i EGE UNIVERSITY INSTITUTE OF NATURAL AND APPLIED SCIENCES (MASTER THESIS)

COPYROLYSIS OF OIL SHALES WITH BIOMASS

Serhat KARAKAYA
Supervisors: Do. Dr. Yurdanur AKGL

Chemistry Department Code of Discipline: 405.02.01 Presentation Date:07.06.2012

Bornova-ZMR 2012

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Sayn Serhat KARAKAYA tarafndan Yksek Lisans tezi olarak sunulan Copyrolysis of Oil shales and Biomass balkl bu alma E.. Lisansst Eitim ve retim Ynetmelii ile E.. Fen Bilimleri Enstits Eitim ve retim Ynergesinin ilgili hkmleri dikkate alnarak tarafmzdan deerlendirilerek savunmaya deer bulunmu ve 07.06.2012 tarihinde yaplan tez savunma snavnda aday oybirlii/oyokluu ile baarl bulunmutur.

Jri yeleri

mza

Jri Bakan

: Do. Dr. Yurdanur AKGL .............................

Raportr ye

: Prof.Dr. Jale YANIK

..............................

ye

:Prof.Dr. Levent BALLCE ..............................

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ZET Bitmlist ve Biyoktlenin Beraber Pirolizi

KARAKAYA, Serhat Yksek Lisans Tezi, Organik Kimya Anabilim Dal Tez Yneticisi: Do. Dr. Yurdanur AKGL Haziran 2012, 56 Sayfa

Bu almada, bitmlistin ve biyoktlenin ve bunlarn beraber olarak sabit yatak reaktrnde ssal dnm allmtr. Bioktle olarak itlenbik kullanlmtr. Bitmlist olarak Gynk bitlisti seilmitir. Bitmlist, sabit yatakl reaktrde 500, 600 ve 700 Cde; bioktle ise 400, 500 ve 600 Cde azot atmosferi altnda pirolizlenmitir. Piroliz rnleri gaz, sv (su faz +biyoya/tar) ve kat olarak ayrlmtr. Bitmlist ve bioktlenin birlikte piroliz deneyleri 500 C 'de 3:1, 1:1, 1:3 gibi bitmlist:bioktle oranlarnda yaplmtr. Bitmlistin ssal dnmnde bioktlenin farkl oranlarda karmnn rn dalm zerine etkisi ve rnlerin yakt zellikleri incelenmitir.

Anahtar Szckler:itlenbik, Bitmlist, bioya - tar, birlikte piroliz

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ABSTRACT COPYROLYSIS OF OIL SHALES WITH BIOMASS

Master in Chemistry Supervisor: Do. Dr. Yurdanur AKGL June 2012, 56pages

In this study, thermal conversion of lignocellulosic biomass, oil-shale and their blends were investigated in a fixed bed reactor. Terebinth berry was used as lignocellulosic biomasses. Goynuk oil-shale was selected as oil shale. The pyrolysis temperatures were selected as 400, 500 and 600 C for biomass samples and 500 , 600 and 700 C for oil shale. Pyrolysis products were separated as gas, liquid (aqueous phase + oil/tar) and char.The effect of temperature on yields and properties of pyrolysis products was investigated. Copyrolysis experiments were carried out at 500 C with the blends consisted of oil shale/ biomass in weight ratio of 1:3, 1:1 and 3:1. The effect of different ratios of biomass in the biomass/oil shale blends on the thermal degradation of oil shale was investigated in terms of both product distribution and fuel properties of products.

Keywords:terebinth berry, oil shale, bio oil - tar, copyrolysis

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ACKNOWLEDGMENT
I gratefully acknowledge Do. Dr. Yurdanur AKGL for her considerable contributions, supports, helpful suggestions and supervision during my study and for her interest in its progress. I am also grateful to Prof. Dr. Jale YANIK, Pelin SEM and Gzde DUMAN for their valuable suggestions, criticism, technical help and supports in interpretation of research.

My special thanks is to my family for their care and patience during the preparation of this thesis.

Serhat KARAKAYA

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CONTENTS

Page

ZET ........................................................................................................ V ABSTRACT .......................................................................................... VII ACKNOWLEDGMENT ......................................................................... IX CONTENTS ............................................................................................ XI LIST OF FIGURES .............................................................................. XIV LIST OF TABLES................................................................................ XVI SYMBOLS AND ABBREVIATIONS ............................................. XVIII

1. INTRODUCTION ................................................................................. 1 1.1 Oil shale ............................................................................................... 1 1.2 Biomass Energy ................................................................................... 8 1.2.1 Biomass conversion process ........................................................... 10 2. LITERATURE REVIEW .................................................................... 20 2.1 Oil shale and coal pyrolysis ............................................................... 20 2.2 Biomass pyrolysis .............................................................................. 21 2.3 Copyrolysis of oil shale or coal and biomass ................................... 23 3. MATERIAL AND METHODS........................................................... 29 3.1 Material .............................................................................................. 29 3.1.1 Feed stocks ..................................................................................... 29 3.1.2 Chemicals ....................................................................................... 29 3.2 Methods ............................................................................................. 30 3.2.1 Pyrolysis ......................................................................................... 30 3.2.2 Analysis .......................................................................................... 32

xii CONTENTS (continue)

Page

4. RESULTS AND DISCUSSION ..........................................................36 4.1 Oil shale Results.................................................................................36 4.1.1 Thermogravimetric Analysis Results ..............................................36 4.1.2 Pyrolysis Results .............................................................................37 4.2 Biomass Results .................................................................................38 4.2.1 Thermogravimetric Analysis Results ..............................................38 4.2.2 Pyrolysis Results .............................................................................40 4.3 Copyrolysis of oil shale and terebinth berry ......................................42 4.3.1 Composition of oil phase ...............................................................43 4.3.2 FT-IR Results ..................................................................................44 4.3.3 H-NMR results ................................................................................46 4.3.4 Fuel characterization of oil and tar .................................................48 4.3.5 Composition of aqueous phase .......................................................49 4.3.6 Fuel characterization of char ...........................................................50 4.3.7 Composition of gas products ..........................................................51 5. CONCLUSION ....................................................................................52 REFERENCES.........................................................................................54

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LIST OF FIGURES

Figure

Page

1.1 General composition of oil shale ......................................................... 3 3.1 Fixed bed reactor ............................................................................... 31 4.1 Tg curve of oil shale .......................................................................... 36 4.2 DTG curve of oil shale ...................................................................... 37 4.3 Product yields (wt.%) from pyrolysis of oil shale ............................. 37 4.4 Composition of liquids obtained from pyrolysis of oil shale ........... 38 4.5 TG curve of biomass.......................................................................... 39 4.6 DTG curve of biomass ....................................................................... 39 4.7 Product yields (wt.%) from pyrolysis of biomass ............................. 40 4.8 Composition of liquids obtained from pyrolysis of biomass ............. 41 4.9 FT-IR spectrums of pyrolysis oil and tar ........................................... 45 4.9 Assignments of the bands in the 1H-NMR spectra of bio-oil and tar samples ................................................................. 47 4.11 Composition of gas products ........................................................... 51

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LIST OF TABLES
Table Page

1.1 Economic oil shale reserves and production in 1999 as reported bt WEC ............................................................................ 6 1.2 Main oil reserves in Turkey ................................................................ 7 1.3 Characteristics of the major oil shale deposits in Turkey ................... 7 1.4 Reactor types and heat transfer ......................................................... 17 3.1 Oil shale properties ........................................................................... 29 3.2 Biomass properties ............................................................................ 30 4.1 Products distributions from the oil shale and copyrolysis of oil shale and biomass ............................................... 43 4.2 Composition of oil phases ................................................................. 44 4.3 H-NMR results of pyrolysis oil and tar............................................. 46 4.4 Some properties of pyrolysis oil and tar ........................................... 48 4.5 Composition of aqueous phase ........................................................ 49 4.6 Properties of char .............................................................................. 50

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SYMBOLS AND ABBREVIATIONS

Abbreviation

Explanation

Db DTG EU GC-FID GC-TCD GCV GW L Mg mL TGA (TG) GOS TB

Dry basis Differential Thermo gravimetric Analysis European Union Gas Chromatography Flame Ionization Detector Gas Chromatography Detector Gross Calorific Value Giga watt Liter Milligram Milliliter Thermo gravimetric Analysis Goynuk Oil shale Terebinth berry Thermal Conductivity

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1.

INTRODUCTION

Rapid increase in world population and energy demand is continuously increasing in line with developing technology. Energy sources will play an important role in the worlds future. The energy sources have been split into three categories: fossil fuels, renewable sources and nuclear sources. Increasing demand for fuels and for chemical feedstock and the awareness of the finite nature of petroleum deposits results in great interest in alternate sources of fossil fuel, such as coal, asphaltite and oil shales. Oil shale represents the main source of solid fossil hydrocarbon compounds in the form of kerogen (M. Sert et al, 2009). Oil can be obtained from kerogen by pyrolysis and retorting processes. The estimated amount of oil recoverable from oil shale is much higher than the resources of crude oil. Like conventional natural energy resources, most organic waste materials such as municipal solid waste (MSW), lignocellulosic waste, and plastic are also potential energy resources. Today, biomass is considered as a renewable resource with high potential for energy production. There are a number of waste and biomass sources being considered as potential sources of fuels and chemical feed stocks. Biomass can be converted to various forms of energy through numerous thermo chemical conversion processes, depending upon the type of energy desired. One of the approaches in utilization of oil shale is coprocessing. The oil shale/biomass co-processing is the one of the most promising options for enhanced oil shale liquefaction and preferable liquefaction products. Coprocessing can also provide the environmental benefits leading to reduction in CO2 emissions.

1.1. Oil Shale

Oil shale, an organic-rich fine-grained sedimentary rock, contains significant amounts of kerogen (a solid mixture of organic chemical compounds) from which liquid hydrocarbons called shale oil can be produced. Shale oil is a substitute for conventional crude oil; however, extracting shale oil from oil shale is more costly than the production of conventional crude oil both financially and

2 in terms of its environmental impact. Deposits of oil shale occur around the world, including major deposits in the United States of America. Estimates of global deposits range from 2.8 trillion to 3.3 trillion barrels (450109 to 520109 m3) of recoverable oil (Survey of energy resources, 2007). Oil shale contains a lower percentage of organic matter than coal. In commercial grades of oil shale the ratio of organic matter to mineral matter lies approximately between 0.75:5 and 1.5:5. At the same time, the organic matter in oil shale has an atomic ratio of hydrogen to carbon (H/C) approximately 1.2 to 1.8 times lower than for crude oil and about 1.5 to 3 times higher than for coals.(Arvo Ots, 2007) Geologists can classify oil shales on the basis of their composition as carbonate-rich shales, siliceous shales, or cannel shales(Sunggyu Lee, 1991). Another classification, known as the van Krevelen diagram, assigns kerogen types, depending on the hydrogen, carbon, and oxygen content of oil shales' original organic matter. Type I refers to kerogen content with a high initial H/C, but a lower O/C ratio. Type I kerogen are mostly aliphatic chains. Oil shales containing type I kerogen provide the highest yield of oil and are the most promising deposits in terms of conventional oil retorting. Type II kerogen is common in many oil shale deposits. This type is also characterized with relatively high H/C and low O/C ratios. In type II kerogen, the poly aromatic nuclei, the hetero atomic ketone and carboxylic groups are more significant than in type I, but still less than type III. Type III kerogen refers to a low H/C ratio, but a high O/C atomic ratio that is derived from terrestrial higher plants. Another distinct characteristic is their relatively higher proportion of polyaromatic nuclei, heteroatomic ketone and carboxylic acid groups. Although resources of oil shale occur in many countries, only 33 countries possess known deposits of possible economic value (K. Brendow, 2003). Wellexplored deposits, potentially classifiable as reserves, include the Green River deposits in the western United States, the Tertiary deposits in Queensland, Australia, deposits in Sweden and Estonia, the El-Lajjun deposit in Jordan, and deposits in France, Germany, Brazil, China, southern Mongolia and Russia. These deposits have given rise to expectations of yielding at least 40 liters of shale oil per tonne of oil shale, using the Fischer Assay.

OIL SHALE

- Quartz - Feldspars - Clays(mainly illite and chlorite) others Pyrite and

- Solubles in CS2

- Insolubles in CS2 - Containing U, Fe, V, Ni, Mo

Figure 1.1 General composition of oil shales (N. E. Altun, 2006) A 2005 estimate set the total world resources of oil shale at 411 giga tons enough to yield 2.8 to 3.3 trillion barrels of shale oil (Survey of energy resources, 2007).This exceeds the world's proven conventional oil reserves, estimated at 1.317 trillion barrels (209.4109 m3), as of 1 January 2007. The largest deposits in the world occur in the United States in the Green River Formation, which covers portions of Colorado, Utah, and Wyoming; about 70% of this resource lies on land owned or managed by the United States federal government. Deposits in the United States constitute 62% of world resources; together, the United States, Russia and Brazil account for 86% of the world's resources in terms of shale-oil content ( K. Brendow, 2003).

Extraction and processing

Oil shale is mined either by traditional underground mining or surface mining techniques. There are several mining methods available, but the common aim of all these methods is to fragment the oil shale deposits in order to enable the transport of shale fragments to a power plant or retorting facility. The main methods of surface mining are open pit mining and strip mining.

4 The extraction of the useful components of oil shale usually takes place above ground (ex-situ processing), although several newer technologies perform this underground (on-site or in-situ processing) (A.K.Burnham, 2006). In either case, the chemical process of pyrolysis converts the kerogen in the oil shale to shale oil (synthetic crude oil) and oil shale gas. Most conversion technologies involve heating shale in the absence of oxygen to a temperature at which kerogen decomposes (pyrolysis) into gas, condensable oil, and a solid residue. This usually takes place between 450 C and 500 C The process of decomposition begins at relatively low temperatures (300 C), but proceeds more rapidly and more completely at higher temperatures. In-situ processing involves heating the oil shale underground. Such technologies can potentially extract more oil from a given area of land than ex-situ processes, since they can access the material at greater depths than surface mines can.

Applications and products

Industry can use oil shale as a fuel for thermal power-plants, burning it (like coal) to drive steam turbines; some of these plants employ the resulting heat for district heating of homes and businesses. Sizable oil-shale-fired power plants occur in Estonia, which has an installed capacity of 2,967 megawatts (MW), Israel (12.5 MW), China (12 MW), and Germany (9.9 MW). In addition to its use as a fuel, oil shale may also serve in the production of specialty carbon fibers, adsorbent carbons, carbon black, phenols, resins, glues, tanning agents, mastic, road bitumen, cement, bricks, construction and decorative blocks, soil-additives, fertilizers, rock-wool insulation, glass, and pharmaceutical products (A study on the EU oil shale industry-viwed in the light of the Estonian experience, May 2007) Based on the EC 2007 report, Estonia was the worlds largest producer of shale oil, producing 345,000 ton of shale oil per year. Approximately 8000 ton of shale oil was utilized for domestic electricity generation; 98,000 ton of oil for heat generation and the remaining 222,000 was exported. In Estonia the solid semicoke byproduct of shale oil production is mostly disposed of in open dumps; currently approximately 300 million ton of solid semi coke waste is present in such dumps.

5 Table 1.1 gives the the reserve amounts, oil-yield potentials and shale-oil production figures for 1999 (WEC, 2001).

Environmental considerations
Both mining and processing of oil shale involve a variety of Environmental impacts, such as global warming and greenhouse gas emissions, disturbance of mined land, disposal of spent shale, use of water resources, and impacts on air and water quality.

Oil shale potential in Turkey

Oil shale comprises the second largest potential fossil fuel in Turkey. The main oil shale resources are located in middle and western regions of Anatolia. The amount of proved explored reserves is around 2.22 billion tons while the total reserves are predicted to be 3 to 5 billion tons. Despite this vast potential, the stated amount cannot be accepted as a the amount of commercial reserves. The deposits vary from 500 to 4500 kcal/kg in calorific value, revealing that each deposit requires a detailed study regarding its possible use (N. E. Altun, C. et al., 2006). In Turkey, the current total reserves of oil shale are the second place, after the lignite reserves. The main oil shale deposits in Turkey are shown in Table 1.2 with the amounts of their geological (proved) and possible reserve. Among the potential resources, Beypazar (Ankara), Seyitmer (Ktahya), Himmetolu (Bolu) and Hatilda (Bolu) deposits are of major importance in terms of quality, amount and exploitability. The characteristics of these four deposits, which constitute around 50% of the total oil shale potential of Turkey are given in Table 1.3

6 Table1.1 Economic oil shale reserves and production in 1999 as reported by WEC

Average shale oil yield (kg

( 106 t ) Shale production in 1999

Estimated additional oil

Proved recoverable oil

Proved Oil shale(x106

potential (x106 tons)

Recovery method

Region/Country

African/Morocco Africa/S.Africa N.America/USA Asia/Thailand Asia/Turkey Europe/Albania Europe/Estonia Europe/Ukraine Middle East/Israel Middle East/Jordan Oceania/Australia

Surface In situ Surface In situ Surface Surface Surface In situ In situ Surface Surface In situ

12300 73 3340000 18668 1640 6 590 910 2674 15360 40000 32400

500 6000080000 810 269 167 300 600 4000 1725

50-64 10 57 50 56

5400 62000

5 167 126 62 100 53 20000 35260 6200 151 -

(x103 tons)

potential

oil/ton)

tons)

7 Table 1.2 Main oil shale reserves in Turkey Name deposits Beypazar Seyitmer Himmetolu Hatlda Mengen Ulukla Bahecik Burhaniye Beydili Dodurga Demirci Sarcakaya eltik TOTAL of the Geological Reserves tons) 327.68 83.32 65.97 78.37 555.34 38.85 289.2 50 130 42 15.6 300 138 172 330 90 1665.65 327.68 122.17 65.97 467.57 50 130 42 15.6 300 138 172 300 90 2220.99 Possible reserves Total (x106 (x106 tons) reserves

(x106 tons)

Table 1.3 Characteristics of the major oil shale deposits in Turkey Deposit Upper calorific value kcal/kg Beypazar Seyitmer Himmetolu Hatlda 812.67 847.90 1991.88 773.86 4.8 6.9 30.9 5.6 5.4 5 43 5.3 60 54.3 482 58 1.4 0.9 2.5 1.3 Total organic carbon % Oil content % Oil content l Total sulphur %

Gynk Himmetolu deposit

The Himmetolu oil shale deposit is located in the southwestern part of province of Bolu, in the neighborhood of the Beypazari, Hatilda Mengen oil shale deposits. The Himmetolu oil shale basin is of Neogene age, and volcanism and tectonic activity have considerable influence on the environmental conditions during the deposition period. The Himmetolu oil shale consists of more than 50% liptinite, 2050% huminite and 020% inertinite maceral groups and is characterized by its high organic content. The origin of the organic matter is mainly algae and land plants. The major inorganic constituents in the organic-rich zones are calcite, dolomite, silica, and considerable amounts of pyrite. The average calorific value of the EGOS zone is around 4900 kcal/kg. The in-place shale oil content of the Himmetolu oil shale is 43% by weight or approximately 482 l/ton of shale. However, the average total sulphur content is high (2.5%) due to considerable pyrite. The Himmetolu oil shale zone is being excavated (2005) to exploit a underlying high-quality lignite seam utilized for domestic heating. On account of its high thermal quality, the Himmetolu oil shale alternative for power generation in Turkey, which relies mostly on poor-quality lignites.

1.2 Biomass Energy

Biomass is the name to given all Earths living matter. Biomass is general term for material derived from growing plants or from animal manure which is effectively a processed form of plant material such as wood from natural forests, waste from agricultural and forestry processes, and industrial, human or animal wastes. The stored energy in the plants and animals, or the waste that they produce is called biomass energy. Plants absorb solar energy, using it to drive the process of photosynthesis, which enables them to live. The energy in biomass from plant matter originally comes from solar energy through the process known as photosynthesis. The energy, which is stored in plants and animals (that eat plants or other animals), or in the wastes that they produce, is called biomass energy. This energy can be recovered by burning biomass as fuels. During combustion, biomass releases heat and carbondioxide that was absorbed while the plants were growing. Essentially,

9 the use of biomass is the reversal of photosynthesis. Is biomass energy a variety of chemical energy? In nature, all biomass ultimately decomposes to its molecules with the release of heat. The release of energy from the combustion of biomass imitates natural process. Therefore, the energy obtained from biomass is a form of renewable energy and, in principle, utilizing this energy does not add carbondioxide to environment, in contrast to fossil fuels. Of all the renewable sources of energy, biomass is unique in that it is effectively stored solar energy. Furthermore, it is the only renewable source of carbon and is able to be converted into convenient solid, liquid and gaseous fuels . Biomass can be used directly (e.g burning wood for heating and cooking) or indirectly by converting it into a liquid or gaseous fuel (e.g. alcohol from sugar crops or biogas from animal waste).The net energy available from biomass when it is combusted ranges from about 8MJ/kg for green wood, to 20MJ/kg for dry plant matter, to 55MJ/kg for methane, as compared with about 27 MJ/kg for coal. Many biomass fired electricity generators use waste materials, such as straw or domestic refuse. Other schemes are based on the idea of cultivating crops of various kinds, especially to provide biomass for fuel. The conversion of biomass to energy (also called bioenergy) encompasses a wide range of different types and sources of biomass, conversion options, end-use applications and infrastructure requirements (McKendry, 2002). Although a wide variety of biomass sources, most importants of their used for energy are: Wood, Vegetable sources, Grease seed crops (sunflower, colza, soybean...), Carbohydrate crops (potato, wheat, corn, beet...), Energy (C4) crops (eucalyptus, sweet corn, miscanthus ...), Aquatic plants (water hyacinth, algae, marine algae, some water grass...), Crop residues (brunch, stalk, straw, root,shell...), Animal wastes, Urban and industrial wastes (Balkanl, 2001). Biomass is the fourth largest source of energy in the world after coal, petroleum and natural gas, providing about 14% of the worlds primary energy consumption. Since the energy crisis in the mid-1970s, the energy utilization from biomass resources has received considerable attention (Bridgwater, 1999).

10 This type of biomass-based resources through different processes of conversion is used to produce biofuels such as biodiesel, ethanol, in heating, in cooking and is used to produce electricity. Biomass energy due to has an extremely important role, renewable and easy availability, socio-economical contribution to development and environmentally friendly.

1.2.1 Biomass conversion process

Biomass cn be converted to fuels and chemical by thermochemicals and biochemical ways. The thermochemical conversion processes have two basic approaches. The first is the gasification of biomass and its conversion to hydrocarbons. The second approach is to liquefy biomass directly by hightemperature pyrolysis, high-pressure liquefaction, ultrapyrolysis, or supercritical extraction. These processes convert the waste biomass into energy rich useful products. Choice of conversion process depends upon the type and quantity of biomass feedstock, the desired form of the energy, i.e., end use requirements, environmental standards, economic conditions and project specific factors. Different thermochemical conversion processes include combustion, gasification, liquefaction, hydrogenation and pyrolysis. Although pyrolysis is still under developing stage but during current energy scenario, pyrolysis has received special attention as it can convert biomass directly into solid, liquid and gaseous products by thermal decomposition of biomass in the absence of oxygen. Pyrolysis offers efficient utilization of particular importance for agriculture countries with vastly available biomass by-products. Pyrolysis will be explained in another section.

1.2.1.1 Combustion
The burning of biomass in air, i.e. combustion, is used over a wide range of outputs to convert the chemical energy stored in biomass into heat, mechanical power, or electricity using various items of process equipment, e.g. stoves, furnaces, boilers, steam turbines, turbo generators, etc. The technology is commercially available and presents minimum risk to investors.

11 Combustion of biomass produces hot gases at temperatures around 800 1000C. It is possible to burn any type of biomass but in practice combustion is feasible only for biomass with a moisture content <50%, unless the biomass is pre-dried. High moisture content biomass is better suited to biological conversion processes.

1.2.1.3 Gasification
Gasification is the conversion of biomass into a combustible gas mixture either by the partial oxidation or by steam or pyrolysis gasification of biomass at high temperatures, typically in the range 800900 C. The low calorific value (CV) gas produced (about 46 MJ=N m3) can be burnt directly or used as a fuel for gas engines and gas turbines. The product gas can be used as a feedstock (syngas) in the production of chemicals e.g. methanol (McKendry, 2001). The process of gasification is a sequence of interconnected reactions; the first step, drying evaporate moisture, is a relatively fast process. The second step, pyrolysis, is also relatively fast but it is a complex process that gives rise to the tars that cause so many problems in gasification processes. Pyrolysis occurs when a solid fuel is heated to 300500 C in the absence of an oxidizing agent, giving a solid char, condensable hydrocarbons or tar and gases. The relative yields of char, liquid and gas mainly depend on the rate of heating and the final temperature. In gasification by partial oxidation, both the gas and liquid and solid products of pyrolysis then react with the oxidizing agent usually air, although oxygen can be used to give the permanent gases CO, CO2, H2, and lesser quantities of hydrocarbon gases. In steam or pyrolytic gasification, the char is burned in a secondary reactor to reheat the hot sand which provides the heat for the gasification.

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1.2.1.3 Liquefaction
Liquefaction is the conversion of biomass into a stable liquid hydrocarbon using low temperatures and high hydrogen pressures (McKendry, 2001). In this process, liquid is obtained by thermo-chemical conversion at low temperature and high pressure using a catalyst in the presence of hydrogen. The interest in liquefaction is low because the reactors and fuel-feeding systems are more complex and more expensive than pyrolysis processes. In liquefaction, feedstock organic compounds are converted into liquid products. In case of liquefaction, feedstock macromolecules compounds are decomposed into fragments of light molecules in the presence of a suitable catalyst. These unstable and highly reactive fragments repolymerize into oily compounds having appropriate molecular weights, whereas in pyrolysis, catalysts are not used and light decomposed fragments are converted to oily compounds through homogeneous reactions in the gas phase. It is an expensive process and also the product is a tarry lump, which is difficult to handle.

1.2.1.4 Supercritical fluid extraction

SCFs have both gas and liquid like properties. They possess gas like mass transfer properties and the salvation characteristic of liquids. Their high diffusivity allows them to penetrate solid materials, and their liquid like densities enable them to dissolve analyses from a solid matrix. SCFs are compressible, and small pressure changes produce significant changes in their density and in their ability to solubilise compounds. Also SCFs have almost no surface tension. Thus, they can penetrate low porosity materials. In addition, their low viscosity provides favorable flow characteristics. These properties enable SCFs to provide excellent extraction efficiency and speed. Supercritical fluid extraction is a fast and efficient method to extract all manner of organic compounds from a wide variety of solid sample matrices. Due to the marked change in its polarity with temperature, water is an interesting

13 alternative to carbondioxide as the extraction fluid. By merely adjusting the temperature, selectivity can be achieved for inorganic or organic compounds and for polar and non-polar organic compounds. Many organic compounds are sufficiently soluble to be extracted under subcritical conditions and in this way, instrumental and other problems, such as the high corrosiveness of supercritical water, can be avoided. Instrumentation for sub- and supercritical water extraction was developed and modified in several ways with the aim of simplifying the procedure while maintaining good recoveries.

1.2.1.5 Pyrolysis
Pyrolysis is the chemical and pysical decomposition of organic material that occurs at high temperatures in the absence of oxygen. The conditions created during pyrolysis cause complex organic molecules to break down into simpler molecules and thus fundamentally and irreversibly alter their properties at a molecular level.

Type of pyrolysis

a. Slow pyrolysis
Conventional slow pyrolysis has been applied for thousands of years and has been mainly used for the production of charcoal. Slow pyrolysis is defined as the pyrolysis that occurs under a slow heating rate. This condition permits the production of solid, liquid, and gaseous pyrolysis products in significant portions. In slow pyrolysis, biomass is heated to about 500 C. The vapor residence time varies from 5 min to 30 min. Because of long residence time of vapor, components in the vapor phase continue to react with each other, as the solid char and any liquid are being formed. The heating rate in conventional pyrolysis is typically much slower than that used in fast pyrolysis. A feedstock can be held at constant temperature or slowly heated. Vapors can be continuously removed as they are formed.

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b. Fast pyrolysis
Fast pyrolysis occurs in a time of a few seconds or less. Therefore heat and mass transfer processes and phase transition phenomena, as well as chemical reaction kinetics, play important roles. The critical issue is to bring the reacting biomass particles to the optimum process temperature and minimize their exposure to the intermediate (lower) temperatures that favour formation of charcoal. One way this objective can be achieved is by using small particles, for example in the fluidized bed processes. Another possibility is to transfer heat very fast only to the particle surface that contacts the heat source as applied in ablative pyrolysis. A critical technical challenge in every case is heat transfer to the reactor of char. The higher yield of desirable liquid product can be obtained by fast pyrolysis. It involves rapid heating of biomass but not as fast as flash pyrolysis. Heating rate is somewhere about 300 C/min. Generally, fast pyrolysis is used to obtain high-grade bio-oil. Fast pyrolysis is successful with most of fluidized bed reactors as it offers high heating rates, rapid devolatilization, easy control, easy product collection, etc. Various reactors like entrained flow reactor, wire mesh reactor, vacuum furnace reactor, vortex reactor, rotating reactor, circulating fluidized bed reactor, etc. were designated for performing fast pyrolysis. Many researchers have contributed in the field of fast pyrolysis of biomass using various reactors. Although fast pyrolysis of biomass has achieved commercial status, there are still many aspects of the process which are largely empirical and require further study to improve reliability, performance, product consistency, product characteristics and scale-up. A wide range of reactor configurations have been investigated that show considerable diversity and innovation in meeting the basic requirements of fast pyrolysis. The `best' method is not yet established with most processes giving between 6575% liquids based on dry wood input. The essential features of a fast pyrolysis reactor are: very high heating and heat transfer rates; moderate and carefully controlled temperature; and rapid cooling or quenching of the pyrolysis vapours. Commercial operation is currently only being achieved from a transport or circulation fluid bed system that are used to produce food

15 favourings. Fluid beds have also been extensively researched and have been scaled up to pilot plant size with plans in hand for demonstration in several locations. Substantial developments can be expected in performance and cost reduction in coming years.

The penalties and interactions are summarized in Table 2.2 below with some speculations on heat transfer modes. The two dominant modes of heat transfer in fast pyrolysis technologies are conductive and convective. Each one can be maximized or a contribution can be made from both depending on the reactor configuration (Bridgwater, 1999)

Bubbling fluid beds usually referred to as just fluid beds as opposed to circulating fluid beds have the advantages of a well understood technology that is simple in construction and operation, good temperature control and very efficient heat transfer to biomass particles arising from the high solids density. Fluid-bed pyrolyzers give good and consistent performance with high liquid yields of typically 7075% wt from wood on a dry-feed basis. Small biomass particle sizes of less than 23mm are needed to achieve high biomass heating rates, and the rate of particle heating is usually the rate-limiting step. Residence time of solids and vapours is controlled by the fluidizing gas flow rate and is higher for char than for vapours. As char acts as an effective vapour cracking catalyst at fast pyrolysis reaction temperatures, rapid and effective char separation/elutriation is important. This is usually achieved by ejection and entrainment followed by separation in one or more cyclones so careful design of sand and biomass/char hydrodynamics is important. Fluidized bed pyrolysis and circulating fluid beds which transfer heat from a heat source to the biomass by a mixture of convection and conduction. The heat transfer limitation is within the particle, thus, requiring very small particles of typically not more than 3 mm to obtain good liquid yields. Substantial carrier gas is needed for fluidization or transport. Circulating fluid beds (CFBs) have many of the features of bubbling beds, except that the residence time of the char is almost the same as for vapours and gas, and the char is more attrited due to the higher gas

16 velocities, which can lead to higher char contents in the collected bio-oil. An added advantage is that CFBs are potentially suitable for very large throughputs even though the hydrodynamics are more complex this technology is widely used at very high throughputs in the petroleum and petrochemical industries. However, heat transfer at higher throughputs has not been demonstrated and offers some challenges. Heat supply is usually from recirculation of heated sand from a secondary char combustor, which can be either a bubbling or circulating fluid bed.

In this respect the process is similar to a twin fluid-bed gasifier except that the reactor (pyrolyser) temperature is much lower and the closely integrated char combustion in a second reactor requires careful control to ensure that the temperature and heat flux match the process and feed requirements. Ablative pyrolysis is substantially different in concept compared with other methods of fast pyrolysis. In all the other methods, the rate of reaction is limited by the rate of heat transfer through the biomass particles, which is why small particles are required. The mode of reaction in ablative pyrolysis is like melting butter in a frying pan the rate of melting can be significantly enhanced by pressing the butter down and moving it over the heated pan surface. In ablative pyrolysis, heat is transferred from the hot reactor wall to melt wood that is in contact with it under pressure. The pyrolysis front thus moves unidirectionally through the biomass particle. As the wood is mechanically moved away, the residual oil film both provides lubrication for successive biomass particles and also rapidly evaporates to give pyrolysis vapours for collection in the same way as other processes.

17
Table 1.4 Reactor types and heat transfer (Bridgwater, 1999).

Reactor type

Suggested mode of heat Advantages/disadvantages/features transfer

Ablative

95%Conduction,

4%

Accepts large size feedstocks; very high mechanical char abrasion from biomass; compact 1% radiation design; heat supply problematical; heat transfer gas not required; particulate transport gas not always required.

convection; 1% radiation.

Circulating fluid 80%Conduction, bed

19%

High heat transfer rates; high char abrasion from biomass and char erosion leading to high char product; char/solid heat in carrier

convection; 1% radiation.

separation required; solids recycle required; increased complexity of system; maximum particle sizes up to 6 mm; possible liquids cracking by hot solids; possible catalytic activity from hot char; greater reactor wear possible.

Fluid bed

90%Conduction

9%

High heat transfer rates; heat supply to fluidizing gas or to bed directly; limited char abrasion; very good solids mixing; particle size limit < 2 mm in smallest dimension; simple reactor configuration

convection; 1% radiation

Entrained flow

4%Conduction

95%

Low heat transfer rates; particle size limit < 2 mm; limited gas/solid mixing

convection; 1% radiation

18 The rate of reaction is strongly influenced by pressure, the relative velocity of the wood and the heat exchange surface and the reactor surface temperature. The key features of ablative pyrolysis are therefore as follows: High pressure of particle on hot reactor wall, achieved due to centrifugal force High relative motion between particle and reactor wall Reactor wall temperature less than 600 C. As reaction rates are not limited by heat transfer through the biomass particles, large particles can be used and, in principle, there is no upper limit to the size that can be processed. In fact, the process is limited by the rate of heat supply to the reactor rather than the rate of heat absorption by the pyrolysing biomass, as in other reactors. There is no requirement for inert gas, so the processing equipment is smaller and potentially lower cost. However, the process is surfacearea-controlled so scaling is more costly and the reactor is mechanically driven, and is thus more complex. Entrained flow fast pyrolysis is, in principle, a simple technology, but most developments have not been as successful as had been hoped, mostly because of the poor heat transfer between a hot gas and a solid particle. High gas flows are required to affect sufficient heat transfer, which requires large plant sizes and entails difficult liquid collection from the low vapour partial pressure. Liquid yields have usually been lower than fluid bed and CFB systems (Bridgwater, 2006).

c. Flash pyrolysis
Flash pyrolysis is the process in which the reaction time is of only several seconds or even less. The heating rate is very high. This requires special reactor configuration in which biomass residence times are only of few seconds. Two of appropriate designs are entrained flow reactor and the fluidized bed reactor. Flash

19 pyrolysis of any kind of biomass requires rapid heating and therefore the particle size should be fairly small, i.e., approximately 105250 mm (Goyal et al., 2008).

d. Vacuum pyrolysis
Vacuum pyrolysis has slow heating rates but removes pyrolysis products as rapidly as in the previous methods which thus simulates fast pyrolysis. Larger particles are needed and the vacuum leads to larger equipment and higher costs. It limits the secondary decomposition reactions, which in turn gives high oil yield and low gas yield.

The Factors that affect Pyrolysis

The factors that affect pyrolysis are pyrolysis temperature, heating rate, catalyst, particle size, reaction conditions of the products and pressure. The amount of volatile matter increase with increasing heating rate. Tar decomposed at high temperatures so that the amount of gas products increase. With Increasing pressure, retention time of volatile substances decreases. The amount of tar increase at middle temperatures with low pressure. Pyrolysis temperature is the important parameter affecting the quantity and composition of volatile substances. Liquid, gas and activated carbon (solid) change by pyrolysis temperature and their chemical composition is also quite different. With the increase in temperature of pyrolysis, H / C and O / C ratio of the liquid product and activated carbon decrease. Volatile products decomposition and again carbon waste gasification observed in long retention times. The pyrolysis process in short retention times, there is a direct correlation between temperature and chemical composition. With the increase temperature, oxygen content in the structure and C / N ratio decrease. With the increase particle size, volatiles migration accelerate to gas

atmosphere so that it is possible that the mass transfer limitation. Volatiles interact longer with the surface and may cause formation of secondary reactions.

20 Polymerization decompositon decreases the efficiency of whole pyrolis process,and

reactions on the suface reduces the liquid efficiency while

increasing the gas efficiency.

21

2. LITERATURE REVIEW

2.1 Oil shale and Coal Pyrolysis

Hans Luik et al. studied two different Estonian oil shales, peat, and willow biomass were submitted to supercritical water conversion at unified operating conditions. The yield and chemical composition of conversion products were investigated by chromatographic, FTIR-spectroscopic and ultimate analysis techniques. The results reveal significant difference in products yield and composition those depending on the feedstock origin and its chemical composition. Common and specific features in conversion of fossil and renewable matter were described. The maximum and the minimum oil yield per organic matter, 62.7 and 18.6%, respectively, were obtained in conversion of oil shales. Willow biomass conversion resulted in the highest yield of gas andwater (50 %). The solubility of oils despite original feedstock increases with solvents used in the raw: dimethyl ketone < water < benzene. The investigation on group composition of the benzene-soluble compounds demonstrated that various oxygen compounds dominate over hydrocarbons in all cases. The majority of hydrocarbons was represented by polycyclic aromatic ones. Aliphatic hydrocarbons, making 611% of the benzene-soluble oil were represented by n-alkanes up to C33. Conversion gases, especially those of peat and willow were characterized by high carbon dioxide content. Supercritical water conversion can be used as an alternative method for the liquefaction and gasification of different feed stocks. Omar S. et al. investigated a modified first order kinetic equation with variable activation energy is employed to model the total weight loss of Ellajjun oil shale samples. Fixed bed retort with 400 g of oil shale sample size is used in this study in 350550 0C temperature range. Variable heating rate, h, in the range 2.65 0C min-1 are tested. Activation energy was allowed to vary as a function of oil shale conversion. The value of the activation energy increased from 98 to 120 kJ mol-1 while the corresponding frequency factor changed from 9.51 -105 to 1.16 - 106. Fischer Assay analysis of the studied samples indicated 12.2 wt.% oil content. The oil shale decomposition ranged from 3.2% to 28.0%. The obtained

22 kinetic data are modeled using variable heating rate, pyrolysis temperature and variable activation energy principle in a nitrogen sweeping medium. Good fit to the obtained experimental data is achieved. Yahya H. et al. investigated In this investigation, spectroscopic (FT-IR, UVVis, 1H NMR) and chromatographic (GC) techniques were used to analyze two Jordanian shale oils, Sultani and El-Lajjun. The oils were extracted at different pyrolysis temperatures (400500 0C) using a fluidized bed reactor. The spectroscopic and chromatographic analyses show that the variation of pyrolysis temperature has no significant effect on the composition of the produced oil. The
1

H NMR results indicate that the protons of methyl and methelyene represent the

bulk of the hydrogen (90%) in most shale oil samples. GC analysis reveals that the oil samples contain n-alkanes with a predominant proportion of n-C25.

2.2 Biomass Pyrolysis

G.A. Romeiro et al. investigated the low temperature conversion (LTC) process applied to a castor seed sample at 380 8C produced pyrolysis oil (50%,w/w), pyrolytic char (29%, w/w), water (13%, w/w) and gas (8%, w/w) fractions. The oil fraction was subjected to analysis of by FTIR, 1H NMR,
13

NMR, GCMS and physicalchemical analysis such as sulfur content, distillation, density, flash-point, kinematic viscosity, Ramsbottom carbon residue, ash content, corrosivity to copper, water content and sediment, cold filter plugging point, and gross calorific value. They were found as conclusion The need for an efficient and renewable source of biomass makes castor seeds an excellent material to be used in the LTC process. After separation of the fractions, the pyrolysis oil was analyzed by FTIR, 1H, 13C NMR and GCMS, demonstrating that the oil possesses long-chain hydrocarbons and also polar components. Nurgul O. et al. investigated apricot pulps was pyrolyzed in a fixed-bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 5 C/min. Final temperature range studied was between 300 and 700 0C and the highest liquid product yield was obtained at 550 0C. Liquid product yield increased significantly under

23 nitrogen and steam atmospheres. For the optimum conditions, pyrolysis of peach pulp was furthermore studied. Liquid products obtained under the most suitable conditions were characterized by FTIR and H-NMR. In addition, gas chromatography/mass spectrophotometer was achieved on all pyrolysis oils. Characterization showed that bio-oil could be a potential source for synthetic fuels and chemical feedstock. Putun E. et al. were studied pyrolysis of hazelnut shells in a fixed-bed tubular reactor. Fixed-bed pyrolysis experiments have been conducted on a sample of hazelnut shells to determine the possibility of being a potential source of renewable fuels and chemical feedstocks. The effects of pyrolysis temperature and well-sweep gas atmosphere (N2) on the pyrolysis yields and chemical compositions have been investigated. The maximum bio-oil yield of 23.1 wt.% was obtained in N2 atmosphere at a pyrolysis temperature of 500C and heating rate of 7 K min-1. The pyrolysis products were characterized by elemental analysis and various chromatographic and spectroscopic techniques and also compared with currently utilised transport fuels by simulated distillation. Bio-oil was then fractionated into pentane soluble and insoluble compounds (asphaltenes). Pentane soluble was then solvent fractionated into pentane, toluene, ether and methanol subfractions by fractionated column chromatography. The aliphatic and low-molecular-weight aromatic subfractions of the bio-oil were then analyzed by capillary column gas-liquid chromatography and GC:MS. Further structural analysis of bio-oil and aromatic and polar subfractions FTIR and 1HNMR spectra were obtained. The chemical characterization has shown that the bio-oil obtained from hazelnut shells was quite similar to the crude oil and shale oil.

2.3 Copyrolysis of biomass with coal or oil shale

Hans Luik et al. (2007) investigated pyrolysis of different types of forest residual biomass such as pine wood, pine bark and spruce needles, and Estonian Kukersite oil shale. Pyrolysis of the individual samples was carried out in a Fischer assay in standard for oil shales semi-coking conditions (under the heating rate 5 min-1 up to 520 0C). The elemental composition of the selected products

24 was examined with Elementar Vario EL analyzer. The functional group composition of liquid fractions was investigated by FTIR-spectroscopy. The group composition of the benzene-soluble fraction was determined by thin-layer chromatography (TLC). The individual composition of volatiles was analyzed by gas chromatography in columns of different polarity with temperature programming. Gas composition, characterizes the bio-gas as especially rich in CO2. The content of CO is considerable also. Common and specific features in biomass and oil shale semi-coking have been described. In comparison with oil shale, the biomass yielded less oil and more gas. Specifically large amounts of reaction water and carbon dioxide were obtained in biomass pyrolysis resulting in formation of significantly deoxygenated liquid and solid products. Bio-oils can be distinguished by the solubility in conventional solvents. Kukersite shale oil and the benzene-soluble fractions of different bio-oils were characterized by similar group composition. Xiumin Jiang et al. (2009) were studied the pyrolysis experiments of the mixture fuels of Huadian oil shale and its shale char prepared at a retorting temperature of 520 0C were conducted using a thermo gravimetric analyzer. Oil shale samples were crushed and sieved to size range of 0-0.6 mm. 50 g of oil shale samples was placed inside a sealed aluminum crucible and heated from room temperature to the retorting temperature of 520 0C in a pure nitrogen atmosphere. In the heating process, steam, hydrocarbon gases, and shale oil evaporation were formed and conducted into a conical flask immerged in a low-temperature trough; after the retorting temperature was kept for a specified residence time of 20 min, the experiment ceased and the standard shale char was obtained. According to The ultimate and proximate analysis of Huadian oil shale and its shale char it was found that, as a result of char production, carbon content (C%) decreases about 10%, but fixed carbon content (FC%) increases almost 2.5 times. carbon element in organic matter is released with the release of volatile matter. As a result, the increase of the mass of fixed carbon and the great decrease of the mass of the sample make FC% of shale char almost 2.5 times as great as that of oil shale. The obtained shale char was mixed with oil shale samples adequately in certain proportions to five samples labeled with S1-S5 in turns with the increase of shale char fraction. Some previous investigations on copyrolysis for thermo

25 gravimetric studies showed the lack of interactions, which have low heating rates. Under very low heating rate conditions, the temperature ranges for pyrolysis of two components differ considerably, indicating that the two processes are well separated and, therefore, obvious synergies cannot be found. According to the thermo gravimetric analysis, the following conclusions can be obtained. The copyrolysis of oil shale and shale char was a complicated multistage process. The release of organic matter tended to decrease while the decomposition of inorganic constituents tended to increase slightly with increasing shale char fraction. At temperatures ranging from 250 to 600 0C, the reactivity of the samples tended to decrease with the increase of shale char fraction due to the lower volatile content and carbon condensation structures in shale char. For each sample, the reactivity increased first and then decreased as the temperature increased, which was attributed to the rearrangement of internal structure of sample particles and forming carbon condensation structures due to the decomposition and release of volatile matter. Between 600 and 800 0C, different ash shells formed inside sample particles of different mixing ratios after the previous pyrolysis, which made the decomposition of minerals more complicated. Sang Done Kim et al. (2010) investigated copyrolysis characteristics of sawdust and coal blend in TGA and a fixed bed reactor. Particle size of the sample was less than 1.0 mm in diameter. The blending weight ratio of sawdust/(sawdust + coal) was 0.4 in the TGA experiments. In a fixed bed reactor, six blending ratios (0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were employed. The fixed bed reactor was heated to a desired temperature under N2 flow. At a desired temperature, the reactor was purging by N2 to eliminate O2 for more than 10 min, thereafter sample (20 g) was fed into reactor under N2 flow of 0.2 m/s for 30 min. The concentrations of CO2, CO and CH4 were analyzed by infrared gas analyzer (and H2 concentration was determined by thermal conductivity gas analyzer. Thermal decomposition of coal appears to start at around 300 0C, and it continued over the whole temperature range at are latively low and constant rate. The maximum weight loss rate is found to be 0.015 min-1 at 460 0C and the total amount of volatiles from coal pyrolysis is 26 wt.% of the initial sample weight on the dry basis. On the other hand, thermal decomposition of sawdust starts at

26 around 200 0C and the maximum weight loss rate is 0.168 min-1 at 3700C. The total volatiles are produced approximately 80 wt.% of the initial sample weight on the db. Cellulose and lignin in the macromolecular structure of biomass are linked together with relatively weak ether bonds (RAOAR, bond energy of 380420 kJ/mol) that will broken at lower temperature. The backbone of coal structure is, however, made of dense polycyclic aromatic hydrocarbons and linked by alternate single and double bonds with extra resonance stability and is more resistant to thermal decomposition with high bond energy of 1000 kJ/mol. Consequently, more volatiles are produced from thermal decomposition of the blend than that from the individual thermal decomposition of coal and sawdust. From copyrolysis of sawdust and coal blend in TGA, the synergy effect to produce more volatiles from coal pyrolysis is pronounced above 400 0C and the catalytic effect of inorganic species in sawdust ash is observed at 700 0C. From the fixed bed reactor experiments, gas products increase up to 39% than that from the additive model by the synergy effect of reduction in char and tar yields. Calorific value of the product gas increases up to 68% with the increase of CO and CH4 yields and it is 35% higher than that of sawdust pyrolysis only.

Anup Kumar Sadhukhan (2008) were studied modelling of lignite coalbiomass such as waste-wood fines blends using thermogravimetric analysis. Lignite coal of Indian origin and waste-wood fines obtained from local saw mills were used in the study. Coal sample was crushed and sieved in the size range of 149210 lm, while the sawdust used was in the range of 354500 lm. Both coal and wood sample were dried in crucibles in an oven at a temperature of 100 0C for 2 h. The samples were then mixed with appropriate proportions to make the blends and then kept in packed condition in desiccators. Blended samples were prepared with coal and biomass ratios of 100:0, 50:50, 40:60, 10:90, and 0:100, respectively. A Perkin Elmer, Pyris Diamond TG/DTA apparatus was used to record the sample mass change with temperature over the course of pyrolysis reaction. The runs were performed with the prepared samples at a slow heating rate of 40 C/min. For all runs 5 mg sample were used with N2 flow of 0.1 L/min to ensure inert atmosphere. Intermolecular dehydration leads to intermediate char

27 formation along with the formation of primary volatiles and char by cracking, cross-linking and re-polymerization reactions. The char further undergoes cracking reaction at high temperature to form gases like CH4, C2H4, and HCN, collectively called secondary volatiles, leaving behind the residual char. A new generalized model was proposed for pyrolysis of biomass with parallel-series reaction scheme, which predicted well the pyrolysis behaviour of biomass over a wide range of temperature covering two thermal events for biomass and one for coal. The weighted average of TG data of pure coal and biomass agreed closely with the TG data of the blends signifying a lack of synergistic effects. Measured TG data indicated a linear relationship between final char yield and fraction of biomass in the blend. Li Zhang et al.(2006) were studied copyrolysis of biomass and coal in a free fall reactor under atmospheric pressure with nitrogen as balance gas. The coal sample selected was Dayan lignite, while the biomass used was legume straw. The operation temperature was over a range of 500700 0C, and the blending ratio of biomass in mixtures was varied between 0 and 100 wt.%. the char yields decrease and consequently the liquid yields increase compared with the calculated values, even the compositions of the gaseous products (e.g. H2, CH4, CO and CO2, etc.) from the blended samples are not in accordance with those of their parent fuels, suggesting that there exist synergetic effects between biomass and coal under the experimental conditions. The largest degree of synergetic effects on the products yields was observed under 600 0C and the blending ratio of 73 wt.% in the copyrolysis of LS/DY. Therefore, it can be concluded that both the higher blending ratio (around 70 wt.%) and the relatively lower temperature (around 600
0

C) are more in favor of obvious synergies during the copyrolysis of biomass and

coal in the free fall reactor.

J.M. Jones et al. (2005) investigated of devolatilisation characteristics of

coal and biomass blends. Three coals and pinewood were used in this study, together with cellulose, lignin, xylan and polywax model compounds. All samples were surface and sieved to 7590 mm size fractions and dried at 60 0C for 12 h prior to analysis. The coal:biomass blends were prepared in 25:75, 50:50 and 75:25 mixtures. PyrolysisGC was performed on each of the fuels, blends and model compounds using GCMSD gas chromatograph. Slow heating rate

28 pyrolysis tests were performed for some of the fuel mixtures. One hundred grams of fuel was pyrolyzed under nitrogen in a static reactor at 520 0C for 1 h at a heating rate of 10 0C min-1. The condensed tars were collected in an ice trap and analyzed by GCMS. The tars were subjected to open column chromatographic separation by gradient elution from an alumina packed column to produce three fractionsaliphatic (from a hexane eluent), aromatic (from a toluene eluent) and polar (from a THF eluent). Thermo gravimetric analysis (TGA) was performed for the individual fuels, the blends and the model compounds. Approximately, 15 mg of sample was heated in nitrogen at a rate of 25 0C min-1 to 900 0C. Nasir Ahmad et al were studied influence of particle grain size on the yield and composition of products from the pyrolysis of oil shales. Oil shales from two regions of Pakistan have been pyrolyzed in a fixed bed reactor in relation to particle grain size. Five size ranges were investigated, B 0.5, 0.51.0, 1.01.7, 1.72.8 and 6.010 mm. The gases were analyzed for their content of CO, CO2, H2, CH4 and other hydrocarbons up to C4. The derived pyrolysis oil was condensed in a series of cold traps and the total oil yield determined. In addition, experiments were carried out on a thermo gravimetric analyzer using the three smallest particle grain sizes under identical heating conditions to the fixed bed reactor. It was found that increasing the particle size up to the largest size used of 10 mm resulted in an increase in oil yield. The total gaseous yield was decreased, reflecting a decrease in concentration for H2, CO, CO2 and the majority of the hydrocarbon gases. The raw oil shale samples of various particle size ranges were analyzed to determine the elemental composition and surface area to determine their influence on the compositional changes in oil and gaseous yield with particle size range. H.B. Vuthaluru investigations into the thermal behavior during copyrolysis of coal, biomass materials and coal/ biomass blends prepared at different ratios (10:90, 20:80, 30:70 and 50:50) have been conducted using a thermo gravimetric analysis (TGA) apparatus. Three thermal events were identified during the pyrolysis. The first two were dominated by the biomass pyrolysis, while the third was linked to the coal pyrolysis, which occurred at much higher temperatures. No interactions were seen between the coal and biomass during copyrolysis. The pyrolytic characteristics of the blends followed those of the parent fuels in an additive manner.

29

3. MATERIALS AND METHODS 3.1 Materials 3.1.1 Feedstocks

Oil shale sample from the Gynk Himmetolu deposit and terebinth berries were grind in 1 mm particle size according to ASTM D2013 and used in experiments as received. The Gynk oil shale consists of more than 50% liptinite, 2050% huminite, and 020% inertinite maceral groups and is characterized by its high organic content. The origin of the organic matter is mainly algae and land plants and the kerogen of the Gynk Himmetoglu oil shale was classified as type I. Some properties of GOS and TB are given in Table 3.1 and 3.2, respectively.

3.1.2 Chemicals
The used chemicals, methanol, n-hexane and dichloromethane, Karl Fischer reagent, were purchased from Merck and used as received. Table 3.1 Oil shale properties Proximate Analysis; as GOS 7.8 34,5 65,5 13,97 54,86 6,61 1,59 3,12
*

Moisture volatile matter fixed carbon Ash Ultimate Analysis; wt %, db C H N S O

*

33,82

calculated from difference

30 Table 3.2 Biomass properties Type of Biomass Proximate Analysis; as 5.52 63.52 36.48 4.33 49.44 6.02 3.21 0.24
*

TB

Moisture volatile matter fixed carbon Ash Ultimate Analysis; wt %. db C H N S O Component Analysis; %wt. db Cellulose Hemicelllulose Lignin Extractives
*

41.09 14.41 30.86 40.2 14.53

calculated from difference

3.2 Methods 3.2.1 Pyrolysis

Pyrolysis experiments were carried out in vertical reactor. Pyrolysis reactor was of a fixed bed design and of stainless steel with 6 cm diameter and 21 cm high. In a typical run, 100 g of CWS or were placed into the reactor. The system was heated to the desired pyrolysis temperature at a heating rate of 5 C min-1, and hold at this temperature for 1 hour. The volatile products were swept by nitrogen gas (25 mL min-1) from reactor to collection flasks cooled with ice where the liquid products were condensed in the traps. Following the condensation distillate (in first two traps), the non-condensable volatiles (gases) were vented to the atmosphere. Experimental setup for pyrolysis is shown in Figure 3.1.

31 After pyrolysis, furnace was cooled to room temperature in a nitrogen gas stream. All traps were weighted before and after each run. Total liquid amount was determined by difference. The liquid and char yields were determined by weighting. The amount of gas was determined by difference. The liquid product consisted of two phases; water phase and oil phase. The aqueous phase in condensate was separated from the organic phase (bio-oil) by funnel.

1
2 3 4 5 6 7

Internal thermocouple Stainless steel reactor High temperature oven External thermocouple Product outlet Liquid products traps Nitrogen entrance

Figure 3.1 Fixed bed reactor

Figure 3.1 Fixed bed reactor

32

3.2.2 Analysis 3.2.2.1 Component analysis of the biomass samples

The analytical methods for extractives, hemicellulose, lignin and cellulose results are given Table 3.2 are as follows. i. Analysis of extractives The dried biomass sample (G0, g) is leached with mixture of toluene/ethanol (2:1 in volume) at a constant temperature for 3 h. After air-drying, the residue is dried in an oven at 105110 C to a constant weight. Then the residue is cooled to room temperature in a desiccators and then weighted (G1, g). The extractive wt. % is calculated as; W1 (wt. %, d) = (G0G1) G0 x 100

ii. Analysis of hemicellulose Put the residue G1 from the extractive analysis above in a flask and then add it into 150 ml NaOH solution (20 g/l). Boil the mixture for 3.5 h with recycled distilled water. Filter and wash the residue till no more Na+, and dry it to a constant weight. The residue is then cooled to room temperature in a desiccator and weighted (G2, g). The hemicellulose wt. % is calculated as;

W2 (wt. %, d) =

(G1G2) G0

x 100

33 iii. Analysis of lignin Put about 1 g of residue after extractives analysis as above into a weighed flask and dry it to a constant weight. The sample is then cooled in a desiccator and weighed (G3, g). Slowly pour 30 ml of sulphuric acid (72%) into the sample. Keep the mixture at 815 C for 24 h. Then transfer it into a flask and dilute it with 300 ml of distilled water. Boil the sample for 1 h with recycled distilled water. After cooling and filtration the residue is washed until there is no more sulfate ion in the filtrate (detected by 10% barium chloride solution). The residue is then dried to a constant weight, cooled to room temperature in a desiccator and weighted (G4, g). The hemicellulose wt. % is calculated as; iv. Analysis of cellulose; The cellulose wt. % is calculated as;

W3 (wt. %, d) =

G4(1W1) G3

x 100

W4 (wt. %, d) = 100-(W1+ W2 +W3)

3.2.2.2 Fixed carbon and volatile matter determination

Fixed carbon and volatile matter were determined in the 1 g product are weighed on the sensible scale. Then it's placed into quartz crucible with cover which was adjusted constant weight before. It is placed into pre-heated oven (850
0

C) then kept for 3 min., then cooled down in the desiccator. After it's down to

room temperature, it was weighted.

34 Fixed carbon and volatile matter are calculated with the formulas below :

% Fixed Carbon =

m m *100 M
2 1

% Volatile matter = 100 ( % Fixed Carbon )

3.2.2.3 Determination of moisture

The samples were determined in terms of moisture, is placed in to Sartorious Therma Control device ,which works infrared rays , as to be 1 g. The moisture in the sample is then calculated as the percentage.

3.2.2.4 Elemental analysis

C, H, N, and S contents of biomass and oil shale, bio-oil, shale-oil and chars were determined by using an elemental analyzer LECO CHNS 932 according to ASTM D5291-96. Oxygen amount was calculated from difference.

3.2.2.5 FT-IR analysis

Fourier transform infrared (FTIR) spectra of pyrolysis oils were recorded using a spectrophotometer (Spectrum 100, Perkin Elmer) in order to qualitatively identify the chemical functionality of oils. Infrared spectra were recorded of the samples placed between KBr plates.

3.2.2.6 1H NMR analysis

1

H NMR Spectra of oils were recorded with a Varian AS-400 using CHCl3

solvent.

35

3.2.2.7Water determination
Water contents of bio-oil and oil phase of shale were determined by KarlFischer titration.

3.2.2.8 Gas product analyses

Pyrolysis gases collected in Tedlar bags were analyzed by gas chromatography using a HP model 5890 series II with a thermal conductivity detector and flame ionization detector. A stainless steel packed column(6.0 m 1/8 in. Propac Q, 2.0 m 1/8 in. 5A molecular sieve, serially connected to each other) was used. The separation of CO2, C1, C2, C3 and C4 gases was achieved by the Propac Q column and the separation of H2, N2 and CO was carried out with the MS 5A column.

3.2.2.9 Thermo gravimetric analysis

Thermo gravimetric analysis of samples was performed in a thermo

gravimetric analyzer (Perkin Elmer Diamond TG/DTA) under N2 atmosphere. The flow rate of purge gas (pure N2, 99.99%) was kept at 200 mL min-1. The sample was heated from the ambient temperature up to 900 C with heating rates of 10 C min-1. Both the thermo gravimetric (TG) and differential thermo gravimetric (DTG) data were used to differentiate the pyrolysis behavior of waste samples at different conditions. In thermo gravimetric analysis, weight loss of sludge samples was calculated according to the below equation. Weight loss, wt. % = (mi ma) x 100 mi

Where mi is the initial mass (g), ma is actual mass (g) of sample.

36

4. RESULTS and DISCUSSIONS 4.1 Oil shale 4.1.1 Thermogravimetric Result

Thermogravimetric analysis of the Goynuk oil shale revealed that major thermal decomposition occurred around 350520 C as shown in Figure 4.1 and 4.2. From pyrolytic differential thermogravimetric (DTG) curves, initial weight loss corresponds to moisture removal, followed by a second degradation event around 330525 C, where the evolution of light volatile compounds occurs from the degradation of kerogen. This is consistent with other published findings (Aboulkasa et al., 2008. ; Yagmur, S. et al., 2006.). At 520 C the yield of residue was about 45 % under these test conditions. TG-DTG results showed that organic matter in oil shale and polymer was completely decomposed at the temperature of below 600 C.

100 90 80 70 60 50 40 30 20 10 0 0 200 400 600 TemperatureC 800 1000 1200

Weight

Figure 4.1 TG curve of Oil Shale

37

0 0,5 0 200 400 600 800 1000 1200

DerivativeWeight%

1 1,5 2 2,5 3 3,5 4 4,5 TemperatureC

Figure 4.2 DTG curve of Oil Shale

4.1.2 Pyrolysis Results

Oil shale was pyrolyzed at three different temperature (500, 600 and 700 C) in a fixed-bed reactor. The effect of temperature on pyrolysis yields are given in Fig 4.3. As seen from fig 4.3 oil shale product distribution did not significantly change as pyrolysis temperature between 500-700 C. There was a little increase in gas and liquid products and decrease in char product yields as the temperature raised from 500 to 700 C.

100 90 80 70 60 50 40 30 20 10 0 500 600 TemperatureC 700

Yields(wt%)

Liquid Char Gas

Figure 4.3 Product yields (wt. %) from pyrolysis of Oil shale

38 Although pyrolysis temperature had no considerable effect on product distribution, liquid composition was changed depending on the pyrolysis temperature. As seen Figure 4.4 tar amount in liquid product considerable decreased (from 87.6 wt% to 71.6 wt %) by increasing the temperature from 500 to 600 C. This shows that tar products decomposed to water soluble compounds and water. As seen Figure4.4, the highest yield of tar was obtained at the pyrolysis temperature of 500 C.

100% 90% 80% 70%

Yields(wt%)

60% 50% 40% 30% 20% 10% 0% 500 600 TempreratureC 700 Tar AqueousPhase

Figure 4.4 Composition of liquids obtained from pyrolysis of Oil shale

4.2 Biomass

4.2.1 Thermogravimetric Results

To understand the thermal conversion behavior of lignocellulosic biomasses under the inert atmosphere, experiment was systematically carried out by means of TGA.

39

100 90 80 70 60 50 40 30 20 10 0 0 200 400 600 TemperatureC 800 1000 1200

Weight%

Figure 4.5 TG curve of Terebinth berry

0 0 1 200 400 600 800 1000 1200

DerivativeWeight%

2 3 4 5 6 TemperatureC

Figure 4.6 DTG curve of Terebinth berry

40 The weight loss (TG curve) and derivative weight loss (DTG curve) for terebinth berry are exhibited in Figure 4.5 and 4.6, respectively. Generally, the occurrence of three weight-loss steps has been reported in literature on the pyrolysis of different lignocellulosic materials (Sentorun-Shalaby et al., 2006). The first weight-loss step is associated with the decomposition of hemicellulose, and the second with cellulose decomposition. On the other hand, lignin degradation occurs over a broad temperature interval (300480 C or higher). It would be mainly responsible for char formation of biomass. The main decomposition of the biomass occurred in the temperature range between 200 and 500 C. The sharp peak at 290 C is attributed to hemicellulose and a second sharp peak at 360 C is belonged to the cellulose. A clear DTG peak of lignin is not observed since lignin decomposes between 200 to 500 C. The mass of residue was ~32 wt %. at the temperature of 500 C.

4.2.2 Pyrolysis Results

100 90 80 70 60 50 40 30 20 10 0 400 450 500 TemperatureC 550 600

Yields(wt%)

Liquid Char Gas

Figure 4.7 Product yields (wt. %) from pyrolysis of biomass

Biomass was pyrolyzed at three different temperatures (400, 500 and 600 C). As seen from figure 4.7 biomass product distribution did not significantly

41 change as pyrolysis temperature between 400-600 C. With increasing temperature, there was a little increase in gas and decrease in char product yields as temperature raised from 400 to 600 C. However, the liquid yield (about 49 wt%) was not changed with the temperature. Similarly, Cao et al who studied the slow pyrolysis of waste corncob, observed a faster changing in products yields between the temperatures 350 and 400 C and a slower changing between the temperatures of 400 600 C whereas the yield of the liquid was nearly constant (Cao Q. et al., 2004.). But, in many literatures related to slow pyrolysis of lignocellulosic materials (Ates, F. et al, 2009.; Gonzalez, J.F.et al., 2005) oil yield reached a maximum value at 500-550 C, and above these temperatures oil yields decreased while gas yield increased. Meanwhile, the char yield continuously decreased with increasing temperature. The differences in the results obtained from present study and previous studies may be due to the difference in the biomass species. The yields of char and gas were approximately 25-30 wt% and 20-25 wt% between the temperatures 400 and 600 C.

100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 400 500 TemperatureC 600

Yields(%wt)

OilPhase AqueousPhase

Figure. 4.8 Composition of liquid obtained from pyrolysis of biomass

42 Although temperature had no effect on liquid yield, oil phase slightly increase (from 43 wt% to 48 wt %) and aqueous phase decreased (from 56 wt% to 52 wt %) as temperature raised from 400 to 500 C. The increase in oil amount may be due to the degradation of lignin in biomass at high temperature.

4.3 Copyrolysis of Oil shale and Terebinth berry

As known, pyrolysis yields depend on many parameters such as temperature, partical size, heating rate and type of feedstock. Temperature plays a major role in biomass pyrolysis. In this study, the copyrolysis of biomass and oil shale was carried out at 500 0C. The copyrolysis temperature was selected according to the result of TG analysis and the results obtained from pyrolysis of each component alone. Table 4.1 shows the char, oil-tar, aqueous fraction and gas yields from the copyrolysis of biomass/oil shale. For comparison purpose, the product yield from pyrolysis of terebinth berry and oil shale alone were also presented in the same table. It is seen that the experimental yields from the copyrolysis are not different from the theoretical ones calculated based on the yields from the pyrolysis of the individual components of the mixtures. This confirmed that there were no synergistic effects between the oil shale and biomass and they had undergone pyrolysis independent of each other. Moghtaderi et al. (2004) and Vuthaluru (2004) observed similar phenomena during the study of pyrolysis of blends of Radiata pine sawdust and Drayton coal and blends of wood waste and Australian coal, respectively. With addition of biomass into oil shale, there was an increase in liquid and decrease in char from pyrolysis of oil shale.

43 Table 4.1 Product distributions from the oil shale and copyrolysis of oil shale and biomass GOS:TB 1:0 3:1 Exp Gaseous* Aqueous phase Oil-Tar Char 29.04 41.74 28.87 40.47 29.03 37.96 24.93 28.20 35.76 34.18 23.26 32.5 26.55 24.07 30.40 26.63 25.10 4.12 20.71 9.95 Teo 24.70 8.31 1:1 Exp Teo 1:3 Exp 26.84 17.40 Teo 23.87 23.46 19.18 25.84 0:1

24.74 24.28 14.57 13.33

*Calculated from mass balance

4.3.1 Composition of Oil phases

The oil derived from lignocellulosic materials has a large number of oxygen containing reactive functional groups which are fragments of cellulose, hemicellulose, and lignin polymers. Because of this, it does not exhibit thermal stability and cannot be effectively fractionated by conventional techniques. It is well known that oils consist of mainly water, carboxylic acids, carbohydrates and lignin-derived substances. On the other hand, shale tar is complex mixtures consisting of organic compounds from wide variety of chemical groups. To characterize the tar / oil, oil phase from pyrolysis were separated into two fractions; hexane soluble and hexane insoluble. In the case of tar from oil sale pyrolysis, hexane solubles and hexane insolubles are called as oil and asphaltenes, respectively. In the case of oil from biomass pyrolysis, hexane solubles are called as extractives which mainly contain hydrocarbons. Hexane insolubles part of bio oil consisted of low molecular weight lignin and high molecular weight lignin compounds.

44

In this study, the pyrolysis oil and tar were firstly extracted with hexane separated as hexane soluble and hexane insoluble. And hexane insolubles were dissolved totally with CH2Cl2. This shows that the compounds derived from biomass in hexane insoluble were low molecular weight lignin compounds. It should be noted that the bio oil from terebinth berry consisted of mainly extractive compounds. However, most bio oil contains extractives less than 30 %. In copyrolysis experiments, no synergic effect observed in terms of oil and tar composition. As expected, the amount of extractives decreased with the increasing amount of terebinth berry in blend.

Table 4.2 Composition of tar and oil phases

Sample(GOS:TB) Hexane Soluble CH2Cl2Solubles

1:0 85.8 14.2

3:1 82.14 17.86

1:1 74.83 25.17

1:3 75.75 24.25

0:1 71.04 28.96

4.3.2 Fourier Transform Infrared Spectroscopy Results

Functional group compositional analysis was determined by FTIR spectrometry, and results are shown in Figure 4.9. FTIR-spectra given in fig 4.9 emphasize rather similarity than specificity of the main functional groups in the corresponding fractions of shale tar and bio-oil and their blends. The O-H stretching vibrations between 3200 and 3400 cm-1 indicate the presence of phenols and alcohols (H. Luik et al., 2007). The strong signals in the range of 28502920 cm-1, corresponding to aliphatic compounds, are present in all samples. In addition, the infrared spectra of the tars and oils presents some bands corresponding to CH2, CH3 bending (1375-1460 cm-1), alkenyl groups (C=C stretching, 16061640 cm-1; CH=CH (trans) 960970 cm-1; CH=CH (cis) 675730 cm-1) and aromatic groups (C=C stretching, 14501464 cm-1). Except 1:1 copyrolysis spectra of tars shows the presence of cm-1) FTIR. CH2, CH3 bending (1260

45

Figure 4.9 FTIR spectrums of pyrolysis oils and tar

46

4.3.3 H-NMR Results

The 1H NMR spectra of the bio-oil, shale tar and their blends and hydrogen distributions are given in Table 4.3, respectively. Results of the 1H NMR analysis show that the biomass mainly contain aliphatic protons at carbon atoms bonded to other aliphatic carbon atoms. 1H NMR analysis for the tar also contains aliphatic protons. Although aliphatic adjacent to oxygen is absence for oil shale and until ratio of 1:3 copyrolysis oil, exist in ratio of 1:3 and only berry. 1H NMR results show that oil and tar consisted of mainly paraffinic. The oils and tar obtained from pyrolysis of oil shale and copyrolysis of some blends (3:1 and 1:1) contained no aliphatic adjacent to oxygen. This may show that the oxygen compounds in these oil and tar are mainly aromatic.

Table 4.3 Assignments of the bands in the 1H-NMR spectra of bio-oil and tar samples GOS:TB Range (ppm) Aromatic Alkene Aliphatic adjacent to oxygen Aliphatic adjacent to aromatic alkene group Other aliphatic (bonded to aliphatic only ) 0.4-1.8 66 61 63 50 59 1.8-3.3 17 21 22 25 21 6.3-9.3 4.5-6.3 3.3-4.5 10 7 11 7 12 3 15 5 5 11 5 4 1:0 3:1 1:1 1:3 0:1

47

Figure 4.10 1H NMR spectra of pyrolysis oil and tar

48

4.3.4 Fuel characterization of oil and tar

Pyrolysis oils were brown in color with irritable odor. The main fuel characteristics of oil and tar are given in Table 4.4. Water levels of oils are shown irregularity. The oils from pyrolysis of individual feed stocks were contained less amount water than that from copyrolysis. One cannot say any reason. The tars obtained from oil shale have higher calorific value than the oils obtained from biomass. In the case of copyrolysis oil and tar, the addition of biomass decreased the calorie of oil obtained from oil shale. Moreover, all oils and tars can be used as fuels for combustion systems in industry. But it is clear that they should be upgraded to receive an improved oil composition for the direct utilization as a transporting fuel.

Table 4.4 Some properties of Pyrolysis Oil and tar

GOS:TB C H N S O* H/C Water, %

1:0 79.59 9.47 1.11 1.91 7.92 0.12 3.98

3:1 79.96 8.94 1.63 1.75 7.72 0.11 12.19 41.62

1:1 77.37 8.51 1.77 1.25 11.10 0.11 2.15 38.86

1:3 76.87 8.92 2.12 0.65 11.44 0.11 8.81 39.23

0:1 73.42 8.86 2.25 0.16 15.31 0.12 3.95 36.54

GCV, kcal 42.24 kg1

*

calculated from difference

49 The properties of oil and tar are given in Table. Gross Calorific value was calculated according to following equation (Friedl, 2005) GCV (MJ kg-1) = (3.55 C2 - 232 C - 2230 H + 51.2 C * H + 131 N + 20600) * 10-3 As it can be seen in Table 4.4, oil and tar contain less amounts of oxygen content than that of the original feed stocks. The significant decrease in oxygen content of the oil and tar compared to the original feedstock is important, because the high oxygen content is not attractive for the production of transport fuels. A further comparison of H/C ratios with conventional fuels indicates that H/C ratios of the oil and tar obtained in this study lie between those of light and heavy petroleum products.

4.3.5 Composition of Aqueous Phase

Analysis of the aqueous phases showed that aqueous phases consisted of mainly water (81-88 %). The other would be water soluble organic compounds such as low molecular weight carbonyl compounds, phenols, alcohols, carboxylic acids etc. To determine the amount of these compounds, aqueous phase was extracted CH2Cl2. The amounts of CH2Cl2 solubles are given in Table 4.5. It is seen that their amounts are not so much. But, most of CH2Cl2 soluble compounds might be evaporated during CH2Cl2 evaporation. Table 4.5 Composition of aqueous phase

GOS:TB Water Content CH2Cl2 Solubles

1:0 83.33 2.36

3:1 89.35 0.63

1:1 88.34 1.32

1:3 88.08 1.40

0:1 81.36 3.43

50

4.3.6 Fuel characteristic of chars

In principle, the char obtained from pyrolysis of materials can be used as fuel, alone or mixed with other fuels. It can be also used as a cheap adsorbent. The characteristic of chars obtained from pyrolysis of oil shale and biomass are mainly depended on the composition of the biomass and oil shale. Some properties of chars from biomass, oil shale and blend (1:1) are given in Table 4.6. GCV were calculated according to following equation (Yanik et al, 2007). H0 = 0,3491C + 1,1783H + 0,10005S - 0,1034O - 0,0151N - 0,0211ASH As expected the char obtained from biomass is appropriate for household briquette production due to the low sulphur and ash content. They can be also burned in a steam boiler with an appropriate emission control. The GCV of char from oil shale was increased while ash content decreased with the addition of biomass. But, both chars from oil shale and blend contain still high sulphur amount. Table 4.6 Properties of chars GOS:TB C H N S O* Ash GCV, kcal kg1 1:0 57.81 2.60 1.96 1.99 35.64 29 19.11 1:1 58.08 2.42 2.24 1.07 36.19 22.65 18.98 0:1 77.2 2.68 2.58 0.04 22.5 11.23 27.51

calculated from difference

51

4.3.7 Composition of gas products

The compositions of gases obtained from pyrolysis of terebinth berry, oil shale and their mixtures are given in Fig 4.11. The gases composed of mainly H2. The content of CO2 is considerable also. The content of C1C5 hydrocarbons, amounting to 40% in shale-derived gas, was very low in bio-gas. By addition of biomass to oil shale,CO2 and CO increased, while H2 decreased. Also there was no difference in alkenes coming from oil shale and biomass gases.

100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 01:00 03:01 01:01 01:03 00:01

H2 CO CO2 1penten 2methyl2butene t2penten 1,3butadiene npentane c2butene iButylene 1butene t2butene nbutane ibutane cyclopropane Propane ethylene ethane methane

Figure 4.11 Composition of gas products

52

5. CONCLUSION

In this study, conversion of biomass and oil shale into the useful production were investigated. To predict thermal behavior of biomass and shale , thermal degradation both of them were investigated by TG/DTG. DTG curve for oil shale exhibits two weight-loss steps between 350-520 C. The shale, devolatilization took place a wide temperature range between 350-520 C with two sharp peaks. The maximum weight loss rate was observed at 520 C. The mass of residue was ~45 wt %. In the case of biomass, DTG curve exhibited two weight loss steps between 200-500 C; first step took place with a maximum weight loss rate at 290 C and second step at 360 C. The mass of residue was ~32 wt at 500 oC. In the first experiments, pyrolysis of oil shale and terebinth berry were investigated by fixed bed reactor. Product distribution from pyrolysis of oil shale did not significantly change as increasing the pyrolysis temperature between 500700 C. There was a little increase in gas and liquid products and decrease in char product yields as temperature raised from 500 to 700 C . The oil yields were around 87 wt% over the range of pyrolysis temperatures. Similarly, temperature has no effect on product distribution from terebinth berry pyrolysis. Liquid yields were approximately 49 wt% in case of terebinth berry. Copyrolysis experiments were carried out with different ratio of oil shale to biomass (1:3, 1:1, 3:1) at 500 C. The experimental yields from the copyrolysis are not different from the theoretical ones calculated based on the yields from the pyrolysis of the individual component of the mixtures. This confirmed that there were no synergistic effects between the oil shale and biomass and they had undergone pyrolysis independent of each other. Functional group compositional analysis of oil/tar was determined by FTIR and NMR spectrometry. Results of the 1H NMR analysis show that the biomass mainly contain aliphatic protons at carbon atoms bonded to other aliphatic carbon atoms. FTIR results also confirm that 1H NMR results. The tars obtained from oil shale have higher calorific value than the oils obtained from biomass. In the case of copyrolysis, the addition of biomass into oil shale decreased the calorie of tar obtained from oil shale. Moreover, all tar/oil can be used as fuels for combustion systems in industry. But it is clear that they should be upgraded to receive an improved oil composition for the direct utilization as a transporting fuel.

53 As expected the char obtained from biomass is appropriate for household briquette production due to the low sulphur and ash content. And copyrolysis of oil shale with biomass give the produce the char having better quality than pyrolysis of oil shale alone.

54

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