TWENTY - THIRD ANNUAL INTERNATIONAL

PITTSBURGH CONFERENCE COAL - ENERGY, ENVIRONMENT AND SUSTAINABLE DEVELOPMENT ABSTRACTS BOOKLET

David L. Lawrence Convention Center

Hosted By

University of Pittsburgh School of Engineering

The Westin Hotel - Convention Center Pittsburgh, PA, USA September 25-28, 2006 TABLE OF CONTENTS

Oral Sessions Page Oral Sessions Page

1: Technologies: Applications and 30: Global : CO Capture – 2: 1 2 25 Economics – 1 Membranes and Solid Sorbents 2: Synthesis of Liquid Fuels, Chemicals, Materials and 31: Gasification Technologies: Advanced Technology 1 26 Other Non–Fuel Uses of Coal: Basics, FT/DME Development – 1 3: Combustion Technologies – 1: Advancing PC Plants 32: Gasification Technologies: Fundamentals and 2 27 to Near-Zero Emissions Simulations – 3 4: Environmental Control Technologies: Mercury 33: Combustion Technologies – 6: Combustion Studies 29 3 Absorption – 1 34: Environmental Control Technologies: Mercury – 1 29 5: from Coal: General Topics 4 35: Gas Turbines and Fuel Cells for Synthesis Gas and 30 6: Global Climate Change: Geologic Carbon Hydrogen Applications – 2 5 Sequestration – 1 36: Coal Production and Preparation – 1 31 7: Gasification Technologies: Applications and 37: Gasification Technologies: Advanced Technology 5 32 Economics – 2 Development – 2 8: Synthesis of Liquid Fuels, Chemicals, Materials and 38: Coal Chemistry, Geosciences and Resources: 6 33 Other Non–Fuel Uses of Coal: Applied FT/CTL Geosciences 9: Combustion Technologies – 2: Mercury Capture 39: Materials, Instrumentation, and Controls – 1 34 7 from Flue Gas 40: Environmental Control Technologies: Mercury – 2 35 10: Environmental Control Technologies: Mercury 41: Coal Utilization By-Products – 1 36 8 Absorption – 2 42: Coal Production and Preparation – 2 37 11: Hydrogen from Coal: Storage/ to Hydrogen 9 43: Gasification Technologies: Advanced Technology 37 12: Global Climate Change: Geologic Carbon Development – 3 10 Sequestration – 2 44: Coal Chemistry, Geosciences, and Resources: 38 13: Gasification Technologies: Applications and Mineral Matter, Coal Ash, Coal Combustion 11 Economics – 3 45: Materials, Instrumentation, and Controls – 2 39 14: Synthesis of Liquid Fuels, Chemicals, Materials 46: Environmental Control Technologies: 40 and Other Non-Fuel Uses of Coal: Coke and 12 Mercury/Others Others 47: Coal Utilization By-Products – 2 41 15: Combustion Technologies – 3: Oxy-Fuel 48: Coal Production and Preparation – 3 42 12 Combustion 49: Gasification Technologies: Advanced Technology 43 16: Environmental Control Technologies: SO , NO , Development – 4 x x 13 Particulate and Mercury – 1 50: Coal Chemistry, Geosciences, and Resources: Coal 44 17: Hydrogen from Coal: Membrane Separation 14 Chemistry 18: Global Climate Change: Greenhouse Gas 51: Materials, Instrumentation, and Controls – 3 45 15 Utilization and Novel Concepts 52: Environmental Control Technologies: General 46 19: Gasification Technologies: Advanced Synthesis Topics 16 Gas Cleanup – 1 53: Coal Utilization By-Products – 3 47 20: Gasification Technologies: Fundamentals and 54: Coal Production and Preparation – 4 48 17 Simulations – 1 21: Combustion Technologies – 4: Coal Co-Fired with 18 Other Fuels 22: Environmental Control Technologies: SO , NO , Poster Sessions Page x x 19 Particulate and Mercury – 2 23: Hydrogen from Coal: Shift Catalyst and 1: Combustion Technologies 49 19 Gasification 2: Gasification Technologies / Hydrogen from Coal 49 24: Global Climate Change: CO Capture – 1: 3: Gas Turbines and Fuel Cells for Synthesis Gas and 2 20 51 Chemical Sorbents Hydrogen Applications 25: Gasification Technologies: Advanced Synthesis 4: Materials, Instrumentation and Controls 52 21 Gas Cleanup – 2 5: Environmental Control Technologies 52 26: Gasification Technologies: Fundamentals and 6: Synthesis of Liquid Fuels, Chemicals, Materials and 22 53 Simulations – 2 Other Non-Fuel Uses of Coal 27: Combustion Technologies – 5: Coal Reactivity and 7: Coal Chemistry, Geosciences and Resources 54 23 Kinetic Studies 28: Environmental Control Technologies: Mercury 24 Oxidation/Catalysts 29: Gas Turbines and Fuel Cells for Synthesis Gas and 25 Hydrogen Applications – 1

A NOTE TO THE READER

This Abstracts Booklet is prepared solely as a convenient reference for the Conference participants. Abstracts are arranged in a numerical order of the oral and poster sessions as published in the Final Conference Program. In order to facilitate the task for the reader to locate a specific abstract in a given session, each paper is given two numbers: the first designates the session number and the second represents the paper number in that session. For example, Paper No. 25-1 is the first paper to be presented in the Oral Session #25. Similarly, Paper No. P3-1 is the first paper to appear in the Poster Session #3.

It should be cautioned that this Abstracts Booklet is prepared based on the original abstract that was submitted, unless the author noted an abstract change. The contents of the Booklet do not reflect late changes made by the authors for their presentations at the Conference. The reader should consult the Final Conference Program for any such changes. Furthermore, updated and detailed full manuscripts are published in the CD-ROM Conference Proceedings, made available to all registered participants at the Conference.

On behalf of the Twenty-Third Annual International Pittsburgh Coal Conference, we wish to express our sincere appreciation to Ms. Heidi M. Aufdenkamp, Ms. Diane McMartin, and Mr. Yannick Heintz for their invaluable assistance in preparing this Abstract Booklet.

Badie Morsi Executive Director International Pittsburgh Coal Conference University of Pittsburgh September 2006

Copyright © 2006 Pittsburgh Coal Conference

1-5 SESSION 1 Environmental Permitting for IGCC Power Plants GASIFICATION TECHNOLOGIES: Stephen Jenkins, URS Corporate, USA APPLICATIONS AND ECONOMICS – 1 Over the past 10 years, power company environmental staff and state and federal environmental agency staff have had extensive experience with the permitting requirements 1-1 for hundreds of -fired combined cycle power plants and some coal-fired power The Gasification Industry: Progress & Prospects plants. Due to the costs of natural gas, stricter environmental requirements, and incentives in James M. Childress, Gasification Technologies Council, USA the Energy Policy Act of 2005, many power companies are now planning to develop Integrated Gasification Combined Cycle (IGCC) power plants that will use coal or blends of The author will review the major factors that have driven the scope of development of coal and other feedstocks. Since there are only two operating IGCC power plants in the U.S., the gasification industry over the immediate past (three years) – energy market, with only 10 years of operating history, there is limited information on environmental environmental regulation, technology development and government policies (at the profiles and performance, and little hands-on experience in power companies and federal and state level – and offer insights into what the future may hold over the near environmental agencies with the air, water, and waste permitting requirements for IGCC and mid term period. The focus will be on the U.S. industry with somewhat less power plants. detailed analysis of international developments in major markets. This paper explains how IGCC technology and environmental profiles are different from natural gas-fired combined cycle and coal-fired power plant technology, as well as how 1-2 permitting procedures are similar to and different from those used for natural gas-fired Polygeneration: Market Barriers and Incentives Considered combined cycle power plant and coal-fired power plant permitting. The paper also discusses Lynn L. Schloesser, Eastman Chemical Company, USA the specific regulations that now apply to IGCC power plants, and provides a summary of key guidelines for air, water, and waste permitting. This will promote the use of standardized The global market has potential for advances in technological efficiency in the approaches and calculation methods in permit applications, making it easier for conversion of coal to energy and materials. Following the rise of “market power” and environmental agency staff to review the applications. This will help assure that the new the technology deployment of combined heat and power (CHP); gasification as fleet of IGCC power plants will be developed based on permits that have comparable coproduction, or polygeneration (production of electricity, process steam, chemical emission limits and utilize effective compliance assurance methods based on the lessons feedstocks or fuels), offers economic opportunity for doubling or tripling efficiency learned over the past 10 years of IGCC power plant operation. (extending the life of coal reserves), achieving near-zero emissions, and building a bridge to the hydrogen economy. Gasification technology as polygeneration is poised to become commercial, particularly in the natural gas dependent, industrial sectors. SESSION 2 Though industrials are motivated by tight natural gas supply and demand, market SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND barriers remain. This paper briefly examines the technology, and the market incentives, OTHER NON-FUEL USES OF COAL: BASICS, FT/DME opportunities, and barriers to polygeneration, with particular emphasis on electricity market barriers and economic incentives in North America. 2-1 1-3 Fischer-Tropsch Synthesis in Microstructured Reactors: the Importance of Flow Quantifying the Real Option Value of Polygeneration Distribution on Both the Process and Coolant Streams Gary Leatherman, Booz Allen Hamilton, USA Kai Jarosch, Anna Lee Tonkovich, Sean Fitzgerald, Velocys, Inc., USA

One of the more promising applications of coal gasification is polygeneration wherein To date, synthetic fuel processes have required enormous economies of scale to produce the technology is configured for the co production of multiple products such as competitively priced products. Systems based on microchannel technology hold the potential electricity, fuels and/or chemicals. The inherent optionality provided by coal to significantly reduce overall costs and enable production of synthetic fuels at smaller scales gasification polygeneration is an attractive source of potential value. Polygeneration is from a variety of low cost feedstock materials. Reactors using this technology are a "real" option that can manifest its value in two ways: 1) arbitrage- wherein the characterized by parallel arrays of microchannels, with typical dimensions in the 0.010-inch relative quantities of the various products are varied in response to the market to to 0.200-inch range. Processes are intensified by reducing heat and mass transfer distances, maximize profits and 2) insurance- wherein a single product gasification plant can be thus decreasing transfer resistance between process fluids and channel walls. Overall system modified to produce another product should production of the primary product no volumes are reduced 10- to 100-fold or more, permitting smaller, lower cost units to produce longer be financially viable. However, the value of this optionality is constrained by commercially significant quantities of synthetic fuel. operational and financial issues. For instance, turn-down ratios, start-up/shut-down At present, several commercial Fischer-Tropsch (FT) processes are used: a tubular fixed bed, cycle time, impact of product cycling on availability, and base-load nature of IGCC slurry bed, fluid bed, and circulating fluid bed. These conventional processes are limited by electricity production can all impact the extent to which the plant operator can modify heat and/or mass transfer performance, and are operated with GHSV less than 1000 hr-1 with production. Among financial constraints are long term power (or other product) selectivity to the undesired side product near 10%. Methane production is a strong purchase agreements, which are almost mandatory for project financing, and the power function of temperature. As the catalyst temperature increases with the exothermic reaction, market context (i.e. regulated, deregulated) in which the plant is located. This paper the methane selectivity continues to rise. attempts to quantitatively assess the inherent economic value of polygeneration The use of microchannel reactors for GTL has demonstrated improved temperature control optionality and examine the impact of real-world operational and financial constraints and reduced methane selectivity. The scale-up challenge of enhanced FT performance in on this value. To this end a simulation model was developed and subsequently used to large scale microchannel reactors has not yet been addressed in the literature. This work will assess the incremental value added by polygeneration optionality through both describe the importance of flow distribution on both the process channels and cooling arbitrage and insurance. channels to maintain performance as the number of parallel process channels increases from one to ten to ten thousand and beyond. 1-4 FT performance in a single microchannel has been reported in the literature, where CO Global Experience with Coal Gasification Coal-To-Gas, conversion approached 70% per pass and methane selectivity less than 11% after more than Coal-To-Liquids, and IGCC Coal-To-Power 1000 hours on stream. Wm. Mark Hart, West Hawk Development Corp., CANADA A catalyst similar to those reported above was evaluated in multi-channel microstructured reactors consisting of more than 10 parallel microchannels interleaved with coolant channels. Coal gasification is globally a ‘hot’ topic for ultra-clean energy, utilization, and Cooling was provided by a cross-flow stream of coolant that was allowed to partially transportation of fuels and IGCC electric power generation. Amid surging energy vaporize thus quickly removing the heat released by the FT reaction. Two reactor designs prices, rising domestic demand, and concerns about energy security, many countries were evaluated both with and without tight control of the coolant flow distribution. In both seek coal gasification to develop and diversify domestic resources. Coal gasification cases the process stream had a flow mal-distribution of less than 10%. been successfully used in the USA, Europe, Russia, and South Africa with plants that In the first case, the reactor design did not achieve tight control of the cool flow distribution convert coal to diesel fuel, power, pipeline quality gas, and various other co-products and when operated the coolant flow rate from channel-to-channel deviated by more than with economics competitive to refining crude oil. Environmentally sound, proven 30%. This mal-distribution resulted in a steep temperature gradient in the catalyst, of more technologies to exploit coal more effectively are now being aggressively applied than 30°C, at the inlet of the process channels. Due to the poor temperature control, the around the globe with US$ billions in new projects now being advanced. Increasing selectivity to methane exceeded 30%. demand for petroleum based fuels along with anticipated increases in natural gas prices The second case, the multi-channel microstructured reactor was designed to provide a tight will continue to drive this trend. This paper discusses coal-to-liquids (CTL), coal-to- control of the flow distribution on the coolant side, and in operation the coolant flow rate gas (CTG), and coal-to-power (CTP/IGCC), projects and technologies around the from channel-to-channel deviated by less than 5%. The resulting process performance world, including from Germany and South Africa and current activities in the USA, mirrored the performance of the single channel microstructured reactor. Canada, and Europe. Scale-up of microstructured reactors for FT synthesis requires careful design of the flow distribution system for both the process channels and the coolant channels. The objective is 1

to review strategies for designing a flow distribution system for the coolant fluid, where of several of these SNG technologies. The knowledge gained over the years has been applied pressure drop is low and phase change occurs as the exothermic reaction in the process to the former technologies resulting in improved efficiency and lower investment cost. channel proceeds.

2-2 SESSION 3 Selectivity Improvement via Nitriding of Iron-Based Fischer-Tropsch Catalysts COMBUSTION TECHNOLOGIES – 1: Michael Claeys, Mark E. Dry, Eric van Steen, Centre for Catalysis Research, ADVANCING PC PLANTS TO NEAR-ZERO EMISSIONS University of Cape Town, SOUTH AFRICA Philip Gibson, Jakobus Visagie, Thato Motjope, Andre van Zyl, Sasol Technology R&D, SOUTH AFRICA 3-1 Deployment of Near-Zero-Emission USC PC Power Plants for CO2 Reduction Iron-based Fischer-Tropsch catalysts have been modified by nitriding at different Tony Armor, John Wheeldon, Electric Power Research Institute, USA conditions in an attempt to affect product selectivity towards valuable chemicals. Mildly pre-reduced catalyst samples nitrided with ammonia at elevated temperature Ultra-supercritical PC plants are being built and operated in Europe and Japan with showed largely improved formation of oxygenates compared to hydrogen reduced superheated steam conditions as high as 4100 psia and 1130°F. These plants are built with catalysts. In addition, and in contrast to early work reported by the Bureau of Mines, ferritic steels and this limits the maximum operating temperature. At US operating nitrided samples in this work also showed increased productivity for long chain 1- conditions and using bituminous coal, the efficiency of these plants is around 40 percent on a olefins. Nitriding was not found to affect overall catalyst activity, shift higher heating value basis. These plants are operating reliably and achieving high activity, methane selectivity and chain growth. The beneficial effects of nitriding can availabilities and low emissions. however decay at Fischer-Tropsch conditions, possibly due to loss of from the The AD700 program in Europe is developing materials and for USC plants with superheated iron nitride phases upon formation of iron carbides. steam conditions as high as 5000 psia and 1290°F and improving boiler and steam turbine designs. To exceed the temperature limit imposed by the ferritic steels, high-nickel alloys 2-3 have to be used. A similar US-DOE program is investigating high-nickel alloys for The Direct Synthesis of Dimethyl Ether over Hybrid Catalysts Composed of temperatures of 1400°F, which are projected to achieve generating efficiencies as high as 48 Cu-Zn Based Catalysts and Solid Acid Catalysts percent (HHV). USC plants operating at these conditions will lower CO2 emissions by 20 Tae Jin Lee, Eun Jin Kim, No-Kuk Park, Gi Bo Han, Si Ok Ryu, Yeungnam percent compared to the current designs. By producing less CO2, the new designs lower the University, National Research Laboratory, SOUTH KOREA cost of CO2 capture. This paper reports on the operation of current USC PC plants, along with their thermal and Dimethyl ether (DME) is primarily used as an aerosol propellant or industrially important environmental performance, and how these designs might be deployed in the US. How the chemical intermediate because of its attractive physical properties. In view of the more advanced USC PC designs might be deployed to achieve near-zero emission power environmental protection, the substitution of DME is unavoidable. Recently, a great attention plants is also discussed. has been paid to its applications as a fuel additive for vehicles and household uses. DME can be not only burned in diesel engine with a modified fuel system at the same efficiency but 3-2 also handled like (LPG). DME has been obtained directly from Requirements and Issues towards Obtainment of Ultra-Low NOx Levels syngas. In this study, the direct synthesis of DME over hybrid catalysts was performed in the Tony Facchiano, EPRI, USA temperature range of 270-290°C. Space velocity (GHSV), molar ratio of [H2]/[CO], and reaction pressure in the experiments were 3000-6000 ml/g-cat.h, 1.0, and 30-50 atm, Several power plants equipped with low-NOx burners and SCR systems are already respectively. Typically, the hybrid catalysts were composed of methanol dehydration obtaining NOx levels under 0.05 lb/MBtu when fired on sub-bituminous coal. However, the catalyst and methanol synthesis catalyst, which were made by a physical mixing in various obtainment of near-zero levels, defined as equal or less than 0.01 lb/MBtu, will require combinations. A series of hybrid catalysts were characterized by BET surface area and XRD significant development effort for both bituminous and sub-bituminous . This paper analysis. will examine the current state of combustion-based and post-combustion NOx control technologies and their accomplishments, operational and design issues currently precluding 2-4 the obtainment of near-zero NOx levels, and the development needed to overcome these Performance of a Non-Sulphided Maximum Distillate Catalyst in limitations. This paper will draw upon full-scale data and experiences, as well as pilot- and Fischer-Tropsch Wax Hydrocracking lab-scale efforts currently underway. Specific issues addressed will include limitations on Jack C.Q. Fletcher, Athanasios Kotsiopolis, Walter Bohringer, University of Cape pollutants that may be consequential to achieving ultra-low NOx levels (e.g., SO3, ammonia Town, Catalysis Research, SOUTH AFRICA slip, PM-10, etc), instrumentation and control challenges, component reliability, and the M. de Boer, Albemarle Catalysts Company B.V., NETHERLANDS impact of fuel properties and their variability. Consideration will be given to the existing C. Knottenbelt, The Petroleum Oil & Gas Corporation of South Africa Ltd, fleet of coal-fired boilers, where furnace design limits combustion-based NOx mitigation SOUTH AFRICA levels and available access limits SCR reactor sizes. Also discussed will be the design of new plants with advanced steam conditions, where greater flexibility to reduce NOx Fischer-Tropsch (F-T) based Gas-to-Liquids (GTL) processing is recognized as an emissions, albeit at increased costs and operational constraints, can be built into the system. industrially proven and economically competitive route to high quality diesel. Furthermore, it is generally accepted that for this purpose, GTL processing is most effective when 3-3 comprising an F-T synthesis driven to wax production, followed by hydrocracking to FGD Designs for High Efficiency: Current Status and Future Challenges produce middle-distillate products. Applying a CoMo/SiO2-Al2O3 catalyst, optimised for George Offen, Charles Dene, John Wheeldon, Electric Power Research Institute, USA hydrocracking crude oil refinery feedstocks in a sulphur-containing environment, to the Robert Keeth, Washington Group International, USA processing of a linear paraffin F-T wax model compound, n-tetradecane, shows that a significant opportunity exists for utilisation of base metal catalyst, having the advantage of Performance and field experience with new, high-efficiency flue gas desulfurization (FGD) producing less branched hydrocracking products, i.e. high cetane number diesel via a systems will be reported. The information presented will be based on recent EPRI visits to hydrogenolytic cracking mechanism. A drawback of such a catalyst, if applied in non- sites that had installed the latest design upgrades at commercial scale or were testing them at sulphided form and in a non-sulphur containing environment, is the comparably high yield large-scale pilot scale. On-site discussions and observations were used to determine the of light gases, in particular methane. It is shown, and proved by a simple kinetic model, that impacts that these design upgrades were having on day-to-day performance of emissions methane is formed via ‘methanolysis’, i.e. successive hydrogenolytic demethanisation control systems as well as balance-of-plant impacts. Sites in Europe, Japan, and the United reaction of the feed compounds, presumably of islands of metallic cobalt on the catalyst. States were visited during the project, and a summary of the major observations will be provided. 2-5 The paper will also present an assessment of the ability of these technologies to achieve Near High Temperature Methanation Process-Revisited Zero Emissions (NZE) goals and suggest additional measures that may be needed to meet Niels Udengaard, Anders N. Olsen, Haldor Topsoe Inc., USA this goal continuously. Qualitatively, NZE is defined as being virtually equivalent to Christian Wix-Nielsen, Haldor Topsoe A/S, DENMARK emissions from gas-fired power plants, with the exception of CO2. It will be shown that state-of-the-art FGD systems achieve very low SO2 emissions when operated optimally, but The rising cost of natural gas has resulted in a strong interest in manufacturing of substitute to maintain these levels continuously provisions may be needed to counter temporary natural gas (SNG) from the less costly and much more abundant coal. deviations in performance. Methanation of synthesis gas mixtures derived from gasification of coal is an essential step in the manufacturing of SNG. Technologies and catalysts for the SNG process were 3-4 developed and tested extensively during the 1970’s, when the energy costs were expected to Advanced Ultra-Supercritical Boiler Design and Boiler Materials increase to unseen levels. This did not happen and the interest in this technology vanished. A James Kutney, The Babcock & Wilcox Company, USA renewed interest today in shifting more energy consumption to coal has resulted in a revival

2

The U.S. pioneered development of supercritical technology with the first boiler 4-2 commencing commercial operation in 1957. This 125-MW B&W Universal Pressure A Novel Process for On-site Production of Mercury Sorbents boiler located at Ohio Power Company's Philo plant delivered 675,000 lb/h steam at Lawrence Bool, Chien-Chung Chao, David R. Thompson, Praxair, USA 4,550 psi. The steam was superheated to 1150°F with two reheats to 1050 and 1000°F. Also installed in the U.S. are 9 x 1300-MW units, the largest single supercritical units Activated carbon injection (ACI) represents a promising method reduce mercury designed, including one that set a record for 607 continuous days of operation. emissions from coal-fired plants. In recent years Praxair has developed a flexible B&W are an actively involved in the US-DOE s ultra supercritical boiler materials process to produce powder activated carbon (PAC) on-site using the plant’s pulverized research program testing stronger more corrosion-resistant materials, such as high- coal. The process is very flexible, allowing both undoped and doped carbons to be nickel alloys, necessary to progress to steam temperatures as high as 1400°F. Such easily produced from the same plant. Third party test results from slipstream tests at progression is essential to preserving pulverized coal technology as the preferred We Energies’ Pleasant Prairie Plant and Xcel Energy’s Comanche Station have shown choice for power generation. Applying these new materials will increase generating removals of 90% or greater. Praxair has continued to refine the process to better efficiency beyond that currently possible with ferritic steels and, by producing less understand the process conditions leading to good mercury capture while minimizing , new units will have lower the costs for carbon capture and the PAC cost. Several parameters have been explored in detail and will be discussed. sequestration. These parameters include the effect of dopant concentration on mercury capture, the This paper will present results from the test programs to certify the new materials. effect of different parent coals on sorbent performance, and the effect of a two-step Fire-side and steam-side corrosion data have been collected from a test loop in an activation process. Additional work planned in cooperation with the U.S. DOE to operating boiler as well as from laboratory simulations, and material weldability and mitigate the impact of PAC produced with the Praxair process on concrete properties fabrication have been evaluated. The paper will also discuss how the materials under will also be discussed. development will be incorporated into the design of new, more efficient boilers. 4-3 3-5 Feasibility of Activated Char Production for Mercury Post-Combustion CO2 Capture from Pulverized Coal Plants Capture from Chicken Waste and Coal John Wheeldon, Electric Power Research Institute; USA Wei-Ping Pan, Hong Cui, Yan Cao, Institute for Combustion Science and Environmental Technology, Western Kentucky University, USA In response to concerns over global warming, technologies need to be developed that capture and store the CO2 released by fossil-fueled power plants. A study carried out in 2000 and co- Chicken waste (CW) and its blending samples with a selected high sulfur coal (E-coal) funded by the US-DOE and EPRI investigated the thermal and economic performance of were used as raw materials for activated char (AC) preparation. Raw samples were supercritical pulverized coal (PC) combustion and an E-Gas™ integrated gasification subjected to the preparation procedures of carbonization in a nitrogen atmosphere and combined cycle (IGCC), using bituminous coal both with and without CO2 removal. The activation in a steam atmosphere. The basic properties of the raw materials, char and general conclusion was that for power plants with CO2 capture, the technology with the activated char were analyzed by components analysis, surface porosity and TGA lowest cost of electricity was IGCC with pre-combustion capture. An implied conclusion analysis. One AC sample was selected for elemental mercury capture tests in a lab- was that supercritical PC with post-combustion capture was not an economic or efficient scale drop tube reactor with air flow. The results show that low-cost and effective way to proceed. activated carbon could be produced by co-process of chicken waste and coal with Since the publication of that study, several improvements have been identified that enhance benefits to increase char yields. The higher removal efficiency is assumed that some the thermal and economic performance of post-combustion CO2 capture technology. activated species of chlorine and sulfur contained in the activated carbon can be of Improvements include those to solvents, CO2 capture plant equipment design, and benefit to elemental mercury capture. However, the assumed capture mechanism integration of the CO2 capture plant with the power plant to improve heat utilization. Once should be proved by the further investigation of detailed surface characteristics. these improvements are incorporated into the DOE/EPRI study, it is shown that a PC plant using post-combustion capture can be competitive with IGCC using pre-combustion capture. 4-4 This is especially the case for sub-bituminous coal where post-combustion capture may be Characterization Mercury Transport and Deposition in Ohio River Valley Region the most economic choice. The latest study also shows a benefit in going to ultra- Myoungwoo Kim, Kevin Crist, Ohio University, USA supercritical steam conditions. The higher efficiency of these PC plants lowers the amount of Rao Kotamarthi, Argonne National Laboratory, USA CO2 produced and so lowers the cost of CO2 capture. This information justifies continued effort to develop materials for use with steam cycles operating at higher temperatures and Ohio University, in collaboration with Argonne National Laboratory, CONSOL Energy, pressures. Significant benefits are also gained from improvements to CO2 capture solvents Advanced Technology Systems, Inc (ATS) as subcontractors, is evaluating the impact of and equipment design, so both these measures also warrant continued development effort. emissions from coal-fired power plants in the Ohio River Valley region as they relate to the The paper reports on the improvements identified for PC plants incorporating post- transport and deposition of mercury, arsenic, and associated fine particulate matter. This combustion CO2 capture and discusses improvements that may be made in the future. evaluation involves two interrelated areas of effort: ambient air monitoring and regional- scale modeling analysis. The scope of work for the modeling analysis includes (1) development of updated inventories of mercury and arsenic emissions from coal plants and SESSION 4 other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric ENVIRONMENTAL CONTROL TECHNOLOGIES: chemical transport model to incorporate recent advancements in the understanding of MERCURY ABSORPTION – 1 mercury transformations in the atmosphere; (3) analyses of the flux of Hg0, RGM, arsenic, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to 4-1 observations in order to evaluate characteristics of specific air masses associated with long- Effectiveness of Sulphur-Impregnated Activated Carbons Produced Using range transport from a specified source region; and (5) evaluation of the sensitivity of these Different Impregnation Methods in Mercury Vapour Adsorption correlations to emissions from regions along the transport path. This will be accomplished by Laura Fuentes de Maria, Shitang Tong, Donald W. Kirk, Charles Q. Jia, University of multiple model runs with emissions simulations switched on and off from the various source Toronto, CANADA regions. The modeling analysis is currently on-going. However an analysis of the base case runs will be presented including mercury wet-deposition patterns for the Ohio River Valley. Adsorption technologies based on sulphur-impregnated activated carbons (SIACs) have been proven an efficient method for vapour-phase mercury removal at coal-fired power 4-5 plants. The enhanced adsorption capacity of SIACs is often attributed to its high specific Field Evaluations of Carbon Sorbents surface area and sulphur species. The effect of sulphur-impregnation methods, which can Nicholas R. Pollack, Calgon Carbon Corporate, USA result in different sulphur species in SIACs, on mercury adsorption, is however not well understood. The present study evaluates the effectiveness of several SIACs produced from Calgon Carbon Corporation has investigated a series of carbon sorbents for the petroleum coke using different activation methods in the adsorption of vapour-phase removal of mercury from flue gas streams of coal-fired power plants. Pilot studies elemental mercury. To analyze the effect of different sulphur species on the adsorption of were conducted at a commercial power plant together with Apogee Scientific, Inc. The mercury, four types of activated carbons are used, a commercially available sulphur-free results represent the performance of the sorbents under real conditions using an actual activated carbon (VAC), a commercially available SIAC (BARRICK), and two adsorbents flue gas stream. A number of parameters were studied: carbon substrate, particle size, (FC1 and FC2) produced in our laboratory using oil-sands fluid coke as raw material. The impregnants, pore volume, and surface modifications. A follow-up study was mercury adsorption experiments are conducted using a laboratory scaled fixed-bed quartz conducted with the most promising candidates in order to maximize the performance reactor. A permeation device is used as the source of mercury vapour. Concentrations of and minimize the cost of the sorbent. Greater than 90% mercury removal was achieved mercury vapour are analyzed based on the dual gold amalgamation technique using a Cold with the best sorbents at normal injection rates. Calgon Carbon Corporation will Vapour Atomic Fluorescence Spectrophotometer (CVAFS). The adsorption capacity of the present the results of these studies. carbons is determined by analyzing mercury concentrations before and after adsorption. The effect of the temperature is studied in this work to better understand mercury adsorption mechanisms by SIACs. 3

5-3 SESSION 5 The Future of Pennsylvania Coal in a Hydrogen Economy HYDROGEN FROM COAL: GENERAL TOPICS Paul Lemar, Resource Dynamics Corporation, USA Eileen M. Schmura, Concurrent Technologies Corporation, USA

5-1 The Department of Energy (DOE) Multi-Year Research, Development and Demonstration US DOE Office of Fossil Energy’s Hydrogen from Coal Activities Plan’s1 overall program goal is to develop hydrogen delivery technologies that enable the Robert Wright, Lowell Miller, Daniel Cicero, US Dept of Energy, USA introduction and long-term viability of hydrogen as an energy carrier for transportation and Mark Ackiewicz, John Anderson, Technology & Management Services, Inc., USA stationary power. Concurrent Technologies Corporation (CTC) and other organizations are Edward Schmetz, John Winslow, Leonardo Technologies, Inc., USA performing research and development (R&D) and infrastructure development tasks in order to assist in meeting this goal. This paper addresses an important objective in this effort to The Hydrogen from Coal Program is part of the Office of Sequestration, Hydrogen, provide a hydrogen delivery tradeoff study for the State of Pennsylvania. One aspect of the and Clean Coal Fuels (OSHCCF) activities in the Department of Energy’s (DOE) tradeoff study addresses the future for Pennsylvania coal in a hydrogen economy. Resource Office of Fossil Energy (FE). The Program manages the Department’s research, Dynamics Corporation (RDC), in conjunction with CTC and Air Products and Chemical development, and demonstration (RD&D) activities for novel coal-based technologies Inc, completed the study; however, this paper was prepared collaboratively by RDC and designed to produce, deliver, store, and utilize hydrogen from coal. Hydrogen research CTC. The hydrogen delivery tradeoff project being lead by CTC for the DOE identifies and is a key element of the Department’s energy research portfolio to meet the qualifies the most important tradeoffs among hydrogen delivery options for the State of Administration’s energy goals and objectives as defined in the National Energy Policy. Pennsylvania. Pennsylvania is a very good case study market because it contains 15 discrete In addition to managing its respective RD&D portfolio, the Program also cooperates metropolitan statistical areas (MSA), as well as a variety of potential fossil fuel based and on joint efforts with other DOE and FE offices on large-scale initiatives such as the renewable hydrogen energy sources and delivery infrastructures. This allows for a structured Hydrogen Fuel Initiative, FutureGen project, Clean Coal Power Initiative and analysis of a variety of meaningful alternative delivery tradeoff scenarios reflective of many Advanced Energy Initiative that were instituted in order to utilize domestic resources, of the challenges the nation faces in moving towards a hydrogen economy. including coal, to address concerns about energy security and greenhouse gas The objectives of this project were to show the lowest cost solution for production emissions. The Hydrogen Fuel Initiative, led by the Office of Energy Efficiency and location/method and delivery methods, and the tradeoffs between these methods. Given that Renewable Energy (EERE), coordinates hydrogen-related activities being performed the State has abundant coal reserves, examining the use of coal as a feedstock for hydrogen by EERE, FE, Office of Nuclear Energy, Science and Technology (NE), and the Office production was a critical aspect of the study. The study approach was designed to use a of Science (SC). The Hydrogen from Coal Program is responsible for hydrogen from scenario-based methodology. Three hydrogen demand scenarios were constructed and coal research activities and participates in joint efforts such as development of the analyzed: an initial scenario focusing on 1 % of the current population of light duty vehicles DOE Hydrogen Posture Plan. This plan outlines DOE’s activities, milestones, and (LDVs) fueled by hydrogen, 10 %, and 30 %. The 1 % case is fleet use and early adopter use deliverables to facilitate the United States’ transition to a hydrogen economy. with the 10 % and 30 % cases representing an increased number of early adopters. Within Additionally, the Hydrogen from Coal Program staff coordinates with the staff of other each of these scenarios, demand centers were identified that in general coincided with the DOE offices on joint R&D solicitations and other appropriate activities. Coordinating major MSAs in the State and were used to define volume and distance relationships. With efforts and sharing of information and experiences are essential if we are to be these parameters defined, a variety of different production and distribution options could be successful in the transition to a hydrogen economy. DOE’s coal RD&D portfolio analyzed and the various tradeoffs identified. For each scenario, the parameters needed for contains technology for energy systems that produce multiple products (i.e., electric lowest delivered cost and for lowest infrastructure investment were identified using a power, hydrogen, fuels, and chemicals). These systems perform with near-zero lifecycle cost analysis and the DOE’s H2A model. The sensitivity analysis examined the emissions, including the capture and storage of carbon dioxide (CO2). A key element potential for the lowest cost options to change based on alternate assumptions and the key of this drive toward zero emissions plants is DOE’s FutureGen project. This project tradeoffs. serves as an integration platform to demonstrate co-production of electricity and 1) Hydrogen, Fuel Cells & Infrastructure Technologies Program Multi-Year Research, hydrogen with CO2 sequestration performed at commercial scale. Development and Demonstration Plan, US Department of Energy, January 21, 2005 This paper reviews (1) the key energy and environmental challenges that the program addresses, (2) the benefits of producing hydrogen from coal while utilizing 5-4 sequestration and (3) the advanced technologies that are under development by the Hydrogen Production through Coal Gasification in Updraft Hydrogen from Coal Program. The goals and milestones of the Program are presented, Gasifiers with Syngas Treating Sections along with recent accomplishments and progress since its inception in FY2004. Alberto Pettinau, Sotacarbo S.p.A., ITALY Finally, key features in the implementation of the program are discussed. VittorioTola, University of Cagliari, ITALY Paolo Deiana, ENEA, ITALY 5-2 Hydrogen-Assisted IC Engine Combustion as a Hydrogen production through coal gasification is becoming one of the most attractive Route to Hydrogen Implementation options for energy production due to the remarkable advantages offered by this Andre Boehman, Daniel Haworth, Elana Chapman, Melanie Fox, Bryan Nese, Saket technology in pollution control and greenhouse gases-emissions monitoring. Priyadarshi, Gregory Lilik, Yu Zhang, Eugene Kung, Pennsylvania State University, With this aim, Sotacarbo, Ansaldo Ricerche, ENEA and the University of Cagliari, are USA developing a research project to design, construct and test a pilot plant for hydrogen production from coal gasification (in particular from high-sulphur Sulcis coal). The This research project (Funded under DOE Cooperative Agreement DE-FC25-04FT42233) project has been funded by the Italian Ministry of Education, University and Research focuses on developing the underlying fundamental information to support technologies that (MIUR) and by the European Commission and the total cost has been estimated in will facilitate the introduction of coal-derived hydrogen into the market. Two paths are about 12 million euros. envisioned here for hydrogen utilization in transportation applications. One is to mix The pilot plant, which is currently under construction in the Sotacarbo Research Centre hydrogen with other fuels, specifically natural gas, to enhance performance in existing located in Sardinia (Italy), includes two updraft fixed-bed Wellman-Galusha gasifiers natural gas-fueled vehicles (e.g., transit buses) and provide a practical and marketable (a 700 kg/h pilot gasifier and a 35 kg/h laboratory-scale gasifier), fed up with high- avenue to begin using hydrogen in the transportation industry. A second is to use hydrogen sulphur Sulcis Coal and low-sulphur South African coal, and a syngas treating process, to enable alternative combustion modes, such as homogeneous charge compression ignition, which includes the raw-gas cleaning section, an integrated CO-shift and CO2 removal in order to permit enhanced efficiency and reduced emissions. This project on hydrogen- system and the hydrogen separation unit. In particular, the raw gas cleaning sections is assisted combustion encompasses two objectives: (1) Optimization of hydrogen-natural gas composed by both hot and cold gas desulphurization processes, which can operate in mixture composition and utilization through laboratory studies of spark ignition engine parallel in order to compare their performances. operation on H2-NG coupled with numerical simulation of the impact of hydrogen blending This paper reports the main results of the process analysis and performance evaluation, on the physical and chemical processes within the engine. The project makes use of facilities in particular the analysis of the updraft moving bed gasifiers has been carried out under developed under a DOE-sponsored hydrogen fueling station project (DOE Cooperative the assumption of chemical equilibrium by using two different simulation models, Agreement No. DE-FC04-02AL67613, “Development of a Turnkey Commercial Hydrogen developed using the Aspen Plus 12.1 and the ChemCad 5.2 software (in both models Fueling Station”) to provide both hydrogen and hydrogen enriched natural gas (HCNG) for the syngas composition has been calculated through the minimization of the Gibbs free the laboratory studies, and (2) Examination of hydrogen-assisted combustion in advanced energy). The results obtained with the two gasification models are very similar and compression-ignition engine processes, such as homogeneous charge compression ignition compare favourably with the expected performance specified by the gasifier (HCCI) engine operation. This includes experiments in a multicylinder engine and manufacturer. multidimensional modeling of in-cylinder aero-thermo-chemical processes. The project will The results obtained with the two gasification models are very similar and compare provide information on the viability and benefits of using hydrogen in an HCCI engine, will favourably with the expected performance specified by the gasifier manufacturer. map out the useful HCCI operating envelope, and will explore the possibilities for As for the syngas treatment line, a detailed simulation dynamic model has been broadening the HCCI operating envelope using direct in-cylinder pilot injection. developed in order to evaluate the performances of each component of the plant (with particular reference to the hot gas desulphurization process and to the integrated CO- shift and CO2 removal system). 4

5-5 Douglas Allen, DOE/NETL, Salem State College, USA Enhanced Hydrogen Production with in-situ CO2 Capture in a Single Stage Reactor Experiments were conducted to determine the solubility of CO2 in a natural brine Liang-Shih Fan, Mahesh Iyer, Shwetha Ramkumar, Danny Wong, The Ohio State solution of the Oriskany sandstone formation under elevated temperature and pressure University, USA conditions. These data were collected at pressures between 100 and 450 bars and at temperatures of 21 and 75ºC. In addition, data on CO2 solubility in pure water were Enhancement in the production of high purity hydrogen from , obtained from coal collected over the same pressure range as a means of verifying reliability of gasification, is limited by thermodynamics of the Water Gas Shift Reaction which is used to experimental technique. Experimentally determined data were compared with CO2 shift the carbon monoxide towards hydrogen. However, this constraint can be overcome by solubility predictions using a model developed by Duan and Sun (2003). Model results concurrent water-gas shift (WGS) and carbonation reactions to enhance H2 production by compare well with Oriskany brine CO2 solubility data collected experimentally, incessantly driving the equilibrium-limited WGS reaction forward and removing the CO2 suggesting that the Duan and Sun model is a reliable tool for estimating solution CO2 product from the fuel gas mixture in-situ. This not only improves the H2 yield but also capacity in high salinity aquifers in the temperature and pressure range evaluated. augments the purity of the product by removing the CO2 co-product and achieving near complete conversion of the CO reactant. This process developed at the Ohio State University 6-4 can effectively and economically produce a pure H2 stream, at high temperature and Evaluation of CO2 Flood on the Geomechanics of Whole Core Samples pressure, via coal gasification while integrating capture of CO2 emissions, for its subsequent Steve Gerdemann, Hank Rush, Bill O'Connor, NETL, USA sequestration. The enhanced water gas shift reaction for H2 production with insitu carbonation was studied using the commercial High Temperature Shift (Iron Oxide) catalyst Geological sequestration of CO2, whether by enhanced oil recovery (EOR), coal-bed and calcium sorbents in an integral fixed bed reactor setup. We have identified a high methane (CBM) recovery, or saline-aquifer injection, is a promising near-term sequestration reactivity patented, mesoporous calcium oxide sorbent for the in-situ CO2 capture. The methodology. While tremendous experience exists for EOR, and CBM recovery has been morphological properties of our patented precipitated calcium carbonate sorbent (PCC) can demonstrated in existing fields, saline-aquifer-injection studies have only recently been be tailored using surface modifiers to demonstrate a high CO2 capture capacity of about 70% initiated. Studies evaluating the availability of saline aquifers suitable for CO2 injection show by weight (~700g of CO2/kgsorbent) at elevated temperatures (600-700°C). Experimental great potential. evidence clearly shows that this proprietary calcium sorbent (PCC) performance dominates This study evaluated the physical and chemical effects on Mt. Simon sandstone core from over that of commercial limestone sorbents at any given time. Thus, product gas the Illinois Basin exposed to simulated deep-aquifer brine saturated with super-critical CO2. composition analyses demonstrate complete carbon monoxide conversion as well as CO2 Conducting these tests on whole core samples rather than crushed core allowed an removal during the initial part of the breakthrough curve, thus demonstrating the synthesis of evaluation of the impact of the CO2 flood on the rock-mechanics properties as well as the pure hydrogen. geochemistry of the core and brine solution. Preliminary results show an increase in porosity and a decrease in crushing strength of the core after exposure to CO2 for 2000 hours.

SESSION 6 6-5 GLOBAL CLIMATE CHANGE: Sequestration of CO2 in Mixtures of Bauxite Residue and Saline Waste Water GEOLOGIC CARBON SEQUESTRATION – 1 with Carbonate Mineral Formation and Caustic Byproduct Neutralization Robert Dilmore, Yee Soong, Sheila Hedges, Angelo Degalbo, DOE/NETL, USA Douglas Allen, DOE/NETL, Salem State College, USA 6-1 Jaw K. Fu, Charles L. Dobbs, ALCOA, USA Effects of CO2 and Aquifer Brine on Well Plugging Cements Chen Zhu, Indiana University, USA Steve Gerdemann, G.E. Rush, Bill O’Connor, NETL, USA Under consideration is a process designed to enhance the CO2 trapping capacity of General consensus is that CO2 at injection pressures in a saline environment will degrade brine solutions through addition of bauxite residue with subsequent carbonation of the portland based well plugging cements. Long term exposure, years or decades are typical caustic mixture. A set of experiments was conducted to explore the concept of utilizing time frames mentioned and modeled. Actual cement samples from CO2 environments such mixtures of bauxite residue and brine to sequester carbon dioxide from industrial gas as oil fields in which CO2 has been used to extend field production are rare, and actual streams such as flue gas from coal fired electric utility boilers. Factors affecting the brackish to saline aquifer rock with CO2 exposure still less common. Laboratory experiments solubility of acid gasses in such mixtures include temperature, pressure, and water to simulate the saline environments were run with interesting results. chemistry properties including pH, ionic concentration, and salinity. Bauxite residue/brine mixture of 90/10 by volume exhibited a CO2 sequestration capacity of 6-2 greater than 9.5 grams per liter when exposed pure CO2 at 20ºC and 100 psig. Calcite Using Pinnate Well Patterns for CO2 Sequestration in formation was verified as a product of bauxite/brine mixture carbonation. Data Allison Unit Reservoir Simulation Study presented herein provide a preliminary assessment of overall process feasibility and Jalal Jalali, Shahab Mohaghegh, West Virginia University, USA probe the influence of several variables on treatment efficiency. It is demonstrated that CO2 sequestration is augmented by adding bauxite residue as a caustic agent to acidic Concerns about rising concentrations of carbon dioxide (CO2) in the atmosphere and the brine solutions, and that trapping is accomplished through solubilization and ultimate necessity of reducing greenhouse gas emissions has led to consideration of large-scale mineralization. storage of CO2 in subsurface. Carbon dioxide is injected into unminable coal seams for enhancing the coalbed methane recovery, which also has the extra advantage of long-term CO2 sequestration. Pilot projects exist in North America and some European countries to SESSION 7 study the feasibility of CO2 sequestration in depleted oil and gas reservoirs. GASIFICATION TECHNOLOGIES: Among different well patterns currently used for primary recovery of coalbed methane, APPLICATIONS AND ECONOMICS – 2 horizontal pinnate wells demonstrate high methane recovery in a short period of time along with cost reductions and smaller footprints. In this study, a pinnate well is first used for primary recovery of methane and then converted 7-1 into an injector for CO2 injection to enhance the methane recovery and eventually long term The Shell Coal Gasification Process sequestration. The large contact area between the wellbore and the formation helps fast Hugo T. P. Bos, F.G. van Dongen, Shell Global Solutions International BV, THE dewatering, hence producing the methane, which is desorbed from the coal matrix into the NETHERLANDS natural fractures. The pinnate pattern distributes the CO2 in a large area of the formation before it reaches the producing wells. Therefore, a larger amount of CO2 could be stored in The latest status of the Shell Coal gasification Process (SCGP) is discussed. the formation before CO2 breakthrough occurs. Applications of gasification for chemicals production and power production are given. In this paper, a feasibility study of CO2 sequestration using pinnate patterns into a coal seam Projects throughout the world are presented including the status of completion/ startup. in the Allison Unit is presented. Several characteristics of the pinnate pattern and the CO2 The latest developments of the Shell Coal gasification Process are presented such as injection strategy are studied and optimized using a numerical reservoir simulator in order to combined oil + coal gasification, biomass/coal to liquids conversion and methods for increase the methane recovery and total CO2 that can be stored before breakthrough. Results CO2 sequestration. will be compared with the results from the well pattern currently used for CO2 flooding in the field. 7-2 The GSP Gasification Process; State-of-the-Art and Further Development 6-3 Manfred Schingnitz, Klaus-Dieter Klemmer, Future Energy GmbH, GERMANY Experimental Measurements of the Solubility of CO2 in the Oriskany Sandstone Aquifer The development of the GSP-Process, a pulverized fuel pressure gasification technology, Robert M. Dilmore, Patrice Pique, Sheila Hedges, Yee Soong, R. J. Jones, was started in 1975 by Deutsches Brennstoffinstitut Freiberg/Sa. (DBI, German Fuel DOE/NETL, USA Research Institute). Main objective for this development was the demand to save crude oil 5

and natural gas which should be partly replaced by using the available lignite. It was the an industrial application. A UCG -IGCC power plant will generate electricity at a much intention of the government in the former GDR to build up several gasification plants in the lower cost than existing or proposed fossil fuel power plants. CO2 emissions of the plant can area of Central Germany to supply major chemical companies through long-distance be reduced to a level 55% less than those of a supercritical coal-fired plant and 25% less than pipelines with syngas from lignite. Because of the low rank of lignite and the high salt the emissions of NG CC. content in the ash of this coal the process had special demands to the feeding system and to the gasifier itself. Passing a period of several owners after the privatization in 1991 the FUTURE ENERGY GmbH belongs to SIEMENS Power Generation since the 1st January SESSION 8 2006. The first test facility with a thermal capacity of 3 MW, built in 1979, was used to SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND examine the technical concept and to test the planned lignite and saliferous lignite for the OTHER NON-FUEL USES OF COAL: APPLIED FT/CTL erection of the large scale demonstration facility in 1984 in the Gaskombinat Schwarze Pumpe /Germany, where the name of the process “GSP” comes from. In the period 1994 to 1998 further test facilities were erected at FUTURE ENERGY site in Freiberg, among this a 8-1 5 MWth cooling screen reactor. Up to now these facilities have been used to gasify more than Coal Conversion - A Rising Star? 90 candidate gasification feeds - among others 35 different coals, 25 sewage sludge’s of C. Lowell Miller, DOE, USA municipal or industrial provenance, petroleum coke, waste oils, bio-oils, bio-slurries and 20 Daniel Cicero, NETL, USA liquid residues, in order to investigate their gasification behavior and to analyze the quality Mark Ackiewicz, John Anderson, Technology & Management, USA and the characteristics of the gasification products. By this systematic research and Edward Schmetz, John Winslow, Leonardo Technologies, Inc., USA development the field of application of the GSP Technology was enlarged from conventional fuels, such as coals and oils, through residual and waste materials and biomass. Coal’s primary use has been for electric power production but it can also be used for other purposes, such as for producing liquid fuels, hydrogen, or chemical intermediates. Coal s 7-3 versatility and flexibility as a feedstock is becoming increasingly recognized, with Orlando Gasification Project: Demonstration of government and industry, jointly and independently, pursuing opportunities to maximize a Nominal 285 MW Coal-Based Transport Gasifier coal s potential as a feedstock for purposes other than power generation. For example, the Frank Morton, Tim Pinkston, Southern Company, USA jointly sponsored, government-industry FutureGen project will develop the world s first Nicola Salazar, KBR, USA electric power and hydrogen co-production plant that produces near-zero emissions and Denise Stalls, Orlando Utilities Commission, USA captures and stores the carbon dioxide that is produced. This paper will review current coal conversion activities that are being pursued by the federal Southern Company, the Orlando Utilities Commission (OUC), and KBR are building an government and industry and the key fundamentals that may be driving these activities. advanced 285-megawatt coal gasification facility near Orlando, Florida with the support of Representative coal to liquid (CTL) concepts and capital and product costs will be reviewed the Department of Energy (DOE) under the Clean Coal Power Initiative (CCPI). The CCPI including discussion of potential activities which could reduce the uncertainties in cost is a cost-sharing partnership between the government and industry designed to accelerate estimation. commercial deployment of advanced technologies to ensure that the United States has clean, Recent legislation may be playing a role in the increased interest in coal conversion reliable, affordable coal-based electricity, which is essential for a strong U.S. economy and technologies. For example, the Energy Policy Act of 2005 (EPACT 2005) contained domestic energy security. The proposed plant will demonstrate an Integrated Gasification provisions related to coal-to-liquid (CTL) technologies or co-production of power and fuels Combined Cycle (IGCC) using an air-blown Transport Gasifier. Southern Company and or chemicals from coal. Additionally, Section 1090 of the National Defense Authorization KBR are developing the Transport Gasifier and related systems for commercial application Act for Fiscal Year 2006 required the Department of Energy to prepare a development plan in the power industry in conjunction with the U.S. Department of Energy (DOE). The Power for coal-to-liquid fuels and the Department of Defense to develop a report on how it would Systems Development Facility (PSDF) is an engineering scale demonstration of the KBR potentially use these fuels. Efforts are also underway by state governments, primarily in Transport Gasifier, a high-temperature, high-pressure syngas filtration system, and gas major coal-producing states, to increase the conversion of coal into fuels and chemicals. cleanup. Built at a sufficient scale to test advanced power systems and components in an Expanded use of coal to produce liquid fuels, hydrogen and chemical intermediates can integrated fashion, the PSDF provides data necessary for commercial scale-up of these increase the security and stability of the nation s liquid fuel supplies, and provide economic technologies. and employment benefits. The Transport Gasifier is an advanced circulating fluidized bed system designed to operate at higher circulation rates, velocities, and riser densities than a conventional circulating bed 8-2 unit. The high circulation rates result in higher throughput, better mixing, and higher mass Review of Competitive and Environmental Challenges to US and heat transfer rates. Since the gasifier uses a dry feed and does not slag its ash, it is Coal-to-Liquids (CTL) Industry Development particularly well-suited for high moisture fuels such as sub-bituminous coal and lignite. Tim Cornitius, Syngas Refiner, USA

7-4 New construction and expansion of Canadian oilsands projects to increase output of Energy investment of the future - Nuon Magnum IGCC Power Plant bitumen-derived synthetic crude oil (SCO) has surpassed the promising potential of Leon Pulles, Nuon, NETHERLANDS producing transportation fuels from coal as the United States continues to neglect the timely Natalie van der Burg, Capgemini, NETHERLANDS and vital development of this vast resource. Unlike other oilsands projects, Canadian Natural Resources Ltd. appears to be staying ahead of budget and it said one move recently “avoided The 21st century is in need of investments in the power generation sector. This article millions of dollars in additional costs.” The first staged of its Horizon project is proceeding describes the economic view on investing in this sector. In addition it entails the well and predicted construction will be 44% completed by the end of the September. Its project development approach of a current investment project, as illustrated by the preplanning is paying off on work for the first stage, budgeted at $6.8 billion with expansion Nuon Magnum IGCC Power Plant project with a generation capacity of 1200 MWe. plans of more than $20 billion over the next dozen years. International oil companies (IOCs) Capgemini is working together with Nuon and delivers project management usually increase production when oil prices are expected to remain high, but a lack of access capabilities. to acreage in some key oil-rich countries has forced them to turn to the Canadian oilsands to increase reserves. The IOCs are using various technologies including gasification to process 7-5 bitumen economically that will mean an increased supply of SCO to US refineries. The Exergy UCG Technology and its Commercial Applications Alternative fuels production is highly sensitive to crude oil price levels. The US Energy Michael S. Blinderman, Ergo Exergy Technologies, Inc., CANADA Information Administration’s Annual Energy Outlook (AEO) 2006 reference case prices increase from $40.49/bbl in 2004 to $54.08/bbl in 2025 ($21/bbl higher than AEO2005) and Underground Coal Gasification (UCG) is a gasification process carried on in non-mined coal to $56.97/bbl in 2030. Higher prices increase demand for unconventional transportation-fuel seams using injection and production wells drilled from the surface, converting coal in situ sources and stimulate coal-to-liquids (CTL) production. With even higher oil prices, US gas- into a product gas usable for chemical processes and power generation. The UCG process to-liquids (GTL) production is also stimulated. developed, refined and practiced by Ergo Exergy Technologies is called the Exergy UCG Technology or UCG Technology. 8-3 The UCG technology is being applied in numerous power generation and chemical projects Use of Cobalt Fischer-Tropsch Catalysts with Coal Derived Synthesis Gas worldwide. These include power projects in South Africa (1,200 MWe), India (750 MWe), Steve LeViness, Fischer Tropsch Reactor Technology, USA Pakistan, and Canada, as well as chemical projects in Australia and Canada. A number of Heinz Robota, Syntroleum Corporation, USA UCG based industrial projects are now at a feasibility stage in New Zealand, USA, and Rafael Espinoza, Rafael Espinoza Consulting, USA Europe. An example of UCG application is the Chinchilla Project in Australia where the technology demonstrated continuous, consistent production of commercial quantities of The production of hydrocarbons by the hydro-polymerization of carbon monoxide was quality fuel gas for over 30 months. The project is currently targeting a 24,000 barrel per day discovered by Fischer and Tropsch in 1923, and – with the exception of 1945-1955 – has synthetic diesel plant based on UCG syngas supply. The UCG technology has demonstrated been in commercial use continuously since 1933. The first commercial Fischer-Tropsch exceptional environmental performance. The UCG methods and techniques of process, practiced in Germany from 1933-1945, employed cobalt based catalysts in fixed environmental management are an effective tool to ensure environmental protection during bed reactors using coal derived synthesis gases. Since 1955 Sasol has practiced FT from coal 6

derived synthesis gases employing iron based catalysts in a variety of different reactors, including fixed, fluidized, and slurry bed variations. Since the late 1980’s and early 1990’s SESSION 9 Mossgas and Shell have practiced FT synthesis from natural gas derived synthesis gases COMBUSTION TECHNOLOGIES – 2: employing iron catalysts in fluidized bed reactors, and cobalt catalysts in fixed bed reactors, MERCURY CAPTURE FROM FLUE GAS respectively. Also since the late 1980’s and early 1990’s, FT synthesis processes from natural gas (“gas to liquids”, or “GTL”) have been developed by BP, ConocoPhillips, ENI/IFP/Agip, ExxonMobil, Rentech, Sasol and Sasol Chevron, Shell, Statoil-PetroSA, and 9-1 Syntroleum, among other. All of these technologies are based upon cobalt catalyst slurry The U.S. Department of Energy’s Phase II Mercury Control phase reactors, with the exceptions of BP and Shell (cobalt catalyst fixed bed reactors) and Technology Field Testing Program Rentech (iron catalyst slurry reactors). The recent dramatic escalation in world-wide Thomas Feeley, III, DOE/NETL, USA petroleum prices, coupled with the passage of a $21/bbl tax credit in the US, has caused a sharp increase in interest in production of FT products from coal derived synthesis gases. Mercury exists in trace amounts in coal. In the United States, coal-fired power plants Current conventional wisdom appears to be that only iron based FT catalysts are appropriate emit about 48 tons of mercury and are the largest point source of emissions. The U.S. for this application, ignoring the fact that the entire German commercial FT industry was in Environmental Protection Agency determined the need to control mercury emissions fact based on cobalt catalysts and coal derived synthesis gases. from power plants and issued regulations on March 15, 2005 under the Clean Air The FT reaction consumes H2 and CO in a ratio slightly higher than 2/1, typically about Mercury Rule. In addition, several states have proposed mercury regulations more 2.15. Depending on the synthesis gas source (especially coal vs. natural gas) and the syngas aggressive than the Federal rule. generation technology, the raw synthesis gas H2/CO ratio can be anywhere in the range of Recognizing the potential for mercury regulations, the U.S. Department of 0.6 to 3.0, or higher. Typical coal gasification raw synthesis gas ratios range from about 0.6 Energy/National Energy Technology Laboratory (DOE/NETL) has been carrying out a to as high as 2.3, again depending on coal source and composition and gasification comprehensive mercury research and development program since the early 1990s. technology. For raw syngas H2/CO ratios below the required FT stoichiometric usage ratio Working collaboratively with EPRI, industry, academia, and EPA, DOE/NETL has of about 2.15, it is necessary to increase the ratio through the use of the water gas shift helped to advance the understanding of the formation, distribution, and capture of (WGS) reaction, either in a separate WGS reactor or in the FT reactor itself through the use mercury. However, uncertainty remains, particularly related to the overall cost and of an FT catalyst with significant WGS activity like iron. In practice, even with iron effectiveness of controlling mercury from a diverse population of coal-fired boilers, as catalysts, a feed synthesis gas H2/CO ratio of 0.6-1.0 is too low, and external WGS must be well as the ultimate fate of mercury once it is removed from the flue gas. employed to avoid excessive FT catalyst requirements and reactor sizes. This presentation will provide an update on DOE/NETL s Phase II mercury field While iron catalysts are preferred for the high temperature FT processes targeting chemical testing program directed at full-scale and slip-stream evaluation of sorbent injection feedstocks and high octane gasoline, the choice of optimum catalyst type for low (e.g., activated carbon) and oxidation processes that have the capability to achieve 50 temperature FT synthesis, targeting middle distillates and other paraffinic products from coal to 70 percent capture of mercury from operating pulverized-coal-fired power plants. In derived syngas is not straightforward, as both cobalt and iron have significant advantages addition, results from the characterization of mercury in coal combustion by-products and disadvantages. In the preferred slurry bed reactors, iron catalysts are characterized by collected from the Phase II field testing program will be presented. low cost, moderate syngas cleanup requirements, relatively low particle strengths (leading to potential catalyst wax separation issues), high deactivation rates and short effective catalyst 9-2 life (leading to high catalyst replacement and solids handling volumes), and low methane but Control of Mercury Emissions from Clean Coal Power Plants with CO2 Capture excessive CO2 selectivities. Cobalt catalysts, on the other hand, are characterized by much Kourosh E. Zanganeh, Ahmed Shafeen, Murlidhar Gupta, Robert Dureau, CANMET higher costs, extremely high syngas cleanup requirements, high particle strength (relatively Energy Technology Centre, CANADA easy catalyst-wax separation), low deactivation rates and long effective life, and somewhat higher methane but much lower CO2 selectivities. The major challenge facing the use of Currently, coal-fired power plants provide about 39% of the global electricity demand and cobalt catalysts is synthesis gas clean-up, which will strongly depend on coal source and this trend is likely to remain the same in the coming decades. According to the International syngas generation (gasification) technology choices. Related coal syngas based catalytic Energy Agency’s predictions, the world’s electricity demand will be doubled between now processes, such as methanation and methanol synthesis, have similar syngas contaminant and 2030. During this period, nearly 1400 GW of new coal-fired power capacity will be specifications and are currently practiced commercially, indicating technical feasibility. required worldwide. With emission standards becoming more stringent, future coal-fired Preliminary results of cobalt catalyzed FT synthesis using a commercial coal gasification power plants will be expected to significantly reduce their emission intensity by utilizing based synthesis gas will be presented. advanced clean coal technologies. The new generation of clean coal power plants with CO2 capture, may include integrated energy conversion systems such as gasification with pre- 8-4 combustion capture, ultra-supercritical steam boilers with post-combustion capture, and oxy- The WMPI Coal-To-Liquids Program fuel combustion systems with integrated capture and compression. The capture component James C. Sorensen, Sorensenenergy, LCC, USA; John W. Rich, Jr., WMPI PTY., of these advance systems could be facilitated by a variety of technologies including LLC, USA membrane separation, absorption, adsorption and cryogenic separation technologies. Some of these technologies such as post-combustion with amine scrubbing would carry significant The Gilberton CTL Project, with plans to begin construction this year, represents the potential for adaptation in the existing fleet of coal-fired power plants through retrofit, while first step in WMPI’s U.S. Coal-To-Liquids program. In parallel with Gilberton, WMPI others such as oxy-fuel combustion and gasification could be effectively deployed in the new has begun exploratory development work on larger capacity CTL projects of a scale state-of-the-art green-field plants with near-zero emissions. not requiring Government subsidy. This paper will provide an update on progress at Controlling the emission of toxic air pollutants such as mercury and other trace metals is one Gilberton, summarize the efforts underway toward commercial project objectives and of several key challenges facing the large-scale deployment of advanced clean coal power some initial conclusions, as well as outlining WMPI’s basic criteria for project success. plants in the next two decades. This is further compounded by the imposed timelines, set in In addition, key drivers behind the current surge of interest in Coal-To-Liquids will be the recent regulations and standards in U.S. and Canada. Currently, there are ongoing discussed. initiatives to demonstrate clean coal technologies for power generation in North America, Europe and other parts of the world by 2012 and beyond. However, any successful 8-5 demonstration of clean coal technologies should also consider the control of primary air Selective Coal Liquefaction through Fischer-Tropsch Synthesis pollutants such as mercury. Hans Schulz, Engler-Bunte-Institute, GERMANY In this paper, we present an overview of mercury emissions from clean coal power plants with CO2 capture, possible pathways for mercury species in gasification, oxy-coal The selectivity of Fischer-Tropsh synthesis to very clean fuels and chemicals makes combustion and post-combustion capture plants, and potential control technologies for the process so attractive today – and also for future application on a coal basis, as reducing mercury emissions from these plants. The CANMET’s oxy-fuel combustion group much against direct coal liquefaction by hydrogenation. Coal gasification and the has been actively pursuing the development of new mercury control technologies for oxy- composition of synthesis gas from coal, in relation to the requirements of the Fischer- coal combustion processes in recent years. The focus of this work is on low rank coals, Tropsch synthesis are regarded together with specific process options of FT-synthesis. mainly, sub-bituminous and lignite coals. In this paper, some results from the recent pilot- Of particular interest is the FT route to diesel fuel as relying strongly on the scale testing at CANMET’s oxy-fuel combustion facility to develop effective mercury combination with “ideal hydrocracking”. But further options are also promising. control technologies for the next generation of oxy-coal power plants are presented. The The mechanistic basis of Fischer-Tropsch synthesis is then regarded, taking into results obtained to date are very encouraging and further work is under progress to optimize account time resolved self-organization of the FT-regime. The fundamental differences these processes. of FT on iron and cobalt are evaluated and the common principle of “frustrated desorption” is established, as on the basis of detailed selectivity studies, seeing the 9-3 highly ordered complexity of product composition. The progress in understanding FT- Mercury Speciation in Exhaust Gases of O2-CO2 Coal Combustion catalysis shall be useful also for progress in commercial application of Fischer-Tropsch Achariya Suriyawong, Pratim Biswas, Washington University in St. Louis, USA synthesis on a coal basis. Carbon dioxide emissions from coal combustion are of particular concern due to their potential effects on global warming and climate change. In most coal combustors, however, 7

carbon dioxide makes up only approximately 15% of the total flue gas by volume; thus, This paper presents validations of the Hg speciation predicted by NEA’s carbon dioxide control methodologies are usually not cost effective. Recently, there have MercuRator™ package with the NETL field test database for over 20 full-scale utility been many studies on O2-CO2 combustion, where CO2 is recycled and used as the diluent gas cleaning systems. It emphasizes SCR/ESP/FGD combinations and activated carbon gas. Recycling effluent flue gas would significantly increase the carbon dioxide injection because these two applications present the best long-term prospects for Hg concentration- thus, making CO2 capture become economically feasible. A change in control by coal-burning utilities. The satisfactory performance with SCR/ESP/FGD combustion gas composition may have numerous effects on pollutants associated with coal combinations paves the way for several important applications, including (i) legitimate combustions. Suriyawong et al.1 found that the aerosol size distribution characteristics of comparisons of data from the same system taken at grossly different times; (ii) very ultrafine and submicrometer particles change when N2 is replaced with CO2. The number accurate predictions for a wide range of fuel quality at particular SCRs and FGDs, concentration and mean size of submicrometer particles are smaller in O2-CO2 coal because the Cl dependence is represented so accurately; and (iii) reliable estimates for 0 combustion. This is due to temperature in the vicinity of burning coal particle is lower in the Hg oxidation with and without NH3 injection. It is now possible to reliably assess the O2-CO2 system, leading to slower burning rate of coal and submicrometer particle formation. benefits of adding an SCR and/or an FGD to any commercial gas cleaning system, for The same study also reported no change in mercury speciation measured at the exit of the any coal type and the full domain of commercial gas cleaning conditions. The status of combustor for O2-CO2 and conventional air combustion. However, a number of studies the validation of ACI performance is similar, in that Hg removal can be accurately found that mercury transformation occurs mostly at lower temperature zone down stream of estimated for the full domain of coal quality, LOI, and ACI rates. the combustor and depends on flue gas composition, such as Cl2, HCl and NO. Since NOx emission significantly decreases for coal combustion in the O2-CO2 system, mercury 10-2 speciation could be affected in the low temperature zone down stream of the combustor. In Enhanced Absorption of Elemental Mercury by Sulphurized this study, the effect of O2-CO2 coal combustion on mercury speciation in the low Activated Lignite HOK ® temperature zone is investigated. Flue gas compositions used in this study are chosen to Mailk Werner, Wolfgang Heschel, Technical University Bergakademie Freiberg, mimic gas compositions that would potentially be in coal combustion system where CO2 is GERMANY recycled. The temperature profile and residence time are selected are based on the typical Jurgen Wirling, Rheinbraun Brennstoff GmbH, GERMANY full-scale coal combustion systems. Mercury emission is measured using the method developed by Hedrick et al.2.The results are compared with those obtained under Adsorptive waste gas cleaning with pulverized activated lignite HOK® by an conventional air combustion conditions. entrained-phase technique is well-known to reduce elemental and ionogenic mercury from the gas phase. Because of the specific surface area and the particular pore 9-4 structure, the favorably-priced mass sorbent is used to treat waste gases from Impact of NO and SO2 on Measurement of Mercury Speciation metallurgical processes, waste combustion plants and those of coal-fired power plants. in a Wet Chemical Conditioning System The decisive point of effective mercury retention by activated carbon or HOK® is the Andrew Fry, JoAnn Lightly, Geoffrey D. Silcox, Brydger Cauch, Jost O.L. Wendt, self-doping of the adsorbent by sulfuric acid during the gas cleaning process. This University of Utah, USA catalytic mechanism usually takes place with the residual SO2 and H2O content in the Constance L. Senior, Reaction Engineering International, USA waste gas. Due to the adsorbed accumulated sulfuric acid in the micropores, highly volatile mercury is separated by means of chemisorption. The objective of this study is The impacts of NO and SO2 on speciated mercury measurements from a wet chemical to develop a low cost adsorbent to ensure mercury deposition in waste gases with SO2- conditioning system were investigated. A reactor previously used to elucidate the impact of reduced and without SO2 content. For this purpose different sulfurization methods have chlorine on mercury oxidation in combustion products was used. NO injected directly into been applied to sulfurize activated lignite HOK®. Additives such as elemental sulfur the KCl impinger of the conditioning system was shown to reduce mercury oxidation by and sulfuric acid have been used. The effectiveness of the produced HOK® samples 44% at concentration of 500 ppmv NO and 200 ppmv Cl exactly matching results where the was measured continuously by the adsorption of elemental volatile mercury Hg0 in a NO was injected into the reactor burner at the same concentration. SO2 was shown to fixed bed reactor with several thin particle layers. essentially eliminate apparent oxidation at concentrations of 300 ppmv SO2 and 200 ppmv Laboratory tests include the temperature-dependent mercury adsorption (60 - 150°C) Cl when injected into the KCl impinger. The effect of NO and SO2 on mercury oxidation and the influence exerted by the SO2, O2 and H2O content in the synthetic waste gas were also predicted using a detailed kinetic model for the reactor conditions of interest. mixture. Experimental results showed an enhancement of the mercury reduction in Model results confirm the observed inhibition does not occur as homogeneous oxidation in absence of SO2 by all sulfurized HOK® samples. The adsorption reached its maximum the reactor. Reduction of Hg2+ in the KCl solution of the wet-chemical conditioning system by using the sulfur-endowed activated lignite at approximately 90°C. Furthermore at by SO2 and NO is likely responsible and is being reported as reduction of oxidation. Due to these samples the mercury separation was independent on the presence of oxygen in this measurement bias, the effects of NO and SO2 can not be elucidated using a mercury the gas stream. analysis system of this type. Further investigation is required to determine the nature and impact of this oxidation-reduction chemistry in the KCl solution. 10-3 Mercury Speciation and Emissions from Bituminous Coal-Fired Facilities: 9-5 A Compilation of CONSOL’s Test Results Since 1994 Adsorption of Trace Elements and Sulfur Dioxide on Ca-Based Sorbents Jeffrey A. Withum, CONSOL Energy, Inc., USA Erdem Sasmaz, Jennifer L. Wilcox, Worcester Polytechnic Institute, USA Beginning in 1994, CONSOL Energy Inc., Research & Development (CONSOL), with Ab initio quantum mechanical tools are used to explain the adsorption mechanism of support from federal and state agencies, trade organizations and private industry, has trace elements on a calcium oxide surface in the gas phase. Density functional theory is performed mercury sampling and analysis test programs at many bituminous coal-fired used to calculate binding energies of elemental mercury, oxidized mercury, selenium plants equipped with various combinations of NOx, SO2, and particulate matter control dioxide and sulfur dioxide molecules with a calcium oxide sorbent using the software devices. With a few exceptions, the Ontario Hydro Flue Gas Mercury Speciation programs, Gaussian 03 and Vienna Ab initio Simulation Package (VASP). Super cells Method was used simultaneously at up to five locations in each plant. At most of the with periodic boundary conditions versus cluster approaches are compared to illustrate plants, solid and liquid samples were collected and mercury mass balances were the potential mechanisms of adsorption. Further, effects of hydrogen chloride on the calculated to confirm the observed removals. This paper will discuss the results of a adsorption of oxidized mercury are investigated to determine how hydrogen chloride comprehensive analysis of the data base developed from all of these test programs. The plays a role in activating the calcium oxide surface to increase potential trace element analysis includes an examination of factors that affect mercury speciation in flue gas adsorption. Our predictions calculated in the gas phase indicate SO2, HgCl2 and SeO2 and coal-to-stack mercury removal at power plants. molecules are capable of adsorbing onto calcium oxide surfaces. However, elemental mercury does not adsorb onto calcium oxide unless it is first oxidized. Moreover, HCl 10-4 inhibits the adsorption of HgCl2 on the calcium oxide surface. These results are in good A New Non-Carbon Sorbent For Removing Mercury agreement with the current data in the literature. Gokhan Alptekin, Margarita Dubovik, Michael Cesario, TDA Research Inc., USA

The U.S. Environmental Protection Agency (EPA) determined the need to reduce mercury SESSION 10 emissions from power plants by implementing maximum achievable control technology. ENVIRONMENTAL CONTROL TECHNOLOGIES: Although, substantial reductions will likely be required over the next decade, there are still MERCURY ABSORPTION – 2 uncertainties, particularly related to the cost and effectiveness of existing mercury control technologies. An ideal mercury abatement system would be easy to retrofit into the existing coal-fired electric utilities. An attractive approach is dry sorbent injection where the sorbent 10-1 injected into the flue gas reacts with gas phase mercury and the mercury-laden sorbent is Predicting Mercury Retention in Utility Gas Cleaning Systems removed with the fly ash either by a fabric filter or by an electrostatic precipitator. The Stephen Niksa, Balaji Krishnakumar, Chitralkumar V. Naik, Niksa Energy Associates, requirements for such a sorbent are straightforward: 1) it should be low cost, 2) it should USA remove mercury with high capacity, and 3) it should not present any environmental problems in its own right. Another less obvious but very important consideration is that the sorbent collected with the fly ash, must not degrade and limit the potential uses of fly ash. 8

Several physical adsorbents, particularly activated carbons, can remove mercury from flue The feasibility of simultaneously producing essentially pure streams of H2 and CO2 gases produced by coal combustion. However, activated carbons are non-selective from synthesis gas using a novel sorption enhanced reaction process concept is being adsorbents; most of the flue gas components adsorb on carbon, competing with mercury, evaluated. The concept is designed to simultaneously carry out the thermodynamically- thus, the efficacy of carbon-based sorbents is severely compromised. To improve the controlled water gas shift reaction (CO + H2O ↔ H2 + CO2) and removal of CO2 from adsorption capacity, it is common to chemically modify the activated carbons with various the reaction zone using a sorber-reactor packed with an admixture of the shift catalyst chemical promoters including sulfur, iodine, chlorine and nitric acid, although the carbon and a CO2 selective chemisorbent in order to circumvent the thermodynamic limitation treatment processes significantly increase the cost of the sorbent. As a result, both for of the reaction and facilitate the rate of forward reaction. K2CO3 promoted hydrotalcite promoted and unpromoted carbons, the projected annual cost of abatement is high in the is initially being tested as the chemisorbent, which selectively sorbs CO2 in presence of order of $38,000 per pound of mercury removed (based on the combined operating and water. This paper outlines the novel process concept, and reports new CO2 annualized capital costs) or over $4 million per year for a 250 MW power plant4. In fact, all chemisorption isotherm and column dynamic data for estimating the kinetics of CO2 these estimates understate the difficulties and costs associated with using carbon-based chemisorption. The CO2 chemisorption isotherm is Langmuirian in the low pressure sorbents. Much of the fly ash collected in the particulate control module is sold as an region with a very large gas-solid interaction parameter. The isotherm deviates from extender to Portland cement: fly ash can replace as much as 80% of the cement in some Langmuir behavior in the high pressure region. A new model to describe the observed grades. However, fly ash that contains carbon is not suitable for use in cement. The problem chemisorption isotherm is proposed. The model simultaneously accounts for is much more serious than lost sales. If the fly ash is not salable for concrete, it has no use at Langmuirian chemisorption of CO2 on the surface of the sorbent and additional all, and immediately becomes an expensive waste problem. reaction between the gaseous and the sorbed CO2. The length of the mass transfer zone TDA Research, Inc. is developing a new sorbent to remove all mercury species from flue for CO2 chemisorption is fairly small. The Linear Driving Force Model is adequate to gas. The sorbent is made of non-carbon based materials and has a high mercury absorption describe the chemisorption column dynamics. capacity, thus will not alter the properties of the fly ash. The sorbent can be produced as an injectable powder for easy integration into the existing power plant infrastructure 11-3 Production of Hydrogen and Carbon Nanotubes by Catalytic Non-Oxidative 10-5 Dehydrogenation of Hydrocarbon Gases and Liquids Feasibility of Generating Sulphur Impregnated Activated Carbon using Gerald Huffman, Yuguo Wang, Naresh Shah, Wenquin Shen, Frank Huggins. Petroleum Coke and Flue Gases from a Copper Smelter University of Kentucky, USA Eric Morris, Charles Q. Jia, University of Toronto, CANADA Shitang Tong, Wuhan University of Science and Technology, CHINA In this paper, we report on non-oxidative catalytic dehydrogenation of methane or to produce pure hydrogen and carbon nanotubes in a single reaction. The Non-ferrous metal smelters are among the largest point-source emitters of gaseous mercury catalysts used are binary Fe-Ni (65% Fe, 35% Ni) or Ni nanoparticles supported on and sulphur dioxide. It has been shown that Alberta oil-sands fluid coke can be effectively Mg(Al) oxide derived from a hydrotalcite-like precursor Mg5Al(OH)11CO3 xH2O. The used to reduce SO2 to elemental sulphur while simultaneously producing sulphur- Ni/Mg(Al)O catalyst exhibited high activity for production of hydrogen and stacked impregnated activated carbon (SIAC). In the capture of mercury from industrial flue gases, cone carbon nanotubes(SCNT) from both methane and ethane at approximately 500°C. SIAC has proven to be a highly effective adsorbent material. The current research aims at However, the activity of the Ni/MgAl(O) catalyst decreased rapidly at a reaction developing an existing SIAC technology to meet the needs of a copper smelter for mitigating temperature of 650°C. Conversely, the (Fe-Ni)/Mg(Al)O catalyst exhibited good both mercury and SO2 emissions while making elemental sulphur as a co-product. The activity and a substantially longer life time for methane and ethane decomposition at challenge behind this undertaking is that these flue gases generally contain percent levels of 650°C. The carbon nanotubes produced were easily purified by dissolving the Mg(Al) O2 and H2O vapour (2-12%), and SO2 concentrations significantly lower than those oxide supported catalysts in 6 M nitric acid at room temperature. Preliminary runs previously used for the activation process. Previous work has shown that it is feasible to showed that unsupported Ni(Fe)O (Ni/Fe=5/1) exhibited self-reduction and high reduce SO2 and produce elemental sulphur in the presence of oxygen and water vapour, but activity at 500ºC for the decomposition of ethane for 110 hours. 1 gram of Ni(Fe)O little work has been done to characterise the SIAC product. The focus of this study is produced 19.5 grams of SCNT+catalyst. The purity of the SCNT therefore exceeds 95 therefore on the optimisation of the SIAC properties under the conditions of the flue gas of a wt% even before removing the catalyst particles. copper smelter. Fluid coke samples are reacted with varying concentrations of SO2 and oxygen or water vapour in a tubular furnace, and the products are analysed for their specific 11-4 surface area, pore size distribution, mass yield, sulphur content, and mercury uptake Coproduction of Hydrogen and Methyl Formate by capacity. The outlet gases from the reactor are examined using gas chromatography in order Dehydrogenation of Methanol to characterise the reactions taking place within the carbon bed. Yulong Zhang, Fan Shi, Xin Fan, John Tierney, Irving Wender, University of Pittsburgh, USA

SESSION 11 Methanol is produced in very large amounts from synthesis gas derived from natural HYDROGEN FROM COAL: STORAGE/SYNGAS TO HYDROGEN gas and coal. It is a hydrogen-rich liquid, providing convenience in storage, transport and handling of hydrogen. The coproduction of hydrogen and chemicals is of potential industrial value. The 11-1 catalytic dehydrogenation of methanol produces hydrogen as well as methyl formate Hydrogen Production from Coal Derived Syn Gas using (MF) according to the following equation: Novel Metal Oxide Particles 2CH3OH = HCOOCH3 + 2H2 L.S. Fan, Luis G. Velazquez-Vargas, Puneet Gupta, Fanxing Li, The Ohio State MF is a stable liquid which is a source of important chemicals such as formaldehyde, University, USA dimethyl formamide, formamide, ethylene glycol, acetic acid and dimethyl carbonate. It is an intermediate in a series of reactions so that fast desorption and diffusion are Syngas Redox process (SGR) is capable of producing H2 from coal derived syngas while essential for high selectivity to MF and hydrogen. In this study, work has started on the providing sequestration ready CO2 stream. A Fe2O3 containing composite particle is used as gas phase dehydrogenation of methanol to produce hydrogen and MF over a series of oxygen carrier to combust coal derived producing, after condensation of water, a nearly pure copper-based catalysts. The effects of supports and promoters are under investigation. CO2 stream. This reaction reduces the Fe2O3 to metallic iron which is then oxidized back Initial results indicate that a Cu/ZrO2 catalyst shows good activity for the coproduction with steam in a second reactor. This generates a nearly pure H2 stream. With this technology, of hydrogen and methyl formate. the cost of energy intensive and expensive CO2 separation process is avoided. Furthermore, depending on the syngas composition, both reactors can operate exothermically which 11-5 favors the heat integration of the system. The process has a high hydrogen production Development of Hydrogen Storage Materials efficiency of about 75% as compared to 64% for the current gasification-WGS technology. S.G. Sankar, Brian Zande, Advanced Materials Corporation, USA In this work, a novel oxygen carrier particle is developed, synthesized and tested. The Long Pan, Jing Li, Rutgers University, USA recyclability, reactivity, and strength of the pellets were characterized. Fixed bed Jinchen Liu, Karl Johnson, University of Pittsburgh, USA experiments for the reduction and oxidation of the pellets ware also performed. It is observed that the newly developed pellets can maintain satisfactory reactivity for multiples cycles and US Department of Energy has embarked on a program to develop hydrogen storage are strong enough for operation in the proposed SGR reactors. Moreover, fixed bed materials for stationary and transportation applications. Hydrogen gas will be derived from a experiments show that particles can be fully oxidized or reduced producing a H2 stream with variety of sources, one of which being the by-product from the Clean Coal Initiative. Future high purity at a reasonable rate. requirements for the utilization of hydrogen in fuel cell vehicles calls for the development of on-board storage systems with a capacity of ~ 6 wt% hydrogen in the near term and of ~ 9 11-2 wt% by 2015. In this talk, we review the work on three families of materials: (a.) Traditional Novel Sorption Enhanced Reaction Process for Production of rare earth intermetallic compounds such as LaNi5, (b.) Light metals such as magnesium and H2 and CO2 from Synthesis Gas (c.) Microporous Metal Organic Frameworks. Each of these families of materials possess Shivaji Sircar, Hugo Caram, K. B. Lee, M. Beaver, Lehigh University, USA distinct advantages and disadvantages; a thorough understanding of the basic properties of

9

these materials is likely to lead to the discovery of new and improved materials for hydrogen In this study a series of computer simulations was conducted with a purpose of storage that meets the challenging specifications set by the US DOE. predicting CO2 transport in a multi-layer environment of typical unmineable coal In the traditional rare earth intermetallic compounds, hydrogen is stored in the interstitial seams. The parameters of three typical coal basins were considered as examples: San- sites of a crystal. The heat of formation of the hydrides is typically about -15 kJ/H, the Juan, Appalachian, and Powder River basins. In the majority of cases it was presumed plateau pressures can be fine-tuned by modifying the alloy compositions, the kinetics of that the upward migration was limited by the lowest permeability layers. An open- hydrogen absorption-desorption are fast ( ~200 sec.) and the volumetric hydrogen capacity is source OpenFOAM CFD solver (openfoam.org) was used in this study to analyze CO2 reasonably high. However, the gravimetric hydrogen storage capacity is only about 1.5 wt%, transport in coal seams. Darcy’s diffusion term was added into the solver, and mass far short of DOE goals. Metallic magnesium chemically reacts with hydrogen to form stable injection was modeled within the framework of compressible flow. To facilitate the MgH2 with a heat of formation of ~-37 kJ/H. The theoretical gravimetric capacity is as high analysis of more complex layer formations in reservoirs a voxel-based geometric as 7 wt%. However, the kinetics of decomposition even in microcrystalline samples is design system was adapted and interfaced with the OpenFOAM and TOUGH2 extremely slow (several thousand seconds at ~300°C). Our recent research work has shown simulators. The study can provide long term projections for the CO2 sequestration that (1) kinetics of decomposition of the hydride increases when the material is reduced to operations in known coal seams. the nanocrystalline size through mechanical milling technique and (2) Addition of small amounts (~2 wt%) of, for example, nanocrystalline iron modifies the plateau pressure 12-3 significantly. More recently, we have begun synthesis, characterization and hydrogen Determination of Coalbed Methane Potential and Gas adsorption studies of Microporous Metal Organic Frameworks (MMOFs). These materials Adsorption Capacity in Western Kentucky Coals are composed of various metals, including selected group-1 and group-2 light elements and Sarah Mardon, Kathy G. Takacs, James C. Hower, Cortland F.Eble, University of transition metals and sp2-carbon based ligands, which form the internal surfaces of the pores. Kentucky, USA We have synthesized several MMOF materials with a number of metals and organic ligands, Maria Mastalerz, Indiana University, USA and studied their hydrogen adsorption properties at room temperature as well as at low temperatures (78 K). For instance, we found that the hydrogen storage capacity is about 3 The Illinois Basin has not been developed for Coalbed Methane (CBM) production. It is w% and 2.25 w% at 78 K and decreases to about 0.29 w% and 0.5 w% at room temperature imperative to determine both gas content and other parameters for the Kentucky portion of for [Co3(bpdc)3bpy] 4DMF H2O (bpdc = biphenyldicarboxylate) and Cu3BTC (BTC = the Illinois Basin if exploration is to progress and production is to occur in this area. This Benzene-1,3,5-tricarboxylate), respectively, at hydrogen pressures of ~30 atm. The hydrogen research is part of a larger project being conducted by the Kentucky Geological Survey to uptake appears to be related, in part, to the pore size and pore structure. Thermal stability, evaluate the CBM production of Pennsylvanian-age western Kentucky coals in Ohio, pore structure and hydrogen storage characteristics of these and other related MMOF Webster, and Union counties using methane adsorption isotherms, direct gas desorption materials will be presented. We have performed atomistically-detailed modeling of H2 measurements, and chemical analyses of coal and gas. This research will investigate adsorption in various MMOF materials and have compared these theoretical predictions with relationships between CBM potential and petrographic, surface area, pore size, and gas experimental data. We have computed both the adsorption isotherms and isosteric heats of adsorption isotherm analyses of the coals. Maceral and reflectance analyses are being adsorption at different temperatures. In general we find qualitative agreement between conducted at the Center for Applied Energy Research. At the Indiana Geological Survey, the simulations and experiments. The simulations indicate that the most attractive sites for surface area and pore size of the coals will be analyzed using a Micrometrics ASAP 2020, adsorption are near the corners of the frameworks, close to where oxygens are bound to the and the CO2 isotherm analyses will be conducted using a volumetric adsorption apparatus in metal atoms. Calculations indicate that substantially higher heats of adsorption are needed to a water temperature bath. The aforementioned analyses will be used to determine site effectively store hydrogen at room temperature. specific correlations for the Kentucky part of the Illinois Basin. The data collected will be Supported by: US DOE Grants: DE-FC26-05NT42446 and DE-FG02-04ER83886 compared with previous work in the Illinois Basin and will be correlated with data and structural features in the basin. Gas composition and carbon and hydrogen isotopic data suggest mostly thermogenic origin of coalbed gas in coals from Webster and Union SESSION 12 Counties, Kentucky, in contrast to the dominantly biogenic character of coalbed gas in Ohio GLOBAL CLIMATE CHANGE: County, Kentucky. GEOLOGIC CARBON SEQUESTRATION – 2 12-4 Effects of Structural Rearrangements on Sorption Capacity of Coals 12-1 Vyacheslav Romanov, Yee Soong, Robert Warzinski, Ronald Lynn, DOE/NETL, USA The Use of Water Injection for CO2 Sequestration in Coalbeds Miguel Tovar, Shahab Mohaghegh, West Virginia University, USA Recently, the problems in practical application of experimental data and modeling to the sequestration of carbon dioxide in coal seams and the concurrent enhanced coalbed Carbon capture and storage in geologic formations has been proposed as a global warming methane (ECBM) recovery have underscored the need for new approaches that take mitigation strategy that can contribute to stabilize the atmospheric concentration of carbon into account the ability of coal for structural rearrangements. Areas of interest include dioxide, the anthropogenic gas with the largest greenhouse effect. Particularly in the US, the plasticization of coal due to CO2 dissolution, the effect of coal swelling on estimation storage of CO2 in unmineable coalbeds is an attractive prospect due to the large amount of of the capacity of a coal-seam to adsorb CO2 (adsorption isotherm), and the stability of coal reserves and the possibility of enhanced coalbed methane recovery. This study the CO2 saturated phase once formed, especially with respect to how it might be introduces a new strategy for the prevention of post-sequestration CO2 seepage to the surface affected by changes in the post-sequestration environment (environmental effects). from the CBM (CoalBed Methane) formations that is named the “Nature’s Sequestration Coals are organic macromolecular systems well known to imbibe organic liquids and Technique”. The idea is to retain the adsorbed CO2 in the coalbed formation by having carbon dioxide. CO2 dissolves in coals and swells them. The problems become more formation water filling the cleat system. Coalbed formations have the capacity to retain prominent in the region of supercritical CO2. We investigated the effects of moisture methane adsorbed on its surface through the geologic time under an appropriated pressure content and pressure cycling history on temporal changes in the coal sorptive capacity condition. This pressure condition is mainly established by water contained in the fracture for a set of Argonne premium coals. The samples were tested as received, dried at network (the cleat system). We can take advantage of this natural occurrence in order to 80°C for 36 hours, and moisture equilibrated at 96-97% RH and 30°C for 48 hours. restore the system’s original conditions by filling the cleat system with water and having The powders were compared to core samples. Additionally, plasticization of coal CO2 adsorbed on the matrix instead of methane. Using a commercial numerical simulator powders was studied by high pressure dilatometer. and data representative of the Appalachian basin region; we investigate whether or not the presence of water on the cleats helps to sequester CO2 in a coalbed for a long period of time 12-5 without significant seepage. Several scenarios were considered for this study, with variations Sorption of Gases by Argonne Premium Coals at Supercritical Pressures of depth, flow mechanism and nature of potential fracture that would work as a conduit for Richard Sakurovs, Stuart Day, Steve Weir, Greg Duffy, CSIRO Energy Technology, the seepage of CO2 to the surface. Results show that water filling the coal cleat system AUSTRALIA decreases significantly the amount of CO2 seeped to the formations above the target formation. Modelling the sorption properties of coals for carbon dioxide under supercritical conditions is necessary for accurate prediction of the sequestering ability of coals in 12-2 seams. We present recent data for sorption curves for three dry Argonne Premium Numerical Modeling of CO2 Sequestration in Unmineable Coal Seams coals using a gravimetric system, and apply a recently developed model to the fitting Guoxiang Liu, Andrei Smirnov, West Virginia University, USA of the excess sorption by these coals of carbon dioxide, methane and nitrogen at two different temperatures at pressures up to 15MPa. The model is unique in that it uses Numerical modeling of CO2 sequestration in deep unmineable coal seams can be used gas density rather than pressure as the main variable. It is a modified Dubinin- for long term predictions of storage capacity of these reservoirs, as well as enables one Radushkevich (DR) equation, using adsorbed phase density rather than saturation to analyze possible CO2 escape routes. In addition to this, the computations can pressure as the upper limit. The fit of this model is generally around 1% of the sorption provide estimates on the possibility of residual methane recovery in CO2 sequestration capacity. The sorption capacity of the coal is found to decrease with increasing operations. The process of CO2 transport in a coal seam can be influenced by many temperature, which disagrees with expectations from simple models of coal sorption factors, such as bounding layers permeabilities, porosities, fracture densities, etc. that predict a sorption capacity that is independent of temperature. This means that sorption capacity should not be considered a direct measure of the surface area of coal. 10

and CO2 price at from $0.50 to $1.20/mcf. The production potential is equal to that achieved SESSION 13 locally over the last 25 years by conventional methods. GASIFICATION TECHNOLOGIES: APPLICATIONS AND ECONOMICS – 3 13-3 2006 Cost and Performance Estimates of Fossil Energy Power Plants Jared P. Ciferno, RDS-Parsons Corporation, USA 13-1 Julianne Klara, NETL, USA GE and Bechtel’s IGCC Reference Plant Update Rich Rapagnani, GE Energy, USA In 1999, the Department of Energy s National Energy Technology Center (NETL) sponsored a report entitled Market-Based Advanced Coal Power Systems in response to a For background, GE Energy purchased ChevronTexaco's gasification technology business in newly deregulated power industry. The study, conducted by Parsons Corporation, compared June of 2004, and soon thereafter formed an IGCC alliance with Bechtel Corporation to the performance and economics of power systems that were advanced, yet market-ready jointly develop and commercialize an IGCC reference plant. Rated nominally at 630 MW, within a 5 year time frame that included Pulverized Coal Boiler (PC), Natural Gas this IGCC Reference Plant provides customers a commercially competitive, cleaner coal Combined Cycle (NGCC), Integrated Gasification Combined Cycle (IGCC) and 2nd alternative for coal to power. Moreover, the GE and Bechtel IGCC Alliance provides this Generation Pressurized Fluidized Bed Combustion (PFBC) power plants. In the 7 years IGCC product on a turnkey basis, including commercial guarantees, thus offering the total since this report was published, natural gas prices have more than doubled while proposed package customers need for successful commercialization of their project. emissions regulations such as EPA s Clean Air Interstate Rule (CAIR) and the Proposed This presentation provides to the conference attendees an update on the GE and Bechtel Power Plant Mercury Rule, have forced the potential inclusion of control devices and IGCC Reference Plant design status, a look at the fuel flexibility benefits inherent in such a operational strategies to lower future power plant emissions. Furthermore, concern over the plant design, a preview of the expanded fuel envelope capabilities under development by GE potential effect of CO2 emissions from fossil fuel power plants on the global climate is a key and a discussion of the business aspects supporting development of IGCC projects. issue for the future of power generation worldwide. With energy demand projected to rise by over 60% through 2030, limiting CO2 emissions from power plants is becoming ever more 13-2 pressing. Finally, technological advances such as the anticipated introduction of a synthesis Beluga Coal Gasification Feasibility Study Phase 1 gas fired gas turbine and expected improvements in the operation of gasifiers will affect the Ronald Schoff, Robert Chaney, RDS-Parsons Corporation, USA overall plant performance. As a result of changing economic, regulatory and technological issues, the 1999 study has become outdated. The effort that is currently underway is the 2006 The Beluga Coal Gasification study aims to determine the economic feasibility of siting a Market-Based Advanced Coal Power Systems study, expanded to include three competitive coal-based gasification plant in the Cook Inlet region of Alaska for the co-production of gasifier technologies, with and without CO2 capture. Economic issues, including the rapid electric power and marketable by-products. The plant products may include synthesis gas, increase in natural gas prices and the shift in the industry back to coal-based plants, are Fischer-Tropsch (F-T) liquids, fertilizers such as ammonia and urea, alcohols, hydrogen, considered here. Pollution control technology advances, brought about by anticipated nitrogen and carbon dioxide, that would be manufactured for local use or for sale in domestic regulation, result in cleaner plants. Advances in gas turbine, gasifier and other balance of and foreign markets. The project was divided into two phases. In Phase 1, the Agrium plant equipment are taken into account. Cost and performance results of the study effort will fertilizer plant in Nikiski serves as the case study site and customer for product gases be discussed in this paper and at the conference presentation. (including hydrogen, nitrogen and carbon dioxide), steam and power from the coal gasification facility. In Phase 2, an assessment of alternative locations and plant designs 13-4 based on local and export markets for the suite of potential products will take place. The Advanced Clean Coal Technologies for Capture Phase 1 case study results, reported here, will feed into the Phase 2 central Alaska regional Minish Shah, Praxair, Inc., USA study. The project may be broken into four major subject areas, described below: Gasification Plant Design: The coal gasification plant investigated in this study is designed In the absence of any regulations on CO2 emissions in the US, the focus is on building new to provide the Kenai Nitrogen Operations (KNO) plant with the following suite of required power plants that are CO2 capture ready. This paper compares and contrasts two advanced products: clean coal technologies for CO2 capture: Integrated Gasification Combined Cycle and Oxy- • 282 million standard cubic feet per day (MMSCFD) of hydrogen at 400 psig and of Coal Fired Boiler. The gasification has been widely promoted and the oxy-fuel combustion suitable quality for ammonia production. is also gaining support as a viable alternative for CO2 capture. Both of these technologies are • Stoichiometric quantity of nitrogen (approximately 100 MMSCFD) at 400 psig and touted for their potential to capture CO2 at low cost. There are significant differences in the 99.99% purity. commercial readiness and the CO2 capture readiness. These issues will be highlighted and • 1,500,000 lb/hr steam at 1500 psig and a minimum temperature of 825°F. the cost and performance with CO2 capture will be presented for both the technologies. All • 300,000 lb/hr steam at 600 psig and 625°F. the individual components of IGCC plant with CO2 capture have been demonstrated in large • 2,500 tpd CO suitable for urea production (25 psig) scale operation in different applications. The main obstacles to commercialization of IGCC 2 are uncertainties related to costs and reliability. Adding CO capture capability to IGCC will • Electric power to satisfy the auxiliary power requirements for the gasification plant 2 impact the performance of all the major sub-units (gasification, combined cycle and ASU). and the KNO facility, to make the entire facility electric power independent. Therefore, to make IGCC CO capture ready, significant preplanning will be required. The Two cases were considered: 2 oxy-fuel technology allows utilities to build power plants based on air-fired PC boiler, Case 1: Process the syngas from the gasification plant to supply required hydrogen and technology they are most familiar with and one which requires lower initial investment nitrogen to the KNO ammonia synthesis loop compressor and produce sufficient steam and compared to IGCC. And for CO capture, two new sub-systems (an air separation unit and a power for the KNO needs. Capital Cost was $1.64 billion. 2 CO clean-up unit) can be installed only when needed further minimizing up-front Case 2: Process the syngas from the gasification plant to supply required hydrogen and 2 investment. However, there has been no large-scale demonstration of some of the sub- nitrogen to the KNO ammonia synthesis loop compressor, but do not produce power from a components of this technology. Although in theory, the oxy-coal fired boiler can be operated gas turbine. Rather, independently produce the required steam and power for the KNO to mimic the air-coal fired boiler, testing at smaller scale will be necessary to understand facility with a CFB coal-fired boiler. Capital Cost was $1.87 billion. flame and heat transfer characteristics and materials compatibility due to different chemical Financial Analysis - The Power Systems Financial Model Version 5.0 (now the standard environment within the boiler. The learnings from such testing will also be needed to used by NETL for IGCC systems analysis) was used to perform the financial analysis. establish whether any design changes are required for the CO -capture ready plant. The CO Factors in the analysis included: coal and limestone supply and cost, by-product markets, 2 2 clean-up will also require further development to address issues related to impurities such as and impact on local natural gas and electric power markets. Project return on equity SO and NO . investment (ROI) and a discounted cash flow analysis were key results. Identification of key x x

model sensitivities also occurred. 13-5 Case 1 possesses superior financial potential relative to Case 2. For Case 1, the ROI was Power Systems Development Facility Update on Six Trig Studies 11.1% with a Payback Year of 2023, assuming start-up in 2011. For Case 2, the ROI was Luke H. Rogers, Southern Company Services, USA 6.0% with a Payback Year of 2031. While both cases produce enough raw materials George S. Booras, Electrical Power Research Institute, USA necessary for ammonia and urea production at the Agrium facility, Case 2 is more Ronald W. Breault, National Energy Technology Center, USA expensive, produces less export power, and requires slightly more coal feed in order to do so. Nicola Salazar, Kellogg Brown and Root, Inc., USA Sensitivity analysis was performed on all model inputs in both cases. The items found to

have the greatest impact on the financial results are the plant EPC cost, system availability, The pursuit of more cost-effective and reliable coal technologies with superior ammonia/urea prices, and coal price. environmental performance continues to drive the development of the Transport Gasifier at Environmental Issues The analysis of the design basis indicates that a proposed IGCC the Power Systems Development Facility (PSDF). This paper presents the results of six facility at the Agrium Kenai Plant is feasible in terms of current environmental permitting updated system and economic studies of Transport Integrated Gasification (TrIG) plants. and compliance requirements imposed by federal, state and local regulations. Southern Company and Kellogg Brown and Root (KBR), in conjunction with the U.S. Carbon Capture/Use - The potential for use of CO for enhanced oil recovery in regional oil 2 Department of Energy (DOE) and other partners, are developing the TrIG process at the fields was a major consideration. It was determined that CO floods could economically 2 PSDF for commercial application in the power industry. The PSDF is an engineering scale produce up to 300 million barrels of oil in Cook Inlet fields with oil prices at $35 to $40/bbl demonstration of the KBR Transport Gasifier along with a high-temperature, high-pressure 11

syngas filter, a gas cleanup process, and related systems. Built at a sufficient scale to test obtaining 46% upgraded coal and 46% extract. It was found that the upgraded coal advanced power systems and components in an integrated fashion, the PSDF provides data contained much less oxygen than the raw coal and its elemental composition was close necessary for commercial scale-up of these technologies. To guide future tests and to higher rank coals. However, the upgraded coal was still not like bituminous coals commercialization of the technologies at the PSDF, a series of conceptual commercial plant and it will need some technique to be utilized more effectively. In this study co- designs has been completed in partnership with the DOE and the Electric Power Research pyrolysis of the upgraded coals and waxes formed from waste plastics was investigated Institute (EPRI). Six TrIG combined cycle cases ha been developed to investigate the as one of the methods of their effective utilization. Waxes were prepared through relative costs and benefits of oxygen-blown or air-blown gasification, of stack gas or syngas pyrolysis of high density polyethylene, polypropylene, and polyethylene terephtalate. cleanup, and of carbon dioxide capture. These cases are all based on a 2x1 GE7FA+e Upgraded coals were then impregnated with the waxes by treatment in an autoclave at combined cycle fueled by syngas from two Transport Gasifiers using Powder River Basin 200°C under pressure. The mixtures of coal and wax were rapidly heated up to 1040°C (PRB) sub-bituminous coal. Detailed performance modeling and cost estimation have shown at about 3000°C/s using a Curie point pyrolyzer in an inert atmosphere. It was found that the optimal configuration for power production without carbon dioxide capture includes that char yield was greatly enhanced by a factor of 1.1 to 1.3 compared to the char air-blown gasification and cold syngas cleanup. Airblown gasification was also shown to be yield of the upgraded coals and waxes when pyrolyzed independently. Even at a slower preferable when carbon dioxide is captured in a TrIG combined cycle system. heating rate (0.17°C/s) the char yields increased by a factor of 1.2 for all waxes. Since no such effect was found when using raw brown coal instead of the upgraded coal, it was suggested that the improvement of the structure of brown coal by our method SESSION 14 could enhance interactions between the coal and the wax when co-pyrolyzed. SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND OTHER NON-FUEL USES OF COAL: COKE AND OTHERS 14-4 Structural Characterization of Alternative Binder Pitches for Carbon Anodes Uthaiporn Suriyapraphadilok, David J. Clifford, Caroline E. Clifford, Harold H. 14-1 Schobert, The Pennsylvania State University, USA Hydrothermal Extraction of Brown Coals for Their Effective Utilization John M. Andresen, University of Nottingham, UNITED KINGDOM Kouichi Miura, Hiroyuki Nakagawa, Masato Morimoto, Ryuichi Ashida, Kyoto University, JAPAN The demand for coal tar binder pitch in the aluminium industry accounts for about 75% of the pitch market. Since the production of coal tars is rapidly decreasing in the United States A novel coal conversion process was proposed: the method combines "a hydrothermal as well as throughout the world, the development of alternative binders should be extraction of brown coal (HT-Extraction, extraction of brown coal by inherent water considered. The objective of the present work was to understand the chemistry of alternative under hydrothermal condition)" and "a catalytic hydrothermal gasification of the pitches from different origins and processes and compare with the well-developed coal tar extract (CHT-Gasification)" both of which are performed under the exactly same binder pitch. The pitch samples studied included a coal tar pitch, coal-extracted pitch, conditions of less than 350°C and less than 20 MPa. The HT-extraction intends to gasification pitch, and laboratory-generated co-coking pitch. Coal tar binder pitches are increase the amount of organic compounds in the aqueous phase and the CHT- traditionally obtained from coal tars that are the by-product of bituminous coal coking Gasification gasifies the organic compounds in the aqueous phase using a novel Ni- process used to make coke for blast furnaces in iron production. Gasification pitches are supported carbon catalyst developed by the authors, producing combustible gas rich in distilled by-product tars produced from the coal gasification process. A production of coal- CH4 and H2. Then the proposed process is expected to be not only a dewatering/ extracted pitches involves a pre-hydrogenation of coal followed by extraction using a dipolar upgrading process of brown coal but also an effective brown coal gasification process. solvent. The co-coking pitch is a unique material derived from co-carbonization of coal and To elucidate the behaviors on the HT-Extraction, several brown coals were treated in decant oil under the conditions simulating a delayed-coker in our laboratory. All samples flowing water or different concentrations of phenol aqueous solutions at temperatures were characterized by nuclear magnetic resonance (NMR) spectroscopy and laser desorption of 350°C. Experiments combining the extraction and the catalytic reaction process mass spectrometry (LDMS). A comparison of average structure and molecular mass of these were also performed using an Australian brown coal to examine the validity of the pitch samples will be presented. proposed concept. 14-5 14-2 Supercritical Fluid Extraction of Diterpenes from Slovak Brown Coal The Characterization of Cokes from Co-coking of Decant Oil and Coal Udmila Turcani, Slovak Academy of Science, SLOVAK REPUBLIC Parvana Gafarova Aksoy, Caroline Burgess Clifford, Leslie Rudnick, Harold H. Franciszek Czechowski, Institute of Organic Chemistry, POLAND Schobert, The Pennsylvania State University, USA Helena Sovava, Institute of Chemical Process Fundamentals AS CR, CZECH REPUBLIC Researchers at The Pennsylvania State University have been involved for the last Franti ek Verbich, Upper Nitra Mines, SLOVAKIA fifteen years in the development of thermally stable jet fuel. The focus of production of Anton Zubrik, Silvia Uvanova, Institute of Geotechnics, SLOVAKIA this fuel is to incorporate coal or coal derived materials into existing oil refinery operations. Penn State’s researchers have clearly shown that the kinds of chemicals in The finely powdered Handlova brown coal was extracted under supercritical the fuel that make it stable at 900°F (hydroaromatics and naphthenes) can be derived in conditions at temperature of 323K with CO2 and at temperatures 573 and 613K with abundant amounts from coal. The overall objectives of refinery integration project are: cyclohexane isopropanol mixture (9:1 v/v). Particles size of the powdered coal used to 1) Investigate and develop an understanding of the most promising refinery integration extraction (Ad = 7.7%, Cd = 54 %) averaged around 6.5m (planetary mill Molinex). of all process streams resulting from the production of a coal-based jet fuel. 2) The coal granularity under 10 m, according to literature, assured highest extract yield. Demonstrate the quality of each of the process streams in terms of refinery The extracted material amounted 0.42, 13.95 and 7.99% of raw coal mass at the above requirements to maintain a stable, profitable refinery operation. 3) Demonstrate the mentioned temperatures, respectively. The supercritical fluid extracts were performance of key process streams in practical testing used for application of these preliminarily separated to three fractions by semipreparative HPLC (HP 1090, streams. Therefore, the project focus is to examine the characteristics and quality of the Hewlett-Packard, Germany) equipped with UV detector (HP 1090, Series II) using streams, such as gasoline, diesel fuel, fuel oil, and coke and to determine the effects of chromatographic column Lichrosphere 100 RP 18 (mobile phase: acetonitrile-water). those materials on other unit operations in the refinery. The work presented will focus The fraction selected on the base of elution time within narrow range found for elution on the blending of coal with decant oil as delayed coker feed. The objective of this time of kaurenoic acid (14.647 minutes, UV wavelength 210 nm) was further analyzed work is to evaluate coke from co-coking of decant oil and coal. The affect of coal to by GC/MS (Agilent Technologies 6890N - Folsom, USA). This fraction constituted coking of decant oil will be examined. The unique pilot-scale coking unit was used for high abundance of diterpenoic compounds: 16 H kaurane - C20H34, kaurenoic acid - performing coking and co-coking experiments. This work mainly focused on C20H30O2, abietatriene C20H30, ferruginol C20H30O and others. The data on fungicidal characterization of uncalcined and calcined coke samples. Densities and ash contents activity of the terpenoic compounds separated from coal will be presented. were determined for calcined and uncalcined coke samples. X-ray diffraction technique was used for evaluation the degree of structural anisotropy in coke samples. SESSION 15 14-3 COMBUSTION TECHNOLOGIES – 3: OXY-FUEL COMBUSTION Co-pyrolysis of Hydrothermally Upgraded Brown Coal and Wax Formed From Waste Plastics Susan Roces, De La Salle University, USA 15-1 Ryuichi Ashida, Masato Morimoto, Kouichi Miura, Monthicha Pattarapanusak, Kyoto Expanding the Clean Coal Portfolio: Oxyfiring to Enhance CO2 Capture University, USA Glen Jukkola, Nsakala Nsakala, Greg Liljedahl, Frank Kluger, Alstom Power, USA

The authors have recently presented a new method that not only removes water from A portfolio of Clean Coal power generation technologies are on path to commercialization in brown coal but also separates the coal into upgraded coal and extract of low molecular response to the need for near-zero emissions and CO2 capture for storage/sequestration. mass compounds. Brown coals were hydrothermally treated using flowing liquid water Technology providers are responding to generators needs with innovations ranging from at around 350°C. The treatment of an Australian brown coal, Loy Yang, resulted in higher efficiency to post-combustion capture to alternative plant designs. Among the 12

promising Clean Coal technologies under development to address CO2 emissions is oxygen cycle was optimized to minimize the overall power plant heat rate and facilitate CO2 combustion. By firing with nearly pure oxygen, atmospheric nitrogen is not introduced into sequestration. Vent gas power recovery and vent gas recycle for O2 recovery are the products of combustion and a concentrated CO2 flue gas stream is produced. This CO2 incorporated to minimize the CO2 removal auxiliary power. The furnace and heat recovery stream can be dried and compressed for sequestration, or further processed into a high purity area components were designed to optimize the location and design of the furnace, burners, CO2 product for varied uses including enhanced oil recover (EOR) or enhanced gas over-fire gas ports, and internal radiant surfaces producing a more compact and efficient recovery. design than air-fired furnaces. A detailed thermal/hydraulic design and analysis of the Oxyfiring is an attractive option for coal combustion for a number of reasons, including: waterwall geometry was conducted to avoid high metal temperatures due to dryout or 1. It uses proven, reliable, commercially available Pulverized Coal (PC) and Circulating departure from nucleate boiling and to avoid flow instabilities. An investigation of the Fluidized Bed (CFB) technology improvement in cycle efficiency and the reduction in CO2 removal penalty due to the 2. Oxygen can be readily produced by commercial cryogenic air separation integration of advanced oxygen separation techniques is also presented. 3. CO2 cleanup, compression, and liquefaction is proven technology It is anticipated that initial deployment of oxyfiring would be for commercial EOR 15-4 application, with co-production of electricity, use of CO2 for oil field stimulation, and use of Numerical Modeling of the Effect of Aerodynamics on NOx Emissions and by-product nitrogen (from oxygen production) for oil field pressurization. Oxyfiring is also a Char Burnout for Combustion of Coal in O2/CO2 stepping stone to additional advanced Clean Coal processes, including chemical looping. Sarma V. Pisupati, Prabhat Naredi, The Pennsylvania State University, USA ALSTOM is actively participating with the US-DOE as well as European partners, Utilities, and academia to design and demonstrate oxyfiring utilizing PC and CFB technologies. This Combustion of coal in O2 and Recycled Flue Gas (RFG) medium is one of the approaches to paper will address the key aspects of the design of oxyfired boilers and the timeline for obtain pure CO2 stream from an existing power plant that can be sequestered to reduce the commercialization. Recent studies have developed important knowledge on heat transfer, greenhouse gas emissions into the atmosphere. Other advantages of this approach are an combustion efficiency, and emissions. This data will form the design basis for scale-up for increase in char burnout and reduction in NOx emissions. However, in order to retrofit the oxyfired demonstration plants. The next step is to demonstrate oxyfiring at a scale of 10 to existing boiler, approximately 30% O2 and 70% CO2 blend is required in the oxidizer 100 MWe. The goal is to provide coal-based power generation options that are clean, cost stream. This leads to a decrease in the volume of combustion gases which subsequently competitive, and reliable. changes the mixing pattern of oxidizer and coal particles inside the boiler. If coal particles and oxygen are not well mixed, NOx emissions will be altered due to local fuel rich pockets. 15-2 In the present paper, an, axi-symmetric, 2-D computational model was developed using Comparisons among Different Implementation Options for Fluent CFD code, for a 1,000 lb steam/hr “A-frame”, water-tube research boiler to identify Coal-Fired Oxyfuel Power Plants and optimize the key variables that influence the NOx emissions. Model predictions were Xinxin Li, Columbia University, USA compared with the experimental measurements of gas temperature, particle speed and gaseous emissions for Upper Freeport (Bituminous) coal fired in air medium. The effects on Climate change concerns over carbon dioxide emissions from fossil fuel combustion have gaseous emissions such as NOx, and CO2 due to change in combustion gas loading and led to the development of carbon dioxide capture technologies for coal fired power plants. presence of increased CO2 are predicted under similar operating conditions. The effect of One particularly promising approach known as oxyfuel-combustion replaces air in the swirl number was analyzed to minimize the NOx emissions from the boiler in enriched combustion chamber with a mixture of pure oxygen and carbon dioxide rich recycled flue O2/CO2 medium. gas. The resulting concentrated stream of CO2 can be pressurized and transported from the plant to a storage site where it is disposed off safely and permanently. Oxyfuel-combustion 15-5 based power plants are shown to be a very competitive option for CO2 capture. This study Experimental and Modeling Study on Particle Size Distribution evaluates three major strategies for introducing oxyfuel power plants: (1) construction of Effects Due to Oxy-Combustion of Coal new oxyfuel plants; (2) retrofit of existing power plants to oxyfuel plants; (3) construction of Achariya Suriyawong, Scott Skeen, Richard Axelbaum, Pratim Biswas, Washington new conventional plants that are designed for a cost-efficient future retrofit. The paper University in St. Louis, USA considers the engineering aspects in the three cases and develops an economic analysis to compare the three options with each other and with a conventional coal fired power plant O2-CO2 coal combustion is a promising technology for mitigating the increase of CO2 that provides the baseline case. The net present values of the different plants are calculated in the atmosphere. Advantages include the potential for CO2 capture, reduction of NOx and compared; a sensitivity analysis is performed and the implications of different emissions, and improvement in combustion efficiency. This paper presents an sensitivities of the key parameters are discussed in the context of long-term investment experimental study developed to examine the effects of O2-CO2 combustion on fine decisions. The study suggests that under a wide range of assumptions building new oxyfuel particle formation and flame stability from both a laminar flow drop-tube furnace and a power plant is the most attractive options for power plant investors. Retrofit options are not piloted coal flame reactor. The results were compared with those obtained under competitive unless the plant has a remaining lifetime of more than twenty years. This is conventional combustion conditions (air) and differences are highlighted. rarely the case for today s power plant fleet in the United States. The situation changes, however, if the upgrade can significantly increase the remaining lifetime of the plant. The sensitivity analysis indicates that the electricity price and CO2 credit price heavily influence SESSION 16 the choice of plant options. An increase in the price of CO2 credit makes new oxyfuel plant ENVIRONMENTAL CONTROL TECHNOLOGIES: even more attractive, the decrease in the price of CO2 credit makes the base plant more SOx, NOx, PARTICULATE AND MERCURY – 1 attractive, the minimum CO2 credit for oxyfuel power plants to be competitive with the base plant is $25.30/ton. An increase in the price of electricity also makes the base plant more attractive; at electricity prices greater than 7.15 c/kWh, new oxyfuel power plant is not 16-1 attractive as the loss in additional electricity outweighs the gain from carbon credits. Under A Multi-Pollutant Wet Scrubber for Capture of SO2, NOx and Hg those conditions, the best investment is a conventional coal-fired power plant. Nick Hutson, Ravi Srivastava, Brian Attwood, US EPA, USA; Carl Singer, Arcadis, USA 15-3 2+ 0 An Optimized Supercritical Oxygen-Fired Pulverized Coal An enhanced wet scrubber that removes SO2, NOx and Hg (both Hg and Hg ) from coal Power Plant for CO2 Capture combustion flue gas has been developed and tested at the EPA/RTP laboratories. In this Andrew Seltzer, Zhen Fan, Foster Wheeler North America Corp., USA multi-pollutant system, a traditional limestone (or other alkali) scrubber solution is enhanced Timothy Fout, DOE/NETL, USA with an additive that promotes the capture of NOx and Hg species. In the optimized system, 0 SO2 (1800 ppm), NOx (200 ppm) and Hg (30 ppb) were all captured at near 100% The Department of Energy and Foster Wheeler have jointly developed a conceptual efficiency. Results from this testing will be provided and discussed in the presentation. supercritical pulverized coal (PC) boiler plant design that will allow practical carbon dioxide (CO2) capture for future CO2 sequestration efforts. CO2 is a major greenhouse gas, which has 16-2 been linked to global climatic change. A novel process for CO2 sequestration is proposed Study on NO Reduction by Coal and Chars in an Entrained Flow Reactor utilizing a supercritical oxygen-fired PC boiler, which, as part of a Rankine steam cycle, Ping Lu, Shengrong Xu, Xiuming Zhu, Nanjing Normal University, P.R. CHINA forms a high efficiency, zero emission, stackless power station. Coal is combusted in the furnace where the oxidizer consists of a mixture of O2 and recycled flue gas, which contains Rapid pyrolysis and NO reduction efficiency of five Chinese pulverized coals and their chars primarily CO2 gas. Recycling of the flue gas is utilized to control flame temperature in the produced at the different conditions under coal reburning were systematically carried out in boiler furnace to maintain acceptable waterwall temperatures. NOx formation is minimized an entrained flow reactor (EFR). The results indicate that the release of carbon and nitrogen by combustion staging via low NOx burners and over-fire gas ports. Virtually all of the flue is almost the same as the coal mass loss, however, hydrogen release fraction is significantly gas sensible and latent heat energy is recovered in the heat recovery area of the boiler where larger than the coal mass loss and the release fraction of carbon, nitrogen. The NO reduction steam superheaters, steam reheaters, gas recuperators, and water economizers are located. efficiency decreases with increasing primary-zone or reburning-zone air: fuel stoichiometry The effluent of the plant is virtually pure CO2, which is condensed, pressurized, and piped ratio. The char contributions to total NO reduction efficiency increase with increasing from the plant to the sequestration site. Overall power plant system and component designs proximate volatile matters. The relative contribution of char to total NO reduction at the are presented for a 475 MW (gross) supercritical coal-fired plant. The power plant system 13

conditions of SR1=1.0 and SR1=1.2 is significantly larger than that at SR1=1.1 for high Argonne National Laboratory (ANL) is developing dense cermet (i.e., ceramic-metal volatile coal at a fixed reburning fraction. composite) membranes for separating hydrogen from mixed gases, particularly product streams generated during coal gasification and/or methane reforming. Hydrogen separation 16-3 with these membranes does not require electrodes or an external power supply, and Low-Temperatures Reduction of NO Using V2O5/AC Catalyst from Flue Gas hydrogen separated from the mixed gas stream is of high purity, so post-separation Zhanggen Huang, Zhenyu Liu, Pingguang Liu, Xianniu Hong, Zenghou Liu, Jue Ge, purification steps are unnecessary. Cermet membranes were prepared by mixing ≈50 vol.% Chinese Academy of Sciences, CHINA Pd with Y2O3-stabilized ZrO2. Using several feed gas mixtures, we measured the nongalvanic hydrogen permeation rate, or flux, for the cermet membranes in the temperature V2O5/AC catalyst showed higher selective catalytic reduction (SCR) activity of NO in range of 500-900°C. This rate varied linearly with the inverse of membrane thickness and 3 2 the presence of SO2 at lower temperatures. Further study showed the V2O5/AC catalyst reached ≈33 cm [STP]/min-cm at 900°C for an ≈15-μm-thick membrane on a porous deactivated easily in the presence of H2O and SO2, which is due to the excess position support structure when 100% H2 at ambient pressure was used as the feed gas. Hydrogen of ammonium-sulfate salts on the catalyst surface. The position rate of ammonium- flux measurements in H2S-containing atmospheres showed that the cermet membranes are sulfate salts is governed by the rate difference between its formation and reaction with stable for up to 1200 h at 900°C in gases that contain 400 ppm H2S. We have also measured NO. Through decrease in the formation rate of ammonium-sulfate salts or increase in the hydrogen flux through the cermet membrane at 500 and 600°C using a feed gas of 73% the reaction rate of ammonium-sulfate salts and NO, such as decrease in V2O5 loading, H2/400 ppm H2S/balance He. Because formation of palladium sulfide (Pd4S) can seriously mineral content of AC and space velocity, or increase in reaction temperature, the degrade hydrogen permeation though Pd-containing membranes, we evaluated the chemical -1 catalyst can be used stably at a space velocity of below 9000 h and temperature of stability of the membranes by equilibrating samples in 73% H2/400 ppm H2S/balance He at 250°C in the presence of SO2 and H2O. In the real existing burner system, a fixed bed temperatures in the range 400-900°C to determine the conditions under which palladium reactor, including reaction and regeneration system, is explored and the catalyst shows sulfide (Pd4S) forms. The present status of membrane development at Argonne will be higher NO conversion at 150°C and 1000 h-1 for 30 day. presented in this paper.

16-4 17-2 SCR/SNCR Optimization with In-Situ Ammonium Single Membrane Reactor Configuration for Separation of Bisulfate Fouling Measurement Hydrogen, Carbon Dioxide and Charles Lockert, Breen Energy Solutions, USA Shain Doong, Raja Jadhav, Gas Technology Institute, USA

Ammonia slip has long been considered one of the primary variables relating to overall The objective of this research project is to develop a novel single membrane reactor process performance of both SCR and SNCR NOx control processes. However, because ammonium that can consolidate two or more downstream unit operations of a coal gasification system in bisulfate generation is related not only to ammonia slip, but the presence of SO3, moisture, a single module for production of a pure stream of hydrogen and a pure stream of carbon and excess O2 as well, its presence cannot be accurately predicted by an ammonia slip dioxide. The overall goals are to achieve higher hydrogen production efficiencies, lower instrument alone. A novel technology has been introduced for the direct measurement of capital costs and a smaller overall footprint than what can be achieved by utilizing separate ammonium bisulfate related fouling tendencies. This instrument directly measures and components for each required unit process/operation in conventional coal to hydrogen reports both the formation temperature and the fouling potential of the ammonium bisulfate systems. This novel membrane reactor process that is under development combines based fouling compounds. Data will be presented on the ammonium bisulfate instrument’s hydrogen sulfide removal, hydrogen separation, carbon dioxide separation and water-gas response, under full scale plant conditions, to varying levels of ammonia slip, its sensitivity shift reaction in a single membrane configuration. The carbon monoxide conversion of the to extremely low levels of ammonia, correlation between detected ammonium bisulfate water-gas-shift reaction from the coal derived syngas stream is enhanced by the activity and site specific air heater fouling as well as correlation between detected complementary use of two membranes within a single reactor to separate hydrogen and ammonium bisulfate activity and ammonia-on-ash concentrations. Further, this carbon dioxide. Consequently, hydrogen production efficiency is increased. The single measurement feedback may be used to optimize the operation of SCR and SNCR systems. membrane reactor configuration produces a pure H2 product and a pure CO2 permeate The measurement would be used to maximize NOx reduction while minimizing fouling stream that is ready for sequestration. In this work, Gas Technology Institute, partnered with across various loads and operating conditions. The specific control actions that can be taken Arizona State University, is evaluating the technical feasibility of this “one-box” concept by include: focusing on membrane material development. A new class of high-temperature nonporous • modifying urea/ammonia injection rates, membranes for separation of CO2 from coal-derived syngas is being developed. Supported • controlling air heater gas outlet temperature by controlling the amount of hot flue gas CO2 membranes are synthesized using a variety of techniques, including in-situ air heater bypass to maintain AH cold-end temperature above the AbS dew point, or impregnation and vacuum infiltration. Additionally, disc-shaped membranes are prepared by • controlling air heater inlet air temperature with air preheating by steam coils to pressure compaction of precursor powders. The prepared membranes are analyzed for maintain AH cold-end temperature above the AbS dew point. physical and chemical properties and evaluated for CO2 permeation. This paper will discuss A grid of AbS measurements may also be used to monitor SCR catalyst fouling as part of a the simulation results for this novel single membrane reactor process in comparison with the catalyst management program. The paper will include performance results from several US conventional H2-selective or CO2-selective membrane reactor process. The modeling generating stations operating either SCR and/or SNCR post combustion NOx systems. approach is based on thermodynamic analysis using a commercial flowsheet simulator to calculate the expected performances. The preliminary results from membrane synthesis and 16-5 characterization will also be presented. The project is sponsored by DOE’s National Energy Current Status of Development of Sieving Electrostatic Precipitator Technology Laboratory and Illinois Clean Coal Institute. Hajrudin Pasic, Zahirul Khan, Ohio University, USA 17-3 The paper describes a recently-proposed Sieving Electrostatic Precipitator (SEP)-- a device Alloy Membranes for Hydrogen Permeation suitable for efficient, cost-effective cleaning of polluted gases of both large and ultra fine Gokhan Alptekin, Sarah DeVoss, Robert Amalfitano, TDA Research, USA particulates in a very broad temperature range. In the last several years, a large number of fly J. Dough Way, Paul Thoen, Mark Lusk, Colorado School of Mines, USA ash collection-efficiency tests have been conducted, first on a bench-size SEP with 6-by-6 inches screens, at room temperature, high temperature (300-350°F), and several tests at U.S. coal reserves nearly equal the total proved world conventional oil reserves – a 250-year 1500°F. Most recently, the SEP has been demonstrated in a laboratory pilot-scale setting supply of U.S. coal at today’s domestic production rates. Hydrogen represents a clean with 6-by-2 foot screens at room temperature. All the results confirm that this technology alternative fuel and its clean production from coal in tandem with carbon sequestration could provides high fly ash collection efficiency, including extremely efficient removal of ultra reduce the environmental concerns associated with the widespread use of coal energy in fine, submicron particulates. Finally, the joint effort of Ohio University (OU), Ohio Coal stationary power applications. Gasification technologies have shown the potential to produce Research Office (OCDO), American Electric Power (AEP), and Electric Power Research clean synthesis gas from coal with virtually zero pollutant emissions, including the emissions Institute (EPRI) is in progress to build and test the SEP pilot unit as a part of a slipstream in of carbon dioxide (CO2). In this approach, coal is first gasified to produce a carbon AEP’s Conesville (OH) Power Plant. Some of those preliminary test results will be monoxide (CO)-rich synthesis gas. In several processing steps the impurities in the syngas presented as well. are removed and the CO content of the syngas is reduced by converting CO to hydrogen (H2) in a two-step water-gas-shift reaction. Finally, the hydrogen is separated from other compounds, mainly CO, CO2 and water. Currently, there are no coal-based facilities that SESSION 17 produce both hydrogen and electric power. However, system level studies indicate that the HYDROGEN FROM COAL: MEMBRANE SEPARATION efficiency of the coal-to-hydrogen plant could be enhanced if the WGS and H2 separation were combined into a single step and carried out at temperatures compatible with the contaminant control step (350-400°C). 17-1 The hydrogen separation membrane should provide robust performance, high hydrogen Dense Cermet Membranes for Hydrogen Separation from Mixed Gas Streams throughput, high selectivity and recovery and long-life at low cost. Palladium (Pd) alloy U. Balu Balachandran, Tae H. Lee, Ling Chen, Sun-Ju Song, Stephen E. Dorris, membranes have all these attributes. The hydrogen separation capability of Pd alloy Argonne National Laboratory, USA membranes is well known with applications in hydrogenation/dehydrogenation reactions and recovery of hydrogen from petrochemical plant streams. Pd alloy membranes provide very 14

high selectivity (theoretically producing a 100% purity H2 product). Unlike the ceramic scanning calorimetry (DSC). X-ray diffraction (XRD) of the sample at different stages of the membranes developed to date (which could only achieve up to 90% H2 selectivity in a single reaction shows that sonicating alone shifts Td to 3400°C, without any chemical changes in pass and requires cascades of membrane modules to provide higher purities), Pd alloy Ni or β-MgH2. However, milling converts a part of β-MgH2 to γ-MgH2. Additional membranes can achieve high selectivity in a single module. Pd alloy membranes also experiments are underway to determine whether the lower Td ≈ 2700°C corresponds to γ- achieve very high hydrogen flux, with at least an order of magnitude higher flux than the MgH2. From our experiments, it is also evident that lowering the crystalline size of both high temperature dense ceramic membranes. The operating temperature of the Pd alloy MgH2 and the Ni catalyst and thorough mixing is likely to further reduce Td. An additional membranes (300-600°C) is also well matched to that of the WGS process (200-600°C), motivation to lower Td is to avoid the formation of Mg2Ni which in our experiments forms where the reaction kinetics and the thermodynamic equilibrium both favor formation of at 2700°C. This may be possible if the amount and crystallite size of the Ni catalyst are hydrogen. The operating temperature for PSA systems (40-80°C) are too low for good WGS further reduced. Results of these experiments, now in progress, will be reported. reaction kinetics and the equilibrium is unfavorable at the high operating temperature of the * Work supported by U.S Department of Energy, Contract # DE-FC26-05NT42456. dense ceramic membranes (600-800°C). However, in spite of these potential benefits, [1] See the review by J. Huot in Nanoclusters and Nanocrystals edited by H.S.Nalwa (Amer. several hurdles inhibit commercial implementation of this membrane technology. To be Sci.Publishers, 2003) pages 53-85. commercially viable: 1) the robustness of these membranes must be improved, 2) the cost of the membrane must be reduced, and 3) the sealing problems encountered when integrating the membrane into the process equipment must be eliminated; a key problem for any SESSION 18 membrane system. GLOBAL CLIMATE CHANGE: TDA Research Inc., in collaboration with Colorado School of Mines (CSM) is developing a GREENHOUSE GAS UTILIZATION AND NOVEL CONCEPTS sulfur and CO-tolerant membrane to produce the clean hydrogen from syngas using Pd membrane films prepared on a variety of supports (e.g., symmetric ceramic supports and porous stainless steel supports). This paper summarizes the results of the membrane 18-1 development and testing efforts. Membranes that showed superior properties in screening Use of Coal Mine Methane in a Microturbine at CONSOL Energy’s Bailey Mine tests using hydrogen/nitrogen mixtures were further evaluated under representative Deborah Kosmack, Richard A. Winschel, CONSOL Energy Inc., USA conditions (the baseline gas composition used in these evaluations were 51% H2, 26% CO2, Patrick Rienks, Jay Johnson, Ingersoll-Rand Energy Systems, USA 21% H2O and 2% CO vol.). In general, membranes showed very good stability in water gas shift environment and were tested for several days with stable permeance and selectivity. We CONSOL Energy Inc Research & Development and Ingersoll Rand Energy Systems, with examined the effect of operating parameters including temperature, pressure and H2 recovery partial funding by the Clean Air Fund provided by the Pennsylvania Department of on membrane performance. We also investigated the impact of CO, CO2 and H2S Environmental Protection, are installing a low-emission 70 kW microturbine generator on a concentration in the reformate gas on the H2 permeation and selectivity of the membrane. large underground coal mine in Pennsylvania to reduce emissions of methane by capturing them and converting them into usable electricity. The generator will be fueled with coal 17-4 mine methane that is currently being vented as part of the mine’s ventilation system. Coal High-Pressure Operation of Dense Hydrogen Transport Membranes for mine methane is one of several major sources of anthropogenic methane, accounting for Pure Hydrogen Production and Simultaneous CO2 Capture about 10% of anthropogenic methane emissions in the United States. Methane is the second Xiaobing Xie, Carl R. Everson IV, Michael V. Mundschau, Harold A. Wright, Paul J. most important non-water greenhouse gas, with a global warming potential 21 times as great Grimmer, Eltron Research Inc., USA as that of carbon dioxide (CO2) on a mass basis. Thus, any coal mine methane that is emitted rather than utilized simultaneously represents a lost potential resource and the emission of a Eltron has developed a family of dense inorganic membranes that enable high H2 separation powerful greenhouse gas. The project objectives are to: 1) convert the low and variable rates with essentially 100% selectivity to H2. The membranes are designed to operate at the concentrations of methane contained in coal mine methane gas that would otherwise be same conditions as high-temperature water-gas shift (WGS) reactors (320−440°C) and can vented to the atmosphere to electricity; 2) provide the generated electric power to an existing be operated with up to 1,000 psi pressure differential across the membrane. In synthesis gas electric power grid; 3) donate the value of the electricity generated during the project period systems that incorporate WGS, the membranes facilitate efficient, low cost separation of H2 to a local school district; and 4) determine the quantity of useful energy that can be and CO2 at high pressure, enabling efficient capture of CO2. The membranes are being economically produced when processing coal mine methane from a working coal mine and developed to work with refinery waste streams as well as synthesis gas derived from natural perform a techno-economic evaluation of the system. When operating at 95% capacity factor gas, liquid hydrocarbons, coal, petroleum coke and biomass. The membranes may be ideal and a heat rate of 13,550 Btu/kWh HHV (higher heating value), the 70 kW generator will for natural gas or coal-based IGCC applications with or without hydrogen export. Compared produce 583 MWh of electricity as it consumes 7,954,000 cubic feet of methane, with a to palladium-based membranes, the Eltron membrane exhibits 20 times the flux for a given global warming potential equivalent to 3,522 short tons of carbon dioxide, each year. Startup set of conditions and costs about 10 times less. The high hydrogen permeability and low cost and commissioning of the system will be followed by 12 months of operations. of the membrane materials allows the use of relatively thick membranes, which is crucial for their operation under high pressure differential. This technology has many advantages over 18-2 competing hydrogen separation technologies. Advantages are listed as follows: (1) the Green Power Technologies for High Ash Indian Coals-Evaluation of membranes allow the capture of CO2 at high pressure. The CO2 is essentially captured at CO2 Mitigation Options, gasification or reforming pressure; (2) the membrane is low cost with long membrane life. D.N. Reddy, Centre for Energy Technology, INDIA; V.K. Sethi, Rajiv Gandhi Stability tests have been conducted for over eleven months on line with high flux retained; Technological University, INDIA (3) the membranes, in principle, will work with synthesis gas generated from any source including coal, petroleum coke, natural gas, or biomass; (4) essentially 100% pure hydrogen The Global concern for reduction in emission of green house gases (GHG) especially CO2 is separated since the membrane works by transporting dissociated hydrogen across the emissions are likely to put pressure on Indian Power System for adoption of improved membrane material; (5) hydrogen recoveries of 90% or higher are possible; (6) the generation technologies. Although India does not have GHG reduction targets, it has actively membranes can be operated under high permeate pressures of pure hydrogen, and thus the taken steps to address the climate change issues. Mitigation options for CO2 reduction which costs associated with hydrogen compression can be substantially reduced; (7) the have been taken up vigorously include GHG emission reduction in power sector through membranes can be integrated with commercial high temperature water-gas shift catalysts. adoption of Co-generation, Combined cycle, Clean Coal Technologies and Coal The integrated membrane/WGS reactor has been demonstrated capable of achieving Beneficiation. CO2 emissions per unit of electricity generated are significantly high in India significantly higher CO conversion over the thermodynamic equilibrium limitation. as large proportion of power generated comes from low sized, old and relatively inefficient Eltron was recently awarded a program from the United States Department of Energy aimed generating units which constitute over 50% of our total installed capacity of about 103,000 at scaling up these membranes for possible use in the FutureGen coal-based power and MW. The technology up gradation through life extension of old polluting units is expected to hydrogen plant. This paper discusses recent advances in the development of these increase the generating efficiency of these units thereby reducing CO2 emissions. Presently membranes including experimental demonstrations of the above mentioned advantages, and about 32 power stations with 106 units of various capacities ranging from 30MW to 200MW membrane performance. totaling to about 10,400 MW dated capacities are taken-up for Life extension (LE) during 10th five year plan (2002-07). In addition to above about 60 Thermal Power plants units 17-5 (13,900 MW) have been taken up for Renovation and Modernization (R&M) in the country, Effect of Nanocrystalline Catalysts on the Desorption Temperature of which is expected to contribute significantly in terms of CO2 reduction. MgH2 for Hydrogen Storage Applications A major thrust on CO2 reduction on long term and sustainable basis would however come M.S. Seehra, P. Dutta, S. Pal, J. Fortune, West Virginia University, USA through adoption of advanced technologies of power generation like Supercritical/Ultra- supercritical power cycles, Integrated Gasification Combined Cycles (IGCC), Fluidized Bed MgH2 is an attractive hydrogen storage material with 7.6 wt% hydrogen capacity and with a Combustion/Gasification Technologies and so on. A beginning towards adoption of super safe endothermic desorption of hydrogen at Td ≈ 4320°C [1]. However for practical critical units has already been made in the country and it is foreseen that super critical applications, this Td is too high. In this work, we will report recent results of our experiments technology would almost universally be adopted for all large sized pithead units in the to lower Td. Our approach is based on the use of nanocrystalline Ni to reduce Td. Our recent country. The attained efficiency gains of these technologies are likely to reduce the experiments using 20 nm Ni nanoparticles mixed ultrasonically in the amount of 1 mol % environmental emissions especially CO2 significantly. Adoption of higher parameters for with a commercial β-MgH2 followed by ball milling of the mixture for 15 minutes, have super critical units after sufficient feedback and operational experience would further reduce yielded Td ≈ 2700°C as revealed by thermogravimetric analysis (TGA) and differential these emissions to a great extent. A total additional efficiency of about 1.5-2% is normally 15

achieved for adoption of super critical parameters of 246-kg/cm2 (g) and 537/565°C, chosen efficiency (> 30%). The integrated combinations were optimized with respect to net power for the first Supercritical Power Plant under planning with unit size of the order of 660 MW. generation efficiency, fraction of CO2 captured, and scale-up considerations. An optimized Adoption of still higher parameters would further enhance the efficiency. Attempts would design balancing those parameters and scale is presented as a solution for a coal-based 500 also need to be made to further enhance the efficiency of conventional pulverized coal fired MWe power plant. plant by adoption of ultra super-critical parameters. The main constraint being faced for adoption of these technologies is the availability of requisite material to withstand 18-5 combination of high Pressures and temperatures encountered. A consortium of several Utilization of Carbon Dioxide from Coal-Fired Power Plant for the equipment manufacturers globally has pooled their resources to develop necessary materials Production of Value-Added Products to overcome the constraints for adoption of ultra super-critical technology. Daniel Van Niekerk, Brandie Markley, Arun Ram Mohan, Victor Rodriguez-Santiago, Another option for CO2 reduction is increased use of natural gas. This provides improvement David Thompson, Derek Elsworth, Jonathan P. Mathews, Sarma Pisupati, Chunshan in generation efficiency together with reduction in CO2 emissions but would facilitate Song, Yan Li,The Pennsylvania State University, USA environmental pollution control only up to a certain extent. With addition of more and more generation capacity and also increasing CO2 emissions from transport and other industrial This paper discusses a few promising physical and chemical technologies for the utilization sectors, progressive de-carbonization of generation resources may have to be adopted in and conversion of CO2 from a 500 MW coal-fired power plant into viable economic certain regions/areas. Already, Natural Gas is being used in a big way in the country for products. The main areas of interest were microalgae biomass production (pond and power generation and GT/CCGT stations accounted for about 10% of total generation in the bioreactor production), supercritical CO2 extraction technology, fixation of CO2 into organic year 2001. The natural Gas resource crunch being faced at present, even though there is compounds (production of various chemical products), and trireforming of CO2 for synthesis quest for quick power generation restricts increased use of Natural gas in Combined Cycle gas production. The value added products that can be produced from these four main mode, limiting it to some specific priority areas only. Research work in this area to increase technologies are: biomass (high and low grade), biomass-derived products (pharmaceutical, the generation efficiency of Combined Cycle to an extent of 60% is already underway and chemical or nutritional), synthesis gas, specialty products (extracted using supercritical this goal is likely to be realized in near future. These technologies can then be adopted as and technology), organic carbonates (linear, cyclic or polycarbonates), carboxylates (formic acid, when available. A much more efficient methodology of generating electricity from Natural oxalic acid, etc), salicylic acid and urea. The method employed for CO2 utilization depends gas is on the anvil i.e. fuel cell technology which looks more promising source of Energy on the desired products. It can be concluded, however, that chemical conversion and tri- option in future. reforming are the leading technologies when the aim is to sequester the most possible CO2. The present study is dedicated to environmentally benign Clean Coal Technologies for Despite the small percentages of CO2 being utilized by biological and scCO2 technologies burning high ash Indian Coals and middling, washery rejects and so on. The paper primarily when compared to the total amount emitted by a 500 MW power plant, the value-added focuses on evaluation of various CO2 mitigation options through use of these Green Power products and yield are considerable. Technologies.

18-3 SESSION 19 Gas Treatment Concepts for IGCC with CO2-Separation GASIFICATION TECHNOLOGIES: Hardy Rauchfuss, Sirko Ogriseck, Mathias Rieger, Bernd Meyer, Technische ADVANCED SYNTHESIS GAS CLEANUP – 1 Universitat Bergakademie Freiberg, GERMANY

Lignite-based power generation plays an essential role for energy supply in Germany. 19-1 Combustion of lignite in conventional PC power plants causes a specific CO2-emission up to Field Testing of a Warm-Gas Desulfurization Process Using a 1,100 kg/MWh averaged [1]. This exceeds the specific CO2-emission of natural gas based Pilot-Scale Transport Reactor System with Coal-Based Syngas power generation by two or three times. The German government intends a reduction of CO2 Jerry Schlather, Eastman Chemical Company, USA emissions by 21 % by 2012 compared to the year 1990. For a notable reduction of the CO2- Brian Turk, Research Triangle Institute International, USA emission of power generation new concepts for high efficient power plants with options for CO2-sequestration or polygeneration are essential. A promising possibility is IGCC with Current Integrated Gasification Combined Cycle (IGCC) power plant designs employ CO2-Separation. All concepts in this investigation are determined for lignite gasification amine-based scrubbing systems to desulfurize the syngas prior to the combustion based on fluidized bed gasification which was been developed for industrial scale in the turbine. Because these systems operate at low temperature relative to the gasifier and HTW-process. An IGCC with CO2-Separation includes nearly the same process steps as a combustion turbine, the overall efficiency of the power plant is reduced by several conventional IGCC without CO2-removal. However, additional equipment is necessary for points. Research Triangle Institute (RTI) has been developing a competing CO-conversion, CO2-separation and compression. Clean gas and raw gas CO-conversion, as desulfurization technology that avoids decreasing overall thermal efficiency by well as alternative concepts have been investigated in accordance with various concepts for operating at temperatures 260ºC (500ºF). This desulfurization technology makes use of raw gas cooling and sour gas removal. Thus specific CO2-emissions in the range of 110 an attrition resistant regenerable desulfurization sorbent and a transport reactor. For kg/MWh and 235 kg/MWh are achievable. This means a carbon retention rate of up to 89 %. temperatures from 260 to 500ºC (500 to 950ºF), RTI has developed a zinc oxide-based The calculations show net efficiencies between 39 and 42 % based on LHV. The costs of sorbent that has been commercially produced and demonstrated to reduce inlet electricity are estimated in the range of 60 to 90 €/MWh. concentrations of H2S and COS totaling 8,000 ppmv (wet basis) to < 5 ppmv (total sulfur wet basis) in extensive bench-scale testing with simulated syngas and in actual 18-4 testing in a pilot-scale transport reactor with real coal derived syngas. Extended testing Optimal Design for Integrating CO2 Capture and Fuel Conversion of the pilot plant transport reactor and desulfurization sorbent was conducted with a Technologies in a 500 MWe Coal-Based Power Plant slip stream of coal-derived syngas from the commercial gasifier at Eastman Chemical Nari Soundarrajan, Meredith A. Hill, Jiahua Guo, Lu-Ming Chen, Vasudha Dhar, Company s facility in Kingsport, TN. This paper will present the results from this Hyun Joe Kim, Ramanathan Sundararaman, Onur Mustafaoglu, Derek Elsworth, extended field test of this pilot-scale desulfurization system and the technical/economic Jonathan P. Mathews, Sarma Pisupati, Chunshan Song, The Pennsylvania State merits of this technology compared to conventional processes. University, USA 19-2 A conceptual study was conducted towards a new design for more efficient fuel conversion Sulfur Removal from E-Gas Gas Streams with S Zorb™ Sulfur and CO2 capture in a future 500 MWe power plant that incorporates both new conversion Removal Technology (SRT) technologies to optimize plant efficiency and new carbon dioxide (CO2) capture methods. Roland Schmidt, Joe Cross, Albert Tsang, Ed Sughrue, ConocoPhillips, USA Conventional means of power generation without CO2 capture (e.g., air-fired pulverized coal Robert Kornosky, DOE/NETL, USA combustion and fluidized bed combustion) formed base cases to evaluate advanced combustion technologies with CO2 capture. The following capture schemes were The SG Solutions (SGS) facility in Terre Haute, IN produces syngas (hydrogen/carbon investigated: 1) Pre-combustion decarbonization consisting of gasification or reforming monoxide stream) for power generation using ConocoPhillips’ E-Gas™ Technology to processes with CO2 separation membranes; 2) Denitrogenation methods such as oxy- gasify coal or petroleum coke. The syngas can contain high levels of sulfur combustion and chemical looping combustion; 3) Post-combustion CO2 recovery using contaminants (>1 weight %). These contaminants must be removed from the gas solvent absorption, membrane separation and solid adsorption. Evaluations were based on: stream prior to power generation. ConocoPhillips’ proprietary S ZorbTM sulfur 1) Efficiency of electricity generation; 2) Fuel consumption and CO2 emitted per unit removal technology (SRT) utilizes proprietary sorbents that can remove these sulfur electricity; 3) Feasibility of scale-up; and 4) Energy penalty associated with capture. Both the contaminants under warm-gas conditions. A slipstream study at the SGS facility methods of CO2 capture and the technology of energy conversion were found to influence demonstrated sulfur reduction to ppm levels under plant operating conditions. The the overall plant efficiency and amount of CO2 that can be captured. Advanced combustion work used ConocoPhillips’ proprietary S ZorbTM sorbents as part of a test program technologies enable the production of concentrated CO2 emission streams, but involve under the “Wabash River Integrated Methanol and Power Production from Clean Coal complex process designs. Gasification-based processes and chemical looping combustion Technologies (IMPPCCT)” Project funded by the U.S. Department of Energy emerged as efficient options for future coal-based power plants. These power generation Cooperative Agreement No. DE-FC26-99FT40659, and managed by the National technologies were integrated with selected CO2 capture technologies to recover a high Energy Technology Laboratory. percentage of the CO2 produced (> 90%) while maintaining reasonable power generation 16

19-3 20-1 Development of Highly Efficient Hot-gas Cleanup Technology for Advanced Issues in Modeling Entrained Flow Coal Gasifiers IGCC System Involving Coproduction of Hydrogen and Liquid Fuels Mike Bockelie, Martin Denison, Hong-Shig Shim, Connie Senior, Adel Sarofim, Michihiro Ishimori, Yoshiharu Yamaguchi, Koichiro Furusawa, Masafumi Katsuta, Reaction Engineering International, USA Waseda University, JAPAN In this paper we describe a mechanistic based engineering process model that can be used for Development studies of hot-gas cleanup system, especially highly efficient desulfurization scoping studies on the performance of entrained flow gasifiers. The model includes technologies have been carried out in order to realize the highly effective coal gasification heterogeneous gasification kinetic rates that account for product/reactant inhibition effects power plants such as IGCC and related systems involving coproduction of hydrogen and/or and pressure effects. Data from the CCSD in Australia has been used to guide selection of liquid fuels (GTL or CTL). In continuing our studies of zinc ferrite and related compounds the kinetic parameters. Commercial scale IGCC plant data has been used to calibrate the as desulfurization agents, we have found several excellent sorbent systems for hot reductive model. Example calculations are provided for a single stage, slurry feed gasifier operating gases such as produced by an entrained-flow gasifier. The performance tests of the across a range of pressures that are representative of current IGCC plant designs and those of sorbent systems were carried out at a fixed-bed type bench-scale reactor at 250-600°C under future CO2 capture ready IGCC plant designs. Demonstrations of the value of the model are atmospheric and pressurized conditions, using simple reductive gas containing hydrogen provided by examining the pressure scaling of gasifiers and the role of residence time versus sulfide and/or related gas. Some sorbent systems composed of zinc ferrite and metal oxides temperature in determining the efficiency of carbon burnout. and/or metal sulfides were found to show excellent desulfurization performance for some representative sulfur compounds; concentrations of hydrogen sulfide, dimethyl sulfide, and 20-2 thiophene involved in the reductive gases were respectively decreased to less than 50 ppbv; A Detailed Look inside a Transport Reactor the performance of the desulfurization agents for synthesis gas is satisfactory with respect to Chris Guenther, Ronald Breault, National Energy Technology Laboratory, USA production of high grade hydrogen and/or liquid fuels such as methanol and DME. The regeneration of the sorbent systems after sulfidation is carried out by oxidation. The feature This investigation uses the Eulerian-Eulerian model MFIX (Multiphase Flow with of breakthrough curves for the sulfuric gases suggests that deactivation of the sorbent Interphase eXchanges; www.mfix.org) developed at the National Energy Technology systems during absorption-regeneration cycles is negligible. The characteristics of zinc Laboratory to investigate the hydrodynamics and chemistry inside a large scale transport ferrite and related systems will be discussed in relation with sorbent systems for hot-gas gasifier. Previous papers used experimental data from the Power Systems Development cleanup process of IGCC power generation system involving coproduction of hydrogen Facility to verify that MFIX can predict accurate exit syngas for both bituminous and sub- and/or liquid fuels; the coproduction process is integrated with IGCC system in parallel with bituminous coals under both air and oxygen-blown operating conditions. In this paper a the combined cycle of gas turbine and steam turbine. detailed look inside the reactor is discussed. Oxygen break-thru into the riser, axial and radial mixing, and exit effects are discussed. A parametric study on reactor height is presented and 19-4 simulation results are presented based on a new reactor design currently under construction Dry Desulfurization of Coal Gas by Partial Oxidation of H2S at the Power Systems Development Facility. Dirk Bauersfeld, Prof. Dr.-Ing.B. Meyer, I. Rochner, Technische Universitat Bergakademie Freiberg, GERMANY 20-3 Part-Load Simulations and Experiments of a Small Coal Gasifier This paper deals with the dry desulfurization of coal gas by partial oxidation of H2S on Ting Wang, Armin Silaen, University of New Orleans, USA high temperature brown coal coke (HOK). H2S is catalytically oxidized by O2: Heng-Wen Hsu, Min-Chain Lo, Industrial Technology Research Institute, TAIWAN H2S+ 1/8 O2 → H2O + 1/8 S8 The formed sulfur is adsorbed on the inner surface on HOK. The operation temperature An oxygen-blown, coal powder-feed, entrained-flow demonstration gasifier was constructed for this dry desulfurization process ranges from 150 to 250°C. A high operation and operated by the Industrial Technology Research Institute (ITRI) in Taiwan. Specific pressure is favorable for the achievable desulfurization level, where more than 99 % tests have been conducted to investigate the gasifier's performance and gain operation can be obtained. The level of desulfurization depends on temperature, pressure and the experience under part-load conditions either caused by reduced load demands or formation of COS. The main limiting factor is COS formation: maintenance needs. Water spray near the exit of the gasifier was employed to test its CO + 1/8 S8 → COS feasibility in tuning H2 content or controlling gas exit temperature. To help understand the This reaction was investigated in a fixed bed reactor, using a typical gasification gas gasifying characteristics of various part-load conditions, computational simulation was from brown coal fluidized bed gasification, at a temperature of 180°C, a pressure up to conducted using the commercial CFD solver FLUENT. The 3-D Navier-Stokes equations 27 bars and a total volume flow of 1.5 to 3 m3/h (STP). The experimental investigation and seven species transport equations were solved with eddy dissipation combustion model. showed that the reaction between CO and elemental sulfur is not the main one. COS is The simulation results provide the velocity, temperature, and species distributions inside the mainly produced by reactions of CO and H2S on HOK. Furthermore, a reaction (COS- gasifier. The results indicate that water spray injection cools down the gas and increases H2 Hydrolysis) was found at lower COS concentrations in the clean gas. These reactions mole fraction at the cost of the reduction of CO and increased production of CO2. It is were observed with increasing residence time. Finally, we determine the amount of recommended that a better way to produce H2 is to inject steam near the feedstock injection COS could be reduced while increasing the desulfurization level. ports where plenty carbon is available and temperature is high and favorable to produce H2 more efficiently via the gasification reaction without producing CO2. The simulated results 19-5 were compared with the experimental data including situations when two of the three fuel Selective Catalytic Oxidation of Hydrogen Sulfide - IGCC Applications injectors were under maintenance. Employing fuel injection through a single injector Maryanne Alvin, Robert Stevens, DOE/NETL, USA unexpectedly performs better than applying three injectors. The results indicate the injection Richard A. Newby, Dale L. Keairns, Science Applications International Corporation, velocity speed and momentum strength of each injector, rather than the total injection USA momentum, are more influential in affecting the gasification efficiency. The results of this study can be used to improve prediction of future part load performance. Selective catalytic oxidation of hydrogen sulfide (SCOHS) to elemental sulfur using activated carbon and NETL-processed metal oxide catalyst systems has been 20-4 investigated under bench-scale, simulated pressurized IGCC conditions for use in dry Effects of Fuel Injection Angles on Performance of a Two-Stage Coal Gasifier and humid gas cleaning process applications. For this technology to be successful, a Armin Silaen, Ting Wang, University of New Orleans, USA 20% cost effective advantage and 1 percentage-point plant efficiency gain over current commercial technology, and <10-15 ppm total gas phase sulfur release into the effluent Numerical simulation of the coal gasification process inside an oxygen-blown, two- gas stream must be demonstrated. The results of our bench-scale catalyst/sorbent stage entrained-flow gasifier are carried out using the commercial CFD solver desulfurization and regeneration efforts for both bulk and polishing sulfur removal FLUENT. The 3-D Navier-Stokes equations and seven species transport equations are indicate that direct selective catalytic oxidation of H2S to elemental sulfur utilizing solved with eddy-breakup combustion model. Simulations are conducted to investigate current activated carbon systems occurs only under conditions of low syngas the effects of coal-slurry injection angles on the performance of a two-stage entrained temperature (<150°C), and in syngas effluent streams containing a low water and CO coal gasifier. The results indicate that the configuration with all injectors positioned content. Thus the SCOHS desulfurization process is considered to be only potentially horizontally gives the best result. By changing the lower injectors to pointing 30 feasible for use in dry gas cleaning conditions for IGCC applications where syngas-CO degrees downward or upward, fuel conversion efficiency is decreased. Altering the is shifted to CO2, and regeneration of the catalyst occurs through heating in warm CO2, upper (second stage) fuel injection directions or eliminating half of the first-stage fuel with simultaneous CO2 sequestration. SCOHS is not considered as a candidate injectors appears to have an insignificant effect on the gasifier performance. desulfurization approach for use in humid IGCC gas cleaning applications. The overall results indicate that the fuel conversion efficiency can be considerably affected by the flow pattern in the gasifier by about 17% in the studied cases.

SESSION 20 20-5 GASIFICATION TECHNOLOGIES: Studies on Hydrodynamic Characteristics of Gas-Solid Tapered Fluidized Beds FUNDAMENTALS AND SIMULATIONS – 1 D.N. Reddy, Osmania University, INDIA

17

Power generation by means of Integrated Gasification Combined Cycle is potentially very considering part of the energy generated during co-firing as renewable energy, the procedure efficient and deserves serious attention as a means of making the best use of available coal for renewable energy share calculation is presented and illustrated with an example. resources. Gas solid fluidization is a subject having wide engineering application overlapping different industries. It is eminently suitable for thermal coal processing and 21-2 could in future play a major role in production of liquid and gaseous fuel from coal using Co-combustion Experiences from the Czech Republic liquefaction and fluidized bed gasification processes. Clean Coal Technologies facilitate the Dagmar Juchelkova, Helena Raclavska, Bohumir Cech, VSB-Technical University of use of coal in an environmentally, satisfactory and economically viable way. For IGCC Ostrava (Integrated Gasification Combined Cycle) further R&D and commercial scale Klaus Koppe, Technical University of Dresden, DEUTSCHLAND demonstrations are needed to encourage commercialization of the technology by improving reliability and availability and reducing costs. Material developments will be important in the The research is focused on the field of combined combustion of coal and waste including above. BHEL was the first organization to take up development of IGCC systems in phases biomass in the fluidized-bed boilers with atmospheric fluidized bed. Special attention will be using PFBG for power generation systems, which has the potential to result in higher given to emissions and possibility of the future utilization on other FCB boilers in the Czech efficiency owing to the possibility of integrating advanced gas turbines to the gasification Republic. Main goals may be outlined in the study of conditions for: system. Cold model rigs have been set up by BHEL to confirm hydrodynamics adopted in - Potential substitution of fuel with less valuable types of coal simultaneously with the design of Pressurised fluidized bed gasifier. The purpose of this study is to investigate the waste and biomass, sustainability of fluidized bed combustion. origin of pressure fluctuations in gas solid tapered fluidized beds using cold model studies. - Actual unit diagnostics development. The study will assess the potential for using pressure fluctuations as an indicator of fluidized - Laboratory studying mechanism for combustion by thermal analysis. bed hydrodynamics in both laboratory scale cold models and industrial scale gasifiers. - Raw material input analysis and dependence of combustion solid residues on raw Many advantages like uniformity of temperature, uniform mixing have been found in material input. fluidized beds. However there exits many problems in fluidized operation carried out in - Combustion inaccuracy assessment in Foster Wheeler FCB unit (temperatures, cylindrical columns, such as non-uniform fluidization in large diameter and deep cylindrical gaseous and solid components, velocities). beds, where there is particle size reduction during operation leading to severe entrainment. - Studying mechanism for fouling deposits formation and composition. Hence there is necessity for the system to have capability of fluidizing particles of different - Balance of combustion elements including . sizes at the same time. The demerits mentioned above in cylindrical beds can be overcome - Verifying a redistribution mode for choice of elements between the fuel and solid by- by using tapered beds. Hydrodynamic characteristics of fluidization in tapered beds differ products of combustion. from those in columnar beds due to variation of superficial velocity in the axial direction of - Quantitative phase analysis and structural analysis of substance especially minerals by the beds. In the former, fixed and fluidized beds could coexist and the sharp peaking of the employing rtg. diffraction methods. pressure could occur, thereby giving rise to a remarkable pressure drop at high flow rates and - Long-term deposit formation on thermal exchanger s walls. hysterisis loop at incipient fludization. Such high velocity regime in tapered fluidized beds - Saturation sludge dosing as a sorbent. can offer better gas to solid contact. In this study, an attempt is made to investigate the various possible regimes in gas solid 21-3 tapered fluidized beds. To explore these unique properties, a series of experiments was Kimberlina - A Zero-Emission Multi-Fuel Power Plant and carried out in gas solid tapered beds with various tapering angles of 5°, 10°, 15°, 20°, using Demonstration Facility particles of different sizes and densities. Detailed visual observations of fluid and particle Scott MacAdam, Roger Anderson, Fermin Viteri, Keith Pronske, Clean Energy behavior and measurements of the pressure drops using Data Acquisition System have led to Systems, USA the identification of 5 flow regimes. The tapering angle of the beds has been found to dramatically affect the beds behavior. Clean Energy Systems, Inc. (CES) has developed a zero-emission power generation Other hydrodynamic characteristics determined experimentally included (peak pressure technology by integrating proven aerospace technology into conventional power systems. A drop, minimum fluidization velocity, minimum velocity of full fluidization, maximum simplified schematic of the process is shown in Figure 1. The core of CES’ process is an velocity of full defluidization, maximum and minimum expansion ratio, hysterisis). The oxy-combustor adapted from rocket engine technology. This combustor burns a clean work on tapered fluidized bed is carried out using distributors of cone angles 60°, 90°, 120°, gaseous fuel with gaseous oxygen in the presence of water. Fuels include syngas from coal, 150° and 180° and varying apex angle from 5° to 20° and compared with that of cylindrical refinery residues, or biomass; natural gas; ; and biodigester gases. The bed. The bed is fixed to a plenum chamber with a distributor. Experiments are conducted in combustion is performed at near-stoichiometric conditions in the presence of recycled water 3-D tapered cold model test rigs. The materials used for the experiments are closely sieved to produce a steam/CO2 mixture at high temperature and pressure. These combustion refractory of density 2965 kg/m3, sand of density 2590 kg/m3, bottom ash of density 1900 products power conventional or advanced steam turbines and may use modified gas turbines kg/m3 and mustard of density 1150 kg/m3 with air as fluidizing medium. In literature, operating at high temperatures for expansion at intermediate-pressures. The gas exiting the correlations are proposed for critical fluidization velocity, peak pressure drop. While there turbines enter a condenser/separator where it is cooled, separating into its components, water have been no correlations for prediction of other parameters such as minimum fluidization and CO2. The recovered CO2 is conditioned and purified as appropriate and sold or velocity of tapered bed with effect to the distributor. Hence it is expected the present sequestered. Most of the water is recycled to the gas generator but excess high-purity water predicted correlation for minimum fluidization velocity would be more useful in design and is produced and available for export. Every component in the CES process, except for the operation of tapered fluidizers. The proposed correlation is found to agree with the combustor and reheater, is commercially proven and is standard in power generation. The experimental results within ± 19%. basic combustor technology has been used successfully in aerospace applications for decades. CES’ innovation has been to adapt that aerospace technology to power generation, much like the process by which aircraft jet engines were adapted for aero-derivative gas SESSION 21 turbines in conventional power plants. COMBUSTION TECHNOLOGIES – 4: COAL CO-FIRED WITH OTHER FUELS 21-4 Research on the Suspension Combustion Rate of Coal Water Slurry Ji Deng-Gao, Taiyuan University of Technology, P.R. CHINA 21-1 Wang Zu-Ne, China University of Mining Technology, P.R. CHINA Biomass Co-firing in Pulverized Coal-fired Utility Boiler Marek Sciazko, Jaroslaw Zuwala, Institute for Chemical Processing of Coal, POLAND The atomization suspension combustion of coal water slurry is the extensive technology of Wojciech Zygmanski, Skawina Power Plant, POLAND its combustion and gasification. Research on coal-water-slurry atomization suspension combustion property is very important. Experiment based on traditional single drop Co-firing tests of sawdust and food processing residue with coal have been carried out at combustion couldn’t reflect true atomization, suspension firing of coal water slurry Skawina Power Plant in Poland (1532 MWth in fuel, currently belonging to CEZ Group). atomization suspension firing test device (ASFTD) was adopted and study on the Skawina Power Plant is a tangentially-fired pulverized coal unit with nine boilers (4 boilers combustion rate of Shenmu coal water slurry suspension combustion was carried out. The of 210 and five boilers of 230 t/h live steam respectively) that produces 590 MW electricity, model of Shenmu slurry suspension combustion rate was proposed under this experiment 600 MW district heat and process steam. condition. The results show that suspension combustion rate gradually increases with the The paper presents an analysis of energy and ecological effects of biomass co-firing in both prolongation of coal water slurry combustion time under different temperature, however, types of coal boilers. Coal and sawdust were blended in the coal yard, and the mixture was different temperature results in distinct suspension combustion rate change. The trend shows fed into the boiler through coal mills. Full scale co-firing trial tests were carried out for two that the suspension combustion rate increases with coal water combustion temperature weeks during February 2005. In the tests, sawdust mass share of 9.5% and food processing heightening. It is helpful to design and operation of coal water slurry combustor. residue of 6.6% (both mass basis) were examined. The co-firing tests were successful. Based on the analysis of the test results, the influence of biomass co-firing on specific components 21-5 of energy balance (e.g. stack losses and boiler thermal efficiency) was discussed, in Utilization of Biomass and Mixtures for the Gas Production comparison to combustion of coal alone. The emission indices during coal combustion were Dagmar Juchelkova, Helena Raclavska, Vaclav Roubicek VSB - Technical University calculated and compared to the emission indices for biomass co-firing. It was shown that of Ostrava, CZECH REPUBLIC biomass co-firing leads to a decrease of CO and SO2 emissions. Due to the possibility of 18

The Aim of the project is the improvement of the collaboration in the gas production Pollutant Removal (IPR) system. Oxy-firing coal produces an exhaust stream and utilization (from various kinds of fuels, incl. biomass and their mixtures). composition dominated by CO2 and water, with particulate matter and small Collaboration between both universities (VŠB-TU Ostrava a SIU Carbondale) was contributions of SOx, NOx, O2, N2, Ar, and Hg. This is followed by the IPR system started at 1993 and there is interest on various themes. Presently is interest on the which uses compression and intercooling to produce a supercritical, transportation- “clean gas” production, the special aspect of this work is environmental improvement ready CO2 fluid suitable for sequestration or for purification, as necessary, to obtain (minimizing of negative people impact to the antroposphere). On the SIU (Southern CO2 for industrial use. Recent theoretical and experimental work at NETL is Illinois University) Carbondale ware gasification engine – pilot with various output – examining three aspects of IPR: acid gas and particulate removal with energy recovery; which can be use for the experiments. Collaboration intensification in the sphere water treatment for recycle and release; and the enhancement of Hg0 capture through “clean gas” production and utilization of the results in the praxis and teaching process oxidation. Because their combination is corrosive, water, associated acid gases and Special interest of the research is given to the estimation of main conditions for the gas particulate matter must be removed from the boiler flue gas in the initial stages of IPR production. to enable compression of the remaining CO2 fluid. This study compared air-fired furnace exhaust and oxy-fired furnace exhaust in flue gas desulfurization experiments. Tests indicate the largest effect is associated with the greater concentration of SO2 in SESSION 22 oxy-fired exhaust, despite the high concentration of CO2 in this flue-gas composition. ENVIRONMENTAL CONTROL TECHNOLOGIES: SOx, NOx, PARTICULATE AND MERCURY – 2 22-4 Photocatalytic Decomposition of NO Originated from Coal Analog Compound Xue Hanling, Li Jianwei, Ge Lingmei, Zhous Anning, Xi’an University of Science & 22-1 Technology, P.R. CHINA Effectiveness of Clean Coal Technology Provisions of EPAct in Addressing Current Environmental Issues Facing Coal Nitric oxide (NO) is the major air pollutant that has to be removed before emitting flue Ben Yamagata, Coal Utilization Research Council, USA gas into the atmosphere. Various processes, such as the selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), are under operation to remove The Energy Policy Act of 2005 (EPAct) includes the enactment of numerous programs NO from flue gas. However, these processes require high operating temperatures and designed to encourage the research, development, demonstration and deployment of clean costs. Recently, a great deal of research work has been carried out on the coal technologies. Except for the enactment of certain tax incentives designed to benefit heterogeneous photocatalytic reactions due to lower energy consumption and operating taxpayers utilizing qualifying clean coal technologies all other clean coal programs included cost for treatment of polluted water and air. This photocatalytic process has the in last year s national energy legislation are authorizations that require appropriations in advantage of complete breakdown of organic pollutants to yield CO2, H2O and the order to become effective. The paper will review the various clean coal technology programs mineral acid. And studies on photocatalytic decomposition of NO have been reported. that are included in EPAct and comment upon the rationale and justification cited by It has been found that Cu+/zeolite catalysts exhibit photocatalytic reactivities for the Congress and industry for enactment of these provisions. With respect to industry s, and decomposition of NOx into N2 and O2 at 275K. In addition, a mixture of TiO2 and particularly CURC s, rationale for these various programs, a Clean Coal Technology activated carbon is found to be an appropriate photocatalyst for the removal of low- Roadmap, first developed by EPRI and CURC, in consultation with the Department of concentration NOx from air. In the study, the photocatalytic oxidation of nitric oxide, Energy, was a guiding document to define what objectives EPAct programs should be which was the oxidation product stemed from the mold compound pyridine of azo- designed to achieve. The Roadmap will be described as well as a discussion as to how the cycle compound in coal structure, over mesoporous loaded nanometer photocatalyst EPAct programs might support achievement of the goals and objectives set forth in the containing metal compounds (MCs) has been studied in a fluidized-bed photoreactor. Roadmap. In order to succeed in achieving the goals of EPAct related to clean coal Stannic oxide (SnO2), zinc oxide (ZnO), cadmium sulfide (CdS), were used as MCs. technologies and to successfully reach the objectives defined in the Roadmap it will be Mesoporous molecule sieve MCM-41 was acted as carrier, and TiO2 was the primary necessary to fully support the clean coal authorizations of EPAct. That is not happening. photocatalyst. The TiO2 treated with MC over support MCM-41 by sol-gel method and Why and what are the potential consequences of a lack of attention to technology dipping process, had the greater efficiency as a NO remover under UV irradiation development especially in light of possible regulation of carbon dioxide? The paper will seek compared with monocomponent TiO2. It is believed that MCM-41 has a high to answer these questions and particularly will focus on the need for successful technology adsorptivity for nitric oxide (NO) to contribute to photocatalytic reaction. The amount development if policy makers choose to create a national or international carbon of NO removed by the loaded photocatalyst including MC showed a tendency to management regulatory scheme. increase with decreasing initial NO concentration. The reaction rate increased with reducing UV light wavelength. The NO decomposition activity depended on the 22-2 amount of semiconductor photocatalysts deposited in channel of MCM-41, too, and the A Novel Ammonia-Based FGD Process: Experiences of a 60MW Demonstration TiO2 loaded with only 10wt%, meanwhile CdS loaded with only 5%, the photocatalyst Wen-De Xiao, East China University of Science and Technology, P.R. CHINA had revealed the highest level of activity in the fluidized-bed photoreactor, NO decomposition reached about 64% at the gas velocity of 200ml/min. Highly dispersed More than 70% of the energy requirements are met by coal combustion in China, resulting in semiconductor photocatalysts in channel of MCM-41 was effective for the severe environmental pollution by huge flue SO2 discharge over 25 million tones a year. The photocatalytic decomposition of NO. well-established and effective procedures to scope with SO2 and acid rain troubles are flue gas desulfurization (FGD). But the well-accepted and widely-applied limestone-based FGD methods have been increasingly blamed where considerable second-hand pollutions SESSION 23 produced. The author and coworkers have been for a decade carried out research for a novel HYDROGEN FROM COAL: SHIFT CATALYST AND GASIFICATION FGD method, based on ammonia and co-producing a useful fertilizer, ammonium sulfate, as displayed by: 2NH3+SO2+H2O+0.5O2=(NH4)2SO4 It is especially suitable for the Chinese situations of huge ammonia and fertilizer industry. Furthermore, ammonia-based method is, 23-1 but limestone-based one is not, accordant to the green chemical principles. Robust, Low-Cost Water-Gas Shift Membrane Reactor for This paper presents the operation experiences with a 60MW demo of the newly-developed High-Purity Hydrogen Production from Coal-Derived Syngas ammonia-based FGD process, shown in Figure 1, characterized by a multiple functional Zhijiang Li, Neng Ye, James Torkelson, Aspen Products Group, Inc., USA column for SO2 absorption to ammonium sulfite, sulfite oxidation to sulfate, and sulfate crystallization. It also overcame shortage of the NH3 slip in the outlet purified gas commonly In an effort to develop a reliable, low-cost membrane water-gas-shift reactor (WGS) appeared in the conventional ammonia-based FGD methods by using two stages in between for hydrogen generation from coal-derived syngas, a sulfur-tolerant transition metal NH3 introduced. WGS catalyst and a low-cost, H2-selective membrane were developed. Tests conducted Figure 2 depicts the operational results during a period of 168 hours for the evaluation of the with synthetic syngas containing 3000 ppm sulfur showed that the WGS catalyst is method when the inlet flue gas SO2 content fluctuated between 200 and 1200 ppmv as the highly active and capable of converting CO at equilibrium conversions at temperatures result of shifting combusted coal from different mines. The FGD column is very robust for from 300 to 500ºC and pressures from 300 to 500 psig. The catalyst displayed higher the SO2 content variation. The ammonium sulfate resulted met the top-grade fertilizer WGS activity than a number of commercial catalysts, especially at lower temperatures. specifications. The stability of the catalyst in the presence of 3000 ppm H2S and 350 ppm HCl was demonstrated for >200 hours. The H2-selective, high-temperature membrane is based 22-3 on a low-cost, hydrogen-selective material. The surfaces of the membrane were Oxy-Firing Flue-Gas Character and Its Effect on FGD - modified by deposition of catalyst layers of desired compositions. H2 permeation tests A Process Study for Integrated Pollutant Removal conducted at 300-500ºC and up to 200 psi H2 partial pressure showed that the -8 Danylo Oryshchyn, Jake Armstrong, Steve Gerdemann, Thomas Ochs, Cathy membrane is highly selective to H2 with a H2 permeability in the range of 1×10 to -7 0.5 Summers, NETL-Albany, USA 1×10 mol H2/(m·s·Pa ), comparable to that of Pd-based membranes. Surface modification increases not only the membrane’s H2 permeability but also its tolerance The National Energy Technology Laboratory (NETL) is investigating combining oxy- to H2S. firing coal, using recirculated flue gas enriched with oxygen, with a unique Integrated 19

23-2 23-5 Gas-Phase Incorporation of Palladium onto Ceria-doped Silica Hydrogen from Coal-Derived Methanol via an Autothermal Reformation Process Aerogel for Water-Gas Shift Catalysis Hyung Chul Yoon, Paul A. Erickson, University of California, Davis, USA Gregory C. Turpin, Brian C. Dunn, Yifan Shi, Eric P. Fillerup, Ronald J. Pugmire, Edward M. Eyring, Richard D. Ernst, University of Utah, USA This paper reports on an investigation of hydrogen production via reformation of coal- Prasanta Dutta, Mohindar Seehra, Vivek Singh, West Virginia University, USA based methanol. We have proven that coal–derived liquids such as commercially available methanol can be converted into hydrogen using both steam and autothermal The Water-Gas Shift (WGS) reaction is a means of producing hydrogen from coal-derived reforming methods. These studies have taken place at the Hydrogen Production & syngas. Palladium-promoted ceria has been investigated recently and has shown potential for Utilization Laboratory at University of California Davis. Through chemical analysis, low-temperature WGS catalysis. One limitation of traditional ceria is an inherent low surface coal-based methanol has shown to have slightly higher amounts of trace hydrocarbons area. While specialty cerias with surface areas as high as 300 m2/g have recently been than chemical grade methanol derived from natural gas. While these trace prepared, they do not show structural stability at relevant temperatures. Supporting ceria on hydrocarbons are typically inconsequential for some energy conversion devices, fuel the surface of silica aerogel can take advantage of the very high surface area of the silica cell applications require ultra pure hydrogen. Steam and autothermal reformers were aerogel as well as the structural integrity of the support. Starting with a silica aerogel having investigated to find the optimal hydrogen production method in the existence of such an approximate surface area of 700 m2/g, ceria can be incorporated onto the surface with trace impurities. Based on experimental results, steam-reforming of coal-based nominal loadings up to 40% (w/w), yielding final surface areas as high as 600 m2/g and methanol has shown significant catalyst degradation caused by the trace impurities. generally above 450 m2/g. Autothermal reformation of coal-derived methanol has demonstrated better Palladium was added via the gas-phase incorporation (GPI) of a volatile organometallic performance with the trace impurities due to its higher operating temperature generated complex, (η3-allyl)(η5-cyclopentadienyl)palladium, which is air-stable and prepared by a by the oxidation step. Autothermal reformation can also avoid some of the energy well-established procedure. Comparisons between GPI and conventional aqueous phase penalties of steam reformation but generally has a lower concentration of hydrogen due incorporation indicate increased activity for GPI-derived catalysts. For example, GPI can to the diluent nature of nitrogen by adding air as the oxidizer. This investigation shows increase the WGS activity in excess of 150% for otherwise identical catalysts. This is that hydrogen production from coal-based methanol is possible using both reformation presumably due to a higher dispersion of the Pd derived from GPI. A XRD analysis of methods when considering fuel cell applications. catalysts derived from the GPI of Pd failed to show well-defined peaks indicative of agglomerated Pd particles, which agrees with the interpretation of high dispersion. SESSION 24 23-3 GLOBAL CLIMATE CHANGE: Mesoporous Metal-Promoted Ceria Catalysts for the Water Gas Shift Reaction CO2 CAPTURE – 1: CHEMICAL SORBENTS Brian Dunn, Jennifer Gasser, Dae-Jung Kim, Eric Fillerup, Gary Hunyh, Gregory C. Turpin, Richard D. Ernest, Ronald J. Pugmire, Edward M. Eyring, Daniel W. Ramirez, University of Utah, USA 24-1 Carbon Dioxide Removal from Flue Gas of Coal-Fired Power Plants Using Dry Metal-promoted ceria catalysts that are active for the Water Gas Shift reaction have Regenerable Carbonate Sorbents in a Thermal-Swing Process received considerable attention in recent years. One drawback to the ceria catalysts is Thomas Nelson, David Green, Paul Box, Raghubir Gupta, Andreas Weber, RTI the relatively low surface area achievable with traditional preparation methods. Two International, USA new types of ceria has been synthesized which possess high surface area and significant catalytic activity when palladium is incorporated into the catalyst. High The reversible reaction between sodium carbonate, carbon dioxide and water vapor, to surface area is attained by either preparing the ceria in an aerogel form or by form sodium bicarbonate (or an intermediate salt) can be used in a thermal swing combining the ceria with a mesostructured silica, SBA-15. The ceria aerogels have cyclic process to recover concentrated carbon dioxide from power plant flue gas for measured BET surface areas as high as ~300 m2/g which is about twice as large as the sequestration or reuse. The process is initially targeted for coal-fired power plants highest surface area ceria prepared via traditional methods. Measured BET surface incorporating wet flue gas desulfurization. The process is also suitable for natural gas- areas of the ceria/SBA-15 composite material can be as high as 800 m2/g, however, the fired power plants. Process modeling suggests that a process of this type offers a lower SBA-15 contributes substantially to this value. Various metals (Pd, Cu, Au) were total energy requirement (and lower overall CO2 capture costs) than existing liquid incorporated into the ceria and the resulting catalysts were evaluated for Water Gas amine- based processes. Shift activity in a 6-channel, laboratory-scale, packed bed reactor. The reactor was Calcined sodium bicarbonate can be used as the sorbent for this process. Alternately, constructed with 6 parallel catalyst beds to allow for the simultaneous evaluation of up sodium carbonate incorporated in an attrition resistant support material can be used. to 6 catalysts under identical reaction conditions (temperature, reactant flow, etc.). The supported sorbent has demonstrated removal of >90% of the CO2 present in a Each bed was equipped with an internal thermocouple to ensure accurate temperature simulated flue gas in a bench-scale co-current down-flow reactor system. The partially measurement and to evaluate thermal cross-talk between reactors that could be caused reacted sorbent can be thermally regenerated, releasing CO2 and H2O. Upon by an exothermic reaction in the catalyst bed. No cross-talk was observed. The condensation of the H2O from the vent stream, a nearly pure CO2 stream can be catalytic activity was measured at 5 temperatures between 150°C and 350°C for 24 produced for reuse or sequestration. This paper discusses the results of a series of lab- hours at each temperature. At the highest temperature, the Pd/ceria aerogel catalyst scale down-flow reactor tests investigating the impact of gas composition, temperature, converted 148 g CO / (hr g-Pd) resulting in the production of 11 g H2 / (hr g-Pd). The sorbent-to-gas ratio, and other important variables on the reaction of CO2 with the Cu and Au catalysts were less active. The Pd-loaded ceria/SBA-15 based catalysts sorbent. This paper also highlights results of field tests confirming that complete were less active than the Pd-loaded ceria aerogel based catalysts at temperatures less sorbent regeneration can be achieved in a heated screw conveyor, with minimal than 300°C, but become more active above 300°C. sorbent attrition. An integrated system incorporating a co-current down-flow absorber, a heated hollow screw conveyor/regenerator, and a hollow screw conveyor/sorbent 23-4 cooler has been designed, constructed and tested Sulfur Deactivation Studies in the High-Temperature Water-Gas Shift Reaction over Chromium-Free Iron-Based 24-2 Lingzhi Zhang, Umit Ozkan, The Ohio State University, USA Developing a New Method for Direct Observation of the Effects of CO2 Injection into Coal Seams Coal is the most abundant fossil fuel in our nation and how to make an efficient and Randal E. Winans, Sonke Seifert, Argonne National Laboratory, USA environmentally acceptable use of coal has become a hot topic considering the Tony Clemens, CRL Energy LTD, NEW ZEALAND increasing energy demands. Hydrogen production through integrated gasification combined-cycle (IGCC) has emerged as a highly promising technology. The Initial investigations to assess the suitability of in situ Small Angle X-Ray Scattering commercialization of these joint power and hydrogen plants needs significant (SAXS) for directly observing changes in coal structure when injected with pressurized improvements in some of the steps following gasification to produce hydrogen more CO2 were carried out at 50 bar pressure and ambient temperature on a suite of New efficiently and economically. Among them is the water gas shift (WGS) reaction. Zealand coals and US coal samples from the Argonne Data Bank. The method requires Development of highly active, sulfur tolerant and chromium free catalysts will bring the use of the Advanced Photon Source (APS) high energy synchrotron at Argonne. about the successful use of coal-derived gas for hydrogen production, resulting in The high level of beam intensity provides the high levels of resolution and enhanced use of our vast coal reserves. Sulfur deactivation studies have been carried observational power required. on over current Fe-based catalysts prepared with different methods. A series of sulfur These initial studies showed that: testing with simulated coal gas were run on the catalysts and different characterization • High energy X-ray beams from the APS can be used to directly observe techniques including BET, XRD, DRIFTS and XPS are used to describe catalyst changes in coal structure as CO2 is injected into the coal at high pressure. properties before and after sulfur poisoning. Those characterizations also give us • The results are very reproducible information about reaction mechanisms and help us explain functions of different • There are clear trends with coal rank. promoters and their relation with reaction activities. These initial successes suggest that it may be possible to develop a robust method for

predicting CO2 sequestration ability of coal seams based on direct observation. 20

24-3 Development of Fluidizable Lithium Silicate-Based Sorbents for SESSION 25 High Temperature Carbon Dioxide Removal GASIFICATION TECHNOLOGIES: Weijiong Li, Santosh Gangwal, Raghubir Gupta, Brian S. Turk, RTI International, ADVANCED SYNTHESIS GAS CLEANUP – 2 USA

One of the key features accelerating the commercial deployment of integrated 25-1 gasification combined cycle (IGCC) systems for producing electricity is that the Synthesis and Reactivity Test of Nanostructure ZnO for addition of CO2 capture and sequestration processes results in the lowest increment in Hot Gas Cleanup on the IGFC capital and operating costs of any of the competing technologies. However, the Si Ok Ryu, No-Kuk Park, You Jin Lee, Gi Bo Han, Tae Jin Lee, Yeungnam commercially available technologies require significant cooling of the syngas to University, SOUTH KOREA effectively capture the CO2 that introduces a significant thermodynamic penalty for Chih Hung Chang, Oregon State University, USA CO2 capture. RTI International (RTI) has been working with regenerable sorbent materials for CO2 capture at elevated temperatures with the potential to produce a high A nano-size zinc oxide was formulated for the effective removal of a very low concentration pressure high purity CO2 product. This process offers the potential to significantly of sulfur compounds (H2S, COS) contained in a gasified fuel gas and their reactivity was reduce any thermodynamic penalty associated with the CO2 capture process. During also investigated in this study. They were prepared by a matrix-assisted method with various the course of this research, RTI has developed Li2SiO4-based sorbents that have precursors. An active carbon was used for a matrix and zinc nitrate, zinc acetate, zinc demonstrated CO2 capture and regeneration in bench-scale testing. Results from this chloride, and zinc sulfate were selected as precursors. Zinc nitrate was the best precursor for testing program were presented at last year’s Pittsburgh Coal Conference. the formulation of the nano-size zinc oxide in the experiments. The size of the formulated Over the last year, RTI has built upon this success by conducting R&D for a fluidized nano-size zinc oxides was in the range of 20-30 nm and its surface area was about 56.2 m2/g. Li4SiO4-based sorbent. The incentive for this work is the knowledge that a transport From TGA(thermal gravity analysis) test, it was found that its sulfur absorption rate was reactor system can be designed to treat high gas throughputs at relatively low capital about 0.363 gS/min·100 g-sorbent. Their reactivity increased with the smaller size and the costs, which will be required to treat the large CO2 content of syngas derived from larger surface area of the sorbents. Most prepared nano-size zinc oxides showed an excellent carbonaceous fuels, especially coal. A CO2 capture technology that offers lower capital performance for the removal of not only H2S but also COS. Their absorption rate was faster cost and higher thermal efficiency becomes more commercially attractive with the than commercial zinc oxides. In order to investigate the sulfur absorption characteristics of potential reward of earlier implementation. The technical challenges for developing a zinc oxide, a series of experiments for various nano-size zinc oxides formulated from fluidized Li4SiO4 sorbent are to achieve a high CO2 reactivity, acceptable different precursors were carried out in a packed-bed reactor system over the temperature hydrodynamic properties and suitable attrition resistance. This presentation will 500°C. The sulfur capacity was about 5.83 gS/100 g-sorbent for H2S. It was concluded that describe the progress made in this R&D program. the zinc oxide prepared by zinc nitrate as a precursor showed the highest sulfur removing capacity. 24-4 Carbon Dioxide Separation through Supported Ionic 25-2 Liquids Membranes in Polymeric Matrixes Desulfurization of High-Pressure Gasified Coal Using the Jeffery Ilconich, David Luebke, Christina Myers, Henry Pennline, DOE/NETL, USA UC Sulfur Recovery Process Diana Matonis, Howard S. Meyer, Dennis Leppin, Gas Technology Institute, USA As compared to other gas separation techniques, membranes have several advantages which can include low capital cost, relatively low energy usage and scalability. While it could be The University of California Sulfur Recovery Process – High Pressure (UCSRP-HP) possible to synthesize the ideal polymer for membrane separation of carbon dioxide from provides the potential to treat high-pressure, warm synthesis gas for the removal of fuel gas, it would be very intensive in terms of money and time. Supported liquid ammonia, hydrogen chloride, and heavy metals including arsenic, mercury, cadmium, and membranes allow the researcher to utilize the wealth of knowledge available on liquid selenium as well as essentially all of the hydrogen sulfide and carbonyl sulfide in a coal- properties. Ionic liquids, which can be useful in capturing CO2 from fuel gas because they derived synthesis gas in a compound contacting tower. In the bottom or scrub section of the posses high CO2 solubility in the ionic liquid relative to H2, are an excellent candidate for tower, the sour gas feed is contacted with a solvent that will absorb some steady state levels this type of membrane. Ionic liquids are not susceptible to evaporation due to their negligible of water, ammonia, and hydrogen sulfide from the gas stream. As a result, the HCl content vapor pressure and thus eliminate the main problem typically seen with supported liquid of the feed gas will be absorbed very effectively to form highly soluble NH4Cl. A small but membranes. significant concentration of NH4HS will also be present in the liquid phase, and the heavy A study has been conducted evaluating the use of the ionic liquid 1-hexyl-3-methyl- metals As, Cd and Hg, will be absorbed to form their respective, very insoluble sulfides. imidazolium bis(trifuoromethylsulfonyl)imide in supported ionic liquid membranes for the Selenium, present in the syngas as H2Se, will be absorbed to form highly soluble (NH4)2Se. capture of CO2 from streams containing H2. In a joint project, the ionic liquid was The solvent is recirculated with a small slipstream being withdrawn, perhaps intermittently, synthesized and characterized at the University of Notre Dame, incorporated into a for filtration and other treatment to remove the accumulated impurities and then returned. polymeric matrix, and tested at the National Energy Technology Laboratory. Initial results The gas stream leaving the scrub section passes into the reactor section through a chimney have been very promising with calculated CO2 permeabilities as high as 950 barrers and that effectively prevents the mixing of the solvent in the two sections. In the upper or reactor significant improvements in CO2/H2 selectivity over the unmodified polymer at 37°C along section of the tower, the UCSRP-HP uses a solvent with high capacity for H2S and SO2 that with promising results at elevated temperatures. In addition to performance, the study also catalyzes the liquid-phase reaction of H2S and SO2 to sulfur and water. Operation is included examining the choice of polymeric supports on performance and membrane above the melting point of sulfur, so the sulfur forms a separate liquid phase and is removed stability in more realistic operating conditions. Also included in this study was an evaluation by simple decantation. The now scrubbed, sour gas, mixed with 10% − 20% excess SO2, is of novel approaches to incorporate the ionic liquid into polymer matrices to optimize the contacted at high pressure (the higher the better) with the UCSRP solvent at about 260 − performance and stability of the membranes. 285°F (125 – 140°C). Substantially all of the H2S reacts to form liquid sulfur, leaving the excess SO2 in the treated gas. The unreacted SO2 is recovered in a separate absorber/stripper 24-5 system, which may optionally also serve to dry the treated gas. The sulfur-free gas may A Parametric Study for Regenerative Ammonia-Based optionally also be passed through a second absorber/stripper system for CO2 recovery. The Scrubbing for the Capture of CO2 recovered SO2 is combined with SO2 produced by burning one-third of the liquid sulfur in a Kevin Resnik, James T. Yeh, Henry W. Pennline, DOE/NETL, USA furnace, compressed and perhaps liquefied, and fed to the reactor column. The furnace William Garber, Deborah C. Hreha, Parsons Project Services, Inc., USA employs either air or oxygen. All of the sulfur formed in the reactor is vaporized as it passes through the furnace; the unburned two-thirds condense in the waste-heat boiler. Any organic A continuous gas and liquid flow, regenerative scrubbing process for CO2 capture is components dissolved in the sulfur will also be burned. The product sulfur has only a small currently being demonstrated at the bench-scale level. An aqueous ammonia-based amount of dissolved SO2 as impurity. This paper will discuss the experimental and solution captures CO2 from simulated flue gas in an absorber and releases a nearly pure engineering studies of UCSRP-HP for syngas desulfurization with optional CO2 recovery stream of CO2 in the regenerator. After the regeneration, the solution of ammonium that include laboratory studies on vapor liquid equilibrium, solvent stability, corrosion and compounds is recycled to the absorber. The design of the continuous flow unit was kinetic studies performed in laboratory scale equipment and column scale-up testing in based on earlier exploratory results from a semi-batch reactor, where a CO2 and N2 gas bench-scale apparatus conducted at GTI and will highlight the potential economic benefits of mixture flowed through a well-mixed batch of ammonia-based solution. Recently, a the process. series of tests have been conducted on the continuous unit to observe the effect of various parameters on CO2 removal efficiency and regenerator effectiveness within the 25-3 flow system. The parameters that were studied include absorber temperature, Sorbents for Mercury Capture from Fuel Gas with regenerator temperature, initial NH3 concentration, simulated flue gas flow rate, liquid Application to Gasification Systems solvent inventory in the flow system, and height of the packed-bed absorber. Results Evan Granite, Henry W. Pennline, Christina R. Myers, Dennis C. Stanko, DOE/NETL, from this current testing campaign conducted in the continuous scrubbing unit as well USA as test results from a 5-cycle semi-batch reactor will be discussed.

21

In gasification for power generation, the removal of mercury by sorbents at elevated IGCC plants and other major utilities are evaluating IGCC s suitability for base-load capacity temperatures preserves the higher thermal efficiency of the integrated gasification combined additions. This recent surge of attention to IGCC power generation is creating a growing cycle system. Unfortunately, most sorbents display poor capacity for elemental mercury at demand for experience with the analysis, operation, and control of commercial-scale IGCC elevated temperatures. Previous experience with sorbents in flue gas has allowed for plants. To meet this need, the National Energy Technology Laboratory (NETL) has judicious selection of potential high-temperature candidate sorbents. The capacities of many launched a project to develop a generic, full-scope, IGCC dynamic plant simulator and sorbents for elemental mercury from nitrogen, as well as from four different simulated fuel establish a state-of-the-art simulator training center at WVU’s National Research Center for gases at temperatures from 204 to 371°C, were determined. The simulated fuel gas Coal and Energy (NRCCE). compositions contain varying concentrations of carbon monoxide, hydrogen, carbon dioxide, In a recently completed scoping study, the authors defined the requirements and features for moisture, and hydrogen sulfide. Promising high temperature sorbent candidates have been an IGCC simulator, and identified potential operator training simulator (OTS) suppliers, identified. Palladium sorbents appear the most promising for high temperature capture of R&D technology collaborators, and members of an advisory board for the project. Key mercury and other trace elements from fuel gases. A collaborative research and development simulator requirements and features identified included: agreement has been initiated between the Department of Energy’s National Energy - High-fidelity, real-time dynamic models of both process (gasification) and power sides Technology Laboratory and Johnson Matthey for optimization of the sorbents for trace - Full-scope OTS capabilities including startup, shutdown, load following and shedding, element capture from high temperature fuel gas. Future directions for mercury sorbent response to fuel and ambient variations, control strategy analysis, malfunctions/trips, development for fuel gas application will be discussed. The work presented in this alarms, scenarios, trending and snapshots manuscript was recently accepted for publication in Industrial & Engineering Chemistry - Unified software modeling platform for engineering analysis and training Research. - Maintainable, flexible, extendable and easy-to-use software and model libraries - Full distributed control system (DCS) emulation 25-4 - Leverage existing NETL equipment/process models and software technology A Novel Sorbent-Based Trace Metal Removal from Coal-Derived - Extendable to FutureGen and zero-emission poly-generation plants Synthesis Gas: Field Demonstration Results The project consists of five phases including: I) Project scoping, II) Detailed planning, III) Gokhan Alptekin, Robert Amalfitano, Margarita Dubovik, Michael Cesario, TDA Simulator development, IV) Simulator deployment, and V) Establishment and support of an Research Inc., USA IGCC Simulator Training Center. The project length from simulator planning through deployment is about three years. Gasifiers convert coal into synthesis gas feed streams that can be used in advanced The IGCC Dynamic Simulator & Training Center will offer much-needed IGCC power cycles to generate electricity and in the production of a wide variety of demonstration, education, and training services such as IGCC plant operation and control chemicals. However, the coal-derived synthesis gas contains a myriad of trace demonstrations, technology familiarization, computer-based training and on-site train the contaminants that cannot be released to the environment if the syngas is burned to trainer programs. Potential users include utilities, engineering firms, technology suppliers, generate power or may poison the catalysts used in the downstream chemical Department of Energy system analysts and engineers, university engineering and training manufacturing processes. Therefore, removal of these contaminants is critical for the R&D community, and others interested in learning more about IGCC plant operations and widespread and environmentally-friendly utilization of coal. TDA Research Inc. control. Because the simulator will be based on a generic IGCC plant design, it is not (TDA) is developing a sorbent that can reduce the concentration of the trace metal intended for training actual plant operators, but IGCC operators may benefit from training on contaminants (i.e., mercury, arsenic, selenium and cadmium) to less than parts per the generic simulator before moving on to plant-specific simulators. billion levels in the coal-derived synthesis gas at elevated temperatures (260°C). The The IGCC Dynamic Simulator & Training Center project will build on and reach beyond sorbent is the key component of an integrated trace contaminant removal system. The existing combined-cycle and conventional-coal power plant simulators to combine for the production of the sorbent is scaled-up under subcontract with a leading U.S. sorbent first time a process/gasification simulator and a combined-cycle simulator together in a manufacturer using commercial manufacturing techniques. The performance single dynamic simulator framework for use in training applications as well as engineering capabilities of the commercially produced sorbent were also confirmed at bench-scale. studies. As a next step, TDA is building an integrated trace metal contaminant removal prototype equipped with all essential items, flow systems and auxiliary components to 26-2 test the operation of the breadboard system using real coal-derived synthesis gas. The CO2 Control Technology Effects on IGCC Plant Performance and Cost proof-of-concept tests will be carried out using a real coal-derived synthesis gas at the Edward S. Rubin, Chao Chen, Michael B. Berkenpas, Carnegie Mellon University, University of North Dakota Energy Environmental Research Center (UNDEERC) in USA their Transport Reactor Demonstration Unit (TRDU). The performance of the sorbent will be tested, and the integration of the process components will be shown in the As part of the US DOE’s Carbon Sequestration Program, we have developed an prototype unit designed to treat 10,000 SCFH coal gas generated from Powder River integrated modeling framework to evaluate the performance and cost of alternative Basin coal. This paper discusses the results of the demonstration tests. carbon capture and storage (CCS) technologies for fossil-fueled power plants in the context of multi-pollutant control requirements. The model (called IECM, for 25-5 Integrated Environmental Control Model) also allows for explicit characterization of Palladium Sorbents for Arsenic Capture from Fuel Gas with the uncertainty or variability in any or all input parameters. Power plant options Application to Gasification Systems currently include pulverized coal (PC) combustion plants, natural gas combined cycle Evan J. Granite, Henry W. Pennline, Christina R. Myers, Dennis C. Stanko (NGCC) plants, and integrated gasification combined cycle (IGCC) plants. This paper uses the IECM to analyze the effects of adding CCS to an IGCC system employing a Arsenic is a semi-volatile trace element present in coal at concentrations of around 15 GE quench gasifier with a water gas shift reactor and Selexol system for CO2 capture. ppm. In the oxidizing environment of flue gas, arsenic forms the oxide As2O3, whereas Parameters of interest include the effects of varying the CO2 removal efficiency, the in the reducing environment of fuel gas, it forms arsine, AsH3. Arsenic is a well known quality and cost of coal, and selected other factors affecting overall plant performance poison for many catalysts such as palladium, platinum, and the NOx selective catalytic and cost. The stochastic simulation capability of the model also is used to illustrate the reduction (SCR) catalysts employed in coal-burning power plants. Arsenic and its effect of uncertainties or variability in key parameters. The potential for advanced compounds are highly toxic and may be subject to future regulations. It has been found oxygen production and gas turbine technologies to reduce the cost and environmental that palladium can adsorb arsine from both nitrogen and a simulated fuel gas over a impacts of IGCC with CCS also is analyzed. wide temperature range. Palladium sorbents have significant potential for high temperature removal of trace metals such as arsenic, mercury, selenium, and cadmium 26-3 from coal-derived fuel and flue gases. Thermodynamic Modeling of Gasification Processes with Respect to Trace Elements Stefan Guhl, Philipp Bruggemann, Bernd Meyer, Technical University Bergakademie SESSION 26 Freiberg, GERMANY GASIFICATION TECHNOLOGIES: Andreas Jockhamann, Sustec Schwarze Pumpe GmbH, GERMANY FUNDAMENTALS AND SIMULATIONS – 2 Trace elements like Na and K and their compounds are known to evaporate in high temperature processes such as gasification. The condensation of their compounds in low 26-1 temperature areas in gasifiers can cause problems. Therefore, it is important to assess their Dynamic Simulation and Training for IGCC Power Plants thermal behaviour. Thermodynamic models can be an excellent tool to carry out this Michael Erbes, Enginomix, LLC, USA assessment. The presented model simulate the BGL-gasification process (British Gas – Stephen E. Zitney, NETL, USA Lurgi) using the thermodynamic software SimuSage in connection with FactSage and Delphi, whereby the Gibbs energy minimisation is used to calculate equilibrium state. The Integrated Gasification Combined Cycle (IGCC) is emerging as the technology of choice for process data and material samples have been obtained from a BGL-gasifier with 200 MW providing clean, low-cost electricity for the next generation of coal-fired power plants and thermal input, which is commercially operated by Sustec Schwarze Pumpe GmbH near will play a central role in the development of high-efficiency, zero-emissions power plants Dresden, Germany. The main feedstock is pelletised municipal solid waste and the synthesis such as FutureGen. Several major utilities and developers recently announced plans to build gas is used to generate methanol and electricity. The gasification process itself is similar to 22 the classical Lurgi-gasifcation process (fixed bed, counter flow, dry ash removal). The major Two optimization methods - genetic algorithm and Powells conjugate directions have been difference lies in an ash removal by a slag bath, where the liquid slag is tapped by a water- coupled in one hybrid procedure to ensure high quality of results and reasonably low cooled copper-nozzle. Hence the temperatures in the combustion zone are very high and lead computational effort. to evaporation of volatile ash components. The model consists of four interacting The whole optimization analysis has been repeated several times for different price scenarios equilibrium stages. Three equilibrium stages describe the classical fixed-bed gasifier zones on the coal, iron and electricity markets. In particular, the impact of rapid change of coal and and include devolatilisation, gasification and combustion. The fourth equilibrium stage iron ore prices due to increased Asia demand has been considered. considers the slag bath. Material flows connect all four stages. The following elements are taken into account: Al, C, Ca, Cu, Cl, Fe, H, K, Mg, N, Na, O, S, Si, Ti, Zn. For the 26-5 description of the molten slag, a solution phase is used, which is based on the quasi-chemical Comparison of Thermodynamic Equilibrium Compositions for Indian Coals model. It therefore considers real interactions between the slag components in the liquid Preeti Aghalayam, Anil Khadse, Mohammed Qayyumi, Sanjay Mahajani, state. As a major result of the model, the capture of volatile ash components can be IIT Bombay, INDIA described. For example the alkalis K and Na evaporate in the hot lower part of the gasifier (slag bath and combustion zone) and will condense in the upper part (devolatilisation zone) A simple model is developed that predicts thermodynamic equilibrium compositions using at the cold solid feedstock. The feedstock will move downward to the hot zones and the the ultimate analysis of coals. Coal is represented as CHxOy. The model is validated with the alkalis will evaporate again. Due to the subsequent accumulation of alkali vapours in the gas pure carbon-steam system by comparison with literature. The thermodynamic equilibrium phase, the solubility of alkalis in the slag will increase. Finally, capture rates and raw gas compositions are predicted for three Indian coals and compared on the basis of product gas concentrations of volatile slag components are calculated. The evaluation of the model was compositions and gross calorific value. The results show that each coal has different done by process data and material samples from the BGL gasifier described above. Practical equilibrium compositions at identical set of operating conditions. Coals containing higher experiences from the operation of the BGL-gasifier are also considered. H/C give more H2 and CH4. The coals containing higher H/C give higher gross calorific value at relatively higher pressures. Thus, high-pressure gasification like Underground Coal 26-4 Gasification may have an advantage over other processes in terms of product calorific value. Economic Optimization of the Integrated Hot Metal, Heat and The inclusion of the energy balance equation in the equilibrium model will enable us to Power Generation Based on the Coal Gasification Process predict the adiabatic gasification temperature. The model becomes complex due to this, but Marcin Liszka, Andrzej Ziebik, Silesian University of Technology, POLAND the additional benefit is that a set of operating conditions is obtained, while reducing one degree of freedom. The worldwide consumption of coal for not hot metal and steel production represents a significant part of total coal demand. On the other hand, the well known possibilities for integration between hot metal and power generation provide a big potential to increase the SESSION 27 fuel utilization efficiency and decrease environment pollution. However, the key problem of COMBUSTION TECHNOLOGIES – 5: such integration is cash flow economy. The steel&power plant, fed with coal is thus COAL REACTIVITY AND KINETIC STUDIES analyzed within the frames of this paper from the thermodynamic and economic points of view. The system taken into consideration consists of the Corex island, combined cycle power 27-1 plant and air separation unit (ASU). The Corex process (trademark of Siemens-VAI) is one THERMACT - A Revolutionary breakthrough in Fire-Side Technology of technologies for cokeless hot metal production belonging to the smelting reduction Swatantra Kumar, Abhitech Energycon Limited, INDIA family. Coal is gasified by oxygen in the hot metal environment, while the produced gas is used as reducing agent (for iron ore) in another shaft reactor. From the power generation Abhitech Energycon, in association with Indian Institute of Technology, Mumbai, has point of view the most important feature of this technology is simultaneous production of hot developed a solid fuel additive-THERMACT, which when mixed with coal improves metal and medium-calorific gas which can be fired in gas turbine combustor. The overall the overall combustion efficiency, thereby reducing coal consumption and pollutants system (Corex, power island, ASU) can be thus perceived as some kind of multi-product like SOx, NOx, SPM etc. THERMACT is added in the proportion of 1 KG for 10-15 IGCC. MT of Coal. Catalysts present in THERMACT convert carbon atoms in coal, into, The case study presented here concerns the location of such an integrated IGCC in southern allotropes by sharing electrons in SP2 hybridization. These allotropes are in Soccer Poland, nearby the existing steel mill and medium size city. Thus, the demands for district ball shapes, known as Buckyballs, each consisting of 60 carbon atoms (C60) linked heat and process steam have been also considered. The power plant becomes in this light a together. Tremendous amount of energy is released when they are burnt. The hollow CHP facility which, among mentioned above, might produce compressed air for high structure of buckyballs traps other atoms inside them like a molecular cage. pressure ASU and consume nitrogen - waste by product of air separation. THERMACT breaks the Oxygen and Hydrogen electronic bond in the water molecule The simultaneous presence of Corex gas fuel (natural gas alternative) and demand for (inherent moisture). This liberated Hydrogen forms transitory methane, which gives different type energy carriers (for internal and external usage) provides large freedom for extra heat on combustion. In the presence of THERMACT the buckyballs formed react optimization of the CHP plant structure and operating parameters. It has been assumed that with SO2 to form polymeric compounds, which come down into ash. This prevents SO3 the Corex export gas is fired in gas turbine (GT) combustor. The GT unit is connected with formation reducing SOx emissions. Sulphur in fly ash is reduced & that in bottom ash heat recovery steam generator (HRSG) and produced steam expands in multi pressure, tap- is increased. THERMACT decomposes metal silicates into silica and metal oxides condensing steam turbine (ST). The GT structure was assumed as a fixed simple cycle while thereby reducing slag and clinker formation. THERMACT prevents formation of V2O5. the HRSG and ST arrangements are free for optimization from point of view of number of THERMACT reduces unburnts in fly ash as well as bottom ash and black smoke as a pressure levels and fractions of appropriate district water heaters in total district heat result of an efficient & complete combustion of coal. THERMACT changes the flame production. The examples of other independent variables selected for optimization are: color to bright whitish yellow from orange indicating optimum combustion of coal. natural gas to Corex gas admixture ratio, GT pressure ratio, GT firing temperature, minimal THERMACT Advantages: temperature differences in HRSG, flow rate of compressed air form GT compressor to ASU, - Improves combustion ST extraction pressure, rate of supplementary firing in HRSG. Finally, 16 independent - Reduces Coal consumption variables have been qualified for optimization. This set of parameters and special techniques - Unburnts in fly and bottom ash of mathematical modeling, based on theory of superstructure allow for generation of - Emissions completely different structures during the optimization process, e.g. it is permissible (for the - Excess air consumption model) to build double pressure combined cycle with reheat or GT unit with district heat - Continuity in the Plant Operations exchanger (no ST) or gas fired steam boiler with ST and extraction connected district heat - CO2 emission also comes down due to reduced coal consumption. exchangers. The Net Present Value (NPV) has been adopted as the objective function of THERMACT is presently being used in Power, Cement and Steel Plants in India. optimization. Even though optimization deals mainly with the parameters of CHP unit, the NPV has been calculated for cash flows crossing the boundary of whole integrated system. 27-2 Such an approach emphasizes the impact of power island parameters on the overall system Coal Characterization in a Drop Tube Furnace performance. Anne-Lise Brasseur, Anne Neveu-Dubosc, EDF R&D, FRANCE The applied computational strategy can be described in following steps: a) selection of Severine Pillet, ITG Consultants, FRANCE values of independent variables being optimized, b) design point simulation of CHP plant at rated conditions, c) off-design simulation including whole year of operation with varying A database on the coal characteristics is elaborated in order to provide the input data required ambient temperature, machines efficiencies and control procedures, d) calculation of to take into account the fuel flexibility (numerous varieties of coals and mixtures) in the 3D objective function on the basis of integrated (during a year) values of substance and energy simulation of pulverized coal boiler. In this frame, the characterization of a series of coals, fluxes, e) selection of new parameters for optimization and return to point a. from different ranks and origins, has been carried out on a drop tube furnace developed by All CHP plant facilities have been modeled on the GateCycle software. The off-design EDF R&D. This test facility is particularly suitable to study the parameters of the reactivity models include, among others, the GT blade cooling and HRSG heat transfer coefficient of coal under experimental combustion conditions closest as possible to those of a PC boiler. analyses. The control procedures and other additional algorithms were integrated as Visual Thus this study reports the characterization of a series of coals both under pyrolysis and Basic macros. combustion conditions, and especially, the coal reactivity constants (Arrhenius constants, Ec and Ac) evaluated through a combustion model. 23

27-3 28-2 Studies in Pyrolysis and Combustion of Indian Coals Experimental Investigation and Theoretical Calculation on Effect of C12 Using Thermogravimetric Analyzer on Mercury Oxidation in Coal Fire Combustion Process Preeti Aghalayam, Anil Khadse, Chinmay Ghoroi, Sanjay Mahajani, IIT Bombay, Wei-Ping Pan, Songgeng Li, Quanhai Wang, Yan Cao, ICSET of Western Kentucky INDIA University, USA

Experiments are performed to study the pyrolysis and combustion reactions for Indian Mercury (Hg) from coal power plants has been identified as the hazardous air pollutant coals using a Thermogravimetric Analyzer (NETZSCH STA 409 PC/PG). Burning of greatest public health concern. Hg in the flue gas occurs as three main forms: the profiles and volatile release profiles are obtained at various heating rates, in both air gaseous elemental mercury Hg(0), the gaseous oxidized Hg(2+), and particulate and inert atmospheres, from 25 to 1000°C for three coal samples. Peak temperatures mercury, Hg(p). Hg(2+) is water soluble, highly absorbable on fly ash and has a low are obtained and activation energies are calculated. The activation energies are in the vapor pressure. Therefore, relative to Hg(0), Hg(2+) is more effectively captured in range 68.49-100.29 kJ/mol at a heating rate of 10°C /min, 66-88.13 kJ/mol at 20°C conventional Air Pollution Control Devices (APCD) such as wet scrubbers (FGD), /min and 52.74-74.93 kJ/mol at 30°C /min, for the combustion reaction. For pyrolysis, fabric filters (FF) and electrostatic precipitator (ESP). However, Hg(0) is firstly activation energies are in the range 34.79-147.99 kJ/mol at 10°C /min, 38.40-166.74 vaporized in the flue gas at higher temperature zone in combustor, followed by kJ/mol at 20°C /min and 36.72-167.46 kJ/mol at 30°C /min. thermodynamically favored oxidation process to major occurrence of Hg(2+) through the homogeneous and the heterogeneous reaction routines at downstream flue gas pass 27-4 as temperature is cooled down. Thus, identifying the mechanism of mercury oxidation Study of the Effect of FeCl3 on the Ignition Point of Coal in the downstream flue gas pass is very important to improve mercury emission control Qiaowen Yang, Dongyao Xu, Wei Li, Aiguo Cheng, Jia Cao, Liying Wang, China efficiencies by APCD in the coal-fired boilers. Based on facts that HgCl2 is the main University of Mining & Technology, P.R. CHINA Hg(2+) in coal-fired combustion process, as well as enormous previous studies on Hg oxidation, it has been generally accepted that chlorine-containing species are the most The combustion supporting alternate agent of three coals was selected by Thermal Gravity important factor on the Hg(0) oxidation in coal-fired flue gas. Chlorine is evolved Analysis (TG) in this paper, it has been found that FeCl3 plays great role on reducing the during coal combustion primarily as hydrochloric acid (HCl), less chance as chlorine ignition point of Guangxi Liang-coal, and FeCl3 could effectively reduce the ignition point molecule (Cl2) through the Deacon reaction under fly ash available conditions. of Xinwen raw coal and Guangxi An-coal also. It also stated that FeCl3 has a good However, the possible concentration of Cl2 is still much higher than request by the Hg combustion supporting action on the coal. At the same time, the relationship of FeCl3 oxidation process. Moreover, the flue gas chemistry may dramatically impact this amount and the ignition point of coal were inspected; the optimum amount of FeCl3 could be oxidation process by the intermediate reactions to affect production of chlorine ion, got. We initially probed into the combustion supporting mechanism of FeCl3, during which is more active in the Hg oxidation process. In this work, isolated effects of Cl2 combustion, the combustion supporting action of FeCl3 was the results of common action of and HCl or their effects including other flue gas species on Hg oxidation under a chloride and iron in chemicals; The combustion supporting action of FeCl3 was individually largely varied temperature window were investigated in a special designed multi-phase achieved by reducing the ignition point of Volatile and Fixed Carbon. flow reactor. A thermal-dynamic and kinetics calculation is used to explore the maxim Hg oxidation rate and possible reaction mechanisms. 27-5 Modeling and Simulation of Single Coal Particle Combustion 28-3 Anil Samale, Arvind Latey, College of Engineering Pune, INDIA A Theoretical Cluster Approach to Understanding Mercury Adsorption to Halogen-Embedded Activated Carbon In the present study, a mathematical model to describe the combustion of single coal particle Bihter Padak, Michael Brunetti, Jennifer Wilcox, Worcester Polytehcnic Institute, is developed by incorporating improvement in the existing models available in the literature. USA This model couples the heat transfer equation with the chemical kinetics equations. The combustion rate has been simulated by considering the first order reaction (C+O2 = CO2). Ab initio methods have been employed for the modeling of activated carbon surface The dependence of the convective heat transfer coefficient on Nusselt number is using a fused-benzene ring cluster approach. Oxygen functional groups have been incorporated in this model. A finite volume method using a TDMA scheme is used for investigated for their promotion of effective elemental mercury adsorption on the solving heat transfer equation and Runge-Kutta fourth order method for the chemical activated carbon surface sites. Lactone and carbonyl functional groups yield the kinetics equations. The model equation is solved for the spherical coal particle of equivalent highest mercury binding energies. Additionally, halogen atoms have been added to the radius ranging from 0.00005 m to 0.0001m and temperature ranging from 300 K to 1000 K. modeled surface, and have found to increase the activated carbon’s mercury adsorption The simulated results obtained by using the present model are in excellent agreement with capacity. The mercury binding energies increase with the addition of the following experimental data, much better than the agreement with earlier model reported in the halogen atoms, F > Cl > Br > I, with the addition of fluorine being the most promising literature. Simulation results capture expected qualitative trends in nature. halogen for increasing mercury adsorption.

28-4 SESSION 28 Survey of Catalysts for Oxidation of Mercury in Flue Gas ENVIRONMENTAL CONTROL TECHNOLOGIES: Evan J. Granite, Albert A. Presto, DOE/NETL, USA MERCURY OXIDATION/CATALYSTS The United States Environmental Protection Agency issued a regulation in March of 2005 for the emission of mercury from coal-burning power plants. In addition, several 28-1 states have also enacted legislation requiring control of mercury emissions from coal- Mercury Transformation Reactions on Model Fly Ashes burning plants. Mercury is a neurotoxin and accumulates within the food chain. Sukh Sidhu, Patanjali Varanasi, University of Dayton Research Institute, USA Elemental mercury is difficult to capture from a gas stream. Much of the mercury contained in power plant flue gas is in the elemental form. Elemental mercury is a From results of our previous mercury oxidation study which was conducted using four semi-noble metal, is insoluble in water, and is not captured efficiently by carbon. different Ohio coal fly ashes, it was observed that the chemical composition of surfaces Mercuric chloride is highly soluble in water, and is more readily removed by carbon. A plays a very important role in mercury oxidation reactions. To further understand catalyst that can oxidize elemental mercury to mercuric chloride (or another mercury oxidation and its dependence on the chemical composition of fly ashes, a compound) would be of tremendous value. A catalyst would enable mercury to be series of experiments were conducted using model fly ashes. These model fly ashes captured by existing air pollution control devices (APCDs) present in coal-burning were prepared using flame soot as carbon source and iron oxide as metal oxide power plants. These existing APCDs include wet scrubbers for acid gas removal, as catalyst. Vanadia supported on titania was also used as a catalyst in order to compare well as electrostatic precipitators (ESPs) and baghouse filters for particulate removal. mercury oxidation observed on the surface of model fly ashes with that on SCR The mercury oxidation catalyst can be located upstream of the appropriate APCD. catalyst. To keep catalytic bed characteristic same for all surfaces the catalytic surface Mercuric chloride is readily removed by the scrubbing solutions employed for acid gas were dispersed on quartz wool. In all experiments, the inlet concentration of Hg0(g) removal. Mercuric chloride is easily removed by adsorption on unburned carbon in fly was maintained at 47 µg/m3 using a permeation device as the source of Hg0(g). All ash captured in ESPs or baghouse filters. Mercuric chloride is also sequestered by experiments were conducted using 4% O2 in nitrogen mix as a reaction gas, and other activated carbon sorbents injected upstream of an ESP or baghouse. Several materials reactants (HCl, H2O) were added as required. The fixed bed catalytic reactor was have been proposed as catalysts for oxidation of mercury. These materials include operated over a temperature range of 300 to 500°C. In each experiment the reactor palladium, gold, iridium, platinum, SCR catalysts, fly ash, activated carbons, Thief effluent was sampled using modified Ontario-Hydro method. After each experiment, carbons, and halogen compounds. Previous results obtained with these catalysts are fixed beds were also analyzed for mercury. It was observed that soot is more active in reviewed. Several mechanisms of mercury oxidation are proposed, and future research mercury oxidation than vanadia/titania and iron oxide catalyst. Results also show that directions are suggested. Alternative catalysts and supports will be suggested, and an over the surface of metal oxide catalysts mercury oxidation is only weakly dependent extensive list of references will be provided. The work presented in this manuscript on temperature. was recently accepted for publication in Environmental Science & Technology.

24

28-5 need customized modifications in order to manage the potential for flame flashback. The A Kinetic Approach to Catalytic Oxidation of Mercury in Flue Gas unique insensitivity of the AVC approach to high through-put velocities will reduce Evan J. Granite, Albert A. Presto, Henry W. Pennline, Andy Karash, William J. hardware modifications and accommodate the extremely fast burning hydrogen-based fuels. O’Dowd, Richard A. Hargis, DOE/NETL, USA In addition, Ramgen’s AVC technology is cross-cutting and capable of delivering benefits to many of the technical areas of concern in zero-emissions combustor-based facilities Several materials have been examined as catalysts for the oxidation of mercury in a including the oxy-fuel Rankine cycle system. bench-scale packed-bed reactor located at NETL. The catalysts examined include activated carbon, Thief carbons, precious metals, fly ash, and halogen compounds. 29-4 Slipstreams of flue gas generated by the NETL 500-lb/hr pilot-scale combustion Catalytic Combustion for Ultra-Low NOx Hydrogen Turbines facility were contacted with the catalysts. An on-line continuous emissions monitor Benjamin Baird, S. Etemad, Sandeep Alvandi, William C. Pfefferle, H. Karim, (CEM) was employed to measure elemental and oxidized mercury entering and exiting Precision Combustion, Inc., USA the bed. The apparent activation energy and reaction order for mercury were Kenneth O. Smith, W. Nazeer, Solar Turbines, Inc., USA determined for several of the catalysts. Future research on catalyst materials will be conducted in a bench-scale packed-bed reactor employing both simulated and real flue Precision Combustion, Inc. (PCI), under sponsorship from the U.S. Department of gas streams generated on-site at NETL. The work presented in this manuscript was Energy, is further developing it’s Rich Catalytic Lean-burn (RCL®) combustion also accepted for publication in Energy & Fuels. system for hydrogen fuels. Rich catalytic operation has successfully demonstrated low single digit ppm NOx and the ability to burn hydrogen fuels in 9 atmosphere subscale tests. The test data show the potential of using rich catalytic combustion for low single SESSION 29 digit emissions. Areas of further work to commercialize this technology has been GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND identified. PCI, in collaboration with Solar Turbines Incorporated and other gas turbine HYDROGEN APPLICATIONS – 1 manufacturers, has a 39 month DOE Fossil Energy Turbine Technology R&D program to develop and demonstrate a low emission rich catalytic combustion system for fuel flexible ultra-low NOx megawatt-scale gas turbines that can utilize hydrogen fuel, 29-1 facilitate high efficiency operation, and be installed or retrofitted into existing turbines. Coal IGCC Turbine Technology Improvements for Carbon Free Fuels This paper presents the status of the rich catalytic application from the combustion Ashok Anand, Benjamin Mancuso, Kevin Collins, Greg Wotzak, GE Energy, USA point of view for MW size engine application.

Reduction of carbon dioxide from Coal-based IGCC Power Plants is rapidly gaining 29-5 increased interest in future installations. Studies have shown that IGCC technology is Development of Turbo Machinery for a Zero CO2 Emissions Oxy-Fuel Cycle able to capture and remove carbon dioxide at lower economic penalty as compared to Mohan A. Hebber, Shiv Dinkar, Juan Pablo Gutierrez, Siemens Power Generation, Inc. conventional pulverized coal fired steam plants. Further improvements in IGCC power Jim Downs, Florida Turbine Technologies, Inc., USA plants with carbon capture, is possible though the development of specific gas turbine cycle designs that increase plant efficiency at reduced costs and emissions. The In 2005 the U.S. Department of Energy-National Energy Technology Laboratory (DOE- performance influence of a typical heavy-duty gas turbine’s cycle parameters on IGCC NETL) awarded a program to Siemens Power Generation (SPG), Inc. to develop turbo plant with carbon capture is presented. An optimization analysis method is described, machinery powered by oxy-fuel combustion, which generates near zero emissions and which can be successfully applied to select a gas turbine cycle design to achieve plant provides for economical CO2 capture capability. (The combustor for this oxy-fuel cycle is to level performance goals. be developed separately by Clean Energy Systems (CES), Inc. of Rancho Cordova, California.). The new working fluid (a mixture of CO2 and steam) and the desire to 29-2 maximize the plant cycle efficiency pose numerous technical challenges not only in Advanced Hydrogen Turbine Development developing the turbine designs and consideration of material systems, but also in the Ed Bancalari, Ihor S. Diakunchak, Pedy Chan, Siemens Power Generation, Inc., USA selection of a plant cycle. The calculation of auxiliary loads for Fuel Processing Plant (gasifier), Air Separation Unit (ASU), O2 compression, CO2 compression, limitations on The Advanced Hydrogen Turbine Development Project objective is to design and develop a metal temperatures and other boundary conditions – all posed difficulties in arriving at fuel flexible (coal derived hydrogen or syngas) advanced gas turbine for Integrated cycles for further consideration. Any turbine design that depends on boundary conditions Gasification Combined Cycle (IGCC) and FutureGen type applications that meets the U.S. higher than the current state-of-the-art poses special challenges in the selection of materials. Department of Energy (DOE) turbine performance goals. The overall DOE Advanced Initial studies indicate that materials in the turbine for the “topping” cycle may have to Power System goal is to conduct the Research and Development necessary to produce CO2 tolerate a Turbine Inlet Temperature (TIT) well in excess of 1500°C with CO2 and H2O as sequestration ready coal-based IGCC power systems with high efficiency (45-50% [HHV]), working fluid. With regards to the steam turbine in the “bottoming” cycle, major challenges near zero emissions (< 2 ppm NOx @ 15% O2) and competitive plant capital cost (< are anticipated in selecting materials for the turbine casing, rotor, blading, valves, sealing and $1000/kW). DOE has awarded Siemens Power Generation a contract for Phases 1 and 2 bolting. Other challenges include innovative cooling techniques including, but not limited to, development work. Phase 1 activities will include identification of advanced technologies the development of serpentine cooling paths; development of start-up procedures and required to achieve the Project goals, detailed Research & Development Implementation algorithms for controls and life consumption. The paper describes approaches planned to Plan preparation and conceptual designs for the new gas turbine components. In Phase 2, the overcome the technical challenges and develop turbine designs that meet the overall identified concepts/technologies will be down selected and a detailed design of the gas objectives of the program including the efficiency goals. An overall time line is also turbine will be completed. Phase 3, which has not yet been awarded, will involve the identified for key milestones. advanced gas turbine and IGCC plant construction and validation/demonstration testing. The end objective is to validate the advanced gas turbine technology by 2015. The starting point for this development effort is the SGT6-6000G gas turbine. This gas turbine will be adapted SESSION 30 for operation on coal and biomass derived hydrogen and syngas fuels, as well as natural gas, GLOBAL CLIMATE CHANGE: CO2 CAPTURE – 2: while achieving high performance levels and reduced capital costs. This paper describes MEMBRANES AND SOLID SORBENTS Phase 1 activities and accomplishments in the first 9 months since the program was initiated.

29-3 30-1 Benefits to IGCC Gas Turbines of Advanced Vortex Combustion Experimental Investigation of a Molecular Gate Membrane for Robert Steele, Pete Baldwin, Ramgen Power Systems, USA Separation of Carbon Dioxide for Flue Gas James Hoffman, Henry W. Pennline, DOE/NETL, USA Ramgen Power Systems is developing an Advanced Vortex Combustion (AVC) technology Shingo Kazama, Teruhiko Kai, Takayuki Kouketsu, Shigetoshi Matsui, Koichi for combustion of hydrogen-based fuels which shows tremendous potential for increased Yamada, RITE, JAPAN energy efficiency and improved asset utilization. The fundamentals of the technology and the potential advantages of incorporating the AVC approach into an IGCC gas turbine will Commercial-sized modules of the PAMAM dendrimer composite membrane with high be presented. The AVC technology can be applied to the efficient and cost-effective CO2/N2 selectivity and CO2 permeance were developed according to the In-situ Modification combustion of hydrogen-based fuels with sub-3 ppmv NOx emissions while maintaining or (IM) method. This method utilizes the interfacial precipitation of membrane materials on the extending simple cycle efficiencies. The AVC technology has the potential for improved surface of porous, commercially available polysulfone (PSF) ultrafiltration hollow fiber turbine efficiency, lower NOx membrane substrates. A thin layer of amphiphilic chitosan, which has a potential affinity for emissions, greater flame stability, high flame speed flexibility, increased durability, and both hydrophobic PSF substrates and hydrophilic PAMAM dendrimers, was employed as a reduced manufacturing costs. This approach can play an important role in the advancement gutter layer directly beneath the inner surface of the substrate by the IM method. PAMAM of future Integrated Gasification Combined Cycle (IGCC) power plants that will require dendrimers were then impregnated into the chitosan gutter layer to form a hybrid active layer hydrogen-enriched fuel burning gas turbines. The flame speed of hydrogen-air mixture is six for CO2 separation. Permeation experiments of the PAMAM dendrimer composite times higher than a natural gas-air mixture. Conventional swirl-based combustion systems membrane were carried out using a humidified mixed CO2 / N2 feed gas at a pressure 25

difference up to 97 kPa at ambient temperature. When conducted with CO2 (5%) / N2 (95%) Combustion of fossil fuels is one of the major sources of the greenhouse gas CO2. Pressure feed gas at a pressure difference of 97 kPa, the PAMAM composite membrane exhibited an swing adsorption/sorption (PSA/PSS) and temperature swing adsorption/sorption -7 3 -2 -1 -1 excellent CO2/N2 selectivity of 150 and a CO2 permeance of 1.7×10 m (STP) m s kPa . (TSA/TSS) are some of the potential techniques that could be utilized for removal of CO2 The impact of various process parameters on the permeability and selectivity was also from fuel gas streams. It is very important to develop sorbents to remove CO2 from fuel gas examined. streams that are applicable for a wide range of temperatures. NETL researchers have developed novel CO2 capture sorbents for both low temperature and moderate temperature 30-2 applications. An Analysis of Dense Hydrogen Membranes as a Means of Producing a CO2 Rich Novel liquid impregnated solid sorbent was developed for CO2 removal in the temperature Stream Consistent with the CO2 Capture Requirements of a Futuregen Plant range of ambient to 60°C. The sorbent is regenerable at 60-80°C. Multi cycle tests conducted Paul J. Grimmer, Carl R. Evenson IV, Xiaobing Xie, Harold A. Wright, Clive in an atmospheric bench scale reactor with simulated flue gas indicated that the sorbent Brereton, Warren Wolfs, Eltron Research Inc., USA retains its CO2 sorption capacity (~ 2 moles of CO2/liter of the sorbent) with CO2 removal efficiency of about 99%. Presence of water vapor did not affect the performance of the Several methods have been proposed for capturing CO2 from coal combustion. Most sorbent. The sorbent was also tested in a high pressure (20 atm.) bench scale flow reactor involve scrubbing CO2 from the low-pressure combustion gases. Eltron, NORAM and with simulated coal gas. The CO2 sorption capacity (~ 6 to 9 moles of CO2/liter of the their partners are developing a system built around Eltron’s hydrogen separation sorbent) at high pressure was significantly higher than that at atmospheric pressure. The CO2 membrane in which the synthesis gas from a coal gasifier is converted to CO2 and H2 absorption capacity was higher at higher concentrations of CO2. It was possible to regenerate prior to combustion and the CO2 and H2 are separated, leaving the H2 for fuel and the the sorbent at 20 atm in the presence of water vapor. The sorbent retained the CO2 sorption CO2 “captured” at high pressure, ready for sequestration. This work is partially funded capacity during a 30 cycle test conducted at 20 atm. Results of the bench scale multi cycle by the DOE as part of the FutureGen clean coal initiative. The system produces flow reactor tests and results of the system analysis will be discussed in the paper. essentially 100% pure H2 which can readily be used in gas turbines, various types of A novel solid sorbent containing mixture of alkali earth and alkali compounds was fuel cells, used in various crude oil refining and petrochemicals or even as a starting developed for CO2 removal at 200-250°C from high pressure gas streams suitable for IGCC point for the “Hydrogen Economy”. Although the membrane and its accompanying systems. The sorbent showed very high capacity (4 moles of CO2/kg of sorbent) for CO2 “no-carb” fuel system have wide application, this paper focuses on use of the system in removal from a gas streams containing 28% CO2 at 200°C and at 20 atm during a lab scale coal gasification. Comparisons are made for capital and operating costs and reactor test. This sorbent can be regenerated at 20 atm and at 375°C utilizing a gas stream performance of the “no-carb” system versus both currently available systems and those containing steam. High pressure and high CO2 concentration enhanced the CO2 sorption still in development. There have been a number of recent advances in the development process. Results of the ten-cycle test with the sorbent and potential applications will also be of these membranes. Experiments have shown that no sweep gas is needed in current discussed in the paper. operation; they have also shown that the H2 permeate pressure can now be up to H2 pipeline pressures for ease of downstream use, and that staged systems with >90% hydrogen recovery with lower hydrogen compression costs are possible. These recent SESSION 31 advances will be examined from an economic perspective. GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGY DEVELOPMENT – 1 30-3 CO2 Adsorption by Dendrimers Bound to Mesoporous Substrates Alan Chaffee, Zhijian Liang, Bandar Fadhel, Caspar J. Schneider, Monash University, 31-1 AUSTRALIA “CoalFleet for Tomorrow” IGCC Research, Development and Demonstration Augmentation Plan Chemical absorption, by amine solvents has long been used by industry for acid gas John Wheeldon, Neville Holt, Jeffrey Phillips, John Parkes, EPRI, USA removal. Amine-based chemical solvents absorb CO2 very selectively. However, regeneration of the solvent is energy-intensive and is also plagued by the generation of The industry initiative “CoalFleet for Tomorrow” was launched in November 2004 to corrosive byproducts. Recently, solid adsorbents based on amine functionalized substrates accelerate the deployment and commercialization of clean, efficient, advanced coal power have been proposed as a possible means of overcoming these limitations via the Pressure systems, thereby preserving coal as a vital component in the electric generation mix. The Swing Adsorption (PSA) process. This paper will report our investigation of CO2 adsorption “CoalFleet” initiative has participation by over 50 organizations including power generators efficiencies for a stepwise growth series of amine terminated melamine dendrimers that have of various types, suppliers, engineering firms, Department of Energy, and other US and been iteratively grown (generations 0 to 4) within the channels of SBA-15 and related international organizations. CoalFleet is tackling the technical and economic/institutional mesoporous silica substrates. The CO2 adsorption efficiencies of the materials were challenges of making advanced coal power plants a prudent investment option both in the determined from thermogravimetric analysis (TGA) and adsorption isotherm measurements. short term and in the long term, while taking into account the potential for future CO2 The adsorption efficiencies were found to be dependent upon both temperature and structure emissions regulations. (support material and dendrimer generation). Heats of CO2 adsorption, measured by As part of the CoalFleet for Tomorrow initiative in 2005, the Electric Power Research differential thermal analysis (DTA), in the range of 40 - 60 kJmol-1, suggest that strong Institute (EPRI) created research, development & demonstration (RD&D) augmentation interactions form during adsorption. Nevertheless, these heats of adsorption are less than plans for IGCC and combustion technologies. The purpose of the plans was to identify those reported for amine solvents, suggesting that, with these materials, the energy RD&D needs, over and above the activity already underway or planned, which is needed to requirement for sorbent regeneration will be lower. foster the early deployment of these advanced coal-based generation technologies. This paper focuses on the long-term roadmap portion of the CoalFleet IGCC RD&D 30-4 augmentation plan and identifies the important technology improvements which could be CO2 Release Property of Lithium Silicate under Reduced Atmosphere implemented to improve the economics of IGCCs incorporating CO2 capture. The roadmap Masahiro Kato, Toshihiro Imada, Kenji Essaki, Yasuhiro Kato, Toshiba Corporation, indicates that IGCCs with CO2 capture could potentially be built at lower $/kW cost and JAPAN with higher thermal efficiency than today’s IGCCs without CO2 capture. This paper will describe the motivation for creating the plan and provide brief descriptions of A novel CO2 separation technique that employs the chemical reaction of lithium-containing the key steps in the long term roadmap. The steps where additional RD&D effort is needed oxide with CO2 has been developed. Because this method is effective in the temperature are identified, and the most appropriate entities (e.g., government, technology suppliers, or range from 450°C to 700°C, it has the advantage of enabling CO2 separation in power plants power industry collaborative) for carrying the various elements of the roadmap are without lowering the temperature. As a result, the energy needed for CO2 capture is expected discussed. to be much lower than with conventional methods such as the amine method. Among all absorbents, lithium orthosilicate (Li4SiO4) shows immediate CO2 absorption and release, 31-2 which results in an obvious weight change of up to 36%. However, in order to remove and Current and Future IGCC Technologies: Bituminous Coal to Electric Power capture high-purity CO2, CO2 release should be conducted in a 100% pure CO2 atmosphere. David Gray, Charles White, John Plunkett, Sal Salerno, Mitretek Systems, USA Under such conditions, the temperature must be more than 800°C, and degradation of Glen Tomlinson, Consultant, USA absorption properties tends to occur. This study focused on reducing the pressure to lower the CO2 release temperature, and cyclic testing was performed for up to 500 cycles. The The United States Department of Energy through the National Energy Technology results showed that the release temperature was lowered to 700°C under 0.7 atm of pure Laboratory (NETL) is funding research & development (R&D) whose objective is to CO2, and the absorption ratio was found to be maintained at about 90% of the initial value. improve the efficiency and reduce the costs of advanced Integrated Gasification Combined Cycle (IGCC) technologies for generation of clean electric power. In order 30-5 to evaluate the benefits of the ongoing R&D, NETL contracted Mitretek Systems to CO2 Capture Utilizing Solid Sorbents utilize their Energy Systems Analysis capabilities and conceptual computer simulation Abbie Layne, Ranjani Siriwardane, DOE/NETL, USA models to quantify the potential impact of successful R&D on the IGCC system. Clark Robinson, Research Development Solutions, USA Mitretek Systems has developed detailed computer simulation models of IGCC configurations. These spreadsheet based models simulate the gasification of coal to clean synthesis gas and the subsequent utilization of this gas in gas turbine and steam 26

turbine cycles. The models provide complete material and energy balances of the laboratory simulated groundwater under anaerobic conditions at ambient temperature system and are flexible with respect to technology and configuration. They also or 37°C. Bacterial count with Epifluorescence methods, pH measurements, volatile estimate capital and operating costs and calculate the required selling price (RSP) of fatty acid content, gas composition and gas volume measurements were conducted the electric power based upon standard discounted cash flow (DCF) analysis. periodically to evaluate methane generation from coal samples over 6 months. Emerging advanced gasification, advanced gas cleaning, and novel gas and steam At ambient temperature, results indicated that gas was generated at an estimated rate of turbine technologies can be incorporated into the baseline (based on current 350 scf/ton of coal/year. However, at 37°C, gas was produced at a higher rate of 900 technologies) IGCC configuration. Also, advanced air separation technology and fuel scf/ton/year as compared to the positive and negative controls. cell technologies can be integrated into the IGCC configuration. Incorporation of these The microscopic observation confirmed the aforementioned results. Mic1 culture advanced technologies into the baseline IGCC plant allows a quantitative estimate of grown in medium with core coal showed higher bacterial count with predominantly the potential benefits of these technologies. These benefits are measured ultimately in filamentous and rod shapes compared to Mic1 grown in groundwater and medium in terms of improved thermal efficiency (reduced heat rate) and in reduction of the cost of the absence of coal. Validation tests were also conducted at simulated high pressure electric power. In this paper, a baseline IGCC configuration that is representative of (300 psi) which also resulted in methane production. An anaerobic fermentation kinetic the current state of the art is first established. Sequential improvements have then been model based on the laboratory results predicted a production potential of 3-7 million assumed for this base plant. These improvements include changing the gasifier feed scf/day from thick Powder River Basin coal seams. This paper will provide a rigorous system from a water slurry to a dry feed pump, greater on-stream time or capacity test protocol for this feasibility study, laboratory tests, procedures, and approach for factor, advanced warm gas cleaning, advanced gas turbine systems, ceramic membrane commercial scale production. technology for air separation, and finally integration of solid oxide fuel cells as a topping cycle before the gas turbine. The order of introduction corresponds with the 31-5 timeline in which R&D for these improvements is expected to be completed. To the Nuclear-Coal Cycle extent possible, the same plant size was used for all configurations analyzed. However, Vladimir Popov, Krzhizhanovsky Power Engineering Institute, RUSSIA because the gas turbine input determines to a great extent the plant size, when advanced turbines were used the overall plant size was adjusted to be compatible with The logic of the present-day power engineering evolution dictates that coal shall be the gas turbine input. considered not only as a conventional fuel for heat and electric energy (e.e.) generation, but also as a material, which can potentially become a source for producing 31-3 some chemical products, motor fuel inclusive. The geography of the coal fields is such Field Trial Results of an Improved Refractory Material for Slagging Gasifiers that in many regions they are the only (or prevailing) source of raw materials (currently James Bennett, Kyei-Sing Kwong, Cynthia Powell, Hugh Thomas, Art Petty, used as fuel). Force majeur situations, that compelled some countries (not without DOE/NETL, USA success) to address coal as a source material for production of motor fuel on industrial H. David Prior, ANH Refractries Corp., USA scale, are known in the history of the past century. Mark Schnake, Harbison-Walker Refractories Company, USA Nonetheless, in the post-war period the relevant technologies did not find extensive use, which was explained by economic reasons, i.e. opening of oil and gas fields. Since Gasifiers are used commercially to react a carbon feedstock with water and oxygen resources of coal in the medium- and long run are incomparable to those of any other under reducing conditions; producing chemicals used as feedstock for other processes, organic energy resource, the today s oil and gas euphoria cannot last long and it will fuel for power plants, and/or steam used in other processes. A gasifier acts as a high pass earlier than one can envision. It will be followed by the coal-nuclear era, that will temperature, high pressure reaction chamber, typically operating between 1250- take up hundreds of years, even if no breeder reactors are used. Incremental growth of 1575°C, and with pressures between 300-1000 psi. Ash that originates from mineral e.e. consumption in time will aggravate the situation still more. Up to the present day impurities in the carbon feedstock becomes a by-product of gasification. In a slagging the use of nuclear and coal energy sources used to be (and still is) absolutely separated gasifier it melts, forming a liquid which flows down the gasifier sidewall; penetrating from each other, conforming to the difference in the nature of nuclear and chemical and wearing away the refractory liner by corrosive dissolution, abrasive wear, or by forces. The difference is very explicitly pronounced in the emerging terminology other processes such as spalling. The refractory liner must withstand the severe service nuclear and coal cycle. The cycles mentioned have their own intrinsic drawbacks and environment, protecting the steel shell against corrosive gases, temperature, and advantages. The technical disadvantage of the first cycle consists in compliance with material wear. Users have identified refractory service life as the most important the most stringent safety requirements (the requirements being followed deliberately limitation to sustained on-line availability of gasifiers, limiting gasifier acceptance and and uncompromisingly) and low efficiency of nuclear energy conversion to e.e., the use by industry. The National Energy Technology Laboratory in Albany, OR, has problem, which is comprehended, but cannot be solved, at least until high-temperature developed and patented (US Patent # 6,815,386) a phosphate containing high chrome gas reactor is constructed. The problems inherent of the coal cycle are well-known and oxide refractory for use in slagging gasifiers. In cooperation with ANH Refractories they cannot be solved either, owing to the lack of industrial methods of carbon dioxide Company, this refractory material has been commercially produced and is undergoing capture. In this context, not quite new, though modernized, approach, i.e. integration of field tests in commercial gasifiers. An analysis of data from these field tests indicates the cycles for enhancing the relevant positive and mitigating the relevant negative that the phosphate containing refractory results in an improved service life over other features, can suggest an alternative way out. The approach is based on setup of an refractory materials currently used as gasifier liners. Results from the post-mortem integrated energy-technological complex, comprising: (1) a pyrolyzer for partial analysis of the field trial in relation to the failure mechanisms in a slagging gasifier catalytic oxidation of the initial brown coal to semi-coke; (2) a modular nuclear will be presented. reactor, generating e.e. and heat (its thermal power 200 MW, its electric power 50 MW, helium temperature (°C) at the core inlet and outlet 300/750-950, helium pressure 31-4 5 MPa, making use of spherical fuel elements); (3) a catalytic gasifier of the semi-coke ITM Oxygen: Enabling Technology for Clean Coal with steam superheated (~800°C;) in the nuclear reactor, producing syngas (H2/CO ≈ Phillip A. Armstrong, ITM Oxygen, USA 45/45); and (4) the Fischer- Tropsch synthesizer. Its catalyst is a cheap product. Partial Douglas L. Benette, EP (Ted) Foster, VanEric E. Stein, Air Products and Chemicals, replacement of coal energy with nuclear energy during generation of e.e., heat and Inc., USA chemical products, motor fuel inclusive, can be mentioned among the main specific features of the process. The use of an energy-technological facility of this type will be Presently over 10% of methane natural gas produced in the United States is from coal especially advantageous in hard to reach places with no transport infrastructure. The seams. Average gas content of coal seams is 50-500 scf per ton of coal in the process is based solely on published domestic developments (both design and Appalachian, Raton, San Juan, and Powder River coal seams. The lowest gas content is experimental ones). in the Powder River Basin. During the past 20 years of increased commercial activities The author is deeply appreciative and grateful to the John D. and Catherine T. in these areas, the gas production is steadily declining in many of the wells. However, MacArthurs Foundation for awarding a grant (No. 04-81306-000-GSS) in support of with increasing energy prices, the demand for natural gas has substantially increased. program of individual research projects. Today the existing reserves of coal exceed 400 billion tons and almost 5.6 trillion tons of coal resources are estimated by the USGS at an unmineable depth. An in situ bioconversion of these vast resources of coal can become a source of large domestic SESSION 32 supply of natural gas. GASIFICATION TECHNOLOGIES: Methane formation is an end product of anaerobic degradation of organic matters FUNDAMENTALS AND SIMULATIONS – 3 including coal in the natural environment. To date biological techniques for production of methane from coal have not been demonstrated on a large scale. The objective of this research is to establish the feasibility of ARCTECH MicGASTM technology for in 32-1 situ enhancement of methane generation in deep coal seams. Impact of Coal Quality and Gasifier Technology on IGCC Performance The feasibility of this approach has been established by utilizing anaerobic microbial Ola Maurstad, Olav Bolland, Norwegian University of Science and Technology, consortia (Mic1) derived from the hind guts and soil eating termites to convert coals NORWAY into methane and CO2. Laboratory tests were conducted with Powder River Basin sub- Howard Herzog, Janos Beer, MIT, USA bituminous core coal samples under simulated subsurface conditions (saturation at 66% coal loading) by growing Mic1 culture (lysed or live) mixed with media or 27

Integrated coal gasification combined cycle (IGCC) plants with pre-combustion and most significant effect on the AFT with the least addition to the coal blend. The capture of CO2 represent one of the most promising near-term options for power effect of SiO2 and TiO2 were very similar with regards to the effect on the AFT. Less generation with carbon capture and storage. This work investigates to what extent Al2O3 was needed to increase the AFT to a similar AFT level in comparison to the IGCC performance (with and without CO2 capture) is affected by coal quality for two SiO2 used and the question still remains why Al2O3 (as pure oxide component) did different entrained flow slagging gasifiers. Based on an IGCC model developed in react different and increased the AFT to a certain temperature with less addition, in Aspen Plus and combined with GTPRO, mass and energy balances were computed. comparison to that of TiO2 and SiO2. The Al2O3 keeps the oxygen molecules stronger Two gasification technologies were considered: A dry feed gasifier with syngas heat bound to the molecule than to the other components, and when the element becomes recovery which represents the Shell technology, and a slurry feed gasifier with full “free”, with free electrons, a different mineral phase can form with a different flow water quench which represents the GE technology. For each gasifier, five different property. Another observation from the AFT results was that the AFT was definitely coals were used and alternatives with and without CO2 capture calculated. It was found non-additive (not a linear weighted calculated average) and not the weighted average that the efficiency, CO2 emissions and net power output of the slurry feed IGCC was AFT as was expected for the other coal properties such as the ash content, for example. strongly dependent on coal type, and had lowest performance for low rank coals. On The ash slagging characteristics is a non-additive property of individual coal sources in the other hand, the dry feed IGCC was little affected by coal type. The slurry feed the blend and therefore difficult to predict. IGCC performed closest to the dry feed IGCC when CO2 was captured and the two In general it can be concluded that the unique opportunity exists to increase the AFT, highest rank bituminous coals were used. was tested, proven and mechanistically outlined in this study on the coal source fed to the Sasol-Lurgi FBDB gasifiers. The AFT can be increased to >1350°C by adding 32-2 AFT increasing minerals or species, for example Al2O3 or kaolinite, to the coal blend Gasification of Lignite in a Transport Reactor before it is fed into the gasification process. By increasing the AFT, the direct effect Michael Swanson, Douglas R. Hajicek, Michael E. Collings, Ann K. Henderson, will be that steam consumption can be decreased, which in turn will improve carbon University of North Dakota, USA utilization. It can be recommended that roof and floor sections, containing mainly Ronald Breault, DOE/NETL, USA siltstone layers, have high AFT properties which might be suitable for use as dilution agent to the current coal in order to increase the AFT of the feed. From a The U.S. Department of Energy (DOE) National Energy Technology Laboratory thermodynamic point of view in the gasification environment, it might be worth to (NETL) Office of Coal and Environmental Systems has as its mission to develop mention that FactSage is able to handle organic and inorganic components and might advanced gasification-based technologies for affordable, efficient, zero-emission be a first decision for further work and development in this area. power generation. These advanced power systems, which are expected to produce near-zero pollutants, are an integral part of DOE’s Vision 21 Program. DOE has also 32-4 been developing advanced gasification systems that lower the capital and operating Gasification of Lignites to Produce Liquid Fuels, Hydrogen and Power costs of producing syngas for chemical production. A transport reactor has shown Michael Swanson, Steven Benson, Michael Jones, Jason Laumb, Michael Holmes, potential to be a low-cost syngas producer compared to other gasification systems University of North Dakota, USA since its high-throughput-per-unit cross-sectional area reduces capital costs. This work Edward Klunder, DOE, USA directly supports the Power Systems Development Facility utilizing the Kellogg, Brown, and Root transport reactor located at the Southern Company Services DOE is investigating various options for removing mercury from warm fuel gas Wilsonville, Alabama, site. Over 2700 hours of operation on 16 different coals ranging conditions at temperatures above the dew point of the moisture in the fuel gas in order from bituminous to lignite along with a petroleum coke has been completed to date in to obtain higher system efficiencies (3). DOE and others have significant investments the pilot-scale transport reactor development unit (TRDU) at the Energy & in other hot-/warm-gas cleanup technologies that are going to require at least warm-gas Environmental Research Center (EERC). The EERC has established an extensive (300 to 700°F [150 to 370°C]) Hg control systems to be developed if these other gas database on the operation of these various fuels in both air-blown and oxygen-blown cleanup technologies are going to be effective. This project will combine demonstrated modes utilizing a pilot-scale transport reactor gasifier. This database has been useful in mercury removal technology from Corning Inc. and the University of North Dakota determining the effectiveness of design changes on an advanced transport reactor Energy and Environmental Research Center. This project team will combine Corning s gasifier and for determining the performance of various feedstocks in a transport high-surface-area impregnated carbon monoliths with the EERC s experience with reactor. The effects of different fuel types on both gasifier performance and the pretreating activated carbon to generate a treated carbon capable of removing greater operation of the hot-gas filter system have been determined. It has been demonstrated than 95% of the mercury from a warm fuel gas at 500°F. This pretreatment should be that corrected fuel gas heating values ranging from 90 to 130 Btu/scf have been able to be readily applied to Corning s impregnated carbon monolith. Depending on the achieved in air-blown mode, while heating values up to 230 Btu/scf on a dry basis have final loading capacity, these monoliths could potentially be utilized as hot-gas filter been achieved in oxygen-blown mode. Carbon conversions up to 95% have also been fail-safe devices while also capturing Hg, As, Se, and Cd on those devices. Control of obtained and are highly dependent on the oxygen– coal ratio. Higher-reactivity (low- these contaminants to 5 ppbw Hg, 5 ppb As, 0.2 ppm Se, and 30 ppb Cd is desired rank) coals appear to perform better in a transport reactor than the less reactive under the project. The project benefit would be to potentially combine multi- bituminous coals. Factors that affect TRDU product gas quality appear to be coal type, contaminant trace metal control with backup particulate control for the protection of a temperature, and air–coal ratios. Testing with a higher-ash, high-moisture, low-rank gas turbine in the event of a candle filter failure. This technology would also provide coal from the Red Hills Mine of the Mississippi Lignite Mining Company have the carbon sorbent in a form that could easily be regenerated in place or removed and recently been completed. Testing with the lignite coal generated a fuel gas with regenerated in a separate process without creating a lot of fines that could adversely acceptable heating value with a high carbon conversion, although some drying of the affect a gas turbine located farther downstream. This has the potential to provide a high-moisture lignite was required before coal-feeding problems were resolved. No ash sorbent in a form that is both compact with a much smaller pressure drop than a packed deposition or bed material agglomeration issues were encountered with this fuel. bed, and could be regenerable to last numerous cycles. If the contaminant loading is not high enough or an in-situ regeneration process is not successfully developed, these 32-3 monoliths could still be utilized in separate multitrain vessels that could be taken off- Manipulation of Gasification Coal Feed in Order to Increase the Ash Flow line and regenerated or replaced depending on the process economics. These monoliths Temperature of the Coal, Enabling the Gasifiers to Operate at Higher could be utilized in either a cross-flow configuration (as a third level of dust protection Temperatures for the turbine) or in a straight-through flow configuration in order to minimize Johan van Dyk, Sasol Technology, SOUTH AFRICA pressure drop. This project will start with monolith production and laboratory testing utilizing a synthesized bottled syngas followed by bench-scale testing with an actual Coal is a crucial feedstock for South Africa’s unique synfuels and petrochemicals coal-derived syngas will be completed. The actual bench-scale gasification testing is industry and used by Sasol as a feedstock to produce synthesis gas via the Sasol-Lurgi important because it will allow the generation of actual trace constituents from coal, Fixed Bed Dry Bottom (FBDB) gasification process. The ash flow temperature (AFT) and at this scale, spiking of the coal to achieve desired metal constituents is possible. gives detail information on the suitability of a coal source for gasification purposes, and specifically to which extent ash agglomeration or clinkering is likely to occur 32-5 within the gasifier. Ash clinkering inside the gasifier can cause channel burning and Experimenting and Operating Coal Gasification in a 2 ton/day Entrained Bed unstable operation. Gasifier Sasol-Lurgi FBDB gasifiers are currently operated with the philosophy of adding an Cheng-Hsien Shen, Heng-Wen Hsu, Min-Chain Lo, Ching-Lin Shieh, Wei-Chung excess of steam to the process to control the H2/CO ratio of the syngas produced, but Chen, Mei-Yen Chen, Industrial Technology Research Institute, P.R. CHINA indirectly also to control the maximum gasifier temperature below the AFT of the coal. An opportunity exists to increase the AFT of the coal fed to the gasifiers by adding Coal is one widely used energy source, which provides 32.5% of energy in Taiwan. AFT increasing minerals to the coal blend before it is fed into the gasification process. Clean coal technology is one of the major discussion topics during National Science For the aim of this study a South African coal source was investigated, as being used meetings from 2000 in Taiwan. The main purpose of this thesis is to develop coal by the gasification operations in Secunda. gasification technology. The pressurized gasification testing facility is located in With the specific aim of this study, to increase the AFT, the determination of the AFT Kaohsiung in Southern Taiwan. Gasifier is a single-stage, refractory-lined, and of the coal blends where some acidic components such as silica (SiO2), alumina entrained bed slagging research reactor designed for the gasification of coal or (Al2O3) and titania (TiO2) were added was conducted. The oxide Al2O3 had the biggest petroleum coke in oxygen-blown gasification modes. The gasifier designs at pressures 28

up to 290 psia and temperatures up to 3000 degree F at a nominal coal feed rate of 2 33-4 metric tons per day. This paper focuses on illustrating some experiences in operating Refurbishment of an Old PC Boiler Confronted with Coal Quality gasifier procedures. It includes preheating gasifier process with air cooling the LPG Degradation by a CFBC Boiler - A Case Study burner header, keeping the pressure difference between coal vessels and gasifier and D. N. Reddy, Osmania University, INDIA setting up oxygen detector at the syngas outlet, which could experiment stably on V.K. Sethi, Rajiv Gandhi Technological University, INDIA operating the gasifier. This study investigates the results of gasifying three imported coal and petroleum coke. One finding is that carbon conversion efficiency at the high The Global concern for reduction in emission of green house gases (GHG) especially gasifying pressure is higher than the low gasifying pressure. This is due to high CO2 emissions are likely to put pressure on Indian Power Sector for adoption of pressure in gasifier enable coal to react with other reactants. Adding steam is helpful to improved power generation technologies. Although India does not have GHG increase the flammable components in syngas, carbon conversion efficiency and cold reduction targets, it has actively taken steps to address the climate change issues. gas efficiency in gasifying procedure. Future research objectives include improving Various options for India for CO2 reduction which have been taken up vigorously carbon conversion and cold gas efficiencies and increasing operating pressure to 235 include, GHG emission reduction in power sector through adoption of Co-generation, psia. Combined Cycle, Clean Coal Technologies (CCTs) and coal beneficiation and Renewable Energy Technologies particularly for Rural Sector. The CO2 emissions per unit of electricity generated are significantly high in India as large proportion of power SESSION 33 generated comes from low sized, old and relatively inefficient generating units which COMBUSTION TECHNOLOGIES – 6: COMBUSTION STUDIES constitute over 45% of our total installed capacity of about 1,18,000 MW. Growing environmental regulations would force many utilities within the country to go in for revamping of these polluting old power plants using environmentally benign 33-1 technology. CFBC offers a promising technology on this front. This technology has The Development of Tangential Coal-Fired Burner to Reduce shown high operational availability even while firing washery rejects and middilings of Unburned Carbon and Enhance Flame Stability high ash content up to 60%. Hyeok-Pill Kim, Si-Hong Song, Sang-Hyeun Kim, Hyuk-Je Kim, Doosan Heavy Industries & Construction Co., Ltd., REPUBLIC OF KOREA 33-5 Experimental Study of Heat Transfer in a Horizontal Swirling Fluidized Bed This report presents a study of the development of an advanced coal nozzle used in Wei-Ping Pan, Ping Lu, Andy Wu, Yan Cao, Western Kentucky University, USA burners to reduce unburned carbon (UBC) in a tangential coal-fired boiler. To understand the mechanism of UBC reduction, experiments using conventional burners In this paper, a horizontal swirling fluidized bed was designed through a specially were carried out to evaluate the effects of air injection velocity, coal fineness and over designed gas distributor and varied secondary air allocation to generate bed material fired air (OFA) on combustion efficiency. It was confirmed that ignition of pulverized swirling in dense zone. The heat transfer coefficients between submerged tube and bed coal particles close to the burner is helpful toward the complete burn of residual carbon material in horizontal fluidized bed were measured with the help of a fast response heat in fly ash. These efforts indicated the additional results that UBC was strongly transfer probe. The influences of fluidization velocity, bed material particle size, bed dependent on the primary air velocity and coal fineness; especially that UBC height, probe orientation and secondary air injection, etc. on heat transfer were dramatically decreased when the weight fraction of pulverized coal under 75μm was intensively investigated. Test results indicated that the heat transfer coefficients over 85%. New coal nozzles, modified from conventional nozzles, were prepared and increase with fluidization velocity, however reach their maximum value at the certain tested to improve the combustion efficiency. Some of these nozzles offered relatively fluidized velocity. The heat transfer coefficient in the backward orientation is higher lower unburned carbon than those of conventional burners and are referred to as HPFS than that in the upward orientation. The heat transfer coefficients decrease with (High Performance Flame Stability) coal nozzles. increasing of bed height. The bed material size is inversely proportional to heat transfer. The secondary air injection generates the preferred hydrodynamics in dense 33-2 zone and enhanced heat transfer. Engineered-Flow Chutes Improve Coal Handling at AmerenUE's Rush Island Plant Michel Schimmelpfenning, AMEREN, USA SESSION 34 Greg Bierie, Martin Engineering Services Group LLC, USA ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY – 1

This presentation will look at an advanced conveyor technology that offer the opportunities for significant improvement in the handling of coal in power plants, and 34-1 in prep plants, bulk transportation facilities, and other coal-handling operations. This Practical Applications of Innovative Mercury Control Technologies technology is flow-engineered chutes. Based on material testing and flow studies, these Brian W. Armet, John E. Batorski, The Mattabassett District, USA chutes allow the development of transfer chute systems that provide better control, continuous coal flow at higher capacities, and dramatic reductions in material spillage The Mattabassett District operates a 20 mgd Regional Wastewater Treatment Facility and the release of airborne dust. By regulating the coal flow path of movement, these located in Cromwell, Connecticut with a 1.55 dry ton/hour biosolids fluidized bed engineered chutes improve the load placement on the belt, eliminate chute blockages, incinerator that runs 24 hours/day, seven days/week. In response to Connecticut reduce safety hazards, and minimize maintenance costs. In this presentation, the Department of Environmental Protection (CTDEP) administrative orders and authors will feature discussions of recent installations of these technologies separately judgments, The District embarked on an ambitious program to evaluate new and and in combination in coal handling facilities. In particular, Mr. Schimmelpfennig will emerging mercury removal technologies to address stricter mercury emissions limits discuss the engineering and installations of flow- engineered chute systems at Ameren planned by CTDEP for municipal sewage sludge (biosolids) incinerators. These s Rush Island Electric Generating Plant, to reduce fugitive material and improve administrative orders and judgments imposed targets of 180 and 150 micro-grams per system performance in the operation s barge unloading and stack-out areas. cubic meter (μg/m³): CTDEP’s goal is 100 μg/m³. The District evaluated a number of technologies including: Sodium tetra sulfide 33-3 injection into the incinerator emissions’ air stream, which has been used in several Influence of Coal Composition on the Release of Na-,K-,Cl- and power generation plants with success; the introduction of foul air containing hydrogen S-species during the Combustion of Brown Coal sulfide, which is believed to oxidize some of the mercury in the incinerator emissions Holger Oleschko, Annette Schimrosczyk, Michael Muller, Forschungszentrum Julich into a more stable form, enhancing overall removal rates; a static carbon bed; and, the GmbH, GERMANY most novel and leading edge technology, a Ultra High Efficiency traveling filter cloth system. The use of brown coal can cause severe problems in combustion systems as far as The Carbon Bed and Ultra High Efficiency filter manufacturer’s experience were with fouling and slagging are concerned. Especially alkali metals that are released during other industries, and the Ultra High Efficiency filter manufacturer’s experience was not combustion are responsible for the formation of sticky deposits in the boiler. In order even related to power generation or sewage sludge incinerators, let alone as an add on to tackle this problem, an increased understanding of the combustion chemistry of following a wet scrubber system. brown coal is necessary. For this reason, laboratory combustion experiments with 7 This evaluation demonstrated that the Ultra High Efficiency traveling filter cloth different German brown coals from the Rheinland area were conducted at temperatures system will remove sub-micron particles as well as mercury, and the carbon canister of 800 and 1200°C. High pressure mass spectrometry (HPMS) was used for the on-line will remove mercury. analysis of the combustion products such as HCl, NaCl, KCl, SO2 and Na2SO4. The This study has value to the industry: Jeffery Holmstead, EPA assistant administrator results show that the release of HCl, NaCl and KCl is strongly dependent on the Cl- for air and radiation, has been quoted stating, “Mercury control technology is not content of the coals. Furthermore, at temperatures of 1200°C, NaCl and SO2 were available on a commercial scale, so the agency was unable to set a MACT standard.” released in two steps, whereas at 800°C these species were released in one step only. Scott Segal, director of the Electric Reliability Coordinating Council, has been quoted as stating, “There is no mercury control technology that exists today that can achieve

29

the reduction levels finalized in the Clean Air Mercury rule, let alone the 90 percent than 95% of the mercury from a warm fuel gas at 500°F (260°C). The EERC and reductions advocated by some activists.” Corning are working together to apply this pretreatment to Corning’s impregnated carbon monoliths and to develop materials to also remove arsenic, selenium and 34-2 cadmium using the monolith system. Target contaminant removal levels are 5 ppbw Mercury Vapor Capture From Coal Derived Fuel Gas in the Hg, 5 ppb As, 0.2 ppm Se, and 30 ppb Cd. Another goal for this technology is to Presence of Hydrogen Chloride Over Iron Based Sorbents provide a process for regeneration in place, or to remove and regenerate the monolith Shengji Wu, Masaki Ozaki, Md. Azhar Uddin, Eiji Sasaoka, Okayama University, system in a separate process without creating a lot of fines that could adversely affect a JAPAN gas turbine located farther downstream. Depending on the final loading capacity, these monoliths could potentially be utilized not only to capture Hg, As, Se, and Cd, but also Laboratory studies were conducted to develop an elemental mercury (Hg0) removal as hot-gas filter fail–safe devices– backup particulate control for the protection of a gas 0 process based on the reaction of H2S and Hg using iron oxide sorbents for coal turbine in the event of a candle filter failure. derived fuel gas. It is well known that hydrogen chloride (HCl) is present in the fuel In this mode, the monoliths would be utilized in a cross-flow configuration. This gases of some types of coal, but the effect of HCl on the Hg0 removal performance of project has begun with monolith production and laboratory testing of the monolith iron based sorbents in coal derived fuel gases is not yet understood. In this study, the system to remove mercury utilizing a simulated syngas. This will be followed by effects of HCl on the removal of Hg0 from coal derived fuel gases over iron based bench-scale testing with an actual coal-derived syngas, which will allow the generation sorbents such as iron oxides, iron oxide-Ca(OH)2, and iron sulfides were investigated. of actual trace constituents from coal to determine their impact on the process early in The iron oxides were prepared by precipitation and conventional impregnation the technology’s development. To date, the lab-scale work has successfully methods. The iron oxide-Ca(OH)2 sample was prepared by mixing iron oxide with demonstrated that treated monoliths can remove mercury at the target temperatures. Ca(OH)2 mechanically. Iron disulfide (FeS2) used in this study was a reagent grade chemical. The Hg0 removal experiments were carried out in a laboratory-scale fixed- 34-5 bed reactor in a temperature range of 60-100°C using simulated fuel gases having the Removing Trace Metals From Coal-Derived Syngas at Elevated 0 composition of Hg (4.8 ppb), H2S (400 ppm), HCl (0-10ppm), CO (30%), H2 (20%), Temperatures: A Progress Report on Sorbent Development H2O (8%), and N2 (balance gas). In the case of iron oxides, the presence of HCl John R. Albritton, Brian S. Turk, Santosh Gangwal, Raghubir Gupta, RTI suppressed the Hg0 removal rate. However, the Hg0 removal rate of iron oxide- International, USA Ca(OH)2 was not affected by the presence of HCl, because Ca(OH)2 reacted with HCl. 0 The Hg removal performance of FeS2 was not suppressed by the presence of HCl in The sustained elevated prices for crude oil and natural gas have generated renewed the coal derived fuel gas. interest in gasification technologies as a means to convert cheaper carbonaceous fuels, primarily coal, into electricity, hydrogen, chemicals and transportation fuels. One of 34-3 the most significant challenges of realizing the potential of gasification for this Nanocrystalline Sorbents for Mercury Removal from Warm Fuel Gas conversion is effectively capturing the variety of contaminants present in these cheaper Raja Jadhav, Howard Meyer, Gas Technology Institute, USA carbonaceous fuels. For the more prominent contaminants like sulfur, chlorine and Slawomir Winecki, NanoScale Materials, Inc., USA nitrogen, commercial technologies are readily available and ongoing R&D efforts are Ronald Breault, National Energy Technology Laboratory, USA spawning new and better technologies. However, control technologies for the trace contaminants have received much less attention. RTI International (RTI) is actively Coal-fired utilities are the single largest source of anthropogenic mercury emissions in developing sorbent-based technologies for removing mercury, arsenic, selenium and the U.S. The mercury regulations currently proposed for coal-combustion systems will cadmium that are specifically designed and optimized for syngas applications. The most likely be extended to the next-generation gasification-based systems. Therefore, a specific objective is to develop sorbents to remove these trace contaminants, from coal significant amount of research work is currently being carried out to address the derived syngas at high pressures between 300 and 700ºF. With RTI’s specialized concern of mercury release from coal-fired power plants. A majority of this research is testing systems for arsenic and mercury, a sorbent screening program has been focused on development of sorbents for mercury capture from “warm” fuel gas. completed and capacity testing and process optimization has begun. Because more Sorbents currently proposed for flue gas application, such as activated carbon, have materials interact with the arsenic in the syngas compared to mercury, the R&D for limited application in fuel gas because of their lower sorption capacity at elevated arsenic has focused on sorbents capable of capturing arsenic in the presence of sulfur temperatures. The presence of reducing components provides additional challenge for for optimal system integration. Similar specialized testing systems have been set up for development of high capacity mercury sorbents for fuel gas applications. In this paper, selenium and cadmium and sorbent screening has begun. The results from these development and evaluation of novel nanocrystalline sorbents for mercury removal different testing programs will be presented in this paper. from warm fuel gas are discussed. Nanocrystalline materials exhibit a wide array of remarkable chemical and physical properties, and can be considered as new materials that bridge molecular and condensed matter. One of their remarkable properties is SESSION 35 enhanced surface chemical reactivity (normalized for surface area) toward incoming GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND adsorbates, which is attributed to extremely large surface areas, unique morphology HYDROGEN APPLICATIONS – 2 and porous nature of the nanomaterials. Gas Technology Institute (GTI), in collaboration with NanoScale Materials, Inc., is evaluating highly reactive nanocrystalline metal oxides/sulfides for capture of mercury from high-pressure (300– 35-1 1000 psi) and high-temperature (300–700°F) fuel gas. The sorbents are evaluated in a A Study of the Transport of Coal Syngas Species through a lab-scale, fixed bed reactor with the outlet mercury concentration monitored by a semi- Solid Oxide Fuel Cell Anode continuous mercury analyzer. This paper discusses unique properties of nanoscale Jason Trembly, Randall S. Gemmen, National Energy Technology Laboratory, USA sorbents and gives preliminary results of mercury capture by these sorbents in David J. Bayless, Ohio University, USA simulated fuel gas conditions. The project is sponsored by DOE’s National Energy Technology Laboratory. High temperature fuel cells, especially solid oxide fuel cells (SOFCs), represent a technology that may be used to more efficiently and cleanly produce both power and 34-4 heat using fossil fuels such as coal. Although technical investigations have shown that Advanced Mercury/Trace Metal Control with Monolith Traps SOFCs may be readily coupled with hydrogen and natural gas to produce power, few Michael Swanson, Edward Olson, Ramesh Sharma, Grant Dunham, Mark Musich, investigations (experimental or theoretical) have focused on the feasibility of operating University of North Dakota, USA SOFCs with gasified coal as fuel. Porous media models provide valuable insight into Jenny Tennant, DOE/NETL, USA the transport of gas species through the anode of a PSOFC and may be adapted to Youchun Shi, Benedict Johnson, Lisa Hogue, Corning, INC., USA investigate the transport behavior of coal syngas species throughout the anode of the PSOFC. Two models, the Mean Transport Pore Model (MTPM) and the Dusty Gas The U.S. Department of Energy (DOE) is investigating warm-gas (300° to 700°F [150° Model (DGM), have been widely used to study steady state and transient transport of to 370°C]) cleanup technologies to remove all coal contaminants at temperature gaseous species through porous materials. While both models have previously been conditions above the dew point in the fuel gas to obtain higher system efficiencies. applied to SOFC applications using both hydrogen and natural gas as fuels, only Mercury is especially difficult to remove at these target warm-temperature conditions, recently has NETL applied the DGM to SOFC anode systems using coal derived but if mercury cannot be removed at warm temperature, the whole warm-gas cleanup syngas as fuel. The following paper presents modeling results from a study of coal scenario will fail. This project is to develop a warm-gas, multicontaminant (including syngas transport under such conditions using the MTPM model. Also a comparison mercury) cleanup system. Furthermore, this technology is expected to be compact, between the MTPM and DGM applied to SOFCs using coal derived syngas as fuel is regenerable, and result in a much smaller pressure drop than possible with a packed presented. bed. This project combines high-surface-area impregnated carbon monoliths from Corning, Inc., with demonstrated mercury removal technology from the University of North Dakota Energy & Environmental Research Center (EERC). The EERC has pretreated activated carbon to generate a treated carbon capable of removing greater 30

35-2 plant which was performed under a co-operative agreement with DOE. As a result, fuel Development of Iron-Based Perovskite Materials as Carbon and cells are one of the most attractive power generating technologies for the future. Sulfur Tolerant SOFC Anodes Advances made under the Fuel Cell Coal-Based Systems program are expected to John Kuhn, Umit Ozkan, The Ohio State University, USA become key enabling technologies for FutureGen, a planned DOE demonstration of advanced power systems that emit near-zero emissions, have double today s electric Current Ni-based solid oxide fuel cells (SOFC) anodes deactivate in the presence of generating efficiency, co-produce hydrogen, and sequester carbon dioxide. This project coal-derived gas because they are easily poisoned by low levels of sulfur and catalyze will take a major step toward enabling the nation to use its ample coal resources more coke formation. Their use requires a large steam to carbon ratio to limit coking. In cleanly and efficiently and to significantly reduce the amount of carbon dioxide addition to these problems, the Ni-based anodes also lose activity through sintering. released to the atmosphere. All of these processes deactivate the anodic reaction rates, cause low power densities, and increase operation costs due to large steam requirements. Thus, the development of 35-4 highly active and carbon and sulfur tolerant materials suitable for use as anodes is Coal-Based, Ultra-Clean, High Efficient Fuel Cell Hybrid Power Generation necessary to bring coal-gas fed SOFC systems closer to commercialization. Ongoing Kevin Litzinger, Siemens Power Generation, USA SOFC cathode research shows iron-based perovskite materials are developed as Brian Attwood, Ravi Srivastava, US Environmental Protection Agency, USA promising materials for use as SOFC cathodes between 500°C and 700°C. The Carl Singer, Arcadis, USA electrochemical activity and oxide ion mobility that make it such a great cathode material can also be harnessed for the oxidation reactions at the anode. The current Siemens Power Generation heads one of three teams engaged in development of ultra- research demonstrates the iron-based perovskite materials are stable in highly reducing clean, highly efficient, fuel cell/gas turbine hybrid power systems in coal-fired power conditions and possess catalytic activity for the direct oxidation of hydrogen and plants. Under the sponsorship of the U. S. Department of Energy s National Energy carbon monoxide in the desired temperature range. The effect of the increased lattice Technology Laboratory, the Fuel Cell Coal-Based Systems initiative targets systems oxygen mobility on the water requirements and the influence of hydrogen sulfide with a minimum plant thermal efficiency of 50% on a high heating value basis, greater concentration on the oxidation activity are discussed. Characterization using X-ray than 90% carbon dioxide capture, and zero emissions of criteria pollutants. diffraction, X-ray photoelectron spectroscopy, simultaneous thermogravimetric and The program extends work already underway in the Department of Energy s Solid differential scanning calorimetric analyses, and temperature-programmed techniques is State Energy Conversion Alliance (SECA) to hybrid fuel cell/turbine plants of greater performed to compliment the anodic oxidation results and correlate the bulk and than 100 MWe scale and operating on coal-based synthesized fuel. The program surface structure-activity relationships. further extends the SECA product cost goal of $400/kWe for the power island in an Integrated Gasified Fuel Cell (IGFC) power plant. The program culminates in system 35-3 demonstrations, at multi megawatt scale, in the FutureGen or other host generating Coal-Based Solid Oxide Fuel Cell Power Plant Development plant. This paper discusses alternative hybrid cycles under consideration, methods for Hossein Ghezel-Ayagh, Fuel Cell Energy, USA carbon dioxide separation, and development steps necessary for fuel cell operation on Jody Doyon, FuelCell Energy Inc., USA synthesized fuels. The paper also discusses test facilities and methodologies for preliminary bench scale verification of Solid Oxide Fuel Cell (SOFC) operation under FuelCell Energy (FCE) has recently been selected by the Department of Energy (DOE) pressurized conditions typical of the hybrid cycles. to initiate a multi-phase program for development of near zero-emission power plants that are very efficient in converting coal to electricity. The primary goal of the program 35-5 is the development of an affordable fuel cell based technology for utilization of The Effect of a Current Collection Layer Containing a Sulfur Tolerant synthesis gas (syngas) from a coal gasifier. One of the key objectives is development Material on the Operation of a PSOFC Utilizing Coal Derived of fuel cell technologies, fabrication processes, and manufacturing infrastructure and Syngas Containing H2S as Fuel capabilities for scale-up of Solid Oxide Fuel Cell (SOFC) stacks for large multi- Jason Trembly, David J. Bayless, Ohio University, USA megawatt base-load power generation plants. The other key objective is Randall S. Gemmen, NETL, USA implementation of an innovative system concept in design of a 100+ MW power plant with anticipated efficiencies approaching 60% of higher heating value (HHV) of coal. High temperature fuel cells, especially solid oxide fuel cells (SOFCs), represent a Combined with existing carbon dioxide separation technologies, the power plant is technology that may be used to more efficiently and cleanly produce both power and expected to achieve greater than 50% overall efficiency while emitting near-zero levels heat using fossil fuels such as coal. The primary problem with the use of coal syngas as of emissions of SOx, NOx, and greenhouse gases to the environment. a fuel source for the PSOFC is the degradation effect of H2S on the anode of the cell. FCE is a world leader in development and manufacture of high temperature fuel cell Traditional PSOFC anodes containing materials such as Ni and Cu sustain large power plants. The Company has developed carbonate fuel cell technology that involves performance losses when the fuel being used contains H2S. Although plans for future large fuel cell areas and 250 kW to MW power plant products. FCE has focused on IGCC power plants use gas clean up systems that will remove H2S below 1ppm, commercialization of its technologies for markets by offering system disturbances may still take place allowing higher concentration of the products of up to 2-MW in capacity. Over 40 commercial units have been installed contaminant to reach the electrochemical module thereby causing costly damage to the worldwide. FCE also heads a project team under the Department of Energy s Solid fuel cell. As a result, there exists an opportunity to investigate ways to introduce State Energy Conversion Alliance (SECA) initiative for development of 3-10 kW reliable passive methods for dealing with such real-world operational risks. To pursue SOFC power plants. FCE and its partner, Versa Power Systems (VPS), have developed this opportunity, we consider in this paper PSOFC anodes that are sulfur tolerant. A a highly efficient, high power density and cost effective anode-supported planar SOFC promising sulfur tolerant material that has recently been demonstrated is the perovskite technology that would form a basis for design of the large-scale hybrid SOFC/Turbine LSV (La0.7Sr0.3VO3). This material demonstrated the ability to oxidize H2S without power plants. VPS, a world-class developer of the solid oxide fuel cells, is developing incurring any significant cell performance degradation. Unfortunately the material can high power density and reliable SOFC cells and stacks. not readily oxidize H2 at the anode and has a low electrical conductivity when FCE s experience with operation of its fuel cells on coal gas dates back to 1992 with compared to traditional anode materials. Since coal syngas contains 30-50vol% H2, operation of a subscale fuel cell power module for over 4000 hours at the Louisiana LSV may not be used alone in an anode for efficient utilization of coal syngas. Since Gasification Technology Inc. site in Plaquemine, LA. Recently, a 2 MW power plant H2S strongly adsorbs onto LSV and the material shows the ability to oxidize the sulfur was designed and fabricated for operation with coal gas. The path forward for contaminant, it may be beneficial to use the material in the current collection layer of development of coal-based multi-MW power plants includes a multi-faceted approach the PSOFC anode and use a standard Ni-GDC interlayer to efficiently oxidize the fuel for both SOFC stack module design as well as development of a hybrid fuel cell/gas species of the syngas. This paper will present the preliminary results from research turbine system. The technical approach consists of an innovative fuel cell stack investigating the effect of PSOFC anode containing an LSV current collection layer on configuration, fabrication of scaled-up cells, newly developed fuel cell seals, novel the performance of the PSOFC utilizing a coal syngas mixture containing up to implementation of a fuel cell clustering concept, and integration of SOFC clusters with 160ppm H2S. a gas turbine. The future development plans include investigation of both fabrication and operational issues related to scale-up of the fuel cell active area to 900 cm2. A unique cell arrangement, C-plate, will extend the planar cell area further to 3600 cm2. SESSION 36 An innovative and patented power cycle will be utilized to achieve very high COAL PRODUCTION AND PREPARATION – 1 efficiencies by integration of the fuel cell with an indirectly heated gas turbine. The proposed system has the flexibility of using both the atmospheric as well as pressurized fuel cells. The eventual driver for the selection will be the cost and 36-1 efficiency of the system. The Efficacy of Dry Coal Cleaning for High-Density Separations The power plant design is projected to have a factory cost of $400/kW, based on a R. Q. Honaker, D. Patil, University of Kentucky, USA production capacity of about 1.4 GW/year or twelve 120 MW power plants per year. G.H. Luttrell, R. Bratton, Virginia Tech, USA This cost is very competitive with today s cost of combined cycle technologies. The basis for the factory cost estimate is a detailed material inventory and the results of a Maximizing the recovery of coal reserves and optimizing coal operations have been a recent cost breakdown analysis for a 40MW hybrid Direct FuelCell®/Turbine power focus of recent attention. Past practices in the western U.S. discarded the coal near the 31

top and floor of large surface mining operations rather than cleaning the material coal beds. Despite being an environmentally friendly source of energy, several issues through a preparation plant. In many situations in the eastern U.S., coal and associated need to be addressed in order to understand environment impacts during its rock are hauled over long distances to the preparation plant where the rock is separated exploitation. The present work was carried out to study the impact of developmental from the coal, hauled and disposed into a refuse area. In an effort to improve coal drilling in Jharia coalfields for extracting methane gas in coal beds. Baseline data on mining economics, an evaluation has been performed to determine the feasibility of different environmental components have been collected and analyzed. Based on the removing high-density rock from the coal using a dry, density-based technology at the site specific conditions and technology used for developmental drilling, environmental mine site. Using a 5 tph mobile unit, approximately 70% of the rock comprised in a impacts arising out of this activity have been predicted and an suitable environmental run-of-mine coal was removed while recovering nearly 100% of the coal. The ash management plan is drawn in order to mitigate the adverse impacts arising out of this content of the tailings stream was greater than 80% in many tests. The results obtained proposed activity. from on-site tests at western and eastern U.S. coal operations will be presented and discussed in the publication. 36-5 Optimization of the Distribution and Blending of Coal-Petroleum 36-2 Coke in a Thermal Power Stations Park How Vibratory Machines Can Improve Coal Handling & Processing Carmen Clemente, Carlos Funez, Universidad Politecnica de Madrid, SPAIN George D. Dumbaugh, Kinergy Corporation, USA The blending of imported coal of different origin with national Spanish coal and Reliably discharging and completely emptying Storage Bins that contain non-flowable petroleum coke is very common in thermal power stations, being the optimum coals, prompting large stock piles to flow even when drenched with rain or happen to determination of these blends the main objective of this research. Besides, the freeze, and unloading Unitrains in 4 hours by means of a large vibrator that becomes determination of the best blend takes implicit the distribution of imported coal among an integral part of the car, are significant improvements in Coal Handling. the power stations in study. This provides an important way of saving, because it For the coal being processed, the Vibrating Feeders, Conveyors, Screens for Scalping, allows to diminish the generation costs and to gain flexibility in the fuel, representing a Washing, Desliming, Dewatering, and Grade Sizing, plus the fluidized beds for Drying main objective to be considered in the investigation of the use of coal as a significant can be provided with a vibratory drive that has a high degree of “energy efficiency” power source of future. The applied optimization tool uses the method "Simplex", that reduces the power consumed, are ecologically friendly because of integrally “dust- creating a matrix of possible results and selecting the optimum solution. When the tight” enclosures, are electrically adjustable over a broad range to enable added restrictions prevail, the matrix of possible results diminishes. Several series of data is operating versatility, are no longer limited in width and length because the driving necessary to be introduced in the optimization tool: national coal, imported coal, fuel forces are better “distributed”, are started and stopped frequently without detriment to and coke prices (€/te); transport price of the imported coal to the generation groups the drive, and are Dynamically Counterbalanced for easier installation. (€/t); fuels characterization; available amount (t) of each fuel used in the optimization; To help make it a more viable fuel for firing a Boiler, a Vibrating Grate that burns premiums to the national coal consumption and plant operative restrictions (for ROM Coal has been developed for this purpose. example the number of mills in which imported coal can be introduced). The design engineering of these vibratory machines is very important. However, the Besides other data have been useful for the determination of the optimum mixture as installed “interface”, particularly at the inlet, and how the vibratory machine is being net specific consumption of the group (kcal/kWh), coal consumption in the period (kt), operated must also be taken into consideration. energy generated in the period (GWh) and the differential cost respect to the national When the engineering design factor is combined with the proper “interfacing” and the coal (M€). If an electrical company applied this methodology of calculation for the best method of operation, any one of these vibratory machines will inherently have the determination of the optimum blend (smaller cost of generation) during a year, taking a following attributes: conservative hypothesis for the improvement of the generation cost (1% for 1. The moisture content can markedly vary over a wide range. The wet, “sticky” improvement), the differential of costs awaited is approximately of 2 million euros. coal caused by the particles becoming very adhesive and cohesive have been The research has been carried out for the distribution of a ship of imported coal uniquely overcome. (Australian) of 150000 tons in three thermal power stations fed with national coal, 2. All the different kinds of coal can be handled. For example, the hard surfaced imported coal and petroleum coke. The imported coal consumption in the evaluated bituminous coals, the soft texture of low sulfur coals such as PRB, and even the power stations, has supposed an improvement in the net specific consumption, partially developed coals such as lignite. reduction of the maintenance costs and improvement of the availability. Also the 3. Abrasive wear can be minimized to where it appears to be practically eliminated. limitations in the capacity of equipment (primary air ventilators and mills) are reduced Particularly, by preventing impact abrasion. with the increase of the imported consumption of coal. There are differences for the 4. The reported productive availability is usually 98% or better. petroleum coke blended with national coal respect to the mixture of coke and imported 5. The initial cost is very competitive, plus the operating costs are reduced and so is coal. When f the coke is blended with national coal, the rate of shutdowns improves the maintenance expense. and the cost of maintenance of mills is reduced, in comparison with the feeding of the Much of this improved vibratory technology is already in productive use handling or 100% national coal. Nevertheless, when the coke is blended with imported coal, these processing coal in the areas surrounding western Pennsylvania, such as West Virginia, parameters get worse, and also the availability, the boiler yield and the emissions. western Maryland, Virginia, and eastern Kentucky. It has been verified that the proposed methodology works correctly, supposing its use The purpose of this paper is to explain why the chosen design of the vibratory machine an improvement in the management of the fuel, giving trustworthy results and must be combined with the appropriate “interface” and the proper “method of observing some differences among the fuel mixtures used in the power stations park operation” to effectively achieve some or all of these beneficial improvements. superior to the 5 % of the total cost of generation.

36-3 Picobubble Enhanced Column Flotation of Fine Coal SESSION 37 S. Yu, R. Honaker, D. Tao, B.K. Parekh, University of Kentucky, USA GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGY DEVELOPMENT – 2 Froth flotation is widely used in the coal industry to clean -28 mesh or -100 mesh fine coal. A successful recovery of particles by flotation depends on efficient particle- bubble collision and attachment with minimal subsequent particle detachment from 37-1 bubble. A fundamental analysis has shown that use of picobubbles can significantly Industrial Size Gasification for Syngas, SNG, Hydrogen and Small improve the flotation recovery of particles by increasing the probability of collision Power Production Using the BGL 1000 Gasifier Module and attachment and reducing the probability of detachment. An experimental study of Victor Shellhorse, Allied Syngas Corporation, USA column and mechanical flotation of fine coal has been conducted to study the effects of Jeffrey Hoffmann, US Department of Energy, USA picobubbles on flotation recovery, clean coal ash, and reagent consumption. Picobubbles were produced based on the hydrodynamic cavitation principle. Experimental results have shown that the use of picobubbles in flotation increased fine Industry is the largest and most diverse energy-consuming sector in the United States, coal recovery by 10-30%, depending on the feed rate, collector dosage, and other using over one-third of all the energy consumed. Most of the energy industry uses is flotation conditions. Picobubbles also acted as a secondary collector and reduced the supplied by natural gas and petroleum products, with electricity a distant third. Based collector dosage by one third to one half. on the 2002 EIA Manufacturing Energy Consumption Survey, industry consumed over 5.7 quads of natural gas and over 964,000 GW-hrs (3.3 quads) of electricity. About 36-4 134,000 GW-hrs of electricity was generated on-site by industry. With the current high Impact of CBM Development on Environment in Jharia Coal Field, India price of natural gas and the projected volatility in natural gas prices in years to come, P. Verma, H.V. Singh, S.R. Wate, S. Devotta, R.N. Singh, National Environmental industry benefits from an abundant, stable cost, reliable energy source. Coal has the Engineering Research Institute, INDIA potential of meeting this need through the use of efficient, industrial size gasification technologies. This paper explores the potential of the British Gas Lurgi (BGL) 1000 Coal Bed Methane (CBM) has emerged as a valuable energy source. Recently in India, fixed bed gasification technology to supply industry with clean fuel gas from coal exploration studies have been initiated to commercially exploit the methane trapped in economically and with virtually no increase in industrial plant air emissions. The 32

features of the BGL 1000 technology that make it particularly attractive for industrial carbonate loop – lime (CaO) / calcium carbonate (CaCO3) loop, integrate it with the application include: A single module producing about 1000 million Btu/hr of a clean gasification loop from Phase I, and ultimately demonstrate the feasibility of hydrogen synthetic fuel gas, a size applicable to a large number of industrial plants. Modular in production from the combined loops. design for small and medium size power applications in the 80 MWe to 250 MWe The main conclusion from Phase 1 and Phase 2 is that the PDU chemistry required for range. Capability of processing essentially all U.S. coals and many opportunity fuels the chemical looping process has been validated. The following processes were including Eastern bituminous, Western sub-bituminous, and lignite coals; petcoke, demonstrated and significant data was generated for each:

biomass, TDF, and other potential fuels whether non-caking or strongly caking, with • CaS – CaSO4 looping low or high ash fusion temperature, or having high sulfur, moisture, or mercury • CaCO3 – CaO looping content. Utilization of solid fuels in the ¼ to 2 size range, typical of as-received coals, • Water gas shift: CO + H2O to H2 +CO2 with minimal preparation (i.e. no drying, pulverizing or slurrying). Demonstrated high • Hydrogen production cold gas efficiency (88 to 92%) among the best of commercial gasification • Sorbent reactivation on line technologies, with low specific consumption of oxygen and steam. Designed for very • CO removal low environmental emissions practically no SO 2 x or particulate emissions; greater than • Char gasification 90% mercury removal; non-leachable slag; and environmental performance unaffected • Coal devolitilization by input quality. Economics were reevaluated based on the results of Phase II testing and were found to

still be valid. 37-2

Recent Developments in Modularized Air-Blown Coal Gasification 37-5 Systems for Industrial Applications Advanced Unmixed Combustion/Gasification: Potential Long Term Technology F. Denis d’Ambrosi, Robert G. Jackson, Econo-Power International Corporation, USA for Production of H and Electricity from Coal with CO Capture 2 2 Parag Kulkarni, Wei Wei, Raul Subia, Vladimir Zamansky, George Rizeq, Greg Coal gasification is receiving a significant amount of interest as the Energy Policy Act Gillette, Zhe Cui, Roger Shisler, Tom McNulty, GE Global Research, USA of 2005 takes effect. Most of the publicized attention is focused on relatively large scale applications for either power generation or for the production of syngas for use as With its abundant domestic supply, coal is one of the most secure, reliable, and a feedstock in the production of either liquid fuels or other chemical products. These affordable energy supplies for the U.S. Today, gasification of coal to produce applications typically are oxygen blown gasification with the attendant requirement to electricity is being commercially introduced as Integrated Gasification Combined include an air separation system in the overall plant design. Recent developments in Cycle (IGCC) power plants. The IGCC technology is well suited to better meet the two stage, fixed bed, air blown gasification systems make this approach very attractive needs for power generation from coal more cleanly than other conventional for smaller, industrial scale applications where the inclusion of an air separator plant technologies. It is also compatible with tomorrow s need for carbon sequestration and would drive operating costs to uneconomic levels. Two stage, fixed bed, air blown production of hydrogen fuel. Looking further into the future, GE along with gasifier plants can reliably and economically support fuel gas production requirements Department of Energy (DOE), is evaluating the feasibility of a novel gasification as low as 120 million BTU per hour. These plants typically include modularized technology called Unmixed Fuel Processing (UFP) of coal to achieve efficiency systems for removal and recovery of particulates, tars and oils and for the removal of advances in meeting the long-range hydrogen and electrical production needs from hydrogen sulfide (H2S). Additional equipment for removal of mercury (Hg) and for coal with CO capture. The evaluation is continuing. The presentation will include H S polishing can be included. Projects using this technology are currently under 2 2 fundamentals of UFP technology and a brief overview of research activities development for a variety of industrial applications including mining and cement kilns, undergoing at GE Global Research including economic and experimental (bench and industrial steam boilers, various types of dryers, glass furnaces and IGCC plants. pilot-scale) feasibility evaluation. This paper will discuss the design features of a modularized two stage, air blown In the UFP technology, coal, steam and air are simultaneously converted into separate gasification plant. The paper will also summarize the development status of the streams of (1) hydrogen-rich gas that can be utilized in fuel cells or turbines, (2) CO - industrial applications mentioned above. 2 rich gas that can be sent for sequestration and (3) high temperature/pressure vitiated air

to generate electricity in a gas turbine expander. While the technology challenges are 37-3 significant, UFP technology has the potential to eliminate the need for the air Chemical Looping Reforming Process for the Production of Hydrogen from Coal separation unit (ASU) using oxygen transfer material (OTM). The UFP technology L.S. Fan, Puneet Gupta, Luis G. Velazquez-Vargas, Fanxing Li, The Ohio State captures CO inherently at higher temperature and pressure using CO adsorbing University, USA 2 2 material (CAM) as compared to the conventional energy intensive low-temperature

CO capture processes. Further, as fuel and air are not mixed together and also because The Chemical Looping Reforming (CLR) process is described. It utilizes direct 2 of the lower gas turbine inlet temperature, the UFP process can potentially produce reduction of iron oxide particles with coal to form metallic iron liberating CO and 2 lower amounts of pollutants such as NO as compared to conventional combustion H O. After condensing the H O, a sequestrable CO stream is obtained. The reduced x 2 2 2 process. Thus the UFP technology offers the potential for reduced cost, increased iron is oxidized with steam in a second reactor producing hydrogen and regenerating process efficiency and lower emissions relative to conventional gasification and the iron oxide. The paper describes the technology in more detail including ASPEN combustion systems. simulations for heat integration and efficiency calculations. The CLR process is GE was awarded a contract from U.S. DOE NETL to evaluate the UFP technology capable of transforming close to 86% of the thermal energy of coal into hydrogen. and address its technical risks. Work on the Phase I program started in October 2000 Economic evaluation of the technology shows a production cost of $0.83/kg H which 2 and work on the Phase II effort started in April 2005. The Phase I R&D program is very competitive with respect to the $1.1/kg H as obtained from SMR of natural 2 established the chemical feasibility of the individual processes of the UFP technology gas. The environmental benefits, the high hydrogen production efficiency and through modeling, lab- and bench- scale testing. The Phase II effort focuses on three significantly lowered production costs put CLR technology at the forefront of high-risk areas: economics, sorbent attrition and lifetime, and product gas quality for emerging clean coal technologies. turbines. The economic analysis includes estimating the capital cost as well as the costs

of hydrogen and electricity for a full-scale UFP plant. These costs will be benchmarked 37-4 with IGCC polygen costs for plants of similar size. Sorbent attrition and lifetime are ALSTOM's Hybrid Combustion-Gasification Chemical being addressed via bench-scale experiments that monitor sorbent performance over Looping Technology Development - Phase II time and by assessing materials interactions at operating conditions. The product gas Herbert E. Andrus, Jr., Paul R. Thibeault, ALSTOM Power, Inc., USA from the third reactor (high-temperature vitiated air) will be evaluated experimentally Suresh C. Jain, DOE, USA in a pilot-scale unit to assess the concentration of particulates, pollutants and other

impurities relative to the specifications required for the gas turbine expander. ALSTOM Power Inc. (ALSTOM) has just completed Phase 2 of a multiphase program "This abstract was prepared with the support of the U.S. Department of Energy, under to developed entirely new, ultra-clean, low cost, high efficiency power plant for the award No. DE-FC26-00FT40974. However, any opinions, findings, conclusions, or global power market. This new power plant concept is based on a hybrid combustion- recommendations expressed herein are those of the authors and do not necessarily gasification process utilizing high temperature chemical and thermal looping reflect the views of the DOE". technology.

The chemical and thermal looping technology can be alternatively configured as 1) a

combustion-based steam power plant with CO2 capture, 2) a hybrid combustion- gasification process producing a syngas for gas turbines or fuel cells or 3) an integrated SESSION 38 hybrid combustion-gasification process producing hydrogen for gas turbines, fuel cells COAL CHEMISTRY, GEOSCIENCES AND RESOURCES: GEOSCIENCES

or other hydrogen based applications while also producing a separate stream of CO2 for use or sequestration. In its most advanced configuration this new concept offers the promise to become the technology link from today’s Rankine cycle steam power plants 38-1 to tomorrow’s energy plants. This paper covers the progress of recently completed A Review-Geology and Coal Resources of Mand Raigarh Phase II Work with the US DOE. The objective for Phase 2 was to develop the Coalfield, District Raigarh, Chhattisgarh D. R. Patel, Geology & Mining Regional Office Bilaqspur (C.G.), INDIA 33

The Mand-Raigarh coalfield (21° 45’ to 22° 42’ N and 83° 01’ to 83° 44’ E) is part of 38-4 the Ib River-Mand-Korba master basin lying within the Mahanadi grabens in A Feasibility Study of MicGAS Technology for in situ Chhattisgarh state. It shows a typical half-Grabens configuration with the southern Enhancement of Coal-Bed Methane boundary marked by major NW-SE trending faults coinciding with the trend of the Shaban Kotob, Daman Walia, Christopher O’Malley, ARCTECH, Inc., USA Mahanadi graben whereas the northern boundary is not faulted. In Mand-Raigarh coalfield, Gondwana sediments comprising of Talchir, Barakar, Presently over 10% of methane natural gas produced in the United States is from coal Barren Measure, Raniganj and Kamthi Formations, rest unconformable over the Pre- seams. Average gas content of coal seams is 50-500 scf per ton of coal in the Cambrian crystalline basement in the northeastern parts. The coal basin has a faulted Appalachian, Raton, San Juan, and Powder River coal seams. The lowest gas content is contact with Proterozoic Chhattisgarh rocks in the south and southwestern part. Inliers in the Powder River Basin. During the past 20 years of increased commercial activities of crystalline rocks are seen at several places. Total thickness of Barakar sediment in in these areas, the gas production is steadily declining in many of the wells. However, the northern part of Mand-Raigarh coalfield as reported by Kamara Guru et. al. (1980) with increasing energy prices, the demand for natural gas has substantially increased. is 706m to 840m while that in the Southern part of Chhal is estimated to be around Today the existing reserves of coal exceed 400 billion tons and almost 5.6 trillion tons 950m. of coal resources are estimated by the USGS at an unmineable depth. An in situ The rocks of Barakar Formation comprises of sandstone and shale interbanded with bioconversion of these vast resources of coal can become a source of large domestic carbonaceous shale and coal seams. Mand-Raigarh coalfield is mainly divided into supply of natural gas. Methane formation is an end product of anaerobic degradation of four major coal sectors viz Chhal, Dharamjaygarh, Kudumkela-Palma and Trans-mand organic matters including coal in the natural environment. To date biological sector. The coal measures lying between Kharsia and Dharamjaygarh exhibit a broad techniques for production of methane from coal have not been demonstrated on a large synclinal structure. The northern limb of the Mand River basin is exposed to the north scale. The objective of this research is to establish the feasibility of ARCTECH in the Sithra-Dharamjaygarh area where the Barakar beds are found to strike broadly in MicGASTM technology for in situ enhancement of methane generation in deep coal a NW-SE direction from the Talchir contact. In the south Limb, the strike is seams. The feasibility of this approach has been established by utilizing anaerobic approximately NW-SE with minor variations and the beds dip towards northwest. microbial consortia (Mic1) derived from the hind guts and soil eating termites to In all XII coal seems have been identified. The grade of coal seams is characterized by convert coals into methane and CO2. Laboratory tests were conducted with Powder non-cocking coal. The ultimate heat value of different coal seams ranges from 1186 River Basin sub-bituminous core coal samples under simulated subsurface conditions kcal/kg to around 6237 kcal/kg (dominantly power grade i.e. E to G). (saturation at 66% coal loading) by growing Mic1 culture (lysed or live) mixed with Geological Survey of India has estimated 19106.04 million tonnes of reserves in this media or laboratory simulated groundwater under anaerobic conditions at ambient coalfield as on 01-01-2006 in coal seams over 0.90 m thickness and up to a depth of temperature or 37°C. Bacterial count with Epifluorescence methods, pH 1200m from surface. This includes 1409.87 million tonnes proved, 15161.84 million measurements, volatile fatty acid content, gas composition and gas volume tonnes of indicated and 2534.33 million tonnes of inferred reserves. measurements were conducted periodically to evaluate methane generation from coal samples over 6 months. At ambient temperature, results indicated that gas was 38-2 generated at an estimated rate of 350 scf/ton of coal/year. However, at 37°C, gas was Genesis of Natural Coke and Its Industrial Utilisation produced at a higher rate of 900 scf/ton/year as compared to the positive and negative Ashok K. Singh, N.K Shukla, Mamta Sharma, S.K. Choudhury, B.N Roy, G. Ghose, S. controls. The microscopic observation confirmed the aforementioned results. Mic1 K. Srivastava, CFRI, INDIA culture grown in medium with core coal showed higher bacterial count with predominantly filamentous and rod shapes compared to Mic1 grown in groundwater Some Indian coalfields were intensely affected due to igneous intrusion in the and medium in the absence of coal. Validation tests were also conducted at simulated geological past. Dykes and sills of lamprophyre and dolerite have intruded the coal high pressure (300 psi) which also resulted in methane production. An anaerobic seams of different rank and type and have caused colossal wastage of the coal fermentation kinetic model based on the laboratory results predicted a production resources by converting it into natural coke and other products, rendering very meagre potential of 3-7 million scf/day from thick Powder River Basin coal seams. This paper marketability. There were series of episodes of volcanic activity during post will provide a rigorous test protocol for this feasibility study, laboratory tests, depositional phase of Gondwana period. As a result there were magmatic intrusions, procedures, and approach for commercial scale production. both concordant and discordant, in the coalfields of this period. Damodar valley coalfields expanding from Raniganj coalfield in the east to Daltanganj coalfield in the 38-5 west, witnessed two major volcanic episodes (Mid Jurassic & Cretaceous) and Preliminary and Post-Working Degassing for Effective and Safe Mining transformed huge amount of coking and non-coking coals into natural coke and char. Nina Kaledina, Valentina Malashkina, Moscow State Mining University, RUSSIA Coking coal during metaplast phase (300-500ºC) due to its viscous nature got intermixed with adjoining shale, sandstone and other rock fragments and produced Co-firing tests of sawdust and food industry residue with coal have been carried out at natural coke, while non coking coal, being non viscous, produced the chars of varying Skawina Power Plant in Poland (1532 MW fuel, currently belonging to CEZ Group). properties. Skawina Power Plant is a tangentially-fired pulverized coal unit with nine boilers (4 Natural cokes are characterised by high ash content (heterogeneous), high inert boilers of 210 and five boilers of 230 t/h live steam respectively) that produces 590 materials, strongly anisotropic, less reactive macerals and more electrically conductive MW electricity, 600 MW district heat and process steam. Skawina plant is equipped (less resistive). The studies carried out on different samples have indicated that the with coal ball mills, over-fire air (OFA) and electrostatic precipitators (ESP). The natural coke or jhama is characterised by moisture (as received) <2.5%, volatile matter paper presents the analysis of energy and ecological effects of biomass co-firing in (as received) <15.0%, hydrogen (as received) 3-4%, real density 1.6-1.9, resistivity both types of coal boilers. Coal and sawdust were blended in the coal yard, and the >80 milliohm centimetre, high crushing strength, low HGI, high AI. Organically, it is mixture was fed into the boiler through coal mills. Full scale co-firing trial tests were generally heterogeneous and composed of altered and unaltered maceral entities; carried out for two weeks during the February 2005. During the tests, sawdust several times the inertinites remain intact, while some times it occurs with alteration proportions of 10% and food industry residue of 6.5% (both mass basis) were into isotropic and anisotropic carbon forms/mosaics. The reactive constituents i.e. examined. The co-firing tests were successful. Basing on the analysis of the tests, the vitrinite and liptinite give rise to mosaics and flow structures with varying degrees of influence of biomass co-firing on the individual elements of energy balance (e.g. stack anisotropy with higher reflectance values. Other coals with higher volatile matter and losses and boiler thermal efficiency) was discussed comparing to combustion of coal hydrogen are categorised under heat affected coals. Keeping the above properties in alone. The emission indices during coal combustion were calculated and compared to view the natural coke samples have been recommended for use in different industries. the emission indices for biomass co-firing. It was shown, that biomass co-firing leads to decreasing of CO and SO2 emissions. Due to the possibility of considering a part of 38-3 energy generated during co-firing as renewable energy, the procedure for renewable Occurrence of Potentially Hazardous Elements in High Sulphur Nagaland Coal energy share calculation was presented and illustrated with an example. The B. P. Baruah, R.L. Goswamee, P.G. Rao, Regional Research Laboratory, INDIA experiences gained from the co-firing tests and the continuous co-firing of biomass since that time was used for developing the new co-firing concept. This concept The coal deposits of Nagaland, India belonging to tertiary age are similar in consists of a separate biofuel combustion system in a pre-furnace. By using this characteristics with other high sulphur coals of North Eastern region. The coals from system, it is possible to utilize many other kinds of biofuels in PC-boilers as well as Melak-Tzurang coalfield, Nagaland, India was found to contain low ash, high volatile increase the share of biofuels, compared to the simultaneous feed of biofuel and coal. matter and high sulphur (low pyritic and more than 90% organic sulphur). Here in this investigation, the presence of fifty-three elements of alkali, alkaline earth and transition metals including lanthanides were determined using Inductively Coupled SESSION 39 Plasma-Atomic Emission Spectrometer (ICP-AES). Sixteen elements (Be, K, Ag, Mn, MATERIALS, INSTRUMENTATION, AND CONTROLS – 1 Cr, Ca, Fe, Mg, Zn, Pb, Sb, Co, Cd, Ni, Cu, Al and Ti) were quantified, out of which eight (Be, Cd, Cr, Co, Mn, Ni, Pb, and Sb) of them were identified as Hazardous Air Pollutants (HAPs) as defined in the 1990 Clean Air Act Amendments (CAAA). XRD 39-1 and FTIR studies indicate the presence of minerals like quartz, pyrite, siderite, gypsum, Diffusion Coatings as Barriers against Corrosion for Gasifier Components rutile, hematite, kaolinite and illite in this coal. Distribution of major mineral phases in Ripudaman Malhotra, Gopala Krishnana, Esperanza Alvarez, Kai Lau, Jordi Perez- coal ash is also reported. Mariano, Angel Sanjurjo, SRI International, USA 34

Heat-exchangers, particle filters, turbines, and other components in integrated coal Promising materials from the laboratory tests were assembled on corrosion probes for testing gasification combined cycle system must withstand the highly sulfiding conditions of the in three utility boilers. Air-cooled, retractable corrosion probes were designed to maintain high-temperature coal gas over an extended period of time. The performance of components metal temperatures using multiple zones, representing USC superheat/reheat temperatures, degrades significantly with time unless expensive high alloy materials are used. Deposition ranging from 650°C (1200°F) to 870°C (1600°F). The probes were installed in utility of a suitable coating on a low-cost alloy may improve its resistance to such sulfidation boilers, equipped with low NOx burners, representing each of the three coal types. This paper attack, and decrease capital and operating costs. The alloys used in the gasifier service presents an update on the current status of this ongoing fireside corrosion advanced materials include austenitic and ferritic stainless steels, nickel-chromium-iron alloys, and expensive research program. nickel-cobalt alloys such as Inconel, Hastelloy and Haynes alloys. Not only are these materials expensive, their machining is also difficult, which makes fabrication of 39-4 components particularly costly. Carbon Molecular Sieve Membrane/Module and its Use for SG Solution's coal gasification power plant in Terre Haute, IN, uses ConocoPhillips' E-Gas Hydrogen Production for Coal technology. The need for corrosion-resistant coatings exists in two areas: (1) the tube sheet Paul Liu, Richard Ciora, Media & Process Technology, Inc., USA of a heat exchanger at ~1000°C that is immediately downstream of the gasifier, and (2) Theodore Tsotsis, University of Southern California, USA porous metal particulate filter at 370°C, which is downstream of the heat exchanger. These components operate at gas streams containing as much as 2% H2S. This corrosion is the Carbon, due to its inertness, is considered an ideal material candidate for handling leading cause of the unscheduled downtime at the plant and hence success in this project will coal-related process streams. Although carbon molecular sieve (CMS) materials have directly impact the plant availability and its operating costs. Coatings that are successfully been used extensively in industry as adsorbents, they have not moved beyond the developed for this application will find use in similar situation in other coal-fired power academic novelty stage as a membrane material. Two major application-related plants. A protective metal or ceramic coating that can resist sulfidation corrosion will extend barriers have prevented industrial acceptance of a CMS membrane, specifically, (i) the life-time of these components and reduce maintenance. poisoning and/or aging by a wide range of contaminants/impurities present in the SRI has developed a low-cost fluidized-bed-reactor chemical vapor deposition (FBR-CVD) atmosphere either during storage or in the stream to be treated and (ii) the lack of a technology to deposit coatings of various metals including Cr, Si, Ti, Al, B, Ni, W, and Mo module that is both cost and commercially/industrially acceptable, particularly for a on metals and ceramics. SRI s method for depositing corrosion-resistant coatings also has high temperature and high pressure applications. Media and Process Technology Inc. advantages over the commonly used techniques such as thermal or plasma spraying, which has overcome these two barriers by choosing appropriate operating conditions and produce coatings with internal porosity and microcracks, so that they must be thick to developing a CMS/ceramic composite membrane/module. One of the major prevent gas penetration to the substrate. The FBR-CVD technology allows (1) both internal application focuses for this CMS membrane/module is hydrogen/electricity co- and external surfaces to be coated, (2) diffusion bonding to the substrate, and (3) formation production from coal. By operating at an intermediate temperatures, i.e., 150 to 300°C, of a dense layer on the surface and increased corrosion protection of the substrate. our unique CMS membrane/module can function as a simple hydrogen separator or as We have successfully deposited coatings of Cr, Cr-Al, Ti, Ti-Al nitrides, and Si-Al nitrides a membrane reactor for water gas shift reaction. Hydrogen permeances of 1 to 3 2 on various steel samples, and tested them in simulated gasifier environments. Coatings on >3 m /m /hr/bar and H2/CO selectivities of 50 to >100 are typical in this operating low carbon steels in the 400 series was most effective as these samples showed minimal temperature range. Based upon the performance of the membrane and the features of corrosion under conditions where Inconel and other coated samples were badly corroded. the module, we have developed several process scenarios for hydrogen production Ferritic steels appear to be more suitable for diffusion barrier coatings than steels containing from coal. Process intensification as a result of the use of our membrane/module will Ni. Some of the coated samples have been placed in the SG Solutions gasifier plant in Terre be presented. Haute, IN, and we await their retrieval at the next scheduled maintenance. 39-5 39-2 FT-IR and XRD Study of Tirap Coal Oxidation of Alloys for Advanced Steam Turbines Binoy K. Saikia, R. K. Boruah, P K Gogoi, Tezpur University, INDIA Gordon Holcomb, Malgorzata Ziomek-Moroz, David E. Alman, NETL, USA Coal sample from Tirap colliery of Assam, India was studied using FTIR and XRD Ultra supercritical (USC) power plants offer the promise of higher efficiencies and methods. FTIR study shows the presence of aliphatic -CH, -CH2 and -CH3 groups, lower emissions. Current goals of the U.S. Department of Energy s Advanced Power aliphatic C-O-C stretching associated with -OH and -NH stretching vibrations and Systems Initiatives include power generation from coal at 60% efficiency, which HCC rocking (single and condensed rings). XRD pattern of the coal shows that it is requires steam temperatures of up to 760°C. This research examines the steam amorphous in nature. Function of Radial Distribution Analysis (FRDA) indicates that oxidation of alloys for use in USC systems, with emphasis placed on applications in coal is lignite in type and there is no evidence of graphite like structure. The first high- and intermediate-pressure turbines. maximum in the FRDA at R = 0.133 nm relates to the C = C bond (Type C – CH = CH – C), the second maximum at R = 0.25 nm relates to the distance between carbon 39-3 atoms of aliphatic chains that are located across one carbon atom. The curve intensity Experimental Evaluation for Fireside Corrosion Resistance of Advanced profiles obtained from FRDA show quite regular molecular packets for this coal. Materials for Ultra-Supercritical Coal-Fired Power Plants Horst Hack, Greg Stanko, Foster Wheeler North America Corp, USA SESSION 40 The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY – 2 co-sponsoring a project, managed by Energy Industries of Ohio (EIO), to evaluate candidate materials for coal-fired boilers operating under ultra-supercritical (USC) steam conditions. Power plants incorporating USC technology will deliver higher cycle efficiency, and lower 40-1 emissions of carbon dioxide (CO2) and other pollutants than current coal-fired plants. Recent Advances in Trace Metal Capture Using Micro and Nano-Scale Sorbents Turbine throttle steam conditions for USC boilers approach 732°C (1350°F), at 35 MPa Jason D. Monnell, Radisav D. Vidic, University of Pittsburgh, USA (5000 psi). The materials used in current boilers typically operate at temperatures below Dianchen Gang, West Virginia University Institute of Technology, USA 600°C (1112°F) and do not have the high-temperature strength and corrosion properties Andrew Karash, Evan J. Granite, DOE/NETL, USA required for USC operation. Materials that can meet the high temperature strength and corrosion requirements for the waterwalls and superheater/reheater sections of USC boilers The adsorption of mercury, arsenic, and selenium on micro and nano-scale sorbents is need to be tested and evaluated. reviewed. In particular, efforts on trace metal capture from coal-derived gas streams The focus of the current work is experimental evaluation of fireside corrosion resistance of using nano-scale sorbents are summarized. A collaborative effort between the candidate materials for use in USC boilers. These materials include high-strength ferritic University of Pittsburgh, WVU Tech, and NETL on the development of novel micro steels (SAVE12, P92, HCM12A), austenitic stainless steels (Super304H, 347HFG, HR3C), and nano-scale sorbents has been initiated with the preliminary results presented and high-nickel alloys (Haynes® 230, CCA617, INCONEL® 740, HR6W). Protective herein. Future research directions are suggested and an extensive list of references is coatings (weld overlays, diffusion coatings, laser claddings) that may be required to mitigate provided. corrosion were also evaluated. Corrosion resistance was evaluated under synthesized coal- ash and flue gas conditions typical of three North American coals, representing Eastern 40-2 (mid-sulfur bituminous), Mid-western (high-sulfur bituminous), and Western (low-sulfur Aqueous Mercury and Lead Removal with Activated Carbons sub-bituminous) coal types. Laboratory testing for waterwall materials was performed at Derived from High Sulfur Carbonaceous Materials 455°C (850°F), 525°C (975°F), and 595°C (1100°F). The superheat/reheat materials were Shitang Tong, Shuqing Zhang, Xiaoqing Wu, Wuhan University of Science and exposed to 650°C (1200°F), 705°C (1300°F), 760°C (1400°F), 815°C (1500°F), and 870°C Technology, CHINA (1600°F). Samples were exposed for 1000 hours, with ash being replenished every 100 Jenny Cai, Loraine Laiyin Chiu, Donald W. Kirk, Charles Q. Jia, University of hours to maintain aggressive conditions. Samples were evaluated for thickness loss and Toronto, CANADA subsurface penetration of the corrosive species. The laboratory testing was useful for screening different alloys in controlled environments, where the different variables of alloy Hg and Pb are of environmental concerns due to their toxic and bioaccumulative content, temperature, fuel/ash and sulfur in the flue gas could be evaluated. nature. Developing cost effective adsorbents for controlling their emissions to the 35

environment is of practical value. In this work, the adsorption of aqueous Hg2+ (200- 41-1 400 ppm) and Pb2+ (570 ppm) onto a series of activated carbons was investigated. The Overview of C2P2, the Industrial Resources Council, and activated carbons used were prepared from high sulfur coal or petroleum coke via the Green Highways Initiative chemical activation processes using alkaline materials such as KOH and its mixture David Goss, American Coal Ash Association, USA; Mark Bryant, AmerenEnergy, with other reagents. Activated carbons were analyzed for specific surface area, porous USA size distribution, total sulfur, as well as sulfur functional groups. The adsorption capacity was determined at controlled pH (5.0~6.0) and temperature (20-60°C) using The use of coal combustion products (CCPs) in a wide variety of applications allows ICP and AAS. The activated carbons had total sulfur contents from 0.16 to 20.14 wt%, for the use, reuse and recycling of nearly 50 million tons annually of these materials. and their specific surface areas varied from 47 to 2232 m2/g. A pseudo first order As new emission control systems are added to coal fueled power plants, there are new model was applied to describe the adsorption kinetics. Experimental data indicated that challenges facing producers and markets of CCPs. The formation of private and public the increase in sulfur content and specific surface area enlarged the adsorption rate and sector partnerships is having a positive impact on developing new markets for CCPs capacity for both Hg(II) and Pb(II). The type of sulfur in activated carbons was found and in increasing the awareness of the value of these products to potential end-users to be the most important factor in determining the effectiveness of adsorbing Hg(II) and specifiers. The Coal Combustion Products Partnership (C2P2), the Industrial and Pb(II). Resources Council and the Green Highways Initiative all are providing information and outreach to those whose decisions could increase the beneficial use of these 40-3 materials. This paper will provide an overview of these partnerships and the results of Novel Sorbents for Removal of Mercury from Flue Gas their efforts. Evan Granite, Albert A. Presto, DOE/NETL, USA 41-2 Numerous materials have been examined as sorbents for the capture of mercury in a Beneficial Land Application Uses of FGD Products lab-scale packed-bed reactor located at NETL. The sorbents examined include Warren Dick, David A. Kost, Liming Chen, The Ohio State University, USA activated carbons, Thief carbons, precious metals, fly ash, metal oxides, and metal sulfides. Simulated flue gases containing sulfur dioxide, nitrogen oxide, oxygen, Combustion of fossil fuels for energy production releases sulfur dioxide (SO2) at a rate carbon dioxide, elemental mercury, and nitrogen were contacted with the sorbents in proportional to the S concentration in the fuel. Industrialized nations have adopted flue the lab-scale packed-bed reactor. Several promising sorbent candidates have been gas desulfurization (FGD) technologies to reduce SO2 emissions. FGD technologies identified. The mechanisms of mercury capture are discussed. Future research on will generate increased amounts of product in the future as more utilities install sorbents will be conducted in a bench-scale packed-bed reactor employing both scrubbers for SO2 control. These FGD products raise economic and environmental simulated and real flue gas streams generated on-site at NETL. issues for which satisfactory solutions still need to be found. The type of coal and desulfurization process used influences the chemical composition and properties of an 40-4 FGD product. The properties of the FGD material have a direct impact on potential Impacts on Trace Metal Leaching from Fly Ash Due to the land application uses. FGD properties most commonly captured for beneficial purposes Co-Combustion of Switchgrass with Coal are (1) ability to neutralize acid, (2) high amounts of soluble calcium and sulfate, (3) Wayne Seames, Mandar Gadgil, Chunmei Wang, Joshua Fetsch, University of North source of plant nutrients, and (4) uniform particle size. Land application uses of FGD Dakota, USA materials are identified by matching the properties of the FGD material with improvement in some ecosystem function (or functions). For beneficial use, the change Biomass/coal blended fuel combustion is gaining popularity as a means to reduce in ecosystem function is assumed to be positive. FGD use must be considered in terms greenhouse gas emissions. The impact of co-combustion upon the solubility of trace of recommended application rates, environmental impact and economic return. metals contained in the various fly ash regimes has yet to be addressed. In this study, Beneficial land application implies the applied FGD material will improve the soil Blacksville coal/switch grass blended fuel is combusted in a 19kW laboratory (primarily) and also the total environment. Often, the intended benefit relates to plant combustor and sampled using a low pressure impactor. Leaching tests of the three growth, but there may be other benefits to soil or water such as reduction of erosion, particle regimes – submicron, fine fragmentation, and bulk ash – were performed. A improved quality of runoff and/or leachate water, or improved internal drainage. The modified TCLP-type leaching method was utilized with acidic, neutral, and basic application rate must be sufficient to cause soil improvement, but not so great as to solvents and the relative solubility of arsenic, selenium, and antimony were determined constitute disposal of the FGD material. Although there is recognition of the potential as a function of solvent and particle regime. The results were then compared to of using FGD materials in agriculture, there is also uncertainty whether this use is comparable results obtained from the combustion of Blacksville coal alone. The results sustainable. Currently, there is a general lack of acceptance in the agricultural suggest that co-combustion may have beneficial effects by lowering the solubility of community for using FGD materials. This barrier can only be overcome by research arsenic, antimony, and to a lesser extent selenium, contained on the surface of and sound knowledge that sometimes already exists in the scientific and technical submicron and fine fragmentation particles into acid and basic solutions. By contrast, literature. To promote use of FGD products, especially FGD gypsum, a national the potential to leach these trace elements from bulk ash collected in disposal piles network of agricultural demonstration and research sites has been established. Network increases. sites, strategically located in the United States, are available to producers, users and marketers of FGD products to provide places where observations can be made as to the 40-5 benefits of FGD product use under regional agricultural conditions. In addition, data on Effect of Hydrogen Chloride in Coal Combustion Flue Gas on the Mercury crop yields, environmental impacts and economic benefits will aid in the marketing of Removal Performance of Activated Carbon from Coal Combustion Flue Gas the FGD products. Toru Yamada, Yuki Yamaji, Eiji Sasaoka, Md. Azhar Uddin, Shengji Wu, Okayama University, JAPAN 41-3 On the Behavior of Coal Combustion By-Products (CCP) under In this study, the effect of HCl on the Hg0 removal performance for coal combustion Different Geotechnical and Geoenvironmental Stress Conditions flue gas system using activated carbons prepared from fly ash and pitch and activated Vincent (Tobi) Ogunro, Mutiu Ayoola, Hilary Inyang, Brian Anderson, John Daniels, carbon derived from coconut shell (a commercial sample) was investigated. Mercury University of North Carolina, USA (Hg0) removal capacity of fly ash-pitch activated carbon was higher than that of coconut shell activated carbon in the absence of HCl, however fly ash-pitch activated Environmental and economic concerns regarding management of coal combustion carbon showed lower mercury adsorption performance compared to the coconut shell products (referred to as Recycled Granular waste Media, RGWMs, in this study) have activated carbon in the presence of HCl. It is suggest that in the absence of HCl, led to several investigations into potential contaminant releases from RGWMs used as surface H2SO4 was produced by the adsorption of SO2, O2 and H2O on the activated substitute materials in construction of geotechnical and geoenvironmental 0 carbon which then reacted with Hg to produce HgSO4 and enhanced the mercury infrastructures. Most of these studies understandably have been focus on assessing the adsorption capacity of the activated carbons. The presence of HCl in the feed gas leaching potential of RGWMs. The results of these studies have provided only limited increased the Hg0 removal performance of the activated carbon sorbents many fold. data on the behavior of RGWMs compared with conventional construction materials. However, the presence of SO2 has an adverse effect on the adsorption capacity of the In order to provide further insight into the engineering behavior and leaching potentials activated carbons in the presence of HCl. of RGWMs especially under unusual stress conditions, series of drained and undrained triaxial compression tests are performed. It was observed that RGWMs exhibit significantly different behavior compared with sand subjected to the same stress SESSION 41 condition. This include significant volumetric contraction of specimen compacted at COAL UTILIZATION BY-PRODUCTS – 1 95% maximum unit weight, deviation from Rowe’s dilatancy theory and steady state concept, static liquefaction of medium dense specimen at low confining stresses, significant loading rate sensitivity and pseudo-viscoelastoplastic behavior within some strain rate regimes. Also, stress-dependent contaminant releases from fresh and aged RGWM are being investigated.

36

41-4 performance of all different types of density based separators, including heavy medium Using Fly Ash-Based Foundry Composition for Molds and vessel, jig, heavy medium cyclone, water only cyclone, spiral etc. This model will be Cores (FASAND) to Pour Iron Castings discussed in comparison to the actual data collected from the aforementioned density Robert Purgert, Energy Industries of Ohio, USA; Andrzej Baliski, Pawel Darlak, Jerzy separators operating in three different coal preparation plants. Sobczak, Foundry Research Institute, POLAND 42-3 The study discusses the results of experiments and trials concerning application of fly Development of Chemical Inhibitors Using Differential Scanning Calorimeter ash as a base material of foundry sands (FASAND mixture) to produce iron castings Equipment for Controlling Spontaneous Heating/Fire in Coal Mines for automotive industry. Two types of fly ashes were examined: the fly ash from R.V.K. Singh, G. Sural, V.K. Singh, Central Mining Research Institute, INDIA Eastlake Plant (USA) and, for comparison, the fly ash from Skawina Power Plant. For these fly ashes detailed investigation was made as regards chemical composition, phase The problem of spontaneous heating/fire is very much serious in Indian coal mines. constitution, density distribution of individual fractions, toxicity, and thermal Due to fire in coal mines, huse quantity of national property like coal is being lost and characteristics. After initial selection of binding systems, the technological properties environment is badly affected due to release of noxious gases. Under this of the FASAND type mixtures were tested. Using the three selected chemical circumstances, chemical inhibitors has played very important role in controlling fire. compositions and fabrication methods, under the local conditions of Energy Industries After carrying out literature survey work, different chemical inhibitors have been of Ohio and Foundry Research Institute - Krakow, some trials were conducted on identified and analysed in Differential Scanning Calorimeter (DSC) equipment. casting the grey and ductile irons, using cores assigned for production of castings for Different proportions of the inhibitors have been analysed in DSC equipment to the automotive industry and the conventional sand casting technology. The ready determine their endothermicity (heat absorbing capacity) at different temperature. castings were subjected to macroscopic examinations to check the surface condition Chemicals like boric acid, di-ammonium phosphate, urea, sodium silicate, sodium and gas content. It has been stated that further work on practical application of chloride has mixed in different proportion and analysed in the DSC equipment. After FASAND mixtures in pouring iron castings should focus on searching for other types that some of the suitable composition has been applied in coal mines to control the of fly ash, characterized by higher thermal characteristics, and on search for other surface as well as overburden dump fire. The objective of this paper is to describe means to improve the permeability of the ready mixtures by raising their open porosity. about the application of chemical inhibitors for controlling spontaneous heating/fire in coal mines. 41-5 42-4 Legal, Ecological and Technological Aspects of the Mass Production of Analysis of the Migrating Laws of Methane in the Mining- Lightweight Concretes Based on High Volume of Coal Ashes Induced Fracture Zones in Overburden Strata Mark Nisnevich, Gregory Sirotin, Tuvia Schlesinger, The College of Judea and Li Shugang, Lin Haifei, Cheng Lianhua, Li Xiaobin, Xi’an University of Science & Samaria, ISRAEL Technology, P.R. CHINA

In an earlier publication in the framework of the 22nd Annual International Pittsburgh In most Chinese coal mines, the inherent permeability coefficient and methane Coal Conference we reported the preliminary results of a R&D program related to the pressure in coal seams are so low that the degasification is more inefficient compare development of a technology for the combined utilization of bottom ash, fly ash and a with other countries. So, first of all, the released methane in the mining induced by-product of stone quarries (unprocessed crushed sand) for the manufacture of fractures should be degassed. It is necessary to study the methane migrating laws in ecologically friendly lightweight concrete with desirable building characteristics. mining-induced fracture zones through research on the storage characteristic of coal In the recent months we made progress in the further development of this technology. bed methane in China. Based on the results of physical modeling and field monitoring, Our efforts are concentrated on the solution of problems related the mass production of the shape of the mining induced fracture zone over the long wall gob can be the ternary lightweight concrete. Special attention has been given to the study of represented by a 3-D elliptic paraboloid function, called the Elliptic Paraboloid Zone. radiological characteristics of coal ashes from different sources and lowering the The coupling mathematical model of the methane delivery law is applied in the mining activity concentrations of radionuclides in the lightweight concrete based on coal fissure Elliptic Paraboloid Zone and the migrating laws of methane is obtained. The ashes. The results of our theoretical and experimental studies will be reported. mining fissure Elliptic Paraboloid Zone is the delivery and collection zone of relieved methane, which is verified by the results of a long wall gob degasification tests at a coal mine of Yangquan in China. This study provides a reasonably basis for designing SESSION 42 the gob-well degasification system for long wall mining operations. COAL PRODUCTION AND PREPARATION – 2 42-5 Simulation Material Experiment Research on the Coupling of 42-1 Seepage Field and Stress Field in Underground Mining Efficiency and Productivity Analysis of Coal Mines Zhang Jie, Hou Zhong Jie, Xi’an University of Science & Technology, P.R. CHINA Subhash C. Sharma, M.K. Mohanty, J. Hirschi, P. Melvin, H. Patil, Southern Illinois University, USA It is important to take solid-liquid coupling simulation material experiment in the research on the coupling of seepage field and stress field in the underground mining. It The technical efficiency of twelve underground coal mines in Illinois is estimated for is difficult to find the suitable coupling simulation material. So the great progress has the period 1989 to 2003 and some factors contributing to inefficiencies at these mines not been made for a long-term. Based on large number of tests, paraffin wax is chosen have been identified in this study by using the stochastic production frontier model. as the cementing material of coupling simulation material model. At the same time, the Next, the output growth is decomposed into its three components: growth due to change law of model physics mechanics parameters has been drawn with different change in technical efficiency, growth due to technological progress, and growth due simulation material’s rate. Shen-Fu mining area coal is in the north of china which is to change in inputs. The overall average technical/productive efficiency of all the covered with rock and water. The mining model is made on the base of the research of mines considered in this study is 69%. There is a clear distinction among the mines. solid-liquid coupling simulation material. Through the simulation material experiment, Three mines are around 80% technically efficient. Four mines are in the 69% to 76% the law of water seepage in destructed rock and the law of rock destructed in seepage efficiency range. The other five mines are in the 50% to 65% range. Besides the field are drawn. The reasonable face advancing distance in water resources amount of labor and capital used in production, other factors which have contributed to preservation mining is gained. It proved that the result of simulation material inefficiency are depth to the coal seam, injury frequency rate and age of the mine. The experiment is consistency with the field through observation. So the research is output growth of these twelve mines was negative between 1991/1992; 1996/1997; important to guide reasonable planning-exploitation of the water resources 2000/2001; 2001/2002 and 2002/2003 and positive the remainder of the time. Negative preservation mining. The success of this experiment provides a new way to research on growth periods were due to negative growth in inputs and negative changes in the coupling of seepage field and stress field. technical efficiencies. Our results reveal that the rate of technological progress has been decreasing throughout the period of study. SESSION 43 42-2 GASIFICATION TECHNOLOGIES: A Unified Model to Characterize the Performance of Density Separators ADVANCED TECHNOLOGY DEVELOPMENT – 3 Manoj K. Mohanty, Pramod K. Sahu, Vishal Gupta, Southern Illinois University, USA

Coal preparation plants clean nearly 90% of the run-of-mine coal using some form of 43-1 density based separators, which are characterized by their partition models. A variety Oxygen Carrier Development for Chemical Looping Combustion of of these models are available, some of which are more suitable for heavy medium Coal Derived Synthesis Gas based separators, whereas some others are better suited for water-based gravity Ranjani Siriwardane, James Poston, DOE/NETL, USA separators. After evaluating many of these available models, a modified log-logistic Karuna Chaudhari, Anthony Zinn, Thomas Simonyi, Clark Robinson, Research model has been developed in this study that is equally suitable for characterizing the Development Solutions, USA 37

In the present work, NETL researchers have studied chemical looping combustion catalyst recovery tests. Three types of laboratory gasifiers have been developed. These (CLC) with an oxygen carrier NiO/bentonite (60 wt.% NiO) for the IGCC systems gasifiers were used to screen catalysts systems, and process variables. Catalyst utilizing simulated synthesis gas. Multi cycle CLC was conducted with NiO/Bentonite recovery screening was conducted in a Soxhlet extractor. The results demonstrate that in TGA at atmospheric pressure and in a high pressure reactor in a temperature range coal can be converted to methane at temperatures as low as 500°C within reasonable between 700- 900°C. Global reaction rates of reduction and oxidation as a function of reaction times of less than 1 hour and as short as 15 minutes. The optimum catalyst conversion were calculated for all oxidation-reduction cycles utilizing the TGA data. system utilized thus far, consists of two catalyst. One catalyst apparently activates a The effect of particle size of the oxygen carrier on CLC was studied for the size second catalyst to accomplish very rapid low temperature conversion of the coal. There between 20-200 mesh. The multi cycle CLC tests conducted in a high pressure packed are many advantageous to the low temperature operation, They include lower steam bed flow reactor indicated constant total production of CO2 from fuel gas at 800°C and requirements, decrease gas separation costs, less catalyst tie-up with mineral 900°C and full consumption of hydrogen during the reaction. constituents, higher catalyst recovery, smaller boiler requirements, higher methane concentration in the product gases, and less gas recycle. Basic thermodynamics will be 43-2 discussed. The paper will report results from batch, high pressure mini-gasifiers, semi from Coal Co-Production Project - A Status Report continuous, high pressure, mini fluid bed gasifier, and a differential bed gasifier. John Ruby, Sheldon Kramer, Nexant, Inc., USA Future development plans will be discussed. Raymond Hobbs, Arizona Public Services, USA Bruce Bryan, Gas Technology Institute, USA 43-5 A Novel Catalytic Coal Gasification Process to Produce SNG The US DOE National Energy Technology Laboratory awarded four co-production Francis Lau, GreatPoint Energy, USA projects in December 2005. This paper presents the status and early results from the project sponsored by Arizona Public Service Company (APS). The 3-year project will GreatPoint Energy is commercializing a novel catalytic process for converting coal research and develop a hydrogasification process to co-produce substitute natural gas (and other carbon-based feedstocks) into high value clean substitute natural gas (SNG). (SNG) and electricity from western coals. The proposed system uses hydrogen instead Coal is available in abundance in the United States and will ensure a secure and an of air or oxygen in the gasification process, an approach that offers higher operating affordable fuel for many generations. GreatPoint converts this low cost, but dirty efficiencies, lower water consumption, and a gas product that is richer in methane than feedstock into the cleanest of all commercially viable fuels. GreatPoint s substitute other gasification processes. The concept has the potential to produce SNG below the natural gas product, called bluegasTM, meets pipeline quality gas requirements, and is projected market price for natural gas. It will separate a carbon dioxide stream ready transported by standard natural gas pipeline. Production can be centralized in close for sequestration. In the first year the project will focus on concept design and proximity to the coal mine, where over half of the carbon (in the form of CO2) can be laboratory tests; the overall objective will be to field test the hydrogasification SNG sequestered. GreatPoint Energy intends to build, own, and operate bluegasTM concept at one of the APS power stations. production facilities and sell bluegasTM to regional distributors and customers in the power generation, industrial, heating and chemical sectors. The company s technology 43-3 is based on the discovery that coal mixed with mixtures of alkali metal catalysts Co-Production of Substitute Natural Gas and Electricity via promotes coal gasification reactions including methanation at mild conditions, around Catalytic Coal Gasification 500 to 700°C. Research into this finding has a led to a one-reactor system which offers Brian S. Turk, Raghubir Gupta, RTI International, USA an efficient and cost-effective route to produce low cost methane from coal. The objective of this paper is to describe the bluegasTM process, the status of the Although coal is well known to be the most abundant fossil fuel available on this technology, and areas of new process development. planet, its reputation as a fuel is tarnished by its inconvenient solid form, complexity for converting into useful energy and work, pollution, and a negative public image that discourages coal use. In a recently funded DOE project, RTI plans to develop key SESSION 44 technologies to convert coal into two more desirable energy forms, namely substitute COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES: natural gas and electricity. RTI’s technology platform is based on extensive research MINERAL MATTER, COAL ASH, COAL COMBUSTION performed by Exxon in the 1970’s for substitute natural gas (SNG) production via catalytic gasification. Unfortunately, this process was not economically viable because an extensive recovery process was necessary to recover the active catalyst from the ash 44-1 to mix with the coal feed, the active catalyst and ash reacted at the operating conditions Characterization of Source Rocks Producing Respirable Quartz and inhibiting effective catalyst recovery, and cryogenic separation was used to separate an Aluminosilicate Dust in Underground US Coal Mines SNG product and a hydrogen and carbon monoxide recycle stream. RTI has adapted a Steven Schatzel, NIOSH, PRL, USA number of newer and novel technologies to overcome these problems and simultaneously achieve near zero emissions, produce a high pressure CO2 product and A research effort has been undertaken at the Pittsburgh Research Laboratory (PRL) of co-produce electricity. In the proposed process, the active catalyst material is loaded on the National Institute of Occupational Safety and Health (NIOSH) to characterize the a support material and remains fixed in a catalytic reactor. The coal is initially source material producing respirable quartz and aluminosilicate dust in coal mines. preprocessed to convert the coal into a mixture of gas phase carbon species, H2 and Mine regulatory personnel suggested that problematic silicate mineral dust solid char fines prior to the catalytic reactor. In the catalytic reactor, the catalyst concentrations were known in some coal mines operating in southern West Virginia, promotes the conversion of the gas phase carbon species and H2 into CH4. Because the Virginia and eastern Kentucky. Six mines were selected in this region for rock and dust ash is trapped in the solid char fines and the catalyst on a support, physical contact sampling by PRL researchers based on elevated quartz concentrations in historical dust between the ash and catalyst is impossible eliminating the potential for reaction. The samples. Four of the coal mines sampled produced elevated respirable quartz dust product gas mixture from the catalytic reactor is cleaned using the hot gas concentrations on active production sections during sampling, the other two mines desulfurization and CO2 capture technologies that have been developed at RTI. The produced about 5% quartz, the regulatory reduced standard limit for quartz. Prior product from the CO2 capture process is a high pressure sequestration ready CO2 research has suggested that the source of respirable silicate dust in underground coal byproduct. More conventional ammonia and methanation processes will be used to mines is typically immediate roof or floor lithology, not mineral matter bound within polish the final SNG to meet pipeline specifications. Finally, the carbon trapped in the the mined coalbed. At some of the sites included in this research there were only char fines is combusted in a pressurized fluid-bed combustor to generate steam and potential quartz source rocks in either the floor or the roof units. At other sites sampled electricity. This presentation will describe the available results from the bench-scale during the study, potential quartz sources existed in both the roof and floor lithologies. testing program for evaluating the technical and economic feasibility of the proposed In the later cases, elemental data have suggested the enrichment of certain cations in process. the roof lithologies compared to floor rock may have the potential to distinguish potential quartz and aluminosilicate sources produced in respirable dust samples. 43-4 Research results from Pennsylvanian-age coalbeds in western Pennsylvania surface Fundamentals of an Optimized Catalyst Gasification System mine sites has suggested the clastically derived mineral matter in the immediate roof Edwin Hippo, Raman Mahato, James May, Narcrisha Norman, Even Odell, Southern rock, coal-bound mineral matter and the immediate floor lithology are derived from a Illinois University, USA common source material. Some of the enrichment of certain cation species in the roof Aarron Mandell, GreatPoint Energy, USA units (i.e., Ca, Fe, Mg, Na) compared to immediate floor rock may be related to the percolation of fluids through the overburden and diminished probability for fluids to GreatPoint Energy has begun the development of a catalytic gasification process. This migrate effectively through the coal or coal precursor and into the floor units. process is aimed at operating at lower gasification temperatures than processes Comparisons of the elemental composition of dust cassette mineral matter and possible previously developed. In conjunction with GreatPoint Energy, The Department of source rocks have shown that the dust composition is not identical to any of the Mechanical Engineering and Energy Processes at Southern Illinois University at sampled potential sources rocks. It is considered likely that the mining process, Carbondale has initiate fundamental studies to determine the feasibility of converting including rock breakage and the entrainment of dust particles in the ventilation air coal into methane while keeping processing temperatures below 700°C. These studies stream have modified the dust composition from the starting parent materials. have included basic thermodynamics, laboratory scale gasification tests and laboratory However, normalizing the data has shown promise in distinguishing potential source 38

rocks using elemental ratios. Data from the single quartz rock sources sites have been previous study based on metal and sulfide geochemistry for the same plant. The fly ash used to assess the viability of the methodology. The elemental data suggests roof strata has a more enriched *34S than the pulverized coal and, in general, the 34S is more as the primary source of mineral-generated respirable dust produced during mining and enriched in fly ashes collected at cooler points in the ash-collection system. This captured by the dust samplers on the cassettes. This finding is contrast to the quartz pattern of 34S suggests an increased isotopic fractionation due to temperature, with the dust sources identified in the field and by x ray diffraction analysis of roof and floor fly ash becoming progressively depleted in 34S and the flue gas sulfur-containing rock where at least one site showed the primary silicate dust source to be in the floor. components becoming progressively enriched in 34S with increasing temperatures. The suite of x ray fluorescence sample data suggests a strong relationship between the Substantially less variation is seen in the C isotopes compared to S isotopes. There is overall amount of Si and the quantity of quartz in the samples. A similar relationship little vertical variation in 13C in the coal bed, with 13C becoming slightly heavier was not found in the parent source rocks. These findings may be significant since the towards the top of the coal seam. An 83 to 93% loss of solid phase carbon occurs potential severity of the silicosis risk to miners is strongly influenced by both the during coal combustion in the transition from coal to ash owing to loss of CO2. Despite quantity of quartz and the clay minerals in the respirable dust fraction. the significant difference in total carbon content only a small enrichment of 0.44 to 0.67 in 13C in the ash relative to the coal is observed, demonstrating that redistribution 44-2 of C isotopes in the boiler and convective passes prior to the arrival of the fly ash in the Studies on Abrasive Propensity of Thermal Coals of India: Effect ash-collection system is minor. of Ash and Quartz Contents Anup Kumar Bandopadhyay, Rajatmay Chatterjee, Central Fuel Research Institute, 44-4 INDIA A Measurement technique for Coal Ash Emissivity in High Temperature Atmospheres A suite of 50 thermal coals from various coalfields of India, viz. Eastern Coalfield Ltd, Miki Shimogori, Hidehisa Yoshizako, Yoshio Shimogori, Babcock-Hitachi.K.Kure Western Coalfield Ltd, Northern Coalfields Ltd and Talcher Coalfields Ltd, used as fuel in Laboratory, JAPAN major thermal power stations,Viz. Farakka Super Thermal Power Project (STPP), Talcher STPP, Talcher TPP, Kahalgaon TPP, Unchahar TPP, Vindyachal STPP, Singarauli STPP, The purpose of our work is to examine the characteristics of coal ash emissivitiy to Rihand STPP, Dadri STPP. Rihand STPP, Majia TPP, Tanda TPP and NSTCL PP, in recent better understand the heat transfer mechanism through ash deposits on tubes in coal- times has been systemically characterized for the first time for the purpose of assessing fired boilers. This paper presents a method for determining coal ash emissivity in high abrasive propensity in terms of their ash and quartz contents. Abrasive propensity of all the temperature atmospheres and the influence of the ash surface temperature on its coals has been determined according to the procedure given in IS: 9949-1986, while the emissivity. Emissivity was determined by comparing theoretical radiation intensities quartz content in each coal has been determine using Fourier Transform Infra for with measurements obtained by a shield tube emissometer. An ash sample was heated quantitative analysis of quartz in minerals. Thermal coal in India is of drift origin and as in an electric furnace during the measurement and the radiation intensity from the such, the mineral contents are high in them. Coals fed to thermal power stations have been sample was measured with a digital pyrometer. Emissivity characteristics of Powder found to contain 30-60% ash and quartz in them varies between 5 and 20% graph plotted River Basin (PRB) coal ash and bituminous coal ash were examined. The main results between quartz and ash contents of the coals shows, statistically, % quartz = 0.25x % Ash, are as follows: (1) Emissivity of deposited ash increases with an increase in deposit i.e., quartz makes one-fourth of the ash. There are poor correlations between abrasion index surface temperature. (2) The emissivity of a sample having fused surface exceeds 0.9. and ash content and between abrasion index and quartz content as suggested by the large (3) PRB deposits have lower emissivities compared with bituminous deposits in the scatter in respective graph with correlation coefficient of 0,56 and 0.31 respectively. range of the surface temperature from 600°C to 1100°C. The commonly occurring minerals found in thermal coal are: kolinite, illite, montmorrilonite and quartz with smaller amounts of carbonate species, pyrite and feldspar. Quartz and pyrite 44-5 are the harder materials present in coal with hardness of 7.0 and 6.5 on Mohs’ scale A Theoretical Study of the Kinetics of Selected Arsenic and Selenium respectively, but as pyrite is present in small amounts, only about 1% of the weight of the Reactions in Coal Combustion Flue Gases coal, its contribution towards abrasive propensity is insignificant compared to that of quartz. Jennifer Wilcox, David Urban, Worcester Polytechnic Institute, USA Quartz is found to occur as rounded and angularly shaped particles of various sizes in coal. Although both size and shape contribute to wear, angular particles are more abrading than As environmental regulations pertaining to mercury are becoming much stricter, other the rounded ones. Poor correlations between abrasion index and quartz to the factors not trace metals, particularly arsenic and selenium, are beginning to be examined as well. being given due consideration. A noted source of compounds containing these elements is coal combustion flue gases The correlation between abrasion index and ash content is, however, found to improve when and, as such, the mechanism(s) of their removal is a topic of much attention. Given that thermal coals are bifurcated into two groups: one with quartz/ash ratio less 0.25 and the other any removal strategy will be dependent upon the speciation, and the speciation in turn greater than 0.25. For the two groups respectively abrasion index (AI) is given by the will be dependent upon the reaction kinetics of the flue gas, determination of the following empirical relations: kinetic parameters of reactions involving these metals is key to developing effective AI = 1.12* Ash + 0.71 (R2 = 0.85) removal techniques. Previous experimental work has been performed to determine the and AI = 1.28* Ash + 6.90 ( R2 = 0.64) speciation for a variety of conditions, however the nature of many of the compounds The factor of 0.25 chosen for bifurcation has been taken from scatter diagram between the created as a result of the combustion process makes them undetectable to current variables. This seems to be plausible as for most of thermal coals the ratio is <0.25 and the experimental techniques. To develop a more complete understanding of the overall AI is given by the first relation above. For coals with the ratio >0.25, the chances for getting speciation it is thus necessary to determine the importance of these compounds. To adventitious quartz from mining operations are higher. Quartz particles from extraneous accomplish this, computational chemistry techniques are employed to determine the sources are characterized by their higher angularity and as such, abrasion of coal containing kinetic parameters of the elementary reactions taking place within the combustion flue these particles over and above the inherent ones is higher. gas environment. The initial phases of the overall project will be presented; namely, The study also shows that there is very poor correlation between AI and HGI. Although HGI the theoretical computations and the development of kinetic rate expressions for a is a technical design parameter and has assumed commercial importance because of its use selection of arsenic and selenium reactions. Additionally, the methodology used for the in coal contract specification, presence of quartz in coal dictates the performance and life calculations will also be discussed. time of a mill. Notwithstanding the limitations, the equations proposed are instrumental in preliminary assessment of abrasive propensity of Indian coals required for maintenance schedules of power plant machinery. SESSION 45 MATERIALS, INSTRUMENTATION, AND CONTROLS – 2 44-3 Sulfur and Carbon Isotope Geochemistry of Coal and Derived Coal Combustion By-Products: An Example From an Eastern Kentucky Mine and Power Plant 45-1 James C. Hower, Ana M. Carmo, Tao Sun, Sarah M. Mardon, University of Kentucky, Co-Coking of Hydrotreated Decant Oil/Coal Blends in a Laboratory Scale USA Coking Unit: Product Distribution of Distillates Erika R. Elswick, Indiana University, USA Omer Gul, Leslie R. Rudnick, Amy Scalise, Harold H. Schobert, Caroline Burgess Clifford, The Pennsylvania State University, USA The isotopic compositions of sulfur (*34S) and carbon (*13C) were determined for the coal utilized by a power plant and for the fly ash produced as a by-product of the coal Delayed coking, used in petroleum refineries throughout the world, is a process that combustion in a 220-MW utility boiler. The coal samples analyzed represent different converts heavy petroleum residua (vacuum residua and decant oil) into light distillate lithologies within a single mine, the coal supplied to the power plant, the pulverized fraction and coke. This is achieved by the pyrolysis and thermal degradation of the feed coal, and the coal rejected by the pulverizer. The ash was collected at various feedstock in a semi-continuous process, at temperatures between 450-500°C, in an 34 stages of the ash-collection system in the plant. There is a notable enrichment in S inert atmosphere, and at pressures around 10 psig. A pilot-scale delayed coker at The from the base to the top of the coal seam in the mine, with much of the variation due to Energy Institute at The Pennsylvania State University is used to provide reliable 34 34 an upwards enrichment in the S values of pyrite. Variations in S and in the amount continuous delayed coking for 4-6 hours to provide acceptable quantities of liquids and of pyritic S in the coal delivered to the plant show that there was a change of source of cokes for the further evaluation. The unit is capable of operating under most delayed coal supplied to the plant, between week one and week two of monitoring, supporting a coking process conditions. The system pressure, temperature and flow rates are 39 monitored by a number of computer-controlled devices, and data from these devices is 45-5 recorded throughout the run. In the present paper, we describe the coking and co- Thermal Stability of Mercury Adsorbed on Sulphur-Containing coking of decant oil and decant oil/coal blends using a pilot-scale delayed coker. Activated Carbon Prepared from Petroleum Coke Decant oil was hydrotreated at several levels of severity for use in the coking/co- Irina Bylina, Charles Q. Jia, University of Toronto, CANADA coking work. The feedstock of the first control experiment contained only decant oil. Shitang Tong, Wuhan University Department of Science and Technology, CHINA The subsequent co-coking experiments used feedstocks in an 80:20 ratio of hydrotreated decant oil to coal. A typical product distribution for a delayed coking The hazards associated with mercury exposure have prompted a tightening of operation is 70% liquids, 20% coke and 10% gas. The boiling point distribution of the regulations governing mercury emissions from utility coal boilers. Accordingly, liquid products was determined using vacuum distillation and simulated distillation. advancements are needed not only in clean-up and control technologies, but also in the ASTM 2887 method was used for the simulated distillation analyses. The results from monitoring of mercury emissions. To meet the need for a real-time, speciating mercury vacuum distillation and simulated distillation reveal that the percentage of the liquid analyzer, we are developing laser-based techniques for stand-off, sensitive detection of products corresponding to jet fuel increases with increasing hydrotreatment. The the two forms of vapor-phase mercury emitted by coal-fired power plants, Hg0 and percentage of liquid products boiling in the jet fuel range, 180-270°C, ranges from 4.5- HgCl2. The approach for measuring HgCl2 concentration in combustion flue gas is to 3 11.3%. The overall yields of jet fuel and diesel in the co-coking run increases with detect emission at 254 nm from Hg (6 P1) fragments produced by the degree of hydrotreating level. The percentage that corresponds to gasoline is photodissociation of HgCl2 at 210 nm. Selection of a laser wavelength that is not approximately 0.5-2.5% and that of diesel is 6.5-15%, whereas the percentage resonant with ground state transitions of Hg0 ensures that the laser photofragment corresponding to fuel oil ranges from approximately 78-48% for low to high degrees of emission (PFE) technique is selective for HgCl2, even in the presence of large hydrotreatment, respectively. Additionally, the total liquid product yield decreases quantities of Hg0. The PFE method was characterized and quantified by evaluating the when coal is present. While this information provides a good basis for determining the potential impact of interference gases, determining the dependence of the HgCl2 PFE relationship between severity of hydrotreating and product yield, further process signal on laser irradiance, and examining the effects of collisional quenching by flue optimization is needed to determine the best co-coking conditions to produce jet fuel gas constituents N2, O2, and CO2. In addition, time-resolved measurements of the 3 range material. The chemical compositions of different fractions, e.g., gasoline, jet atomic emission provide insight into both the preparation and decay of the Hg (6 P1) fuel, will be discussed. state. Extension of the PFE technique to a fieldable instrument requires a UV laser source that is not subject to the physical limitations of conventional laboratory laser 45-2 systems. In addition to producing high average and peak powers with excellent beam High Temperature Corrosion Probes: How Well Do They Work? quality, the laser source must be compact, rugged, and light weight. Frequency Sophie Bullard, Albany Research Center, USA conversion of pulsed, rare-earth-doped fiber lasers has the potential to meet these Bernard Covino, Gordon Holcomb, Margaret Ziomek-Moroz, NETL-Albany, USA requirements for a practical laser source. Recent experiments in our laboratory using the frequency-quintupled output of a Sandia-built fiber laser at 213 nm have The ability to monitor the corrosion degradation of key metallic components in fossil demonstrated the ability to detect trace amounts of HgCl2 in an environment fuel power plants will become increasingly important for FutureGen and ultra- characteristic of flue gas. Using this source, we achieved a detection limit of 0.5 ppb supercritical power plants. A number of factors (ash deposition, coal composition for a signal acquisition time of 5 minutes. While this detection sensitivity meets the changes, thermal gradients, and low NOx conditions, among others) which occur in the requirements for real-time monitoring of the HgCl2 concentration in a flue gas high temperature sections of energy production facilities will contribute to corrosion. environment, ongoing efforts to increase the output power of fiber lasers will enable Several years of research have shown that high temperature corrosion rate probes need the realization of equivalent detection limits with decreased signal acquisition times to be better understood before corrosion rate can be used as a process variable by and/or greater stand-off distances. power plant operators. Our recent research has shown that electrochemical corrosion probes typically measure lower corrosion rates than those measured by standard mass loss techniques. While still useful for monitoring changes in corrosion rates, absolute SESSION 46 probe corrosion rates will need a calibration factor to be useful. Continuing research is ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY/OTHERS targeted to help resolve this situation. This paper will present the results of this research. 46-1 45-3 Semi-Continuous Detection of Mercury in Flue Gas by Photo-Deposition Application of a Diode-laser-based Ultraviolet Absorption Sensor for In Situ Evan J. Granite, DOE/NETL, USA Measurements of Atomic Mercury in Coal Combustion Exhaust Jesse K. Magnuson, Robert P. Lucht, Thomas N. Anderson, Purdue University, USA The United States Environmental Protection Agency issued a regulation in March of Udayasarathy A. Vijayasarathy, Kalyan Annamalai, Hyukjin Oh, Texas A&M 2005 for the emission of mercury from coal-burning power plants. In addition, several University, USA states have also enacted legislation requiring control of mercury emissions from coal- burning plants. Methods for the detection of mercury in flue gas are needed in order to A diode-laser-based ultraviolet absorption sensor was successfully demonstrated for determine compliance with state and federal regulations. Photo-deposition of mercury both in situ and extractive sampling atomic mercury measurements in a laboratory upon a quartz substrate is shown to be a simple and inexpensive method for the semi- scale 30 kWt coal combustor at Texas A&M University. Laser sensor measurements continuous determination of total mercury in coal-derived flue gases. were compared to measurements from a commercial mercury analyzer. A 375-nm A small particulate-free slipstream of flue gas is heated to temperatures above 950oF, single-mode laser and a 784-nm distributed feedback (DFB) laser are sum-frequency converting all of the mercury to the elemental form. A small stream of oxygen or air is mixed in a nonlinear beta-barium borate crystal to generate a 254-nm beam. By tuning blended into the slipstream, which is cooled to temperatures below 280oF. Short-wave the frequency of the DFB laser, the ultraviolet beam is tuned across the transition 254-nm ultraviolet (UV) light is applied to the resulting gas mixture, yielding frequency of mercury at 253.7-nm, leaving an off-resonant baseline on either side. No quantitative deposition of mercuric oxide upon a quartz substrate, and forming the pretreatment is required for either the in situ or extractive sampling configurations; the basis for a SCEM. The quartz substrate can be a surface acoustic wave (SAW) mass effects of broadband absorption can be effectively eliminated during data analysis. sensor, allowing for near instant detection of total mercury in the flue gas. Extractive sampling was demonstrated to improve the detection limit of the sensor and The UV-SAW combination results in a simple SCEM for total mercury in flue gas. It to demonstrate the feasibility of total mercury concentration measurements in the has the advantages of being a dry environmentally friendly system which is reliable, future through extractive sampling. Significant variation in the atomic mercury inexpensive, and has the potential for being fully automated. concentration of coal-combustion exhaust was observed over short time periods during our in situ measurements. The sensor detection limits for in situ and extractive 46-2 sampling are 0.3 and 0.1 parts per billion over a one meter path length, respectively. Sulphur Transformation during Chemical Activation of High Sulphur Petroleum Coke 45-4 Jenny Cai, Charles Q. Jia, University of Toronto, CANADA Detection of Mercuric Chloride Using a Fiber Laser Shitang Tong, Wuhan University of Science and Technology, P.R. CHINA Thomas Reichardt, Alexandra A. Hoops, Dahv A. V. Kliner, Jeffrey P. Koplow, Sean W. Moore, Sandia National Laboratories, USA High sulphur petroleum coke was used to produce sulphur-impregnated activated carbon (SIAC) which had been proven to be more effective than virgin activated We demonstrate photofragment emission with a compact fiber-laser source to measure carbon for Hg adsorption. The purpose of this work was to study the behaviour of gaseous HgCl2 concentration with the goal of developing a real-time stand-off sulphur compounds in high sulphur petroleum coke during chemical activation and to speciating mercury emissions monitor. Assuming typical flue gas concentrations (74% determine how sulphur was retained in the activated coke and what types of sulphur N2, 12% CO2, 8% H2O, and 6% O2) at 200°C, we calculate a stand-off detection limit reaction were involved. This is needed for producing SIACs that contain certain of 0.7 ppb for a fieldable monitoring instrument. sulphur functional groups particularly active in mercury adsorption. Two types of petroleum cokes containing 5-7 wt% of sulphur were used to produce SIAC by potassium hydroxide (KOH) activation in the presence of sulphur dioxide (SO2) at 40

600-900°C. Changes in the amount of different sulphur types were determined by wet Coals with Middle and high sulfur content have been prepared into coal water mixture chemical analysis. The sulphur functional groups in the raw coke and activated coke (CWM) to reduce the sulfur dioxide emission. In order to increase the sulfur-fixing were quantitatively analyzed using X-ray Photoelectron Spectroscopy (XPS). The efficiency, the role of promotion to sulfur-fixing capability with alkali metal salt in results showed that more sulphur formed on coke surface at the temperature around CWM combustion has been investigated. In this experiment, three coal samples were 700°C. The main sulphur functional groups and their fractions changed after from Xinjiang, Gaoyang and Shuiyu. Xinjiang coal with the sulfur content of 1.32% activation. Sulphur transformation under various activation conditions was observed was low sulfur content coal, and contain 76.52% of inorganic sulfur; Gaoyang coal and the role of sulphur in coke activation was discussed. was middle sulfur content coal, with the sulfur content of 1.85%, and contain 60.37% of organic sulfur; Shuiyu coal was high sulfur content coal, with the sulfur content of 46-3 3.28%, and contain 59.46% of organic sulfur. Experimental results showed that the Preparation of High-Performance Activated Carbon from Shenfu Coal sulfur-fixing efficiency could be increased obviously by alkali metal salt. The sulfur- for Absorptive Desulfurization of Liquid Hydrocarbon Fuels fixing capability could be increased by 6%~9% when alkali metal dosage was one Anning Zhou, Xiaoliang Ma, Chunshan Song, The Pennsylvania State University, percent of calcium carbonate dosage. With the increase of alkali metal salt dosage, the USA aperture of calcium oxide increased too, when the aperture increased excessively, the surface area of calcium oxide would reduced notably, which would be unfavorable to A novel method for preparing an ultra-high-surface-area activated carbon from Shenfu the sulfur-fixation reaction. The reason for alkali metals could improve the sulfur- coal by chemical activation with NaOH and KOH as activating agents was explored in fixing efficiency of CWM was: Alkali metal can improve the aperture of calcium this study. The preparation method was optimized based on examination of diverse oxide, helped sulfur dioxide and oxygen through calcium sulphate surface layer to experimental variables such as impregnation time, activating-agent/coal ratio, diffuse into calcium oxide inside, enhanced the sulfur-fixing efficiency. KOH/NaOH ratio, activating temperature. The adsorptive performance of the prepared activated carbons was evaluated for removal of sulfur compounds from a liquid hydrocarbon fuel. The results indicate that effects of the activating-agent/coal ratio, SESSION 47 KOH/NaOH ratio, activating temperature and time are significant for improvement of COAL UTILIZATION BY-PRODUCTS – 2 the adsorptive desulfurization performance of the activated carbons. The chemical activation with two activating agents (NaOH-KOH mixture) might be a more efficient method to develop an activated carbon with high desulfurization 47-1 capacity in comparison with the chemical activation with KOH or NaOH alone. The A Technical Review of the Final Report of the National Academy of specific surface of the activated carbon prepared by using the two activating agents can Sciences "Managing Coal Combustion Residues in Mines" be up to 3000 m2/g. Kemery C. Vories, U.S. DOI Office of Surface Mining, USA

46-4 On March 1, 2006, the National Research Council released to the public its final report Catalytic Direct Oxidation of Coal-Gasification Syngas: Conversion of Hydrogen by the National Academy of Sciences “Managing Coal Combustion Residues (CCRs) Sulfide to Elemental Sulfur with Concomitant Capture of Mercury in Mines.” Based on the news release of the National Academy of Sciences (NAS), James Aderhold, Raj Palla, Dennis Leppin, Gas Technology Institute, USA putting coal ash back into mines for reclamation is a viable option for disposal, as long as precautions are taken to protect the environment and public health. The report also This paper presents the results of an experimental study on the use of catalytic direct acknowledged that CCRs could serve a useful purpose in mine reclamation, lessen the oxidation (DO) for the upgrading of syngas generated from the gasification of coal in need for new landfills, and potentially neutralize acid mine drainage. The report an IGCC system. This work was sponsored by the Illinois Clean Coal Institute (ICCI) recommends development of enforceable Federal standards that give the States and conducted by the Gas Technology Institute (GTI). The DO approach would be authority to permit the use of CCRs at mines but allows them to adopt requirements for expected to have significant cost savings for syngas versus the current technology for local conditions. The report lists 40 findings or recommendations under 12 categories. removing sulfur from coal gasifier syngas, which involves an amine or physical- This paper addresses these findings on a case by case basis to evaluate their merits solvent treating system, followed by Claus and Tail Gas Treating of the off-gas. against the extensive record of data and scientific studies on the subject. The NAS has The overall objectives of these studies were (1) to define processing conditions for chosen to use the term “Coal Combustion Residues” where OSM has historically used bulk removal of sulfur compounds as elemental sulfur from the syngas and (2) to the term “Coal Combustion By-Products.” The terms are interchangeable. The author accomplish simultaneous removal of other contaminants, such as mercury from the is in agreement with the NAS findings that support: (1) the use of these materials in syngas. A bench-scale testing system has been constructed at GTI to measure the mine reclamation; (2) the need for specific Federal regulations under the Surface performance of full-particle-size catalysts at elevated pressures and temperatures. A Mining Control and Reclamation Act of 1977 (SMCRA) that spells out the minimum blended gas stream, which contains the primary components of syngas, is combined permitting, bonding, and environmental performance standard requirements when they with oxygen (in the form of air), and passes over hot catalyst. From measured changes are placed on active coal mines; (3) the research priorities to specifically address the in composition of the syngas stream, the activity and selectivity of the catalyst are hydrogeologic fate of CCBs and any leachate generated by those CCBs in relation to evaluated. Processing conditions were found where the added oxygen reacted public health and environmental quality; and (4) to develop mining appropriate selectively with the hydrogen sulfide in the syngas, with minimal oxidation of the leachate tests. A limitation of the report is in its inability to: (1) acknowledge the valuable syngas components of carbon monoxide and hydrogen. Considerable testing profound differences between regulatory environments that control placement of CCBs was done at temperatures below the estimated dew-point of the elemental sulfur in the at mines; (2) evaluate available ground water monitoring data and scientific research product gas. There was evidence of considerable yield of elemental sulfur, but within the context of the applicable regulatory environments; and (3) acknowledge the significant levels of the undesirable side reaction to carbonyl sulfide (COS) were also volumes of scientific studies and State regulatory data that shows no degradation of noted in the initial studies. A diffusion-tube system was incorporated into the catalyst- water quality due to placement of CCBs at SMCRA mines for the last 29 years. The testing system to add mercury vapor into the blended feed to the catalyst. With a following review is strictly the opinion of the author and carries no institutional considerable effort, procedures were developed so that ppb levels of mercury could be endorsement. added consistently to the blended syngas feed, at the relatively-high pressures utilized for catalyst testing. However, in "blank" testing, the mercury in the feed was 47-2 completely removed before reaching the product sampling system. Therefore, the Evaluation of the Effects of Treating Waynesburg Surface Mine Spoil with catalyst testing system was modified in respects: first, the hold-up volume (and thus Fluidized Bed Combustion Ash to ControlAcid Mine Drainage also the internal surface area) was greatly reduced, and second, an inert coating was Paul Ziemkiewicz, West Virginia University, USA applied the piping and vessels in the reactor and product recovery sections of the experimental system. In "blank" testing subsequent to these modifications, mercury Surface mining of the Waynesburg Coal seam in northern West Virginia has typically capture by the catalyst testing system was greatly reduced. In testing with a resulted in acid mine drainage (AMD) generation. The Office of Surface Mining s commercially-available catalyst in the upgraded experimental system, process Acid Mine Drainage Policy of 1998, proscribed permitting of mines with the prospect conditions were found where high conversion of hydrogen sulfide selectively to of indefinite generation of AMD. In 2002 Patriot Mining Co. began to develop elemental sulfur was measured, with concomitant removal of mercury. Data from the Waynesburg reserves and sought a means of controlling AMD in compliance with the laboratory catalyst test unit experiments, as well as the GTI experience in introducing policy. The reserves were to serve a newly constructed fluidized bed combustion and measuring Hg at high-pressure and high temperatures, will be presented and (FBC) plant in nearby Morgantown WV. The selected control method included discussed. complete mining of all coal and immediately adjacent carbonaceous shales for shipment to the FBC unit. This accounted for the bulk of pyritic material on site. FBC 46-5 ash was then to be used as a compacted, cementitious barrier applied to the mined pit Promotion of Sulfur-fixing Capability in Coal Water Mixture floor, against the highwall and as a compacted cap over the regraded spoil. The Combustion by Alkali Metal Salt objective was to direct most water flow away from the regraded spoil to minimize Huang Bo, China University of Mining & Technology, P.R. CHINA AMD formation. Monitoring data are shown indicating that since treatment with the FBC cap, AMD has been controlled to the extent that the site s NPDES permit is in compliance without treatment. The NPDES permit contaminants include Al, Fe, Mn 41

and pH. Additional elemental monitoring required by the WV Department of the Mid-Atlantic Highlands. Lime sources required for pozzolan stabilized CCP Environmental Protection indicates that levels of As, Se, Ba, Cu, Pb, Ni and Hg are cement grout are plentiful throughout the Mid-Atlantic Highlands. CCP use in below drinking water or aquatic life standards as appropriate indicating that the subsurface void stabilization provides stowage for the continuous and voluminous CCP benefits with respect to AMD remediation are not offset by the introduction of other waste stream in a beneficial, safe and environmentally benign manner to mitigate contaminants. hazards from abandoned underground mines common to the Mid-Atlantic Highlands. Hazards from abandoned mines include subsidence, acidic water production, and 47-3 drastically disturbed hydrogeology. Abandoned mine hazards include subsidence (sink Environmental Concerns Related to the Use of Coal holes) in addition to the release of radon gas and increased likelihood of groundwater Combustion By-products in Mine Placement pollution. As a waste product, CCP material can be obtained for little to no cost. Using Tamara Vandivort, Paul F. Ziemkiewicz, WV Water Research Institute, USA CCP material presents an economic as well as an environmental incentive for large volume grouting projects required of abandoned underground mine lands. Earlier this year, the National Academy of Sciences Committee on Mine Placement of Through a cooperative effort of public and private sectors, the Maryland Power Plant Coal Combustion Wastes, released a report on Managing Coal Combustion Residues in Research Project (PPRP) has developed a program to beneficially use CCPs in an Mines. The Committee found placing coal combustion residues in mines to be a viable environmentally safe and effective manner. As a part of this program, PPRP developed way of disposing these materials as long as placement avoids adverse impacts to a cost optimization study to examine and minimize costs associated with CCP grouting human health and the environment. The Committee indicated advantages of doing so projects. This cost optimization evaluates the use of CCPs as subsurface void including assisting with mine reclamation, lessening the need for new landfills, and stabilization and identifies the optimal means, methods, and associated budget costs to neutralizing acid mine drainage. The Committee recommended that minefills be transport, manage, mix, and inject CCP grout. Given the resources available in the designed in such a way that water movement through the residues is minimized. This is Mid-Atlantic Highlands, existing technology, the success of PPRP mine grouting not based on any actual damage cases associated with minefilling, but on data on projects, and clearly demonstrated economical feasibility of using CCPs, a new environmental effects from surface impoundment and landfill sites which indicate that business opportunity exists in the Mid-Atlantic Highlands to restore thousands of adverse environmental impacts can occur when coal combustion residues have contact square miles of potentially hazardous real estate to productive use through subsurface with water or when the residues are not properly covered. void stabilization. A U.S. Department of Energy - National Energy Technology Laboratory-funded program, the Combustion Byproducts Recycling Consortium (CBRC), seeks to promote and support the commercially viable and environmentally sound recycling of SESSION 48 CCBs for productive and sustainable uses of resources, through scientific research, COAL PRODUCTION AND PREPARATION – 3 development, and field testing. Since its inception in 1998, the CBRC has funded 52 CCB research projects nationwide. Several of those projects include using CCBs in mine filling, surface mine reclamation, and the mobility and control of metals in CCB 48-1 leachate. This paper will focus specifically on the projects related to using CCBs in New Coals Collections. The First Results and Prospects mining operations. Svetlana A. Aiphtein, D.L. Shirochin, V.I. Minaev, Moscow State University of Mining, RUSSIA 47-4 Influence of Residence Time on Fly Ash Leachability: Long-Term Implications The new coals collection made of representative seems probes from Kuznetsk and Gautham Das, Mark E. Hill, John L. Daniels, Vincent O. Ogunro, University of North Donetsk basins are submitted. The collection consists of vitrinite coals with the Carolina at Charlotte, USA reflection index from 0.5 up to 1.5 %. Within the framework of similar rank, the coals differing on facial conditions of primary coalification, chemical composition, A considerable body of research has been conducted regarding the use of coal thermoplastic and physical properties are submitted. According to the Russian combustion byproducts (CCBs) in general and leachability in particular. There are classification these coals concern to different genetic types on a reducing degree. The many leach tests available as recommended by various agencies and described in the similar coals are allocated in the countries of Europe and the USA name «perhydrous open literature. Many of these have been used to characterize the leaching potential of coals». The coal collection constantly replenishes and at the moment includes 22 CCBs when considered for highvolume use in civil and highway engineering samples. The coals have the full characteristic on technical, maceral and element applications. The majority of this work suggests that CCBs tend to leach various structure, on caking ability, on sorption and strength properties. constituents, often metals, boron, sulfates and chlorides, at concentrations above applicable regulatory standards. However, in typical leaching tests, the leaching 48-2 solution composition, solid:liquid (L/S) ratio, residence time, temperature and level of Application of Bacteria Thiobacillus Ferrooxidans by Desulphurization of Coal effective stress often has little in common with the field condition. As such, there is a Peter Fecko, Zuzana Sitavancova, Lukas Cvesper, Lukas Koval, VSB-TU Ostrava, level of uncertainty regarding the true behavior of CCBs used as embankment or fill CZECH REPUBLIC material. This uncertainty tends to encourage disposal, even when all other technical and financial constraints for reuse are met. As part of a broader research program to The aim of this paper is the suitability of bacterial leaching applied on the coal sample better predict in situ performance of CCBs in construction, this paper reports on the from mine Most. The results of this work show that using clean cultures of influence of pH and flowrate on fly ash leachate data. In particular, column Thiobacillus ferroxidans is in the case very good if we evaluate desulphurisation from experiments were conducted at three levels of pH (4.3, 6.9 and 9.0) and at three point of view of pyrite sulphur, which, after one month of leaching is almost gone from different flowrates (500, 1000 and 2000 mL/day). The results show differences in sample contains much organic sulphur which is produced by bacteria Thiobaicllus conductivity, pH and Eh as the flowrate is increased. In general, these results suggest ferrooxidans degraded only a little. Applying bacterial leaching it is possible to remove that laboratory testing to determine field leachability should use flowrates similar to approximately 36% of total sulphur and 32% of pyritic sulphur from the coal; better that expected in situ. Such an approach has the added advantage of accounting for results are obtained eliminating sulphate sulphur, i.e. up to 63% desulphurization and time-dependent changes in mineralogy, which in turn dictate the chemical and physical desulphurization of organic sulphur is complicated; it fluctuates around 10%. performance of CCBs. 48-3 47-5 Clean Coal Technology for the Future - NEDO's Challenge A Business Opportunity in the Mid-Atlantic Highlands: An Environmentally Shunichi Yanai, New Energy and Industrial Technology Development Organization, Sound and Cost Effective Solution for Filling Underground JAPAN Voids to Mitigate Hazards Kyoichi Kohgami, Yusuke Tadakuma, Ichiro Fujiwara, Sadao Wasaka, NEDO, John Jenkins, iLF Engineers, USA JAPAN Joseph F. Giacinto, Lenny G. Rafalko, Environmental Resources Management, Inc., USA In the paper, the activities of clean coal technology development by New Energy and Paul Petzrick, Maryland Deparmtent of Natural Resources, USA Industrial Technology Development Organization (NEDO), Japan are introduced. We have three main projects as follows; 1) a high efficiency coal gasification This paper outlines the sources and problems associated with abandoned mines, the technology development (EAGLE), 2) ash-free coal production technology proximity of these mines to power plants producing CCPs and the beneficial utilization development (Hyper-coal), and 3) clean fuel production technology development from of the CCPs to mitigate problems with abandoned underground mine lands. Coal asphalt (ATL). In the EAGLE project, a gasifier, that can produce multi-purpose coal Combustion by-Products (CCPs), a waste product of coal fired power plants, have been derived synthesis gas efficiently, has been developed. The features of the gasifier are used for several years as material for subsurface void stabilization projects. CCP that it has high efficiency and wide variety of coals is acceptable in the gasifier. The material exhibits chemical reactions similar to commercially available Portland cement progress of the development is explained in the paper. Hyper-coal is a challenging when mixed with water and lime with dry strength properties more than sufficient to technology development project, that produces completely ash-free coal (less than support overlying rock strata and man made structures. Approximately 30 million tons 200ppm) by the solvent de-ashing technology. In the paper, the progress of its of CCPs are produced in close proximity to the 6,000 abandoned underground mines in technology and its applications are introduced. ATL stands for Asphalt To Liquids. 42

ATL process has three stages, namely gasification stage, FT synthesis stage, and funded research project comprises three phases, Phase I for design and testing of a hydrocracking stage. In the project, high activity FT catalyst and hydrocracking device to feed coal into 300 psi, Phase II for feeding into 500 PSI and Phase III with a catalyst are developed. 1000 PSI injection target. The first phase target was achieved in December 2003 with results reported at this conference in 2004. In January 2005, the Phase II feeder 48-4 achieved a new record pressure for continuous injection of coal, 560 psi, exceeding the Behavior of the Solid-Liquid Removal to Make the Ash-Free Coal Phase II target. Following success in reaching the Phase II pressure target, the program Noriyuki Okuyama, Atsushi Furuya, Nobuyuki Komatsu, Takuo Shigehisa, KOBE addressed fuel flexibility of the machine. Testing was carried out on a range of Steel, Ltd., JAPAN carbonaceous fuels from bituminous to lignite, as well as renewable fuel samples, all of which were successfully fed into pressure. To assess long-term reliability of the Hyper-coal is an ash-free coal produced by applying the solvent de-ashing technology. Stamet pump, the Phase II unit has been installed at the DOE-funded Power Systems Coal is thermally extracted in the coal-derived solvent, which consists with 2-ring Development Facility (PSDF) in Wilsonville AL for extended testing. This is currently aromatics at 360-380°C. The coal-extracted slurry, which consists with the coal ongoing. Stamet is now undertaking design and assembly of the Phase III feeder. solution and the insoluble solid including ash, is introduced into the settler. The solid is Additionally, in order to accommodate the latest pressure target and allow flexibility in settled down by gravity and concentrated in the bottom. Inversely, the solution is future developments, a new and up-rated test rig with a 1500 psi pressure rating is clarified in the top of the settler. After solvent removal, the ash-free coal, which is being fabricated. This paper will present selected results of Phase II, including the named Hyper-coal (HPC), and the ash condensed residue coal (RC) are produced. 1000-hour testing being undertaken at PSDF, along with a review and evaluation of the This paper concerns with the settling behavior of RC and the clarification behavior phase III program to the date of the conference and extended semi-scale commercial using the batch-type and the continuous settler. The influences of the settling time, the testing which should have concluded by the date of the conference. solid concentration were examined. We understood that the one to two hours of settling time was needed for converging the solid-liquid separation under the conditions of 310 49-3 ~ 380°C, 10 ~ 25 wt.% of the initial coal concentration. The ash concentration in HPC The PWR/DOE High-Pressure Ultra-Dense Phase Feed System and converged around one to three thousand PPM by remaining of the microscopic Rapid-Mix Multi-Element Injector for Gasification, particles. The maximum RC concentration in underflow was 35 ~ 40 wt.%, regardless Kenneth Sprouse, David R. Matthews, Pratt & Whitney Rocketdyne Inc., USA of the initial ash concentration in raw coal and coal extraction rate. Greg F. Weber, University of North Dakota, USA The operations using the continuous system (0.1t/d bench scale unit, BSU) were carried out. The clarification grade of the overflow was almost same as the batch This paper provides the status of a high pressure ultra-dense phase feed system and system. The connecting filtration unit further clarified the overflow. The continuous rapidmix multi-element injector currently being developed by Pratt & Whitney operations successfully demonstrated the targets, negligible small amount of ash (300 Rocketdyne Inc. (PWR) and the U.S. Department of Energy (DOE) under a ~ 600 PPM in HPC), high yield of HPC (60wt.% on daf) and stable operation. cooperative agreement. The high pressure feed system is part of PWR’s advanced gasification program to improve overall performance and reduce capital and operating 48-5 costs. This effort scalesup work initiated by PWR in the 1970’s (at nominal coal flow Advanced Efficient Equipment for Coal Concentration in China rates of 6 to 24 tons/day) -- see, e.g., Oberg and Hood (1980) and Sprouse and Xianguo Li, Keping Chen, Mingxu Zhang, Anhui University of Science and Schuman (1983, 1986) – to near commercial sizes of 400 to 1200 tons/day. Technology, CHINA Construction of a new high pressure (> 1200 psia) test facility at the University of North Dakota Energy and Environmental Research Center (UNDEERC – Grand Forks, China is a big coal producer in the world, with a total output amounting to about 2100 ND) is in progress with testing expected to commence in January 2007. The dry feed Mt/a, of which 40% is prepared now. This paper gives a detailed description of system minimizes the amount of carrier gas to only that residing within the interstices different types of modern high-efficient coal preparation equipment including a jigging of a static coal pile (void fractions nominally 55 vol%). This carrier gas minimization machine, dense medium cyclone, flotation machine, flotation column, and dry allows the use of rocket engine style rapid-mix multi-element injectors having coal separation equipment. These equipments have been used in China in recent years in flow non-uniformities among the elements below 2 %RSD (relative standard order to raise the qualities of various kinds of coal. deviation). The program will test both a 6-element and 18- element injector design using multiple short-duration (4 minute long) batch mode tests. A continuous high- pressure discharge solids pump at 400 tons/day is also being developed for future long- SESSION 49 duration feed system testing in 2008. Uniform flow splitting in dry ultra-dense phase is GASIFICATION TECHNOLOGIES: an enabling technology for rapid-mix compact gasifier operation. This technology ADVANCED TECHNOLOGY DEVELOPMENT – 4 produces flame temperatures in excess of 5,500°F within a few inches of the injector face for fast reactions.

49-1 49-4 High Efficiency Coal Plant that Meets the DOE 2020 Goals - One Decade Early The Exergy Optimization of the Reverse Combustion William S. Rollins, NovelEdge Technologies, LLC, USA Linking in Underground Coal Gasification Michael Blinderman, Ergo Exergy Technologies Inc., CANADA The DOE has set goals in its Clean Coal Power Initiative (CCPI) for a clean, efficient, Dmitry Saulov, Alexander Klimenko, The University of Queensland, AUSTRALIA and cost effective coal facility that can separate and sequester CO2 by 2020. This plant is intended to demonstrate high efficiency, ultra-low emissions, and moderate cost. In Underground Coal Gasification (UCG) is a gasification process carried on in non- addition, it is to have the ability to produce hydrogen for external use, and separate mined coal seams using injection and production wells drilled from the surface, which CO2 for sequestration. To meet this objective, the DOE has funded development enables the coal to be converted into product gas. A key operation of the UCG is programs for numerous technologies that are intended to help power plant constructors linking the injection and production wells. Reverse combustion linking (RCL) is a attain the 2020 CCPI objective. However, by employing only a select few of these new method of linking the process wells within a coal seam, which includes injection of an technologies, along with technology that has been developed independently by oxidant into one well and ignition of coal in the other so that combustion propagates industry, it is possible to meet the essence of the 2020 CCPI objective almost 10 years towards the source of oxidant thereby establishing a low hydraulic resistance path early. Not only does this new plant have the ability to meet the CCPI objectives at an between the two wells. The new theory of the RCL in typical UCG conditions has been early date, but it also demonstrates a new system for separation of CO2 that is recently suggested. The key parameters of the RCL process are determined using the significantly less energy and cost intensive than other CO2 separation methods. The technique of Intrinsic Disturbed Flame Equations (IDFE). This study is concerned with potential exists for this technology package to provide a coal-fueled power plant, extending the results of the RCL theory to incorporate hydro- dynamics of air injection which includes CO2 removal at pipeline pressure, that is 20% more efficient, yet less and flow during RCL operation to derive mass flow rate of air to the combustion front costly than a conventional supercritical pulverized coal plant of today that includes no as a function of the injection pressure. The results enabled an optimization procedure CO2 removal whatsoever. maximizing the exergy efficiency of the RCL process. The optimization has been performed on a model case using a quasi-two-dimensional air flow model in the coal 49-2 seam. The results have been compared to the industrial operational data of RCL in the Development of a Coal Feeder for Continuous Injection into Gasification conditions of the Chinchilla UCG project in Australia. The comparison has indicated a Operating Pressures of 1000 psi - DOE Funded Phase III Program Review reasonable conformity of the modeling with the operational results. The preliminary Tim Saunders, Derek Aaldred, Stamet Inc., USA outcomes of the study will be further refined to incorporate more realistic air flow models in the coal seams. The DOE, working through the National Energy Technology Laboratory, has funded a research project to develop the unique Stamet “Posimetric Solids Pump” to a level able 49-5 to feed coal into current and planned gasification system operating pressures. The Process Analysis and Performance Evaluation of Updraft Coal Gasifiers program’s research objective is a mechanical rotary device for continuously feeding Vittorio Tola, Giorgio Cau, University of Cagliari, ITALY coal into pressurized environments up to 1000 pounds per square inch. The DOE- 43

Coal gasification is becoming commercially even more important due to its potential High Performance Engineering plastics are being touted as materials of the future. application in hydrogen, ammonia, methanol and other chemicals and clean fuels Already quite a few such polymers are already in the market e.g. Kevlar from Dupont, production, other than power generation, together with carbon dioxide capture and Xydar from Amoco, Vectra from Hoechst Celanese. Polyethylene Napthalate (PEN) sequestration. In this framework the technological development is also addressed, with from Teijen and Amoco. Most of the high performance polymers are aromatic a renewed interest, to simplified processes and plant solutions based, for example, on polymers or liquid crystal polymers, both of which are derived from aromatic gasification with air (or air enriched with oxygen) and on moving or fluidised bed monomers. However mass use of such polymers are inhibited by their much higher gasifiers, of interest for small and medium scale plants. The design, analysis and cost. However with rapidly growing market demand of such polymers the demand of performance evaluation of the overall system (gasification, gas clean-up, aromatic monomers are also increasing rapidly and will continue to so in the near desulphurisation, CO-shift conversion, CO2 and hydrogen separation, etc.) require a future. However contrary to this increasing demand this availability of aromatics preliminary estimation of gasifier mass and energy balances and raw gas composition, particulars, 2-4 ring compounds has declined significantly due to world wide decline in which influence the whole downstream gas clean-up and treatment systems. The production of coal tar which continues to be major source of 2-4 aromatic ring present study reports a process analysis and performance evaluation of updraft moving compounds. The main reason for the decline in coal tar production is linked with the bed gasifiers, which have been carried out by a computer simulation model developed worldwide decline in steel production, which concomitantly reduces coke production, using the Aspen Plus 12.1 software, The model schematises the gasifier in several and this in effect reduces coal tar production. Furthermore development of newer steel different zones: coal preheating and drying, devolatilization, gasification, combustion technologies like direct coal injection etc. have decreased this demand of coke and and oxidant preheating, under the hypothesis of char gasification at thermodynamic with adoption of these technologies coke product and as a result tar product is likely to equilibrium. The model allows to appraise the mass and energy balance of the gasifier fall rapidly in the coming decades. Moreover by product coke oven opera is now and the main characteristics of the syngas produced by the gasification process sensed to be an extremely environment unfriendly operations and with enforcement of (composition, mass flow, temperature, lower heat value, etc.), being assigned coal more stringent environmental standards blast furnace steel technologies which is composition and coal, steam and oxidant (air eventually enriched with oxygen) mass directly related with coke making is expected to be replaced by these newer flows. In this paper the model is applied to predict the performance of two updraft technologies. moving bed gasifiers (sized respectively for 35 kg/h and 700 kg/h of low sulphur coal Although coal tar still continues to be the major source (about 95% of the world and high sulphur coal (Sulcis). The gasifiers are part of a small pilot gasification and production) for 2-4 ring aromatics, the total process is not very efficient vis a vis gas treatment plant for hydrogen production under construction at the Sotacarbo production of chemicals considering that good quality bituminous coal produces only Research Centre in Sardinia. around 30 liters of tar which then consists only of about around 25% of two to four ring aromatics of which are present in very small quantities. Furthermore coal tar is an extremely complex mixture and separation of various components particularly those SESSION 50 present in lower concentration make it a rather costly operation However as such COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES: technological trends which is leading to reduction in tar production are an anti thesis of COAL CHEMISTRY the trend of increasing demand of 2-4 aromatics and therefore there is urgent need for development of newer technologies for their production in on sustainable if not on mass scale. Two broad strategies have been proposed in this regard, one being the 50-1 indirect route and the other direct. The indirect route consists of coal conversion route The Pore Structure of Coals Dewatered by Mechanical and coal liquefaction, which involves basically separation of the coal liquids obtained, Thermal Expression (MTE) followed by further conversion if necessary to produce the chemicals of interest. Short Alan L. Chaffee, Janine Hulston, Yuli Artano, Monash University, AUSTRALIA contact time coal liquefaction followed by catalytic de-alkylation to obtain aromatic Christian Bergins, Christian Vogt, Karl Strauss, University of Dortmund, GERMANY monomers as suggested by some authors (1,2) is a good example of such a concept. However coal liquefaction products are again complicated mixtures which will require The mechanical thermal dewatering (MTE) process has been shown to effectively complicated and time consuming separation techniques which will add to the cost of dewater high moisture low rank coals via the application of mechanical force at the chemicals produced, an inhibiting factor in mass production as discussed before. elevated temperatures. The MTE process produces a low porosity product coal, which However direct sourcing of coal for production of value added products particularly for undergoes further shrinkage upon drying. In this study, the porosity and its production of monomers for high performance engineering plastics is a much bolder development within MTE products has been probed through a combination of and challenging strategy, although definite technologies have yet to be fully developed. geometric measurements, helium pycnometry and mercury intrusion porosimetry Coal is predominantly an aromatic material, the structure of which contains crosslinked (MIP). An advantage of MIP is that it allows pore size distributions to be determined polyaromatic units of three or more rings having hydroaromatic and aliphatic over a broad pore size range, spanning several orders of magnitude. The technique structures as peripheral groups. Unfortunately for the chemical industry the aromatic however has its limitations, in that samples need to be completely dry. Thus porosity part contributes solely to coke formation and is not therefore available for preparation and pore size distribution data can only be obtained for dried MTE products, which of aromatics. The direct sourcing route proposes to use these aromatic units in coal have undergone shrinkage. Moreover, care must be taken when interpreting the macromolecule available as aromatic monomers (of three or more rings) or precursor mesopore diameter range (2-50 nm), as the high intrusion pressures required to of such monomers. The methods proposed envisage processes for scission of certain measure pore sizes in this region may also lead to sample compression. This can be target bonds (mainly bridging bonds) between the polyaromatic units. A similar compensated if the inherent compressibility, κ, of the sample is known and the raw method suggested by Song and Schobert (3) for generating high yields of benzene data is adjusted accordingly. Most prior work in the literature has taken no account of carboxylic acids from selective oxidation of low rank coals is a good example. the coal’s compressibility, κ; or, if κ has been considered, it has been determined by In NorthEastern region of India about 900 million tones of high sulfur coal is available extrapolation of the intrusion portion of the MIP curve in the high pressure region but that has to be judiciously utilized. About 75-90% of the total sulfur is in the (>100MPa, at least) where there (sometimes) appears to be a linear relationship organic form that also mostly in thiophenic & thio-ketonic form, which is very difficult between the cumulative intrusion volume and pressure. However, if mesopore filling is to remove. The pyretic sulfur is highly disseminated in the organic matrix of coal still occurring in this region the compressibility, κi, determined by this method will hence can not be separated by physical processes. Therefore use of high sulfur NE clearly be compromised. Consistent with this understanding, the values of κ region coal in any industry possess a limitation. Hence its gainful utilization in an determined in this study from the intrusion portion of the curve varied from sample to environment friendly way is the need of the day. sample and were observed to increase as the proportion of pores in the mesopore size This paper explores the method of coal oxidation with dilute nitric acid as a possible domain increased. In contrast, the compressibilities determined from the extrusion method for oxidative degradation of coal to produce benzene carboxylic acids as portion of the curve, κe, were relatively constant for all MTE products prepared from precursors for such monomers. The coals used for these studies are coals from NE the same coal. Thus, it is inferred that the extrusion data provide a better measure of region of India which have limited application in conventional coal based industries, in the true compressibility of a coal and more correctly account for elastic deformations spite of substantial reserves (about 900 MT), considering it high organic sulfur content in the coal’s macromolecular network (consisting of not only coal, but also closed or combined with highly disseminated pyrite which is difficult to remove physically. inaccessible pores and unfilled micropores) that occur under the influence of high fluid pressures. Moreover, the skeletal densities determined from MIP, after correcting for 50-3 the compressibility (using κe), are lower than the He densities determined by Transformation of the Fe-Mineral Associations in Coal during Gasification pycnometry, in accord with physical reality (and unlike the skeletal densities Frans Waanders, North-West University, SOUTH AFRICA determined using κi). Elimination of the compressibility effects then facilitates the John Bunt, Sasol Technology, SOUTH AFRICA calculation of micropore (pores < 2nm diameter) volumes which are physically sensible and appear consistent with values determined by other approaches. The mineral matter associated with coal undergoes various transformations during the coal gasification process. Optimisation of the gasification process is necessary in the 50-2 coal to liquids technology. The principle aim of this investigation was to determine the Direct Sourcing of Coal: Part-I -Solubilization of Coal changes that the Fe-containing minerals and mineral associations undergo during from North Eastern Region of India gasification of coal. Due to the complexity of the counter-current coal-gas process Debapriya Choudhury, Raja Sen, Gora Shosh, Sunil K. Srivastava, Central Fuel used, a gasifier dissection was undertaken on one of the Sasol gasifiers. Detailed Research, INDIA characterisation profiles of various properties of the coal were undertaken after a 44

commercial-scale gasifier was shutdown for routine maintenance of which the Ordered mesophase pitch was prepared by thermal polymerization of a fluid catalytic Mössbauer spectroscopy technique will be described here. Representative samples cracking (FCC) slurry stock. Thermal conversion experiments were performed on a from the gasifier were extracted after sufficient cooling was done to allow the safe multi-tube well-shape crucible programmed heated furnace. Optical microscope turn-out of the gasifier. In the coal samples that entered the gasifier, pyrite was the observation and solvent extraction separation were used to elucidate formation abundant Fe-containing mineral, whilst the pyrite changed gradually to form, in behaviors of ordered mesophase. It has been indicated from our work that there are conjunction with the SiO2 and Al2O3 present in the coal, a Fe-containing glass and three steps, i.e., containing the formation of the mesophase micro-crystal, the growth hematite at the bottom, or ash grate of the gasifier. of mesophase micro-crystals and the coalescence of mesophase spherules. The former two steps are slow, whilst the last is a fast one. In addition, a novel tubular reactor 50-4 reducing in the central section was designed to guide the ordered growth of mesophase Uneven Distribution of Sulfurs and Their Transformation during Coal Pyrolysis spherules under the oriented flowing gas stream by thermal cracking. The optical Baoqing Li, Fenrong Liu, Wen Li, Haokan Chen, Chinese Academy of Sciences, P.R. structure observation showed that anisotropic mesophase fibrous structures were first CHINA formed radial-in-ward around the reaction tube wall. At prolonged time on stream (TOS), such structures further developed from the wall toward the centre of the tube Two Chinese coals, Liuzhi high pyrite coal with high ash content (LZ) and Zunyi high and thus form a ring-shape structure. organic sulfur coal (ZY), were pyrolyzed in a fixed-bed reactor under nitrogen and hydrogen at temperature ranging from 400 to 700ºC. The effects of heat rate, 51-2 temperature and gas atmosphere on sulfur transformation and sulfur uneven Effect of KOH in Preparation of Activated Carbon with Low Ash Content and distribution were examined by XPS combined with traditional sulfur analysis method. High Specific Surface Area from Law Rank Bituminous Coal The ratio of surface S to bulk S is used to describe the uneven distribution of sulfurs. It Jin Lei, Qiang Xie, China University of Mining and Technology, P.R. CHINA is found that oxygen is rich on the surface, while S in the bulk. The increasing ratio of surface S to bulk S with increasing temperature clearly indicates the sulfur transfer An experimental study on the effect of K-containing compounds in preparation of coal- from the bulk to the char surface during pyrolysis. The ratios are higher at all based activated carbon was conducted in this paper. KOH was used in the co- temperatures studied for ZY coal than for LZ coal, which may be related to the higher carbonization with coal, changes in graphitic crystallites in chars derived from ash content in LZ coal. The ratio of surface S to bulk S increases with increasing carbonization of coal with and without KOH were analyzed by X-ray diffraction heating rate for LZ coal, while it decreases for ZY coal. In the presence of H2, the S on (XRD) technique, activation rates of chars with different contents of K-containing the surface is much lower than that under N2 and surface S in sulphidic, thiophenic and compounds were deduced, and resulting activated carbons were characterized by sulfoxide forms is totally disappeared for LZ coal at various temperatures and heating nitrogen adsorption isotherms at 77 K and iodine numbers. The results showed that the rates, while the surface S in thiophenic and sulfoxide forms is not totally disappeared introduction of KOH into the coal feedstock before carbonization can realize the for ZY coal, which may be related to the high rank of ZY coal. The ratio of surface S intensive removal of inorganic matters from chars under mild conditions, especially for to bulk S decreases before 600ºC with increasing temperature for both coals in the the efficient removal of dispersive quartz, an extremely difficult separated mineral presence of H2, showing that gaseous H2 can easily react with the surface S to form component in other processes else. Apart from this, KOH demonstrates a favorable H2S, while above 600ºC it increases because the supply of H2 cannot match the rate of effect in control over coal carbonization with the goal to form nongraphitizable formation of HS· free radicals at high temperature. isotropic carbon precursor, which is a necessary prerequisite for the formation and development of micro pores. However, the K-containing compounds such as K2CO3 50-5 and K2O remaining in chars after carbonization catalyze the reaction between carbon Advanced Carbon Foams from Coal and steam, which leads to the formation of macro pores. In the end an innovative Drew Spradling, Touchstone Research Laboratory, USA method, in the light of which KOH is added in coal feedstock before carbonization and K-containing compounds are removed by acid washing after carbonization, was Carbon foams manufactured from bituminous coal feedstocks have seen increasing proposed for the synthesis of coal-based activated carbon with ash content less than application in composites manufacturing and in naval shipbuilding, due to the unique 10% and specific surface area more than 1600 m2/g. properties of these lightweight materials. In the unique manufacturing process, pulverized coal is converted into a lightweight, high strength, open cell carbon foam 51-3 with highly uniform pore size distribution, and tailorable electrical and mechanical Effect of the Coking-Coal Property Change on Blend properties. A state-of-the-art manufacturing facility is being commissioned and large Quality and Coke Microstructure cross-sections of carbon foam are being consistently produced on a limited commercial Gaifeng Xue, Peng Chen, Shangchao Liu, Wuhan Iron and Steel volume scale. Many advanced applications ranging from aerospace composites to Corporation, P.R. CHINA naval shipbuilding have been demonstrated through subscale component qualification testing. As an example, carbon foam is being tested as a potential material for the new By studying the vitrinite reflectance and its distribution, technical indexes of the single Navy DDX class warship. Prototype testing in the deckhouse composite structure is coal and blended coal for coking in WISCO in recent years, it was discovered that the underway, with the carbon foam providing low radar cross-section, corrosion- single coal quality changed obviously, especially the metamorphism, its changes resistance, excellent electromagnetic shielding effectiveness, and the ability to meet obviously affected blended-coal qualities and coke microstructure. fire, toxicity, and smoke requirements. The material has been demonstrated that it can be integrated into the ship s planned composite and steel structures. In the development 51-4 of the carbon foam materials, extensive coal chemistry studies were performed, leading Experimental Research on Coke Braise as a Cokemaking Additive to a comprehensive understanding of the controlled coking nature of the manufacturing Shizhuang Shi, Wuhan University of Science and Technology, CHINA process. During manufacturing, the fluid and devolatilization properties of the coals Xueying Zhou, Wuhan Iron and Steel Corporation, P.R. CHINA are manipulated with precise control of the heating, pressure, and atmosphere variables necessary to produce large quantities of highly uniform foam. High pressure autoclaves The experiment of suitability of coke braise with coking coal was carried out firstly and atmosphere furnaces have been custom designed for this unique manufacturing and then cokemaking experiment, coke braise as an additives and petroleum coke for a process. Extensive characterization of the different carbon foam grades produced, comparison, was carried out in a semi-commercial scale. The influence of particle size allows for advanced material application such as those found in the aerospace and and its distribution, proportion of coke braise and property of coke-oven charge on defense industries. Mechanical, electrical, and acoustical properties of the foam were coke quality was researched. The experimental results show that there is a good extensively characterized, leading to the selection of appropriate application in areas suitability between coking coal and coke braise; For high quality of coke, the particle where conventional materials are inferior. A brief overview of the carbon foam size of coke braise should be less than 0.45mm. The addition of 3% coke braise is production process, as well as some of the unique applications of this advanced carbon feasible under the condition of routine production in Coking plant of WISCO. The material will be presented. effect of addition of 3% coke braise is superior to the effect of addition of 3% petroleum coke.

SESSION 51 51-5 MATERIALS, INSTRUMENTATION, AND CONTROLS – 3 Study of CH4-H2O In Coke-Oven Reforming to Produce Syngas Catalyzed by Carbon Catalyst Yongfa Zhang, Wei Zhao, Huawei Zhang, Xiling Miao, Yan Liang, Guojie Zhang, 51-1 Yaling Sun, Kechang Xie, Taiyan University of Technology, P.R. CHINA Studies on the Preparation of Mesophase Pitchs by Thermal Conversion of a FCC Slurry Coke-oven gas that contains mainly 57~62% H2, 25~28% CH4, and ~6% CO is a high Xiaolong Zhou, Jing Chen, Guoxian Yu, Cheng-lie Li, East China University of quality hydrogen resource. However, coke-oven gas that contains more organic sulfur Science and Technology, P.R. CHINA such as COS, thiophene S, and more tar can not be converted into syngas easily by Ni- Minglin Jing, Zuo Zhang, Shanghai Institute of Technology, P.R. CHINA catalyst process. Based on this limitation a new kind of catalyst, carbon catalyst for reforming CH4.in coke-oven gas to syngas was studied. The research of CH4-H2O (in 45

coke-oven gas) reforming was taken in a Plug Flow Reactor (PFR). The research For agricultural application, the mine spoil area (6000 m2) having a randomized block indicated that: 1) in the uncatalyzed CH4-H2O reforming, the conversion rate of CH4 is design and 18 treatments (T1-T18), crop rotation (rice-green gram-rice-sun hemp-rice- lower. At the reaction temperature of 1100°C the conversion rate is about a half. rice) was selected. Biometric observation of the growth and development stages of rice However, in the carbon catalyzed CH4-H2O reforming, the conversion rate of CH4 at crops revealed that overall growth condition of rice plants was luxuriant, with less 1100°C is 97.4%. The carbon catalyst can accelerate the reaction of CH4-H2O incidence of pest, uniform and early maturity, intense colour of green leaves and reforming; 2) In the process of CH4-H2O reforming, the reaction of water gas shift bigger size of panicle in the plots amended with fly ash alone and in combination with happened because of the existence of H2O and the component contents of the product press mud in one time and repeat applications. The crop yield (grain and straw) was gas have been changed. At lower temperatures, the water gas shift reaction has the found to be increased in the range from 3.0 to 42.0% over corresponding control from trend of reduce the content of CO and increase the content of H2 in the product gas; 3) 5 to 20 t/ha, however repeat applications of fly ash at lower dosages (up to 20 t/ha) Because of the existence of water gas shift reaction, in the CH4-H2O reforming were more effective in increasing the yield apart from improvement in the texture and reaction, as the ratio of H2O/CH4 was towards 1, the content of methane in coke-oven fertility of mine spoil and the nutrient content of crop produce than the corresponding gas appeared towards highest; At 1200°C, with the staying time 0.5 seconds, the one-time applications and repeat applications up to 50 t/ha. Some increase in the methane conversion rate in carbon catalyzed reaction is 85.5%. When the resident time content of trace and heavy metals and the level of g emitters in mine spoil and crop lengthens to 1 second, the conversion rate of methane in coke-oven gas can reach produce was observed, but well within the permissible limits. The residual effect of fly above 95.0%. 4) At the temperature about 1000°C carbon catalyst shows the catalytic ash on succeeding crops was also encouraging in an eco-friendly manner. For forestry activity on water gas shift reaction. When the reaction temperature reaches above plantations, about 6000 plants consisting 17 different species were planted on the mine 1050°C, the amount of CO2 will rapidly decrease to below 0.5%. This could be due to spoil/over burden dump (BCCL) along with fly ash and other amendments (cow dung, that at the temperature, the reaction between C and CO2 could rapidly increase, i.e. the coco peat, humic acid, biofertilizer, etc.) which evinced that the physico-chemical and CO2 from shifting reaction reacts with the C in catalyst, rapidly decreasing CO2 biological characteristics of mine spoil was significantly (p<0.05) improved with contents. 5) The result of element analysis and specific surface area analysis of the progressive growth of planted species apart from accompanied reduction in the CO2 carbon catalyst indicated that the contents of S and N in the carbon catalyst decreased concentration (up to 20%), SPM (up to 16%), SOx (up to 55%) and NOx (53%) where sharply and the pore specific volume and the surface area increased after the reaction Sissoo (Dalbergia sissoo), Siris (Albizzia lebbek) and Acacia (Acacia auriculaeformis) of CH4-H2O reforming. play very important role. Based on the above and other demonstration trials, CFRI has successfully developed fly ash soil amendment technology (FASAT)-capable of significantly improving the SESSION 52 fertility status and biological activity of the agricultural/mine spoil, with promising ENVIRONMENTAL CONTROL TECHNOLOGIES: GENERAL TOPICS yield/growth performance of a variety of crops/plant species in eco-friendly manner.

52-3 52-1 CO2 Sequestration through a Novel Aqueous Mineral Carbonation Process Polycyclic Aromatic Hydrocarbon in Soil from Beijing, China Dirk Van Essendelft, Harold H. Schobert, The Pennsylvania State University, USA Xiaobai Xu, Ma Ling-Ling, Xu Xiao-bail, Li Xing-Hong, Chinese Academy of Sciences, CHINA Sequestration of anthropogenic CO2 emissions remains an important and viable Cheng Hang-Xin, Institute of Geophysical & Geochemical Exploration, CHINA strategy in the worldwide effort to reduce the human contribution to climate change. With fossil fuel energy production likely to uphold a significant portion of total CO2 The rapid urbanization and industrialization of Beijing has resulted in significant stress emissions well into the future, a practical strategy for emission reduction may begin by to Beijing environments. In the present study, 16 priority polycyclic aromatic considering limiting and non-limiting factors in the design of a sequestration system hydrocarbons (EPA-PAHs) in the surface soils from Beijing were determined using for a single fossil fuel burning process. Aqueous mineral carbonation lends itself well gas chromatography and mass spectrometry (GC–MS). The total concentration of 16 to chemical process development. A process has been developed that shows strong EPA-PAH varied from 0.016 to 5.470 μg g-1 in soil of Beijing. The spatial distribution potential to make aqueous mineral carbonation both practical and cost effective. Many of PAHs was displayed by the contour plot, which clearly showed that the sites with research efforts have been made to maximize the carbon dioxide sequestration rate by higher content of PAHs are located in the urban areas and northwest outskirts and mineral carbonation. However, most have been shown to be impractical due to the those with lower content are distributed in the south and northeast outskirts. requirement of unfavorable process conditions or prolific process steps. The focus of Compounds profiles presented that the 4-, 5- and 6-ring PAHs were major the current design is chemical simplicity, saleable product isolation and purity, energy compositions and represented about 76%. It was worth noticing that the level of BaP, efficiency, and the incorporation of low temperature heat utilization. These things the most potent carcinogenic PAHs, was from less than limits of detection to 0.402 μg allow the process to be easily integrated into existing or new fossil fuel burning g-1 in soils. The correlation analysis showed that PAHs have the similar source in most processes in an economical and practical way. In the modeled process, serpentine or sampling sites and BaP might be considered as the indicator of total PAHs. olivine is digested in a specialized reactor which creates a magnesium rich liquor. The Characteristic ratios of PAHs indicated that the PAHs pollutants probably mainly came magnesium rich liquor is pH adjusted with ammonium hydroxide and carbonated in the from the pyrogenic origins, especially coal combustion and vehicular emission. The second stage. Finally, waste heat from the fossil fuel combustion process is used to level of PAHs in our study area was also compared with other studies. The information produce ammonium based, dry fertilizer. All products can be isolated in pure form and from this study is significantly for understanding PAHs pollution in the environment of sold to offset capital and operating costs. integrated Beijing city. 52-4 52-2 Comparison of Integrated Gas Cleanup Technologies for Eco-Friendly Reclamation of Mine Spoil for Agro-Forestry Gasification-Based Energy Systems through Fly Ash and Biological Amendments Maryanne Alvin, U.S. DOE/NETL, USA Lal Chand Ram, Nishant Srivastava, S.K. Jha, A.K. Sinha, Central Fuel Research Richard A. Newby, Dale L. Keairns, Science Applications International, USA Institute, INDIA Two basic approaches are used for cleaning the syngas from gasification processes – The generation of huge quantities of mine spoil comprising unwanted shaly matter, cleaning the syngas below its dew point (dry gas cleaning), or operating at higher stones, etc. in the ratio (1:4, coal:mine spoil) produced from open cast coal mining temperatures above the syngas stream dew point (humid gas cleaning). The benefit contributing about 70% of total coal extraction is a big challenge for environmental from a humid gas cleaning system is significant and represents an important system managers apart from utilization of huge amount of fly ash (110 million tones/annum) advance required to achieve the DOE coal program performance targets. Dry and being generated from 85 thermal power plants (TPPs) in our country. Such problems of humid gas cleaning operating conditions are compared, and integrated system concepts management/disposal and utilization of mine spoil and fly ash will continue to for humid gas cleaning are illustrated. Process requirements for achieving a humid gas compound in near future in view of ever increasing demand of energy. As such the cleaning system for gasification energy systems are presented along with perspective development of an eco-friendly technology for reclamation of mine spoil through on the development status and technical challenges. Technology is available to amendment of fly ash will be of much significance. Fly ash being alkaline and demonstrate particulate and halide removal at humid gas cleaning conditions. endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has Sulfur removal at humid gas cleaning conditions has been investigated for many years the potential to improve the texture, fertility and crop productivity of mine spoil. and with the successful completion of current pilot scale tests could be demonstrated. Extensive field demonstration trials on the reclamation of mine spoils of Neyveli Experimental data and concepts are available to support removal of volatile metals. Lignite Corporation (NLC), Tamil Nadu and Bharat Coking Coal Ltd., Dhanbad was Carbon capture concepts for pre-combustion humid gas cleaning have been proposed. carried out for three years using fly ash from NLC and Santhaldih TPPs. For Further work is required to permit an assessment of these concepts and how they will agricultural purpose fly ash from NLC was applied at varying doses (@ 0, 5, 10, 20, compete with other approaches for carbon capture. 50, 100, 200 t/ha) alone and in combination with press mud and other amendments, where repeat application was made up to 50 t/ha. For forestry plantations Santhaldih TPP ash was applied at selective dose of fly ash with other amendments.

46

52-5 can develop respiratory diseases over time. Here we examine crystalline quartz in coal Pilot-Scale Demonstration of Upgrading Waste Sulfuric Acid From Acid fly ash by computer controlled scanning electron microscopy (CCSEM). Washing Process for Crude Benzol Production in a Coke Plant Both the size and shape of the quartz particles are related to their toxicity. In the Shitang Tong, Cui Zhengwei, Wuhan University of Science and Technology, P.R. present study, energy-dispersive x-ray (EDX) spectra identify quartz particles as those CHINA that contain > 90% Si. CCSEM size distributions are then used to classify respirable Zhanghua Zhen, Hua Qi, Jinan Iron and Steel Corperation, CHINA quartz particles as those having a mean particle diameter of < 4μm. Shape is also very Charles Q. Jia, University of Toronto, CANADA important since crystalline quartz particles will generally be more angular and elongated than glassy SiO2 particles. Such angular and/or elongated particles will more To process crude benzol from coke oven gas, the acid washing process is widely used readily penetrate cell walls to cause biological damage. In order to classify particle in coke manufacturers in China. Although the hydrogenation process was known to be shape quantitatively by CCSEM, we define another parameter called circularity. a superior process due to its better quality control of the final benzene products and the Glassy ash particles are very often in the form of spheres, near-spheres, or at least avoidance of the generation of waste sulfuric acid containing coal tar, many coke smooth equant particles. The parameter circularity is therefore defined as the ratio of manufacturers still hesitate to adapt the technology due to its high cost. Containing the radius determined from the particle perimeter to that obtained from the particle area acidic tar, the waste sulfuric acid generated from the acid washing process is a pinkish subtended by the electron beam. A perfect sphere would have a circularity of 1. black liquid that has an odious smell and a rather high COD value. With nearly 50 wt% CCSEM data for these parameters for ~2,000 3,000 fly ash particles are then combined of sulfuric acid, it contains sulfonic surfactant, saturated and unsaturated hydrocarbons. into plots that display volume percentages of Si-rich particles as a function of size and Despite its troublesome nature and potential impacts on the environment, nothing was circularity. Regions of interest can be highlighted based on parameter definitions. On practically done to deal with this waste stream. Recently, we have developed an the basis of a CCSEM examination of NIST K-411 Glass Microspheres standard environment-friendly process for upgrading the waste sulfuric acid. A 30 L installation reference material, we conclude that SiO2 glass particles have a circularity < 2. The was built and successfully demonstrated in Jinan Iron and Steel Co., China, where 3.5 SiO2 particles that are then classified as respirable quartz are those with mean million tons of coke are produced each year. The process consists of two major diameters < 4 µm and circularity >2. Based on our investigation of four power plant operation units: polymerization and extraction. In the first unit, a specific catalyst is ashes using this method, the percentage of the total SiO2 particles that would be used for inducing the polymerization of unsaturated organic species and the classified as respirable quartz is relatively small and constitutes a very small fraction of precipitation of a coke-like solid material. In the second unit, the filtrate from the first the total ash. unit is extracted with an organic solvent obtained from coal tar distillation to clear off most of the remaining organic compounds in the sulfuric acid. To reduce the amount of 53-3 the solvent used in the primary extraction step, a secondary extraction with another A Study on the Ash from Coal Gangue Fired Power solvent obtained from the crude benzol processing may be used. Upon the treatment Plant-Characteristics and Application using the two-stage process, the COD value was reduced from 200 g/l to 20g/l, a Jianglong Yu, Hui Song, Shenyang Institute of Aeronauctical Engineering removal of over 80 %. Color index was reduced by up to 96%. The yield of the coke- Liping Chang, Wei Xie, Kechang Xie, Taiyuan University of Technology, P.R. like solid sludge was 15-25 % of the mass of the waste acid. The purified acid was then CHINA used to produce ammonia sulfate crystals of a satisfactory quality, without encountering any engineering problem. The coke-like material was used as a precursor Coal will continue to dominate China s energy supply in the future. The mining of coal for activated carbon production. creates large amount of gangue which not only occupies a large area of land but also generate environmental problems. On the other hand, coal gangue is a low calorific fuel which should be utilized properly. A few small power plants are current running SESSION 53 or under construction in China. However, due to its high ash content, coal gangue COAL UTILIZATION BY-PRODUCTS – 3 generates a large amount of ash when it is combusted in power plants. The ash from power stations not only contributes to emissions of fine particulates in the air but also results in the contamination of soil. The utilization of coal gangue ash is therefore 53-1 important to reduce China s environmental pollution. In this paper, current status of the Investigation of the Relationship between Particulate Bound Mercury and research and development of gangue ash utilization in China is reviewed. The gangue Properties of Fly Ash in a Full-scale 100 MWe Pulverized ash has found its application in a wide range of areas, such as road construction, Coal Combustion Boiler chemicals, agriculture fertilizers, etc. Some ash samples were collected by the authors Wei-Ping Pan, Chin-Min Cheng, Yan Cao, Western Kentucky University, USA from a coal gangue fired power plant in Fuxin, northeast China. Characteristics of the Sen Li, Purdue University, USA ash were analyzed by using XRD, SEM, Laser sizer and other techniques. Because of its physical structure (e.g., large surface area and porosity) and its composition (i.e., The properties of fly ash in coal-fired boilers influence the emission of mercury containing mainly SiO2, Al2O3 and CaO) the gangue ash has a potential in the pollutant from power plants into the environment. In this study, fly ash samples were application of iron-based sorbents for high temperature removal of hydrogen sulfide collected from mechanical hopper (MHP) and electrostatic precipitator hopper (ESP) from coal gas. A desulphurization sorbent was prepared by using the mixture of iron of a full-scale 100-MWe, pulverized coal combustion boiler. The mercury content, oxide and the gangue ash collected from the power plant. The structure and property of specific surface area (SSA), unburned carbon, and elemental composition of the fly ash the surbent were examined using XRD, SEM and other techniques. samples were analyzed to evaluate the correlation between the concentration of particulate bound mercury and the properties of fly ash in coal combustion boilers. For 53-4 a given coal, it was found that the mercury content in the fly ash collected from ESP Flotoreagent on Base of the Products of the By-Product Coke Plant was greater than in the fly ash samples collected from MHP. This phenomenon may be Viktor Saranchuk, The Litvinenko L.M. Institute of Physical-Organic Chemistry and due to higher sulfur, unburned carbon, and manganese contents, as well as SSA, of Coal Chemistry, UKRAINE ESP fly ash than of MHP fly ash. Comparison of the fly ash samples generated from Igor Arovin, Pilot-line Production, UKRAINE seven different coals by using the statistical Pearson Correlations indicates that the mercury adsorbed on both MHP and ESP fly ashes has a highly positive correlation Flotation method is used for enrichment of ordinary coal having small part less 0,5 with the unburned carbon and manganese contents of those fly ashes, respectively. mm. In connection with deficit of flotoreagent has got up the question about creation Moreover, no significant correlations were found between particulate bound mercury flotoreagent on the base own non-deficit products and waste-products by-product coke and other elemental compositions of fly ash. The high SSA and unburned carbon production. Such work was done in laboratory condition on flotomachine 240-FL-À. contents are beneficial for fly ash to catch gaseous mercury by physical adsorption, As complex flotoreagent were trieded usual and formilin straw oil, polymers of while sulfur will aggregate with gaseous mercury. Manganese in fly ash is believed benzene department, formilin polymers, non-phenol butter, stillage bottoms and their participating in oxidizing volatile elemental mercury (Hg0) to mercury (Hg2+). The mixture. The best results are received when use formilin straw oil, on base which is oxidized mercury in flue gas can form a complex with the fly ash and then get removed created flotoreagent UR-410. Efficiency of the work flotoreagent was explored on before the flue gas get out from the stack of the boiler. charge of Avdeevka by-product coke plant.

53-2 53-5 Distinguishing Free Crystalline Quartz in Coal Fly Ash using Geology and Mineralogy of Coal and Combustible Shale World Deposits as a Electron Microscopy Techniques Resources Forecast Basement of Energy-Chemical and Mineral Raw Materials in Gerald Huffman, Nick Cprek, Naresh Shah, Frank Huggins, University of Kentucky, View of Valuable and Potentiality Toxic Rare Elements it Contains USA Mikhail Povarennykh, Russian Academy of Sciences, RUSSIA Mikhail Shpirt, Institute of Fossil Fuels, Ministry of Natural Resources, RUSSIA Determination of the amounts and classification of the types of silica contained in coal fly ash is a subject of interest because of the adverse health effects caused by Inevitable in the nearest future exhausting of oil and gas deposits in view of the inhalation of crystalline quartz. Workers with prolonged exposure to this carcinogen modern constantly increasing industrial consumption forces us to pay maximum attention to significantly more huge world resources of hard fossil fuels (HFF) (coals 47

and combustible shales, C&CS) much more evenly distributed along the Earth’s Hyper-Coals can be produced by thermal extraction from various coals with organic territory. In contrast to oil and gas, the production and usage of HFF is significantly solvent, and by the gravity settling the soluble. HPC is an ash-less coal, and has an connected with prospects of a by-product obtaining of huge resources of mineral raw excellent thermal plasticity, and has high total dilatation by Audibert-Arnu dilatometer. materials for production of building materials, commercial aluminium compounds as These characters of HPC are advantages in coke manufacturing. So, effective well as compounds and concentrates of rare and trace elements (R&TE)(Ge, Ga, Re, utilization of the HPC as a coke making material was investigated. Adding a small TR) and valuable metals (VM)(Au, Ag, PGE). At the same time, realization of amount of the HPC to blended coals could be improved the strength (I-type drum energetical potential of HFF is connected with environmental pollution in several index: IDI) of the coke manufactured with the coal blends. Possibility of substituting regions of the world by significant amounts of sulphur compounds and potentially the HPC for coking coals in coke manufacturing process was investigated in this study. toxic R&TE (As, Be, Cr, Zn, Pb, Sr, Mn a.o.). In view of the above mentioned We confirmed that HPC could be substituted for high fluidity coal, and blending of problems, it seems very important to make a world C&CS reserves and resources HPC into coal blend increased blending ratio of poorly-coking coal in coal blend distribution analysis as well as to create databese on their compositions and without change of the IDI. The quality of industrial coke is usually evaluated as DI technological properties based on detailed geological and geochemical-mineralogical (Drum Index). Preparation of 10 kg of coke sample is needed to obtain the DI. When knowledge of C&CS basins and estimation of potentially toxic R&TE compounds' the amount of HPC is too small to manufacture coke for DI test, another evaluating outburst volumes. As it is planned by the international team of specialists of C&CS method is necessary to get the strength of cokes manufactured with coal blend geology, during nearest three years it is expected to achieve the following results: containing HPC. Therefore we tried to evaluate the coke strength as tensile strength - Creation of GIS and databases of different categories resources, organic and (St) of small cylindrical coke sample in the case of the smallest test in our study. mineral components compositions, parameters of quality and concentrations of Correlations between St and IDI, DI and IDI, St and DI were investigated for same valuable and potentially toxic R&TE for the world main C&CS deposits; coke samples manufactured with coal blend containing HPC. We confirmed high - Choice of promising utilization directions of each C&CS deposit under detailed correlation coefficient in these correlations. By using of these correlations, it becomes analysis; possible to estimate DI when we are not able to get enough amount of HPC sample for - GIS and set of maps of the world C&CS deposit distribution; DI test. In this study, estimated St of small cylindrical coke sample carbonized in test - Expert auto express analysis of C&CS deposits for revealing of economically tube (φ15mm) was 5.5-6.0 MPa corresponding to DI of industrial coke. promising reserves and resources of by-product valuable R&TE, environmental outburst volumes of toxic sulphur compounds and trace elements during their 54-4 mining and utilization as well as volumes and compositions of ash&slag wastes Surface Modification of Fe3O4 Nanoparticles produced as a result of combustion and gasification of HFF. Yongjian Liu, Hong Zhuang, University of Science & Tech of Suzhou, P.R. CHINA Hongyi Jia, CUMT, P.R. CHINA

SESSION 54 This article discusses the surface modification process of Fe3O4 nanoparticles in details COAL PRODUCTION AND PREPARATION – 4 through a series of experiments. And on the basis of the surface modification coating mechanism, the theoretical analysis is done to the experimental phenomena and the effects on the variation of size, magnetism and stability of Fe3O4 nanoparticles 54-1 produced by the different of pH value, temperature and added dosage of surfactant. Low Rank Coal Upgrading with Syncrude Oil Production using "SynCrude-SynCoal™" Medium Temperature Pyrolysis Processing 54-5 Ebbe Skov, Hetagon Energy Systems, Inc., USA The Strategic Thinking of the Coal Resources for Wuhan Steel Group Franklin G. Rinker, Keith A. Moore, ConvertCoal, Inc., USA Shangguo Liang, Wuhan Steel Group, P.R. CHINA

The coal-to-liquid (CTL) conversion of low-sulfur Western Low Rank Coals by Wuhan Steel Group (Wusteel for short) is a large iron and steel corporation with steel medium-temperature processing called SynCrude-SynCoal™ (SC2) produces both a capacity of 14 million of tons now and 18 million of tons in near future. In the last few syncrude for oil refining and a low-emissions coal-char fuel for power-boiler electrical years, as a result of fast development of national economy, the need of domestic generation. A 10,000-ton/day SC2 CTL project will produce 8000-barrels/day oil and market for the coal, electricity, oil, transportation has significant growth. Along with 5500-tons/day coal-char sufficient for a 600-MW electric power plant. Conceptually, the metallurgy productivity fierce extend, the metallurgy industry is sturdy to pull the ten SC2 projects could provide the US a new secure domestic oilfield resource of metallurgy coal demand. The market price of coal increases continuously. The coal 80,000 barrels/day. The SC2 processing significantly upgrades the quality of the coal- supply is gradually tense up. At the same time, be subjected to influence of the rapid char fuel by removing moisture, fuel sulfur, nitrogen and mercury. This product can increase of the goods, the shortage of conveyance capacity and the circuit direction potentially meet EPA’s stringent new Clean Air Interstate Rules (CAIR) for SO2 restrict etc, the national railroad carry ability was serious hard up. It is anticipated that compliance and increase the power plant’s boiler efficiency and capacity. The yield within the short period, the situation could not alleviate. Under the restrict of both coal and quality of coaltar oil produced by SC2 mild pyrolysis of LRC differs substantially resources and the railroad conveyance, how do the work well to supply the coal at from high temperature coal-tars produced by other processes. Conventional petroleum present and in a period of aftertime, to insure the energy and materials supplies for refining and hydro-treatment will convert the SC2 coal-oil into syncrude and provide Wusteel’s productivity growth need is a strategic topic that the company needs solve feedstock for added-value chemical intermediates products. The SC2 CTL technology urgently. Firstly the paper introduces the coal yield of the world mainly producers, is based on earlier mild pyrolysis demonstration projects and requires only main coal consumers and their consumption in the world, coal import and export commercially mature equipment. The SynCrude-SynCoal™ process, its products and circumstance in China, the Coking coal resources distribution in China and the yield applicability to the energy supply industries are described herein. growth circumstance of coke from 1994 to 2004, and the yields of iron, steel & coke in China within 1994-2004. Secondly the paper predict the coal demand in China, 54-2 including electric power industry, iron & steel making industry, architectural material Characteristics of Hyper-Coal (Ash Free Coal) for Coke Production industry, chemical industry and other industries; as well as the trend about average Nobuyuki Komatsu, Noriyuki Okuyama, Atsushi Furuya, Takuo Shigehisa, Kobe selling price of merchandise coal for state- owned pivot coal mine. Then the paper Steel, Ltd., JAPAN introduces the coal resource species constitute of Wusteel, the strategic supply chains of the medium and long-term agreement and cooperate relations and the predict of coal Hyper-coal means ash free coal that is produced by coal extraction and solid-liquid supply structure when steel yield reaches 18 million. Lastly the paper introduces the separation treatment. The autoclave (AC) for batch test and the small-scale continuous new technology used in Wusteel for coke quality improvement including coke dry process of Hyper-coal (BSU : Bench Scale Unit, capacity : 0.1 t/d) were developed and quenching technique, the hriquette coking process, the coal expert system etc; and operated in Kobe Steel, Japan. Using this AC and BSU, several kinds of coal, from compare Wusteel’s coke quality with baosteel’s and the advanced level in the world; lignite to bituminous coal, were tested and evaluated for Hyper-coal process and lots of and points out the difficulties and measures of coal strategic supply of Wusteel. samples were produced to investigate the utilization for power generation, coke for blast furnace iron production and others materials. Especially, Hyper-coal has some merits to strengthen the coke materials and has possibility to reduce the production cost of coke. This paper discusses the characteristics of Hyper-coal suitable for the coke production.

54-3 Evaluation of Strength for Metallurgical Coke Manufactured with Hyper-Coal Kanji Matsudaira, Yuko Nishibata, Masaru Nishimura, The Kansai Coke & Chemicals Co, Ltd., JAPAN Noriyuki Okuyama, Takuo Shigehisa, Kobe Steel, Ltd., JAPAN

48

minimizing harmful emissions. From the results of experiments and thermal modeling POSTER SESSION 1 it is clear that near 38 % of energy grasses can be used in the large fluidized-bed COMBUSTION TECHNOLOGIES boilers located in the Czech Republic. From energetic point of view has a growing importance the grass and permanent grass covers for production. According to research projects the grass is the most suitable material for biogas generation because P1-1 its high biological activity, high content of nutrients and easy cells degradability in all Importance of the Lignite for Energy in Turkey stages of moisture. The origin of solution is based on determination of grass mixtures Ilker Senguler, Mineral Research Institute (MTA), TURKEY suitable for combined combustion, determination of technological processes of Hayrullah Dagistan, General Directorate of Mineral Research and Exploration, growing, harvest and fuel preparation and further determination of grass mixture TURKEY suitable for biogas production. This paper presents only the results from the experiments of combustion of energy grasses. Energy is the main input for industrialization and development. In electrical power generation, the share of thermal plants is 64%. Because of their low capacity and high P1-4 initial investment cost renewable energy sources are not preferred. CO2 Reduction Potential on the Czech Condition Since the coal resources comprise 27% of all the energy sources, it will continue to Dagmar Juchelkova, Helena Raclavska, Vaclav Roubicek, Pavel Kolat, Jiri Bilik, take a role in the 21st Century. 1.75% of these resources are located in Turkey and most Darja Noskievicova, Pavlina Pustejovska, Jarmila DolezalovaVSB-Technical of the electrical power generation is based on thermal power stations. University of Ostrava, CZECH REPUBLIC Most of the known lignite deposits in Turkey are of low calorific value, high percentage of ash, volatile matter, moisture and sulphur. Almost 75% of the total At present the task of minimizing carbon dioxide emissions in relation to its influence reserves are with a calorific value of below 2500 kcal/kg. 17% are between 2500 and on environment belongs to the priorities of EU research activities. For achieving the 3000 kcal/kg. While only the 8% are over 3000 kcal/kg. Therefore, it is inevitable that best possible results it is necessary to focus attention on information concerning input the majority of such lignites which are feasible technically and economically for materials character study of production as well as manufacturing processes and exploitation must be enriched by washing before marketing. subsequent returning the products back to environment (anthroposphere). The highest Total installed capacity of based on lignite thermal power plants is 6390 MW in degree utilization of domestic energetic sources and supply the information important Turkey. In addition to 1760 MW (Can and Elbistan) is under testing. It is planned to for energetic conception of individual country and regions is the main request of EU have thermal power plants with capacities of power 13810 MW in 2010 and 16060 in government on research. Reduction of CO2 production can begin if following 2020. information will be known: Coal exploration studies will be accelerated to correspond the energy deficiency of - Character of input materials (content of C, H, N, S and TOC - total organic carbon), Turkey. General Directorate of Mineral Research and Exploration of Turkey (MTA) pollutants, physical-chemical properties, determination of phase occurrence, amount of will carry out a series of coal exploration projects in different regions of Turkey. As a input materials etc.). result of these studies including drilling activities, the coal reserves will have been - Production and technological processes (energy demand technological limits for increased importantly. realization of IPPC and LAC etc.). United Nations Framework Convention on Climate Change (UNFCCC) regulations - The utilization and character of by-products (evaluation of properties → processing stipulates that the green gas emissions should be dropped to 1990’s level. Therefore for other kind of utilization or alternative technology for disposal). new combustion technologies are required for energy resources. The thermal power plant in Can, Canakkale, capacity of power 2x160 MW with fluidized bed combustion P1-5 technology will be a good example for the future use of this application. The Rheology of Coal-Oil Mixtures (COM) Turkey possesses a large lignite potential with 8.3 billion tons. New combustion Gunduz Atesok, Mustafa Ozer, Feridun Boylu, Istanbul Technical University, technologies and coal mining applications will make this potential more attractive in TURKEY the near future. The sensibility to the environmental problems in Turkey can be taken as a guarantee that we will not face the environmental problems industrialized Today 90% of electricity in the world is produced from fossil fuels such as coal, oil countries had faced before. We should not forget that “a living society is one that and natural gas. Oil equivalent of fossil in the world is calculated to be 68% coal, 18% obtains its current needs without destroying the belongings of the next generations”. oil and 14% natural gas. According to these figures the lifetime of oil, natural gas and coal is 40, 60 and 220 years respectively. Coal water slurries (CWS) and coal oil P1-2 mixtures (COM) may be an alternative energy source to fuel-oil. In COM or CWS technology, the coal loading rate is an important factor and it depends on the rheology The Char-CO2 Reaction at High Temperatures and Pressures Elizabeth Hodge, Daniel Roberts, David Harris, CSIRO Energy Technology – QCAT, of mixtures. AUSTRALIA In this study, the COM was prepared using fuel-oil(#6) and high rank bituminous coal John Stubington, UNSW, AUSTRALIA at a temperature range 20 to 90°C and coal loading rate were examined. The results of the study showed that the rheology of COMs loaded with high amount of coal as much The rate of coal conversion in an entrained flow gasifier is limited by the rate of as 60% could be advanced by increasing the mixture temperature to 90°C. However, for slurries with suitable viscosity, the mixture temperature at 60°C is found to be reaction of char with steam and CO2. Under these conditions, rates of carbon conversion depend on the chemical reaction rate on the char surface and the rate of gas enough with lower coal loading rates such as 50%. diffusion to the surface of, and within the pores of, the particle. For pulverised coal In conclusion, it was found that fuel-oil can be loaded with high amount of solids using particles, at low temperatures (below about 900–1000°C) the conversion rate depends high rank coals. Thus, the consumption rate of fuel-oil could be decreased without only on the chemical reaction rate. As temperatures increase, the influence of gas sacrificing on the heating value of the new fuel, COM. diffusion becomes significant and the conversion process becomes more complicated. Whilst the rate of the char–CO2 reaction at high pressures has been investigated at low temperatures, few data exist that allow quantification of this reaction at high POSTER SESSION 2 temperatures and pressures relevant to full-scale entrained flow gasifiers. This paper GASIFICATION TECHNOLOGIES / HYDROGEN FROM COAL presents new data from measurements of the rate of the char–CO2 reaction at temperatures up to 1400°C and pressures up to 20 bar in a pressurised entrained flow reactor. The data have been compared to reaction rates obtained at lower temperatures P2-1 in order to begin to develop the link between low and high temperature reaction rates. Carbon Dioxide Capture and Separation Techniques for Advanced Power Generation Point Sources P1-3 Henry Pennline, David Luebke, Badie Morsi, Yannick J. Heintz, Kenneth L. Jones, Utilization of Energy Grasses for Combustion Jeffery B. Ilconich, DOE/NETL, USA Dagmar Juchelkova, Helena Raclavska, Bohumir Cech, Jan Frydrych, David Andert, VSB-Technical University of Ostrava, CZECH REPUBLIC The capture/separation step for carbon dioxide (CO2) from large-point sources is a critical one with respect to the technical feasibility and cost of the overall carbon The highest degree utilization of domestic energetic sources and supply the sequestration scenario. For large-point sources, such as those found in power information important for energetic conception of individual country and regions is the generation, the carbon dioxide capture techniques being investigated by the in-house main request of EU government on research. Utilization of energy grasses is very research area of the National Energy Technology Laboratory possess the potential for important because of various reasons - social benefit, environmental benefit, country improved efficiency and costs as compared to more conventional technologies. The benefit, etc. The energy utilization of the energy grasses is one of the main topics for investigated techniques can have wide applications, but the research has focused on future developments of recoverable sources in the European Union and in the Czech capture/separation of carbon dioxide from flue gas (postcombustion from fossil fuel- Republic. The aim of research is combustion tests in the boilers of various producers fired combustors) and from fuel gas (precombustion, such as integrated gasification located in the Czech Republic. The experiments are carried out for Czech grasses and combined cycle – IGCC). With respect to fuel gas applications, novel concepts are wastes including analyses and recommendations for optimal thermal utilization and being developed in wet scrubbing with physical absorption; chemical absorption with 49

solid sorbents; and separation by membranes. In one concept, a wet scrubbing structures. The overlapping degradation temperature interval between coal and plastic technique is being investigated that uses a physical solvent process to remove CO2 is beneficial to hydrogen transfer from plastic to coal. The difference of weight loss from fuel gas of an IGCC system at elevated temperature and pressure. The need to (ΔW) between experimental and theoretical ones, calculated as a algebraic sums of define an ideal solvent has led to the study of the solubility and mass transfer those from each separated component, is about 5-6% at 550-650°C. These properties of various solvents. Fabrication techniques and mechanistic studies for experimental results indicate on significant synergistic effect during plastic and hybrid membranes separating CO2 from the fuel gas produced by coal gasification are biomass co-pyrolysis at the high temperature region. In addition, a kinetic analysis was also being performed. Membranes that consist of CO2-philic silanes incorporated into performed to fit thermogavimetric data, the global processes being considered as one an alumina support or ionic liquids encapsulated into a polymeric substrate have been to three consecutive first order reactions. A reasonable fit to the experimental data was investigated for permeability and selectivity. An overview of two novel techniques is obtained for all materials and their blends. presented along with a research progress status of each technology. P2-5 P2-2 Solvent Extraction of South African Coal-A Review Selective Catalytic Oxidation of Hydrogen Sulfide - Johan van Dyk, TJ van de Walt, Sasol Technology, SOUTH AFRICA Systems Analysis for IGCC Application Richard A. Newby, Dale L. Keairns, Science Applications International Corporation, Sasol’s Secunda plants in South Africa are very conveniently placed with respect to the USA vast coal reserves of the Mpumulanga region. Sasol converts these coal reserves, via its Maryanne Alvin, DOE/NETL, USA indirect liquefaction process, into liquid fuels and various chemicals. This process is operated under severe process conditions, and the concomitant release of big volumes Selective catalytic oxidation of hydrogen sulfide (SCOHS) has been evaluated of CO2 presents environmental problems. In addition to this, these plants consume conceptually for IGCC applications, and the theoretical limits of reaction performance, utilities other than coal (such as water) and need the support of a well developed process performance, and economic potential in IGCC have been estimated. Syngas infrastructure (like e.g. a good roads network). Other, more remote (with respect to the conditions that have high partial pressures of total sulfur result in substantial liquid Secunda plants) coal reserves may be in need of a different kind of coal conversion sulfur retention within the catalyst bed, with relatively complex processing being technology before these can be monetised. Such is the case for the Waterberg coal required. Applications that have much lower total sulfur partial pressure in the process reserves – coal that is high in vitrinite content and may be eminently suitable for gas might permit SCOHS operation under conditions where little liquid sulfur is conversion via coal solvent extraction. The coal solvent extraction process is mild retained in the catalyst, reducing the processing complexity and possibly improving the (with respect to process conditions) and CO2 release is low; coal is the major utility desulfurization performance. The results from our recent IGCC process evaluations consumed in light of the process being self-sustainable in terms of the solvent that is using the SCOHS technology and conventional syngas cleaning are presented, and required. The product from solvent extraction (mild coal dissolution) is a lowash and alternative SCOHS process configurations and applications that provide greater low-sulphur solid or pitch and is suitable for use as a fuel in new technology power performance and cost potential are identified. generation plants, or as a reductant in the metallurgical industry, and even as a precursor for several carbon products. Coal solvent extraction is a well known P2-3 technology and the majority of literature is based on vitrinite rich coal. Little work is Optimization of Heat Recovery Steam Generators for IGCC Power Plants reported on the mild solvent extraction of inertinite rich coals, or the role of other D. N. Reddy, Osmania University, INDIA reactive macerals (besides vitrinite). Thus, work on South African coal, also rich in other reactive macerals, is reviewed. Basic human needs can be met only through industrial growth, which depends to a great extent on energy supply. The large increase in population during the last few P2-6 decades and the spun in industrial growth have placed tremendous burden on the Regenerable Sorbent Development for Sulfur and Chloride electrical utility industry and process plants producing chemicals, fertilizers, Removal From Coal-Derived Synthesis Gas petrochemicals, and other essential commodities, resulting in the need for additional Ranjani Siriwardane, DOE/NETL, USA capacity in the areas of power and steam generation throughout the world. Steam is Thomas Webster, Research Development Solutions, USA used in nearly every industry; and it is well known fact that steam generators and heat recovery boilers are vital to power and process plants. It is no wonder that with rising A large number of components in coal form corrosive and toxic compounds during fuel and energy costs engineers in these, fields are working on innovative methods to gasification processes. According to the U.S. Department of Energy, National Energy generate electricity, improve energy utilization in these plants, recover energy Technology Laboratory (DOE NETL) goals, contaminants have to be reduced to parts efficiently, from various waste gas sources, and simultaneously minimize the impact per billion in order to utilize gasification gas streams in fuel cell applications. Even these processes have on environmental pollution and the emission of harmful gases to more stringent requirements are expected if the fuel is to be utilized in chemical the atmosphere. Heat recovery boilers, also known as waste heat recovery boilers or production applications. Regenerable hydrogen sulfide removal sorbents have been heat recovery steam generators (HRSGs), form an inevitable part of chemical plants, developed at DOE NETL. These sorbents can remove the hydrogen sulfide to parts per refineries, power plants, and process systems. They are classified in several ways, billion range at 316°C and at 20 atmospheres. The sorbent can be regenerated with according to the application, the type of boiler used, whether the line gas is used for oxygen. Reactivity and physical durability of the sorbent did not change during the process or mainly for energy recovery, cleanliness of the gas, and boiler configuration, multi-cycle tests. Results of the multi-cycle, benchscale tests utilizing simulated coal to mention a few. The main clarification is based on whether the boiler is used for gas and results of the tests with real coal gas will be discussed in the paper. process purposes or for energy recovery. Process waste heat boilers are used to cool Regenerable hydrogen chloride removal sorbents have also been developed at DOE waste gas streams from a given inlet temperature to a desired exit temperature for NETL. These sorbents can remove HCl to parts per billion range at 300°C to 500°C. further processing purposes. An example can be found in the chemical industry in a The sorbent can be regenerated with oxygen. Results of thermogravimetric analysis sulfuric acid or hydrogen plant- where the gas steam is cooled to a particular gas and bench-scale flow reactor tests with both regenerable and non-regenerable HCl temperature and then taken to a reactor for further processing. The exit gas temperature removal sorbents will be discussed in the paper. from the boiler is an important parameter affecting the downstream process reactions and hence is controlled by using a gas bypass system. Steam generation is of secondary P2-7 importance in such plants. In energy recovery applications, on the other hand, the gas Assessment and Environmental Performance of Coal and Biomass is cooled as much as possible while avoiding low temperature corrosion and steam Based Combined Heat and Power Plants (CHP) generation throughout the world. Steam is used in nearly every industry; and it is well D.N. Reddy, K. Basu, Osmania University, INDIA known that steam generators and heat recovery boilers are vital to power and process plants. It is no wonder that with rising fuel and energy cost engineers in these, fields Shortage and quality of grid power prompted Indian Industries to go for captive power are working on innovative methods to generate electricity, improve energy utilization plants. For process industries, uninterrupted steam supply becomes a necessity. in these plants, recover energy efficiently, from various waste gas sources, and Generally, coal based captive power plants are employed for these duties. These plants simultaneously minimize the impact these processes have on environmental pollution have efficiency range between 5% to 10%. Biomass based Combined Heat and Power and the emission of harmful gases to the atmosphere. plant (CHP) could improve both generation efficiency and environmental performance. Biomass based power generation using reciprocating engine is well established P2-4 technology. However, low life expectancy and higher cost of generation slowed down Thermogravimetric characteristics and kinetic of coal/plastic blends co-pyrolysis the wider adaptation of this technology. Gas turbine manufacturers are pursuing Limin Zhou, Yipin Wang, Qunwu Huang, Junqing Cai, Tianjin University, CHINA development of burning Low Btu gas in combustor. Biomass gasifier integrated to gas turbine as topping cycle and steam Turbine as bottoming cycle could provide power Co-pyrolytic behaviours of different plastics(high density polyethylene, low density cycle efficiency of 2% to 4% higher than that of conventional power plant. Centre for polyethylene and polypropylene) and low volatile coal (LVC) were investigated using Energy Technology carried out designs of a CHP plant utilizing the existing TGA. The results indicated that coal was decomposed at in the temperature range 174- equipment. In spite of limitation on component efficiency, power block can attain a net 710°C, while the thermal degradation temperature of plastic is 438-521°C. Plastics thermal efficiency of 9.9 and CHP efficiency of 49.79 for a plant capacity of 51.72 showed similar pyrolysis behaviors due to similar chemical bonds in their molecular kWe. The validation of the mathematical models was carried out by using 50

experimental data available in literature and data from the equipment available at CET. - Benzothiophene (850), very weak poisoning effect, slightly improved activity The report presents the considerations for equipment selection and sensivity analysis of after removal. down-draft Gasifier and design of HRB. The strength of the poisoning effects reflects the basicity of the respective poison compounds and their adsorptive strength on the acid sites of the catalyst. From these P2-8 findings it is apparent which gasifier impurities are problematic, and require removal, Removal of H2S in Gas from Coal Gasification Using a Polymer and which may be adequately managed during solid acid processing. Sorbent Supported on Mesoporous Molecular Sieves Xiaoxing Wang, Xiaoliang Ma, Chunshan Song, The Pennslyvania State University, USA POSTER SESSION 3 GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND The deep removal of H2S from natural gas, coal/biomass gasification gas and the HYDROGEN APPLICATIONS reformate is one of the major challenges in the hydrogen production process and utilization of these fuel gases. In order to develop a more efficient sorbent with high capacity, selectivity and regenerability, a series of polyethylenimine (PEI) sorbents P3-1 supported on mesoporous molecular sieves, including SBA-15, MCM-41 and MCM- Syngas Fuel Composition Sensitivities of Combustor Flashback and Blowout 48, have been prepared and characterized by XRD and N2 physisorption. The sorption David Noble, Quingguo Zhang, Tim Lieuwen, Georgia Institute of Technology, USA performance of the prepared sorbents for removing H2S from a simulated coal gasification gas, which contains 4000 ppmv H2S and 20 vol% H2 in nitrogen, has been This paper reports experimental data detailing the fuel composition sensitivities of tested in a fix-bed system at a temperature range from 22 to 75°C. The effects of flashback and lean blowout limits of syngas (H2/CO/CH4 mixtures). Data were operating conditions, including temperature, gas hourly space velocity (GHSV), on the obtained over a range of fuel compositions at fixed approach flow velocity, reactant sorption performance have been examined in detail. It is found that the increase in temperature, and combustor pressure at several conditions up to 7.1 atm and 500 K temperature and GHSV resulted in the decrease of the breakthrough capacity. The inlet reactants temperature. Consistent with prior studies, these results indicate that the breakthrough capacity and the saturation capacity of the supported PEI sorbents percentage of H2 in the fuel dominates the mixture blowout characteristics. These change with the PEI loading. A positive synergetic effect between SBA-15 support and blowout characteristics can be captured with classical Damköhler number scalings to loading PEI on H2S sorption was observed. The maximum breakthrough capacity of predict blowoff equivalence ratios to within 10%. Counter-intuitively, the percentage 1.97 mmol/g-PEI was obtained at a PEI loading of 50 wt %, while the maximum of hydrogen had far less effect on flashback characteristics, at least for fuels with saturation capacity of 4.65 mmol/g-PEI was obtained at a PEI loading of 65 wt %. The hydrogen mole fractions less than 60%. This is due to the fact that two mechanisms of comparison of the supports indicates that the higher porous volume and the three- “flashback” were noted: rapid flashback into the premixer, presumably through the dimension channel structure favor improving the sorption performance. The desorption boundary layer, and movement of the static flame position upstream along the and regeneration of the spent sorbents have also been conduced in the fix-bed system centerbody. The former and latter mechanisms were observed at high and low at 22 and 75°C, respectively. It indicates that desorption of the saturated sorbents can hydrogen concentrations. In the latter mechanism, flame temperature, not flame speed, be conducted easily at 75°C and the sorbent is stable during the adsorption-desorption appears to be the key parameter describing flashback tendencies. cycles. The results imply that the developed sorbent is a promising sorbent for removing H2S from gas streams at more environmentally friendly and energetically P3-2 efficient conditions. In addition, the mechanism for the sorption of H2S on the Effect of Syngas Composition on Emissions from an supported PEI is also discussed on the basis of the experimental and computational Idealized Gas Turbine Combustor results. Timothy C. Williams, Christopher R. Shaddix, Robert W. Schefer, Sandia National Laboratories, USA P2-9 Investigating Reactive Ball Milling of Anthracite Coal Future energy systems based on gasification of coal or biomass for co-production of Apurba Sakti, Caroline E. Burgess Clifford, Angela D. Lueking, The Pennsylvania electrical power and gaseous or liquid fuels may require gas turbine operation on State University, USA unusual fuel mixtures. In addition, global climate change concerns may dictate the production of a CO2 product stream for end-use or sequestration, with potential Development of alternative energy technologies is the key to address future energy impacts on the oxidizer used in the gas turbine. In this study the operation at concerns of depleting fossil fuel reserves and the hydrogen economy is one of the atmospheric pressure of a small, optically accessible swirl-stabilized premixed forerunners amongst the various options being considered. A combined hydrogen combustor, burning fuels ranging from pure methane to conventional and H2-rich and production and storage process using coal as a precursor and ball milling it in the H2-lean syngas mixtures is investigated. Both air and CO2-diluted oxygen are used as presence of a hydrogen donating solvent is investigated here. Tests of our current the oxidizers. CO and NOx emissions for these flames have been determined over the hypotheses that ball milling induces cross links in the coal structure facilitated by the full range of stoichiometries from the lean blow-off limit to slightly rich conditions (φ evolution of hydrogen will be presented. The effect of mineral matter present in the ~ 1.03). The presence of hydrogen in the syngas fuel mixtures results in more compact, coals has been investigated as well and will be presented along with the possible higher temperature flames, resulting in increased flame stability and higher NOx commercial applications. emissions. The lean blowoff limit and the lean stoichiometry at which CO emissions become significant both decrease with increasing H2 content in the syngas. For the P2-10 investigated mixtures, CO emissions near the stoichiometric point do not become The Impact of Trace Impurities in Coal Gasification Products on the significant until φ > 0.95. At this stoichiometric limit, where dilute-oxygen power Performance of Solid Acid Catalysts for Phenolics Transformations systems would preferably operate, CO emissions rise more rapidly for combustion in Jack C. Q. Fletcher, Walter Bohringer, University of Cape Town, SOUTH AFRICA O2-CO2 mixtures than for combustion in air. Cathy L. Dwyer, Sasol Technology Research and Development, SOUTH AFRICA P3-3 The effect of impurities as potential catalyst poisons in the raw phenolics stream from Low Temperature Oxygen Activation and Transport over Doped a Lurgi coal gasifier was investigated for the transformation of phenolic compounds Lanthanum Ferrites for Use as SOFC Cathodes over zeolite H-MFI as a solid Brønsted acid catalyst. A model mixture of light John Kuhn, Umit Ozkan, The Ohio State University, USA phenolics, representing the major constituents of such a stream, was converted at 350ºC and 60 bar in the liquid phase. A series of potential catalyst poisons were added, Current Ni-based solid oxide fuel cells (SOFC) anodes deactivate in the presence of individually, each representing the ‘parent compound’ of one of the families of typical coal-derived gas because they are easily poisoned by low levels of sulfur and catalyze impurities in such a stream. Conversion of p-cresol was monitored vs. time-on-stream coke formation. Their use requires a large steam to carbon ratio to limit coking. In as a catalyst activity indicator. After the introduction of poison, the response in catalyst addition to these problems, the Ni-based anodes also lose activity through sintering. activity, i.e. the conversion of p-cresol, ranged from a steeply declining behaviour to All of these processes deactivate the anodic reaction rates, cause low power densities, showing no effect at all. Upon re-introduction of poison-free feed, catalyst activity and increase operation costs due to large steam requirements. Thus, the development of recovered, completely or in part, and was more or less rapid. Potential poisons that highly active and carbon and sulfur tolerant materials suitable for use as anodes is were evaluated, their applied concentrations (in wt -ppm) and the results obtained are necessary to bring coal-gas fed SOFC systems closer to commercialization. Ongoing as follows: SOFC cathode research shows iron-based perovskite materials are developed as - Pyridine (200), strong poisoning effect, partially reversible promising materials for use as SOFC cathodes between 500°C and 700°C. The - Benzonitrile (3700), strong poisoning effect, presumably by the decomposition electrochemical activity and oxide ion mobility that make it such a great cathode co-product NH3 from hydrolysis with moisture, reversible material can also be harnessed for the oxidation reactions at the anode. The current - Aniline (200), weak poisoning effect, improved activity after removal research demonstrates the iron-based perovskite materials are stable in highly reducing - Indole (200), very weak poisoning effect, improved activity after removal conditions and possess catalytic activity for the direct oxidation of hydrogen and - Thiophenol (850), no poisoning effect, no effect after removal carbon monoxide in the desired temperature range. The effect of the increased lattice oxygen mobility on the water requirements and the influence of hydrogen sulfide 51

concentration on the oxidation activity are discussed. Characterization using X-ray flow of pyrolysis gas, the order growth of mesophase was achieved by leading gas diffraction, X-ray photoelectron spectroscopy, simultaneous thermogravimetric and flow. The influences of reactor structure and process conditions on orderly growth of differential scanning calorimetric analyses, and temperature-programmed techniques is mesophase were studied by microscope. performed to compliment the anodic oxidation results and correlate the bulk and surface structure-activity relationships. P4-2 Performance Difference of Coke from CDQ and CWQ P3-4 Shizhuang Shi, Wei Xu, Wuhan University of Science and Technology, CHINA SOFC Reaction Process Suitable for Use with Sulfur-Containing Fuels Matthew Cooper, David Bayless, Ohio University, USA In order to make clear the performance difference between cokes from CDQ and CWQ, the contrastive study was carried out on normal analysis, granularity analysis, Growing concerns over the environment as well as political instability in oil-producing strength analysis, thermal performance, catalytic analysis and optical texture analysis regions of the world have ignited a large degree of interest in converting the of cokes from CDQ and CWQ from WISCO. The experimental results show that, electrochemical energy from coal-derived fuel streams using fuel cells. One specific compared with coke from CWQ, the performance of coke from CDQ was improved type of fuel cell, known as the solid oxide fuel cell (SOFC), has the ability to produce obviously such as mean granularity, granularity coefficient, mechanical strength, energy from hydrocarbon fuels at efficiencies far greater than traditional combustion thermal performance etc.; the ash component catalytic index (MCI), optical texture engines. However, hydrogen sulfide (H2S), a common component of hydrocarbon index (OTI) etc. are unchanged basically; its alkali absorptance is strong, and its alkali fuels, poisons conventional SOFCs and necessitates costly fuel treatment, preventing resistance is weak, but its thermal performance is still superior to coke from CWQ the utilization of SOFCs for distributed power from being financially feasible. The aim after alkali absorption; and its boron absorptance is weak, and its passivation effect is of this research is to develop a SOFC reaction process which will allow the use of a bad, and its thermal performance is even somewhat inferior to coke from CWQ after H2S-containing fuel derived from coal reserves known as coal syngas. In the proposed boron absorption. process, a two-stage SOFC reaction system will be used. In the first stage, SOFCs will utilize an electrode material known as lanthanum strontium vanadate (LSV), which has P4-3 shown high activity toward consuming H2S; it is hypothesized that these LSV SOFCs Sulfur Transfer Law From Coking Coal to Coke will scrub any H2S present in the syngas stream via electrochemical oxidation while Shizhuang Shi, Wuhan University of Science and Technology, CHINA leaving behind non-H2S species such as hydrogen (H2) and carbon monoxide (CO). Zhiping Liu, Wuhan Iron and Steel Corporation, CHINA The outlet gases from this LSV SOFC will then be fed to another SOFC utilizing conventional Ni anodes; these conventional anodes have been shown to readily oxidize Sulfur is a harmful ingredient in coke and coke sulfur is from coal sulfur. In order to H2 and CO, leading to the hypothesis that the combined process will efficiently reduce sulfur content of coke, the sulfur transfer law from coal to coke must be produce electricity even when using a H2S-contaminated fuel stream. It should be understood fully. For that, the sulfur content of various forms in coal and total sulfur noted that this research is still in preliminary stages; feedback from the scientific transfer law from coal to coke are researched. The experimental results show that the community on the merit of the effort is desired. sulfur in coal principally organic sulfur, secondly sulfide sulfur and least sulfate sulfur, and the organic sulfur content increases with the volatile content of coal; and that P3-5 sulfur conversion ΔS from coking to coke and the ratio of coke sulfur content to coal Development of a Fuel Flexible Catalytic Combustor for IGCC Applications sulfur content ΔS/K all decrease with the increase of the volatile content of coking Walter R. Laster, Pratyush Nag, Elvira Anaoshkina, Siemens Power Generation, Inc., coal, for both single coking coals and their blends. USA Bruce C. Folkedahl, University of North Dakota, USA P4-4 Effect of Coking Coal Ash Composition on the Coke Thermal Performance Siemens has been working on the development of an ultra low NOx catalytic Shizhuang Shi, Wuhan University of Science and Technology, CHINA combustor for the SGT6-5000F gas turbine using the Rich Catalytic Lean (RCLTM) Meicheng Jin, Wuhan Iron and Steel Corporation, CHINA design. By operating the catalyst section fuel rich, this design shows considerable promise for robust operation over a wide range of fuel compositions including syngas. The coke thermal performance, including the coke reactivity index CRI and the coke Under the sponsorship of the U. S. Department of Energy’s National Energy strength after reaction CSR, is an important quality index of metallurgical coke. They Technology Laboratory (DE-FC26-03NT41891), Siemens is conducting a three year are affected by the property of coking coal and the ash composition. In order to program to develop an ultra low NOx, fuel flexible catalytic combustor for gas turbine research the influence of ash composition on the coke thermal performance, firstly the application to Integrated Gasification Combined Cycle (IGCC) plants. The goal of this catalytic index MCI is defined; then cokemaking experiments in laboratory and program is to significantly reduce the emissions levels for the current diffusion flame industrial coke experiments are carried out successively. According to experimental based IGCC combustion systems down to 2 ppm NOx without the requirement for results, the mathematical models are established. The experimental results show that dilution flow. This paper addresses the current status of the fuel flexible catalytic the influence of ash catalytic index MCI on the thermal performance of coke, CRI and combustor development program. Performance of the catalytic coating materials have CSR, is very obvious; there is a positive relativity between the ash catalytic index MCI been verified for natural gas, typical syngas fuels and hydrogen. The initial verification and the coke reactivity CRI; there is a negative relativity between the ash catalytic testing of the subscale SGT6-5000F combustion module on syngas was performed and index MCI and the coke strength after reaction; and that the mathematical models the design changes necessary for the full basket design have been identified. The (regression equations) established from the experiment reveal the essence of the effect program is on track for full scale basket verification next year. of various factors on the thermal performance of coke. They can be used to predict the thermal performance of coke, CRI and CSR, and to guide the production of coke.

POSTER SESSION 4 MATERIALS, INSTRUMENTATION AND CONTROLS POSTER SESSION 5 ENVIRONMENTAL CONTROL TECHNOLOGIES

P4-1 Study on the Orderly Growth of High-Content Mesophase Pitch P5-1 Minglin Jin, Haiqi Zhang, Zhuo Zhang, Jing Chen, Shanghai Institute of Technology, A New Approach for Semi-Dry Flue Gas Desulphurization CHINA Fan Wang, Hongmei Wang, Fan Zhang, Junfang Wang, Yongli Hao, Jun Lin, Di Jin, Hexing Li, Shanghai Normal University, CHINA Chinese Research Academy of Environmental Sciences, CHINA

The preparation of high content mesophase pitch was one of key techniques to develop A new semi-dry flue gas desulphurization (FGD) system was established to a 35t/h the needle coke, carbon fibre as well as new carbon materials. High content mesophase coal-fired boiler, in which SO2 sorbents were activated by steam during conveyance, pitch has been previously synthesized from coal tar pitch in more tubes well-crucible the steam temperature was about 200-350°C, with the pressure of about 0.4 MPa. stove. It was found that changes of TI-QS content were as parabola during non- To investigate behavior of steam activation, experiments were also conducted to isothermal polymerization of coal tar pitch. Meanwhile the microstructure changes of examine changes of surface structure, size distribution, and chemical components of mesophase pitch was observed by microscope with the changes of TI-QS content, such SO2 sorbents before and after steam preparation. BET surface area analysis results as the nuclear appearance of mesophase micro-crystal, the growth of mesophase micro- show that the sum of specific surface area increases from 7.8688m2/g to 10.0715m2/g crystal as well as the coalescence in different reaction time. As a result, the key factor during SO2 sorbent activation by steam conveyance. The porous structure gives rise to of preparation of high content mesophase was the reaction time and temperature and specific surface area, which enhances desulphurization process. It is obvious that not comparatively low reaction temperature as well as prolonged reaction time were only changes of external and internal structures of fly ash occur, but also the chemical propitious to preparation of high-content mesophase. As the growth of mesophase was compositions. Mixture of lime and fly ash (lime to fly ash ratio was 1:8) was used for a spontaneous process the another one of key techniques was how to make orderly SO2 sorbent, and analysis results were obtained that the content of Ca(OH)2 was 9.1 % growth of high content mesophase. The special tube reactor was designed with single of initial SO2 sorbent, while 16.9 % of Ca(OH)2 content was attained after steam 52

activation. It was concluded that Ca(OH)2 content increased after SO2 sorbent The vast quantities of waste coal in this country present us an opportunity to recover activation by means of steam conveyance. Experiments were conducted regarding the them as an alternative energy source. This paper describes a newly developed multi- factors that closely related with operating performance, which were reacting stage loop-flow flotation column (the MSTLFLO Process) as an effective means for temperature, CaO/SO2 molar ratio, and SO2 sorbents, where SO2 sorbents using lime recovering waste coal from disposal sites and to produce a clean coal product for only and other two different compounds of lime to fly ash ratio were considered. electricity generation. Experimental tests under different column operation conditions Testing results show that when CaO/SO2 molar ratio is 1.2, and SO2 removal efficiency were carried out with three different waste coal samples. The results have is attained as high as 85.1%, and an efficiency of 88.3% is achieved when CaO/SO2 demonstrated that the MSTLFLO process is capable of producing low ash (<10% ash) molar ratio is 1.4. Adding fly ash to lime for SO2 sorbent can improve desulphurization clean coal product with greater than 85% heating value recovery. Moreover, the cost of process. Experimental results SO2 removal efficiency increase from 67.43 % to 76.24 producing clean coal product from waste coal using the MSTLFLO process in a 2,000 % is achieved when the ratio of fly ash to lime increases from 0 to 3:1. A ton/day plant is estimated to be $2.38/ton. This cost compares very favorably with desulphurization efficiency of 81.07 % was attained when fly ash to lime ratio is 8:1. other fine coal cleaning processes, particularly in view of the fact that it not only adds positive values to a waste resource but also minimizes one of the key environmental P5-2 impacts related to coal mining. Metal Compounds of Benzene-1,3-diamidoethanethiol (BDETH2), a thiol based ligand David Atwood, Kamruz Zaman, University of Kentucky, USA POSTER SESSION 6 SYNTHESIS OF LIQUID FUELS, CHEMI–CALS, MATERIALS AND Heavy metal pollution is a serious threat to natural ecosystems. Various methods and OTHER NON–FUEL USES OF COAL technologies are in use to remove heavy metals from the environment. They include phytoremediation, bioremediation, activated carbon adsorption, extractions, and others. More recently the use of chemical reagents to combat heavy metal pollution has come P6-1 into play. Some of them, the thiol-based ligands in particular, have proven effective in Study of Temperature-Programme-Reduction (TPR) on Bifunctional precipitation heavy metals from aqueous systems. The latest and most versatile Catalysts for Conversion of Synthesis Gas to Dimethyl Ether chemical precipitation reagent is known as Benzene-1,3-diamidoethanethiol Yunlai Su, Hua Wang, Y.-M. Tian, Y.-Q. Guo, Zhengzhou University, CHINA (abbreviated as BDETH2). Marketed with the common name MetX this ligand has L. Xu, Z.-M. Liu, Chinese Academy of Sciences, CHINA been found effective in binding heavy metals in a variety of settings. Synthesis, and characterization of this relatively inexpensive an dnon-toxic multidentate ligand and its Synthesis of methanol, oxygenates, fuels and other hydrocarbon products from bonding arrangement to the metals Cd, Hg, and Pb along with the full characterization synthesis gas continues to be an area of both academic and industrial activity. These data of the BDET-M compounds will be presented here. processes are also important for utilisation of remote natural gas or clean coal conversion. Dimethyl ether (DME), currently used as a propellant, has received P5-3 growing attention owing to its potential as a useful chemical intermediate and its Conceptual Design of a Supersonic CO2 Compressor application as an alternative clean fuel [1-6]. Recently, a novel method called STD Robert Steele, Shawn Lawlor, Peter Baldwin, Ramgen Power Systems, USA (syngas to dimethyl ether) process was developed by Topsøe for the direct DME production from syngas [1,2]. The catalyst used in this process is composed of a Ramgen Power Systems, Inc. is developing a family of high performance supersonic methanol-synthesis catalyst and an HZSM-5 catalyst treated with ammonia which compressors (RampressorTM) that combine many of the aspects of shock compression poisons strong acid sites to prevent the formation of hydrocarbons. It is well accepted systems commonly used in supersonic flight inlets with turbo-machinery design to be a bifunctional catalyst. In this study, the reduction behavior of the bifunctional practices employed in conventional axial and centrifugal compressor design. The result catalyst were investigated with TPR and the modification of solid acid (SA) and is a high efficiency compressor that is capable of single stage pressure ratios in excess methanol-synthesis catalyst (MSC) were examined to promote the STD reaction. of those available in existing axial or centrifugal compressors. A variety of design configurations for land-based compressors utilizing this system have been explored. P6-2 A proof-of-concept system has been designed to demonstrate the basic operational Coal Pyrolysis under Synthesis Gas, Hydrogen and Nitrogen characteristics of this family of compressors when operating on air. Based on the Baoquing Li, Wen Li, Fenrong Liu, Zongqing Bai, Gang Wang, Chinese Academy of results from that effort a compressor specifically designed for the high pressure ratios Sciences, CHINA required to support CO2 Capture and Storage has been proposed. The basic theory of Alyeksandr Ariunaa, B. Purevsuren, Sh. Munkhjargal, Mongolian Academy of operation of this new family of compressors will be reviewed along with the Sciences, MONGOLIA performance characteristics and conceptual design features of the proposed CO2 compressor systems. Chinese Xundian, Mongolian Shiveeovoo lignites and Khoot oil shale are pyrolyzed under synthesis gas (SG) at temperature range from 400ºC to 800ºC for lignite and P5-4 from 300ºC to 600ºC for oil shale with heating rate of 10ºC min-1 in a fixed bed Dynamics of Gas Isolation at Pyrolysis reactor. The results were compared with those obtained by pyrolysis under hydrogen Victor Saranchuk, Olga Chernova, Evgeniy Zbykovskiy, Donetsk National Technical and nitrogen. The results showed that unlike pyrolysis at high pressure, there are only University, UKRAINE slight different in the yields of char and tar among pyrolyses under various gases at room pressure for lignite, while higher liquid yield with lower yields of char and gas Need of the reception alongside with coke of the coke gas as marketable products has was obtained in pyrolysis under SG and H2 than under N2. It is found that the pyrite S puted the question about study dynamics of the gas emission of the pyrolysis of the can be easily removed to partially convert to organic S under various gaseous separate coals and charge of them. For study was an applying installation with mass of atmosphere and the total sulfur removal for oil shale is much less than lignite, which the loading 1400 g. Were received correlation amount stood out separate gas during might be related to its high ash content. The higher total sulfur removal and less undertaking the experience. Exists the certain dependency of the mass stood out gas organic S content in the presence of SG in comparison with those under N2 and even from coal metamorphism degree. Is it also built curves of the separation separate under H2 in pyrolysis of Xundian lignite might result from the action of CO in SG. component pyrolysis gas of coals of the different marks and charge, formed from these However, CO does not show its function in pyrolysis of khoot oil shale, which might coals. The Curves of the separation individual pyrolysis gas of coal of the mark DG also be related to the high ash content. The results reported show the possibility of and OS have one maximum. On crooked separations coal gas marks G, ZH, K exists using synthesis gas instead of pure hydrogen as the reactive gas for coal two maximums. The Observed phenomena of the origin one or two maximums of the hydropyrolysis. gas emission possible with two affecting factor. The First - a process of the emoving moisture from coal loading. The First maximum of the gas emission of coals G, ZH P6-3 and K appears exactly at moment, when in the centre of the coal loading else lasts the Copper, a Selectivity Promoter in Iron Based Fischer-Tropsch Synthesis? process of the drying and the temperature continues to remain constant. After Michael Claeys, Peter S. Cairns, Mark E. Dry, Eric van Steen, Centre for Catalysis completion of the process of the drying temperature coal loading continues to increase, Research, University of Cape Town, SOUTH AFRICA but intensity of the gas emission falls. The Second factor is an origin, existence and consolidation plastic layer since arising the second maximum of the gas emission A study of copper promotion on co-precipitated iron catalysts has been conducted. complies with the temperature of the existence or origin plastic layer in the centre to Catalysts with a wide range of iron to copper ratios were prepared. The addition of coal loading. I.e. mutual or separate influence of the separation and existence plastic copper in the co-precipitation of iron leads to the formation of small iron crystallites layer causes origin one or two maximums. that are X-ray amorphous; at low copper loadings the copper is also amorphous. The effect of copper on reduction promotion has been confirmed and the affinity of the P5-5 potassium promoter for iron rather than copper has been identified. On examination of MSTLFLO Process for Waste Coal Beneficiation the hydrocarbon product, copper has no effect on the overall activity, methane J.F. Zhong, A. Antoine, L. Hong, B. I. Morsi, M. H. Cooper, S. H. Chiang, selectivity and chain growth probability (α). Promotion with high concentrations of University of Pittsburgh, USA copper can lead to greatly enhanced alcohol formation, while the hydrocarbon product 53 is only slightly affected with increased paraffin formation, which is believed to be due studies on some of the gravity fractions having medium to high volatile matter and less to a slight shift of primary product selectivity as well as effects of secondary to moderate ash content lead to the conclusion that the natural coke may be used for hydrogenation. It is further shown that these effects are not due to uneven potassium blending with power coal. Lower VM fractions may be recommended for cement promotion and that the iron and copper need to be co-precipitated in order to achieve industry. maximum oxygenate promotion. P7-2 P6-4 X-Ray diffraction analysis on the macerals of coals with different type-reductivity A Gaming Framework for Analyzing Market Potentials and Risks of CTL Haizhou Chang, Chuange Wang, Jun Li, Wenying Li, Kechang Xie, Fangui Zeng, A. Tuzuner, Zuwel Yu, Purdue University, USA Taiyuan University of Technology, CHINA

Coal-to-liquids (CTL) has been attracting a lot of attention due to persisting high crude In this article, X-ray diffraction (XRD) was carried out to study the crystallite oil prices, energy security concerns, large reserves of coal in many oil importing characteristics of the vitrinite and inertinite from Pingshuo and Shendong coals with countries etc. Both the direct coal liquefaction (DCL) and indirect coal liquefaction similar coal rank and petrographical composition but with different reductivity (ICL) processes are proven technologies. However, whether the CTL business will revealing the influence of the reductivity on macerals crystallite. Pingshuo (PR) coal survive in an open global market depends on many factors, which can be mapped to was with stronger reductivity. Compared with vitrinite (PV) there was bigger risks. The most determining factor of the viability of the CTL business is future oil crystallite size, higher regularity and aromaticity (ƒa) in inertinite (PI). Shendong (SR) price movement. According to many studies, oil prices will have to be above $35- coal was with weaker reductivity, its inertinite’s crystallite size and regularity were 40/bbl for the CTL business to survive, depending on the location and coal use of the more obvious than vitrinite (SV), but almost same ƒa value. The crystallite parameters CTL business. An immediate question is: Do oil exporting countries have the incentive of PV and SV are alike, which shows a good relationship with the petrographical to reduce oil prices? The answer is: If there is no threat of entry to snatch the market likeness of PV and SV. Compared with PI, there is fewer aromatic layers and lower ƒa shares of these oil exporting countries, they may not have the incentive to reduce oil in Shendong inertinite (SI). The content of highly disordered material called prices by increasing their production. Hence, CTL can be regarded as a threat of entry amorphous carbon was investigated. Results showed that PV was obviously higher into oil market to force the oil exporting countries to reduce prices through production than PI, SV is slightly higher than SI and PV, SI is obviously higher than PI. The expansion. Therefore, building the CTL capacity can be used as a gaming approach to characteristic that there were relatively lower ƒa as well as more amorphous carbon in reducing crude oil prices, which may benefit the oil importing countries in many SI with weaker reductivity indicated that SI contains more active components, which aspects, including reduced oil prices, increased energy security, plus many other might be related to the fact that SI contained plentiful semifusinite. benefits such as job creation, balancing trade, cash flows improvement etc. The paper proposes a gaming model to find the equilibrium solution to the CTL P7-3 capacity building. A stochastic mean-reversion price model is used, and the Nash- Comparison of Microwave-Assisted Extraction and Soxhlet extraction equilibrium can be found using a stochastic root finding approach. In the equilibrium, Chen Hong, Lu Junqing, Ge Lingmei, Li Jianwei, Zhou Anning, Xi'an University of the “best” CTL capacity will be calculated based on the “long-run” marginal cost of Science and Technology, CHINA the total CTL capacity in the world. In order to compare extraction yields and the extracts, extraction with several single P6-5 organic solvents under microwave-assisted and Soxhlet extraction were conducted for Novel Magnetic Method for Separation of Iron Catalysts 5 typical Chinese coals –Shenfu, Tongchuan, Huating, Yitai, Panzhihua coal. Above from Fischer-Tropsch Wax 50% extraction yield was acquired for ethylenediamine under microwave-assisted R.R. Oder, EXPORTech Company, USA extraction, conversely only 40% extraction yield were the highest for Soxhlet extraction. Extracts were analyzed by GC/MS. Influence of temperature, solvent, coal We describe a novel continuous magnetic method for separation of nano-meter size type on microwave-assisted extraction are also studied. The cause of different iron catalysts from Fischer-Tropsch wax (patent pending). The method has been scaled extraction yield on different coals was discussed. up from the bench scale to prepare clean wax containing 0.1 to 0.5 wt.% catalyst from slurries containing 20- 25 wt.% catalyst at the rate of 50 barrels per day (BPD) feed P7-4 wax at 500oF.1 We will discuss the operating mechanism of the separator which is R&D of a New Technology of Conversion of Coke Oven Gas housed between the poles of an electromagnet producing magnetic fields in the range from Bituminous Coal into Syngas of 0.2 to 0.5 Tesla throughout the working volume. The method achieves high levels of Yongfa Zhang, Kechang Xie, Taiyuan University of Technology, CHINA catalyst separation from the wax by promoting magnetic agglomeration throughout the Ping Wan, Changchun Technology College, CHINA volume of the vertically oriented elongate cylindrical separation vessel. Downwardly- Guangliang Liu, Xiaofei Chen, Yan Liang, Jia Zhang, Li Yang, Shanxi Sunrise Coal directed high velocity jet flows located adjacent to the inside walls of the separation Technology Ltd., CHINA vessel nearest the magnet poles are used to sweep the catalyst agglomerates from the magnetized volume of the separator. The jets are controlled to promote movement of A kind of new technology with an integrated apparatus (IA) for producing syngas from the agglomerates without causing turbulent mixing. Clean wax with a low bituminous coal is developed. In the integrated apparatus three processes: coal concentration of catalyst is continuously issued from the top of the separator while wax pyrolysis, partial coal gasification and conversion of coke oven gas (COG) into syngas slurry with a high concentration of catalyst is issued from the bottom of the vessel. Use are completed and three products: syngas, ferro-alloy coke (semi-coke) and tar are of a supplemental separation method such as batch operated high gradient magnetic produced in an environmental friendly manner. In this paper, the status of China’s separation to treat the product of the first stage continuous magnetic separator has semi-coke industry and coke oven gas utilization are introduced; the principle of produced clean wax containing 0.01 wt.% catalyst. conversing CH4-rich gas such as COG into syngas with the assistance of H2O-O2 in a high temperature carbon catalytic system are analyzed; and other technological issues, such as the process, main technical specifications of the integrated apparatus, product POSTER SESSION 7 quality, energy consumption, financial estimation, and environmental protection etc. COAL CHEMISTRY, GEOSCIENCES AND RESOURCES are discussed. It has been shown by research that the main technical specifications of the integrated apparatus are as following: coal processing capability 23 T/d, coke yield 3 14.7 T/d, tar yield 1.15 T/d, syngas yield 11960 Nm /d. The syngas quality shows CH4 P7-1 content <1.0% and (H2 + CO) content > 86.5%. The semi-coke is favored product used Cleaning Potentality of natural Coke (jhama) through washability for Si-Fe alloy and carbide production. Its volatile rate is lower than 4.00% and Investigation and Its Suitability for Different End Uses electrical resistance is higher than 1506Ω.mm2.m-1 at 1300°C. The content of phenol in Ashok K. Singh, N.K. Shukla, Amrita Mukherjee, Mamta Sharma, N. Choudhury, T. the tar is 16.25%. The integrated apparatus, a clean technology is energy and resource Gauricharan, D.D. Haldar, Central Fuel Research Institute, INDIA efficient.

Substantial reserves of natural coke (jhama) are available in Indian coalfields, but due P7-5 to its peculiar physical and chemical properties, its suitability for different end uses has Niobium and tantalum content at Kuzbass coals not been established. Earlier workers have attempted to find out new avenues for Boris F. Nifantov, Vadim P. Potapov, Anatoliy N. Zaostorvskiy, Olga P. Zanina, The utilization of this material by producing coke from different blends of jhama with Institute of the Coal and Coal Chemistry SB RAS, RUSSIA coking coal fines, obtained from coal washeries. In the present study, authors have attempted to study the washability characteristics of a typical natural coke from seam At all deposits of the world coals contain niobium and tantalum which maintenance as XIV A of Jharia coalfield. Results of conventional float and sink tests have been used a rule do not exceed clark levels. Last years the data of high contents of these metals at to determine the yield of cleans at 10% and 15% ash content. The washability data various coal-mining regions were published. In the present message are considered reveals that a theoretical yield of ~20% and >80% is achievable at 10% and 15% ash metal logenic and the geochemical data of niobium and tantalum contents levels. Different gravity fractions were further characterized (chemically and accompanied by Sc, Ti, Fe, Y, Zn, Ce, Hf, Th, U at III - XVII layers of Tom-Usa microscopically) to find out their suitability for carbon artefact industries. These Kuzbass region. 54