Nanostructure of Bitumen Produced from Heavy Oil: monograph 9786010427662

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AL-FARABI KAZAKH NATIONAL UNIVERSITY

Ye. Tileuberdi, Ye. K. Ongarbayev, F. Behrendt, Z. A. Mansurov

NANOSTRUCTURE OF BITUMEN PRODUCED FROM HEAVY OIL Monograph

Almaty «Qazaq university» 2017

UDC 665.6.03; 547.917/.918; 577.114; 577.124 N 29 Recommended for publication by the Academic Council (Protocol №4 dated by 26.12.2016) and the decision of the Editorial-Publishing Council of the al-Faraby Kazakh National University (Protocol №2 dated by 29.12.2016) Reviewer: Doctor of chemical science, professor, R.M. Iskakov (KazNRTU) Doctor of chemical science, professor, G.A. Mun (KazNU) Ph.D. in chemistry, acting ass. prof. K.K. Kudaibergenov (KazNU) Ye. Tіleuberdі – Chapters 1, 2, 3, 4 Ye.K. Ongarbayev, F. Behrendt and Z.A. Mansurov – Paragraph 4.3, Chapter 5

N 29 Nanostructure of Bitumen Produced from Heavy Oil: monograph / Ye. Tileuberdi, Ye.K. Ongarbayev, F. Behrendt, Z.A. Mansurov. – Almaty: Qazaq University, 2017. – 164 pp. ISBN 978-601-04-2766-2 The monograph is devoted to study of nano/microstructures of bitumen produced from high viscous heavy oil. It studied and developed processing technology of Kazakhstan oil sands: Extracting natural bitumen from oil sands and examining their all the physical and chemical properties, studying structures of oil sands, precipitating nanosized aspahltene aggregates of bitumen materials and studying asphaltene composition and surface morphology, producing synthetic oil and high-quality oxidized bitumen from natural bitumen and preparing asphalt concrete with oil sands. Also investigated bitumen modification with rubber crumb: studying surface morphology of rubber crumb from worn tires, preparing rubber-bitumen compounds and asphalt concrete on the based rubber crumb, analyzing gas composition on released during the preparation of RBC and asphalt concrete with rubber crumb, studying surface morphology of rubber-bitumen compounds The monograph can be useful to a wide range of professionals involved in petrochemistry and nanotechnology as well as bachelors, masters and Ph.D. students.

UDC 665.6.03; 547.917/.918; 577.114; 577.124 ISBN 978-601-04-2766-2

© Tileuberdi Ye. et al., 2017 © Al-Farabi KazNU, 2017

CONTENTS LIST OF ABBREVIATIONS .............................................................................6 ILLUSTRATIONS...............................................................................................7 ACKNOWLEDGMENTS ...................................................................................13 INTRODUCTION................................................................................................14 I. PETROLEUM, OIL SAND AND HEAVY OIL............................................16 1.1. Petroleum and Oil, Properties of Hydrocarbons .....................................16 1.1.1. Definition and general characteristics of petroleum .....................16 1.1.2. Petroleum processing, refined product consumption ....................21 1.1.3. Oil producing sector of Kazakhstan..............................................23 1.2. Oil Sand and Natural Bitumen ................................................................26 1.2.1. Unconventional hydrocarbon: oil sands .......................................26 1.2.2. Industrial technologies of the oil extraction from the oil sand .....30 1.2.3. Kazakhstan’s oil sand ...................................................................32 1.3. Study Kazakhstan’s Oil Sand Organic Part .............................................33 1.3.1. Materials and separating methods of organic part from oil sands..........................................................................................33 1.3.2. Composition and characteristics of oil sand bitumen ..................35 1.4. Structures of Oil Sand and Its Mineral Parts ...........................................42 1.4.1. Microscopic study of oil sand structure ........................................42 1.4.2. Mineral part of oil sands ...............................................................45 1.4.3. Clay composition in oil sand .......................................................51 References 1 ...........................................................................................................53 II. BITUMEN PRODUCING AND ASPHALTENE ........................................56 2.1. Properties and Structure of Bitumen .......................................................56 2.1.1. Definition of bitumen ....................................................................56 2.1.2. Main bitumen manufacturing methods .........................................58 2.1.3. Bitumen application and consumption .........................................60 2.2. Producing Bitumen from Oil Sands ........................................................61 2.2.1. Physical and mechanical characteristics of natural bitumen ........61 2.2.2. Production of oxidized bitumen from natural bitumen of oil sand .........................................................................................................64 2.3. Investigation of Asphaltene Aggregates in Bitumen ..............................67 2.3.1. Definition of asphaltene ................................................................67 2.3.2. Asphaltene and its properties ........................................................68 2.3.3. Role of asphaltene in bitumen ......................................................72 2.4. Precipitation of Asphaltene from Bitumen ..............................................74

3

2.4.1. Asphaltene precipitation method ..................................................74 2.4.2. Composition of asphaltene precipitated from bitumen ................75 2.4.3. Structure of asphaltene surface .....................................................79 2.4.4. Thermal study of asphaltene .........................................................82 References 2 ...........................................................................................................84 III. USING RUBBER CRUMB FOR THE PRODUCTION OF RUBBER MODIFIED BITUMEN.......................................................................................87 3.1. Rubber crumb and Bitumen Modification ...............................................87 3.1.1. Crumb rubber from worn tires and their characteristics ...............87 3.1.2. Ways of recycling and utilization .................................................89 3.1.3. Bitumen modification with crumb rubber based modifier and interaction study .....................................................................................91 3.2. Producing Rubber Bitumen Compounds with Rubber Crumb................93 3.2.1. Rubber crumb which used in the work ........................................93 3.2.2. Preparation of rubber-bitumen compounds ..................................95 3.2.3. Discussion and comparison of RCMB characteristics .................100 3.2.4. Microscopic study of rubber-bitumen compounds .......................102 References 3 ...........................................................................................................104 IV. NANOTECHNOLOGY, ROAD BUILDING AND ASPHALT CONCRETE .........................................................................................................106 4.1. Nanoscience and Nanotechnology in Road Building ............................106 4.1.1. Nanoscience and nanotechnology is modern field ........................106 4.1.2. Application of nanotechnology in road building materials ..........108 4.2. Asphalt Concrete Materials ....................................................................113 4.2.1. Composition and condition of asphalt concrete............................113 4.2.2. Types of asphalt concrete..............................................................114 4.2.3. Structures of asphalt concrete .......................................................116 4.3. Preparation of Asphalt Concrete with Oil Sand and Rubber Crumb ......117 4.3.1. Preparation of asphalt concrete with oil sands..............................117 4.3.2. Preparation of asphalt concrete with rubber crumb ......................120 4.3.3. The results of gas composition analysis on released during the preparation of RBC and asphalt mixtures based on rubber crumb ...123 References 4 ...........................................................................................................128 V. PRODUCING SYNTHETIC OIL FROM OIL SAND BITUMEN ............130 5.1. Oil sand, bitumen and synthetic oil .........................................................130 5.1.1. Denomination of unconventional oil ...........................................130 5.1.2. Classification of the organic sediments ........................................132 5.1.3. Methods of fuel deriving from oil sand bitumen ..........................134 5.2. Catalytic hydrogenation of oil sand’s natural bitumen ...........................138 5.2.1. Hydrogenation experiment ..........................................................138 5.2.2. Preparation of catalyst for the hydrogenation process .................140 5.2.3. Hydrogenation to Munayli-Mola natural bitumen ........................141

4

5.2.4. Hydrogenation to Beke natural bitumen .......................................144 5.2.5. Conclusion of phenomena ...........................................................146 5.3. Thermal processing of oil sands and characteristics of products ............147 5.3.1. Providing experiment by thermal method ....................................147 5.3.2. Thermal processing of oil sands ...................................................148 5.3.3. Comparison fractional composition of organic part of oil sands separated by extraction and thermal processing .....................................150 5.3.4. Semi-industrial plants for thermal processing of oil sands ...........151 5.4. Thermocatalytic cracking of natural bitumen..........................................152 5.4.1. Providing experiment....................................................................152 5.4.2. Cracking process of oil sand bitumen ...........................................154 5.4.3. Compositions of cracking products of natural bitumen ................156 5.4.4. Molecular weights of cracking products ......................................158 References 5 ...........................................................................................................159 CONCLUSION ....................................................................................................162

5

LIST OF ABBREVIATIONS OS

–

Oil sand

NB

–

Natural Bitumen

SEM

–

Scanning Electron Microscopy

RC

–

Rubber Crumb

RBC

–

Rubber Bitumen Compounds

IR

–

Infra-Red

ST –

Standard

RK

–

Republic of Kazakhstan

R:O

–

Rubber: Engine oil

TEM

–

Transmission Electron Microscopy

OPEC

–

Organization of the Petroleum Exporting Countries

ASTM

–

American Society for Testing and Materials

SAGD

–

Steam Assisted Gravity Drainage

SARA –

Saturates, aromatics, resins and asphaltene

SBS

–

Styrene butadiene styrene

CRM

–

Crumb rubber modifier

AC

–

Asphalt concrete

HMAC

–

Hot mix asphalt concrete

WMAC

–

Warm mix asphalt concrete

AFM

–

Atomic force microscopy

PDM

–

Phase detection microscopy

LPG

–

Liquefied petroleum gas

EOR methods

–

Enhanced recovery methods

FCC

–

Fluidized catalytic cracking

HO

–

Hydrogenated oil

BET –

Brunauer, Emmett and Teller

I.B.

–

Initial of boiling point

E.B.

–

End of boiling point

DTBP –

Di-tert-butyl peroxide

Wt. %

Weight percentage

–

6

ILLUSTRATIONS Figures 1

Total world oil reserves

15

2

Boiling point-carbon number profile for petroleum

16

3

Petroleum Industry Segments

18

4

Map of oil and gas basin of Kazakhstan

20

5

Oil production in Kazakhstan

21

6

Oil pipelines: current and future routes

22

7

Photography of the oil sands

23

8

Diagram of the petroleum formation process

24

9

Trend in the extent of biodegradation of heavy oil and bitumen

25

10

Schematic of a SAGD in situ development

26

11

Oil sands located area in Kazakhstan

27

12

Photograph of oil sand samples

28

13

Scheme of Soxhlet apparatus

29

14 Image of natural bitumen extracted from oil sands

30

15

IR spectrum of Munayli-Mola natural bitumen

33

16

IR spectrum of Beke natural bitumen

33

17

Apparatus for elemental analyses

34

18 Image of after extracted mineral part of oil sands

36

19 SEM image of oil sand and after thermal extracted sand

36

20 Optical microscopic images of Beke oil sands

37

21 Composition and structure of oil sands

38

22 X-ray phase analyses of mineral part of oil sands

40

23

Optical microscopic image of mineral part of Beke oil sand

42

24 SEM image of oil sand’s mineral part

43

25 Experimental scheme of clay separation

44

26 Optical microscopic image of clay mineral composition of Beke oil sand

46

27 Representative structures of bitumen fractions

51

7

28 Evolution of molecular weights and structures as a function of the boiling point

51

29 Main processing methods in the production of bitumens

53

30 Graphic of bitumen consumption

54

31 Apparatus for determination of depth of needle penetration of samples

56

32 Scheme of apparatus for oxidizing bitumen

57

33 Bitumen samples

57

34 Schematic illustration of SARA analysis

60

35 Cross-sectional model of the structure of the asphaltene

61

36 Scheme of the formation of nanoclusters of asphaltene molecules

62

37 High resolution image of the structure of the asphaltene aggregates

63

38 Image of precipitated asphaltene samples

65

39 The IR-spectrum of asphaltenes precipitated from natural bitumen of Munayli-Mola deposit

66

40 Hypothetical asphaltene molecule and its interaction with metalloporphyrins

67

41 The detail of diffraction diagram of asphaltenes

68

42 SEM images of asphaltene surface precipitated from natural bitumen

69

43 SEM images of asphaltene surface precipitated from paving bitumen

69

44 TEM images of asphaltene surface precipitated from natural bitumen

70

45 TEM images of asphaltene surface precipitated from paving bitumen

71

46 SEM images of asphaltene products after heated at 600 oC

72

47 Worn tires in open landfills

76

48 Model of typical tire rubber mix

77

49 Chemical structures of principal organic components of crumb rubber

78

50 Schematic diagram of the utilization of car and heavy-duty tires as chips

79

51 Simplified nano-mechanical model of SBS Poly-Styrene-ButadieneStyrene modified bitumen

80

52 SEM image of rubber bitumen

80

53 Optical microscope images of rubber crumb with particle size less than 0.6 mm

81

54 Optical microscope images of rubber crumb with particle size 0.6-1.0 mm

82

55 SEM images of rubber crumb

82

8

56 Scheme of apparatus for preparing RBC

83

57 Dependence of penetration on the rubber-oil content of RBC

87

58 Dependence of softening point on the rubber-oil content of RBC

88

59 Dependence of ductility on the rubber-oil content of RBC

88

60 Optical microscopic image of RBC

90

61 Scale diagram of objects, tools, models and forces at varies different scale

94

62 AFM topographic and PDM images of bitumen

96

63 ESEM image of bitumen (B 50=70 and (b) PmB 60=90)

97

64 Structural layers model of asphalt concrete

101

65 Asphalt concrete with oil sands

102

66 Asphalt concrete with rubber crumb

104

67 Asphalt pavement with rubber crumb on the experimental plot of the 107 Institute of Combustion Problems 68

Chromatograms of hydrocarbon gases allocated in the preparation of stone-mineral mixture

108

69

Chromatogramsof hydrocarbon gasesallocatedin the preparation of asphalt mixwith the addition of RBC

108

70 Chromatograms of oxygen and methane, isolated in the preparation of 110 stone-mineral mixture 71

Chromatograms of oxygen and methane, isolated in the preparation of 111 asphalt mix with the addition of rubber bitumen compounds

72

Classification of fossil fuel as organic sediments

73

Classification of fossil fuels as hydrocarbon resources and hydrocarbon- 117 producing resources

74

Schematic representation of the properties and recovery methods for 118 crude oil, heavy oil, tar-sand bitumen, and coal

75

Typical route of bitumen to refinery

120

76

Heavy oil–upgrading options

121

77

Photography of autoclave installations for hydrogenation of natural 123 bitumen

78

Typical hydrogen reaction

123

78

SEM image of active carbon supported catalyst

124

79

Profiles of temperature and pressure over time hydrogenation process of 125 Munayli-Mola natural bitumen

80

Fraction of hydrogenated natural bitumen

9

117

126

81 Profiles of temperature and pressure over time hydrogenation process of 128 Beke natural bitumen 82

Radical chain mechanism for homolysis of a hypothetical molecule M

129

83

Scheme of apparatus for the thermal processing oil sands

130

84

Diagram of fractional composition of organic part

132

85

Semi-industrial plants for thermal processing

133

87

Scheme of the experiment

135

10

Tables 1

Total refined product consumption

19

2

Characteristics of solvents

29

3

Organic content of oil sands extracted by variety of solvents

30

4

Physical and chemical properties of natural bitumen

31

5

Comparison results of ash content determination and extraction

32

6

Elemental composition of Munayli-Mola bitumen

34

7

Elemental composition of Beke natural bitumen

35

8

X-ray phase analysis results of samples of oil sand minerals

39

9

The results of semi-quantitative analysis of oil sand’s mineral composition

41

10 Elemental composition of clay minerals of oil sand

45

11 Physical and mechanical characteristics of Munayli-Mola natural bitumen

55

12

58

Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 230 °С

13 Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 240 °С

58

14 Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 270 °С

59

15 The results X-ray fluorescent analysis of asphaltenes

67

16 Physical and mechanical characteristics of rubber-bitumen compounds on the based bitumen BND 60/90 with the addition of crumb rubber (particle size less than 0.6 mm)

84

17 Physical and mechanical characteristics of rubber-bitumen compounds on the based bitumen BND 60/90 with the addition of crumb rubber (0.61.0 mm)

84

18 Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (less than 0.6 mm)

85

19

86

Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (0.6-1 mm)

20 Properties comparison of crumb rubber (particle size less than 0.6 mm) modified bitumen with base bitumen

89

21 Particulate composite of asphalt concrete with micro- and nanoparticles

95

22 The physical and mechanical characteristics of samples

103

11

23 Physical and mechanical characteristics of rubber-asphalt with rubber 105 crumb (less than 0.6 mm) 24 Physical and mechanical characteristics of rubber-asphalt with no rubber 106 crumb (0.6-1.0 mm) 25 The concentrations of gases allocated in the preparation of rubberbitumen compounds

109

26 The concentrations of gases allocated in the preparation of asphalt mixtures

110

27 Fractional composition of hydrogenated oil from Munayli-Mola, while 125 vacuum distillation 28 Comparative characteristics of natural bitumen extracted from oil sand 127 before and after the hydrogenation process 29 Fractional composition of hydrogenated oil from Beke, while vacuum 128 distillation 30 Physicochemical properties of thermal processing products of Beke oil 131 sand 31 Product characteristics of obtained from Munayli-Mola oil sand by 132 thermal processing, the average heating rate 16.7  32 Main technical characteristics of semi-industrial plants

134

33 Characteristics of synthetic oil produced from Beke bitumen

134

34 Material balance and composition of cracking products of natural bitumen 137 35 Fractional composition of cracking products of natural bitumen

138

36 Gas composition of cracked products

139

37 Molecular weights of cracking products, a.m.u.

140

12

ACKNOWLEDGMENTS We would like to acknowledge everyone that has contributed to this monograph. Specifically, We would like to thank the colleagues at the «Chair of chemical physics and materials science» and at the «Open type National nanotechnological laboratory» of Al-Farabi Kazakh National University. We would like to express our gratitude to everyone at the «Institute of combustion problems» of Ministry of Education and Science of RK. We want to start expressing a sincere acknowledgement to colleagues at the «Institute for Energy Engineering» of Berlin Technical University (Germany).

13

INTRODUCTION Today a complex conversion and rational using of hydrocarbon raw material for the producing of the valuable chemical materials and qualitative petroleum product are one of the priority ways of the turning the Republic of Kazakhstan in the market economies. Petroleum products play an important role in economic development of any nation. At present Kazakhstan is one of the large world oil exporter and oil producing sector takes a leading position in the structure of national economy of Kazakhstan. As time passes, reserves of fossilized carbon are being depleted for use as energy and more attention is being focused on alternate energy sources. One such energy source is oil sand. This valuable resource can be found in several locations in the world such as Canada, Venezuela and other. In the Western part of Kazakhstan has more reserves of oil sand, currently over 50 fields of oil sands have been discovered. Nanotechnology entered the oil and gas industry not so long ago, but many of its applications have become not many of integral part, the seemingly traditional technological processes. For example, the use of nanostructured zeolites allowed increase 40% yield of gasoline fraction compared using conventional catalysts. The use of materials with a selected nanostructure allows doing for lighter, durable and strong equipment. Bitumen is a mixture of organic liquids that is viscous, black and sticky. It is a complex mixture of high boiling point range of compounds and molecules with a relatively low hydrogen-to-carbon ratio. Oil bitumen is widely used in many industries. The main problem with road building is the poor quality of bitumen used in asphalt-concrete pavements. One of the ways to improve the quality of the binders is their modification with rubber crumb from worn tires. Thus, the efficient processing of worn tires makes it possible not only to solve environmental problems but also to perform economically rational utilization processes. In our country the satisfaction of need for a bitumen material occurs due to its import and bitumen characteristics completely mismatch climatic conditions of our State, i.e. Therefore investigation of domestic heavy hydrocarbon and unconventional oil, finding out 14

perspective processing methods, producing high quality of bitumen materials on the based domestic raw materials are an actual problem. This Monograph outlines the fundamental aspects of oil sands and natural bitumen for the benefit of scientists, engineers and students who interested in learning on unconventional hydrocarbon resources. The monograph is devoted to the study of composition and structure of oil sand and natural bitumen, created new ways of processing and application rubber bitumen compounds and asphalt concrete. Also have precipitated nano-sized aspahltene aggregates of bitumen materials and continuously studied asphaltene composition and surface morphology. Oil and bitumen is considered colloidal dispersion system, and their components – asphaltenes and resins are considered as nanoscale systems. For the production of light oil products natural bitumen is subjected to thermal processing, thermolysis in the presence of catalyst, hydrogenation in the presence of nanocatalysts. The analysis and evaluation of the data done by authors showed highly promising science and technology for an excellent studying of bitumen structure.

15

I. PETROLEUM, OIL SAND AND HEAVY OIL

1.1. Petroleum and Oil, Properties of Hydrocarbons 1.1.1. Definition and general characteristics of petroleum Term of petroleum and oil Petroleum or crude oil is any naturally-occurring flammable mixture of hydrocarbons found in geologic formations, such as rock strata. Petroleum is complex mixture of hydrocarbon compounds, high-molecular tar and asphaltene substances. Usually with minor amounts of nitrogen-, oxygen-, and sulfur-containing compounds as well as trace amounts of metal-containing compounds. The word petroleum, derived from the Latin petra and oleum, means literally “rock oil” and refers to hydrocarbons that occur widely in the sedimentary rocks in the form of gases, liquids, semisolids, or solids. Petroleum (crude oil, conventional crude oil) is found in the microscopic pores of sedimentary rocks, such as sandstone and limestone. Not all of the pores in a rock contain petroleum and some pores will be filled with water or brine that is saturated with minerals [1-6]. The terms “oil” and “petroleum” are sometimes used interchangeably. Technically, the term petroleum only refers to crude oil, but sometimes it is applied to describe any solid, liquid or gaseous hydrocarbons. So, we can say that the petroleum is the broad category that includes both crude oil and petroleum products. Crude oil is a mixture of hydrocarbons that exists as a liquid in natural underground reservoirs and remains liquid when brought to the surface [7-9]. Petroleum reserves of the world A reserve of the conventional oil is 30 % and most of the world’s oils are unconventional as shown at figure 1. As time passes, reserves of fossilized carbon are being depleted for use as energy, growth in consumption of petroleum products on a global scale and more attention is being focused on alternate energy sources. Not all of the oil 16

fields that are discovered are exploited since the oil may be far too deep or of insufficient volume or the oil field may be so remote that transport costs would be excessively high. Conventional oil is a mixture of mainly pentanes and heavier hydrocarbons. Unconventional oil is petroleum produced or extracted using techniques other than the conventional (oil well) method. Unconventional oil included extraheavy oil, oil sands, kerogen oil, shale oil. It is in semi-solid form mixed with sand and water, as in the Athabasca oil sands in Canada. Heavy crude oil is oil that is highly viscous, and cannot easily flow to production wells under normal reservoir conditions. It is referred to as “heavy” because its density or specific gravity is higher than that of light crude oil. Extra heavy crude oil is oil that is highly viscous, and cannot easily flow to production wells under normal reservoir conditions, too. Venezuela has large amounts of oil in the Orinoco oil sands, although the hydrocarbons trapped in them are more fluid than in Canada and are usually called extra heavy oil [7-10].

Figure 1 – Total world oil reserves

In addition to the definitions of petroleum, heavy oil, and oil sand bitumen presented below, there are two definitions that need to be addressed which also speak to the difference between petroleum and heavy oil on the one hand and oil sand bitumen on the other. These are (1) reservoir and (2) deposit and will be presented first in order to affirm the differences between petroleum/heavy oil and oil sand bitumen. Petroleum is derived from aquatic plants and 17

animals that lived and died hundreds of millions of years ago. Their remains became mixed with mud and sand in layered deposits that, over the millennia, were geologically transformed into sedimentary rock. The World Petroleum Congress adopted definition of international group of the United Nations, in 1987, with minor modifications. Later, Venezuela added its own definition of extraheavy oil, as a crude that is less than 10° API, with viscosity less than 10,000 cP. By contrast, Canadian heavy oil, which is obtained from the oil sands or carbonates, has an API gravity less than 10° and a viscosity above 10,000 cP at reservoir conditions. It is the most viscous hydrocarbon and is practically a solid at room temperature, now recognized all over the world as bitumen [10]. Content and composition of hydrocarbons Its main components are carbon (83-87%), hydrogen (10-14%) , as well as, oxygen (0.05-2%), nitrogen (0.1-2%), sulfur (0.05-6%) and various microelements (metal< 0.1%)such as nickel, vanadium, iron, calcium, magnium, aluminum, silicon and copper [1-5]. Thus the purely hydrocarbon content may be higher than 90% by weight for paraffinic petroleum and 50% by weight for heavy crude oil and much lower for natural bitumen. Due to the hydrogen and carbon are mail component that the petroleum called “hydrocarbons”, too. Under surface pressure and temperature conditions, lighter hydrocarbons, methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids. However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface conditions. The molecular boundaries of petroleum cover a wide range of boiling points and carbon numbers of hydrocarbon compounds (figure 2) and other compounds [8, 11-13]. The main part of the oil consists of three groups of hydrocarbons – alkanes, naphthenes and arenas. Alkanes (in the literature you can also encounter the names of saturated hydrocarbons, saturated hydrocarbons, paraffins) are chemically the most stable. Their general formula is CnH (2n + 2). If the number of carbon atoms in the molecule is not more than four, then at atmospheric pressure the alkanes will be gaseous. At 5-16 carbon atoms, these are liquids, and above – already solid substances, paraffins. Naphthenes include alicyclic hydrocarbons of the composition CnH2n, CnH (2n-2) and CnH (2n-4). The oils contain mainly cyclopentane C5H10, cyclohexane C6H10 and their homologues. 18

And finally, the arenas (aromatic hydrocarbons). They are much poorer in hydrogen, the carbon / hydrogen ratio in the arenas is the highest, much higher than in oil as a whole. The content of hydrogen in oils varies widely, but on average it can be taken at 10-12% while the hydrogen content in benzene is 7.7%. They form on the basis of resins, asphaltenes and other precursors of coke, and being extremely unstable, complicate the lives of oil refiners. Look at the structure of the molecules of pentane C5H10, cyclohexane C6H12 and benzene C6H6 – typical representatives of each of these classes:

Figure 2 – Boiling point-carbon number profile for petroleum [8]

Pentane

19

Cyclohexane

Benzene

In addition to the carbon part, there is an asphalt-tar component in oil, porphyrins, sulfur and an ash part. Asphalt-resinous part – a dark dense substance, which is partially soluble in gasoline. The dissolving part is called asphaltene, but insoluble, clearly, resin. Porphyrins are special organic compounds containing nitrogen in their composition. Many scientists believe that they were once formed from plant chlorophyll and hemoglobin of animals. Sulfur in oil is quite a lot – up to 5%, and it brings a lot of trouble to the oil industry, causing corrosion of metals [14]. The demand for high value petroleum products such as middle distillate, gasoline and lube oil is increasing, while the demand for low value products such as fuel oil and residua based products is decreasing. Therefore, maximizing of liquid products yield from 20

various processes and valorization residues is of immediate attention to refiners. At the same time, environmental concerns have increased, resulting in more rigorous specifications for petroleum products, including fuel oils. These trends have emphasized the importance of processes that convert the heavier oil fractions into lighter and more valuable clean products [15].

1.1.2. Petroleum processing, refined product consumption Petroleum industry and its classification The petroleum industry is involved in the global processes of exploration, extraction, refining, transporting and marketing petroleum products (figure 3). The largest volume products of the industry are fuel oil and petrol. Petroleum refinery is a complex system of multiple operations and the operations used at a given refinery depend upon the properties of the crude oil to be refined. The petroleum refining industry converts crude oil into more than 2500 refined products. A refinery’s processing flow scheme is largely determined by the composition of the crude oil feedstock and the chosen slate of petroleum products [16-17]. The petroleum industry generally classifies crude oil by the geographic location it is produced in, its density, and its sulfur content. Crude oil may be considered light if it has low density or heavy if it has high density; and it may be referred to as sweet if it contains relatively little sulfur if it contains substantial amounts of sulfur [18]. There are numerous possible refinery configurations and each is designed to achieve the specific target of transforming crude oil into useful products such as liquid petroleum gas, fuels and a large number of other products that are used as raw material in the petrochemical industry [15]. All refineries have three primary sections: separation, conversion and finishing. The first step in any refinery is separation of the crude oil into component streams in a distillation unit. Modern conversion refineries typically have two distillation towers in series, a tower operating close to atmospheric pressure followed by a vacuum unit. The most widely used process in the finishing steps is hydrotreating a generic name given to a wide range of hydrogenation or hydrogen21

addition steps. In addition to removing a substantial amount of sulfur, hydrotreating may also target other compounds containing metals and nitrogen and occasionally olefins and aromatics may be hydrogenated [15].

Figure 3 – Petroleum Industry Segments [16]

Petroleum products Petroleum products are omnipresent in today’s our life, and have become almost natural parts of the modern world. A lot of products we use daily are derived from petroleum, just think of all kinds of fuels, oils and the wide range of petrochemicals. Petroleum provides not only fuel for energy, industry, heating, and transportation but also basic materials used for the manufacture of synthetic fibers for clothing and in plastics, paints, solvents, fertilizers, insecticides, soaps, synthetic rubber, lubricants, grease, wax, and the distillation residuum asphalt, which is used for highway surfaces and roofing materials. The uses of petroleum as a source of raw material in manufacturing are central to the functioning of modern industry and it perhaps the most important substance consumed in modern society [6, 8, 15, 19]. Refined product consumption According to development of technology and industry, the consumption for oil products is year-by-year increasing. Table 1 is 22

presenting the refined product consumption in some selected regions of the world [20]. Table 1 Total refined product consumption, millions tonnes/year [20] Location European Union USA China India Middle East North Africa Russia Kazakhstan

1995 y. 679 809 152 79 187 50 136 20

2000 y. 702 897 206 108 209 57 129 35

2005 y. 727 942 316 121 254 68 133 60

2010 y. 747 969 439 139 283 71 164 79

2020 y. 789 1039 731 173 346 88 200 150

The table shows the differences in scale of growth in the study regions, with the largest growth-taking place, perhaps unexpectedly, in China and the smallest in -North Africa, which is also the smallest market of the study regions. Consumption in the study region is expected to grow to 3.37 billion tonnes in 2020, representing 77% of global consumption by 2020. The inclusion of some of the fastest growing economies results in the study region results in the higher than average growth [20]. Petroleum-based liquid fuels remain the largest fraction of world energy consumption. It is estimated by International Energy Outlook 2007 that the world use of petroleum and other liquids will grow from 83 million barrels oil equivalent per day in 2004 to 118 million barrels per day in 2030 [21].

1.1.3. Oil producing sector of Kazakhstan Oil and gas basin of Kazakhstan Petroleum products play an important role in economic development of any nation. At present oil producing sector takes a leading position in the structure of national economy of Kazakhstan. The oil and gas basins of Kazakhstan were classified (see figure 23

4). According to information resources, it can be grouped into four revealed or prospective oil and gas provinces in the Republic of Kazakhstan [22]. They are: 1. The Pre-Caspian Basin lies in the western part of the country, behind the Mugodzhary Mountains. The geology of this province is made up of Paleozoic sediments covering a Proterozoic basement. 2. The Mangistau-Usturt Basin lies in the Mangistau and Aqtobe areas of Kazakhstan. 3. The Central Kazakhstan Basin lies in the eastern and southern areas of Kazakhstan. 4. The Western Siberian Basin is in the northern and northeastern region of Kazakhstan, north of the Kokshetau Mountains. The geology is of a platform type, with a Mesozoic cover overlying a Paleozoic basement.

Figure 4 – Map of oil and gas basin of Kazakhstan [22]

Exploration in those provinces in which oil and gas has already been extracted had, by 2010, led to the discovery of more than 200 oil, gas, oil-and-gas and condensate hydrocarbon accumulations. Of these, the Kashagan, the Tengiz and the Karachaganak fields can be considered giants. 24

Academician Nadirov N.K. reported in own study [2, 23] that the currently in Kazakhstan known 16 major sedimentary basins. They are namely: the Caspian, Usturt-Bozashi, Mangistau, Aral, Syrdarya, South Torgay, North Torgay, North Kazakhstan, Teniz, Shu-Sarysu, Western Ile, East Ile, Balkhash, Alakol, Zaisan, Yertys basins, which is due to more than 160 oil and gas fields. Oil producing sector of Kazakhstan Oil industry played the main role in modernization. The share of oil in industry is 49%, in structure of imports the share of oil is 60%. Exports incomes influenced to Astana decision for diversification of energy, routes of oil transportation according to strategy of many vectors in Foreign policy of Kazakhstan [24, 25]. Kazakhstan’s oil producing sector is quickly developing and figure 5 shows the oil production amount in near 20 years.

Figure 5 – Oil productions in Kazakhstan

Crude oil production grew from 40 in 2001 to 80 million tons in 2014 i.e. for 2 times. Oil production growth and large oil-fields development of Caspian sea offshore demand appropriate infrastructure. Currently, main pipelines in Kazakhstan are Tengiz-Novorossiysk (Caspian pipeline consortium), Kalamkas-Uzen-Atyrau, AtyrauSamara, Zhanazhol-Kenkiyak-Orsk, Pavlodar-Shymkent, KarakoyinKumkol, Atasu-Alashankou. Moreover, priority route is Baku-Tbilisi25

Ceyhan oil pipeline. Oil-pipelines extend up to 5.8 thousand kilometers with capacity of 120 million tons (figure 6) [25, 26].

Figure 6 – Oil pipelines: current and future routes

1.2. Oil Sand and Natural Bitumen 1.2.1. Unconventional hydrocarbon: oil sands The term of oil sand Oil sands (figure 7) have different terms in the world, for example: oil-bituminous sands, tar sands, extra heavy oil, oil-bituminous mineral (rock). There is term natural asphalt, it refers to a wide variety of materials found in nature and containing varying amounts of bitumen. According to EN 12597, natural asphalt is defined as relatively hard bitumen found in natural deposits, often mixed with fine or very fine mineral aggregates [27]. From a practical viewpoint, it is convenient to classify these asphalts into three groups according to their bitumen content: – Gilsonite. Natural asphalt was discovered in Utah, United States, in 1882 and later developed commercially by S.H. Gilson, after whom it was named. This material, which varies somewhat from one vein to another, is characterized by its high softening point and low mineral matter content. 26

– Trinidad asphalt. Trinidad lake is situated on the island of Trinidad, West Indies. It covers a surface area of about 400000 m2 and is about 90 m deep at its center. – Rock Asphalt and Oil Sands. Kentucky rock asphalt is found in deposits or beds 2-15 m thick in horizontal strata below an overburden of clay soil. It contains between 4 and 15% bitumen and is recovered by simple quarrying, broken into lumps, and then crushed to a coarse powder.

Figure 7 – Photography of the oil sands

Oil sand and its location As time passes, reserves of fossilized carbon are being depleted for use as energy and more attention is being focused on alternate energy sources. One such energy source is oil sand. This valuable resource can be found in several locations around the globe, including the USA, Canada, Venezuela, Russia, China, Cuba, Indonesia, Brazil, Trinidad, Tobago, Jordan, Madagascar, Colombia, Albania, Romania, Spain, Portugal, Nigeria, Argentina and Kazakhstan. However, the largest deposits of the world oil sands are located in Canada and Venezuela. Bitumen in the Athabasca oil sands deposit is an increasingly important source of synthetic crude oil in North America. Because the cost of oil production from oil sands is significantly higher than that 27

for conventional crudes, there is an increasing need to develop the resource in amore efficient and cost effective manner. Venezuela also has large amounts of oil in the Orinoco oil sands and they are usually called extra heavy oil, although the hydrocarbons trapped in them are more fluid than in Canada [28, 29]. According to the Alberta Energy and Utilities Board, Alberta’s oil sand deposits contain 1.7 trillion barrels of bitumen, of which over 300 billion are recoverable by current technology (hot water extraction process or by in situ methods). The total amount is greater than the known reserves of Saudi Arabia. Natural bitumen reserves are estimated at as following: Total: 250 billion barrels Canada: 177 billion barrels Kazakhstan: 42 billion barrels U.S. (Utah): 32 billion barrels Russia: 28 billion barrels Congo: 0.5 – 2.5 billion barrels These oil sands resources are called unconventional oil to distinguish them from oil that can be extracted using traditional oil well methods. Because compared to conventional crude oil, heavier crude oils from oil sands have too much carbon and not enough hydrogen, these processes generally involve removing carbon from or adding hydrogen to the molecules, and using catalytic cracking to convert more complex molecules in the oil to the shorter, simpler ones in the fuels. Most deposits of oil sands contain mixtures of bitumen, coarse sand, water, fine solids, small amounts of heavy metals and other contaminants. Oil sands solids are mostly silica but include smaller amounts of kaolinite, illite, chlorite and smectite (montmorillonite). In making synthetic crude oil, special refining processes are used to remove impurities and correct the carbon-hydrogen imbalance [28-34]. Petroleum formation When it comes to explain the origin from the different oil sands from the world there are two main theories. The first one suggest that the oil sands come from the degradation of conventional petroleum during long periods of time by microbes that left behind some bitumen and converted the lighter crude into heavier fractions. The second one does not assume that the petroleum formation cycle was completed 28

and explains the origin of bitumen as the incomplete or anomalous process of formation of oil from organic matter [35, 36]. The figure 8 shows the process of bitumen formation including the two possibilities:

Figure 8 – Diagram of the petroleum formation process [35]

According to the first theory, the petroleum formation process was completed and then it was transformed in bitumen due to the activity of the microbes. But according to the second theory, Catagenesis did not occur because the organic matter was not buried deep enough and the kerogen was not transformed into hydrocarbons and it was just under very long periods of time that some portion of the kerogen was transformed into bitumen [35]. Bitumen is so heavy, thick, and viscous that it is virtually immobile at normal conditions. The formation started before the time of the dinosaurs, in the Devonian period. One of the most widely accepted hypotheses is that bitumen was formed because of biodegradation of conventional oil that migrated across a distance, carried by marine waters. The degree of biodegradation varies considerably across the length and depth of the deposits. In support of this hypothesis, scientific evidence has shown that the extent of biodegradation in bitumen is directly related to the amount of remaining hydrocarbons of molecular range less than C20 n-alkanes and mono-aromatic hydrocarbons present. Undegraded oil in the same region found to have higher percentage of n-alkanes as compared to degraded oil. Scientists usually measure biodegradation by measuring the concentration of below C20 n-alkanes. Cyclic saturated hydrocarbons are not affected by biodegradation. Figure 9 shows the trend of relative percentages of C17-C18 as biomarkers, used by the scientists, to determine the degree of biodegradation. The concentrations of C17–C18 are highest in conventional heavy oil, as compared to unconventional heavy oil 29

(extraheavy oil), and are lowest in bitumen. So far, the common belief is that biodegradation is mostly responsible for the heterogeneity of the subsurface formation because biotransformation reactions are highly dependent on the environment [37].

Figure 9 – Trend in the extent of biodegradation of heavy oil and bitumen [37]

1.2.2. Industrial technologies of the oil extraction from the oil sand Main industrial technologies of the extraction of oil from oil sand use a hydrodynamic, thermal and chemical influence. Well known, hot water extraction is used for the commercial bitumen recovery from oil sand. The effects of several factors on the bitumen recovery have been investigated, including solid-liquid ratio, NaOH concentration, stirring time. The solvent extraction is only used in the experimental work. No any solvent extraction process is commercialized in the world at present because of the difficulty of solvent recovery and solvent loss. Retorting is a process in which oil sand is heated to around 500 0C under the condition of oxygen to produce oil. After retorting, oil sand bitumen is thermally cracking process. Alberta Taciuk Process was invented for oil sand retorting, but it is now used for oil shale retorting. With the goal of processing heavy oil, bitumen, and residue to obtain gasoline and other liquid fuels, an in-depth knowledge of the constituents of these heavy feedstocks is an essential first step for any 30

technological advancement. Compared to conventional oil (obtained from traditional, easily accessible sources), however, synthetic crude from bitumen is expensive and complicated to produce [32, 38-40]. The surface mining extraction method is similar to many coal mining operations. Traditional extraction methods are not suitable for bitumen recovery so, when the Canadians started to extract oil sands from their deposits, they had to remove the layer of ground that is over the wanted ore (including trees and all kind of life that could exist in that level) so that the oil sands could be extracted as a surface mine. However, more modern extraction methods have been developed to overcome this problem such as “in situ” extraction methods that are more environmentally friendly and avoid the need to remove the upper layer of the ground. Steam Assisted Gravity Drainage (SAGD) and Cyclic Steam Stimulation are the two major methods used nowadays as in situ extraction methods [41, 42]. In the next figure (figure 10) is shown the surface mining of schematic of a SAGD in situ development.

Figure 10 – Schematic of a SAGD in situ development [42]

31

The two main drawbacks of this process are the big amounts of water required for making one barrel of oil and the big amount of tailings produced. Besides, the energy consumption is also very important. For producing one barrel of oil the industries that use this process require from 17 to 21 barrels of water, however, the majorities of this water is recycled and just from 2 to 4.5 barrels are needed [8]. There are 1.7 trillion barrels of bitumen in place in Canadian oil sands and the resource will become a major source of petroleum products in the near future. Extra heavy oil has been commercially produced from Alberta’s massive oil sands resources for four decades. Through the evolution of technology, the efficiency and performance of oil sands extraction, separation and upgrading technology has advanced, while operating costs have fallen. In 2005, Alberta produced more than 1 million barrels per day of upgraded crude oil and bitumen from oil sands, and projections are that over three million barrels per day could be produced in 2030. The evolution of Alberta’s oil sands industry contributes both technology and lessons learned to guide further development of North America’s heavy oil resources. In 2003, samples of Lloydminster oil sands (oil-water-solids ratio of 19: 40: 41) considered particularly stubborn to separation were tested with exposure to variable frequency microwaves [43, 44].

1.2.3. Kazakhstan’s oil sand As it was written before, in Kazakhstan discovered huge amount of oil sands, its reserve more than conventional oil of Republic. They are accumulated in three region of Kazakhstan (Western part). Namely, Aqtobe, Atyrau and Mangistau regions (figure 11). According published dates that the in West Kazakhstan at depths up to 120 m occurs more than 1 billion tons of natural bitumen and over 15-20 billion tons of oil sands. Pioneer of complex study on processing oil sands was in 80-90s of last century. The problem of development of Kazakhstan oil sand in 1980-1985 was conducted in four main areas: investigation of geology and geochemistry of mineral and organic components of the oil sand deposits; development of technologies of oil sand and tools for use in road construction; study 32

of organic mineral constituents of the oil sand as an additional source of energy and chemical resources.

Figure 11 – Oil sands located area in Kazakhstan

Compared to Canadian oil sands, the Kazakhstan oil sand deposits are situated far from water source. Therefore, the traditional extraction methods are not suitable for processing this “black gold” [45, 46].

1.3. Study Kazakhstan’s Oil Sand Organic Part 1.3.1. Materials and separating methods of organic part from oil sands Oil sand samples The objects of research work were oil sands from two deposits. One of the samples is oil sand of deposits Munayli-Mola (figure 12 a), which located in Atyrau region. LLP “Dortechnika” supported us Munayli-Mola oil sands for experiment. Second sample is oil sand of deposits Beke (figure 12 b). Beke oil sands located in Mangistau region. It was supported to research by LLP “Altyn KDT”.

33

а

b

а – Munayli-Mola oil sand, b – Beke oil sand Figure 12 – Photograph of oil sand samples

Laboratory bitumen extraction method For the separation of organic part from oil sands the extraction method was used. The hexane, benzene, trichloromethane (chloroform), toluene, ethanol and benzene mixture (the ratio of ethanol: benzene was equal to 1:4) was used as a solvent. Extraction was carried out in Soxhlet apparatus (figure 13) till termination of solvent coloring. Content of organic species (natural bitumen) in oil sands q’B were calculated as following equation:

qB' 

( G1  G )  ( G 2  G ) G1  G

100% (1)

where, G – mass of dried filtration paper with cotton, g; G1– mass of oil sand samples and filtration 1 – reflux condenser, 2 – Soxhlet apparatus, paper with cotton until extraction, g; 3 – flask, 4 – heating plate, G2 – mass of dried mineral waste 5 – upright (sands) and filtration paper with cotton after Figure 13 – Scheme of extraction, g. Soxhlet apparatus

34

Used organic solvents for extraction process Separation of organic part from oil sand was carried out by extraction method at apparatus Soxhlet. For the extraction process variety of solvents were used, which characteristics are showing in table 2. Table 2 Characteristics of solvents Solvents

Molecular formula

Boiling point, 0C

Hexane

C6H14

69

Toluene

C7H8

111

Benzene

C6H6

80.1

Ethanol

C2H6O

78.37

As showing table, hexane has lower boiling point (69 оC) and toluene has higher boiling point (111оC). The equal of ethanol and benzene mixture was 1:4 and their boiling points closest each other (80.1 and 78.37 оC).

1.3.2. Composition and characteristics of oil sand bitumen Organic part of oil sand is natural bitumen Including three kinds of samples, organic substances extracted by toluene has higher content. The medium content of organic part in oil sands of Munayli-Mola deposits are 16 wt.%. Whereas, it is determined that the Beke oil sand has 11 wt.%. of organic substances [45]. Other parts (without organic part) of oil sands are consists solid and sand mixture. Table 3 is presenting results of extraction and some analyses. Organic part of oil sand is black with glitter, characteristic like petroleum bitumen. And it is natural raw material. Therefore it called “natural bitumen” (NB), also called as “bitumen” (Figure 14). Some characteristics of NB are presenting in the table 4.

35

Table 3 Organic content of oil sands extracted by variety of solvents, wt.% Samples Munayli-Mola oil sand Beke oil sand

Extracted by hexane

Extracted by toluene

15.5

16.5

Extracted by ethanol and benzene mixture 15.9

10.6

11.3

11.2

Medium organic content of OS 16 11

Тable 4 Physical and chemical properties of natural bitumen Oil sand samples

Characteristics

Density, g/cm3 Munayli-Mola Heating value, OS j/g Density, g/cm3 Beke OS Heating value, j/g

NB extracted by hexane

NB extracted by toluene

0.997

1.090

NB extracted by the ethanol and benzene mixture 0.987

43006

42464

41857

0.917

0.925

1.002

42728

43264

42536

Figure 14 – Image of natural bitumen extracted from oil sands

36

Density is important properties of petroleum and petroleum products. At experiment pycnometer was used for the determination of density of oil samples. Water (distilled) were added into weighted pycnometer untill selected volume and was weighted all mass. After cleaned dish, the oil samples were added hydrocarbon and weighted again pycnometer with oil. At last, density of products calculated by following formula:

ߩ௢௜௟ ൌ

୫మ ି୫బ ୫భ ି୫బ

ή ɏ୵ୟ୲ୣ୰

(2)

As tabulated dates, the results of density presented the object of research is heavy oil. Because of density of heavy oil produced by hexane are 0.997 g/cm3 and by the ethanol and benzene mixture are 0.987 g/cm3. Heating value of natural bitumen was tested at IKA oxygen bomb calorimeters C 200. Medium heating value of natural bitumen produced from Munayli-Mola oil sand was 42442 j/g and produced from Beke oil sand was 42842 j/g. The heating value or calorific value of hydrocarbons is the amount of heat released during the complete combustion of a specified amount of them. Usually, the heat value of crude oil expected around 42-44 Mj/kg. Comparison extraction results with ash determination In order to prove the extraction results, the process were compared with results of ash content determination (in table 5). About one gram of sample (in duplicate) was weighed into porcelain dishes. They were placed in the muffle furnace “Nabertherm”. It installed maximal temperature at 815 ˚C. After that the muffle was turned off, the dishes were transferred to desiccators to avoid picking up moisture from the atmosphere. Dishes were weighed after samples were cooled. The ash g % content was calculated by: Ash content (g %) = (Weight of ashed samples/ Weight of Fresh Samples) × 100. It is describing as formula:

‫ܣ‬ൌ

୫మ ି୫భ ୫

ൈ ͳͲͲΨ

(3)

where, m – mass of oil sample, m1 – mass of crucible, m2 – mass of after burnet crucible with ash.

37

Table 5 Comparison results of ash content determination and extraction Research object

Munayli-Mola oil sands

Methods

Contents

Extraction method

Extracted oil, wt. %

After extracted sands, wt. %

16

84

Determination of ash content

Organic part, wt. %

Ash content, wt. %

16.7

83.3

As the table, ash content of oil sands was 83.3 wt.%, so its organic part is 16.7 wt.%. and extracting results close to them. In general, same organic content in oil sands using extraction methods with ash determining method (16 and 16.7 wt.%). It means, while extraction process the solvents separated almost organic substances from mineral part of oil sands. Depending on the concentration of bitumen, the oil sands are usually divided into three main classes [37], as follows: – Low-grade oil sands – bitumen content 6-8 wt% – Medium-grade oil sands – bitumen content 8-10 wt% – Rich oil sands – bitumen content >10 wt%. As experimental results, Munayli-Mola and Beke oil sands consists more than 10 wt% of bitumen content. It allows concluding, that the both oil sand are rich oil sand. It was reported that the percentage of bitumen in oil sand can range from 30%. It is depended deep level of feedstock. Infrared spectroscopic analyses Chemical composition of natural bitumen was identified by a Fourier transform infrared spectroscopy Spectrum-65 in cells of KBr and tablets with KBr. It is used to obtain an infrared spectrum of absorption, emission, photoconductivity or Raman scattering of a solid, liquid or gas. A spectrometer simultaneously collects spectral data in a wide spectral range. The spectra with 400-4000 cm-1 range were obtained. The IR-spectrums of oil sand bitumen are showing at figure 15 and 16.

38

Figure 15 – IR spectrum of Munayli-Mola natural bitumen

100,0 95 90 85 80

874,95

536,58 469,34

1603,62

75

813,99 1706,44

721,48 1031,84

70 65 60 55

1376,77

%T 50 45 40 35

1461,19

30 25 20 15 10 2853,34

5 3,2 4000,0

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

cm-1

Figure 16 – IR spectrum of Beke natural bitumen

39

800

600

450,0

In the IR spectrum of Munayli-Mola bitumen, that the absorption bands characteristic for alkyl substituents (-CH3,-CH2), with minima at 2856, 2922 cm-1 and spectrum of Munayli-Mola bitumen with a minimum at 2853.34 cm-1. It should be noted a high enough intensity stretching bands groups C-O-C and C-OH at 1032 cm-1, 1156 cm-1 (figure 12) and 1031.84 cm-1 (figure 13). As well as, in combination with an intense absorption band at the 1604, 1706 cm-1 (figure 12) and 1603.62, 1706.44 cm-1 (figure 13) of the carbonyl groups. Oxygenates (1100-1300, 1706 cm-1) and aromatic structures (747, 1032, 1604 cm1 ) are most clearly seen the asphaltene and asphaltogenic acids content of Munayli-Mola bitumen. In the Beke bitumen they are according to dates 1706.44 cm-1 1031.84, 1604 cm-1. In the both spectrum at 1377, 1376.77cm-1and 1456, 1461.19 cm-1have absorption bands belonging to stretching vibrations of the methylene groups and characterize the degree of branched paraffin [45]. Elemental compositions The elemental compositions of natural bitumen from the oil sands were compared with elemental composition of petroleum bitumen BND 60/90. Carbon, hydrogen, nitrogen, oxygen and sulfur analyses were performed using a Elementar Vario EL III (figure 17).

Figure 17 – Apparatus for elemental analyses

40

The oil samples in elemental analysis were sealed in the capsule. Air in the capsule was forced out the capsule via a gas stream of oxygen. The mean blank values of several samples were subtracted for evaluation.Macro elements of Munayli-Mola bitumen and standard bitumen are shown in table 6. Table 6 Elemental composition of Munayli-Mola bitumen Content, wt. %

Type of bitumen

Ash content. wt. %

C

H

S

N

O

Natural bitumen extracted by hexane

0.082

84.36

12.16

1.294

0.29

1.814

Natural bitumen extracted by toluene

1.3

85.00

12.34

1.010

0.30

0.15

Natural bitumen extracted by ethanol/benzene

0.13

84.69

11.39

1.292

0.38

2.118

Standard paving bitumen BND 60/90

0.167

84.91

11.01

3.050

0.52

0.343

A distinctive feature of the Munayli-Mola natural bitumen is almost the same content of carbon (between 84 and 85) and hydrogen (11-12) with standard bitumen. Meanwhile, all bitumen derived by variety of solvents has less than BND 60/90 on the sulfur and nitrogen content. The elemental composition of natural bitumen from the Beke oil sand is presenting in table 7. Table 7 Elemental composition of Beke natural bitumen Samples

Natural bitumen extracted Natural bitumen extracted by hexane by toluene

Elemental composition Carbon, wt.%

85.25

84.49

Hydrogen, wt.%

11.54

11.39

Sulfur, wt.%

0.436

0.482

Nitrogen, wt.%

0.44

0.47

Oxygen, wt.%

1.214

1.998

Ash content, wt.%

1.02

1.17

41

There are showing the Beke natural bitumen has same content of carbon and hydrogen with standard bitumen, too. Meanwhile, all bitumen derived by variety of solvents has less than BND 60/90 on the sulfur and nitrogen content. It can conclude from the results of table 8 and 9, that the Munayli-Mola and Beke natural bitumen have same content of C, H2 and N2. But, Munayli-Mola has higher S (more than 1 wt.%) and Beke has higher ash (more than 1 wt.%) [45].

1.4. Structures of Oil Sand and Its Mineral Parts 1.4.1. Microscopic study of oil sand structure Oil sands consist of quartz sand, organic substances as natural bitumen, water, clay and minerals. Organic part separated oil sand residue consists of solid and sand mixture as in the figure 18. Figure 19-21 shows the comparing of oil sand with after solvent extracted sand grain surface appearance and morphology. As present figure 19 and 20 A-D, sand grains of oil sand surrounded by natural bitumen and wetted water. It was published that the thin layer of water, around 10 nm across (figure 21 A and figure 20 E, F), between the quartz and the bitumen. This layer makes the oil sands water-wet.

1 – extracted by hexane; 2 – extracted by toluene; 3 – extracted by ethanol/benzene Figure 18 – Image of after extracted mineral part of oil sands

42

A

B

C

D

Figure 19 – SEM image of oil sand and after thermal extracted sand

The water wet containing clay fines and other minerals, as discussed over. It should be noted, there are air avoid between sand particles without bitumen covered (figure 20 C, D and figure 21 B). Study of linkage between natural bitumen and sand grains in oil sand is important. This phenomenon is more useful at processing and developing of oil sand [45, 46].

43

A

B

C

D

E

F Figure 20 – Optical microscopic images of Beke oil sands

44

A

B

Figure 21 – Composition and structure of oil sands [37, 46]

1.4.2. Mineral part of oil sands Sand composition The medium content of organic part in selected oil sands are 11-16 wt.%. Therefore, their mineral parts 84-89 % by weight in oil sands. Mineral aggregates of Munayli-Mola oil sands after extraction were studied at apparatus X-ray phase analysis. They are presenting at figure 22 and in the table 8. X-ray phase analyses to mineral samples were tested on the diffractometer DRON-3М. X-ray pattern of samples obtained digitally. When analyzing the base of ICDD diffraction data was used. At preparing the sample was deposited on a silicon single-crystal substrate, therefore on the diffraction pattern presents diffraction line d = 1.361 Å, which belongs to the silicon.

45

Table 8 X-ray phase analysis results of samples of oil sand minerals Sample A

Sample B

Sample C

Angle

d value

Intensity

Angle

d value

Intensity

Angle

d value

Intensity

2-Theta °

Angstrom

Count

2-Theta °

Angstrom

Count

2-Theta °

Angstrom

Count

24,239

4,2603

2173

24,261

4,2564

1662

24,302

4,2494

1434

25,554

4,0445

290

25,630

4,0326

215

25,739

4,0159

407

26,152

3,9536

239

26,259

3,9377

253

27,426

3,7732

310

27,437

3,7717

418

26,786

3,8616

230

28,300

3,6589

388

28,244

3,6660

367

27,398

3,7770

253

31,112

3,3353

7151 1143

30,711

3,3778

1221

28,175

3,6749

420

32,111

3,2341

30,965

3,3507

11336

30,720

3,3768

1159

32,455

3,2008

891

32,010

3,2441

1135

31,018

3,3451

9835

35,141

2,9630

252

32,578

3,1890

1339

32,072

3,2380

1292

42,732

2,4551

698

35,357

2,9454

324

32,565

3,1903

1399

46,167

2,2814

491

35,955

2,8980

341

35,947

2,8987

237

47,164

2,2358

379

42,680

2,4580

808

40,298

2,5967

275

49,752

2,1264

557

46,177

2,2809

715

42,677

2,4581

696

53,742

1,9790

359

47,163

2,2359

613

46,196

2,2800

719

58,979

1,8170

893

48,896

2,1612

255

47,147

2,2365

436

59,571

1,8006

202

49,763

2,1259

647

49,731

2,1272

657

64,746

1,6706

409

53,768

1,9781

400

53,725

1,9795

398

65,307

1,6578

676

58,975

1,8171

1265

58,960

1,8176

841

70,949

1,5413

651

59,558

1,8010

246

59,538

1,8015

291

75,968

1,4534

303

64,689

1,6719

539

60,286

1,7812

161

80,644

1,3823

550

65,272

1,6586

223

64,705

1,6715

443

81,361

1,3722

510

70,953

1,5412

949

65,231

1,6595

183

87,969

1,2880

212

75,951

1,4536

281

70,959

1,5411

1139

90,837

1,2558

550

80,666

1,3820

597

75,990

1,4530

275

81,249

1,3738

773

80,681

1,3818

436

83,398

1,3446

246

81,310

1,3729

657

87,996

1,2877

223

87,921

1,2885

191

90,777

1,2565

298

46

Sample A

d=1,8171

d=1,9781

d=2,2809 d=2,2359 d=2,1612 d=2,1259

d=2,4580

d=2,9454

d=3,3778 d=3,1890

d=4,2603 d=4,0445 d=3,7717

INTENSITY counts

10000

0 21

30

40

50

60

2 THETA degrees N2 zak6 2013 - File: N2 zak6 2013.RA

C

SiO2

KAlSi3O8-Microcline

NaAlSi3O8-Albite

Sample B

d=2,1272

d=2,2800 d=2,2365

d=2,4581

d=2,5967

d=2,8987

d=3,3768 d=3,2380 d=3,1903

d=4,2564 d=4,0326 d=3,8616 d=3,6749

INTENSITY counts

10000

0 21

30

40

50

2 THETA degrees N3 zak6 2013

NaAlSi3O8

SiO2

C

KAlSi3O8

Sample C

1000

d=1,8170

d=1,9790

2000

d=2,2814 d=2,2358 d=2,1264

3000

d=2,4551

4000

d=2,9630

5000

d=3,2341

6000

d=4,2494 d=4,0159 d=3,7732

INTENSITY counts

7000

0 22

30

40

50

60

2 THETA degrees N4 zak6 2013

KAlSi3O8

SiO2 NaAlSi3O8

Figure 22 – X-ray phase analyses of mineral part of oil sands

47

According to the tabulated dates, after extracted mineral part of oil sands consists of silicon and aluminum oxide composites (table 9). Namely, consists 72-79 % of quartz (SiO2), 11-14 % of albite (NaAlSi3O8) and 9-13 % of microcline (KAlSi3O8). The chemical composition of the mineral part, also studied by atomic absorption spectrophotometers presented components, wt. %: Na2O (2.70), K2O (4.10), Fe2O3 (0.37), Al2O3 (9.30), CaO (0.22), SiO2 (82.16), TiO2 (0.06). Table 9 The results of semi-quantitative analysis of oil sand’s mineral composition Sample

Mineral aggregates of Munayli-Mola OS after extracted by hexane

Name of the composition

Chemical formula

Content, %

Quartz

SiO2

79.1

Albite

NaAlSi3O8

11.8

Microcline

KAlSi3O8

9.0

Footprints of carbon

C

0.1

Quartz

SiO2

72.1

Albite

NaAlSi3O8

14.1

Microcline

KAlSi3O8

13.8

Footprints of carbon

C

0

Quartz

SiO2

75,5

Albite

NaAlSi3O8

11.2

Microcline

KAlSi3O8

13.3

Footprints of carbon

C

0

Total

Mineral aggregates of Munayli-Mola OS after extracted by toluene

100

Total

Mineral aggregates of Munayli-Mola OS after extracted by B/E mixture

Total

100

100

Microscopic study of sands Microscopic analyses were provided to after extracted sands of oil sand. The samples were taken by Leica DM 6000 M optical microscope on optical reflection. It uses visible light and a system 48

of lenses to magnify images of small samples. The Leica DM6000 M is available with a 6”x 6” stage for microelectronics inspection. The images from an optical microscope were captured by normal light-sensitive cameras to generate a micrograph. Figure 19 is optical microscopic image of Beke oil sand’s mineral part. Figure 23 shown that the almost particle size of the sand grains are about 200 μm, but, some particle size is 400-500 μm, although it varies a bit too. Microscopic image shows a lot of bitumen free sand grains, however, some of them are quite black, that is because some bitumen remained attached to the grains through the pores.

Figure 23 – Optical microscopic image of mineral part of Beke oil sand

Scanning electron microscopic (SEM) image described more information about selected objects (figure 24). The SEM uses a focused beam of high-energy electrons to generate a variety of signals at the surface of solid specimens. The signals that derive from the electron-sample interactions reveal information about the sample, including external morphology, chemical composition, crystalline structure, and the orientation of materials making up the sample. SEM (Quanta 3D 200i) at an accelerated voltage of 20 kV and pressure at 0.003 Pa. Figure is presenting not only particle size of sand grain (variety of size until 400-500 μm), but also is presenting grain surface structure. Mineral part of oil sand has dense surface layer and micro porous structure. Also shown at sand surface white substances and it is describing metal composition of mineral parts. In this reason the clay minerals was separated from sand particle.

49

Figure 24 – SEM image of oil sand’s mineral part

50

1.4.3. Clay composition in oil sand Clay separation method After extracted mineral part oil sand were mixed with 200 ml of water to perform a simple stage extraction of the clay present in the oil sands. Since the clay is slightly soluble in water (due to the hydrogen bonds between the oxygen of the silicates and the hydrogen of the molecules of water) the insoluble sands would not dissolve and the clay will form a solution with the distilled water used. After mixing the distilled water and the sand properly, a filtration was made to separate the suspended insoluble materials of the water collecting the solution of water and clay in a flask. A simple funnel and filter paper was used for the filtration and the filtrate was collected into an Erlenmeyer flask. At last, the dried clay from the Petri dish was collected and weighted. Experimental scheme of clay separation is presenting in figure 25.

Figure 25 – Experimental scheme of clay separation

Clay composition and structure The retained solution of the remaining sands after the extraction with water has the same concentration of clay as the solution filtered before, but no washing of the refines was performed. That happened, because the amount of retained solution was thought to be very 51

small and the amount of clay in that solution considered negligible. However, it might have been the cause for getting such a low value in the fraction of clay. Besides, it must also be considered the absorption of solution by the filter paper that also retains clay inside it. X-ray fluorescent analysis of clay mineral composition were carried out on a spectrometer “Focus – M2”, through the measure of analytical lines of chemical elements and by counting them, determine the mass concentration of the elements contained in the sample. The results of elemental analysis are presented in the table 10. Table 10 Elemental composition of clay minerals of oil sand Element

Concentration, %

Intensity, cps

Fe

0.349

3.95

K

1.270

2.26

Ca

60.304

255.13

S

29.799

17.78

Cl2

3.987

2.24

P

3.773

1.09

Sr

0.329

3.85

Mn

0.189

1.58

It is easy to see from the table 10, that the clay mineral compositions are formed in a 90% by Calcium and Sulfur, 3-4 % of Cl2 and P, as well as very small content of Fe, Sr and Mn. But, that it is not coherent with the chemical formula of the clay, which is Al2O3·2SiO2·H2O. The calcium and the sulfur suggest that the chemical formula of the clay composition inside the oil sands from Beke is CaSO4·2H2O, which is expected main content of gypsum. This composition can be useful for many applications, most of them medical, but also for making pieces of art and many other practical uses. It must be said that hydrogen and oxygen are not detected by this method and the rest of the elements shown in the list belong to other molecules and substances that are mainly impurities and are present in a very small fraction. Figure 26 is optical microscopic image of clay minerals of oil sands. As it is shown in figure 26 the particle size of the clay is very varied and can be extremely small and quite big. The range is difficult 52

to estimate, but is obvious their small particles is 0.46 μm. However, it’s difficult to conclude surface structure, the composition have both crystal and amorphous structure.

A

B

C

D Figure 26 – Optical microscopic image of clay mineral composition of Beke oil sand

References 1 1. Ongarbaev Ye., Mansurov Z.:Study of composition and properties of oil pollution. B. Faye and Y. Sinyavskiy (eds.), Impact of Pollution on Animal Products. SpringerScience + BusinessMediaB.V. – 2008. – P. 3-12. 2. Надиров Н.К. Высоковязкие нефти и природные битумы: в 5 т. – Алматы: Ғылым, 2001. – Т.1. – 360 с. 3. Mansurov Z.A., Ongarbaev E.K., Tuleutaev B.K.: Utilization of Oil Wastes for Production of Road-building materials // Eurasian Chemico-Technological Journal. – 2000. – № 2(2). – P. 161-166.

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4. Fuel Chemistry Public Education. Petroleum. http://www.ems.psu.edu. 25/10/2014. 5. Нуржанова С.Б. Новые доходы в технологии извлечения ценных металлов из Высоковязких нефтей, природные битумов и горючих сланцев // труды РГП национального центра КПМС РК. – Алматы, 2013. – С. 613-634. 6. Petroleum processing and refining. http://www.answers.com. 06.04.2014 7. FAQ – U.S. Energy Information Administration (EIA). http://www.eia.gov. 8. JAMES G. SPEIGHT. Handbook of Petroleum Product Analysis. – John Wiley & Sons, Inc., Hoboken, –New Jersey, 2002. –P. 454. 9. Hussein Alboudwarej et al. highlighting heavy oil. https://www.slb.com 10. James G. Speight. Oil sand production processes. Elsevier Inc. – 2013. – 175 p. 11. Киинов Л. Перспективы развития нефтегазовой отрасли Казахстана // Нефть и газ. – 2010. – № 6 (60). – С. 83-88. 12. Калыбаев А. А. Глубокая конверсия нефти путем турбулентно – волновой молекулярной деструкции // Нефть и газ. – 2003. – № 3. – С. 72-79. 13. Мансуров З. А., Онгарбаев Е. К., Тулеутаев Б. К. Разработка способа утилизации нефтеотходов и дорожно -строительные материалы на их основе // Нефть и газ. – 2000. – № 1. – С. 67-75. 14. Химический состав нефти и газа. http://www.ngfr.ru. 20.10.2016. 15. Eman A. Emam. Clays as Catalysts in Petroleum Refining Industry // ARPN Journal of Science and Technology. – 2013, – Vol. 3, – No. 4, –P. 356-375. 16. Ma.tthew R. Harrison. Theresa M. Shires, Richard, A. Baker. and Christopher J. Loughran. Methane Emissions from the U. S. Petroleum Industry. REPORT NO. EPA- 600 / R- 99-010 17. Petroleum Refining. http://www.epa.gov. 20.09.2014. 18. Онгарбаев Е. К. Научные основы комплексной переработки тяжелых нефтей, нефтяных остатков и отходов: автореф. ... докт. хим. наук: 02.00.13. – Алматы: Əрекет-Принт, 2010. – 39 с. 19. Онгарбаев Е.К., Досжанов Е.О., Мансуров З.А. Переработка тяжелых нефтей, нефтяных остатков и отходов. – Изд. 2-е, допол. – Алматы: Қазақ университеті, 2011. – 254 с. 20. Study on oil refining and oil markets. Prepared for: European commission. – 2008 (January).– P. 377. http://ec.europa.eu. 06.04.2014. 21. Bei Zhao. High Temperature Behaviours of Asphaltene Aggregates in Heavy Feedstocks and in Mixtures with Diluents. PhD thesis. – University of Alberta, 2008. – P. 197. 22. Oil and gas basins of Kazakhstan. https://www.google.ru. 16.11.2014. 23. Надиров Н. К. Высоковязкие нефти и природные битумы: в 5 т. – Алматы: Ғылым, 2001. – Т.5. – 360 с. 24. Алшанов Р. Нефть и мировая экономика // Нефть и газ. – 2008. – № 5. – С. 73-77. 25. Gabdullin K., Bek Ali Y., Aldabek N. Oil Prices Impact on Energy Policy of Kazakhstan // International Journal of Social, Human Science and Engineering. – 2012.– Vol. 6, No. 6. – P. 1-4.

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26. Стратегический план развития Казахстана до 2020 года http://www. minplan.kz. 10.11.2014. 27. Asphalt and bitumen. Encyclopedia of chemistry (Ullmann’s). –2012. – Vol. 4. – P. 273-294. DOI: 10.1002/14356007.a03_169.pub2 28. Wik S., Spark B.D., Ng S., Yu Y., Li Z., Chung K.H.. Effect of process water chemistry and particulate mineralogy on model // Fuel. – 2008. – Vol. 87. – P 1394–1412. 29. Dusseault M.B.. Comparing Venezuelan and Canadian heavy oil and tar sands. www.southportland.org. 04.11.2014. 30. Wang Qing, Jia Chunxia, Jiang Qianqian, Wang Yin, Deyin Wu.: Combustion characteristics of Indonesian oil sands // Fuel Processing Technology. – 2012. – Vol. 99. – P. 110–114. 31. Надиров Н. К. Высоковязкие нефти и природные битумы: в 5 т. – Алматы: Ғылым, 2001. – Т.5. – 337 с. 32. Parviz M. Rahimi and Thomas Gentzis. The chemistry of bitumen and heavy oil processing. National Centre for Upgrading Technology, Oil Patch Drive, Suite A202, Devon. – Alberta: Canada T9G 1A8, – 2008. – P. 149-186. 33. Andy Hong P.K., Zhixiong Cha, Xinyue Zhao, Chia-Jung Cheng, Willem Duyvesteyn.: Extraction of bitumen from oil sands with hot water and pressure cycles// Fuel Processing Technology. – 2013. – Vol. 106. – P. 460–467. 34. Oil Sands Mining and Processing. www.slidedoc.us. 18.10.2016. 35. Fuel Chemistry Public Education. Research sequence: (with Google as browser) Fuel Chemistry Public Education-Oil sands 10.07.2014. 36. Saúl Domínguez Negreira. Study about oil sands and bitumen extraction methods. Report in the institute of combustion problems. – Almaty, 2014. – P. 35. 37. Banerjee, Dwijen K. Oil sands, heavy oil and bitumen.– Tulsa, USA: RenWell, 2012. – P. 185. 38. Abramov O.V., Abramov V.O., Myasnikov S.K., Mullakaev M.S. Extraction of bitumen, crude oil and its products from tar sand and contaminated sandy soil under effect of ultrasound // Ultrasonics Sonochemistry. – 2009. – Vol. 16. – P. 408-416. 39. Yue Ma, Shuyuan Li. The pyrolysis, extraction and kinetics of Buton oil sand bitumen // Fuel Processing Technology.– 2012. – Vol.100. – P. 11–15. 40. Tileuberdi Ye., Ongarbaev Ye., Tuleutaev B., Mansurov Z., Behrendt F. Study of Natural Bitumen Extracted from Oil Sands // Applied Mechanics and Materials. –2014. – Vol. 467. – P. 8-11. 41. Rada de Malherbe. Synthetic Crude from oil sands. – VDI Verglag, Dusseldorf, 1983. – P. 102. 42. In Situ Methods used in the Oil Sands. www.ramp-alberta.org. 11/07/2014. 43. Sateesh Mutyala et. al. Microwave applications to oil sands and petroleum: A review. Fuel Processing Technology. 91. (2010). 127–135 44. Mansurov Z.A. Study and processing of oil sands // Journal of Petroleum and Environmental Biotechnology. – 2016. – Vol. 7 (4). – P. 31. 45. Ye. Tileuberdi. Nanostructure of Bitumen Produced from Heavy Oil: Ph.D. thesis, –2014. – P. 102. 46. Ye. Tileuberdi, Z. Mansurov, Ye. Ongarbayev, B. Tuleutaev. Structural study and upgrading of Kazakhstan oil sands // Eurasian Chemico-Technological Journal. – 2015. – Vol. 17 (1). – P. 41-45.

55

II. BITUMEN PRODUCING AND ASPHALTENE 2.1. Properties and Structure of Bitumen 2.1.1. Definition of bitumen Bitumen is a mixture of organic liquids that is viscous, black and sticky. It is a complex mixture of high boiling point range of compounds and molecules with a relatively low hydrogen-to-carbon ratio. In the United States the terms asphalt and bitumen are synonymous, while in other areas, e.g. in Europe and Asia, both terms have different meanings [1-5]. According to European Standard EN 12597 definition that the bitumen is a virtually in volatile, adhesive and water proofing material derived from crude petroleum, or present in natural asphalt, which is completely or nearly completely soluble in toluene, and very viscous or nearly solid at ambient temperature, whereas asphalt is defined as a mixture of mineral aggregates and bituminous binder. It is not known to present any safety, health or environmental hazard. Meanwhile, the American Society for Testing and Materials (ASTM) defines bitumen as a generic class of amorphous, natural or manufactured, dark colored, cementitious substances composed principally of high molecular mass hydrocarbons, soluble in carbon disulfide. Asphalt also is defined as a cementitious material in which the predominating constituents are bitumens. The terms bituminous and asphaltic then refer to materials that contain or are treated with bitumen or asphalt [2, 6]. The residue of many refinery processes, asphalt – a once-maligned by-product – is now a premium value product for highway surfaces, roofing materials, and miscellaneous waterproofing uses. The term bitumen includes a wide variety of reddish-brown to black materials of semisolid, viscous to brittle character that can exist in nature with no mineral impurity or with mineral matter contents that exceed 50% by weight. It is also, on occasion, referred to as native asphalt and extra heavy oil. Bitumen is frequently found filling pores and crevices of sandstone, limestone, or argillaceous sediments, in which case the organic and 56

associated mineral matrix is known as rock asphalt [7-8]. A widely adopted separation methodology of bitumen composition known as the SARA method. Representative structures of bitumen fractions are shown at figure 27. By the hydrocarbon group types they are isolated as saturates, aromatics, resins, and asphaltenes. Maltenes, also called petrolenes are the remaining portion of the bitumen material after the precipitation of asphaltene aggregates with the normal paraffins. The aromatic portion is mostly naphtheno-aromatic hydrocarbons with three or four naphthenic rings per molecule and is nonpolar.These oils are the liquid part of the bitumen and consist of normal-, iso-, and cyclo-paraffins and condensed naphthenes with some alkyl aromatics. The oils have a key feature of dispersing polar agglomerations of asphaltenes and resins [9].

Figure 27 – Representative structures of bitumen fractions [9]

Bitumen is a complex combination of organic compounds with high carbon numbers. This family of molecules can be found in many heavy crude oil. In its simplest form bitumen manufacturing separates the higher fraction from the residuum, the required molecules being already present in the crude oil [10]. Crude heavy fractions are defined as molecules containing more than 25 carbon atoms (C25), presenting a structural complexity which increases with the boiling point (see figure 28) as well as the molecular weight, the density, the viscosity, the aromaticity and the contents of heteroatoms and metals [11]. 57

Figure 28 – Evolution of molecular weights and structures as a function of the boiling point [11]

2.1.2. Main bitumen manufacturing methods Several manufacturing methods are available to produce specification bitumens depending on the crude source(s) and processing capabilities available. The processes used in bitumen production are illustrated in Figure 29. Often used bitumen manufacturing technologies are selected [10, 12]: – Distillation. The most common refining process used for producing bitumen is straight reduction to grade from petroleum crude oil or a crude blend, using atmospheric and vacuum distillation. The lighter fractions are removed at atmospheric equivalent temperatures of 345-400 °C and 370-450 °C leaving a high boiling point hydrocarbon residue. The atmospheric equivalent temperature to yield the vacuum residue is up to 535 °C. – Oxidised bitumen, also known commonly as blown bitumen, is made in a manufacturing unit known as the bitumen blowing unit or air blowing unit or oxidiser. Depending on the feedstock viscosity and the processing conditions. The processes achieve this through varying degrees of chemical reactions which result in an increase in the average molecular weight of the bitumen leading to higher viscosity bitumen. 58

– Solvent deasphalting uses solvents to remove asphaltene fractions from distillation residues for the production of lubricating oil base stocks. The principal deasphalting processes use propane, butane, isobutene, pentane, or supercritical solvent extraction.

Figure 29 – Main processing methods in the production of bitumens

– Vacuum distillation of thermal cracked residue. In a visbreaking unit, a residue stream is heated to temperatures between 440-500 °C, although process conditions can vary depending upon the feedstock and the desired properties of the thermally cracked material, to avoid coke formation. When used for bitumen production the thermal59

ly cracked residue is subjected to vacuum distillation to remove the distillate fractions which are then further treated and used in production of fuels. The product obtained after vacuum distillation is typically a hard material which can be used as a blending component for bitumen production. – Other processes. A number of other refinery processes are used to produce small amounts of residual materials that can be used in the production of bitumen. The processes, including solvent extraction, hydrodesulphurisation and hydrogenation, are not commonly used and hence represent only a minor part of the overall bitumen production. 2.1.3. Bitumen application and consumption Oil bitumen are widely used in many industries. The primary use of bitumen is for paving and roofing applications [10, 13]: – 85% of all the bitumen is used as the binder in various kinds of asphalt pavements: pavements for roads, airports, parking lots, etc. – About 10% of the bitumen is used for roofing. – The rest of the bitumen, approximately 5% of the total, is used for a variety of purposes, each very small in volume. This sector is referred to as “Secondary Uses”. Therefore their production is the important economic problem and requires constant perfection. The main problem with road building is the poor quality of bitumen used in asphalt-concrete pavements. Kazakhstan is the ninth largest country in the world, covering an area of 2717300 km2 and government programs have been agreed for the improvement of infrastructure and road construction across the country [14]. Statistic dates showed that the bitumen consumption is year by year increasing in the Republic (see figure 30). The volume paraffinic and high viscous heavy oil increases recently. Processing of such hydrocarbonic raw material for production of qualitative oil products leads to significant expenses in connection with increase in a share of secondary processes. Produced bitumen is characterized by a low extensibility and low temperature properties. Therefore the rests of high paraffinic oils are considered unsuitable for production of qualitative road bitumens. Nevertheless, there are works where technologies of production of bitumens from paraffinic raw 60

material are described. Necessity of development of the production technology of bitumens from paraffinic raw material demands search of conditions and ways of new nonconventional methods of processing and preparation of raw material [8, 15].

Figure 30 – Graphic of bitumen consumption

In our country the satisfaction of need for a bitumen material occurs due to its import Russia and Iran. Characteristics of imported bitumen completely mismatch climatic conditions of our country, i.e. do not maintain sharp differences of temperatures from -40 up to +40 °С. And also with a view of preservation of quality and technological properties, bitumen is not recommended to be transported on greater distances. In this connection, production of bitumens of various marks on the basis of domestic raw material is an actual problem [16].

2.2. Producing Bitumen from Oil Sands 2.2.1. Physical and mechanical characteristics of natural bitumen Physical and mechanical characteristics of natural bitumen were determined as bitumen according to standard 22245-90. They are presenting in table 11. 61

Table 11 Physical and mechanical characteristics of Munayli-Mola natural bitumen Characteristics

Results

Units

Penetration, at 0 °C

20

0.1 mm

Softening point

28

°C

Ductility, at 0 °C

100

cm

Penetration involves the determination of the extent to which a standard needle penetrates a properly prepared sample of bitumen under specified conditions of temperature, load, and time. The unit of penetration is 0.1 mm, which is generally omitted in favor of reporting just the measured number. It was determined by a apparatus Penetrometer PNB-03 (Figure 31) in accordance with standard 1150178. For the analyses the bitumen sample cup was placed in a water bath at a temperature of 25 0C for 1 hour and determined by a standard needle penetration depth when the load of 100 g for 5 sec. At standard BND 60/90 means a standard paving grade bitumen with a penetration range between 61 and 90 0.1 mm. Softening temperature-the temperature at which the bitumen of a relatively solid state into the liquid state. The softening point was determined by the method of “ring and ball” according to standard 11506-73. It is a measure of the temperature at which a steel ball passes through a disk of the sample and falls a distance of 25.0 mm when the specimen, ball, and bath of distilled water were heated on a hot plate at a rate of 5 °C per minute. The Ductility test gives a measure of adhesive property of bitumen and its ability to stretch. Tensile properties were determined at apparatus Ductilometer CDB-974 N according to standard 1150575. Ductility of a bituminous material is a measure of the distance in centimeters that it elongates before breaking when the two ends of a briquette specimen are pulled apart at a specified rate and temperature. Water bath was maintained within 0 °C or 25.0 ±0.1 °C of the specified test temperature.

62

Figure 31 – Apparatus for determination of depth of needle penetration of samples

As showing in table 10, depth of needle penetration of natural bitumen at 0 °C was 20·0.1 mm and softening point is 28 °C. Ductility of NB at 0 °C was 100 cm. At room temperature the bitumen characteristics could not determinate, because of more sticky. On physical and mechanical characteristics is not satisfaction to requirement of any mark of paving bitumen. However, the natural bitumen is high viscously hydrocarbons [17].

63

2.2.2. Production of oxidized bitumen from natural bitumen of oil sand Oxidation process carried out at 3 L of cylindrical reactor (1) made by stainless steel. Figure 32 is shown scheme of the reactor. Heat it up at burner (2) with the propane-butane mixture. At process, the heated air blowing (3) given to the raw material from compressor (8). Oxidation of natural bitumen was spent at temperatures from 230 up to 270 °С. Through the certain time intervals (1; 1.5; 2 h) were selected tests of oxidation product.

1 – reactor, 2 – heater, 3 – air bubbling tube, 4 – thermometer, 5 – bitumen receiving tube, 6, 7 – rotameters, 8 – compressor, 9 – gas opening tube, 10 – balloon of propane-butane Figure 32 – Scheme of apparatus for oxidizing bitumen

Oxidation of Beke natural bitumen was at temperatures 230, 240 and 270 °С. Through the certain time intervals (60; 90; 120; 150 minutes) were selected tests of oxidation product (figure 33) and its characteristics. Tables 12-14 are shown the main physical and mechanical properties of the oxidized samples from Beke natural bitumen at variety temperature. 64

Figure 33 – Bitumen samples

Tables 12 Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 230 °С Name of the Sample № 1 indicators

BND 90/130

Penetration at 25 оС, 0,1 mm

115

91-130

46

40-60

30

Softening point, оС

44

not less than 43

52

not less than 51

65

Ductility, cm

76

at least 65

45

at least 45

8

Flash point, о С

237

not less than 230

235

not less than 230

220

Sample № 2 BND 40/60 Sample № 3

The oxidation time of the sample number 1 was 60 minutes, the resulting on its physical and mechanical parameters of bitumen is consistent with the requirements of state standard, which mark is BND 90/130. Sample number 2 was oxidized for 90 minutes, its products corresponds to the mark of petroleum bitumen BND 40/60. Further increase oxidation time up to 150 minutes leads to deteriorate the quality of the bitumen (sample number 3). 65

Tables 13 Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 240 °С Name of the indicators

Sample №1

BND 60/90

Sample №2

BND 40/60

Sample №3

BN 70/30

Penetration at 25 о С, 0,1 mm

62

61-90

43

40-60

29

21-40

Softening point, оС

53

not less than 47

61

not less than 51

70

70-80

Ductility, cm

64

at least 55

31

at least 45

12

at least 3,0

Brittle point,оС

-16

not more than -15

-10

not more than-12

-

-

Flashpoint, оС

225

230

232

230

239

not less than 240

Tables 14 Physical and mechanical characteristics of bitumen, obtained from the organic part of Beke oil sand at a temperature of 270 °С Name of the Sample № 1 indicators

BD 70/30

Sample № 2

BD 90/10

Sample № 3

Penetration at 25 оС, 0.1 mm

32

21-40

12

5-20

7

Softening point, оС

72

70-80

85

90-105

92

Ductility, cm

18

at least 3,0

4,0

at least 1,0

2,1

Flash point, о С

238

not less than 240

235

not less than 240

-

66

The samples are listed in table 13 were oxidized at a temperature of 240 °C, while the oxidation of the sample number 1 time was prolonged to 90 minutes, the sample number 2 – 120 minutes, the sample number 3 – 150 minutes. The characteristics of the samples are compared with the state standard on various grades of bitumen. Oxidation products at temperature of 270 °С were according bitumen standard. Thus, analysis of experiment results showed that the from organic part of the Beke oil sand allows produce bitumens of different marks, as road petroleum bitumen BND 40/60, BND 60/90, BND 90/130, as well as building bitumen marks of BN 70/30 and BN 90/10 [17].

2.3. Investigation of Asphaltene Aggregates in Bitumen 2.3.1. Definition of asphaltene Asphaltenes are a fraction of crude oil defined operationally by their solubility in toluene and solubility in n-heptane. They are usually named along with the solvent used for their precipitation, because every asphaltene is different in quality and quantity on the basis of the solvent used.This fraction has been studied extensively because of its role in oilfield flow assurance and more recently. Because, its application as a geochemical marker that can indicate the geologic structure of oil reservoirs. Asphaltene is the most refractory and often the heaviest component, highly aromatic and polar of hydrocarbon. Because of these fundamental characteristics, it is considered an important factor that causes hindrance in many petroleum operations, production, transportation, refining, even wax crystallization, crude oil emulsification, and de-emulsification. Though many of these claims are not fully proved or understood, asphaltene does have a negative effect on many of the above operations. The term asphaltenedoes not imply any particular molecular structure or molecular weight.It is natural to attribute these negative impacts to particular molecular and thermodynamic properties associated with asphaltene. Additionally, asphaltenes are known to be a complex mixture containing thousands of distinct molecular formulas. Despite this scrutiny, some fundamental aspects of 67

asphaltene chemistry are still debated. Asphaltenes are a group of molecular species, whose exact molecular weight is still unknown and varies from 500 to 15000 depending on the analytical technique used [18-21]. In nature, asphaltenes are hypothesized to be formed as a result of oxidation of natural resins. Asphaltenes comprise a heterogeneous fraction consisting of largely polycondensed aromatic rings and cyclic naphthenes, containing most of the heteroatoms (S, N, and O) and metals of the bitumen. Almost all of the heteroatoms and the metals in the asphaltenes are present in five- or six-member ring structures, in a layer of blocks lying one after another.At temperature of 300400 oC the asphaltene does not melt, only decompose, formed carbon and volatile products. They react with sulfuric acid forming sulfonic acids, as might be expected on the basis of the polyaromatic structure of these components. The color of dissolved asphaltenes is deep red at very low concentration in benzene as 0.0003 % makes the solution distinctly yellowish. The color of crude oils and residues is due to the combined effect of neutral resins and asphaltenes. The black color of some crude oils and residues is related to the presence of asphaltenes which are not properly peptized [21, 22]

2.3.2. Asphaltene and its properties Asphaltenes are present in most petroleum materials, and in all heavy oils and bitumens from oil sands. So, they are widely using in many industries. For analytical purposes, the concentration of asphaltene in a crude oil is defined by precipitation with either n-pentane (C5) or n-heptane (C7). For example, n-C5-asphaletene or n-C6-asphaltene means that the asphaltene was precipitated using normal pentane or normal hexane, respectively, as solvents. A standard method exists to quantify resins by a completely different approach. It involves a time-consuming chromatographic separation of de-asphalted oil into saturates, aromatics, and resins, the so-call6ed SARA analysis [23]. It is presenting at figure 34.

68

Crude oil dilute with n-alkane solution

Maltenes precipitate

adsorb on chromatographic column elute with: (1) alkane

Saturate s

(2) aromatic

Aromati cs

(3) Polar solvent

Resins

Asphaltenes

Figure 34 – Schematic illustration of SARA analysis [23]

In the study [24] summarized data on the structure of the petroleum asphaltenes molecules and methods of aggregation. A review of materials on possible phase transitions in asphaltene nanoaggregates and examined their effect on the properties of the oil disperse systems. In recent years the industry that form aggregates of colloidal sizes in the crude with a wide range of molecular weights (1000-50000) and diameters ranging around 3 – 5 nm. In a commercial process, lower hydrocarbons – such as propane, butane, or a mixture of the two – are used as solvents. Yields of asphaltenes depend on the solvent or mixture of solvents used, their solubility in that solvent, and the bitumento-solvent ratio [21, 25]. G.A. Camacho-Bragado et al. offered the cross-sectional model of the structure of the asphaltene (figure 35).

69

Figure 35 – Cross-sectional model of the structure of the asphaltene [25]

In the form of individual molecules of asphaltenes present in the oil media at concentrations of less than 2.1 mg/l [26, 27], according to some sources [28] – at concentrations less than 5.10 mg/l. Stable nanoaggregates size 2-10 nm are formed from 6-10 asphaltene macromolecules [29, 30] at the critical concentration of nano aggregation, value of which amounts to 50-200 mg/l for different asphaltenes [31-34]. Further increasing the concentration of asphaltenes results in more nanoaggregates, but their dimensions do not vary. When the concentration of asphaltenes in the solution to 2-5 g/l the formation of clusters of nanoaggregates (Figure 36). Clusters are represented by fractal structures consisting of 8-10 nanoaggregates [30, 35]. Cluster sizes are in the range of 6-30 nm, sometimes up to 100 nm. 70

Given a polydisperse composition of asphaltenes in petroleum systems and intermolecular interactions of various types, proposed the following model of asphaltene nanoaggregates [24]. Lateral substituents include linear or branched aliphatic, hydroxyl, carboxyl group. These molecules are adsorbed on staching aggregates by hydrogen force and form their aliphatic groups, forming a shell resistant to 200 о С. Thus, was formed «colloidal chain» to capture the oil components (free radicals, resins and others). Cluster formation and flocculation is carried out by Van der Waals interactions.

Figure 36 – Scheme of the formation of nanoclusters of asphaltene molecules [24]

Sunyaev [36] studied the effect ofthe phase state (size and structure) supramolecular structures on the physicochemical properties of petroleum systems. Theyproposed a model of the particles of the dispersed phase of the oil system- a complex structural unit. Thus, it is found that the phase state of the asphaltenes affects the rate of coke formation and the yield of light oil. Nowadays, research activities are more focusing on the properties and structure of asphaltene. In the publication was applied high resolution transmission electron microscopy and energy dispersive 71

spectrometry in the study of asphaltenes. It was found that when the asphaltenes are well separated from the resins the sample consists of a carbon structure containing S, V, Si, related to fullerenic carbon [25, 37]. Graphene-like layers (0.39 nm) and 1.5-nm sized two-shell structures are shown at figure 37.

Figure 37 – High resolution image of the structure of the asphaltene aggregates [25]

During observation in the microscope (figure 30) it was possible to see the formation of fullerenes such as onions and C @ C structures. The fact that they decomposed under further irradiation suggests that they are metastable structures. Since the heteroatoms are still present they are likely to cause instability to the structure [25].

2.3.3. Role of asphaltene in bitumen Asphaltenes are the most poorly defined class of compounds in bitumen but play an important role in characterization and processing. By definition, asphaltenes are in the fraction of the bitumen that is insoluble in normal- paraffin solvent and soluble in benzene or toluene. They are usually named along with the solvent used for their precipitation, because every asphaltene is different in quality and quantity on the basis of the solvent used. For example, n-C5-asphaletene or n-C6asphaltene means that the asphaltene was precipitated using normal pentane or normal hexane, respectively, as solvents. In a commercial process, lower hydrocarbonssuch as propane, butane, or a mixture 72

of the twoare used as solvents. Yields of asphaltenes depend on the solvent or mixture of solvents used, their solubility in that solvent, and the bitumen-to-solvent ratio. The term asphaltene does not imply any particular molecular structure or molecular weight. Rather, asphaltenes are a group of molecular species, whose exact molecular weight is still unknown and varies from 500 to 15,000 depending on the analytical technique used [17, 21, 38]. Asphaltenes comprise a heterogeneous fraction consisting of largely polycondensed aromatic rings and cyclic naphthenes, containing most of the heteroatoms (S, N, and O) and metals of the bitumen. Almost all of the heteroatoms and the metals in the asphaltenes are present in five- or six-member ring structures, in a layer of blocks lying one after another. As the molecular weight of asphaltenes increases, the nonaromatic nature of their structure also increases.Asphaltene molecules are grouped together in a layer of sheets that are dissolved in the maltenes fraction. If either the structure of the asphaltenes is disturbed or the maltenes are partially removed, then the asphaltenes start to agglomerate and settle as solid. The asphaltenes comprise the heaviest part of the heavy oil resid and play a negative role in bitumen recovery, in transportation, and, most important, in the upgrading and refining processes. Asphaltene plays a threefold role in the fouling process [21, 38]: – First and foremost, it has the tendency of precipitating out in the presence of lighter paraffinic hydrocarbon fractions, making the crude s mobility restricted. This creates fouling in the production well during the recovery process, as well as in the pipeline during the transportation of bitumen. – Second, once the structure of the asphaltene is disturbed, the fouling tendency increases (e.g., thermally cracked asphaltenes foul at a higher rate than unprocessed asphaltenes). – Finally, an increase in asphaltene concentration in the feedstock results in a high rate of fouling on furnace walls. The high density and high viscosity of bitumen are also attributed to its asphaltene content. Asphaltenes are so complex that no single research group can complete a study or answer all the questions about them. Scientists are still debating the molecular weight of asphaltenes, which can vary from hundreds to millions in some cases. It is still debated whether the physical nature of asphaltenes presents as an aggregate, a colloid, or an association with resins. 73

Asphaltenes are a contentious area among researchers, with longstanding battles still raging. Asphaltenes are very sensitive to atmospheric oxygen. It has been observed that just the handling of asphaltenes in the atmosphere oxidizes the sample rapidly enough that its characteristics change. Visually, one can observe the asphaltene color change rapidly with the time of exposure, and any chemical properties measured will be influenced by the length of time of exposure to air. Due to the nature of the asphaltenes, which are made of polycondensed layers of aromatic structures, their average molecular weight and density are both expected to be the highest among all fractions. Clearly, asphaltenes comprise the heaviest (average molecular weight above 2,000) and the most dense (density above 1,200 kg/m3) fraction and are mostly responsible for the increase in mass and density of the whole bitumen. Asphaltenes and resins both have molecular weights and densities higher than the average values of the whole bitumen [17, 38].

2.4. Precipitation of Asphaltene from Bitumen 2.4.1. Asphaltene precipitation method During the experimental work we carried out the precipitation of asphaltenes from oil sand of Munayli-Mola deposit. The extracted natural bitumen was mixed with a small quantity of toluene in order to dissolve it. Then we added a 40-fold amount of petroleum ether in relation to the initial hitch of bitumen and put it to the dark place that it couldn’t reached by light to allow the precipitation of insoluble components. The resulting precipitate is dissolved again in toluene and petroleum ether. The procedure is repeated several times, and each step eliminates resins. This changes the external appearance of the precipitate from glassy black solid to brownish carbonaceous material. The separation was continued until no more changes in the residue were observed. Visual analysis of the precipitated asphaltenes showed that the samples are like a brownish fine powder with a distinctive black gloss. It is presenting at figure 38. 74

Figure 38 – Image of precipitated asphaltene samples

2.4.2. Composition of asphaltene precipitated from bitumen IR-spectroscopic analyses The chemical composition of precipitated asphaltenes has been studied by IR spectroscopy. According to the IR-spectrum (figure 39), it can be concluded that the broad absorption band of asphaltenes at 3000-3600 cm-1 are characterizing the presence of polycyclic aromatic hydrocarbons and aliphatic chains in the samples of asphaltens. These hydrocarbons have free functional groups (carboxyl, carbonyl, hydroxyl) at their ends, which are forming the hydrogen bonds. The peak of the absorption band at 3570 cm-1 determines the stretching vibrations of the-OH group, which is actively involved in the formation of intermolecular hydrogen bonds. In IR – spectrum we can also see the presence of specific absorption bans which can characterize the presence of the alkyl substituents (-CH3, -CH2) with minima at 2853, 2922 cm-1. Also presented the stretching and bending vibrations and the groups -CH2-CH3 at 1451 and 1376 cm-1. 75

Figure 39 – The IR-spectrum of asphaltenes precipitated from natural bitumen of Munayli-Mola deposit

The IR-spectroscopic analyzes helped to approximately determine the chemical, group composition of received asphaltenes. X-ray fluorescent analysis Also during the research was made the attempt to establish the elemental composition of the samples of asphaltenes on the installation of x-ray fluorescent spectrometer “Focus – M 2”. The results of elemental analysis are presented in the following table 15. Table 15 shows the presence of certain elements in the asphaltenes received from natural bitumen of Munayli-Mola deposit. From the table, it can be concluded that this natural bitumen, exactly its heavy residue after various treatment processes in the future can be used as an alternate resource for such important elements as vanadium, titanium, nickel and zinc, because the amount of these element in bitumen is enough to be mastered.

76

Table 15 The results X-ray fluorescent analysis of asphaltenes Element

Fractional concentration, %

Intensity, cps

Fe

42.445

34.81

S Ca Ni Zn Ti

28.0 11.672 2.640 6.332 0.644

0.71 3.10 1.21 2.85 0.24

As

1.756

0.64

K V

3.517 2.994

0.37 2.28

Figure 40 – Hypothetical asphaltene molecule and its interaction with metalloporphyrins [39]

77

It has been reported that in general, the asphaltene microstructure is a large aromatic sheet, having high molecular weight. Additionally, few metalloporphyrins are also associated with asphaltene molecule via a p-electronic interaction as shown in Figure 40. It allows observe how to linkage metal elements with hydrocarbon compound of asphaltene [17, 39]. X-ray diffraction analysis The following X-ray diffraction analysis of the samples was carried out on a installation of DRON-3M digitally. According to the results of X-ray diffraction analysis (Figure 41) it was found that the basis of a sample of asphaltenes precipitated from natural bitumen Munaily-Mola, is X-ray amorphous phase. Also found the presence of two crystalline phases. One – quartz content is less than one percent. Another phase is also present in very small quantities and is represented by a single line of diffraction d = 4.158 Å. As known, it cannot be carried out the X-ray diffraction analysis by one phase line, because it may belong to a plurality of phases which are not present in the sample [40].

Figure 41 – The detail of diffraction diagram of asphaltenes

78

2.4.3. Structure of asphaltene surface SEM analyses To study the structure and aggregation of asphaltene surface, the produced samples were examined by scanning electron microscopy. The resulting surface images are given some information about the characteristics of asphaltogenic aggregation. Figure 42 and 43 shows SEM image of precipitated asphaltene from bitumen. As seen in figure 42 A and B, derived asphaltenes have a mediumordered structure, the main component of the surface is represented by amorphous carbon. There are more subtle areas of carbon layers, about structure and aggregation, which electron microscopy data does not seen.

A

B

Figure 42 – SEM images of asphaltene surface precipitated from natural bitumen

When visually comparison images of the asphaltenes surface of natural bitumen with asphaltene of BND 60/90, immediately noticeable that the degree of ordering of asphaltenes BND60/90 is much lower, has large monolithic switching, weakly focused on a major surface, provided with amorphous carbon [17, 40].

79

A

B

Figure 43 – SEM images of asphaltene surface precipitated from paving bitumen

TEM analyses Scanning electron microscopy does not give us complete information about the processes of aggregation of asphaltenes, and therefore asphaltenes continue studied by transmission electron microscopy. Results of the TEM analyses of the asphaltene surface precipitated from natural bitumen were shown at figure 44. TEM uses an electron beam to interact with a sample to form an image on a photographic plate or specialist camera. Also the study was performed on a transmission electron microscope JEM 100CX, at an accelerating voltage of 100 kV (vacuum, a small temperature). Preparations were prepared by dry preparation. Asphaltene sample of natural bitumen consists mainly of fragments sufficiently dense film (figure 44 B). For some annealing of the sample occurs thinning of the film and occasionally there are sample substance of formation, having a crystal lattice (figure 44 3 A). At the edge of the film may be dense large and thin particles (figure 44 C). Meanwhile on the 3 C are present traces of the transformation of the particles. Microdiffraction image that reflect the crystalline order of the substance, give evidence of presented bulk amorphous material. As the TEM images, after annealing asphaltenes of natural bitumen of Munayli-Mola oil sands going appearance two types of nano-dimensional structures: the capsule in the capsule and the ribbon80

like structure. Figure 38 are presenting the TEM images of asphaltene, which precipitated from paving bitumen. Sample submitted asphaltene of BND 60/90, is mainly composed of rounded particles, most of which are extremely small (figure 45 A). The substance of the sample has no structural order – an amorphous structure (figure 45 B). Often there are large round particles and sufficiently dense particles (figure 45 C). Single-crystal particles and traces the transformations of the particles were observed [17].

A

B

C

D

Figure 44 – TEM images of asphaltene surface precipitated from natural bitumen

81

A

B

C

D

Figure 45 – TEM images of asphaltene surface precipitated from paving bitumen

2.4.4. Thermal study of asphaltene As the molecular weight of asphaltenes increases, the nonaromatic nature of their structure also increases. Thermal properties of asphaltene were discussed in published paper. On heating above 300-400 oC, asphaltenes are not melted, but decompose, forming carbon and volatile products. They react with sulfuric acid forming sulfuric acids, as might be expected on the basis of the polyaromatic structure of these components. The asphaltene, precipitated from oil sand bitumen were thermal studied under inert gas. When experiment providing, that the process 82

temperature installed at temperature 600 oC and its products analyzed by microscopic technique (figure 46).

A

B

C

D

Figure 46 – SEM images of asphaltene products after heated at 600 oC

Figure 46 shows the structure of asphaltene product after heated at 600 oC and it has amorphous carbon structure. It was formed 5.12 nm of nanoparticles at high temperature heating [17].

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III. USING RUBBER CRUMB FOR THE PRODUCTION OF RUBBER MODIFIED BITUMEN 3.1. Rubber crumb and Bitumen Modification 3.1.1. Crumb rubber from worn tires and their characteristics Crumb rubber (CR) is a term usually applied to recycled rubber from automotive and truck scrap tires. CR is the recycled rubber obtained by mechanical shearing or grinding of scrap tires into small particles. During the recycling process steel and fluff is removed leaving tire rubber with a granular consistency. The utilization of spent rubber materials, including automobile tires, is currently one of the most important environmental problems on a global scale because of the rapid growth of the automobile industry. Tires are bulky, they are highly toxic, they do not undergo natural degradation and decay; therefore, they are accumulated in open landfills to occupy considerable ground areas or scattered in ravines, forests, and water bodies to pollute the environment (figure 47) [1-3]. According to available data, the world reserves of scrap tires are estimated at 25 million tons with an annual increment of 12 million (at least 7 million) tons. In Russia and the Commonwealth of Independent States, the annual volume of discarded automobile tires is greater than 1 million tons, about 1.5 million tons from China. For fully utilizing natural resources and protecting environment, many countries give priority to the reuse of waste rubber in recent twenty years [5, 6]. Scrap tires are valuable secondary raw materials containing 65-70% rubber, 15-25% technical-grade carbon, and 10-15% highquality metal. Eng. Vasco Pampulim, et.al offered the model of typical tire rubber mix (figure 48).Thus, the efficient processing of scrap tires makes it possible not only to solve environmental problems but also to perform economically rational utilization processes [5, 7]. 87

Figure 47 – Worn tires in open landfills [4]

Figure 48 – Model of typical tire rubber mix [7]

88

Straight out of the tree, natural rubber latex (polyisoprene) is not good for much. It gets runny and sticky when it is warm, and it gets hard and brittle when it is cold. Figure 49 shows the chemical structures of principal organic components of crumb rubber. As literatures review, classified the range of tire materials as following: – Whole tires – Shred and chips: Fragmented irregular tire pieces by a mechanical process. Shred 75-300 mm, Chips 15-75 mm. – Granules: Finely dispersed particles (1-10 mm) produced by ambient or cryogenic method. – Powders: Fine granules (< 2 mm) through ambient or cryogenic processing At the experiment and industry size from 74 μm (200 mesh) to 10 mm crumb rubber have been using on the asphalt paving [8].

Figure 49 – Chemical structures of principal organic components of crumb rubber [8]

3.1.2. Ways of recycling and utilization In the world, scientists have been offered variety ways of recycling and utilization of rubber crumb from worn tires. A well-known method is to burn the rubber waste to produce energy while producing cement. This kind of “recycling” has to be reduced in future. Due to its irreversible network, the different compounds and ingredients the 89

recycling of rubber is not comparable with the recycling of plastics [9]. Crumb rubber is often used in astroturf as cushioning, where it is sometimes referred to as astro-dirt. CR was used to remove ethylbenzene, toluene and xylene from aqueous solutions at room temperature [4]. Rubber crumb also goes into the manufacturing of several auto parts such as brake pads, brake shoes and vehicle acoustic insulation. Small percentages of crumb rubber go into manufacturing new tires. A revolutionary nanotechnology process developed by the British group Dena Technology is gearing up worldwide to produce high quality building material as wood-replacement products from used tires. Also uses to paper-replacement materials are investigating [10].

1 – sorting floor, 2 – side strip remover, 3 – cutter-type chipper, 4 – electromagnetic apparatus, 5 – hammer mill, 6 – tank with a solvent spent oil, 7, 7a – chip fluidization reactor, 8 – magnetic separator, 9 – mixer homogenizer, 10 – tank with petroleum residue, 11 – zeolite shale crushing and dispensing unit, 12 – furnace, 13 – thermolysis reactor, 14 – separator, and 15 – rectification column Figure 50 – Schematic diagram of the utilization of car and heavy-duty tires as chips [5]

90

Cut tires are used for the manufacture of drainage tubes, tapes for the protection of cables and pipelines, and soundproof walls along highways and for the protection of downslopes from erosion. Thermal methods for the secondary use of scrap tires are known, in particular, the combustion of tires to generate energy and pyrolysis under conditions of relatively low temperatures to produce light distillate, solid fuel, and metal. However, toxic organic substances, carbon monoxide, sulfur dioxide, soot, and volatile heavy metal compounds are released into the atmosphere with flue gases because of incomplete combustion. Therefore, this method is not widely used. In addition, the following technologies are available: the processing of tires to obtain rubber crumbs and powders for the manufacture of polymer mixtures and construction materials and the production of reclaim for the manufacture of rubber mixtures and asphalt-rubber compositions for insulating and roofing materials [5, 11, 12]. Schematic diagram of the utilization of tires as rubber crumb was offered (figure 50).

3.1.3. Bitumen modification with crumb rubber based modifier and interaction study There are many modification processes and additives that are currently used in bitumen modifications, such as styrene butadiene styrene (SBS), styrene-butadiene rubber, ethylene vinyl acetate and crumb rubber modifier (CRM). Figure 51 is representing a linked network of polymeric macromolecules with the bitumen. Using the alternative materials in road and pavement construction, such as CRM, will definitely be environmentally beneficial, and not only it can improve the bitumen binder properties and durability, but it also has a potential to be cost effective and increase the construction cost as they are highly expensive materials [13]. The development of modified asphalt materials to improve the overall performance of pavements has been the focus of several research efforts made over the past few decades. They have been investigating that the properties of CRM binders at a wide range of temperature are consider to be somewhat unclear due to the various interaction effects of CRM with bitumen binder, largely depending on the chemistry of the bitumen, the CRM percentage, particle size, effect 91

of mixing type, dimensional changes of crumb rubber with binder, texture service of CRM and the blending interaction temperature and time [14-16, 17-19].

Figure 51 – Simplified nano-mechanical model of SBS Poly-Styrene-Butadiene-Styrene modified bitumen [13]

It was studied that the physical and chemical reactions between rubber powder and bitumen. Through scanning electron microscope (SEM), fluorescence microscope, environmental scanning electron microscopy, spectral analysis, and component analysis tests, the interaction theory between asphalt and rubber was discussed. Figure 52 shows the SEM image of rubber modified bitumen.

Figure 52 – SEM image of rubber bitumen [14]

It is concluded that rubber powder become soft and bond together with each other after being mixed with bitumen. Bitumen changes from 92

a smooth homogeneous matter to a continuous mixing system. The interaction is mainly physical diffusion, but there are some chemical reactions in the process, especially at long reaction time [15, 20]. Researches and applications of CRM and other modifications in the world showed that the bitumen binder has many advantages characteristics like improved resistance to rutting due to high viscosity, high softening point and better resilience, improved resistance to surface initiated and, reduce fatigue/ reflection cracking, reduce temperature susceptibility, reduce noise, resistance to fissure propagation, improved resistance to ultra-violet, improved resistance to oxygen or ozone, improved durability and lower pavement maintenance costs, and saving in energy and natural resource by using waste products [7, 14, 21]. Asphalt concrete prepared with RubberBitumen Compounds exhibits high performance, enhanced wear and heat resistance, and resistance to aging. As a result, the pavement quality grows, and its service life becomes a factor of 1.5-2 longer [1, 15-16].

3.2. Producing Rubber Bitumen Compounds with Rubber Crumb 3.2.1. Rubber crumb which used in the work Rubber crumb from spent tires (from Kazakhstan Rubber Recycling LLP (in Astana)) which have two different particle sizes: one of the rubber crumb particle size less than 0.6 mm. It is showing on the figure 53. The other one particle sizes are between 0.6 mm and 1mm. It is showing on the figure 54. These figures were taken by Leica DM 6000 M optical microscope on optical reflection.

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Figure 53 – Optical microscope images of rubber crumb with particle size less than 0.6 mm

Figure 54 – Optical microscope images of rubber crumb with particle size 0.6-1.0 mm

Figure 55 – SEM images of rubber crumb

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The microstructures of rubber crumb were investigated with a Scaning Electron Microscopy (SEM) at an accelerated voltage of 20 kVand pressure at 0.003 Pa. Microscopic analyzes showed that crumb rubber has variety of morphological structures (figure 53, 54). It was determined, the RC very low pores heterogeneous material (figure 55) [3].

3.2.2. Preparation of rubber-bitumen compounds Modification of bitumen with RC For the preparing rubber-bitumen compounds, the bitumen materials heated till 160-170 оС. The apparatus were heated electrically (4), and the temperature of reactor fixed by thermo regulator (8). Then the 3, 5, 7 and 10 wt. % of rubber crumb were added in to bitumen. The compound was mechanically stirred for 5 minutes at 165-180 оС. The stirrer (1 and 5) allows for mechanical mixing of raw materials for process intensification. It is presenting in figure 56. At first we tested only rubber crumb (particle size less than 0.6 mm) modified bitumen. But, results of analyses showed that the samples on the physical and mechanical characteristics were poor indicator (Table 16), because of lower extensibility. Ductility of rubber modified products was between 7 cm and 14 cm. Standard accordance of rubber modified bitumen was determined according to “Recommendation on the application of crumb rubber in road con- 1 – motor stirrer, 2 – pipe for gas outlet, struction R RK 218-76-2008”. 3 – a cylindrical reactor, 4 – electric oven, 5 – agitator, 6 – a branch pipe for the In fact, all of the samples were withdrawal of products, 7 – Cabinet, close to standard or mismatch 8 – thermo regulator, 9 – thermocouple. standard requirements of the rubber-bitumen compounds. Figure 56 – Scheme of apparatus for preparing RBC

95

Particle size between 0.6-1 mm rubber crumb modified bitumen was investigated same method and same experimental conditions with activated rubber-crumb modified samples (table 17). There are kindred phenomena, too: poor indicators, lower extensibility. Prepared samples were mismatch standard requirements of the rubber-bitumen compounds. Table 16 Physical and mechanical characteristics of rubber-bitumen compounds on the based bitumen BND 60/90 with the addition of crumb rubber (particle size less than 0.6 mm) Name of the

BND

RBC with the addition of CR

indicators

60/90

3%

5%

7%

10 %

RBC 90/130

RBC 60/90

RBC 40/60

Penetration at 25 оС, 0.1 mm

78

82

82

64

52

91-30

61-90

40-60

Softening point, оС

47

50

52

54

57

Ductility at 25 о С, cm

96

14

11

8

7

Standard requirements

not less not less not less than 48 than 52 than 56 at lest 14

at lest 12

at lest 10

Table 17 Physical and mechanical characteristics of rubber-bitumen compounds on the based bitumen BND 60/90 with the addition of crumb rubber (0.6-1.0 mm) RBC with the addition of CR

Name of the

BND

indicators

60/90

3%

5%

7%

10 %

RBC 90/130

RBC 60/90

RBC 40/60

Penetration at 25 оС, 0.1 mm

78

92

70

63

52

91-130

61-90

40-60

Softening point, оС

47

51

55

57

67

not less not less than 48 than 52

not less than 56

Ductility at 25 о С, cm

96

17

10

8

7

at least 14

at least 10

96

Standard requirements

at least 12

The dispersion degree and the swelling capacity of crumb rubber in the bitumen have an important effect on improving properties of bitumen. The swelling of crumb rubber in bitumen is the process that light components in bitumen, such as saturated component, aromatic component, permeate into the crumb rubber. Obviously, the swelling can promote the formation of the elastic network of crumb rubber modified bitumen. So the better the swelling of bitumen to crumb rubber, has the better properties of crumb rubber modified bitumen [5-6, 14-15]. Modification of bitumen with RC and its composition Aim of improving the physical and mechanical characteristics of RBC was used spent engine oil as additional modifying agent. Rubber-oil mixtures were prepared by mixing spent engine oil into rubber crumb with a ratio in 5:6, 1:1 and 3:2. After a day it used for preparing rubber-bitumen compounds. Bitumen samples were heated at 160-170 оС and variety content of (10; 15; 20; 25 wt.%) rubber-oil mixtures were added in bitumen. The compound was stirred for 5 to 60 minutes at 165-180 оС. Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (less than 0.6 mm) and spent engine oil (rubber:engine oil=1:1 and rubber:engine oil=3:2) are given in table 18. We can see from table 18, physical and mechanical characteristics of RBC with 20 wt.% rubber-oil corresponds to grade of paving rubber-bitumen compounds RBC 90/130 and 25 wt.% rubber-oil modified sample is according to standard RBC 130/200. The table showing physical and mechanical characteristics of RBC with 10 wt.% rubber-oil corresponds to grade of paving rubber-bitumen compounds RBC 60/90. Then RBC with 20 wt.% rubber-oil added sample according to standard RBC 90/130 and 25 wt.% rubber-oil modified bitumen corresponds to grade of paving rubber-bitumen compounds RBC 130/200. Whereas the 15 wt.% modified sample mismatch any standard of RBC. Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (0.6-1 mm) and spent engine oil (rubber:engine oil=1:1 and rubber:engine oil=3:2) are given in table 18. When we use no rubber crumb (06-1mm) in ratio R:O=1:1 only one composition is a according to standard RBC 60/90. This is the 15 wt%, which is shown in table 19. 97

Table 18 Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (less than 0.6 mm) Name of indicators

Penetration At 25 °C, 0.1mm

Softening point, °C

Ductility at 25 °C, cm

Penetration index Changing of softening temperature after heated, °C Standard accordance

Rubberoil ratio

Rubber-oil percentage in bitumen 10 wt. %

15 wt. %

20 wt. %

25 wt. %

R:O=1:1

90

127

126

170

R:O=3:2

75

130

109

150

R:O=1:1

51

46

50

48

R:O=3:2

58

47

55

46

R:O=1:1

25

19

26,5

22

R:O=3:2

19

31

17

25

R:O=1:1

0.6

0.3

1.5

2.2

R:O=3:2

1.7

0.7

2.2

0.9

R:O=1:1

5

5

5

5

R:O=3:2

4

5

5

6

R:O=1:1

–

–

RBC 90/130

R:O=3:2

RBC 60/90

–

RBC 90/130

Methods of testing According to standard 11501 According to standard 11506 According to standard 11505 By empirical formula According to standard 18180

RBC According 130/200 to R RK 218-76RBC 2008 130/200

We can see from the table 19 that the sample of RBC added 10 wt. % rubber-oil mixtures are according to standard RBC 60/90, with 15 wt. % and with 20 wt. % rubber-oil modified bitumen corresponds to grade of paving rubber-bitumen compounds RBC 130/200. As seen from tabulated dates, all the Changing of softening temperature after heated results are according to standard requirements, which not more than 5 and 6 °C. Penetration index are normal, too. Thus, all the tabulated results are allows knowing in ratio 3:2 rubber-oil mixture modified bitumen better than ratio of 1:1. 98

Table 19 Physical and mechanical characteristics of rubber-bitumen compounds with rubber crumb (0.6-1 mm) Namesofindicators

Rubberoil ratio

Rubber-oil percentage in bitumen 10 wt. %

15 wt. %

20 wt. %

25 wt. %

R:O=1:1 Penetrationat25°C, 0.1mm R:O=3:2

67

71

90

91

87

160

195

108

R:O=1:1

50

59

51

58

R:O=3:2

53

45

45

52

R:O=1:1

12

13.5

12.5

11.5

R:O=3:2

17

20

18

13

R:O=1:1

-0.5

1.8

0.6

2.3

R:O=3:2

1.0

0.9

1.8

1.5

R:O=1:1

4

4

5

5

R:O=3:2

4

6

6

5

R:O=1:1

–

RBC 60/90

–

–

R:O=3:2

RBC 60/90

Softeningpoint, °C

Ductilityat25°C, cm

Penetration index Changing of softening temperature after heated, °C Standard accordance

RBC RBC 130/200 130/200

–

Methodof testing According to standard 11501 According to standard 11506 According to standard 11505 By empirical formula According to standard 18180 According to R RK 21876-2008

The resulting rubber-bitumen compounds (RBCs) exhibit elasticity, increased softening point, decreased brittle point, and enhanced strength. These properties allow RBCs to be used both as binders for asphalt concretes and as mastics for pavement repair [3, 22].

99

3.2.3. Discussion and comparision of RCMB characteristics Physical and mechanical characteristics of prepared rubberbitumen compounds were compared. Dependence of depth of needle penetration on the rubber-oil content of RBCs is showing in figure 57.

Rubber-oil ratio: 1 – 1:2, 2 – 2:3, 3 – 1:1, 4 – 3:2 Figure 57 – Dependence of penetration on the rubber-oil content of RBC

As seen from figure 57, with increasing content of rubber-oil mixture from 5 wt. % to 25 wt. % in bitumen, the penetration of rubber-bitumen compounds were increased. Otherwise softening point of RBC isn’t more changing in any content of rubber-oil mixture (figure 58). Dependence of ductility on the rubber-oil content of rubber-bitumen compounds is presenting at figure 59. It was shown that the ductility of RBC are decreasing depended to increase content of rubber-oil mixture in bitumen. This is due to the action of rubber particles as stress concentrators. It means the viscosity of bitumen compounds increased and starts to harden. These bitumen composition functions as a liquid or pseudo-thermoplastic matrix, the rubber particles provide resilient power frame in the amount of binder. 100

Rubber-oil ratio: 1 – 1:2, 2 – 2:3, 3 – 1:1, 4 – 3:2 Figure 58 – Dependence of softening point on the rubber-oil content of RBC

Rubber-oil ratio: 1 – 1:2, 2 – 2:3, 3 – 1:1, 4 – 3:2 Figure 59 – Dependence of ductility on the rubber-oil content of RBC

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The properties of crumb rubber modified bitumen, including the RC and crumb rubber with spent engine oil in ratio 1:1, are summarized in table 20. They were compared with base bitumen. By comparison, the properties of modified bitumen with the rubber-oil mixture are best, because of it is according to standard mark RBC 90/130. Its penetration and ductility is highest, while softening point decrease. And RC modified bitumen due to poor extensibility (7 cm) were mismatch standard requirements of the rubber-bitumen compounds. It can be describe elasticity properties of engine oil for preparing modified bitumen based rubber crumb [3, 23]. Table 20 Properties comparison of crumb rubber (particle size less than 0.6 mm) modified bitumen with base bitumen Kind of modifier

Penetration, 0.1mm Softening point, ºС

Ductility, cm

Base bitumen

78

47

96

Rubber crumb, 10 wt.%

52

57

7

Rubber-oil mixture, 20 wt.%

126

50

26.5

Thus, according to the results, rubber modified bitumen samples made are more adhesive than base bitumen and have more ability to stick aggregate together with rubber based modifier.

3.2.4. Microscopic study of rubber-bitumen compounds Surface structure of bitumen compound materials was studied at microscopic technique and they are presenting at figure 60. They describe interaction between bitumen and rubber in rubber bitumen compounds. It is shown that the appearance of original bitumen is very smooth. The bitumen appearance becomes uneven after adding of rubber crumband the rubber crumb became sticky after mixing with base bitumen (figure 60 A, B). During the preparation of rubber and bitumen, the bitumen aggregation almost covered the swelled rubber crumb when heating and stirring the mixture(figure 60 C, D). The 102

reason may be that rubber powder swelled by absorbing some light components or more liquid part of bitumen. Because of the rubber crumb has 1.474 m2/g of surface area, 0.300 nm of medium pore size. It is important for react rubber crumb with bitumen [3].

A

B

C

D Figure 60 – Optical microscopic image of RBC

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References 3 1. Shunin D. G., Filippova A. G., Okhotina N. A., Liakumovich A. G., and Ya. D. Samuilov. Possibilities of Production and Use of Rubber-Bitumen Compounds // Russian Journal of Applied Chemistry. – 2002. – Vol. 75,No. 6. – Р. 1020-1023. 2. Gorlova E. E., Nefedov B. K., Gorlov E. G., and Ol’gin A. A. Reprocessing of Industrial Rubber Waste in a Mixture with Shale// Solid Fuel Chemistry. – 2008. – Vol. 42,No. 2. – P. 93–94. 3. Ye. Tileuberdi. Nanostructure of Bitumen Produced from Heavy Oil: Ph.D. thesis, – 2014. – P. 102. 4. Alamo-Nole L.A., Roman F. and Perales-Perez O. Sorption of Ethylbenzene, Toluene and Xylene onto Crumb Rubber from Aqueous Solutions. http://www.nsti. org/BioNano2007. 5. Gorlova E. E., Nefedov B. K., and Gorlov E. G. Manufacture of an Asphalt– Rubber Binder for Road Pavements by the Thermolysis of Tire Chips with Heavy Petroleum Residues // Solid Fuel Chemistry. – 2009. – Vol. 43, No. 4. – P. 224–228. 6. YE Zhigang, ZHANG Yuzhen, KONG Xianming. Modification of Bitumen with Desulfurized Crumb Rubber in the Present of Reactive Additives // Journal of Wuhan University of Technology – Mater. Sci. Ed. Mar. – 2005. – Vol. 20, No. 1. – P. 95-97. 7. Eng. Vasco Pampulim. “Use of Rubber Powder cryogenically recovered from end-of-life tires in Asphalt Rubber for high performance road paving // International Theoretical and Practical Conference on “Contemporary Approaches to Rubber Goods and Tires Recycling” (slide.) – Moscow, 2011(1 -2 June). – P. 42. 8. Xiaohu Lu. Crumb Rubber in Asphalt Pavements and Recycling. www.rknet. it. 13.07.2012. 9. Mareike Hess, Harald Geisler, and Robert H. Schuster. Devulcanization as an opportunity to recycle rubber. Chem. Listy 103, s1−s148 PMA 2009 & 20th SRC. – 2009. – P. 58-60. 10. Nanotech turns used tyres into building material. http://www.dena.co.uk. 31.01.2012. 11. Background on Artificial Playing Fields and Crumb Rubber. http://www. ct.gov. 31.01.2012. 12. Waste Tire Disposal. http://www.state.tn.us. 17.03.2012. 13. Nuha S. Mashaan, Asim Hassan Ali, Mohamed Rehan Karim and Mahrez Abdelaziz. An overview of crumb rubber modified asphalt // International Journal of the Physical Sciences. – 2012. – Vol. 7(2). –P. 166 – 170. 14. AO Ying, CAO Rongji. Interaction Theory of Asphalt and Rubber // Journal of Wuhan University of Technology-Mater. Sci. Ed. Oct. – 2010.– P. 853-855. 15. YE Zhi-gang, KONG Xiang ming,YU Jian-ying, WEI Lian-qi. Microstructure and Properties of Desulfurized Crumb Rubber Modified Bitumen // Journal of Wuhan University of Technology-Mater. Sci.Ed. Mar. – 2003. – Vol.18, No.1. – P. 83-85. 16. Austruy F., Tileuberdi Ye., Ongarbaev Ye., Mansurov Z. Use of rubber-oil mixture for production of rubber-bitumen compounds // Programe and Scientific ma-

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terials of VI international symposium on «Combustion and plasmachemistry». – 2426 August 2011. – P. 137-138. 17. Feipeng Xiao, Bradley J. Putman, Serji N. Amirkhanian. Laboratory Investigation of Dimensional Changes of Crumb Rubber Reacting with Asphalt Binder. http://www.clemson.edu. 16.10.2014. 18. Herda Yati KATMAN, Mohamed Rehan KARIM, Mohd. Rasdan IBRAHIM, Abdelaziz MAHREZ. Effect of mixing type on performance of sobutene porous asphalt // Proceedings of the Eastern Asia Society for Transportation Studies. – 2005. – Vol. 5. – P. 762 – 771. 19. Тілеуберді Е., Қозбакарова С., Оңғарбаев Е.К., Төлеутаев Б.К., Мансұров З.А. Резеңке үгінділерін асфальт бетон қоспасын алуға пайдалану // ҚазҰУ хабаршысы, химия сериясы. – 2012. – № 1 (65). – С. 196-199. 20. Elvira Joana Ferreira Peralta. Study of the Interaction Between Bitumen and Rubber: diss. For master science. – Escola de Engenharia, 2009. – P. 266. 21. Mullins O.C. The Modified Yen Model // Energy Fuels. –2010. – Vol. 24. – P. 2179-2207. 22. Tileuberdi Ye., Ongarbaev Ye.K., Mansurov Z.A., Tuleutaev B.K., Akkazyn E.A. Physical and Mechanical Characteristics of Rubber-Bitumen Compounds // Chemical and Materials Engineering. – 2013. – Vol. 1, No. 4. – P. 105-110. 23. Онгарбаев Е.К., Тилеуберди Е., Иманбаев Е. Асфальтобетонные смеси на основе вяжущих с добавкой резиновой крошки // Материалы международной научно-практической конференции «Проблемы и перспективы развития химии, нефтехимии и нефтепереработки» // Нижнекамск. – 25 апреля 2014 г. – С. 283286.

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IV. NANOTECHNOLOGY, ROAD BUILDING AND ASPHALT CONCRETE 4.1 Nanoscience and Nanotechnology in Road Building 4.1.1 Nanoscience and nanotechnology is modern field Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular and macromolecular scales. Nano is a Greek word and means “Dwarf”. The application of nanoscience to “practical” device is called nanotechnology. Nanotechnology is a field that is dominated by developments in basic physics and chemistry research. A more accurate definition of nanotechnology was presented in 1981 by Drexler, such as the production with dimensions and precision between 0.1 and 100 nm. In other words, nanotechnology are the design, characterization, production and application of structures, devices and systems by controlling shape and size at nanometer scale. Nowadays in the world there is no standard that describes what nanotechnology and nanoproducts [1-5]. The European Commission established a Task Force to develop a classification of nanoproducts. In the ISO / TC 229 Nanotechnology refers to the following [3, 6]: 1. Understanding and control of matter and processes at the nanoscale, typically, but not exclusively, below 100 nanometres in one or more dimensions where the onset of size-dependent phenomena usually enables novel applications, 2. Utilizing the properties of nanoscale materials that differ from the properties of individual atoms, molecules, and bulk matter, to create improved materials, devices, and systems that exploit these new properties. Nanotechnology is not a new science and it is not a new technology, it is rather an extension of the sciences and technologies that has been applied in ancient manufacturing by adding gold/silver or during careful manufacturing using carbon nanotubes [7]. The evolution 106

of challenging technologies and sophisticated instrumentations as well as broadening of basic scientific knowledge are making the research on nanotechnology fast moving and evolutionary. In nanolevelelectrostatic forces take over and quantum effects come in. Further, as particles become nano-sized, the proportion of atoms on the surface increases relative to those inside and this leads to novel properties [8]. Scale diagram of objects, tools, models and forces at varies different scale are presenting in the figure 61.

Figure 61 – Scale diagram of objects, tools, models and forces at varies different scale [10]

107

Nanotechnology is still in an early phase of development, and fundamental understanding and tools are still in the pipeline of new ideas and innovations. Key research themes have been driven by open discovery in the last decade. In the next decade, nanotechnology research and development is likely to shift its focus to socioeconomic needs – driven governance, with significant consequences for science, investment, and regulatory policies [9]. Nanoscience and nanotechnologies are widely seen as having huge potential to bring benefits to many areas of research and application, and are attracting rapidly increasing investments from Governments and from businesses in many parts of the world. Their application may raise new challenges in the safety, regulatory or ethical domains that will require societal debate. Industries of using and enable application this fields are in energy, chemical, sport, telecommunication, computers, construction, transportation, health care, pharmaceutical, aerospace, defense, biotechnology, agricultural and food industries [4].

4.1.2. Application of nanotechnology in road building materials Bituminous materials are mainly used on a large scale and in huge quantities for road constructions, the mechanical behavior of these materials depend to a great extent on structural elements and phenomena which are effective on a micro- and nanoscale [11]. Nanoscience and technology may lead to significant improvements and further development in asphalt pavement technology and help to find answers to many questions of the material behavior, which are not well understood. In particular, progress appears possible in the field of materials design, testing, modeling and manufacturing as well as pavement construction and sensoring. Research on a microscale has already started and needs to be intensified significantly whereas research on a nano-scale is still at the very beginning of being established for this important type of building materials. As previous said, asphalt concrete is a particulate composite typically made of bitumen or modified binder, rigid cubical particles such as mineral filler down to a nanoscale range, sand and stone mineral aggregates, additives and air. In the table 21 are showing particulate 108

composite of asphalt concrete with micro- and nanoparticles. In some cases other particles such as fibers, crumb rubber, glass, slag and other are added in order to fulfill special functional requirements in terms of visibility, friction or to improve mechanical and climatic long-term performance, e.g. by reducing the risk of rutting, low temperature and fatigue cracking. However, some components are no longer applied or under very restricted use in many countries for health and environmental reasons [5, 11]. Table 21 Particulate composite of asphalt concrete with micro- and nanoparticles [11] Binders Hot Process • Bitumen • Polymer Bitumen (Elastomers, Plastomers, Natural Latex, Reclaimed Synthetic Rubber,..) • Extenders (Sulfur, Lignin) • Synthetic Binders for Colored Asphalt • …. Cold/Warm Process • BitumenEmulsions (Cold Water) • Foam Bitumen (Cold Water with Hot Bitumen) • ….

Additives

Particles

• Bonding Agents (Hydrated Lime, Amine Derivatives,..) • Hydraulic Cement • Natural Asphalt (Gilsonite, Trinidad Lake Asphalt) • Rejuvenators • Emulsifiers • Oxidants • Antioxidants • Polymer Additives • Reactive NanoCeramics • Self-Deicing Agents (CaCl Flakes,..) •…

Micro/nano particles •Filler (Crusher Fines, Baghouse Fines, Fly Ash, Carbon Black, Silica Fume, ..) • Fibers (Cellulose, Mineral, Polymer,..) • Pigments • Crumb Rubber • …. Macro Particles • Sand, Stones • Crushed Recycl. Glass • Slag • Recycled Tire Particles • Fibers (Steel, Fiberglass, Polyester, Polyprop.,..) • Reclaimed Asphalt Pavement

109

Air voids • Closed pores • Inter-Connected Pores

The morphology and structures of bitumen have been studied using the present available technology such as microscopes. During the Masson et al. study described use of cryogenic atomic force microscopy (AFM) and phase detection microscopy (PDM) to characterize bitumen nano- and microstructures [12]. Figure 62 shows the AFM topographic (top) and PDM images of bitumen AAS at 22 °C under vacuum (15 μm x 15 μm). Respective differentials are 165 nm and 175°. The results were interpreted in light of glass transition temperatures for bitumen fractions. The domains visible by microscopy, bitumen phases, were attributed to domains rich in bitumen composition.

Figure 62 – AFM topographic and PDM images of bitumen [12]

Typical imaging temperatures were 22 °C, -10 °C, -27 °C, -55 °C and -72 °C. These domains were found in the paraphase rich in saturates and in the periphase rich in naphthene aromatics and polar aromatics as shown at the figure 62. Other research group was studied bitumen morphology. Microstructure and micromechanical properties were determined using an environmental scanning electron microscope and the nanoindentation technique. Modulated differential scanning calorimetry was used to determine phase-change temperatures and endo/exotherms associated with molecular movement. It is presented (figure 63) that the higher molecular weight fraction remain and become visible in the form of string-like structure [12-13]. Currently developing the production technology of asphalt mixtures is using the modifier of “Unirem.” Asphalt modifier 110

“Unirem” is a loose composite material based on the active powder discretely devulcanized rubber produced by high shear grinding used tires [14-15]. The modifier “Unirem” does not require preheating and is introduced into the mixer asphalt mix simultaneously with bitumen or immediately after the introduction bitumen. With the introduction of the modifier “Unirem” in hot bitumen occurs instantaneous decay particle modifier microblocks. Introduction “Unirem” in the road bitumen leads to the formation of a structured nano-level of rubber bitumen compounds, no tendency to delamination and possessing high adhesion properties, as well as high crack resistance in a wide temperature range.

Figure 63 – ESEM image of bitumen (B 50=70 and (b) PmB 60=90) [13]

The company “Advanced Technologies” provides development in microreactor universal technology of carbon nanotubes, fullerenes, nanodiamonds, sobuten, metal nanoparticles, their oxide compounds, nanoparticles carbides, nitrides etc. [16]. An important distinguishing feature of this technology is the direct absorption of nanoparticles substantially at their formation with specially designed liquid organic medium, that hinder their aggregation for a long time – more than six months. Basic Product ArmCap, containing multi-walled carbon nanotubes and nanodiamonds are currently used to obtain nanomodifier ArmBit for bitumen and asphalt mix. Concentration of nanomodifier of ArmBit in bitumen was 0.005. %. The modified asphalt mix has a somewhat high performance in comparison with the requirements of state standard. 111

The advantage of the considered methods for modifying bitumen in asphalt concrete is the ability to implement them without changing the composition of the requirements of state standard on the content of asphalt mix and production technology. The results showed that the nanomodificators are to increase the impact of technical and properties of asphalt concrete. The same effect is achieved by structuring asphalt binder [17]. In this case the effect is achieved by reducing the content of bitumen in the asphalt mix at the ordered arrangement of the mineral powder particles asphalt binder. In contrast to the modification of asphalt concrete, where the self-organization structure due to the introduction of modifiers, when structuring asphalt binder ordered structure is realized by mechanical action on the particles of the material in the process of balling granules. On the possibility of the inclusion technology of structuring asphalt binder in nanotechnology note the following. In accordance with the above classification limiting factor in deciding this question is the size of the object, forming new material properties. In the technology in question is the subject of this bituminous film in the asphalt binder between particles of mineral powder and controlled parameter – the thickness of the film. The specific surface area of mineral powders is averaging 300-350 m2/kg. Then one can determine the thickness of the bituminous film necessary for the distribution of 13% of bitumen by the weight of asphalt binder. Thus, the surface layer of substances – specific surface phase of a thickness was several nanometers. For this indicator, it could be attributed to the nanostructure. However, typical nanostructures are considered only separate body – threads, tapes, films, tubes of the same thickness. The surface layer on only one side has interphase boundary separating it from other substances. Therefore, the surface layer is a specific surface phase material, but not typical nanostructure. As published literature on the this field, asphalt construction methods with the use of nanomaterials can be classified into two general ways. Advancement in the procedure involves the use of a fibre sheet (matrix) containing nano-silica particles and hardeners. These nanoparticles penetrate and close small cracks on the concrete surface and, in strengthening applications, the matrices form a strong bond between the surface of the concrete and the fibre reinforcement [18-19]. 112

Tests performed on binders and dense asphalt mixtures proved that the cloisite nanoclay modifications helped to increase the stiffness, to improve the rutting resistance of the standard 40/60 binder. This is especially true if the 6% cloisite modification is used. In addition, the indirect tensile strength and fracture energy values are increased due to 6% cloisite modification. The nanofill (6%) modification helps to improve the ageing resistance of the 70/100 binder in the short term and long term too [20]. The addition of small amounts (1 wt. %) of carbon nanotubes can improve the mechanical properties of samples consisting of the main Portland cement phase and water. Oxidized multi-walled nanotubes show the best improvements both in compressive strength and flexural strength compared to the reference samples without the reinforcement. It is theorized the high defect concentration on the surface of the oxidized multi-walled nanotubes could lead to a better linkage between the nanostructures and the binder thus improving the mechanical properties of the composite rather like the deformations on reinforcing bars [5, 19, 21].

4.2. Asphalt Concrete Materials 4.2.1. Composition and condition of asphalt concrete Typically, asphalt concrete (AC) is a mixture of inorganic filler (crushed stone, sand, gravel, limestone) and petroleum-derived binder (bitumen). Bitumen serves primarily as a binder in asphalt concrete, the viscous nature of bitumen allows the asphalt to sustain significant flexible, creating a very durable surface material. Typically bitumen is containing approximately 4-7 % by weight in holly mixture. It consists of mineral aggregate bound together with binder, laid in layers, and compacted. This composite material commonly used to surface roads, street, runway, revetment, port facilities, recreational (bikeways, tennis courts, tracks), hydraulic structures, parking lots, and airports [22]. The process was refined and enhanced by Belgian inventor and U.S. immigrant Edward de Smedt. Asphalt concrete has several synonymous in the world. AC commonly called asphalt, blacktop, asphalt (or asphaltic) concrete, bituminous asphalt concrete or bituminous mixture. As well as 113

pavement (in North America), tarmac (in Great Britain and Ireland) and asphaltbeton (in Kazakhstan). In 1870 a Belgian chemist named Desmedt first true asphalt pavement, a mixture of sand, which was established in the City Hall in New York. Desmedt in highway design in France in 1852 and was modeled [23]. The durability of asphalt concrete is greatly influenced by the environmental changes during the year between hot and cold temperatures as well as between day and night. Usually high temperatures can soften the bitumen and reduce the stiffness of AC making the mix more susceptible to rutting. Otherwise, low temperature can increase the stiffness of bitumen and reduce the flexibility of the asphaltic concrete, hence, inducing fatigue failure. Thus, high temperature stiffness and low temperature flexibility are important properties in asphalt concrete respectively to avert rutting and cracking [24]. These roads should be lower in cost and produce lower noise making it more suitable for regular usage with safety. It also offers higher traffic speed and is easy to repair as well. Moreover engineers must take care of certain factors such as the traffic volume and traffic type. Based on these factors the thickness of the road may be decided. The sub base and its load carrying capacity should also be considered before building the roads. Another major advantage of the asphalt is that it is almost hundred percent recyclable and recycling has increased significantly in recent years. Asphalt is routinely milled and re-laid along with fresh materials, saving money and preserving non-renewable natural resources [25].

4.2.2. Types of asphalt concrete There are many different types of asphalt concrete, each with its own combination of different amounts and type of bituminous binder and mineral aggregates, and each asphalt has performance characteristics appropriate for specific application. Main types asphalt concrete, which have been using in infrastructure as following: – Hot mix asphalt concrete (HMAC). It is type of AC, produced by heating the asphalt binder to decrease its viscosity, and drying the aggregate to remove moisture from it prior to mixing. Mixing is generally performed with the aggregate at around 120-150 °C for virgin asphalt, at 160-170 °C for polymer and rubber modified asphalt 114

and at 90-100 °C for the asphalt cement. HMAC is the form of asphalt concrete most commonly used in any nations [26]. – Warm mix asphalt concrete (WMAC) is a group of technologies that allow a reduction in the temperatures at which asphalt mixes are produced and placed. These technologies tend to reduce the viscosity of the asphalt and provide for the complete coating of aggregates at lower temperatures. It is produced by adding either zeolites, waxes, asphalt emulsions, or sometimes even water to the asphalt binder prior to mixing at temperatures 20 to 55 °C lower than typical hot-mix asphalt [27]. – Cold mix asphalt concrete is made by emulsifying asphalt in water with soap before mixing. While in its emulsified state the asphalt is less viscous and the mixture is easy to work and compact. The emulsion will break after enough water evaporates. However, it is not as durable as HMAC or WMAC. They are generally used in the roads where traffic volume is low and road is not used very regularly. – Cut-back asphalt concrete is another type of asphalt concrete which is made by adding kerosene or other petroleum prior to mixing with the aggregate. While in its dissolved state the asphalt is less viscous and the mix is easy to work and compact. After the mix is laid down the lighter fraction evaporates. However, use of such petroleum products causes a lot of pollution, therefore, they are generally not a preferred materialfor building roads. – Mastic asphalt concrete is produced by heating hard grade blown bitumen in a green cooker (mixer) until it has become a viscous liquid after which the aggregate mix is then added. Polymers or other additives may also be added to increase the quality of the final product. The mix is cooked for six to eight hours and then the whole mixture structure is taken to the site of work. The whole mixtureis emptied on the site where road is supposed to be built. – Natural asphalt concrete constitutes bituminous rock, found in some parts of the world, where porous sedimentary rock near the surface has been impregnated with upwelling bitumen. Another asphalt pavement materials have been developed to meet specific needs, such as stone-matrix asphalt, which is designed to ensure a very strong wearing surface, porous asphalt pavements, which are permeable and allow water to drain through the pavement for controlling storm water and tarmac for using especially at airfields. 115

4.2.3. Structures of asphalt concrete A typical asphalt road construction is multilayered in form, comprising bitumen-bond and unbonds materials. Asphalt pavement materials consists main three structural layers [28], and figure 64 is representing them.

Figure 64 – Structural layers model of asphalt concrete [28]

Main structural layers of asphalt pavement materials as following [29]: – First structural layer is asphalt layer, which top layer of road. As figure 64, it consists of three tiers – a surface course, a binder course and a asphalt base course. The surface course mixture must be designed to have sufficient stability and durability to withstand the appropriate traffic loads and the detrimental effects of environmentally-increased stress. The binder course is an intermediate layer in structural layer. It is designed to reduce rutting and withstand the highest stresses that occur about 50-70 mm below the surface course layer. The asphalt base course mixtures have a maximum aggregate size (up to 75 mm) and even lower asphalt binder content. – The second layer road base course is the most important structural layer. The road base course should exhibit long-life characteristics, ensuring that fatigue of the structure are resisted for as long as possible and no damage develops. – The third layer sub-base course (and sub-grade layers) constitutes the foundations of the road structure. They are unbound materials, such as indigenous soil, crushed or uncrushed aggregate, or re-used secondary material. 116

Most pavement failures are caused by a combination of these factors: environmental factors, poor drainage and soils, traffic loadings, deficient materials, poor construction practices and other. Thus, Asphalt pavement failures are typically divided into four classes: 1) cracking 2) distortion 3) disintegration 4) surface defects Within each class there are several subcategories, each with different causes [5, 29].

4.3. Preparation of Asphalt Concrete with Oil Sand and Rubber Crumb 4.3.1. Preparation of asphalt concrete with oil sands According to all of the results, the natural bitumen from oil sands clothest to paving bitumen by physical and mechanical characteristics. Regarding to this reason, asphalt mix samples were prepared by addition of oil sands deposits Munayli-Mola (figure 65) and studied their properties. For the requirement of analyses mass of stone-mineral mixtures (mineral aggregates) were 7 kg. Including crushed stone – 35 wt.%, sand – 58 wt.%, mineral powder – 7 wt.%. The content of bitumen in the mineral aggregates were 4, 7 and 10 wt.%. All of the samples prepared without adding petroleum bitumen. Because of natural bitumen from oil sands estimated for petroleum paving bitumen. Mineral aggregates in oil sands estimated for screenings. Because of they have same size and its main component is quartz. At experiment 3 samples were prepared by 4, 7 and 10 wt.% natural bitumen in holly mix. The physicochemical characteristics of samples tabulated in table 22. Sample number 1 – a mixture containing 4 wt.% of bitumen. Mineral part of asphalt mix consists 2.45 kg of crushed stone, 0.49 kg of mineral powder, 2.3 kg of sand. 2 kg of oil sands are used, in the composition of them 0.3 kg of natural bitumen and 1.7 kg of mineral parts. Because, content of organic part in oil sands were 16 wt.%. The content of oil sands in the initial mixture was 28 wt.%. 117

Figure 65 – Asphalt concrete with oil sands

Sample number 2 – a mixture containing 7 wt.% of bitumen. For the preparation of the samples were mixed in 2.45 kg of crushed stone, 0.49 kg of mineral powder and 1 kg of sand. 3.5 kg of oil sands are added. In this material consists of 0.5 kg of natural bitumen and 3 kg of mineral parts. The content of the oil sands in the initial mixture was 47 wt.%. Sample number 3 – a mixture containing 10 wt.% of bitumen. This sample prepared by 2.45 kg of crushed stone, 0.49 kg of mineral powder and without sand. In the asphalt mix 4.7 kg of oil sands were used. As parts of the organic species are 0.7 kg, the amounts of the mineral part are 4 kg. The content of the oil sands were – 60 wt.%. Thus, the test asphalt mix prepared by proven performance to meet the requirements ST RK 1225-2003 showed that a mixture containing 28 wt. % oil sands on all physical and chemical characteristics correspond Porous asphalt concrete grade 2. Asphalt mix prepared with the addition of 47 wt. % oil sands according to standard of dense asphalt concrete grade 3 [5, 30-31]. 118

Table 22 The physical and mechanical characteristics of samples

Name of indicators

Content of oil sands in asphalt mix

Basic requirements for the ST RK 1225-2003

28 %

47 % 60 %

Medium density, g/ cm3

2.29

2.30

2.22

not rated

Water saturation, %

6.1

2.4

2.6

for the dense type of B, V, G from 1.5 to 4.0 for the porous type from 5 to 10

Compression strength, MPа, at 20 оС 8.7

4.6

4.2

not less than 2.5 for М1 not less than 2.2 for М2 not less than 2.0 for М3

Compression strength, MPа, at 20 оС watersaturated

6.5

4.7

4.8

not rated

Compression strength, MPа, at 50 оС

2.1

1.1

0.6

not less than 1.3 for B М1 not less than 1.2 for B М2 not less than 1.1 for B М3 not less than 0.7 for the porous М1 not less than 0.5 for the porous M2

Compression strength, MPа at 0 оС

14.9

13.0

5.1

no more than 13.0 for the porous not rated

Water resistance

1.0

0.75

0.64

not less than 0.85 for the dense М1 not less than 0.80 for the dense М2 not less than 0.7 for the porous М1 not less than 0.6 for the porous М2

Water resistance with prolonged water saturation

0.55

0.78

0.43

not less than 0.75 for the dense М1 not less than 0.7 for the dense М2 not less than 0.6 for the porous М1 not less than 0.5 for the porous М2

Adhesion of binder to the mineral portion of the mixture

–

–

–

braves (at least ¾ surface of the mixture covered with foil binder)

119

4.3.2. Preparation of asphalt concrete with rubber crumb Use of rubber bitumen compounds as a pavement material was started in 1960s by the city of Phoenix, Arizona on several area freeways because of its high durability. Since then it has garnered interest for its ability to reduce road noise. Several samples of rubber-bitumen compounds were used for preparing hot asphalt mix (Figure 66), because of their best physical and mechanical characteristics in all of prepared RBC. For the requirement of analyses mass of stone-mineral mixtures was 7 kg. Including crushed stone – 35 wt.%, sands (screenings) – 58 wt.%, mineral powder – 7 wt.%. Stone-mineral mixtures were heated to 180 оС and RBC was added into mixture, which was stirred till get uniform black color. Rubber-bitumen compounds in the mineral aggregates were 7 wt.%. Physical and mechanical characteristics of these samples are presented in table 23.

Figure 66 – Asphalt concrete with rubber crumb

120

As is evident from the table 23, medium densities of four samples are fundamentally identic, which are between 2.33g/cm3 and 2.35 g/ cm3. Compression strength of sample №1 at 50 оС lower than other. Whereas, all samples on characteristics of compression strength at 0 о С refers to the A, B type of asphalt concrete, they aren’t more than 13.0 Mpa. On indicator of water resistance of sample № 1 and № 4 was closest to standard (0.89). For the results of analyses on characteristics of water resistant of all samples with prolonged water saturation (not less than 0.8) were according to requirements of standard. Table 23 Physical and mechanical characteristics of rubber-asphalt with rubber crumb (less than 0.6 mm)

№ 1 RBC R:O=5:6 20 wt.%

№ 2 RBC R:O=1:120 wt.%

№ 3 RBC R:O=3:210 wt.%

№4 RBC R:O=3:220 wt.%

Asphalt mix with rubber crumb

Medium density, g/cm3

2.34

2.33

2.35

2.33

Not rated

Water saturation, %

0.7

0.5

0.4

0.7

For the dense type from 1.5 to 4.0

Compression strength, MPa, at 20 оСwatersaturated

2.4

2.0

3.1

2.1

Not rated

Compression strength, MPa, at 50 оС

0.7

0.8

0.9

1.1

For the dense type, Mpa, not less than: А – 1.5 B – 1.8

Compression strength, MPa, at 0 оС

5.7

2.3

7.6

6.9

No more than 13.0 for the A, B type of asphalt concrete:

Name of indicators

Standard requirements

Water resistance

0.89

0.83

0.97

0.89

Not less than 0.9

Water resistant with prolonged water saturation

0.85

0.92

0.94

0.90

Not less than 0.8

121

Asphalt concrete was tested prepared by rubber-bitumen compounds on the based RC of particle size 0.6-1.0 mm (table 24). For the results of analyses on characteristics of medium density of four samples are fundamentally identic, too. On water saturation at № 2 and № 3 are according to standard, whereas, result of sample №1 mismatch requirements of the norms. And sample № 1 got lower indicator on compression strength, at 0 оС and 50 оС. We can see from the table 24 on characteristics of water resistant with prolonged water saturation (not less than 0,8) were according to requirements of standard. But, on indicator of water resistance at sample № 2 refers to the standard requirements of asphalt concrete [5, 32]. Table 24 Physical and mechanical characteristics of rubber-asphalt with no rubber crumb (0.6-1.0 mm)

№2 RBC R:O=1:1 15 wt.% №3 RBC R:O=3:220 wt.%

Name of indicators

№1 RBC R:O=5:6 25 wt.%

Asphalt mix with rubber crumb Standard requirements

Medium density, g/cm3

2.30

2.31

2.28

Not rated

Water saturation, %

1.3

2.4

3.0

For the dense type from 1.5 to 4.0

Compression strength, MPa, at 20 оС water-saturated

1.5

2.3

2.1

Not rated

Compression strength, MPa, at 50 оС

0.6

0.8

0.8

For the dense type, Mpa, not less than: А – 1.5 B – 1.8

Compression strength, MPa, at 0 оС

3.6

6.8

6.7

No more than 13.0 for the A, B type of asphalt concrete:

Water resistance

0.88

0.96

0.78

Not less than 0.9

water resistant with prolonged water saturation

1.0

1.2

0.93

Not less than 0.8

122

At the factory LLP “Asphaltobeton-1” in Almaty was produced 10 tons of asphalt mix with the addition of crumb rubber (particle size less than 0.6 mm) in an amount of 7 mas.%. This mixture was laid on the experimental plot of the Institute of Combustion Problems. Length of laid asphalt pavement is 20 m, width 5 m, thickness of 6 cm. Figure 67 is photograph of the pavement.

Figure 67 – Asphalt pavement with rubber crumb on the experimental plot of the Institute of Combustion Problems

4.3.3. The results of gas composition analysis on released during the preparation of RBC and asphalt mixtures based on rubber crumb Gas composition and concentration, when producing rubber bitumen compounds and preparing rubberized asphalt were investigated at apparatus gas chromatography. Figure 68 shows chromatograms of gases selected when preparing gravel and mineral mixture. Here the gas chromatography method were identified hydrocarbon gases whose concentrations are shown in tables 25-26. Figures 69 shows the chromatogram of gases extracted in the preparation of asphalt mixture with the addition of rubberbitumen compounds. 123

Figure 68 – Chromatograms of hydrocarbon gases allocated in the preparation of stone-mineral mixture

Figure 69 – Chromatograms of hydrocarbon gases allocated in the preparation of asphalt mix with the addition of RBC

124

As can be seen from the figures, in the chromatogram detected peaks corresponding to n-alkanes: methane, ethane, propane and butane, isoalkanes: isobutane, alkenes: ethylene and propylene [5, 33]. Table 25 The concentrations of gases allocated in the preparation of rubber-bitumen compounds

Gases

Bitumen BND 60/90

Bitumen with rubber crumb of 7 wt. %

Bitumen with rubber-oil mixture of 20 %, 1:1

Gas concentration, ml Methane

1.4

3.2

13.3

Ethan

0.4

0.6

2.6



0.7



1.3

Ethylene

0.2

Propane

0.7

0.6

2.1

Propylene

0.4

0.4

4.1

Isobutane

0.1

0.1

0.3

N-butane





0.7

0.3

0.3

As seen from table 25, gas phase released during heating of bitumen and the preparation of rubber-bitumen compounds, mainly consists of saturated hydrocarbons: methane, ethane, propane, n-butane and isobutene. Also, there is some amount of unsaturated hydrocarbons, such as ethylene and propylene. However, the concentration of all gaseous hydrocarbons was negligible and stored at 10-6. Comparing gas concentrations showed that addition of crumb rubber to the bitumen, then once the waste oil results in higher gas concentrations. Especially significant increase in gas concentration is observed when adding the waste oil. For example, the methane concentration with the addition of crumb rubber to bitumen increases with from 1.410-6 to 3.210-6, while adding more waste oil to 13.310-6, increased to 9 times. If the content of ethane in bitumen with rubber crumb is almost unchanged, with the addition of the waste oil is increased 6 times. The ethylene concentration in the first case is increased by 3 times in the second case also by 6 times. The concentration of propylene initially unchanged, but the additive waste oil led to an increase in its concentration of 10 times. 125

A concentration of C4 hydrocarbons (n-butane and isobutane) is increased slightly. In general, when preparing RBC concentration of gaseous hydrocarbon increases, but the numerical value is within regulatory limits. Next, we measured the concentrations of gas allocated in the preparation of asphalt mixtures with the addition of rubber-binding. Here is bucking the trend, rubber-binder additive to stone-mineral mixture led to various changes in the concentration of gaseous hydrocarbons. While stirring the mixture, dropout and mineral powder with rubber-bitumen binder in the composition of the gas phase methane is detected, ethane concentration is increased by 3 times, ethylene, propane and propylene is reduced. The concentration of n-butane and sobutene increases. Table 26 The concentrations of gases allocated in the preparation of asphalt mixtures Gases

Stirring crushed stone, sand and mineral powder

Stirring crushed stone, sand and mineral powder with RBC

Methane

2.110

-

Ethan

-6

0.510

1.810-6

Ethylene

2.810-6

0.910-6

Propane

1.010

1.110-6

Propylene

14.210-6

10.010-6

Isobutane

0.110-6

0.210-6

N-butane

0.310

0.510-6

Gas concentration, ml -6

-6

-6

On the figures 70 and 71 are chromatograms of the gas mixture, highlighted in the preparation of stone-mineral mixture and with the addition of rubber-binder, where there are peaks, corresponding methane and oxygen. By chromatographic data with the addition of rubber-binder the concentration of oxygen and methane slightly increase. It should be noted there are not seen the toxic gas such as COx and NOx [5, 33]. 126

Figure 70 – Chromatograms of oxygen and methane, isolated in the preparation of stone-mineral mixture

Figure 71 – Chromatograms of oxygen and methane, isolated in the preparation of asphalt mix with the addition of rubber bitumen compounds

127

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19. Saurav. Application of nanotechnology in building materials// International Journal of Engineering Research and Applications. – 2012. – Vol. 2(5). – P.10771082. 20. Daniel Beyene Ghile. Effects of Nanoclay Modification on Rheology of Bitumen and on Performance of Asphalt Mixtures: Thesis for master science. – Delft, 2006. – P. 151. 21. Akbari Motlagh A., Kiasat A., Mirzaei E. and Omidi Birgani F. Bitumen modification using carbon nanotubes // World Applied Sciences Journal. – 2012. – Vol.18 (4). – P. 594-599. 22. Тилеуберди Е., Козбакарова С.М., Онгарбаев Е.К., Тулеутаев Б.К., Мансуров З.А. Дорожные покрытия с резиновой крошкой отработанных шин // Программа и материалы VII Международного симпозиума «Физика и химия углеродных материалов / Наноинженерия». – Алматы, 19-21 сентября 2012 г. – С. 208-210. 23. Никонова О.Н.. Исследование свойств битума при его совместном модифицировании резиновым порошком и серой. http://rosdornii.ru. 08.02.2012. 24. Онгарбаев Е.К., Тилеуберди Е., Козбакарова С.М., Иманбаев Е.И., Мансуров З.А. Приготовление асфальтобетонных смесей с добавкой резиновой крошки // Материалы Международной научно-практической конференции «Нефтегазопереработка-2013». – Уфа, 22 мая 2013 г. – С. 139-140. 25. Hot Mix Asphalts 101. www.state.nj.us. 30.10.2012. 26. Amiri Parviz. Nano Materials in Asphalt and Tar// Australian Journal of Basic and Applied Sciences. – 2011. – Vol. 5(12). – P. 3270-3273. 27. Abdullahi Ali Mohamed. A study on the physical and mechanical properties of asphaltic concrete incorporating crumb rubber produced through dry process// PhD thesis, July 2007. – P. 48. 28. Applications – roads. http://www.eurobitume.eu. 22.11.2011. 29. Heemun Park, Jewon Kim, Yeonbok Kim, Hyunjong Lee. Determination of the layer thickness for long-life asphalt pavements // Proceedings of the Eastern Asia Society for Transportation Studies. – 2005. – Vol. 5. –P. 791 – 802. 30. Ye. Tileuberdi, B.K. Tuleutaev, Ye.K. Ongarbayev, Ye.I. Imanbayev, Z.A. Mansurov. Preparation of asphalt concrete with Beke oil sands. // Сборник материалов VIII Международный симпозиум «Горение и плазмохимия» и Международная научно-практическая конференция «Энергоэффективность-2015». – Алматы, 2015. – С. 142-144. 31. Патент РК № 84185. Способ приготовления асфальтобетонной смеси / Тілеуберді Е., Мансуров З.А., Онгарбаев Е.К., Тулеутаев Б.К.,; опубл. 31.10.2013 г. 32. Тілеуберді Е., Қозбакарова С., Оңғарбаев Е.К., Төлеутаев Б.К., Мансұров З.А. Резеңке үгінділерін асфальтбетон қоспасын алуға пайдалану // ҚазҰУ хабаршысы, химия сериясы. – 2012. – № 1 (65). – С. 196-199. 33. Онгарбаев Е.К., Тілеуберді Е., Акказин Е.А., Тулеутаев Б.К., Мансуров З.А., Досумов К. Состав газов при приготовлении резинобитумных материалов и асфальтобетонных смесей на их основе // Материалы VIII Международного симпозиума «Горение и плазмохимия» и международной научно-технической конференции «Энергоэффективность-2015». – Алматы, 17-18 сентября 2015 г. – С. 443-445.

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V. PRODUCING SYNTHETIC OIL FROM OIL SAND BITUMEN 5.1 Oil sand, bitumen and synthetic oil 5.1.1 Denomination of unconventional oil Unconventional oil comprises bitumen from oil sands, as well as extra heavy oil and crude oil from coal and/or oil shale. They are more discussed in the chapter 1. Thus the denomination unconventional can refer as below: – Geological aspects of the formation; – Properties of the deposits; Technical necessities for an ecologically acceptable, economic exploitation, and more appropriately to the method of recovery. In addition to the definitions of petroleum, heavy oil, and oil sand bitumen presented below, there are two definitions that need to be addressed which also speak to the difference between petroleum and heavy oil on the one hand and oil sand bitumen on the other. These are reservoir and deposit and will be presented first in order to affirm the differences between petroleum/heavy oil and oil sand bitumen [1-6]. Organic matters gradually decomposed and eventually formed petroleum (or a related precursor), which migrated from the original source beds to more porous and permeable rocks, such as sandstone and siltstone, where it finally became entrapped. Such entrapped accumulations of petroleum are called reservoirs. A series of reservoirs within a common rock structure ora series of reservoirs in separate but neighboring formations is commonly referred to as an oil field. A group of fields is often found in a single geologic environment known as a sedimentary basin or province. Not all of the pores in a rock contain petroleum and some pores will be filled with water or brine that is saturated with minerals [1, 2]. The term deposit is typically applied to an accumulation of ore in which the ore is part of the rock. Oil sand (tar-sand) deposits (or, more technically, bituminous sand deposits) are loose sand or partially consolidated sandstone containing naturally occurring mixtures 130

of sand, clay, and water, saturated with a dense and extremely viscous hydrocarbonaceous material technically referred to as bitumen (or colloquially as tar due to its similar appearance, odor, and color to tar produced thermally from coal). The bitumen contained in oil sand deposits exists in the semisolid or solid phase and is typically immobile under deposit conditions of temperature and pressure, unless heated or diluted with low boiling hydrocarbon solvents. Attempts to define oil sand bitumen based on a single property such as API gravity or viscosity are, at best, speculative and subject to inaccuracies [1, 2]. However, not all of the oil fields that are discovered are exploited since the oil may be far too deep or of insufficient volume or the oil field may be so remote that transport costs would be excessively high. Most heavy oil reservoirs originated as conventional oil that formed in deep formations, but migrated to the surface region where they were degraded by bacteria and by weathering, and where the lightest hydrocarbons escaped. Since there is a wide variation in the properties of crude petroleum, the proportions in which the different constituents occur vary with the origin and the relative amounts of the source materials that form the initial protopetroleum as well as the maturation conditions. Thus, some crude oils have higher proportions of the lower boiling components and others (such as heavy oil and bitumen) have higher proportions of higher boiling components (asphaltic components and residuum) [1, 2, 7]. The name heavy oil can often be misleading as it has also been used in reference to as: (1) fuel oil that contains residuum left over from distillation, that is, residual fuel oil; (2) coal tar creosote; (3) viscous crude oil. Very simply, heavy oil is a type of crude oil which is very viscous and does not flow easily. The common characteristic properties (relative to conventional crude oil) are high specific gravity, low hydrogen to carbon ratios, high carbon residues, and high contents of asphaltene constituents, heavy metal, sulfur, and nitrogen. Specialized recovery and refining processes are required to produce more useful fractions, such as naphtha, kerosene, and gas oil. Bituminous rocks (oil sand) generally have a coarse, porous structure, with the bituminous material in the voids. A much more common situation is that the organic 131

material is present as an inherent part of the rock composition insofar as it is a diagenetic residue of the organic material detritus that was deposited with the sediment. The organic components of such rocks are usually refractory and are only slightly affected by most organic solvents. Generally, the bitumen found in oil sand deposits is an extremely viscous material that is immobile under reservoir conditions and cannot be recovered through a well by the application of secondary or enhanced recovery techniques [1, 2, 4, 8].

5.1.2. Classification of the organic sediments Use of the term organic sediments is more correct and to be preferred. It is presenting in the figure 72. The inclusion of coal and oil shale kerogen in the category hydrocarbon resources is due to the fact that these two natural resources (coal and oil shale kerogen) will produce hydrocarbons on high-temperature processing (see figure 73). Therefore, if either coal or oil shale kerogen is to be included in the term hydrocarbon resources, it is more appropriate that they be classed as hydrocarbon-producing resources under the general classification of organic sediments [1, 2].

Figure 72 – Classification of fossil fuel as organic sediments [2]

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Figure 73 – Classification of fossil fuels as hydrocarbon resources and hydrocarbon-producing resources [2]

Thus, fossil energy resources divide into two classes: (1) naturally occuring hydrocarbons (petroleum, natural gas, and natural waxes) (2) hydrocarbon sources (oil shale and coal) which may be made to generate hydrocarbons by the application of conversion processes. Both classes may very aptly be described as organic sediments. A method that uses the pour point of the oil and the reservoir temperature adds a specific qualification to the term extremely viscous as it occurs in the definition of oil sand. In fact, when used in conjunction with the recovery method (Figure 74), pour point offers more general applicability to the conditions of the oil in the reservoir or the bitumen in the deposit and comparison of the two temperatures (pour point and reservoir temperatures) shows promise and warrants further consideration [1-4]. In summary, heavy oil is more viscous than conventional petroleum but the resources are in plentiful supply and different methods of production are required. However, heavy oil (like conventional petroleum and oil sand bitumen) cannot be defined using a single property. Oil sand bitumen cannot be defined using a single property, but it can be defined by the recovery method; bitumen can be defined by the recovery method. Furthermore, heavy oil is usually mobile in the reservoir, whereas oil sand bitumen is immobile in the deposit [1, 2, 9]. 133

Figure 74 – Schematic representation of the properties and recovery methods for crude oil, heavy oil, tar-sand bitumen, and coal [2]

5.1.3. Methods of fuel deriving from oil sand bitumen Synthetic crude is one of many misnomers in the oil industry. It is neither a synthetic material nor a crude; rather, it is a thermally processed liquid derived from bitumen. Properties of synthetic crude oil will highly depend on the history of the processing conditions [1]. The synthetic oil or fuels derived from petroleum contribute approximately one- third to one-half of the total world energy supply and are used not only as transportation fuels such as gasoline, diesel fuel, and aviation fuel, among others, but also to heat buildings. Petroleum products have a wide variety of uses that vary from gaseous and liquid fuels to near solid machinery lubricants. In addition, the residue of many refinery processes – a once-maligned by-product, is now a premium value product for highway surfaces, roofing materials, and miscellaneous waterproofing uses. Conventional petroleum production can include up to three distinct phases: primary, secondary, and 134

tertiary (or enhanced) recovery. During primary recovery, the natural pressure of the reservoir, or gravity, drives oil into the wellbore, which, when combined with artificial lift techniques (such as pumps), brings the oil to the surface [1-3, 10]. Primary recovery occurs as a result of the generation of natural energy from expansion of gas and water within the producing formation, pushing fluids into the wellbore and lifting them to the surface. Typically, approximately 10% v/v of the original oil in place in the reservoir is produced during primary recovery. Secondary recovery occurs as artificial energy is applied to lift fluids to the surface. This may be accomplished by injecting gas down a hole to lift fluids to the surface, installation of a subsurface pump, or injecting gas or water into the formation itself. Secondary recovery is effected when well, reservoir, facility, and economic conditions permit. Secondary recovery methods result in the recovery of an additional 20-40% v/v of the original oil in place. Tertiary recovery methods (enhanced recovery methods, EOR methods) are applied when the means of increasing fluid mobility in oil reservoirs within the reservoir are introduced in addition to secondary techniques. This may be accomplished by introducing additional heat into the formation (such as by the injection of steam—steam flood) to lower the viscosity, i.e., thin the oil, and improve its ability to flow to the wellbore. Tertiary recovery technique involves injecting bacteria into the oil field. Some bacteria produce polysaccharides that reduce the permeability of the water-filled pores of the reservoir rock and this effectively forces injected water into the oil-filled pores, pushing the oil out [1, 2]. Quality of the bitumen from oil sand deposits is poor as a refinery feedstock. As in any field in which primary recovery operations are followed by secondary or enhanced recovery operations and there is a positive change in product quality, such is also the case for oil sand recovery operations. Thus, product oils recovered by thermal stimulation of oil sand deposits show some improvement in properties over those of the bitumen in place. Upgrading of bitumen comprises two stages: primary and secondary upgrading as shown in figure 75. Primary upgrading is usually carried out either thermally, by the coking process, or catalytically, by the resid-hydrocracking process. In the primary upgrading step the bigger molecules are cracked into lower-molecular-weight molecules to make a desirable distillable product. In both cases, the processed 135

oil’s composition is fundamentally different from the virgin oil’s composition in terms of sulfur, nitrogen, oxygen, and hydrogen. The gaseous components consist of lighter hydrocarbons, or liquefied petroleum gas (LPG), that are separated and used as fuel [1].

Figure 75 – Typical route of bitumen to refinery [1]

In the secondary-upgrading stage, the resulting liquid oil from the primary step is further processed to produce a syncrude that meets the refinery feedstock specifications. The most common process to remove heteroatoms and metals, as well as to saturate the aromatics, is hydroprocessing. Thus, syncrude quality depends not only on the properties of the bitumen as feedstock but also on the history of the thermal and catalytic processes that took place. Hence, the syncrude is drastically different from the conventional oil with the same boilingpoint distribution. Conventional refineries cannot always handle syncrude owing to its limited catalyst performance [1-4]. As shown in figure 76, there are two major upgrading processes: carbon rejection and hydrogen addition. There are several carbonrejection options available in the market, and they are all commercially proven and economically attractive residue upgrading options as compared to hydrogen addition. However, carbon-rejection processes typically have a substantial reduction in liquid volume yield, since part of the crude is converted into solid coke or pitch [1]. Syncrude at the refinery gate mainly consists of naphtha, distillate, and heavy gas oil. The naphtha fraction goes to a reformer to be converted intohigh-octane gasoline. The distillate fraction is treated in a hydrotreater to meet the specifications of diesel, kerosene, and jet fuel. The cetane number of the diesel fraction of a synthetic crude 136

is less than that of a conventional crude, and the diesel fraction requires further treatment before use. Paraffin in the bitumen usually moves into the naphtha range after cracking instead of into the diesel range, where it is needed to be for cetane improvement. Aromatic hydrogenation is another way to improve diesel quality; however, it reaches thermodynamic equilibrium and limits the process of naphthenic compound formation [1, 2, 9].

Figure 76 – Heavy oil–upgrading options [1]

When hydrocracking is used instead of coking in the primary upgrading, there will be lower amounts of sulfur and nitrogen in the distillate. Still, secondary hydrotreating is required in order to meet the refinery specifications. Heteroatoms that migrate to the syncrude are resistant to further hydrotreating. Hydroprocessing of syncrude is a major process in a refinery. It is also difficult, because several reactions occur simultaneously (e.g., the removal of S, N, O, and metals, along with the saturation of aromatics and olefins). Above 400 °C, the coking reaction competes with the hydrogenation reaction, and the availability of hydrogen and the reaction pressure dictate which reaction dominates. Thermal cracking processes offer attractive methods of bitumen conversion at low operating pressure without requiring expensive catalysts. Currently, the most widely operated residuum conversion processes are visbreaking and delayed coking, and other processes which have also received some attention for bitumen upgrading include partial upgrading (a form of 137

thermal deasphalting), flexicoking, the Eureka process, and various hydrocracking processes [1-3]. The most economical and easiest thermal process is visbreaking. (The terminology comes from viscosity breaking.) It is the oldest technology, in which the heavy feedstock is subjected to mild thermal cracking at a lower severity to reduce the viscosity and to produce fuel oil. In the visbreaking process, bigger molecules are partially broken, so that the viscosity of the crude is decreased to such an extent that the liquid becomes mobile. This process has its limitations, and the most common problem is the relative instability of the visbroken product. Most syncrude is produced by a delayed-coking process. The product is more aromatic and olefinic as compared to conventional crude. This requires sufficient hydrotreating, which a conventional refinery may not be able to handle without major capital investment. The gas oil fractionis directed to a fluidized catalytic cracking (FCC) unit or to a hydrocracker, to convert the heavier feedstock into diesel and gasoline range products [1-5].

5.2. Catalytic hydrogenation of oil sand’s natural bitumen 5.2.1. Hydrogenation experiment For obtaining light petroleum fractions is necessary to process the hydrogenation of natural bitumen, which allows improved characteristics and simplify of the obtained product. The processing of heavy crude in the presence of hydrogen is a major step in the upgrading of heavy oil or bitumen. Because bitumen is highly deficient in hydrogen and contains high concentrations of heteroatoms and metals, it is imperative to improve the quality of the upgraded product by removing the impurities, this is done by means of adding hydrogen [1, 11]. Therefore, the hydrogenation was tested to natural bitumen recovered by extraction with hexane. Hydrogenation process was carried out to NB of oil sands on the apparatus “Autoclave” (in figure 77). The hydrogenation experiments of natural bitumen extracted from oil sands were carried out in a «Autoclave». Around 200-300 g of NB was charged into the reactor together with active coal supported 138

catalyst. The process provided under 350 mbar of H2 pressure and a temperature of 430 – 460 °C. After loading the sample, the reactor was sealed and flushed 3 times with hydrogen followed by tuning the system to the desired initial pressure of H2. The reactor agitated at 120 rpm, which had been heated to the desired temperature and maintained for 40 – 160 min. After the processes the hydrogenated products in the reactor were removed out.

Figure 77 – Photography of autoclave installations for hydrogenation of natural bitumen

Hydrogenation is a chemical reaction of great importance to the petrochemical and fine chemical industries. Usually hydrogenation refers to the addition reaction of molecular hydrogen with an unsaturated carbon-carbon double bond. There are first compound – alkene is converted into the corresponding alkane [4, 12]. It illustrate as following:

139

Figure 78 – Typical hydrogen reaction [12]

All hydrogenation reactions are highly exothermic. The heat released per mole of hydrogen consumed varies in the range of 60-70 kilojoules per mole (kj/mol). Well known the importance of catalyst on the hydrocarbon processing. A number of metal catalysts are available for hydrogenation reactions. Among the most commonly used metals are nickel, chromium, tungsten, molybdenum, palladium, cobalt, iron, and copper. Metal catalysts get poisoned easily in the presence of sulfur and nitrogen. Therefore, oxides or sulfides of the metals are usually used, to avoid poisoning [4, 12].

5.2.2. Preparation of catalyst for the hydrogenation process For the purpose of adding to hydrogenation process, the active coal supported catalyst – molybdenum oxide (MoO3) was prepared. At first, 10 ml of distilled water added in flask and 3 g of molybdenum oxide (MoO3) added to water and stirred them for 2-3 minutes by magnetic mixer. Then 25% of ammonia solution added slowly (drop by drop) till all catalyst solved. At last, 10 g of active coal were added to mixture and heated until water evaporation. Finally, prepared catalyst dried under vacuum and oven. The catalyst has 699.807 m2/g of surface area, 0.0635 nm of medium pore size. BET surface area of the active coal supported catalyst was determined by nitrogen adsorption at – 196 oC using a sorbtometer-M adsorption analyzer. Total pore volume was calculated from the amount of nitrogen adsorbed at a relative N2 pressure (P P01) of 0.99. The average pore size was assumed to be 4V/BET. All the samples were degassed at 150 oC for 12 h before the measurement. 140

Microscopic structure of catalyst is presenting at figure 79. SEM image of catalyst showed that the catalyst consisting different sizes agglomeration of plate-like structure [4, 11].

Figure 79 – SEM image of active carbon supported catalyst

5.2.3. Hydrogenation to Munayli-Mola natural bitumen Munayli-Mola oil sands processed by hydrogen at a temperature 460 °C, hydrogen pressure of 350 bar and the process time of 2 h 40 min. At the experiment, 2 g of activated carbon supported molybdenum oxide (MoO3) was used. Figure 80 shows the profiles of temperature and pressure over time the hydrogenation process of natural bitumen. We can see from the figure, the temperature of reactor was raised gradually to 450 оС, then stabilized at this temperature and after 2 hours and 40 minutes begins to decline. The hydrogen pressure in the reactor (lower line) increases until the end of the process, and reaches 375 bar. Thus during the hydrogenation the pressure of hydrogen ranges from 250 to 375 bar.

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Figure 80 – Profiles of temperature and pressure over time hydrogenation process of Munayli-Mola natural bitumen

Due to separate out synthetic oil from heavy residue with catalyst, the products of hydrogenation were provided vacuum distillation. Results of fractional composition of hydrogenated natural bitumen (hydrogenated oil), while vacuum distillation are presenting in table 27. Table 27 Fractional composition of hydrogenated oil from Munayli-Mola, while vacuum distillation Characteristics Temperature interval, оС

Oil fractions at selected temperatures interval 1st fraction

2nd fraction

Vacuum residue

I.B. – 215 С

216 – 316 С

316 оС – E.B.

о

о

Pressure, mbar

808

805 – 60

60

Mass of fraction, g

80.39

72.72

43.88

Yield of fraction, %

40.81

36.91

22.27

142

As can be seen from table 27, the yield fraction of hydrogenated oil (HO) from Munayli-Mola bitumen, which boiled out from the start of boiling to 215 оС is 40.8 wt. %. Fraction of hydrogenated oil at the temperature range from 216 to 316 оС formed in amount of 36.9 wt. %. These data confirm the positive effect on the hydrogenation process of the natural bitumen, resulting in an increased yield of volatile petroleum products. The divided products of distillation of HO are showing at figure 81. The 1st and 2nd fractions are extremely light hydrocarbons, their mix called hydrogenated oil and 3d fraction estimated as vacuum residue (after 320 оС under vacuum).

Figure 81 – Fraction of hydrogenated natural bitumen

Table 28 shows the comparative characteristics of natural bitumen extracted from oil sand before and after the hydrogenation process. As seen from the tabulated data, after hydrogenation process decreases the density and ash content of natural bitumen, which also confirms the change in the fractional composition of the bitumen. The yield of light fractions of hydrogenated natural bitumen significantly increased compared to the original natural bitumen. This shows the need to hydrogenation process for expanding the range of products derived oil 143

sands. The only limiting factor may be the high cost of the process in connection with the use of hydrogen [4, 13]. Table 28 Comparative characteristics of natural bitumen extracted from oil sand before and after the hydrogenation process Characteristics

Natural bitumen

Hydrogenated NB

Density, g/cm

0.992

0.883

Ash content, wt. %

0.5

0.07

Yield of fraction, % I.B. – 180 оС 180 – 240оС 240 – 300оС 300оС – E.B.

1.39 0.96 97.68

50.0 20.0 12.6 17.4

3

5.2.4. Hydrogenation to Beke natural bitumen Hydrogenation process was examined to natural bitumen of Beke oil sand as Munayli-Mola feedstock. The process provided same installation method on the apparatus “Autoclave”. There is some changing on experimental condition in comparison with hydrogenation of Munayli-Mola bitumen: has lower process temperature (460 °C) and short time, only 40 minutes (not 2 h 40 min). For the experiment, 1.5 g of activated carbon supported catalyst – molybdenum oxide (MoO3) was used. The H2 pressure didn’t change, process provided under 350 bar as before. The yield of hydrogenated natural bitumen was 91%. Figure 82 is presenting the profiles of temperature and pressure over time the hydrogenation process of natural bitumen. The figure 81 shows the temperature of reactor was raised gradually to 430 оС (red line), and then stabilized at this temperature. The hydrogen pressure in the reactor (blue line) increases until the end of the process, and reaches 350 bar. As seen this picture, the hydrogen pressure didn’t decrease. It means in the process don’t more consuming hydrogen for saturating of hydrocarbons. In this reason, process time prolonged only 40 minutes. When vacuum distilled to hydrogenation products of Beke bitumen, the fractions were received (table 29).

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Figure 82 – Profiles of temperature and pressure over time hydrogenation process of Beke natural bitumen

Table 29 Fractional composition of hydrogenated oil from Beke, while vacuum distillation Characteristics Temperature interval, 0C Pressure, mbar

Oil fractions at selected temperatures interval 1st fraction

2nd fraction

Vacuum residue

I.B. – 215 С

216 – 316 С

316оС – E.B.

о

о

808

805 – 60

60

Mass of fraction, g

24.64

85.78

77.37

Yield of fraction, %

13.12

45.68

41.20

As shown table 29, the yield fraction of hydrogenated productd of Beke bitumen, which 1st fraction is 13.12 wt. %. It is lower than sample of Munayli-Mola. Yield of 2nd fraction increased, that the temperature range from 216 to 316 оС formed in amount of 45.68 wt. %. 145

5.2.5. Conclusion of phenomena The fact that thermal hydroprocessing of bitumen and heavy oils can be accomplished at a much lower temperature and a relatively high conversion indicates that the cleavage of C-C bonds is not a rate determining step. The initiation step may involve cleavage of the C-S bond, or the breakage of the C-C bonds must be accomplished by a mechanism other than homolytic cleavage. There are a number of mechanisms proposed for the initiation step of the cleavage of strong C-C bonds (figure 83) [4, 14].

Figure 83 – Radical chain mechanism for homolysis of a hypothetical molecule M [14]

It is also difficult, because several reactions occur simultaneously (e.g., the removal of S, N, O and metals, along with the saturation of aromatics and olefins). Above 400 °C, the coking reaction competes with the hydrogenation reaction, and the availability of hydrogen and the reaction pressure dictate which reaction dominates [1, 4]. Thus, results indicate the possibility of using oil sands not only as a raw material for road-construction materials (bitumen, asphalt mixture), but also useful for producing synthetic oil or light petroleum products [4, 11-15].

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5.3. Thermal processing of oil sands and characteristics of products 5.3.1. Providing experiment by thermal method World’s conventional oil reservoirs are depleting on an alarming rate and we must find alternate sources to keep the supply undisturbed. Currently the best alternative is the heavy oil which can be extracted by applying different techniques which are different from the conventional methods [3, 16]. Thermal processing of oil sand was conducted in the installation from room temperature to 560 0C. Feedstock heating rate was varied from 6 to 16,7 0C per minute. The average duration of processes was 45 minutes. The reactor is a cylindrical basin with a length of 20 cm and an inner diameter of 8 cm (in the figure 84).

1 – cylindrical reactor, 2 – tube, 3 – Perforated diaphragm, 4 – raw material, 5 – connecting pipe for output gas and products, 6 – refrigerator, 7 – electric furnace, 8 – thermoregulator, 9 – receptacle. Figure 84 – Scheme of apparatus for the thermal processing oil sands

The thermal apparatus consists of a cylindrical reactor (1) with a length of 20 cm and an inner diameter of 8 cm. At the bottom of the reactor has a tube for supplying bubbling gas (2). Gas from the air reservoir fed to the reactor through a perforated diaphragm (3) upwards by the raw material (4). Then gases and vapors enter through tube (5) 147

in the refrigerator (6) being cooled with water. The reactor is heated by an electric furnace (7). The process temperature was controlled by thermoregulator (heat controller) (8). The condensed liquid products flow from the refrigerator to the receptacle (9).

5.3.2. Thermal processing of oil sands The individual product yield and physicochemical characteristics of the liquid distillate obtained from oil sand was defined (table 30). It was determined that the 12 % of organic part in Beke oil sand. As seen from table 30, the derived liquid part is 9.6 % by weight of oil sand and around 2.4 wt.% of gas products were separated out. Due to the high temperature achieved inside the reactor, all the organic fractions of the bitumen boiled and just the inorganic sands will remain in the basin. The exhaust tube of the reactor leads to a heat exchanger where the vapors are condensed and poured into an Erlenmeyer flask. Table 30 Physicochemical properties of thermal processing products of Beke oil sand Parameters

Contents

Yield of products, wt. % Gaseous

2.4

Liquid

9.6

Solid residue

88.0

Characteristics of the liquid fraction: Density, g/cm3 Molecular weight Ash, % Flash point, °С

0.862 261 0.38 42

Fractional composition, wt. %: Boiling point – 180 оС 180-250 оС 250-350 оС 350- end of boiling

19.6 24.0 33.0 23.4

148

A liquid product of the processing seems synthetic oil, which has 0.8620 g/cm3 of density. As well as boiling end fraction after 350 оС was 23.4 mass, %. From the qualitative characteristics of wide fraction of products thermodestructive processing oil sand can be seen that it is in many physicochemical characteristics similar to petroleum fractions [17, 18]. Oil sand of deposits Munayli-Mola were processed by thermal method as Beke oil sand. Table 31 shows the yield of the products of the thermal processing Munayli-Mola oil sand. From the table it can be concluded that the processing oil sand maximum yield of the desired amount of liquid products has not been achieved. After establishing the optimal mode of thermal processing Munayli-Mola oil sand was set fractional composition of the obtained products. Results of the analysis on the fractional composition of the derived products are of great importance for the study, as the basis of these data, it is possible to judge the depth of processing of the breed [19-21]. Table 31 Product characteristics of obtained from Munayli-Mola oil sand by thermal processing, the average heating rate 16.7 оС/ min Parameters

Contents

Yield of products, wt. % Gaseous

1.5

Liquid

13.5

Solid residue

85

Fractional composition, wt. %: Boiling point – 180 оС 180-250 оС 250-350 оС 350- end of boiling

6.1 15.1 46.8 28.8

As indicators of table 31, the values of fractional composition of the products, obtained by thermal method, allow to carry out further studies on the effect of heating rate factor of raw materials on the yield of light fractions [4, 22]. 149

5.3.3. Comparison fractional composition of organic part of oil sands separated by extraction and thermal processing Fractional composition of oil sand bitumen were compared, which separated by organic solvent extraction and thermal processing. It is showing at figure 85.

Figure 85 – Diagram of fractional composition of organic part

Comparative analysis of the data from figure 84 shows that the fraction of natural bitumen composition varies with thermal processing method increases the amount of low-boiling fractions (until 180 0C) with 8.9 %, amount of products by extraction was 19.6 %. Number fraction boiled at 180-250 0C increased around 2 times: fraction of extracted products are 13% and fraction of thermal processing products are 24 %. The fraction boiling at 250-320 0C are increased from 35 to 43 %. However, the amount of fractions above 350 0C reduced from 34.5 to 13.4 %. The products of thermal processing have better properties as synthetic oil. Its density was 0.850 g/cm3. The extracted products with solvents were highly viscous black substances as heavy oil residue. Its density was 1.025 g/cm3 [16-24]. 150

5.3.4. Semi-industrial plants for thermal processing of oil sands Next were conducted determining the detonation characteristics of fraction obtained from synthetic oil of Beke oil sands through thermal method at a semi-industrial apparatus. It is presenting at the figure 86 and its main technical characteristics are tabulated in the table 32.

Figure 86 – Semi-industrial plants for thermal processing

Table 32 Main technical characteristics of semi-industrial plants Reactor volume Product performance Power consumption Process temperature Process time Overall dimensions Operation mode Modifications

80 L 500 kg/h 7,5 kW 450-560 оС 45 min 2.1м*2.5м*1м periodic stationary, mobile

151

It must be note, in a little extent, the thermal method is also catalytic, the clay and the heavy metals present in the mineral phase of the oil sands act as catalyst so that heavy fractions of the bitumen react to form lighter parts. Characteristics of obtained products showed that their suitability as a motor fuel. The data are given in table 33. Table 33 Characteristics of synthetic oil produced from Beke bitumen Parameters

The initial sample

Gasoline fraction 80180 °С

Diesel Gasoil fraction 180- fraction 250250 °С 320 °С

Octane number

-

80

not defined

not defined

Cetane number

-

-

above 45

not defined

Flash, °С

-

-

35-40

-

Density at 20 °С, kg/m

0.870

0.754

0.817

0.864

Pour point, °С

-40

not defined

-50-55

-45

not defined

above -40

above -25

1

not defined

not defined

3

Filterability temperature above -35limit, °С 40 Benzene volume, %

-

Table 33 shows that the gasoline fraction correspond gasoline AI80 and diesel fraction has a low melting point and a good indicator on the limiting filterability temperature, which is favorable for diesel in the winter time. Gasoil fraction can be used as furnace fuel. It follows that the synthetic oil is produced from Веке oil sand, also of interest for further investigations in this direction. Thus, experiment results showed that the thermal process is one way for producing synthetic oil from oil sands [4, 22-25].

5.4. Thermocatalytic cracking of natural bitumen 5.4.1. Providing experiment There is a growing interest in upgrading heavy oil due to an increased demand on liquid fuel coupled with the need to improvethe transportability of heavy crude. The presence of asphaltenes, the 152

constituents of heavy oil with the highest molecular weightand polarity, complicates heavy oil recovery, transportability and processing. Upgrading of heavy oil involves a conversion oflow value feedstock, the heavy fraction, to high value light fractionswith higher H:C ratio. Thermal cracking is an example of carbon rejection upgrading process at temperatures higher than 350 °С. It targets maximizing the yield of the light fractions and lowering the viscosity of the liquid product at the expense of producing some coke. One of the perspective methods for producing synthetic oil is thermocatalytic conversion of heavy hydrocarbons in the presence of catalytic additives such as iron oxides [26-28]. In thermal degradation processes of heavy oil can increase the yield of low-boiling liquid products. The object of investigation was selected sample of bitumen Munayli-Mola and Beke deposits. Extracting natural bitumen was carried out in the Soxhlet apparatus by chloroform solvent. The scheme of the cracked experiment and analysis of the products is shown in Figure 87.

Figure 87 – Scheme of the experiment [28]

Cracking was carried out in bitumen autoclave reactor of 12 cm3; the bitumen was weighed 7 g cracking duration of 60 minutes at a temperature of 450 °С. After the thermolysis, all samples from the 153

reactor were quantitatively extracted, then yield of gas, liquid cracking products and coke were determined. Group composition of the initial bitumen and liquid cracking products installed on the traditional pattern: first, determine the content of asphaltenes in the sample by «cold» method Golde. Then, the concentration of resins obtained by adsorption method with putting the analyzed product ASK silica, placing the mixture in a Soxhlet extractor and subsequently washing out components of hydrocarbon (oil) by n-hexane and resin by an ethanolbenzene mixture from silica (ratio 1:1 STF technique SZHSHI 12172005, IPC SB RAS).

5.4.2. Cracking process of oil sand bitumen The thermal destruction processes of heavy hydrocarbon raw materials make it possible to increase the yield of low boiling liquid products with the formation of coke and gas as by products. Cracking processes in the presence of different catalysts are of special interest. Table 34 summarizes the material balance and composition of cracking products of natural bitumen. As seen from table 34, the cracking of natural bitumen and liquid products formed amount of coke and appear gas. Yield of cracking liquid products from Munayli-Mola deposits was higher than in the processing of bitumen from Beke deposits for 6 wt. % and coke was lower 4.7 wt. %. Cracking has led to increased yield of oil components and the amount of high molecular weight components of bitumen decreases: resin content was decreased. Apparently, this is caused by an increase in coke formation and destruction of resinous components to lighter products. The content of oils in the composition of the liquid cracking products from Munayli-Mola deposit is more for 22 % than the bitumen of Beke deposits and content of resin is less for 15 %, asphaltenes content is lower 7 %. These number shows that the bitumen from Munayli-Mola deposit more acceptable for cracking than the bitumen from Beke deposit [28, 29]. In the form of microspheres of the catalyst chosen and for cracking process was given 10 % weight mass of the catalyst. Microspheres are ferrospheres energy ashes with a high content of iron oxides. Selection ferrospheres due to the fact that they contain the iron oxide phase, represented mainly hematite and spinel ferrite, which can initiate the 154

degradation of high molecular weight components. Ferrospheres are one of the most common types of microspheres in volatile ash from pulverized coal combustion in thermal power stations. The formation of a globular structure is a result of the thermochemical transformation of mineral coal forms droplets to form complex high-iron melts (FeO-CaO-MgO-SiO2-Al2O3) macroelement of partial oxidation and crystallization phases separate on cooling. Table 34 Material balance and composition of cracking products of natural bitumen Cracking conditions

Stotal in oil, wt. %

Composition of liquid products, wt. %

Yield, wt. % Gas

Liquid

Coke

Oil

Resin

Asphaltene

Natural bitumen from Beke deposit Natural bitumen

0.30

0.0

100.0

0.0

49.17

44.89

5.94

450 °С, 60 min.

0.43

1.4

67.7

30.9

61.29

28.27

10.44

450 °С, 60 min. with catalysis

0.34

1.3

63

35.7

60.05

32.24

7.71

450 °С, 60 min. with DTBP

0.35

1.1

70.3

28.6

63.27

24.81

11.92

Natural bitumen from Munayli-Mola deposit Natural bitumen

0.7

0.0

100.0

0.0

47.58

46.37

6.05

450 °С, 60 min.

0.57

0.2

73.6

26.2

83.61

13.39

3.0

450 °С, 60 min with catalysis

0.64

0.5

64.8

34.7

77.53

14.39

8.08

450 °С, 60 min. with DTBP

0.65

1.5

87.6

10.9

77.07

15.23

7.71

Presence of a catalyst in a cracking process had a negative impact on the yield of liquid products and content of oil components: for bitumen both of deposits yield of liquid products decreased, and yield of coke increased for 4-8 %. Oil content decreased, while the total amount of resin-asphaltene components increased for 1 and 6 %, respectively, for the bitumen Beke and Munayli-Mola deposits. 155

Catalyst intensified condensation and consolidation reaction in cracking products. One of the methods to achieve a more profound transformation of resin-asphaltene components to target products and as a consequence, increase the yield of distillate fractions in the cracking process is a radical-additive component, which are the initiators of radical chain processes of low-temperature cracking. Di-tert-butyl peroxide (DTBP) was added 3 wt. % as the radical-additive addition. This organic peroxide initiates the reaction to the destruction of high-molecular compounds and provides to yield of light products. The addition of peroxide favorably influenced the cracking process: the yield of liquid products is increased; especially in the case of cracking bitumen increasing was 14 % from Munayli-Mola deposit. Yield of coke is reduced; in this case the decrease was 15 %. In part of the liquid cracking products of bitumen from Beke deposits content oil components increased for 2 %, the amount of resin content decreased for 3.4 %. However, the processing of bitumen Munayli-Mola deposits despite the significant increase yield of liquid products is showed a decrease the amount of oil and the increase content of resin-asphaltene substances. It appears that the cracking with radical-additive addition involved not only resins and asphaltenes for degradation processes, but also the oil.

5.4.3. Compositions of cracking products of natural bitumen After the thermal and catalytic thermal processing of natural bitumen of oil sands from Munayli-Mola and Beke deposits were investigated fractional composition of the obtained products. Results of the analysis on the fractional composition of the obtained products are major importance for the study, as the basis of these data we can judge the depth of processing of the bitumen. Content of distillate fractions in the initial bitumen and cracking products was estimated by thermogravimetric analysis. Thermogravimetric analysis was performed in air derivatograph MOM firm (Hungary), which allows fixing the weight loss of the sample with the analytical sample with rising temperature until 350 °C at a heating rate of 10 degree/min [28]. 156

Table 35 Fractional composition of cracking products of natural bitumen Composition, wt. %

Sample

Tb.p., °С

B.p.-200

200-360

> 360

Natural bitumen of Beke deposit Natural bitumen

116.8

5.1

20.2

74.7

After cracking

77.9

2.3

18.9

78.8

With catalysis

73

16.1

26.8

57.1

With DTBP

77.4

4.9

14.6

80.5

Natural bitumen of Munayli-Mola deposit Natural bitumen

96.5

2.2

15.6

82.2

After cracking

92

9.3

34.2

56.5

With catalysis

75

7.1

23.3

69.6

With DTBP

82.7

6.5

21.4

72.1

Analysis of the fraction composition of the bitumen cracking products (table 35) showed that a reduction the boiling point fractions under cracking as compared with the initial bitumen. The cracking of bitumen from Beke deposits elevation of boiling point – 360 fractions observed in the case of the catalyst, while the number of fractions of B.p.-200 оC increased for 11 %, the fraction in the range of 200-360°С increased for 6.6 %. Cracking bitumen of Munayli-Mola deposits in all cases leads to the increase the B.p.-200 fractions, indicating an increase in the proportion of destructive processes in the reaction medium. Here, the maximum increase in the content of light fractions occurred during the cracking of bitumen without addition of catalyst and peroxide: the fraction of B.p.-200 increased for 7.1 %, and the fractions 200-360 increase for 18.6 %. The presence of a catalyst and an initiator additive resulted to higher contents of such light fractions. Gas composition of cracking products was determined by gas adsorption chromatograph (see table 36). The main gaseous cracking products include methane, that its content greater than 30 wt. % of Beke deposit and another deposit from Munayli-Mola deposit is more 10 wt. % of methene, in addition has ethane, propane, iso-butane and hydrogen. And the hydrogen content after cracked gases is 2.5-4.5 wt. %. 157

Table 36 Gas composition of cracked products Composition, wt. % Gas

H2

Munayli-Mola OS

Beke OS

After cracking

With catalysis

With DTBP

After cracking

With catalysis

With DTBP

4.53

4.16

4.1

2.71

2.97

2.53

O2

3.43

3.59

5.69

3.86

4.84

3.19

N2

13.43

15.81

24.57

22.78

22.38

15.55

CH4

24.39

24.93

21.97

30.28

35.87

33.14

С2Н6

17

13.33

9.16

10.14

11.62

8.12

СО2

24.79

28.56

19.18

23.77

14.22

16.99

С3Н8

8.88

7.15

6.8

5.16

6.34

5.26

С3Н6

0

0

0

0.02

0.07

0.08

i-С4Н10

2.05

1.41

7.93

0.76

0.97

14.53

n-С4Н10

0.08

0.05

0.04

0.03

0.04

0.03

i-С5Н12

0.96

0.69

0.32

0.3

0.36

0.4

n-С5Н12

0.46

0.32

0.24

0.19

0.32

0.18

5.4.4. Molecular weights of cracking products Molecular weight of resin and asphaltenes of natural bitumen and cracking products was measured by method cryoscopies in naphthalene in installation “Kryon” that is created in IPC SB RAS. Its results are presenting in the table 37. The thermolysis is lead to a deep changing of the structural characteristics of average molecules of resin and asphaltenes than in subcritical conditions. Asphaltene molecules more destroyed by addition of a catalyst to produce lighter products such as: coke, gas and resin compounds [28]. Thus, to conduct process cracking is allowed to increase yield of liquid products of production natural bitumen. A significant reduction in the initial boiling point of liquid products is during cracking. The presence of the catalyst and additive di-tert-butyl peroxide led to increased yield of light fractions and to improve the content of cracking products [28-30]. 158

Table 37 Molecular weights of cracking products, a.m.u. Sample

NB from Munaily-Mola deposit

NB from Beke deposit

Asphaltenes

Resin

Asphaltenes

Resin

Natural bitumen

1803

566

2044

751

After cracking

677

437

1304

499

With catalysis

1045

586

1003

550

With DTBP

869

552

1042

564

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CONCLUSION For the extraction of natural bitumen (organic part) from oil sands the extraction method was used and carried out in Soxhlet apparatus. The medium content of NB in oil sands of Munayli-Mola deposits were 16 wt.%. Whereas, it is determined that the Beke oil sand has 11 wt.%. of organic substances. Characteristics of natural bitumen presented like heavy oil and its elemental composition close to standard paving bitumen BND 60/90. The optimum content of the oil sands in the asphalt concrete are 28 and 47 mass %, the mixes prepared under these conditions satisfy requirements of the state standard. Visual analysis of the precipitated asphaltenes showed that the samples are like a brownish fine powder with a distinctive black gloss. According to the IR-spectrum of asphaltens, that the broad absorption band of asphaltenes at 3000-3600 cm-1 are characterizing the presence of polycyclic aromatic hydrocarbons and aliphatic chains. The peak of the absorption band at 3570 cm-1 determines the stretching vibrations of the-OH group, which is actively involved in the formation of intermolecular hydrogen bonds. In IR- spectrum we can also see the presence of specific absorption bans which can characterize the presence of the alkyl substituents (-CH3, -CH2) groups -CH2-CH3. Microscopic images showed that the asphaltenes have a mediumordered structure, the main component of the surface is represented by amorphous carbon. In the study production of rubber-bitumen compounds based on spent rubber items and spent engine oil and same time use it to preparing rubber-asphalt mixture were investigated. It is established that the quantity of entered binders depending on physical and chemical conditions, which was optimal composition of rubber-oil at a ratio of 1:1 and 3:2 and introduction to bitumen in amount of 15-25 wt.%. It is improving to characteristics of rubberized asphalt. At that time, rubber crumb and spent engine oil use to road construction will allow the amount of rubber crumb produced by reclaiming facilities to be considerably increased and decrease environmental pollution with industrial wastes. It was produced state standard satisfied paving bitumen during short time with a wide interval of plasticity by oxidation natural 162

bitumen from Beke oil sand. Also, studied and developed technology for producing synthetic oil by the method of hydrogenation, thermal processing and catalytic cracking. It was found that the optimum content of the oil sands in the asphalt concrete were concluded at 28 and 47 mass %, the mixes prepared under these conditions satisfy requirements of the standard. As results of microscopic analyses, on the RBC the bitumen aggregation almost covered the swelled rubber crumb when heating and stirring the composition. It is important for react rubber and bitumen compounds. Sand grains of oil sand surrounded by natural bitumen and very thin layer of wetted water, keeping it separate each other. This phenomenon more is useful, at processing and developing of oil sand.

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Scientific issue Yerbol Tileuberdi Yerdos Kkalimullauly Ongarbayev Frank Behrendt Zulkhair Aimukhametuly Mansurov

NANOSTRUCTURE OF BITUMEN PRODUCED FROM HEAVY OIL Monograph Computer page makeup and cover designer A. Aldasheva IS No.11123 Signed for publishing 16.08.17. Format 60x84 1/16. Offset paper. Digital printing. Volume 20,0 printer’s sheet. Edition 500. Order No.4238 Publishing house «Qazaq university» Al-Farabi Kazakh National University, 71 Al-Farabi, 050040, Almaty Printed in the printing office of the «Qazaq university» publishing house