Advances in Synthesis Gas: Methods, Technologies and Applications, Volume 2: Syngas Purification and Separation 0323918778, 9780323918770

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Advances in Synthesis Gas: Methods, Technologies and Applications

Advances in Synthesis Gas: Methods, Technologies and Applications Volume 2: Syngas Purification and Separation Edited by Mohammad Reza Rahimpour Department of Chemical Engineering, Shiraz University, Shiraz, Iran

Mohammad Amin Makarem Methanol Institute, Shiraz University, Shiraz, Iran

Maryam Meshksar Department of Chemical Engineering, Shiraz University, Shiraz, Iran

Contributors Mitra Abbaspour Department of Chemical Engineering, Shiraz University, Shiraz, Iran Of
elia de Queiroz Fernandes Arau´jo Escola de Quı´mica, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil M.A.A. Aziz Centre of Hydrogen Energy, Institute of Future Energy, Universiti Teknologi Malaysia (UTM), Johor Bahru, Johor, Malaysia Ali Behrad Vakylabad Department of Materials, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman, Iran Enrico Bocci Marconi University, Rome, Italy Hudson Bolsoni Carminati Escola de Quı´mica, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Jos
e Luiz de Medeiros Escola de Quı´mica, Federal University of Rio de Janeiro, Rio de Janeiro, Brazil Silvio de Oliveira Junior Department of Mechanical Engineering, Polytechnic School of University of Sa˜o Paulo, Sa˜o Paulo, Brazil Andrea Di Carlo L’Aquila University, L’Aquila, Italy Meire Ellen Gorete Ribeiro Domingos Department of Chemical Engineering, Polytechnic School of University of Sa˜o Paulo, Sa˜o Paulo, Brazil Mois
es Teles dos Santos Department of Chemical Engineering, Polytechnic School of University of Sa˜o Paulo, Sa˜o Paulo, Brazil Alberto Figoli CNR-ITM, University of Calabria, Rende, Cosenza, Italy Daniel A. Flo´rez-Orrego Department of Mechanical Engineering, Polytechnic School of University of Sa˜o Paulo, Sa˜o Paulo, Brazil; Faculty of Minas, National University of Colombia, School of Processes
and Energy, Medellin, Colombia; Department of Mechanical Engineering, Ecole Polytechnique F
ed
erale de Lausanne, Switzerland Xingyuan Gao Department of Chemistry and Material Science, Guangdong University of Education, Engineering Technology Development Center of Advanced Materials & Energy Saving and Emission Reduction in Guangdong Colleges and Universities, Guangzhou, China; Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore Behnam Ghalei Institute for Integrated Cell-Material Sciences (iCeMS); Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, Japan Mohsen Ghasemian Department of Chemical Engineering, Isfahan University of Technology, Isfahan, Iran Kamran Ghasemzadeh Urmia University of Technology, Urmia, Iran

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Contributors Foroogh Mohseni Ghaleh Ghazi Department of Chemical Engineering, Shiraz University, Shiraz, Iran Jonathan Harding Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool, United Kingdom C.N.C. Hitam Centre of Hydrogen Energy, Institute of Future Energy, Universiti Teknologi Malaysia (UTM), Johor Bahru, Johor, Malaysia Adolfo Iulianelli CNR-ITM, University of Calabria, Rende, Cosenza, Italy Baishali Kanjilal Bioengineering, University of California, 217 Materials Science and Engineering Building, Riverside, CA, United States H. Enis Karahan Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University, Maslak, Istanbul, Turkey; Institute for Integrated Cell-Material Sciences (iCeMS); Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, Japan Sibudjing Kawi Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore Hadiseh Khosravani Department of Chemical Engineering, Shiraz University, Shiraz, Iran Parvin Kiani Department of Chemical Engineering, Shiraz University, Shiraz, Iran Matteo Manisco CNR-ITM, University of Calabria, Rende, Cosenza, Italy Arameh Masoumi Bioengineering, University of California, 217 Materials Science and Engineering Building, Riverside, CA, United States St
ephanie Mathieu Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool, United Kingdom Maryam Meshksar Department of Chemical Engineering; Methanol Institute, Shiraz University, Shiraz, Iran Rafael Nogueira Nakashima Department of Mechanical Engineering, Polytechnic School of University of Sa˜o Paulo, Sa˜o Paulo, Brazil Iman Noshadi Bioengineering, University of California, 217 Materials Science and Engineering Building, Riverside, CA, United States Hasancan Okutan Department of Chemical Engineering; Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University, Maslak, Istanbul, Turkey Shuxian Qiu Department of Chemistry and Material Science, Guangdong University of Education, Engineering Technology Development Center of Advanced Materials & Energy Saving and Emission Reduction in Guangdong Colleges and Universities, Guangzhou, China Hamid Reza Rahimpour Department of Chemical Engineering, Shiraz University, Shiraz, Iran Mohammad Reza Rahimpour Department of Chemical Engineering, Shiraz University, Shiraz, Iran Maryam Koohi Saadi Department of Chemical Engineering, Shiraz University, Shiraz, Iran Alper Sarıo glan Department of Chemical Engineering; Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University, Maslak, Istanbul, Turkey Elisa Savuto L’Aquila University, L’Aquila, Italy Kambiz Taghaddom Department of Chemical Engineering, Shiraz University, Shiraz, Iran

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Contributors Ş. Birg€ ul Tantekin-Ersolmaz Polymer Science and Technology Graduate Program, Istanbul Technical University; Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University; Department of Chemical Engineering, Istanbul Technical University, Maslak, Istanbul, Turkey Xin Tu Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool, United Kingdom Abdullah Z. Turan TUBITAK Marmara Research Center, Energy Institute, Kocaeli, Turkey Sadiye Velio glu Institute of Nanotechnology, Gebze Technical University, Kocaeli, Turkey Cansu Yıldırım Polymer Science and Technology Graduate Program, Istanbul Technical University; Synthetic Fuels & Chemicals Technology Center (ITU-SENTEK), Istanbul Technical University, Maslak, Istanbul, Turkey Shabnam Yousefi Department of Chemical Engineering, Shiraz University, Shiraz, Iran

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Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2023 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. ISBN: 978-0-323-91877-0

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Preface Vol. 2: Syngas Purification and Separation Synthesis gas (syngas) and its products such as hydrogen are indispensable in chemical, oil, and energy industries. They are important building blocks and serve as feedstock for the production of many chemical compounds such as ammonia and methanol. Hydrogen is expected to become a common energy carrier no later than the middle of the 21st century since it offers considerable energy density and releases negligible pollutants. It is also utilized in petroleum refineries for producing clean transportation fuels, and its consumption is expected to increase dramatically in the near future as refineries need to intensify production capacities. Many publications have hitherto focused on syngas production and purification methods, as well as its applications in industrial production units. Despite the fact that extended studies have been undertaken, there is still room for improvement. The four volumes of this book series explain the conventional and state-of-the-art technologies for the production, purification, and conversion of syngas meticulously. Depending on the feedstock type and production technology, the produced syngas may comprise a large number of impurities including particulate matters, acidic gases (such as CO2 and H2S), nitrogen-containing compounds (such as N2, NH3, and HCN), halogen-containing derivatives (such as HCl, HBr, and HF), and tar compounds, which should be eliminated stepwise in order to avoid catalyst poisoning or reducing the quality of downstream products. Accordingly, it is of great significance to address the challenges, as well as state-of-the-art concepts, in syngas purification, conditioning, and quality enhancement. These topics fall within the scope of this book, which aims to connect the scientists in research laboratories and the operators in industrial plants to solve the problems of syngas cleaning and upgrading operations. To do so, various common syngas purification methods such as absorption, adsorption, and membrane techniques are described in distinct sections, each of which includes specific chapters discussing concepts meticulously. Absorption techniques consider the role of common solvents, ionic liquids, deep eutectic solvents, and nanoparticles-modified solvents. Adsorption-based processes for syngas purification include swing technologies, metal-oxide sorbents, zeolite and molecular sieves, and carbon materials. Membrane technology is divided into ionic liquid membranes, polymeric membranes, MOF-mixed matrix membranes,

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Preface molecular sieving membranes, and dense metal membranes. Other alternatives such as oxidation process, plasma technology, thermal tar removal, and particulate separation methods are also covered in this volume. The editors feel obliged to sincerely appreciate the authors of the chapters for their contributions, hard work, and great assistance in this project. Furthermore, the authors, as well as the editors, are grateful to all the Elsevier staff for their invaluable and irreplaceable step-by-step assistance in preparing this book.

Mohammad Reza Rahimpour Mohammad Amin Makarem Maryam Meshksar

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Reviewer Acknowledgments The editors feel obliged to appreciate the dedicated reviewers (listed below) who were involved in reviewing and commenting on the submitted chapters and whose cooperation and insightful comments were very helpful in improving the quality of the chapters and books in this series. Dr. Mohammad Hadi Sedaghat School of Mechanical Engineering, Shiraz University, Shiraz, Iran Dr. Ali Bakhtyari Chemical Engineering Department, Shiraz University, Shiraz, Iran Dr. Javad Hekayati Department of Chemical Engineering, Shiraz University, Shiraz, Iran Ms. Parvin Kiani Department of Chemical Engineering, Shiraz University, Shiraz, Iran Ms. Samira Zafarnak Department of Chemical Engineering, Shiraz University, Shiraz, Iran

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About the Editors Prof. Mohammad Reza Rahimpour is a professor in Chemical Engineering at Shiraz University, Iran. He received his PhD in Chemical Engineering from Shiraz University in cooperation with the University of Sydney, Australia, in 1988. He started his independent career as assistant professor at Shiraz University in September 1998. Prof. Rahimpour was a research associate at the University of California, Davis, from 2012 to 2017. During his stint at the University of California, he developed different reaction networks and catalytic processes such as thermal and plasma reactors for upgrading lignin bio-oil to biofuel with the collaboration of UCDAVIS. He has been a chair of the Department of Chemical Engineering at Shiraz University from 2005 to 2009 and from 2015 to 2020. Prof. Rahimpour leads a research group in fuel processing technology focused on the catalytic conversion of fossil fuels such as natural gas and renewable fuels such as bio-oils derived from lignin to valuable energy sources. He provides young distinguished scholars from developing countries with perfect educational opportunities in both experimental methods and theoretical tools to undertake in-depth research in the various fields of chemical engineering including carbon capture, chemical looping, membrane separation, storage and utilization technologies, novel technologies for natural gas conversion, and improving the energy efficiency in the production and use of natural gas in industries.

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About the Editors Dr. Mohammad Amin Makarem is a research associate at Methanol Institute, Shiraz University. His research interests are focused on gas separation and purification, nanofluids, microfluidics, catalyst synthesis, reactor design, and green energy. In the gas separation field, his focus is on experimental and theoretical investigation and optimization of the pressure swing adsorption process, and in the gas purification field, he is working on novel technologies such as microchannels. Recently, he has investigated methods of synthesizing bio-template nanomaterials and catalysts. He has collaborated in writing and editing various books and book chapters for famous publishers such as Elsevier, Springer, and Wiley, in addition to guest editing journal special issues. Maryam Meshksar is a research associate at Shiraz University. Her research is focused on gas separation, clean energy, and catalyst synthesis. In the gas separation field, she is working on membrane separation processes, and in the clean energy field, she has worked on different reforming-based processes for syngas production from methane experimentally. She has also synthesized novel catalysts for these processes, which have been tested for the first time. She has reviewed novel technologies such as microchannels for energy production. Recently, she has written various book chapters for famous publishers such as Elsevier, Springer, and Wiley.

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CHAPTER 1

Characteristics of syngas impurities; Physical and chemical properties Hadiseh Khosravani, Hamid Reza Rahimpour, and Mohammad Reza Rahimpour Department of Chemical Engineering, Shiraz University, Shiraz, Iran

1. Introduction Synthesis gas (H2 and CO) can currently be made in a variety of ways and feedstock. Syngas can be generated from natural gas, coal, waste, wood, or biomass. Gasification plants can be found in every continent, with the majority of them in China [1–4]. A variety of factors influence the syngas production process including raw material availability, cost, and most crucially, the ultimate product’s composition. The H2/CO ratio is the most fundamental factor that determines syngas composition [5–7]. The gasification process is a method that turns carbon-containing materials into synthesis gas, which may then be utilized to generate energy and other useful products such as chemicals, fuels, and fertilizers [8]. B-XTL technologies based on Fischer-Tropsch (FT) are promising candidates for future energy production. The goal of these procedures is to transform lignocellulosic biomass into energy. After adjusting the H2/ CO ratio and removing CO2, the input is converted into synthesis gas, which is then subjected to the FT reaction. However, numerous contaminants in synthesis gas must be eliminated to avoid FT catalysts poisoning. Significant changes in the composition of the synthesis gas are expected due to the wide range of feedstock that can be treated. Feedstock type has an impact on the nature of the existent impurities, as well as their relative contents. Furthermore, due to the high sensitivity of the FT catalyst, strict syngas purity criteria are necessary. As a result, synthesis gas purification is a significant barrier to the development of B-XTL methods. This chapter focuses on the different types and content of syngas impurities, their relations with the nature of feedstock, as well as their primary obstacles, which must be removed or overcome. The sulfur and nitrogen produced during the gasification process have significant economic and environmental implications. The existed nitrogen in the fuel is primarily transformed to molecular hydrogen cyanide (HCN) and N2, rather than the respective oxides, whereas the sulfur in the fuel creates carbonyl sulfide (COS) and HCN. The principal chemical reactions decompose and oxidize hydrocarbon derivatives to produce CO, CO2, H2, and water as product Advances in Synthesis Gas: Methods, Technologies and Applications. https://doi.org/10.1016/B978-0-323-91877-0.00015-5 Copyright # 2023 Elsevier Inc. All rights reserved.

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Chapter 1

gases. Hydrogen sulfide (H2S), different carbon and sulfur compounds, low-molecular-weight hydrocarbon derivatives, ammonia, and tar are also the major impurities in the syngas [8]. The destructive effects of nitrogen compounds, sulfur compounds, transition and heavy metals, and halides are discussed in this chapter. Besides, the main synthesis gas purification technologies (based on catalytic processes, adsorption, absorption, and so on) are described, along with the issues that these processes are provided [9].

2. Syngas impurities As previously discussed, the produced syngas from biomass feedstock must first be thoroughly cleaned to eliminate impurities and potential catalyst-toxic materials, before being sold for use in various applications [10]. The composition of syngas produced from the gasification process, as per different sources, is summarized in Table 1. The produced syngas is usually saturated by water vapor and includes varying levels of H2S in addition to various amounts of other pollutants, depending on the nature of the biomass resources and the process variables used to produce the gas [11–13]. Contaminants have qualities that make the gas useless and potentially toxic in certain processes, if they are not removed. For example, hydrogen sulfide is a poisonous gas with a distinct, unpleasant odor reminiscent of rotten eggs [14]. When combined with the existed water vapor in the syngas, it forms acidic compounds that can cause corrosion of instruments. To avoid this, and other negative effects of other impurities, the syngas must be dried and any contaminants removed before it is transported to a conversion unit or sold [19,20]. H2S, CO2, H2O, and halogenated chemicals are the most common (but not always the only) impurities that may need to be removed in gas cleaning equipment. Desulfurization is used to protect pipelines and other equipment from corrosion and to reduce harmful H2S levels in the workplace and in the usage units [21,22]. Simultaneously, the existence of SO2 in the gas stream reduces the dew point of the stack gas (the temperature at which the gas must be chilled Table 1 Composition of produced syngas, as per various sources. Content

Vol% [14]

Mole fraction [15]

Vol% [16]

Mole fraction [17]

Mole fraction [18]

CH4 H2 CO2 CO C2H4 N2 C3H6 C2H6

10.000 40.000 21.000 25.000 2.500 1.500 – –

0.000 0.293 0.118 0.287 0.272 0.030 – –

4.527 80.667 1.571 1.176 1.884 – 7.433 1.867

0.045 0.109 0.115 0.222 – 0.509 – –

0.001 0.733 – – – 0.266 – –

Characteristics of syngas impurities 5 to become saturated with water vapor). H2SO3 and H2CO3 are another two corrosive impurities of syngas that are produced by the reaction of water and SO2 or water and CO2, respectively [23]. Besides the mentioned syngas impurities, the produced syngas contains some other contaminants including particulate matter (PM), alkali metals (i.e., Na, K) condensable hydrocarbon derivatives (i.e., tar products), nitrogen-containing derivatives (i.e., NH3, HCN), sulfur-containing derivatives (i.e., H2S, COS, CS2), and halogen-containing derivatives (i.e., HCl, HBr, HF) that should be eliminated before the syngas is being used in different processes [24]. The problems caused by each of these impurities, as well as their maximum allowable amounts for the FT process, are indicated in Table 2 [25].

3. Properties of syngas impurities The physical properties of different existed impurities in the produced syngas are listed in Table 3. The chemical compound hydrogen sulfide (H2S) is a colorless chalcogen-hydride gas that is toxic, corrosive, and flammable. Furthermore, as previously stated, trace concentrations of this hazardous chemical in the ambient atmosphere have a horrible rotten eggs odor. Regardless, the human body creates modest amounts of this sulfide and its mineral salts, which it employs as a signaling molecule [31]. Hydrocyanic acid has the chemical formula HCN and is a liquid made up of hydrogen cyanide and water. It’s a colorless, very deadly, and combustible liquid that boils at 25.6°C, just above room temperature. HCN that has been vaporized is lighter than air and evaporates quickly. Commercially, it’s commonly offered as an aqueous solution containing 2%–10% hydrogen cyanide. Hydrogen cyanide in aqueous solutions decomposes slowly to generate ammonium formate. It’s a highly deadly gas with a distinct bitter almond scent. It’s a hazardous translucent liquid that can’t be stored or transported [33]. Ammonia (CH3) is known to behave as a weak base since it combines with many acids to form salts. For example, when it is reacted with hydrochloric acid, ammonia is converted into ammonium chloride. All the salts that are produced from such acid-base reactions are known to contain the ammonium cation, denoted as NH4 +. It’s worth noting that ammonia has some weak acidic properties and can thus be classified as an amphoteric chemical. Ammonia’s acidic properties allow it to produce amides with alkali metals and alkaline earth metals. It’s also worth noting that when dissolved in water, the NH3 molecule undergoes self-dissociation. The conjugate base (NH2
) and conjugate acid (NH4 + ) are formed when the ammonia molecule undergoes molecular autoionization [34].

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Chapter 1

Table 2 The syngas impurities with their maximum allowable amounts for FT process and their caused problems [25–30]. Impurity classification

Impurities

Halide containing compounds

HF HCl HBr

Organic compounds (tars)

BTX

Alkali metals containing compounds

Nitrogen containing compounds

Refs. [29,30]

Ref. [28]

Ref. [25]

Ref. [27]

HF + HCl + HBr < 0.01 mol ppm –

HCl < 0.01 ppm

HF + HCl + HBr < 10 ppbv

–

–

–

–

Na + K< 0.01 ppm

Below dew point