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A SYSTEMS ANALYSIS OF PYROLYSIS SYSTEMATICS TO SERVE ENERGY REQUIREMENTS

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A SYSTEMS ANALYSIS OF PYROLYSIS SYSTEMATICS TO SERVE ENERGY REQUIREMENTS
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2008

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Biomass ( jstor )
Coal ( jstor )
Combustion ( jstor )
Energy ( jstor )
Energy technology ( jstor )
Environmental technology ( jstor )
Gasification ( jstor )
Liquids ( jstor )
Pyrolysis ( jstor )
Raw materials ( jstor )

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University of Florida
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A SYSTEMS ANALYSIS OF PYROLYSIS SYSTEMATICS TO SERVE ENERGY REQUIREMENTS By SAI SANKAR MUDULODU A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2002

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Dedicated to My Parents and Sister

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ACKNOWLEDGMENTS I thank the Almighty for all that he has bestowed on me. I would like to express my deepest and sincere gratitude to my advisor, Dr. Alex E. S. Green, for his encouraging support and continuous guidance during my graduate studies, which otherwise would have made my master’s degree an impossible task. I am deeply grateful to Dr. Green for his belief in me and giving me financial support without which I would have great difficulty continuing my studies. Also, I take this opportunity to extend my sincere thanks to Dr. Jack Elzinga and Dr. Joseph Geunes for their support and advice from time to time. I thank my parents and sister for their love, support and constant encouragement. Also, I would like to convey my thanks to my friends for all their ideas and suggestions. I can never thank enough all the sources that directly or indirectly added value to my research efforts and favored a successful completion of this thesis. iii

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iv TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iii LIST OF TABLES............................................................................................................vii LIST OF FIGURES.........................................................................................................viii ABSTRACT ...................................................................................................................... .x CHAPTER 1 INTRODUCTION...........................................................................................................1 USA As a System............................................................................................................1 What Is Biomass?...........................................................................................................3 Renewable Energy Paradigm..........................................................................................3 The Advantages of Using Biomass..........................................................................5 Need for an Omnivorous Feedstock Converter........................................................5 What Are The Basics To Biomass Conversion?......................................................8 What is gasification?..........................................................................................8 What is pyrolysis?..............................................................................................9 What is liquifaction?..........................................................................................9 Gasificationthe trends in gasification ............................................................10 What Is Our Model?...............................................................................................11 Most Prominent Gasification Technology In The USA The IGCC..................... 12 Applications of Gasification..................................................................................12 2 THE SEMI-EMPIRICAL MODEL FOR PYROLYSIS................................................14 The ICAAS-CCTL Program.........................................................................................14 Reason For The Difficulty In Modeling.......................................................................15 Apparatus And Experimental Procedure......................................................................16 Description of Gasifi cation Test Rig......................................................................16 Experimental Procedure.........................................................................................17 Rice Husk Pyrolysis Experiments That Led To The Final Model................................18 Discussion and Conclusion...........................................................................................21 Introduction To The ModelingA Walk Through........................................................22 CCTL Laboratory Pyrolyzers Results....................................................................23 The Wt% Representation.......................................................................................26 Yield Sytematics....................................................................................................27

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v Dulongs Formula....................................................................................................29 Liquid Yields..........................................................................................................29 SEM Feedstock-Product Correlations....................................................................30 Organic Products....................................................................................................31 Parameter Adjustments..........................................................................................32 An Objective of Coal Cl assification Was Met....................................................... 33 A Few Insights From Table 2-3 ............................................................................. 34 3 CO-UTILIZATION AND APPLICATIONS................................................................44 What Is Co-utilization?.................................................................................................44 Some of The Applications of Co-utilization..........................................................44 The Co-firing alternative..................................................................................44 The Co-gasification alternative........................................................................45 Biomass alternative..........................................................................................45 Phytoremediation.............................................................................................46 Special applications to the co-utilization.........................................................47 Examples of Some Co-utilization applications......................................................48 Why the kinetics of the co-gasif ication process are important........................50 Demonstration of Co-gasification of Lignite Coal With The MSW................51 Gasification Technologies In The USA........................................................................51 Some Accomplishments In The A pplication Of Gasification................................53 Gasification By Technology..................................................................................55 4 CO-UTILIZATION IN TH E CONTEXT OF INDIA...................................................57 Status and Achievement in Specific Sectors – Biomass Power............................. 59 Energy From Waste.........................................................................................61 Stand-alone/Off-grid Applications...................................................................63 Cleaner Coal Technologies For India ................................................................... 63 India's Clean Coal Technology Progress...............................................................64 Factors Favoring The Renewable Energy Paradigm..............................................65 Foreign Investment:.........................................................................................65 National RE Policy .........................................................................................65 Co-utilization in the context of India.....................................................................66 5 RECOMMENDATIONS FOR FUTURE......................................................................68 6 CONCLUSIONS............................................................................................................69 APPENDIX PREVIOUSLY UNDOCUMENTED WORK ON VARIOUS CO-UTILIZATION METHODS ..............................................................70 Compendium of Co-utilizati on Work Around The World.....................................70 Co-pyrolysis, Co-gasification: Coal(Helper) –Biomass/MSW (helpee) European Union......................................................................................................................70 Co-pyrolysis,Co-gasificatio n: Coal (Helper) –Bioma ss/MSW (helpee) USA.......76

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vi References From ICAASCCTL’s Work (USA)..................................................76 Miscellaneous Compounds Account ed For In The Modeling...............................79 Search For A q That Depends On Temperature.....................................................80 LIST OF REFERENCES...................................................................................................91 BIOGRAPHICAL SKETCH.............................................................................................95

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LIST OF TABLES Table page 1-1 Biomass and other Opportunity Fuels .........................................................................4 2-1 The main parameters of rice hull logistics .................................................................21 2-2 Proximate Analysis and Ultimate Analysis of a few compounds .............................25 2-3 Properties and trends through feedstocks at different oxygen levels. .......................36 2-4 Shows the various functional groups and their representation ..................................43 2-5 Shows the parameters for the basic gases...................................................................43 A-1 The parameters for the equations of q.......................................................................80 A-2 The parameters and predictions at 950 Deg. C..........................................................81 A-3 The data set used in our discovery of the [H] wt% leveling off at 6%......................85 vii

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LIST OF FIGURES Figure page 1-1 Total Annual USA energy consumption in quads at the millennium ..........................2 1-2 Omnivorous Feedstock Converter.................................................................................6 2-1 The Experimental set-up used for the Pyrolysis of Rice Hulls....................................18 2-2 Experimental Rice hull product yields vs. temperature and analytical fits.................21 2-3 Bagasse yields for 5 gram samples vs. time at three temperatures..............................25 2-4 Weight percentages of hydrogen [H] vs [O]...............................................................36 2-5 Total volatile weight percentages vs [O] for 185 DASNF carbonaceous materials from proximate analysis.............................................................................................37 2-6 Higher heating values (HHV) of 185 carbonaceous materials (corrected to DASNF) vs. [O]. The smooth curve represents HHV= A([C]/3+[H]-[O]/8)..............................37 2-7 Yields for 5 gram samples of various opportunity fuels. VT is taken as limiting yields (intersection with right vertical scale).............................................................38 2-8 Yields of the basic gases and the sum of the others at 950 C, the proximate volatiles.38 2-9 The basic gases, the sum of the others and the Total voaltiles at 300, 600, 900 and 1200 Deg. C................................................................................................................39 2-10 The sum of the functional groups and the sum of all the series all at 300, 600, 900 and 1200 Deg. C......................................................................................................40 2-11 Members of the Paraffin series,Olefin series, Alkanol series and Ether series.........41 2-12 Weight percentages of hydrogen [H] for 185 DASNF carbonaceous materials vs [O]. Given are Rank labels are given on bottom scale and [O] values.....................42 3-1 The basic gasification process for various applications..............................................53 3-2 The Tampa Electric Polk Station Project....................................................................54 3-3 The Wabash River Coal Gasification Repowering Project.........................................54 viii

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3-4 The Air Products Liquid Phase Methanol Project in Kingsport..................................55 3-5 The Commercial Gasification technologies and their spread......................................55 4-1 The estimated biomass power potential in Megawatt.................................................58 4-2 Estimates of technical potential for renewable energy technologies...........................58 4-3 The particular technologies that were used to get the energy utilized.........................59 4-4 The renewable energy power achievement sector wise...............................................60 4-5 Potential for bagasse based cogeneration in some Indian states.................................61 4-6 Status of projects commissioned and under implementation......................................61 ix

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Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science A SYSTEMS ANALYSIS OF PYROLYSIS SYSTEMATICS TO SERVE ENERGY REQUIREMENTS By Sai Sankar Mudulodu August 2002 Chair: Dr. D. Jack Elzinga Cochair: Dr. Alex E.S. Green Major Department: Industrial and Systems Engineering Energy has always been a focus, so has energy management and, specifically, reducing the USA’s (and other nations) excessive dependence upon foreign oil. During the past thirty-five years, considerable efforts have been invested in fundamental research on the thermo-chemical conversion of alternative solid fuels and on its areas of application. Today, the attempt is being made to develop processes for upgrading those fuels to become easily accessible energy sources of high efficiency. Our long recognized need to reduce our dependence on imported oil has been realized and given more importance. In the near and middle term we must clearly develop environmentally acceptable alternatives to oil using our available domestic fuels. Developing the technology and infrastructure for co-utilizing, co-firing, co-gasifying fresh and fossil biomasses is quite an ordeal as the knowledge gained in this field is still in primitive stages. The current lack of understanding of the fundamental pyrolysis processes of x

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biomass or coal combustion or gasification/liquefaction is a major impediment to the design of optimum thermo-chemical systems. My thesis focuses on dealing with the modeling and development of the systematics of pyrolysis that would be useful to a large number of energy applications. It states the benefits in the context of nationally co-utilizing/co-pyrolysing biomass and coals through pyrolysis. The ultimate goal has been to develop a realistic analytical model that can represent all the CHO compounds observed among pyrolysis products for all carbonaceous feedstock. Apart from a comprehensive review of the pyrolysis/gasification methodologies and applications, the presentation covers certain important issues concerning the various means of utilizing the semi empirical model. In addition, results of the model reported may be taken as approximately correct; specific topics that directly affect the model are discussed. Specifically, at the end the thesis stands to point out and expand on applications not already considered, provide a good bibliography on co-utilization, particularly via gasification and liquefaction, expand on systems that would be helped by co-utilization and document matters not already documented. xi

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CHAPTER 1 INTRODUCTION If one of the duties of an industrial engineer is to make a more efficient use of resources with a properly modeled system in place, I look into the whole of the USA as a system, whose resources need to be conserved and utilized efficiently. USA As a System As a result of the "Oil Crises" of 1973 and 1979 the Clean Combustion Technology Laboratory (CCTL) was formed to search for ecofriendly alternatives to oil. CCTL-ICAAS (Interdisciplinary Center for Aeronomy and other Atmospheric Sciences) undertook a state supported study directed toward reducing Florida utilities use of oil while minimizing the environmental impacts of increased coal use. It led to Dr. Green’s 1980 book Coal Burning Issues [1]. It also led to his appointment in 1986 to the National Coal Council, possibly as its first academic. The 1981 book An Alternative to Oil, Burning Coal with Natural Gas [2] began his search for ecofriendly ways of co-utilizing domestic fuels and his sojourn in the environmental-energy crossfire. Figure 1-1 shows a diagram of annual energy consumption of the USA at the millennium extrapolated from Energy Information Agency documents. The numbers are in quadrillion (a million billion or 10 15 ) BTU (quads). We consumed 95 quads and with the 5 exported quads the total in round numbers was 100 quads. We would very soon exhaust our domestic oil at present consumption rates if we relied entirely on it for transportation. Our natural gas would follow later but how much later depends upon who 1

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2 makes the estimate. Our coal reserves will last two or three centuries. Nuclear and renewables are smaller energy sources at this time. Renewables have the greatest public appeal since they appear to have minimal environmental impact. Dr. Green’s conclusion is that biomass is the renewable with the greatest near term prospect for alleviating some of our national energy and environmental problems. USA Energy Consumption Natural Gas 21.5 Renewable 7.5 Nuclear 7.5 Coal 21.5 Domestic Oil 14 Imported Oil 23at the Millennium 01234 Renewables Biomass 3.5 Hydro Electric 3.6 Geothermal 0.3 Solar 0.07 Wind 0.03 Figure 1-1. (Top) Total Annual USA energy consumption in quads at the millennium (Bottom) Renewables[3].

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3 What Is Biomass? Biomass includes all waterand land-based vegetation and trees, or virgin biomass, and all waste biomass such as municipal solid waste (MSW), municipal biosolids (sewage) and animal wastes (manures), forestry and agricultural residues, and certain types of industrial wastes. Unlike fossil fuels, biomass is renewable in the sense that only a short period of time is needed to replace what is used as an energy resource It isn't surprising to note that the Global Energy potential of virgin biomass is so large that its about 100 times the world's total annual energy consumption [4]. It is certainly a lot of Biomass Carbon we are looking at to utilize as the energy resource here. Renewable Energy Paradigm The table shown next page as well as parts of the text that follow are obtained from the paper by Dr. Alex Green in a report published [5] lists the potential sources that should be considered in the USA. Types of biomass and other opportunity fuels that should be considered in the United States. Energy crops (No.1) and agricultural residues (No.2) probably have the largest potential for biomass to energy while potentially providing agricultural benefits. Because biomass is more oxygenated than coal it is more easily converted to liquids and gases. These forms of biomass have been considered since the 1973 oil crisis but interest seems to increase or wane depending upon the price of oil set by the OPEC cartel or socio-political factors. Forestry residue and forest under story (No.3) are usually handled by "controlled burning" that leads to high levels of soot pollution and sometimes-disastrous losses of property. Numbers 4-8 are mainly sent to landfills usually leading to adverse environmental impacts that are larger than if the waste were used for energy with ecofriendly technologies. The wood energy in No. 9 is substantial but the technology

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4 used must include an effective way of capturing the toxics. The same can be said for the energy opportunities and potential environmental problems with Nos.10-12. Here reducing environmental impacts would probably represent the greater public service. In the Everglade restoration effort No. 13, Meleluca, an invasive woody exotic, would be a big cost item if treated only as a re-mediation problem. However, if treated as an opportunity fuel its disposal could proceed at a much faster pace and with some cost recovery. On the other hand the energy opportunities in Nos. 14 and 15 are very substantial and conversion to liquid fuels might well be the optimum technology. Category 16, coal fines is an example of a non-plant matter type of opportunity. Ecofriendly fuel blending with natural gas, good coal or dry waste wood, if available nearby, could help extract useful energy from this marginal coal. Table 1-1. Biomass and other Opportunity Fuels [3] 1. Energy crops on underutilized or marginal lands. 2. Agricultural residues 3. Forestry residues and forest understory. 4. Infested trees, pine beetles, citrus canker, oak spore 5. Cellulosic components of municipal solid waste. 6. Urban yard waste, 7. Construction and deconstruction debris. 8. Food processing waste. 9. CCA and other treated wood. 10. Biosolids (sewage sludge). 11. Plants grown for phytoremediation of toxic sites. 12. Algae from water remediation. 13. Invasive species (Melaluca in the Everglades), 14. Used Tires. 15. Waste plastics. 16. Coal Fines.

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5 The Advantages of Using Biomass The energetic and industrial usage of biomass is becoming more and more technologically and economically attractive. The use of biomass offers the advantage of benefits too that we see below: Biomass is available in every country in various forms and thus assures a secure supply of raw material to the energy system. Maintaining biomass as a significant contributor to the national energy supply is, for many countries, the best way of ensuring greater autonomy and a cheap energy for the industry. Socio-economic benefits including the creation of new employment opportunities in rural districts. Environmental benefits include the utilization of biomass for energy is an alternative for decreasing current environmental problems such as CO2 increase in the atmosphere caused by the use of fossil fuels. Furthermore, bio-fuels contain minimal sulphur, thus avoiding SO2 emissions. Need for an Omnivorous Feedstock Converter Please refer to figure 1-2. while we discuss the following strategies to go by. So, when we concentrate on the domestically available resources that include natural gas (NG), coal (Co), biomass (Bm), municipal solid waste (MSW) and bio-solids (BS). Unfortunately most of the research and development (R&D) on alternatives to oil are specialized efforts within individual industrial or governmental fuel sectors. Now energy, environment, and economic (EEE) strategies are urgently needed that take an overall national systems perspective. Since apart from natural gas most of our available domestic energy sources are solid fuels that cannot directly be used for efficient vehicles, combustion turbines, or fuel cells, we greatly need "omnivorous" fuel converters to

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6 change blends of domestic feedstock into clean gaseous or liquid fuels suitable for efficient vehicles or electrical generators. Two strategies are available. 1. Marginal but abundant fuels such as BS, MSW or AW (agricultural waste), that are now wasted or that present costly disposal problems are brought to a local electrical generator to be co-fired or co-gasified in small proportions with the main coal or natural gas fuel. 2. BS, MSW or AW are blended as needed in robust facilities with small proportions of high caloric fuels such as NG, Co or Ti (tires) to produce clean gaseous or liquid fuels. To develop both of these fuel-blending strategies, knowledge of pyrolysis products at various temperatures as it depends upon the compositions of solid fuels would be very helpful. Unfortunately such correlations still are not available, even for biomass and coal, traditional fuels that have been used for millennia. Co, Bm, RDF, Bs CO2, NG, St, Air,O2 Processor, Ct, Ab, Re Gasifier/Liquifie r Filter Dis tiller GCU Combustion Turbine Liquid Fuels Specialty Chemicals Generator HRSG AC,Hu,CO2Sc, Coke, Ash Steam Turbine Generato r Co=Coal, Bm=Biomass, RDF=Refuse Derived Fuel, Bs=Biosolids Ct=Catalyst, Ab=Absorbents, Re= Reactants, CO2=Carbon Dioxide, St=Steam, NG=Natural Gas, O2= Oxygen, GCU=Gas Clean Up, HRSG=Heat Recovery Steam Generator AC=Activated Carbon, Hu=Humates, CO2Sc=CO2 scrubber Figure1-2. Omnivorous Feedstock Converter [5] By 1986, the work at ICAAS concluded that it is possible to reduce pollutants and increase our national reliance on domestic fuels, such as coal, natural gas, biomass and municipal solid waste by co-gasification or co-liquefaction. Figure 1-2 shown previously illustrates conceptually an "omnivorous feedstock converter." Granting that such facilities are or soon will be available to apply these fuel-blending strategies, knowledge of the pyrolysis products of available fuels at various temperatures would be very helpful.

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7 Unfortunately, even though biomass and coal have been used by humankind for millennia one still can only guess at the pyrolysis products of various feed-stocks. This lack of knowledge is probably due to the many variables that control pyrolysis products, the lack of consistent data in the literature on products of pyrolysis or simply the general lack of attention to the basic steps in thermo-chemical processes. In efforts to overcome this age old problem we have attempted to organize major features of experimental pyrolysis data with analytical models. The intent was to use the analytical models to find or test possible semi-empirical models (SEM) of pyrolysis and eventually develop a more fundamental model. This scientific method is nicely illustrated in the development of planetary astronomy through Tycho Brahe's observations, Kepler's analytical laws, Newton's gravitational model and Einstein's general theory of relativity.This analytical work has its roots in attempts to study coal pyrolysis in early CCTL coal-natural gas co-firing studies[6,7,8,9]. The objective of co-utilizing, co-pyrolyzing , co-firing, co-gasifying all boil down to one thing, the greater utilization of Biomass, or rather BIO-FUELS and towards achieving the primary goals of the Energy advisory committee's three primary goals for bio-fuels: By 2010 triple production of fuel from biomass sources, from 2000 levels, by removing technology and policy barriers. Provide benefits to farmers and forest landowners by increasing the value of agricultural and forestry products and assisting rural communities with economic development. Encourage investment by mitigating the financial risk involved in biofuels.

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8 What Are The Basics To Biomass Conversion? The conversion processes of biomass usually involve a reduction of the water content of the material, resulting in the simultaneous increase in its thermal value and preservation potential, and in an improving of the handling characteristics of the biomass, for example turning it into a fluid, which may be either gas or liquid. Oxygen removal from the biomass in the form of carbon dioxide (and carbon monoxide) will result in products with high hydrogen to carbon (H/C) ratio. Wood and other biomass can be treated in a number of different ways to provide such fuels. In general such methods are divided into biological and thermal. The biological conversion processes are hydrolysis, fermentation and anaerobic digestion. The main thermal conversion processes are combustion, gasification, pyrolysis and liquefaction. What is gasification? Gasification and pyrolysis represent partial processes of combustion, where the product mix (gas, liquid and solid) can be controlled by altering temperature, particle size, residence time, pressure and composition of the atmosphere under which the biomass is treated. Gasification is a high temperature process in which a solid fuel is reacted with steam, carbon dioxide, air or hydrogen under oxygen-deficient conditions giving a mixture of gases including hydrogen and carbon monoxide. The most important reactions during gasification are as follows: C + O2 = CO H = 109 kJ C + O2 = CO2 H = 390 kJ C + H2O (g) = CO + H2 H = + 130 kJ C + 2 H2O (g) = CO2 + 2 H2 H = + 88 kJ

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9 C + CO2 = 2 CO H = + 172 kJ CO + H2O (g) = CO2 + H2 H = 41kJ CO + 3 H2 = CH4 + H2O (g) H = 205kJ C + 2 H2 = CH4 H = 71kJ What is pyrolysis? Pyrolysis of biomass is the heating of solid biomass in an inert atmosphere to produce gaseous products (mainly CO2, H2, CO, CH4, C2H2, C2H4, C2H6, benzene, etc.), liquid products (tars, high molecular hydrocarbons and water) and solid products (char). By changing the rate of heating and the final temperature it is possible to modify the proportions of the gas, liquid and solid product. Pyrolysis is the thermal degradation of wastes, either in the complete absence of an oxidizing agent, or with such a limited supply that gasification does not occur to an appreciable extent. Reaction temperatures vary between 500 0 C and 800 0 C, compared to values of between 800 0 C and 1000 0 C for gasification. Three main products are usually produced: gas, pyrolysis oil and charcoal, the relative proportions of which depend on the pyrolysis method, the characteristics of the waste and the reaction parameters. What is liquifaction? Conversion of feedstock organic compounds into liquid products by liquefaction is a relatively low temperature (250C-500C), high-pressure (5-35 MPa) catalytic process, carried out in a reducing atmosphere (hydrogen or carbon monoxide) or using a hydrogen donor system. Gasification also provides a fuel gas that can be combusted, generating heat, or used in an engine or turbine for electricity generation. The produced gas can be also

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10 further processed towards methanol or towards liquid hydrocarbons by Fisher-Tropsch synthesis. Gasification: The Trends in Gasification Since gasification has strategic emission, efficiency, and economic flexibility for the future, gasification is alive and well and continues to grow. current annual growth in gasification is about 3,000 MWth of synthesis gas, or about 7% of the total operating worldwide capacity. Planned gasification projects show this growth will likely continue. Western Europe is the leading region for gasification based on MWth of synthesis gas output of real and planned projects. Asia and Australia comprise the second largest region. North America stands third. When we look into gasification by primary feedstock, we note that they fall in the following order: Coal-Petroleum-Gas-Pet coke-Biomass. We definitely want to get more out of biomass. The idea is to increase biomass and get it up the order in the list. To utilize the advantages that biomass offers and harness advantages of the process in removing poisonous/ hazardous elements from the feedstocks such as CCA-treated wood or arsenic-infused plant matter. Continuing convergence of oil, gas, and electric power marketing with deregulation improves the potential for gasification. Increasing interest in improved energy efficiency, reduced emissions, and increased recycle of wastes also helps gasification. One of the reasons why co-firing and other means of co-utilization are not commercial yet is that insufficient R&D has been done to understand the long term effects of co-firing biomass, especially agricultural residues, in power plants. But now, with such a predicting model and defining systematics , we know what's going to come

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11 out beforehand. This should pave a good way in towards utilizing the least expensive way of utilizing the potential to vastly expand biomass use for power generation. What Is Our Model? With the aim of utilizing different kinds of biomass as raw material to substitute or partly replace fossil fuels in a way that is economically, technologically and environmentally acceptable, the research in the area of biomass pyrolysis and gasification has been advanced at CCTL-ICAAS by developing a model that tells what's in the volatiles at any given temperature. The model focused on both the low temperature and high temperature pyrolysis and since it's more logistical in nature, adjustments have been made to suit the results of all the empirical data available with the present state of art of the science. The model can now predict quite precisely the products of slow pyrolysis given just the oxygen content of the feedstock. The comprehensive list of products accommodates all the major functional groups and a separate set of miscellaneous products that are significant but do not fall into any of the groups. This is perhaps the most advanced predictor -model for the pyrolysis products. In the words of my advisor, "This work has so much significance that it was to be done more than a hundred years ago but no one took to the challenge of creating a model/predicting guide owing to the difficulty of multiple spheres of knowledge needed to successfully get thru. There is a need for a conference specially dedicated to this type of work" (incidentally, there is the first one at the University of Florida -The International Conference on Co-utilization of Domestic Fuels (ICCDF) February 5-6, 2003).

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12 Most Prominent Gasification Technology In The USA: The IGCC According to the manager for process power plant product and market development, GE Power systems, IGCC (Integrated Gasification Combined Cycle) is currently the most competitive new power plant option in the USA and will remain a significant participant in the near future power market. In fact, Coal IGCC beats Natural gas combined cycle when the NG prices are above US$4.1/MMBTU. For the past few years, the rising prices of natural gas and the new technology developments have made IGCC competitive over the conventional combined cycle and steam turbine cycles. The co-production of Hydrogen, Sulfur, Ammonia, Methanol etc. adds to the advantages and furthering the list of applications to the IGCC. Finally, a dualor co-fired IGCC plant with natural gas and Syngas (derived from petroleum coke , coal or residues) can be effectively employed by the power producers to hedge against the exaggerated fuel market price fluctuations. Applications of Gasification Gasification of biomass and production of electricity and heat. The most common thermal conversion of biomass is combustion. In some circumstances it is advantageous to gasify biomass. When electricity is produced from biomass, the electrical energy efficiency is increased by gasification and use of a gas turbine and a steam turbine, in comparison with combustion followed by a steam turbine. Internal combustion engines for producing energy can be run on gasification gas. Synthesis gas for production of methanol, ammonia and H2 can be produced by gasification of biomass. The gas volume after gasification is considerably smaller than after combustion, so, in some cases, there are possibilities for simpler and less expensive gas cleaning.

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13 Increasing use of gasification for waste disposal. There is now increasing movement towards solid waste disposal by pyrolysis and gasification. There is also a great need to learn how to convert domestic solid fuels into gaseous and liquid fuels suitable for combustion turbines or fuel cells and increasing attention is being given to blending opportunity fuels with coal. Thus the need to predict the output when pyrolysing various feedstock and blends of disparate fuels in combustors, pyrolysers, gasifiers, liquifiers, and carbonizers is developing rapidly.

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14 CHAPTER 2 THE SEMI-EMPIRICAL MODEL FOR PYROLYSIS The ICAAS-CCTL Program Environmental/Energy (EE) strategies have been the main concern of the Interdisciplinary Center for Aeronomy and other Atmospheric Sciences (ICAAS) since its founding at the University of Florida in 1970. At the outset it was clear that most atmospheric emission problems are associated with energy use. A state-supported interdisciplinary study [1] examined from many perspectives environmental and technical problems associated with replacing oil use in Florida with coal in industrial and utility boilers. This study and the 1979 oil crises led to a focus on co-firing coal and natural gas in boilers designed for oil. Questions raised by the potentially harmful anthropogenic emissions from this response to USA's excessive dependence on imported oil led to the formation of the Clean Combustion Technology Laboratory (CCTL). Its goal was to pursue R&D on various problems associated with co-utilization of domestic fuels. Considerable co-firing progress was made at an industrial scale until oil prices plummeted and interest in oil backout declined. Then CCTL's undertook studies of waste disposal and broader aspects of co-utilization. CCTL first emphasized co-firing arrangements to take advantage of existing capital facilities . However, for greater environmental benefits, including climate change mitigation

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15 The focus moved towards cogasification and co-liquifaction systems to convert solid fuels into clean gaseous or liquid fuels suitable for efficient combustion turbines, fuel cells or efficient vehicles. The European Union has been pursuing co-gasification and co-liquification rather aggressively [10-12]. On the other hand while co-firing is finally gaining attention in the USA there has been very little interest in co-utilization via gasification or liquification. CCTL-ICAAS has been seeking the systematics of pyrolysis that must eventually underlie applications of co-utilization technology by pooling the large coal and biomass data base of proximate and ultimate analysis. Proximate analysis gives total volatile yields, both non-condensable gases and condensable liquids and tars from 7-minute anoxic heating at 950 C. However, for co-utilization applications it is very important to know the composition of the gaseous and liquid products from various feed stocks over a broad temperature range and this data-base is limited. Reason For The Difficulty In Modeling The very reason for the difficulty in modeling of the pyrolysis systematics is due to the involved substance-specific-complex mechanics for which one needs a good grasp of various fields like organic chemistry, reaction kinetics, mathematical modeling perspectives and the science of thermal conversion. Let us consider for example, the case of pyrolysis of Cellulose, the basic building block of all matter. The pyrolysis is a fast reaction at temperatures above 300C. Pyrolysis of cellulose proceeds through two types of reactions: a gradual degradation, decomposition and charring on heating at lower temperatures, and a rapid volatilization accompanied by the formation of levoglucosan on pyrolysis at higher temperatures . The initial degradation reactions include depolymerization, hydrolysis, oxidation, dehydration and decarboxylation .

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16 The high char yield obtained at low heating rate and low temperature can be explained by a predominance of the dehydration reactions. At temperatures below 300C the dominating reaction of cellulose is dehydration. The gaseous products are carbon dioxide, water and carbon monoxide, while the cellulose is converted to more stable anhydrocellulose. The anhydrocellulose is more stable than cellulose, which results in a high char production. At temperatures above 300C cellulose depolymerizes producing mainly levoglucosan. High heating rates provide shorter time for the dehydration to take place, which results in a more unstable material left for depolymerization to primary volatiles and therefore lower final char yields. This certainly speaks of volumes of data required for our ultimate goal to be accomplished and bring our ongoing research to fruition. Apparatus And Experimental Procedure Description of Gasification Test Rig The gasification test rig consists of four main units [13], which are the vertical indirect gasifier reactor, the hot gas-condensing unit, gas clearing units and the respirometer. This testrig was constructed with replaceable stainless steel tube with a fixed heating system. The heating system consists of a ceramic furnace connected to power source controlled by means of a regulator. The experimental setup is shown in figure.2-1.A stopper is provided at the top of the reactor for dropping sample and a platform at the middle is provided to hold the sample. The platform is constructed form stainless steel and tube having screen fastened at its top and with a thermocouple inside which again connected to a multimeter to read the temperature. The height or the position of the sample holder is adjustable so that samples of different lengths can be centered in the gasifier. The hot product gas comes out from the reactor top and enters at the top of the condenser unit and is cooled. Subsequently, it passes through a

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17 liquid collector and a tar filter. The gas is collected in the respirometer. This is essentially a bell inverted in water that displaces upward when gas is introduced into it. The counterbalanced rising bell results in the downward translation of an ink pen, which traces the volume generated as a function of time on a rotating drum onto which the chart paper is fixed. The sample from the respirometer was taken and analyzed using gas chromatography (GC), the known method of determining the composition of a mixture of gases in the product gas. The apparatus and procedure used for each gas sample is in accordance with the ASTM D1946-90, Analysis of reformed gas by gas-chromatography. The gas chromatography used was a variant 3700 series, model # 374000-00. The samples were analyzed using Helium as the carrier gas and corrections were carried out for Hydrogen. Experimental Procedure To begin an experiment, the furnace is turned on and allowed to heat to the desired temperature is reached; the feedstock capsule is introduced into the heating zone of the reactor. Heating the samples could be considered instantaneous once the reactor has reached the run temperature. Simultaneously, the respirometer is switched on for a slow run for the volume measurement. The experiment was run over a period of 7-min. After cooling down to ambient temperature, the weight of char remaining in the capsule, the amount of liquid and the tar in the filter is measured. In this experiment, the pyrolysis and gasification of oak chips/rice hulls has been conducted with the aim of determining the quantity of gases formed, liquids produced and the solids accumulated at temperatures ranging from 300 Deg. C to 900 Deg. C.

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18 Figure 2-1. The Experimental set-up used for the Pyrolysis of Rice Hulls[13] Rice Husk Pyrolysis Experiments That Led To The Final Model In pursuit of indirectly heated converters to produce useful gas, liquids and chars the CCTL has fabricated about ten batch type laboratory scale systems and two continuously fed systems. The experimental component of this study uses a simplified and improved version of one of our batch fed converters (see Figure 2-1 above). This gasifier test rig consists of four main units: 1) a vertical indirect gasifier reactor, 2) a hot gas-condensing unit, 3) a gas clearing units and 4) a respirometer for volume measurements. This simple test rig was constructed with a replaceable stainless steel tube with a heating system consisting of a ceramic furnace and a variac controlled power source. A stopper is provided at the top of the reactor for sealing the system after dropping the sample. A platform at the middle is provided to hold the sample in the high temperature zone. The platform is constructed from a stainless steel tube having a screen fastened at its top with a thermocouple inside that is connected to a millivoltmeter to determine the temperature. The height or the position of the

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19 sample holder is adjustable so that samples of different lengths can be centered in the gasifier. Provisions are made for steam, CO2, air, oxygen or other gasification agent injection from below. However, the experiments reported here were basically in the pyrolysis mode. The hot volatiles comes out from the reactor top and enters at the top of the condenser unit. The volatiles passing downward are cooled and subsequently passed through a liquid collector and a tar filter. The gas is finally collected in the respirometer whose counterbalanced downward translation of an ink pen, traces the volume generated as a function of time on chart paper fixed on a rotating drum. To begin an experiment, the furnace is turned on and allowed to heat to the desired temperature. The feedstock capsule is introduced into the heating zone of the reactor and the respirometer simultaneously switched on for the volume measurement over a period of 7-min. After cooling to ambient temperature, the weight of char remaining in the capsule and the amount of liquid and the tar in the filter is measured. In this experiment, the pyrolysis and gasification of rice hulls has been conducted with the aim of determining the quantity of gases formed, liquids produced and the solids accumulated at various temperatures. Samples from the respirometer was taken and analyzed using a Varian 3700 gas chromatograph (GC) with a thermal conductivity detector (TCD). The samples were analyzed using helium as the carrier gas. Approximate corrections were made for hydrogen yields and for discounting initially entrained air. Figure 2-2 summarizes the data and presents fits with our analytical model of the influence of temperature on yields. Figure 2-2 (first six graphs) illustrates the experimental results and our logistic fits to H2, CO, CH4, CO2, C2H4 and C2H6 data from our batch studies with rice hulls. Table 2 shows the logistic parameters for all of them. Figure 4g gives

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20 the sum of the experimental gaseous weight percentages, the sum of the analytic gas weight percentages and a single logistic representation of the total analytic gas yield. Figure 4h shows our fit (Ych) to the char data which is compatible with TGA measurements at low heating rates like in Gaur & Reed, 1998. Figure 4i shows the analytic Ych, the total volatile Yv, total gas Yg and the difference L (for liquids) as given by Ych = 100 Yv and L = Yv Yg (10) We have not yet analyzed the break down of our short list assignment of liquid products. [14] list some 200 primary, secondary and tertiary liquids and tars that must eventually be considered. Our semi-empirical model divides these in various categories according to their normalized signatures such as in figure but does not give the ki factor. We are tentatively assuming that the five individual liquid yields in the figure can be represented for all temperatures by the proportions chosen on the basis of ultimate and proximate analysis data. However, adjustments to satisfy mass and C, H, and O balances have not yet been made. Our pyrolysis data for rice husks illustrate the use of logistic functions for representing temperature dependencies of pyrolysis yields. We have found similar results with experimental pyrolysis data on a variety of substances as well as with a number of experiments reported in the literature [15, 16, 17 and references therein].

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21 Figure 2-2. Experimental Rice hull product yields vs. temperature and analytical fits. [18] Table 2-1. The main parameters of rice hull logistics tot gastot volW6266To510255D12060CH4H2C2H4C2H6COCO2w61.6613319p11.51.51.510.8q0001.500Table 2 logistic parameters for rice husk Discussion and Conclusion Volatile amount and composition have a major impact on the design of combustors, gasifiers and liquifiers. Volatiles released in pyrolysis have been the subject of several major coal reviews [11,19,9]. These have made it clear that many variables have an influence but that this subject is still very unsettled. Despite many recent biomass gasification and liquification efforts [20,21,8], we have found no efforts on correlating feedstock and product

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22 compositions. Our attempts to fill this important need throughout the entire CHO range are admittedly exploratory and subject to improvements. They are presented here as a challenge to ourselves and to coal and biomass pyrolysis specialists to develop better common coal-biomass engineering models to serve the expanding needs of co-utilization applications. While it will probably take some time to organize and assess the influence of many other variables upon fast pyrolysis one might surmise that for slow pyrolysis, as in proximate analysis, empirical or semi-empirical approaches such as used in this work can be driven home much sooner and would fulfill many long standing needs. Improved knowledge of the energy and compositional systematics of pyrolysis products can particularly have important applications in integrated gasifier combined cycle systems (IGCC) systems or in liquefaction systems based upon blended feedstocks. Introduction To The ModelingA Walk Through Achieving a better description of the expected pyrolysis products of materials consisting mainly of carbon, hydrogen and oxygen would provide a broad base that could also support ground based solid waste disposal and other solid fuel conversion applications that have taken on urgency since September 11, 2001. The background of CCTL’s pyrolysis and gasification studies is summarized in our ICES-2001paper. Our pyrolysis systematics studies began by using the thermo-gravimetric analysis (TGA) data of Tromp, Kapteijn and Moulijn [22] (to be referred to as TKM) for five coals that range in rank from anthracite to a high volatile bituminous coal [23]. TKM presented the production rates of CO, CO2, CH4, and H2 as functions of temperature up to 1050 K. We integrated TKM rates to obtain the total weight percent yields at various temperatures and fit these results with the three parameter (W, T o , D) logistic function. Y = W L (T) where L (T) =1/{1 + exp ((T o -T)/D) (1)

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23 We assembled a collection of fitting parameters for the four gases and the five ranks of coal. This was the start of our search based upon the faith that some order must underlie the apparent chaos of pyrolysis yields of carbonaceous materials. Our ultimate goal has been to develop a realistic analytical model that can represent all the CHO compounds observed among pyrolysis products for all carbonaceous feedstock. Following this study we analyzed cellulose pyrolysis yields measured by Graham, Bergongnou and Freel (to be referred to as GBF)] at various residence times from 50 to 1000 milliseconds (ms) and temperatures from 650 to 900C, with the ultra-pyrolysis system at the University of Western Ontario. GBF obtained total gaseous pyrolysis yields Y(t,T), in weight percent, that they fit as a function of residence time and temperature using the first order decay representations. Y(t,T) = V*(T)[1-exp(-k t)] (2) Green, Zanardi and Mullin, [16] fit GBF's tabular results for V* with the logistic representation (Eq.1) with W = 94%, Tc=950 K= 677 C and D = 70 K (or C). GBF and GZM also found reasonable analytic fits to GBF tabular values of k using the usual Arrhenius rate constant k(T) = A exp-E/RT = k o exp(a-qu) (3) Where k0 = 1s -1 , a = ln A/k 0 , q = E/1000R and u = 1000/T, with T in Kelvin and the parameters a = 13.49, and q = 11.75 for the second form of Eq. 3. CCTL Laboratory Pyrolyzers Results After working with literature data the CCTL constructed many simple laboratory scale indirectly heated pyrolyzer/gasifiers and obtained reproducible gaseous yields vs time at various furnace temperatures. Figure 2-3 shows an example of gaseous yields (in liters) at

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24 three temperatures for a 5 gram sample of bagasse dropped into a vertical tube furnace.. The tube is quickly sealed apart from a line to a Collins respirometer that collects the gas in a water-sealed cylinder giving a record of gas volume vs time on graph paper. Gas samples are analyzed with a Varian 3700 gas chromatograph (GC) with a thermal conductivity detector (TCD). Figures 2-3 shows data and quadratic fits obtained for bagasse at 800 o C, 900 o C, and 1000 o C. [24]. Table 2-2 top part is a summary of yield results at 1000 C obtained at the CCTL. The ultimate analyses are taken from the literature for comparable materials. These yields undoubtedly are the result of a complex interplay of pyrolysis, heat transfer, phase change, dissociation, chemical decomposition and diffusion processes. In modeling data mass loss vs. time data it is often assumed that dm/dt = k m p or dm/ m p = -k dt (4) where m = M(t)/Mo and Mo is the initial mass. Integration gives m(t) = 1 / [1 + (p-1)kt] 1/(p-1) exp –kt (5) where the arrow points to the result for the case p = 1. As noted in Figure 1 in most measurements made at the CCTL it was found that the yield Y = 1m(t) = at bt 2 usually represent the data very well. By algebra it can be shown that this is equivalent to using the value p = 1/2 in Eqs. 1and 2 which becomes Y(t) = Ym [kt (kt) 2 /4] = at bt 2 (6) where a = Y m k and b = Y m k 2 /4 (7) While Eq. (6) mplies that Y(t) increases to a parabolic peak Y m at t p = 2/k and then descends, in fitting our data we replace the descending part of the parabola by the constant Ym. We will refer to this as the slow pyrolysis saturation yield although in some cases a much slower additional yield has been observed (see 1000 C case in Figure 5).

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25 0.000.501.001.502.002.503.003.50020406080Time (s)Yield (liters ) Sugarcane Bagasse8009001000 100 Figure 2-3. Bagasse yields for 5 gram samples vs. time at three temperatures. [18] Table 2-2. Proximate Analysis and Ultimate Analysis of a few compounds [18] Proximate Analysis Name %VM %Liq FC Ash C% H% O% Bagasse 59.2 9.8 20 11 45.71 5.89 40.37 Melaluca 75 3.5 20 1.5 48.61 5.83 43.36 Leuceana 82 1.15 14 2.85 48.61 5.83 43.36 Elephant grass 72 0.35 19 8.65 44.58 5.35 39.18 Pine bark 55 10.5 34 0.5 56.3 5.6 37.7 Lignin powder 50 13.8 35 1.2 61.2 6.12 32.6 Bond paper 61.93 18.7 8.4 11 41.2 5.5 41.9 Newsprint 56.66 25.5 15.4 2.4 49.14 6.1 43.03 Coal 22.02 13.6 57.2 7.2 76.9 5.1 6.9 Wood pelletts 61.34 23.1 15 0.5 47.84 5.8 45.76 Polyolefin 56.58 42.4 1 0 85.7 14.3 0 PETG 51.8 43.7 4.5 0 62.5 4.2 33.3 Ultimate Analysis Mass Percent at 1000 C Name H2 CO CH4 CO2 C2H2 C2H4 C2H6 Bagasse 1.26 28.92 5.75 18.66 0.32 3.72 0.37 Melaluca 1.7 39.45 8.85 23.09 0.88 5.2 0.55 Leuceana 1.81 38.85 8.66 26.67 0.45 4.82 0.49 Elephant grass 1.48 31.84 7.64 24.66 0.38 5.1 0.65 Pine bark 1.62 29.58 5.38 15.22 0.37 2.56 0.12 Lignin powder 1.43 25.15 8.95 10.64 0.33 3.1 0.29 Bond paper 1.56 27.41 5.59 23.42 0.36 3.34 0.25 Newsprint 1.3 29.25 5.93 16.19 0.6 3.24 0.15 Coal 1.26 8.74 6.48 3.48 0.19 1.63 0.22 Wood pelletts 1.37 33.29 6.52 15.96 0.51 3.44 0.25 Polyolefin 1.17 4.72 16.09 6.01 0.76 25.39 2.44 PETG 0.64 15.52 4.63 29.06 0.2 1.7 0.06

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26 At some later point it would be fruitful to join slow pyrolysis to fast pyrolysis by using equations like Eq. 2 or Eq 6 or by using multi-step decay models such as presented at the 1996 Houston IJPGC [23]. The Wt% Representation In last year's ICES effort [17] resumed the search for analytic representations of the systematics of pyrolysis volatiles and again used atomic ratios O/C and H/C representations [15,16] We refined our previous coalification formula and total volatile formula while seeking formulas for individual gaseous yields. To maintain CHO balances we made use of [C], [H] and [O], the carbon, hydrogen and oxygen weight percentages (wt%) as given in ultimate analysis data. While doing so we found that the coalification formula and curve expressed in terms of wt% are simpler than those given in terms of atomic ratios. Furthermore, wt% have advantages when systematizing higher heating values (HHV) and other feedstock and pyrolysis product properties. Figure 6 shows an [H] vs [O] plot of for 185 representative DANSF CHO materials taken from ultimate analysis data sets in Gaur and Reed [7], Schultz and Kitto, [8] and Singer [25] and other sources. It actually covers major categories of coals and ultimate and proximate analyses as measured in industry for over a century. On the bottom scale we give rank names that have been used for coals and some potential names that might be used for the biomass region. Also shown on Fig. 6 by the open squares (read on right scale) are the data for [C] vs[O]. The near constancy of [H] and the smooth decline of [C] with increasing [O] provide strong reasons for treating peat and biomass simply as lower rank coals. In view of the many differing coal classification systems used throughout the world it would be well to simply rank CHO fuels by [O] in 2% steps as shown in Figure 2-4 and [H] in say 0.5% steps. An intriguing aspect of this [H] vs [O] coalification plot is the fact that apart from the anthracite region all feedstocks have [H]

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27 values close to 6%. Indeed one can now capture the essence of the entire biomass to coal domain with an analytic coalification curve and a carbon constraint given by [H] = 6{1exp-([O]/2) (8) [C] = 100 [O] [H] (9) Accepting Eq. 8 and Eq. 9 reduces the search for systematics of CHO substances along the coalification path to the single independent variable [O]. In what follows we will find it helpful to chose [O]s =25, [H]s=6 and [C]s = 69 to serve as a reference CHO point and to use the dimensionless variables x = [O]/25 h =[H]/6 and z = [C]/69 (10) Yield Sytematics Apparently in our previous use of H/C and O/C coordinates we were following a path pioneered by Van Krevelin in pyrolysis studies. Recently these coordinates were used by Hurt [7] in a review of the structure, properties and reactivity of solid fuels. Our work is differentiated in part by its heavy use of analytic relationships a trend used more extensively in the slide rule computer era [27] than in this electronic computer age. However, atomic ratios feedstock representations can be directly converted to the [H], [O] representation using [C] = 100/{(H/C)/12) + (4/3)(O/C) + 1}, [H] = [C](H /C)/12 and [O] = [C](4/3)(O/C) (11) Also shown on Figure 2-12, (see end of chapter) are the approximate boundary for CHO material softening and carbon formation in practical pyrolysis experiments translated from Hurt's graphical H/C vs O/C representations . They can be represented approximately by (x=[O]/25) [18] [H](soft) = 20 x 2 (12) [H](char) = 11.5{ 1(x 1) 2 /2} 2/3 (13)

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28 Shown also on the figure at the end of the chapter are the [H], [O] positions of lignin (6.12,32.6), cellulose (6.15,49.4) and hemi-cellulose (6.66,53.3), the three main components of all plant matter. These are based upon the compositions C5H6O2, C6H10O5 and C6H10O5 as assumed in many of our previous papers. The closeness of these [H] positions to 6% is a great advantage of the wt% percent representation with respect to the atomic ratio representation. From proximate analyses data collected for various fuels for almost a century, large data sets of the weight percent of volatile matter (%VM), fixed carbon (FC), ash and higher heating values (HHV) are also available over the entire coalification curve ranging from biomass to peat to lignite to bituminous and anthracite coal. In proximate analysis the weight loss after exposure to 950 o C for 7 minutes in an anoxic medium determines %VM and the residual represents the weight of FC and ash. A weight measurement after this residual is burnt gives the ash wt%. Figure 3 shows an empirical smooth fit (VTe) to rather "noisy" data and the corresponding empirical function for FC given respectively by VTe = 62 h x 1/2 (14) FC= 100 V Te (15) Also shown on Figure 2-5 are the 185 experimental values of [C] and [O] from ultimate analyses and the analytical representation of FC given by Eqs 14 and 15 for natural materials. The first question we address in this work is what are the yields in wt% of the many specific gaseous and liquid volatiles in proximate analysis total volatiles. Whether the volatiles are mainly H2O and CO2 or combustible gases CO, CH4, H2 etc. should obviously be important in many situations.

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29 Dulongs Formula Most proximate analyses reports also give the higher heating value (HHV) of the fuel as measured with a bomb calorimeter. The systematics of HHVs has been represented by Dulong's formula in the coal, biomass, food calorimetry and chemistry literature as linearly dependents upon the mass fraction or wt% of the constituents While the coefficients of [C] used in the biomass sector and the coal sector [8] agree within 3% the coefficients of [H] and [O] differ by 20% and 70 % respectively. Assuming a dry ash, sulfur and nitrogen free (DASNF) fuel, we have proposed as simple and convenient compromise between coal and biomass sectors [8]. HHV = A{[C]/3) + [H] ([O]/8)} (16) where A = 1.08 MJ/kg = 464 BTU/lb Note that the carbon energy content (A[C]/3) is generally much larger than the hydrogen energy contribution (6A). Oxygen contributes negatively, (-A [O]/8). This compromise, unlike most Dulong representations gives zero HHV for CO2 and H2O, the end products of hydrocarbon combustion. The corresponding formula for HHV in terms of atomic ratios is more complex [17]. Liquid Yields The slow pyrolysis gas yields of a variety of feedstocks using the drop tube pyrolysis system described by Green [17] with a volume measuring device (respirometer) were accompanied by char yield measurements. These were assigned by weighing the solid residue after the sample is allowed to cool in an anoxic environment. Then following traditions in pyrolysis studies we assigned the difference between total mass loss and gas

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30 yield as liquids (condensible gases or tar yields) with the balance as the fixed carbon i.e. we use 100 = Gas + Liq + FC + Ash (18) The assignments in Table 3a were made in this way. Table 3b shows our gaseous weight percentage assignments converted from our original volume and GC-TCD measurements. SEM Feedstock-Product Correlations In various earlier attempts [15,17] to find feedstock-product correlations we assumed that CHO materials consist of basic molecular units CnHmOp each having the same molecular weight (MW = 10,000). After several attempts to represent correlations empirically we found a plausible semi-empirical model (SEM) that assumes volatiles from CnHmOp feedstock relate to CaHbOc products according to Y(n,m,p: a,b,c) = k (n/n s ) a (m/m s ) b (p/p s ) c (19) Here s denotes a standard reference point along the coalification curve and k is an adjusted constant for each product species intended to be applicable over the entire [O] domain. Taking advantage of identities n/ns = [C]/Cs , m/ms = [H]/Hs and p/ps = [0]]/Os and working in [C], [H], [O] space and chosing the central Os = 25, Hs = 6 and Cs = 69 as the standard normalization point the working formula becomes y(CaHbOc) =k{[C]/69} a {[H]/6} b {[O]/25} c = k z a h b x c (20) In CCTL’s most recent efforts to simulate the variation of the main volatile product yields with [O] have concentrated on the systematics of the 5 big volatiles (CO, CO2, CH4, H2, and H2O) that in most regions of [O] account for most of the [C], [H] and [O] of the feedstock. This SEM implies that the wt% of these big 5 vary as [CO] =k 1 z x [CO2] = k 2 z x 2 ,

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31 [H2] = k 3 h 2 , [CH4] = k 4 z h 4 and [H20] = k 5 h 2 x (21) where we hoped the k's could be fixed for each compound over the entire coalification path. Organic Products Milne’s list of over 200 organic compounds [26] that have been identified in the gases, liquids and tars from biomass pyrolysis. Solomon and Hamblen have suggested that these products should be divided into important functional groups. In our effort to accommodate these many organic pyrolysis products we used rules for a, b and c that join functional group products (CaHbOc) while recognizing that isomers (groups with identical a, b and c) can differ in detailed properties. Table 2-4 shows the functional group subdivisions now being used in this effort and the a,b,c rules that connect these groups. We have subdivided these groups into aliphatic and aromatic products and into pure hydrocarbons i.e. (CaHb) and the oxygenates (CaHbO, CaHbO2, CaHbO3 etc). We are using j = 1, 2, 3 etc to denote the first, second, third, etc. members of each group. In using this functional group approach we hypothesize that the yields of successive group members follow some regular pattern that could be simulated by appropriate rules for the parameters in our analytical model. Thus far we have chosen a common To and D for all members and have adopted simple rules for the ps and qs for successive family members. It is known from polymer degradation studies that heavier products appear in yields at low temperature and these break up into smaller parts at high temperatures. Thus in our model we progressively decrease p with j which makes the yield rise successively at lower temperatures. We progressively increase q with j, which makes the peak associated with finite qs move toward lower temperatures at higher j. As to the k parameter to lower the yield of higher group members we are now pursuing the rule that

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32 k = 100/(a+ )(b+1)(c+1) (22) where is an adjustable parameter for each family. Our rules accommodate each individual group member and facilitate the calculation of a wt% sum of any functional group. Then the final wt% of all feedstock products can be given in terms of a reasonable number of functional group families rather than the much larger number of individual product members. Parameter Adjustments The volatiles CO, CO2, CH4, H2 and H2O have major roles in a study of the relation between feedstock and pyrolysis product composition and usually are a substantial part of the total volatile weight. We generally chose parameters for the first four that are reasonable in relation to our experimental data (refer to Appendix work B). Since we have little data to fix H2O we have used fragmentary reports of water yields in the literature, hydrogen and oxygen balance and total volatiles to fix its parameters. The p parameters have largely been chosen based upon GZM’s fits to GBF cellulose pyrolysis data in which the volatiles are released in the order H2O, CO2, CO, CH4 and H2. The qs were chosen to reflect the decline in H2O and CO2 at high temperatures by interaction with carbon and the continued rise of CO and H2 at very high temperatures [26] presumably with some decomposition of CH4. In many hours of parameter searches to date we have come close to the goal of using fixed ks for the big 5 volatiles. However, as yet we have only achieved a good balance of the wt% of C, H and O and total volatiles by letting k(CO) and k(CO2) have some residual dependence on [O] (see Table 6). For the organic functional group families we are currently holding to d = 1 for all families and the rules p = exp (-0.05(j-1))

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33 q = 0.60 a exp T/718 (23) The rule for q,a is a tentative one made after several attempts to find temperature independent q’s, brings us to a point that we can examine applications of an analytic model that gives the composition of products of CHO pyrolysis for various feedstock compositions and temperatures. Figure 2-8 shows our model output for the Big 5 volatiles and the sum of the others (Soth) at 950 C, the temperature used for proximate analysis. In effect it is our tentative breakdown the volatiles in proximate analysis reports. Figure 2-8 shows the breakdown of Soth in terms of functional group sums. Figures 2-9 gives outputs of the Big 5 at 300, 600, 900, and 1200 C and Figure 2-10 give the functional group sums for the corresponding temperatures. These results seem to be in reasonable relationship to experience. There are many other useful outputs that can now be generated. For example knowing the weight percentages of the individual volatiles we can calculate their contributions to the heating values of the gaseous or liquid products using enthalpy tables. We can also estimate the heating value of the char knowing the CHO wt%s and using our Dulong formula. Substantial data has been gathered indicating that “additivity” will be the zeroth order thermo-chemical effect and that physical or chemical synergisms or antagonisms, will probably represent first or second order effects. Perhaps of greatest importance to any blend-conversion program is that by using an additivity rule we can get estimates of the relative abundances of the various pyrolysis products from knowledge of the CHO mixtures represented at any time in waste generated in the blending. An Objective of Coal Classification Was Met We have seen in the above discussion that the whole of the Oxygen range falls into one family and can hence be classified on a basis they all acceptably vary with. In using blends of

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34 solid feedstock in gasification systems it is useful to quantify the concept of coal rank. After corrections for moisture, ash and minor species content we show that oxygen weight percentage [O] and hydrogen weight percentage [H] can provide a quantitative basis for a ranking system that includes peat (developing coal) as a lower rank coal and biomass, (infant coal) as the lowest rank coal. The differing coal classification systems used throughout the world causes confusion in R&D and in global coal trade. Thus it would be good to develop some simple quantitative ranking system for natural carbonaceous (CHO) fuels. The oxygen weight percentage (i.e. 10-O for bituminous, 44-O for wood) as given in Table 2-3, perhaps with the hydrogen weight percentage with one decimal place (i.e. 5.7-H) would see to provide an unambiguous quantitative index. Words or numbers could be used to give physical characteristics and the moisture, ash and minor species content. For qualitative discussions high O coal, HiO coal, or HiO CHO or just HiO for biomass and low O coal or LoO, for the coal region could be used. For the middle region midO or MiO would be good for sub-bituminous and lignite. A Few Insights From Table 2-3 The eighth column of Table 2-3 gives nominal densities (in Kg/liter) for the various CHO fuels. The ninth column gives E/vol, the product of the heating value times the density in MJ/liter. The higher densities of LoO vs HiO fuels are advantageous from the transportation standpoint. Indeed its low energy density is what limits the economic transport distances of biomass. The tenth and eleventh columns of Table 2-3 show some properties of CHO materials that are not yet well quantified but are relevant to co-utilization issues. The tenth column gives relative char re-activities [26]. In thermal processing and in steam, oxygen or CO 2

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35 gasification HiO char has advantages. The eleventh column gives a qualitative picture of the free H and OH radicals that are released in high temperature pyrolysis. Since high char reactivity and free radicals facilitate thermo-chemical processes, HiO materials have advantages on both scores. Blending HiOs with LoOs provides a simple way of applying useful properties of one rank to assist thermal processing of another, a valuable technical reason for co-utilization. The twelfth column suggests a quantitative coal ranking system

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36 Table 2-3. Properties and trends through feedstocks at different oxygen levels. [3] Ultimate,[H] = 6 [1-exp -[O]/2], Proximate V T = 62 hx 1/2 where h=[H]/6 and x=[O]/25, HHV = A {[C]/3 + [H] -[O]/8}, where A=1.08MJ/Kg, Density= 1.680.64x ; E/ vol = 70 exp -x , RelchR = exp 3.7x Ultimate Analysis Proximate Analysis Other properties Name C H O HHV VT FCCh Dens E/vol RelchR H,OH Rad Q Rank Anthracite 94 3 3 36 7 93 1.6 58 1.5 v. low 3 -O Bituminous 85 5 10 35 33 67 1.4 49 5 Low 10 -O Sub Bitum 75 5 20 30 51 49 1.2 36 16 Med 20 -O Lignite 70 5 25 27 58 42 1 27 50 Interm 25 -O Peat 60 6 34 23 69 31 0.8 18 150 High 34 -O Wood 49 7 44 18 81 19 0.6 11 500 v. high 44 -O Cellulose 44 6 50 10 88 12 0.4 9 1600 v v.high 50 -O 02468100102030405020406080100 carbonmetaantanth r subanthlvbitmvbithvbitahvbitb bita bitbsubita subitblignitealignitebbrownleonardpeatapeatbpeatcbarkshellswoodawoodbEcrop ag wasteagric H=6(1-exp(-O/2))C =100H O OLDMATUREYOUNGDEVELOPINGINFANTCOALSCOALSADULTHi OLo OMi O 0 Figure 2-4. Weight percentages of hydrogen [H] vs [O] for 185 DASNF carbonaceous materials (blue diamonds) vs oxygen wt% (read left scale) the upper curve and data shows [C] vs [O] (right scale) [3]

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37 Vol and FC vs. O0102030405060708090100010203040 FC[O] 50 Figure 2-5. Total volatile weight percentages vs [O] for 185 DASNF carbonaceous materials (squares) from proximate analysis. The curve through the data points satisfies V T =62([H]/6)([O]/25) 1/2 [18] HHV vs O 101520253035400102030405[O]HHV 0 Figure 2-6 Higher heating values (HHV) of 185 carbonaceous materials (corrected to DASNF) vs. [O]. The smooth curve represents HHV= A([C]/3+[H]-[O]/8) [13]

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38 Figure 2-7. Yields (in liters) for 5 gram samples of various opportunity fuels. VT is taken as limiting yields (intersection with right vertical scale) [24] Figure2-8. Yields of the basic gases and the sum of the others at 950 C, the proximate volatiles. [18] 0.11.010.0100.001020304050 TotalCOCO2CH4H2Soth.H20950Big 5 0.0100.1001.00010.0000510152025303540455055 Spara Solef Sacty Sarom Spna Salcoh Ccarbo Sether Saldeh Sphen Sform Sguaic Ssyring Ssyri2 Ssug1 Ssug2 Smisc. Sum 950SothTotal

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39 1. 0. 10. 1. 0. 1010.0100.001020304050 tot CH4 CO CO2 H2 H2O Soth 300Big 5 0.11.010.0100.001020304050 tot CH4 CO CO2 H2 H2O Soth 600Big 5 100100.001020304050 tot CH4 CO CO2 H2 H2O Soth 900Big 5 0.11.010.0100.001020304050 tot CH4 CO CO2 H2 H2O Soth 1200Big 5 Figure 2-9. the basic gases, the sum of the others and the Total voaltiles at 300, 600, 900 and 1200 Deg. C [18]

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40 0.0010.0100.1001.00010.0000510152025303540455055 Spara Solef Sacty Sarom Spna Salcoh Ccarbo Sether Saldeh Sphen Sform Sguaic Ssyring Ssyri2 Ssug1 Ssug2 Smisc. Sum 300Soth 0.010.101.0010.00100.000510152025303540455055 Spara Solef Sacty Sarom Spna Salcoh Ccarbo Sether Saldeh Sphen Sform Sguaic Ssyring Ssyri2 Ssug1 Ssug2 Smisc. Sum 600Soth 0.0010.0100.1001.00010.0000510152025303540455055 Spara Solef Sacty Sarom Spna Salcoh Ccarbo Sether Saldeh Sphen Sform Sguaic Ssyring Ssyri2 Ssug1 Ssug2 Smisc. Sum 900Soth 0.0010.0100.1001.00010.0000510152025303540455055 Spara Solef Sacty Sarom Spna Salcoh Ccarbo Sether Saldeh Sphen Sform Sguaic Ssyring Ssyri2 Ssug1 Ssug2 Smisc. Sum 1200Soth Figure2-10. The sum of the functional groups and the sum of all the series all at 300, 600, 900 and 1200 Deg. C [18] Figure 2-11A illustrates the results for the four gases and the total gas yield and Figure 2-11B the results for the first four liquids and the total liquid yield of the paraffin family. The results for the olefins and acetylene gases and liquids and for the alkanols, and ethers liquids are given in figures . 2-11A to 2-11F

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41 paraffin gases012345678902004006008001000 SumCH4C2H6C3H8 0.000.100.200.300.400.500.600.700.800.9002004006008001000 Paraffins liquidsC5H12C6H14C7H16Sum Olefin gases0.00.51.01.52.02.53.03.502004006008001000 C2H4C3H6C4H8Sum 0.000.200.400.600.801.001.2002004006008001000 Olefins liquidsSumC5H10C6H12C7H14 A B C D E F Figure 2-11. A) First four Gaseous members of Paraffin series and total gas. B) First four liquid members of Paraffin series and total liquid. C) First four gaseous

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42 members of Olefin series and total gas. D) First four Liquid members of Olefin series and total liquid. E) First four members of Alkanol series and total liquids F) First four members of Ethers series [13] 0246810121416010203040506 [H][H](soft)[H](char) carbonmetaantanthsubanthlvbitmvbithvbitb bita bitbsubita subitblignitealignitebbrownleonardpeatapeatbpeatcbarkshellswoodawoodbEcrop ag wastea g ric [H][O]PEPSPUBSMSWLi.Ce.HChvbita 0 Figure 2-12. Weight percentages of hydrogen [H] for 185 DASNF carbonaceous materials (blue diamonds) vs oxygen wt% . Rank labels are given on bottom scale [O] values on top scale. {tranformed from Hurt [1998] Van Krevelen representation the black circles represent PE polyethylene, PS polystyrene, PU polyuathane, Li lignin, Ce cellulose, Hc hemicellulose, BS biosolids, MSW, municipal solid waste, Hsoft softening boundary, Hchar, char boundary. [18]

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43 Table 2-4 Shows the various functional groups and their representation [18] aromatics a b c Aromatics 5+j 4+2j 0 polynuclear aromatics 6+4j 6+2j 0 Phenols 5+j 4+2j 1 Guaiacols 6+j 6+2j 2 syringols 1 7+j 8+2j 3 syringols 2 8+j 10+2j 4 sugars 1 4+j 10 5 sugars 2 5+j 10+2j 5 f unctional g roup as CaHbOc , j=1,2,3 aliphatics a b c paraffins j 2a+2 0 Olefins j+1 2a 0 acetylenes j+1 2a-2 0 aldehydes j+1 2a 1 carbonyls j 2a 1 alcohols j 2a+2 1 ethers j+1 2a+2 1 Formic acids j 2a 2 Table 2-5 Shows the parameters for the basic gases.[18] Basic p q A B CO 1 -0.03 18 2.25 CO2 0.66 0.02 4 0.38 H2 1.66 -0.03 2 0 H2O 0.5 0.02 6 0 CH4 1 0.02 10 0 Others Exp(-0.05 (j-1))

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CHAPTER 3 CO-UTILIZATION AND APPLICATIONS What Is Co-utilization? The use of biomass together in certain applications, such as for electric power generation with coal and wood or coal and RDF (refuse derived fuel) in a dual fuel combustion or co-combustion plants can be called co-utilization. Simply, it is employing two or more fuels into an application, here in our context is for energy production. Some of The Applications of Co-utilization Most of the following are cited from the NCC article of Dr. Alex Green [3] The Co-firing Alternative Many of the problems associated with biomass utilization that lie in exclusive use of the biomass can be overcome if these fuels were co-fired at a nearby utility or industrial plant in relatively small proportions (say 5-15% by energy) with the coal or natural gas normally used. Some problems might develop such as increased fouling/slagging. However, several of the major forms of biomass previously listed can be handled at standard industrial or utility plants with modest retrofit costs. There are many variations of co-firing technology. For smaller utilities, factory fabricated robust solid fuel systems can serve a valuable role. Since biomass is relatively easy to gasify one could build a separate HiO gasifier at the coal or NG plant and direct its gaseous products into a suitable combustion zone of the coal or natural gas flame. Co-firing biomass or biomass-generated gas in the coal fireball can lower NOx emissions. 44

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45 The Co-gasification Alternative The omnivorous feedstock conversion system conceptually illustrated by Figure 2 in chapter 1 is intended to change solid fuels into gaseous or liquid forms to make them suitable for use with efficient energy systems. Examples are combustion turbines, co-gen systems, combined cycle systems, fuel cells and even fuel cell-turbine combinations. A major environmental advantage of the co-gasification option comes when using or disposing of CHO materials laden with toxic materials. Here it should be possible to condense out, chemically scrub or adsorb toxic elements such as arsenic, mercury, lead etc after the gasifier but before the turbine. The volume of gas that must be scrubbed is then much smaller than the volume involved in combustion followed by stack gas scrubbing A recent economic analysis indicating that coal's mercury problem can be brought under control with much lower capital costs via the gasification route supports this general conclusion [8,9] Biomass Alternative Liquifiers of biomass, mostly under development in Europe and Canada provide a complementary path to gasification for biomass utilization. Because of their high oxygen content biomass is easier and requires less energy to bring into liquid (or gaseous) forms. Liquids are easier to store than gaseous fuel and to use than solid fuels. These advantages, well recognized in the transportation sector, can also apply to industries and utilities. Thus when liquid production exceeds needs the pyrolysis liquifier can be maintained at full production rate and the stored fuel can be used in times of high demand or sold to nearby utilities or industry. Technologies for improving the shelf life of these pyrolysis liquids are under development. Co-liquifying biomass with coal would bring

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46 more abundant resources into the "pot" and use the reactive properties of the HiOs to facilitate the conversion of the LoOs.It is well known and obvious from Figure 1 that the main energy problem in the USA is our excessive reliance on imported oil. A survey made by my advisor 5 years ago found that among the commercial organizations working on pyrolysis of biomass to liquid fuels and chemicals only one commercial firm out of 18 was based in the USA. The USA program to generate ethanol via fermentation of corn to produce high value gasoline additives probably consumes more liquid fuel than it generates. It might do more for our liquid fuel deficit if the residue, xylage, were also converted to liquid fuels perhaps with HiO-LoO co-liquefying technology. Using the xylage for cattle feed might lead to over-production of beef and foster obesity, a national problem that has reached epidemic proportions. Another liquid co-utilization technology worthy of pursuit would be to blend used vegetable oil with pyrolysis liquids for use in diesel engines. Since there is not enough used vegetable oil, developing technologies for blending with pyrolysis liquids from HiO-LoO mixtures would substantially multiply the impact of the used vegetable oil. [28,29,30] Phytoremediation The Science Times section of the NY Times of March 6, 2001 summarizes the large potential of phytoremediation, the use of plants as pollution sponges to cleanse toxic sites and contaminated bodies of water. The article points to specialized plants that 1. Remove metal contaminants, 2. Treat organic contaminants, 3. Remove radioactive contaminants and 4. Extract contaminants from sewage sludge. The technology is growing rapidly and with all the toxic sites that need remediation the plant matter produced should be very substantial.

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47 The mining community could benefit by developments in phytoremediation and corresponding plant processing advances. In addition to remediation of used mine lands, the industry could make use of phyto-mining, a new technology for extraction of valuable metals that will also benefit from the development of phytoremediation technologies. This NY Times article also describes the work of Professor Lena Ma (UF), who discovered a fern that thrives on arsenic. Pyrolysis/gasification is the only promising proposed way to dispose of toxic laden biomass without re-contaminating the environment. Since widely differing plants are being examined for phytoremediation it is essential to bring order into the chaotic science of pyrolysis. It is quite likely that spiking the phyto-remediating plant with a higher heating value feedstock (i.e. a MiO or LoO CHO material would improve the process and the gaseous product. Knowing what's in the volatiles would facilitate LoO-HiO blending decisions in thermo-chemical processing of toxic laden biomass. Special applications to the co-utilization Applied Science Inc. Applied Sciences, Inc. [31], is an advanced materials research firm fully equipped with development and complementary diagnostic facilities for a carbon fiber production. Approximately 75% of the activities at ASI are related to carbon nanofibers and composites in one form or another. They manufacture Buckyballs, nanotubes, and nanofibers all of which form a continuum of carbon nanomaterials. Co-utilization analyses will help this company obtain the data on the requisite yeilds and gases to produce effectively. A greater knowledge of the catalysts in Pyro studies would help extend our model to predict their required inputs too.

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48 Advanced Life Support Applications Thermo-chemical-mechanical (TCM) feedstock conversion (FC) systems originally developed for high temperature conversion of domestic solid feedstock or blends to useful liquid and gaseous fuels are examined for advanced life support (ALS) applications in spacecraft. Recently, exploratory investigations with these TCM-FC systems to use or sequester CO 2 have led also to a focus on the production of useful chemicals and chars (activated carbon, humates, CO 2 scrubbers, chelating and detoxifying agents, etc). TCM systems can process solid blends with catalysts, adsorbants, reactants, carbon dioxide, steam, air, oxygen, natural gas and liquids. This study considers applications of CCTL’s laboratory scale TCM-FCs for the conversion of the solid waste into sterile and useful gases, liquids or chars on long space missions. TCM units are extrusion systems, and are more adaptable to zero gravity than fluidized bed systems or other systems that rely on gravity. The fact that TCM systems can process solid waste in minutes whereas biochemical conversion requires weeks should be advantageous when time is important. The ALS system here referred to is responsible to convert wastes into useful gases and liquids and since the feed-stocks aboard the space ship would be a blend of various waste, this stands as a very special kind of Co-utilization. Examples of Some Co-utilization applications Coal and biomass utilization. Co-combustion of coal is the most economic way of biomass utilization, as long as there are no restrictions by operational problems. In a study by Dr. Hein, K.R.G, IVD, Univ. of Stuttgart, (report # JOR3-CT95-0057), he compares the simulations of PF combustion (1900K-773k) and FB combustion (1573K-673k) Their model predicts general trends and they say that the two combustion modes have distinctly different patterns of behavior. In the former case, high temperatures lead to the breakdown of fuel primary volatiles into light olefins, particularly ethyne, which subsequently recombine to create problematic hydrocarbon species as the burnt gases

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49 cool. Whereas, in the latter case, the primary volatiles dissociate into two ringed aromatic species such as naphthalene. However, the most important overall conclusion is that dioxins are the result of poor combustion conditions, i.e. with respect to air: fuel mixing, rather than a property of any particular fuel. The notable conclusions Regarding Emissions is that ‘No increase in trace element or dioxin emissions in biomass co-combustion could be observed’. This calls for more and more of the co-combustion and co-utilization projects. Biomass and coal, co-gasification experiment to cite synergies. In an investigative study by the Royal Institute of Technology, Stockholm, Sweden on co-gasification of biomass-coal blends they carry out an experiment in oxygen containing atmosphere in a pressurized fluidized bed gasifier and noted that char from woody biomass is very sensitive to the thermal annealing effect which occurred at relatively low temperature (around 650 C in the investigation) and short soak time (less than 8 minutes). Interesting synergies occurred during co-gasification of woody biomass with coal in the pressurized fluidized bubbling bed reactor. The fuel mixture of birch and coal and their char formed in situ demonstrated unexpected high reaction rate of gasification in an oxygen-containing atmosphere under the studied conditions. The yield of char diminished and consequently the production of gas increased. Furthermore, it was also seen that the formation of both tar and ammonia from fuel-nitrogen were seemingly affected synergistically in the co-gasification experiments of the fuels. The yields of both tar and ammonia were lower than expected.

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50 Why the kinetics of the co-gasification process are important It is addressed in the study that the reaction rate of char gasification with reactive gaseous agents such as steam, carbon dioxide, hydrogen, oxygen, and so on, is much lower than that of the de-volatilization reaction. In most cases once the char is formed it is relatively difficult to be gasified. Therefore gasification of char can be the limiting step (controlled by either reaction kinetics or diffusion of reactive agents and products) of the whole process of pyrolysis/gasification of the solid fuel. Hence the study of the kinetics of the reactions between char and reactive gas agents is of great importance for the development of the process. An other interesting application of pyrolysis to obtain hydrocarbons from biomass that may be considered similar to a co-utilization effort. The study was made by Tanja Barth and others, for the Joule III program (JOR3-CT97-0176), ‘Project: Aqueous Thermal Conversion Of Biomass to Hydrocarbons in the Fluid fuel RangeHydrocarbons from biomass’. It is an investigation to determine the efficiency of the conversion into petroleum compatible fluid fuels specially hydrocarbons from the Pyrolysis of biomass and organic wastes in the presence of water. The results show that the aqueous pyrolysis can be a viable process for conversion of wet biomass into fluids. Good yields of light oils that are compatible with petroleum products are obtained from many raw materials, but the hydrocarbon content (in the strict chemical sense) is not necessarily high. The product profile is most dependent on the biomass type used, less on the pyrolysis conditions. Alternative products like phenols and acetic acid are produced more easily than hydrocarbons. Hydrogen is produced in good yields at relevant conditions, and is also a potentially very interesting product. The technique of pyrolysis in aqueous media is considered to have a potential for application

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51 in waste management and valorization of biomass and organic wastes with high water contents. Demonstration of Co-gasification of Lignite Coal With The MSW The co-gasification of pre-treated municipal solid waste (of differing origins) and lignite was demonstrated in a commercial scale during normal production in the HTW demonstration plant at Berrenrath, Germany. [32] No unusual phenomena occurred during the gasification of municipal waste and no significant differences from the gasification of 100 % lignite were noted, even when the municipal waste portion was increased to 50%. This is substantiated by the comparison in between gasification of just the brown coal and the co-gasification of MSW that tells that they are not much different for the max. gasification temperature and the quantity of synthesis gas produced for pure lignite operation and the tests with municipal waste. The traces were just the same except for a little higher CH 4. The pollution abatement requirements are easily met by the technology used. The modular structure permits the plant to be tailored for the particular locality and minimizes the investments. The co-gasification process permits a substantial improvement of the plant economy by substituting municipal solid waste for primary energy. The savings that can be realized depend on various criteria such as plant location, energy and feedstock costs and credits etc. and can therefore not be quantified here within. Overall, The very positive results are a motivation for continued development of the overall concept. Gasification Technologies In The USA Coal gasification represents the next generation of coal-based energy production. With the first pioneering coal gasification power plants now operating in the United States and other nations, coal gasification is gaining increasing acceptance as a way to generate extremely clean electricity and other high-value energy products.

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52 Rather than burning coal directly, coal gasification reacts coal with steam and carefully controlled amounts of air or oxygen under high temperatures and pressures. The heat and pressure break apart the chemical bonds in coal's complex molecular structure, setting into motion chemical reactions with the steam and oxygen to form a gaseous mixture, typically hydrogen and carbon monoxide. (Gasification, in fact, may be one of the best ways to produce clean-burning hydrogen fuel in the future.) Pollutant-forming impurities and greenhouse gases can be separated from the gaseous stream. As much as 99% of sulfur and other pollutants can be removed and processed into commercial products such as chemicals and fertilizers. Unreacted solids can be collected and marketed as a co-product such as slag (used, for example, in road building). The primary product, fuel-grade coal-derived gas, rivals natural gas in environmental quality. Today's conventional combustion plants are typically 33-35% efficient (fuel-to-electricity). Coal gasification offers the prospects of boosting efficiencies to 45-50% in the short-term and potentially to nearly 60% with technological advancements. Higher efficiencies translate into better economics and inherent reductions in greenhouse gases. Coal gasification offers a much more efficient way to generate electricity than conventional coal-burning power plants. The basic gasification process can also be applied to virtually any carbon-based feedstock such as biomass, petroleum coke, municipal waste, or blends of these fuels. (Information, figure obtained from the following website link accessed on July 21, 2002 http://www.fe.doe.gov/coal_power/gasification/index.shtml Dept. of Energy.)

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53 Figure 3-1. The basic gasification process for various applications Some Accomplishments In The Application Of Gasification Gasification represents clean, efficient, and flexible ways to use the Nation’s abundant coal reserves. First generation Integrated Gasification Combined Cycle plants have already demonstrated the efficiency and environmental performance benefits. Working with a broad range of industrial, university, and national laboratory stakeholders, the program will establish the technology capability to expand the success to a new generation of technology that will serve broader markets — for electricity, fuels, chemicals, hydrogen, and steam — with improved economics. At Tampa's Polk County plant, a Texaco-supplied pressurized, oxygen blown, entrained flow gasifier will convert coal into a combustible gas. It is this combined cycle using two turbines that accounts for the technology's high efficiencies. The Polk Power Station is the first in the Nation to use this advanced technology in a new "grassroots"

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54 power plant. The technology developed by General Electric will process about 10% of the syngas as part of the first-of-a-kind test program. The remainder of the gas will be cleaned by more conventional means The Wabash River Coal Gasification Repowering Project was the first full-size commercial gasification combined-cycle plant built in the United States that repowered an existing pulverized coal plant. Located outside West Terre Haute, Indiana, the plant is one of the world’s largest single-train gasification combined-cycle plants operating commercially. The project received the 1996 Power plant Award from Power magazine. Figure 3-2. The Tampa Electric Polk Station Project [33] Figure 3-3 The Wabash River Coal Gasification Repowering Project [33] The Air Products Liquid Phase Methanol Project in Kingsport, Tennessee has successfully demonstrated the production of methanol from coal gas at commercial scale. The methanol can be used directly as a fuel product or as an intermediary for a wide range of petrochemical products. This technology could be the forerunner of stand-alone

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55 facilities to produce liquids from coal. In emerging market areas, it could be the liquids-producing module of a multi-product energy plant such as DOE’s Vision 21 plant. Figure 3-4The Air Products Liquid Phase Methanol Project in Kingsport [33] Figure 3-5. The Commercial Gasification technologies and their spread [34] Gasification By Technology The commercially well proven Texaco, Shell, and Lurgi (Dry Ash) gasification technologies represent a major portion of the total worldwide gasification capacity, as illustrated in Figure above. Texaco is the leading licensor of gasification technology based on total capacity, representing nearly 40% of the real capacity, with 63 projects accounting for 16,483 MWth of synthesis gas output. The Lurgi Dry Ash and Shell

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56 gasification technologies represent nearly 28% and 21% of real capacity, respectively, with seven projects generating 11,842 MWth and 28 projects generating 8,967 MWth, respectively. Texaco and Shell continue to add new projects, with 7,559 MWth and 3,000 MWth, respectively, of synthesis gas output planned in new projects. There appears to be little interest in new Lurgi DryAsh gasifiers, which is likely due to the feedstock limitation, large steam addition, and extensive waste liquids clean-up requirements of Lurgi Dry Ash gasifiers.These limitations do not exist for the Texaco and Shell technologies. The surge in refinery polygeneration projects also helps the Texaco and Shell technologies,as both are well known in this industry and are quite experienced with processing low-value refinery feedstocks. Texaco has the added advantage of more experience with petcoke. (This information has been obtained from National Energy Technology Laboratory’s Gasification—Worldwide Use and Acceptance, January 2000) A compendium of various co-utilization work around the world has been appended at the end of this thesis for reference.

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CHAPTER 4 CO-UTILIZATION IN THE CONTEXT OF INDIA A Brief Survey of Renewable Energy In India. Information and text obtained in part from [TERI Project Report No. 2000RT45]. After a decade, in 1992, the Department of non-conventional Energy sources was upgraded to the status of a Ministry, named the Ministry of Non-conventional Energy Sources (MNES) to increase the deployment of RE technologies. (The Ministry is the nodal agency of the Government of India for all matters concerning the promotion of non-conventional/renewable energy. The span of its activities covers policy making, planning, promotion and co-ordination of various demonstration and commercial programmes, designing and implementing fiscal and financial incentives, creation of industrial capacity, promotion of R&D and technology development, intellectual property protection, human resource development and international relations. The ministry also deals with emerging areas; such as, fuel cells, electric vehicles, ocean energy and hydrogen energy. All multilateral and bilateral government-to-government linkages related to renewables are enacted through this Ministry.) In order to provide concessional financial support to the renewable energy sector, the Ministry has set up under its fold a financial institution, viz., Indian Renewable Energy Development Agency Ltd. (IREDA).This agency has been playing a very significant role in improving the renewable energy sector of India. 57

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58 Potential and Current Installed capacity for various RETs in India. India is generously endowed with renewable energy resources viz. solar, wind, biomass. Small Hydro, that are widely distributed across the country and can be utilized through commercially viable technologies to generate power/ energy. Figure 4-1. The estimated biomass power potential in Megawatt [28] Figure 4-2.Estimates of technical potential for renewable energy technologies [28] Compared to the estimated potential, the utilization of these resources has been low as indicated in the figure next page. The figure actually tells us that the gasification projects are the highest in the world for India and that the potential to further enhance this is quite evident now.

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59 Figure 4-3. The particular technologies that were used to get the energy utilized. [28] Status and Achievement in Specific Sectors – Biomass Power In India, about 46 percent of the total energy consumption is estimated to be met from various biomass resources i.e. agricultural residues, animal dung, forest wastes, fire and wood. India produces a huge quantity of agricultural residues, which can be converted into energy. The age-old practice of direct burning of agricultural residues to generate energy for domestic as well as industrial applications is very inefficient. In this

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60 context gasification of biomass for decentralised power generation, water pumping as well as thermal applications is important. India plans to generate an additional 3,000 MW of grid power from renewables between 1999-2002. Biomass is available in the country in large quantities in the form of agricultural, forestry and agro-industrial residues. More than 500 million tons of crop residues are produced every year, a large portion of which is either wasted or used inefficiently. Conservative estimates indicate that even with the present utilization pattern of these residues and by using the surplus biomass material, more than 16000 MW of grid-quality power can be generated for de-centralised applications. In addition, around 3500 MW of power can be produced if all the 430 sugar mills in the country switched over to modern techniques of co-generation. According to preliminary estimates, the country has a biomass power potential of about 19,500 MW. Refer to the figures and tables that follow. Figure 4-4 The renewable energy power achievement sector wise. [28]

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61 Figure 4-5. Potential for bagasse based cogeneration in some Indian states [28] Figure 4-6. Status of projects commissioned and under implementation [28] Energy From Waste Naturally, unless the garbage is properly disposed off, there is a risk of environmental degradation and health hazards to the public. On a conservative estimate, about 30 million tons of solid waste and 4400 million cubic metres of liquid waste are generated every year in urban areas from household and commercial activities. In addition to this, the manufacturing sector makes its own contribution to the quantum of waste generated. Technologies are now available to treat the garbage to meet the required

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62 pollution control standards, besides generating power. From the present estimated availability of garbage, there is potential to generate about 1700 MW of power MW from urban and municipal wastes and 700 MW from industrial wastes. The break-up of the estimated potential is shown in Fig. Below. Figure 4-7 The potential of waste from the urban & industrial sectors Figure .4-8 The power generation from renewable forms in MW.

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63 Stand-alone/Off-grid Applications Bagasse-based cogeneration in sugar mills offers immense possibilities. The surplus power generation potential of the 400 and odd sugar mills through bagasse-based cogeneration is estimated at 3500 MW. To facilitate this process new initiatives have been taken. These include the Lead Partnership Programme and Joint Venture model. The latter, in particular, is meant for groups of sugar mills in the cooperative and State sectors. Besides bagasse, there are quite a few biomass materials, which can be used for production of producer gas or briquettes. The potential for biomass power generation is estimated at 16,000 MW. Technologies for gasification and briquetting have been developed and R & D projects have been sponsored through a number of institutions for improving these technologies. So far, about 1700 gasifier systems with an aggregate capacity of about 34 MW have been installed. These have helped in providing electricity to remote villages for home lighting and street lighting. Cleaner Coal Technologies For India: The Indian energy sector is dominated by coal. The coal reserves of India are supposed to last well for 250 years. Not only does India meet 55-60% of its energy needs from coal, but also the amount of coal consumed in absolute terms has increased by almost 5% per year over the last decade and is expected to continue to increase for the foreseeable future. This strong dependence on coal represents a major challenge to both India’s environment and the global environment. In this context, India can benefit greatly from adopting the wealth of UK cleaner coal technologies that are suitable for India. With a developed manufacturing sector, India has the technical expertise and capability to harness these technologies.

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64 India's Clean Coal Technology Progress India and has made strides toward boosting its biomass-powered generation. In India, the ministry of non-conventional energy sources estimated an annual availability of about 500 mt of biomass from crop residues, bagasse, other agricultural residues and forest sources. About 170 mt already is being used for power generation. India currently has 222 MW of bagasse-based co-generation capacity and another 332 MW or so is being constructed. Growing environmental concerns and the need to improve conversion efficiency levels have led to the development of clean coal technologies in India. The most popular of these technologies are fluidized bed combustion (FBC), pressurized fluidized bed combustion combined cycle (PFBC) and integrated gasification combined cycle (IGCC). In India, gasification and fluid bed combustion are of greater importance as these processes can help generate power with considerable efficiency, even from the low quality coal abundantly found in the country. The gasification technologies developed elsewhere are not adaptable for the gasification of high-ash, low-grade Indian coals. IGCC technology compares favorably with other technologies. It is independent of the fuel quality. Depending on the type of gasifier, liquid residues, slurries and coal can be used. The technology is also environment friendly. Pollutants like sulphur dioxide and oxides of nitrogen are reduced to very low levels, without the implementation of downstream plant components and without additives like limestone. The low NOx values are achieved by dilution of the purified syngas with nitrogen from the air separation unit and by saturation with water. Bharat Heavy Electricals Limited (BHEL) has been working on IGCC technology and has developed an appropriate gasification process for Indian coal feedstock. The

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65 company's research has revolved around air-blown fluidized bed gasification owing to the high mineral matter in the coal. Factors Favoring The Renewable Energy Paradigm Foreign Investment: During the current financial year, the Government of India further liberalised the policies for foreign investment in renewable energy sector. A foreign investor can enter into a Joint Venture not only for the manufacture of renewable energy devices and products, but also for setting up power generation projects based on renewable energy. For the entire non-conventional energy sector, 100% foreign direct investment is allowed under the automatic route without prior information to the government. No prior approval of government is required toset up an industrial undertaking with FDI/NRI/OCB1 investment. The investor can bring funds directly, incorporate and Indian company, allot shares to foreign investors and inform the Reserve Bank of India (RBI) within 30 days. At present investment is mainly in the areas of solar photovoltaics, co-generation, wind energy, waste-to-energy projects and battery-operated vehicle. An investment of the order of Rs 300 crore is expected as a result of implementation of such projects. National RE Policy: The government is keen on increasing the share of RE in country's installed power generation capacity by an additional 10% or 12,000 MW by 2012. A draft of the RE policy statement has been submitted by MNES for approval. In effect, around one tenth of the 1,20,000 MW expansion in energy generation capacity planned for the country by the Central Electricity Authority (CEA) for the 11th plan (2007-2012) is expected to come from the RE sector.

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66 Co-utilization in the context of India It has been concluded that India has reasonable coal reserves for not less than 250 years to come and holds the third place among the world coal producers. It is now a definite time when there needs to be a shift in the way biomass is being utilized. Traditionally, biomass is being used in rural areas for low-grade energy purposes only and they inherently hold the low-efficiency equipment along. Since the power generation demands outstrip the supply capacity, the way to go would be to co-utilize the coals and the biomass together to generate clean fuels and generate power in a more economical way. Since most of the coals used are low-grade coals, India has the problem of high ash content and to solve this, one can actually go for the utilization sequences for the ash into various applications like for making concrete mixes in rural areas, making pavements in the cities etc. What we say in the context of India actually applies to all the countries of south Asia because all of them sail the same boat. India is in a better position in many respects. If India goes with the co-utilization option, it will probably cut the below-demand-numbers down and satisfy more of the 30% of the unmet demands. With de-regulation in the electricity and power generation, industry sees a growth in more number of separately generating facilities that can add more to the nation’s energy needs. The main aim is to at least supply the 20% of the population that is not yet having access to electricity obtain electricity. The advantages that India stands now namely being the first in the world for biomass gasifiers and it can definitely extend that to the power generation for local use to begin with and then later combine the local power generation facilities to the national grid. Other factors to keep in mind here are that the subsidies that the Indian government has been giving on the petroleum products are cut

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67 off and this leaves with no fuels in the reach for the common man. Another advantage of co-utilizing of the biomass with coal will reduce the threat of the already increasing nine-fold-carbon emissions. The observation that one often makes in the case of India’s coal-powered generation strategies is that it has the low-energy efficiency of the coal-fired generation plants that mean high energy consumption per unit output. Also, since there is very high cost involved in the replacing of existing plants, they will all probably run for a couple or more decades. So, the right thing to do it to introduce in these plants the very basic needs to co-fire or co-gasify the biomass and try to get the whole set-up to break even with the previous expenses and get the economics better. Only, the measures and better means like this one suggested can cause a nation like India to break free from the constraints of economic development – power outages and unreliable electricity supplies.

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CHAPTER 5 RECOMMENDATIONS FOR FUTURE Interesting synergies occur during co-gasification and this can as well be studied further and be implicated to solve more applications. The process of solid fuel gasification is very complicated and is affected not only by the types of different gasifiers but also by treatment conditions such as temperature, pressure, heat exchange time, heating rate (which is associated with the nature of feedstock, particle size of the feed and temperature, etc.) and pyrolysis atmosphere and so forth. Now covering all these factors into one simple model is quite an ordeal and shall be accomplished with time. Factors such as the critical influences exerted by time temperature-environment history of char formation on the reactivity and/or yield of the char is another step for future in our work. Additional studies can actually make the spectrum of feedstocks even to include non-DASNF fuels too. This would require a great depth and understanding of the Sulfur and Nitrogen compound systematics, their effect on catalysts and so on. An easier way of defining the feedstocks and their products would be to base all the feedstocks into the three building block-weight percents (Cellulose, Hemi-cellulose and Lignin) and apply the additivity rules to obtain the product set. This extension to the model would come by very soon after the product compositions are obtained and verified. 68

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CHAPTER 6 CONCLUSIONS Knowing correlations between feedstock composition and pyrolysis products would be particularly useful when pyrolyzing the variable blends that appear in solid waste. The framework we are pursuing can now give estimates of product yields at 20 temperatures between 200 to 1200 o C, for 200 or so products and 25 values of [O] and eventually for 10 values of [H]. Thus in effect we could calculate 20*200*25*10= 1000,000 output numbers from a model that has only 20 or so adjustable parameters, a rather economical input to output ratio. Clearly additional data is needed and hopefully this work will stimulate measurements that could be used to test this model, better adjust its parameters or suggest improved models. In presenting this preliminary SEM , ICAAS and me pose it as a challenge to ourselves and to experts in biomass or coal processing to find better models that could account for more observations, use fewer parameters, are better based in the fundamental physics and chemistry of CHO materials. Such models are needed to reduce time and costs in designing systems for ground based waste disposal and energy generating systems. 69

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APPENDIX PREVIOUSLY UNDOCUMENTED WORK ON VARIOUS CO-UTILIZATION METHODS Compendium of Co-utilization Work Around The World The following is a list of work done by people all over the world in the field of co-utiliztion. Most of these are funded experimental studies carried out recently. Co-pyrolysis, Co-gasification: Coal(Helper) –Biomass/MSW (helpee) European Union Adlhoch,W., Hoffman,H., Klossek, K.,Schiffer,H,(1994) Rheinbraun AG, ‘Use of sewage sludge in the HTW Process’, C1, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Ahlroth Mikael, Gunnar Svedberg,(1998) Royal Institute of Technology, Stockholm, Sweden, 'Case Study on Simultaneous Gasification of Black Liquor and Biomass in a PulpMill', 98-GT-350 Andre,Rui (2002) Co-gasification Study and Optimization of Coal, Biomass, and Plastic Wastes Mixtures, Lisboa, Portugal, GT-2002-30011 Anne-Galle Collot,(1998) Athanasios Megaritis, Alan A. Herod, Denis R. Dugwell, Raphael Kandiyoti, University of London, London, UK, 'Co-Pyrolysis and Co-Gasification of Coal and Biomass in a Pressurized FixedBed Reactor', 98-GT-162, Bemtgen, J.M., K.R.G. Hein and A.J.Mincher, (1994), ‘Cogasification of coal/biomass and coal/waste mixtures’, Volume 3 , final reports of a comprehensive survey through , 70

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71 Berge N, Carlsson M, Kallner P, Stromberg B,(1994), TPS Termiska Processor AB; ‘Re-burning of a Pulverized Coal Flame with LCV Gas’, C7, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Born, M., (1998), ‘Co-Gasification of Municipal Wastes and Lignite’ Acta Montana, ser. B, No. 8 (110), Prague, p.15, Czech Republic Buchtele,J., et.al, (1998), ‘Co-Processing: Co-Pyrolysis of Coal with OrganicWastes’, Acta Montana, ser. B, No. 8 (110), Prague, p. 29 , Czech Republic Buchtele, J., et.al, (1999), 'Comparative co-pyrolysis coal/waste plastics.',Prospects for Coal Science in the 21st Century, S. 1211-1214.,International Conference on Coal Science /10./. Taiyuan (CN), 99.09.12-99.09.17, Czech Republic Carugati A, Del Piero G, Pederzani G, Pollesel P (1994), Eniricherie, ‘Evaluation of Coal Refuse and Coal Biomass Residues as H 2 S Sorbents’, C6, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Cermkov, P., J. Buchtele, (2000), 'Utilization of solid biomass waste through co-pyrolysis with coal'.,5th Conference on Environment and Mineral Processing.Vysok kola bnsk Technick univerzita (Ostrava, Czechia)S. 19-25. Chen Guanxing, Qizhaung Yu, Claes Brage, Christer Rosn, Krister Sjstrm(1999), Royal Institute of Technology (KTH), Stockholm, Sweden; 'Co-Gasification of Coal/Biomass Blends in a Pressurized Fluidized-Bed Gasifier The Advantageous Synergies in the Process' , 99-GT-191 Collot, A.G.,et.al, (2000), "Co-pyrolysis and Co-gasification of Coal and Biomass in Bench-scale Fixed Bed and Fluidised Bed Reactors", Fuel, 78, 667-679

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72 Darmstadt, H.,et.al, (2001), ‘The Co-Pyrolysis Under Vacuum of Sugar Cane Bagasse and Petroleum Residue. Properties and Potential Uses of the Char Product’ Carbon, 39 815-825. Gang Pan,Y.et.al, (1995), ‘Pyrolysis of blends of biomass with poor coals’, Fuels journal volume 75, No 4, Chemical Engineering Department, Universitat Politicnica de cataluya, Barcelona, Spain Garcia, A.N., et.al, (1995), ‘ Gas production by Pyrolysis of municipal solid waste at high temperature in a fluidized bed reactor’, Energy and Fuels 1995, 9, pp 648-658, Spain. Hoppesteyn P.D.J., J. Andries, K. R. G. Hein, (1998), Delft University of Technology, Delft, The Netherlands, 'Biomass/Coal Derived Gas Utilization in a Gas Turbine Combustor', 98-GT-160 Huth, A M., Heilos, G. Gaio, J. Karg, (2000),Siemens AG Power Generation Group (KWU), Mlheim, Germany, Operation Experiences of Siemens IGCC Gas Turbines Using Gasification Products from Coal and Refinery Residues, 2000-GT-0026 Jong W. de, J. Andries, K.R.G. Hein,(1998), Delft University of Technology, Delft, The Netherlands, 'Coal-Biomass Gasification in a Pressurized Fluidized Bed Gasifier', 98-GT-159 Kaloc,M., J. Pavelka, (1998), ‘Research of Co-Pyrolysis of Coal Pitch Products with Wasteplastic’ Acta Montana, ser. B, No. 8 (110), Prague, p. 51, Czech Republic Kandiyoti R,G P Reed et al., (2002),'Modeling Trace Element Emissions in Co-gasification of Sewage Sludge with Coal', paper GT-2002-30672 Kiel JHA, Bos A, Den Uil H, Plaum JM ,(1994), ECN Fossil Fuels, ‘the Development of Cogasification for Coal/Biomass and for other-Coal/Waste Mixtures and

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73 the reduction of emissions from the Utilization of the Derived Fuel Gas’, C8, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Kelsall GJ, Laughlin K,(1994), CRE Group Ltd., ‘The Development of Co-gasification for Coal and for other-Coal /Waste mixtures’, C10, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Kurkela E, Stahlberg P,(1992) ‘Air Gasification of Peat, Wood and Brown coal in a Presurrized Fluidized-Bed Reactor’, Carbon Convertion , Gas yields and Tar formation, Fuel Processing Technology, No 31. Kurkela, E.(1994), VTT gasification research group, Finland.‘Co-gasification of Biomass and Coal’, C9, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Madsen, M.,Christensen,E ; Elsam/Elkraft (1994) ‘Combined gasification of coal and straw Coal’ C2, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Madsen, M., (1997?) ‘Gasification of biomass and coal for power production in Denmark’, SK power Company, Denmark pp. 1062-1067, conference proceedings TBF Marco Kanaar ,(2002),Operating experience from beggenum IGCC plant and future plans for Co-gasification of Bioamass , Buggenum, Haelen, Netherlands Mastral, F.J.,et.al, (2000?), ‘Co-pyrolysis and Co-gasification of polyethylene and sawdust mixtures in a fluidised bed reactor; Temperature influence’, Spain. Meesri,C., B.Moghtaderi, (2001), ‘Pyrolytic characteristics of biomass/coal mixtures’, corporate research center for black coal utilization., University of New Castle, Callaghan, Australia

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74 Minchener, A.J., (1998), CRE Group Limited, UK, ‘An Overview of Recent Clean Coal Gasification Technology R&D Activities Supported by the European Commission’ proceedings of ASME TURBO EXPO '98, June 2-5, Stockholm, Sweden Minchener, A.J., (1999), CRE Group Ltd., England, ‘Syngas Europa’ Featured article, Mechanical Engineering , July Michener, A et al. EC research project: APAS Contract CoalCT92-0001, European commission IEA Coal Research, ‘News letter’, (2001), November, Number 36., (www.iea-coal.org.uk) , London, United Kingdom Munoz, A (2002), Meat and Bonemeal Co-Gasification in IGCC Technology, Elcogas, Puertollano, Spain, GT-2002-30010 Paterson, N.,(2002),'Testing of Sewage Sludge and Coal/Sewage Sludge Mixtures in a Pilot Scale Air Blown Gasifier', paper GT-2002-30013 Pavel, S., J. Srogl, (1992), 'Co-pyrolysis of solid organic waste with hard coal', pub. Uhli-Rudy 1 , p. 351-355, ISSN/ISBN: 0041-5812 Czech Republic Ree, R. van, (1997), ECN. Brandstoffen, Conversie en Milieu [BCM], 'Co-gasification of coal and biomass waste in entrained-flow gasifiers: phase 1: preliminary study', pub. BCM: ECN-C--97-021, April,The Netherlands Reinoso C et al. (1994), CIEMAT Group; ‘Fluidized Bed Combustion and Gasification of Low-Grade Coals and Biomass in Different Mixtures in Pilot Plants Aiming ot High Efficiency and Low Emission Processes’, C5, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7

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75 Rudiger H, Greul U, Spliethoff H, Hein KRG (1994); IVD Stuttgart, ‘Co-pyrolysis of Coal/Biomass and Coal/Sewage Sludge Mixtures in an Entrained Flow Reactor’, C4, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Sakata, Y., (1998), Co-pyrolysis of waste polymers with coal, Macromol. Symp., Vol. 135, pp. 1 373 , IUPAC 38th Micro-symposium on Recycling of Polymers Simon Harvey,(2000), Chalmers University of Technology, Gteborg, Sweden, Performance of a Biomass Integrated Gasification Combined Cycle CHP Plant Supplying Heat to a District Heating Network, 2000-GT-0023. Sorum, L.,et.al, (2000), ‘Pyrolysis characteristics and kinetics of municipal solid wastes’, Fuels Journal, volume 80, Elsevier publications, Institute of Thermal energy and hydropower, Norwegian University of Science and technology, Norway Sjstrom K, Bjornbom E, Chen G, Brage C, Rosen C yu Q (1994) ; KTH, 'Synergistic effects in co-gasification of Coal and Biomass', C3, European Commission, APAS Contract COAL-CT92-001, ISBN 3-928123-15-7 Storm, C., et.al, (1999), 'Co-Pyrolysis of Coal/Biomass and Coal/Sewage Sludge Mixtures',Vol 121 No 1 Jan 1999,Journal of Engineering for Gas Turbines and Power. Storm, C., H. Rudiger, (1998), ‘Co-pyrolysis of coal/ Biomass and coal/sewage sludge mixtures’, proc. of the IGTI, sweden, , Institute of process engineering and power plant technology (IVD), Stuttgart, Germany Straka,P., J. Kovrov, (1998), ‘Co-Pyrolysis of Waste PVC with Coal’, Acta Montana, ser. B, No. 8 (110), Prague, p. 45, Czech Republic Waldemar Liebner,(2000), Lurgi oel gas chemie Gmbh, Frankfurt am Main, Germany , MPGMulti Purpose Gasification in IGCCService

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76 Wanzl, W., (1994), DMT Institute for coke making and Field tech., Germany, ‘Techniques for studying and modeling of coal pyrolysis and their relevance to biomass and wastes’, Biomass and Bioenergy,JBB-MS097, 1994, Elsevier Science Ltd. Co-pyrolysis,Co-gasification: Coal (Helper) –Biomass/MSW (helpee) USA Brown, R.C., et.al, (2000), Biomass and Bioenergy, 18, 499-506, ‘Catalytic effects observed during the Co-gasification of coal and Switch grass’, Ames Laboratory, Iowa State University, USA Hurt,R. (2001), (National Energy Technology Laboratory) NETL Publications, (2001), US DOE, Conference Proceedings 'Minimizing Net CO2 Emissions by Oxidative Co-Pyrolysis of Coal/Biomass Blends ',Brown University. Kate, R., (2000), The Ninth Biennial Bioenergy Conference, Bioenergy, October 15-19 ‘Pyrolytic aspects in thermo-chemical conversion of biomass fuel mix’, USA Spath, P.L. and R.P. Overend, (1997?), ‘Biomass utilization in cofiring scenarios with a gas turbine integrated combined cycle system’, National Renewable Energy Laboratory, Golden, CO, USA References From ICAASCCTL’s Work (USA) Green A., Peres S., Mullin J., Xue H. (1995) "Cogasification of Domestic Fuels," Proceedings of Inter. Joint Power Generation Conf., Vol. 1, Minneapolis, MN. ASME-FACT New York, NY. Green A., Zanardi M., Peres S., Mullin J. (1996) "Cogasification of Coal and Other Domestic Fuels," Proc. 2 Int Inter. Conf. on Coal Utilization, Clearwater FL, pp. 569-580.

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77 Green A., Zanardi M., Peres S.,(1996), “Thermal conversion of Biomass”, Proc. Of Indo –US workshop on Ecofriendly Technologies for Biomass Conversion to Energy and Industrial Chemicals,Tirupati, AP India. Sept., pp 57-78 Green A., Zanardi M., Krzyszic, K.,Peres S., Mullin J. (1996) "Cogasification of Solid Fuels” Proc. ASME Joint Power Generation Conf. Houston TX, Oct. Green A, Peres S., Mullin J., Anderson R. 1997. "Solid Fuel Gasifiers for Gas turbines," 97-GT-62 ASME IGTI Conference, Orlando, Florida, June Green, A., J. Mullin,(1998), ‘’Feedstock Blending with Laboratory Indirectly Heated Gasifiers”, ASME , Inter. Gas Turbine InstituteTurbo Expo 1998 June, Stockholm Green A., Mullin J. (1999) “Feedstock Blending Studies with Laboratory Indirectly Heated Gasifiers”, Journal of Engineering for Gas Turbines and Power, Vol.121, Oct., pg1-7 Green A., Schaefer G. (1999) "Feedstock Blending in Indirectly Heated Gasifier/Liquifiers," ASME paper 99-GT-81. Green A., Schaefer G. (2000) "Feedstock Blending in a continuously fed gasifier" ASME paper Turbo Expo 2000, Munich, Germany May 8-11. Green, A., J. Mullin, G. Schaefer and W. Zhang, (2001) “Feedstock Blending, A Clean Coal Technology”,Proc.26 th Intern Technical Conference on Coal Utilization & Fuel Systems pp191-202. Green, A.E.S., Venkatachalam P, M Sai Sankar, (2001) “Pyrolysis Systematics for Co-utilization Applications”, IASTED's PES 2001 conference, Tampa,FL. Nov 19-22,2001.

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78 Green A., Venkatachalam, P. and M. S. Sankar, (2001) “Feedstock Blending of Domestic Fuels in Gasifier/Liquifiers”, , IGTI, , 2001. Green A., Sai S Mudulodu, (2002), “Co-gasification of Coals of Various Ranks”, International Technical Conference on Coal Utilization & Fuel Systems, Clearwater, FL. Green A, W Zhang and S Mudulodu (2002) “Alternatives to Oil, Co-utilization of Domestic Fuels, ASEE-SE Gainesville FL April 7-9 Green A and Sai S Mudulodu, (2002) “Feedstock Blending in Gasifiers/Liqufiers, Proc. ASME Turbo Expo 2002, Amsterdam.

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79 Miscellaneous Compounds Accounted For In The Modeling 1. FURAN 2. 2METHYLFURAN 3. FURANONE 4. FURFURAL 5. FURFURAL ALCOHOL 6. HYDRO.METHYL FURALDEHYDE 7. METHYL FURFURAL 8. GLYOXAL 9. HYDROXY ETHANAL 10. ETHYLENE GLYCOL 11. PROPANAL 2-ONE 12. ACETOL 13. METHANOLACETALDEHYDE 14. 2,3 BUTANEDIONE 15. 2,3, PENTENEDIONE 16. CATECHOL 17. RESORCINOL 18. HYROQUINONE 19. VANILLIN These are the list of compounds that have been grouped under the miscellaneous set because they did not precisely fit into a functional group that the model accommodated. Such a set would facilitate furthering of certain special compounds that do not have a functional group in specific.

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80 Search For A q That Depends On Temperature In search of a well-fitting temperature dependant “q” equation:, the following work was carried out. Table A-1. The parameters for the equations of q. Alpha 0.001 Qo > 0.25 0.5 0.6 A11 .8 .13 To > 115 B45 00 32 for the others eqn. 1 eqn. 2 eqn. 3 t hru data fit. 1 1A p r T q Eqn.1 Eqn.2 Eqn.3 200 0.45 0.44 0.41 0.53 300 0.40 0.37 0.37 0.49 0000 .397 .6 .850 .643 400 0.35 0.33 0.34 0.45 000 .5 .662 .533 500 0.3 0.31 0.30 0.41 000 .5 .516 .441 600 0.26 0.30 0.27 0.38 0000 .262 .5 .402 .366 700 0.25 0.29 0.25 0.34 000 .33 .313 .303 800 0.19 0.29 0.22 0.30 000 .25 .244 .251 900 0.16 0.28 0.20 0.26 0000 .173 .15 .190 .208 1000 0.14 0.28 0.18 0.23 000 .15 .148 .172 1100 0.13 0.28 0.17 0.19 000 .09 .115 .143 1200 0.12 0.28 0.15 0.15 0000 .114 .09 .090 .118 950 0.28 0.19 0.24 .161 A -0.00125 B=-0.0019 q = a*exp (b*T)is Eqn.4 0 Eqn.1. q= Qo*Exp(To/T) Eqn.2. q=Qo*Exp(-*T) Eqn.3. q=Qo-0.38(T/800) Eqn.4 q=-0.00125*(-0.0019T) is the equation given by datafit. 00.10.20.30.40.50.60.70.820040060080010001200 Figure A-1. Graph shows the curves fitting the q-values at different temperatures.

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Table A-2. The parameters and predictions at 950 Deg. C. 81 Pyrolysis Model results at 950.00 Deg. C Ultimate Proximate Weight percentage (wt %) Name C H O Vol. HV CO CO2 CH4 H2 H2O Soth. Anthracite 92.34 4.66 3.00 7.29 36.79 3.83 0.08 0.76 0.42 0.14 1.79 Bituminous 84.04 5.96 10.00 32.57 35.02 11.60 0.78 6.33 1.29 1.42 16.68 Sub Bituminous 74.00 6.00 20.00 51.13 30.39 21.04 2.88 7.90 1.57 3.47 16.43 Lignite 69.00 6.00 25.00 57.76 27.94 25.15 4.34 7.73 1.63 4.52 14.75 Peat 60.00 6.00 34.00 69.16 23.49 31.57 7.58 7.26 1.75 6.67 13.59 Wood 50.00 6.00 44.00 81.06 18.54 37.15 11.93 6.71 1.91 9.68 14.01 Volatiles Char Name C H O wt % Enc HV C H O wt% Enc HV R reac. Anthracite 3.80 0.78 2.43 7.01 1.88 26.86 90.04 2.38 0.57 92.99 34.91 37.54 3 Bituminous 24.03 4.59 9.49 38.10 12.32 32.34 60.46 0.92 0.51 61.90 22.69 36.66 10 Sub Bituminous 27.98 5.56 19.74 53.29 13.42 25.18 46.06 0.40 0.26 46.71 16.97 36.33 32 Lignite 27.87 5.52 24.73 58.12 12.66 21.77 41.14 0.47 0.27 41.88 15.28 36.49 100 Peat 29.00 5.58 33.83 68.42 11.90 17.39 31.00 0.42 0.17 31.58 11.59 36.70 300 Wood 31.26 5.89 44.24 81.38 11.64 14.30 18.74 0.11 -0.24 18.62 6.90 37.06 1000 Gases liquids excluding water Name C H O wt % Enc HV C H O wt% Enc HV Anthracite 3.51 0.74 2.24 6.49 1.76 27.10 0.28 0.03 0.07 0.38 0.12 32.55 Bituminous 15.10 3.57 7.20 25.87 8.32 32.17 8.93 0.85 1.03 10.82 4.00 36.98

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82Table A-2 (continued) Gases liquids excluding water Name C H O wt %Enc HV C H O wt% Enc HV Sub Bituminous 20.84 4.2814.1239.2310.22 26.047.150.902.5410.593.2030.24 Lignite 22.26 4.2117.5344.0010.1923. 175.610.813.199.612.4625.63 Peat 24.54 4.0623.5652.1610.0419. 254.460.784.359.591.8619.39 Wood 26.82 3.9629.9160.699.8916.30 4.430.865.7311.021.7515.85 Sums Aliphatics Name para olef acty aldehcarboalcohetherformSum misc. Anthracite 0.04 0.20 1.17 0.00 0.100.02 0.000.00 1.54 0.04 Bituminous 1.05 1.70 3.22 0.121. 020.53 0.070.13 7.85 0.29 Sub-bit 1.30 1.79 2.88 0.272. 191.33 0.190.60 10.55 0.34 Lignite 1.15 1.57 2.52 0.312. 641.62 0.220.94 10.97 0.37 Peat 0.89 1.22 1.95 0.363.31 2.03 0.261.72 11.74 0.48 Wood 0.66 0.90 1.45 0.393.91 2.40 0.282.84 12.84 0.67 Sums Aromatics Name arom pna phen guaic syrin g syri 2 Sum sug1 sug 2 Anthracite 0.15 0.05 0.01 0.00 0.000.000.21 0.00 0.00 Bituminous 4.90 3.08 0.52 0.03 0.000.008.54 0.00 0.00 Sub-bit 3.72 0.85 0.83 0.110. 010.005.53 0.00 0.00 Lignite 2.25 0.36 0.66 0.110. 010.003.41 0.01 0.00 Peat 0.83 0.08 0.36 0.080. 010.001.36 0.02 0.00 Wood 0.24 0.01 0.15 0.040.01 0.000.45 0.04 0.00

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83Table A-2 (continued) Enco Energy content HV Higher heating value R reac. Relative reactivity 0.00 950.0 0 CH4 CO CO2H2 H2O aliphati cs aromati cs 1.00 1.00 p 1.00 1.00 0.662.000.50 factor of q q 0.02 -0.02 0.02-0.020.030.17 0.03 A 0.00 0.00 0.000.000.00

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84 This sheet is a list of parameters that gave the above values for the Pyrolysis of the six feedstocks at 950 Deg C. this gets auto-generated by taking values from the main-code sheet. Such a summarized result sheet would benefit one concerned with specific goals of making liquids, generating pyrolysis oils and cases where the goal is to see how much of the aromatics than aliphatics come out

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Table A-3. The data set used in our discovery of the [H] wt% leveling off at 6%. The following is a data set that came in handy for the coalification curve)Name of feedstock O 6*H(O/2) C(O/2) C H O/C Volatiles cor-fixc cor-vola cal-fc cal-vola HHV H/C coal-hhv bio-hhv hhv-calc Cotton gin waste 50.40 6 49 43.44 6.160 0.87 83.41 15.22 84.78 91.48 8.52 17.48 1.70 14.32 17.08 16.26 Bagasse 48.34 6 51.1 45.37 6.286 0.80 64.60 25.49 74.51 91.82 8.18 15.68 1.66 15.38 18.01 15.96 Bean straw 48.06 6 51.3 45.96 5.979 0.78 75.30 19.95 80.05 91.87 8.13 17.46 1.56 15.53 18.14 16.61 Millet straw 47.68 6 51.7 46.15 6.176 0.77 78.28 17.37 82.63 91.93 8.07 18.05 1.61 15.73 18.31 17.11 Cotton stalk 47.01 6 52.4 46.76 6.226 0.75 70.89 24.04 75.96 92.03 7.97 18.26 1.60 16.07 18.61 17.90 Corn stover 46.81 6 52.6 47.18 6.010 0.74 75.17 20.39 79.61 92.06 7.94 17.65 1.53 16.18 18.70 17.41 Corn stalks 46.56 6 52.8 47.23 6.213 0.74 73.30 21.69 78.31 92.10 7.90 18.25 1.58 16.31 18.82 17.91 Corncobs 46.43 6 53 47.57 5.995 0.73 80.10 18.80 81.20 92.12 7.88 18.77 1.51 16.37 18.88 18.37 Rice Husk ( patni 23) 46.26 6 53.1 47.52 6.226 0.73 69.30 17.70 82.30 92.14 7.86 15.67 1.57 16.46 18.95 15.51 Cotton stalk 46.10 6 53.3 47.77 6.136 0.72 62.90 24.03 75.97 92.17 7.83 15.83 1.54 16.55 19.03 15.65 Canion Live Oak 46.04 6 53.4 48.13 5.835 0.72 88.20 11.36 88.64 92.17 7.83 18.98 1.45 16.58 19.05 17.61 Mango Wood 45.92 6 53.5 47.80 6.285 0.72 85.64 11.71 88.29 92.19 7.81 19.17 1.58 16.64 19.11 18.09 Cabernet Sauvignon 45.57 6 53.8 48.36 6.072 0.71 78.63 19.63 80.37 92.24 7.76 19.03 1.51 16.82 19.27 18.83 Rice Husk bran 45.50 6 53.9 48.16 6.336 0.71 61.83 24.00 76.00 92.25 7.75 15.42 1.58 16.86 19.30 15.99 Eucalyptus Grandis 45.43 6 54 48.65 5.929 0.70 82.55 17.02 82.98 92.26 7.74 19.35 1.46 16.90 19.33 18.70 Rice hulls 45.38 6 54 49.03 5.582 0.69 63.60 19.90 80.10 92.27 7.73 14.89 1.37 16.92 19.35 13.66 Almond Shells 45.34 6 54.1 48.25 6.404 0.70 73.45 22.84 77.16 92.27 7.73 19.38 1.59 16.94 19.37 19.35 Tan Oak 45.24 6 54.2 48.61 6.154 0.70 12.40 87.10 12.46 87.54 92.29 7.71 19.12 1.52 16.99 19.41 18.75 Manzanita 45.22 6 48.77 6.012 0.70 17.89 81.29 18.04 81.96 92.29 7.71 19.30 1.48 17.00 19.42 19.00 Madrone 45.22 6 54.2 48.71 6.069 0.70 15.10 84.50 15.16 84.84 92.29 7.71 19.14 1.50 17.00 19.42 18.90 Tan Oak 45.13 6 54.3 48.82 6.049 0.69 9.20 90.60 9.22 90.78 92.31 7.69 18.93 1.49 17.05 19.46 18.30 Wheat straw 44.98 6 54.4 49.32 5.708 0.68 19.80 71.30 21.73 78.27 92.33 7.67 17.51 1.39 17.13 19.53 17.00 Eucalyptus Globulus 44.95 6 54.4 49.02 6.024 0.69 17.30 81.60 17.49 82.51 92.33 7.67 19.23 1.47 17.14 19.54 19.02 Madrone 44.88 6 54.5 49.08 6.047 0.69 12.00 87.80 12.02 87.98 92.34 7.66 19.51 1.48 17.18 19.58 18.71 White Fir 44.87 6 54.5 49.13 5.996 0.68 16.58 83.17 16.62 83.38 92.34 7.66 19.95 1.46 17.18 19.58 19.10 Cotton gin trash 44.79 6 54.6 48.74 6.475 0.69 15.10 67.30 18.33 81.67 92.35 7.65 16.42 1.59 17.23 19.62 16.33 Poplar 44.59 6 54.8 49.44 5.970 0.68 16.35 82.32 16.57 83.43 92.38 7.62 19.38 1.45 17.33 19.71 18.92 Ponderosa Pine 44.54 6 54.9 49.45 6.014 0.68 17.17 82.54 17.22 82.78 92.39 7.61 20.02 1.46 17.36 19.73 19.34 Eucalyptus Camald 44.49 6 54.9 49.58 5.939 0.67 17.82 81.42 17.96 82.04 92.40 7.60 19.42 1.44 17.38 19.76 19.18 fixed C 14.97 22.10 18.77 16.45 22.43 19.25 20.30 18.54 14.90 19.90 11.30 11.36 19.20 85 19.53 16.93 15.80 21.74 54.2

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86Table A-3 (continued) Pine needles 44.3965548.946.6700.6826.1272.38 26.5273.4892.417.5920. 121.6417.4319.8021.49 Casuarina 44.34655.149.705.9610.6719.6678. 9419.9480.0692.427.5819. 441.4417.4619.8219.36 Casuarina 44.27655.149.566.1720.6719.5878. 5619.9580.0592.437.5718. 771.4917.5019.8519.72 Almond Hulls 44.25655.149.915.8420.6622.8971. 3324.2975.7192.437.5718. 221.4017.5019.8618.59 Pistachio shells 44.25655.249.736.0240.6716. 8482.0317.0382.9792.437.57 19.261.4517.5119.8619.28 Chinkapin 44.19655.249.865.9510.6612.8086. 9012.8487.1692.447.5619. 351.4317.5419.8918.88 Olive pits 44.13655.349.546.3240.6721.2075. 6021.9078.1092.447.5621. 391.5317.5719.9119.98 Sugarcane bagasse 44.09655.349.945.9640.6614.95 73.7816.8583.1592.457.55 17.331.4317.5919.9316.88 Rice straw 44.07655.350.355.5800.6617.2569. 3319.9280.0892.457.5516. 281.3317.6019.9415.92 Red Alder 44.05655.449.856.0970.6612.5087. 1012.5587.4592.467.5419. 301.4717.6119.9519.18 Plywood 44.02655.449.906.0850.6615.7782.14 16.1183.8992.467.5418. 961.4617.6319.9719.18 White Oak 44.01655.450.495.4900.6517.2081. 2817.4782.5392.467.5419. 421.3017.6319.9718.26 Sudan grass 43.97655.450.036.0040.6618.6072. 7520.3679.6492.477.5317. 391.4417.6519.9917.97 Peach pits 43.96655.449.646.4040.6619.8079. 1020.0279.9892.477.5319. 421.5517.6619.9920.51 Bagasse 43.89655.549.706.404 0.6616.8775.1018.3481.6692.48 7.5219.501.5517.6920.0218.76 Alfafa seed straw 43.84655.650.345.8140.6520. 1572.6021.7378.2792.487.52 18.451.3917.7220.0518.10 English walnut pr 43.80655.650.485.7160.6518. 1080.8218.3081.7092.497.51 19.631.3617.7420.0719.00 Walnut shells 43.77655.650.465.7650.6521.16 78.2821.2878.7292.497.51 20.181.3717.7520.0819.55 Chenin Blanc Pr 43.75655.750.106.1460.6520.21 77.2820.7379.2792.507.50 19.131.4717.7620.0919.81 Black Walnut Pruning 43.74655.750.375.8870.6518. 5680.6918.7081.3092.507.50 19.831.4017.7720.0919.48 Coconut shell 43.68655.750.585.7410.6522.10 77.1922.2677.7492.517.49 20.501.3617.8020.1219.61 Chaparral 43.59655.850.905.5130.6418.6875.19 19.9080.1092.527.4818. 611.3017.8520.1617.68 Peanut hulls 43.57655.850.416.0140.6521.0973. 0222.4177.5992.527.4818. 641.4317.8620.1719.01 Corn stover 43.13656.350.55 6.3170.6414.5078.1015.6684.3492. 587.4219.001.5018.0920.3718.76 Douglas Fir 43.08656.350.736.1910.6412.6087. 3012.6187.3992.597.4120. 381.4618.1120.3919.85 Wheat dust 43.07656.350.686.2460.6416.4769. 8519.0880.9292.597.4116. 201.4818.1120.3917.54 Black Locust 42.62656.851.575.8050.6218.2680. 9418.4181.5992.647.3619. 711.3518.3520.6019.74 Western Hemlock 42.24657.251. 805.9610.6115.2084.8015.2084.8092. 697.3120.051.3818.5520.7720.04 Groundnut shells 42.14657.351.856.0180.6121.60 72.7022.9177.0992.717.29 19.851.3918.6020.8219.70 Almond Prunings 41.95657.452.625.4260.6021.54 76.8321.9078.1092.737.27 20.011.2418.7020.9019.47 Coconut fibre 41.73657.752.955.3170.5929.70 66.5830.8569.1592.767.24 20.051.2118.8121.0019.81

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87Table A-3 (continued) Douglas Fir 40.87658.552.776.3570.5817.7081. 5017.8482.1692.877.1321. 051.4519.2621.3921.45 Redwood 40.4265953.665.9180.5616.1083.5016. 1683.8492.927.0821.031.3219.4921.5920.67 Cedar 40.25659.153.746.0060.5621.9073.00 23.0876.9292.947.0620. 031.3419.5821.6720.55 Spruce 40.17659.253.905.9310.5626.6069.60 27.6572.3592.957.0520. 331.3219.6221.7121.23 Macadamia shells 40.05659.354.915.0360.5523. 6875.9223.7876.2292.967.04 21.011.1019.6821.7619.99 Peach pits 39.92659.554.066.0180.5519.8579. 1220.0679.9492.987.0220. 821.3419.7521.8221.32 Cocoa Hulls 38.30661.155.666.0360.5223.8067. 9525.9474.0693.166.8419. 041.3020.5922.5520.85 Loblolly Pine bark 37.85661.556.535.6220.5033.90 54.7038.2661.7493.226.78 21.781.1920.8222.7620.69 Slash pine bark 37.71661.756.835.4600.5033.40 56.9036.9963.0193.236.77 21.771.1520.8922.8220.74 Long leaf pine bark 37.66661.756.805.5390.5032.30 67.0032.5367.4793.246.76 21.771.1720.9222.8422.67 Peat S-H3 37.30662.157.095.6040.4926.8770. 1327.7072.3093.286.7222. 001.1821.1123.0121.84 Douglas Fir bark 37.15662.356.885.9720.4925.80 73.0026.1173.8993.296.71 22.101.2621.1923.0822.82 Palm Beach Everglades107 35.86663.558.026.1220.46 9.5026.4026.4673.5493.436. 577.231.2721.8623.668.50 Palm Beach Everglades36 35.3666459.515.1310.4528. 8061.3031.9668.0493.486.52 18.981.0322.1123.8920.42 Swedish fuel peat 35.29664.158.546.1680.4530. 4067.0031.2168.7993.496.51 18.901.2622.1523.9223.97 Grape pomace 34.55664.859.176.2790.4421.4074. 4022.3477.6693.566.4421. 801.2722.5324.2523.07 Palm Beach Everglades103 32.96666.461.505.5310.40 30.8063.0032.8467.1693.716. 2921.491.0823.3624.9722.85 Palm Beach Everglades98 32.90666.561.665.4400.40 23.3057.7028.7771.2393.726. 2817.791.0623.3925.0019.20 Palm Beach Everglades39 32.87666.561.895.2450.40 30.6058.5034.3465.6693.726. 2820.141.0223.4125.0121.39 Palm Beach Everglades129 32.23667.262.515.2570.39 31.9058.9035.1364.8793.786. 2220.931.0123.7425.3022.10 Palm Beach Everglades117 32.21667.262.665.1340.39 30.8058.8034.3865.6393.796. 2120.170.9823.7525.3121.53 Palm Beach Everglades37 32.12667.362.665.2210.38 33.1057.9036.3763.6393.796. 2121.171.0023.7925.3522.24 Sumter Jumper Creek Marsh142 31.98667.461.936.0910. 3921.3063.4025.1574.8593.816. 1919.051.1823.8725.4121.13 St. Johns Shingle Bay Swa112 31.82667.662.955.2270. 3817.1028.0037.9262.0893.826. 1810.351.0023.9525.4910.94 POLK-Near west lake#162 31.61667.862.695.6990.38 29.4050.7036.7063.3093.846. 1619.071.0924.0625.5820.49 Palm Beach Everglades104 31.57667.862.815.6180.38 30.9061.6033.4166.5993.846. 1621.751.0724.0825.6023.14 Palm Beach Everglades35 31.54667.962.505.9580.38 28.0061.4031.3268.6893.856. 1521.541.1424.0925.6122.74 Palm Beach Everglades118 31.29668.162.596.1220.38 19.0042.4030.9469.0693.876. 1314.471.1724.2225.7316.22 Palm Beach Everglades101 31.24668.263.175.5870.37 32.0059.7034.9065.1093.876. 1321.211.0624.2525.7523.13 Palm Beach Everglades38 31.05668.363.235.7170.37 31.8060.7034.3865.6293.896. 1122.261.0924.3525.8323.54 Palm Beach Everglades99 30.84668.663.755.4090.36 32.8057.6036.2863.7293.916. 0921.101.0224.4625.9322.76

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88Table A-3 (continued) Seminole SOUTH of Oviedo88 30.3966963.995.6190.36 31.4059.7034.4765.5393.956. 0521.771.0524.6926.1323.23 Lignite San Miguel 30.33669.161.937.7420.3710. 0021.2032.0567.9593.956.05 23.861.5024.7226.1611.92 Palm Beach Everglades95 30.30669.162.966.7340.36 25.4068.4027.0872.9293.966. 0423.281.2824.7426.1725.02 Putnam Florahome Area1 29.82669.664.086.0980.35 30.7063.2032.6967.3194.006. 0023.261.1424.9926.3924.68 Palm Beach Everglades102 29.61669.864.925.4670.34 33.9057.4037.1362.8794.025. 9822.051.0125.0926.4923.50 Seminole East of Oviedo128 29.466 69.965.225.3220.3428.5056.8033.4166. 5994.035.9720.000.9825.1826.5621.46 Putnam Florahome Area111 29.3867064.276.3550.3426. 5060.9030.3269.6894.045.96 21.841.1925.2226.5923.39 POLK-Near west lake7 29.35670.164.815.8420.34 28.0047.9036.8963.1194.045. 9619.001.0825.2326.6120.30 Palm Beach Everglades96 29.31670.164.296.4040.34 26.1058.9030.7169.2994.045. 9621.121.2025.2526.6222.94 Palm Beach Everglades106 28.82670.665.575.6170.33 30.0056.1034.8465.1694.085. 9220.891.0325.5126.8522.43 Palm Beach Everglades105 28.71670.765.116.1810.33 24.1052.0031.6768.3394.095. 9119.171.1425.5626.8920.63 POLK-Near west lake161 28.48670.965.975.5490.32 32.4051.4038.6661.3494.115. 8921.331.0125.6827.0022.19 POLK-Near west lake160 28.26671.166.385.3620.32 29.0042.6040.5059.5094.135. 8717.720.9725.8027.1019.02 Putnam Florahome Area110 27.94671.565.766.3040.32 26.9057.2031.9968.0194.165. 8421.861.1525.9627.2423.00 Seminole SOUTH of Oviedo89 26.89672.567.175.9340.30 29.5054.2035.2464.7694.245. 7620.981.0626.5027.7222.86 YOGOSLAVIAN BROWN COAL 26.63672.868.115.260.29 45.851.147.2752.7394.265. 7425.80.9326.6427.8426.4 German Braun. Lig 26.27673.168.405.3210.2946.03 49.4748.2051.8094.295.71 25.100.9326.8328.0026.34 OSTELBE 25.25674.169.175.580.2742.156.5 42.7057.3094.375.6326.50.9727.3528.4627.2 ISLAND OF EUBOEA 24.61674.870.035.360.2641 56.142.2257.7894.425.58 270.9227.6928.7526.6 RHINE REGION 24.57674.870. 444.990.2642.855.343.6356.3794. 425.5826.90.8527.7128.7726.5 BELGIUM FLORENNES 23.83675.671.105.070.2544. 853.845.4454.5694.475.53 27.70.8628.0929.1027.1 URALBOGOSLOVSK 23.78675.671.434.80.25554 356.1243.8894.485.5227.20.8128.1229.1327.7 FAR EASTKIRDINSKY 23.55675.872.084.370.2557. 54158.3841.6294.495.5126.80.7328.2429.2327.5 NEYVELI LIGNITE 23.4367671.305.270.2541.557. 142.0957.9194.505.5027.50.8928.3029.2827.1 Lignite Bryan 23.03676.470.126.8460.2518.10 31.5036.4963.5194.535.47 27.961.1728.5129.4616.71 Spain 22.26677.172.365.3750.2314.2445.27 23.9376.0794.595.4114. 180.8928.9129.8116.30 Lignite N Dakota 21.89677.572.935.1840.2345. 3043.6050.9649.0494.615.39 27.810.8529.1029.9825.69 ND J 21.53677.973.614.8610.2230.8028.2052. 2047.8094.645.3616.770.7929.2930.1417.42 TX J 20.97678.473.665.3730.2129.7029.30 50.3449.6694.685.3217. 100.8829.5830.4018.16 Spring Creek 19.02680.475.605.3770.1951.2043. 1054.2945.7194.805.2029. 870.8530.5831.2828.35 Lignite S Hallsville 18.54680.975.865.6060.1844. 4045.2049.5550.4594.845.16 29.490.8930.8431.5027.04

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89Table A-3 (continued) WY I 18.4468176.265.3070.1839.7033.3054. 3845.6294.845.1621.910.8430.8931.5422.63 Wyoming Elkol 18.04681.476.315.6560.1846.60 43.0052.0147.9994.875.13 29.570.8931.1031.7227.44 Decker 17.57681.877.085.3530.1754.0040.80 56.9643.0494.905.1030. 540.8331.3431.9429.01 Indonesia 17.18682.277.185.6390.1728.7645.57 38.6961.3194.925.0822. 890.8831.5432.1122.41 SPANISH COALSSUB BITU 16.92682.577.545.530.16 41.748.746.1353.8794.945. 0629.40.8631.6732.2327.1 CO I 16.31683.178.615.0800.1645.9030.50 60.0839.9294.985.0223. 560.7831.9932.5024.12 RIO ESCONDIDO 16.16683.278.025.830.1651.1 46.752.2547.7594.995.01 30.80.9032.0732.5730.2 SPANISH COALSHIGH VOL BITU 15.87683.579.154.98 0.1561.536.862.5637.4495.00 5.0030.70.7632.2232.7030.4 PUXTREES 15.58683.878.825.60.1551.746.5 52.6547.3595.024.9831.40.8532.3732.8330.2 RIO ESCONDIDO 15.4268478.625.960.154948. 350.3649.6495.034.9731.80.9132.4532.9130.2 SELANGOR, BATU ARANG 15.4168478.675.920.1549.3 48.750.3149.6995.034.97 32.20.9032.4632.9130.3 NORTHERN BOHEMIA 14.98684.479.105.910.1449. 14950.0549.9595.064.9432.30.9032.6833.1030.4 POLAND 14.73684.780.025.250.1453.14454. 6945.3195.074.9331.50.7932.8133.2229.8 ARGENTINARIO TURBIO AREA 14.4568579.156.410. 1451.247.152.0947.9195.094. 9132.60.9732.9533.3431.5 TUNCBILEK-SUB BITUMINOUS 14.3868579.586.040.14 51.544.553.6546.3595.094. 9132.20.9132.9933.3830.5 BAYSWATER 14.30685.180.804.90.1361.936 63.2336.7795.104.9031.70.7333.0333.4130.5 China 13.455.9985.981.535.021 0.1247.2430.9260.4439.5695.15 4.8524.980.7433.4733.7925.09 WY G 11.965.9887.482.395.643 0.1149.8040.5055.1544.8595.24 4.7630.140.8234.2334.4628.99 Ilinois #6 11.925.9887.582.24 5.8400.1145.0044.2050.4549.5595. 244.7632.590.8534.2534.4828.50 TX F 11.305.9888.181.377.329 0.1034.9048.9041.6558.3595.28 4.7228.451.0834.5634.7528.36 OH G 11.075.9888.383.215.7180.1048.7036.10 57.4342.5795.294.7128. 280.8234.6834.8627.96 Australia 11.005.9888.483.815.1830.1044.3024. 8064.1135.8995.304.7022. 470.7434.7234.8923.49 S. Africa 10.925.9788.583.67 5.4020.1050.3035.3058.7641.2495. 304.7028.310.7734.7634.9227.91 France 10.605.9788.883.935.468 0.0954.9636.1160.3539.6595.32 4.6830.570.7834.9235.0629.71 UT F 10.435.978983.665.9100.0951.8037.20 58.2041.8095.334.6730. 210.8535.0135.1429.54 IA H 10.335.9789.183.935.739 0.0939.3035.6052.4747.5395.34 4.6624.930.8235.0535.1824.99 WA F 10.275.9689.183.216.522 0.0947.1037.7055.5444.4695.34 4.6629.330.9435.0935.2128.97 IN H 10.095.9689.384.205.7100.0942.3036.60 53.6146.3995.354.6526. 560.8135.1735.2926.16 MI H 9.525.9589.984.685.792 0.0847.0035.0057.3242.6895.39 4.6127.590.8235.4535.5327.52 IL G 9.415.959085.025.5690.0850.6033.00 60.5339.4795.404.6028. 210.7935.5135.5827.98 Pittsburgh #8 9.085.9490.385.065.8620.0850.7040. 2055.7844.2295.434.5733. 840.8335.6735.7229.96

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90Table A-3 (continued) IL H 8.925.93 90.584.866.2160.0839.1040.20 49.3150.6995.444.5626. 700.8835.7535.7926.73 OK F 8.835.93 90.685.705.475 0.0857.0035.0061.9638.0495.45 4.5531.700.7735.7935.8330.42 Green IN #3 8.525.92 90.984.926.5560.0841.5340. 9350.3649.6495.474.5327. 360.9335.9435.9628.16 OH F 8.355.91 91.185.805.8470.0751.2036.60 58.3141.6995.484.5230. 210.8236.0236.0329.45 KYG 8.195.9 91.285.666.1460.0745.3037.70 54.5845.4295.504.5028. 100.8636.0936.0928.20 KY F 7.845.88 91.686.275.8820.0758.9035.00 62.7337.2795.534.4733. 240.8236.2536.2431.70 CO F 7.655.87 91.886.356.0000.0754.3032.60 62.4937.5195.554.4530. 730.8336.3436.3229.90 NM F 7.605.87 91.886.525.8820.0750.6033.50 60.1739.8395.554.4529. 420.8236.3636.3428.76 MO G 7.145.83 92.387.095.7690.0644.6032.00 58.2241.7895.604.4026. 280.7936.5636.5126.45 TN F 6.755.79 92.787.405.8490.0656.1035.90 60.9839.0295.654.3532. 310.8036.7236.6631.10 VA F 6.415.76 9387.615.9780.0558.0036.0061. 7038.3095.694.3133.750.8236.8636.7831.94 KS F 6.235.73 93.288.045.7290.0552.4031.80 62.2337.7795.724.2829. 470.7836.9336.8528.98 Korea 5.945.69 93.592.841.2210.0568.567.46 90.199.8195.764.2421. 960.1637.0336.9423.73 Pittsburgh Seam 5.745.66 93.788. 415.8550.0555.8033.9062.2137.7995. 804.2031.750.7937.1037.0130.74 WV F 5.295.57 94.289.085.623 0.0460.0033.0064.5235.4895.88 4.1233.380.7637.2337.1431.67 MO F 5.215.56 94.288.835.9550.0453.5032.10 62.5037.5095.904.1030. 210.8037.2637.1629.82 AL F 4.705.43 94.889.825.4810.0460.9030.80 66.4133.5996.013.9933. 050.7337.3837.2831.40 PA F 4.575.39 94.989.705.7380.0458.3030.00 66.0233.9896.053.9531. 660.7737.4137.3130.73 German-Anna 4.105.23 95.492.52 3.3820.0379.6012.0086.9013.1096. 193.8133.000.4437.4737.3931.02 RI A 4.015.19 95.595.390.5940.0365.302.50 96.313.6996.213.7921. 660.0737.4837.4021.32 MD D 3.374.89 96.191.864.7670.0370.4018.20 79.4620.5496.463.5432. 100.6237.4737.4431.12 Nuthumberland #8 A 3.154.76 96.492.893.9520.0382. 599.0990.099.9196.563.44 32.860.5137.4437.4332.18 VA C 2.904.59 96.692.894.2160.0266.7010.60 86.2913.7196.693.3127. 560.5437.3937.4127.76 VA E 2.754.48 96.891.865.3900.0267.9021.80 75.7024.3096.783.2232. 630.7037.3537.3831.91 PA E 2.744.48 96.892.125.1370.0270.0020.50 77.3522.6596.783.2233. 290.6737.3437.3832.00 Anthracite 2.624.38 96.995.222.1620.0283.10 6.4092.857.1596.863.14 33.470.2737.3037.3629.82 AR C 1.993.78 97.694.033.9810.0278.809.80 88.9411.0697.302.7031. 870.5136.9737.1531.32 ****B 1.533.21 98.196.342.125 0.0182.203.7095.694.3197.72 2.2829.820.2636.5836.8829.10 NM B 1.513.18 98.295.483.0160.0182.705.50 93.766.2497.752.2531. 030.3836.5536.8630.64 *** B 1.012.37 98.896.872.1230.0187.703.10 96.593.4198.331.6731. 490.2635.9236.4230.82 CO A 0.801.98 9995.893.3140.0183.805.70 93.636.3798.611.3931. 910.4135.5936.1931.48

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91 LIST OF REFERENCES 1) Green A, ed. (1980), Coal Burning Issues, University Presses of Florida,Gainesville, FL,USA 2) Green A, ed. (1981), An Alternative to Oil, Burning Coal with Gas, University Presses of Florida, Gainesville, FL,USA. 3) Green A (2002), National Coal Council Re port, Appendix; and the Florida Public service commission Presentation. 4) Klass D. L. (1998), Biomass for Renewable Energy, Fuels, and Chemicals, 234-236. Academic Press, San Diego, CA 5) Green A, M Sai Sankar (2002), Co-gasification of Coals of Various Ranks, 26th International Conf. on Coal Utilization and Fuel Systems, Clearwater, FL. Mar 58,2002 6) Green A, ed. (1991), Solid Fuel Convers ions for the Transportation Sector, ASMEFACT, New York, NY. 7) Gaur S, Reed .T (1998), Thermal Data for Natural and Synthetic Fuels, Marcel Dekker Inc., New York. 8) Stultz S., Kitto J., ed. (1992), Babcock & Wilcox, Steam 40th Edition, Barberton, Ohio., Babcock and Wilcox publishers. 9) Solomon S and Hamblen D.G., Chemistry of Coal Conversion, Pyrolysis, pg.121232, NATO ASI Series, Plenum 10) Kurkela E, (1996), Recent Results and Plans Concerning Co-Gasification of Biomass and CoalAn Overview, Proc. Biomass for Energy and the Environment, 9th EU Bioenergy Conf. 11) Karaca F., Bolat E (2000), Coprocessing of Turkish Lignite With a Cellulosic Waste Material, Fuel Process Technology, v. 64: n1-3 pp. 47-55. IGTI 2002 12) Storm C., Rudiger H, Spliethoff H, Hein K.R. G, 1998, Co-pyrolysis of Coal/Biomass and Coal/Sewage Mixtures, 98-GT-103, ASME Turbo-Expo 1998, Stockholm

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92 13) Green A, J. P. Mullin (1999), Feed stock Blending Studies with Laboratory Indirectly Heated Gasifiers, Journal of Engineering for Gas Turbines and Power, Oct 1999,vol-121,Transactions of the ASME. 14) Milne .T, Overend R (1994), Fast Pyrolysis, Biomass and Bioeneregy, Vol 7, No.1-6. 15) Green A, Zanardi M., Krzyszic .K.,Peres S., Mullin J (1996c) Cogasification of Solid Fuels,ICES 30th Conference, SAE publication 16) Green A, Zanardi M., Peres S., Mullin J. 1996b. Cogasifying Biomass with Other Domestic Fuels, Bioenergy 96, Nashville TN June. 17) Green A, Mulllin J.P., Schaefer G.P., M.S. Sankar (2001), Life Support Applications of TCM-FC Technology, ICES 31St Conference, Orlando. 18) Green A, Mudulodu. Sankar, Ritesh C (2002b), Multipurpose Solid Waste Disposal for the ISS, ICES 32nd Conference, San Antonio, TX , July 2002. 19) J. Bemtgen, K. Hein, A. Minchener, (1994), Cogasification of Coal/Biomass and Coal/Waste Mixtures, European Union Clean Coal Technology Programme 19921994, Stuttgart. 20) Bridgewater, A. Peacocke (2000), Fast Pyrolysis Processes for Biomass, Renewable & Sustainable Energy Reviews, v. 4,1 1-73 21) Klass D L., An Introduction to Biomass Energy – A Renewable Resource for the website http://www.bera1.org , biomass energy research association., accessed on 08/01/2002. 22) Green A, Peres S., Mullin J., Xue H. 1995. Cogasification of Domestic Fuels, Proceedings of IJPGC, Vol. 1, Minneapolis, MN. ASME-FACT New York, NY. 23) Green A, ed. (1988), Co-Combustion, Fuel and Combustion Technology (FACT) Division of the American Society of M echanical Engineers (ASME), New York, NY. 24) Green A, , J. Mullin(1999) ,Feedstock Bl ending Studies With Laboratory Indirectly Heated Gasifiers, Journal of Engineer ing for GasTurbines and Power, Oct 1999, Vol-121, pp 151-162, Transactions of the ASME, 25) J. Singer, ed. (1981), Combustion-Fossil Power Systems, pp. 16-23 Combustion Engineering Inc., Windsor. 26) T. Milne, N. Abatzoglou, R. Evans (Nov 1998), Biomass Gasifier "Tars": Their Nature, Formation, and Conversion, National Renewable Energy Laboratories /TP570-25357.

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93 27) Green A (2001) A Physicist with the Air Force in World War II, Physics Today, Aug ,v 54, No 8, at link http://www.physicstoday.org/pt/vol-54/iss-8/p40.html accessed from Gainesville, FL on Aug 01,2002. 28) Tata Energy Research InstituteNew Delhi,(2000) , Survey of Renewable Energy in India, Energy Information administration reportsTERI Project Report No. 2000RT45. URL reference for more info: http://www.teriin.org. 29) Sato. H, Wolff J, Radtke .K (2000), High Temperature Winkler Gasification of Municipal Solid Waste, 2000-Gasification Technologies Conference, San Francisco, CA, USA 30) Bridgewater (2001) ThermoNet =PyNe + Gas Net, No. 12, the Pyne news magazine. 31) Applied Sci, Inc.(2002) http://www.apsci.com/home.html , accessed from Gainesville, FL on July 15th , 2002. 32) Howard J. (1981) Fundamentals of Coal Pyrolysis and Hydropyrolysis, Chapter 12, pg. 665, Chemistry of Coal Utilization (2nd Supplement) Wiley NY 98 33) National Energy TechnologyLaboratory Report (2001), Gasification Technologies A Program to Deliver Clean, Secure, and Affordable Energy, Nov 2001. 34) National Energy TechnologyLaboratory Report (2000), Gasification-Worldwide Use and Acceptance, Jan 2000.

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BIOGRAPHICAL SKETCH Sai Sankar Mudulodu born on the 16th of May 1978 at Kakinada, AP, India, finished his high school in May 1995 and decided to go into engineering. This marked the start of his career as a mechanical engineer. In summer 1999, he graduated with a Bachelor of Engineering (BE) degree from Nagpur University, MS, India. Following a year of work as a CAD engineer, Mr. Mudulodu began his graduate studies at the University of Florida’s Department of Industrial and Systems Engineering. His Master of Science in ISE is expected in August 2002. Mr. Mudulodu started out with administrative duties and research on March 12th, 2001, as an hourly employee after quitting his work for the College of Education. He was appointed as a half time graduate research assistant in summer 2001. This was when he first signed up for his MS thesis with Dr. Green. He is interested in working in the areas of manufacturing and logistics, supply chain management, energy management and consulting. 94