca⅔⅔ie⅔. On the othe⅔ hand, the c⅔oss-linkinμ conditions a⅔e intense and the immobilized lipase shows lowe⅔ activity [ ]. The hiμh λ⅔ee λatty acid content oλ waste cookinμ oil λo⅔m wate⅔ by este⅔iλication with alco‐ hol which cause aμμlome⅔ation oλ lipase and lowe⅔inμ biocatalysis eλλiciency [ ]. Hence, λ⅔ee Geτtriθhum sp. lipase was not a suitable enzyme catalyst λo⅔ t⅔anseste⅔iλication oλ waste cookinμ oil. Yan et al. [ ], ⅔epo⅔t a modiλication p⅔ocedu⅔e λo⅔ p⅔epa⅔ation oλ c⅔oss-linked Geτtriθhum sp. The obtained lipase exhibited imp⅔oved pH and the⅔mostable stability com‐ pa⅔ed to λ⅔ee lipase. The ⅔elative biodiesel yield was % λo⅔ t⅔anseste⅔iλication oλ waste cookinμ oil with methanol. Kuma⅔i et al. [ ] studied the p⅔epa⅔ation oλ Pseudτmτσζs θepζθiζ lipase c⅔oss-linked enzyme aμμ⅔eμates. It was shown that c⅔oss linked lipases has a μ⅔eate⅔ stability than λ⅔ee enzymes to the denatu⅔inμ conditions. The enzyme also used to catalyze madhuca indica oil, which s t⅔anseste⅔iλication is diλλicult by chemical ⅔outes due to its hiμh λ⅔ee λatty acid content. “s a ⅔esult, % conve⅔sion was obtained aλte⅔ . h. Immobilization oλ Cζσdidζ ruμτsζ lipase on λine powde⅔ oλ Sci⅔pus μ⅔ossus L.λ. by μluta⅔alde‐ hyde by c⅔oss linked techni⅓ue λo⅔ biodiesel p⅔oduction λ⅔om palm oil, as al⅔eady investiμat‐ ed by Kensinμh et al. [ ]. It was concluded that immobilized lipase yielded hiμhe⅔ conve⅔sion oλ biodiesel than that oλ λ⅔ee lipase. Lo⅔ena et al. [ ] investiμated the immobilization oλ the “lθζliμeσes spp. lipase on polyethyle‐ nimine aμa⅔ose, μluta⅔aldehyde aμa⅔ose, octyl aμa⅔ose, μlyoxyl aμa⅔ose, Sepabeads® by the aμμ⅔eμation and c⅔osslinkinμ method. The t⅔anseste⅔iλication oλ canola oil was achieved with a yield % usinμ a six-step addition oλ methanol and lipase immobilized on Sepa‐ beads® by the aμμ⅔eμation method. “ll these methods a⅔e shown schematically in Fiμu⅔e .

Figure 2. Schema“ic diagram of enzyme immobiliza“ion me“hods: a)Adsorp“ion me“hod b)Covalen“ binding me“hod c)En“rapmen“ me“hod d) Crosslinking me“hod

217

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . . Whτle θell immτηilizζtiτσ The applicability oλ lipases λo⅔ the bulk p⅔oduction oλ λuels was limited siμniλicantly by the hiμh cost oλ lipases [ ]. Utilizinμ mic⅔obial cells such as λunμi, bacte⅔ia, and yeasts cells con‐ taininμ int⅔acellula⅔ lipase instead oλ ext⅔acellula⅔ lipases λ⅔ee and immobilized lipase is an easie⅔ and a cost eλλective way oλ enzymatic biodiesel p⅔oduction. Compa⅔ed to conventional enzymatic p⅔ocesses, the use oλ whole cells p⅔ovides excellent ope⅔ational stability and avoids the complex p⅔ocedu⅔es oλ isolation, pu⅔iλication and immobilization [ , ]. The μene⅔al p⅔epa⅔ation steps λo⅔ immobilized ext⅔acellula⅔ enzymes and whole cell enzymes showed in Fiμu⅔e . ”iomass suppo⅔t pa⅔ticles have been used λo⅔ immobilization oλ whole cells.

a

b

Figure 3. The prepara“ion s“eps of a) immobilized ex“racell”lar lipase and b) whole cell bioca“alys“

“spe⅔μillus and Rhizopus have been most widely used as whole cell biocatalyst. ”an et al. [ ], used λi⅔st a whole cell biocatalyst, immobilized Rhizopus o⅔yzae IFO a , -posi‐ tional speciλicity lipase cells within biomass suppo⅔t pa⅔ticles, λo⅔ the p⅔oduction oλ biodie‐ sel and . % methyl este⅔ content was attained which was a simila⅔ ⅔esult as that usinμ the ext⅔acellula⅔ lipase. Many ⅔esea⅔che⅔s have expe⅔imented on the use oλ whole cells to cata‐ lyze t⅔anseste⅔iλication ⅔eaction summa⅔ized in Table . “ techni⅓ue usinμ μluta⅔aldehyde c⅔oss-linkinμ t⅔eatment on whole cell catalyst λo⅔ metha‐ nolysis oλ soybean oil was developed by Sun et al. [ ]. The μluta⅔aldehyde c⅔oss linkinμ t⅔eatment ⅔esulted in hiμhe⅔ methanol tole⅔ance and hiμh catalytic activity with the ⅔atio oλ methanol to oil ⅔eachinμ . “lso, a novel methanol addition st⅔ateμy was p⅔oposed as step‐ wise addition oλ diλλe⅔ent amounts oλ methanol . , . , . , and . M e⅓uivalent oλ oil ev‐ e⅔y h. It was λound that the hiμhest methyl este⅔ yield could ⅔each . % aλte⅔ h ⅔eaction by . mol, . M and . mol methanol additions at , , and h. In μene⅔al, the whole cell catalyzed p⅔ocess is slowe⅔ than ext⅔acellula⅔ lipase catalyzed p⅔ocess. Sun et al. [ ], also ⅔epo⅔ted that the ⅔eaction time could be sho⅔tened by this way. It is clea⅔ that siμ‐ niλicant ⅔eduction in the cost oλ biodiesel p⅔oduction can be achieved by combininμ the whole cell biocatalyst p⅔ocess with stepwise addition oλ methanol.

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

Lipase Source

Carrier

Acid/Oil Source

Alcohol

Maximum

Reference

Performance (%) Aspergill”s niger

BSPs

a

Was“e Cooking

Me“hanol

86.4

[96]

(yield) Aspergillus niger

Poly”re“hane

Palm

Me“hanol

BSPsa Aspergill”s niger

BSPsa

>90

[97]

(yield) Palm

Me“hanol

87

[98]

(yield) Aspergill”s oryzae NS4 BSPsa

Soybean

Me“hanol

98

[99]

(conversion) A. oryzae carrying r-

BSPsa

Palm Soybean

Me“hanol

CALB

85

[100]

90

b

(conversion) Aspergillus oryzae

BSPs

a

Rapeseed

expressing r-FHLc

Escherichia coli BL21

-

Rapeseed

Me“hanol

96 (yield)

E“hanol

94 (yield)

1-Propanol 1-

96 (yield)

B”“anol

97 (yield)

Me“hanol

97.7

[101]

[102]

(conversion) Rhizopus chinensis

-

Soybean

Me“hanol

CCTCC M201021 Rhizomucor miehei

"/>86

[103]

(yield) -

Soybean

Me“hanol

displaying Pichia

83.14

[104]

(yield)

pas“oris Rhizopus oryzae IFO

BSPsa

4697

Rhizopus oryzae IFO

Refined Rapeseed

Me“hanol

~60(yield)

Cr”de Rapeseed,

~60(yield)

Acidified Rapeseed

~70(yield)

[105]

a

BSPs

Soybean

Me“hanol

~90(yield)

[106]

BSPsa

Soybean

Me“hanol

~85(yield)

[107]

-

Soybean

Me“hanol

71

[108]

4697 Rhizopus oryzae IFO 4697 Rhizopus oryzae IFO4697 Rhizopus oryzae IFO 4697 and Aspergill”s oryzae niaD300 (combined ”se)

(conversion) BSPsa

Soybean

Me“hanol

~100 (conversion)

[109]

219

220

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Lipase Source

Carrier

Acid/Oil Source

Alcohol

Maximum

Reference

Performance (%) Rhizopus oryzae ATCC -

Soybean

24563

(Free Fa““y Acid Con“en“

Me“hanol

97

[110]

(conversion)

5.5%) Rhizopus oryzae IFO

BSPs

a

Soybean

Me“hanol

4697 Rhizopus oryzae

72

[111]

(yield) Poly”re“hane foam Soybean

Me“hanol

BSPsa

90

[112]

(conversion)

Rhizopus oryzae

BSPsa

Ja“ropha C”rcas

Me“hanol

80 (conversion)

[113]

Rhizopus oryzae IFO

-

Soybean

Me“hanol

86

[114]

4697 Rhizopus oryzae

(yield) BSPsa

Rapeseed

Me“hanol,

83,

E“hanol,

79,

1-Propanol, 1-

93,

B”“anol

69

[101]

(yield) Serra“ia marcescens

-

YXJ-1002

Grease

Me“hanol

97

[115]

(yield)

BSPs:Biomass s”ppor“ par“icles

a

r-CALB: Candida an“arc“ica lipase B

b

r-FHL: F”sari”m he“erospor”m lipase

c

Table 6. Comparison of biodiesel prod”c“ion performance ”sing whole cell bioca“alys“s

Whole cell biocatalysts will be a way to indust⅔ialization oλ biodiesel p⅔oduction but the limited mass t⅔ansλe⅔ eλλiciency oλ p⅔oduct and subst⅔ate is a hu⅔dle to λu⅔the⅔ in‐ vestiμations [ ].

. Feedstocks The main aim oλ ⅔esea⅔ches is to obtain a biodiesel, which will have a competitive p⅔ice com‐ pa⅔ed to othe⅔ conventional sou⅔ces oλ ene⅔μy [ ]. “t this point, selectinμ the λeedstock, ⅔ep⅔esents mo⅔e than - % oλ the ove⅔all biodiesel p⅔oduction cost, is a vital step to ensu⅔e a cost eλλective biodiesel p⅔oduction. Diλλe⅔ent kinds oλ λeedstock with va⅔ied ⅔anμe oλ edible and inedible veμetable oil, animal λats, waste oil, mic⅔obial oil and mic⅔oalμae oil can be used λo⅔ enzyme catalyzed t⅔anseste⅔iλication [ ].

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

. . Vegetable oils Veμetable oils a⅔e candidates as alte⅔native λuels λo⅔ diesel enμines with thei⅔ hiμh heat con‐ tent [ ]. ”ut, di⅔ect use oλ veμetable oils is not possible because oλ the hiμh kinematics vis‐ cosity oλ them which a⅔e va⅔ies in the ⅔anμe oλ cSt at °C and a⅔e about times hiμhe⅔ than oλ diesel λuel G⅔ade No. D leads to many p⅔oblems [ , ]. The⅔eλo⅔e, mod‐ iλication oλ veμetable oil is necessa⅔y and the valuable p⅔oduct oλ this modiλication is named biodiesel . The edible veμetable oils such as soybean [ , ], sunλlowe⅔ [ ], palm [ , ], co⅔n [ ], cottonseed [ ], canola [ , , ] and olive [ , ] oils have been widely used in enzymatic t⅔anseste⅔iλication. In developed count⅔ies, edible oils constitute mo⅔e than % oλ biodiesel p⅔oduction λeedstock because the p⅔oduced biodiesel λ⅔om these oils have p⅔ope⅔ties ve⅔y simila⅔ to pet⅔oleum-based diesel [ ]. “lso, the count⅔y and its climate, the oil pe⅔centaμe and the yield pe⅔ hecta⅔e a⅔e eλλective pa⅔amete⅔s in selectinμ the potential ⅔enewable λeedstock oλ λuel [ , ]. Fo⅔ example, while ⅔apeseed oil p⅔evailinμ the EU p⅔oduction, soybean oil p⅔evailinμ the US and Latin “me⅔ican p⅔oduction, and palm oil mainly beinμ used in “sia [ ]. Inedible oils do not λind a place in human consumption due to includinμ toxic components. The⅔eλo⅔e, inedible oils do not compete with λood c⅔ops. Thus, inedible veμetable oils a⅔e an alte⅔native λeedstock λo⅔ biodiesel p⅔oduction. ”abassu O⅔binya ma⅔tiana , Jat⅔opha cu⅔cas Linnaeus , neem “zadi⅔acta indica , polanμa Calophyllum inophyllum ,ka⅔anja Ponμa‐ mia pinnata , ⅔ubbe⅔ seed t⅔ee Hevea b⅔asiliensis , mahua Madhuca indica and Madhuca lonμiλolia , tobacco Nicotina tabacum , silk cotton t⅔ee, etc. a⅔e p⅔omisinμ inedible veμeta‐ ble oil sou⅔ces. Jat⅔opha cu⅔cas is an att⅔active λeedstock between va⅔ious oil bea⅔inμ seeds as it has been developed scientiλically and λound to μive bette⅔ biodiesel yield and p⅔oduc‐ tivity [ ]. C⅔ude Jat⅔opha oil contains about % oλ λ⅔ee λatty acid that is too hiμh λo⅔ alka‐ line catalyzed biodiesel p⅔oduction [ ]. Howeve⅔, hiμh λ⅔ee acid content is not a p⅔oblem in the p⅔oduction p⅔ocess oλ biodiesel via usinμ enzyme catalysts. ”esides Jat⅔opha cu⅔cas, species oλ λatty acid methyl este⅔ oλ oils oλ includinμ “zadi⅔achta indica, Calophyllum in‐ ophyllum, and Ponμamia pinnata we⅔e λound most suitable λo⅔ use as biodiesel, which ad‐ just to the majo⅔ speciλication oλ biodiesel standa⅔ds oλ Eu⅔opean Standa⅔d O⅔μanization, Ge⅔many, and US“ [ ]. Modi et al. ⅔epo⅔ted conve⅔sion oλ c⅔ude oils oλ Ponμamia pinnata ka⅔anj , Jat⅔opha cu⅔cas jat⅔opha via immobilized Novozym to biodiesel λuel with yield , and . %, ⅔espectively [ ]. . . Animal oils/fats “nimal λats a⅔e anothe⅔ μ⅔oup oλ λeedstock λo⅔ biodiesel p⅔oduction. “nimal λats used to p⅔oduce biodiesel via enzymatic ⅔oute include la⅔d [ ], lamb meet [ ] and beeλ tallow [ ]. “nimal λats a⅔e economically λeasible λeedstocks compa⅔ed to veμetable oils. “nimal λat methyl este⅔ also has many λavo⅔ably p⅔ope⅔ties such as non-co⅔⅔osive, hiμh cetane num‐ be⅔, and ⅔enewable [ , ]. Howeve⅔, animal λats satu⅔ated compounds lead to a tendency to oxidation and c⅔ystallization unacceptably at hiμh tempe⅔atu⅔es [ ].

221

222

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

. . Waste oils/fats In μene⅔al, a⅔ound the wo⅔ld only halλ oλ the discha⅔μed edible oils ⅔ecycled as animal λeed o⅔ as ⅔aw mate⅔ial λo⅔ lub⅔icant and paint and the ⅔emainde⅔ is discha⅔μed into the envi‐ ⅔onment [ ]. Hence, the use oλ waste oils/λats λo⅔ biodiesel p⅔oduction is ve⅔y impo⅔tant to ⅔educe and ⅔ecycle the waste oil [ ], to eliminate the envi⅔onment and human health ⅔isk caused by waste oils [ ] and to lowe⅔ the biodiesel p⅔oduction cost. Waste cookinμ oil, animal λats, yellow μ⅔ease, b⅔own μ⅔ease obtained λ⅔om hiμhly oxidized yellow μ⅔ease o⅔ ⅔ecove⅔ed waste μ⅔ease λ⅔om plumbinμ t⅔ap and waste sludμe o⅔ soap-stock λ⅔om the veμetable oil ⅔eλininμ p⅔ocess we⅔e the majo⅔ sou⅔ces oλ waste oil have been used λo⅔ bio‐ diesel p⅔oduction [ ]. The selection oλ a catalyst to be used λo⅔ the p⅔oduction oλ biodie‐ sel λuel is mostly inλluenced by the amount oλ λ⅔ee λatty acid content in va⅔ious λeedstocks [ ]. The lipase-catalyzed ⅔eaction is a p⅔omisinμ method λo⅔ conve⅔tinμ waste oils which contains hiμh pe⅔centaμe oλ λ⅔ee λatty acids and hiμh wate⅔ content, into biodiesel with hiμh yield [ ]. It has been ⅔epo⅔ted that Novozym is capable oλ conve⅔tinμ the used olive oils [ ]. . . Algae oils The⅔e is a conside⅔able inte⅔est in the use oλ alμae mic⅔o and mac⅔o oils λo⅔ synthesis oλ biodiesel. ”ecause these oils a⅔e cheap ⅔aw mate⅔ials besides animal λats and have ⅔apid μ⅔owth ⅔ate and p⅔oductivity when compa⅔ed to conventional λo⅔est⅔y, aμ⅔icultu⅔al c⅔ops, hiμh lipid content, tole⅔ance λo⅔ poo⅔ ⅓uality wate⅔, smalle⅔ land usaμe up to o⅔ times less when compa⅔ed to ⅔apeseed o⅔ soybean c⅔ops [ , ]. The smalle⅔ land usaμe b⅔inμs the advantaμe oλ ⅔educinμ the competition λo⅔ a⅔able soil with othe⅔ c⅔ops, in pa⅔tic‐ ula⅔ λo⅔ human consumption [ ]. Howeve⅔, the⅔e a⅔e still some d⅔awbacks λo⅔ utilization oλ alμae λo⅔ biodiesel p⅔oduction. “ conside⅔able investment in technoloμical development and technical expe⅔tise is needed to optimize the mic⅔oalμae ha⅔vestinμ and oil ext⅔action p⅔ocesses, to use cheap sou⅔ces oλ CO λo⅔ cultu⅔e en⅔ichment [ ]. “lμae oils contain about - % oil [ ]. Seve⅔al ⅔esea⅔che⅔s have been expe⅔imented on mic⅔oalμal oils as ⅔aw mate⅔ial λo⅔ biodiesel p⅔oduction. T⅔an et al. [ ], investiμated the conve⅔sion oλ mi‐ c⅔oalμal oil λ⅔om Chlo⅔ella vulμa⅔is ESP- to biodiesel by usinμ immobilized ”u⅔kholde⅔ia lipase and a hiμh λatty acid methyl este⅔s conve⅔sion eλλiciency oλ . wt% oil o⅔ . wt % biomass was obtained λo⅔ h ⅔eaction. It is p⅔oposed that mic⅔oalμal oil has μood po‐ tential λo⅔ application in the comme⅔cial p⅔oduction oλ biodiesel. The enzymatic conve⅔sion oλ mic⅔oalμal oils to biodiesel in ionic li⅓uids was λi⅔stly studied by Lai et al. [ ]. Fou⅔ mic⅔oalμae two st⅔ains oλ ”ot⅔yococcus b⅔aunii ”” and ”” , Chlo⅔ella vulμa⅔is, and Chlo⅔ella py⅔enoidosa have been catalyzed by two immobilized lipases, Penicillium expan‐ sum lipase and Candida anta⅔ctica lipase ” Novozym , in two solvent systems an ion‐ ic li⅓uid -butyl- -methylimidazolium hexaλluo⅔ophosphate, [”MIm][PF ] and an o⅔μanic solvent te⅔t-butanol . Penicillium expansum lipase was λound mo⅔e eλλicient λo⅔ this appli‐ cation and the ionic li⅓uid [”MIm] [PF ] showed a μ⅔eate⅔ conve⅔sion yield . % and . % obtained ⅔elative to the one obtained in the commonly used o⅔μanic solvent te⅔t-bu‐ tanol . % and . % .

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

. The effect of reaction parameterson enzymatic transesterification . . The effect of temperature on enzymatic transesterification Enzymatic t⅔anseste⅔iλication takes place at low tempe⅔atu⅔es va⅔yinμ λ⅔om to °C. In μene⅔al, initially the ⅔ate oλ ⅔eaction inc⅔eases with ⅔ise in ⅔eaction tempe⅔atu⅔e, because oλ an inc⅔ease in ⅔ate constants with tempe⅔atu⅔e and less mass t⅔ansλe⅔ limitations [ , ]. Neve⅔theless, inc⅔eased tempe⅔atu⅔e aλte⅔ the optimum tempe⅔atu⅔e p⅔omotes to denatu⅔ation and hiμhe⅔ the⅔mal deactivation oλ the enzyme, since it dec⅔eased the catalytic activity [ ]. Va⅔ious ⅔esea⅔ches have been ca⅔⅔ied out to λind out the eλλect oλ tempe⅔atu⅔e on biodiesel p⅔oduction with immobilized enzymes. It is clea⅔ that immobilization p⅔ovide mo⅔e tempe⅔‐ atu⅔e ⅔esistance compa⅔ed to λ⅔ee enzymes due to supplyinμ a mo⅔e ⅔iμid exte⅔nal backbone λo⅔ lipase molecule [ , ]. Howeve⅔, optimum tempe⅔atu⅔e is speciλic λo⅔ each p⅔oduc‐ tion. The studies about the eλλect oλ tempe⅔atu⅔e λo⅔ enzymatic t⅔anseste⅔iλication a⅔e shown in Table . Lipase

Oil Source

Alcohol

Performed

Optimum

Temperatures In

Temperature (°C)

Reference

The Range (°C) Immobilized Aspergill”s Palm

Me“hanol

25-50

40

[153]

Me“hanol

25-50

30

[154]

Babass”

E“hanol

39-56

39

[155]

Candida an“arc“ica

Co““on Seed

T-B”“anol

30-50

50

[156]

Candida an“arc“ica

Acid

Me“hanol

30-50

30

[157]

Me“hanol

27-50

40

[158]

niger Immobilized Aspergill”s Was“e Cooking niger Immobilized B”rkholderia cepacia

Immobilized Candida Sp. Salad 99–125 Candida Sp. 99–125

Was“e Cooking

Me“hanol

35-50

40-50

[159]

Immobilized

Ja“ropha

T-B”“anol

30-55

55

[160]

Cr”de Rapeseed

E“hanol

25-50

35

[161]

Lipozyme RM IM

Soybean

B”“anol

20-50

30

[162]

Lipozyme RM IM

Soybean

Me“hanol and 40–60

50

[163]

En“erobac“er aerogenes Immobilized En“erobac“er aerogenes

E“hanol Lipozyme RM IM

Soybean Oil

E“hanol

45-78

50

[164]

Deodorizer Dis“illa“e Lipozyme TL IM

Rapeseed

N-B”“anol

30-60

40

[165]

Lipozyme TL IM

Soybean

E“hanol

20-50

35

[162]

223

224

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Lipase

Oil Source

Alcohol

Performed

Optimum

Temperatures In

Temperature (°C)

Reference

The Range (°C) Lipozyme TL IM

Palm

E“hanol

30-78

50

[166]

Novozyme 435

Rapeseed

Me“hanol

25-55

40

[167]

Novozyme 435

T”ng and Palm

Me“hanol and 45-55

55

[168]

30-55

50

[169]

[170]

E“hanol Novozym 435

Co““onseed

-(Dime“hyl Carbona“e As Organic Solven“)

Novozym 435

Canalo

Me“hanol

25-65

38

Novozym 435

Olive

Me“hanol

30-70

40

[129]

Novozym 435

Soybean

T-Amyl

30-60

40

[171]

Novozym 435

S”nflower

Me“hanol

25-65

45

[172]

Novozym 435

S“illingia

Me“hanol

30-60

40

[173]

Novozym 435

Co““on Seed

Me“hanol

30-70

50

[174]

E“hanol

25-60

25

[175]

T-Amyl

25-55

35

[176]

Me“hanol and 25–60

35

[177]

Novozym 435, Lipozyme Soybean TL IM and Lipozyme RM IM Immobilized Penicilli”m Was“e expans”m Immobilized

Soybean

Pse”domonas cepacia

E“hanol

Pse”domonas cepacia

Soybean

Me“hanol

20–60

30

[178]

Immobilized

Triolein

1-Propanol

40-70

60

[48]

Soybean

Me“hanol

30-60

40

[49]

Soybean

Me“hanol

30-40

30

[179]

Canola

Me“hanol

30-70

40

[69]

Pse”domonas fl”orescens Pse”domonas fl”orescens Rhizop”s chinensis CCTCC M201021 Thermomyces lan”ginos”s Table 7. Da“a on op“im”m “empera“”re for enzyma“ic biodiesel prod”c“ion

. . The effect of water content on enzymatic transesterification Wate⅔ content is one oλ the key λacto⅔s λo⅔ enzymatic t⅔anseste⅔iλication ⅔eaction that have a st⅔onμ eλλect on lipase s active th⅔ee-dimensional conλo⅔mational state [ , ]. ”iocatalysts, needs a small amount oλ wate⅔ to ⅔etain thei⅔ activities [ ]. Lipase has an uni⅓ue λeatu⅔e on the wate⅔-oil inte⅔λace, and the lipase activity depends on this inte⅔λace. The p⅔esence oλ an oil wate⅔ inte⅔λace ⅔e⅓ui⅔ed because it p⅔ovides a suitable envi⅔onment λo⅔ enzyme acti‐ vation which occu⅔s due to the unmaskinμ and ⅔est⅔uctu⅔inμ the active site th⅔ouμh conλo⅔‐

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

mational chanμes oλ the lipase molecule [ , ]. When the addition oλ wate⅔ inc⅔eased, the amount oλ wate⅔ available λo⅔ oil to λo⅔m oil wate⅔ d⅔oplets also inc⅔eases, hence inc⅔easinμ the available inte⅔λacial a⅔ea [ ]. Thus, enzymatic activity can not be possible in a wate⅔ λ⅔ee media. Howeve⅔, excess wate⅔ cause ⅔eve⅔se ⅔eaction oλ hyd⅔olysis. The amount oλ ⅔e‐ ⅓ui⅔ed wate⅔, to p⅔ovide an optimum enzyme activity, diλλe⅔s acco⅔dinμ to the type oλ en‐ zyme and ⅔eaction medium composition. Enzymes, subst⅔ates, o⅔μanic solvent and also immobilized suppo⅔t have a c⅔ucial ⅔ole on optimal wate⅔ activity λo⅔ lipase [ ]. Optimum wate⅔ content not only p⅔ovides keepinμ the hyd⅔olysis oλ este⅔ linkaμes at the minimum level, but also ensu⅔es the hiμhest deμ⅔ee oλ t⅔anseste⅔iλication [ ]. Thus, a bette⅔ cont⅔ol oλ wate⅔ content is ve⅔y impo⅔tant λo⅔ enzymatic p⅔ocess. Wate⅔ activity aw is deλined as λ⅔ee boundness wate⅔ in the system, which is a ⅔atio oλ va‐ po⅔ p⅔essu⅔e ove⅔ the μiven system ve⅔sus that ove⅔ pu⅔e wate⅔ [ ]. The⅔modynamic wate⅔ activity is the best p⅔edicto⅔ oλ ⅔eaction ⅔ate that can be dete⅔mined in any phase by diλλe⅔ent kinds oλ senso⅔s such as holoμ⅔aphic senso⅔, Weiss LiCl humidity senso⅔ [ , ]. “lso, seve⅔al methods have been developed λo⅔ cont⅔ol oλ wate⅔ activity, λo⅔ example, e⅓uilib⅔a‐ tion with satu⅔ated salt solutions [ ], addition oλ salt hyd⅔ate pai⅔s [ , ] and int⅔oduc‐ tion oλ ai⅔ o⅔ nit⅔oμen into the ⅔eacto⅔ [ ]. Recently, Pete⅔son et. al. developed a p⅔actical way λo⅔ cont⅔ol oλ wate⅔ activity in la⅔μe-scale enzymatic ⅔eactions by usinμ a p⅔oμ⅔amma‐ ble loμic cont⅔olle⅔. On the othe⅔ hand, pe⅔centaμe wate⅔ content is anothe⅔ exp⅔ession which is used widely in t⅔anseste⅔iλication, μene⅔ally assayed by Ka⅔l-Fische⅔ coulomete⅔. In μene⅔al, lipases show hiμhe⅔ activity with hiμhe⅔ wate⅔ activities in solvent λ⅔ee systems instead oλ Candida anta⅔ctica lipase Novozym [ ]. Fo⅔ Candida sp. lipase, the optimum wate⅔ content is % based on the oil weiμht to maintain the hiμhest t⅔anseste⅔‐ iλication activity [ ]. Salis et al., investiμated p⅔oduction oλ oleic acid alkyl este⅔s by usinμ Pseudomonas cepacia and dete⅔mined that aw in the ⅔anμe . . , -butanol t⅔iolein we⅔e the best conditions to ⅔each maximum enzymatic activity. It was also λound that at the hiμhe⅔ values oλ wate⅔ activity, no hyd⅔olysis ⅔eaction was occu⅔⅔ed [ ]. Nou⅔eddini and Philkana [ ] tested immobilized Pseudomonas cepacia λo⅔ the t⅔anseste⅔i‐ λication oλ soybean oil with methanol and ethanol and obse⅔ved that inc⅔eased addition oλ wate⅔ p⅔ovide a conside⅔able inc⅔ease in the este⅔ yield. The optimal conditions we⅔e dete⅔‐ mined λo⅔ p⅔ocessinμ μ oλ soybean oil by mμ lipase in h as . oil/methanol mola⅔ ⅔atio, . μ wate⅔ in the p⅔esence oλ methanol that ⅔esulted in % yield and . oil/etha‐ nol mola⅔ ⅔atio, . μ wate⅔ in the p⅔esence oλ ethanol that ⅔esulted in % yield. “l-Zuhai⅔ et al. studied the este⅔iλication oλ n-buty⅔ic acid with methanol in the p⅔esence oλ Muco⅔ miehei lipase, and λound simila⅔ ⅔esults with lite⅔atu⅔e [ ] that hiμhe⅔ wate⅔ con‐ tent, makes lipase mo⅔e eλλicient [ ]. Shah and Gupta used immobilized Pseudomonas cepacia lipase λo⅔ ethanolysis oλ Jat⅔opha oil and noted that the best yield % μained by in the p⅔esence oλ % w/w wate⅔ in h. The yield was only % in absence oλ wate⅔ [ ].

225

226

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Kawakami et al. dete⅔mined the eλλect oλ wate⅔ content λo⅔ t⅔anseste⅔iλication oλ Jat⅔opha oil and methanol to cha⅔acte⅔ize ”u⅔kholde⅔ia cepacia lipase immobilized in an n-butyl-substi‐ tuted hyd⅔ophobic silica monolith. The autho⅔s ⅔epo⅔ted that biodiesel yield ⅔eached % with wate⅔ content oλ . % w/w aλte⅔ h usinμ a stoichiomet⅔ic mixtu⅔e oλ methanol and oil [ ]. Chen et al. investiμated the eλλect oλ wate⅔ content λo⅔ p⅔oduction oλ biodiesel with oleic acid with methanol catalyzed by soluble lipase NS , p⅔oduced by modiλication oλ “spe⅔μil‐ lus o⅔yzae mic⅔oo⅔μanism, in the biphasic a⅓ueous-oil systems and λound that the este⅔iλica‐ tion yield is low iλ the wate⅔ was scant. The hiμhe⅔ ⅔eaction ⅔ate and λatty acid methyl este⅔ yield was obtained with wt % wate⅔ by oleic acid weiμht [ ]. It is clea⅔ that du⅔inμ the past decade nume⅔ous investiμations have been made to dete⅔mine the optimal wate⅔ content λo⅔ t⅔anseste⅔iλication. “s a ⅔esult, the necessa⅔y amount oλ wate⅔ content is an impo⅔tant λacto⅔ to c⅔eate an inte⅔λacial su⅔λace between oil and wate⅔ and to ensu⅔e optimal enzymatic activity. “lso, wate⅔ has a st⅔onμ inλluence on st⅔uctu⅔al inteμ⅔ity, active site pola⅔ity, and p⅔otein stability oλ lipase [ , ]. Howeve⅔, it diλλe⅔s λ⅔om enzyme to ⅔eaction conditions. . . The effect of acyl acceptors on enzymatic transesterification Methanol, sho⅔t chain alcohol, usually used as an acyl accepto⅔ due to its low p⅔ice and availability. Insoluble and a ⅔elatively hiμh amount oλ methanol with ⅔espect to oil, have a neμative inλluence on the stability oλ lipases and could be solved by a stepwise addition oλ the alcohols [ , ]. To eliminate inhibito⅔y eλλects oλ methanol some co-solvents a⅔e add‐ ed to the ⅔eaction mixtu⅔e. Te⅔t-butanol is one oλ the impo⅔tant co-solvents which is added to enzymatic ⅔eaction. Usaμe oλ te⅔t-butanol, a pola⅔ solvent, is also a possible solution λo⅔ eliminatinμ the inhibito⅔y eλλects oλ methanol and μlyce⅔ol both oλ them soluble in te⅔t-bu‐ tanol and suμμested instead oλ usinμ butanol [ ]. Liu et al. [ ], t⅔anseste⅔iλied waste baked duck oil by th⅔ee diλλe⅔ent comme⅔cial immobilized lipases Novozym , Lipozyme TLIM and Lipozyme RMIM with diλλe⅔ent monohyd⅔ic alcohols methanol, ethanol, p⅔opa‐ nol, isop⅔opanol, isobutanol, isoamyl alcohol and λusel oil-like alcohol mixtu⅔e containinμ % isobutanol, % isoamyl alcohol, % methanol in solvent-λ⅔ee and te⅔t-butanol sys‐ tems. It was ⅔epo⅔ted that each lipase p⅔esented a diλλe⅔ent kinetic patte⅔n dependinμ on the monohyd⅔ic alcohols. The ⅔esults showed that Lipozyme TL IM and Novozym μave hiμh conve⅔sion ⅔ate with isobutanol and isoamyl alcohol eithe⅔ in solvent-λ⅔ee o⅔ in te⅔t-bu‐ tanol system. Thus, the combined use oλ lipases, Novozym and Lipozyme TLIM, as cata‐ lyst and λusel oil-like mixtu⅔e as ⅔aw mate⅔ial λo⅔ biodiesel synthesis was λound eλλective in view oλ cost savinμ oλ biodiesel p⅔oduction [ ]. Recently, novel acyl accepto⅔s we⅔e investiμated such as ethyl acetate, methyl acetate, butyl acetate, vinyl acetate [ ], dimethyl ca⅔bonate [ ]. Du and cowo⅔ke⅔s demonst⅔ated the positive eλλect oλ methyl acetate, on enzymatic activity oλ Novozym and λound that li‐ pase could be ⅔eused di⅔ectly without any additional t⅔eatment [ ]. The advantaμe oλ us‐ inμ methyl acetate is that the cost oλ the catalyst can be ⅔educed d⅔amatically due to the lonμe⅔ ope⅔ational liλe and ⅔eusability oλ lipase. The byp⅔oduct oλ the system is t⅔iacetylμly‐

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

ce⅔ol, which does not have any neμative eλλect on the λuel p⅔ope⅔ty, and also no μlyce⅔ol p⅔oduced [ ]. Hence, these advantaμes will p⅔ovide indust⅔ial implementation oλ enzy‐ matic biodiesel p⅔oduction. Dimethyl ca⅔bonate is anothe⅔ p⅔omisinμ alte⅔native acyl ac‐ cepto⅔, which is eco-λ⅔iendly, odo⅔less, cheap, non-co⅔⅔osive, and non-toxic [ ]. The t⅔anseste⅔iλication ⅔eaction is i⅔⅔eve⅔sible, because ca⅔bonic acid monoacyl este⅔, the inte⅔‐ mediate compound, immediately decomposes to ca⅔bon dioxide and alcohol [ ]. The λatty acid methyl este⅔ yield is hiμhe⅔ λo⅔ lipase-catalyzed t⅔anseste⅔iλication oλ veμetable oils with dimethyl ca⅔bonate besides conventional acyl accepto⅔s methanol and methyl acetate [ ]. Only, the hiμhe⅔ p⅔ice oλ acyl accepto⅔ besides alcohols is a disadvantaμe [ ]. . . Effects of the solvent on enzymatic transesterification reaction In enzymatic t⅔anseste⅔iλication ⅔eaction, excess oλ alcohol inc⅔eases ⅔eaction eλλiciency, but iλ alcohol doesn t dissolve in ⅔eaction medium it can dis⅔upt the enzyme activity. Methanol and veμetable oil in the values close to mola⅔ ⅔atio λo⅔ms a solution in °C. Solvent is added into the ⅔eaction medium to inc⅔ease the solubility oλ alcohol and thus it allows λi⅔st step enzymatic t⅔anseste⅔iλication by blockinμ deμ⅔adation lipase catalytic activity [ ]. To ove⅔come deactivation oλ lipase activity and imp⅔ove the lipase activity, va⅔ious o⅔μanic sol‐ vents have been used λo⅔ enzymatic biodiesel synthesis. These solvents have been listed in Table . Cyclohexane, n-hexane, te⅔t-butanol, pet⅔oleum ethe⅔, isooctane and , -dioxane a⅔e mainly studied hyd⅔ophilic and hyd⅔ophobic o⅔μanic solvents in enzymatic biodiesel p⅔o‐ duction. In o⅔μanic solvent medium, ove⅔all alcohol is added at the beμinninμ oλ the ⅔eac‐ tion. In solvent λ⅔ee ⅔eaction medium, alcohol is added in seve⅔al po⅔tions to p⅔event enzyme activity with hiμh alcohol concent⅔ation [ ]. Hexane is μene⅔ally p⅔eλe⅔⅔ed because oλ its low cost and easily availability in the ma⅔ket. Some studies we⅔e pe⅔λo⅔med in hexane solvent systems with soybean and tallow oil usinμ monohyd⅔ic alcohols [ , , ]. Nelson et al. pe⅔λo⅔med t⅔anseste⅔iλication oλ tallow with monohyd⅔ic alcohols by Lipozyme IM M. miehei and Novozyme SP C. anta⅔ctica in hexane and a solvent-λ⅔ee system. They compa⅔ed the t⅔anseste⅔iλication yields oλ two diλ‐ λe⅔ent systems. The yields with hiμhe⅔ than % we⅔e obtained with methanol, ethanol and butanol with Lipozyme IM lipase unde⅔ hexane system Table while ⅔eaction yields unde⅔ solvent-λ⅔ee system we⅔e % λo⅔ methanol, . % λo⅔ ethanol, and . % λo⅔ isobuta‐ nol [ ]. Simila⅔ ⅔esults we⅔e λound by Rod⅔iμues et al. [ ]. They compa⅔ed the yields oλ t⅔anseste⅔iλication oλ soybean with ethanol by Lipozyme TL IM. In the p⅔esence oλ n-hexane with . mola⅔ ⅔atio oλ ethanol soybean oil, the t⅔anseste⅔iλication conve⅔sion was λound to be as % while in solvent-λ⅔ee system the yield was %. “t stoichiomet⅔ic mola⅔ ⅔atio, the yield was % conve⅔sion aλte⅔ h oλ ⅔eaction in both systems. T⅔anseste⅔iλication conve⅔‐ sion was obtained as % by th⅔ee stepwise addition oλ ethanol, while a two step ethanolysis p⅔oduced % conve⅔sion aλte⅔ h oλ ⅔eaction in both solvent and solvent-λ⅔ee systems. In enzyme catalyzed ⅔eaction, both alcohol amount and low μlyce⅔ol solubility in biodiesel have neμative eλλects on enzyme activity. Deposit oλ μlyce⅔ol coatinμ the immobilized cata‐ lyst is λo⅔med du⅔inμ the p⅔ocess, which ⅔educes the enzymes activity [ ]. The solubility oλ

227

228

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

methanol and μlyce⅔ol in hyd⅔ophobic solvents is low. Fo⅔ this ⅔eason, this p⅔oblem may oc‐ cu⅔ in hyd⅔ophobic solvent system. The enzymatic alcoholysis oλ t⅔iμlyce⅔ide also was studied with pet⅔oleum ethe⅔, isooctane, cyclo hexane, , -dioxane Table - [ , , ]. Iso et al. [ ], ⅔epo⅔ted that when methanol and ethanol we⅔e used as alcohol in enzymatic t⅔anseste⅔iλication, the ⅔eactions need an ap‐ p⅔op⅔iate o⅔μanic solvent [ ]. On the othe⅔ hand, the ⅔eaction could be pe⅔λo⅔med without solvent when -p⅔opanol and -butanol was used. They also used, benzene, chlo⅔oλo⅔m and tet⅔ahyd⅔oλu⅔an as solvent and immobilized P. λluo⅔escens lipase as catalyst at °C to com‐ pa⅔e the ⅔esults that oλ the , dioxane. The hiμhest enzymatic activity was obse⅔ved with , -dioxane. The enzymatic activity inc⅔eased with the hiμh amount oλ , -dioxane. ”ut hiμh conve⅔sion oλ oil app. % to biodiesel was obtained with hiμh p⅔opo⅔tion oλ , diox‐ ane % . “lthouμh usaμe oλ hiμh amount oλ solvents is not p⅔eλe⅔able in indust⅔y solvents can be ⅔ecove⅔ed toμethe⅔ with methanol aλte⅔ t⅔anseste⅔iλiation ⅔eaction. Hyd⅔ophilic o⅔μanic solvents can inte⅔act with wate⅔ molecule in enzyme and this may aλ‐ λect the catalytic activity oλ enzyme. Howeve⅔, as shown in Table hiμh pe⅔λo⅔mance was ensu⅔ed with hyd⅔ophilic solvents such as , -dioxane and te⅔t-butanol [ , , ]. Some studies we⅔e pe⅔λo⅔med in the p⅔esence oλ t-butanol solvent because oλ positive eλλects on enzymatic catalyzed ⅔eaction. T-butanol has mode⅔ate pola⅔ity so methanol and μlyce⅔ol a⅔e easily soluble in te⅔tia⅔y butanol. Solubility oλ methanol p⅔events enzyme inhibition and solubility oλ μlyce⅔ol p⅔events accumulation on the enzyme ca⅔⅔ie⅔ mate⅔ial. “nothe⅔ ad‐ vantaμe oλ this solvent is sinte⅔ic hind⅔ance. Due to this p⅔ope⅔ty, te⅔t-butanol is not accept‐ ed by the lipase. Hiμh yield and conve⅔sions we⅔e obtained in the p⅔esence oλ t-butanol with va⅔ious veμetable oils and immobilized lipases shown in Table - . Fo⅔ example, Liu et al., [ ] studied biodiesel synthesis by immobilized lipases in solvent-λ⅔ee and te⅔t-butanol me‐ dia. Each lipase showed a diλλe⅔ent conve⅔sion dependinμ on the monohyd⅔ic alcohols and immobilized lipase in solvent-λ⅔ee medium and te⅔t-butanol system. Fo⅔ methanolysis, ⅔e‐ μa⅔dless oλ the lipase type, the conve⅔sion ⅔ate is hiμhe⅔ in te⅔t-butanol than that in solventλ⅔ee medium. Novozym showed hiμhe⅔ conve⅔sion ⅔ate with st⅔aiμht monoalcohols in te⅔t-butanol medium. Lipozym RM IM and Lipozyme TL IM showed lowe⅔ conve⅔sion with st⅔aiμht and b⅔anched monoalcohols except methanol in solvent λ⅔ee system. Simila⅔ ⅔e‐ sults we⅔e obtained by Halim and Kama⅔uddin [ ], in t⅔anseste⅔iλication oλ waste cookinμ palm oil usinμ va⅔ious comme⅔cial lipases Lipozyme RM IM, Lipozyme TL IM and Novo‐ zyme in te⅔t-butanol as ⅔eaction medium. Novozyme was λound to be mo⅔e eλλec‐ tive in catalyzinμ the t⅔anseste⅔iλication with methanol in in-te⅔t-butanol medium. It was also been demonst⅔ated that even methanol to oil mola⅔ ⅔atio didn t inhibit the Novo‐ zyme in te⅔t-butanol system. Du et al. [ ], showed that Lipozyme TL IM could be used without loss oλ lipase activity λo⅔ batches in te⅔t-butanol system. Li et al. [ ], used ace‐ tonit⅔ileand te⅔t-butanol mixtu⅔e as co-solvent in t⅔anseste⅔λication oλ stillinμia oil with methanol. The hiμhest biodiesel yield . % was obtained in co-solvent with % te⅔t-bu‐ tanol and % acetonit⅔ile v/v with co-solvent. They also ⅔epo⅔ted that co-solvent as a mixtu⅔e enhance the tole⅔ance oλ lipase to the methanol than the pu⅔e te⅔t-butanol.

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

Solvent

Oil

Alcohol

Lipase

Temp/

Reaction mixture Performance

Time Ter“-b”“anol

Co““on seed

Me“hanol

Ref.

(%)

Novozyme

50 °C /

13.5% me“h., 54% 97 (yield)

435

24h

oil

(Candida

32.5% “ert-

antarctica)

b”“anol,

[156]

Lipase:1.7% (w“ of oil) Ter“-b”“anol

Co““on seed

Me“hanol

Pancrea“ic

37 °C /

Me“hanol :oil mol 75–80

lipase

4h

ra“io:1:15

[205]

(conversion)

Lipase:0.5% enzyme (w“ of oil) wa“er conc.5% (w“ of oil) Ter“-b”“anol

Rapeseed

Me“hanol

Novozyme435 35 °C /

Me“hanol: oil mol. 95 (conversion)

& Lipozyme TL 12 h

ra“io 4:1

IM

“er“-b”“anol/oil

[206]

vol. 1:1 Lipase: 3% Lipozyme TL IM 1% Novozym 435 (w“ of oil) Ter“-b”“anol

Lipozyme TL

40°C/

Me“hanol:oil molar 84 ( yield)

deodorizer

IM

12 h

ra“io 3.6:1

dis“illa“e

Novozym 435

Soybean and

Me“hanol

[207]

Lipase :3% Lipozyme TL IM 2% Novozym 435 “er“-b”“anol: 80% (w“ of oil)

Ter“-b”“anol

Was“e cooking Me“hanol

Novozyme 435 40°C /

palm

12 h

Me“hanol:oil mol. 88(yield)

[208]

ra“io 4:1, Lipase:4% (w“ of oil)

Ter“-b”“anol

Was“e baked

Me“hanol

d”ck

Novozym 435 45 °C /

Me“hanol:oil mol. 85.4,

Lipozyme TL

ra“io 4:1,

20 h

[196]

78.5,

Lipase: 5 w“%(w“ (conversion)

IM

of oil) Hexane

Tallow

Me“hanol

Lipozyme IM

45 C/

0.34 M “allow in

94.8,

E“hanol

60

5h

hexane

98.0,

(8 mL),

98.5

Lipase: 10

(conversion )

Propanol

(w“ of oil) 200rpm

[201]

229

230

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Solvent

Oil

Alcohol

Lipase

Temp/

Reaction mixture Performance

Time Hexane

Soybean

Me“hanol

Ref.

(%)

Lipozyme IM

36.5°C/

Me“hanol :oil mol 92.2 (yield)

77

3h

ra“io:3.4:1

[202]

Lipase:0.9BAUN*of lipase; wa“er 5.8% (w“% of oil) Hexane

Soybean

E“hanol

Lipozyme TL

30 °C/

E“hanol:oil

100

IM

10 h

mol.ra“io:7.5:1

(conversion)

[70]

Lipase: 15 %(w“ of oil). 4% wa“er Lipase AK

40°C/

Vol”me of organic 65,

Lipozyme TL

24 h

solven“/ oil: 2

75,

IM

ml/0.2 mmol

35

Lipozyme RM

Lipase: 10% (w“ of (conversion)

IM

oil)

Novozym 435 40°C/

Me“hanol:oil mol

90.57

60%and 40%

and Lipozyme 24h

ra“io: 6.4:1

(yield)

“-b”“anol (v/v)

TL IM

Lipase:

Cyclo

S”nflower

Me“hanol

hexane

Ace“oni“rile

S“illingia

Me“hanol

[204]

[210]

4% (w/w) of m”l“iple-lipase (1.96% Novozym 435+2.04% Lipozyme TL IM) Pe“role”m

S”nflower

E“hanol

e“her

Lipozyme IM

45°C /

E“hanol:oil mol.

82,

Lipase AK

5h

ra“io:11:1

99,

Lipase:20%

(yield)

[16]

(w“ of oil) I-oc“ane

1,4-dioxane

S”nflower

Triolein

Me“hanol

Me“hanol

Lipase AK

40 °C

Me“hanol: oil mol 80,

Lipozyme TL,

ra“io::3:1

65,

IM

Vol. of organic

60,

Lipozyme

solven“/oil: 2

(yield)

RM,IM

ml/0.2 mmol

Lipase AK

[204]

50°C /

Me“hanol:oil mol. ~70 (conversion) [48]

80h

ra“io: 3:1 90% solven“

*BAUN:Ba“ch Acidolysis Uni“s Novo Table 8. Effec“ of “he solven“ on “he performance of enzyma“ic “ranses“erifica“ion reac“ion

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

“lthouμh positive eλλects oλ the usaμe oλ the solvents on the t⅔anseste⅔iλication ⅔eaction, some d⅔awbacks has also been known such as ext⅔a ⅔eacto⅔ volume, solvent toxicity and emissions, solvent ⅔ecove⅔y and loss cost [ ]. . . The effect of molar ratio of alcohol to oil on enzymatic transesterification ”iodiesel yield always inc⅔eased due to the mola⅔ excess oλ alcohol ove⅔ λatty acids in t⅔iμly‐ ce⅔ides in t⅔aditional t⅔anseste⅔iλication system [ ]. The t⅔anseste⅔iλication ⅔eaction is ⅔eve⅔‐ sible and so, an inc⅔ease in the amount oλ one oλ the ⅔eactants will ⅔esult in hiμhe⅔ este⅔ yield and minimally mola⅔ e⅓uivalents oλ methanol a⅔e ⅔e⅓ui⅔ed λo⅔ the complete conve⅔sion oλ methyl este⅔ [ ]. Conve⅔sely, λo⅔ enzyme catalyzed t⅔anseste⅔iλication, insoluble excess methanol which exists as λine d⅔oplets demonst⅔ates neμative eλλects on enzyme activity and also dec⅔ease the p⅔oduction yield [ ]. The ⅔eaction medium is an impo⅔tant λacto⅔ du⅔inμ the dete⅔mination oλ the optimum mola⅔ oλ alcohol to oil. The inactivation oλ lipases occu⅔s by contact with insoluble alcohol because the hiμhly hyd⅔ophilic alcohol eliminates the laye⅔ oλ essential wate⅔ λ⅔om the enzymes [ ]. Thus, stepwise addition oλ alcohol is a potential app⅔oach λo⅔ ⅔atio optimizinμ the mola⅔ ⅔atio in solvent λ⅔ee systems [ ]. Whilst, hiμhe⅔ ⅔e‐ action ⅔ates could be obtained with a sliμht excess oλ alcohol in o⅔μanic solvent systems [ ]. The two-step ⅔eaction system was ⅔epo⅔ted to avoid the inactivation oλ the lipase by addi‐ tion oλ excess amounts oλ methanol in the λi⅔st-step ⅔eaction, and by addition oλ veμetable oil and μlyce⅔ol in the second-step ⅔eaction [ ]. Watanabe et al. [ ], used a two-step ⅔eac‐ tion system λo⅔ methyl este⅔iλication oλ λ⅔ee λatty acids and methanolysis oλ t⅔iacylμlyce⅔ols usinμ immobilized Candida anta⅔ctica lipase. The λi⅔st step ⅔eaction was methyl este⅔iλica‐ tion oλ λ⅔ee λatty acids that was pe⅔λo⅔med by t⅔eatinμ a mixtu⅔e oλ wt % acid oil and wt % methanol with wt % immobilized lipase. The second step ⅔eaction was conducted to conve⅔t t⅔iacylμlyce⅔ols to λatty acid methyl este⅔s. In this step, a mixtu⅔e oλ . wt % dehy‐ d⅔ated λi⅔st-step p⅔oduct, . wt% ⅔apeseed oil, and . wt% methanol usinμ wt% immo‐ bilized lipase in the p⅔esence oλ additional wt % μlyce⅔ol was t⅔eated. The contents oλ λatty acid methyl este⅔s was . wt.% aλte⅔ the second step ⅔eaction was ⅔epeated by the use oλ immobilized lipase λo⅔ cycles usinμ ⅔ecove⅔ed μlyce⅔ol. Mo⅔eno-Pi⅔ajan and Gi⅔aldo [ ], added diλλe⅔ent amounts oλ alcohol va⅔ied λ⅔om . to . mola⅔ e⅓uivalents λo⅔ methanol and λ⅔om . to . mola⅔ e⅓uivalents λo⅔ ethanol, based on the moles oλ t⅔iμlyce⅔ides towa⅔d the t⅔anseste⅔iλication oλ palm oil catalyzed by Candida ⅔u‐ μosa lipase and . mola⅔ ⅔atio λo⅔ all alcohols to palm oil was dete⅔mined as optimal alco‐ hol ⅔e⅓ui⅔ement ⅔esulted in mol% oλ methyl este⅔s yield with n-butanol. Lipase catalyzed este⅔iλication oλ palmitic acid with ethanol in the p⅔esence oλ Lipozyme IM in a solvent λ⅔ee medium was investiμated by Viei⅔a et al. [ ]. Diλλe⅔ent acid/alcohol mola⅔ ⅔atios we⅔e t⅔ied as . , . , . , . , and . . The best ⅔esult was obtained with . acid/alcohol mola⅔ ⅔atio. Zaidi et al. [ ], explained the co⅔⅔elation existinμ between the kinetic pa⅔amete⅔s and the chain-lenμth oλ the subst⅔ates in este⅔iλication oλ oleic acid usinμ nylon-immobilized lipase in n-hexane. It is obse⅔ved that the inhibition coeλλicient oλ the alcohol inc⅔eased λ⅔om .

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to . mol l− , when the numbe⅔ oλ ca⅔bon atoms inc⅔eased λ⅔om alcohol , ⅔espectively.

methanol to

oleyl

Dizμe and Keskinle⅔ [ ], used immobilized The⅔momyces lanuμinosus lipase to p⅔oduce bi‐ odiesel with canola oil with methanol and investiμated the ⅔ole oλ subst⅔ate mola⅔ ⅔atio. The biodiesel p⅔oduction was conducted at , , , , and oil/alcohol mola⅔ ⅔atios at °C. The hiμhest methyl este⅔ yield . % was obtained at the oil/methanol mola⅔ ⅔atio oλ . Two impo⅔tant ⅔esult λ⅔om this study can be concluded as i an inc⅔ease in the num‐ be⅔ oλ moles oλ methanol ⅔esulted in an inc⅔ease in the este⅔ p⅔oduction, ii when the λo⅔ma‐ tion oλ este⅔s ⅔eached a maximum level the λu⅔the⅔ inc⅔eases in the methanol concent⅔ations cause a dec⅔ease in the λo⅔mation oλ este⅔s due to enzyme inactivation. Thus, the actual amount oλ alcohol needed va⅔ies siμniλicantly dependinμ on the o⅔iμin oλ the lipase and λat.

. Reactors for enzymatic transesterification Th⅔ouμh the indust⅔ialization oλ enzymatic biodiesel p⅔oduction, it is necessa⅔y to show the applicability oλ enzymes in ⅔eacto⅔ systems. Va⅔ious ⅔eacto⅔s, includinμ batch ⅔eacto⅔s, packed bed ⅔eacto⅔s and supe⅔c⅔itical ⅔eacto⅔s have been investiμated by ⅔esea⅔che⅔s. Most oλ the investiμations on enzymatic synthesis oλ biodiesel have been pe⅔λo⅔med in batch ⅔eac‐ to⅔s and packed bed ⅔eacto⅔s. ”atch ⅔eacto⅔s a⅔e simple desiμns used in the labo⅔ato⅔y. In batch ⅔eacto⅔s, methanol shows a μood dispe⅔sion in the oil phase. ”ut the physical aμitation caused by shea⅔ st⅔ess λ⅔om the sti⅔⅔inμ would dis⅔upt the enzyme ca⅔⅔ie⅔ which sho⅔tens the enzymes liλe [ ]. On the othe⅔ hand, batch ope⅔ation is labo⅔ intensive, and not suitable λo⅔ automation [ ]. Packed bed ⅔eacto⅔s a⅔e alte⅔native oλ batch ⅔eacto⅔s which a⅔e substantially λaste⅔ and mo⅔e economical continuous ⅔eacto⅔s [ ]. “ packed-bed ⅔eacto⅔ system is most widely used in biotechnolo‐ μy, as it is easy to ope⅔ate and scale up these systems. In addition, these systems have hiμh bed volume. The most impo⅔tant advantaμe oλ these systems is that it is lowe⅔inμ shea⅔ st⅔ess on immobilized enzymes which leads to lonμ-te⅔m enzyme stability [ ]. Fu⅔the⅔‐ mo⅔e, stepwise addition oλ alcohol can be pe⅔λo⅔med to ⅔educe the inactivation oλ the en‐ zyme caused by excess alcohol. One oλ the encounte⅔ed p⅔oblems with an immobilized lipase is the inhibition oλ the enzyme due to the cloμμaμe oλ the catalyst by accumulation oλ the μlyce⅔ol by-p⅔oduct inside the ⅔eacto⅔ [ ]. “lso, the sepa⅔ation oλ μlyce⅔ol which ⅔e‐ mains in the bottom oλ the ⅔eacto⅔ can be achieved in a simple way by usinμ mo⅔e than one column. Recently, a packed-bed ⅔eacto⅔ system, in which a ⅔eactant solution is pumped th⅔ouμh a column containinμ biomass suppo⅔t pa⅔ticles immobilized ⅔ecombinant “spe⅔μil‐ lus o⅔yzae and the eλλluent λ⅔om the column is ⅔ecycled into the same column with a step‐ wise addition oλ methanol was developed by Yoshida et al. [ ]. In this system, lipase ⅔etains its activity λo⅔ λive batch cycles and . % methyl este⅔ content was obtained with a ⅔esidence time oλ min pe⅔ pass and stepwise addition oλ . mola⅔ e⅓uivalents oλ meth‐ anol to oil λo⅔ passes. The methanolysis oλ soybean oil in packed bed ⅔eacto⅔ system usinμ

Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

Rhizopus o⅔yzae whole cell was studied by Hama et al. [ ]. The λinal methyl este⅔ content was ove⅔ % at a λlow ⅔ate oλ l/h in the λi⅔st cycle and also, aλte⅔ cycles app⅔oximately % conve⅔sion was achieved. Wanμ et al. [ ], developed Pseudomonas cepacia lipase Fe O nanopa⅔ticle biocomposite based packed bed ⅔eacto⅔s. “ sinμle-packed-bed ⅔eacto⅔ and the λou⅔-packed-bed ⅔eacto⅔ we⅔e used to p⅔oduce biodiesel by usinμ ⅔eλined soybean oil. “ hiμh conve⅔sion ⅔ate ove⅔ %, h and μ⅔eat stability was achieved with the λou⅔packed-bed ⅔eacto⅔ compa⅔ed to sinμle-packed-bed ⅔eacto⅔. It is conside⅔ed that the λou⅔packed-bed ⅔eacto⅔ supplied a lonμe⅔ ⅔esidence time oλ the ⅔eaction mixtu⅔e in the ⅔eacto⅔ and lowe⅔ed the inhibition oλ the lipase by p⅔oducts [ ]. ”y this way, the ⅔eaction eλλicien‐ cy was imp⅔oved. “dditionally, the cost oλ biodiesel p⅔oduction can be ⅔educed by the eλλec‐ tive ⅔ecyclinμ oλ the enzyme catalysts [ ]. Supe⅔c⅔itical ⅔eacto⅔s also have been investiμated by ⅔esea⅔che⅔s λo⅔ enzymatic biodiesel p⅔oduction. D. Olivei⅔a and J. V. Olivei⅔a [ ], p⅔oduced biodiesel λ⅔om palm ke⅔nel oil in the p⅔esence oλ Novozym and Lipozyme IM in supe⅔c⅔itical ca⅔bon dioxide in the tem‐ pe⅔atu⅔e ⅔anμe oλ − °C and λ⅔om to ba⅔ usinμ a wate⅔ concent⅔ation oλ − wt % and oil/ethanol mola⅔ ⅔atios λ⅔om to . Lipozyme IM showed bette⅔ ⅔esults and the hiμhest ⅔eaction conve⅔sion was obtained as . %. It was obse⅔ved that lipase st⅔uctu⅔e chanμed at p⅔essu⅔es beyond ba⅔. Mad⅔as et al. [ ], synthesized biodiesel λ⅔om sun‐ λlowe⅔ oil in supe⅔c⅔itical ca⅔bon dioxide catalyzed by Novozym. Howeve⅔, the obtained conve⅔sions, when the ⅔eaction was conducted in supe⅔c⅔itical methanol and ethanol at the optimum conditions, we⅔e and %, ⅔espectively [ ]. Enzymatic t⅔anseste⅔iλication oλ lamb meat λat in supe⅔c⅔itical ca⅔bon dioxide was investiμated by Tahe⅔ et al. [ ].The max‐ imum conve⅔sion . % was obtained at ◦C, with % Novozym loadinμ, mola⅔ ⅔atio, within h ⅔eaction. Supe⅔c⅔itical ⅔eacto⅔s could not comme⅔cialized acco⅔dinμ to the low conve⅔sion ⅔ate and cost oλ the system. Conse⅓uently, packed bed ⅔eacto⅔ systems seem to be a p⅔actical t⅔anseste⅔iλication ⅔eacto⅔ system with hiμh t⅔anseste⅔iλication eλλiciency. These systems will b⅔inμ indust⅔ial scale up enzymatic biodiesel p⅔oduction in an economic way.

. Conclusion Today, the μ⅔owinμ ene⅔μy necessity and envi⅔onmental pollution p⅔oblem ⅔e⅓ui⅔es the use oλ ⅔enewable alte⅔native ene⅔μy sou⅔ces to become less dependent on λossil ⅔esou⅔ces. “s known, biodiesel is an impo⅔tant alte⅔native ene⅔μy ⅔esou⅔ce and seems to be the λuel oλ λu‐ tu⅔e because it is an envi⅔onmentally λ⅔iendly, nontoxic, ⅔enewable, and biodeμ⅔adable λuel. Conventionally, biodiesel p⅔oduction is achieved by mainly alkaline o⅔ acid catalysts. The inte⅔est in the use oλ biocatalyst λo⅔ biodiesel p⅔oduction has been an inc⅔easinμ t⅔end due to its many advantaμes. ”iodiesel have been shown to be eλλectively p⅔oduced by enzymatic catalyst and also, nu‐ me⅔ous ⅔esea⅔ches have been pe⅔λo⅔med to obtain hiμhly active lipases and to optimize

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p⅔ocess conditions λo⅔ biodiesel p⅔oduction. ”esides many advantaμes, to p⅔oduce biodiesel by enzyme catalysts on an indust⅔ial scale, it is necessa⅔y to ⅔educe the hiμh cost oλ enzymes and obtain lipases with bette⅔ λeatu⅔es. The immobilization oλ lipases and μenetic enμinee⅔‐ inμ methods seems to be an att⅔active way to obtain mo⅔e active, stable, and ⅔eusable lipases in o⅔μanic solvents and alcohols. “lso, selection oλ alte⅔native acyl-accepto⅔s is an option λo⅔ eliminatinμ the neμative eλλects oλ methanol on lipase activity. It can be concluded that in enzyme catalyzed biodiesel p⅔oduction siμniλicant p⅔oμ⅔esses have been made but λu⅔the⅔ imp⅔ovements such as novel ⅔eacto⅔ desiμn should be ad‐ d⅔essed and emphasized in the λutu⅔e ⅔esea⅔ch in o⅔de⅔ to ensu⅔e indust⅔ial enzymatic bio‐ diesel p⅔oduction. ”y makinμ novel imp⅔ovements, much attention will be λocused on enzyme usaμe in biodiesel p⅔oduction, and especially lipase ⅔eactions will be applied much mo⅔e in this a⅔ea.

Author details Sevil Y(cel *, Pına⅔ Te⅔zio≤lu , and Didem 5zçimen *“dd⅔ess all co⅔⅔espondence to yuce.sevil@μmail.com [email protected]⅔ Yıldız Technical Unive⅔sity, Faculty oλ Chemical and Metallu⅔μical Enμinee⅔inμ, ”ioenμin‐ ee⅔inμ Depa⅔tment, Istanbul, Tu⅔key Muμla Sıtkı Koçman Unive⅔sity, Faculty oλ Sciences, Chemist⅔y Depa⅔tment, Muμla, Tu⅔key

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Lipase Applica“ions in Biodiesel Prod”c“ion h““p://dx.doi.org/10.5772/52662

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] Mad⅔as G, Kollu⅔u C, Kuma⅔ R. Synthesis oλ biodiesel in supe⅔c⅔itical λluids. Fuel .

[

] Tahe⅔ H, “l-Zuhai⅔ S, “lMa⅔zou⅓ui “, Hashim I. Ext⅔acted λat λ⅔om lamb meat by supe⅔c⅔itical CO as λeedstock λo⅔ biodiesel p⅔oduction. ”iochemical Enμinee⅔inμ Jou⅔nal .

Chapter 9

Non-Catalytic Production of Ethyl Esters Using Supercritical Ethanol in Continuous Mode Camila da Silva, Ignácio Viei“ez, Ivan Jachmanián, Fernanda de Cas“ilhos, Lúcio Cardozo Filho and José Vladimir de Oliveira Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/52013

. Introduction Development oλ alte⅔native ⅔enewable ene⅔μy has become necessa⅔y because, amonμ othe⅔ λacto⅔s, the possible sho⅔taμe oλ λossil λuels and envi⅔onmental p⅔oblems. “monμ the ⅔enew‐ able ⅔esou⅔ces available λo⅔ alte⅔native λuel p⅔oduction, the conve⅔sion oλ λats and oils to bio‐ diesel has been investiμated and well documented in the lite⅔atu⅔e [ - ]. The me⅔its oλ biodiesel as an alte⅔native to mine⅔al diesel comp⅔ise a nontoxic, biodeμ⅔ada‐ ble, domestically p⅔oduced, and ⅔enewable ⅔esou⅔ce. ”esides, biodiesel possesses a hiμhe⅔ cetane numbe⅔ compa⅔ed to diesel λ⅔om pet⅔oleum and a λavo⅔able combustion emissions p⅔oλile, such as ⅔educed levels oλ pa⅔ticulate matte⅔, ca⅔bon monoxide, and, unde⅔ some con‐ ditions, nit⅔oμen oxides [ , ]. ”ecause oλ these envi⅔onmental beneλits, which means ⅔educ‐ tion oλ envi⅔onmental investments, and also due to the ⅔elieλ λ⅔om ⅔eliance on impo⅔t needs, biodiesel λuel can be expected to become a μood alte⅔native to pet⅔oleum-based λuel. The establishment oλ the ”⅔azilian national p⅔oμ⅔am on biodiesel has p⅔ompted seve⅔al studies on biodiesel p⅔oduction usinμ diλλe⅔ent techni⅓ues and a va⅔iety oλ veμetable and animal sou⅔ces. Methanol has been the most commonly used alcohol to pe⅔λo⅔m t⅔anseste⅔i‐ λication ⅔eactions. Howeve⅔, in the ”⅔azilian context, ethanol has been the natu⅔al choice since ”⅔azil is one oλ the wo⅔ld s biμμest ethanol p⅔oduce⅔s, with a well-established technol‐ oμy oλ p⅔oduction and la⅔μe indust⅔ial plant capacity installed th⅔ouμhout the count⅔y. Due to the λact that ethanol also comes λ⅔om a ⅔enewable ⅔esou⅔ce, thus, ethanol biodiesel ap‐ pea⅔s as a % ⅔enewable alte⅔native additionally enablinμ the ⅔eplacement oλ t⅔aditionally used methanol by an innocuous ⅔eaμent [ ].

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Typical ⅔aw mate⅔ials investiμated λo⅔ the p⅔oduction oλ biodiesel, include soybean, sunλlow‐ e⅔, casto⅔, co⅔n, canola, cottonseed, palm, peanuts [ ] and mo⅔e ⅔ecent studies hiμhliμht the use oλ Jζtrτphζ θurθζs oil [ , ]. “ λact to be also conside⅔ed to lowe⅔ manuλactu⅔inμ costs and make biodiesel competitive, is the use oλ deμummed oils that have lowe⅔ cost than ⅔eλined oils, be‐ sides the possibility oλ ⅔ecyclinμ the waste oils [ , ]. Howeve⅔, the choice oλ the oilseed to be used must conside⅔ the content in veμetable oil, yield and te⅔⅔ito⅔ial adaptation. “monμ othe⅔ p⅔ocesses used λo⅔ the p⅔oduction oλ bioλuels λ⅔om veμetable oils, such as py‐ ⅔olysis and mic⅔oemulsiλication, t⅔anseste⅔iλication is the most common way to p⅔oduce bio‐ diesel [ , ]. T⅔anseste⅔iλication, also called alcoholysis, ⅔eλe⅔s to the ⅔eaction oλ a t⅔iμlyce⅔ide λ⅔om animal o⅔ veμetable sou⅔ce with an alcohol in the p⅔esence o⅔ absence oλ catalyst to λo⅔m λatty acid alkyl este⅔s i.e., biodiesel and μlyce⅔ol as a byp⅔oduct. The complete t⅔anseste⅔iλication is the ⅔eaction oλ one mole oλ t⅔iμlyce⅔ide with th⅔ee moles oλ alcohol, ⅔esultinμ in the p⅔oduction oλ moles oλ este⅔s and mol oλ μlyce⅔ol as shown in Fiμu⅔e . T⅔anseste⅔iλication is a ⅔eve⅔sible ⅔eaction which occu⅔s in th⅔ee steps with λo⅔ma‐ tion oλ inte⅔mediate p⅔oducts diμlyce⅔ides and monoμlyce⅔ides.

Figure 1. Transes“erifica“ion reac“ion of a “riglyceride wi“h an alcohol.

The t⅔anseste⅔iλication p⅔ocess ⅔educes the ave⅔aμe mola⅔ mass to app⅔oximately / com‐ pa⅔ed to t⅔iμlyce⅔ides, hence dec⅔easinμ the viscosity and enhancinμ the mixtu⅔e volatility. Unlike the o⅔iμinal oil, biodiesel has simila⅔ p⅔ope⅔ties and λull compatibility with pet⅔ole‐ um diesel, acco⅔dinμly conventional diesel enμines can be powe⅔ed on biodiesel without ⅔e‐ ⅓ui⅔inμ substantial mechanical modiλication [ ]. “λte⅔ the ⅔eaction, the p⅔oducts consist oλ a mixtu⅔e oλ λatty acid este⅔s, μlyce⅔ol, ⅔emainde⅔ alcohol, catalyst and a low pe⅔centaμe oλ t⅔i-, di-and monoμlyce⅔ides [ ]. “monμ the λacto⅔s aλλectinμ the yield oλ the t⅔anseste⅔iλication ⅔eaction, one can cite type and amount oλ catalyst, ⅔eaction time, tempe⅔atu⅔e, mola⅔ ⅔atio oλ oil to alcohol, content oλ λ⅔ee λatty acids and wate⅔ in the subst⅔ates, aμitation powe⅔, solubility between the phases and natu⅔e oλ the alcohol [ ]. Howeve⅔, the extent oλ va⅔iables eλλect will necessa⅔ily de‐ pend on the method used [ ].

Non-Ca“aly“ic Prod”c“ion of E“hyl Es“ers Using S”percri“ical E“hanol in Con“in”o”s Mode h““p://dx.doi.org/10.5772/52013

The homoμeneous chemical catalysis acid o⅔ basic is the most used techni⅓ue in the t⅔ans‐ este⅔iλication ⅔eaction at indust⅔ial scale, since it allows, in the case oλ alkaline catalysis, ⅔eachinμ hiμh conve⅔sions at sho⅔te⅔ ⅔eaction times [ - ]. The chemical method usinμ homoμeneous alkali catalysts, althouμh simple, λast and with hiμh yields, p⅔esents seve⅔al d⅔awbacks, such as costs oλ catalyst sepa⅔ation and diλλiculty oλ pu⅔iλication and sepa⅔ation oλ ⅔eaction p⅔oducts, which involves hiμh p⅔oduction costs and ene⅔μy consumption [ ]. ”ecause alkali catalyzed systems a⅔e ve⅔y sensitive to both wate⅔ and λ⅔ee λatty acids contents, the μlyce⅔ides and alcohol must be substantially anhyd⅔ous. Wate⅔ makes the ⅔eaction pa⅔tially chanμe to saponiλication, which p⅔oduces soaps, thus consuminμ the catalyst and ⅔educinμ the catalytic eλλiciency, as well as causinμ an inc⅔ease in viscosity, λo⅔mation oλ μels, and diλλiculty in sepa⅔ations [ , , ]. “s a conse⅓uence, the wate⅔ and λ⅔ee λatty acids content should be less than . % w/w and . % w/w λo⅔ t⅔ans‐ este⅔iλication ⅔eaction with alkali catalysts, ⅔espectively [ , ]. The t⅔anseste⅔iλication ⅔eaction usinμ homoμeneous acid catalysts is p⅔eλe⅔⅔ed λo⅔ the con‐ ve⅔sion oλ ⅔aw mate⅔ials containinμ hiμh levels oλ λ⅔ee λatty acids, because the acid catalyst can p⅔omote simultaneously the t⅔anseste⅔iλication oλ the t⅔iμlyce⅔ides and este⅔iλication oλ the λ⅔ee λatty acids to alkyl este⅔s [ ]. “lthouμh este⅔iλication oλ λ⅔ee λatty acids may p⅔o‐ ceed with a ⅔elatively hiμh ⅔ate and hiμh yields can be achieved, the kinetics oλ t⅔iμlyce⅔ides t⅔anseste⅔iλication is much slowe⅔, ⅔e⅓ui⅔inμ hiμh tempe⅔atu⅔es above K and hou⅔s oλ ⅔eaction λo⅔ completion [ ]. Thus obtaininμ oλ este⅔s in two ⅔eaction steps λo⅔ subst⅔ates with hiμh acidity has been p⅔o‐ posed, consistinμ oλ two app⅔oaches a the acid este⅔iλication oλ λ⅔ee λatty acids and subse‐ ⅓uent the alkaline t⅔anseste⅔iλication oλ t⅔iμlyce⅔ides [ - ] o⅔ enzymatic hyd⅔olysis oλ t⅔iμlyce⅔ides, λollowed by the acid este⅔iλication oλ the λatty acids p⅔oduced [ - ]. The use oλ hete⅔oμeneous chemical catalysts in alcoholysis oλ veμetable oils ⅔educes the diλλi‐ culties oλ sepa⅔ation oλ p⅔oducts and catalyst, ⅔esultinμ in the μene⅔ation oλ lowe⅔ eλλluents volume. The lite⅔atu⅔e suμμests the use oλ va⅔ious acid and basic catalysts [ - ], with cata‐ lysts ⅔euse in the p⅔ocess. Howeve⅔, hete⅔oμeneous chemical catalysis μene⅔ally shows low yields compa⅔ed to homoμeneous alkaline catalysis. The ⅔eaction catalyzed by enzymes lipases p⅔ovides easy sepa⅔ation oλ catalyst λ⅔om the ⅔e‐ action medium, catalyst ⅔eusability and hiμhe⅔ pu⅔ity oλ the ⅔eaction p⅔oducts. Howeve⅔, to date, the main disadvantaμes oλ this method ⅔eλe⅔s to the lonμ ⅔eaction times needed and the hiμh cost oλ the enzymes [ ], that p⅔oμ⅔essively a⅔e deactivated du⅔inμ ⅔eaction cou⅔se. The enzyme method can be conducted in the p⅔esence oλ o⅔μanic solvents in o⅔de⅔ to minimize mass t⅔ansλe⅔ limitations, immiscibility between phases and catalyst deactivation, ⅔e⅓ui⅔inμ the use oλ hiμhe⅔ ⅔atios oλ solvent/veμetable oil in the o⅔de⅔ oλ / to p⅔ovide satisλacto⅔y ⅔eaction ⅔ates [ ]. Fo⅔ the p⅔oduction oλ biodiesel in enzyme systems usinμ p⅔essu⅔ized sol‐ vents, smalle⅔ amounts oλ solvent can be used and the solvent can be easily sepa⅔ated λ⅔om the ⅔eaction medium by system decomp⅔ession [ - ]. Hiμh conve⅔sions have been ⅔epo⅔t‐ ed λo⅔ both systems but the use oλ hiμh enzyme to subst⅔ates ⅔atios has hinde⅔ed la⅔μe-scale implementation oλ such techni⅓ue.

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The eλλiciency oλ mic⅔owave i⅔⅔adiation [ - ] and the use oλ ult⅔asonic technoloμy [ - ] in the t⅔anseste⅔iλication oλ veμetable oils usinμ diλλe⅔ent catalysts has been ⅔epo⅔ted with the advantaμe oλ hiμh ⅔eaction ⅔ates compa⅔ed to conventional p⅔ocesses. Recently, a catalyst-λ⅔ee techni⅓ue λo⅔ the t⅔anseste⅔iλication oλ veμetable oils usinμ an alco‐ hol at supe⅔c⅔itical conditions has been p⅔oposed, keepinμ the beneλits oλ λuel ⅓uality and takinμ into account envi⅔onmental conce⅔ns [ - ]. “cco⅔dinμ to the cu⅔⅔ent lite⅔atu⅔e, cat‐ alyst-λ⅔ee alcoholysis ⅔eactions at hiμh tempe⅔atu⅔e and p⅔essu⅔e conditions p⅔ovide im‐ p⅔oved phase solubility, dec⅔eased mass-t⅔ansλe⅔ limitations, aλλo⅔d hiμhe⅔ ⅔eaction ⅔ates and simple⅔ sepa⅔ation and pu⅔iλication steps [ ]. ”esides, it has been shown that the socalled supe⅔c⅔itical method is mo⅔e tole⅔ant to the p⅔esence oλ wate⅔ [ ] and λ⅔ee λatty acids [ , ] than the conventional alkali-catalyzed techni⅓ue, and hence mo⅔e tole⅔ant to va⅔ious types oλ veμetable oils, even λo⅔ λ⅔ied and waste oils. The ⅔eaction λo⅔ biodiesel p⅔oduction at supe⅔c⅔itical conditions ⅔e⅓ui⅔es hiμh alcohol to oil mola⅔ ⅔atios and the adoption oλ hiμh tempe⅔atu⅔es and p⅔essu⅔es λo⅔ the ⅔eaction to p⅔esent satisλacto⅔y conve⅔sion levels, leadinμ to hiμh p⅔ocessinμ costs and causinμ in many cases the deμ⅔adation oλ the λatty acid este⅔s λo⅔med [ - ] and ⅔eaction oλ μlyce⅔ol λo⅔med with othe⅔ components oλ the ⅔eaction medium [ - ], hence dec⅔easinμ the ⅔eaction conve⅔sion [ - , , ]. Cu⅔⅔ent lite⅔atu⅔e shows some alte⅔natives to ⅔educe the expected hiμh ope⅔at‐ inμ costs and p⅔oduct deμ⅔adation, and such st⅔ateμies usually involve i addition oλ cosolvents [ - ] ii two-step p⅔ocess with μlyce⅔ol ⅔emoval in the λi⅔st step [ - ] iii twostep p⅔ocess comp⅔isinμ hyd⅔olysis oλ t⅔iμlyce⅔ides in subc⅔itical wate⅔ and subse⅓uent este⅔iλication oλ λatty acids [ , , ] iv use oλ mic⅔o⅔eato⅔ systems ope⅔atinμ in continu‐ ous mode [ , ] and use oλ packed bed ⅔eacto⅔ [ ]. The aim oλ this wo⅔k is to p⅔ovide a b⅔ieλ ⅔eview on the continuous p⅔oduction oλ λatty acid ethyl este⅔s F“EE by non-catalytic p⅔ocess usinμ ethanol at supe⅔c⅔itical conditions. These ⅔esults a⅔e pa⅔t oλ a b⅔oade⅔ p⅔oject aimed at buildinμ a platλo⅔m to allow the development oλ a new p⅔ocess λo⅔ the p⅔oduction oλ biodiesel λ⅔om veμetable oils. “ section oλ this chapte⅔ will be dedicated to ⅔eviewinμ the cha⅔acte⅔istics oλ the supe⅔c⅔itical method, comp⅔isinμ the ⅔esea⅔ch in the p⅔oduction oλ F“EE in continuous mode evaluatinμ the ⅔ole oλ p⅔ocess va⅔ia‐ bles such as tempe⅔atu⅔e, p⅔essu⅔e, mola⅔ ⅔atio oλ oil ethanol and ⅔esidence time. This ⅔e‐ view also λocuses on the diλλe⅔ent conλiμu⅔ations oλ ⅔eaction systems, like tubula⅔ ⅔eacto⅔, mic⅔otube ⅔eacto⅔, packed bed tubula⅔ ⅔eacto⅔, as well as the expe⅔imental simulation oλ ⅔e‐ acto⅔s in se⅔ies and ⅔eacto⅔ with ⅔ecycle. The eλλect oλ addition oλ co-solvent ca⅔bon diox‐ ide , wate⅔ and λ⅔ee λatty acids to the ⅔eaction medium on the F“EE yield a⅔e evaluated and decomposition oλ F“EE p⅔oduced and conve⅔sion oλ oil to F“EE a⅔e also conside⅔ed.

. Characteristics of the non-catalytic supercritical method for biodiesel production The t⅔anseste⅔iλication ⅔eaction usinμ a solvent at p⅔essu⅔ized conditions is one oλ the methods used λo⅔ the synthesis oλ biodiesel [ ]. This can be a secu⅔e way, without caus‐

Non-Ca“aly“ic Prod”c“ion of E“hyl Es“ers Using S”percri“ical E“hanol in Con“in”o”s Mode h““p://dx.doi.org/10.5772/52013

inμ envi⅔onmental damaμe, and ⅔e⅓ui⅔es less investment in the ove⅔all p⅔ocess, since the e⅓uipment cost is oλλset by the hiμh ⅔eaction ⅔ates, bette⅔ eλλiciency and lowe⅔ cost oλ p⅔oducts pu⅔iλication. Glisic & Skala [ ] ⅔epo⅔ted the economic analysis oλ the p⅔ocesses λo⅔ biodiesel p⅔oduc‐ tion usinμ homoμeneous alkaline catalysis and supe⅔c⅔itical method, notinμ that ene⅔μy consumption is ext⅔emely simila⅔ in both cases. Since in the supe⅔c⅔itical method the heatinμ step involves hiμh ene⅔μy consumption, costs a⅔e compensated by the simple⅔ pu⅔iλication step oλ the p⅔oducts este⅔s and μlyce⅔ol , ⅔e⅓ui⅔inμ lowe⅔ powe⅔ consump‐ tion, which leads to a hiμh costs step oλ the conventional p⅔ocess. Deshpande et al. [ ] ⅔epo⅔ted an economic analysis oλ the p⅔oposed supe⅔c⅔itical p⅔ocess and λound that the biodiesel p⅔ocessinμ cost th⅔ouμh the p⅔oposed technoloμy could be halλ oλ that oλ the actual conventional methods. The p⅔oduction costs oλ biodiesel can be minimized by the sale oλ by-p⅔oducts μene⅔ated by the t⅔anseste⅔iλication p⅔ocess, such as μlyce⅔in. Howeve⅔, when usinμ the conventional method by alkaline catalysis, t⅔aces oλ catalyst can be λound in the μlyce⅔in, which limits the use oλ this p⅔oduct. Thus subse⅓uent pu⅔iλication steps a⅔e ⅔e⅓ui⅔ed [ , ], a λact that is not needed in the supe⅔c⅔itical method, which p⅔oceeds with simple pu⅔iλication and sepa⅔ation oλ the bioλuel p⅔oduced and μene⅔ates a hiμh-pu⅔e μlyce⅔in [ , , ]. Ma⅔chetti & E⅔⅔azu [ ] evaluated diλλe⅔ent p⅔ocesses λo⅔ biodiesel p⅔oduction usinμ veμ‐ etable oils with hiμh content oλ λ⅔ee λatty acids, includinμ the supe⅔c⅔itical method and stated that the supe⅔c⅔itical method is an att⅔active alte⅔native λ⅔om a technoloμical point oλ view. “dditionally, λ⅔om the economic point oλ view, less wastewate⅔ is p⅔oduced and a hiμh ⅓uality μlyce⅔in is μene⅔ated as a byp⅔oduct, howeve⅔ hiμhe⅔ ene⅔μy is ⅔e⅓ui⅔ed by the ⅔eaction step. The ⅔eactivity in the supe⅔c⅔itical state is hiμhe⅔ than in the li⅓uid o⅔ μas, which λacilitates the t⅔anseste⅔iλication ⅔eaction [ ]. The supe⅔c⅔itical point oλ ethanol and methanol a⅔e K and . Mpa [ , ] and K and . Mpa [ ], ⅔espectively. The non-catalytic p⅔oduc‐ tion oλ biodiesel with supe⅔c⅔itical alcohol p⅔ovides hiμh ⅔eaction yields, since it p⅔omotes the simultaneous hyd⅔olysis and t⅔anseste⅔iλication oλ t⅔iμlyce⅔ides and este⅔iλication oλ λ⅔ee λatty acids p⅔esent in veμetable oil [ ]. The supe⅔c⅔itical method has the λollowinμ advantaμes ove⅔ othe⅔ methods used λo⅔ biodie‐ sel p⅔oduction [ ] a.

Catalyst is not used in the ⅔eaction and pu⅔iλication p⅔ocedu⅔es a⅔e much simple⅔, since the sepa⅔ation p⅔ocess oλ the catalyst and the saponiλied p⅔oduct is not ⅔e⅓ui⅔ed

b.

The supe⅔c⅔itical ⅔eaction ⅔e⅓ui⅔es sho⅔te⅔ ⅔eaction time than the t⅔aditional catalytic t⅔anseste⅔iλication and the conve⅔sion ⅔ate is hiμh. The catalytic t⅔anseste⅔iλication ⅔e‐ ⅓ui⅔es, in some cases, hou⅔s to ⅔each the ⅔eaction e⅓uilib⅔ium, while supe⅔c⅔itical meth‐ od only minutes

c.

Low ⅓uality subst⅔ates oλ can be used in the supe⅔c⅔itical method, since hiμh levels oλ λ⅔ee λatty acids and wate⅔ do not have a neμative eλλect on the ⅔eaction.

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The alcohol in the supe⅔c⅔itical state solves o⅔ ⅔educes the possible λo⅔mation oλ two phases to λo⅔m a sinμle homoμeneous phase, by dec⅔easinμ the dielect⅔ic constant oλ alcohol in the supe⅔c⅔itical state, which ⅔esults in inc⅔eased solubility oλ the oil [ ]. Ma & Hanna [ ] ⅔e‐ po⅔ted that the solubility oλ t⅔iμlyce⅔ides in methanol inc⅔eases at a ⅔ate oλ to % w/w oλ K inc⅔ease in tempe⅔atu⅔e. Some disadvantaμes oλ supe⅔c⅔itical method a⅔e neve⅔theless pointed out hiμh alcohol to oil ⅔atios a⅔e ⅔e⅓ui⅔ed in the o⅔de⅔ oλ , best ⅔esults a⅔e obtained at tempe⅔atu⅔es above K and hiμh p⅔essu⅔es, typically MPa, which leads to hiμh p⅔ocessinμ costs and ene⅔μy consumption. In addition, the ⅓uality oλ biodiesel may be comp⅔omised by the low stability oλ ce⅔tain λatty acid este⅔s exposed to the d⅔astic ⅔eaction conditions ⅔e⅓ui⅔ed. Thus, due to d⅔astic inc⅔ease in costs associated with the use oλ excess alcohol and e⅓uipment due to op‐ e⅔ation at hiμh tempe⅔atu⅔es and p⅔essu⅔es, imp⅔ovements to the supe⅔c⅔itical method λo⅔ p⅔oducinμ biodiesel a⅔e ⅔e⅓ui⅔ed [ ]. Kiwja⅔oun et al. [ ] investiμated the biodiesel p⅔oduction p⅔ocesses by supe⅔c⅔itical metha‐ nol combined with and alkaline catalyst and the impacts μene⅔ated by each p⅔ocess on the envi⅔onment, usinμ LC“ liλe cycle analysis as a tool. It was obse⅔ved by these ⅔esea⅔che⅔s that the supe⅔c⅔itical method is advantaμeous compa⅔ed to conventional method due to the less amount oλ wastewate⅔ μene⅔ated, howeve⅔, c⅔eates a hiμh impact on the envi⅔onment, mainly due to the la⅔μe amount oλ alcohol used in the p⅔ocess, emphasizinμ the need λo⅔ ⅔e‐ sea⅔ch ⅔eμa⅔dinμ the ⅔eduction in ope⅔atinμ conditions tempe⅔atu⅔e, p⅔essu⅔e and the amount oλ alcohol used in the p⅔ocess. Ma⅔ulanda [ ] evaluated the potential envi⅔onmen‐ tal impact assessment oλ the p⅔ocess λo⅔ biodiesel p⅔oduction by non-catalyst supe⅔c⅔itical method and conventional base-catalyzed p⅔ocess. The envi⅔onmental assessment ⅔esults in‐ dicated the supe⅔c⅔itical p⅔ocess, even when wo⅔kinμ at a mola⅔ ⅔atio, has a lowe⅔ im‐ pact than the conventional base-catalyzed p⅔ocess. . . Decomposition Du⅔inμ supe⅔c⅔itical t⅔anseste⅔iλication, the hiμh tempe⅔atu⅔es above lonμ ⅔eaction pe⅔iods, a dec⅔ease in the conve⅔sion can be obse⅔ved [ ,

,

K employed and - , ].

He et al. [ ] evaluated the ⅔esults obtained λo⅔ the t⅔anseste⅔iλication oλ soybean oil in supe⅔c⅔itical methanol and concluded that the ⅔eason λo⅔ the dec⅔ease in ⅔eaction yield is the dec⅔ease in the content oλ unsatu⅔ated este⅔s, caused by isome⅔ization, hyd⅔oμenation and the⅔mal decomposition that would consume such este⅔s, especially C linoleic and C linolenate . Imaha⅔a et al. [ ] evaluated the the⅔mal stability oλ diλλe⅔ent samples oλ biodiesel and λatty acid este⅔s in diλλe⅔ent conditions oλ tempe⅔atu⅔e and p⅔es‐ su⅔e. The autho⅔s λound that the⅔mal deμ⅔adation is mo⅔e p⅔onounced λo⅔ the unsatu⅔at‐ ed este⅔s above K and MPa and the⅔mal stability oλ satu⅔ated este⅔s is also aλλected. Kasim et al. [ ] ⅔epo⅔t that the pe⅔centaμe oλ t⅔ans isome⅔s can ⅔each levels up to % unde⅔ ce⅔tain ⅔eaction conditions MPa, K λo⅔ the t⅔anseste⅔iλication oλ ⅔ice b⅔an oil in methanol.

Non-Ca“aly“ic Prod”c“ion of E“hyl Es“ers Using S”percri“ical E“hanol in Con“in”o”s Mode h““p://dx.doi.org/10.5772/52013

“t the supe⅔c⅔itical ⅔eaction conditions, side ⅔eactions with the pa⅔ticipation oλ the μlyce⅔ol λo⅔med as byp⅔oduct can cause the deμ⅔adation oλ othe⅔ components p⅔esent in the ⅔eaction medium. Fo⅔ instance, “nistescu et al. [ ] pe⅔λo⅔med the alcoholysis ⅔eactions usinμ supe⅔c⅔itical methanol at tempe⅔atu⅔es a⅔ound K and ⅔epo⅔ted the absence oλ μlyce⅔ol in the ⅔eaction p⅔oducts, the autho⅔s coμitated that ⅔eaction oλ μlyce⅔ol with othe⅔ compounds may have occu⅔⅔ed. “ima⅔etti et al. [ ] evaluated the ⅔eaction oλ ⅔eλined soybean oil with supe⅔c⅔itical methanol at diλλe⅔ent ⅔eaction condi‐ tions and at the conditions studied by the autho⅔s, μlyce⅔ol was not λo⅔med. It is ⅔e‐ po⅔ted that μlyce⅔ol is conve⅔ted into lowe⅔ molecula⅔ weiμht p⅔oducts and wate⅔ at the beμinninμ oλ the ⅔eaction and that wate⅔ ⅔eacts with t⅔iμlyce⅔ide to λo⅔m λ⅔ee λatty acid, thus inc⅔easinμ the acidity oλ the p⅔oduct. In the cou⅔se oλ the ⅔eaction, these λat‐ ty acids a⅔e conve⅔ted into methyl este⅔s. “lso, the μlyce⅔ol may ⅔eact in diλλe⅔ent ways i decomposition to p⅔oduce p⅔oducts oλ lowe⅔ molecula⅔ weiμht, such as ac⅔o‐ lein, acetaldehyde, acetic acid, amonμ othe⅔s, ii polyme⅔ization to λo⅔m polyμlyce⅔ols, which occu⅔ at hiμh tempe⅔atu⅔e conditions and iii ethe⅔iλication with methanol to p⅔oduce ethe⅔s oλ μlyce⅔ol, thus consuminμ the alcohol in the ⅔eaction medium. Lee et al. [ ], in the synthesis oλ biodiesel λ⅔om waste canola oil, ⅔epo⅔ted that side ⅔eaction was obtained by ⅔eactinμ μlyce⅔ol and supe⅔c⅔itical methanol at K/ MPa λo⅔ , and minutes. The expe⅔imental ⅔esults showed that these ⅔eactions could posi‐ tively aλλect the ove⅔all biodiesel yield by p⅔ovidinμ oxyμenated compounds such as methoxy- , -p⅔opanediol, dimethoxymethane, and , -dimethoxyp⅔opane as well methyl palmitate and methyl oleate. In Vieitez et al. [ ] a novel and simple GC method was p⅔oposed to evaluate de pe⅔‐ centaμe oλ ove⅔all decomposition. Samples we⅔e t⅔eated with ”F /MeOH [ ] to de⅔iva‐ tize all oλ the λatty acids mono-, di-, and t⅔iμlyce⅔ides, λ⅔ee λatty acids, and also ethyl este⅔s to the co⅔⅔espondinμ methyl este⅔s, and then analyzed by GC. Fo⅔ the evalua‐ tion oλ the deμ⅔adation pe⅔centaμe, palmitic acid was assumed not liable to deμ⅔ada‐ tion, conside⅔inμ its hiμh stability, and was taken as ⅔eλe⅔ence as an inte⅔nal standa⅔d "native" . Thus, deμ⅔adation was estimated as Deθτmpτsitiτσ % =

×

−

∑ Pi P

S

×

P

∑ Pi

O

whe⅔e ΣPi was the summation oλ all λatty acid methyl este⅔ pe⅔centaμes, P was the pe⅔‐ centaμe oλ ethyl este⅔, and subsc⅔ipts s and o indicate that the exp⅔essions between b⅔ackets we⅔e evaluated conside⅔inμ the composition oλ the sample p⅔oduct and the o⅔iμinal oil, ⅔espectively [ ]. The use oλ the te⅔m "decomposition" oλ λatty acids ⅔eλe⅔⅔ed to the dec⅔ease in its pe⅔centaμe dete⅔mined by μas ch⅔omatoμ⅔aphy due to the λo⅔mation oλ othe⅔ compounds not neces‐ sa⅔ily imply that they have "b⅔oken" but have suλλe⅔ed some type oλ alte⅔ation . Since the⅔e is no inλo⅔mation about the dete⅔mination oλ this pa⅔amete⅔ type, the method desc⅔ibed be‐ low can be conside⅔ed a new cont⅔ibution to the a⅔ea oλ the synthesis oλ biodiesel in supe⅔‐ c⅔itical alcohols.

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. . Addition of co-solvent “ ⅓uestion to be conside⅔ed is the addition oλ co-solvents to the ⅔eaction medium that can p⅔ovide milde⅔ ope⅔ation conditions, since the use oλ co-solvents ⅔educes the limitations oλ mass t⅔ansλe⅔ between phases involved [ ] and inc⅔eases the ⅔eaction ⅔ate oλλe⅔inμ an ho‐ moμeneous ⅔eaction media [ , ]. “s co-solvents in supe⅔c⅔itical t⅔anseste⅔iλication it can be used non-pola⅔ comp⅔essed μases, λo⅔ example, ca⅔bon dioxide, methane, ethane, p⅔opane, n-butane and thei⅔ mixtu⅔es [ ]. Some studies have ⅔epo⅔ted the use oλ heptane/hexane as co-solvent [ - ]. “monμ these the use oλ CO at supe⅔c⅔itical conditions has shown a p⅔omisinμ λutu⅔e λo⅔ envi⅔onmentally λ⅔iendly chemical p⅔ocesses, because it comp⅔ises a nonλlammable solvent, nontoxic, inex‐ pensive and ⅔eadily available in hiμh pu⅔ity. Indeed, besides beinμ a μood solvent λo⅔ ext⅔ac‐ tion, ca⅔bon dioxide has also p⅔oved useλul as solvent ⅔eaction medium [ ]. Howeve⅔, a limitinμ λacto⅔ λo⅔ the use oλ ca⅔bon dioxide is low mutual solubility CO -t⅔iμlyce⅔ides, which means that hiμh p⅔essu⅔es a⅔e ⅔e⅓ui⅔ed to solubilize the ⅔eaμents [ ]. The use oλ p⅔opane and n-butane as comp⅔essed solvent o⅔ even in the supe⅔c⅔itical state seems to be a nice substitute λo⅔ a va⅔iety oλ solvent in ⅔eactive systems. These μases oλλe⅔ as the main advantaμe the low p⅔essu⅔e t⅔ansitions systems λound mainly in veμetable oils due to the hiμhe⅔ solubility exhibited compa⅔ed to that the use oλ CO [ , ]. Pe⅔eda et al. [ ] ⅔epo⅔ted that the use oλ p⅔opane in the hyd⅔oμenation oλ t⅔iμlyce⅔ides inc⅔eases the miscibil‐ ity oλ the components oλ the mixtu⅔e, allowinμ the ⅔eaction to occu⅔ unde⅔ conditions oλ a sinμle homoμeneous phase. Yin et al. [ ] ⅔epo⅔ted that este⅔s yield λo⅔ the ⅔eaction usinμ supe⅔c⅔itical methanol in‐ c⅔eased when usinμ ca⅔bon dioxide as cosolvent. Imaha⅔a et al. [ ], in the alcoholysis oλ canola oil in methanol with the addition oλ supe⅔c⅔itical CO , λound that the addition oλ cosolvent inc⅔eases the ⅔eaction yield, howeve⅔, hiμh mola⅔ pe⅔centaμe oλ CO above . CO / methanol led to a dec⅔ease in ⅔eaction conve⅔sion. . . Two-step reaction ”ased on the ⅔epo⅔ts available in the lite⅔atu⅔e it is suμμested that the t⅔anseste⅔iλication oλ veμetable oils at supe⅔c⅔itical conditions can be conducted on alte⅔native systems in o⅔de⅔ to ⅔educe ⅔aw mate⅔ial costs and ope⅔atinμ costs. The⅔e is a μ⅔owinμ emphasis on the p⅔oposed system with a two-step ⅔eaction usinμ ⅔eacto⅔s in se⅔ies, with hiμhe⅔ conve⅔sions to the sys‐ tem in one step [ ] at mild ope⅔atinμ tempe⅔atu⅔es and p⅔essu⅔es and dec⅔easinμ the amount oλ alcohol used in the p⅔ocess [ ]. Kusdiana & Saka [ ] and Minami & Saka [ ] p⅔oposed the continuous synthesis oλ bio‐ diesel λ⅔om canola oil in two ⅔eaction steps, which consists p⅔ima⅔ily in the hyd⅔olysis oλ t⅔iμlyce⅔ides in p⅔essu⅔ized wate⅔ and subse⅓uent este⅔iλication oλ λatty acids in supe⅔‐ c⅔itical methanol, with μlyce⅔ol ⅔emoved p⅔io⅔ to FF“ methyl este⅔iλication. This p⅔ocess is ca⅔⅔ied out unde⅔ mo⅔e mode⅔ate tempe⅔atu⅔e and p⅔essu⅔e compa⅔ed to the p⅔ocess in one step.

Non-Ca“aly“ic Prod”c“ion of E“hyl Es“ers Using S”percri“ical E“hanol in Con“in”o”s Mode h““p://dx.doi.org/10.5772/52013

”usto et al. [ ] ⅔epo⅔ted that tubula⅔ ⅔eacto⅔s λo⅔ supe⅔c⅔itical t⅔anseste⅔iλication must ope⅔ate in o⅔de⅔ to minimize the axial dispe⅔sion, and as suμμested by the autho⅔s, to satisλy this condition ⅔eactions in a tubula⅔ ⅔eacto⅔ with sepa⅔ation step oλ un⅔eacted p⅔oducts, with ⅔ecycle the same o⅔ two o⅔ mo⅔e ⅔eacto⅔s in se⅔ies with inte⅔mediate sepa‐ ⅔ation oλ μlyce⅔ol μene⅔ated. One advantaμe oλ ⅔emovinμ the μlyce⅔ol λo⅔med in the ⅔eac‐ tion mixtu⅔e is to allow the ⅔eaction to occu⅔ at lowe⅔ ⅔atios oλ alcohol to oil inc⅔easinμ the ⅔eaction ⅔ate λo⅔ the p⅔oduction oλ biodiesel [ ]. “s cited by “ima⅔etti et al. [ ], alonμ the ⅔eaction, the alcohol used in the p⅔ocess is ⅔e⅓ui⅔ed by seconda⅔y ⅔eactions, which occu⅔ with μlyce⅔ol. D'Ippolito et al. [ ] evaluated theo⅔etically the non-catalytic p⅔ocess λo⅔ p⅔oducinμ bio‐ diesel λ⅔om expe⅔imental data and inλo⅔mation available in the lite⅔atu⅔e to dete⅔mine an ope⅔atinμ mode and ope⅔atinμ conditions that ⅔educe ene⅔μy consumption and inc⅔ease p⅔oduct ⅓uality. Results obtained suμμest that the two-step p⅔ocess with inte⅔mediate ⅔e‐ moval oλ μlyce⅔ol dec⅔eases the ⅔atios oλ methanol to oil to about - times. Fu⅔the⅔‐ mo⅔e, not only the system p⅔essu⅔e can be ⅔educed as ene⅔μy costs. In the p⅔ocess p⅔oposed by C⅔awλo⅔d et al. [ ], it is suμμested that the obtained este⅔es by supe⅔c⅔iti‐ cal ⅔oute can be made by t⅔anseste⅔iλication oλ t⅔iμlyce⅔ides with continuous ⅔emoval oλ μlyce⅔ol λo⅔med in the p⅔ocess, pe⅔iodically o⅔ continuously, inc⅔easinμ the ⅔ate oλ este⅔ λo⅔mation. These autho⅔s a⅔μued that the ⅔eaction p⅔oceeded in this way can μ⅔eatly de‐ c⅔ease the amount oλ alcohol to be used in the p⅔ocess. . . Intensification technologies in continuous biodiesel production In the t⅔anseste⅔iλication oλ veμetable oils, ⅔eaction ⅔ate can be limited by mass t⅔ansλe⅔ be‐ tween oil and alcohol because the ve⅔y poo⅔ mutual miscibility. Hence, some p⅔ocess inten‐ siλication technoloμies have been developed and applied to imp⅔ove mixinμ and mass/heat t⅔ansλe⅔ between the two li⅓uid phases in ⅔ecent yea⅔s. Reaction ⅔ate is μ⅔eatly enhanced and thus ⅔esidence time may be ⅔educed. Some oλ the technoloμies have been applied successλul‐ ly in comme⅔cial p⅔oduction [ ]. To ⅔educe the limitations oλ mass and heat t⅔ansλe⅔ in chemical ⅔eactions, lite⅔atu⅔e indicates to conduct these ⅔eactions in mic⅔o⅔eacto⅔s [ ] and in packed bed ⅔eacto⅔s [ ]. In mic⅔o⅔eacto⅔s, mass and heat t⅔ansλe⅔ inc⅔ease due to the small size and la⅔μe contact a⅔ea [ ] and the lowest inte⅔nal diamete⅔s p⅔omote inte⅔action with the ⅔eaμents at the molecu‐ la⅔ level [ ]. The inte⅔nal diamete⅔ oλ mic⅔o⅔eacto⅔s, a⅔e typically m[ , ]. Sun et al. [ ] used ⅔eacto⅔s with . to . cm inne⅔ diamete⅔ and Guan et al. [ ] used ⅔eacto⅔s with diλλe⅔ent inne⅔ diamete⅔s . , . , . and . cm, callinμ them as mic⅔otube ⅔eacto⅔s. Fu⅔the⅔mo⅔e, hiμhe⅔ conve⅔sion and selectivity a⅔e obtained in a sho⅔te⅔ ⅔eaction time as compa⅔ed to batch system [ , ]. The ⅔ates oλ t⅔anseste⅔iλication λo⅔ biodiesel p⅔oduction a⅔e cont⅔olled by the ⅔ate oλ mass t⅔ansλe⅔ between phases [ ], beinμ applied hiμh ⅔ates oλ aμitation λo⅔ the batch system. Sun et al. [ ] studied the p⅔oduction oλ biodiesel usinμ alkaline catalysis with capilla⅔ies mic⅔o⅔eacto⅔s, and ⅔epo⅔ted that the ⅔esidence time is siμniλicantly ⅔e‐ duced by the use oλ these ⅔eacto⅔s compa⅔ed to the conventional p⅔ocess in batch

259

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

mode. Guan et al. [ ] investiμated the synthesis oλ biodiesel usinμ mic⅔otube ⅔eac‐ to⅔s λo⅔ the alcoholysis oλ sunλlowe⅔ oil by basic catalysis, evaluatinμ the inλluence oλ the lenμth and inte⅔nal diamete⅔ oλ the ⅔eacto⅔. The conve⅔sion oλ the oil was st⅔onμly inλluenced by ⅔eacto⅔ μeomet⅔y and the best ⅔esults we⅔e obtained λo⅔ the ⅔eacto⅔ with smalle⅔ diamete⅔ and μ⅔eate⅔ lenμth. “lthouμh the phenomenon ⅔elated to mass t⅔ansλe⅔ is a key pa⅔amete⅔ to obtain bette⅔ yields in biodiesel by the supe⅔c⅔itical method and one app⅔oach suitable is the use oλ packed bed ⅔eacto⅔. The packed bed system maximizes the inte⅔λacial su⅔λace a⅔ea between the two phases oil and alcohol and the contact oλ the immiscible li⅓uid-li⅓uid two phases a⅔e im‐ p⅔oved towa⅔ds achievinμ excellent mass t⅔ansλe⅔ pe⅔λo⅔mance, which is obtained by ex‐ t⅔udinμ one phase into anothe⅔, as the two phases λlow th⅔ouμh the pa⅔ticles openinμs, as commonly λound in a packed bed ⅔eacto⅔ [ , , ]. “taya et al. [ ] ⅔epo⅔ted the acid-catalyzed t⅔anseste⅔iλication oλ canola oil with metha‐ nol usinμ a packed bed ⅔eacto⅔ and showed that the mass-t⅔ansλe⅔ limitations λo⅔ twophase expe⅔iments can be eλλectively ove⅔come usinμ a li⅓uid-li⅓uid packed bed ⅔eacto⅔. Santacesa⅔ia et al. [ ] pe⅔λo⅔med the t⅔anseste⅔iλication ⅔eactions in a simple tubula⅔ ⅔e‐ acto⅔ λilled with stainless steel sphe⅔es oλ diλλe⅔ent sizes and obtained that the ⅔eactions like methanol soybean oil t⅔anseste⅔iλication, mass t⅔ansλe⅔ ⅔ate can μ⅔eatly be inc⅔eased also by λavo⅔inμ an intense local tu⅔bulence. The eλλects oλ packed bed ⅔eacto⅔ can be ob‐ se⅔ved in othe⅔ chemical ⅔eactions, λo⅔ instance, Su et al. [ ] evaluated the eλλect oλ packed mic⅔ochannel ⅔eacto⅔s to pe⅔λo⅔m the nit⅔ation oλ o-nit⅔otoluene with mixed acid and ⅔epo⅔ted that the yield oλ this li⅓uid-li⅓uid multiphase ⅔eaction is inc⅔eased by con‐ ductinμ the ⅔eaction usinμ the packed ⅔eacto⅔.

. Configuration of reactors in continuous mode for supercritical ethanolysis The λollowinμ sections a⅔e dedicated to p⅔ovide an ove⅔view oλ ⅔esults obtained in supe⅔c⅔it‐ ical ethanolysis in diλλe⅔ent ⅔eacto⅔ conλiμu⅔ations. The schematic diaμ⅔am oλ the expe⅔imen‐ tal setup, developed by ou⅔ ⅔esea⅔ch μ⅔oup, is shown in Fiμu⅔e . In these expe⅔iments, the ⅔esidence time was simply computed dividinμ the volume oλ the ⅔eacto⅔ mL by the λlow ⅔ate oλ subst⅔ates mL/min set in the li⅓uid pump. Results ⅔epo⅔ted a⅔e in ⅔elation to content oλ este⅔s in the sample dete⅔mined by μas ch⅔oma‐ toμ⅔aphy, λollowinμ the Eu⅔opean no⅔mative EN [ ]. The data ⅔elated to decomposi‐ tion ⅔eλe⅔ to de⅔ivatization oλ the samples with ”F /methanol [ ] to de⅔ivatize all oλ the λatty acids mono-, di-, and t⅔iμlyce⅔ydes, λ⅔ee λatty acids, and also ethyl este⅔s to the co⅔⅔espond‐ inμ methyl este⅔s and then analyzed by μas ch⅔omatoμ⅔aphy. Fo⅔ the evaluation oλ the de‐ composition pe⅔centaμe, palmitic acid was assumed not liable to deμ⅔adation, conside⅔inμ its hiμh stability [ , ]. These expe⅔imental p⅔ocedu⅔es as well as analytical methods used a⅔e desc⅔ibed in detail in the wo⅔k oλ Vieitez et al. [ ] and Silva et al. [ ].

Non-Ca“aly“ic Prod”c“ion of E“hyl Es“ers Using S”percri“ical E“hanol in Con“in”o”s Mode h““p://dx.doi.org/10.5772/52013

Figure 2. Schema“ic diagram of “he experimen“al appara“”s. RM - reac“ional mix“”re; MS - mechanical s“irring device; LP - high-press”re liq”id p”mp; CV - check-valve; A - solven“ reservoir; B - “hermos“a“ic ba“hs; SP - syringe p”mp; F f”rnace; R - reac“or; T1 - “empera“”re indica“or a“ “he reac“or inle“; T2 - “empera“”re indica“or a“ “he reac“or o”“le“; DA - da“a acq”isi“ion sys“em; CS - cooling sys“em; V1 - feed valve; PI - press”re indica“or; PIC - con“roller; V2 - press”re con“rol valve; S - glass collec“or; G - gas o”“p”“. Taken wi“h permission from Silva e“ al. [79].

. . Tubular reactor The tubula⅔ ⅔eacto⅔ utilized was made oλ stainless steel tubinμ L / in. OD inte⅔nal di‐ amete⅔ oλ . mm HIP , beinμ used in the wo⅔k oλ Silva et al. [ ], Vieitez et al. [ ], Vieitez et al. [ ], ”e⅔toldi et al. [ ], Vieitez et al. [ ], Vieitez et al. [ ], Vieitez et al. [ ], Silva et al. [ ], Vieitez et al. [ ] and Vieitez et al. [ ]. In these wo⅔ks, seve⅔al app⅔oaches we⅔e made in o⅔de⅔ to optimize t⅔anseste⅔iλication ⅔eactions λo⅔ biodiesel p⅔oduction in supe⅔c⅔iti‐ cal ethanol in continuous tubula⅔ ⅔eacto⅔ and the bette⅔ yields achieved λo⅔ each study a⅔e p⅔esented in Table . Silva et al. [ ] investiμated the eλλect oλ the va⅔iables tempe⅔atu⅔e, p⅔essu⅔e, oil to ethanol mo‐ la⅔ ⅔atio and ⅔esidence time on the yield oλ ethyl este⅔s in the t⅔anseste⅔iλication ⅔eaction oλ ⅔e‐ λined soybean oil. In that wo⅔k, it was obse⅔ved that an inc⅔ease in tempe⅔atu⅔e led to a sha⅔p enhancement oλ ⅔eaction conve⅔sions and λaste⅔ initial ⅔eaction ⅔ates. “lso, as ⅔eaction time de‐ velops, a decline in the conve⅔sion ⅔eaction was obse⅔ved λo⅔ the tempe⅔atu⅔e oλ K. The ⅔e‐ action p⅔essu⅔e had inλluence on the F“EE yields, with bette⅔ yields obtained at MPa. Reμa⅔dinμ the eλλect oλ oil to ethanol mola⅔ ⅔atio, ⅔esults obtained by that study demonst⅔ated that aλte⅔ a ce⅔tain pe⅔iod oλ time hiμhe⅔ values oλ mola⅔ ⅔atio oλ ethanol to oil aλλo⅔d bette⅔ con‐

261

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

ve⅔sions in sho⅔te⅔ ⅔eaction times. This λact could be expected to a ce⅔tain extent because in cat‐ alyst-λ⅔ee ⅔eactions an inc⅔ease in the alcohol-to-oil mola⅔ ⅔atio should p⅔ovide μ⅔eate⅔ contact between subst⅔ates, thus λavo⅔inμ ⅔eaction conve⅔sion. ”esides, an excess oλ ⅔eactant could also shiλt the ⅔eaction to ethyl este⅔s λo⅔mation. In the expe⅔imental ⅔anμe investiμated the autho⅔s ⅔epo⅔ted ~

% in ethyl este⅔s at the ope⅔atinμ conditions shown in Table .

Vegetable oil

Conditions and additional information

Refined

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa;

soybean oil

35 min

Refined

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa;

soybean oil

28 min and wa“er con“en“ of 2.5 w“%

Refined

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa;

soybean oil

28 min and wa“er con“en“ of 2.5 w“%

Refined

1:40 oil “o e“hanol molar ra“io; 573 K; 20 MPa;

soybean oil

52.5 min and wa“er con“en“ of 5 w“%

Deg”mmed

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa;

soybean oil

28 min and wa“er con“en“ of 10 w“%

Cas“or oil

1:40 oil “o e“hanol molar ra“io; 573 K; 20 MPa; 28 min and wa“er con“en“ of 5 w“%

S”nflower oil

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa; 42 min and wa“er con“en“ of 5 w“%

High oleic

1:40 oil “o e“hanol molar ra“io; 623 K; 20 MPa;

s”nflower oil

42 min and wa“er con“en“ of 5 w“%

Refined

1:40 oil “o e“hanol molar ra“io; 573 K; 20 MPa;

soybean oil

~48 min and addi“ion of 10% of free fa““y

FAEE yield

Decomposition

[%]

[%]

~80.0

NR

70.0

~ 14.0

70.0

~ 14.0

70.0

3.0

[7]

55.0

NR

[117]

75.0

~11.0

[58]

~69.0

~14.0

~75.0

minutes . In a late⅔ study, Vieitez et al. [ ] λocused on the dependence oλ este⅔s yield and decompo‐ sition as a λunction oλ veμetable oil composition Table . The ⅔esults obtained show a ⅔ela‐ tion between the composition oλ veμetable oil and content oλ este⅔s. Note that the content oλ este⅔s, ⅔eμa⅔dless oλ ⅔esidence time conside⅔ed, dec⅔eases in the λollowinμ o⅔de⅔ hiμh oleic sunλlowe⅔ oil> sunλlowe⅔ oil> soybean oil> casto⅔ oil. This o⅔de⅔, except by casto⅔ oil, is in‐ ve⅔sely with the deμ⅔ee oλ unsatu⅔ation oλ each oil, which conλi⅔ms that the eλλiciency oλ the p⅔ocess dependency oλ the stability oλ the oil used. The casto⅔ oil has a hiμh pe⅔centaμe oλ decomposition. This pe⅔centaμe inc⅔eases in the λollowinμ o⅔de⅔ λo⅔ the veμetable oils stud‐ ied hiμh oleic sunλlowe⅔ oil wate⅔.

Figure 11. Principle of biogas p”rifica“ion

373

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Usinμ two adso⅔ption towe⅔s λilled with the abso⅔bent desc⅔ibed above, concent⅔ated meth‐ ane with a low dew point can be seamlessly obtained by alte⅔nately ⅔epeatinμ the adso⅔p‐ tion and ⅔eμene⅔ation p⅔ocesses. . . . . Deviθe speθiλiθζtiτσs Fiμure i.

Ent⅔ance bioμas conditions .

Flow ⅔ate

.

P⅔essu⅔e

.

”ioμas composition

CH

%, CO

. Nm /h mm H O

%, wate⅔ satu⅔ated

T⅔ace ⅓uantities oλ inμ⅔edients e.μ., hyd⅔oμen sulλide and ammonia ii.

ppm o⅔ less

Exit p⅔oduct μas conditions .

Methane pu⅔ity at least

%

.

Methane collection ⅔ate at least

%

Figure 12. The adsorp“ive, isola“ed me“hane concen“ra“ing device

. . . . Chζrζθteristiθs τλ methζσe θτσθeσtrζtiτσ The abso⅔bent used λo⅔ methane concent⅔ation is a ca⅔bon molecula⅔ sieve CMS with a mic⅔opo⅔e diamete⅔ adjusted to be app⅔oximately . to . nm [ ]. Iλ it is used to sepa⅔ate ca⅔bon dioxide and methane, then the diλλe⅔ence in adso⅔ption ⅔ate is used instead oλ the diλλe⅔ence in e⅓uilib⅔ium adso⅔ption capacity. Table and Fiμu⅔e show the data λo⅔ the e⅓uilib⅔ium amount adso⅔bed and adso⅔ption ⅔ate cu⅔ve, ⅔espectively [ ]. “s Fiμu⅔e indicates, the amount oλ ca⅔bon dioxide ⅔eached % oλ the e⅓uilib⅔ium adso⅔ption capacity within one minute, while almost no methane was abso⅔bed. This p⅔inciple can be used to pe⅔λo⅔m adso⅔ption sepa⅔ation.

U“iliza“ion of Cr”de Glycerin from Biodiesel Prod”c“ion: A Field Tes“ of a Cr”de Glycerin Recycling Process h““p://dx.doi.org/10.5772/52171

Adsorp“ion amo”n“ (ml/g)

CO2

Me“hane

55.2

26.9

Table 1. Eq”ilibri”m adsorp“ion capaci“ies (”nder one a“mosphere press”re)

Figure 13. Adsorp“ion ra“e c”rves for carbon dioxide and me“hane

. . . Operζtiτσζl testiσμ λτr ηiτμζs .

Ove⅔view

Reλined bioμas can be eλλectively used as a λuel in vehicles and cookinμ appliances. In the plant, we ve⅔iλied the establishment oλ eλλective systems that allow bioμas to be used as a λuel in liμht ca⅔s λo⅔ λood sales, se⅔vice buμμy ca⅔s used within the campus and λo⅔ moto⅔cycles, as well as a λuel λo⅔ cookinμ in the caλete⅔ia and othe⅔ λacilities. Usinμ a λille⅔, we cha⅔μed app⅔oximately % bioμas ⅔eλined th⅔ouμh PS“ into a typical natu⅔al-μas liμht ca⅔, on-campus se⅔vice buμμy ca⅔s, moto⅔cycles e⅓uipped with a λuel caniste⅔ λilled with an abso⅔bent, and adso⅔ptive sto⅔aμe cylinde⅔s λo⅔ t⅔ansλe⅔ λilled with an abso⅔bent. The λillinμ e⅓uipment used cha⅔μes μas unde⅔ a low λillinμ p⅔essu⅔e oλ . MPa o⅔ less, and is not, the⅔eλo⅔e, ⅔est⅔icted by any laws o⅔ ⅔eμulations in Japan. “s methane vehicles, we used on-campus liμht minivans, on-campus adso⅔ptive se⅔vice buμμy ca⅔s, and adso⅔ptive moto⅔cycles. La⅔μe ⅓uantities oλ bioμas must be sto⅔ed unde⅔ a hiμh p⅔essu⅔e. This ⅔e⅓ui⅔es adhe⅔ence to the Hiμh P⅔essu⅔e Gas Saλety “ct and othe⅔ laws and

375

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

⅔eμulations, causinμ the unit p⅔ice oλ bioμas to ⅔ise. The system ve⅔iλied in this ⅔esea⅔ch p⅔oject eliminates the need to add⅔ess this matte⅔, p⅔ovidinμ saλe t⅔ansλe⅔ oλ la⅔μe volumes oλ bioμas. Fiμu⅔e shows the λlow cha⅔t λo⅔ ext⅔actinμ methane λ⅔om a methane adso⅔ptive sto⅔aμe tank λo⅔ use as a λuel in vehicles. Usinμ these systems, bioμas is expected to be able to be used in a wide⅔ ⅔anμe oλ applications, includinμ the consume⅔ seμment.

Figure 14. Flow char“ for “he ”se of biogas as a f”el in vehicles and cooking

.

Ove⅔views oλ the devices

[”ioμas λille⅔] Fiμu⅔e • Type Low-p⅔essu⅔e λillinμ e⅓uipment λo⅔ bioμas • Discha⅔μe λlow ⅔ate oλ the μas comp⅔esso⅔ . Nm /h o⅔ mo⅔e • Fillinμ p⅔essu⅔e .

MPa G o⅔ less

• Ent⅔ance bioμas composition Methane

%, CO

%

U“iliza“ion of Cr”de Glycerin from Biodiesel Prod”c“ion: A Field Tes“ of a Cr”de Glycerin Recycling Process h““p://dx.doi.org/10.5772/52171

Figure 15. The biogas filler

[Liμht minivan] Fiμu⅔e • Fuel tank • Sto⅔aμe p⅔essu⅔e .

MPa

• Sto⅔aμe capacity “pp⅔ox. . m • T⅔avel ⅔anμe km

Figure 16. A ligh“ minivan

[On-campus adso⅔ptive se⅔vice buμμy Fiμu⅔e • Fuel tank • Sto⅔aμe p⅔essu⅔e .

MPa

377

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

• Sto⅔aμe capacity . m • T⅔avel ⅔anμe km

Figure 17. An on-camp”s adsorp“ive service b”ggy

[“dso⅔ptive Moto⅔cycle] Fiμu⅔e • Fuel tank • Sto⅔aμe p⅔essu⅔e .

MPa

• Sto⅔aμe capacity m • T⅔avel ⅔anμe km

Figure 18. An adsorp“ive mo“orcycle

U“iliza“ion of Cr”de Glycerin from Biodiesel Prod”c“ion: A Field Tes“ of a Cr”de Glycerin Recycling Process h““p://dx.doi.org/10.5772/52171

. Conclusion . . Consideration of business sizes Vehicle

Vehicle

Motorcycle

Buggy

Biogas s“orage capaci“y [m3]

1

3.5

0.5

12.5

Mileage [km]

50

80

7

175

Mileage per day [km]

5

10

7

50

200

200

200

200

506

2212

2528

18057

9.74

42.6

48.7

348

Ann”al n”mber of opera“ion days [days] Req”ired mon“hly n”mber of cafe“eria ”sers [people] Ann”al disposal amo”n“ of glycerin [L]

(wi“hin “he premises) (o”“side “he premises)

Ann”al

BDF

170

744

850

6075

red”c“ion of CO2

Biogas

44.1

193

221

1577

emissions [kg]

To“al

214

937

1071

7651

Use

Delivery of mail, e“c.

Travel wi“hin “he premises

Ma“erial

Ma“erial

“ranspor“a“ion

“ranspor“a“ion

wi“hin “he premises from/“o “he premises

Table 2. U“iliza“ions of biogas and “heir effec“s on CO2 emissions red”c“ion

”ased on nume⅔ical values ⅔eμa⅔dinμ bioμas uses and utilizations λ⅔om p⅔oduct cataloμ data , we conside⅔ed the ⅔e⅓ui⅔ed business sizes. In the model, we used the numbe⅔ oλ use⅔s oλ the co-op caλete⅔ia and the amount oλ waste cookinμ oil μene⅔ated. The co-op caλete⅔ia oλ Osaka P⅔eλectu⅔e Unive⅔sity is used by , people pe⅔ month on ave⅔aμe and , lite⅔s oλ waste cookinμ oil a⅔e discha⅔μed annually. We conside⅔ed the amount oλ μlyce⅔in de⅔ived λ⅔om ”DF p⅔oduction to be one ⅓ua⅔te⅔ oλ the amount oλ waste cookinμ oil. Table summa⅔izes the uses and utilizations oλ the bioμas alonμ with thei⅔ eλλects on CO emissions ⅔eduction. ”ased on the data in the table, we estimated that the business model p⅔oposed by this ⅔esea⅔ch can be applied to any business place that has a dininμ λacility used by hund⅔eds oλ people a month. With inc⅔eases in the numbe⅔ oλ use⅔s, the λo⅔m oλ use and utilization develops iλ a business place has a dininμ λacility o⅔ λacilities used by mo⅔e than , people a month, then it is expected that the business can expand the use ⅔anμe to include the utilization oλ business vehicles.

379

380

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

”⅔azil, an excellent exempla⅔ λo⅔ biomass ene⅔μy powe⅔ μene⅔ation, has sta⅔ted to make eλ‐ λo⅔ts to ⅔educe λossil λuel use by blendinμ % ”DF into liμht oil, simila⅔ to the use oλ bioe‐ thanol in the past. The p⅔ocess p⅔oposed can be applied to all vehicles, includinμ natu⅔al-μas and diesel vehicles, as lonμ as they use an inte⅔nal combustion enμine. The la⅔μest challenμe is λuel sto⅔aμe. ”ecause μas chanμes volume with tempe⅔atu⅔e, it is impo⅔tant to inc⅔ease the amount oλ bioμas sto⅔ed pe⅔ unit volume. Ou⅔ pa⅔tne⅔, Osaka Gas Enμinee⅔inμ, owns lead‐ inμ-edμe technoloμy λo⅔ bioμas sto⅔aμe and its application, which is expected to popula⅔ize the business model. . . Future challenges ”elow a⅔e the λutu⅔e challenμes associated with business p⅔ojects that use bioμas as a λuel and othe⅔ uses .

Dec⅔easinμ the λuel p⅔ice pe⅔ unit heatinμ value to o⅔ below that oλ city μas In many cases, the use oλ bioμas as a λuel is compa⅔ed with the use oλ city μas in te⅔ms oλ cost because they exhibit simila⅔ p⅔ope⅔ties [ ]. The compa⅔ison, howeve⅔, no⅔mally indicates that bioμas has no clea⅔ advantaμe. On the othe⅔ hand, to achieve sustainable development, it is impo⅔tant to use bioμas a ⅔ecyclable, ca⅔bon-neut⅔al λuel. Fo⅔ this ⅔eason, it is necessa⅔y to μive a p⅔eλe⅔ential tax ⅔ate acco⅔dinμ to its use and implement a system that λacilitates subsidies λo⅔ e⅓uipment installation, λo⅔ example.

.

Developinμ a comp⅔ehensive plan cove⅔inμ the enti⅔e su⅔⅔oundinμ a⅔ea when const⅔uct‐ inμ a bioμas μene⅔ation λacility To use bioμas, a waste-de⅔ived λuel, at low cost, it is impe⅔ative that the ⅔aw mate⅔ial waste can be collected intensively and that local λacilities can use the μene⅔ated bioμas. This means that it is necessa⅔y to develop a comp⅔ehensive plan cove⅔inμ all neiμhbo⅔inμ a⅔eas when const⅔uctinμ a bioμas μene⅔ation λacility. ”ased on the cha⅔acte⅔istics oλ the unive⅔sity, this ⅔esea⅔ch cove⅔s all p⅔ocesses ⅔anμinμ λ⅔om the μene⅔ation oλ waste and the p⅔oduction oλ bioμas and ”DF to thei⅔ uses, so it may p⅔ovide an excellent case study λo⅔ developinμ a ⅔eμional plan.

.

Eliminatinμ ⅔est⅔ictions to the use oλ bioμas th⅔ouμh λuel t⅔ansλe⅔, based on an adso⅔ptive sto⅔aμe technoloμy Cu⅔⅔ently, the sewaμe plants in Osaka city use sludμe diμestion to dispose oλ sludμe. Fo⅔ the eλλective use oλ the bioμas μene⅔ated the⅔e, elect⅔ic powe⅔ μene⅔ation and many othe⅔ applications a⅔e beinμ conside⅔ed and implemented. On the othe⅔ hand, when sewaμe plants and othe⅔ λacilities make eλλective use oλ bioμas, that use is subject to many laws and ⅔eμulations e.μ., Hiμh P⅔essu⅔e Gas Saλety “ct, Gas ”usiness “ct, and ”uildinμ Standa⅔ds “ct , dependinμ on the installation site, and the⅔eλo⅔e is ⅔est⅔icted in some cases. Iλ elect⅔ic powe⅔ is μene⅔ated within the p⅔emises oλ a sewe⅔ plant, the μene⅔ation eλλiciency is lowe⅔ than that oλ la⅔μe elect⅔ic powe⅔ μene⅔ation

U“iliza“ion of Cr”de Glycerin from Biodiesel Prod”c“ion: A Field Tes“ of a Cr”de Glycerin Recycling Process h““p://dx.doi.org/10.5772/52171

λacilities, and the location whe⅔e the collected hot wate⅔ should be used must be consid‐ e⅔ed. The bioμas t⅔ansλe⅔ system based on the adso⅔ptive sto⅔aμe techni⅓ue is an eλλective solution to these p⅔oblems. Examples oλ useλul applications may include a sewe⅔ plant o⅔ a methane λe⅔mentation λacility that cannot make eλλective use oλ bioμas because it is located in a non-indust⅔ial a⅔ea bioμas μene⅔ated the⅔e can be t⅔ansλe⅔⅔ed to a la⅔μe elect⅔ic powe⅔ μene⅔ation λacility usinμ an adso⅔ptive sto⅔aμe tank installed in an ISO-deλined containe⅔ λo⅔ use as a λuel. In this case, the use oλ bioμas is not subject to the va⅔ious laws and ⅔eμulations and it is possible to saλely t⅔ansλe⅔ la⅔μe volumes oλ bioμas. ”ioμas has simila⅔ p⅔ope⅔ties to natu⅔al μas and can be used at powe⅔ plants and othe⅔ λacilities that use natu⅔al μas as λuel. The⅔eλo⅔e, its use is expected to μ⅔ow.

Acknowledgements This ⅔esea⅔ch was conducted with the conside⅔able help oλ P⅔oλesso⅔ Taketoshi Okuno, P⅔esident oλ Osaka P⅔eλectu⅔e Unive⅔sity, and P⅔oλesso⅔ Masakazu “mpo, Vice-P⅔esident oλ the unive⅔sity. In addition, the ⅔esea⅔ch was subsidized by Osaka City as a p⅔oject to help ve⅔iλy the p⅔acticality oλ envi⅔onmental and ene⅔μy-⅔elated technoloμies. We would like to exp⅔ess ou⅔ hea⅔t-λelt thanks to all oλ the above.

Author details Hayato Tokumoto *, Hi⅔oshi ”andow , Kensuke Ku⅔ahashi and Takahiko Wakamatsu *“dd⅔ess all co⅔⅔espondence to tokumoto@chemenμ.osakaλu-u.ac.jp Depa⅔tment oλ Chemical Enμinee⅔inμ, Osaka P⅔eλectu⅔e Unive⅔sity, Gakuen-cho, Sakai, Osaka, Japan Osaka P⅔eλectu⅔e Unive⅔sity Colleμe oλ Technoloμy, Saiwai, Neyaμawa, Osaka, Japan Ene⅔μy and Envi⅔onment ”usiness Div, Ene⅔μy ”usiness and Enμinee⅔inμ Dept, Osaka Gas Enμinee⅔inμ Co., Ltd., Japan

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U“iliza“ion of Cr”de Glycerin from Biodiesel Prod”c“ion: A Field Tes“ of a Cr”de Glycerin Recycling Process h““p://dx.doi.org/10.5772/52171

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] Patte⅔son T, Esteves S, Dinsdale R, Guwy “. “n evaluation oλ the policy and technoeconomic λacto⅔ aλλectinμ the potential λo⅔ bioμas upμ⅔adinμ λo⅔ t⅔anspo⅔t λuel use in the UK. Ene⅔μy Policy -

th Ed. . New

383

Section 4

Biodiesel Applications in Engines

Chapter 14

Application of Biodiesel in Automotive Diesel Engines Yanfei Li, G”ohong Tian and Hongming X” Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/ 53222

. Introduction . . background Diesel enμines due to the bette⅔ λuel economy have been widely used in automotive a⅔ea. Howeve⅔, the limited ⅔ese⅔ve oλ λossil λuel and dete⅔io⅔atinμ envi⅔onment have made scien‐ tists seek to alte⅔native λuels λo⅔ diesel while keepinμ the hiμh eλλiciency oλ diesel enμine. Fuel consumption is expected to inc⅔ease λ⅔om million ba⅔⅔els pe⅔ day to million ba⅔‐ ⅔els pe⅔ day by acco⅔dinμ to the ⅔epo⅔t published by US Ene⅔μy Inλo⅔mation “dminis‐ t⅔ation in [ ]. The limited ⅔ese⅔ve cannot aλλo⅔d this usaμe. “nothe⅔ challenμe is envi⅔onmental dete⅔io⅔ation and climate chanμe. Excessive emissions oλ ca⅔bon dioxide CO to the atmosphe⅔e a⅔e ⅔eμa⅔ded as the leadinμ cause oλ μlobal wa⅔minμ. In addition, othe⅔ emissions, such as NOx, SO , also have a close ⅔elationship with othe⅔ λo⅔ms oλ climate chanμe, such as photochemical smoμ and acid ⅔ain. Due to these, the ⅔eμulations on λuel economy and emission limits a⅔e inc⅔easinμly st⅔inμent. Table shows the EU emissions ⅔eμulations λo⅔ passenμe⅔ ca⅔s came into λo⅔ce since . Tier

Date

E”ro 1†

J”l-92

2.72 (3.16)

-

-

-

0.97 (1.13)

0.14 (0.18)

E”ro 2

Jan-96

1

-

-

-

0.7

0.08

E”ro 3

Jan-00

0.64

-

-

0.5

0.56

0.05

E”ro 4

Jan-05

0.5

-

-

0.25

0.3

0.025

E”ro 5

Sep-09

0.5

-

-

0.18

0.23

0.005

Sep-14

0.5

-

-

0.08

0.17

0.005

E”ro 6 (f”“”re)

HC+NOx

Table 1. E”ropean emissions reg”la“ions for passenger cars (Ca“egory M*), g/km

388

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Howeve⅔, it is not a lonμ-te⅔m solution even thouμh these measu⅔es can help alleviate o⅔ ⅔e‐ duce the emissions and extend the liλetime oλ λossil λuel in indust⅔y, because one day λossil λuel would ⅔un out iλ the λuel consumption is kept at nowadays ⅔ate. In addition, the de‐ c⅔ease in λossil λuel ⅔ese⅔ve would lead to the inc⅔ease oλ oil p⅔ice. The ⅔isinμ λuel p⅔ice ⅔aised the cost-competiveness oλ othe⅔ ene⅔μy sou⅔ces, such as wind ene⅔μy and sola⅔ ene⅔‐ μy. Hence some secto⅔s, such as indust⅔ial and buildinμs, a⅔e d⅔iven towa⅔ds othe⅔ substi‐ tute ene⅔μy sou⅔ces when possible, whe⅔eas in t⅔anspo⅔tation secto⅔, li⅓uid λuel is still the p⅔eλe⅔⅔ed choice. Conse⅓uently, the t⅔anspo⅔tation sha⅔e oλ the total li⅓uid λuels inc⅔eases in the p⅔ojected pe⅔iod, accountinμ λo⅔ % oλ the total inc⅔ease in li⅓uid λuel p⅔oduction [ ]. The⅔eλo⅔e, the eλλo⅔ts have been made to seek the alte⅔native λo⅔ λossil λuel, especially aλte⅔ the ene⅔μy c⅔isis in s. People a⅔e t⅔yinμ to λind a sustainable way to powe⅔ the enμines. . . Biodiesel “monμ the alte⅔natives λo⅔ λossil diesel, biodiesel has been widely investiμated due to its ⅔enewability, compa⅔able p⅔ope⅔ties to λossil diesel and the ⅔eduction in main emission p⅔oducts. ”iodiesel is mainly comp⅔ised oλ mono-alkyl este⅔s oλ lonμ chain λatty acids and it was de‐ λined in standa⅔d “STM D . No⅔mally λeedstock such as veμetable oil and animal λat is used to p⅔oduce biodiesel th⅔ouμh t⅔anseste⅔iλication method. With the on-μoinμ development oλ biodiesel, the cateμo⅔ization oλ biodiesel is developed. Gene⅔ally biodiesel can be cateμo⅔ised by the ⅔eadiness oλ λeedstock and p⅔oduce technolo‐ μies. The biodiesel made λ⅔om veμetable oil and animal λats usinμ t⅔anseste⅔iλication method is no⅔mally ⅔ecoμnised as λi⅔st-μene⅔ation biodiesel. The second-μene⅔ation biodiesel, ”io‐ mass to li⅓uid ”TL λuel is to tu⅔n cellulose into λuel components enzyme λe⅔mentation o⅔ μasiλication th⅔ouμh Fische⅔-T⅔opsch synthesis , and the λeedstock theo⅔etically can be any bio mass such as waste aμ⅔icultu⅔e, wood chips etc. Some biodiesel λ⅔om jat⅔opha, alμae, etc., despite beinμ p⅔oduced by t⅔anseste⅔iλication method, is widely ⅔eμa⅔ded as secondμene⅔ation due to the technical challenμe oλ λeedstock plantinμ and ha⅔vestinμ. No⅔mally the second-μene⅔ation biodiesel can supplement the d⅔awbacks oλ the λi⅔st-μene⅔ation bio‐ diesel pa⅔ticula⅔ly beinμ non-competitive with λood. Diλλe⅔ent λ⅔om above deλinition, anothe⅔ new λuel, Hyd⅔o-t⅔eated veμetable oil HVO , usinμ the same λeedstock as st μene⅔ation biodiesel, is viewed as second μene⅔ation biodiesel, and ”TL is thi⅔d-μene⅔ation [ ]. The autho⅔s still cateμo⅔ize it into second-μene⅔ation biodiesel because HVO sha⅔es the same λeedstock with λi⅔st-μene⅔ation biodiesel even thouμh it is made th⅔ouμh diλλe⅔ent way and has bette⅔ ⅓uality than λi⅔st-μene⅔ation biodiesel th⅔ouμh t⅔anseste⅔iλication. . . . Histτry Veμetable oil has been used in diesel enμine lonμ time aμo. In aλte⅔ the invention oλ die‐ sel enμine, , D⅔. Diesel used peanut oil to ⅔un one oλ his enμines at the Pa⅔is Exposition oλ . Veμetable oils we⅔e used in diesel enμines until s. The ⅔ecent use oλ veμetable oil

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

as the alte⅔native λo⅔ diesel sta⅔ts λ⅔om ea⅔ly s due to the conce⅔n about the ene⅔μy sup‐ ply. ”ut biodiesel is not comme⅔cialised until late s.Fo⅔ the di⅔ect use oλ veμetable oil, seve⅔al diλλiculties occu⅔, includinμ the hiμh viscosity, acid composition, λ⅔ee λatty acid con‐ tent, and μum λo⅔mation due to oxidation and polyme⅔ization du⅔inμ sto⅔aμe and combus‐ tion, ca⅔bon deposition, and oil thickeninμ Ma and Hana, . The⅔eλo⅔e, the di⅔ect use oλ veμetable oil may not be satisλacto⅔y and p⅔actical. The technoloμies to imp⅔ove the veμeta‐ ble oil appea⅔ed. . . . Prτduθtiτσ prτθess The⅔e a⅔e seve⅔al ways used to p⅔oduce F“ME th⅔ouμh veμetable oil, py⅔olysis, c⅔ackinμ and t⅔anseste⅔iλication. The common method is t⅔anseste⅔iλication. Fiμu⅔e shows the chem‐ ical ⅔eaction oλ F“ME p⅔oduction. T⅔iμlyce⅔ides, the main component in veμetable oil and animal λat, ⅔eacts with alcohol in a caustic envi⅔onment and p⅔oduce Fatty “cid Methyl Es‐ te⅔ F“ME o⅔ Fatty “cid Ethyl Este⅔ F“EE and the byp⅔oduct μlyce⅔ol. “s a ⅔esult, biodie‐ sel is a mixtu⅔e oλ este⅔s, small amount oλ μlyce⅔ol, λ⅔ee λatty acids, pa⅔tially ⅔eacted acylμlyce⅔ol, and ⅔esidual ⅔aw mate⅔ials. No⅔mally methanol is used λo⅔ the ⅔eaction λo⅔ the hiμhe⅔ ⅔eaction ⅔ate and lowe⅔ p⅔ice. The λuel ⅓ualities may be va⅔ied in te⅔ms oλ alcohol used. Methyl este⅔ was bette⅔ than ethyl este⅔ λ⅔om the point oλ enμine pe⅔λo⅔mance hiμhe⅔ powe⅔ and to⅔⅓ue could be achieved.

Figure 1. Transes“erifica“ion reac“ion in ca”s“ic environmen“

Diλλe⅔ent λ⅔om t⅔anseste⅔iλication, Hyd⅔o-t⅔eatinμ oλ veμetable oil o⅔ animal λat HVO have been developed by seve⅔al companies, such as Neste Oil, “xens IFP, and Honeywell UOP. In the hyd⅔o-t⅔eatinμ p⅔ocess, veμetable oil o⅔ animal λat is also the λeedstock. Hyd⅔oμen is added into the plant to ⅔emove the oxyμen content and satu⅔ate the C=C and the λinal p⅔od‐ ucts a⅔e pa⅔aλλin, p⅔opane, wate⅔ and CO . P⅔opane is also a p⅔omisinμ and valuable λuel p⅔oduct. Due to the excellent p⅔ope⅔ties,

Figure 2. Prod”c“ ro”“es of “ranses“erifica“ion and hydro-“rea“ed me“hod

389

390

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Fische⅔-T⅔opsch FT method is anothe⅔ way to p⅔oduce synthetic λuel, usinμ va⅔ious liμno‐ cellulosic λeedstock. ”TL biomass-mass-to-li⅓uid λuel, GTL Gas-to-li⅓uid λuel, and CTL Coal-to-li⅓uid λuel a⅔e p⅔oduced with this method. GTL and ”TL a⅔e not sustainable λuels λo⅔ natu⅔al μas and coal a⅔e not ⅔enewable. Howeve⅔, in this chapte⅔ GTL is included late⅔ because it sha⅔es the simila⅔ p⅔oduction p⅔ocess and has simila⅔ physiochemical p⅔ope⅔ties with ”TL. Fiμu⅔e shows the manuλactu⅔inμ p⅔ocess oλ FT synthetic λuel. The solid λeed‐ stock coal and biomass a⅔e initially μasiλied, then the composition oλ the synμas and CO and sulphu⅔ compounds a⅔e ⅔emoved beλo⅔e the synthesis p⅔ocess. “λte⅔ the synthesis p⅔oc‐ ess, the p⅔oducts a⅔e ⅔eλined and the ⅔eλined p⅔oducts includes the synthetic diesel and μaso‐ line blendstock.

Figure 3. FT f”el man”fac“”ring process

. . Biodiesel standards Due to the diλλe⅔ence in the λeedstock and manuλactu⅔inμ p⅔ocess, the F“ME p⅔oducts may va⅔y ve⅔y much. Table lists seve⅔al main standa⅔ds used in the wo⅔ld, aiminμ at ⅔each the satisλaction and the e⅓uipment compatibility. Austrian Bio-Diesel

Unit

Standard C1190 Feb. 91

Densi“y a“ 15°C Viscosi“y a“ 40°C Flash poin“

g/cm3 mm2/s

0.86 - 0.90 6.5 - 9.0 (20°C)

°C

Min. 55

(°F)

-131

Australian Biodiesel Standard

DIN 51606 (1997/9/1)

U.S. Quality Specification NBB/ASTM

Euro Standard EN 14214

0.86 – 0.89

0.875 - 0.90

/

0.86 - 0.90

3.5 – 5.0

3.5 - 5.0

1.9 - 6.0

3.50 - 5.00

Min. 110

Min. 100

Min. 120

-230

-212

-248

120.0°C

°C (°F) CFPP

s”mmer win“er

To“al s”lph”r Conradson (CCR) a“ 100% a“ 10%

mg/kg % mass

Max. 0 (32) / Max. -8

Max. 0 (32)

/

Max. -20 (-4)

(17.6) Max. 200

Max. 50 mg/kg Max. 100

Max. 500

Max. 0.1

Max 0.05

Max. 0.05

Max. 0.05

Max. 10.0 /

/

Max 0.30

/

/

Max. 0.30

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

Ce“ane n”mber

-

S”lfa“ed ash con“en“ % mass

Min. 48

Min. 51

Min. 49

Min. 40

Min. 51

Max. 0.02

Max. 0.02

Max. 0.03

Max. 0.02

Max. 0.02

Max. 300

/

Max. 500

free of Wa“er con“en“

mg/kg

deposi“ed wa“er

Wa“er & sedimen“

vol. %

/

Max. 0.05

/

Max. 0.05

/

To“al con“amina“ion

mg/kg

/

Max. 24

Max. 20

/

Max. 24

Copper corrosion ( 3

degree of

hs, 50°C)

Corrosion

1

No. 3b max.

1

Ne”“ralisa“ion val”e

mg

Max. 0.5

Max. 0.8

Max. 0.50

< 10mg/kg s”lph”r – 1

/

"/ 10mg/kg s”lph”r – 3 max

Max. 1

/

Oxida“ion s“abili“y

h

/

Min 6 @ 110°C /

/

Min. 6.0

Me“hanol con“en“

% mass

Max. 0.30

0.2

Max. 0.3

Max. 0.2

Max. 0.20

Es“er con“en“

% mass

/

Min 96.5

/

/

Min 96.5

Monoglycerides

% mass

/

/

Max. 0.8

/

Max. 0.80

Diglycerides

% mass

/

/

Max. 0.4

/

Max. 0.20

Triglycerides

% mass

/

/

Max. 0.4

/

Max. 0.20

Free glycerine

% mass

Max. 0.03

Max. 0.02

Max. 0.02

Max. 0.02

Max. 0.02

To“al glycerine

% mass

Max. 0.25

Max. 0.25

Max. 0.25

Max. 0.24

Max. 0.25

/

/

Max. 115

/

Max. 120

% mass

/

/

/

/

Max. 12.0

% mass

/

/

/

/

Max. 1

mg/kg

/

Max. 10

Max. 10

/

Max. 10.0

mg/kg

/

/

Max. 5

/

Max. 5.0

mg/kg

/

/

/

/

Max. 5.0

Iodine val”e Linolenic acid ME Poly”nsa“”ra“ed ("/ =4db) Phosphor”s con“en“ Alkaline con“en“ (Na +K) Alkaline ear“h me“als (Ca + Mg)

Table 2. Biodiesel S“andards

. . Pros and Cons The λollowinμ summa⅔ised the advantaμes oλ biodiesel • Renewable ene⅔μy sou⅔ce in compa⅔ison with t⅔aditional λossil λuel • Deμ⅔adability • Much less sulphu⅔, leadinμ to lowe⅔ toxic substances in the exhaust • “bsence oλ P“Hs and a⅔ound • Va⅔ious λeedstock

% oλ oxyμen help the ⅔eduction oλ HC and CO

391

392

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

The use oλ bio-diesel λuels cannot occu⅔ without adoptinμ a se⅔ies oλ p⅔ecautions. Indeed, unless the p⅔ope⅔ p⅔ecautions a⅔e taken, biodiesel λuels can cause a va⅔iety oλ enμine pe⅔‐ λo⅔mance p⅔oblems includinμ λilte⅔ pluμμinμ, injecto⅔ cokinμ, piston ⅔inμ stickinμ and b⅔eak‐ inμ, seal swellinμ and ha⅔deninμ/c⅔ackinμ and seve⅔e lub⅔icant deμ⅔adation. ”io-diesel also ⅔e⅓ui⅔es special t⅔eatment at low tempe⅔atu⅔es to avoid an excessive ⅔ise in viscosity and loss oλ λluidity. Lonμ-te⅔m sto⅔aμe p⅔oblems can be obse⅔ved as ⅔esult oλ the poo⅔ oxidation stability oλ bio‐ diesel λuels. Thus additives may be needed to imp⅔ove sto⅔aμe conditions. Fu⅔the⅔mo⅔e, bio‐ diesel is an excellent medium λo⅔ mic⅔obial μ⅔owth. “s wate⅔ accele⅔ates mic⅔obial μ⅔owth and is mo⅔e p⅔evalent in biodiesel than in pet⅔oleum based λuels, special ca⅔e must be taken to ⅔emove wate⅔ λ⅔om λuel sto⅔aμe tanks to avoid ope⅔ational p⅔oblems such as sediment build-up, p⅔ematu⅔e λilte⅔ pluμμinμ o⅔ sto⅔aμe tank co⅔⅔osion. . . Security of supply “nothe⅔ ⅔eason λo⅔ the sea⅔ch oλ alte⅔native λuel is the ene⅔μy secu⅔ity. The economical μ⅔owth can p⅔omote the demand λo⅔ ene⅔μy. Table listed c⅔ude oil ⅔eliance on impo⅔ted oil oλ US and China. The ⅔eliance oλ the two count⅔ies a⅔e up to . % and . %, ⅔espectively. The ene⅔μy supply can be well alleviated iλ biodiesel can be p⅔oduced and used in comme⅔‐ cial scale. Fu⅔the⅔ analyses a⅔e needed to unde⅔stand the λuel diλλe⅔ence and can help λuel desiμn du⅔inμ the biodiesel p⅔oduction p⅔ocess. The Commission G⅔een Pape⅔ CEC, ⅔epo⅔ted an ambitious EU p⅔oμ⅔amme on the usaμe oλ biodiesel that % alte⅔native λuel substitution by in conventional λuel in the ⅔oad t⅔anspo⅔t secto⅔ is set. On anothe⅔ hand, the utilisation oλ biodiesel leads to conce⅔ns oλ land use, deλo⅔estation and neμative eλλect on bio-dive⅔sity needs λu⅔the⅔ explo⅔ation. Year 2007

Year 2008

Year 2009

Year 2010

US1

58.2%

57.0%

51.5%

49.2%

Year 2011 44.8%

China

47.2%

49.8%

52%

54.8%

56.5%

Table 3. 1 US Depar“men“ of Energy, Energy Informa“ion Adminis“ra“ion, Mon“hly Energy Review, Washing“on, DC, March 2012, Table 3.3aCr”de oil reliance of US and China from 2007 - 2011

. Fuel properties . . Fuel composition Due to the va⅔ious λeedstocks λo⅔ biodiesel, the λuel composition va⅔ies in a wide ⅔anμe. Gene⅔ally the λats and oils contain common types oλ λatty acid consistinμ oλ - to ca⅔bon chain, and ove⅔ % a⅔e between - and -ca⅔bon chains [ ]. Table shows the composition oλ some common F“ME. Some oλ these a⅔e satu⅔ated, some a⅔e monounsatu‐ ⅔ated and othe⅔s a⅔e poly-unsatu⅔ated. The composition oλ biodiesel dete⅔mined the chem‐ ical and physical p⅔ope⅔ties, such as the λuel viscosity, su⅔λace tension, cetane numbe⅔ CN ,

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

oxidation stability, low-tempe⅔atu⅔e p⅔ope⅔ties, as well as the λollowinμ combustion and emission cha⅔acte⅔istics. . . Viscosity Viscosity is a measu⅔e oλ ⅔esistance to λlow oλ a li⅓uid due to inte⅔nal λ⅔iction and it is one oλ the most impo⅔tant pa⅔amete⅔s in evaluate the λuel ⅓uality. Viscosity aλλects enμine wo⅔kinμ p⅔ocess ve⅔y much. Hiμhe⅔ viscosity would p⅔ohibit atomisation and instability oλ λuel d⅔op‐ lets, and p⅔omote the λo⅔mation oλ deposit. This also explains why neat veμetable oils have diλλiculty when used in diesel enμines di⅔ectly. The viscosity can be measu⅔ed acco⅔dinμ to the standa⅔ds such as “STM D o⅔ ISO . The viscosity oλ individual satu⅔ated λatty acid este⅔ inc⅔eases with ca⅔bon chain lenμth and non-linea⅔ly dec⅔eases with the inc⅔ease oλ numbe⅔ oλ double bonds [ ]. In addition, the position oλ C=C double bond and the b⅔anch‐ inμ in the este⅔ moiety has less eλλect on viscosity. ”iodiesel has a hiμhe⅔ viscosity than λossil diesel. “t lowe⅔ blend ⅔atio, the viscosities oλ diesel and biodiesel/diesel blend a⅔e ve⅔y close. “s the blend ⅔atio continues to inc⅔ease, biodiesels show a much hiμhe⅔ value. This can pa⅔tly explain why biodiesel/diesel blends with lowe⅔ blend ⅔atio a⅔e widely used in diesel enμines.

h““p://www.dieselne“.com/“ech/f”el_biodiesel_app.h“ml Table 4. Composi“ion of common FAME.

. . Cetane number CN CN is used to evaluate λuel iμnition ⅓uality dete⅔mined by the time between sta⅔t oλ injec‐ tion and sta⅔t oλ combustion. Hiμhe⅔ CN indicates sho⅔te⅔ time aλte⅔ the injection. CN is mainly dete⅔mined by the λuel composition and can aλλect enμine sta⅔tability, noise and

393

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

emission cha⅔acte⅔istics. Gene⅔ally, biodiesel has a hiμhe⅔ CN than mine⅔al diesel. This can be att⅔ibuted to the lonμe⅔ ca⅔bon chain lenμth oλ biodiesel. Unsatu⅔ation and ca⅔bon chain lenμth a⅔e the most two inλluential λacto⅔s oλ CN [ , , ]. Hiμhe⅔ satu⅔ation deμ⅔ee and lonμe⅔ λatty acid chain lenμth can lead to a lowe⅔ CN. The positions oλ chemical μ⅔oup may also inλluence the CN. The CNis the hiμhest when the ca⅔bonyl μ⅔oup is at the end oλ the ca⅔bon chain and lowest in the middle oλ the ca⅔bon chain. In addition, a hiμhe⅔ level oλ hy‐ d⅔ope⅔oxides inc⅔eases CN and a sho⅔te⅔ chain lenμth oλ the alcohol moiety may also in‐ c⅔ease CN [ , ]. . . Low-temperature property Diesel enμines may encounte⅔ the sta⅔t-up and pe⅔λo⅔mance p⅔oblems at low tempe⅔atu⅔es. “s ambient tempe⅔atu⅔es dec⅔ease towa⅔ds the λuel satu⅔ation tempe⅔atu⅔e, hiμh-molecula⅔weiμht compound beμin to nucleate and λo⅔m was c⅔ystals. The existence oλ was c⅔ystals may aλλect the λuel supply and enμine pe⅔λo⅔mance. Th⅔ee pa⅔amete⅔s, cloud point CP , pou⅔ point PP , and cold λilte⅔ pluμμinμ point CFPP a⅔e used to desc⅔ibe low-tempe⅔atu⅔e p⅔ope⅔ties. The tempe⅔atu⅔e at which c⅔ystals become visible is called CP because the c⅔ys‐ tals lead to a cloudy suspension. iλ the tempe⅔atu⅔e continues to dec⅔ease, the c⅔ystals would λuse toμethe⅔ and λo⅔m la⅔μe⅔ aμμlome⅔ates. The tempe⅔atu⅔e at which c⅔ystal aμμlome⅔a‐ tion is la⅔μe enouμh to p⅔event λ⅔ee pou⅔inμ oλ λluid is called PP. “ mo⅔e complicated test p⅔ocedu⅔e is involved in o⅔de⅔ to obtain CFPP. The test uses a vacuum to d⅔aw a cc λuel sample th⅔ouμh a mic⅔on sc⅔een within a seconds. The lowest tempe⅔atu⅔e that the λuel can still λlow th⅔ouμh the λilte⅔ is called CFPP. This is an ve⅔y conce⅔ninμ issue in application oλ biodiesel into diesel enμines. Neat biodie‐ sel has poo⅔e⅔ low-tempe⅔atu⅔e pe⅔λo⅔mance than conventional diesel. The⅔eλo⅔e, when bio‐ diesel is used in cold condition, the biodiesel c⅔ystaλdl may block the λuel pipe and the λuel λilte⅔, and even ab⅔ade the hiμh-p⅔essu⅔e λuel pump, sho⅔tinμ the liλetime oλ vehicle enμines. Resea⅔ch has shown that the cold λlow p⅔ope⅔ty is associated with the satu⅔ated F“ME in veμetable oil based biodiesel. The hiμhe⅔ the p⅔opo⅔tion oλ satu⅔ated F“ME and the lonμe⅔ chain F“ME in satu⅔ated F“ME, the poo⅔e⅔ the cold tempe⅔atu⅔e pe⅔λo⅔mance is [ ]. Gene⅔ally, the low-tempe⅔atu⅔e p⅔ope⅔ties can be imp⅔oved by λollowinμ methods • ”lendinμ with λossil diesel • blendinμ with additives • C⅔ystallization λ⅔actionation by dec⅔easinμ the satu⅔ated alkyl este⅔ content in the biodiesel. • Employinμ b⅔anched este⅔s

. Application in Diesel Engines The enμine pe⅔λo⅔mance λuelled with biodiesel is c⅔ucial λo⅔ the application oλ biodiesel. The mainly involved p⅔oblems may include co⅔⅔osion, mate⅔ial deμ⅔adation, injecto⅔ cokinμ, λil‐

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

te⅔ pluμμinμ and piston ⅔inμ stickinμ, enμine deposits etc. the⅔eλo⅔e, in the λollowinμ section, the studies λocusinμ on these issues we⅔e int⅔oduced. . . Fuel spray characteristics Injection sp⅔ay is the p⅔ocess that λuel is injected λ⅔om nozzle, and it is associated with λollowinμ λuel atomisation, inte⅔action with su⅔⅔oundinμ μas, mixtu⅔e λo⅔mation and com‐ bustion. Reμa⅔dinμ to a new λuel applied into the diesel enμine, the sp⅔ay p⅔ocess is diλλe⅔‐ ent due to the diλλe⅔ent p⅔ope⅔ties λ⅔om diesel, and the cont⅔ol st⅔ateμy should be chanμed acco⅔dinμly in o⅔de⅔ to achieve the optimum pe⅔λo⅔mance. Viscosity, su⅔λace tension and density a⅔e the th⅔ee main pa⅔amete⅔s, which inλluence λuel sp⅔ay cha⅔acte⅔istics. Hiμhe⅔ viscosity and su⅔λace tension will p⅔ohibit the atomisation and instability oλ λuel d⅔oplets. Due to the diλλe⅔ent biodiesels p⅔ope⅔ties λ⅔om diesel, studies on the sp⅔ay cha⅔acte⅔istics a⅔e necessa⅔y. . . . Neζr-λield sprζy θhζrζθteristiθs In the nea⅔-λield oλ nozzle, the sp⅔ay is dominated by the injection dynamics while the sp⅔ay is aλλected by the ambient conditions in the λa⅔ λield. “cco⅔dinμ to Hi⅔oyasu s model, beλo⅔e the t ηreζkup, which ⅔ep⅔esents the time λo⅔ λuel jet b⅔eakup, the penet⅔ation lenμth is p⅔opo⅔tion‐ al to the time aλte⅔ sta⅔t oλ injection, namely “SOI. Howeve⅔, the non-linea⅔ phenomenon has been obse⅔ved by a numbe⅔ oλ ⅔esea⅔che⅔s. The accele⅔ation p⅔ocess has been λound to be diλλe⅔ent amonμ λuels. Fiμu⅔e compa⅔es the mo⅔pholoμy oλ the sp⅔ay p⅔ocess oλ the th⅔ee tested λuels, ULSD, RME and GTL and Fiμu⅔e shows the sp⅔ay tip penet⅔ation lenμth evolution aλte⅔ sta⅔t oλ injection “SOI usinμ an ult⅔ahiμh-speed CCD came⅔a oλ up to million shots pe⅔ second. The initial non-linea⅔ penet⅔ation can be obse⅔ved, indicatinμ the accele⅔ation pe⅔iod at the initial sp⅔ay staμe. GTL λuel has lonμe⅔ penet⅔atinμ lenμth than RME and die‐ sel even thouμh it was ove⅔taken by RME s “SOI. Seve⅔al publications have ⅔epo⅔ted that GTL with lowe⅔ density has a sho⅔te⅔ penet⅔ation delay. Howeve⅔, these we⅔e based on the μlobal λuel sp⅔ay cha⅔acte⅔istics usinμ a ⅔elatively low speed came⅔a [ , ]. The tempo⅔al ⅔esolution is not hiμh enouμh to captu⅔e the nea⅔-λield sp⅔ay p⅔ocess.

Figure 4. Seq”ence of spray images in a single “ime-resolved ULSD spray (Pinj=120 MPa, Pamb =3.0 MPa and “d”r=1.5 ms)

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Figure 5. Spray “ip pene“ra“ion leng“h evol”“ion agains“ “ime ASOI (Pinj=120 MPa, Pamb =3.0 MPa and “d”r=1.5 ms)

. . . Mζθrτsθτpiθ sprζy θhζrζθteristiθs No⅔mally, biodiesel shows a lonμe⅔ penet⅔ation and na⅔⅔owe⅔ sp⅔ay anμle than λossil λuel due to the hiμhe⅔ viscosity, su⅔λace tension and density. The penet⅔ation lenμth oλ biodiesel inc⅔eases with the blend ⅔atio, hiμhe⅔ biodiesel content ⅔e⅓ui⅔es lonμe⅔ b⅔eakup time [ ]. The diλλe⅔ence between the two type λuels can be va⅔ied at diλλe⅔ent conditions. Senato⅔e et al. [ ] expe⅔imentally studied biodiesel sp⅔ay cha⅔acte⅔istics at diλλe⅔ent ambient p⅔essu⅔es. The autho⅔s showed that little diλλe⅔ence can be obse⅔ved at the ambient p⅔essu⅔e oλ . MPa while the penet⅔ation lenμth siμniλicantly inc⅔eased in cont⅔ast to diesel sp⅔ay at the ambient p⅔essu⅔e oλ . MPa. In addition, biodiesel may have a lowe⅔ penet⅔ation velocity due to the neμative eλλect oλ λuel density on sp⅔ay velocity [ ]. . . . Sζuter Meζσ diζmeter SMD SMD is one oλ the pa⅔amete⅔s to evaluate λuel atomisation ⅓uality and ⅔ep⅔esents the ⅔atio oλ total d⅔oplet volume to su⅔λace a⅔ea. Smalle⅔ SMD indicates mo⅔e small λuel d⅔oplets and the la⅔μe⅔ contact a⅔ea with su⅔⅔oundinμ μas. Due to the hiμh viscosity and su⅔λace tension, SMD oλ biodiesel is hiμhe⅔ than λossil diesel. “llen et al. [ ] conducted the compa⅔ative anal‐ ysis on biodiesels and a la⅔μe⅔ SMD, between %- %, can be obse⅔ved and concluded an empi⅔ical e⅓uation to estimate SMD SMD = .

+ .

σ

whe⅔e is λuel dynamic viscosity Pa.s and σis λuel su⅔λace tension N/m . Fiμu⅔e compa⅔ed diesel with neat RME and GTL at diλλe⅔ent injection p⅔essu⅔e alonμ the sp⅔ay axis in te⅔ms oλ SMD. It can be seen that the injection p⅔essu⅔e has a siμniλicant impact on d⅔oplet size. The SMD dec⅔eases d⅔amatically when the injection p⅔essu⅔e inc⅔eases λ⅔om MPa to MPa. GTL has the lowest SMD amonμ all the th⅔ee measu⅔ed λuels at the μiv‐

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en conditions while RME has the la⅔μest d⅔oplet size. The SMD evolution also dec⅔eases with the inc⅔ease oλ the axial distance downst⅔eam oλ the nozzle even thouμh the⅔e is a sliμhtly inc⅔ease λ⅔om mm to mm at the MPa condition. This may be caused by the d⅔oplet coalesce.

Figure 6. SMD dis“rib”“ion along “he spray axis ”nder injec“ion press”re of 80 MPa (Lef“) and 120 MPa (Righ“)

. . . Weζr Perλτrmζσθe ζσd Durζσθe In diesel enμines, the enμine pa⅔ts a⅔e lub⅔icated by the λuel itselλ. In o⅔de⅔ to meet diesel enμine emission standa⅔ds, Ult⅔a-low sulphu⅔ diesel ULSD a⅔e p⅔oduced, which has a maximum sulphu⅔ content oλ ppm. Howeve⅔, the ⅔elatively poo⅔ lub⅔icity oλ ULSD may lead to the λailu⅔e oλ enμine pa⅔ts, such as λuel pumps and injecto⅔s. The inhe⅔ently μ⅔eate⅔ lub⅔icity oλ ”iodiesel can oλλset the d⅔awback oλ ULSD, and a small pe⅔centaμe oλ biodiesel can ⅔esto⅔e the lub⅔icity oλ diesel [ ]. It is also necessa⅔y to study the enμine endu⅔ance in o⅔de⅔ to λully apply biodiesel into vehi‐ cle ope⅔ation. G⅔aboski et al. [ ] ⅔eviewed p⅔evious studies and concluded that nit⅔ile ⅔ub‐ be⅔, Nylon / and hiμh-density polyp⅔opylene exposed to methyl soyeste⅔ and D- blends exhibited chanμes in physical p⅔ope⅔ties and λluo⅔inated elastome⅔ must be adopted λo⅔ bio‐ diesel application. Te⅔⅔y et al. [ ] examined the du⅔ability oλ a set oλ λive commonly used elastome⅔s in automotive λuel systems in diλλe⅔ent biodiesel blends ” and ” and the eλ‐ λect oλ a hiμhly oxidized biodiesel blends on the elastome⅔s was studied. The ⅔esults demon‐ st⅔ated that it appea⅔ed to be compatible with these elastome⅔s, λo⅔ hiμhly oxidized and unoxidized ” and unoxidized ” , but ” p⅔epa⅔ed λ⅔om hiμhly oxidized biodiesel shows the potential λo⅔ siμniλicant p⅔oblems. . . Engine Output performance The adaptability oλ biodiesel in diesel enμines has been well studied λ⅔om low blend ⅔atio to neat biodiesel. Due to the potential damaμe oλ biodiesel on vehicle, no⅔mally biodiesel blended with diesel we⅔e mostly studied. In μene⅔al, typical heatinμ value λo⅔ biodiesel is lowe⅔ than that oλ λossil diesel. “ μ⅔eate⅔ amount oλ λuel is subse⅓uently ⅔e⅓ui⅔ed to main‐ tain the same enμine output. G⅔eate⅔ λuel consumption oλ up to % with heavy-duty en‐ μines ove⅔ the United States Fede⅔al Test P⅔ocedu⅔e US-FTP cycle was obse⅔ved. Due to

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the lowe⅔ heatinμ value, enμine powe⅔ loss is expected and the loss inc⅔eases with the blend ⅔atio oλ biodiesel in diesel [

,

]. Fiμu⅔e

shows the output powe⅔ oλ an -cylinde⅔ com‐

mon-⅔ail diesel enμine with diλλe⅔ent biodiesel blends at two enμine speeds. With the in‐ c⅔ease oλ biodiesel blend concent⅔ation, maximum out powe⅔ was μ⅔adually ⅔educed, especially in the hiμhe⅔ blend ⅔atio. Fiμu⅔e

p⅔esents the b⅔ake speciλic λuel consumption

”SFC co⅔⅔espondinμ to the condition oλ Fiμu⅔e . The obvious inc⅔ease in λuel consump‐ tion has been obse⅔ved usinμ hiμhe⅔ biodiesel/diesel blends. F⅔om Fiμu⅔e

and Fiμu⅔e , it

can be λound that the output pe⅔λo⅔mance and λuel economy oλ biodiesel/diesel blends a⅔e ve⅔y close to those oλ diesel when the blend ⅔atio is unde⅔ blends with lowe⅔ blend ⅔atio a⅔e p⅔eλe⅔⅔ed.

Figure 7. O”“p”“ power of differen“ biodiesel blends a“ “wo speeds [33]

Figure 8. BSFC of differen“ biodiesel blends a“ “wo speeds [33]

%. The⅔eλo⅔e, biodiesel/diesel

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

. . Combustion characteristics In diesel enμines, combustion is to ⅔elease ene⅔μy contained in λuel, then impa⅔t wo⅔k on piston, and powe⅔ the enμine. Facto⅔s aλλectinμ combustion cha⅔acte⅔istics include λuel p⅔op‐ e⅔ties and in-cylinde⅔ conditions. ”iodiesel has a hiμhe⅔ CN and the eλλect oλ CN on combus‐ tion has been discussed in p⅔evious section. The ave⅔aμe peak cylinde⅔ p⅔essu⅔e inc⅔eases when biodiesel o⅔ its blends a⅔e used. Fo⅔ the application oλ biodiesel into diesel enμines, advanced injection timinμ and inc⅔eased injection p⅔essu⅔e have been no⅔mally used. This is due to thei⅔ diλλe⅔ences in density and bulk modulus oλ comp⅔essibility. Combustion and emissions cha⅔acte⅔istics have been investiμated by Chuepenμ et al. [ ] usinμ diλλe⅔ent RME blends λ⅔om ” to ” in a sinμle-cylinde⅔ diesel enμine in te⅔ms oλ enμine load, EGR Ex‐ haust μas ⅔eci⅔culation , and injection timinμ. “t the same enμine load, the p⅔opo⅔tion oλ λuel bu⅔nt in the p⅔emixed phase inc⅔eases and the sta⅔t oλ combustion is advanced as the p⅔opo⅔tion oλ RME in ULSD inc⅔eases. With the same ope⅔atinμ conditions, inc⅔ease in EGR ⅔ate oλ up to %, sliμhtly ⅔educes the peak p⅔essu⅔e and inc⅔eases iμnition delay. . . Emissions . . . Reμulζted emissiτσs “ numbe⅔ oλ studies on the enμine emissions oλ enμines powe⅔ed by biodiesel o⅔ blends have been ca⅔⅔ied out. Envi⅔onmental P⅔otection “μency EP“ in the United States co⅔⅔elat‐ ed the biodiesel ⅔atio with the chanμes in pollutants usinμ statistical ⅔eμ⅔ession analysis and also the ave⅔aμe eλλect oλ biodiesel on heavy-duty diesel enμines [ ]. The NOx emissions in‐ c⅔eased with the concent⅔ation oλ biodiesel and the inc⅔ease is by % at ” while HC, CO and PM we⅔e μ⅔eatly ⅔educed. The siμniλicant ⅔eduction oλ emissions oλ HC, CO and PM can be att⅔ibuted to the oxyμen content in biodiesel. It has been widely ⅔epo⅔ted that NOx inc⅔eases as biodiesel is used in diesel enμines. “ num‐ be⅔ oλ eλλo⅔ts have been made in o⅔de⅔ to unde⅔stand the λo⅔mation mechanism and elimi‐ nate this penalty. The⅔e a⅔e seve⅔al main ⅔easons have been suμμested • “dvanced injection timinμ • Oxyμen content in biodiesel • Double bond • Radiative heat t⅔ansλe⅔ • Hiμhe⅔ adiabatic λlame tempe⅔atu⅔e “n advanced injection timinμ due to the hiμhe⅔ bulk modulus oλ biodiesel in pump-in-line injection system leads to the ea⅔lie⅔ sta⅔t oλ combustion, ⅔esultinμ in hiμhe⅔ in-cylinde⅔ tem‐ pe⅔atu⅔e, which can inc⅔ease NOx emission [ , ]. Howeve⅔, it is well unde⅔stood that ad‐ vanced injection timinμ inc⅔eases NOx emission in diesel enμine [ ], and this seems not to be the main cont⅔ibution to NOx inc⅔ease as b⅔oad application oλ common ⅔ail injection sys‐ tem, which can well cont⅔ol the injection timinμ. Schmidt et al. [ ] expe⅔imentally studied

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the eλλect oλ concent⅔ation oλ oxyμen in intake μas on NOx emission, and λound that NOx emission inc⅔eases with the oxyμen content in mixtu⅔e. Howeve⅔, the eλλect oλ oxyμen con‐ tent in ai⅔ on combustion is diλλe⅔ent λ⅔om that oλ oxyμen content in biodiesel itselλ. The ⅔a‐ diative heat t⅔ansλe⅔ may also play a ⅔ole in the NOx inc⅔ease. Soot ⅔adiation is the p⅔ima⅔y way oλ heat loss λ⅔om in-cylinde⅔ λlame and biodiesel can ⅔educe this heat loss and will in‐ c⅔ease the λlame tempe⅔atu⅔e and p⅔oduce mo⅔e NOx [ ]. The double bond in biodiesel com‐ position is anothe⅔ potential to inc⅔ease NOx emission. The double bonds lead to hiμhe⅔ adiabatic λlame tempe⅔atu⅔e, and the biodiesel with hiμhe⅔ unsatu⅔ated este⅔ pe⅔centaμe co⅔‐ ⅔esponded to hiμhe⅔ NOx emission [ , ]. ”an-Weiss et al. [ ] also ⅔evealed that sliμht diλ‐ λe⅔ence in the adiabatic λlame tempe⅔atu⅔e can lead to a measu⅔able inc⅔ease in NOx. Muelle⅔ et al. [ ] suμμested that NOx inc⅔ease in biodiesel-λuelled enμine is the ⅔esult oλ a numbe⅔ oλ mechanisms, and the ⅔elative impo⅔tance oλ each mechanism may va⅔y unde⅔ diλλe⅔ent op‐ e⅔atinμ conditions and indicated that ai⅔/λuel mixtu⅔e close to stoichiomet⅔ic at iμnition and in the standinμ p⅔emixed auto-iμnition zone nea⅔ λlame liλt-oλλ lenμth may be the key λacto⅔s in explaininμ the NOx inc⅔ease, whose eλλect could cause hiμhe⅔ local and ave⅔aμe in-cylin‐ de⅔ tempe⅔atu⅔e and lowe⅔ ⅔adiative heat losses. The⅔eλo⅔e, th⅔ee main st⅔ateμies to alleviate the NOx emission can be p⅔oposed one is to de‐ te⅔mine the biodiesel compound that can lowe⅔ NOx emission o⅔ use a p⅔ope⅔ base λuel and additives, anothe⅔ is to desiμn the combustion system to p⅔ohibit NOx p⅔oduction by lowe⅔ the combustion tempe⅔atu⅔e, and the thi⅔d one is to ⅔ecalib⅔ate the enμine by tuninμ the in‐ jection st⅔ateμy. . . . Uσreμulζted emissiτσs Fo⅔ othe⅔ un⅔eμulated emissions λ⅔om an enμine λuelled with biodiesel, polycyclic a⅔omat‐ ic hyd⅔oca⅔bon P“H and nit⅔o P“H compounds a⅔e substantially ⅔educed, as well as the lowe⅔ levels oλ some toxic and ⅔eactive HC species [ ]. The PM composition i.e. volatile mate⅔ial and elemental ca⅔bon λ⅔om the combustion oλ RME-based biodiesel blend ” in a tu⅔bo-cha⅔μed enμine with EGR ope⅔ation was studied usinμ the⅔mo-μ⅔avimet⅔ic analy‐ sis TG“ [ ]. Gene⅔ally, total PM mass λ⅔om ” combustion was lowe⅔ than that λo⅔ die‐ sel in all enμine ope⅔atinμ conditions. Elemental ca⅔bon PM mass λ⅔actions we⅔e sliμhtly lowe⅔ λo⅔ the ” . The volatile mate⅔ial po⅔tions oλ the ” pa⅔ticulates a⅔e μ⅔eate⅔ than those oλ diesel pa⅔ticulates i⅔⅔espective oλ enμine ope⅔atinμ condition. Fo⅔ both λuels used in the test, volatile mate⅔ial was obse⅔ved to be hiμhe⅔ at idle speed and liμht load when exhaust emissions we⅔e at low tempe⅔atu⅔e. In p⅔evious ⅔eμulations on PM, mass is the only conce⅔n. With the inc⅔easinμ conce⅔n on exhaust emissions, the PM size and numbe⅔ a⅔e to be limited by λutu⅔e emission ⅔eμulations. [ ] studied the pa⅔ticulate matte⅔ cha⅔acte⅔istics oλ RME and GTL . It was λound that the application oλ RME and GTL leads to a ⅔eduction in both total pa⅔ticle numbe⅔ and nonvolatile pa⅔t numbe⅔ ove⅔ the test conditions. The obtained imaμes λ⅔om SEM Scanned Elec‐ t⅔onic Mic⅔oscopy λo⅔ the th⅔ee test λuels a⅔e shown in Fiμu⅔e . The imaμes show the mo⅔pholoμy oλ PM at two maμniλications. The autho⅔s λound that PM λ⅔om diesel combustion has mo⅔e cluste⅔s than those λ⅔om RME and GTL λ⅔om Fiμu⅔e a , c and e , indicatinμ that p⅔ima⅔y pa⅔ticle size oλ the tested λuels is a⅔ound mm Fiμu⅔e . b , d and λ .

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

Figure 9. Exha”s“ par“ic”la“e n”mber concen“ra“ion (“o“al)

Figure 10. Par“icle morphology (cap“”red ”nder engine mode of 1800 rpm, 30 Nm): (a) Diesel magnifica“ion of 10000; (b) Diesel magnifica“ion of 65000; (c) RME 10 magnifica“ion of 10000; (d) RME magnifica“ion of 65000; (e) GTL10 magnifica“ion of 10000; (f) GTL10 magnifica“ion of 65000

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. . Engine emission optimisation Two popula⅔ methods have been used to ⅔educe the enμine out emission λo⅔ biodiesel-λuel‐ led enμines injection st⅔ateμy and EGR. Fo⅔ the λo⅔me⅔, the combustion p⅔ocess can be con‐ t⅔olled by injection timinμ and injection p⅔essu⅔e. Fo⅔ the time beinμ, the common ⅔ail injection system has been widely used and multiple injections up to oλ times can be ⅔eal‐ ised. Th⅔ouμh this way, the λuel injection ⅔ate is cont⅔ollable. The NOx can be ⅔educed th⅔ouμh p⅔e-injection with small amount λuel this p⅔events a lonμ pe⅔iod oλ iμnition delay and the⅔eλo⅔e leads to a lowe⅔ peak p⅔essu⅔e λo⅔ the latte⅔, EGR is always an eλλective way to ⅔educe NOx emission. Due to the induction oλ exhaust μas, the μlobal in-cylinde⅔ tempe⅔a‐ tu⅔e is ⅔educed, avoidinμ the the⅔mal conditions λavou⅔ed by NOx λo⅔mation. Ladommatos et al. [ ] also ⅔evealed that the ⅔eduction in combustion tempe⅔atu⅔e is a conse⅓uence oλ the ⅔educed peak ⅔ate oλ the p⅔emixed phase combustion due to the lowe⅔ oxyμen availability.

. Conclusions ”iodiesel is the most p⅔omisinμ λuel in the nea⅔ λutu⅔e as an alte⅔native to λossil diesel. De‐ spite oλ its advantaμes, it still has some disadvantaμes such as sou⅔ce λo⅔ massive λeedstock, ⅔elatively poo⅔ low-tempe⅔atu⅔e p⅔ope⅔ties, inc⅔ease in NOx emissions, etc. These issues should be so⅔ted out beλo⅔e biodiesel is applied into diesel enμines in a la⅔μe scale. The⅔e‐ λo⅔e, in-depth studies on the application oλ biodiesel into diesel enμines a⅔e necessa⅔y. The ⅔esea⅔ch on alte⅔native λeedstocks is also an impo⅔tant a⅔ea and the second-μene⅔ation bio‐ diesel is mo⅔e p⅔omisinμ made λ⅔om alμae and the μenetic modiλication is a potential way to solve this p⅔oblem oλ sou⅔ce oλ massive λeedstock. The low-tempe⅔atu⅔e λuel p⅔ope⅔ties can be imp⅔oved by additives o⅔ the p⅔oduction ⅔outine. In addition, diesel enμines should also be optimised in o⅔de⅔ to achieve the optimal pe⅔λo⅔mance and emissions. “ηηreviζtiτσs: ASOI

Af“er s“ar“ of injec“ion

BTL

Biomass-“o-liq”id

BSFC

Brake specific f”el cons”mp“ion

CCD

Charge-co”pled device

CN

Ce“ane n”mber

CO

Carbon monoxide

CTL

Coal-“o-liq”id

EPA

Environmen“al Pro“ec“ion Agency

FAME

Fa““y acid me“hyl es“er

GTL

Gas-“o-liq”id

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

HC

Hydrocarbon

HVO

Hydro-“rea“ed vege“able oil

NOx

Ni“ric oxide

PAH

Polycyclic aroma“ic hydrocarbon

RME

Rapeseed me“hyl es“er

ULSD

Ul“ra-low s”lph”r diesel

Author details Yanλei Li , *, Guohonμ Tian and Honμminμ Xu , *“dd⅔ess all co⅔⅔espondence to yanλei.lee@μmail.com School oλ Mechanical Enμinee⅔inμ, Unive⅔sity oλ ”i⅔minμham, UK State Key Labo⅔ato⅔y oλ “utomotive Saλety and Ene⅔μy, Tsinμhua Unive⅔sity, China Si⅔ Joseph Swan Cent⅔e λo⅔ Ene⅔μy Resea⅔ch, Newcastle Unive⅔sity, UK

References [ ] Inte⅔national Ene⅔μ Outlook.

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[ ] “lam, M., Sonμ, J., et al. . Combustion and Emission Pe⅔λo⅔mance oλ Low Sul‐ λu⅔ Ult⅔a-Low Sulλu⅔ and ”iodiesel ”lends in a DI Diesel Enμine. S“E pζper - . [ ] “llen, C. “. W., & Watts, K. C. . Compa⅔ative analysis oλ the atomization cha⅔‐ acte⅔istics oλ λiλteen biodiesel λuel types. Trζσsζθtiτσs τλ the “sζe, , . [ ] “llen, C. “. W., Watts, K. C., et al. . P⅔edictinμ the viscosity oλ biodiesel λuels λ⅔om thei⅔ λatty acid este⅔ composition. Fuel, , . [ ] ”an-Weiss, G. “., Chen, J. Y., et al. . “ nume⅔ical investiμation into the anoma‐ lous sliμht NOx inc⅔ease when bu⅔ninμ biodiesel “ new old theo⅔y. Fuel Prτθessiσμ Teθhστlτμy, , . [ ] Chenμ, “., Upatnieks, “., et al. . Investiμation oλ the impact oλ biodiesel λuel‐ linμ on NOx emissions usinμ an optical di⅔ect injection diesel enμine. Iσterσζtiτσζl Jτurσζl τλ Eσμiσe Reseζrθh, , .

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[ ] Chuepenμ, S., Tsolakis, “., et al. . “ Study oλ ⅓uantitative impact on emissions oλ hiμh p⅔opo⅔tion oλ RME-based biodiesel blends. S“E teθhσiθζl pζper - . [ ] Chuepenμ, S., Xu, H. M., et al. . Pa⅔ticulate emissions λ⅔om a common ⅔ail λuel injection diesel enμine with RME-based biodiesel blended λuellinμ usinμ the⅔moμ⅔avimet⅔ic analysis. S“E teθhσiθζl pζper - . [ ] Desantes, J. M., Pay⅔i, R., et al. . Inλluence on Diesel Injection Cha⅔acte⅔istics and ”ehavio⅔ Usinμ ”iodiesel Fuels. S“E - . [

] EP“. . “ Comp⅔ehensive “nalysis oλ ”iodiesel Impacts on Exhaust Emissions. Eσvirτσmeσtζl Prτteθtiτσ “μeσθy.

[

] EP“. GO-

[

] Ge⅔pen, J. V.

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] Gonμ, G., Sonμ, C., et al. . Sp⅔ay cha⅔acte⅔istics oλ diesel λuel, Fishch-T⅔opsch diesel λuel and thei⅔ blend. Eleθtriθζl ζσd Cτσtrτl Eσμiσeeriσμ ICECE , Iσterσζtiτσζl Cτσλereσθe τσ.

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] G⅔aboski, M. S., & Mc Co⅔mick, R. L. . Combustion oλ λat and veμetable oil de‐ ⅔ived λuels in diesel enμines. Prτμress iσ Eσerμy ζσd Cτmηustiτσ Sθieσθe, , .

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] G⅔imaldi, C., & Post⅔ioti, L. . Expe⅔imental Compa⅔ison ”etween Conventional and ”io-de⅔ived Fuel Sp⅔ays λ⅔om a Common Rail Injection System . S“E teθhσiθζl pζ‐ per - .

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] Knothe, G., Matheaus, “. C., et al. . Cetane numbe⅔s oλ b⅔anched and st⅔aiμhtchain λatty este⅔s dete⅔mined in an iμnition ⅓uality teste⅔[small sta⅔, λilled]. Fuel, , - .

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] Ku⅔onen, M., Mikkonen, S., et al. . Hyd⅔ot⅔eated Veμetable Oil as Fuel λo⅔ Heavy Duty Diesel Enμines. S“E teθhσiθζl pζper - .

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] Ladommatos, N., “bdelhalim, S. M., et al. diesel combustion. S“E technical pape⅔

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] Mc Co⅔mick, R. L., Tennant, C. J., et al. Tested in Heavy-Duty Enμines Meetinμ - .

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] Muelle⅔, C. J., ”oehman, “. L., et al. . “n Expe⅔imental Investiμation oλ the O⅔i‐ μin oλ Inc⅔eased NOx Emissions When Fuelinμ a Heavy-Duty Comp⅔ession-Iμnitio with Soy ”iodiesel. S“E pζper - .

[

] Nμuyen, D. N., Ishida, H., et al. . Iμnition and Combustion Cha⅔acte⅔istics oλ Gas-to-Li⅓uid Fuels λo⅔ Diλλe⅔ent “mbient P⅔essu⅔es. Eσerμy & Fuels, , .

-

. ”iodiesel Handlinμ and Use Guidelines. .

th Editiτσ, EP“. DOE/

. Cetane Numbe⅔ Testinμ oλ ”iodiesel.

.

. Eλλects oλ EGR on heat⅔elease in

. Reμulated Emissions λ⅔om ”iodiesel Emission Standa⅔ds. S“E pζper

Applica“ion of Biodiesel in A”“omo“ive Diesel Engines h““p://dx.doi.org/10.5772/ 53222

[

] Schönbo⅔n, “., Ladommatos, N., et al.

. The inλluence oλ molecula⅔ st⅔uctu⅔e oλ

λatty acid monoalkyl este⅔s on diesel combustion. Cτmηustiτσ ζσd Flζme, [

.

] Schmidt, K., & Ge⅔pen, J.

. The eλλect oλ biodiesel λuel composition on diesel

diesel combustion and emissions. S“E pζper [

] Senato⅔e, “., Ca⅔done, M., et al.

.

. Expe⅔imental Cha⅔acte⅔ization oλ a Common

Rail Enμine Fuelled with Diλλe⅔ent ”iodiesel. S“E teθhσiθζl pζper [

] Sha⅔p, C. “., Howell, S. “., et al. S“E pζper

-

-

] Sha⅔p, C. “., Howell, S. “., et al.

. The eλλect oλ biodiesel λuels on t⅔ansient ,

] Sheehan, J., Camob⅔eco, V., et al.

un⅔eμulated emissions and chemical -

] Sukjit, E., & Dea⅔n, K. D.

[

“p⅔ Medium ED Size vp.

. Enhancinμ the lub⅔icity oλ an envi⅔onmentally

λ⅔iendly Swedish diesel λuel MK . Weζr, ] Szybist, J. P., & ”oehman, “. L. odiesel Fuel. S“E pζper

-

-

-

-

.

.

] Te⅔⅔y, ”., Mc Co⅔mick, R. L., et al.

] Wu, M., Wu, G., et al.

,

. ”ehavio⅔ oλ a Diesel Injection System with ”i‐

. Impact oλ ”iodiesel ”lends on Fuel System

Component Du⅔ability. S“E teθhσiθζl pζper [

.

. “n Ove⅔view oλ ”iodiesel and Pet⅔oleum

Diesel Liλe Cycles. Othe⅔ Inλo⅔mation P”D

[

-

-

.

. Low-Tempe⅔atu⅔e Fluidity oλ ”io-Diesel Fuel P⅔epa⅔ed

λ⅔om Edible Veμetible Oil. Petrτleum prτθessiσμ ζσd petrτθhemiθζls, [

] Zhanμ, J., Xu, H., et al.

[

-

,

-

.

. The Pa⅔ticle Emissions Cha⅔acte⅔istics oλ a Liμht Duty

% “lte⅔native Fuel ”lends. S“E Iσterσζtiτσζl Jτurσζl τλ Fuels ζσd

Diesel Enμine with Luηriθζσt [ ],

.

.

cha⅔acte⅔ization. S“E Trζσsζθtiτσ,

[

-

Reμulated emission and pe⅔λo⅔mance.

emissions λ⅔om mode⅔n diesel enμines, Pa⅔t

[

-

. The eλλect oλ biodiesel λuels on t⅔ansient

emission λ⅔om mode⅔n diesel enμien~Pa⅔t

[

,

.

] Zhanμ, X., Wanμ, H., et al.

. Cha⅔acte⅔istics oλ Output Pe⅔λo⅔mances and Emis‐

sions oλ Diesel Enμine Employed Common Rail Fueled with ”iodiesel ”lends λ⅔om Wasted Cookinμ Oil. S“E Teθhσiθζl Pζper

-

-

.

405

Chapter 15

Simulation of Biofuels Combustion in Diesel Engines Andrey Marchenko, Alexandr Ose“rov, Oleg Linkov and Dmi“ry Samoilenko Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/52333

. Introduction In the study oλ the wo⅔kinμ p⅔ocess, the development oλ new enμine const⅔uction o⅔ mode⅔n‐ ization oλ an existinμ one is necessa⅔y to use simulation with mathematical models. Modelinμ oλ the p⅔ocesses inside the cylinde⅔ allows in a λi⅔st app⅔oximation to evaluate enμine pe⅔‐ λo⅔mance, choose the ⅔ational value oλ adjustment o⅔ const⅔uctive pa⅔amete⅔, to ⅔educe mate⅔ial, labo⅔ and time ⅔e⅓ui⅔ed to conduct expe⅔imental ⅔esea⅔ch. One oλ the most diλλicult p⅔ocess λo⅔ simulation is the combustion p⅔ocess in diesel enμines. This p⅔ocess is dete⅔mined and accompanied by a numbe⅔ oλ othe⅔ p⅔ocesses and phenomena. The⅔e is intense inte⅔action between the motion oλ the λuel jets and ai⅔ λlow in the cylinde⅔, heat t⅔ansλe⅔ between the combustion chambe⅔ zones and walls, volume evapo⅔ation λ⅔om the su⅔λace oλ li⅓uid d⅔oplets. “ll this leads to the λo⅔mation oλ the active nucleus oλ the λuel oxidation and its iμnition, volumet⅔ic and then the diλλusion combustion. Cu⅔⅔ently, the⅔e a⅔e a numbe⅔ oλ hypotheses about the behavio⅔ oλ each oλ these p⅔ocesses and thei⅔ inte⅔action. Fo⅔ each hypothesis p⅔oposed mathematical desc⅔iption oλ a diλλe⅔ent deμ⅔ee oλ accu⅔acy. The most complex model implemented technoloμy oλ Computational Fluid Dynamic CFD th⅔ee-dimensional simulation oλ μas λlow and the injected λuel in the cylinde⅔s and maniλolds oλ inte⅔nal combustion enμines [ - ]. The most popula⅔ p⅔oμ⅔ams a⅔e KIV“ Los “lamos National Labo⅔ato⅔y, Los “lamos, New Mexico ST“R-CD CD-adapco, head⅓ua⅔te⅔ Melville, New Yo⅔k, US“ FIRE “VL, head⅓ua⅔te⅔ in G⅔atz, “ust⅔ia VECTIS Rica⅔do, head⅓ua⅔te⅔ Sho⅔eham-by-Sea, Enμland, United Kinμdom . Fo⅔ example, the soλtwa⅔e packaμe “VL FIRE Enμine includes ove⅔ diλλe⅔ent models oλ λo⅔mation and sp⅔ead oλ the jet, its decay, c⅔ushinμ d⅔ops, collisions between them, the

408

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

evapo⅔ation oλ λuel and its inte⅔action with the wall oλ the combustion chambe⅔ [ ]. The λo⅔mation oλ li⅓uid λilms, thei⅔ dist⅔ibution and evapo⅔ation, the inte⅔action with the walls and the li⅓uid λuel to⅔ches a⅔e also simulated. Seve⅔al models desc⅔ibe the p⅔ocesses oλ iμnition, combustion and the λo⅔mation oλ ha⅔mλul substances, takinμ into account detailed chemical kinetics oλ ⅔eactinμ systems. “ siμniλicant technical challenμe oλ CFD models is the complexity oλ calculations and the need λo⅔ powe⅔λul compute⅔s. Data p⅔epa⅔ation only λo⅔ one simulation with hiμhly skilled pe⅔sonal could takes a λew days. Calculation time λo⅔ one va⅔iant oλ the enμine - a λew hou⅔s and sometimes days. Implementation oλ these p⅔oμ⅔ams λo⅔ optimization calculations is p⅔oblem‐ atic because optimization p⅔ocess has to count thousands oλ desiμn options. The⅔modynamic and phenomenoloμical models that use the - o⅔ -dimensional ⅔ep⅔esenta‐ tions, ⅔e⅓ui⅔e less time and ⅔esou⅔ces. The most popula⅔ p⅔oμ⅔ams we⅔e GT-Powe⅔ Gamma Technoloμies, Inc, head⅓ua⅔te⅔ Westmont, Illinois, US“ , ”OOST “VL,G⅔atz, “ust⅔ia , W“VE Rica⅔do, Sho⅔eham-by-Sea, Enμland, United Kinμdom , DIESEL RK Moscow State Technical Unive⅔sity named aλte⅔ ”auman, Moscow, Russian Fede⅔ation . These soλtwa⅔e p⅔oducts usually include a one-dimensional model oλ μas exchanμe. To calculate the mixinμ and combustion in a diesel enμine used empi⅔ical o⅔ semi-empi⅔ical models [ - ]. The most sophisticated models oλ combustion used in the⅔modynamic models a⅔e models oλ H. Hi⅔oyasu [ ], as well as Razleytsev N.F. and Kuleshov “.S. models[ , ]. In these models, the p⅔opaμation oλ λuel jet is desc⅔ibed by the c⅔ite⅔ial e⅓uations obtained on the basis oλ expe⅔imental data. It has been assumed in this modelsthat the main inλluence on the ⅔ate oλ heat μene⅔ation ⅔ate has d⅔ops evapo⅔ation ⅔ate and the speed oλ the ai⅔ penet⅔ated in the combustion zone. “lso, the eλλects oλ ai⅔ swi⅔l on the development oλ λuel sp⅔ays is conside⅔ed. In models oλ mixinμ, combustion and evapo⅔ation usinμ an ave⅔aμe diamete⅔ oλ the d⅔oplet on the Saute⅔. The λuel jet is conside⅔ed as a set oλ zones, each oλ which has a cha⅔acte⅔istic tempe⅔atu⅔e, the volume, λuel-to-ai⅔ ⅔atio. These models allow us to investiμate the inλluence on the combustion oλ comp⅔ession, timinμ and du⅔ation oλ the injection, hole diamete⅔ and the numbe⅔ oλ sp⅔ays in the λuel injecto⅔, cha⅔acte⅔istics oλ λuel injection, combustion chambe⅔ shape, co⅔⅔elate the di⅔ection oλ λuel jets with combustion chambe⅔ and swi⅔l intensity, take into account the inte⅔action oλ jet λuel with the walls and to each othe⅔ and λinally allow you to pe⅔λo⅔m multi-λacto⅔ multi-c⅔ite⅔ia optimization. Howeve⅔, the use oλ this class oλ models ⅔e⅓ui⅔es detailed desiμn inλo⅔mation oλ the simulated enμine, settinμ up empi⅔ical ⅔elations and coeλλicients to make a ⅔elatively labo⅔-intensive ve⅔iλication. Widesp⅔ead empi⅔ical o⅔ semi-empi⅔ical models oλ combustion, which desc⅔ibe the μeomet⅔ic shape oλ the heat μene⅔ation cu⅔ve [ - ] second μ⅔oup a⅔e also p⅔esented. Such models a⅔e easy to desc⅔ibe and ve⅔satility oλ use. Fo⅔ example, in a model oλ p⅔oλ. VibeI.I. [ ], the ⅔ate oλ combustion and the p⅔opo⅔tion oλ bu⅔nt λuel a⅔e desc⅔ibed by semi-empi⅔ical dependencies

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333 m+ dx m+ m j exp Cj = -C jz dj

x = - exp Cj ¯= whe⅔e φ

φ

m+

,

φz , φ, φz - ⅔espectively, ⅔elative du⅔ation oλ combustion, the cu⅔⅔ent du⅔ation oλ

combustion λ⅔om the sta⅔t oλ combustion and combustion du⅔ation shown in anμles oλ ⅔otation oλ the c⅔ankshaλt C - constant λo⅔ example, at the end oλ the combustion when x = x Z = . - ,

, C = ln

- ,

=

m-index oλ combustion cha⅔acte⅔. Featu⅔e oλ empi⅔ical models is that all input values oλ the calculation λo⅔mulas a⅔e constant values and a⅔e μiven by expe⅔imental data o⅔ chosen λ⅔om the ⅔ecommended by investiμato⅔s ⅔anμes. Fo⅔ example, in λi⅔st app⅔oximation, p⅔oλ. Vibe I.I. ⅔ecommends m , λo⅔ diesel enμines, and in the wo⅔k oλ scientists λ⅔om ”auman Moscow state Unive⅔sity Moscow, Russian Fede⅔ation values oλ m ⅔anμe λ⅔om - . to . . Use oλ this class oλ models suitable λo⅔ desc⅔ibinμ the combustion in a speciλic enμine ⅔unninμ on one mode oλ his wo⅔k.When chanμinμ a const⅔uctive pa⅔amete⅔ and adjustinμ the enμine o⅔ the conditions oλ his wo⅔k empi⅔ical models stop p⅔oducinμ an accu⅔ate ⅔esult. The d⅔awback oλ empi⅔ical models oλ combustion is the complexity oλ thei⅔ use in calculations oλ the ha⅔mλul substances λo⅔mation in diesel enμines, in pa⅔ticula⅔ nit⅔oμen oxides. NO output in acco⅔dance with the the⅔mal theo⅔y oλ ZeldovichU.”. [ ] is ext⅔emely sensitive to the maμnitude oλ the tempe⅔atu⅔e in the cylinde⅔. The⅔eλo⅔e, in these calculations, it is impo⅔tant to accu⅔ately dete⅔mine the tempe⅔atu⅔e and, conse⅓uently, the heat μene⅔ation cu⅔ve. This cu⅔ve, calculated by the empi⅔ical models as a ⅔ule have one peak that does not comply with the combustion p⅔ocess in diesel enμines λo⅔ most modes oλ ope⅔ation. “cco⅔dinμly, the accu⅔acy oλ the calculation output oλ ha⅔mλul substances by usinμ models oλ this class is ⅔elatively low. Most oλ the p⅔oblems that a⅔ise in the p⅔actice oλ desiμn and ⅔esea⅔ch oλ va⅔ious diesel enμines can be solved usinμ "inte⅔mediate" type models [ , - ] thi⅔d μ⅔oup . These models combine the advantaμes oλ computational methods λ⅔om λi⅔st and second μ⅔oups. “ numbe⅔ oλ models desc⅔ibes the combustion p⅔ocess by usinμ Vibe I.I. ⅔elationships and [ , ], but unlike empi⅔ical models the indices oλ combustion du⅔ation φz and combustion cha⅔acte⅔ m a⅔e λunctions oλ desiμn pa⅔amete⅔s and ope⅔ation modes. The data obtained by p⅔ocessinμ the expe⅔imental indicato⅔ diaμ⅔ams, conλi⅔m the co⅔⅔ectness oλ this app⅔oach Fiμ.

409

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 1. The change in “he index of comb”s“ion charac“er m d”ring opera“ion cycle in “he 4 s“roke a”“o“rac“or diesel engine wi“h “”rbocharger (SMD-23)

“cco⅔dinμ to the va⅔iable natu⅔e oλ the index oλ combustion cha⅔acte⅔m λo⅔ the diλλe⅔entiation oλ e⅓uation the next dependence was obtained which is diλλe⅔ent λ⅔om e⅓uation dx dm m+ ¯ ¯m + φ ¯ m+ lnφ ¯ = − Cexp Cφ m+ φ ¯ dφ φz dφ Filipkovsky “. I.p⅔oposed to dete⅔mine the index oλ combustion cha⅔acte⅔m and the du⅔ation oλ the combustion φzin Vibe I.I. dependencies and as a λunction oλ the pa⅔amete⅔s oλ the evapo⅔ation, diλλusion and chemical kinetics oλ ⅔eaction [ ]. The model takes into account the main λacto⅔s that dete⅔mine the combustion p⅔ocess • desiμn λeatu⅔es oλ the combustion chambe⅔ chambe⅔ shape, the diamete⅔ oλ the cylinde⅔ and the neck chambe⅔, swi⅔l ⅔atio • cha⅔acte⅔istics oλ the λuel injection and atomization diamete⅔ and the eλλective c⅔oss section oλ nozzle holes, du⅔ation, and mean p⅔essu⅔e oλ injection, amount the λuel du⅔inμ ope⅔ation cycle, the physical cha⅔acte⅔istics oλ the λuel • the⅔mo-and μas-dynamic pa⅔amete⅔s oλ the cha⅔μe in cylinde⅔ p⅔essu⅔e and density oλ cha⅔μe at the end oλ a conditional extended to top dead cent⅔e TDC comp⅔ession, the tanμential velocity oλ the cha⅔μe in the combustion chambe⅔ • mode pa⅔amete⅔s oλ the enμine speed, excess ai⅔ ⅔atio . The model assumed that the development oλ chain ⅔eactions beμins with the sta⅔t oλ λuel injection into the diesel cylinde⅔, ⅔athe⅔ than the beμinninμ oλ combustion, as in the model oλ p⅔oλ. VibeI. I. The cu⅔ve oλ heat μene⅔ation ⅔ate, calculated by the model, has one peak.

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Calculations oλ heat cu⅔ves by the model oλ Filipkovsky “.I. λo⅔ medium-speed λou⅔-st⅔oke diesel enμines with tu⅔bocha⅔μinμ, cm bo⅔e and st⅔oke cmand λou⅔-st⅔oke diesel enμines with tu⅔bocha⅔μinμ, cm bo⅔e and st⅔oke cm with volume mixinμ p⅔ocesses have shown μood aμ⅔eement with expe⅔imental data. Howeve⅔, p⅔actical application oλ this model λo⅔ hiμhspeed automotive diesel with a volume-λilm-mixinμ p⅔ocesses did not p⅔oduce positive ⅔esults. The disc⅔epancy between the calculated and expe⅔imental data is μ⅔eatest in the pa⅔tial modes, whe⅔e the cu⅔ve has a two-peak heat μene⅔ation ⅔ate in natu⅔e Fiμ. . Finally, this method μives a siμniλicant e⅔⅔o⅔ in the calculations λo⅔ bioλuels because oλ siμniλicant diλλe⅔ences in the physicochemical p⅔ope⅔ties oλ diesel λuels and bioλuels.

1 0,8 0,03

0,6

0,02

0,4

0,01

0,2

Heat generation, Х

Differential characteristics of heat generation, dx/dφ [deg-1]

0,04

0

0 342

362

382

402

φ [deg] Figure 2. Comparison of experimen“al and calc”la“ed hea“ genera“ion charac“eris“ics of “he e“hyl es“ers of rapeseed oil – Calc”la“ion by “he me“hod of Dr. Filippovsky A.I.; – Experimen“al da“a

Despite these p⅔oblems, the Filipkovsky “.I. model, in ou⅔ opinion, has the potential λo⅔ λu⅔the⅔ imp⅔ovement. Obviously, it is necessa⅔y to adapt this model to inteμ⅔ate λeatu⅔es oλ mediumspeed diesel enμines, physicochemical p⅔ope⅔ties oλ bioλuels, as well as ope⅔ation modes oλ small and medium loads, whe⅔e the heat μene⅔ation ⅔ate has two-peak cha⅔acte⅔. Siμniλicant inλluence on the combustion p⅔ocess have physical and chemical p⅔ope⅔ties oλ λuel. In p⅔esent study, the λeatu⅔es oλ the p⅔ocesses in the enμine cylinde⅔ associated with the use oλ bio-λuels oλ plant-based o⅔iμin, in pa⅔ticula⅔ mixtu⅔es oλ ⅔apeseed oil RO with diesel λuel DF and the ethyl este⅔ oλ ⅔apeseed oil EERO . In conducted by autho⅔s expe⅔imental studies have shown that the p⅔esence oλ oxyμen in the molecule oλ bioλuels will intensiλy the p⅔ocess oλ diλ‐ λusion combustion, which should be conside⅔ed when developinμ a mathematical model. This chapte⅔ desc⅔ibes the ⅔esults oλ expe⅔imental studies oλ bioλuels in diesel enμines, the mathematical model oλ combustion in the diesel enμinecylinde⅔ and the ⅔esults oλ ve⅔iλication.

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. Experimental studies of biofuels in diesel engines Expe⅔imental studies a⅔e needed to obtain basic data λo⅔ modelinμ, μettinμ a numbe⅔ oλ empi⅔ical coeλλicients in the model e⅓uations and ⅔eλinement oλ physical laws, compa⅔ison oλ expe⅔imental and calculated data. . . Investigation of physicochemical properties of biofuels Physicochemical p⅔ope⅔ties oλ the investiμated bioλuels a⅔e p⅔esented in Table . “nalysis oλ the data in Table. shows that the p⅔ope⅔ties oλ plant-based λuels a⅔e siμniλicantly diλλe⅔ent λ⅔om the p⅔ope⅔ties oλ diesel λuel PM and EEROaλte⅔ compa⅔ison with DFhave ⅔espectively and . % less low heat values, λo⅔ and . % hiμhe⅔ density, λo⅔ . and . % hiμhe⅔ su⅔λace tension, and λo⅔ . and . times hiμhe⅔ viscosity. Fo⅔ the combustion oλ kμ oλ RO and EERO ⅔e⅓ui⅔ed ⅔espectively . and . % less ai⅔, which is associated with the p⅔esence oλ oxyμen in the st⅔uctu⅔es oλ thei⅔ molecules. It should be noted that the t⅔ial set oλ EERO contained un⅔eacted ⅔aped oil, so the physical and chemical p⅔ope⅔ties oλ ethyl diλλe⅔ a⅔e diλλe⅔ent λ⅔om those μiven in the technical lite⅔atu⅔e [ ]. Property

Diesel fuel Rape oil (DF)

(RO)

Ethyl ester of rapeseed oil (EERO)

Mixtures DF: RO

DF: RO

DF: RO

(3:1)

(1:1)

(1:3)

Elemen“al composi“ion, %: carbon (C)

87

77,9

77,6

84,5

82

79,8

hydrogen (H)

12,6

11,9

12

12,3

12

11,8

oxygen (O)

0,4

10,2

10,4

3,2

5,9

8,5

s”lf”r (S)

0,04

0

0

0,03

0,02

0,01

The amo”n“ of air for comb”s“ion per mass

14,4

12,7

12,7

13,9

13,5

12,9

High hea“ val”e Qv, MJ / kg

44,95

39,3

39,2

43,4

42,0

40,6

Low hea“ val”e of Qn, MJ / kg

42,2

36,8

36,9

40,7

39,3

38,0

The densi“y ρ, g/m3 (20 ˚ C)

825

915

895

849

872

894

The kinema“ic viscosi“y ν, mm 3 / s (20 ˚ C)

3,8

87

32,48

26,3

47,6

67,8

The s”rface “ension σ * 103 N / m (20 ˚ C)

28,9

33,3

36

30,1

31,2

32,3

”ni“ of f”el Lo, kg / kg

Table 1. Physicochemical proper“ies of biof”els.

The diλλe⅔ence between the physical and chemical p⅔ope⅔ties oλ bioλuels on the p⅔ope⅔ties oλ diesel λuel is the cause oλ chanμes in diesel wo⅔kinμ p⅔ocess and pe⅔λo⅔mance, which should be conside⅔ed when simulatinμ p⅔ocesses inside the cylinde⅔.

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

. . Studies of dispersion atomized biofuels To cla⅔iλy the empi⅔ical and c⅔ite⅔ial ⅔elationships that cha⅔acte⅔ize the ⅓uality oλ atomization oλ bioλuels, an expe⅔imental study was made oλ atomizationdispe⅔sion. Sinμle injections we⅔e made on μlass plates coated with a laye⅔ oλ soot and ke⅔osene and on a top side cove⅔ed with a laye⅔ oλ maμnesium oxide which has a b⅔iμht white colo⅔ λo⅔ cla⅔ity oλ p⅔ints λuel d⅔oplets. The studies we⅔e conducted on the λollowinμ λ⅔e⅓uencies oλ hiμh p⅔essu⅔e λuel pump camshaλt ⅔otation , and ⅔pm. Fuel ⅔ack settinμ was made λo⅔ maximum λuel delive⅔y. Mic⅔oμ⅔aphswe⅔e obtained in the expe⅔imental study oλ dispe⅔sion oλ the atomization oλ va⅔ious λuels and shown on Fiμ. . Photomic⅔oμ⅔aphs a⅔e p⅔ocessed acco⅔dinμ to the p⅔ocedu⅔e [ ]. The ⅔elative λuel atomization cha⅔acte⅔istics we⅔e obtained as the ⅔esults Fiμu⅔es - Diλλe⅔ential R - ⅓uantitative R su⅔λace R - volume and inteμ⅔al S - ⅓uantitative S - su⅔λace S - volume . The data obtained allowed to estimate the ave⅔aμe diamete⅔ oλ λuel d⅔oplets oλ diλλe⅔ent composition. The most commonly used pa⅔amete⅔ λo⅔ calculatinμ the evapo⅔ation oλ λuel is the ave⅔aμe volume-su⅔λace d⅔oplet diamete⅔ Saute⅔ diamete⅔ d

= E dθ M

.

/ ( r We )

.

,

whe⅔e E is a constant λacto⅔ dependinμ on the desiμn oλ the nozzle and the method oλ ave⅔aμinμ the d⅔oplet size dθ-diamete⅔ oλ atomized holes M-c⅔ite⅔ion, which cha⅔acte⅔izes the ⅔atio oλ su⅔λace tension and viscosity We- Webe⅔ c⅔ite⅔ion ρ- ai⅔ density to λuel ⅔at⅔io Calculations oλ Saute⅔ diamete⅔ oλ d⅔oplets λo⅔ a λou⅔-st⅔oke auto-t⅔acto⅔ tu⅔bocha⅔μed diesel enμine, which has a cylinde⅔ diamete⅔ mm and mm st⅔oke ⅔unninμ on standa⅔d diesel λuel usinμ the standa⅔d λuel system show that the value oλ d on nominal powe⅔ mode ⅔anμes λ⅔om to mic⅔ons. G⅔eate⅔ d⅔oplet diamete⅔ values obtained in expe⅔imental studies Fiμ. , due to the λact that the injection was made into the envi⅔onment unde⅔ atmosphe⅔ic conditions. It is obvious that in a ⅔unninμ diesel enμine a hiμh tempe⅔atu⅔e oλ the cha⅔μe in the cylinde⅔ causes a μ⅔eate⅔ atomization and evapo⅔ation oλ λuel d⅔oplets. The⅔eλo⅔e, when ⅔eλinement dependencies λo⅔ the case oλ bioλuels, ⅔elative not absolute values oλ d Table was used. “nalysis oλ the data in Table. shows that the dependence with app⅔eciable e⅔⅔o⅔ desc⅔ibes the va⅔iation oλ d λo⅔ plant-based λuels. “utho⅔s have p⅔o‐

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

posed an empi⅔ical co⅔⅔ection λo⅔ the dependence

, dependinμ on the viscosity oλ the λuel

and allows to do mo⅔e accu⅔ate calculation oλ the ave⅔aμe volume-su⅔λace diamete⅔ oλ d⅔ops k λ (n ) = - ,

×n + ,

×n + ,

.

Figure 3. Micrograph of a“omized f”el drople“s (n = 900 rpm): a s“andard diesel f”el (a) a mix“”re of diesel f”el and rapeseed oil in “he ra“io 1:1 (b); p”re rapeseed oil (c); e“hyl es“er of rapeseed oil (d)

Diesel Fuel

Mixture

Rape Oil

Ethyl ester of rapeseed

(DF)

DF: RO (1:1)

(RO)

oil(EERO)

d¯ 32(experimen“)

1,00

1,509

2,000

1,877

d¯ 32(calc”la“ed by “he form”la (3))

1,00

1,537

3,176

1,488

d¯ 32(adj”s“ed val”e)

1,00

1,509

1,927

1,541

Table 2. The rela“ive diame“ers of “he drople“s of differen“ f”els

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Figure 4. The rela“ive a“omiza“ion charac“eris“ics of diesel f”el (high press”re f”el p”mp camshaf“ ro“a“ion speed 900 rpm)

Figure 5. The rela“ive charac“eris“ics of spray mix“”re DF and RO (1:1) (high press”re f”el p”mp camshaf“ ro“a“ion speed 900 rpm)

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 6. The rela“ive a“omiza“ion charac“eris“ics of RO (high press”re f”el p”mp camshaf“ ro“a“ion speed 900 rpm)

Figure 7. The rela“ive a“omiza“ion charac“eris“ics EERO (high press”re f”el p”mp camshaf“ ro“a“ion speed 900 rpm)

Dependence

, co⅔⅔ected to

becomes

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

=

d

k λ × dθ × E × M

( r × We )

.

.

.

. . Experimental investigations of biofuels implementation in diesel Expe⅔imental studies oλ the enμine ⅔unninμ on t⅔aditional and bioλuels pe⅔λo⅔med on a test bench with a diesel enμine SMD-

, e⅓uipped with a tu⅔bocha⅔μed and inte⅔coole⅔ system.

”⅔ieλ technical cha⅔acte⅔istics oλ a diesel enμine SMD-

is shown in Table. , the pictu⅔e oλ

expe⅔imental λacility is shown in Fiμ. .

Parameter

Value

N”mber of cylinders

4

Bore, mm

120

S“roke, mm

140

The geome“ric compression ra“io

15,5

Ra“ed power, kW

120

Ra“ed speed rpm

2000

Table 3. S”mmary of “echnical charac“eris“ics of a diesel engine SMD-23

Figure 8. Experimen“al s“and

Enμine tests we⅔e conducted on the modes oλ enμine load cha⅔acte⅔istic ⅔elated to ⅔ated powe⅔ mode with enμine speed

⅔pm and peak to⅔⅓ue mode with enμine speed

⅔pm.

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Du⅔inμ the tests on each mode, the pa⅔amete⅔s oλ ai⅔ and λuel delive⅔y systems, exhaust μas, coolant and oil we⅔e measu⅔ed. Enμine speed and to⅔⅓ue we⅔e also detected. Indexinμ, the deλinition oλ st⅔oke in injecto⅔ idle and measu⅔inμ the p⅔essu⅔e in the λuel injection pipe was ca⅔⅔ied out. “lso emissions we⅔e measu⅔ed and included NO , CO and smoke ⅔eμist⅔ation. The values oλ injection timinμ anμle and adjust λuel pump adjustments ⅔emained unchanμed. Main diesel indices that ⅔unninμ on a diλλe⅔ent λuels a⅔e shown in Fiμ. .Lets conside⅔ the eλλect oλ physicochemical p⅔ope⅔ties oλ bio-λuels on the pe⅔λo⅔mance oλ diesel.

Figure 9. Effec“ of load on “he performance of diesel exha”s“ gas SMD-23: engine speed 2000 rpm (a); engine speed 1500 rpm (b) -DF; - EERO; RO: DF (1:1)

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Injected λuel and ai⅔ mixinμ. Injection oλ plant-based λuel into the combustion chambe⅔ is ca⅔⅔ied out with the hiμhe⅔ maximum p⅔essu⅔e than the injection oλ diesel λuel, which is explained by the inλluence oλ lowe⅔ comp⅔essibility and hiμhe⅔ viscosity oλ plant-based λuels. G⅔eate⅔ su⅔λace tension λo⅔ce and μ⅔eate⅔ kinematic viscosity see Table. p⅔ovide mo⅔e late⅔ decay oλ injected plant-based λuel on the d⅔oplets and λo⅔mation oλ smalle⅔ atomizinμ cone in compa⅔ison with diesel λuel. This d⅔amatically inc⅔eases the diamete⅔ oλ λuel d⅔oplets. “s shown in [ , , ], atomizinμ cone is ⅔educed by % usinμ mthyl este⅔ oλ ⅔apeseed oil and the ave⅔aμe volume-su⅔λace d⅔oplet diamete⅔ d inc⅔eases, ⅔espectively, in , - , times when usinμ pu⅔e RO, a mixtu⅔e oλ RO and DF to and EERO . Injection oλ plant-based λuels with the hiμhe⅔ maximum p⅔essu⅔es μ⅔eate⅔ diamete⅔s oλ d⅔op‐ lets in combination with a μ⅔eate⅔ speciλic weiμht inc⅔ease penet⅔atinμ powe⅔ and the ⅔anμe oλ λuel jet. The du⅔ation oλ injection oλ plant-based λuelsφiinc⅔eases sliμhtly - c⅔ank anμle as a ⅔esult oλ siμniλicant inc⅔ease in injection p⅔essu⅔e with a small inc⅔ease in a λuel delive⅔y. The above λacto⅔s lead to the λact that in the case oλ usinμ plant-based λuels the volume λ⅔action oλ mixinμ is ⅔educed and the λ⅔action oλ wall-λilm mixinμ is inc⅔ease. The ⅓uality oλ volume mixinμ become lowe⅔ed in this case. The pe⅔iod oλ iμnition delay. “s a ⅔esult oλ p⅔ocessinμ the expe⅔imental indicato⅔ diaμ⅔ams, inteμ⅔al and diλλe⅔ential cha⅔acte⅔istics oλ heat μene⅔ation in the cylinde⅔ we⅔e obtained ove⅔ the enti⅔e ⅔anμe oλ investiμated λuel mixtu⅔es and ⅔eμime cha⅔acte⅔istics oλ the enμine. In Fiμ. shows the ⅔elative heat μene⅔ation cha⅔acte⅔istics when bu⅔ned pu⅔e diesel λuel, and mixtu⅔es EERO,RO DF on hiμh load Pe = . MPa and Pe = . MPa and medium Pe = . MPa and MPa load at enμine speed ⅔pm and enμine speed ⅔pm. F⅔om the analysis oλ these cha⅔acte⅔istics is diλλicult to see any leμitimate diλλe⅔ences in the iμnition delay pe⅔iod oλ plant-based λuels and diesel λuel. Conse⅓uently, we can conclude that the λlammability oλ plant-based λuels is almost unchanμed in compa⅔ison with diesel λuel λlammability. The λi⅔st peak oλ heat μene⅔ation ⅔ate. “s we can see λ⅔om Fiμ. , on the most modes the maximum heat μene⅔ation ⅔ate λo⅔ plant-based λuel in this pe⅔iod is lowe⅔ than λo⅔ diesel λuel. In addition, the a⅔ea unde⅔ the λi⅔st peak oλ the cu⅔ve dx / dφsmalle⅔, and hence smalle⅔ the amount oλ λuel bu⅔ned out in this pe⅔iod. This λact is obviously ⅔elated to the dete⅔io⅔ation oλ the mixinμ between the iμnition delay when usinμ mixtu⅔es oλ RO with the DF and EERO. Reduction in the anμle oλ λ⅔ame dive⅔‐ μence, inc⅔easinμ the ⅔elative amount oλ λuel that ente⅔s the wall oλ the combustion chambe⅔, a siμniλicant inc⅔ease in the ave⅔aμe diamete⅔ oλ d⅔oplets leads to a dete⅔io⅔ation in mixinμ λo⅔‐ mation and ⅔educe the ⅔elative amount oλ λuel vapo⅔ized du⅔inμ the pe⅔iod oλ iμnition delay. The second peak oλ heat μene⅔ation ⅔ate. “λte⅔ bu⅔ninμ the λuel, evapo⅔ated du⅔inμ the pe⅔iod oλ iμnition delay, the⅔e is a diλλusion combustion oλ the λuel d⅔oplets in the λuel to⅔ch, as well as the λuel evapo⅔atinμ λ⅔om the walls oλ the combustion chambe⅔ aλte⅔ the contact oλ the to⅔ch and the wall. The natu⅔e oλ the combustion p⅔ocess in this pe⅔iod dete⅔mines the indicato⅔ pe⅔λo⅔mance oλ the cycle [ ].

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In an expe⅔imental enμine used a cylind⅔ical combustion chambe⅔, that implements volumeλilm mixtu⅔e λo⅔mation. Obtained data is cont⅔adicto⅔y ex λacte see Fiμ. . Inc⅔easinμ the amount oλ λuel ⅔eachinμ the wall, la⅔μe diamete⅔ d⅔ops, the hete⅔oμeneity oλ atomization when usinμ plant-based λuels should lead to a dec⅔ease in the ⅔ate oλ evapo⅔ation and combustion oλ λuel, especially in the modes oλ small loads, when the wall has a lowe⅔ tempe⅔atu⅔e. Howeve⅔, it is clea⅔ that almost on all modes the⅔e is an inc⅔ease in the ⅔ate oλ combustion as compa⅔ed to DF. The dete⅔io⅔ation in the amount oλ mixinμ in this case does not lead to a dec⅔ease in combustion ⅔ate and it can be seen not only in the modes oλ hiμh loads, but also in modes oλ low loads. Intensiλication oλ the diλλusion combustion oλ plant-basedλuels, can obviously be explained by the p⅔esence oλ oxyμen in the st⅔uctu⅔e oλ the molecule. When bu⅔ninμ λuel d⅔oplets oλ bioλuel, the oxyμen is in the molecule oλ λuel. This oxyμen is mo⅔e active than molecula⅔ oxyμen. That is why, even at low tempe⅔atu⅔es oλ plant-based λuel oxidation ⅔ate oλ its "own" oxyμen is ve⅔y hiμh. “ll this p⅔obably leads to an inc⅔ease in diλλusion combustion ⅔ate in μene⅔al. The inc⅔ease in the ⅔ate oλ combustion oλ plant-based λuels in the main pe⅔iod oλ combustion in most cases leads to a sliμht inc⅔ease in ave⅔aμe tempe⅔atu⅔es and p⅔essu⅔es in the cylinde⅔. In addition, the exhaust μas tempe⅔atu⅔e ⅔ise in the exhaust maniλold see Fiμ. . . The pe⅔iod oλ slow combustion. Du⅔inμ this pe⅔iod the⅔e was bu⅔ninμ oλ λuel in the cylinde⅔. F⅔om Fiμ. diλλicult to see the end oλ the combustion oλ diλλe⅔ent λuels. Howeve⅔, it is clea⅔ that the diλλe⅔ences between the test λuel at the end oλ the combustion is low. “ccele⅔ated bu⅔n‐ inμ oλ plant-based λuels, du⅔inμ the second pe⅔iod oλ combustion, appa⅔ently compensate by slow combustion in the λi⅔st pe⅔iod. So the total du⅔ation oλ combustion is p⅔actically un‐ chanμed. Eλλective pe⅔λo⅔mance. “s it can be seen λ⅔om Fiμ. , the use oλ plant-based λuels leads to an inc⅔ease in b⅔eak speciλic λuel consumption because oλ ⅔eduction in thei⅔ low heat value compa⅔ed to diesel λuel. Chanμinμ in eλλective eλλiciency oλ the diesel enμine is not so clea⅔. The inc⅔ease in the ⅔ate oλ diλλusion combustion, hiμh ⅓uality λilm mixinμ on the hiμh loads modes lead to an inc⅔ease in the eλλective eλλiciency iλ we use plant-based λuels. “t low load modes mixtu⅔e λo⅔mation dete⅔io⅔ates in the volume oλ the combustion chambe⅔. In addition, the sha⅔e oλ plant based λuel bu⅔ninμ in the ⅔elatively cold wall su⅔λace a⅔eas oλ combustion chambe⅔, which explains the dec⅔ease in the eλλective eλλiciency at low load modes. The toxicity oλ exhaust μases. When usinμ supplements oλ veμetable-based oils to diesel λuel, and iλ diesel enμine ope⅔atinμ on pu⅔e EERO on modes oλ hiμh and medium loads the smokeemission ⅔educed in . - times and NO emissions inc⅔ease λo⅔ - %. In most modes oλ low-load smoke and NO a⅔e ⅔educed in . - times , o⅔ ⅔emain unchanμed. CO emissions usinμ diλλe⅔ent λuels a⅔e compa⅔able. Expe⅔imental studies have p⅔ovided initial inλo⅔mation on the physicochemical p⅔ope⅔ties oλ plant-based λuels, low oλ λlow injection, atomization, mixinμ and combustion in the cylinde⅔, the data λo⅔ mathematical modelinμ p⅔ocessesinside the cylinde⅔.

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Figure 10. Hea“ genera“ion charac“eris“ics in “he diesel cylinder: engine speed 1500 rpm: Pe = 1.25 MPa (a) Pe = 0.67 MPa (b); engine speed 2000 rpm: Ре = 1,01 MPa (c), Ре = 0,57 MPa (d); -DF; - EERO; RO: DF (1:1)

These diλλe⅔ences in the physicochemical p⅔ope⅔ties oλ bioλuels and thei⅔ impact on λlow p⅔ocesses in the cylinde⅔ oλ a diesel enμine λo⅔m the basis λo⅔ the developed mathematical model oλ combustion. . Description of the proposed mathematical model of combustion Lets conside⅔ the λeatu⅔es oλ the p⅔oposed model oλ combustion.

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Diλλe⅔ential cha⅔acte⅔istic oλ heat μene⅔ation p⅔oposed to desc⅔ibe by two cu⅔ves co⅔⅔espond‐ inμ to the pe⅔iods oλ iμnition o⅔ "λast" combustion and the diλλusion combustion mI + mI mI + dmI ù æ dx ö σé ln j I ê mI + j I + j I ú ç ÷ = - “ × C × exp C × j I j zI êë dj I ûú è dj ø I mII + æ dx ö σ ç ÷ = -C × x v × S × exp Cj II jz è dj ø II II

é mII mII + dmII ù ln j II ê mII + j II + j II ú dj II úû êë

whe⅔e “ - coeλλicient takinμ into account the inλluence oλ the p⅔opo⅔tion oλ vapo⅔ized λuel du⅔inμ the iμnition delay at the ⅔ate oλ λast combustion C - coeλλicient takinμ into account the completeness oλ combustion ξv - the deμ⅔ee oλ eλλicient use oλ ai⅔ cha⅔μe S - coeλλicient takinμ into account the sha⅔e oλ λuel bu⅔ned λo⅔ the pe⅔iod oλ the iμnition linkinμ the two pe⅔iods . The index «I» ⅔elated to pa⅔amete⅔s that identiλied iμnition, the index «II» - the p⅔ocess oλ diλλusion combustion. Dynamics indicato⅔s λo⅔ the ⅔espective pe⅔iods oλ combustion j mI ö æ mI = × j mI × ç - j ÷ è ø j mII æ mII = × j mII × ç - j è

ö ÷, ø

¯ mI and φ ¯ mII ⅔elative moments oλ maximum heat μene⅔ate ⅔ate whe⅔e -φ ¯ I and φ ¯ II - the ⅔elative anμles oλ the c⅔ankshaλt⅔otation φ ¯ I = φ / φZI , φ ¯ II = φ / φZII φ φ - the cu⅔⅔ent anμle oλ the c⅔ankshaλt ⅔otation λ⅔om the sta⅔t oλ combustion φZI, φZII - ⅔espectively, the du⅔ation oλ λast and diλλusive combustion. “t each calculated section the values heat μene⅔ation ⅔ate

dx dφ

I

and

dx dφ

II

was compa⅔inμ. The λinal calculated

dx took the value oλ μ⅔eate⅔ meaninμ oλ two ⅔ates. dφ

The total amount oλ bu⅔nt λuel a⅔e dete⅔mined by inteμ⅔atinμ the λunction dx / dφ in the a⅔ea oλ combustion

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

x=

jk

ò dj dj ,

jN

dx

whe⅔e φN, φk - ⅔espectively the beμinninμ and the end oλ combustion. In λo⅔mulas the⅔e a⅔e the pa⅔amete⅔s “ and, φZI and φZII, ξv, which, unlike the pa‐ ⅔amete⅔s oλ the known λo⅔mulas Vibe I.I. accounted speciλic p⅔ocesses oλ λuel injection, mix‐ inμ, evapo⅔ation, combustion, and the inte⅔action oλ these p⅔ocesses with each othe⅔. In μene⅔alizinμ the data obtained by p⅔ocessinμ the expe⅔imental indicato⅔ diaμ⅔ams, empi⅔‐ ical co⅔⅔elations was p⅔oposed to dete⅔mine the ⅔elative moment oλ maximum heat μene⅔a‐ tion ⅔ate du⅔inμ pe⅔iods oλ combustion

j mI = , +

.

× ηè × jZI j mII = , ×σ

+

.

× ηè × jZII , ×σ

whe⅔e ηи- a constant oλ ⅔elative evapo⅔ation. The ⅔elative constant oλ evapo⅔ation ηu = Кu / d whe⅔e Кu - constant oλ evapo⅔ation, calculated λo⅔ the ave⅔aμe diamete⅔ d oλ the d⅔oplet un‐ de⅔ Saute⅔. P⅔oλ. Razleytsev [ ] estimated, that du⅔inμ the evapo⅔ation oλ λuel in a diesel enμine cylinde⅔ the ave⅔aμe evapo⅔ation constant KuT =

pθ

-

whe⅔e pθ - the p⅔essu⅔e in the cylinde⅔ at the end oλ a conditional extension to TDC comp⅔ession. Theo⅔etical constant КuТ does not include an inc⅔ease in the ⅔ate oλ evapo⅔ation oλ d⅔oplets du⅔inμ combustion, the eλλect oλ size oλ d⅔ops, speed and λ⅔e⅓uency oλ tu⅔bulent vo⅔tices a⅔isinμ in the diesel cylinde⅔. This dependence is in p⅔actical calculations can be taken into account by co⅔⅔ection λunction Υ Kи = Y ⋅ K иT . In [ ] p⅔oposed the λollowinμ λo⅔mula λo⅔ dete⅔mininμ the co⅔⅔ection λunction

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Y = y ( WT d

)

.

p

. C

,

whe⅔e y - constant empi⅔ical coeλλicient dependinμ on the desiμn oλ the combustion chambe⅔ and takinμ into account the eλλect oλ unaccounted seconda⅔y λacto⅔s. WT - the tanμential velocity oλ the cha⅔μe in the combustion chambe⅔ pθ - the calculated p⅔essu⅔e at the end oλ a conditional extension to TDC comp⅔ession. It should pay pa⅔ticula⅔ attention to the coeλλicient oλ y. It is obvious that the⅔e a⅔e pe⅔manent λacto⅔s that deλined y coeλλicient - enμine desiμn, adjustments and settinμs mode. On the othe⅔ hand, while usinμ diλλe⅔ent λuels - the value oλ this ⅔atio will be dete⅔mined by physical and chemical p⅔ope⅔ties oλ λuels. “s shown in Section , an impo⅔tant p⅔ope⅔ty oλ plant-based λuelsthat have a mate⅔ial eλλect on the combustion p⅔ocess is the oxyμen content in the molecule. Inc⅔easinμ the numbe⅔ oλ bound oxyμen in the molecule leads to an inc⅔ease in the ⅔ate oλ diλλusion combustion. “cco⅔dinμly, the simulation oλ combustion is expedient to inc⅔ease the coeλλicient y p⅔opo⅔‐ tional to the sha⅔e oλ the oxyμen in the molecule oλ λuel. In this study, a constant value y was adjusted λo⅔ each λuel type on the basis oλ p⅔ovidinμ the best aμ⅔eement between calculated and expe⅔imental data. Fo⅔ all the calculations λo⅔ one type oλ λuel y constant has not chanμed. In acco⅔dance with the o⅔iμinal model [ ] the du⅔ation oλ diλλusion combustion

t

zII

=j +j , i η

whe⅔e φi - the du⅔ation oλ λuel injection φη- the du⅔ation oλ bu⅔n-out λuel aλte⅔ the injection. The du⅔ation oλ bu⅔n-out λuel ϕη cha⅔acte⅔ized by the time oλ evapo⅔ation and combustion oλ

la⅔μe d⅔oplets delive⅔ed in the diesel enμine cylinde⅔ at the end oλ injection. This time depends on the λineness oλ atomization, the dist⅔ibution oλ d⅔ops, the pa⅔amete⅔s oλ the wo⅔kinμ λluid in the cylinde⅔, ai⅔-λuel ⅔atio, etc. ϕη can be calculatedλ⅔om the λo⅔mula [ ]

j = Ka × j , η e whe⅔e ϕe - the du⅔ation oλ the evapo⅔ation oλ la⅔μe d⅔oplets oλ λuel K α - co⅔⅔ection λunction which takes into account the time oλ λuel vapo⅔s bu⅔ninμ. The du⅔ation the la⅔μe d⅔oplets evapo⅔ation oλ λuel

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

je =

dK Ku

whe⅔e dK - an ave⅔aμe diamete⅔ oλ la⅔μe d⅔ops oλ λuel injected into cylinde⅔ by the end oλ the λuel delive⅔y. In [ ] p⅔oposed to dete⅔mine the diamete⅔ oλ the la⅔μe d⅔ops by the λo⅔mula dK = ” × d In this λo⅔mula, the size λacto⅔ is

(

”= . + .

exp Dp λ.i

),

whe⅔e Δ p λi - the ave⅔aμe p⅔essu⅔e d⅔op du⅔inμ injection, MPa. Co⅔⅔ection λunction at the time oλ bu⅔ninμ-out oλ λuel vapo⅔s can be dete⅔mined λ⅔om the dependence [ ] K = +

l

“ Ku

l-

whe⅔e - is the ⅔atio oλ actual ai⅔-to-λuel ⅔atio to stoichiomet⅔y λo⅔ a μiven mixtu⅔e “ - coeλλicient, which is dete⅔mined by identiλyinμ a numbe⅔ oλ expe⅔imental data λo⅔ deλined ⅔ow oλ enμines and can be taken e⅓ual to . •

.

We p⅔oposed to dete⅔mine the du⅔ation oλ the λast combustion as a λunction oλ the du⅔ation oλ the iμnition delay pe⅔iod

t whe⅔e

i

zI

=t ×K , i l

- the pe⅔iod oλ iμnition delay in seconds.

Iλ to μo to the c⅔ank anμle, the du⅔ation oλ λast and diλλusive combustion a⅔e dete⅔mined by the λollowinμ λo⅔mulas

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jZI = t ZI σ jZII = qi + jη σ, whe⅔e

i

- injection advanced anμle.

In developed model has been assumed that bu⅔n ⅔ate du⅔inμ the iμnition mostly depends on the amount oλ λuel vapo⅔ized du⅔inμ the pe⅔iod oλ iμnition delay. In tu⅔n, the calculation oλ the λi⅔st peak heat μene⅔ation ⅔ate coeλλicient takinμ into account the inλluence oλ the p⅔opo⅔tion oλ vapo⅔ized λuel du⅔inμ the iμnition delay pe⅔iod. “ = KI × s I whe⅔e σI - the ⅔elative amount oλ λuel injected du⅔inμ iμnition delay pe⅔iod φI KI - coeλλicient oλ p⅔opo⅔tionality. In [ ] p⅔oposed the dynamics oλ heat μene⅔ation du⅔inμ diλλusion combustion e⅓uation to adjust with the ⅔atio ξv, which is a deμ⅔ee oλ eλλicient use oλ ai⅔ cha⅔μe in cylinde⅔

xV = whe⅔e

m

- the ave⅔aμe

lò , l

coeλλicient in the combustion zone

the estimated value oλ cylinde⅔.

in the cylinde⅔ λo⅔ λull combustion oλ the λuel injected into the

The coeλλicient ξV takes into account the inte⅔action oλ λuel to⅔ch with the wall oλ the combus‐

tion chambe⅔ and othe⅔ λacto⅔s that ⅔educe the amount oλ oxidant ente⅔inμ the combustion zone. In [ , ] desc⅔ibes a method oλ dete⅔mininμ this ⅔atio.

The mathematical model oλ combustion is inteμ⅔ated into the the⅔modynamic model oλ the closed-loop wo⅔kλlow enμine with a tu⅔bocha⅔μe⅔.

. Implementation of mathematical models for practical calculations Compa⅔ison oλ calculated and expe⅔imental cha⅔acte⅔istics oλ heat μene⅔ation and indicato⅔ diaμ⅔ams usinμ diλλe⅔ent λuels is shown in Fiμ. - . It can be seen that the p⅔oposed mathe‐ matical model p⅔ovides a satisλacto⅔y aμ⅔eement between the calculated and expe⅔imental data in a wide ⅔anμe oλ bioλuels, loads and enμine speeds. “ p⅔ecise desc⅔iption oλ the combustion p⅔ocess is impo⅔tant in modelinμ the λo⅔mation oλ ha⅔mλul substances in the cylinde⅔. Fo⅔ example, the e⅔⅔o⅔ in dete⅔mininμ the tempe⅔atu⅔e in

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

the cylinde⅔ - K leads to a chanμe in the calculated NO output by %, e⅔⅔o⅔ in dete⅔mininμ the tempe⅔atu⅔e oλ K chanμe in the calculated NO output is . times [ ]. Obviously, usinμ the p⅔oposed mathematical model ⅔athe⅔ than empi⅔ical o⅔ semi empi⅔ical models p⅔ovide a mo⅔e accu⅔ate calculation oλ the λo⅔mation oλ ha⅔mλul substances in the diesel enμine cylinde⅔. The ade⅓uacy oλ the developed mathematical model was tested also λo⅔ its ⅔esponse to the chanμinμ inλluence oλ pa⅔amete⅔s - the comp⅔ession ⅔atio, injection du⅔ation and injection delay anμle Fiμ. . It is seen that the obtained nume⅔ical data t⅔ends and loμical and do not conλlict with simila⅔ data oλ othe⅔ ⅔esea⅔che⅔s [ - ]. We can conclude that the developed mathematical model allows us not only to desc⅔ibe the dynamics oλ heatμene⅔ation with suλλicient accu⅔acy, but also to ade⅓uately ⅔espond to chanμes in desiμn and adjustments in the pa⅔amete⅔s oλ diesel.

. Conclusion “ctual and pe⅔spective task λo⅔ mode⅔n enμine buildinμ has been int⅔oduced and solved in the chapte⅔. This task included the development oλ mathematical model oλ alte⅔native bioλuels and λossil λuel diesel combustion calculation in the cylinde⅔ oλ diesel enμine. It is shown that the physical-chemical p⅔ope⅔ties oλ bioλuels diλλe⅔ siμniλicantly λ⅔om the p⅔ope⅔ties oλ diesel λuel, which leads to chanμes in the p⅔ocesses oλ λuel injection, mixtu⅔e λo⅔mation and combustion. “ll this has a siμniλicant impact on the eλλicient and envi⅔onmental pe⅔λo⅔mance oλ diesel enμines. “utho⅔s have p⅔oposed mathematical model that ade⅓uately desc⅔ibes the p⅔ocess oλ com‐ bustion oλ conventional diesel and bio-λuel in the cylinde⅔ oλ diesel enμine. It was conλi⅔med by the ⅔esults oλ calculation and expe⅔imental studies. The mathematical model p⅔oposed by the autho⅔s can be used to solve optimization tasks in inte⅔nal combustion enμines ⅔unninμ on a diesel λuel, as in this model combustion p⅔ocesses a⅔e linked with pa⅔amete⅔s oλ enμine desiμn and enμine wo⅔kinμ p⅔ocess pa⅔amete⅔s. The model is developed in a pa⅔amet⅔ic λo⅔m and ⅔eλlects the chanμe in desiμn and adjustment pa⅔amete⅔s oλ the diesel enμine. “n impo⅔tant cha⅔acte⅔istic oλ a new mathematical model is an ade⅓uate desc⅔iption oλ the λi⅔st phase oλ the combustion p⅔ocess λi⅔st peak , which is associated with λuel bu⅔n-out, accumulated du⅔inμ the iμnition delay, which allows mo⅔e ⅔eliable to calculate the tempe⅔atu⅔e oλ the wo⅔kinμ λluid in the cylinde⅔ oλ diesel enμine and, conse⅓uently, with μ⅔eate⅔ ⅔eliability to calculate by Zeldovich methoda numbe⅔ oλ nit⅔oμen oxides that a⅔e λo⅔med in the cylinde⅔ oλ diesel enμines. The p⅔oposed model can be used in unive⅔sity t⅔aininμ p⅔oμ⅔ams λo⅔ p⅔oλessionals in the λield oλ inte⅔nal combustion enμines, as well as in p⅔actice oλ λi⅔ms pa⅔ticipatinμ in the mode⅔niza‐ tion oλ existinμ and development oλ advanced diesel enμines.

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 11. Verifica“ion of “he model of calc”la“ion of hea“ genera“ion process. Diesel: engine speed 2000 rpm,Pe = 1.1 MPa (a); engine speed 2000 rpm,Pe=0.56 MPa (b); engine speed 1500 rpm, Pe=1.35 MPa (c); engine speed 1500 rpm,рe=0.67 MPa (d); Experimen“; Calc”la“ion of “he refined model

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Figure 12. Verifica“ion of “he model of calc”la“ion of hea“ genera“ion process. A mix“”re of RO: DF (1:1): engine speed 2000 rpm, pe =1.1 MPa (a); engine speed 2000 rpm, pe =0.56 MPa (b); engine speed 1500 rpm, pe =1.35 MPa (c); en‐ gine speed 1500 rpm, pe =0.67 MPa (d); Experimen“; Calc”la“ion on “he refined model

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Figure 13. Verifica“ion of “he model of calc”la“ion of hea“ genera“ion process. EERO: engine speed 2000 rpm, pe =1.1 MPa (a); engine speed 2000 rpm, pe =0.56 MPa (b);engine speed 1500 rpm, pe =1.35 MPa (c);engine speed 1500 rpm, pe =0.67 MPa (d); Experimen“; Calc”la“ion of “he refined model

Sim”la“ion of Biof”els Comb”s“ion in Diesel Engines h““p://dx.doi.org/10.5772/52333

Figure 14. Effec“ of changing “he compression ra“io ε (a, b), “he injec“ion d”ra“ion φi (c, d) and injec“ion delay angle Θi (e, f) a“ “he ra“e of hea“ genera“ion and press”re in “he cylinder of diesel engine

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Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Author details “nd⅔ey Ma⅔chenko, “lexand⅔ Oset⅔ov, Oleμ Linkov and Dmit⅔y Samoilenko National Technical Unive⅔sity "Kha⅔kiv Polytechnic Institute", Uk⅔aine

References [ ] P⅔ieschinμ, P., Ramusch, G., Ruetz, J. and Tatschl, R., D-CFD Modelinμ oλ conven‐ tional and “lte⅔native Diesel Combustion and Pollutant Fo⅔mation - “ Validation Study. S“E - . [ ] Tatschl, R., P⅔ieschinμ, P., Ruetz, J. and Kamme⅔diene⅔, Th., DoE ”ased CFD “naly‐ sis oλ Diesel Combustion and Pollutant Fo⅔mation. S“E - . [ ] Dahlen, L. and La⅔sson, “., CFD Studies oλ Combustion and In-Cylinde⅔ Soot T⅔ends in a DI Diesel Enμine - Compa⅔ison to Di⅔ect Photoμ⅔aphy Studies. S“E - . [ ] Konμ, S.-C., Han, Z.Y. and Reitz, RD, The Development and “pplication oλ a Diesel Iμnition and Combustion Model λo⅔ Multidimensional Enμine Simulations. S“E . [ ] Kolade ”., Thomas M., Konμ SC, "Coupled D/ D analysis oλ λuel injection and diesel enμine combustion", S“E Inte⅔national, vol. , . [ ] FIRE v

Manual. “VL List GmbH, G⅔az

.

[ ] Razleytsev N.F. Modellinμ and optimization oλ the combustion p⅔ocess in diesel en‐ μines. - Kha⅔kov Kha⅔kov unive⅔sity p⅔ess. . [ ] Kuleshov “.S. The p⅔oμ⅔am λo⅔ calculatinμ and optimizinμ the inte⅔nal combustion enμine DIESEL-RK. Desc⅔iption oλ mathematical models, solvinμ optimization p⅔ob‐ lems. M. ”auman. ”auman . [ ] Hi⅔oyuki Hi⅔oyasu, Toshikazu Kadota and Masataka “⅔ai. Development and Use oλ a Sp⅔ay Combustion Modelinμ to P⅔edict Diesel Enμine Eλλiciency and Pollutant Emissions. JSME . [

] Wiebe I.I.New about wo⅔kinμ cicle oλ enμines. Moscow

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] Watson, N., Pilley, “.D., Ma⅔zouk, M. “ Combustion Co⅔⅔elation λo⅔ Diesel Enμine Simulation. Diesel Combustion and Emissions . S“E Society oλ “utomotive Enμi‐ nee⅔s - .

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] Goncha⅔ V.M. Nume⅔ical simulation oλ the wo⅔kinμ cicle in Diesel. Powe⅔ machine buildinμ - .

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] Ramos JI. Inte⅔nal Combustion Enμine Modelinμ. Hemisphe⅔e Publishinμ Co⅔po⅔a‐ tion .

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] ”lumbe⅔μ P., Kumme⅔ I.T. P⅔ediction oλ NO Fo⅔mation in Spa⅔k-Iμnited Enμines “n “nalisys oλ Methods oλ Cont⅔ol.Combustion and Flame - .

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] Lino Guzzella and Ch⅔istophe⅔ H. Onde⅔. Int⅔oduction to Modelinμ and Cont⅔ol oλ IC Enμine Systems. Sp⅔inμe⅔ .

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] ZeldovichY.”., Ga⅔dene⅔sP.Y., F⅔ank-KamenetskyD.“. Oxidation oλ nit⅔oμen du⅔inμ combustion. Moscow - Leninμ⅔ad “N USSR .

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] Semenov V.S. Cu⅔⅔ent p⅔oblems oλ the theo⅔y oλ ma⅔ine diesels. M. I / O Mo⅔tehin‐ λo⅔m⅔eklama .

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] Va⅔banets R. The pa⅔amet⅔ic diaμnostics oλ diesel enμines S”V M / R. Va⅔banets. “e⅔ospace technic and technoloμy -

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] Filipkovsky“.I. Imp⅔ovement oλ wo⅔kinμ p⅔ocess in diesel tipe physical and mathematical simulation.PhDthesis. HIIT .

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] Taldy G.”., K⅔ivobokov “. Nume⅔ical Simulation oλ the combustion p⅔ocess in die‐ sel. “e⅔ospace Enμinee⅔inμ and Technoloμy .

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] Lotko”., LukaninV., Khachiyan, “. Theuseoλalte⅔nativeλuelsininte⅔nalcombustionen‐ μines. Moscow M“DI TU .

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] Lyshevsky.Thep⅔ocessesoλatomizationoλdieselλuelinjecto⅔s. Moskow Mashμiz

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] Linkov O. Selection and validation oλ the pa⅔amete⅔s oλ mixtu⅔e λo⅔mation and com‐ bustion oλ diesel enμine ope⅔atinμ on alte⅔native λuels. PhDthesis. NTU "KPI"

[

] Ma⅔chenko“., SemenovV., Sukachev I.I., Linkov O. Simulation oλ λeatu⅔es oλ the wo⅔kinμ p⅔ocess in SMD- diesel enμine ⅔unninμ on t⅔aditional diesel λuel and methyl este⅔s oλ ⅔apeseed oil. “e⅔ospace Enμinee⅔inμ and Technoloμy .

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] The theo⅔y oλ inte⅔nal combustion enμinesEd. DyachenkoN.H. L. Mechanical Enμi‐ nee⅔inμ .p.

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] Zvonov V.“. The toxicity oλ inte⅔nal combustion enμines. -M. Mechanical Enμinee⅔‐ inμ, .

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] Ma⅔kovV., KislovV., Khvatov V.“. Cha⅔acte⅔istics oλ λuel delive⅔y in diesel enμines. Moscow Publishinμ House oλ the MSTU”auman .

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] Pa⅔sadanovI.V. Imp⅔ovinμ the ⅓uality and competitiveness oλ diesel enμines th⅔ouμh an inteμ⅔ated λuel eλλiciency and envi⅔onmental c⅔ite⅔ia the monoμ⅔aph . Kha⅔kov NTU "KPI" .

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and Peμaso .

on the basis oλ

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Chapter 16

An Analysis of Physico-Chemical Properties of the Next Generation Biofuels and Their Correlation with the Requirements of Diesel Engine Ar“”r Malinowski, Joanna Czarnocka and Krzysz“of Bierna“ Addi“ional informa“ion is available a“ “he end of “he chap“er h““p://dx.doi.org/10.5772/53685

. Introduction The⅔e is a p⅔essinμ need to haste developinμ advanced ene⅔μy technoloμies to ⅔educe dependency on c⅔ude oil and climate p⅔otection. ”ioλuels li⅓uid and μaseous λuels de‐ ⅔ived λ⅔om o⅔μanic matte⅔ can play an impo⅔tant ⅔ole in ⅔educinμ oλ ca⅔bon dioxide CO emissions in the t⅔anspo⅔t, and can ⅔aise the ene⅔μy secu⅔ity. ”y , bioλuels could p⅔ovide % oλ total t⅔anspo⅔t λuel. The use oλ bioλuels could avoid a⅔ound . μiμatonnes Gt oλ CO emissions pe⅔ yea⅔ when p⅔oduced sustainably. To meet this vi‐ sion, most conventional bioλuel technoloμies need to imp⅔ove conve⅔sion eλλiciency, cost and ove⅔all sustainability. Conventional bioλuel technoloμies include well-established that a⅔e al⅔eady p⅔oducinμ bioλuels on a comme⅔cial scale. These bioλuels, commonly ⅔e‐ λe⅔⅔ed to as λi⅔st-μene⅔ation, include suμa⅔- and sta⅔ch-based ethanol, oil-c⅔op based bio‐ diesel and st⅔aiμht veμetable oil, as well as bioμas μained th⅔ouμh anae⅔obic diμestion. The Inte⅔national Ene⅔μy “μency has unde⅔taken an eλλo⅔t to develop a se⅔ies oλ μlobal technoloμy ⅔oad maps cove⅔inμ advanced technoloμies, commonly ⅔eλe⅔⅔ed to as sec‐ ond- o⅔ thi⅔d-μene⅔ation. This new technoloμies a⅔e still in the ⅔esea⅔ch and develop‐ ment R&D , pilot o⅔ demonst⅔ation phase [ ].Siμniλicant dec⅔ease oλ λossil λuels and lack oλ new ones becomes the basis λo⅔ the Olduvai theo⅔y, published by R.C. Duncan [ ]. The theo⅔y postulated that in the yea⅔s , because oλ sho⅔taμe oλ ene⅔μy, the wo⅔ld would μo th⅔ouμh an economic c⅔isis. This c⅔isis would lead to collapse oλ indust⅔ial civilization. So, the⅔e is a need to look λo⅔ alte⅔native, ⅔enewable sou⅔ces oλ ⅔aw mate⅔ials.

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“cco⅔dinμ to the cu⅔⅔ent EU Di⅔ective on p⅔omotinμ the use oλ ene⅔μy λ⅔om ⅔enewable sou⅔‐ ces [ ], pet⅔ochemical companies a⅔e obliμed to ma⅔ket λuel containinμ biocomponents / /EC . ”iomass means the biodeμ⅔adable λ⅔action oλ p⅔oducts, waste and ⅔esidues λ⅔om bioloμical o⅔iμin, λ⅔om aμ⅔icultu⅔e, λo⅔est⅔y and ⅔elated indust⅔ies includinμ λishe⅔ies and a⅓uacultu⅔e, as well as the biodeμ⅔adable λ⅔action oλ indust⅔ial and municipal wastes. “ssuminμ biomass as the basic sou⅔ce oλ mate⅔ials λo⅔ the p⅔oduction oλ bioλuels, two main mate⅔ial pathways and the suitinμ mate⅔ial p⅔ocessinμ technoloμies have been conside⅔ed in the Eu⅔opean deλinition. That is ⅔eλe⅔⅔ed to as ”tL biomass-to-li⅓uid o⅔, as an alte⅔native, ”tG biomass-to-μas and WtL waste-to-li⅓uid o⅔, as an alte⅔native, WtG waste-to-μas . ”ioλuels a⅔e divided into μ⅔oups acco⅔dinμ to thei⅔ state oλ matte⅔. “cco⅔dinμ to “nnex to Communication λ⅔om the Commission oλ the Eu⅔opean Communities No. oλ , COM λinal, bioλuels have been divided into li⅓uid, μas, and othe⅔s, with λi⅔st and second μene⅔ation bioλuels havinμ been int⅔oduced in this Communication λo⅔ the λi⅔st time. How‐ eve⅔, an idea oλ synthetic bioλuels has been int⅔oduced and deλined as synthetic hyd⅔o‐ ca⅔bons o⅔ mixtu⅔es oλ synthetic hyd⅔oca⅔bons p⅔oduced λ⅔om biomass, λo⅔ example SynGas p⅔oduced λ⅔om μasiλication oλ λo⅔est⅔y biomass o⅔ SynDiesel.

. Classification of biofuels In the Eu⅔opean classiλication, the λollowinμ bioλuels have been sepa⅔ated because oλ the state oλ matte⅔ .

Li⅓uid bioλuels

• ”ioethanol μot λ⅔om biomass o⅔ biodeμ⅔adable waste λ⅔actions, possible λo⅔ use as bioλuel E oλ % ethanol and % pet⅔ol contents o⅔ as bioλuel E oλ % ethanol and % pet⅔ol contents • ”iodiesel containinμ methyl-este⅔s [PME pu⅔e veμetable oils , RME ⅔apeseed methyl este⅔s , F“ME λatty acid methyl este⅔s ] p⅔oduced λ⅔om veμetable oil, animal oil o⅔ ⅔e‐ cycled λo⅔ example post-λ⅔yinμ λats and oils, meetinμ the ⅔e⅓ui⅔ements oλ ⅔elevant ⅓uali‐ ty standa⅔ds λo⅔ ” diesel oils oλ % este⅔ and % pet⅔oleum-based diesel contents, ” diesel oils oλ these p⅔opo⅔tions beinμ % and %, ⅔espectively, and ” exclusively consistinμ oλ pu⅔e este⅔s oλ p⅔ope⅔ties meetinμ the ⅔elevant standa⅔d speciλications • ”iomethanol p⅔oduced λ⅔om biomass, λo⅔ use as bioλuel o⅔ a λuel inμ⅔edient • ”ioET”E, that is Ethyl-te⅔tio-butyl-ethe⅔ p⅔oduced λ⅔om bioethanol, used as a pet⅔ol addi‐ tive to inc⅔ease the octane ⅔atinμ and to ⅔educe knockinμ and added to pet⅔ol at a pe⅔cent‐ aμe ⅔ate oλ % • ”ioMT”E, that is Methyl-te⅔tio-butyl-ethe⅔ p⅔oduced λ⅔om biomethanol, used λo⅔ the same pu⅔poses as those oλ the ”ioET”E and added to pet⅔ol at a pe⅔centaμe ⅔ate oλ % • ”tL, that is Li⅓uid λ⅔actions o⅔ mixtu⅔es oλ li⅓uid λ⅔actions p⅔oduced λ⅔om biomass, λo⅔ use as bioλuels o⅔ λuel inμ⅔edients

An Analysis of Physico-Chemical Proper“ies of “he Nex“ Genera“ion Biof”els... h““p://dx.doi.org/10.5772/53685

• Pu⅔e veμetable oils PVO p⅔oduced th⅔ouμh p⅔essinμ, ext⅔action o⅔ simila⅔, inclusive oλ ⅔eλininμ, but chemically unmodiλied, which can be used as bioλuel when compati‐ ble with the enμine involved and when meetinμ the matchinμ envi⅔onmental p⅔otec‐ tion ⅔e⅓ui⅔ements. .

Gaseous bioλuels

• ”ioDME t⅔anspo⅔t λuels μained λ⅔om Renewable Ene⅔μy Sou⅔ces RES , that is Dimethy‐ lethe⅔ p⅔oduced λ⅔om biomass, λo⅔ di⅔ect use as bioλuel λo⅔ comp⅔ession-iμnition enμines • ”ioμas, that is ”ioλuel p⅔oduced λ⅔om biomass o⅔ the biodeμ⅔adable λ⅔actions oλ waste, pu⅔iλied to natu⅔al μas ⅓uality • ”iohyd⅔oμen as bioλuel p⅔oduced λ⅔om biomass o⅔ the biodeμ⅔adable λ⅔actions oλ waste. .

Othe⅔ ⅔enewable λuels, that is ”ioλuels not named above, o⅔iμinatinμ λ⅔om sou⅔ces as deλined in Di⅔ective / /EC and suitable to powe⅔ t⅔anspo⅔t.

This division ⅔esulted λ⅔om the ⅔easons discussed above, in pa⅔ticula⅔ λ⅔om assessment oλ the usability oλ speciλic λuels in the p⅔esent-day enμine technoloμies, availability oλ the λeed‐ stock needed, and envi⅔onmental impact oλ the λuels. The λo⅔mal division oλ bioλuels into speciλic μene⅔ations has been published in the ⅔epo⅔t titled ”ioλueels in the Eu⅔opean Un‐ ion, a Vision λo⅔ and ”eyond . “cco⅔dinμ to this ⅔epo⅔t, bioλuels have been divided in‐ to λi⅔st μene⅔ation bioλuels, ⅔eλe⅔⅔ed to as conventional bioλuels, and second μene⅔ation bioλuels, ⅔eλe⅔⅔ed to as advanced bioλuels. The λi⅔st μene⅔ation

conventional

bioλuels include

• ”ioethanol ”ioEtOH, ”ioEt , unde⅔stood as conventional ethanol μot th⅔ouμh hyd⅔olysis and λe⅔mentation λ⅔om ⅔aw mate⅔ials such as ce⅔eals, suμa⅔ beets. • Pu⅔e veμetable oils, μot th⅔ouμh cold p⅔essinμ and ext⅔action λ⅔om seeds oλ oil plants • ”iodiesel, consistinμ oλ RME o⅔ F“ME and λatty acid ethyl este⅔s F“EE oλ hiμhe⅔ λatty acids oλ othe⅔ oily plants and μained as the ⅔esult oλ cold p⅔essinμ, ext⅔action and t⅔anses‐ te⅔iλication • ”iodiesel, consistinμ oλ methyl and ethyl este⅔s and μained as the ⅔esult oλ t⅔anseste⅔iλica‐ tion oλ post-λ⅔yinμ oil • ”ioμas, μot by pu⅔iλication oλ wet landλill o⅔ aμ⅔icultu⅔al bioμas • ”ioET”E, μot by chemical p⅔ocessinμ oλ bioethanol. The idea oλ second μene⅔ation bioλuels development is based on an assumption. Feedstock to be used λo⅔ p⅔oducinμ such λuels should e⅓ually include biomass, waste veμetable oils and animal λats, as well as any waste substances oλ o⅔μanic o⅔iμin that a⅔e useless in the λood and λo⅔est⅔y indust⅔ies. The second μene⅔ation advanced bioλuels includes • ”ioethanol, biobutanol, and blends oλ hiμhe⅔ alcohols and de⅔ivative compounds, μot as the ⅔esult oλ advanced oλ hyd⅔olysis and λe⅔mentation oλ liμnocellulosic biomass exclud‐ inμ the λeedstock λo⅔ λood p⅔oduction pu⅔poses

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• Synthetic bioλuels, beinμ p⅔oducts oλ biomass p⅔ocessinμ and μained by μasiλication and p⅔ope⅔ synthesis into li⅓uid λuel inμ⅔edients ”tL and p⅔oducts oλ p⅔ocess biodeμ⅔adable indust⅔ial and municipal wastes, includinμ ca⅔bon dioxide WtL • Fuels λo⅔ comp⅔ession-iμnition enμines, μot λ⅔om biomass th⅔ouμh Fische⅔-T⅔opsch, inclu‐ sive oλ synthetic biodiesels μot by blendinμ oλ liμnocellulosic p⅔oducts • ”iomethanol, μot as the ⅔esult oλ liμnocellulose t⅔ansλo⅔mation, inclusive oλ Fische⅔T⅔opsch synthesis, as well as with the use oλ waste ca⅔bon dioxide • ”iodimethylethe⅔ bioDME , μot by the⅔mochemical p⅔ocessinμ oλ biomass, inclusive oλ biomethanol, bioμas, and synthetic bioμases beinμ de⅔ivative p⅔oducts oλ biomass t⅔ans‐ λo⅔mation • ”iodiesel as bioλuel o⅔ a λuel inμ⅔edient λo⅔ comp⅔ession-iμnition enμines, μot by hyd⅔o⅔e‐ λininμ hyd⅔oμenation oλ veμetable oils and animal λats • ”iodimethylλu⅔an bioDMF , obtained λ⅔om suμa⅔ t⅔ansλo⅔mation, inclusive oλ t⅔ansλo⅔m‐ inμ cellulose in to the⅔mochemical and biochemical p⅔ocesses • ”ioμas as synthetic natu⅔al μas SNG o⅔ biomethane, obtained in ⅔esult oλ liμnocelluloses μasiλication, co⅔⅔ect synthesis, o⅔ pu⅔iλication oλ aμ⅔icultu⅔al, landλill, and sewaμe sludμe bioμas • ”iohyd⅔oμen μot in ⅔esult oλ μasiλication oλ liμnocellulose and synthesis oλ the μasiλication p⅔oducts o⅔ as the ⅔esult oλ biochemical p⅔ocesses. The Eu⅔opean Commission Di⅔ecto⅔ate-Gene⅔al λo⅔ Ene⅔μy and T⅔anspo⅔t p⅔oposed to sepa‐ ⅔ate thi⅔d μene⅔ation bioλuels, deλininμ them as those λo⅔ which the technoloμy oλ unive⅔sal μain and int⅔oduction oλ such λuels may be developed in s o⅔ even late⅔, acco⅔dinμ to the estimates. P⅔elimina⅔ily, biohyd⅔oμen and biomethanol have been classiλied in this μ⅔oup. The thi⅔d μene⅔ation bioλuels may be obtained by the methods simila⅔ to those used in the second μene⅔ation bioλuels, but λ⅔om the λeedstock biomass havinμ been modiλied at the plant μ⅔owinμ staμe with the use oλ molecula⅔ bioloμy techni⅓ues. The objective oλ such chanμes is to imp⅔ove the conve⅔sion oλ biomass into bioλuels biohyd⅔oμen, biomethanol, biobutanol by λo⅔ example cultivation oλ t⅔ees oλ low liμnin content, development oλ c⅔ops with enzymes inco⅔po⅔ated as ⅔e⅓ui⅔ed, etc. Sepa⅔atinμ a new, λou⅔th μene⅔ation oλ bioλuels was p⅔oposed because oλ the need to close the ca⅔bon dioxide balance o⅔ to cut out the envi⅔onmental impact oλ this compound. The⅔e‐ λo⅔e, the λou⅔th μene⅔ation bioλuel technoloμies should be developed with conside⅔inμ the CCS Ca⅔bon Captu⅔e and Sto⅔aμe at the ⅔aw mate⅔ial p⅔epa⅔ation and bioλuel p⅔oduc‐ tion staμes. The ⅔aw mate⅔ials used λo⅔ p⅔oduction oλ such λuels should be the plants oλ in‐ c⅔eased CO assimilation ⅔ates at the plant μ⅔owinμ staμe and the technoloμies applied must be devised conside⅔inμ the captu⅔e oλ ca⅔bon dioxide in p⅔ope⅔ μeoloμical λo⅔mations by causinμ the ca⅔bonate staμe to be ⅔eached o⅔ the sto⅔aμe in oil and μas exploitation caμes.

An Analysis of Physico-Chemical Proper“ies of “he Nex“ Genera“ion Biof”els... h““p://dx.doi.org/10.5772/53685

. The main directions of advanced fuel technology’s development Within the planned pe⅔spective oλ the p⅔oduction and use oλ bioλuels, the λuels a⅔e ⅔e⅓ui⅔ed to be available in enouμh la⅔μe ⅓uantities to have acceptable technical and ene⅔μy cha⅔acte⅔‐ istics λo⅔ beinμ suitable λo⅔ λuelinμ enμines o⅔ heatinμ to be inexpensive at both the p⅔oduc‐ tion and sale staμes to cause smalle⅔ envi⅔onmental haza⅔d in compa⅔ison with the conventional λuels to imp⅔ove ene⅔μy independence. ”ased on the expe⅔ience and on ⅔esults oλ the ⅔esea⅔ch wo⅔k ca⅔⅔ied out, we should st⅔ive in the nea⅔est λutu⅔e to μet bioλuels as hyd⅔oca⅔bon blends p⅔oduced by deλinite pathways. Such pathways will make it possible to μet alte⅔native λuels λo⅔ IC enμines with simultane‐ ous closinμ oλ the CO cycle. The⅔eλo⅔e, the advanced bioλuels should be • Synthetic bioλuels made as blends oλ hyd⅔oca⅔bons p⅔oduced in ⅔esult oλ biomass μasiλica‐ tion and py⅔olysis [ ] λiμu⅔es and

Lignocellulosic residues

Pretreatment

Gasification

Syngas

Combustion

Electricity and heat

FT synthesis

Synthetic biofuels

Figure 1. Schema“ic diagram of biomass “o liq”id process in Choren, Germany.

The main piece oλ biomass μasiλication technoloμy is the patented Ca⅔bo-V p⅔ocess that al‐ lows to p⅔oduce ta⅔-λ⅔ee synthetic μas, a b⅔eakth⅔ouμh λo⅔ biomass to ene⅔μy chanμe. The μas consistinμ mainly oλ CO and H can be used as a combustion μas λo⅔ the μene⅔ation oλ elect⅔icity, steam o⅔ heat, o⅔ λo⅔ the make oλ t⅔anspo⅔t λuels ”tL . Compa⅔ed with λossil die‐

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sel, the combustion oλ ”tL diesel ⅔educes PM s pa⅔ticulate matte⅔s emissions by to % and hyd⅔oca⅔bon emissions by up to %. It achieves supe⅔io⅔ combustion cha⅔acte⅔istics while no enμine adjustments a⅔e needed. ”ut pe⅔haps its most impo⅔tant λeatu⅔e is the abili‐ ty to ⅔ecycle atmosphe⅔ic CO into the λuel thus closinμ the sustainability cycle.

Lignocellulosic residues

Pretreatment

Pyrolysis ( 450 – 500oC)

Pyrolytic liquid

Hydrogenation/ upgrading

Synthetic biofuel

Separation/ fractionation

Chemical reactions

Combustion

Polymers (resins)

Food (flavourings)

Electricity and heat

Figure 2. Schema“ic diagram of Rapid Thermal Processing (RTP) TM “echnology in On“ario, Canada (owner Ensyn). I“ is commercial ins“alla“ion.

“nothe⅔ p⅔omisinμ technoloμy is ⅔elated to py⅔olysis. Rapid The⅔mal P⅔ocessinμ RTP is a λast the⅔mal p⅔ocess whe⅔e biomass is ⅔apidly heated without oxyμen. The biomass is vapo⅔‐ ized and ⅔apidly cooled to p⅔oduce hiμh yields oλ py⅔olysis oil. The py⅔olysis oil is λ⅔actio‐ nated into chemicals λo⅔ enμinee⅔ed wood p⅔oducts ⅔esins and λuel λo⅔ the⅔mal applications. The ⅔esultinμ cha⅔ and μases a⅔e used λo⅔ ene⅔μy. RTP™ typically yields to wt% py⅔olysis oil λ⅔om d⅔ied woody biomass. • ”ioλuels ea⅔ned λ⅔om biomass in ⅔esult oλ othe⅔ the⅔mochemical p⅔ocesses, such as py⅔ol‐ ysis o⅔ p⅔ocesses oλ depolyme⅔isation and hyd⅔oμenation oλ biomass decomposition p⅔od‐ ucts hyd⅔othe⅔mal upμ⅔adinμ-HTU p⅔ocesses • Fuel blends composed oλ hyd⅔oca⅔bons μained λ⅔om biomass, includinμ those di⅔ectly o⅔ indi⅔ectly obtained λ⅔om suμa⅔s in ⅔esult oλ bioloμical o⅔ chemical p⅔ocesses, • ”ioλuels beinμ othe⅔ suμa⅔ de⅔ivatives • ”iomethane and othe⅔ μaseous λuels μot λ⅔om biomass μasiλication p⅔ocesses o⅔ aμ⅔icul‐ tu⅔al, landλill, and sewaμe sludμe t⅔eatment p⅔ocesses

An Analysis of Physico-Chemical Proper“ies of “he Nex“ Genera“ion Biof”els... h““p://dx.doi.org/10.5772/53685

• ”ioethanol and hiμhe⅔ alcohols -biobutanol and thei⅔ de⅔ivatives, obtained λ⅔om biomass in ⅔esult oλ biochemical o⅔ catalyzed the⅔mochemical p⅔ocesses λiμu⅔e

Figure 3. Processes of biochemical biomass conversion.

• ”ioλuels obtained by utilization oλ ca⅔bon dioxide λo⅔ p⅔oduction oλ mic⅔oo⅔μanisms o⅔ by di⅔ect o⅔ indi⅔ect synthesis oλ ca⅔bon dioxide oλ natu⅔al o⅔iμin in the⅔mochemical and bio‐ chemical • ”ioλuels obtained λ⅔om synthetic μas p⅔oduced as a p⅔oduct oλ di⅔ect o⅔ indi⅔ect th⅔ouμh methanol conve⅔sion oλ biomass o⅔ GHG • ”ioλuels HVO, hyd⅔oμenated veμetable oils μot by hyd⅔oμenation oλ waste veμetable and animal λats.

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. Application of selected types of biofuels of the first and second generation “monμ the p⅔oposed alte⅔native λuels, veμetable oils have ⅔eceived much attention in ⅔ecent yea⅔s λo⅔ diesel enμines owinμ to thei⅔ advantaμes as ⅔enewable and domestically p⅔oduced ene⅔μy. The majo⅔ disadvantaμe oλ pu⅔e veμetable oils is thei⅔ inhe⅔ently hiμh viscosity, leadinμ to poo⅔ λuel atomization, incomplete combustion, cokinμ oλ λuel injecto⅔s, ⅔inμ ca⅔‐ bonization, and accumulation oλ veμetable oil in the lub⅔icatinμ oil. Seve⅔al methods a⅔e conse⅓uently beinμ used to ⅔educe veμetable oil s viscosity. ”lendinμ oλ veμetable oils with an alcohol oλ lowe⅔ viscosity is one oλ the methods [ , ]. Main alcohols used as a λuels inμ⅔edient a⅔e methanol, ethanol and n-butanol. These alco‐ hols have diλλe⅔ent p⅔ope⅔ties. Some oλ them a⅔e p⅔esented in Table . They a⅔e compa⅔ed to conventional enμine λuels. Fuel

Energy density

Heat of vaporization

Kinematic viscosity at 20°C

Diesel

38.6 MJ/l

0.47 MJ/kg

"/>3 cS“

Gasoline

32.0 MJ/l

0.36 MJ/kg

0.4–0.8 cS“

B”“anol

29.2 MJ/l

0.43 MJ/kg

3.64 cS“

E“hanol

19.6 MJ/l

0.92 MJ/kg

1.52 cS“

Me“hanol

16.0 MJ/l

1.20 MJ/kg

0.64 cS“

Table 1. The proper“ies of differen“ alcohols and engine f”els

It is inte⅔estinμ the butanol has simila⅔ ene⅔μy density as pet⅔ol. ”utanol is μood solvent oλ heavy hyd⅔oca⅔bons such diesel λuels . The mixtu⅔e oλ these components is homoμeneous and doesn t sepa⅔ate aλte⅔ seve⅔al months. In cont⅔ast, ethanol is sliμhtly soluble in diesel λuel. It is impo⅔tant the wate⅔ is nea⅔ly insoluble in butanol, in cont⅔ast to ethanol which dis‐ solves wate⅔ in any p⅔opo⅔tion. The old and new technoloμy oλ butanol p⅔oduction is known as an “”E p⅔ocess “cetone”utanol-Ethanol and the second μene⅔ation p⅔ocess usinμ liμnocellulosic waste mate⅔ials, ⅔espectively. The conventional “”E λe⅔mentation p⅔ocess is based on suμa⅔ s mate⅔ial cane o⅔ beet o⅔ sta⅔ch wheat, co⅔n o⅔ ⅔ice which is easily b⅔oken down into suμa⅔s. Du⅔inμ the λe⅔mentation λo⅔med the th⅔ee components acetone, n-butanol and ethanol in ⅔atio oλ as main p⅔oducts. The p⅔ocess is pe⅔λo⅔med by anae⅔obic μ⅔am- positive bacte⅔ia oλ the μen‐ eus clost⅔idia mainly Clost⅔idium acetobutylicum, but also C. ”eije⅔inckii, C. butylicum and othe⅔s . The “”E p⅔ocess is not p⅔oλitable because oλ low p⅔oductivity and poo⅔ selec‐ tivity. One oλ the cou⅔ses cove⅔s metabolic enμinee⅔inμ issues, that is modiλication oλ meta‐ bolic pathway to inc⅔ease ⅔esistinμ clost⅔idia bacte⅔ia to hiμhe⅔ concent⅔ations oλ λe⅔mentation p⅔oducts, and imp⅔ove the eλλiciency and selectivity. Low yield oλ the λe⅔men‐ tation oλ butanol synthesis ⅔e⅓ui⅔es ⅔esea⅔ch on butanol ⅔ecove⅔y techni⅓ues. The⅔e a⅔e

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many sepa⅔ation techni⅓ues oλ λe⅔mentation p⅔oducts, e. μ. li⅓uid-li⅓uid ext⅔action, pe⅔st⅔ac‐ tion, pe⅔vapo⅔ation memb⅔ane sepa⅔ation with μaseous pe⅔meate discha⅔μe combined with immobilization oλ bacte⅔ial cells, adso⅔ption o⅔ ⅔eve⅔sed osmosis. It is estimated that eλλective solutions development can help to inc⅔ease oλ p⅔oλitability up to - %. The ideal λeedstock λo⅔ bioconve⅔sions could be waste biomass, λo⅔ example st⅔aw, wood chips and pape⅔ pulp eλλluent. “lso c⅔ops specially μ⅔own λo⅔ thei⅔ hiμh biomass p⅔oduction ⅔ate kenaλ, miscanthus and sho⅔t ⅔otation woody c⅔ops . Such sou⅔ces oλ ⅔aw mate⅔ials can be desc⅔ibed as cellulosic biomass because oλ thei⅔ hiμh cellulose and hemicellulose con‐ tent. The λeedstock used in λe⅔mentation dete⅔mines the selection oλ st⅔ains and p⅔ocess con‐ ditions. The company G⅔een ”ioloμics is developinμ biobutanol p⅔oduction λ⅔om μlyce⅔ol and othe⅔ wastes λ⅔om indust⅔y and aμ⅔icultu⅔e, usinμ μenetically modiλied the⅔mophilic bacte⅔ia oλ the μenus μeobacillus and sells de⅔ived λuel named ”utaλuel λiμu⅔e .

Feedstocks

corn starch, molasses, glycerine, hemicelulose

bagasse, wheat straw, corn strover

Pretreatment and hydrolysis

Saccharification

FERMENTATION thermofilic bacteria

Product recovery

Acetone

Butanol

Ethanol

Hydrogen

High value chemicals

Figure 4. Schema“ic diagram of GBL’s “echnology, Green Biologics L“d. Biob”“anol ”sed “o prod”ce f”els, pain“s, coa“‐ ings, resins, polymers and solven“s.

”utanol, like ethanol, can blend well with μasoline. ”iobutanol can ⅔eplace μasoline in E λuel. “lso, butanol could be a λutu⅔e λo⅔ blendinμ with diesel. ”utanol contains mo⅔e oxyμen compa⅔ed to the biodiesel, leadinμ to λu⅔the⅔ decline oλ soot. NOx emissions can also be ⅔e‐ duced because oλ its hiμhe⅔ heat oλ evapo⅔ation, which ⅔esults in a lowe⅔ combustion tem‐

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pe⅔atu⅔e. The butanol has mo⅔e advantaμes than the widely used ethanol and F“ME. Howeve⅔, the main disadvantaμe oλ butanol is low p⅔oduction. ”iobutanol is nonco⅔⅔osive and can be shipped via pipeline. No.

Butanol isomers

1

1-b”“anol

2

2-b”“anol

3

iso-b”“anol

4

“er“-b”“anol

Main application Gasoline addi“ive, solven“s, plas“icizers, chemical in“ermedia“e, cosme“ics Solven“s, chemical in“ermedia“e, ind”s“rial cleaners, perf”mes or in ar“ificial flavors Gasoline addi“ive, solven“ and addi“ive for pain“, ind”s“rial cleaners, ink ingredien“ Gasoline addi“ive for oc“ane boos“er and oxygena“e; in“ermedia“e for MTBE, ETBE, THBP; dena“”ran“ for e“hanol; solven“

Table 2. The main applica“ion of b”“anol isomers. Ref. [7]

This wo⅔k p⅔esents a novel way oλ usinμ alcohols and pu⅔e veμetable oil as λuels λo⅔ a diesel enμine. It was shown the possibility oλ use oλ hiμhe⅔ alcohols as a solvent λo⅔ st⅔aiμht veμeta‐ ble oil the mixtu⅔e was named ”M . Such a mixtu⅔e, aλte⅔ μettinμ the density simila⅔ to the density oλ diesel λuel, was mixed with diesel λuel D μivinμ biomixdiesel ”MD . Fo⅔ ”MD p⅔epa⅔ation was used the n-butanol and iso-amyl by-p⅔oduct oλ ethanol λe⅔mentation as an alcohol, ⅔apeseed oil and conventional diesel λuel. “nothe⅔ bioλuels as an example oλ second μene⅔ation we⅔e obtained by nonoxidative the⅔mal/py⅔olytic c⅔ackinμ oλ st⅔aw nea⅔ly mic⅔ons λollowed by biooil hyd⅔ot⅔eatinμ. The last one- HVO diesel was obtained by cata‐ lytic hyd⅔oconve⅔sion oλ veμetable oil mixtu⅔es. Hyd⅔ot⅔eated veμetable oils do not have the ha⅔mλul eλλects oλ este⅔-type biodiesel λuels, like inc⅔eased NOx emission, deposit λo⅔mation, sto⅔aμe stability p⅔oblems, mo⅔e ⅔apid aμinμ oλ enμine oil o⅔ poo⅔ cold p⅔ope⅔ties. HVOs a⅔e st⅔aiμht chain pa⅔aλλinic hyd⅔oca⅔bons that a⅔e λ⅔ee oλ a⅔omatics, oxyμen and sulλu⅔ and have hiμh cetane numbe⅔s. “ll th⅔ee bioλuels we⅔e examined acco⅔dinμ to ENstanda⅔d [ ] . . Experimental and results . . . “ssessmeσt τλ the physiθτ-θhemiθζl prτperties τλ the ”MD ηiτλuel To assess the ⅓uality oλ bioλuel containinμ components such as hiμhe⅔ alcohol and ⅔apeseed oil we⅔e p⅔epa⅔ed two expe⅔imental blends based on p⅔evious wo⅔ks [ , ]. Majo⅔ scientiλic wo⅔ks ⅔eμa⅔ds diesel-biobutanol mixtu⅔es [ ] and mino⅔ t⅔iple mixtu⅔es with veμetable oil. The main component oλ mixtu⅔es was conventional diesel in % vol. , made up to % with two mentioned above biocomponets. Expe⅔iment was ca⅔⅔ied out with two hiμhe⅔ alco‐

An Analysis of Physico-Chemical Proper“ies of “he Nex“ Genera“ion Biof”els... h““p://dx.doi.org/10.5772/53685

hols n-butyl alcohol and iso-amyl alcohol. Fi⅔st we⅔e p⅔epa⅔ed blends consistinμ oλ selected alcohol and ⅔apeseed oil in a ⅔atio oλ ”ioMix , and then ⅔eceived blend was int⅔oduced into diesel λuel D . P⅔epa⅔ed samples a⅔e ma⅔ked with symbols ”MD- with n-butanol and ”MD- with iso-amyl alcohol . Mixtu⅔es oλ ”MD- and ”MD- we⅔e clea⅔, without haze and sediment. New bioλuels sto⅔ed λo⅔ seve⅔al days at ⅔oom tempe⅔atu⅔e showed no λeatu⅔es oλ sepa⅔ation. Diesel λuel used to compose bioλuels met all ⅓uality ⅔e⅓ui⅔ements ac‐ co⅔dinμ to EN- . Table shows the basic λeatu⅔es oλ diesel, and Table compa⅔es p⅔ope⅔‐ ties oλ n-butyl alcohol and iso-amyl. No.

Property

Result

1.

Ce“ane n”mber

53,0

2.

Densi“y a“ 15oC, kg/m3

836,2

3.

Flash poin“, oC

63

4.

Carbon resid”e (on 10% dis“illa“ion resid”e), %(m/m) Dis“illa“ion %(V/V) recovered a“ 250oC,

5.

%(V/V) recovered a“ 350oC, 50%(V/V) recovered a“ , oC 95%(V/V) recovered a“ , oC finish boiling poin“, oC

nm we⅔e obse⅔ved with an inc⅔ease in load λo⅔ both the λuels. Fo⅔ the stationa⅔y enμine ⅔unninμ with ULSD at λull load, nucleation % , accumula‐ tion % and λine pa⅔ticles % sha⅔ed almost a simila⅔ λ⅔action oλ pa⅔ticles to the total PNC. Howeve⅔, λo⅔ ”D, nucleation % and accumulation mode pa⅔ticles % we⅔e ma‐ jo⅔ cont⅔ibuto⅔s to the total numbe⅔ concent⅔ations. The λ⅔action oλ accumulation mode pa⅔‐ ticles inc⅔eased λ⅔om % du⅔inμ idle mode to % at λull load in the case oλ ULSD, and a simila⅔ inc⅔ease was obse⅔ved λo⅔ biodiesel as well λ⅔om % at idle mode to % at λull load . This obse⅔vation implies that diesel enμines emit mo⅔e accumulation pa⅔ticles at hiμh‐ e⅔ loads. “t hiμhe⅔ loads, mo⅔e λuel is injected into the combustion chambe⅔ to μene⅔ate ad‐ ditional to⅔⅓ue needed and also the ⅔esidence time λo⅔ the pa⅔ticles in the combustion chambe⅔ dec⅔eases ⅔elatively. The⅔eλo⅔e, the oxidation oλ pa⅔ticulate soot tends to be ⅔e‐ duced, leadinμ to the ⅔elease oλ a la⅔μe λ⅔action oλ accumulation and λine pa⅔ticles. In the case oλ biodiesel, the inhe⅔ent oxyμen in the λuel imp⅔oves the oxidation oλ soot. The⅔eλo⅔e, the pe⅔centaμe inc⅔ease oλ λine pa⅔ticles is ⅔elatively less λo⅔ ”D.

. Chemical properties of particulate emissions Since diesel enμines a⅔e one oλ the most siμniλicant ai⅔ pollutant sou⅔ces in u⅔ban a⅔eas Cass, , chemical composition oλ diesel exhaust has been widely investiμated. The chemical p⅔o‐ λile oλ PM plays a c⅔ucial ⅔ole in health and envi⅔onmental impacts. Va⅔iations in the chemical composition oλ ae⅔osols alte⅔ thei⅔ hyμ⅔oscopicity and can lead to chanμes in the cloud-active λ⅔action oλ the ae⅔osols, o⅔ cloud condensation nuclei CCN numbe⅔ concent⅔ation Wa⅔d et al., . Some ca⅔cinoμenic and toxic chemical compounds p⅔esent in DEP when bioloμically

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available can aλλect human health. Diesel enμine emissions consist oλ a wide ⅔anμe oλ o⅔μanic and ino⅔μanic compounds in μaseous as well as pa⅔ticulate phases ”(nμe⅔ et al., . Con‐ cent⅔ations oλ most pa⅔ticle-bound chemical constituents depend on the type oλ enμine, enμine load, λuel and lub⅔ication oil p⅔ope⅔ties Dwivedi et al., . La⅔μe su⅔λace a⅔ea oλ DEP ena‐ bles adso⅔ption oλ o⅔μanics and ino⅔μanic compounds λ⅔om the combustion p⅔ocess and/o⅔ the adso⅔ption oλ additional compounds du⅔inμ t⅔anspo⅔t in the ambient ai⅔. DEP consists mainly oλ elemental ca⅔bon EC % , o⅔μanic ca⅔bon OC % and small amounts oλ sulλates, ni‐ t⅔ates % and metals & Elements % Fiμu⅔e EP“, a.

Figure 3. Frac“iona“ion of par“icle emi““ed from ULSD WCOB (B100) for vario”s loads (Be“ha e“ al., 2011a).

Physico-Chemical Charac“eris“ics of Par“ic”la“e Emissions from Diesel Engines F”elled wi“h Was“e Cooking Oil Derived Biodiesel and Ul“ra Low S”lph”r Diesel h““p://dx.doi.org/10.5772/53476

Figure 4. Typical chemical composi“ions for diesel par“ic”la“e ma““er (PM2.5) (EPA, 2002a)

. . Particle-bound polycyclic aromatic hydrocarbons PAHs Pa⅔ticulate-bound o⅔μanic compounds, especially P“Hs, a⅔e hiμhly ca⅔cinoμenic. P“Hs and thei⅔ de⅔ivatives nit⅔o-P“Hs toμethe⅔ comp⅔ise less than % oλ the mass oλ DEP EP“, a . The emissions oλ these compounds a⅔e comp⅔ehensively studied λo⅔ diesel enμines λuelled with diesel and ”D Junμ et al., ”aμley et al., Co⅔⅔ea et al., Ka⅔avala‐ kis et al., Tu⅔⅔o-”aldassa⅔i et al., Zou and “tkinson, Ka⅔avalakis et al., . “ majo⅔ity oλ studies have λound a siμniλicant dec⅔ease in P“Hs emissions with ”D compa⅔ed to that with diesel ”aμley et al., Co⅔⅔ea et al., Ka⅔avalakis et al., . Howeve⅔, a couple oλ studies have indicated only statistically insiμniλicant ⅔eduction in P“Hs Tu⅔⅔o-”aldassa⅔i et al., Zou and “tkinson, when ”D is used. The ⅔educ‐ tion in P“H emission may be att⅔ibuted to the p⅔esence oλ excess oxyμen in ”D and the ab‐ sence oλ a⅔omatic and polycyclic a⅔omatic compounds in the λuel. One study Ka⅔avalakis et al., was λound in lite⅔atu⅔e ⅔epo⅔tinμ hiμhe⅔ P“Hs emissions when usinμ ”D. Ka⅔ava‐ lakis et al. tested ”D made λ⅔om soybean oil and used λ⅔yinμ oil. They λound lowe⅔ P“H emissions with ”D made λ⅔om soybean oil. Howeve⅔, ”D made λ⅔om used λ⅔yinμ oil emitted mo⅔e P“H compounds compa⅔ed to those λ⅔om diesel. They att⅔ibuted the inc⅔ease in P“Hs to dime⅔s, t⅔ime⅔s, polyme⅔ization p⅔oducts, and cyclic acids p⅔esent in the biodie‐ sel made λ⅔om used λ⅔yinμ oil. . . Particulate-bound elements and trace metals Studies on pa⅔ticulate-bound metals emitted λ⅔om ”D combustion a⅔e not as comp⅔ehensive as P“Hs, despite a st⅔onμ co⅔⅔elation between human health ⅔isk and pa⅔ticulate-bound

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metals Hu et al., Ve⅔ma et al., . Ve⅔y λew studies Dwivedi et al., Cheunμ et al., we⅔e λound in lite⅔atu⅔e investiμatinμ pa⅔ticulate-bound metals in ”D. Dwivedi et al. conducted a compa⅔ative assessment and cha⅔acte⅔ization oλ pa⅔ticulate-bound t⅔ace elemental emissions λ⅔om diesel and ⅔ice b⅔an oil de⅔ived ”D. Elements such as C⅔, Ni, Pb, Cd, Na, “l, Mμ, and Fe we⅔e investiμated. The autho⅔s obse⅔ved that concent⅔ation oλ metals such as C⅔, Fe, “l, Zn, Mμ inc⅔eased while othe⅔s Pb, Cd, Na, Ni we⅔e ⅔educed with the usaμe oλ ” % ”D . Cheunμ et al. also obse⅔ved hiμhe⅔ concent⅔ations oλ Fe, Zn, Mμ when usinμ ”D. Howeve⅔, C⅔, “l, Pb, Cd, Na, Ni we⅔e lowe⅔ in ”D emission com‐ pa⅔ed to diesel. In both the studies, the pa⅔ticulate-bound elemental concent⅔ations we⅔e mainly att⅔ibuted to the λuel and lub⅔icatinμ oil composition apa⅔t λ⅔om enμine wea⅔. Metals and elements that we⅔e λound hiμhe⅔ in λuel we⅔e also λound hiμhe⅔ in the emissions. Since the pa⅔ticulate-bound elements la⅔μely depend on λuel ⅓uality and composition apa⅔t λ⅔om enμine wea⅔, thei⅔ concent⅔ation in the exhaust is expected to va⅔y with λeedstock oλ ”D. In anothe⅔ study ”etha et al. b investiμated the pa⅔ticulate bound elements λ⅔om WCO” ” , ULSD and thei⅔ blend ” . They obse⅔ved that pa⅔ticulate emissions we⅔e ⅔educed with the usaμe oλ WCO”. Howeve⅔, most oλ the elements which a⅔e known to be toxic such as Zn, C⅔, Ni we⅔e ve⅔y hiμh in the WCO” exhaust compa⅔ed to ULSD. Elements such as “s, Co, “l, Mn we⅔e λound to be in hiμhe⅔ levels in ULSD. Elements such as C⅔, Cu, Fe, ”a, Zn, Mμ, Ni, and K we⅔e λound in hiμhe⅔ concent⅔ations in ” compa⅔ed to ULSD. Simila⅔ λindinμs we⅔e ⅔epo⅔ted by Dwivedi et al. . They λound that concent⅔ations oλ Zn, Fe, and C⅔ we⅔e hiμhe⅔ in biodiesel compa⅔ed to those in diesel. The hiμhe⅔ concent⅔ations oλ elements, especially Cu, Fe, Zn, in ” used in this study can be att⅔ibuted to the ⅔aw mate‐ ⅔ial λ⅔om which biodiesel was p⅔epa⅔ed. ”D used in this study was de⅔ived λ⅔om WCO μen‐ e⅔ated in ⅔estau⅔ants and λood cou⅔ts. The oil has been used λo⅔ cookinμ and λ⅔yinμ oλ va⅔ious λood p⅔oducts. Elements such as Cu, Fe, Zn and Mn we⅔e λound in veμetables, Ka‐ washima and Soa⅔es, Cu, Fe, and Zn in meat Lomba⅔di-”occia et al., and Cu, Zn and Cd in λish “tta et al., . These elements miμht have been ⅔eleased into the oil du⅔‐ inμ cookinμ and the⅔eλo⅔e, the concent⅔ations oλ Fe, Zn, Cu, Mn in ”D we⅔e λound to be siμ‐ niλicantly hiμh. In addition, these elements can also be leached out λ⅔om the cookinμ utensils due to heatinμ Kuliμowski and Halpe⅔in, .

. Estimation of health risk due to particulate emissions Human health ⅔isk assessment was conducted based on the mean concent⅔ations oλ pa⅔ticu‐ late-bound elements dete⅔mined th⅔ouμh the expe⅔imental study. Health ⅔isk assessment is especially useλul in unde⅔standinμ the health haza⅔d associated with inhalation exposu⅔e to PM emitted λ⅔om ” compa⅔ed to that oλ ULSD. The details and steps involved in health ⅔isk assessment a⅔e desc⅔ibed in detail elsewhe⅔e See and ”alasub⅔amanian, . ”⅔ieλly, it involves λou⅔ impo⅔tant steps NRC, as desc⅔ibed below. Haza⅔d identiλication elements which have known toxicity values a⅔e conside⅔ed. “l, C⅔, and Mn induce non-ca⅔cinoμenic eλλects while “s, Cd, C⅔, Ni and Co induce ca⅔cinoμenic health eλλects.

Physico-Chemical Charac“eris“ics of Par“ic”la“e Emissions from Diesel Engines F”elled wi“h Was“e Cooking Oil Derived Biodiesel and Ul“ra Low S”lph”r Diesel h““p://dx.doi.org/10.5772/53476

Exposu⅔e assessment This involves estimation oλ ch⅔onic daily intake CDI oλ these ele‐ ments calculated λ⅔om the λollowinμ e⅓uations. CDI mμ kμ - day - =

Total dose TD,mμ m - x inhalation ⅔ate IR, m day ”ody weiμht ”W,kμ TD = C x E

whe⅔e C is concent⅔ation oλ pollutant and E is deposition λ⅔action oλ pa⅔ticles by size μiven by Volckens and Leith, , E=- .

+ .

ln D p

+ .

s⅓⅔t D p

whe⅔e Dp is the diamete⅔ oλ pa⅔ticles. In this study, PM . “e⅔odynamic diamete⅔ . m was used i.e. Dp is . m. IR is typically assumed to be m day- and ”W to be kμ λo⅔ adults. “s λo⅔ child⅔en, the IR and ”W a⅔e assumed to be m day- and kμ, ⅔espectively. Dose-⅔esponse assessment- It is the p⅔obability oλ health eλλects acco⅔dinμ to the dose oλ pollutant oλ conce⅔n. “ssuminμ only inhalation as the majo⅔ exposu⅔e ⅔oute, the ⅔eλe⅔ence dose RλD, mμ kμ- , day- λo⅔ toxic elements that a⅔e non-ca⅔cinoμenic was calculated λ⅔om ⅔eλe⅔ence concent⅔ations RλC, mμ/m p⅔ovided by USEP“. Likewise, λo⅔ ca⅔cinoμenic ele‐ ments the inhalation slope λacto⅔ SF, mμ- kμ day was calculated λ⅔om inhalation unit ⅔isk values IUR, mμ- m p⅔ovided by USEP“. Risk cha⅔acte⅔ization o⅔ estimation oλ health ⅔isk - was calculated based on the exposu⅔e and dose ⅔esponse assessments. Fo⅔ non-ca⅔cinoμenic metals, it is indicated by United States Depa⅔tment oλ Ene⅔μy, Haza⅔d Quotient ( HQ ) = CDI/RλD

Fo⅔ ca⅔cinoμenic metals, total ca⅔cinoμenic ⅔isk is estimated in te⅔ms oλ excess liλe time can‐ ce⅔ ⅔isk ELCR μiven by United States Depa⅔tment oλ Ene⅔μy, . ELCR = CDI x SF The human health ⅔isk assessment was ca⅔⅔ied out to ⅓uantiλy the ⅔isk associated with the pa⅔ticulate-bound metals emitted λ⅔om ULSD and WCO” at λull load λ⅔om a stationa⅔y en‐ μine λo⅔ illust⅔ation. The pe⅔tinent inλo⅔mation oλ the TD and RλD, HQ, inhalation SF and ELCR λo⅔ adults and child⅔en a⅔e shown in Tables and . The concent⅔ations oλ metals used λo⅔ this illust⅔ation

477

478

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

a⅔e adopted λ⅔om ”etha et al. b shown in Table and CDI is calculated usinμ E⅓ns . The concent⅔ations ⅔epo⅔ted in ”etha et al., b ⅔ep⅔esent those emitted λ⅔om the ⅔aw enμine exhaust. Howeve⅔, in ⅔eality the enμine exhaust is diluted by ambient ai⅔ once it is ⅔eleased to the atmosphe⅔e. The dilution λacto⅔ is typically times when exhaust is ⅔e‐ leased to the ambient atmosphe⅔e on ⅔oad conditions Zielinska, . The mean concent⅔a‐ tions oλ elements we⅔e divided by to be used in health ⅔isk calculations. The deposition eλλiciency E λo⅔ pa⅔ticle with . m is nea⅔ly . . The CDI is calculated by λi⅔st estimatinμ the TD oλ the each element Tables and . ULSD CDI

RfD

(mg kg-1 day-1)

(mg kg-1 day-1)

Al

9.84 x 10-6

1.43 x 10-3

6.88 x 10-3

Cr

1.22 x 10-6

2.86 x 10-5

4.26 x 10-2

Mn

9.18 x 10

1.43 x 10

6.42 x 10-3

Metals

SF

HQ

(mg kg-1 day)

ELCR

Non carcinogenic me“als

-8

-5

Carcinogenic me“als As

2.51 x 10-8

15.1

3.79 x 10-7

Cd

-9

3.79 x 10

6.3

2.39 x 10-8

Cr

1.22 x 10-6

4.2

5.12 x 10-6

Ni

8.02 x 10

84

6.74 x 10-6

-8

∑=5.59 x10-2

∑ =12.3 x10-6

WCOB CDI

RfD

(mg kg-1 day-1)

(mg kg-1 day-1)

Al

6.42 x 10-6

1.43 x 10-3

4.49 x 10-3

Cr

2.18 x 10-6

2.86 x 10-5

7.63 x 10-2

Mn

3.85 x 10

1.43 x 10

2.69 x 10-3

Metals

SF

HQ

(mg kg-1 day)

ELCR

Non carcinogenic me“als

-8

-5

Carcinogenic me“als As

9.57 x 10-9

15.1

1.45 x 10-7

Cd

-9

2.31 x 10

6.3

1.45 x 10-8

Cr

2.18 x 10-6

4.2

9.16 x 10-6

Ni

8.72 x 10-8

84

7.33 x 10-6

∑=8.34x 10

-2

∑=16.6 x 10-6

Table 2. Es“ima“ion of h”man heal“h risk in ad”l“s d”e “o par“ic”la“e bo”nd elemen“s from PM2.5 emi““ed from WCOB and ULSD (Be“ha e“ al., 2011b)

Physico-Chemical Charac“eris“ics of Par“ic”la“e Emissions from Diesel Engines F”elled wi“h Was“e Cooking Oil Derived Biodiesel and Ul“ra Low S”lph”r Diesel h““p://dx.doi.org/10.5772/53476 ULSD Metals

CDI

RfD

(mg kg-1day-1)

(mg kg-1day-1)

SF

HQ

(mg kg-1day)

ELCR

Non carcinogenic me“als Al

2.30 x 10-5

1.43 x 10-3

1.61 x 10-2

Cr

2.85 x 10-6

2.86 x 10-5

9.95 x 10-2

Mn

2.14 x 10-7

1.43 x 10-5

1.50 x 10-2

Carcinogenic me“als As

5.85 x 10-8

15.1

8.84 x 10-7

Cd

8.85 x 10

-9

6.3

5.58 x 10-8

Cr

2.85 x 10-6

4.2

1.20 x 10-5

Ni

1.87 x 10

84

1.57 x 10-5

-7

∑= 1.31 x 10-2

∑ = 28.6 x 10-6

WCOB Metals

CDI

RfD

(mg kg-1day-1)

(mg kg-1day-1)

SF

HQ

(mg kg-1day)

ELCR

Non carcinogenic me“als Al

1.50 x 10-5

1.43 x 10-3

1.05 x 10-2

Cr

5.09 x 10

2.86 x 10

-5

1.78 x 10-1

Mn

8.98 x 10-8

1.43 x 10-5

6.28 x 10-3

-6

Carcinogenic me“als As

2.23 x 10-8

15.1

3.37 x 10-7

Cd

5.38 x 10-9

6.3

3.39 x 10-8

Cr

5.09 x 10

4.2

2.14 x 10-5

Ni

2.04 x 10-7

84

1.71 x 10-5

-6

∑ = 1.95 x 10

-1

∑ = 38.8 x 10-6

Table 3. Es“ima“ion of h”man heal“h risk in children d”e “o par“ic”la“e bo”nd elemen“s from PM2.5 emi““ed from WCOB and ULSD (Be“ha e“ al., 2011b)

“s shown in Tables and , the levels oλ non-ca⅔cinoμenic ⅔isk total HQ we⅔e estimated to be . λo⅔ ULSD and . λo⅔ WCO” and ca⅔cinoμenic ⅔isk total ELCR to be . x - λo⅔ ULSD and . x - λo⅔ WCO” λo⅔ adults. In the case oλ child⅔en, non-ca⅔cinoμenic and ca⅔‐ cinoμenic ⅔isks λo⅔ both the λuels a⅔e hiμhe⅔ than those in adults. Total HQ was estimated to be . λo⅔ ULSD and . λo⅔ ” , while total ELCR was . x - λo⅔ ULSD and . x λo⅔ WCO”. It implies that to child⅔en o⅔ to adults in a million can μet cance⅔ aλte⅔ exposu⅔e to the toxic t⅔ace metals in PM . emitted λ⅔om the combustion oλ ULSD. In the case oλ biodiesel, it is even hiμhe⅔, to child⅔en o⅔ to adults out oλ a million can μet cance⅔ aλte⅔ exposu⅔e to PM . by ” λuel.

479

480

Biodiesel - Feeds“ocks, Prod”c“ion and Applica“ions

Element

ULSD (mg/m3)

WCOB(mg/m3)

Al

147.6

96.3

Mn

1.4

0.6

Cr

18.3

32.7

Ni

1.2

1.3

Cd

0.06

0.03

As

0.4

0.14

Table 4. Concen“ra“ion of par“ic”la“e bo”nd elemen“s in raw exha”s“ of a s“a“ionary engine

F⅔om the ⅔esults it can be deduced that the non-ca⅔cinoμenic ⅔isk indicated by HQ was hiμh‐ e⅔ λo⅔ WCO” compa⅔ed to ULSD λo⅔ both μ⅔oups oλ people. Howeve⅔, λo⅔ both ULSD and WCO”, the total HQ was ve⅔y low λo⅔ adults compa⅔ed to child⅔en and λo⅔ both the μ⅔oups total HQ was below acceptable levels, “cceptable levels λo⅔ total HQ = . On the othe⅔ hand ca⅔cinoμenic ⅔isk indicated by ELCR was λound to be much hiμhe⅔ than the acceptable limit λo⅔ both μ⅔oups and λo⅔ both λuels i.e., in a million and that ELCR λo⅔ WCO” was μ⅔eate⅔ than ULSD. F⅔om the ⅔isk assessment ⅔esults made in this study, it appea⅔s that exposu⅔e to PM . emitted λ⅔om biodiesel poses hiμhe⅔ ⅔isk when compa⅔ed to PM . emitted λ⅔om ULSD. Howeve⅔, it is to be noted that in this study the ca⅔cinoμenic ⅔isk due to pa⅔ticulate bound elements was used as a measu⅔e to evaluate the total ca⅔cinoμenic ⅔isk. “ mo⅔e comp⅔ehen‐ sive and extensive ⅔esea⅔ch needs to be done to evaluate the complete ⅔isk assessment in‐ cludinμ many othe⅔ ca⅔cinoμenic compounds such as P“Hs and nit⅔o-P“Hs. Studies have shown that P“H emissions λ⅔om biodiesel a⅔e ve⅔y much lowe⅔ compa⅔ed to diesel Jalava et al., Ka⅔avalakis et al., Lin et al., Tu⅔⅔io-”aldassa⅔⅔i et al., . The⅔eλo⅔e, the total ca⅔cinoμenic ⅔isk oλ WCO” exhaust pa⅔ticles miμht be actually lowe⅔ than ULSD. In the case oλ P“Hs the the ⅔isk assessment λo⅔ P“Hs that a⅔e p⅔obable and possible human ca⅔cinoμens we⅔e calculated usinμ petency e⅓uivalency λacto⅔ PEF ⅔elative to ”aP and the CDI calculated λ⅔om E⅓ . Table shows the P“Hs with know PEFs Collins et al., . PAH

Group

PEF

Benz(a)an“hracene, BaA

2A

0.1

Benz(a)pyrene, BaP

2A

1

Benzo(b)fl”oran“hene, BbF

2B

0.1

Benzo(k)fl”oran“hene, BkF

2B

0.01

Indeno(1,2,3-cd)pyrene, Ind

2B

0.1

2A: Probable H”man Carcinogen 2B: Possible H”man Carcinogen Table 5. Classifica“ion of PAHs by IARC and Po“ency eq”ivalency fac“or (PEF)

Ca⅔cinoμenic ⅔isk due to individual P“Hs is calculated as p⅔oduct oλ CDI and PEF. The total ca⅔cinoμenic ⅔isk is the summation oλ individual ⅔isk.

Physico-Chemical Charac“eris“ics of Par“ic”la“e Emissions from Diesel Engines F”elled wi“h Was“e Cooking Oil Derived Biodiesel and Ul“ra Low S”lph”r Diesel h““p://dx.doi.org/10.5772/53476

. Summary Pa⅔ticle. physical and chemical p⅔ope⅔ties play a key ⅔ole in dete⅔mininμ the health eλλects associated with PM emissions. Smalle⅔ pa⅔ticles can penet⅔ate deep inside the alveola⅔ ⅔e‐ μions oλ lunμs. ”io-available pa⅔ticulate-bound compounds pose se⅔ious health p⅔oblems. WCO” had lowe⅔ PNC compa⅔ed to that oλ ULSD. Howeve⅔, WCO” had a hiμhe⅔ λ⅔action oλ nucleation mode pa⅔ticles ⅔elative to that oλ ULSD, and the⅔eλo⅔e, a la⅔μe λ⅔action oλ PM emitted λ⅔om WCO” can deposit in ⅔espi⅔ato⅔y system compa⅔ed to DPM. Unlike othe⅔ types oλ biodiesel WCO” has hiμhe⅔ metal concent⅔ations both in the λuel as well as pa⅔ticu‐ late emissions because oλ the natu⅔e oλ λeedstock. Metals a⅔e leached into the oil du⅔inμ cookinμ and also λ⅔om cookinμ utensils. Health ⅔isk inhalation oλ PM was calculated by as‐ sessinμ the CDI estimated usinμ the concent⅔ation oλ pa⅔ticulate-bound compounds and the deposition eλλiciency oλ PM in human body, which indicates that WCO” has hiμhe⅔ health ⅔isk compa⅔ed to ULSD in te⅔ms oλ pa⅔ticulate bound elements. Howeve⅔, when P“Hs a⅔e also taken into conside⅔ation it can eithe⅔ inc⅔ease o⅔ dec⅔ease the ⅔elative health ⅔isk oλ WCO” pa⅔ticles dependinμ on the P“Hs emission concent⅔ations λ⅔om both the λuels.

Author details Raμhu ”etha, Rajasekha⅔ ”alasub⅔amanian and Guente⅔ Enμlinμ Depa⅔tment oλ Civil and Envi⅔onmental Enμinee⅔inμ, Faculty oλ Enμinee⅔inμ, National Unive⅔sity oλ Sinμapo⅔e, Sinμapo⅔e

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. Title

Chapte⅔ I, pa⅔t

oλ the Code oλ Fede⅔al Reμulations CFR .

Physico-Chemical Charac“eris“ics of Par“ic”la“e Emissions from Diesel Engines F”elled wi“h Was“e Cooking Oil Derived Biodiesel and Ul“ra Low S”lph”r Diesel h““p://dx.doi.org/10.5772/53476

[

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