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 will be sent to all registered participants following the Conference. On behalf of the Twenty-Fifth Annual International Pittsburgh Coal Conference, we wish to express our sincere appreciation to Ms. Heidi M. Aufdenkamp, Mr. Yannick Heintz and Mr. Laurent Sehabiague for their invaluable assistance in preparing this Abstract Booklet. Thank you,

Badie I. Morsi, Editor Professor and Executive Director of the Conference

Copyright 2008 Pittsburgh Coal Conference

TABLE OF CONTENTS

Oral Sessions 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 21: 22: 23: 24: 25: 26: 27: 28: 29: 30: 31: 32: 33: 34: 35: 36: 37: 38: 39: 40:

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Oral Sessions

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Gasification Technologies: General Session 1...............1 Special Symposium: NETL-University Consortium.........1 Combustion Technologies 1...........................................3 Gas Turbines and Fuel Cells for Synthesis Gas and Hydrogen Applications 1 ...............................................3 Coal Production and Preparation 1 ................................4 Synthesis of Liquid Fuels: GTL, CTL and BTL 1 .........5 Gasification Technologies: General Session 2...............6 Hydrogen from Coal 1 ....................................................7 Combustion Technologies 2...........................................8 Gas Turbines and Fuel Cells for Synthesis Gas and Hydrogen Applications 2 ...............................................9 Coal Production and Prepartion 2 ................................10 Synthesis of Liquid Fuels: GTL, CTL, and BTL 2 ......11 Gasification Technologies: Substitute Natural Gas ........12 Hydrogen from Coal 2 .................................................13 Combustion Technologies 3.........................................14 Coal Chemistry, Geosciences, and Resources 1 ..........15 Coal Production and Prepartion 3 ................................16 Synthesis of Liquid Fuels: GTL, CTL, and BTL 3 ......17 Gasification Technologies: Fundamentals 1 ................18 Underground Coal Gasification 1 ................................19 Combustion Technologies 4.........................................20 Coal Chemistry, Geosciences, and Resources 2 ..........21 Global Climate Change: Science, Sequestration, and Utilization 1 ...................................22 Synthesis of Liquid Fuels: GTL, CTL, and BTL 4 ......23 Gasification Technologies: Fundamentals 2 ................23 Underground Coal Gasification 2 ................................24 Environmental Control Technologies: Mercury Capture, Noncarbon .........................................25 Coal Chemistry, Geosciences, and Resources 3 ..........26 Global Climate Change: Science, Sequestration, and Utilization 2 ...................................27 Synthesis of Liquid Fuels: GTL, CTL, and BTL 5 ......28 GasificationTechnologies: Fundamentals 3 .................29 Underground Coal Gasification 3 ................................30 Environmental Control technologies: Mercury Capture, Carbon, NOx ......................................31 Coal Chemistry, Geosciences, and Resources 4 ..........32 Global Climate Change: Science, Sequestration, and Utilization 3 ...................................34 Gasification: PNNL-China..............................................35 GasificationTechnologies: Advanced Technologies 1............................................36 Gasification Technologies: Synthesis Gas Cleaning 1.............................................37 Environmental Control Technolgies: Multipollutant Control ....................................................38 Coal Chemistry, Geosciences, and Resources 5 ..........39

41: Global Climate Change: Science, Sequestration, and Utilization 4...................................40 42: Coal Utilization By-Products 1....................................40 43: Gasification Technologies: Advanced Technologies 2............................................41 44: Gasification Technologies: Synthesis Gas Cleaning 2 ............................................42 45: Environmental Control Technologies: NOx/SOx Control Strategies............................................43 46: Chemicals, Materials, and Other Non-Fuel Uses of Coal 1..............................................................44 47: Gloval Climate Change: Science, Sequestration, and Utilization 5...................................45 48: Coal Utilization By-Products 2....................................46 49: Gasification Technolgies: Advanced Technololgies 3...........................................47 50: Gasification Technologies: Co-Gasification...................48 51: Environmental Control Technologies: Combustion Byproduct Applications, SOx .....................50 52: Chemicals, Materials, and Other Non-Fuel Uses of Coal 2..............................................................51 53: Global Climate Change: Science, Sequestration, and Utilization 6...................................51 54: Coal Utilization By-Products 3....................................52

Poster Sessions 1: 2: 3: 4: 5: 6: 7: 8: 9:

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Combustion Technologies ..............................................53 Gasification Technologies and PNNL-China .................54 Environmental Control Technologies .............................55 Global Climate Change...................................................56 Synthesis of Liquid Fuels: GTL, CTL, and BTL ............57 Chemicals, Materials, and Other Non-Fuel Uses of Coal....................................................................58 Coal Chemistry, Geosciences, and Resources ................59 Gas Turbines and Fuel Cells for Synthesis Gas and Hydrogen Applications ...................................................60 NETL-University Consortium ........................................61

SESSION 1 GASIFICATION TECHNOLOGIES: GENERAL SESSION 1

1-1 Worlds Largest IGCC Celebrates 10th Anniversary Wolfgang Schellberg, Uhde GmbH, GERMANY; Francisco Garcia Pea, ELCOGAS, S.A., SPAIN; Max Hooper, Uhde Corp. of America, USA This paper describes the worlds largest IGCC based on solid feedstock, a mixture of petcoke and coal at ELCOGAS in Puertollano, Spain. Uhdes PRENFLOTM process is used for the gasification of high-sulfur petcoke and high-ash coal. Operational results and lessons learnt in the last 10 years are described. For more than 65 years Uhde (incorporated with Heinrich Koppers and Krupp Koppers) is now active in the field of coal gasification technology, especially entrained-flow gasification with dry coal dust feeding. At the moment Uhde is involved in several projects in the United States based on PRENFLO coal gasification, for the generation of electric power and the production of liquid fuels. In addition, the new PDQ process (PRENFLO with Direct Quench) will be presented. It is a total water quench mainly for chemical application. 1-2 ZeroGen - Clean Coal Power Initiative with CCS Martin Oettinger, Zvonko Pregelj, Stanwell Corp., AUSTRALIA; Michael DeLallo, Jay White, WorleyParsons Group, Inc., USA; Rik van der Ploeg, Shell Global Solutions International, THE NETHERLANDS ZeroGen Pty Ltd, completed the initial phase of a multiple phase Feasibility Study (the project) for the design of an Integrated Gasification Combined Cycle (IGCC) incorporating carbon dioxide (CO2) capture and geosequestration. The project is located adjacent to the Stanwell Corporation thermal generation station in Queensland, Australia. The ZeroGen Project is a demonstration IGCC (Integrated Gasification Combined Cycle) Power Plant that will incorporate the capability to capture and sequester carbon dioxide (CO2) in geological formations. The primary objective of the facility s operational and demonstration program is to validate the application of CO2 capture and geosequestration in a coal based power generation facility. The Initial designs are based on the application of Shell gasification technology provided by Shell Global Solutions International. The focus of the initial phase, Phase 1A, of the project was the selection and confirmation of key process systems, the process design criteria and parameters for defining the process configuration. Shell Global Solutions International together with ZeroGen Pty Ltd and WorleyParsons Group Inc established the project process configuration; defined major system components, developed heat and mass balances, plant performance and emissions profiles, and characterized the carbon dioxide geosequestration. This paper provides an overview of the project and actities completed to-date including sequestration definition that has been carried out at the ZeroGen project location. 1-3 Developing Global Coal-Based Fuel, SNG & Chemical Projects Tim Cornitius, Zeus Development Corporation, USA Sustained higher energy prices and growing demand are driving alternative fuel development. Large-scale 80,000-b/d CTL projects that have been in the study phase of development are now being pulled off the shelves in China, India, Australia and South Africa. China is quickly building a coal-to-methanol-based fuel/chemical infrastructure to supply the growing demand for DME cooking fuel/LPG substitute, synthetic diesel, ammonia fertilizers, olefins, acetic acid and other products. US developers are focusing on coal/petcoke-based production of fuels, substitute natural gas and power as well as using CO2 for enhanced oil recovery and other applications rather than geological sequestration. 1-4 The Business Case for Coal Gasification with Co-Production David R. Berg; Brian Oakley, Scully Capital Services, Inc.; Andrew Paterson, Econergy, Inc., USA The Business Case for Coal Gasification with Co-Production quantifies the economics of coal gasification with co-production, with and without carbon sequestration; examines the market, policy/regulatory, and technical risks associated with developing large-scale early commercial U.S. co-production facilities; and evaluates the cost-effectiveness of incentives that could improve the financial prospects of early commercial projects. The results of this unique multi-sponsor

analysis suggest that coal gasification with co-production projects could be competitive and assured sources of transportation fuels, electricity, and other products over the long term. Sales of Fischer-Tropsch (FT) fuels from a plant (in late-2005 dollars, +/- 30 percent, and without taking into account recent cost escalation) must be priced in the range of $68$73 per barrel, or $52$56 per barrel in crude-equivalent price, to make construction and operation financially attractive. Compressing, transporting, and permanently sequestering carbon dioxide could increase the cost of synthetic fuel by approximately $10.00 per barrel, although revenues from enhanced oil recovery (EOR) could offset part or all of this increase for plants sited near EOR opportunities. However, energy prices have exhibited price volatility over at least the past 30 years and the credit rating agencies utilize a conservative long-term crude oil price expectation which reflects the likelihood that prices will fall, for periods of time, to prices significantly below todays energy prices. As a result, plants are likely to require the support of a purchase agreement with a creditworthy counterparty and, in some cases, government incentives to address a range of significant business risks, including price volatility in energy markets, high and escalating capital cost and operational uncertainties, and uncertainties about carbon policy. Thus, given the countrys vast coal reserves, the cost advantage co-production plants are likely to have in sequestering carbon dioxide, and the demonstrated commercial track record of coal gasification technologies, coal gasification with co-production affords the nation an opportunity that is worthy of careful consideration. 1-5 Cleanly Unlocking the Value of Coal Synthesis Energy Systems, J. Mathew Whitaker, USA Synthesis Energy Systems, Inc. is a global industrial gasification company whose business is to build, own and operate coal gasification plants utilizing its proprietary UGAS fluidized bed gasification technology to convert low rank coal and coal wastes into higher value energy products, such as transportation fuels. Its technology is the only commercial gasification technology that can process low rank and waste coals, which further advances project returns and unlocks extraordinary value from the coal resource. With its ability to process waste coal and the inherently friendly emissions profile of its facilities, SES is poised to make a positive impact on the overall environmental sustainability of coal conversion projects. And, with approximately fifty percent of the worlds coal falling into the low rank category, SES is positioned to facilitate resource owners in Cleanly Unlocking the Value of (their) Coal.

SESSION 2 SPECIAL SYMPOSIUM: NETL-UNIVERSITY CONSORTIUM

2-1 Robust and Efficient Oxygen Carriers for Chemical Looping Combustion Rahul Solunke, Tengfei Liu, Goetz Veser, University of Pittsburgh, USA Chemical looping combustion (CLC) is an emerging technology for clean energyproduction from fossil and renewable fuels. In CLC, an oxygen carrier (typically a metal) is first oxidized with air. The hot metal oxide is then reduced in contact with a fuel in a second reactor, thus combusting the fuel. Finally, the reduced metal is transferred back to the oxidizer, closing the materials loop. CLC is a green combustion technology since it allows for flame-less and completely NOx-free combustion without requiring expensive air separation. Furthermore, CLC produces sequestration-ready CO2-streams without significant energy penalty. Combined with sequestration, CLC thus enables high-efficiency, CO2 emissions-free combustion of fossil fuels, or combustion processes with negative CO2-footprint from biomass-derived fuels. However, CLC currently suffers from insufficient thermal stability of the oxygen carriers and slow re-oxidation kinetics. We present a significant step towards overcoming these hurdles through the development of novel nanocomposite oxygen carriers. Nanostructured oxygen carriers were synthesized, characterized (via SEM, TEM, XRD, BET, and chemisorption), and evaluated for their performance in the chemical looping combustion of coal-derived syngas streams via multi-cycle TGA experiments. The present contribution focuses on Ni-based carriers, where nanoscaled Ni particles are embedded in a high-temperature stable ceramic matrix. Both high-temperature stabilized alumina and silica matrices were synthesized and evaluated. Results are compared to that of conventional Nibentonite carrier. The nanocomposites show exceptional high temperature stability, highly reproducible oxidation-reduction cycles, and a significant acceleration of the reoxidation kinetics as compared to conventional carrier. The accelerated redox kinetics can be traced back to the elimination of solid-state diffusion limitations in the NiO overlayer, and the unusual stability of these materials is explained via a nano-caging effect.

Beyond the performance of these materials in the combustion of clean syngas streams, we recently extended these studies onto the performance of these carrier materials in the presence of sulphur contamination. The sensitivity of the metal as well as the carrier to S-contamination was evaluated over a wide temperature range, and its effect on structural stability of the materials as well as the reversibility of S-poisoning was investigated. Synthesis, characterization, and kinetic evaluation of the materials will be discussed in detail in the presentation. 2-2 Synthesis and Characterization of Bimetallic Nanocatalysts for Fuel Processing Applications Anmin Cao, Goetz Veser, University of Pittsburgh, USA Bimetallic nanoparticles (NPs), composed of two different metal elements, are of great interest from both scientific and technological perspective. The existence of a second metal can introduce new properties and, in particular, lead to significant improvements of catalytic properties compared to the monometallic catalyst. As a result, bimetallic catalysts have been the topic of intense research for many decades, and recent advances in the controlled synthesis of bimetallic nanoparticles have lead to a renewed interest in these systems. Our investigation of bimetallic nanocatalysts for fuel processing applications builds onto our previous work on supported nanocatalyst. We had previously successfully demonstrated the synthesis of a series of monometallic nanoparticles embedded in a nanostructured ceramic matrix, resulting in highly active and exceptionally stable nanocomposite catalysts. In the present work, we are extending this approach by transforming this nanocomposite into bimetallic catalysts via simple and efficient solution-based synthesis routes, either through a polyol-mediated process or a galvanic replacement route. In this approach, a monometallic nanocomposite such as Platinum Bariumhexaaluminate (Pt-BHA) is first synthesized via a micro-emulsion based sol-gel process and then transformed into different kinds of bimetallic catalysts as PtM/BHA (M=Fe, Sn, Cu, Au etc.). The resulting materials were characterized by a wide range of characterization techniques (SEM, TEM, XRD, BET, chemisorption, and TPD). The results demonstrate that the transformation process does not affect the morphology of the nanocomposite. The bimetallic particles are well dispersed in the ceramic matrix and retain the very high specific surface area of the monometallic precursor (>300 m2/g). However, their catalytic properties are fundamentally changed, as evidenced by CO-TPD (temperature programmed desorption) experiments. A strong peak shift occurs on both PtFe/BHA and PtSn/BHA while PtCu/BHA shows a linear superposition of the monometallic Pt-BHA and Cu-BHA equivalents. It is noteworthy that the temperature decrease for CO desorption on PtSn/BHA is as high as 194C, which corresponds to a reduction of the CO desorption energy by ~57.4 kJ/mol. Overall, we see this work as a first step towards the synthesis of highly efficient and stable multicomponent catalysts for fuel processing applications. 2-3 Nanostructured Water-Gas Shift Catalysts Yanan Wang, Shuang Liang, Goetz Veser, University of Pittsburgh, USA The water gas shift reaction (WGS) is a key reaction in the production of liquid fuels or hydrogen from fossil and renewable resources. It is widely used to adjust the CO:H2 ratio in synthesis gas for the production of chemicals and liquid fuels, and to reduce the carbon monoxide content in order to produce hydrogen-rich streams for fuel cells. While WGS is at high temperatures limited only by thermodynamic equilibrium limitations, at lower temperatures (<400C) the activity and stability of the catalysts is currently the limiting factor. Additionally, typical syngas-based feed streams contain significant amounts of contaminants, in particular S-compounds, which adds further constraints on the lifetime of WGS catalysts. In recent years, Au has received much attention as a potentially highly active WGS catalyst, in particular in combination with a CeO2-based support. Building onto these reports, we are currently working on the synthesis of highly robust nanostructured WGS catalysts in which noble metal nanoparticles are embedded into a nanostructured ceramic matrix. The work is an extension of our previous work in which we demonstrated the unusual stability of nanocomposite noble metal/alumina nanocomposite materials for the production of synthesis gas via catalytic partial oxidation of methane. The synthesis is based on a reverse microemulsion-templated sol-gel synthesis, in which the embedded metal nanoparticles are synthesized simultaneously with the ceramic matrix. Based on this approach, we have been able to synthesize a range of CeO2- and La2O3based nanostructured ceramic supports with very high surface area and good thermal stability over the relevant temperature range. Au, Ni, and Pt nanoparticles were successfully embedded into these structures, and the resulting materials were characterized via SEM, TEM, XRD, BET, and chemisorption. Main factors that affect the pore structure will be discussed in the presentation. In particular, we will demonstrate that the Ce:La ratio in mixed Ce/La-oxides has a profound impact on the surface area and morphology of the resulting materials, and that the pore structure of the materials can be further tailored via changes in the water:alkoxide ratio. We are

currently in the process of evaluating the activity of these nanostructured catalysts in WGS, as well as their stability in S-containing feed streams. 2-4 Exceptional Activity of Nanostructured Pt Catalysts in Low-Temperature CO Oxidation Yi Zhang, T. Sanders, G. Veser, University of Pittsburgh; S. Natesakhawat, C. Matranga, DOE-NETL, USA Nanomaterials have found much attention in catalysis over the past decade due to the very high surface area, and sometimes even completely novel reactivity, observed in the nanosize regime. One of the major hurdles in studying and utilizing the potential of nano-catalysts, however, is their insufficient stability at realistic reaction conditions. We have recently been able to overcome this barrier by synthesizing highly active and sintering-resistant nanocomposite catalysts, in which metal nanoparticles are embedded into a high-temperature stabilized alumina matrix. These materials thus combine the high reactivity of nano-sized noble metal particles with the excellent high-temperature stability of barium hexa-aluminates (BHA). Here, we present a study of CO oxidation at low-temperature conditions (T < 300 K) over a 1 wt% Pt-BHA nanocomposite catalyst. CO oxidation is a key reaction in any fuel processing scheme and has recently gained much attention in the context of preferential CO oxidation for the production of PEM-fuel cell ready hydrogen streams. At the same time, CO oxidation also serves as a relatively simple model reaction for fundamental studies of size effects in nano-sized catalysts. Low-temperature CO oxidation was performed by saturating a Pt-BHA sample with CO at 300 K followed by evacuation, cooling, and backfilling the chamber with O2 to 0.5 Torr. The reaction progress was monitored in-situ via FTIR over a temperature range of 200-300 K. We find an activation energy of ~ 9 kJ/mol for CO oxidation over Pt-BHA, which is about three times lower than previously published values for conventional supported Pt catalysts, indicating the exceptionally high reactivity of these nanocomposite catalysts. These FTIR results are further supported by ambientpressure kinetic studies which were conducted in parallel in a conventional fixed-bed reactor configuration. In order to gain deeper insights into this observation, we synthesized size-controlled Pt-BHA with Pt particles sizes in the range of ~2.5-5 nm. These materials were further studied via chemisorption and CO-TPD (temperature-programmed desorption). The TPD results shows a strong dependence of CO desorption energies on particle size, with an abrupt increase in CO bond energies by ~20 kJ/mol from particles with diameters above 4 nm to particles with diameters below 3 nm. The results confirm that nano-sized metals could hold a large potential as next generation fuel processing catalysts, and that nanostructuring may be a viable way to harvest this potential at realistic process conditions. 2-5 Analysis of Extracted Selenium from Coal-Combustion By-Products Lisa M. Horvath-Lohr, Dorothy J. Vesper, West Virginia University and DOENETL; Robert L. Thompson, DOE-NETL Site Support Contractor, Parsons; Karl T. Schroeder, DOE-NETL, USA Selenium found in coal utilization by-products (CUBs), such as coal fly ash, can be released into the environment. Separate analysis of species is crucial because Se toxicity and mobility are species dependent. Extractions mechanisms, such as column leaching experiments, can predict the retention of selenium species in coal combustion by-products. Analysis of the supernatant for total selenium and speciated inorganic forms can show if all species are accounted for from the extracted fly ash samples. The NETL CUB group conducted column leaching experiments on fly ash samples. The procedure consisted of four fly ash samples being placed in columns and leached with acetic acid, nitric acid and sodium carbonate, separately over a four-month time period. Supernatant samples were taken every two to three days throughout the four month period and analyzed for both total and speciated selenium along with other major and trace elements. Speciation of the supernatant for oxyanions selenite (SeO3-2) and selenate (SeO4-2, was conducted using a reverse-phase column coupled to a Perkin Elmer ICP-MS with DRC system. These ions have been reported as the most likely Se species associated with fly ash samples (Mattigod and Quinn, 2003). Separation of selenite and selenate is achieved within 2 minutes on a Brownlee C8 column using a 50 L injection loop and a flow rate of 1.0 mL/min at 25C. The mobile phase consists of an acetic acidammonium acetate buffer plus tetrabutylammonium hydroxide for the ion-pairing agent, and 5% methanol, resulting in a pH of 5.2. Initial results show a large mass balance deficit between the total Se and the sum of the Se-species concentrations. This indicates that there is a loss of species during the extraction or speciation, or there are other species present that are not accounted for using this method such as elemental selenium or organic phases, or instrument interferences. The presence of a deficit has been reported by other researchers (EPRI, 2006) although many studies have been focused on these species alone (Jackson and Miller, 1998; EPRI, 2006; NSMP, 2006). References: EPRI (2006) Speciation and attenuation of Arsenic and Selenium at coal combustion by-product management facilities. USDo Energy. 3: 69.

Jackson BP, Miller WP (1998) Arsenic and selenium speciation in coal fly ash extracts by ion chromatography-inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry 13: 1107-1112. Mattigod SV, Quinn TR (2003) Selenium content and oxidation states in flys ashes from western U.S. coals, in KS Sajwan, ed., Chemistry of trace elements in fly ash: New York, Kluwer Academic/Plenum Publishers, p. 143-156. NSMP (2006) A comparison of methods for measuring total selenium and selenium species in water. Updated May 8, 2006, Retrieved 09/2007, from http://www.ocnsmp.com/pdf/Se_Speciation_Methods_Final%20Report_8May06.pdf.

studies, weldability and fabricability evaluations, and review of applicable design codes and standards. These evaluations are nearly completed and are providing the confidence that currently-available materials can meet the challenge. Key findings from the study will be presented. 3-4 Post-Combustion CO2 Capture Technologies John Wheeldon, EPRI, USA This paper provides a review of selected post-combustion CO2 capture technologies and processes under development. The majority of current efforts are focused on regenerative capture processes identifying new solvents and adsorbents with the balance of activities proposing new processes. A wide range of options is required as there is no guarantee that improvements being identified or technologies emerging will prove to be economically viable. 3-5 DOE/NETLs Mercury Control Technology R&D Program - Recent Results from Phase III Testing Lynn A. Brickett, Thomas J. Feeley, III, B. Andrew OPalko, DOE-NETL; Andrew P. Jones, Science Applications International Corporation, USA DOE/NETL has worked with industry, research organizations, and academia to develop advanced mercury control technology for coal-based power systems. Over the past seven years, this research has focused on the full-scale and slip-stream field testing of activated carbon injection (ACI) and flue gas desulfurization enhancements at nearly 50 U.S. coal-fired power plants. The goal of the field testing was to demonstrate high levels (50-90%) of mercury capture over an extended period of operation, while also reducing the cost of mercury removal. The field testing program has successfully met this goal. Due in large part to this success, coal-fired power plant operators have begun to install mercury control technology in response to state regulations. As of April 2008, orders have been placed for over 44 gigawatts of ACI. This paper will provide an update on DOE/NETLs mercury control technology R&D program, including an assessment of the cost of capture.

SESSION 3 COMBUSTION TECHNOLOGIES 1

3-1 Engineering and Economic Evaluation of a 1300F Series UltraSupercritical Pulverized Coal Plant John Wheeldon, EPRI, USA The strategy for lowering the cost of CO2 capture from coal-based power plants includes raising generating efficiency. For pulverized coal (PC) plants this means progressing to ultra-supercritical (USC) steam conditions, arbitrarily defined as having temperatures above 593C (1100F). Currently, USC steam temperatures are limited to approximately 627C (1160F) by the use of ferritic steels, the most advanced commercially available steels. To go to higher temperatures, high-nickel alloys must be used, and these are still under development. EPRIs UltraGen Initiative is a proposed series of projects to advance commercialization of USC PC power plants with near-zero emissions of criteria pollutants. One of these projects is UltraGen II, a 750-MW 1300F Series plant design, and this study was formulated to support its development. The objectives included establishing the plants generating efficiency and capital and operating costs to determine the cost-effectiveness of USC PC plants as a means of reducing the cost of CO2 capture and storage. Included is an assessment of additional development needs that may be required before demonstrating the technology. Finally, design concepts that could potentially result in further increases in efficiency and decreases in emissions are discussed. 3-2 Reducing CO2 Emissions by Improving the Efficiency of the Existing Coalfired Power Plant Fleet Chris Nichols, Gregson Vaux, Connie Zaremsky, James Murphy, Massood Ramezan, DOE-NETL, USA In 2005, coal-fired power plants in the United States built before 1980 accounted for 26% of total U.S. CO2 emissions. Analysis of GHG mitigation policies indicates that for CO2 taxes under 30-40 $/mtCO2 most of the existing coal-fired power plants will choose to operate as they are and pay the tax. If so, they will operate under a greatly enhanced economic incentive for efficiency improvements. The average efficiency of the pre-1980 sub-critical fleet is 31%, while the top 10% of this group achieves around 36%, showing that significant improvement is possible for older plants. This paper sets forth an estimate of the aggregate CO2 emissions reductions that could be achieved through efficiency upgrades, taking into account the limitations at each plant. Individual power plants are grouped according to coal grade, boiler technology, pollution control equipment, altitude, water source, and other factors. The efficiency improvement opportunity is estimated as the difference between the best performers in each group and the rest. 3-3 Materials for Advanced Ultra Supercritical Fossil Plant R. Viswanathan, Electric Power Research Institute; Robert Purgert, Energy Industries of Ohio; Patricia Rawls, DOE-NETL, USA One of the pathways for achieving the goal of utilizing the available large quantities of indigenous coal, at the same time reducing emissions, is by increasing the efficiency of power plants by utilizing much higher steam conditions. The US Ultra-Supercritical Steam (USC) Project funded by US Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) promises to increase the efficiency of pulverized coalfired power plants by as much as nine percentage points, with an associated reduction of CO2 emissions by about 22% compared to current sub-critical steam power plants, by increasing the operating temperature and pressure to 760C (1400F) and 35 MPa (5000 psi), respectively. Preliminary analysis has shown such a plant to be economically viable. The current project primarily focuses on developing the materials technology needed to achieve these conditions in the boiler. The scope of the materials evaluation includes mechanical properties, steam-side oxidation and fireside corrosion

SESSION 4 GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND HYDROGEN APPLICATIONS 1

4-1 DOEs SECA Program: Progress & Plans Wayne A. Surdoval, DOE-NETL, USA Developing technology to ensure that the use of coal is an economic energy source while maintaining Americas ever tightening environmental and climate requirements is of crucial U.S. national importance for solving todays energy security concerns. The U.S. Department of Energys (DOE) is sponsoring the research and development (R&D) of solid oxide fuel cells (SOFCs) under the Solid State Energy Conversion Alliance (SECA). SECA is leading the way to low-cost, environmentally-friendly, fuel-flexible SOFCs and coal-based SOFC power generation systems for stationary markets. SECA is managed by the DOEs National Energy Technology Laboratory (NETL) Program Office, in partnership with private industry, educational institutions and national laboratories. SECA has three major focus areas: Cost Reduction, Coal-Based Systems, and Core Technology R&D. The SECA Cost Reduction goal is to reduce the manufactured cost of SOFC power systems to $400 per kilowatt by 2010. Concurrently, Coal-Based Systems is pursuing the scaling, aggregation and integration of the technology for use in large Integrated Gasification Fuel Cell (IGFC) systems for central power generation applications in order to efficiently and cleanly utilize the nations large coal reserves. The performance of IGFC systems will be consistent with Fossil Energys Advanced Power Systems goals, including over 45 percent efficiency (coal higher heating value HHV to electricity) with 90 percent carbon capture. Megawatt-class proof-of-concept systems will be demonstrated no later than 2012 and 2015. In support of these goals, SECA Industry Teams are establishing the requisite manufacturing base, and the SECA Core Technology Program is providing vital R&D to further improve on the substantial progress made through the SECA program. The first series of SOFC system prototypes fielded by the SECA Industry Teams surpassed SECAs intermediate-targets for efficiency, reliability and production cost. Furthermore, NETL analyses show that an IGFC system with a pressurized SOFC and catalytic gasification with recycle permits a high net efficiency approaching 60 percent HHV with carbon capture greater than 90 percent. Separate fuel and air streams to the SOFC substantially reduce the amount of water required to condense, recycle and reuse process water, and without a steam cycle, there is virtually no external water requirement. The high efficiency maintains an economic cost of electricity (COE) due to less fuel per megawatt hour and a smaller plant. Meeting SECA goals result in the lowest COE coal option with environmental regulation compliance and the ability to

capture greater than 90 percent of the carbon. This technology makes substantial strides in permitting clean economic energy production from coal in any state in the U.S. 4-2 Development of an Efficient Coal-Fueled Solid Oxide Fuel Cell Power System Concept Equipped for CO2 Separation Wayne L. Lundberg, Larry A. Shockling, Stephen E. Veyo, Eugene E. Smeltzer, Gordon A. Israelson, Arun K. S. Iyengar, Siemens Power Generation, Inc., USA A baseline, clean, coal-fueled, high-efficiency, fuel cell-based electric power system concept has been developed as part of U.S. Department of Energy contract no. DEFC26-05NT42613. Key system design objectives were high electric efficiency with CO2 separation at a plant capacity greater than 100 MWe. The efficiency was to be greater than 50% (net AC/coal HHV) and it was required that at least 90% of the carbon exiting the coal gasification system in syngas must be separated (in CO2 form), ready for sequestration. The selected baseline power system cycle concept integrates pressurized SOFC generator modules with a gas turbine and a steam turbine bottoming cycle. To maximize the system electric efficiency, a high degree of subsystem heat integration is employed. CO2 separation from syngas is accomplished prior to utilization by power generation components. The power system cycle concept is described, major system components are identified and characterized, the component physical arrangement is discussed, and results of the system electric performance and conceptual-level cost evaluations are presented. A power system proof-of-concept demonstration is planned at a capacity level of approximately 5 MWe. 4-3 Progress in Development of Coal-Based Solid Oxide Fuel Cell Power Plants Hossein Ghezel-Ayagh, Jody Doyan, Jim Walzak, Sven Tobias Junker, Dilip Patel, Allen Adriani, Peng Huang, FuelCell Energy, Inc; David Stauffer, Vladimir Vaysman, WorleyParsons Group Inc.; Brian Borglum, Eric Tang, Randy Petri, Versa Power Systems; Chakravarthy Sishtla, Gas Technology Institute, USA FuelCell Energy (FCE) is involved in Phase I of a multiphase project for development of very efficient coal-to-electricity power plants with near-zero emissions. The project is being carried out through a cooperative agreement with the Department of Energys Solid Energy Conversion Alliance (SECA) program. The primary objective of the project is to develop an affordable, multi-MW-size SOFC-based power plant system for utilization of synthesis gas (syngas) from a coal gasifier with near-zero emissions. Some of the key project objectives are the development of SOFC technologies, cell and stack size scale-up, SOFC performance optimization, increased stack manufacturing capacity development and MW-class module engineering design. The project is organized in three phases: Phase I of the project will focus on cell and stack development. This will include the scale-up of existing SOFC cell area and stack size (number of cells) and performance improvements. Preliminary engineering design and analysis for multiMW power plant systems will also be conducted. The Phase I deliverable will be test demonstration of a SOFC stack building block unit that is representative of a MW class module on simulated coal syngas. Upon successful completion of Phase I and selection by DOE to continue, Phase II of the project will focus on modularization of the Phase I stack building block units into a MW-size module. Detailed design engineering and analysis for multi-MW power plant systems will also be conducted. The Phase II deliverable will be the test demonstration of a MW-size representative SOFC stack module on simulated coal syngas. Upon successful completion of Phase II and selection by DOE to continue, Phase III of the project will focus on the design and fabrication of a proof-of-concept multiMW power plant. The Phase III deliverable will be tested for at least three years at a suitable SECA selected site. FCE utilizes the planar cell and stack technology of its SOFC provider, Versa Power Systems Inc (VPS) for all its SOFC development programs. VPS has well established processes, quality control procedures and equipment for the manufacture of small to intermediate size cells and stacks. This serves as a solid basis for cell area and stack size scale-up. The other key objective is implementation of an innovative system concept in design of a multi-MW power plant with anticipated coal-to-AC efficiencies approaching 60% on a coal HHV basis. Combined with existing carbon dioxide separation technologies, the power plant is expected to achieve ultra high efficiencies while emitting near-zero levels of emissions of SOx, NOx, and greenhouse gases to the environment. The development of this technology will significantly advance the nations energy security and independence interests, address pollution and greenhouse gases concerns, and help enhance the nations economic growth. The advances in stack scale-up, fuel cell module design, and system configurations including integration with gasification and coal gas clean-up processes will be presented.

4-4 System Tradeoffs and Sensitivities in an Integrated Gasification Fuel Cell Combined Cycle with Carbon Capture Eric Grol, DOE-NETL; Dale Keairns, Richard Newby, Science Applications International Corporation (SAIC), USA The U.S. Department of Energys National Energy Technology Laboratory (NETL) conducts research of solid oxide fuel cells (SOFC) as part of an advanced power generation portfolio. Part of this research involves the evaluation of integrated system concepts that can maximize the potential offered by solid oxide fuel cell technology. SOFC technology enables the use of advanced gasification technology to achieve system efficiencies targeted at 60% while capturing greater than 90% of carbon dioxide emissions. Solid oxide fuel cells can increase overall system performance with significant methane content (e.g. 15-25%) in the fuel gas. An example is the use of low temperature catalytic gasification technology, which has the potential to achieve improved gasifier performance with methane concentrations that benefit the fuel cell system operation. System concepts are presented to achieve high efficiency electric power generation while capturing carbon dioxide. Material and energy balances for these systems are summarized. 4-5 Micro-mixing Fuel Injection for Low Emission Combustion of Hydrogen for Gas Turbine Applications Adel Mansour, Erlendur Steinthorsson, Brian Hollon, Parker Hannifin Corporation; Steven Hernandez, Qing Wang, Howard Lee, Vincent McDonell, University of California, Irvine, USA The performance of a set of micro-mixing fuel injectors operating on hydrogen fuel is investigated using experiments and computational fluid dynamics. A micro-mixing fuel injector consists of multiple, small (thimble size) and closely spaced mixing cups, within which fuel and air mix rapidly at a small scale. The goal of the research is to develop injectors capable of ultra-low NOx emissions-performance when operating on hydrogen and syngas fuels. In the present work, flame structure, flash-back performance and emissions results are presented for a number of mixing-cup configurations at various equivalence ratios and pressures up to 5 atm. The structure of the hydrogen/air flame is captured using OH* chemiluminescence and emissions are measured using EPA certified approach. The results demonstrate that a number of configurations produce low single-digit NOx emissions for a range of adiabatic flame temperatures, inlet temperatures and pressures while remaining robust relative to flashback and lean blowout. Specifically, emissions in the range from 2 ppm to 5.5 ppm were demonstrated at adiabatic flame temperature of 1750 K and at pressures up to 5 atm, without flashback on 100% hydrogen fuel. Based on the results obtained to date, the micro-mixing approach appears promising relative to achieving low emissions while maximizing scalability and fuel flexibility.

SESSION 5 COAL PRODUCTION AND PREPARATION 1

5-1 Future Impacts of Coal Distribution Constraints on Coal Costs David McCollum, Joan Ogden, University of California-Davis, USA Coal consumption in the United States is projected to rise significantly over the next few decades. About two-thirds of all coal in the U.S. is transported via rail, but certain coal-carrying rail corridors are already up against their capacity limits. Any future increase in coal demand will probably necessitate significant capital investment by rail companies. This study seeks to identify existing capacity and potential constraints within the U.S. coal distribution network and to estimate the costs of alleviating those constraints under several scenarios of coal demand growth. We consider coal demand both for electricity generation and production of hydrogen fuel for transportation applications. Using a model of the U.S. rail network, we estimate the costs of adding new rail capacity to meet growing coal demand. Total railroad capital investments could be on the order of $1.5$11.0 billion over the 20042050 timeframe, depending on the particular scenario we model. While these infrastructure investments are substantial, it does not seem likely that the delivered cost of coal will necessarily increase throughout the country as a result. Hence, on a cost basis our analysis shows that investment in coal distribution infrastructure should not be a barrier to a coalbased Hydrogen Economy.

5-2 A Rheological Study on the Pumpability of Co-Mingled Biomass and Coal Slurries Wei He, Chan S. Park, Joseph M. Norbeck, University of California, Riverside, USA There is considerable interest in the gasification and subsequent conversion of coal and biomass mixtures to synthetic liquid fuels as a means of reducing the overall net life cycle CO2 emissions when compared to petroleum. Our laboratory has developed a steam hydrogasification technology which has been shown to be very efficient for gasification of biomass and coal feedstocks and mixtures. However, the pumpability of coal and biomass slurries in gasification processes is a critical issue that needs to be more fully understood in order to maintain the high efficiencies of the technology. The pumpability is dependent on the slurrys rheological properties (e.g. shear rate, shear stress and viscosity) which in turn are related to the slurrys physical properties. In this study, wood was initially hydrotreated to make a high solid content biomass paste and then mixed in varying percentages with a coal-water slurry. The effect of solid particle size of the slurry, the initial coal and wood particle size distribution, and the solid/water ratio on shear rate and viscosity were determined using a rotational rheometer. Our experimental results show that larger particle size offers better pumpability. The presence of a high percentage of biomass in solid form significantly decreased slurry pumpability. The optimum solid/water ratio has been determined with various coal/biomass mixtures. The results of these experiments will be presented. 5-3 Application of Flotation by Ecological Loads of the Cerny Prikop Stream Peter Fecko, Iva Janakova, Anna Kovalova, Monika Madrova, Lucia Kovalova, VSB-Technical Univerzity of Ostrava, CZECH REPUBLIC The stream Cerny prikop is located in the Ostrava city districts of Marianske Hory, Moravska Ostrava and Privoz. This locality belongs among the most polluted areas in Ostrava as the locality is unbearably polluted by the Coking Plant of Jan Sverma, company BorsodChem MCHZ (the chemical plant), City Waste Water Treatment Plant and a number of other companies in the given territory all the way to its mouth to the Odra River. Moreover, the area is also affected by the construction of motorway D 47. The sediments of Cerny prikop represent a significant ecological burden within the Ostrava urban area. They are contaminated by a wide range of organic pollutants which have never been exactly identified. The proposed project shall deal with the removal of selected organic pollutants, such as GRO, PCBs and PAHs by means of typical preparation method of flotation. The basic research should bring minimization of the content of selected hazardous substances from the Cerny prikop sediments. It is apparent from the laboratory experiment results that after flotation test there is a cca 80% removal of PAHs, 90% removal of PCBs and 78% removal of GRO. 5-4 Removal of Heavy Metals from Industrial Waste Water by Mineral Resources as Adsorbents Nikolas Mucha, Vladimr ablk, Kateina Cechlov, Alena Sochorkov, Iva Jankov, VSB-Technical University of Ostrava, CZECH REPUBLIC Sewage treatment prior to their discharge into water courses is a vital precondition for the preservation of surface and ground water sources quality. It is necessary to eliminate the influence of various inorganic and organic contaminants to the minimum, to clean up their effects or minimize them at least. One way to remove such substances from water are adsorption technologies. These technologies of water purification are implemented especially in cases when biological treatment is unsuitable or insufficient. Among the most tested adsorbents of heavy metals there are for example zeolites, carbonates, clays, peat, iron oxides, etc. With regard to the fact that currently recycling and waste minimization technologies are being enforced, efforts are made to make the most efficient use of all materials. Thus, earlier unused materials are becoming significant resources for todays industry. Among those materials there are also waste rocks produced during brown coal extraction in the North Bohemian and Sokolov Basin, which can be used as adsorbents. Their advantages are their natural origin, low price, high abundances and improvements to economic effectiveness of mining. Moreover, as they are processed they need not be dumped and do not strain the environment. 5-5 Studies on Reducing Low Rank Coal Moisture by Drying Wenhui Zhang, Huijun Xu, Shun Lu, Shunwei Gao, Xiaodian Wang, Xirong Qiao, China Shenhua Energy Company LTD, CHINA In order to reduce moisture of low rank coal produced by Shenhua, a process of drying coal process with mixture of air and flue gas has been developed. The Characteristic of drying coal process with mixture of air and flue gas is that the temperature of the mixture of air and flue gas is below 210C which is below the ignition temperature of low rank coal. The content of oxygen in mixture of air and flue gas is below 19%. The explosion and combustion during coal drying do not take place below 210C and

oxygen content of 19%. The relative humidity of mixture of air and flue gas effect the rate of drying coal. In order to increase the rate of drying coal, the size of particle of coal is below 30 mm. Compared with other kind of drying coal process, the process of drying coal developed by shenhua is safe, high efficient and low cost. Shenhua drying coal process is one of most promising drying coal processes for low rank bituminous coal. It is feasible to dry larger quantities of low rank bituminous coal for use at the power plant.

SESSION 6 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL 1

6-1 The Most Effective Coal-To-Gasoline Conversion - Where Coal and Nuclear Come Together Heinz Termuehlen, USA; W. Jaeger, H.-J. Hamel, GERMANY We can become independent of any oil import by producing gasoline from coal utilizing nuclear energy. Because conventional coal combustion adversely effects the environment, it is important to minimize this effect when using coal in the future. Coal as well as nuclear fuel are available for centuries to come. Presently, nuclear fuel is used for power generation, with about 20% of the electric power in the US being generated in nuclear power plants. This paper shows a way to most effectively combine the utilization of coal and nuclear fuel for the production of domestic gasoline. Coal, as the most abundant fossil fuel in the US (about 95% of all fossil fuel), can be converted to gasoline. However, the conversion process must be most effective with the highest gasoline production per specific coal consumption, leading to the lowest adverse effect on the environment. Integrated coal gasification combined cycle (IGCC) power plants are in operation for power generation. In these plants coal is gasified for combustion in a gas turbine of a combined cycle power plant to generate power. An IGCC plant could also be designed for the production of methanol, which can be converted to gasoline. In such IGCC plants the coal gasification is an exothermic process demanding a large amount of heat energy from the coal for this process. To minimizing the coal consumption for the production of a maximum of methanol and then gasoline, the combination of a high temperature gas cooled reactor (HTGR) with a coal-to-gasoline conversion plant has been developed. This process features a highly endothermic coal gasification process, which utilizes the high temperature gas discharge from the reactor in a steam reformer. A hydro-gasifier is utilized. This paper describes such combined plant. The capital and operating costs for this plant have been estimated and as result, gasoline production costs below $2.80 per gallon based on coal costs of $50 per ton can be expected. With this plant concept the discharge of pollutants from the use of coal is minimized. 6-2 Rentechs Coal-To-Liquids Process: GHG Life-Cycle Inventory Relative to Conventional Crude Oil Derived Distillate Fuels Robert L. Freerks, Rentech, Inc., USA Rentech presented information at the 2007 International Pittsburgh Coal Conference on its initial assessment of the life-cycle greenhouse gas (GHG) emissions for a Coal-toLiquids (CTL) project in Natchez, MS. The Natchez project will process petroleum coke and/or coal and biomass in a modern CTL plant designed by Rentech based on a proprietary iron-based Fischer-Tropsch (FT) catalyst. The capture of CO2 is an integral part of the plant design. The CO2 will be sequestered in existing oil fields as part of planned enhanced oil recovery (EOR). This presentation updates the life-cycle inventory with emissions estimates for coal and petroleum coke processing into summer and winter-grade diesel fuel and kerosene-based jet fuel. Naphtha produced at the plant will be sold as an ethylene/propylene feedstock. Comparisons are made to typical crude oils and the average crude slate refined in the U.S. Gulf Coast region. Ranking of the various distillate fuel alternatives is dependent on how emissions are allocated for the various refined products and feedstocks being compared. Relative to the marginal quality crude processed in the region, the GHG emissions for the CTL plant with CO2 sequestration are significantly lower. The emissions are even lower if credit is taken for the displacement of petcoke in the electric power market and for the superior quality of the FT naphtha, diesel and jet fuel. 6-3 Plants for Conversion of Coal to Heavy Crude Elliot B. Kennel, Mayuri Mukka, Alfred. H. Stiller, John W. Zondlo, West Virginia University, USA; Gilbert Chalifoux, Quantex Energy Inc., CANADA Conversion of coal feedstocks from the solid to liquid state generally involves adding hydrogen and cracking molecules in the coal via different processes. Alternatively, solvent extraction is one means by which this can be accomplished. A commodity solvent such as a coal tar distillation product or petrochemical dilutent is hydrogenated

to enhance its ability to digest coal. Crushed coal is then digested in the solvent resulting in conversion of up to 90% of the dry, ash-free coal to the liquid state. Solids are removed from the slurry via centrifugation. The centrifuged solids could be blended with other forms of coal or biomass, and would make up only a small percentage of the total fuel feed. The resultant synthetic crude is to be distilled to produce a binder pitch. The overhead liquids can be recycled as a coal solvent, or alternatively, upgraded to produce value-added fuels and chemicals. The distillation bottoms can be utilized as a binder pitch. Alternatively, a delayed coker can be used to thermocrack the heavy molecules to produce lighter liquids in addition to an anode grade coke residue. 6-4 Measurement of Coal Slurry Viscosities at High Temperature and High Pressure Yan Wu, Zhi Guo, Ke-jian Li, Shi-dong Shi, Ping He, Beijing Research Institute of Coal Chemistry, China Coal Research Institute, CHINA An apparatus for measuring coal slurry viscosity at high temperature and high pressure were set-up. Two calculation methods named power number method (at Re < 300)and shearing strength dissociation method for processing experiment data of the apparatus have been made in this paper. The two calculation methods are calibrated with some reagents such as glycerin etc. The fundamental work provides viscosity data of coal slurry at liquefaction conditions. Viscosity-temperature curves for a Chinese brown coal slurry and a heavy coal liquefaction stream produced from hot separator bottom of bench scale test unit under H2 pressure were obtained. The study results showed that the slurry viscosities are strongly affected by coal characteristics, heating rate and temperature. Curves of apparent viscosity versus temperature are suit for Vogel equation.

Improve the integration with downstream applications such as shift for chemical applications, water is added directly to the syngas, not via a saturator cycle in the shift section. Allow power applications with integrated SCGP and downstream CO2 sequestration Allow gasification of high-fouling coals (with high alkaline contents and high chlorine), which cannot easily be processed with a syngas cooler. Allow the choice between keeping the ash dry to a large extent or go fully wet. Since the gasifier design is kept the same, the key advantages of SCGP are retained, such as its membrane wall (heat protection of the gasifier via water cooling and steam production), a separate gas outlet and slag outlet for processing high-ash coals, and multiple burners, which allow large single-unit capacities and an efficient slag removal. 7-3 Co-Generation - Opportunities in the Integration of Chemicals Production and IGCC Power Production Esben Lauge Srensen, Poul Erik Hjlund-Nielsen, Martin Dan Palis Srensen, Jrgen Madsen, Haldor Topse A/S, DENMARK Coal is becoming an increasingly important raw material for the power and chemicals production. Attractive synergies can be obtained by combining power generation with the production of chemicals. In an Integrated Gasification Combined Cycle (IGCC) plant, power is produced by burning the synthesis gas produced by gasification in a gas turbine. This synthesis gas is also an excellent raw material for the production of valuable chemicals such as methanol, hydrogen, high-grade DiMethyl Ether (DME) and ammonia, or fuels with practically no market saturation such as gasoline, fuelgrade DME, synthetic natural gas (SNG) and Fischer-Tropsch (FT) diesel. By combining the IGCC power production with chemical production, the plant becomes less sensitive to changes in the price of power because alternative products may be produced. Some of these products can be exported or stored and used as fuel to accommodate peak loads when the price of power is high. In many gasification processes, partial substitution of coal with suitable sources of biomass will result in an efficient way of meeting future power and transportation fuel requirements from renewable energy sources. The process impacts of doing so should however be carefully considered. Due to the concern for the possible effect of carbon dioxide (CO2) on the global climate, it is also necessary to analyse the effect of CO2 capture on the integration schemes. Many studies have focused on the options for CO2 sequestration from IGCC plants. This paper presents examples of attractive systems obtained by a combination of power and chemicals production, as well as options for CO2 capture. 7-4 Effect of Gas-Turbine ASU Integration in Dynamics and Control of IGCC Power Plants Priyadarshi Mahapatra, B. Wayne Bequette, Rensselaer Polytechnic Institute, USA Gas turbines will certainly play a major role in future power generation and several well justified concepts have been developed or are the subject of major feasibility studies. However, the combined cycle is now well established and offers superior performance to any of the competing systems that are likely to be available in the medium term for large scale power generation applications. In Integrated Gasification Combined Cycle (IGCC) power plants, integration between gas-turbine and air separation unit is determined by the percentage of total air separation unit (ASU) air required coming from GT compressor which has a common shaft with the gas turbine. This integration is a tradeoff among efficiency, investment cost, operational flexibility, power, and startup/shutdown times. In this study, a pressure-driven dynamic model for gas-turbine/gas-compressor (using ASPEN DYNAMICS) has been developed to investigate feasibility and applicability of integration with the ASU during varying load demands. The gas-turbine model analysis incorporates internal surge-prevention controllers and inlet guide vanes (IGVs) to prevent exceeding maximum power output per turbine. The ASU is a cryogenic heat-integrated double column, with the condenser of the high pressure column supplying the heat for the reboiler of the low pressure column. The process variables operating at different time scales are responsible for the difficulties with commonly used PID-based control scheme with disturbances in syngas and injected nitrogen feed pressure. In this paper we present a detailed operability analysis to better understand inherent control system performance limitations. Further, we develop a model predictive control strategy that handles rateof-change and multiple time-scale constraints imposed by the process design of the air separation and gas turbine/compressor units. Finally we close with a discussion of future work on the simulation and control of an entire IGCC power plant.

SESSION 7 GASIFICATION TECHNOLOGIES: GENERAL SESSION 2

7-1 Application of Siemens Fuel Gasification Technology for Different Types of Coal Frank Hannemann, Manfred Schingnitz, Joachim Lamp, Baoting Wu, Siemens Fuel Gasification Technology GmbH & Co. KG, GERMANY The Siemens Fuel Gasification (SFG) technology can gasify a wide range of feedstocks including petcoke, hard coal, lignite, and low rank fuels like refinery residuals and biomass. The technology has been selected for a number of projects in the last years. Applications range from chemicals & hydrogen production to IGCC. Commissioning of Siemens first SFG-500 gasifiers is expected to start in 2009. This paper will review the SFG technology and current projects. An extensive research and development program is underway to improve design features of Siemens gasification technology which in particular focuses on customer requirements such as high availability and low maintenance. The paper will describe Siemens approach to provide gasification solutions depending on rank of coal, ash composition and ash content. These particular parameters define operability and applicability of entrained flow gasification systems which operate well above ash melting point. Slag characterization is essential for slag flowing behavior, agglomeration and leachability. Gasification test runs in combination with slag viscosity analysis and determination of fusion temperature provide sufficient confidence to decide on optimal gasification temperature and potential addition of well selected flux material. Assuming a wide range of coal feedstock opportunities worldwide the Siemens Fuel Gasification test center in Freiberg represents a unique facility which offers a 5 MW gasification pilot plant to investigate slag fusion and agglomeration behavior and in addition two test rigs for slag viscosity analysis and high dense phase pulverized coal conveyance. 7-2 A Water Quench for the Shell Coal Gasification Process Guillaume Fournier, Wouter Harteveld, Mark Prins, Thomas Von Kossak, Rob Van den Berg, Shell Global Solutions International B.V., THE NETHERLANDS The Shell Coal Gasification Process has been developed for a high efficiency and minimum emissions to the environment and as part of integrated coal gasification combined cycle. The standard arrangement of the gasifier and syngas cooler internals has been licensed many times in China and Europe. The syngas cooler is instrumental to achieve these high efficiencies and minimum emissions, yet the current situation in syngas manufacturing calls for the application of a water quench downstream the coal gasification reactor as this would have several advantages: Reduce the SCGP capital expenditure due to line-up simplification: no syngas cooler, no candle filter and a simpler shift line-up

SESSION 8 HYDROGEN FROM COAL 1

8-1 Development of Membranes for Purifying Hydrogen Produced by Coal Gasification and/or Methane Reforming U. (Balu) Balachandran, T. H. Lee, Y. Lu, C. Y. Park, S. E. Dorris, Argonne National Laboratory, USA Hydrogen, the fuel of choice for both electric power and transportation sectors, can be produced from fossil and renewable resources by various technologies. Because it is produced in gas streams with numerous components, purification is a critical step in producing hydrogen. Argonne National Laboratory is developing dense cermet (i.e., ceramic-metal composite) hydrogen transport membranes (HTMs) for separating hydrogen from mixed gases, such as the product streams that are generated during coal gasification and/or methane reforming. Hydrogen separation with Argonnes HTMs is nongalvanic (i.e., it does not use electrodes or an external power supply to drive the separation), and it yields high purity hydrogen, thereby eliminating the need for postseparation purification steps. HTMs were prepared by mixing 50 vol.% 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 range of 500-900C. This rate varied linearly with the inverse of membrane thickness and reached 33 cm3[STP]/min-cm2 at 900C for an 15-mthick membrane on a porous support structure when 100% H2 at ambient pressure was used as the feed gas. Because good chemical stability is critical for HTMs, due to the corrosive nature of product streams from coal gasification and/or methane reforming, we evaluated the effect of various contaminants on the chemical stability of cermet membranes. Hydrogen sulfide (H2S), a particularly corrosive contaminant, impedes hydrogen permeation through cermet membranes by reacting with them to form palladium sulfide (Pd4S). To evaluate the chemical stability of membranes, the Pd/Pd4S phase boundary was determined in the temperature range 450-650C in tests using various feed gases that contained 10-73% H2 and 8-400 ppm H2S. Hydrogen flux measurements showed that at 900C, the cermet membranes are stable for up to 1200 h in gases that contain 400 ppm H2S. The present status of HTM development at Argonne will be presented in this paper. 8-2 Development and Testing of a Coal to Fuel Cell Grade Hydrogen Technology Package and a Pathway for Hydrogen Uptake in New Zealand Anthony H. Clemens, Tana Levi, Ruben Smit, CRL Energy Limited; Alister Gardiner, Industrial Research Limited; Jonathan Leaver, Unitec New Zealand, NEW ZEALAND The coal to fuel cell grade hydrogen technology development programme is entering its final stages with the testing of the fully integrated low rank coal gasifier, syngas clean-up and hydrogen production line and fuel cell assembly. The paper describes the new technology, considers several issues that arose during its development and how these were addressed. The paper also considers likely pathways whereby hydrogen may be taken up within the future New Zealand energy system. The methodology was similar to that used within the European Union as part of its HyWays project. A series of potential individual hydrogen supply chains were identified in consultation with energy stakeholders from government and industry and the contributions of each chain in achieving future energy scenarios (out to 2050) were identified using a system dynamics modeling package. The results of the individual chain selection process and the subsequent modeling are discussed along with their implications for the future uptake of hydrogen in New Zealand. 8-3 A Regional Model of Coal-Based Hydrogen Infrastructure Deployment with Carbon Capture and Storage (CCS) Nils Johnson, Joan Ogden, Christopher Yang, University of California, Davis, USA Hydrogen produced via coal gasification with CCS is an alternative transportation fuel that promises to both reduce CO2 emissions in the transportation sector and improve energy security by utilizing a domestic primary energy source. However, this fuel pathway will require significant investments in new infrastructure for producing and distributing the gaseous fuel. Although several organizations have explored the cost of individual infrastructure components and integrated systems, these studies are largely static models that examine generic spatial layouts at fixed hydrogen demands. As a result, there is significant uncertainty surrounding the cost of hydrogen infrastructure deployment through time in real geographic regions. This paper attempts to address this issue by describing a model, developed with support from NETL, to estimate the cost of infrastructure deployment over time to meet a growing hydrogen demand in a specific region.

We combine a detailed engineering economic model of infrastructure components with spatial data in a geographic information system (GIS) to optimize the design of hydrogen infrastructure and to quantify the investments associated with its deployment. We examine a case in which hydrogen is centrally produced via coal gasification with CCS and distributed by pipeline to individual hydrogen demand centers as hydrogen vehicle market penetration increases from 5% to 75% over a 30year period. The study region is defined by the jurisdiction of the Midwest Regional Carbon Sequestration Partnership (MRCSP), which includes Pennsylvania and several neighboring states. Using the model, we are able to quantify the annual revenue requirements as infrastructure is built through time, which allows us to identify the levelized cost of hydrogen over pre-defined planning periods. In addition, cash flow analysis is used to identify the years in which the project might break even given different hydrogen prices. The model is also used to examine the impact of various policy instruments on the cost of hydrogen, including carbon taxes, tax credits, direct subsidies, and depreciation schedules. This paper summarizes the results with an emphasis on the estimated cost of hydrogen and the impacts of various policy instruments and technological improvements on these costs. We will also examine the sensitivity of hydrogen costs to feedstock and construction cost escalation rates. 8-4 Hydrogen Production from Coal Direct Chemical Looping Process Process Simulation L.-S. Fan, Liang Zeng, Fei Wang, Fanxing Li, Fu-Chen Yu, Andrew Tong, The Ohio State University, USA The traditional hydrogen production from coal via a gasification and WGS process is costly and relatively inefficient. This is especially the case when under a carbon constrained scenario due to the energy consuming CO2 capture and compression steps. In this paper, a clean and efficient coal to hydrogen/electricity conversion scheme, known as the Coal Direct Chemical Looping (CDCL) process, is discussed. Utilizing iron oxide as an oxygen carrier, the CDCL process produces hydrogen with in-situ CO2 capture under elevated pressure. Hence the carbon management cost of the coal conversion process is drastically reduced. Novel thermodynamic models are developed for analysis on individual CDCL reactor using ASPEN Plus. Based on these results, process simulations are performed to further illustrate the energy management in the CDCL process. The process simulation for the conventional gasification process for hydrogen production was also performed based on identical assumptions. The simulation results show that ~ 78% HHV efficiency can be achieved with 100% CO2 capture. The high energy conversion efficiency of the CDCL process results from the process intensification coupled with the optimized energy management. 8-5 Co-Production of Pure Hydrogen and Electricity from Coal Syngas via the Steam-Iron Process Using Promoted Iron Based Catalysts Jason Trembly, Raghubir Gupta, Dharmesh Kumar, RTI International, USA The reversible reaction between iron oxide, CO, and H2 to form metallic iron, CO2, and H2O can be used in a redox cycle process with steam to produce pure high pressure hydrogen. A process based on this reversible reaction- RTI s Steam-Iron Process, has been developed and is targeted as an addition to IGCC power plants for the coproduction of hydrogen and electricity. This presentation will detail the laboratory development of a fluidizable iron-based material for the production of hydrogen from coal syngas. Fixed fluidized-bed benchscale experiments were conducted at 500C and 300 psig using simulated coal derived syngas, including H2S, to determine optimal iron and promoter loadings for the catalyst. The catalysts were shown to be able to produce over 8.0 scc H2.gcat-1. Additionally the catalysts were shown to be able to sustain production for over 100 cycles and produce a pure hydrogen product. Currently, a dual fluidized-bed circulating system is being developed to further evaluate the feasibility of the RTI Steam-Iron Process to be used for the co-production of H2 and electricity in an IGCC power plant. This work was accomplished under a cooperative agreement with the U.S. DOE. The project is part of DOE NETL s Hydrogen and Syngas Program which seeks to develop advanced energy technologies to facilitate the transition to the hydrogen economy though use of our nations vast reserves of coal.

SESSION 9 COMBUSTION TECHNOLOGIES 2

9-1 Reactivity of Pulverised Coals in Simulated Air (O2/N2) and Oxy-Fuel (O2/CO2) Atmospheres Renu Kumar Rathnam, Terry Wall, Behdad Moghtaderi, The University of Newcastle, AUSTRALIA; Karin Eriksson, Lars Stromberg, Vattenfall Research and Development AB, SWEDEN The study of combustion characteristics of pulverised coals under oxy-fuel (O2/CO2) conditions is a topic of current interest as data on oxy-fuel combustion is required to model oxy-fuel combustors. This study deals with the measurement of reactivity of pulverised coal in simulated air (O2/N2) and oxy-fuel (O2/CO2) conditions using a laboratory drop tube furnace (DTF) and a thermogravimetric analyser (TGA). In the TGA, the fuel sample (~ 10 mg) was heated from 30 to 1100C, at a heating rate of 10C/min, in various gas atmospheres that simulate pyrolysis (100% N2, 100% CO2) and combustion conditions. Combustion conditions in air and oxy-fuel atmospheres were simulated by varying the O2 concentration in N2 and CO2 respectively. The mass loss rates measured in O2/CO2 conditions in the TGA were slightly lower at higher O2 concentrations and lower temperatures. However, higher reactivity was observed at lower O2 concentrations and higher temperatures under O2/CO2 conditions in comparison to O2/N2. The higher mass loss observed in O2/CO2 and not observed in O2/N2 conditions is attributed to the reaction of the residual char with CO2. The apparent volatile yields measured in the DTF in 100% CO2 were found to be higher than the volatile yield measured in 100% N2 for Coal B and Coal C. The coal burnouts, measured at various O2 concentrations, in the DTF were also higher in O2/CO2 conditions in comparison to the burnouts obtained in O2/N2 conditions for Coal B and Coal C. Both TGA and DTF results from the present study show that the coal burnout under O2/CO2 conditions could be higher in comparison to O2/N2 conditions probably due to the occurrence of the char-CO2 gasification reaction, especially at high temperatures and comparatively low O2 levels. Isothermal experiments at higher temperatures are required to study the effect of the char-CO2 gasification reaction on reactivity and confirm the mechanisms of coal combustion in oxy-fuel (O2/CO2) conditions. 9-2 Assessment of Radiation Models in the Prediction of Heat Transfer in Coal Combustion and Oxy-Fuel Firing Rachael Porter, Mohamed Pourkashanian, Alan Williams, L. Ma, University of Leeds; Gerry Hesselmann, Norman Simpson, Brian Smith, David Smith, Doosan Babcock, UNITED KINGDOM The accurate prediction of heat transfer in modern utility furnaces is a notoriously difficult problem to solve. Performance prediction methods for pf utility furnaces developed over the years have tended to be based on plant experience and empirical formulations. The accurate prediction of heat transfer involves the solution of the Radiative Transfer Equation (RTE), a formidable task requiring considerable computational resources. An exact solution of the RTE is not feasible except in the very simplest cases and therefore a variety of different methods have been developed to approximate the solution of the RTE. The difficulty of estimation of heat transfer from pulverised coal flames increases because of the nature of the medium within the furnace volume. The presence of fly-ash, char particles, soot and radiation from gases within the volume means that the medium is absorbing, emitting and scattering. The problem is further complicated when the successful prediction of the heat transfer is required for oxy-pf combustion. Current proposals for oxy-pf technologies involve recycling a portion of the flue gases and therefore the main component of the medium becomes carbon dioxide (CO2) instead of nitrogen (N2). The radiative properties within the medium will change considerably when oxy-pf firing is used and to create a method for adaptable solution for heat transfer is a great challenge. The increase in CO2 in oxy-pf means that the radiative properties of the medium will be significantly changed. The heat capacity of CO2 is greater and the thermal diffusivity lower. Crucially to the calculation of heat transfer, absorption and emission properties of the medium will be different. The interaction of molecules with the radiation must be considered because of the increased concentration. The radiative properties of the medium are key in the solution of the RTE. Successful prediction of these parameters in oxy-fuel firing is difficult because many emissivity models are based on data for CO2 and H2O that apply to conventional combustion environments only. The accurate prediction of heat transfer during oxy-pf firing is important because of retro-fitting oxy-pf combustion practices to existing power stations. For this to be successful the heat transfer to the steam side should be unchanged so that current setups can be maintained or only marginally altered. For new plant builds, the nature of boiler design means that the methods used are often empirically based and hence there is potential that heat transfer prediction in oxy-pf firing will be imprecise. A radiation

model with accurate results for heat transfer will provide verification of current boiler design programs. Modelling of a CTF has been carried out using CFD simulation to assess the impact of various aspects of radiation modelling including the importance of soot, particle emissivity, gaseous absorption coefficients and choice of radiation models. Improvements required to produce better agreement with experimental values have been established. 9-3 Effect of Operating Parameters in Pressurized Mills on Coal Flow Distribution Between the Outlet Pipes Harun Bilirgen, Can Koroglu, Aly Elshabasy, Edward Levy, Lehigh University, USA Control of the pipe-to-pipe distribution of pulverized fuel (PF) has been difficult to achieve in pulverizers with multiple outlet pipes connected directly to the discharge turret at the top of the pulverizer. The current research has focused on understanding the flow behavior of coal and air mixtures in multiple-outlet pressurized pulverizers. Experimental tests were performed with 1:7 scale pulverizer models with 4 and 6 outlet pipes. Each outlet pipe was connected to a separate cyclone to accurately measure the PF and air flows in each outlet pipe. Effects of primary air flow rate, classifier vane angle, and air-to-fuel ratio on the coal flow distributions between the outlet pipes were investigated. Moreover, the sensitivity of coal and primary air flow rates in each outlet pipes to orificing was studied in the 4 outlet pulverizer model. The results indicate that coal flow in any outlet pipe varied as much as 30 percent as a function of pulverizer operating parameters. Use of orifices was found to be an ineffective method for adjusting coal flow distributions among the outlet pipes since the primary air flow was much more sensitive to the orifices than the coal flow. 9-4 Differences in Chars Formed from Coal Pyrolysis under N2 and CO2 Atmospheres Dong Zeng, Shengteng Hu, Hamid Sarv, The Babcock & Wilcox Company Research Center, USA Oxy-combustion of coal is a viable technology for power generation and production of a concentrated CO2 stream for sequestration. Because of its demonstrated potential for carbon capture, oxy-combustion has gained considerable popularity and become the subject of numerous bench and pilot-scale investigations. Replacement of N2 with CO2 can affect coal devolatilization and char formation reactions. Detailed knowledge of char reactivity, swelling ratio, and pore structure is important to the accurate determination of char burnout and the development of efficient oxy-combustion systems. However, despite the growing interest in oxy-combustion, fundamental research in this area has been sporadic. Babcock and Wilcox (B&W) used a newly-constructed entrained-flow reactor to study changes in physical properties and intrinsic reactivities of chars formed under oxycombustion conditions. For comparison, pulverized samples of a lignite coal, a subbituminous coal, and an eastern high-volatile bituminous coal were devolatilized at different temperatures in N2entrained and CO2entrained flows. Effects of pyrolysis temperature and residence time were also investigated. Coal mass loss during pyrolysis experiments was determined from ash analysis. Elemental char analysis was also carried out. Average swelling ratios were determined from the mass release and density measurements. Both BET and CO2 surface areas of the collected char samples were measured. Char morphology was studied using a Scanning Electron Microscope. Reactivities of generated char samples were measured at isothermal and oxidizing conditions using a Thermo Gravimetric Analyzer. Intrinsic char oxidation rates were determined from the reactivity measurements. Measured and calculated changes in char properties and reactivities due to switching from N2 to CO2 during coal devolatilization are discussed in the paper. 9-5 Study of Coal Predrying and its Impact to Operational Parameter of 600 MW Coal Fired Power Plant Mochamad Choliq, Tonny Sarief, PT PLN (Persero) Research and Development, INDONESIA In general the preparation of coal prior to feeding to the boiler is reducing its size and moisture content in the pulverizer. However, the air which is used for coal drying will be used as combustion air in the furnace. Whenever moisture content in the coal increase, the moisture content in the air also increase, as the result they will reduce the advantage of heat generated from combustion process and increasing the flue gas volume. The increasing flue gas volume affect the temperature and heat transfer distribution in the furnace that will reduce plant capability capacity, increasing pulverizer power consumption, reducing boiler efficiency, induced draft fan increase and finally increasing overall heat rate. The improvement of as mentioned condition it is needed by developing coal drying outside pulverizers by using flue gas as dryer agent prior to discharge to the environment.

Simulation result showing that by 10% reducing moisture content in coal using flue gas will reduce flue gas volume from combustion process and improve heat transfer efficiency around 4%, in addition the number pulverizer operation required reduced from 6 to 5 pulverizer for 600 MW coal fired power plant. The flue gas required to drying the coal prior to feeding to the pulverizers is about 10% of total flue gas discharge to the stack and the flue as quality under acceptable limit. The reducing moisture content prior to feeding to the pulverizers by using flue gas is possible to be implemented due to amount flue gas reasonably abundant and to reduce the risk of implementation of as mentioned project in the power plant it is necessary to perform modeling in the laboratory scale.

porous media which separates the fuel and tin. Fuel is introduced into a hot zone surrounding the cell and is subject to a sort of internal gasification. This indirect approach has been used for CellTech Gen 2 and Gen 3. Each approach may have application depending on factors such as plant size and impurity levels. 10-3 Materials and Component Development for Advanced Turbine Systems Mary Anne Alvin, DOE-NETL, USA Hydrogen-fired and oxy-fueled land-based gas turbines are currently targeting inlet operating temperatures of ~1425-1760C (~2600-3200F). In view of natural gas or syngas-fired engines, advancements in both materials, as well as aerothermal cooling configurations are anticipated prior to commercial operation in 2015. This paper reviews recent technical accomplishments resulting from NETLs bond coat development effort, and provides a comparative assessment of their high temperature, cyclic oxidation, bench-scale performance to that of current state-of-the-art (SOTA) thermal barrier coatings (TBCs). 10-4 Development of a Low-Swirl Burner for Syngasand H2 Gas Turbines Robert K. Cheng, David Littlejohn, Lawrence Berkeley National Laboratory; Peter Strakey, Todd Sidwell, DOE-NETL; David R. Noble, Tim Lieuwen, Georgia Institute of Technology, USA The low-swirl injector (LSI) is an ultra-low NOx technology based on a novel lean premixed combustion concept. It has been developed for gas turbines operating on natural gas and has the potential for adaptation to fuel-flexible gas turbines operating on a variety of gaseous fuels. Under the sponsorship of the US Dept. of Energy (DOE) Clean Coal program, this technology is being developed for the gas turbines in Integrated Gasification Combined Cycle (IGCC) coal power plants that burn syngases and/or fuels with very high H2 constituents when the IGCC plant is equipped with carbon capture and sequestration technologies. The LSI technology evolved from laboratory research and its operating principle has been characterized by laser-based diagnostics. The application of the fundamental knowledge has facilitated the transfer of this combustion method from the laboratory to the market place. To adapt LSI to the IGCC turbines, the first step is to gain an understanding of the effects of syngas and H2 on the flame behaviors. The experiments were conducted in three facilities. Open and enclosed laboratory flames at atmospheric conditions were used to investigate the lean-blow off limits, global flame characteristics, emissions, the flowfield structures and the turbulent flame speeds. Verification of syngas operation at elevated temperatures and pressures were performed with a reduced scale LSI in a small pressurized combustion channel at Georgia Institute of Technology. Verification of hydrogen operation at elevated temperatures and pressures were performed with a full scale LSI in a research combustor at National Energy Technology Laboratory in West Virginia. These studies show that the basic LSI design is amenable to burning syngases and pure hydrogen. The main effect of increasing H2 concentration in the fuel is an upstream shift in the LSI flame position. This upstream shift is consistent with the prediction from a top order analytical model for the coupling between the flowfield and the turbulent flame speed. The LSI also shows a higher resistance to H2 flame flashback than an idealized high-swirl injector. However, prior to flashback, the high diffusivity and reactivity of the H2 fuel alter the LSI flame stabilization mechanism and thus the flame shape. The NOx emissions from syngas flames and from H2 flames show log-linear dependency on the adiabatic flame temperature and are comparable to those from other hydrocarbon gaseous fuels. These studies demonstrated the feasibility of the LSI concept for IGCC gas turbine and the potential for meeting the DOE goal of operating at < 2 ppm NOx (@15% O2) with high H2 fuels. 10-5 Advanced Hydrogen Turbine Development Update Joseph Fadok, Siemens Power Generation; Ihor Diakunchak, CDI Corp, USA Siemens Power Generation (SPG) has completed Phase 1 of the U.S. Department of Energy (DOE) Advanced Hydrogen Turbine Development Program and is currently in year one of Phase 2. The 3-phase (only Phases 1 and 2 have been awarded to date), multi-year program goals are to develop an advanced syngas, hydrogen and natural gas fueled gas turbine fully integrated into coal-based Integrated Gasification Combined Cycle (IGCC) plants. The program objectives are to demonstrate by 2010 a 2 3 percentage point efficiency improvement over the baseline, <2 ppm NOx @ 15% O2 on syngas fuel and 20-30% reduction in combined cycle capital cost in $/kW. By 2015, the objectives of 3-5 percentage points efficiency improvement over the baseline, <2 ppm NOx @ 15% O2 on H2 fuel, and CO2 sequestration readiness are to be demonstrated. This paper describes the Phase 1 accomplishments, Phase 2 first years activities, and plans for the remainder of Phase 2. The two-year Phase 1 included identifying the advanced technologies required to achieve the program goals, novel or enhanced technologies development initiation and Research and Development Implementation Plan preparation. Phase 2 (5-year duration) will focus on advanced technologies development, downselection and validation, as well as the Hydrogen Turbine conceptual design. In Phase 3, if awarded, the advanced gas turbine detailed

SESSION 10 GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND HYDROGEN APPLICATIONS 2

10-1 Effects of Coal Syngas Impurities on Anodes of Solid Oxide Fuel Cells: A Review Fatma Cayan, Mingjia Zhi, Suryanarayana Pakalapati, Ismail Celik, Nianqiang Nick Wu, West Virginia University; Randall Gemmen, DOE-NETL, USA A literature review is conducted to summarize the studies on the identification of impurities in coal syngas and their effects on the performance of Ni-yttria stabilized zirconia (Ni-YSZ) anode of solid oxide fuel cells (SOFCs). Coal syngas typically contains major species, CO, H2, CO2, H2O, CH4, N2, and H2S as well as trace impurities. Thermodynamic equilibrium calculations have indicated that trace impurities species such as Be, Cr, K, Na, and V in the coal syngas form condensed phases under warm gas cleanup conditions and can be effectively removed by the cleanup processes. For meaningful data comparison, a practical parameter is formulated to quantify the level of degradation normalized with respect to the relevant experimental parameters. Experimental results show that the existence of Hg, Si, Zn and NH3 in the coal syngas does not significantly affect the performance of the NiYSZ anode. The presence of Cd and Se in the syngas impacts the SOFC anode performance to some extent. Impurity species such as Cl, Sb, As, and P cause severe cell voltage degradation due to attack on the Ni-YSZ anode. Sb, As and P have the potential to react with Ni to form secondary phases in the Ni-YSZ anode, which deteriorate the catalytic activity of the anode. 10-2 Direct Coal Fuel Cell Jeff Bentley, CellTech Power LLC, USA The Liquid Tin Anode (LTA) Fuel Cell can operate on gaseous, liquid and solid fuels containing hydrogen, carbon or hydrocarbon compounds. The current version of the LTA, called Gen 3.1 was developed specifically to generate electricity from liquid hydrocarbon fuel. It has been shown to operate directly on military logistics fuel (JP8) for over 100 hours with peak efficiency greater than 40%. The LTA has also demonstrated the ability to operate in the presence of sulfur and under sooting conditions. The LTA can also generate power directly from solid fuels. The power production in the LTA comes from the conversion of liquid tin to tin oxide: [1] Sn(l) + 2 O2- = SnO2 (s) + 4 e A solid fuel such as carbon can be used to reduce tin oxide back to tin via one of the following pathways. [2] SnO2(s) + 2 C = 2 CO(g) + Sn SnO2(s) + C = 2 CO2(g) + Sn SnO2(s) + CO(g) = CO2(g) + Sn [3] [4]

CO2(g) + C = 2 CO(g) [5] Equations [2] and [3] describe direct oxidation of carbon, which has been demonstrated by CellTech Power. The Generation 3.1 cell incorporates a porous ceramic which provides containment of the tin anode and allows only gaseous products to interact with the tin. In this case, Eqs [4] and [5] describe the oxidation process. The LTA also makes power from hydrogen. The pathway in LTA for power production from hydrogen, with water as the product is described elsewhere. Generation 2 LTA uses a porous separator to contain the tin anode. The equations superimposed on the micrograph show the location of reactions for a complex hydrocarbon (in this case coal) utilizing indirect oxidation. CellTech is evaluating the use of LTA operating directly on carbon, coal, petroleum coke, biomass and other carbonaceous feedstocks. For solid feedstocks, two approaches are being evaluated. In one approach, a larger tin reservoir allows fuel and tin to be directly mixed (fuel is introduced and mixed directly into the liquid tin anode). This approach allows the direct reduction of tin oxide by carbon (Eq 3) or hydrogen and was used in CellTech s Gen 1 fuel cell. The second approach uses a

design will be completed, the prototype engine manufactured and installed into an IGCC plant for validation testing to demonstrate the projects commercial viability and that the DOE program goals have been achieved. The development effort so far has focused on cycle performance calculations, engine and plant cost estimates, gas turbine-IGCC plant integration studies, combustion concepts development, turbine aerodynamics/cooling concepts development, modular turbine component construction concepts evaluation, novel materials/coatings technologies development and engine system integration/flexibility considerations. In Phase 1, four combustion concepts (diffusion flame, catalytic, and two premix systems) were investigated and down selected to two for further development in Phase 2 and eventual downselection to one successful candidate for incorporation into the Hydrogen Turbine. This paper provides details on the combustion development testing, test results and the downselection process. Considerable effort was devoted to identifying advanced turbine aerodynamic and airfoil cooling concepts for development and incorporation into the advanced gas turbine. A study was carried out on the performance benefits to be derived from a significant increase in the turbine annulus height in excess of current state-of-the-art (SOTA), which was necessitated by the substantial increase in turbine mass flow resulting from the IGCC application. This study concluded that this concept is feasible from both mechanical integrity and manufacturability considerations. Substantial progress was made in advanced bondcoat, thermal barrier coating and fabricated airfoil development. Conceptual design reviews and risk analyses were conducted on the new gas turbine components. Studies were carried out on the gas turbine-IGCC plant integration and different gasification and air separation technologies that should be considered and evaluated. The results of these studies and developments provided a firm basis for completing the advanced Hydrogen Turbine technologies development in Phase 2.

water. This paper examines the application of dry beneficiation technology to the separation of coal and mineral matter in a novel air-fluidized bed. The Reflux Classifier (RC) is an innovative design that incorporates an inclined settler above a conventional fluidized bed to achieve increased segregation rates and a higher throughput than separators with an equivalent footprint. The RC has been successfully implemented as a water based system for processing -2+0.25 mm coal in Australia. In this study, the effectiveness of magnetite and sand as dense media for the separation of coal in an air fluidized RC was evaluated. The effect of vibration on the separations obtained using both these media was also examined. A vibrated fluidized bed has a lower minimum fluidization velocity and smaller bubbles resulting in a more consistent bed density. A single channel RC was used in this study in batch and semi-batch operation. It was established that multiple separations stages were required when using a magnetite medium, but that a single stage semi-batch separation with sand medium and vibration was demonstrated to out perform all magnetite separations. Vibration acts to significantly improve the separation efficiency in a sand system, but made no improvement to the magnetite system. The effect of the direction and frequency of the vibration on the Ep and cut point of the separation are reported. On -8+1 mm coal using sand medium with vibration, the beneficiation achieved an ash reduction from a feed of 30% ash coal to a 15% ash product corresponding to a yield of 76% and a combustibles recovery of 92%. This compares well with a water separation in the RC which has a product ash of about 13.5%. The separation performance increased with increasing particle size with Ep values of 0.067 for 6.35+4 mm particles compared with 0.125 for the -2+1 mm fraction. The coal separation results are reported and compared with coal washability data. 11-3 Dry Processing of Fine Coal D.P. Patil, B.K.Parekh, Center for Applied Energy Research, USA

SESSION 11 COAL PRODUCTION AND PREPARATION 2

11-1 Coal Grinding & Drying for Coal Gasification Plants Tobias Korz, Carsten Schoessow, Loesche GmbH, GERMANY Since more than 100 years Loesche supplies pulverizers and complete grinding and drying plants to the cement, steel and power industry. Loesche grinding plants utilise energy and resources efficiently, and their quality and reliability are recognised internationally. The modular structure of large roller grinding mills enables utilisation of the same components in different mill sizes. Module components include grinding rollers, rocker arms, pedestals and spring assemblies. The principle behind this structure was patented in1970 and is employed for coal grinding mills and mills in the cement and industrial minerals industry. 2, 3, 4 or even 6 grinding roller configurations for a single grinding table can be realised. In 1990 Loesche supplied the first coal grinding plant for an IGCC power plant in Buggenum, Netherlands. With this experience Loesche is the first choice for the now upcoming coal gasification projects all over the world. Our paper describes the technical features of the Loesche vertical roller mill for the grinding and drying of coal, petcoke, anthracite or lignite. Within the next months Loesche will commission the biggest coal mill of the world, a LM 43.4 D with a name plate capacity of 210 t/h. Additionally, we will describe the function of our Loma hot gas generator which produces the necessary heat to dry the coal. Furthermore, the safety of coal-grinding plants must be ensured in all operating situations. Safety aspects are laid down in regulations and ordinances. Nowadays inert and pneumatically-operated grinding plants can be designed with incorporated operational safety characteristics. Self-inert grinding plants that utilise recirculated gases occurring in the installation system itself. The required process heat is provided by a hot gas generator that is an intrinsic part of the grinding plant. We will explain in detail the function of a so called self-inerted coal grinding plant which enables safe and reliable operation under inert conditions. This includes the necessary supervision of oxygen and CO contents, as well as the automatic control of the plant in case of hazardous situations like emergency shut down or power failure. The presentation will end with an outlook into the future where even bigger mills will be used to reduce the investment costs of coal gasification plants. 11-2 The Effect of Vibration on Dry Coal Beneficiation in the Reflux Classifier Siubhan Macpherson, Kevin Galvin, The University of Newcastle, AUSTRALIA Coal preparation has traditionally involved separating coal and mineral matter particles using a variety of water based gravity beneficiation methods. As the reliability of water supplies decreases, new methods for the dry beneficiation of coal are being sought. A dry beneficiated coal has the advantage of a reduced moisture content compared with conventionally processed coal. Further advantages include negligible process water requirements and less capital equipment for dewatering processes and the recovery of

Mechanization in the underground coal mining industry has increased the amount of fine size coal and waste (refuse) in the mined coal. Processing of run-of-mine coal is done at a coal preparation plant located away from the mine which means that a significant amount of rocks are also transported along with coal. Also, in certain parts of USA due to the scarcity of water only selective mining is being done while neglecting coal containing high ash and sulfur. This type of mining reduces the mine productivity and proper use of natural resources. In these scenarios, dry coal processing will be economical as it will not utilize water and thus no dewatering or drying of the product will be required. The goal of this study was to evaluate a dry separation process for processing coal finer than 1/4 inch. High ash coal samples from two (Mine 1 and Mine 2) Western Kentucky mines were selected for the present study. Statistical design experiments were conducted to assess the effect of operating parameters of the dry separator on product yield for a given ash content. The tests showed that for Mine 1 coal, the air table was able to reduce the ash from 27% to 10-12% ash with a clean yield of about 75-80%. The ash rejection was about 77-80% with a combustible recovery of about 95% indicating excellent separation efficiency. The pyritic sulfur was reduced from 2.65% to about 1.5%. Processing of the combined -1/4 x 6 mesh coal reduced the ash content from 25.5% to 10.9%. The total sulfur was reduced from 4.05% to 3.35%. The heating value of the coal was increased from 10326 Btu/lb to 12623 Btu/lb. For the Mine 2 coal, the clean coal yield was as high as 78% for 1/4 x 6 mesh size fraction. The 6x14 mesh fraction provided a clean coal product contaning 9% ash at a yield of 86%. The total sulfur was reduced from 3.36% to 3.05%. In summary, the air table was effective in reducing ash by 65% and sulfur by about 25-35%. 11-4 Rotating Coal Drying Kiln Thomas A. Menditto, James R. Heitman, Energy Prep Inc., USA Energy Prep Inc is a coal preparation company offering services for intellectual license to a process of a rotating coal drying kiln that will upgrade the quality of coal, and therefore offer energy companies that use lower quality coal an opportunity to make a net profit of at least ten million a year. The incredible profits offered by our process are a direct result of our tested procedure, whose economic value is far superior to many other processes on the market. The IB-50 was in operation at the Wabash Valley Energy mine in 1983 by James R. Heitman. At that time James R. Heitman was the president of Wabash Valley Energy, Inc. and the founder of Energy Prep, Inc. which is a subsidiary of United Engineering and Contracting Company, Inc. The IB-50 was capable of removing 10% to 20% of moisture from sub-bituminous coal at a rate of 50 tons per hour. Several samples of the Indiana coal were sent to labs for testing. Feed conditions had been varied between 20% and 40% moisture and product dried to between 5% and 10% moisture. On one occasion coal was dried to 0.12% moisture. On the same equipment feed rates were varied from 5 tons per hour to over 70 tons per hour. It is the unique design of the apparatus that enables a product with low investments costs and great profit margins. Our process sufficiently dries the coal without causing combustion through the use of a digitally controlled rotating kiln drier. The most marketable part of our process is the fact that it does not require an additional fuel source to run. Gasoline and an electric generator are used as backup sources of energy to get the machine started, but due to

10

our process the majority of fuel used is only 5% to 10% of the coal being dried. In fact, during the testing it was determined that to achieve a 20% reduction in moisture less than 5% of the product was consumed for fuel. The apparatus is small enough that permits can be avoided, and therefore our initial start-up and maintenance cost are not more than $3/ton, which makes our process economically valuable on many levels. Energy Preps apparatus has many economic benefits that would interest energy companies around the world. The upgraded fuel quality has been shown through tests at Leigh University to increase boiler efficiency and decrease emission costs. Furthermore, the reduction in moisture content leads to weight reductions which drastically reduce the rail costs. In addition, our apparatus is eligible for tax credits for providing an enhanced coal product. The summation of all these savings could lead to yearly net profits of at least ten million for energy companies around the globe. Energy Prep, therefore believes that our apparatus would catch the interests of many within the coal and energy sector. 11-5 The Investigation of the Breakage Patterns of Coal Under Simulated Impact and Attrition Breakage Conditions in Order to Predict Fines Generation During Transport and Handling Q.P Campbell, North-West University; V. Claassens, Sasol Research and Development, SOUTH AFRICA This project was done to gather data and develop models to predict the breakage characteristics of coal (and specifically fines generation) during the normal handling and transport of freshly mined coal from the coal face to the end user. Two types of breakage events have been investigated: impact breakage (at transfer chutes, dropping into hoppers and silos, etc.) and attrition breakage (during transport on long conveyer belts, railroad trucks, etc.). Freshly mined coal, from a number of different South African sources, was used and subjected to single particle freefall tests where high speed video photography was used to characterize the breakage during impact. Breakage product distributions were measured and related to a variety of factors, like kinetic energy, coal type, and particle orientation during impact. Additionally, the attrition breakage due to motion during transport was simulated for extended times, and results were correlated with some of the physical coal properties. These results are being used to establish a statistically based model to predict fines generation in an entire coal transportation system.

beneficial to improve dispersing degree, catalysis activity and selectivity for C5+ hydrocarbon. The CO conversition are 90.61% 97.81%, the selectivity for C5+ hydrocarbon is 76.8% 84.7%, and the alkene/alkane rate in tail gas is close to zero at the condition of temperature 240C, pressure 2 MPa, and airspeed 500 h-1. 12-3 The Liquefaction Reactivity of the Shangwan Parent Coal and its Lithotypes from the ShenHua Coal Zhou Jianming, Wang Naiji, Beijing Research Institute of Coal Chemistry, China Coal Research Institute; Wang Yonggang, Yang Zhengwei, Wang Caihong, China University of Mining and Technology, CHINA The hydro-liquefaction behaviors of Shangwan (Shenhua Coal) coal and its vitrain and fusain of lithotypes were investigated in a high pressure microautoclave at the different temperature (ranging from 400 to 450C) and pressure (ranging from 7 to 11 MPa). Results showed that with increasing in the temperature and initial hydrogen pressure, the total conversion and oil yield increased. At the 7 MPa initial hydrogen pressure, the temperature raising from 400C up to 450C, the total conversion were increased by 23.74%, 26.67% and 32.08%, respectively. At the same conditions, the liquefaction reactivity order of Shangwan coal and its lithotypes is: parent coal>vitrain>fusian. At 450C and 7 MPa, the total conversion and oil yield of the parent coal were 82.96% and 47.93%, while those of vitrain and fusain were 80.69%, 43.83%, 61.24%, and 27.68% respectively. The highest oil yield of vitrain was 48.12% at the temperature of 440C. The liquefaction reactivity of parent coal, which has higher ash content and catalytic component, was higher than that of the vitrain. 12-4 Low Temperature Fischer-Tropsch Synthesis Using Iron-Based Catalysts in Slurry Bubble Column Reactor Hak-Joo Kim, Dong-Hyun Chun, Jung-Hoon Yang, Ho-Tae Lee, Heon Jung, Korea Institute of Energy Research, KOREA Recently, the high oil price above 100$/barrel results in the deep interest of developing alternative technology for manufacturing clean and economic synthesis fuel for transportation. Coal-to-liquid (CTL) process can be one promising and effective route of producing synthesis fuel in mass production. Development of Fisher-Tropsch synthesis (FTS) catalyst and reactor system is one of core technologies of the CTL process. In this work, modified iron-based catalysts were developped with enhanced reducibility at low temperatures. Modified iron-based catalysts were prepared by conventional co-precipitation method with the addition of small amount of precious metal and transition metal for enhancing the reducibility of the catalysts at low temperature. The catalysts were characterized by TPR, TEM, ICP, XRD, BET, PSA methods. The reaction was carried out in a slurry bubble column reactor with 2 inch of diameter and 1.5 m of height. Catalyst was suspended in mineral oil and introduced to the reactor using high pressure pump. Catalyst slurry was bubbled with the synthesis gas purged from the gas distributor specially designed for proper control of bubble size. Precise flow control of reactants (H2/CO=2/1 molar ratio) was attained with the aid of mass flow controller (Brooks, 5850E) under pressurized reaction condition controlled by a back pressure regulator (Tescom). At the exit of the reactor, liquid products were collected from the liquid collector prior equipped with a heat exchanger working with a cold liquid (0C) circulating system. The volumetric flow rate of gas phase product and unreacted feed gas was measured by the dry gas meter (Shinogawa, 1 L/rev.). The gas was sampled with a gas-tight syringe in the sampling port located prior to the dry gas meter. Collected liquid products were analyzed with the aid of gas chromatographies. Addition of small amount of precious metal and transition metal was effective for increasing the reducibility of iron-based catalysts at low temperature of 220C. In the reaction condition without mass transfer limitation, modified ironbased catalyst with enhanced reducibility was effective for producing higher waxy hydrocarbons. TPR profiles of the calcined catalysts showed two main peaks. Peak at lower temperature was assigned to the reduction of Fe2O3 to Fe3O4, the higher temperature peak to the reduction of Fe3O4 to metallic Fe. Addition of precious metal and transition metal was effective for reducing the reduction temperature range. The chain growth probability of the modified iron-based catalysts, based on the A-S-F distribution, was higher than the conventional iron-based catalyst, showing high potentials for catalyst design to produce longer chain length hydrocarbons. 12-5 Kinetic Modeling of a Fischer-Tropsch Reaction Over a Cobalt Catalyst in a Slurry Bubble Column Reactor for Incorporation into a Computational Multiphase Fluid Dynamics Model Anastasia Gribik, Donna Guillen, Daniel Ginosar, Idaho National Laboratory, USA Currently multi-tubular fixed bed reactors, fluidized bed reactors, and slurry bubble column reactors (SBCRs) are used in commercial Fischer Tropsch (FT) synthesis. There are a number of advantages of the SBCR compared to fixed and fluidized bed reactors. The main advantage of the SBCR is that temperature control and heat recovery are more easily achieved. The SBCR is a multiphase chemical reactor where a synthesis gas, comprised mainly of H2 and CO, is bubbled through a liquid

SESSION 12 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL 2

12-1 Effect of Pretreatment on the Activity, Selectivity and Life-time of Iron Catalyst Supported on Carbon Nanotube for Fischer-Tropsch Synthesis Ajay Dalai, Reza M. Malek Abbaslou, Ahmad Tavasoli, University of Saskatchewan, CANADA This paper presents the effects of acid treatment on the activity, product selectivity and life span of iron Fischer-Tropsch (FT) catalysts supported on carbon nanotubes (CNTs). Two different types of CNTs with low surface area (~25 m2/g) and high surface area (~170 m2/g) were prepared and treated with 35 wt% HNO3 at 25C and 110C for 16 hours. Fe/CNTs were prepared using incipient wetness impregnation method with iron loading of 10 wt%. The CNT supports and catalysts were characterized by nitrogen adsorption, ICP, TPR, XRD, SEM, TEM and Raman spectroscopy. The acid treatments at 25C and 110C increased the BET surface area by 18% and 31%. The results of Raman analysis revealed that the acid treatment increased the number of defects which are considered as anchoring site for metal particles. TEM analysis showed that the major parts of the iron particles were homogenously distributed inside the acid treated nanotubes. According to the XRD analysis, the acid treatment on both families of CNTs resulted in decrease in metal particle sizes. The FT synthesis was carried out in a fixed-bed micro reactor (275C, 2 MPa, CO/H2 = 2) for 120 h. Among the catalysts studied, Fe catalyst supported on pretreated CNTs at 110C was stable and active while, the other catalysts experienced rapid deactivations. The Fe catalyst supported on CNTs low surface area and larger diameter showed much lower CH4 and higher C5+ selectivities. 12-2 Study on Eggshell Co/ZrO2/SiO2 Catalysts for the Fischer-Tropsch Synthesis Cui-wei Xiao, Nai-ji Wang, Peng Miao, Ren-shan Ji, China Coal Research Institute, CHINA Cobalt-based eggshell catalysts were prepared from support of formless SiO2. The structure and reductionp roperty of the catalysts were characterized by SEM, EDS, and Brunner-Enunett-Teller (BET) techniques. The results show that the catalysts reacting activity depend on available oxide cobalt amounts to a great extent, and lesser crystal particle of cobalt is in favor of selectivity for liquid hydrocarbon. Additive of ZrO2 is

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hydrocarbon wax containing solid catalyst particles to produce specialty chemicals, lubricants, or fuels. The FT synthesis reaction is the polymerization of methylene groups [-(CH2)-] forming mainly linear alkanes and alkenes, ranging from methane to high molecular weight waxes. The Idaho National Laboratory is developing a computational multiphase fluid dynamics (CMFD) model of the FT process in a SBCR. This paper discusses the incorporation of absorption and reaction kinetics into the current hydrodynamic model. A phased approach for incorporation of the reaction kinetics into a CMFD model is presented here. Initially, a simple kinetic model is coupled to the hydrodynamic model, with increasing levels of complexity added in stages. The first phase of the model includes incorporation of the absorption of gas species from both large and small bubbles into the bulk liquid phase. The driving force for the gas across the gas liquid interface into the bulk liquid is dependent upon the interfacial gas concentration in both small and large bubbles. However, because it is difficult to measure the concentration at the gas-liquid interface, coefficients for convective mass transfer have been developed for the overall driving force between the bulk concentrations in the gas and liquid phases. It is assumed that there are no temperature effects from mass transfer of the gas phases to the bulk liquid phase, since there are only small amounts of dissolved gas in the liquid phase. The product from the incorporation of absorption is the steady state concentration profile of the absorbed gas species in the bulk liquid phase. The second phase of the model incorporates a simplified macrokinetic model to the mass balance equation in the CMFD code. Initially, the model assumes that the catalyst particles are sufficiently small such that external and internal mass and heat transfer are not rate limiting. The model is developed utilizing the macrokinetic rate expression developed by Yates and Satterfield (1991). Initially, the model assumes that the only species formed other than water in the FT reaction is C27H56. Change in moles of the reacting species and the resulting temperature of the catalyst and fluid phases is solved simultaneously. The macrokinetic model is solved in conjunction with the species transport equations in a separate module which is incorporated into the CMFD code.

desired range of methane compositions for maximizing SNG production. The details are described in the body of the paper. KBR has developed proprietary technologies around the core oxygen-blown TRIG gasifier to maximize water recovery and process heat utilization. The present configuration for SNG production incorporates these novel heat and water integration schemes, while minimizing the environmental footprint. Carbon dioxide is captured at a purity level suitable for enhanced oil recovery (EOR) and/or sequestration. Robustness, enhanced flexibility, reduced energy and water consumption are key features. 13-3 Production of Bio-CNG by Gasification Christiaan van der Meijden, B.J. Vreugdenhil, A. van der Drift, R.W.R. Zwart, Energy Research Centre of the Netherlands (ECN); H.J. Veringa, University of Twente, THE NETHERLANDS Compressed Natural Gas (CNG) is becoming more and more important as a transport fuel. The number of cars using CNG instead of liquid fuels is increasing rapidly (to 8 million in 2008). CNG is a relatively clean transport fuel. The emissions of CO2, particles and sulfur are significantly lower than for other conventional fossil fuels. Fossil CNG can easily be replaced by CNG produced from biomass (Bio-CNG), because the composition of the gas and the heating value are similar. Replacing CNG by Bio-CNG will reduce fossil CO2 emissions to zero. Bio-CNG even has the potential to become a CO2 negative transport fuel, as part of the carbon from the biomass is separated as pure CO2 from the fuel during the production of Bio-CNG. If this pure CO2 stream is sequestrated, Bio-CNG becomes CO2 negative. The production of Bio-CNG via digestion has been developed and is implemented (mainly) in small-scale installations. The limited amount of suitable digestible feed stock demands for development of a technology which can convert a wider range of biomass, like wood residue, into Bio-CNG. Gasification is such a route that can convert a wide range of (cellulosic) biomass into CH4 with a high energetic efficiency of 70%. A promising alternative second generation bio-fuel is Fischer- Tropsch Diesel produced by gasification of biomass, but the overall efficiency of biomass to FischerTropsch Diesel is significantly lower (below 50%). Several biomass gasification technologies are available or under development to produce gas that can be upgraded into Bio-CNG. The overall system from biomass (wood) to SNG was modeled using Aspen Plus. The results showed that indirect gasification gives the highest overall efficiency to Bio-CNG. The Energy research Centre of the Netherlands (ECN) decided to continue the development of an indirectly heated (allothermal) biomass gasification process (MILENA), because of its high overall efficiency to Bio-CNG. The foreseen scale for a commercial Bio-CNG production facility is between 50 and 500 MWth or between 3 and 30 ton/h of Bio-CNG. The MILENA technology is suitable to be scaled up to this scale. ECN also develops and tests the required gas cleaning equipment. The gas from the final gas cleaning step can directly be upgraded into CH4 by conventional and commercially available methanation catalysts. ECN has built and tested the Bio-CNG installation on a lab-scale of 6 kg/hour biomass input (30 kWth). A pilot scale gasification unit of 160 kg/hour (0.8 MWth) was built in 2008. First tests in biomass combustion and gasification mode showed that the installation is behaving as expected. The results from the lab-scale installation are promising. The gasifier and connected gas cleaning were operated successfully during several 100 hour duration tests. Progress has been made in selecting the appropriate process conditions to obtain cleaned producer gas that can be sent to a commercial methanation process. 13-4 Development of a Hydrogasification Process for Co-Production of Substitute Natural Gas (SNG), Biofuel and Electricity from Western Coal Raymond Hobbs, Xiaolei Sun, Fuyuki Noguchi, Arizona Public Service; Elaine Everitt, Chris Guenther, NETL/DOE, USA The Advanced Hydrogasification Process (AHP) process is being developed by Arizona Public Service (APS) to utilize the U.S.s abundant coal supply to address concerns of diminishing domestic oil and natural gas resources as energy providers, while also incorporating a renewable theme to address regulations in western states. A fully integrated five-step process Integrated Energy Strategy (IES) includes (1) Hydrogen production without CO2 emissions; (2) Substitute Natural Gas (SNG) generation by flash Hydrogasification of coal; (3) Oxy-combustion of coal/char to produce electricity, (4) Carbon recycling of CO2 emissions through biological processes, and (5) Biofuels production from carbon recycling. The combination of these steps creates an integrated process that delivers energy and fuel in a long-term sustainable fashion. During the current phase of this study, effort has been focused on design and fabrication of a bench scale reactor system for generating data on hydrogasification kinetics, coal conversion, product yield and composition. Extensive Computational Fluid Dynamic (CFD) simulations have been conducted to assist with reactor design, especially hydrogen nozzle design. Test operations are expected to begin in late fall 2008. Investigation of a concept for using Algae as biological CO2 capture method is discussed.

SESSION 13 GASIFICATION TECHNOLOGIES: SUBSTITUTE NATURAL GAS

13-1 The Case for Synthetic Natural Gas from Coal Gary Leatherman, Booz Allen Hamilton, USA The production of pipeline quality synthetic natural gas (SNG) from coal is a potentially attractive application of gasification technology. This paper examines the economics of SNG production using current state-of-the-art technology (entrained flow gasification and catalytic methanization) with and without carbon capture and storage. The potential economic viability of this approach is then compared to a number of natural gas price scenarios. The potential of emerging gasification technologies to create a step change in economics are also assessed. The paper then examines how SNG from coal with CCS can contribute to CO2 emission reductions. Details on the scale of market penetration required for significant CO2 impact are analyzed. 13-2 KBRs Transport Gasifier (TRIG) An Advanced Gasification Technology for SNG Production from Low-Rank Coals Siva Ariyapadi, Philip Shires, Manish Bhargava, David Ebbern, KBR, USA The KBR Transport Gasifier (TRIG) operating in the oxygen-blown mode can provide clean, particulate-free synthesis gas (syngas) for a wide variety of coal-based chemicals and fuels applications. This advanced gasification technology was jointly developed by KBR and Southern Company Services, Inc. in an effort to offer a less energy-intensive gasifier for the processing of low-rank coals. The TRIG gasifier is based on years of commercial operating experience from KBR s fluid catalytic cracking (FCC) reactors and features dry feed injection/ dry ash handling systems. An engineering-scale prototype of the Transport Gasifier has been in successful operation since the mid-1990s at the Power Systems Development Facility (PSDF) in Wilsonville, Alabama. A range of low-rank coals has been successfully tested in this facility under both air-blown and oxygen-blown modes. More recently, the TRIG technology was selected for an advanced 600 MWe, two-gasifier IGCC facility for Mississippi Power. The project is based on air-blown gasification of lignite and is currently in the detailed engineering phase. The focus of this article will be on oxygen-blown operation of TRIG to produce syngas suitable for Substitute Natural Gas (SNG) applications. The Transport Gasifier operates at elevated pressures and moderate temperatures. The moderate temperature operation of TRIG is an important advantage for SNG production in comparison to the various high temperature slagging gasifiers in particular, the specific-oxygen consumption is low, resulting in higher cold gas efficiencies. Moreover, by slight modifications in gasifier operating conditions, it is possible to provide syngas with a

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13-5 Overview of Viresco Energys Coal Pilot Plant Using Steam Hydrogasification Technology Joseph M. Norbeck, Jim Guthrie, Viresco Energy LLC, USA A multi-step process based on steam hydrogasification to convert coal and coal/biomass mixtures to liquid fuels has been shown to have some significant advantages over current gasification technologies. It is an integrated system of three different chemical processes. In the current configuration a steam hydrogasification (SHR) step is followed by a steam methane reforming (SMR) step followed by a Fischer-Tropsch reaction (FTR) step. This technology has been successfully demonstrated at the process demonstration unit scale at the University of California Riverside. The University of California has filed 12 full patent applications on this technology and Viresco Energy LLC has an exclusive global option of this technology. The Department of Energys National Energy Technology Laboratory (NETL) has completed a detailed review of this technology, the results of which will be presented at the conference in another presentation. The next critical step in the commercialization process is to design, construct and operate a pilot plant of the size of between fifteen to twenty tons/day. This facility will be constructed in Utah and use a feed of Utah coal with the flexibility to use coal and biomass mixtures. A technical team has been formed to lead in the commercialization that includes Viresco, the University of California, Riverside, Research Triangle Institute, Technip, and NETL. This paper will present an overview of the technology, the anticipated design of the Utah facility, and details of the projected yield and capital cost of the pilot facility. 13-6 Co-Production of Substitute Natural Gas and Electricity via Catalytic Coal Gasification Brian S. Turk, Raghubir Gupta, Andreas Weber, RTI International, USA The convenience and clean-burning features associated with the use of natural gas has allowed this fuel to become invaluable for industrial, commercial, and residential energy and heating needs. The challenge is that the domestic supply of this natural resource is dwindling, which has driven up the cost of this resource. One approach for supplementing domestic resources of natural gas that is receiving considerable attention is the conversion of coal into a methane-rich gaseous product or substitute natural gas (SNG), which meets current natural gas pipeline specifications. The main advantage of this approach is that this SNG product can be added to the extensive network of existing natural gas pipelines increasing supply without any noticeable effect by the end user. The technical challenge is to develop processes for converting coal into SNG that are thermally efficient, environmentally attractive and economically competitive. With DOE/NETL funding, RTI has been exploring a novel process that converts low ranked coals, like sub-bituminous coal and lignite, into a SNG product meeting pipeline specifications. Several key features of this process are the novel two-stage gasification approach that targets increasing carbon conversion with enhanced selectivity for methane formation and use more effective warm syngas cleaning technologies that actually generate a pure CO2 by-product that is sequestration ready. In this two-stage coal conversion process, coal is initially preprocessed to convert the coal into a mixture of gas phase carbon species, H2 and solid char fines prior to the catalytic reactor. In a second catalytic reactor, the catalyst promotes the conversion of the gas phase carbon species and H2 into CH4. Because the ash is trapped in the solid char fines and the catalyst on a support, physical contact between the ash and catalyst is impossible eliminating the potential for reaction and deactivation of the catalyst. The product gas mixture from the catalytic reactor is cleaned using the hot gas desulfurization and CO2 capture technologies that have been developed at RTI. The product from the CO2 capture process is a high pressure sequestration ready CO2 byproduct. With a final polishing methanation and gas cleaning process, an SNG product meeting pipeline specifications is produced. During Phase I of this project, RTI has focused on bench-scale testing of the technical feasibility of the different pieces of this coal conversion process. This presentation will describe the results from this bench-scale testing program for evaluating the technical and economic feasibility of the proposed process.

while reducing pollutants in an indirect but highly effective manner, hence the cost for the hydrogen product is greatly reduced. Extensive demonstrations of the SCL process have been carried out under a fixed bed reactor using coal syngas as feedstock. Hydrogen with an average purity higher than 99.8% was produced. The key concepts of SCL process utilizing iron oxide based composite particles are proved to be feasible. 14-2 Effect of Reaction Temperature on the Performance of Thermal Swing Sorption Enhanced Reaction Process for Simultaneous Production of Fuel Cell Grade H2 and Compressed CO2 from Synthesis Gas Michael Beaver, Ki Bong Lee, Shivaji Sircar, Hugo Caram, Lehigh University, USA A novel cyclic thermal swing sorption enhanced reaction (TSSER) process concept was recently proposed for simultaneous production of fuel-cell grade H2 and compressed CO2 from a synthesis gas containing CO and H2O [1, 2]. The process carried out the catalytic water gas shift (WGS) reaction (CO + H2O CO2 + H2) with simultaneous removal of CO2 from the reaction zone by a reversible, hydrophobic, CO2 selective chemisorbent in order to circumvent the thermodynamic limitation of the WGS reaction and enhance the rate of the forward reaction. The chemisorbent was periodically regenerated using the principles of thermal swing adsorption by purging the sorber-reactor with super heated steam at different pressures and temperatures. Several intermediate process steps were employed to produce a pure and compressed CO2 by-product during the thermal desorption process. The present work reports (a) new experimental data demonstrating the concept of sorption enhanced WGS reaction at different temperatures using a commercial WGS catalyst and Na2O promoted alumina as the CO2 chemisorbent, and (b) the effect of the sorption-reaction temperature on the TSSER process performance estimated by model simulation. Relatively slower kinetics of the sorption-enhanced WGS reaction imposes a lower bound (~ 200C), while the thermal stability of the chemisorbent and the use of carbon steel sorber-reactors sets the upper bound (~ 550C) of temperatures for practical operation of the TSSER process. Simulated process performances (sorptionreaction at 200 and 400 C, and regeneration at 550C) show that the operation of the sorption-reaction step at 200 C increases the H2 and CO2 productivities of the process by, respectively, ~ 38% and 35% without changing the (a) moles of H2 produced per mole of CO in the feed gas, and (b) net CO2 recovery as a compressed by-product gas. The total steam duty for the sorbent regeneration increases by ~ 14% for the lower sorption-reaction temperature operation. Another major benefit of the lower reaction temperature operation was a very large increase in the pressure of the CO2 by- product (e.g. 40 and 21 bars at, respectively, 200 and 400C) when the reactor feed gas contained 20% CO + 80% H2O at a total pressure of 15 bar. 14-3 Studies on the Reduction Mechanism of the Iron Oxide Based Composite Particle in the Syngas Chemical Looping Process Liang-Shih Fan, Deepak Sridhar, Fanxing Li, Hyung Kim, Liang Zeng, Thomas Yeh, The Ohio State University, USA Syngas Chemical Looping (SCL) is a novel process developed to convert coal derived syngas into hydrogen of very high purity with integrated CO2 separation. The technology developed at the OSU revolves around the ability of the Iron based oxygen carrier to perform the multiple tasks. There are three major reactors in the SCL process, namely, the Reducer, The Oxidizer and, the combustion train. The oxygen carrier passes through all three units mentioned above and gets involved in the critical reactions that enable the highly efficient process. The iron based composite particle synthesized at The Ohio State University maintains high reactivity for more than 100 reduction-oxidation cycles and has strength that can sustain commercial operations. These superior properties compared to commercial Fe2O3 make the iron oxide composite particle an ideal choice to be adapted in the SCL process. In this paper, the reduction kinetics of the iron based composite particle using CO and H2 are investigated. An ionic oxygen transfer mechanism is proposed to explain the kinetic results as well as the superior performance of the particle. SEM-EDX studies are also discussed to further validate the proposed mechanism. This understanding of the mechanism is vital for the optimization of particle that will make the SCL more efficient as well as economically attractive. 14-4 Calcium Looping Process for High Temperature High Pressure Hydrogen Production with Insitu CO2 and Sulfur Capture Shwetha Ramkumar, L. S. Fan, Mahesh V. Iyer, The Ohio State University, USA The world energy demands for transportation, industry, electricity, etc are projected to increase from 420 quadrillion BTU in 2003 to well over 720 quadrillion BTU by the year 2030. Currently, the United States is dependent on foreign oil for 56% of its energy needs which is estimated to increase to 70% by 2025. This rising energy demand coupled with the depleting global oil reserves and the dependence on foreign oil has brought processes which convert coal into hydrogen as well as cleaner, high

SESSION 14 HYDROGEN FROM COAL 2

14-1 Syngas Chemical Looping Process for Hydrogen Production L. -S. Fan, Fanxing Li, Deepak Sridhar, Hyung Kim, Liang Zeng, Fei Wang, The Ohio State University, USA The Syngas Chemical Looping (SCL) process is a novel chemical looping process that can efficiently convert gaseous fuels such as syngas and hydrocarbons into hydrogen with in-situ CO2 capture. Through the assistance of a specially tailored Fe2O3 based composite particle, the SCL process simplifies the overall fuel conversion scheme

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energy density fuels to the forefront. The United States has the worlds largest coal reserves and hence the development of an energy efficient coal to hydrogen, electricity and liquid fuels technology is essential. Gasification provides options for the efficient and environmentally benign conversion of coal to liquid fuels, hydrogen and electricity. The calcium looping process is based on the syngas obtained from the gasification of coal and integrates the water gas shift (WGS) reaction with in-situ carbon dioxide (CO2), sulfur and hydrogen halide remove at high temperatures in a single reactor. Thus the integrated process combines several unit operations, such as the WGS reactor, CO2 capture system, sulfur removal step, halide removal, and hydrogen purification in one process module thereby reducing the overall foot print of the process. In this process, the thermodynamic limitation of the WGSR is overcome by the in-situ removal of CO2 by the calcium oxide sorbent obtained from the Ohio State University patented Precipitated Calcium carbonate (PCC) sorbent. Besides, the calcium oxide sorbent has also demonstrated superior performance in the removal of sulfur impurities. The morphological properties of the PCC sorbent can be tailored using surface modifiers to form a mesoporous structure that results in superior performance over naturally occurring limestone and dolomite sorbents that are plagued by pore mouth closure leading to lower conversions. The PCC sorbent demonstrates a high CO2 capture capacity of about 70% by weight while removing H2S impurities at high temperatures to ppm levels and producing high purity hydrogen at elevated pressures in the absence of a catalyst. Life cycle testing of the sorbent over multiple cycles of carbonation-calcination reactions shows that PCC sorbent attains a capture capacity of 40-36 wt% over 50-100 cycles, which is significantly higher than most of the high temperature sorbents reported in literature. Calcium carbonate which is formed in the process due to the reaction of calcium oxide with CO2 is separately calcined to yield a pure CO2 stream for its subsequent sequestration and the calcium oxide is recycled back. Thus, the calcium looping scheme not only improves the hydrogen yield and purity but also integrates a gas cleanup and CO2 management scheme in the hydrogen production process. Process Evaluation and optimization of the calcium looping system for the production of hydrogen from coal has been conducted using the commercial ASPEN Plus process simulation software. The over all efficiency of this process for the production of 99.999% pure hydrogen from coal is 63% (HHV) when compared to the state-ofthe-art, hydrogen from coal process which has an efficiency of 57% (HHV). The purity of hydrogen is increased by a large extent when the carbonation reaction is integrated with the WGSR. The steam addition for the WGSR can also be reduced to stoichiometric quantities which aids in reducing the parasitic energy consumption of the process. In addition, the extent of H2S removal by the CaO sorbent is also enhanced by operating at lower steam partial pressures. Experiments conducted in a bench scale system have revealed the superior performance of PCC sorbent for the production of H2. High purity hydrogen of 99.7% with less that 1 ppm sulfur impurity has been obtained in a bench scale fixed bed reactor system. The calcium looping process results in the production of high purity H2 at high temperatures and pressures, simultaneous removal of CO2 as well as sulfur impurities, production of a sequestrable CO2 stream by sorbent regeneration, reduction in excess steam requirement and flexibility in carbon monoxide conversion to produce H2:CO ratios of varying compositions suitable for fuels/chemical synthesis. 14-5 A Feasibility Study of Ni-Fe-Cr Based Metal Alloys as WGS Catalysts for Catalytic Membrane Reactors at 700C San Shwe Hla, Greg Duffy, Jim Edwards, Alex Ilyushechkin, Leigh Morpeth, Daniel Roberts, Dongchan Park, CSIRO Energy Technology, AUSTRALIA Ni.Fe.Cr based metal alloys (Ni70Fe9Cr19, Ni64Fe1Cr21, and Ni10Fe69Cr19) in the form of fine powders have been examined for their water-gas-shift catalytic activity at significantly higher temperature (700C) than can be achieved with conventional high temperature WGS catalysts. This study was performed in order to identify candidate materials for the fabrication of high temperature catalytic membrane reactors for hydrogen production from coal-derived syngases. It has been confirmed that the Ni FeCr alloy powders tested promote CO conversion through the WGS catalytic reaction to various extents and that this level of activity is to some extent dependent of the type of pre-treatment applied to the powders. While it was observed that the bulk NiFeCr powder remains phase-stable and chemically inert, surface chemistry characterisation confirmed the enrichment of metal oxide layers on the surface of the powder as chromium oxides and iron oxides, which are believed to be the active components for WGS reactions.

SESSION 15 COMBUSTION TECHNOLOGIES 3

15-1 CFD Modeling of Oxy-Fuel Combustion in a Utility Coal-Fired Boiler Zumao Chen, Alan Sayre, Rick Wessel, Denny K. McDonald, Babcock & Wilcox, USA Power generation from fossil fuel combustion results in the emissions of greenhouse gases, primarily carbon dioxide (CO2), which is generally believed to contribute to global climate change. Oxy-fuel combustion provides an approach in which CO2 in the flue gas may be concentrated to permit more efficient and economical capture and disposal. Traditionally, air is used as the medium for combustion in coal-fired boilers. A large amount of nitrogen from the air results in a low concentration of carbon dioxide in the flue gas. The low concentration of carbon dioxide makes CO2 recovery or capture more difficult and costly due to the large volume of flue gas that must be processed. In the case of oxy-fuel combustion, the oxygen in air is replaced by nearly pure oxygen from an air separation unit (ASU). The oxygen is then diluted by recycled flue gas, leading to a gas mixture with a lower oxygen concentration, to ensure that there is sufficient gas volume to control flame temperature and achieve the desired heat transfer within the boiler. The resulting flue gas leaving the boiler is a CO2-rich stream ready for processing (compression and purification) and sequestration. In this paper, the results of a computational fluid dynamics (CFD) modeling study are reported. In-house comprehensive software, COMOSM, is used to simulate pulverized coal combustion in a 520 gross MWe opposed-wall fired boiler. The combustion performance of the boiler is evaluated, and the heat transfer characteristics of the boiler under oxy-firing conditions are discussed and compared with those under airfiring conditions. 15-2 Novel Air Separation Sorbents Gokhan Alptekin, Ambal Jayaraman, Margarita Dubovik, Lauren Brickner, TDA Research, Inc., USA Oxy-fuel combustion has the potential to dramatically decrease the environmental impact of producing electrical power, especially because it can be retrofit to existing pulverized coal power plants. In this technology, oxygen combustion replaces the traditional combustion environment of coal in air. This results in an off gas of steam and pure CO2, which can be easily sequestered rather than released into the atmosphere where it contributes to the green house effect. However, the technology is not yet used in spite of its promise, primarily because pure oxygen is currently too expensive. TDA Research, Inc. (TDA) is developing a low cost, high capacity sorbent for air separation to supply low cost oxygen for oxy-fuel combustion. The regenerable sorbent can remove oxygen from air with very high capacity, and the sorbent maintains its capacity for over 200 absorption/regeneration cycles under representative conditions. TDAs oxygen sorbents also would find application in IGCC plants. 15-3 Oxy-Coal Combustion: Effects of PO2 on Coal Jet Stability in O2/CO2 Environments Jingwei Zhang, Eric G. Eddings, Jost O. L. Wendt, University of Utah, USA The purpose of this research is to understand and predict the effects of the near burner zone environment on ignition characteristics of a turbulent axial pulverized coal jet. In oxy-coal combustion this environment consists of O2 and CO2 (instead of N2). Ultimately it is planned to provide data for subsequent simulation validation studies that can be used to predict how air fired combustors may be retrofitted to oxy-coal. Specifically the objective is to explore effects of variations in the partial pressure of O2 and CO2 on coal jet ignition and flame stability. During the oxy coal jet ignition process, the partial pressure of oxygen, PO2, in the transporting fluid, comprised one additional degree of freedom in controlling flame aerodynamics, and enhancing coal ignition, flame attachment/detachment and modifying pollutant formation. The experimental investigations are carried on in a 100 kW laboratory furnace outfitted with an axial burner and arrays of electrically-heated panels in the burner zone in order to control variations in near-burner heat loss. The furnace also has visual access to the burner zone through quartz windows. Sufficient supply of O2 and fresh CO2 are supplied through special utility infrastructure in the laboratory. A special CMOS sensor based camera is used to capture Type 0 axial turbulent diffusion flame shape for the use of statistical studies of flame length at different operational parameters, with special emphasis on systematic variations of partial oxygen pressure in both transport and secondary oxidant streams. Our experimental data show how flame attachment increased with PO2 in either primary or secondary oxidant streams. These variables were also shown to have a first-order influence on fuel NOx. Future work will use these data to validate CFD simulations of axial coal jet ignition in turbulent flows.

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15-4 Numerical Investigation of Oxy-Coal Combustion in Pilot Scale and the Challenges Maryam Gharebaghi, Lin Ma, Mohamad Pourkashanian, Alan Williams, University of Leeds; Ben Goh, Power Technology Centre, UNITED KINGDOM Sequestration as the process of capture and storage of carbon dioxide (CO2) is an alternative for decreasing the green house effect, producing mostly by coal-fired power plants. If coal combustion is performed using oxygen instead of air, the product will be rich in CO2 and therefore ready for sequestration and the process is known as Oxy-coal combustion. Oxy-coal combustion could be applied to the conventional coal combustion plants that will require some modifications. In order to minimize the modification required to the plant, the use of Oxy-pulverized fuel (Oxy-PF) combustion combined with Recycled Flue Gas (RFG) is an alternative option. In this study, to find out the extent of the modifications, by applying Computational Fluid Dynamics (CFD) capabilities, the major challenges in numerical modelling of Oxy-PF combustion with RFG are identified. It has been found that with the presence of high concentration of CO2 in the combustion test facility, the flue gas temperature decreases dramatically. Char combustion and particularly carbon in ash are influenced as well. It has been found that the effect of C-CO2 and C-H2O reactions on char reactivity cannot be disregarded. In order to improve the validity of the CFD code for the design purposes, further modelling improvements for accurate predictions are addressed. 15-5 Study on Simultaneous Removal NOx and SO2 in an Entrained Flow Reactor During Biomass Reburning Ping Lu, Yongqiao Wang, Xiuming Zhu, Shengrong Xu, Nanjing Normal University, CHINA It is well known that the emission of SO2 and NOx from coal-fired electrical power plant have been recognized as acid rain precursors that impose a significant threat to the environment. Among the general methods aiming at the removal of SO2 and NOx, reburning and dry sorbent injection technologies have the advantages of being simple with less equipment, lower capital and operation costs, higher SO2 and NOx removal efficiencies and limited secondary waste generation. Generally speaking, SO2 and NOx removals reported are in the range 60~90% and 50~65% respectively. The optimum injection temperature is about 1100C ~ 1150C. Calcium-based furnace sorbent (such as limestone) injection for SO2 removal is the most popular technology. Reburning is a mature NOx control technology that has been demonstrated on several coal-fired boilers worldwide. Reburning is a three-step process, involving combustion of majority of the fuel under normal fuel-lean conditions, followed by injection of a reburning fuel to establish a fuel-rich zone in which nitrogen oxides formed in the primary combustion zone are reduced to N2, and finally injection of over-fire air to oxidize CO, H2, any remaining hydrocarbons and nitrogenous radicals (NHi, HCN, etc.) exiting in reburning zone. Natural gas, oil, pulverized coal and biomass can be effective reburn fuels. Biomass (such as wood, corn straw, rice husk, etc.) is a regenerable energy. Because of biomass containing low nitrogen content and little sulfur content, high volatiles, relatively low ash contents and, and zero net CO2 emissions, biomass reburning technology to reduce NOx is more attractive. As is well know NOx reduction reactions with solid fuels (coal, biomass) include homogeneous mechanisms involving NOx reacting with volatiles and heterogeneous mechanisms involving NOx reacting with chars. In biomass reburning process, there will produce a large fraction of the volatiles and high activity of fly-ash which will enhance the NO heterogeneous reduction and partly absorb SO2 in flue gas through activated biomass fly-ash. The objective of this research was to study simultaneous removal of SO2 and NOx by biomass reburning and furnace calcium-based sorbents (such as limestone) injection in an entrained flow reactor (EFR). The effects of biomass type and particle size, temperature, residence time, Ca/S ratio, stoichiometric ratio (SR), and additives were investigated. 15-6 Estimation of Thermal and Kinetic Parameters to Model Coal Dust Ignition Ali Rangwala, Haejun Park, Nicholas Dembsey, Kulbushan Joshi, Worcester Polytechnic Institute; Evan Granite, DOE-NETL, USA The ignition temperature of a dust layer can depend on many parameters including: thickness of layer, particle size, moisture content, and particle shape. Three separate models of dust ignition, based on different geometrical configurations have been widely employed in the literature [1]. Based on the configuration of these models, three different types of experiments have been used in the past to perform dust ignition tests on samples: the constant temperature oven, the hot plate, and dust suspended in a furnace within a wire mesh cube. Generally speaking, the data obtained by these methods provide useful benchmark values, but do not provide the fundamental properties required for a broader understanding of dust thermal ignition theory. Most of these tests are based on determining a reference minimum temperature necessary for the ignition of a dust. This is normally performed by exposing a sample, with standard dimensions and boundary conditions, to a fixed ambient temperature and observing whether ignition occurs. Common criteria for ignition in hot plate tests are visible

signs of combustion or glowing, or the sample temperature rising 20 to 50C above the hot plate temperature. This study develops an experimental methodology to use the standard ASTM E2021 test apparatus [2] to obtain thermal and kinetic parameters of Pittsburgh seam coal subject to thermal ignition. Parameters include thermal conductivity, activation energy, coupled pre-exponential factor and heat of reaction term. These terms are required, but rarely known, input values for modeling hot surface ignition of dust layers. Thermal conductivity was estimated by equating heat flux from the hot plate with heat loss on the boundaries at a low enough hot plate temperature where heat generation of dust layer is negligible. Activation energy, and coupled pre-exponential factor and heat of reaction term were obtained by a best fit temperature distribution of a 1D steady state, numerical model with experimental results. Numerically estimated values for thermal conductivity, activation energy, and coupled pre-exponential factor and heat of reaction term were 0.09 W/m-K, 73.2 kJ/mole, and 3.99107 kJ/kg-s, respectively. These values are in good agreement with previous values reported in literature [3]. References: 1. P. C. Bowes, Self-heating: Evaluating and Controlling the Hazards, ed. B.R. Establishment. 1984: Elsevier. 2. ASTM E 2021, Standard Test Method for Hot-Surface Ignition of Dust Layers, A. International, Editor 2001. 3. P.D. Reddy et al. Effect of Inerts on Layer Ignition Temperatures of coal dust, Combustion and flame 114 (1998) 41-53.

SESSION 16 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 1

16-1 Swelling of Coals in Different Gases at High Pressures Richard Sakurovs, Stuart Day, Robyn Fry, CSIRO Energy Technology, AUSTRALIA If carbon dioxide can be sequestered in coal seams and it simultaneously results in enhanced coal bed methane (ECBM) production, some of the sequestration costs can be recovered in the generation of a useful gas. One potential difficulty with ECBM is that carbon dioxide is known to swell coal, which may reduce its permeability. Coals also swell in other gases (St George and Barakat, 2001) though not to the same extent. However, the relationship between the degrees of swelling of coal in different gases has not been examined in any detail. Here we report on the swelling of a subbituminous and bituminous coal in carbon dioxide, methane, nitrogen, argon and krypton. We find the maximum extent of swelling is proportional to the critical temperature of the gas. This indicates that swelling of these coals by all of these gases has a similar basic mechanism: carbon dioxide is only different in the extent to which it swells coal. 16-2 Effects of Texture and Porosity on Diffusion and Sorption in Coal Lumps and Powder Vyacheslav Romanov, Yee Soong, DOE-NETL, USA Typically, the CO2 sorption measurements are conducted on crushed and pulverized coal powder. The differences in texture and porosity between the powder and lumps may affect the transport and interaction of the sorbate fluids and coal. We address macroscopic and mesoscopic structural differences between powdered and nonpowdered coals that influence the rates of the fluid sorptiondesorption kinetics and the pressure dependence of the coal sorption capacity. In this work, experimental longterm sorption isotherms for Argonne premium Upper Freeport coal powder and lumps have been interpreted in terms of the coal swelling, shrinkage, and changes in the pore structure and interconnectivity. We propose a thermodynamic approach for modeling certain structural rearrangements of the macromolecular network of coal, which is tied to the fundamental molecular-scale CO2coal interaction. 16-3 Differential Swelling of Coal Majewska Zofia, G.Ceglarska-Stefaska, S. Majewski, J. Zitek, K. Czerw, AGH University of Science and Technology, POLAND The aim of this study was to investigate the volumetric strain induced in coal by sorption/desorption of carbon dioxide and methane. Rectangular specimens (40 mm x 20 mm x 20 mm) were prepared from lumps of coal taken from the Budryk mine in the Upper Silesia Basin, Poland. The coal was a high volatile bituminous C coal. Specimens were cut with the long axis perpendicular to the bedding plane. Sorption/desorption measurements were carried out by the volumetric method, at 298 K, for gas pressures from 1.5 MPa to 4.0 MPa. During sorption/desorption tests expansion and contraction of the coal specimens were continuously monitored by four resistance-type strain gauges, attached to the sample

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surface on opposite sides at mid-height, at right angles to one another, to pick up strain parallel and perpendicular to the bedding. The volumetric changes for the coal spacimen were calculated from the measured strain. The major findings were as follows. Sorption kinetics indicated that the coal tested showed comparable affinities for CH4 and CO2. None the less, sorption of CO2 led to swelling at least twice that induced by the sorption of CH4, even when considered with respect to the volume of the sorbed gas. The maximum volumetric strain varied from about 0.7 - 1.4% for CO2 and 0.3 - 0.45% for CH4. Strain anisotropy was observed; strain measured perpendicular to the bedding was higher than in the plane parallel to it. The measured strain for gas sorption clearly showed a non-linear relationship between coal matrix swelling and the volume of gas sorbed. In the case of CO2, a rapid increase in the volumetric strain occurred at the beginning of the test, swelling passed through a fairly flat maximum and then started to fall while the volume of gas sorbed went on increasing. Such behavior was unusual and, as far as we know, has not yet been reported. Swelling due CH4 sorption increased in the early stages of sorption, but soon approached an apparent equilibrium level. However, during desorption, shrinkage of the coal matrix was approximately a linear function of the volume of gas desorbed. This was true for both sorbates used. These findings support the results of some other studies, but contradict others. Swelling of the coal tested was additionally characterised by the time required to reach half of the maximum swelling (T1/2). For CO2 the values of T1/2 lay in the range of 0.4 1.0 hour, while for CH4 this was approximately 8 hours. The present study has demonstrated that differential swelling of coal matrix can take place and that the sorption-induced swelling is a non-linear function of the volume of the sorbed gas. The results could have implications for the sequestration of CO2 in coal seams and CH4 recovery from coalbeds (ECBM). Swelling/shrinkage of the coal matrix should be included in models used to predict coal permeability and gas flow rates. 16-4 The Thermogravimetric Analysis of Chinese Coals with High Hydrogen Content Shaoqing Wang, Harold H. Schobert, Gareth D. Mitchell, The Pennsylvania State University, USA; Yuegang Tang, China University of Mining and Technology (Beijing), CHINA Selected Chinese coals, rich in barkinite, were studied by thermogravimetric analysis in a nitrogen atmosphere at three heating rates (10, 15 and 25C min-1). Proximate analysis, ultimate analysis and maceral composition were also measured according to ASTM procedures. The values of hydrogen content and H/C atomic ratio of coal samples studied are, separately >6 and 0.8. A good correlation between hydrogen and barkinite content was observed. When the coals are heated under an inert atmosphere, mass loss occurs in the region 300~550C. The thermal profile shows a monotonic weight loss, however, the reaction is intense. In addition, two good linear relationships were found between H/C atomic ratio and the total mass loss as well as the maximum rate of mass loss. The results also showed that the TGA curves were not greatly influenced by heating rate employed, especially for those coal samples rich in barkinite content. 16-5 An Energy Basin in Turkey: Thrace Region Ilker Senguler, Yusuf Ziya Cosar, General Directorate of Mineral Research and Exploration of Turkey, TURKEY Thrace Basin (Europen part of Turkey) is one of the most important basins because of coal and hydrocarbon potential. Coal explorations have been conducted by General Directorate of Mineral Research and Exploration (MTA), oil and natural gas explorations usually by Turkish Petroleum Corporation (TPAO). Coal formations in Thrace Basin of Tertiary are within Danismen Formation of Oligocene. Danismen Formation has a lithology including gray-green claystone, sandstone, conglomerate, tuff and lignite, and was named as lignitic sandstones in the region by first studies. There are lignite occurrences on foothills of Istranca Mountains in N of Thrace Basin, and these are mentioned as Saray, Vize, Kirklareli and Demirhanli fields in general, and Kesan, Malkara, Uzunkopru and Meric fields in the south. With drilled explorations at significant depths from 1950 to 1980 performed by General Directorate of Mineral Research and Exploration, about 400 million tons of lignite reserves were estimated. Lignites exposed at N and S of the basin gradually deepen toward center of the basin, and reach to 10 000 meters of sedimentary sequence in central parts of the basin and extend to depths below 600 meters. Survey and drilling studies conducted in the region since 2005 by General Directorate of Mineral Research and Exploration aim at exploring coal potential in deeper parts of the basin. Lignite occurrences at depths between 300 and 500 m in the basin will significantly increase lignite potential of the Thrace Basin. Turkey s energy demand is increasing by 6-8% every year, and electricity demand to be expected in 2020 would be estimated as 500 billion kWh. This also denotes that additional 3000-4000 MW power plants would be for electricity production every year.

Besides this, taking into consideration our energy insurance, lignites in our country have a significant potential. Studies conducted by General Directorate of MTA since 2005 facilitated the construction of Saray Coal Power Plant and hence it is considered that any plant construction could be made in other regions on same basin. As were in foundation years, MTA has again undertaken a mission on energy supply, and this project, an important milestone for conversion of Thrace Basin to an Energy Basin, proceeds at present.

SESSION 17 COAL PRODUCTION AND PREPARATION 3

17-1 Burning Unprepared Run Of Mine Coal to Efficiently Fire a Stoker Boiler George Dumbaugh, Kinergy Corporation, USA Mined coal can now be directly and efficiently used to fire a Stoker Boiler. This uncleaned, so-called ROM kind of 2 size stoker coal can have a high percentage of fines. It can be wet and adhesive (sticky) and it can contain more than a normal amount of non-combustible clays or other impurities. All that matters is the rate of coal being fed has heat content needed by the Boiler. This very beneficial accomplishment is intended to make coal a more viable fuel. This timely progress is being achieved with a new Water Cooled Vibrating Grate. It uniquely has an enclosed, underside plenum that is used to receive the incoming air. In turn, this zone controlled combustion air is permeated up through the firing deck that burns the coal. Since it vibrates as a complete unit, it is equipped with a dynamic counterbalance to virtually eliminate transmitting any vibration to the exterior structure. This Vibrating Grate can accommodate Boilers, because the vibratory forces are effectively spread across its width and along its length. The vibratory action is very energy efficient, which is why the Grates motor consumes very little power. By utilizing a simple method of electrical control, the fuel feed rate can be varied from virtually zero to the maximum capacity wanted. This control also provides operating versatility. Flexible connections around the perimeter of the firng deck seal it with the Boiler above. Because the ash is continually being discharged over one end of the firing deck, collecting hoppers under the Grate are no longer needed. Since the vibratory action prompts the fuel to more thoroughly burn, it inherently reduces the amount of ash particulant in the high temperature flue gas being passed to the scrubbers. In turn, the amount of pollutants such as CO, CO2, NOx are proportionally less. This kind of Vibrating Grate can be retrofitted to existing Stoker Boilers. While it was designed for burning coal, it can also be used to fire Boilers with the bio-mass fuels such as shredded wood waste, cotton plants, palm trees, municipal solid waste, refuse derived fuel, and the like. Waste coals, which include culm, silt, and gob can also be burned. This remarkable power engineering feat is the result of the cooperative effort of the Illinois Department of Energy (DOE), the Riley Power Group in Worcester, Massachusetts, and Kinergy Corporation in Louisville, Kentucky. 17-2 Evaluating the Achievable Benefits of Extending Technologies for Uneconomical Coal Resources in South Africa Mikolaj Zieleniewski, Sasol Synfuels; Alan Brent, University of Pretoria, SOUTH AFRICA As the South African economy relies heavily on its coal resources, these resources should be utilised and managed in the best possible manner. Underground coal gasification (UCG) is one of the leading technologies used where conventional mining techniques are uneconomical. UCG delivers gas suitable for synthesis, production of fuels and electricity, or for home usage. The method is perceived as being environmentally friendly and safer than traditional mining. The study summarised in this paper was conducted so as to create a simple model that would allow for the evaluation of UCG process-related costs versus expected benefits in a wider context under different circumstances. The parameters of the model are: feasibility definition, i.e. maximum possible gas calorific value, based on geological surveys and gasification agents; direct process derived from the expected capital and operational expenditures and compared with the gas volume propensity; and assessment of externality costs. The externalities concept should encourage governmental agencies to consider investment in UCG technology as a vehicle for delivering, potentially, high savings in terms of expenditure on national health and of the reduction in the costs of environmental damage resulting from gaseous emissions into the atmosphere.

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17-3 Emissions Reduction and Plant Efficiency Improvement Using the MagMill Robin R. Oder, Ron Hurst, Russell E. Jamison, MagMill Co. LLC, USA We will report recent results obtained with use of a commercial scale MagMill demonstration unit located at the DTE Energy Services facility in Vicksburg, MS. The unit consists of a CE Raymond 352 pulverizer fitted with a dynamic classifier joined to a two stage ParaMag magnetic separator. The MagMill is being developed commercially by MagMill LLC, a joint venture between NALCO Mobotec and EXPORTech Company, Inc. The demonstration unit is operated jointly by DTE Energy Services and MagMill LLC. The MagMill is a dry method for cleaning coal at pulverized coal-fired power plants and other facilities such as direct injection steel furnaces. It consists of a pulverizer and a continuous dry magnetic separator operating together as one unit to clean coal. The technology removes hard to grind mineral impurities from the coal fed to the pulverizer before they are ground to product specification of 7080% passing 200 mesh. Minerals such as iron pyrite denser and harder to grind than the relatively soft hydrocarbon component of coal concentrate on the grinding table inside the pulverizer. They require more passes through the grinding zone to reach particle size specification; hence their concentration is higher on the table than it is in the incoming coal. This concentrated material is withdrawn through the wall of the pulverizer at the elevation of the table top and sent to a continuously operating dry magnetic separator. The separator rejects the mineral component and recovers clean carbon for return to the mill for additional grinding. In addition to carrying sulfur and hazardous trace metals such as mercury and arsenic, these abrasive minerals limit the throughput of the pulverizer, consume extra power for grinding, and lead to problems of abrasive and erosive wear throughout the entire plant. This abrasiveness has been known to lead to plant derating. Pyrites and many of the other minerals found in coal are paramagnetic while the coal is diamagnetic, making continuous dry magnetic separation feasible. Magnetic separation significantly lowers levels of ash, sulfur, and trace metals such as mercury and arsenic before the pulverized coal is fed to the burner. In earlier measurements on Eastern US bituminous coal employing a prototype MagMill, reductions in ash ranging up to 48% and total sulfur up to 54% were measured on a pounds per million Btu basis. Decreases up to 61% on a pound per tera BTU basis were observed in mercury. More recently, direct measurements of dry magnetic separation of a 0.36 wt.% pyritic sulfur sub-bituminous coal from New Mexico showed decreases in ash of 30% and sulfur of 8% on a pounds per million Btu basis and mercury reductions up to 70% on a pounds per Tera Btu basis. This novel technology applicable to all coals and all types of coal pulverization has the potential to increase production up to 70% while lowering power draw by 40% with simultaneous reduced emissions of ash, sulfur and mercury. At an estimated capital cost of $30 per kW for a 760 MW unit, this is an attractive method of increasing MWHr. output compared to the cost and time delay incurred when building a new coalfired plant. Recent results obtained from processing sub-bituminous and lignite coals from the western US and Canada and metallurgical quality coal from the southern US at the Vicksburg MagMill demonstration facility will be presented. 17-4 Gas-Liquid Two-Phase Bubbly Flow in Structured Packing Column for Coal Preparation Chunjiang Liu, Jie Cheng, Tianjin University, CHINA; Fan Shi, University of Michigan, USA Coal preparation or coal cleaning in froth flotation involves the selective separation of clean coal particles, which is naturally hydrophobic, from mineral matter, such as kaolinite, montmorillonite and illite, which are hydrophilic. In practice of flotation, coal particles will attach to and rise with the froth after their collision, and then be recovered from the top of operating unit. The flotation separation relies on the exploitation of the fundamental physics of multiple bubble-particle collisions. In this paper, bubble columns packed with structured packing (Mellapak 350Y structured packing) present different hydrodynamic behavior from traditional empty bubble columns. Three-dimensional Laser Doppler Velocimetry (LDV) and computational fluid dynamic (CFD) method was used to simulate the liquid velocity distribution in structured packing bubble column. The influence of gas flow rate and geometry of inner packing on time-averaged velocity distribution is investigated. The results of 2D model indicated that rising bubbles oscillated and coalesced with increasing of gas inlet rate. The velocity of liquid surrounding the bubble increased and vortexes at different scales were observed. The velocity of single point in liquid fluctuated more and more frequently as the gas inlet velocity increased. In threedimensional unsteady simulation, the break-up of bubbles at crisscrossing section of the packing could be clearly observed in the animation of the bubbly flow. The velocity of liquid surrounding bubbles was larger than that of else region in the horizontal cross-section. Besides, the bubble trajectory changed when it passed through the crisscrossing section of the packing and liquid recirculation cells appeared in upper and lower locations. Both flow characteristics allowed for excellent transverse mixing and alleviated fluid back mixing.

The results of this study are critical for coal preparation as well as other minerals by using structured packing flotation column process. 17-5 Numerical Calculation and Determining Mechanizability of Coal Seams Using Fuzzy Logic Mohammad Bitaraf, Islamic Azad University, IRAN Mineral region of tabas is in east of central iran in yazd province. In this article to observe the mechanizability of coal seams located in this region and degree of improving level of mechanization, factors affecting on mechanizability are studied. Studies shows that thickness, dip, uniformity, roof and floor rock criteria and coal strength are important factors effect of mechanizability of one seam. So considering above factors a fuzzy model using fuzzy tech 5,12 software is made. In this model mechanizability of coal seams regarding effective factors is calculated as a numerical index without dimension. The range of index of mechanizability model changes between 0-100. This comparative scientific suggestion categorize seams to low, medium and high, each one is espicific by limitations of certain numbers. As a case study mechanizability of coal seams in tabas coal mine using this method has been analyzed. The study shows that the mechanizability of seam B1 is medium, seam C1 is high, and seams C2, D is low. 17-6 Qualitative Analysis of Hanging Wall Caving in Longwall Mining; Case Study: Tabas Parvarde Coal Mine Mehrshad Rostami, Islamic Azad University, IRAN Longwall mining is one of the commonest underground mining methods in coal mining worldwide. Longwall is a caving method and the caving process is one of the most important parts of the extraction sequences. Therefore qualitative analysis of the caving can be a useful study to observe and predict the conditions of the hanging wall behavior during the face advance and planning the extraction operation. In this study first of all the parameters affecting on the caving has been classified in four groups. These groups are: mechanical, geometrical, operational and geological parameters. Then the quality of caving according to these parameters and the factors resulting by them such as stability time, bulk factor, average particle size of the caved strata in the gob area and overhanging has been analyzed by using the Tabas Parvarde coal mine conditions. Tabas Parvarde coal mine is located in Parvarde district, Yazd province in Iran. There are five coal seams in this area named B1, B2, C1 and C2. Now only the C2 is under the operation and the results of analysis on this seam show that caving quality in C2 is medium to low.

SESSION 18 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL 3

18-1 Effect of Changing Temperature and Inlet Gas Ratio on Water Gas Shift Activity and Methane Selectivity in Fischer-Tropsch Synthesis Thierry Musanda, Diane Hildebrand, David Glasser, University of the Witwatersrand, SOUTH AFRICA The effect of temperature and inlet gas ratio on the water gas shift activity and methane selectivity was studied since the degree to which equilibrium is attained. If a high water gas shift activity is achieved then the H2 in the inlet gas can be supplemented by the production of more H2 from the conversion of water and CO to H2 and H2 and CO2. The percentage approach to equilibrium is defined as the CO2 that is actually produced divided by the amount that would be expected if equilibrium had been attained. Increasing the temperature increases the percentage approach to equilibrium. Methane is an undesired product in Fischer-Tropsch Synthesis because it has very little use as a fuel or as a chemical feedstock and it is very expensive to be reformed. Therefore, its production is preferred to be kept as lower as possible. An increase in temperature only has a marginal effect on the production of methane at the lower inlet gas ratio but the effect increases as the ratio increases. This is probably due to the fact that an increase in temperature probably increases the amount of dissociation of the CO resulting in more active carbon on the catalyst surface which is then available for direct hydrogenation to methane. This paper will look at the impact of changing temperature and inlet gas ratio on water gas shift activity and methane selectivity in Fischer-Tropsch synthesis. Thermodynamic constraints, kinetics and graphical method will be used to understand this effect.

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18-2 Syngas Conversion to Ethanol over La and/or V Oxide Promoted RhSiO2 Catalysts James J. Spivey, Nachal Subramanian, Louisiana State University; Jia Gao, Xunhua Mo, James G. Goodwin, Jr., Walter Torres, Clemson University, USA In the last thirty years, much attention has been paid to synthesis of higher alcohols from coal-derived syngas due to their potential use as a fuel blend or alternative motor fuel for the reduction of exhaust emissions [1]. Methanol is a common product produced from syngas conversion using copper/zinc based catalysts. However, higher alcohols may be more desirable products, due to their fuel and blending properties. In particular, ethanol is desirable because of the large market that has been created for its use as a fuel. Another interesting application is its potential use as a hydrogen carrier to supply fuel cells. By far the most widely studied catalysts for the hydrogenation of CO to oxygenates are based on Rh [2]. Among supported metal catalysts, Rh appears to be the most active and selective for the synthesis of ethanol and higher alcohols from syngas. Of particular interest are vanadium promoted Rh catalysts, which have been reported to have a high selectivity (typically at low CO conversions) for the production of ethanol [3]. In this work, we have studied the effects of promoters on Rh/SiO2 catalysts under different reaction conditions. A series of La and/or V oxide promoted Rh/SiO2 catalysts were tested for CO hydrogenation to ethanol in a packed bed reactor. Of the catalysts tested, the doubly promoted La-V-Rh/SiO2 catalyst exhibits the highest activity and selectivity towards ethanol at H2/CO: 2/1, 14 bar and 270C -- CO conversion was 7.5% and ethanol selectivity was 44%. Tests at two reaction temperatures (230C and 270C) indicate that both the ethanol selectivity and CO conversion are higher at 270C whereas tests carried out by varying the H2/CO ratios (2/1 and 4/1) suggest that H2/CO : 2/1 and 14 bar gives a higher selectivity towards ethanol relative to methane. [1] Run Xu, Cheng Yang, Wei Wei, Wen-huai Li, Yu-han Sun, Tian-dou Hu, J. Molec. Catal. A, 221(2004) 51-58. [2] James J. Spivey, Adefemi Egbebi, Chem. Soc. Rev., 36 (2007) 1-17. [3] G.van der lee, B. Schuller, H. Post, T. Favre, and V. Ponec, J.Catal., 98(1986) 522529. 18-3 Study on the Effect of Co2O3 Modified Fe-Cu Catalyst for Synthesis of Higher Alcohols from Syngas Yun-lai Su, Xiao-fen Zhu, Zhengzhou University, CHINA It is a very economical attractive method to produce higher alcohols from CO and H2 (syngas). For its high octane and volatility control, higher alcohols can act as fuel and chemical raw material. In our previous work, alcohols can be synthesized over (promoted by) Fe-Cu based catalysts from syngas under temperate operation condition, which is made with low cost and shows high catalytic performance. In this work, based on original batch formula Fe-Cu catalyst, series of different amount cobalt were introduced by impregnation after the co-precipitation process. Catalytic evaluation were performed in a fixed bed high-pressure flow reactor under the conditions: T=350C, P=6.0 MPa, GHSV=10000 h-1, n(H2)/n(CO)=2.3. H2-TPR, H2-TPD, XRD characterization technique were applied to interpretive surface texture of catalysts. In this study, the effect of Fe-Cu catalysts with cobalt loaded was discussed in its activity performance over synthetic reaction of syngas. The experimental result shows that the cobalt loading can obviously enhance the selectivity of higher alcohols and yields of alcohol. Too little or too more cobalt was bad for its catalytic performance over CO hydrogenation. A maximum alcohol yield (Yalcohol) is 0.98 g/mL-1h-1, and the ethanol selectivity at the most is 34.13 w% and the C2+OH selectivity (SC2+OH) at the most is 59.00 w% when catalyst with 1.00 w% cobalt loaded at this reaction conditions. H2-TPR profiles show that when the catalyst is loaded with 1.00 w% cobalt, the reduction temperatures of both reduction peaks are lowest: the first reduction peak is at the temperature of 266C, and the second is at 400C. H2-TPD shows that all catalysts have two active centers, and the second dehydrogenation peak of the catalyst modified changes larger and moves to higher temperature. XRD spectrum declares 2=36.5 is diffraction peak of crystals of Cu2O, and its crystal is dispersion and thin. 18-4 Higher Alcohols Synthesis from Syngas over Promoted Copper-Iron Catalysts Yuhan Sun, Minggui Ling, Kegong Fang, Yao Xu, Debao Li, State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, CHINA In the last 30 years, several catalytic systems have been developed for higher alcohols synthesis from syngas due to the potential application as a gasoline blend or alternative motor fuel for the reduction of exhaust emission. Recently, an efficient copper-iron based catalyst had been developed at our laboratory. In this work, a series of model catalysts were prepared by co-precipitation method and evaluated in the fixed-bed reactor to study the promotional effect of zinc and manganese on the synergetic effect between Cu and Fe.

Firstly, it was observed by in situ diffuse reflectance infrared spectroscopy (DRIFT) that an acetyl intermediate was detected over CuFe catalyst. The existence of such intermediate suggested the validity of adsorbed CO insertion into metal-alkyl (M-C) bond, a mechanism popular for the Rh catalysts and CuCo clusters. Therefore, the present finding confirmed the existence of synergistic effect between Cu and Fe. Based on these observations, a bi-function mechanism was proposed over the co-precipitated CuFe bimetallic system, by which Cu site was a center for adsorbing undissociated CO molecular and Fe site was acted as the roles in producing hydrocarbon and promoting the chain growth. Secondly, the results of N2 adsorption and XRD found that Cu and Fe phases highly dispersed over CuFe catalyst, showing a surface area of 99.6 m2/g. The addition of zinc into CuFe catalyst led to a decease in surface area and the appearance of a new wellresolved diffraction peak, characterizing as ZnFe2O4. However, the existence of manganese in CuFe bimetallic system appears to be another picture: the higher dispersion of active phases after manganese introduction must be a contributor of higher surface area. The zinc and manganese co-promoted CuFe catalyst did not display other change apart from these mentioned above. In the process of H2-TPR, it was seen that over CuZnFe catalyst, the reduction peak position of CuO phase had been shifted to higher temperature related to CuFe catalyst as a result of the low dispersion of Cu phase after zinc addition. In the case of Fe reduction, the manner of the H2-consumption peak changed into broader one, comparing with CuFe catalyst, due to the appearance of a less re. Lastly, the catalytic performance for higher alcohols synthesis over various CuFe catalysts, following the activation by syngas at 300C for 12 h, had been evaluated. It was found that alcohols and hydrocarbons were main product over CuFe based catalysts, and the production of either alcohols or hydrocarbons followed A-S-F distributions, and their parameters, being dependent on the synergistic effect between copper and iron, were essentially different due to the impact of free carbon deposited on the surface of catalyst. The addition of zinc changed the catalytic behavior of CuFe catalyst markedly, i.e. increasing CO conversion and alcohols yield. This finding must be due to the formation of ZnFe2O4, enhancing the activation ability of Fe towards CO molecular as detected by FT-IR. However, the low dispersion of active phase after zinc addition weakened the synergistic effect between Cu and Fe, leading to the lower parameter of alcohols synthesis.

SESSION 19 GASIFICATION TECHNOLOGIES: FUNDAMENTALS 1

19-1 Gasification Kinetics: Model Development and Validation Vladimir Zamansky, Boris Eiteneer, GE Global Research, USA; JS Ravichandra, GE Global Research, INDIA; Cai Zeng, GE Global Research, CHINA; Thomas Fletcher, Brigham Young University, USA GE Global Research is conducting an international R&D program on gasification kinetics. The goal of the program is to develop and validate predictive models describing the chemical processes in the gasification and post-gasification zones of practical gasification systems. In this program, the processes in the gasifier are modeled by detailed chemical reactions, which in turn are validated by experiments. We examined existing models of coal devolatilization, char gasification, soot formation and growth, and homogeneous gas-phase interactions. After detailed analysis, several of these models were selected and adopted as the initial individual sub-models. The Chemical Percolation Devolatilization model and Char Burnout Kinetics model were adopted for the initial description of coal devolatilization and char conversion, respectively. A detailed mechanism of gasification and combustion of benzene was selected to describe tar formation/conversion processes. The benzene model was updated to include all reactions of gaseous products, including tar, and their conversion to soot precursors. The selected initial sub-models were integrated in Chemical Workbench kinetic code developed by Kintech in Russia. The initial integrated gasification kinetic model will be first utilized for parametric modeling of the gasification process and later for experimental validation and improvement of the individual sub-models. These improved sub-models will be integrated in subsequent advanced versions of the gasification kinetic model. The experimental validation program has started. It will include testing of different coal samples in bench-scale gasifier, high-pressure wire mesh reactor, high-pressure thermogravimetric analyzer, and novel and unique entrained flow reactor, capable of reaching hightemperature, high-pressure conditions of industrial gasifiers. 19-2 Modeling Entrained Flow Coal Gasifiers Mike Bockelie, Martin Denison, Dave Swensen, Connie Senior, Adel Sarofim, Reaction Engineering International, USA In this paper we describe a model for ash vaporization that is being implemented into Computational Fluid Dynamic (CFD) models for entrained flow coal gasifiers that can be used in studies to improve gasifier performance. The CFD models provide detailed

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information about gasifier performance including the gasifier flowfield, carbon conversion, slagging behavior, heat transfer, soot and tar formation, etc.. Ash vaporization has not been included in the model. Ash vaporization occurs in high temperature regions of the gasifier and results in sub-micon aerosol formation that can re-condense and deposit on downstream equipment. The developed model is appropriate for evaluating the performance of one or two stage coal gasifier fired with either a slurry or dry feed. 19-3 Effect of Turbulence Models on Gasification Simulation Ting Wang, Armin Silaen, University of New Orleans, USA Numerical simulations of coal gasification process inside a generic entrained-flow gasifier are carried out using the commercial CFD solver FLUENT. The NavierStokes equations and seven species transport equations are solved with three heterogeneous global reactions and two homogeneous reactions. Finite rates are used for the heterogeneous solid-to-gas reactions, while eddy-breakup combustion model is adopted for homogeneous gas-to-gas reactions. Kobayashis two competing rates model is used for devolatilization process. Since the reactions are affected by the fluid mechanics and the turbulence eddy dynamics, the effects of various turbulence models on the calculated results are investigated. Seven different turbulence models are employed for comparison including Standard k-, Spalart-Allmaras, RNG (ReNormalized Group) k-, Realizable k-, Standard k- Model, Shear Stress Transport (SST) k- Model, and Reynolds Stress Model (RSM). The flow and temperature fields and distributions of species concentrations are compared and analyzed. The gasification performance is also compared including carbon conversion, fuel conversion efficiency, syngas composition, and cold gasification efficiency. 19-4 Quantification of Oxygen Capture in Mineral Structure During Gasification Johan van Dyk, JHP van Heerden, Sasol Technology; Frans Waanders, NorthWest University, SOUTH AFRICA It has been observed that during the transformation of minerals at higher temperatures (>1000C), mineral species are formed containing a high number of oxygen molecules, i.e. gehlenite (Ca2Al2SiO7), mullite (Al6Si3O15), margarite (CaAl4Si2O10(OH)2) and almandine (Fe3Al2Si3O12). Results of the coal sources evaluated in this investigation indicated significant differences in mineral elemental composition, i.e. the CaO content varied between 5 mass % and 10 mass %, the Fe2O3 content varied between 1.6 mass % to more than 5 mass %, as well as differences in the TiO2, P2O5 and MgO content. The coal sources producing the highest concentration of Ca-Al-Si species (CaAl2Si2O8 anorthite and CaAl4Si2O10(OH)2 margarite), which crystallized from the slag-liquid phase during the combustion stage, also contained the highest amount of acidic components or highest percentage of kaolinite. The highest concentration of mullite and free SiO2 after the gasification reaction (before the combustion zone), also resulted in the highest concentration of Ca-Al-Si compounds forming during the oxidation phase. The freeSiO2 in the mineral structure of the coal sources resulted then in the formation of mineral structures with Mg, Na or Ca when present in the mineral structure, to form new mineral compounds such as KAl3Si3O10(OH)2 (muscovite), Mg5Al2Si3O10(OH)8 (clinochlore), or other high oxygen molecule-containing mineral compounds. Thus, if free-SiO2 was not present after the gasification phase, and mostly taken up in the form of anorthite (due to high or higher CaO contents or Fe-contents in high Fe-containing coal sources), the concentration of Si-oxygen capture compounds are relatively low. An acceptable linear correlation between oxygen capture tendencies (increase in mineral matter content during the combustion phase) versus CaO-content was obtained with the South African coal sources evaluated. This confirmed the observations obtained based on HT-XRD and FactSage modelling. It can be concluded that the linear model to predict oxygen capture behavior from CaO-content is acceptable and can be used as a predictive tool. The SiO2 content, for example, has an inverse affect on oxygen trends up to a specific concentration of CaO in the coal. However, this model is only valid for the coal types tested (South African Highveld coal sources), and additional test work will have to be conducted for other coal types, i.e. northern hemisphere coal. 19-5 Simulation of IGCC Technologies: Influence of Operational Conditions (Environmental and Fuel Gas Production) Csar Nieto, Erika Arenas, Andrs Arrieta, Zulamita Zapata, Universidad Pontificia Bolivariana; Carlos Londoo, Carlos Valds, Farid Chejne, Universidad Nacional de Colombia - Sede Medelln, COLUMBIA Integrated Gasification Combined Cycle (IGCC) is one of the most promising technologies for power generation; the environmental benefits and the higher energy conversion efficiency distinguish it from traditional coal generation technologies. IGCC performance is affected by different technological and operational aspects, e.g. gasification technologies, gasifier agent, coal rank, environmental conditions, and power demand. This group of conditions hinders the assessment process and conduces necessarily to the use of thermodynamic simulation tools. In this work

thermodynamics analysis simulations were conduced in Hysys and GateCycle. Simulations in Hysys were carried out for different gasification technologies, kinetic reactions, gasifying agents and coal types. Syngas composition and lower heat values were calculated for the all different conditions and had been loaded into GateCycle in which Combined Cycle efficiency were studied for different environmental conditions. Results show behavior for IGCC technologies at different places according to its environmental and operational conditions, and coal rank.

SESSION 20 UNDERGROUND COAL GASIFICATION 1

20-1 The Future Prospects for Underground Coal Gasification Michael Green, UCG Partnership Ltd, UNITED KINGDOM Underground coal gasification is now an important option for coal exploitation and large-scale syngas production in most countries with substantial coal resources. UCG offers the opportunity to exploit the natural coal reserves, which would otherwise be left in the ground as uneconomic or physically unmineable coal. The alternatives for coal supply are conventional mining, often difficult in regions like the European Union, or the importing of coal at much increased prices from the major world suppliers. UCG has been the subject of intense research and field trials in many countries since the Second World War, not least in the United States, where the development program in the 1970s and 1980s extended to 32 separate tests, and a supporting program in National Government laboratories. The program led eventually to detailed proposals for commercial production of chemicals and SNG. Although technically proven, UCG could not compete with low price natural gas at the time and it was left to the Europeans in the 1990s and the Australians after 1999 to conduct further field trials in the coal fields relevant to these Regions. Increased gas prices and concerns about security of supply have produced a resurgence of interest in UCG in many countries. UCG offers an alternative to conventional coal mining, which is safer, more environmentally attractive and, like oil and gas extraction, is more efficient in the use of production manpower. Furthermore, syngas is a flexible fuel and a potential feedstock for poly-generation plant supplying energy, fuel and chemicals from the same complex. The position today (2008) is that UCG feasibility studies and demonstrations are underway in countries as far apart as Mongolia, South Africa, Australia Latin America and the United States, and almost all the studies are in the hands of large mining or power companies who are applying inhouse or investor resources. Those companies are reporting that the unit energy cost for UCG is now substantially below the alternatives of natural gas or surface gasification. Other studies suggest that world coal reserves could be increased by more than two thirds when large scale commercialization of UCG becomes a reality. Environmental issues for UCG tend to focus on the likely impact on ground water, and there is evidence from earlier trials that contamination can occur. However, UCG in deeper coal seams, combined with careful site selection, and the use of active pressure control of the cavity will minimize the underground environmental impact. Those already engaged with National or Regional regulators are confident that UCG under these conditions can meet the stringent ground water regulations now in place in Europe and most other developed regions of the world. Low carbon emissions are another major consideration for fossil fuel usage. Fortunately, UCG already compares well with other coal processes in terms of its emissions per unit of electrical energy and the fact that UCG syngas can be used in combined cycle power generation. Moreover, the syngas is particularly well suited to pre-combustion capture, because of the high pressure of the gases at surface and the favorable partial pressure of the CO2. Partial CO2 capture and the production of hydrogen- methane mixtures, with low carbon content are particularly attractive process options for UCG syngas. CO2 from the separation plant is compressed to pipeline pressure for transportation to storage in abandoned gas reservoirs, saline aquifers and for use in enhance oil recovery. Storage of CO2 back in the abandoned UCG cavity, overlying coal seams and surrounding stressed areas is also potentially feasible under the right conditions. An EU sponsored study to examine hydrogen production and low carbon emissions from UCG has commenced. The 3.2M project aims to investigate hydrogen production and CO2 capture and storage, which involves a variety of academic and research groups throughout Europe. The project is scheduled to last three years and if successful, field trials are likely to follow. Meanwhile the UK has its own study of UCG under the Firth of Forth which is investigating the possibility of operating the process offshore in combination with CCS.

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20-2 UCG & Surface Gasification Comparisons and Contrasts Eric Redman, HellerEhrman LLP, USA Surface gasification, which is possible using several technologies, and underground coal gasification (UCG) represent different methods of achieving similar objectives. These include creating new energy supplies, producing and capturing carbon dioxide for enhanced oil production or other sequestration, and producing valuable gases (e.g., synthetic natural gas, hydrogen, and argon), byproduct hydrocarbons, and other chemicals. Importantly, the objectives also include protecting the local and global environments through reduced air emissions of criteria pollutants, and through muchreduced net CO2 emissions when compared with power plants that burn coal. Both forms of gasification surface and underground are technically suited to specific situations. Both can be conducted in an air-blown or oxygen-blown manner. But the two gasification approaches are not complete alternatives to one another. For example, UCG can be carried out only where suitable coal deposits exist (an easily satisfied requirement, fortunately, in North America). Surface gasification can be conducted far from the nearest coal field, and close to load centers and needed infrastructure, but requires significant coal mining, transport, and higher capital investment than UCG. Among developers of gasification projects, the Summit Power Group may be unique in developing both surface gasification projects (two types at two different scales) and power plants for UCG projects. This experience allows a compare and contrast look at UCG and surface gasification, and some conclusions about the comparative features of each. This presentation will provide that look, with particular focus on cost, efficiency, reliability, scale, commercial readiness, related commercial and financing matters (such as warrantability), environmental impact, and importantly carbon management. The author, an energy sector lawyer, serves as a business consultant to Laurus Energy (a licensee of Ergo Exergys UCG process) and as a leader of Summits gasification group. 20-3 Hydrogen Oriented Underground Gasification of Coal Jan Rogut, GIG - Central Mining Institute, POLAND; Marc Steen, Institute for Energy, Joint Research Centre, European Commission, THE NETHERLANDS Underground coal gasification (UCG) is a technology with more than one century of history. Recently, it has attracted renewed interest triggered by increasing global energy security concerns and stringent environmental regulations on energy production from fossil fuels. HUGE, the Hydrogen Oriented Underground Coal Gasification for Europe project, co-financed by the European Coal and Steel Research Fund is a major clean coal technology R&D project in the European Union. HUGE raises high expectations because of the potential of its specific UCG concept to integrate large scale in situ production of hydrogen-rich gases with on site geological storage of carbon dioxide. This would allow transferring underground generated low carbon and partly purified hydrogen or synthesis gases to the surface as major product, while leaving behind the wastes generated during their conversion from coal. The project, which primarily addresses a European issue, also has a global dimension because of the environmental constraints related to the technologies involved. Major attention in the technology oriented project HUGE is paid to optimizing the integration of mature elements of coal gasification and hydro-gasification processes with heat and mass transfer phenomena taking place in geological multiphase systems of complex geometry. Because the coal to hydrogen conversion process may be carried out at high depths in the composite geological structures of coal seams, aquifers and surrounding strata, only a limited number of methods and tools are available for controlling the conversion processes. Hence, valuable expertise from in situ coal gasification, from geological carbon dioxide storage, from geothermy and from enhanced oil recovery are compiled, critically assessed and used as building blocks in designing and constructing the hydrogen oriented UCG plant. In the context of HUGE, the novel concept of geo-reactor, which stands for an underground, environmentally safe coal gasification plant intentionally integrated with geothermal heat exchange and with carbon capture and storage, is investigated for exploitation of synergies between various geological technologies. 20-4 Environmental Issues of UCG-Study of Some of the Indian Coal / Lignite Deposits Rajinder Kumar Sapru, Rakesh Kumar Sharma, Dinesh Kumar Mathur, Oil & Natural Gas Corporation Limited, INDIA Indian economy is growing at more than 8% and presuming similar rate of growth till 2031, the requirement of primary energy shall increase by 3-4 times and that of electricity supply by 5-7 times of todays consumption. In order to meet the huge requirement, all the options of potential energy sources of India need to be explored and exploited. India is the fourth largest producer of coal in the world. Unfortunately, almost 75% of the resource is at an un-mineable depth. Similarly, out of 38 billion tones of lignite, only about 6 billion tones of lignite are mineable and the rest are un-mineable.

Underground Coal Gasification (UCG), which is a process of in-situ conversion of coal/lignite into Syngas, could allow exploitation of the un-mineable resource. UCG process is an improvement over the combination of conventional mining and surface combustion of coal. As the process is being carried out underground, there is lower particulate emission, lesser water requirement, no waste (ash) generation, no venting of green house gases as in the mining, etc. However, there are environmental issues that arise from the process and can broadly be classified as surface and subsurface issues. Pollutants like phenols, tars, aromatic hydrocarbons etc. are co-produced along with Syngas. If the pollutants escape from the underground reactor and find a pathway, they could contaminate a nearby aquifer. If the un-treated surface water gets mixed with the ground water, the latter can get polluted. The creation of void in the subsurface due to consumption of coal can lead to subsidence. In order to minimize these surface and subsurface impacts, various parameters like geology and depth of coal seam, overburden thickness and properties, hydrogeology of the coal seam and surrounding strata etc. are studied. The study of these parameters and selecting a suitable site is the most important step for minimization of impacts on the environment. Of course, an overall appraisal including size and market of the resource decide the suitability of a site for the process of UCG. Whole suite of the parameters like proximate & ultimate analysis, depth of the deposit, rank, seam dip, geology and lithology, hydrogeology, tectonics, permeability, geomechanical properties etc. were studied for a large number of coal / lignite fields spread across India. The aim of the study was to identify the site(s) that has sufficient quantity of tectonically less disturbed resource and where the impact on the environment due to the process of UCG is minimized. The screening process was a rigorous one and only one site out of several sites was identified as a suitable site for the process of UCG. Further, general geology showed isolation of the lignite seam in the thick layer of clay and this envelope of clay shall act as an impervious layer preventing escape of pollutants from the underground gasifier. The hydrological data showed absence of major aquifers. The unsuitable areas were either tectonically disturbed or indicated presence of major aquifers besides other unfavourable factors. Subsidence parameters have also been predicted. Various parameters shall be monitored through special wells drilled for the purpose. The application of technology of UCG to a number of potential suitable sites could open up a huge opportunity of exploiting the large un-mineable coal / lignite deposits in India. 20-5 Linking Underground Coal Gasification to CCS and the Downstream Opportunities Dermot Roddy, Newcastle University, UNITED KINGDOM This paper starts by surveying the range of integration opportunities that have been developed over a number of years in North East England for surface gasification of coal, linking into power generation, petrochemicals, synthetic fuels, fuel cells and renewable energy production. It then draws on all of this to explore a range of ways in which an Underground Coal Gasification (UCG) project can be linked into similar activities to create a range of value-adding opportunities. Conclusions are then drawn about the scope for replication elsewhere.

SESSION 21 COMBUSTION TECHNOLOGIES 4

21-1 A Process for Clean Combustion or Hydrogen Production Using Coal Jinsheng Wang, Edward J. Anthony, Natural Resources Canada, CANADA The chemical looping process has been developed for combustion of gaseous fuel, whereas clean combustion of solid fuels is of greater interest. Moreover, in chemical looping combustion of gaseous fuel such as natural gas, large amount of water has to be separated from the CO2 product. The condensed water would potentially be corrosive and thus add cost to the process. The oxy-fuel combustion is for solid fuels, but it requires large quantity of pure oxygen. Moreover, the current approach of reducing combustion temperature with CO2 lowers the thermal efficiency. We propose a chemical looping process for clean combustion of coal, or hydrogen production from coal. The process is based on coal gasification with CO2 to produce CO. The CO will then reduce a metal oxide in a separate reactor to give CO2 and pure metal or a lower oxide. Part of the CO2 is recycled for the gasification and the rest is for disposal. The metal or lower oxide is sent to another reactor for oxidation. Heat or power generation can be achieved through this highly exothermic reaction. The overall thermal effect is the same as the combustion of coal, but separation of CO2 is achieved. Comparing with the chemical looping combustion of natural gas, very little water is present in the CO2 product of the coal process. The gasification process can also be used for hydrogen production, via water gas shift reaction of CO. A membrane reactor is evaluated, where the hydrogen product is

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separated from CO, CO2, and steam. Existing fluidized bed technology is considered suitable for the proposed process. 21-2 Thermoeconomic Comparison of Coal-Based Oxy-Fuel and PostCombustion CO2 Capture - Case Study for Polish Conditions Marcin Liszka, Andrzej Ziebik, Silesian University of Technology, POLAND The carbon capture and storage (CCS) is perceived in many countries as mid-term (2020) reality. As CCS technology has not yet been implemented in full-scale plant the comparison of different methods for CO2 removal would be helpful for forthcoming decision-making processes. The study presented here is addressed to the thermodynamic and economic comparison of two newly built pulverized coal (PC) units. One of them is equipped in CCS based on chemical CO2 absorption from the flue gas while another one applies oxy-fuel combustion. For both cases the same steam cycle parameters have been assumed. Both CCS options have been evaluated from the point of view of cumulative energy consumption. This analysis takes into account among others energy expenditures for fuel mining and transport, preparation of sorbents as well as energy incomes due to byproducts generation. Applied cumulative calculus makes thus possible determination of the primary energy consumption for electricity generation which is crucial for thermodynamic comparison of both analyzed systems. The economic CCS aspects have been investigated taking discounted cash flow method as main tool. The cost of electricity production has been calculated assuming the value of modified internal rate of return (MIRR) for electricity producer equal to 10%. An other economic parameter included in this study is cost of CO2 avoidance calculated for both CCS options in two versions: including cost of CO2 transport and storage and neglecting this parameter. The application of the presented system and economic approaches requires information on mass and energy fluxes passing the power units boundary. To calculate all necessary parameters, simulation models of both analyzed PC systems have been prepared. All models have been built on EES software. Most of them are composed of elementary components like heat exchangers, groups of turbine expansion stages, CO2 compressors and coolers, etc. In case of CO2 chemical absorption unit and the cold box for cryogenic air separation the literature-based index models have been applied. The parameters of economic and technical environments have been assumed to values typical for southern Poland conditions. Obtained results indicate that the average increase of cumulative energy consumption caused by CCS inclusion in PC power plant is equal to ca. 30% while the increase of electricity cost amounts to 45% (post-combustion) and to 48% (oxy-fuel). The cost of CO2 avoidance is equal respectively to 47 and 43 Euro/Mg CO2. 21-3 Chemical-Looping Combustion of Coal with Metal Oxide Oxygen Carriers Ranjani Siriwardane, George Richards, DOE-NETL; Thomas Simonyi, Hanjing Tian, Parsons, USA Chemical looping combustion (CLC) is an emerging technology for clean energy production from fossil and renewable fuels. In CLC, an oxygen carrier (typically a metal oxide) is first oxidized with air. The hot metal oxide is then reduced in contact with a fuel in a second reactor, thus combusting the fuel. Finally, the reduced oxygen carrier is transferred back to the oxidizer. CLC thus allows for flame-less, NOx-free combustion without requiring expensive air separation. Most importantly, CLC produces sequestration-ready CO2-streams without significant energy penalty. A Solid fuel such as coal is rarely used in CLC since the process with solid fuels faces many challenges. However, if we address these challenges CLC would be a very economical way for utilization of coal. Research work on feasibility of utilizing oxygen carriers for coal combustion will be presented in this paper Samples of coal mixed with bulk and supported metal oxides (NiO, CuO, MnOx, Co2O3) and metal sulfates were heated up to 1000C in a Thermo Gravimetric Analyzer equipped with a mass spectrometer. Three steps of weight losses were observed: the moisture loss at about 100C, coal partial pyrolysis at 400-500C, and coal-combustion at 600-1000C. The results strongly supported the feasibility of coal combustion utilizing oxygen carriers. Multi cycle tests conducted with CuO as the oxygen carrier showed very promising results. Effect of CO2 and other additives were also investigated. Thermodynamic calculations to understand the feasibility of the concept will also be presented. 21-4 Improving Thermal Efficiencies in Steam Power Plants by Replacing Steam Turbines with New Generation Prime Mover Jerry F. Willis, Admiral Air, Inc., USA Despite the fact that many believe that burning fossil fuels has a significant negative impact on our environment, coal fired steam power plants continue to be the standard bearer for generating electric energy. With thermal efficiencies at approximately 35%, only 35 of every 100 railroad carloads of coal consumed generate electrical power. It is time to ask the question Is the steam turbine still the best technology to drive electric generators?

Utilizing todays steam turbines in coal fired steam generating facilities requires a huge investment in natural resources and auxiliary equipment. Increasing efficiency in steam power plants will substantially reduce the need for coal, thereby reducing emissions and extending fossil fuel resources well into the future. A way to achieve this objective is to replace steam turbines with more efficient prime movers through retrofit programs and construction of new power plants utilizing a prime mover that will increase the efficiency of coal fired steam generating plants. There is now a new concept prime mover available. With the new W2 Prime Mover developed by AAI, a typical 250 mw electric generator can be driven with approximately 50% of the steam required by the typical steam turbine. This will elevate the thermal efficiency of a coal fired steam plants to approach 60% thermal efficiency. 21-5 Clean Energy Systems Zero Emissions Oxy-Fuel Power Generation Process Scott MacAdam, Roger E. Anderson, Fermin Viteri, Keith L. Pronske, Clean Energy Systems, Inc., USA Clean Energy Systems, Inc. (CES) has a developed a novel oxy-fuel power generation concept that uses proven aerospace technology to enable zero-emissions power generation from fossil fuels. The core of the technology is a high-pressure oxycombustor that burns gaseous fuels with oxygen in the presence of water to produce a steam/CO2 working fluid for steam turbines or modified gas turbines. Carbon capture is achieved by separating CO2 from the turbine exhaust in a condenser, and delivering the conditioned, compressed CO2 to a storage site such as an enhanced oil recovery (EOR) field, a depleted gas reservoir, or a saline aquifer. CES has demonstrated the oxy-combustor for over 2,000 hours, mainly on natural gas, while supplying power to the grid at CESs 20 MWth Kimberlina Power Plant outside Bakersfield, California. Under a $4.6 million award from the Department of Energy, CES is developing the oxy-combustion technology for coal-based power plants that use synthesis gas as the fuel. It is closely associated with a DOE award to Siemens Power Generation to develop high-temperature turbines that would be powered by steam/CO2 working fluid from the CES oxy-fuel combustor. In Phase I of the project, CES performed system studies of future oxy-syngas plants, and tested the existing combustor at firing rates of up to 5 MWth on simulated syngas mixtures. In Phase II of the project, CES is performing a detailed design of a 100 MWth syngas combustor, which will be fabricated and tested in Phase III. CES has fabricated a commercial-scale 170 MWth natural gas combustor and plans to test this unit with a modified GE J79 gas turbine at Kimberlina in mid-2008. These components will be deployed in first generation CES power plants that would generate approximately 40-70 MWe of clean power, and 900-1800 tons/day CO2 that will be delivered to nearby EOR operations or stored in saline aquifers. One of these plants is the proposed site for the West Coast Regional Carbon Sequestration Partnership (WESTCARB) Phase III test that would capture CO2 from the process and inject it into a deep saline aquifer.

SESSION 22 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 2

22-1 Element Affinity to Organic Part of Coal Zdenk Klika, Lenka Ambruov, Ivan Kolomaznk, Jana Seidlerov, Jiina Vontorov, VB-Technical University Ostrava; Ivana Skorov, Institute of Rock Structure and Mechanics AS CR, CZECH REPUBLIC The organic element affinities (OEA) were studied on example of Ga and Ge in lignite. Bulk sample of lignite was fractionated using sink-float technique and lignite fractions with different ash content were obtained. All lignite fractions were air-dried and characterized by ash content (An) and the yield of the n-th fraction (fC,n), petrographic and chemical analyses. The data were processed by factor and regression analyses and very high correlation coefficients among some characteristics were obtained. Correlation coefficients of Ga to organic part of coal to huminite and to ulminite are 0.848, 0.803 and 0.833, respectively and correlation coefficients of Ge to organic part of coal to huminite and to U are 0.828, 0.810 and 0.954, respectively. From tested regression equations the best one was selected:

cC ,i , n = cU ,i .U n + cMA,i MAn
where cC,i,n is the concentration of the i-th element in the n-th coal fraction, cU,i is the concentration of the i-th element in the ulminite (U), Un - content of ulminite in the nth coal fraction; cMA,i is the concentration of the i-th element in the mineral admixture (MA), MAn is content of mineral admixture in the n-th coal fraction. From the data for n lignite fraction the coefficients cU,i for Ga (18.2 ppm) and Ge (149 ppm) and coefficient cMA,i for Ga and Ge (10.0 ppm) were calculated. Using the Eq.(1) and relating data of each of n lignite fractions the organic element affinities OEA of Ga and Ge have been calculated. The obtained results of OEA (77% for Ga and 97% for

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Ge) are in good agreement with those ones calculated using former subroutine based on different principle (Klika and Kolomaznk, 2000). 22-2 Occurrence and Distribution Patterns of Trace Elements in Black Rock Series of Yutangba, Hubei Province, P.R. China Yuegang Tang, Sujuan Shi, Fenghua Zhaou, Shaoqing Wang, Weiwei Li, Huimin Hou, China University of Mining and Technology (Beijing), CHINA Mineralogy, geochemistry, and petrology of the selenium-rich black rocks in Yutangba of Enshi county, Hubei Province of southern China were studied using inductively coupled plasma mass spectrometry, powder X-ray diffraction. The author researched patterns of distribution, modes of occurrence, character and mechanism of enrichment of Selenium in black rocks. Regularities of distribution and association of trace element in bed succession of research area were discussed in detail by correlation. And it can be used to study cause of formation of Selenium. The results indicate that Yutangba black rock series are not only rich in Se, but also enriched in V, Cr, Cu, Mo, Cd, Sb, and U. There are six types of distribution pattern of trace element on Yutangba profile section. 22-3 Temperature Dependence of Lead (II) Adsorption from Aqueous Solutions on Subbituminous Coal Boleslav Taraba, Roman Marlek, Zuzana Kniezkov, Ostrava University, CZECH REPUBLIC Adsorption behavior of lead (II) ions on subbituminous coal sample was investigated at temperatures 30 and 60C. Batch adsorption experiments were used to study the shape of adsorption isotherms as well as the adsorption kinetics. SETARAM C80 calorimeter equipped with mixing vessel was then applied to determine heat effects accompanying the interactions of lead (II) ions with coal surface. As a result, the most significant effect of temperature was ascertained for the kinetics of adsorption process. On the other hand, practically no shift in adsorption capacity of coal to Pb(II) ions with temperature was found. Simultaneously, enthalpy of adsorption was confirmed to be slightly exothermic with value of isosteric adsorption heat - 7 + 2 kJ/mol.

successful financial mechanisms. Significant to understanding the challenges is to examine and discuss the lessons learned from similar deployments. Addressed are the major topics associated with CCS commercialization. To advance broad base commercialization of carbon sequestration, projects need to consider the issues debated by industry, the financial community, and the U.S. Congress. The topics addressed are CCS Congressional Initiatives,, the governmental incentives to support the early phases of CCS commercialization; Geologic Storage Regulatory Frameworks, the statutory and regulatory framework to support the injection of CO2; Environmental Financial Mechanisms, the funding mechanisms previously used to support energy and environmental projects that may also be utilized to support CCS technologies; and Carbon Accounting, the process to verify and ensure the secure capture and storage of carbon dioxide. Much can be learned from these lessons learned. 23-3 Energy Project Risk Amidst Climate Change Regulatory Uncertainty James Ekmann, Robert Dolence, Leonardo Technologies, Inc., USA For anyone considering an energy-related project that emits greenhouse gases (GHGs) or that offsets such emissions, the path forward is filled with uncertainty. Compare todays development concerns with the 1970s. In 1970 the primary uncertainties were future electric demand, the cost of capital, and the return on investment granted by a public utility commission. In 2008, uncertainties include a global fuel market; resource depletion; future environmental policies, including traditional pollutants, GHGs, and issues that might appear over the long life of the project; rapidly escalating capital and labor costs; unproven technology options; and geopolitical upheavals arising beyond energy and environment. Lawmakers and regulators are increasingly asked to ensure clean, reliable and fairly-priced energy supply and energy security. How does one balance between the need to add new capacity while enhancing the sustainability of the energy system? The signatories to the Kyoto Protocol have entered the first budget period. The European Union Emission Trading System has been in operation since 2005. Experience from this trading system offers valuable lessons for emerging carbon markets. Discussions are underway to develop GHG reduction programs that might include the United States and the developing nations while the EU is moving ahead with plans for reductions of 20 to 30% below 2005 levels. In the United States, regulation of GHGs is no longer considered a question of if., but when. Laws aimed at carbon reduction will be works in progress with amendments likely to follow. The RGGI initiative starts its first budget period on January 1, 2009. Globally, financial institutions are developing risk standards or investment policies to incorporate risks arising from potential new GHG regulations or to the impact of climatic changes. Insurers are establishing means to share risks and are seeking ways to hedge against these perceived risks. We will contrast real world events with idealized mitigation strategies, technological options essential to these strategies and their projected costs. The IPCCs 4th Assessment reports examined mitigation strategies under various scenarios. Assumptions underlay these analyses, assumptions that are often overlooked in discussions of policy, time lines for reductions, and metrics for success. These and related assessments raise important questions about the efficacy of current efforts and the pace of change. Can sound application of assessment tools improve the ability of project developers to communicate with the spectrum of regulators and interested parties that routinely become involved in decision making? Examination of key assessment studies argues that: Fossil fuels will be needed to meet societal needs for many years. Significant cuts in GHG emissions are essential for pragmatic reasons and must start soon. New technologies paired with enhanced performance of existing infrastructure can address both energy security and environmental concerns. Careful assessments of risks and of interactions amongst technologies are critical to ensure progress against both goals. A strong array of tools is available to support assessments. But these all carry uncertainties and can be compromised by biased assumptions. We will survey case studies that offer key insights, prevalent assumptions that underlie many major assessments, and statistical gaps while summarizing policy and technology risks. 23-4 Quantification of Mine Land Reclamation and Carbon Sequestration: New Technology for Non-Destructive, In-Situ Measurement Lucian Wielopolski, Brookhaven National Laboratory; Richard C. Stehouwer, Penn State University, USA For the coal industry as a major energy source to remain viable and to grow, it must be responsive to public concerns with; a) land disturbance from surface coal mining, and b) the massive emissions of CO2 and other greenhouse gasses from the combustion of coal. While the industry has devoted considerable efforts toward both land reclamation and emissions control, the present need to mitigate atmospheric CO2 increases gives mine soil restoration a new emphasis and importance. Based on 1992 NRI data land disturbed by mining was assessed at 4.4 Mha at United States alone. Implementation of reclamation strategies on these lands as well as on abandoned mined lands which focus on establishment of sustainable production of biomass and carbon sequestration would

SESSION 23 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 1

23-1 Global Warming: The Electric Utility Challenge Frank Princiotta, USEPA, USA The control of greenhouse gases presents a monumental challenge. Industrialization and population growth provide strong drivers for accelerating emissions of greenhouse gases, especially carbon dioxide. In light of the long lifetime of CO2, major reductions of emissions over time will be necessary to stabilize atmospheric concentrations at protective levels. The presentation quantifies the degree of emission control needed for several target CO2 global concentrations and warming increments. The paper then focuses on electricity production and the technologies currently and potentially available to mitigate emissions from this source. Conventional coal boilers with CO2 capture and sequestration, integrated combined cycle gasification (IGCC) with capture and sequestration, solar, wind and nuclear options are compared. For these key technologies, the paper describes the state of development, current and projected costs, projected technology penetrations, and the projected ability to contribute to quantifiable CO2 emission reductions in identifiable time frames. 23-2 Policy and Financial Issues Surrounding Carbon Capture and Storage: Lessons Learned and the Path Forward Jesse E. Gandee, C. David Locke, Patrick R. Esposito, Augusta Systems, Inc., USA In the 110th U.S. Congress, there have been more than 100 bills proposed that address Greenhouse Gases (GHG)s and Carbon Capture and Storage (CCS) technologies. The interest in these topics is reflective of the countrys motivation to resolve climate change issues. In fact, given the collection of GHG and CCS-related policy proposals, the U.S. energy industries, such as coal and natural gas, could soon be functioning in a carbon constrained world. CCS is a viable option to reduce any hurdles associated with GHG requirements but to do so effectively, it must be allowed to evolve in a coherent legal and regulatory climate. Previous research reveals that a full-scale commercial CCS industry will allow for coal companies to meet the energy needs of future generations while simultaneously addressing any carbon constraints. Nevertheless, there are several financial and project-cost factors that will influence the development of a commercial CCS industry, including government funding, market incentives, and

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be beneficial; a) to the mining industry in the eyes of the public, b) in supplementing land needs for potential biofuels and crop production, c) to trading with carbon credits, and d) in sequestering some of the atmospheric CO2. 23-5 Global Climate Change; The Challenge of Mitigating Three Trillion Tons of CO2 Frank Princiotta, USEPA, USA Anthropogenic emissions of greenhouse gases, especially carbon dioxide, CO2, have led to increasing atmospheric concentrations which are the primary cause of the 0.8C warming the earth has experienced since the industrial revolution. With industrial activity and population expected to increase for the rest of the century, large increases in greenhouse gas emissions are projected, with additional and potentially substantial subsequent global warming predicted. While much literature exists on various aspects of this subject, this presentation provides a succinct integration of the projected warming the earth is likely to experience in the decades ahead, the emission reductions that may be needed to constrain this warming, and the technologies needed to help achieve the three trillion tons of CO2 mitigation that may be required. This paper uses available, transparent modeling tools and the most recent existing literature, to draw broad conclusions about the challenge posed by climate change and potential technological remedies over the next century. The presentation provides an overview of the forces driving CO2 emissions, how different CO2 emission trajectories could affect temperature this century, and a concise sector-by-sector summary of mitigation options, and R&D priorities.The author will then quantify the emission reductions potentially available from two major and distinct categories in order to achieve such mitigation. The first involves the accelerated use of existing technologies, especially in the building and transportation sectors. The second, and most important category, involves development and utilization of new energy production and end use technologies, with a focus on power generation and mobile sources. Key technologies will be characterized regarding their mitigation potential and developmental status.

and other contaminants that are detrimental to the steam reforming and FischerTropsch catalysts. The feedstock used in the simulations is sub-bituminous coal from southern regions of the state of Utah. The simulation includes a Fischer-Tropsch unit complete with hydrotreating units and hydrocracking units. The CTL facility produces approximately 5,488 bbl/day of commercial-grade diesel liquid and 2,352 bbl/day of naphtha liquid, which could be shipped to a refinery for further upgrading into commercial-grade end products or to produce other chemicals of commercial value. The CTL plant also generates 107 MW of electric power that can be exported. Simulations were also performed to explore a plant design that includes equipment to separate and compress carbon dioxide for injection into a pipeline and potential sequestration. Facility with CO2 capture and sequestration off-site (65% capture) is included in this analysis. The overall plant thermal effective efficiency for the process configuration is 53.4 percent, on an HHV basis. This paper presents the overview of the material & energy balances and the other results of the simulation. 24-3 Study of Co-liquefaction of Chinese Bituminous Coal and Lignin Wang Zhi-hong, He Xu-wen, Xu De-ping, Wang Yong-gang, Guo Xiang-kun, China University of Mining & Technology, CHINA Co-liquefaction of Shenhua bituminous coal and lignin from black liquor of paper mill was studied. In present work, tetralin was employed as hydrogen-donor solvent. The experiments were carried out in a 250 ml micro-autoclave. Effects of reaction temperature, time, different initial pressure of hydrogen, lignin/Shenhua coal ratios on the conversion, liquid and yields, asphaltene and preasphaltene yields, hydrogen consumption and effective hydrogen were investigated. The results show that the addition of lignin can promote the conversion of coal effectively compared with direct coal liquefaction. The greatest extent promotion is in lignin/Shenhua of 2:8. Conversion and oil yield increase obviously when initial hydrogen pressure is less than 9 MPa. If the hydrogen pressure continue to increase, conversion and oil yield will not be obvious to increase. Oil yield increases at first and then reduces with the increase of temperature. Optimum coliquefaction temperature is at 440C. Conversion and oil yield of co-liquefaction increases at first and then reduces with reaction time, and reached maximum value of 82.66% and 51.49% at 60 min., respectively, under optimum conditions of temperature 440C, initial hydrogen pressure of 9 MPa, Lignin/bituminous coal of 2:8 and reaction time of 60 min.

SESSION 24 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL 4

24-1 Hydrogenation of Naphthalene using Nickel-Molybdenum Catalyst in a Trickle-Bed Reactor Abhijit Bhagavatula, Elliot B. Kennel, Alfred H. Stiller, John W. Zondlo, West Virginia University, USA; Robert W. Svensson, Chalmers Lindholmen University College, SWEDEN The hydrogenation of coal-tar distillates has been carried out in a Trickle Bed Reactor, in which the liquid is allowed to flow through the catalyst bed in the presence of hydrogen. The purpose of these experiments is to reduce the residence time of the disitillates in the reactor, taking advantage of the geometry of the trickle-bed system. Specifically, in trickle bed reactors, part of the catalyst surface is covered by gas and part by liquid. The liquid phase and the gas phase are allowed to flow co-currently downwards through the reactor. A co-current operation allows for better distribution of the liquid over the catalyst and higher liquid flow rates without flooding problems. Part of the catalyst surface is simultaneously covered by gas and liquid. Hence, it is expected that the kinetics of the reaction would be much faster. Thus, the determination of the minimum practical residence time, order of the reaction and rate of reaction for the desired catalytic hydrotreatment of coal tar distillates is the proposed topic of research. 24-2 Baseline Technical and Economic Assessment of a Small Scale Steam Hydrogasification Process with Fischer-Tropsch Liquids Facility Chan S. Park, Arun SK Raju, Joseph M. Norbeck, University of California, Riverside; Larry Rath, Walter Shelton, DOE-NETL, USA A combination of Steam Hydro-gasification Reaction (SHR) and Steam Methane Reforming (SMR) can be used to produce synthesis gas (H2+CO) from carbonaceous feedstock. This technology, developed at the University of California Riverside, Center for Environmental Research and Technology (CE-CERT) operates at moderate temperatures and pressures when compared to other similar processes and can be used to produce Fischer-Tropsch liquids. The technical and economic feasibility of a commercial 4,000 metric ton per day Coal To Liquids (CTL) facility using this new technology is being evaluated by CECERT and the National Energy Technology Laboratory (NETL). Detailed ASPEN Plus simulations have been performed for a plant with a capability of 4000 tons/day coal feed. The simulations include a reactor and a regenerator section for the SHR. The SHR is assumed to be a fluidized bed reactor and the sand material is heated in the regenerator section to enable heat supply to the reactor. The simulation also has a gas cleanup system that will remove the sulfur SESSION 25 GASIFICATION TECHNOLOGIES: FUNDAMENTALS 2

25-1 Preventing Agglomeration Problems During Gasification of High-Sodium Lignite Robert S. Dahlin, Southern Research Institute; Johnny R. Dorminey, WanWang Peng, Roxann F. Leonard, Pannalal Vimalchand, Southern Company Services, USA Previous gasification studies have shown that sodium vapor released from high-sodium lignites can react with silica to form sticky sodium silicates. These sticky sodium silicate compounds naturally tend to glue particles together leading to the formation of agglomerated deposits in the gasifier. Laboratory studies reported in our previous paper suggested that the formation of these sticky sodium silicates was responsible for the agglomeration and deposition problems encountered during the use of high-sodium lignite in a previous test run (TC13) at the Power Systems Development Facility. The previous laboratory studies also suggested that the agglomeration could be minimized by eliminating the sand bed material, reducing the gasifier operating temperature, and introducing an inert particulate material (e.g., dolomite or limestone) to reduce the contact between sticky particles. To take advantage of these observations, a subsequent test run (TC16) was performed with the sand bed material eliminated, the gasifier operating temperature limited to about 930C (1700F), and with the addition of dolomite into the gasifier recycle loop. With these remedial steps in place, the highsodium lignite was successfully gasified without any signs of agglomeration or deposition problems. After the successful gasification run in TC16, another run (TC21) was attempted with the same lignite. In TC21, however, the sodium content of the lignite was somewhat higher (about 8 to 9 wt% as Na2O in the ash versus about 6 to 7 wt% in TC16). With the higher sodium content, the problems with agglomeration and deposition recurred. To better understand the nature of the deposit formation in TC21, samples of the deposits taken from the lower mixing zone of the gasifier after TC21 were subjected to various lab tests. First, the deposit chunks were pulverized and heated to various temperatures to determine the minimum temperature required for reconsolidation. These tests showed that the deposits reconsolidated even at temperatures as low as 540C (1000F). Given the relatively low temperatures at which reconsolidation was observed, it was clear that reduction of the gasifier operating temperature alone would not be a viable means of preventing the agglomeration seen in TC21. Moreover,

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because of the relatively large reconsolidation tendency of the TC21 deposit, it was clear that any additives used to prevent agglomeration would need to be even more effective than the dolomite used in TC16. With these factors in mind, a series of experiments was conducted to evaluate various additives that might help minimize agglomeration and deposition problems. The additives tested included: dolomite, amorphous silica fume, bauxite, vermiculite, kaolinite, waste-derived kaolinite, and meta-kaolin. The laboratory tests showed that a coarse form of meta-kaolin (mean size 920 microns) could prevent reconsolidation of deposits at temperatures as high as 982C (1800F). SEM/EDX analysis confirmed that the metakaolin was able to capture sodium vapor without consolidation. Based on these results, it was decided to conduct another gasifier run with the high-sodium lignite, this time with the meta-kaolin used as an additive. The successful gasification run (TC23) was started with PRB coal to replace any sand bed material with coarse coal ash. After the sand was eliminated from the system, the gasifier was transitioned to high-sodium lignite feed with the simultaneous addition of meta-kaolin. The meta-kaolin was added with the lignite at a rate roughly equivalent to the ash content of the lignite. During the run, the gasifier operating conditions and solids samples were closely monitored to detect any signs of agglomeration or deposition. The monitoring included visual inspection of the samples, examination of the samples under the optical microscope, and baking of the samples in a laboratory muffle furnace to determine whether exposure to higher temperatures would cause sintering and agglomeration. No evidence of sintering or agglomeration was found using any of these procedures. 25-2 Pilot Plant for Fluidised Bed Gasification of Carbon Products with the High-Temperature-Winkler (HTW) Gasifier at the Department of Ferrous Metallurgy Stephan Geimer, Dieter Senk, Thomas Baur, Department of Ferrous Metallurgy, RWTH Aachen University, GERMANY Since several decades gasification of coal with HTW process is state of the art. The increasing energy costs in connection with higher demand on energy lead to new developments for energy production. The good flexibility of the High-TemperatureWinkler gasification process and the ability to use many different carbon and hydrogen containing materials are some advantages. At the Department of Ferrous Metallurgy, RWTH Aachen University a pilot plant for the investigation of gasification behaviour exists. The gasification of up to 40 kg per hour carbonaceous material is possible. In 2007 the complete refractory and all control and measurement units have been revamped. All process units are now computer controlled and a continuous data acquisition enables to calculate the complete mass balance. Due to the size of the pilot plant a prediction for the coal consumption in industrial plants is possible. A wide range of different lignite coals, plastics and waste material in combination with different reaction gas containing of oxygen, air and steam have been applied. A stable operation for these products was archived to find optimum set of process parameters. The production gas was online analysed to record its applicability for power plants but also for industrial application or ore reduction in the metallurgy. 25-3 Gasification Reactivity of Solvent Extracted Ash Less Coals and Raw Coals with K2CO3 at 650C Under Steam Atul Sharma, Hiroyuki Kawashima, Ikuo Saito, Toshimasa Takanohashi, National Institute of Advanced Industrial Science and Technology, JAPAN HyperCoal is a clean coal with ash content <0.05 wt%.Oaky Creek [OC] (C=82%), and Pasir [PAS] (C= 68%) coals were subjected to solvent extraction method to prepare Oaky Creek HyperCoal [OCHPC], Pasir HyperCoal [PasHPC]. Experiments were carried out to compare the gasification reactivity of HyperCoals and parent raw coals with the 20, 40, 50 and 60% K2CO3 as a catalyst at 600 and 650C with steam. Catalyst was loaded by first dissolving K2CO3 on the surface of the HyperCoal by capturing moisture from air followed by physical mixing method. Gasification rates of both coals and HyperCoals were strongly influenced by the temperature and catalyst loading. H2 and CO2 made about 99% of the product gases. Catalytic steam gasification of HyperCoals was found to be chemical reaction controlled in the 600~650C temperature range for all catalyst loadings. Gasification rates of HyperCoals were found to be always higher than parent coals at any given temperature for all catalyst loadings. XRD results showed that microstructure of chars prepared from coals and HyperCoals were similar. NMR results show no significant difference between the chemical compositions of the chars. SEM images showed that chars from HyperCoals are like porous zeolite while dense chars were observed for coals. The difference in reactivity of HyperCoal and coal could be best explained by the macroscopic difference in chars from HyperCoals and coals.

25-4 Preparation and Characterization of Sr(Mn1-xNix)O3 Solid Solution in Relation to Their Use in Chemical Looping Oxygen Transfer Ewelina Ksepko, Jan Figa, Institute for Chemical Processing of Coal; Ewa Talik, University of Silesia, POLAND Chemical looping (CL) using interconnected beds is a new promising combustion technology for production of power with inherent separation of greenhouse gas CO2. The technique involves the use of metal oxide as an oxygen carrier which transfers oxygen from air to fuel. In the concept no extra energy is needed for CO2 separation. The CL idea could be extended to the combustion of solid fuel and CO2 free H2 production. The important role in the mentioned process is played by simple solid oxygen carriers like: NiO, MnO2, Fe2O3. There are only few papers about complex potential CL material as perovskite-type La0.8Sr0.2Co0.2Fe0.8O3. New perovskite-type materials were obtained and characterized by means TG, SEM, XRD, XPS measurements and melting points study. Solid state reaction of oxides was used for preparation. In order to investigate the oxidation/reduction of the materials thermogravimetric measurements were performed. The mentioned perovskite material change very quickly oxygen content with maintaining chemical properties during oxidized and reducing cycles. So it is believed to be suitable candidate for chemical looping. XPS measurements were used to study electronic structure and chemical composition of the obtained perovskites. The obtained samples show deviations from the nominal concentration due to a presence of the additional phases (e.g. carbonates coming from starting materials). The decrease of the carbon and oxygen content was observed during the thermal measurements of the SrMnO3 electronic structure in the range of 20C-700C. Significant changes start above 350C. XRD technique measurements confirmed to be perovskite-type phase. The solid solution Sr(Mn1xNix)O3 effected extremely high melting temperatures in reduction atmosphere, from 1370C to 1590C. Promising results obtained from reduction and oxidation measurements by means of TG, melting points, XPS and XRD research allow us to conclude that Sr(Mn1-xNix)O3 is a capable and suitable candidate for Chemical Looping Combustion- Chemical Looping Gasification processes. 25-5 Pressure Drop Predictions in a Fixed-Bed Coal Gasifier Adam Luckos, John Bunt, Sasol Technology R&D, SOUTH AFRICA In the Sasol Synfuels plant in Secunda, Sasol-Lurgi fixed-bed dry bottom gasifiers are used for the conversion of low-grade bituminous coals to synthesis gas (syngas). The gasifiers are fed with lump coal having a particle size in the range of 5 to 100 mm. Operating experience shows that the average particle size and particle size distribution (PSD) of fresh coal, char and ash influence the pressure drop across the bed and the gas-flow distribution within the bed. These hydrodynamic phenomena are responsible for stable gasifier operation and for the quality and production rate of the syngas. The counter-current operation produces four characteristic zones in the gasifier, namely, drying, devolatilization, reduction and combustion. The physical properties of the solids (i.e. average particle size, PSD, sphericity and density) are different in each of these zones. Similarly, the chemical composition of the syngas, its properties (temperature, density and viscosity) and superficial velocity vary along the height of the bed. The most popular equation used to estimate the pressure drop in packed beds is that proposed by Ergun. The Ergun equation gives good predictions for non-reacting, isothermal packed beds made of uniformly sized, spherical or nearly spherical particles. In the case of fixed-bed gasifiers, predictions by the Ergun equation based on the average or inlet values of bed and gas flow parameters are unsatisfactory because the bed structure and gas flow vary significantly in the different reaction zones. In this study, the Ergun equation is applied to each reaction zone separately. The total pressure drop across the bed is then calculated as the sum of pressure drops in all zones. It is shown that the total pressure drop obtained this way agrees better with the measured one.

SESSION 26 UNDERGROUND COAL GASIFICATION 2

26-1 North America Prospects for UCG in a Carbon Constrained, Energy Secure World Samuel Friedmann, LLNL, USA Underground coal gasification (UCG) has re-emerged as an energy technology of note. This is part is due to UCGs attractive production economics, ability to use otherwise inaccessible resources, and ability to produce syngas that can be converted into electricity, fuels, hydrogen, and other high-value products. These importance of these attributes have increased in light of increased emphasis on secure domestic energy supply, limitations to natural gas production in North America, and increased focus on environmental concerns such as mercury, sulfur, and CO2 emissions.

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Recent research suggests that the US can dramatically increase its domestic coal reserves by gasifying unmineable coals at depth (300-1500 m). Cursory assessment of major coal basins in North America (e.g., Powder River Basin, Illinois, Alberta Basin) suggests a conservative estimate of a four-fold increase in coal resource. These resources could realistically be used to generate assured fuels for military supplies with a substantially lower cost than equivalent surface facilities. Similarly, there is a high coincidence between North American coal resources and potential sites for carbon capture and sequestration (CCS). Initial estimates of sequestration resource published by the DOE and others suggest >75% of previous UCG pilots lay within 50 km of suitable saline aquifers, depleted oil and gas fields, and EOR possibilities. Case studies in key basins demonstrate the potential pairing of conventional CCS with UCG projects. The attractive, preliminary economic assessments for UCG suggest that it would be possible to fully or partially decarbonize many UCG product streams to deliver low-carbon coal energy to markets. 26-2 Underground Coal Gasification Activities in China Sohei Shimada, The University of Tokyo, JAPAN; Jie Liang, China University of Mining and Technology, CHINA UCG (Underground Coal Gasification) is an ultimate energy recovery method from coal seam without exploiting coal. UCG has long history with different gasification scales from fundamental laboratory experiments and theoretical studies to pilot scale field tests and semi-commercial operation. Recent booming of UCG is strongly depends on the natural gas shortage and energy market situation mainly on the oil price. For the UCG is an unconventional way to recover the energy stored underground coal seam and it is rather expensive way to recover energy compared to other conventional energy resources. Incomplete technological maturity including environmental protection technology is one of the key factors in commercializing UCG. Many field tests were carried out in many countries in the world. China is one of the advanced UCG country where UCG is commercialized and assigned one of the national important technology development items. Many UCG technologies have been developed in China. The feature of the UCG system in China is to use the used mine roadway as linking channel. Therefore, this is called Long and Large Tunnel Gasification Method. Air and steam is usually used as an injection gas and in some cases underground water acts as hydrogen source. Recent technology target in UCG in China is to recover high concentration hydrogen for the future hydrogen society. Two stage UCG method was developed to maintain high gasification temperature. Air and steam is injected repeatedly for obtaining high temperature distribution in coal seam with air injection and hydrogen production with steam injection. In steam injection stage the hydrogen with 50-60% concentration was produced. Recent technology challenge is oxygen-rich air injection. China University of Mining and Technology established the UCG Research Center. The Center has a large experimental apparatus with the dimension of 4.45 m (length) 1.17 m (width) 1.57 m (height). This experimental apparatus enables the measurement of gasification process and temperature distribution at combustion and gasification zone with time. The experiments in this apparatus make the reproduction of gasification process underground in more realistic situation. This paper summarizes the UCG technology development and present situation in practice and researches in China. 26-3 Application of the Exergy UCG Technology in International Industrial Projects: The Status Update M. Blinderman, A. Blinderman, G. Elliott, A. Metz, V. Pashenko, I. Saptikov, P. Bedi, Ergo Exergy Technologies, Inc., CANADA Underground Coal Gasification (UCG) is a gasification process carried on in nonmined coal seams using injection and production wells drilled from the surface, converting coal in situ into a product gas usable for chemical processes and power generation. The UCG process developed, refined and practiced by Ergo Exergy Technologies is called the Exergy UCG Technology or UCG Technology. The UCG methods and techniques of environmental management are an effective tool to ensure environmental protection during an industrial application. A UCG-IGCC power plant will generate electricity at a much lower cost than existing or proposed fossil fuel power plants. CO2 emissions of the plant can be reduced to a level 55% less than those of a supercritical coal-fired plant and 25% less than the emissions of NG CC. The UCG technology is being applied in numerous power generation and chemical projects worldwide. These include power projects in South Africa (1,200 MWe), India (750 MWe), Pakistan, and Canada, as well as chemical projects in Australia and Canada. A number of UCG based industrial projects are now at a feasibility stage in New Zealand, USA, and Europe. This paper provides an update on current status of these projects, with primary focus on the Majuba UCG project in South Africa, SENZ project in New Zealand, Two projects in India and the projects in North America targeting power generation and provision of energy and raw materials for production and upgrading of petroleum products from tar sands in Western Canada.

26-4 Underground Coal Gasification (UCG) Project Development in the Australasian Region L.K.Walker, Cougar Energy Ltd., AUSTRALIA Activity in UCG in Australia over the past 10 years has had a significant impact on the revitalization of the technology internationally. This paper summarizes the background to this work, including the gaining of environmental approvals for the successful Chinchilla project, significant commercial aspects of its operation, and its impact in the current climate of global warming concerns. The paper also describes the activities on a number of specific UCG projects in the region, which confirm the certainty behind the eventual commercialization of the technology.

SESSION 27 ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY CAPTURE, NONCARBON

27-1 Mercuric Chloride Based Catalysts for Oxidation of Mercury in Flue Gas Evan J. Granite, John P. Baltrus, DOE-NETL, USA A promising method for the removal of mercury involves catalytic oxidation or chlorination of elemental mercury. Elemental mercury is insoluble in water, whereas oxidized forms such as mercuric chloride are soluble. The catalytic oxidation of elemental mercury to mercuric chloride, upstream of a wet scrubber, could be an attractive strategy for the control of mercury emissions from coal-burning power plants. Many materials have been examined as potential catalysts for the oxidation of mercury in flue gas [1-2]. These materials include: 1.) noble metals such as palladium, gold, platinum, and iridium, 2.) activated carbons, 3.) fly ashes, and 4.) SCR catalysts. There are significant differences in the performance of the catalysts in terms of active life in flue gas. However, the differences between the classes of catalysts, at least in terms of initial level of mercury oxidation achieved, are typically rather small. This suggests the possibility of a common reaction mechanism for the oxidation of mercury. One possibility is that gas phase HCl and/or Cl2 are highly reactive, readily adsorb on most surfaces, and thereby allow many materials to act as catalysts. It was recently found that the study of the homogeneous oxidation of elemental mercury by the halogens is extremely difficult because of wall effects [3-5]. The walls of the reactor, even if chosen or coated to be especially inert, were found to readily catalyze the oxidation of mercury. Medhekar has suggested that mercuric chloride deposits on the wall surfaces act as an active site for the oxidation of mercury, rendering many different materials to behave as catalysts with similar levels of activity for the formation of mercuric chloride [3-5]. Schofield has suggested mercuric oxide or mercuric sulfate as a common active adsorbate in the catalytic oxidation of mercury [6-7]. Mercuric chloride dispersed upon activated carbons is well-known and widely employed catalysts for the hydrochlorination of acetylene [8-12]. Acetylene and hydrogen chloride are reacted over the mercuric chloride catalyst. The loading level of mercuric chloride is typically between 5-10% by weight, and the reaction temperatures are usually around 120C. The extensive literature on the mercuric chloride catalysts for hydrochlorination may provide useful insights on the oxidation of mercury in flue gas. The structure of mercuric chloride adsorbed upon gold has also been previously determined [13]. In addition, other metal chlorides have been employed as catalysts for the polymerization or selective chlorination of organic compounds [14-15], and this also may provide insight into the catalytic oxidation (chlorination) of elemental mercury. The efficacy of mercuric chloride treated activated carbon, as well as other chloride treated catalysts, will be determined, possibly through collaborative efforts. Literature Cited 1. Presto, A.A.; Granite, E.J. Survey of Catalysts for Oxidation of Mercury in Flue Gas, Environmental Science & Technology 2006, 40(18), 5601-5609. 2. Presto, A.A.; Granite, E.J.; Karash, A.; Hargis, R.A.; ODowd, W.J.; Pennline, H.W. A Kinetic Approach to the Catalytic Oxidation of Mercury in Flue Gas, Energy & Fuels 2006, 20, 1941-1945. 3. Wang, J.; Anthony, E.J. An Analysis of the Reaction Rate for Mercury Vapor and Chlorine, Chem. Eng. Technol. 2005, 28(5), 569-573. 4. Ariya, P.A.; Khalizov, A; Gidas, A. Reactions of Gaseous Mercury with Atomic and Molecular Halogens: Kinetics, Product Studies, and Atmospheric Implications, J. Phys. Chem. A 2002, 106, 7310-7320. 5. Medhekar, A.K.; Rokni, M.; Trainor, D.W.; Jacob, J.H. Surface Catalyzed Reaction of Hg + Cl2, Chemical Physics Letters 1979, 65(3), 600-604. 6. Schofield, K. Let them eat fish: Hold the mercury, Chem. Phys. Lett. 2004, 386, 65. 7. Schofield, K. Mercury emission chemistry: The similarities or are they generalities of mercury and alkali combustion deposition processes? Proc. Comb. Inst. 2005, 30, 1263.

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8. 9.

10. 11. 12. 13. 14. 15.

Ogunye, A.F; Ray, W.H. Optimization of a Vinyl Chloride Monomer Reactor, Ind. Eng. Chem. Process Des. Develop. 1970, 9(4), 619-624. Ghosh, A.K.; Agnew, J.B. Kinetics and Mechanism of the Catalytic Hydrochlorination of Acetylene to Vinyl Chloride by Use of a Transient Response Technique, Ind. Eng. Chem. Process Des. Develop. 1985, 24(1), 152159. Hutchings, G.J.; Grady, D.T. Hydrochlorination of Acetylene: The Effect of Mercuric Chloride Concentration on Catalyst Life, Applied Catalysis 1985, 17, 155-160. Hutchings, G.J.; Grady, D.T. Effect of Drying Conditions on Carbon Supported Mercuric Chloride Catalysts, Applied Catalysis 1985, 16, 411-415. Dazhuang, L. The Loss Rate by Sublimation of Mercuric Chloride Adsorbed on Activated Carbon, Carbon 1993, 8, 1237-1242. Laakso, A.; Lahtinen, J.; Levlin, M.; Hautojarui, P. Adsorption of HgCl2 on Au (111) surfaces studied by scanning tunneling microscopy, J. Chem. Phys. 2001, 115(8), 3763-3768. Singh, A.P.; Kumar, S.B. Para selective chlorination of toluene with an L-zeolite catalyst, Applied Catalysis A: General 1995, 126, 27-38. Cai, T.; Liu, S.; Qu, J.; Wong, S.; Song, Z.; He, M. Chlorinated alumina and its catalytic behavior in selective polymerization of isobutene, Applied Catalysis A: General 1993, 97, 113-122.

changes of outlet mercury concentration. Experimental results show that, mercury adsorption in the surface of activated coke is physisorption process. And one makes an in-depth research on thermodynamics and kinetics of Hg0 adsorption in active coke. Research shows that Hg0 adsorption is perfect to accord with Freundlich and Henrys law models in the original coke because of lower concentration, but results are poor with using Langmuir adsorption model, that is, the initial stage can not be used to determine the whole adsorption isotherm. Its not suitable for the prediction of mercury adsorption capacity of high concentration. Researching the mathematical model of mercury adsorption process, the mercury mass balance reads

C C 1 q +u + =0 t Z t

(1). Mass transfer includes

internal diffusion and external diffusion. The overall mass-transfer velocity can be written as:

q = K s av q q t

) (2).The rate of external diffusion and internal

by

diffusion

are

simply

given

27-2 The Binding of Flue Gas Pollutants on Pd-Au Alloys and Monolayers Jennifer Wilcox, Erdem Sasmaz, Shela Aboud, Stanford University, USA Density Functional Theory calculations have been performed to predict the binding mechanism of flue gas pollutants such as SO2, Hg0, HgCl2, HgO and SeO2 on pure Pd (001) and Au (001) and their binary alloys. The vast majority of the mercury released from coal combustion is elemental (Hg0) and its binding on PdAu (111) has been investigated. Additionally, the temperature effect on the binding mechanism of Hg0 has been investigated on pure Pd (001). It has been found that the Pd surface is more reactive than the Au surface to the pollutants of coal combustion flue gas. A weak interaction has been obtained for SO2 and HgCl2 molecules on Pd (001), whereas Hg0, HgO and SeO2 bind strongly to the Pd (001) surface. Calculations for Hg0 binding on PdAu (111) have shown that small additions of Au to Pd increases the binding energy by improving the surface reactivity of the alloy. Further studies showed that using a monolayer of Pd overlayed on an Au substrate enhances binding compared to the PdAu alloys. The use of monolayers not only removes the dependence on the random atomic arrangement, but it may also lead to a higher capacity because of the surface composition uniformity and subsequent increased number of binding sites. 27-3 Development of Novel Catalyst for Mercury Oxidation under PostCombustion Zone Conditions D Patanjali Varanasi, Sukh Sidhu, University of Dayton, USA The results of our previous mercury oxidation study conducted using six different Ohio coal fly ashes and model fly ashes show that the chemical composition of surfaces plays an important role in mercury oxidation reactions. Mercury speciation depends on fly ash surface constituent like carbon, iron and calcium. It was also noted that fly ash behavior for mercury adsorption/oxidation is based on its carbon content at lower temperature and on its metal content at higher temperature. The mercury should be present in its oxidized form for it to be effectively removed in the wet scrubbers. An oxidation catalyst is needed to ensure oxidation of mercury before it enters the wet scrubber. The present study investigates the applicability of -iron oxide, copper oxide and copper chloride as mercury oxidation catalyst. The mercury oxidation and mercury adsorption/desorption capabilities of these catalyst were also examined in the presence of coal fly ash. In all experiments, the inlet concentration of Hg0(g) was maintained at 33 g/m3 using a diffusion cell as the source of Hg0(g). A 4% O2 in nitrogen mix was used as a reaction gas, and HCl was added to reaction gas as required. The fixed bed catalytic reactor was operated over a temperature range of 200 to 400C. In each experiment the reactor effluent was sampled using modified Ontario-Hydro method. After each experiment, fixed beds were also analyzed for mercury. The results show that copper oxide and copper chloride were highly effective in oxidizing mercury. However the -iron oxide catalyst only showed high mercury adsorption and significant mercury oxidation was only observed after long exposure in the presence of HCl. 27-4 Research on Kinetics of Mercury Capture with Active Coke Yin-wu Xiong, Beijing Research Institute of Coal Chemistry; Ya-na Bai, CUMTB, CHINA Active coke (AC) has eximious adsorption properties, which has maken great development in flue gas purification. Active coke not only removal of major pollutants in flue gas such as SOx, NOx, but also removal of elemental mercury (Hg0). It is put in fixed-bed reactor, then mercury vapor from the Hg0 permeation tubes mixed with other simulated flue gas components pass through samples layer, at last, measure the

q = k s av (qi q ) t

q = k g av (c ci ) t

(3)

and

(4), respectively. Following the Henrys law, surface

adsorption process has the following equation:

q = Kc

(5). Finite difference

method calculation for the eqs 1-5 is used to adjust mathematical simulation parameters K and Ksav. The results show that, the smaller particle size and the more mesopore of adsorbent, the bigger mass transfer coefficient and physisorption capability. With the adsorption temperature increasing, the mass transfer coefficient is larger, which accelerates the mass transfer process, but reduces the adsorption capacity. 27-5 Evaluation of Decomposition Characteristics of Mercury Compounds Using Mass Spectrometer Md. Azhar Uddin, Saori Nagano, Masaki Ozaki, Eiji Sasaoka, Okayama University, JAPAN; Shengji Wu, Hangzhou Dianzi University, CHINA Understanding the decomposition characteristics of mercury compounds is very important for the development of sorbents for mercury removal from coal derived flue gas and fuel gas. The information concerning to the stability of mercury compound are valuable data necessary for the design of solid sorbents. However, there are not enough data available on mercury compounds stability in the flue or fuel gas conditions. The decomposition behavior of mercury compounds such as HgS, HgO, HgSO4, HgCl2, Hg2Cl2 were investigated by TPDD (temperature programmed decomposition and desorption) technique using a mass spectrometer (TPD-Mass method). Especially, the stability and reactivity of mercury chloride (HgCl2) was mainly examined in coal combustion flue gas and coal derived fuel gas conditions. The mercury compounds were diluted with solids (diluents) such as SiO2, SiC, Al2O3, TiO2 and activated carbon for TPD-Mass experiments. The following results were obtained: (1) the order of the main peak temperature of mercury evolution from the decomposition of mercury compound in He flow was as follows: HgS (meta-cinnabar) = HgO < HgS (cinnabar) < HgSO4; (2) HgSO4 was hydrolyzed by H2O; (3) HgO was reduced by SO2 in the presence of H2O and O2; (3) HgCl2 and Hg2Cl2 were decomposed more easily over the SiO2 than the other mercury compounds; (4) HgCl2 was most easily decomposed over the SiO2 and stabilized over the AC; (5) HgCl2 gas could be converted to Hg0 over quartz wool, Pyrex wool, ceramics (SiO2-Al2O3) wool, carbon fiber and AC.

SESSION 28 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 3

28-1 The Oxygen and its Influence on Coal Surface Roman Marsalek, Univerzity of Ostrava, CZECH REPUBLIC Various types of oxidation of carbonaceous materials were evaluated. The zeta potential of different kinds of carbonaceous materials was studied with respect to the content of oxygen. Samples of sub-bituminous, bituminous, altered bituminous coal, activated carbon and graphite were used. It was found, that zeta potential of coal samples decreases to more negative values with increasing native amount of oxygen. This trend was confirmed on samples of partially oxidized coal, for which the zeta potential decreases with increasing temperature of oxidation and increasing amount of chemisorbed oxygen. Similar relation was found for samples of graphite oxidized by nitric acid. A surface of carbonaceous materials was also modified by surfactant - SDS

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(sodium dodecyl sulphate). We followed relationship between adsorbed amount of SDS and changes of the zeta potential. Amount of oxygen in carbonaceous materials affects hydrophobicity of these samples. Decrease in oxygen content leads to increase of adsorption of SDS. 28-2 Study on the Properties of Huangling Coal and its Application in Coking Shizhuang Shi, Gang Shi, Feng Shi, Cheng Zhang, Wei Xu, Wuhan University of Science and Technology; Yubao Guo, Shiqiang Ma, Huangling Ming Group Corporation Ltd.; Jun Wang, Shangguo Liang, Xinhong Lei, Wuhan Iron and Steel Co. Ltd, CHINA Huangling coal is a new kind of coal mined from a colliery with more than ten million tons per annum. In order to use it better, firstly, its properties are studied systematically, including preliminary analysis, ultimate analysis, ash component analysis, maceral (petrographic) analysis, vitrinite reflectance analysis, technological property analysis, Hardgrove grindability analysis, coking property analysis, harmful element analysis (e.g. phosphorus, arsenic, hydrargyrum, chromium, plumbum etc.) and so on. It is found that the huangling coal is a gas coal with low ash content, low sulfur content, medium phosphorus content, low arsenic content, low chromium content, low plumbum content, medium hydrargyrum content according to Chinese classification standard of coal. Then the huangling coal is used to blend and to coke. The effect of the ratio and fineness of Huangling coal in blend on coke quality, including mechanical strength (M40, M10), thermal performance (CRI, CSR), microstrength (MSI), porosities, densities, optical texture etc., is studied systematically. Experimental results show that the huangling coal possesses good coking property. When its proportion ranges from 2%-20% and under the conditions of different fineness, the various indexes of coke quality are stable basically. 28-3 Determination of Gieselers Plasticity Parameters of Coal Based on Dielectric Property Tetsuo Aida, Ken-ichi Fujita, Toyokazu Shinkai, Kinki University; Izumi Shimoyama, JFE Steel Corporation, JAPAN It has been developed a reliable methodology to determine the plasticity parameters of coal, so-called, Gieseler s Initial Softening Temperature (ST), Maximum Fluidity Temperature (MFT), and Re-solidification Temperature (RT), based on the dielectric properties. The thermal behavior of dielectric property of coal was evaluated by using our instrumentation which has capability to determine a capacitance and electric conductivity with a function of temperature. Because of the physical definition of these properties, the thermal mobility and polarizability of the macromolecular network structure of coal is thought to be more reasonably reflected on the plasticity of coal than viscosity. A typical example of the measurement of the capacitance of the Argonne Premium Illinois No.6 coal is demonstrated below, with the scheme determining ST- and MFTvalues, as 371C and 410C, of which Gieseler s determination were 367C and 417C, respectively. The Re-solidification Temperature (RT) of Illinois No. 6 coal has also been determined by the same manor from the thermal behavior of electric conductivity of coal, as 447C, (cf. Gieseler s 444C). This paper will present details of the instrumentation, and discuss its potentiality in the coal science with data of other Argonne Premium Coal Samples, comparing with Gieselers. 28-4 The Definitions of Catalytic Index of Ash Component of Coking Coal and their Interrelations Shizhuang Shi, Cheng Zhang, Feng Shi, Wei Xu, Hui Wang, Wuhan University of Science and Technology; Xinhong Lei, Coking Co. Ltd, Wuhan Iron and Steel Group Corporation, CHINA In order to comprehensively estimate the influence of ash component of coking coal on catalysis of carbon solution loss reaction of coke, various catalytic indexes were defined and named by different researchers. The number of ash components used in the definition range from 4 to 10. In order to study the correlation among the various definitions, firstly the ash component data of about 100 primary coking coals of China were determined; and the catalytic indexes of each coal according to various definitions were calculated. Then the regression analyses between them were carried out. The results show that there are very good correlativity between some catalytic indexes, for example, the correlation coefficient between the mineral catalytic index MCIb of Baosteel Co. and Yangs mineral catalytic index MCIy is 0.9996, the mineral catalytic index MCIb of Baosteel Co. and the mineral basicity index MBI of Canadian CCRA is 0.9723 etc. Therefore they can be interchanged in a way.

28-5 Maastrichtian Coals from Nigeria: Notes on the Origins of the Inertinite Macerals, with Attention to Macrinite Formation as a Consequence of Fungal Degradation James C. Hower, University of Kentucky (CAER); Susan J. Tewalt, Harvey E. Belkin, U.S. Geological Survey; Jennifer M.K. OKeefe, Morehead State University; J.D. Stucker, Allison R. Richardson, University of Kentucky, USA; Samson Adeleke Oke, Federal University of Technology, NIGERIA; Irena J. Kostova, University of Sofia St. Kliment Ohridski, BULGARIA Subbituminous to high volatile C bituminous Maastrichtian coals from the Enugu and Okaba Odagbo coal fields, Anambra Basin, and the Orukpa coal field, Benue Trough, Nigeria, were collected for the U.S. Geological Surveys World Coal Quality Inventory. Petrology was done at the University of Kentucky Center for Applied Energy Research. The coals show wide variation in the maceral percentages, from 34 to 82% huminite/vitrinite and 7.6 to 31% fusinite + semifusinite + inertodetrinite. The inertinite group contains not only relatively abundant fusinite and semifusinite, with lesser amounts of inertodetrinite; but also secretinite, micrinite, macrinite, and funginite. The fusinite + semifusinite and each of the other maceral varieties can have distinct origins and it is misleading to consider all inertinites as having a more or less common origin. In particular for this set of Cretaceous coals, macrinite, often a rare maceral, is present in amounts up to 3.8%. In these coals and in others we have examined, macrinite can be associated with funginite. Whether or not this is a causal association is debatable, but it has been suggested by other researchers that there could be a genetic connection between the two macerals. Fungal degradation of woody and other material is a plausible origin for the amorphous to (marginally) detrital structure found in the associated macrinite.

SESSION 29 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 2

29-1 Low-Cost, High-Efficiency CO2 Compressor Peter Baldwin, Ramgen Power Systems, USA Ramgen Power Systems, Inc. is developing a family of high performance CO2 compressors that combine many of the aspects of shock compression systems commonly used in supersonic flight inlets, with turbo-machinery design practices employed in conventional axial and centrifugal compressor design. Shock wave compression technology has the potential to develop very high compression ratio per stage and very high efficiency, simultaneously. This capability allows Ramgen to configure a 2-stage CO2 compressor for a pressure ratio of 100:1, while conventional technology will typically require 8-stages of compression. The input power to Ramgens 2-stage compressor will be comparable to the 8-stage conventional approaches, but the individual compressor stage discharge temperature will be 450500F vs. the conventional 8-stage 200F, allowing for cost effective heat recovery of 80% of the input Btu. The all-in capital cost is expected to be 1/3 of the conventional approaches. Ramgen will present an update on its technical and commercial status. 29-2 A Comparison of In-Line and Integrally-Geared Centrifugal CO2 Compressors Kevin W. Kisor, MAN TURBO Inc., USA For gasification plants with carbon-capture capability, one of the problems that must be solved is how to compress the CO2 after it has been separated from the syngas stream. Because the volume of gas is so large, a centrifugal compressor is the most realistic solution for that task. Whether injected into the aquifer or transported via pipeline to an enhanced oil recovery location, the CO2 must be compressed from approximately atmospheric pressure at the separation unit up to pressures in the range of 2,000 3,000 psi. Traditional in-line centrifugal compressors could be used, and have a long history of reliability in critical process and oilfiled services. Integrally-geared centrifugals have a lower capital cost and require less power, but have fewer references in this high pressure range. Our presentation would describe the basic differences between the two compressor types in terms of design philosophy, construction details, and comparative performance. We would finish with a case history of the CO2 pipeline compressors in operation at Dakota Gas Company in North Dakota.

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29-3 CO2 Sequestration in Unminable Coal Seams: Characterization, Modeling, Assessment and Testing of Sinks in Central Appalachia Michael Karmis, Nino Ripepi, I. Miskovic, Virginia Tech; J. Matthew Conrad, Michael J. Miller, Chris Shea, Marshall Miller & Associates, Inc., USA This paper describes the work of the Central Appalachian Coal Seam Sequestration group of the Southeast Regional Carbon Sequestration Partnership (SECARB) on the characterization, modeling, assessment and testing of unminable coal seams in Central Appalachia that can serve as carbon dioxide sinks, while also stimulating enhanced coalbed methane recovery (ECBM). Managed by the Southern States Energy Board, SECARB is one of the seven regional carbon sequestration partnerships established and supported by the National Energy Technology Laboratory, U.S. Department of Energy. Assessment of CO2 sequestration and enhanced recovery potential of coalbed methane (CBM) reservoirs in the Central Appalachian Basin has indicated that more than 1.3 billion tons of carbon dioxide (CO2) can be sequestered, while increasing coalbed methane reserves by as much as 2.5 trillion cubic feet (Tcf). Since some of the Central Appalachian coalbed methane fields are approaching maturity, CO2-enhanced coalbed methane recovery has the potential to add significant recoverable reserves and extend the life of these fields. Based on geologic characterization results, a carbon dioxide injection site was selected in Russell County, Virginia, where an existing CBM well was donated by CNX Gas. Prior to injecting carbon dioxide, two monitor wells will be drilled in close proximity to the injection well to procure important geologic and engineering parameters required for reservoir modeling. Core hole testing will include a thorough suite of geophysical logs, gas desorption tests, adsorption isotherms (carbon dioxide, methane and nitrogen), and petrographic analyses. As part of the field test, 1,000 tons of CO2 will be injected into the CBM well in order to evaluate the ability of coal seams to sequester and adsorb CO2. This paper presents an overview of the characterization, modeling and assessment of the region and provides an update on testing protocols and procedures to further assure the success of coal seam sequestration with ECBM recovery in Central Appalachia. 29-4 Profile of Mineral Characteristics for Geological Seals at Field Demonstration Sites for Carbon Dioxide Sequestration in Saline Aquifers Craig Griffith, Yee Soong, Sheila Hedges, DOE-NETL; Gregory Lowry, David Dzombak, Carnegie Mellon University, USA In 2003, the U.S. Department of Energy initiated regional partnership programs to test promising carbon sequestration technologies and enable large scale implementation of CO2 sequestration. Five of the seven partnerships are planning site demonstrations for CO2 sequestration in deep saline aquifers. A mineralogical profile of the seals overlying the target porous rock storage units across seven of the nine sites was generated to identify minerals of interest with rock-brine-CO2 interactions that would be relevant in assessing seal integrity. The most abundant minerals present in these seal rocks, as reported in literature, include: Quartz, illite, dolomite, calcite, and glauconite along with significant levels of organic carbon. The types of formations in which these minerals occur, and their relative abundance will be discussed. In addition, initial studies of the extent and rate of reactivity of selected minerals with CO2-saturated brine solutions under sequestration conditions will be described. 29-5 Comparative Study of Bituminous and Lignite Coals in Application to CO2 Sequestration Igor V. Haljasmaa, Robert McLendon, Sinisha A. Jikich, Hema Siriwardane, Yee Soong, Gino Irdi, DOE-NETL; Anastasia Dobroskok, EERC, University of North Dakota, USA Unmineable coal seams have been proposed for carbon dioxide sequestration. In order to assess the possible suitability of a particular coal type (or specific coal seam) for sequestration there are key parameters that are necessary to know. Among them are permeability and the sorption capacity of the coal seam. In addition, if there are interactions between the coal seam and the carbon dioxide, an estimate of the time constant for such interactions is essential. Formation permeability is most accurately determined by well testing. Fluid flow through coal seams is primarily Darcy type flow through fractures, cleats, etc. However, carbon dioxide transport into the bulk of the coal matrix (to enable sorption) is best determined in specialized equipment in controlled conditions in a laboratory setting. The National Energy Technology Lab (NETL) has such equipment. A modified Autolab 1500 unit (New England Research, Inc.) for handling very low permeability cores and a CT scanner for measuring sorption rates of carbon dioxide in coal cores were used to test bituminous and lignite cores. Times for sorption were determined at different confining and pore pressures. Profiles of sorption gradients were determined. Qualitatively, over certain range of confining and pore pressures, the sorption process in coal cores may require days to approach equilibrium. Comparisons were made to powder studies for sorption isotherms (Langmuir or BET type 1). Measurements of permeability in coal cores were highly

variable. Besides being affected by pressure variations and presence of cracks/ cleats, permeability was strongly dependant on the CO2 exposure time. Coal swelling due to the carbon dioxide sorption caused, at times, dramatic drops in permeability (sometimes by an order of magnitude). Often, the effects of carbon dioxide sorption were almost immediate; it would happen before the first carbon exposure test was completed. Over the time period of several days, permeability would sometimes decrease by another order of magnitude. This phenomenon can significantly slow down penetration of CO2 to the final sequestration target (coal matrix) and, thus, would strongly affect the sequestration rates.

SESSION 30 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL 5

30-1 Coal to Liquids vs. CO2 Management Qingyun Sun, Jerald J. Fletcher, West Virginia University, USA High crude oil prices have again resulted in significant interest in coal-to-liquids (CTL) technologies as an alternative source for liquid fuels in the US. While some concerns related to the technical feasibility and economical viability of CTL remain, CO2 management has become a significant constraint to potential development. Current CTL processes generate significant amounts of CO2. The ability to manage CO2 emissions is expected to directly impact the financial and business decisions of investors and developers. This paper discusses the quantity and quality of the CO2 generated during the liquefaction process and explores alternative CO2 management options for CTL projects. The CO2 streams generated by direct and indirect coal liquefaction technologies are compared both qualitatively and quantitatively. This assessment and the related discussion will proved a better understanding of CO2 constraints and possible solutions relevant to future CTL development. 30-2 Performance, Economics, and Greenhouse Gas Emissions from Coal and Biomass Synthetic Fuel Production Thomas J. Tarka, DOE-NETL; David Gray, Charles White, Noblis, Inc., USA Record high oil prices and increasing concerns about energy security have prompted a renewed interest in the production of transportation fuels from alternative or unconventional sources. The fuels vary, as do their feedstocks, with consideration being given to everything from hydrogen to cellulosic ethanol and natural gas-based liquids. Numerous studies are currently underway evaluating the economics, scale, and energy conversion efficiency of producing these fuels. Furthermore, the growing awareness of global climate change has intensified the need for any fuel under consideration to have life-cycle greenhouse gas (GHG) emissions which either match or are reduced when compared to conventional petroleum fuels. One potential pathway is the production of diesel fuel and naptha from coal and biomass. This pathway enables the use of a renewable, low-carbon fuel with an existing technology for liquid fuels production. The process looks economically attractive given the availability and cost of coal (as compared to oil) but has the drawback of increased GHG emissions compared to petroleum. The National Energy Technology Laboratory (NETL) initiated a study in 2007 to better explore the potential for the production of these unconventional liquids, with the goal of understanding the trade-offs between fuel cost, GHG footprint, and scale achievable. Over 16 different scenarios were examined, including the use of different plant configurations, various coal and biomass types, a representative selection of biomass to coal ratios (ranging from CTL only to BTL only), and the integration of Carbon Capture and Storage (CCS). This paper details the findings of this extensive study. 30-3 Fischer-Tropsch Fuels from Coal and Biomass Eric D. Larson, Guangjian Liu, Robert H. Williams, Thomas G. Kreutz, Princeton University, USA We present results of detailed process design, simulation, and cost analysis of facilities producing Fischer-Tropsch Liquid (FTL) fuels from biomass and coal, with capture and deep underground storage of by-product CO2. Biomass and coal are co-gasified in an oxygen-blown dry-feed entrained flow reactor, and following gas cleaning and conditioning, the resulting synthesis gas is fed to an iron-catalyzed FT reactor where it is converted into a raw syncrude that is refined to finished transportation fuels, primarily diesel and gasoline substitutes. We present results for four process configurations, each with a different percentage of biomass in the biomass-plus-coal feedstock. The percentage ranges from 0 to 100. We report energy and carbon balances for each configuration, along with levelized FTL production costs as a function of assumed cost of carbon emissions. With the percentage of biomass in the input feedstock equal to zero, there are net positive lifecycle carbon emissions

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associated with the FTL product. With the biomass percentage at 100, there are net negative lifecycle carbon emissions. 30-4 Effect of Gasification Conditions on Fischer-Tropsch Liquid and Power Production S. Srinivas, Anil Khadse, Preeti Aghalayam, Ranjan K. Malik, Sanjay M. Mahajani, IIT Bombay, INDIA It is well-known that syngas composition from a gasification reactor depends on the operating conditions and the feed stock. The aim is to compare the overall performance of a flowsheet consisting of the following blocks - a gasifier, an FT reactor and a power generator. Simulations are performed in Aspen Plus for a given set of operating conditions (pressure and temperature) in different gasifiers and at different FT reactor temperatures by considering liquid yield from the FT process, power generation potential from the reactor tail-gas and steam generation capability from the exothermic heat of the FT reactor. A simple equilibrium model is used to predict the syngas composition from different gasifiers. A detailed kinetic model reported in literature is used for the FT reactor simulations. The analysis of these simulation results and observed trend between gasifier operating features and FT liquid yields/power production is reported.

31-3 An Improved Thermodynamic Factsage Simulation to Simulate Mineral Matter Transformation During a Fixed Bed Counter-Current Gasification Process, Validated with Ht-Xrd JC van Dyk, Sasol Technology; Frans Waanders, North-West University, SOUTH AFRICA In a previous study by Van Dyk, et. al., (2006) and Van Dyk (2006), a FactSage model was developed to understand the chemistry and interpret mineral matter transformation during a fixed bed counter-current gasification process. It was concluded that the FactSage model developed, compared with HT-XRD experimental results and that the FactSage thermodynamic modeling supplies insight into specific mineral reactions and slag formation. The specific value for Sasol in using FactSage, in combination with HT-XRD is that it can be used to analyze equilibrium conditions for reactions occurring between inorganic and organic materials together, as well as to provide insight into mineral transformation and slag formation. The purpose of the present study was to improve the current FactSage modeling approach, by combining specific zones in the gasification process. This can improve and speed-up the interpretation of mineral matter transformations and flow properties of reacted mineral matter in coal and assist in identifying and quantifying slag formation in the gasifier operation at temperatures not reflected by normal AFT analyses. The updated and improved FactSage model compared favorably with the original model as well as with HTXRD results and thus will be able to supply results in a faster and more convenient manner. In the new FactSage model, supported by HT-XRD experimental findings, it is indicated that feldspar formation (including anorthite) correlated with slag formation at temperatures around 1000C and no slag formation in the base case coal was observed in the drying and devolitilization zone, as was to be expected. Feldspar is one is the mineral species which has the lowest AFT causing the most slag-liquid formation and forms probably as a product between the SiO2, Al2O3 and Ca-containing species. In the gasification zone it was clear that slag-liquid formed at a temperature of 1000C, with a decrease in the feldspar content. Mullite formation was also observed in the base case sample in the temperature range 1000C and 1100C. The decrease in the amount of SiO2 at 1100C is related to the formation of mullite, but also that the slag-liquid phase also contains an amount of SiO2 in the molten form. 31-4 Effect of Mineral Transformation on the Surface Tension, Viscosity, and Size Fraction of Char Particles LaTosha Gibson, Narasimhan Soundarrajan, Sarma V. Pisupati, The Pennsylvania State University; Lawrence J. Shadle, DOE-NETL, USA Controlling ash deposition and handling slag disposal in an entrained flow gasifier is a general concern. Excessive Ash/char deposition in the convective section is an issue since it can lead to unplanned shutdowns until the deposits are cleared. Excess amount of char captured in the slag can render the slag useless for the cement industry. Therefore, the behavior of coal must be analyzed from the stage of injection to its final form (fly ash, component of slag, or bottom ash). To characterize this behavior of coal within the entrained flow gasifier, the Discrete Phase Model will be used. The Discrete Phase Model is a computational model that uses Eulerian flow to represent the gas phase but employs the Lagrangian method to determine the trajectories of the solid phase particles. As a requirement of the Discrete Phase Model, the boundary conditions for the particle phase must be characterized through the coefficient of restitution. The coefficient of restitution (COR) is defined as the ratio of the rebounding velocity to the impacting velocity. However, in literature describing ash and particulate behavior, the impacting velocity is also known as the deposition velocity. For an entrained flow gasifier, boundary conditions for the COR would have to be established for the refractory wall of a gasifier as well as the developing slag. Through an extensive literature review of particle wall collision models, the surface tension was found to be a main component that determines whether a particle adheres or rebounds for a wall or substrate. The surface tension has often been used to determine the force of adhesion in particle-wall collision models. Once the surface tension, particle size fraction, and density of a particle are known, a force of energy balance is prescribed in determining the deposition velocity prior to impact. Surface tension models developed by Hanoa and Tanaka on the basis of the Butlers equation for binary solutions could prove useful-if the molar fractions of the mineral composition of the slag (and char particles) are known. The main challenge in employing this surface tension model and any one particle wall collision model (that includes the force of adhesion) within the entrained flow gasifier is the mineral transformation of the parent coal. Issues in quantitatively characterizing mineral transformations include describing surface reactions inclusive of mineral distribution at the surface, differentiating the behavior between extraneous and inherent minerals, and incorporating the effects of the reducing environment in the gasifier on the transformation of minerals. Determining the reactions at the surface would require an understanding of the surface area to volume ratio of the ash particles in interest. Meanwhile the inherent mineral matter undergoes transformation at the particle temperature. This requires the temperature profile for the inherent mineral matter that is separate from that of the extraneous mineral matter -- for which the temperature is governed by the gaseous medium. As for the effects of a reducing environment, the existence of hydrogen and carbon monoxide in lieu of water and

SESSION 31 GASIFICATION TECHNOLOGIES: FUNDAMENTALS 3

31-1 A Simplified Phase Equilibrium Algorithm Used to Predict Ash/Slag Behaviors in Slagging Gasifiers/Combustors Bing Liu, Humberto E. Garcia, Idaho National Laboratory; Larry L. Baxter, Brigham Young University, USA Ash/slag behavior is one of the major technical issues in entrained-flow gasification processes. For example, low temperature in slagging gasifiers may cause plugging due to serious ash deposition, which may lead to abnormal shutdown of the process; at sufficiently high temperatures, slag will dissolve refractory liners, possibly resulting in material corrosion problems. Knowledge of ash/slag phase equilibrium is needed to keep normal operation of gasification processes and to estimate and possibly prolong the remaining useful life of refractory liners. In the present work, a simplified phase diagram algorithm is introduced to calculate the melting point of the ash based on its composition and the solubility of the refractory in slag at typical operating temperatures. Melting points of several binary and ternary systems are used to test and verify the correctness and efficiency of the proposed algorithm. A CaO-Al2O3-SiO2 ternary system is used as an example to explore the solubility of Al2O3- and Cr2O3based refractory materials. This algorithm has proven to be computationally efficient and can be used to predict ash/slag-related behaviors, such as ash melting points and refractory corrosion rates in slagging gasifiers. 31-2 An Empirical Viscosity Model for Coal Slags Josef Matyas, Scott Cooley, S.K. Sundaram, Carmen Rodriquez, Autumn Edmondson, Benjamin Arrigoni, Pacific Northwest National Laboratory, USA Slags of low viscosity readily penetrate the refractory lining in slagging gasifiers, causing rapid and severe corrosion through spalling. In addition, a low-viscosity slag that flows down the gasifier wall forms a relatively thin layer of slag on the refractory surface, allowing the corrosive gases in the gasifier to participate in the chemical reactions between the refractory and the slag. In contrast, a slag viscosity of <25 Pas at 1400C is necessary to minimize the possibility of plugging the slag tap. There is a need to predict and optimize slag viscosity so slagging gasifiers can operate continuously at temperatures ranging from 1300 to 1650C. The approach adopted in this work was to statistically design and prepare simulated slags, measure the viscosity as a function of temperature under reducing conditions, and develop a model to predict slag viscosity based on slag composition and temperature. Statistical design software was used to select compositions from a candidate set of all possible vertices that will optimally represent the composition space for 10 main components. A total of 21 slag compositions were generated, including 5 actual coal slag compositions. The Arrhenius equation was applied to measured viscosity versus temperature data of 17 slags, and the Arrhenius coefficients (A and B in ln(vis) = A + B/T) were expressed as linear functions of the slag composition. The viscosity model was validated using 1) data splitting approach, and 2) viscosity/temperature data measured at Pacific Northwest National Laboratory for four selected slag compositions from the literature.

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carbon dioxide can lead to more reactive components for the mineral matter. Aside from mineral reactions agglomeration, fragmentation, and coalescence also play a role. Because the magnitude of forces determining the deposition velocity is dependent on the particle size and gravity, these factors must also be addressed. This paper will discuss a method to determine an approximation for the surface tension, viscosity, and resulting size fraction over the expected residence time in an entrained flow gasifier. Agglomeration, fragmentation, and coalescence will also be discussed. 31-5 High Temperature X-ray Diffraction Studies for Various Coal Sources in Order to Simulate Mineral Transformations During Gasification Adam Baran, Johan Van Dyk, Sasol Technology (Pty) Ltd, SOUTH AFRICA; Stefan Melzer, Corus Technology B. V., THE NETHERLANDS Coal is generally accepted to be a heterogeneous resource where coal properties can vary extensively between geological sites or within a mine. Therefore detail coal characteristics are essential to predict the gasification performance of a particular coal. Mineral matter transformations in coal with temperature and slag formation are specific properties of a coal source that determine its suitability for combustion or gasification processes, where ash flow temperature (AFT) is a parameter that specifically gives information in this regard. High temperature X-ray diffraction (HT-XRD) analysis for coal provides information about mineral matter transformation in coal with temperature. HT-XRD can be used to analyze reactions occurring between inorganic and organic matter in coal, as well as provide insight into mineral transformations and slag formation. This can improve the interpretation of flow properties of the reacted mineral matter in coal and assist in identifying and quantifying slag formation in gasifier operation at temperatures not reflected by normal AFT analysis. In order to study mineral matter transformations in coal from various locations by HTXRD, five non South-African, northern hemisphere coal samples with known detailed characteristics and variability in properties, were selected for the present study. Detailed room temperature X-ray diffraction (RT-XRD) analysis revealed that the predominant phases present in original coal samples were quartz, kaolinite and muscovite, in various proportions. For calcium bearing minerals, in most cases calcite but also dolomite were identified. Pyrite and siderite were present for iron bearing minerals. Traces of rutile, anatase, brushite and albite were also observed. HT-XRD showed that decomposition of the minerals occurred according to expected routes. It was observed that the temperature sensitive pyrite decomposed first at 500600C, followed by kaolinite at 650-750C and calcite at 750-850C. Temperature resistant quartz, albite and anatase decomposed at much higher temperatures between 1100-1450C. It is commonly accepted that kaolinite decomposes to the intermediate amorphous phase known as meta-kaolinite, which at higher temperatures gives rise to mullite. Indeed, occurrence of mullite was observed in two samples in temperature range of 1150-1500C. Other minerals that crystallised in the samples at high temperatures were anorthite and cristobalite. Formation of anorthite was only observed in one sample in temperature range of 1200-1350C. Anorthite forms due to the decomposition of the SiO2, Al2O3 and CaO-containing species. It is accepted that anorthite has the lowest AFT, causing the most slag-liquid formation. Cristobalite, which is a high temperature polymorph of silica, was observed only in one sample in temperature range of 1300-1450C. Minerals which were formed in the samples in the intermediate temperature range were anhydrite and hematite. Anhydrite occurred in various samples between 400-1250C probably as a result of decomposition of pyrite and calcite. Hematite was formed in number of samples in temperature range of 500-1350C from decomposition of iron bearing minerals. In one sample traces of lime were observed between 800-1200C. It can be concluded that HT-XRD does supply insight into specific mineral interactions and slag formation in coal. 31-6 Investigation of Coal Char-Slag Transition at High Temperature Suhui Li, Kevin Whitty, University of Utah, USA Performance of high temperature slagging entrained-flow coal gasifiers is in large part dictated by coal burnout behavior. In particular, the transition from porous, relatively low density char to liquid slag affects overall carbon conversion and relative residence times of material on the wall and in the gas phase. In this work, a laminar entrained flow reactor was used to study the char-slag transition during the gasification process under atmospheric pressure. Coal particles were fed into the reactor for devolatilization by a pure nitrogen flow or gasification by a premixed nitrogen-air flow under various heating temperatures. Specific carbon conversions were achieved by varying the residence time of coal particles in the reactor. Devolatilized and oxidized char particles were collected by a cyclone and a filter for further analysis. The carbon content and the corresponding carbon conversion were determined by the loss-on-ignition test. The specific surface area and pore size distribution of the particles were determined by gas adsorption analysis. The morphological changes of the particles were observed with a scanning electron microscope. These analyses provide information concerning the influence of reaction temperature on the char-slag transition of the coal particles during the gasification process. The

sharp decrease of the surface area of the char particle was a mark of char-slag transition. The morphological change revealed by scanning electron microscope agreed well with this surface area change. Qualitative comparison with several pore models showed that ash fusion effect should be considered for describing the porous structure evolution during late stage of gasification at elevated temperatures.

SESSION 32 UNDERGROUND COAL GASIFICATION 3

32-1 An NGO Perspective on Underground Coal Gasification Mike Fowler, Kurt Waltzer, Clean Air Task Force, USA Recent studies suggests that underground coal gasification (UCG) with carbon capture and storage (CCS) may be able to provide low-carbon electricity at a cost comparable to that for existing coal technologies without CCS, and therefore may be able to play a meaningful role in reducing global greenhouse gas emissions. Recent studies also suggest that environmental impacts of UCG, especially groundwater contamination, can be reduced or eliminated by proper site selection, operational controls, and proper site closure. A rational approach to deploying this potentially game-changing technology would include both early commercial characterization burns, co-located carbon dioxide capture and injection tests, and thorough real-time groundwater monitoring. An NGO perspective on these issues is advanced, and potential trade-offs for UCG commercialization are discussed in the context of sound environmental stewardship principals. 32-2 TEXYNs Santa Barbara Mining System Tom Tillman, TEXYN, USA TEXYN is developing a new technology that will create low-cost hydrogen products from ultra-deep coal, using a combined drilling/gasification method. The hardware is an underground coal gasifier. We will turn the gasifier concept inside out, and then bring the gasifier to the coal. The result is the lowest-cost path to industrial-scale hydrogen production and to carbon-free electricity. The defining characteristics are (1) simplicity, (2) low capital costs, and (3) the most benign environmental profile of any fossil fuel. TEXYNs Technology TEXYN has developed two processes that complement each other:

The first process is a deep, electrically powered, underground coal gasifier that creates its own steam and oxygen at the point of the reaction. This method provides at least a 10X increase in reaction temperature, pressure, depth, flow-rate, cleanliness, etc, as compared to current Underground Coal Gasification (UCG) methods. Our target fuel source is an indigenous, stranded, and ubiquitous resource, which is beyond the physical reach of other extraction technologies. The zones in yellow and turquoise, in the map at left, indicate the location of such deep coal deposits. The gasification process works by deploying the tool into a horizontal bore in an extremely deep (3000 to 8000 ft) coal seam. Water is injected at the surface in an injection well. Power is provided by a high-voltage umbilical to the tool. The tool creates its own steam from the injected water. Much of this steam is reduced to oxygen and hydrogen by the extreme conditions created in the tool. Steam and oxygen

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react with the coal to produce carbon monoxide and more hydrogen. The highpressure product gasses are collected at a distant production well, for subsequent surface processing. The second process is a method to create and capture CO2 waste in the most economical manner. This is a highly streamlined process as compared to the status quo. In order to achieve near-total CO2 capture, the method requires that the energy carrier be limited to hydrogen gas. However, that is not a negative, considering the low expected cost is projected for the hydrogen. AGR systems and gas compressors are eliminated from the process. Energy Products METRICS OVERVIEW ($/mmBTU) TEXYN-based Status-Quo Technology Gasification Coal Cost $0.01 ~$0.50 - $2.00 Gasification Cost ~$1.30 ~$2 - $3 Raw Syngas Cost ~$1.30 ~$3 - $5 Hydrogen Cost ~$2 - $2.50 The intermediate (well-head) product is a synthesis gas, is projected at ~$1.30 per mmBTU. This compares favorably to the cost of raw coal, delivered at approximately $1.801, and to the cost of raw synthesis gas from a traditional surface gasifier at $3 to $5. The capital-burdened cost of hydrogen is projected at less than $2.50 per mmBTU. An important byproduct is 98% enriched carbon dioxide (CO2), used for Enhanced Oil Recovery (EOR) operations in underserved oil fields known to require vast amounts of CO2. The TEXYN process is not just Carbon Capture Ready; rather, it was set up expressly for the immediate low-tech capture of carbon at high pressure, for ultimate sequestration. CO2 recovery is projected at greater than 99%.
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less expensive and easier option to determine UCG process performance at any given time. 32-5 Estimation of Chemical Reaction Occurred in Underground Coal Gasification Sohei Shimada, The University of Tokyo; Mamoru Kaiho, Osamu Yamada, National Institute of Advanced Industrial Science and Technology, JAPAN National Institute of Advanced Industrial Science and Technology (AIST) has developed a method to determine the coefficients to in the chemical equation coal gasification, CHmOn+O2+ H2O -> H2+CO+CO2+CH4, based on the results of ultimate analysis of coal and chemical analysis of gas composition (H2O and N2 free), in order to evaluate the process of reaction of actual coal gasification process. Since the numerical expressions used to calculate to were derived based on the stoichiometry of the chemical equation without any arbitrary assumption and approximation, the method is thought to be applicable to the estimation of reactions of underground coal gasification (UCG). In the published results of gas composition produced by UCG, however, very few cases was found that comprised the data of ultimate analysis of coal. The result of UCG carried out in Fushin coal mine in China was investigated. Gasifier was constructed utilizing mining gallery and air was used as a gasifying agent. Chemical equation was determined using the method above mentioned. Since the value of in the formula and the amount of oxygen reacted were relatively small and , amount of water reacted, was estimated to be positive, gasification reaction was concluded to proceed in favorable conditions. Water may be decomposed by the reaction of C+H2O -> CO+H2 and CO+H2O -> CO2+H2O. Since water was not fed in the gasifier as a gasifying agent, water decomposed is considered to have come from ground water or moisture in coal seam. Chemical equation of UCG was compared with that of conventional fixed bed gasifier and characteristic of UCG gasification process was discussed. 32-6 Development of a UCG Based Project in Canada Simone Maev, Laurus Energy Inc., CANADA Underground Coal Gasification technology is getting significant attention around the globe as a new mining method to extract energy of stranded coal where other methods are not applicable. Laurus Energy is an exclusive Canadian licensee of the Exergy UCG. UCG technology provided by Ergo Exergy Technolgies Inc. from Montreal, Canada. The UCG technology is being successfully applied in a number of commercial UCG projects around the world. Laurus Energy is developing its first commercial project based on UCG technology in North America. The project is targeting power generation and supply of fuel and hydrogen for the local industrial markets. Laurus Energy has large coal holdings in Alberta, Canada and started execution of its first Tomahawk I project development program, including regulatory and environmental approvals, Site Selection and Pre-Feasibilty and Site Characterization program.

http://www.netl.doe.gov/energyanalyses/pubs/Bituminous%20Baseline_Final%20Report.pdf 32-3 Geomechanical Simulations Related to UCG Activities Joseph Morris, Oleg Vorobiev, Tarabay Antoun, S. Julio Friedmann, Lawrence Livermore National Laboratory, USA This paper will present results from a recent investigation into a range of geomechanical processes induced by UCG activities. The mechanical response of the coal and host rockmass plays a role in every stage of UCG operations. For example, cavity collapse during the burn has significant effect upon the rate of the burn itself. In the vicinity of the cavity, collapse and fracturing may result in enhanced hydraulic conductivity of the rock matrix above the burn chamber. Even far from the cavity, stresses due to subsidence may be sufficient to induce new fractures linking previously isolated aquifers. These mechanical processes are key in understanding the risk of unacceptable subsidence and the potential for groundwater contamination. These mechanical processes are inherently non-linear, involving significant inelastic response, especially in the region closest to the cavity. In addition, the response of the rock mass involves both continuum and discrete mechanical behavior. To better understand these effects, we have applied a suite of highly non-linear computational tools in both two and three dimensions to a series of UCG scenarios. Our calculations include combinations of continuum and discrete mechanical responses by employing fully coupled finite element and discrete element capabilities. We will discuss the features of our geomaterial modeling framework including our treatment for rock failure. Finally, we will present results of mechanical simulations covering the range of a single burn up to multiple modules in a range of geologic settings. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. 32-4 Compartment Modeling for Underground Coal Gasification Cavity Preeti Aghalayam, D. Sateesh, Ramesh Naidu, Sanjay Mahajani, Anuradda Ganesh, IIT Bombay; R.K. Sapru, R.K. Sharma, UCG Group, IRS, INDIA Underground coal gasification (UCG) is the in-situ gasification process carried on in un-mineable coal seams using injection and production wells drilled from the surface, which enables the coal to be converted into combustible gas. UCG process may provide a secure energy supply and reduce green house gas emissions and is capable of producing commercial quantities of gas to be used as a chemical feedstock or as fuel for power generation. As gasification proceeds, an underground cavity is formed. The volume of the cavity increases progressively with coal spalling from the roof and getting consumed. As underground coal gasification cavities are of irregular threedimensional shapes, computational fluid dynamics studies (CFD) are essential in order to understand the complex flow patterns involved. The characterization of the nonideal flow patterns in UCG is an important aspect as it is likely to influence the process performance significantly. The main objective of this work is to understand the velocity distribution and perform residence time distribution (RTD) studies in the UCG cavity. Based on the RTD studies, the actual UCG cavity at different times has been modeled as a simplified network of ideal reactors, which may offer a computationally

SESSION 33 ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY CAPTURE, CARBON, NOx

33-1 Understanding the Binding Mechanism of Mercury on Activated Carbon Bihter Padak, Jennifer Wilcox, Stanford University, USA Coal combustion power plants constitute a significant amount of mercury released into the atmosphere. Oxidized mercury is captured by wet scrubbers, while gaseous elemental mercury passes through the scrubbers readily. Particulate matter such as fly ash, unburned carbon and activated carbon can be used to capture elemental and oxidized mercury through adsorption processes. Activated carbon is currently used in many power plants effectively. Understanding the mechanism that mercury adsorbs on activated carbon is crucial to develop better capture technologies for mercury. In this study we examine the possible binding mechanism of mercury on activated carbon, performing ab initio energetics calculations using Gaussian03. Activated carbon surface is modeled by a single graphene layer in which the edge atoms on the upper side are unsaturated in order to simulate the active sites. In some cases, chlorine atoms are placed at the edge sites to see the effect of chlorine on mercury binding and investigate a possible surface reaction between mercury and chlorine.

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33-2 Mercury Emission Control with Gas-Phase Brominated PAC Sorbents Qunhui (Emma) Zhou, Sid Nelson Jr., Ron Landreth, Jon Miller, Arlen Overholt, Xin Liu, Tang Zhong, Yinzhi Zhang, Sorbent Technologies Corporation; Lynn Brickett, DOE-NETL, USA B-PAC, C-PAC, and H-PAC compose the family of gas-phase brominated powdered activated carbon sorbents specially developed for reducing mercury from flue gas of power plants with standard configurations, plants selling fly ash for concrete use, and plants having hot-side electrostatic precipitators, respectively. This series of sorbents has been proven cost-effective for mercury emission control at more than twenty coal power plant units and industrial boilers that burn different types of coals and that are configured with different pollution control devices. For example, an average of 91% of gas phase mercury was removed with 3 lbs/MMacf of B-PAC for 30-days at the Detroit Edisons St. Clair power station, which burns a blend of bituminous coal and subbituminous coal and has a cold-side ESP. Injecting 4.6 lbs/MMacf of C-PAC upstream of a very small cold-side ESP (112 m2/kacf SCA) achieved 81% of average mercury removal during a one-month full-scale tested trial at the Midwest Generation Crawford Unit 7 and allowed the fly ash containing the CPAC to continue to be used in concrete as the substitute for cement. This paper will (1) briefly introduce the data from the full-scale mercury trials which injected B-PAC, C-PAC, and H-PAC sorbents in flue gas of power plants, (2) compare the efficiency of B-PAC family with that of other sorbents in comparative trials, (3) discuss how the properties such as bromine species, particle size, and pore structure of these activated carbon-based sorbents influence mercury capture, and (4) discuss how to optimize sorbent use to comply with strict mercury reduction regulations. 33-3 Temperature Programmed Decomposition Desorption of Mercury Species over Activated Carbon Sorbents for Mercury Removal from Coal Derived Fuel Gas Md. Azhar Uddin, Masaki Ozaki, Eiji Sasaoka, Okayama University, JAPAN; Shengji Wu, Hangzhou Dianzi University, CHINA Mercury (Hg0) removal process for coal derived fuel gas in the IGCC process will be one of the important issues for the development of a clean and highly efficient coal power generation system. Recently iron based sorbents such as iron oxide (Fe2O3), supported iron oxides on TiO2, and iron sulfides were proposed as active mercury of the main impurity compounds in coal derived fuel gas, therefore H2S injection is not necessary in this system. HCl is also another impurity in coal derived fuel gas. In this study, the contribution of HCl to the mercury removal from coal derived fuel gas by a commercial activated carbon (AC) was studied using a temperature programmed decomposition desorption (TPDD) technique. TPDD technique was applied to understand the decomposition character of the mercury species on the sorbents. The Hg0 removal experiments were carried out in a laboratory-scale fixed-bed reactor at 80-300C using a simulated fuel gas. The following results were obtained from this study: 1) HCl contributed to the mercury removal from the coal derived fuel gas by the AC; 2) H2S suppressed the mercury removal with HCl by the AC; 3) The stability of the mercury surface species formed on the AC in the presence of H2S was different from that in the absence of H2S. 33-4 Impact of Acid Gases and Temperature on Mercury Oxidation and Uptake Catalyzed by Activated Carbon Surface Ravi Bhardwaj, Gwin, Dobson and Foreman Inc.; Jason D. Monnell, Radislav D. Vidic, University of Pittsburgh, USA The impact of acidic gases (NO, NO2, SO2, HCl), water, and temperature on mercury oxidation and uptake by novel carbon-based sorbent was evaluated. Carbonaceous sorbent was exposed to simulated coal-fired power plant flue gas in a packed-bed configuration at 140 C and the tail gas was monitored for mercury after acid gas cleaning. Limited (up to 10%) homogeneous oxidation of elemental mercury was observed. However, the presence of carbon surface led to a significant (above 50%) increase in the oxidation of elemental mercury. The absence of water from the flue gas further increased mercury uptake capacity of the novel sorbent, but it also caused a decrease in elemental mercury oxidation. Removal of SO2 from the flue gas led to a tremendous increase in mercury uptake by the sorbent since no mercury was observed in the effluent gas for 24 hours. Absence of NO from the flue gas led to a significant decrease in the elemental mercury oxidation and faster breakthrough of mercury; however an increase in the overall mercury uptake capacity was observed due to more pronounced tailing effect. On the other hand, removal of NO2 led to no significant change in mercury uptake or in mercury oxidation. Removal of HCl reduced the breakthrough time by a half, but it increased the overall mercury uptake capacity of the sorbent by nearly 70%. Moreover, removal of HCl also caused a significant decrease in elemental mercury oxidation. Upon increasing the fixed-bed temperature from 140C to 240C, an instant breakthrough of mercury was observed. Also, at 240C, almost no elemental mercury oxidation was observed, as compared to 50% oxidation at 140C under similar simulated flue gas condition.

The results obtained in this study suggest that the presence of water, NO and HCl in the flue gas facilitate oxidation of elemental mercury but their presence also leads to a decrease in the mercury uptake capacity. The presence of SO2 leads to a significant decrease in mercury uptake by the activated carbon sorbent. Increase in temperature leads to a significant decrease in mercury uptake as well as decrease in elemental mercury oxidation. This paper provides data that is critically needed to manage flue gases for optimal mercury removal by carbonaceous materials. 33-5 Effects of Hcl and SO2 Concentration on Mercury Removal by Activated Carbon Sorbents in Coal Derived Flue Gas Ryota Ochiai, Md. Azhar Uddin, Eiji Sasaoka, Okayama University, JAPAN; Shengji Wu, Hangzhou Dianzi University, CHINA In this study, the effect of presence of HCl and SO2 in the simulated coal combustion flue gas on the Hg0 removal by a commercial activated carbon (coconut shell AC) was investigated in a laboratory scale fixed bed reactor in temperature range of 80 to 200C. The characteristics (thermal stability) of the mercury species formed on the sorbents under various adsorption conditions were investigated by temperature programmed decomposition desorption (TPDD) technique. It was found that the presence of HCl and SO2 in the flue gas affected the mercury removal efficiency of the sorbents as well as the characteristics of the mercury adsorption species. The mercury removal rate of AC increased with HCl concentration in the flue gas. In the presence of HCl and absence of SO2 during Hg0 adsorption by AC, a single Hg0 desorption peak at around 300C was observed in the TPDD spectra and intensity of this peak increased with HCl concentration during mercury adsorption. The peak at around 300C may be derived from the decomposition and desorption of mercury chloride species. The presence of SO2 during mercury adsorption had an adverse effect on the mercury removal by AC in the presence of HCl. In the presence of both SO2 and HCl during Hg0 adsorption by AC, the major TPDD peaks temperatures changed drastically depending on the concentration of HCl and SO2 in flue gas during Hg0 adsorption. 33-6 Optimization of Scr System at Cayuga Unit 1 Carlos Romero, Zheng Yao, Fengqi Si, Eugenio Schuster, Lehigh University; Robert Morey, Jacob Peter, AES Cayuga, LLC; Barry N. Liebowitz, New York State Energy Research and Development Authority, USA AES Cayuga Unit 1 is a 160 MW unit, equipped with a low-NOx firing system and an anhydrous ammonia (NH3), Selective Catalytic Reduction (SCR) system for NOx emissions control. A combined boiler/SCR/air preheater (APH) optimization was performed to minimize the cost of NOx emissions control. Boiler and low-NOx system control settings, and SCR and air preheater (APH) operating conditions were included in a parametric test program. Information from a Breen Energy Solutions ammonium bisulfate (ABS) probe was also included for monitoring of ABS formation in real-time and as a constraint to the SCR optimization. The parametric test data were used as the basis for the optimization that consisted of an approach that incorporates accurate online support vector regression (AOSVR) modeling for adaptive learning, and genetic algorithms for implementation of the multi-objective optimization. The results indicate that optimal operating conditions can be achieved for a coordinated boiler/SCR/APH operation, and minimal NH3 consumption, maximum SCR performance, and optimal net unit heat rate, subject to minimal impact on fly ash unburned carbon content, mitigated ABS formation, and other operational and environmental constraints. The optimal conditions resulted in reduced NH3 usage of the order of 25 percent, with improved APH fouling management.

SESSION 34 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 4

34-1 Potential Respirable Quartz and Silica Dust Sources in Underground Coal Mines Identified by Geochemical Analyses Steven Schatzel, NIOSH, USA Silicosis represents a significant health hazard to workers in US underground coal mines. Prior research has suggested that the primary respirable silica dust source does not typically reside within the coal seam being mined. Mines which had a history of high silica content in respirable dust samples (over 5% of the sample mass) were chosen for a new study which sought to identify the parent rock of respirable silica dust material using geochemical methods. All of the coalbeds being mined at the study sites were found to have relatively low mineral matter contents. An experimental methodology based on alkali and alkaline earth elemental concentrations in respirable dust samples was devised to distinguish mine roof from mine floor horizons in room and pillar mine sites. Some of the enrichment of these cation species in the roof units compared to immediate floor rock may be related to the percolation of fluids through the overburden and the difficulty of fluids to migrate effectively through the coal or

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coal precursor and into the floor units. It is recognized that in the application of these techniques, some of the rock being characterized is removed as mined material and that the transportation of dust through the ventilation system is a complex process whereby all material is not conserved within a closed system. The calcium, magnesium, sodium and potassium concentrations from this study suggest that roof strata is the primary source of mineral-generated respirable dust produced during mining and captured by the dust samplers on conventional dust filter cassettes. Compositional comparisons between the silica in the respirable dust sample and the potential source rocks may indicate that modification during the mining process may be responsible for the mineralogical proportions found in the respirable dust fraction. The consequences of this process may be very pronounced in the silicate mineral fraction. Quartz grains are denser and tend to form generally equant fragments upon breakage where kaolinite and illite tend to form long or platy fragments and are of much lower density which could result in differing transport characteristics of the mineral matter. The range of silicate mineral matter sources may not contribute uniformly to the different particle size fractions. These findings may be significant since the potential severity of the silicosis risk to miners is strongly influenced by both the amount of quartz and the clay minerals in respirable dust. 34-2 Oxidative Decomposition of Formaldehyde to Carbon Dioxide and Molecular Hydrogen Catalyzed by Bitunineous Coals Haim Cohen, Uri Green, Ariel University Center at Samaria, ISRAEL Self heating of large coal piles stored for long periods (1-6 months), due to atmospheric oxidation (chemisorption\oxidation) raise a maintenance problem in the storage sites near large power stations which use bitumineous coals as the fuel. Thus hot spots are formed resulting in reduction in calorific value of the coals and in extreme cases eruption of fires. The main gas released during the storage is carbon dioxide but also some carbon monoxide, low molecular weight organic molecules (C1-5) and water are produced. It has been established that moreover, bituminous coal exposed to mild oxidation conditions (temperature range 40-120C in air atmosphere) emit also molecular hydrogen as a side product. These reactions have been observed for a variety of bituminous coals worldwide. The amount of molecular hydrogen formed (which is a reduction product) is surprisingly linear to the amount of oxygen (oxidation reagent) consumed by the coal. It has been suggested that the low temperature oxidation produces some surface hydroperoxide groups which do oxidize formaldehyde (which is also released by the self heating of the coal) to yield the ustable cyclic intermediate dioxirane, CH2O2, which subsequently decomposes to molecular oxygen and carbon dioxide. The mechanism of reaction and the effect of water addition to inhibit molecular hydrogen production will be discussed in detail. 34-3 Reconnaissance of Coal-Mine Fires in Perry County, Eastern Kentucky James C. Hower, University of Kentucky Center for Applied Energy Research; Glenn B. Stracher, East Georgia College; John K. Hiett, Office of Mine Safety & Licensing; Sarah M. Mardon, Kentucky Division of Water; Jennifer M.K. OKeefe, Morehead State University; Paul A. Schroeder, University of Georgia; Donald R. Blake, University of California, Irvine; Stephen D. Emsbo-Mattingly, NewFields Environmental Forensics Practice, LLC, USA Hundreds of underground and open pit coal-mine fires burning across the United States are destroying a valuable natural resource while spewing noxious vapors and particulate matter into the atmosphere from gas vents and ground fissures, frequently encrusted with the solid-by-products of combustion. These fires have destroyed faunal and floral habitats, poisoned and killed people, destroyed towns, metamorphosed and melted rock adjacent to coal seams, and caused land subsidence. The fires usually ignite by explosives and electrical work, the accidental ignition of methane and hydrogen during mining, surface fires, lightening strikes, and spontaneous combustion. Numerous mine fires have been reported in the coalfields of Kentucky. During reconnaissance work in eastern Kentucky at the Ruth Mullins and Laura Campbell fires near Hazard, yellow-green smoke was observed to be billowing or continuously exhaled from ground fissures and gas vents. In both cases, the fire is in abandoned underground and auger mines in the Pennsylvanian Breathitt Formation Hazard No. 7 coalbed. Ignited by a forest fire in 2006, smoke from the Ruth Mullins fire, near the town of Bulan, north of Hazard, was observed along the highwall in 2007. This fire is a health hazard to families living nearby and could damage Kentucky Route 80 if coal was not removed during construction in 1980. West of Hazard, the Laura Campbell fire, thought to have started by the spontaneous combustion of coal, could destabilize a nearby water tank and affect the public water supply. Gas-vent temperatures, measured within select vents, ranged between 165 and 385C. Several vents and fissures were encrusted with creosote, sulfur, and other solid-by-products of combustion, currently being analyzed along with the gas. In situ analyses of CO and CO2 at one vent were 100 ppm and 0.1% by volume, respectively.

34-4 New Achievements in the Field of Preventing the Spontaneous Combustions, Applied at the Level of the Pitcoal Mines in Jiu Valley Romania Aronel Matei, Ioel Veres, Adrian Zvanca, University of Petrosani; Lorand Toth, I.N.S.E.M.E.X. PETROSANI, ROMANIA The coal is and will always be a main source of energy. The coal is integrated in the strategies that were conceived and implemented in the purpose of promoting the development of sustainable energy in the CEE area and in the rest of worlds area. In our country, the field of energetic coal must function in the condition of competitivity and reduction of the production costs. This thing was achieved by the reorganization and the modernization of the mining activity. The growth of the extraction capacity at the viable mines was achieved by introducing the methods of exploitation of high quality, such as the method of coal exploitation with undetermined sand bar. This method amplifies some risk factors such as apparition of spontaneous combustions. In order to reduce the risk factor that was mentioned above, after the study of the coals composition, the theories of the production of the spontaneous combustion and the way to initiate the oxidation reaction, a series of substances were tested, substances with an action of inhibitor during the process. Unlike the classical interpretation of prevention of the spontaneous combustions with the help of cold agents, the way of action the inhibition efficiency are different and the transpose in practice of the technology of prevention with the help of the inhibitors which leaded to a significant diminution of the numbers of fires (spontaneous combustions) at the level of pit coal mines from Jiu Valley Romania. This work deals with the theoretical part and the laboratory experiments of the test of the inhibitors in situ. For the works that were done, as new ones, there were made documentations in order to obtain licenses. 34-5 Molecular Hydrogen Formed via Low Temperature Oxidation of Bituminous Coals as the Source of Explosions in Underground Coal Mines Haim Cohen, Ariel University Center at Samaria, ISRAEL Explosions in deep mines (or other confined spaces containing bituminous coals) are usually attributed to methane gas concentrations above the LEL or accumulation of fine coal dust which can undergo fast radical reactions. In order to avoid occurrence of such conditions in deep coal mines, methane detectors are installed and good ventilation is required. Coal piles stored for long periods at ambient temperatures might undergo autocatalytic heating if the rate of heat dissipation from the pile is lower than the heat release due to the chemisorption/oxidation of atmospheric oxygen inside the pores of the coal. Some (5-10%) of the reacting oxygen produces carbon dioxide but some carbon monoxide, low molecular weight organic molecules (C1-5) and water are also released. It has been established that bituminous coal exposed to mild oxidation conditions (temperature range 40-120C in air atmosphere) emits also molecular hydrogen as a side product. These reactions have been observed for a variety of bituminous coals worldwide. Surprisingly, the amount of hydrogen released (which is a reduction product) are linear to the amount of oxygen consumed. The hydrogen is produced via oxidative decomposition of formaldehyde groups with surface hydroperoxides and is catalyzed by the coal surface. Thus if there is an accumulation of hydrogen in a crack in the coal seam in a underground mine and the concentration increases to 4.1% (LEL in air) initiation of explosion by electrostatic charge or a spark is feasible. Indeed in the last decade several unexplained explosions have been reported in coal mines worldwide despite appropriate ventilation and no detection of methane had been observed. We have checked if accumulation of hydrogen in a deep coal mine might reach the LEL of 4.1%. The results show that in extreme cases this is indeed the case and furthermore that during transportation of bituminous coal by sea hydrogen concentrations might reach levels of up to 10% in ship holds (which are also a confined space). These observations may indicate that molecular hydrogen accumulation in confined spaces might increase the risk to explosions and that appropriate measure should be taken in order to check this possibility.

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35-3 SESSION 35 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 3 First U.S. Field Trial of Oxidation Technology for Coal Mine Ventilation Air Methane Deborah A. Kosmack, CONSOL Energy Inc.; Kenneth P. Zak, MEGTEC Systems, USA CONSOL Energy Inc., in conjunction with MEGTEC Systems, Inc., the U.S. Department of Energy, and the U.S. Environmental Protection Agency, designed, built, and operated a commercial-size thermal flow reversal reactor (TFRR) to evaluate its suitability to oxidize coal mine ventilation air methane (VAM). Coal mining, and particularly coal mine ventilation air, is a source of anthropogenic methane emissions, a greenhouse gas. The concentration of methane in the ventilation air is very small (<1.5%) and flow rates can sometimes exceed 300,000 scfm for a single mine fan, so oxidation of this methane is difficult. This test program was conducted with simulated coal mine VAM in advance of deploying the technology on active coal mine ventilation fans. The demonstration project team installed and operated a 30,000 scfm MEGTEC VOCSIDIZER oxidation system on an inactive coal mine in West Liberty, WV. The performance of the unit was monitored and evaluated during months of unmanned operation at mostly constant conditions. The operating and maintenance history and how it impacts the implementation of the technology on mine fans will be discussed. Emission tests showed very low levels of all criteria pollutants at the stack. Parametric studies showed that the equipment can successfully operate at the design specification limits. The results verified the ability of the TFRR to oxidize 95% of the low and variable concentration of methane in the ventilation air. This technology provides new opportunities to reduce greenhouse gas emissions by the reduction of methane emissions from coal mine ventilation air. An economic evaluation of the technology as applied to both methane oxidation and to energy recovery on a working coal mine will be discussed. A large commercial-size installation (180,000 scfm) on a single typical mine ventilation bleeder fan would reduce methane emissions by 14,200 to 23,700 short ton per year (the equivalent of 236,000 to 394,000 metric tonne carbon dioxide). 35-4 Carbon Dioxide Capture Technology Plan and Development in Taiwan Wan-Hsia Liu, Heng-Wen Hsu, Jyh-Feng Hang, Chin-Ming Huang, Hou-Chuan Wang, Industrial Technology Research Institute, TAIWAN Taiwan is part of a group that suffers from highly dangerous Climate Changes as note in a U.N. report. In the past century Taiwan has experience a 1.3 increase in temperature, which is twice of the global average. The government of Taiwan, not a signatory of the Kyoto Protocol, strives to comply with international treaties voluntarily. Taiwan also understands CO2 decrement is various countries common responsibility. Related government agencies are already actively promoting various domestic reduction measures, including the Climate and Kyoto Protocol response working group, Greenhouse Gas Reduction Act (draft) in 2006, Greenhouse gas reduction nationwide energy conference in 2005, education and other measures that are in the planning stages. This article will introduce the carbon dioxide (CO2) capture technology plan and carbon dioxide capture technologies research in Industrial Technology Research Institute (ITRI) in Taiwan. According to the Bureau of Energy (BOE), Ministry of Economic Affairs Statistic show CO2 emissions of 110 million metric tons and 265 million metric tons in 1990 and 2006 with an annual CO2 emission growth rate of 5.62% in Taiwan. ITRI has surveyed Taiwan CO2 capture technologies development that show research chiefly on absorption technology and adsorption technology and membrane diffusion technology developed by academia. A gasification technology (2 tons of coal per day of pressure entrained bed) is done on a pilot scale in ITRI (Kaohsiung). In the future, power generation, petrochemical industry and steel and iron industries are the first to be considered for reduction of CO2 emissions. Our goal is to establish a 1 to 3 MW (5 to 15 hundred tons CO2 every year) pilot plant in 2012, 10 to 30 MW (50 to 150 thousand tons CO2 every year) demonstration plant in 2020 and a commercial plant in 2027 for post-combustion capture. In addition, ITRI has to research and develop the CO2 capture technologies from flue gases including Gasification or Integrated Gasification Combined Cycle (IGCC), Carbonation and calcination recycle (CCR) and innovative meso-porous nanomaterials for CO2 adsorption. 35-5 Dakota Gasification Company An International Energy Venture Claudia Miller, Steve Pouliot, Dakota Gasification Company, USA The Great Plains Synfuels Plant, located near Beulah, North Dakota, is the only commercial-scale gasification plant operating in the United States that produces Synthetic Natural Gas (SNG) from coal. The plant is owned and operated by Dakota Gasification Company (DGC), which is a wholly owned subsidiary of Basin Electric Power Cooperative (BEPC), based in Bismarck, North Dakota. The concept for the Synfuels Plant began in the 1970s and grew from a desire to alleviate the United States dependence on foreign oil. Today upwards of 150 million standard cubic feet per day of SNG are produced and exported to consumers

35-1 Application of Molecular Modeling for CO2 Sequestration in Coal Tim Tambach, Frank van Bergen, TNO Built Environment and Geoscience, THE NETHERLANDS Underground storage of carbon dioxide (CO2) in deep coal beds is one of the options for reducing the CO2 emission to the atmosphere and the greenhouse effect. A beneficial side effect of CO2 injection in the subsurface is the enhanced release of methane (CH4) which can then be produced as fuel. This technique is referred to as CO2-enhanced coal bed methane (ECBM). The results of field and laboratory experiments are showing discrepancies with the current ideas on the interaction between CO2 and coal. Therefore, it is difficult to model these experiments with the present-day numerical reservoir models. The discrepancies can be partly attributed to the heterogenic character of coal and to the observed coal swelling, which both need further investigation. Additionally, the (Langmuir) adsorption model that is currently implemented in reservoir models is a clear simplification of the process, especially for the supercritical CO2. For example, the (extended) Langmuir model implies sorption at a homogenous surface where preferential adsorption is solely determined by the partial pressures of the different gasses. For considering the effect of the heterogeneity of the coal surface we went down to the microscale level. Based on the literature we built a molecular model of coal using Hyperchem (v7.51), which confirms the heterogeneity and complexity. We coupled the software with our own in-house interface and computed the affinity of CO2 and CH4 molecules for the coal surface. The idea is that the coal behaves as a solid phase with the CO2 and CH4 molecules moving around it. The results show that the molecules can either be in the free gas phase or adsorbed to the coal. One can understand that this adsorption is not straightforward. To get an idea of this adsorption we computed the coordinates of all the molecules after each simulation (time) step. We observed that the molecular density of is higher around the coal surface, but also adsorption is taking place inside the micropores in the coal structure. The results further show that there is a preference of CO2 adsorption, which is in agreement with experimental measurements. We expect that is it very difficult to release the molecules from the micropores. In our future work we aim to confirm these insights and further study the influence of water, the type of coal, and coal swelling. This will be helpful for developing relations between pore size distributions and adsorption isotherms. Such relations can then be incorporated in reservoir models. 35-2 Geomechanical Simulations of CO2 Storage Integrity using the Livermore Distinct Element Method Joseph Morris, Scott Johnson, S. Julio Friedmann, Lawrence Livermore National Laboratory, USA Large-scale carbon capture and sequestration (CCS) projects involving annual injections of millions of tons of CO2 are a key infrastructural element needed to substantially reduce greenhouse gas emissions. The large rate and volume of injection will induce pressure and stress gradients within the formation that could activate existing fractures and faults, or drive new fractures through the caprock. We will present results of an ongoing investigation to identify conditions that will activate existing fractures/faults or make new fractures within the caprock using the Livermore Distinct Element Code (LDEC). LDEC is a multiphysics code, developed at LLNL, capable of simulating dynamic fracture of rock masses under a range of conditions. As part of a recent project, LDEC has been extended to consider fault activation and dynamic fracture of rock masses due to pressurization of the pore-space. We will present several demonstrations of LDEC functionality and applications of LDEC to CO2 injection scenarios including injection into an extensively fractured rockmass. These examples highlight the advantages of explicitly including the geomechanical response of each interface within the rockmass. We present results from our investigations of Teapot Dome using LDEC to study the potential for fault activation during injection. Using this approach, we built finite element models of the rock masses surrounding bounding faults and explicitly simulated the compression and shear on the fault interface. A CO2 injection source was introduced and the area of fault activation was predicted as a function of injection rate. This work presents an approach where the interactions of all locations on the fault are considered in response to specific injection scenarios. For example, with LDEC, as regions of the fault fail, the shear load is taken up elsewhere on the fault. The results of this study are consistent with previous studies of Teapot Dome and indicate significantly elevated pore pressures are required to activate the bounding faults, given the assumed in situ stress state on the faults.

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throughout the Midwest via the Northern Border Pipeline. Numerous by-products and co-products, including anhydrous ammonia, ammonium sulfate fertilizer, phenol, cresylic acid, krypton/xenon, naphtha and carbon dioxide (CO2) enhance the viability of the facility. The Great Plains Synfuels Plant has operated 14 Lurgi Mark IV gasifiers for over twenty years. On April 24, 1984 the gasification plant began producing an intermediate raw gas. Subsequently, the first synthetic natural gas entered the nations interstate pipeline network on July 28, 1984. While the facility had its challenges, it is a technical success story. Under current energy markets, it is an economic success as well. The idea for selling CO2 from the gasification plant arose well before the project was being built in the early 1980s. This became a reality in October of 2000 when Dakota Gasification Company began exporting up to 95 million standard cubic feet per day high pressure CO2 from the Synfuels Plant. Today the plant has two Canadian customers and exports approximately 150 million standard cubic feet of CO2 per day. This paper discusses the original project and the expansion. A general overview of the gasification process is included to define the steps required to concentrate the CO2 into a usable product.

respectively. The results in the cold fluidized bed showed single biomass particles are difficult to be fluidized, while a good fluidization can be gained with the addition of coal particles as long as the mass fraction of biomass particles was less than 50 wt%. Similar trend was observed to the mixture of biomass char and coal char. A better fluidization quality was gained when coal ash was added to the mixtures of coal char and biomass char, the minimum fluidization velocity of the mixtures of biomass char, coal char and coal ash increased with the increase of mass fraction of coal ash. The minimum fluidization velocities of two components and three components systems both could be predicted well by the empirical formulas. The thermal gravity results showed biomass char has higher reactivity than coal char. Co-gasification can be described by one order kinetics equation. In the self-heating fluidized bed, the effects of oxygen equivalence ratio, steam/carbon ratio, biomass/coal ratio and biomass type on the gasification characteristics were studied in the temperature range of 8501050C. The results showed a relatively lower oxygen equivalence ratio is advantageous to gasification efficiency. There is an optical steam/carbon ratio for cogasification process. A rise of biomass ratio favors carbon conversion and gasification efficiency. A stable operation can be obtained when the biomass ratio in mixtures is less than 50 wt%. Among the three types of biomass used, the order of the carbon conversion of various fuels is as follows: coal/pine sawdust > coal/sorghum stalk > coal/rice straw > coal, which is consistent with the reactivity of the fuel carbon. 36-3 Modeling Slag Penetration and Refractory Degradation Using the Finite Element Method Kenneth Johnson, Rick Williford, Josef Matyas, Siva Pilli, S.K. Sundaram, Vladimir Korolev, Pacific Northwest National Laboratory, USA Refractory degradation due to slag penetration can significantly reduce the service life of gasifier refractory linings. This paper describes a modeling approach that was developed to predict refractory spalling as a function of operating temperature, coal feedstock and refractory type. The model simulates the coupled thermal, diffusion, and mechanical interactions of coal slag with refractory ceramics. The heat transfer and slag diffusion solutions are directly coupled through a temperature-dependent effective diffusivity for slag penetration. The effective diffusivity is defined from slag penetration tests conducted in our laboratories on specific coal slag and refractory combinations. Chemically-induced swelling of the refractory and the buildup of mechanical stresses are functions of the slag penetration. The model results are compared with analytical spalling models and validated by experimental data in order to develop an efficient refractory degradation model for implementation in a systems level gasifier model. The ultimate goal of our research is to provide a tool that will help optimize gasifier performance by balancing conversion efficiency with refractory life. 36-4 Modeling of Time Varying Slag Flow in Coal Gasifiers Siva P. Pilli, Kenneth Johnson, Ralph Williford, S. K. Sundaram, Vladimir Korolev, Jarrod Crum, Battelle - PNNL, USA There is considerable interest within government agencies and the energy industries across the globe to further advance the clean and economical conversion of coal into liquid fuels to reduce our dependency on imported oil. To date, advances in these areas have been largely based on experimental work. Although there are some detailed systems level performance models, little work has been done on numerical modeling of the component level processes. If accurate models are developed, then significant R&D time might be saved, new insights into the process might be gained, and some good predictions of process or performance can be made. One such area is the characterization of slag deposition and flow on the gasifier walls. Understanding slag rheology and slag-refractory interactions is critical to design and operation of gasifiers with extended refractory lifetimes. Slag rheology and slag-refractory interactions is also important to better control the operating parameters so that the overall gasifier performance with extended service life can be optimized. In the present work, the literature on slag flow modeling was reviewed and a model similar to Seggianis was developed to simulate the time varying slag accumulation and flow on the walls of a Prenflo coal gasifier. This model was further extended and modified to simulate a refractory wall gasifier including heat transfer through the refractory wall with flowing slag in contact with the refractory. The model was used to simulate temperature dependent slag flow using rheology data from our experimental slag testing program. These modeling results as well as experimental validation are presented. 36-5 Models for Refractory Spalling in Coal Gasifiers Rick Williford, Ken Johnson, S.K. Sundaram, Siva Pilli, Pacific Northwest National Lab, USA Spalling degradation of hot-face refractories in slagging coal gasifiers has a major impact on refractory lifetime, and thus on the economics of coal gasification. Models are needed to help optimize gasifier performance by balancing conversion efficiency with refractory life. Two predictive models for spalling are proposed in this paper. The two models treat spalling caused by volume expansion and by volume shrinkage, due

SESSION 36 GASIFICATION: PNNL-CHINA

36-1 Design & Development of a Novel Research Gasifier George Muntean, Mike Dodson, Bob Robertus, Pacific Northwest National Laboratory, USA The Pacific Northwest National Laboratorys (PNNL) strategy is based on a commitment to solve world-class problems by rapidly translating science into solutions. One of the primary laboratory mission statements guiding the execution of this strategy relates to our increasing domestic energy demands. The laboratory recognizes the critical need for the United States to effectively utilize its domestic hydrocarbon resources in an environmentally benign manner. In support of this mission, the laboratory has numerous ongoing research programs. Project examples include: the use of millimeter-wave technology for corrosion, slag viscosity, and temperature measurements in gasifiers; approaches to predict and control slag viscosity; development of metal oxides and or pure metal polishers to remove H2S from warm syngas; separations agents for mercury capture from the gasifier outlet gas and liquid streams; new Fisher-Tropsch catalysts and vessel configurations; CO2 capture using advanced solid sorbents, liquid solvents and membranes; advanced computer modeling of coal gasifiers; development of a CO2/coal slurry pump for feeding gasifiers While initial proof-of-concept tests for each of these projects can be performed at small scales using simulated gases in pressurized bottles or other artificial conditions, actual gasification gases are needed to prove that the processes will work satisfactorily in a commercial environment. Gaseous products from coal contain trace amounts of many impurities whose effects are unknown and not easily determined using synthetic bottled gases. In short, the mission as a whole and the individual projects within it require the credibility that comes with operating a real gasifier processing coal in a high oxygen environment and testing new approaches in that realistic environment. Ultimately, the scale-up of novel technologies requires testing at commercially acceptable levels of demonstration such as the DOE-FE supported facilities at the PSDF (Power Systems Development Facility). We believe that efficient technology development benefits from an additional, intermediate level of testing between bench scale and commercial scale. To this end, PNNL has designed and procured a novel and unique engineering-scale coal gasifier. The gasifier is a small entrained flow, slagging design. The gasifier will be capable of processing up to 100 lbs/hr of coal at pressures up to 500 psig and converting it into a suitable syngas test stream for the evaluation of novel separations and synthesis technologies. This talk will describe the design and operation of this unique test bed including lessons learned and initial test results. 36-2 Process Development on Co-Gasification of Coal and Biomass in a Fluidized Bed Jicheng Bi, Rong Zhang, Kezhong Li, Institute of Coal Chemistry, Chinese Academy of Sciences, CHINA Investigations on fluidization quality, gasification reactivity and operational parameters optimization in coal and biomass co-gasification process were performed in a cold fluidized bed, a thermalgravity analyzer and a self-heating fluidized bed gasifier,

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to chemical reactions of slag components with the porous refractory. Both models express molten slag ingress into the porous refractory in terms of an effective diffusivity, which is formulated in terms of the simultaneous transport of reactive species by capillary action through the pores and by diffusive transport through the slag and the solid refractory material. The effective diffusivity depends on the total pressure gradient across the refractory, the temperature and chemistry dependence of the slag viscosity, the refractory porosity, the pore tortuosity, and the average pore radius. The modeling results appear useful for large scale simulations to predict the lifetimes of refractories in slagging coal gasifiers, and for determining whether an observed spall originates from tensile or compressive mechanisms. 36-6 Sensor Concepts and Development for Coal Gasification S. K. Sundaram, J. V. Crum, Pacific Northwest National Laboratory; P. P. Woskov, MIT, USA Gasification or partial oxidation combines coal, oxygen and steam to produce synthesis gas which will be further processed to get the final product. Several advancements are needed for cost-effective and environmentally-benign gasifier processes and operation, e.g., novel catalysts, membranes, and materials for advanced, lower cost separations of hydrogen from carbon dioxide and other contaminants. In addition, improvements in many technological areas will be needed, e.g., gasifier design, materials and feed systems, sensors, and advancements in carbon dioxide capture and sequestration technology. An overview of sensor needs and challenges of coal gasification will be summarized. Additionally, progress made on sensors and capabilities development for gasification under the Energy Conversion Initiative (ECI) at Pacific Northwest National Laboratory (PNNL) will be highlighted. It is shown that new millimeter-wave technologies and methods can address many of the sensors needs for advancing coal gasification systems.

SESSION 37 GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES 1

37-1 The Potential Impact of Developing Technologies on the Economics and Performance of Future IGCC Power Plants John Plunkett, David Gray, Charles White, Noblis, USA This paper presents the results of a study funded by the National Energy Technology Laboratory (NETL) to quantify the impacts of advanced technologies on the performance and economics of future IGCC power plants. A reference IGCC power plant that consists of currently available technology is used as the benchmark by which to measure the improvements provided by incorporating the advanced technologies. The advanced technologies that are analyzed in this study are: dry coal feed pumping system to introduce the coal into the gasifiers and to replace water slurry feeding, warm gas cleaning to replace conventional acid gas and trace element removal, direct sulfur recovery to replace the Claus unit, high temperature ionic membrane air separation to replace cryogenic air separation, advanced syngas gas turbines, and stationary solid oxide fuel cells. These technologies are under development within NETLs research and development (R&D) program. Aspen Plus simulations were used to conceptualize the IGCC plants and estimate the performance improvement in terms of overall thermal efficiency, capital cost, and the levelized cost of electricity. The novel technologies being developed through NETLs R&D program will provide coal-based power plants for the future, which generate low-cost electricity with significantly improved efficiency and reduced environmental footprint. 37-2 Progress on HydroMax Breakthrough Molten-Metal Coal Gasification Technology Phillip Brown, Jeff Hassannia, Steven Schenk, Diversified Energy Corporation, USA HydroMax is a patented, breakthrough gasification technology that utilizes a unique chemical pathway to produce syngas (CO + H2) and hydrogen (H2) in separate and distinct streams, resulting in process and economic benefits. Using two distinct steps, the HydroMax process begins with a molten Iron/Tin (FeSn) bath heated to 1300C. In Step 1, steam is injected into the molten bath, which is then thermo-chemically split (i.e. traditional steaming of iron) resulting in H2 gas (released) and oxidized Fe (FeO). After the Fe is oxidized, steam injection ceases and coal is injected into the reactor (Step 2). Carbon, with its high affinity to oxygen, reduces the oxidized FeO to its pure form (Fe) and produces a CO-rich syngas, which is either used as a fuel gas or combined with hydrogen from Step 1 to produce Fischer Tropsch fuels. Based on these fundamental processes of steaming-iron and metal-bath-smelting, the oxidation and reduction steps are then repeated in a cyclic fashion thus resulting in no molten-metal consumption.

Furthermore, the tin (Sn) in the molten metal serves to capture sulfur as tin-sulfide gas that is subsequently roasted to tin-dioxide and reintroduced into the molten-metal bath, therefore maintaining the tin composition integrity and operating temperature of the reactor. Several unique attributes of the HydroMax gasification technology result in significant operational and economic benefits compared to existing gasification approaches, including: Capital cost reductions as a result of a simple and proven reactor design Smaller gasification footprint due to the high thermal inertia of the molten-metal reactor Flexibility to utilize any carbon feedstock due to the high thermal inertia associated with a molten-metal bath Flexible and tailored outputs as a result of producing syngas and pure hydrogen in separate streams Ability to accept high sulfur coals due to the unique sulfur removal approach via tin-sulfide Commercial and industrial HydroMax applications are numerous, including: utilityscale power generation, synthetic natural gas production, coal-to-liquid-fuels, and large-scale hydrogen production for oil refineries or the fertilizer industry. Currently, the HydroMax team is pursuing an initial market entry point focused on small industrial scale applications for converting coal and/or biomass into a fuel-gas for process heating and drying applications used by a number of manufacturing companies. Diversified Energy is cooperating with two industrial firms, in different markets, to design a HydroMax gasification system to supply a natural gas substitute for process heating and to explore the economic feasibility of incorporating HydroMax as a source for low-cost fuel gas. Previous laboratory and proof-of-concept tests have successfully demonstrated the fundamental science and approach of the HydroMax technology. Capital cost analysis conducted by Aker Kvaerner indicates that significant cost reductions are achievable using the HydroMax approach. Since the 2007 Clearwater conference, the HydroMax technology team has made significant development progress. A dynamic simulation model was created to assess the technology performance using a variety of carbon feedstocks. Initial results from this model indicate that HydroMax performs better than existing commercial gasifiers, particularly when using low-rank western coals or highmoisture content biomass as a feedstock. Also since 2007, HydroMax was selected by three different government organizations for development funding. The U.S. Department of Energy is funding bench-scale HydroMax tests using PRB and Illinois #6 coals. These tests will be completed in January 2008. The U.S. Department of Defense is funding a HydroMax to liquid fuels feasibility study. This study will focus on waste gasification and conversion to diesel and jet fuel. Finally, the State of California is funding a HydroMax pilot demonstration at a pulp mill in Eureka, CA. DEC will construct and install a HydroMax system at Evergreen Pulp to gasify waste wood fines and provide syngas for process heating. The HydroMax presentation will include: 1) A brief overview of the HydroMax coal gasification technology 2) An introduction to the HydroMax development team 3) Previous test results and analyses including the January 2007 DOE funded tests 4) Analyses conducted using models developed from AspenPlus and a discussion of HydroMax performance compared to commercially available gasifiers 5) Summary of the industrial applications being pursued and evaluated 6) Progress status of DOD and State of California contracts 7) Future development plans and activities. 37-3 ALSTOMs Hybrid Combustion-Gasification Chemical Looping Technology Development - Phase III Herbert Andrus, John Chiu, Paul Thibeault, ALSTOM Power Plant Laboratories; Ronald Breault, DOE-NETL, USA ALSTOM Power Inc. (ALSTOM) has just completed Phase III of a multiphase program to developed entirely new, ultra-clean, low cost, high efficiency power plant for the global power market. This new power plant concept is based on a hybrid combustion-gasification process utilizing high temperature chemical and thermal looping 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 combustiongasification process producing a syngas for gas turbines or fuel cells or 3) an integrated hybrid combustion-gasification process producing hydrogen for gas turbines, fuel cells or other hydrogen based applications while also producing a separate stream of CO2 for use or sequestration. This paper covers the progress of recently completed Phase III Work with the US DOE. The objective for Phase III was to investigate the solids handling system for the multiple solids streams, to develop an automatic control methodology for the process components, and to generate enough information to design and build the prototype Chemical Looping system to be built in the next Phase of the program. These objectives were met. The main conclusion from Phase 1 and Phase 2 was that the PDU chemistry required for the chemical looping process has been validated. The main conclusion from Phase III is that it is possible to design an integrated Chemical looping system with all of the components necessary for successful operation and it is also possible to design a control system to operate the multiple

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solids transport loops. Economics were reevaluated based on the results of Phase I, II and III testing and were found to still be valid. 37-4 Coal Direct Chemical Looping Process for Hydrogen Production Experimental Studies Liang-Shih Fan, Hyung Kim, Fanxing Li, Deepak Sridhar, Liang Zeng, Fei Wang, The Ohio State University, USA The Coal Direct Chemical Looping (CDCL) process is a novel technology producing hydrogen from coal with integrated CO2 separation. The CDCL uses the composite iron oxide particle as an oxygen carrier to combust coal. These particles are reduced by coal to capture CO2 in the reducer. Then, these reduced particles are used in the second reactor to produce hydrogen through oxidation, as they react with high temperature steam. The indirect combustion of coal with composite iron particles significantly enhances the efficiency of the hydrogen production process. These composite iron particles are uniquely synthesized by the Ohio State University to sustain the high temperature reactions and transportation. The experimental results on the combustion of coal with iron particles show more than 90% conversion of coal and >95% CO2 are achieved under optimized reaction conditions. In addition, effect of sulfur and ash on the recyclability of the composite iron oxide particle was also studied. 37-5 Retrofitting Existing Coal-Fired Power Plants with Plasma Gasification to Meet Clean Air Act Environmental Standards Shyam Dighe, Tom Gdaniec, Westinghouse Plasma Corp.; Alan Sawyer, NRG Energy, Inc., USA Retrofitting existing coal power plants with plasma gasification results in modernized clean energy facilities. Plasma gasification technology offers an environmentally responsible solution for older power plants allowing old power plants to meet increasingly stringent regulatory and environmental standards. Plasma Gasification technology converts coal / biomass into syngas, which is cleaned of impurities i.e. sulfur and mercury, and then combusted in the existing facility s steam electric generating equipment (typically boilers). By retrofitting plasma gasification technology into the older power plants, much of the existing facility infrastructure is retained and reused; thereby reducing repowering costs and the amount of air pollutants emitted is drastically reduced. As well, by replacing some of the coal with renewable biomass feedstock, construction and demolition waste or municipal solid waste, significant greenhouse gas reductions can also be attained. Retrofitting coal fueled facilities using plasma gasification system is expected to reduce harmful air emissions below US environmental guidelines, with significant reductions of nitrogen oxides (NOx), mercury (Hg) and sulfur oxides (SOx). Reductions in greenhouse gas emissions from retrofitted facilities are possible by combining biomass into the feedstock to displace the need for coal and further reduction may be possible with the future add-on of carbon capture and sequestration technology. As well, it enhances power generation on Brownfield sites in areas of high power demand. Most importantly, it makes it unnecessary to abandon older power plants, the people who operate them, the vendors who sell goods and services to them, and the communities who benefit from them. As well, as it is a more time and cost efficient solution than building new facilities NRG Energys power plant in Somerset, MA currently produces 110 megawatts (MW) with a pulverized coal combustion boiler and associated steam turbine. NRG has proposed and received required approvals from the Commonwealth of Massachusetts Department of Environmental Protection for the design, construction, and operation of a plasma gasification system at Somerset and the refueling of the existing boiler from pulverized coal to clean syngas firing using the plasma gasification technology developed by Westinghouse Plasma Corp (WPC). WPC is a wholly owned subsidiary of Alter Nrg. The approval also allows the use of up to 45% biomass, on a heat input basis to displace coal, thereby earning both Renewable Energy Credits and significantly reducing the emissions of greenhouse gas (GHG). There are close to 600 small to medium size coal-fired generation units in North America that are nearing the end of their economic life because they can t meet new emissions standards. NRG Energy together with Alter NRG has identified more than 320 coal-fired units that are suitable for retrofitting using WPC plasma technology. NRG Energy s Somerset plant will be the world s first plasma gasification retrofit of a coal-fired power plant. Our paper will explain how plasma gasification works, the application to and benefits of plasma gasification for power plant retrofits, the experiences with plasma gasification of waste feed materials in commercial plants in Japan and India and the industry trends which are heightening interest in North America and around the world for plasma gasification application for power generation.

SESSION 38 GASIFICATION TECHNOLOGIES: SYNTHESIS GAS CLEANING 1

38-1 250 MW IGCC Demonstration Start Up MHI Gas Clean-Up System Shintaro Honjo, Mitsubishi Heavy Industries America, Inc., USA; Makoto Susaki, Susumu Okino, Toshinobu Yasutake, Mitsubishi Heavy Industries, Ltd., JAPAN September 2007, 250 MW scale air-blown Integrated coal Gasification Combined Cycle (IGCC) plant has successfully started up at Nakoso in Japan. This is first Japanese commercial scale IGCC demonstration test to verify its performance and reliability. All main components such as Gasifier, Turbine and Gas clean-up system are designed and/or manufactured by Mitsubishi Heavy Industries, Ltd (MHI) for Japanese Clean Coal Power R&D Co., Ltd (CCP). Since the startup of September 2007, MHI confirmed this demonstration plant exceed the entire performance target relate with pollution control (SOx, NOx and PMs). Plant is now running continuous basis to proof its reliability. This paper describes on its advanced cold gas clean-up process which also improves plant efficiency by 0.6% compared with conventional system. The demonstration test will be continued till end of 2009. 38-2 UCSRP-HP - an Integrated Multi-Contaminant Removal Process for Treating Coal-Derived Syngas Howard S. Meyer, Diana Matonis, Timothy Tamale, Dennis Leppin, Gas Technology Institute; Scott Lynn, University of California Berkeley, USA The University of California Sulfur Recovery Process-High Pressure (UCSRP-HP) testing program is developing an integrated, multi-contaminant removal process for coal-derived syngas at 275F to 300F and at the given sour gas pressure. The process will remove H2S, NH3, HCl and heavy metals, including Hg, As, Se and Cd, to partsper-million (ppm) or in some cases parts-per-billion (ppb) levels in a single process. Contaminates, such as NH3, HCl and trace contaminants, are removed in the first section of a compound reactor column. This is accomplished by a common solvent absorbing H2S, NH3, HCl and trace metals from the feed gas. NH3 and HCl form a highly soluble NH4Cl salt and the absorbed heavy metals, As, Cd and Hg, precipitate out as their very insoluble sulfides. The Se trace metal, present in the syngas as H2Se, forms a highly soluble (NH4)2Se under these conditions and remains dissolved in the solvent. A slipstream of the solvent will be treated to remove the soluble and insoluble components. In the second section of the column, H2S is converted directly into elemental sulfur by reaction with sulfur dioxide in the liquid phase. The liquid sulfur formed rapidly separates from the solvent phase, allowing the Claus reaction to continue without equilibrium limitations that controls gas-phase catalytic systems. The proposed process is tightly integrated and is expected to be significantly more economical both in terms of capital and operating costs because it replaces the sulfur removal processes, acid-gas removal, Claus and SCOT, as well as the trace components removal processes used or proposed in conventional schemes by a single unit. This paper will include an (i) investigation of long-term (i.e., 1000 hrs) solvent stability by exposure of the solvent to a gas simulating synthesis gas from the gasification of Illinois No. 6 coal containing all the contaminants that may be present in the feed to UCSRP reactor, (ii) investigation of metal corrosion related issues for selecting suitable material of construction for UCSRP reactor, (iii) investigation of the removal of the trace metal components from the syngas by the selected solvent, (iv) investigation of the fate of COS in the system, (v) development of an Aspen-Plus based computer simulation model, and (vi) techno-economic evaluation of the process applied to syngas cleanup. 38-3 Development of a Warm Syngas Clean-Up Technology Platform for Power and Chemicals Production Brian S. Turk, John R. Albritton, Jason Trembly, Raghubir Gupta, Lora Toy, Paige Pressler-Jur, RTI International; Jerry Schlather, Jeremy Gibson, Joshua Keller, Eastman Chemical Company, USA Gasification is a proven commercial process for converting carbonaceous feedstocks, particularly low value and dirty feeds such as coal, lignite, petroleum coke and biomass into synthesis gas. The challenges for gasification are efficient utilization of this synthesis gas for power or chemical production, achieving acceptable environmental performance and competitive capital and operating costs. For gasification of dirty feeds like coal, the syngas cleanup process plays a vital role in meeting these challenges. The list of syngas contaminants, which includes sulfur, nitrogen, chlorine, mercury, alkali metals, selenium, cadmium, and arsenic, makes the importance of the syngas cleanup process to gasification apparent. Furthermore, although the carbon dioxide is not considered a contaminant, being able to capture and sequester the carbon dioxide in a cost-effective manner is becoming an important

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decision factor in selecting gasification over other technologies in todays carbon constrained world. As the scope of syngas cleaning expands beyond sulfur, conventional commercial technologies are challenged to achieve the environmental performance and high energy efficiencies at competitive capital and operating costs. RTI International (RTI) has strong multi-faceted R&D program focused on developing a technology platform for syngas cleaning. The key features of this technology platform are removing all contaminants including sulfur, ammonia, mercury, arsenic, chlorine, alkali metals, and even carbon dioxide. The primary focus for syngas cleaning is for the entire platform to operate at temperatures >250C. RTI and Eastman Chemical Company (Eastman) have successfully demonstrated a transport reactor-based desulfurization technology suitable for warm syngas. In addition, field testing of other syngas cleaning technologies have been completed this year. This paper will present new technical development and feasibility analysis of this syngas cleaning technology platform, along with commercialization plans. 38-4 CrystaSulf-DO Process for Sulfur Removal from Warm Coal-Derived Gas Diana Matonis, Howard S. Meyer, Timothy Tamale, Dennis Leppin, Gas Technology Institute; David Seeger, CrystaTech Inc., USA This paper presents the results of an on-going experimental study on the catalytic direct oxidation (DO) section of the CrystaSulf-DO process for the removal of sulfur compounds as elemental sulfur from syngas generated by the gasification of coal. This hybrid process concept places the DO bed upstream of the CrystaSulf unit. This approach allows for 80-95% of the hydrogen sulfide in the inlet gas stream to be converted to elemental sulfur and removed before entering the CrystaSulf absorber. The primary benefit of this approach on the overall sulfur removal/recovery system is an 80% or greater reduction in the CrystaSulf units circulation rate, and the size of the crystallizer, sulfur filter and associated equipment. Consequently, overall utilities and chemical consumption rates should be dramatically reduced. By tailoring the O2 to H2S ratio in the DO process we can (1) minimize the loss of combustibles in the gas and (2) control the amount of elemental sulfur versus SO2 in the exit. With this additional integration, the sulfur dioxide needed for the liquid phase reactions in CrystaSulf may be produced in the same catalyst bed, further simplifies the overall process and lowering its cost. The CrystaSulf- DO approach could offer a significant cost advantage over the amine/Claus/tail gas approach for syngas applications for coal feed rates up to 250 tons/day (tpd). Experiments were conducted to select a suitable catalyst; investigate the effect of major operating parameters, including water vapor content, on H2S removal efficiency; determine optimum operating parameters; and ultimately develop a reactor design and perform a preliminary economic analysis. A bench-scale testing system at Gas Technology Institute (GTI) was used to measure the performance of full-particle-size catalysts at pressures to 2.8 MPa (400 psi), and temperatures primarily between 124149C (255 300F). A blended gas stream, which contains the primary components of syngas, is combined with oxygen (by air addition) and passed over hot catalyst. From measured changes in composition of the syngas stream, the activity and selectivity of the catalyst are evaluated. Optimal process conditions are determined by varying the amount of oxygen added that reacts selectively with hydrogen sulfide in the syngas minimizing the consumption of the valuable syngas components of carbon monoxide and hydrogen as will be shown. 38-5 Innovative Hot-Gas Cleanup Processes for Advanced IGCC Systems and for Hydrogen Production Processes Michihiro Ishimori, Yuya Mezaki, Seiji Terashita, Masafumi Katsuta, Waseda University, JAPAN Development of a hot-gas cleanup system, especially highly efficient desulfurization technology has been studied to realize effective coal gasification plants such as advanced IGCC systems for electricity and advanced processes for high-grade hydrogen production. We have explored innovative desulfurization agents composed of zinc ferrite, metal oxides and/or metal sulfides for hot-gas cleanup processes, using simulated coal gas by an entrained-flow gasifier. It was shown that by use of the above agents, hydrogen sulfide itself is almost completely removed and that sulfur atoms of sulfuric substances such as COS involved in coal gas are also catalytically reduced to hydrogen sulfide and subsequently removed; total concentration of H2S and COS involved in the simulated coal gas could be decreased to less than detection limit (PFD/GC; 20 ppbv). The desulfurization agents can be satisfactorily used to realize advanced IGCC and IGFC plants having extremely high thermal efficiencies, and for advanced processes of high-grade hydrogen production for PEFC.

SESSION 39 ENVIRONMENTAL CONTROL TECHNOLOGIES: MULTIPOLLUTANT CONTROL

39-1 Assessment of the Alternative Oxidation-Reduction and OxidationAbsorption Chemical Process Modes in Integrated SO2, NOx and Hg Removal William Ellison, Ellison Consultants, USA The presentation, after defining the two chemical processes, will review recent, early, breakthrough commercial application of these principal, generic, chemical engineering technologies that afford means of simultaneous removal of NOx and elemental mercury in FGD scrubbing operations, wet, dry or semi-dry, and existing or new. Details will be given of: Principal system design challenges in engineering of a commercial, flue gas, chemical pre-oxidation facility Key elements in achieving acceptable pre-oxidation system design and performance Oxidation-reduction process design Advantages of use of oxidation reduction scrubbing chemistry Disadvantages in use of oxidation-reduction scrubbing chemistry Emphasis for this mode on merits of scrubber system design that achieves surface renewal, i.e. continuous, in-situ renewal of chemically active gas/liquid contact surface Oxidation-absorption process design Disadvantages in use of oxidation-absorption scrubbing chemistry. 39-2 Cost-Effective Retrofitting of Fossil Fueled Power Plants with Raw Flue Gas Pre-Oxidation in Meeting Nitrogen Oxides, Mercury and Sulfur Dioxide Emission Limits William A. Walsh, Jr., VGA Nozzle Company; William Ellison, Ellison Consultants, USA Oxidizing of nitric oxide (NO), the principal flue-gas NOx component, to a higher oxide (NO2, N2O3 or N2O5) is a key step in gaining NOx emission control in downstream dry and semi-dry scrubbing systems. The pre-oxidation step also simultaneously converts elemental mercury to an oxidized form and sulfur dioxide (SO2) to sulfur trioxide (SO3) for their dry-mode removal. The proprietary Variable Gas Atomization (VGA) nozzle-lance system described provides a cost-effective means of performing this pre-oxidation. It injects mixtures of chemicals, fed in-duct, that interact to yield highly activated radical forms as they are being formed and released. These further react with the non-dedusted, raw flue gas. Candidate oxidants include hydrogen peroxide (H2O2), yielding its reactive components as radicals, and sodium chlorate (NaClO3), yielding chlorine dioxide (ClO2). Oxidation may be accomplished either in the raw-flue-gas duct directly upstream of scrubbing or, if higher reaction temperature is desired, upstream of the air pre-heater. It has application in conjunction with combustion of all fossil fuels that emit acid gases and mercury. It is suitable for retrofitting to existing boiler/scrubber facilities, boilers scheduled for scrubber addition and for new power generating sources. The paper will describe the processes and equipment to achieve in-situ formation of the reactive chemical radicals effective in pre-oxidation. It will delineate the nozzlelance system design effectively utilized to achieve a uniform distribution of these reactive agents throughout the raw flue gas stream. In addition, it will outline modest modifications to existing power plant flue gas ducts and dry/semi-dry scrubbers that enable cost-effective emission control. 39-3 Use of Advanced Process and Mechanical Engineering Means for Flue Gas Treatment in SO2 and Hg Removal with an Optional Measure of Secondary Denox Kevin Furnary, LEEP Holdings, LLC; William Ellison, Ellison Consultants, USA Of Australian commercial origin, LEEP gas treatment technology to be detailed is based in part on international integration of commercially successful, American and overseas, mechanical and chemical engineering design technology. This novel scrubber is a high gas velocity chemical reactor that creates large surface area for reaction between flue gas and multiple recirculating chemical scrubbing media to be used. Inflow of scrubbing media and their kinetic energy occurs stepwise along the course of a circular reaction vessel at several sequential contact stations, each of which comprises a ring of nozzles that brings about intense mixing and interaction augmented by pronounced, fluid shearing leading, in turn, to continuous scrubbing surface renewal. To advantage, the final contact station optionally uses a chemically reducing scrubbing medium in high-sulfur service making possible the effective application of newly field-

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proven, generic, oxidation-reduction chemical process operation that achieves simultaneous SO2, NOx, and Hgo removal. Examples are to be given of attractive chemical process and mechanical engineering design features utilized: Sub-atmospheric pressure scrubber operation arising from mechanical engineering design devoid of booster fan use Commercial state-of-the art in advanced, horizontal-gas-flow, scrubber mist eliminator design and operation of European origin Zero-effluent, calcium-based scrubbing operation yielding output sulfite-solids cake to be intermixed with the pre-collected dry fly ash for advantageous disposal via construction of a structural landfill monolith Possible alternative use of newest technological advancements in application of ammonia scrubbing including a finished yield of high-value, agricultural fertilizer, by-product solids of true granular form Optional, high-velocity, existing, stack discharge of scrubbed, water saturated flue gas, that is hot by-pass gas reheated via advanced aerodynamic gas mixing means Optional use of the alternative oxidation-absorption chemical process mode of scrubber operation in applications in which NOx ppm reduction, as when augmenting SCR, is minimal. 39-4 Regenerable Molecular Basket Sorbents for NO2 and SO2 Removal from Flue Gas Xiaoxing Wang, Xiaoliang Ma, Chunshan Song, Penn State University, USA Molecular Basket Sorbent concept has been used to develop a new nanoporous composite sorbent, which is able to remove NO2 and SO2 selectively from flue gas and other gas streams at ambient conditions and can be regenerated easily. The present study may open a new window for development of the high performance of sorbents for gas separation. 39-5 The Greenidge Multi-Pollutant Control Project: Demonstration Results and Deployment of Innovative Technology for Reducing Emissions from Smaller Coal-Fired Power Plants Dan Connell, CONSOL Energy Inc. R&D; Doug Roll, AES Greenidge LLC; Rich Abrams, Roderick Beittel, Babcock Power Environmental Inc.; Wolfe Huber, DOE-NETL, USA There are more than 420 coal-fired electric generating units (EGUs) in the United States with capacities of 50-300 MW that currently are not equipped with selective catalytic reduction (SCR), flue gas desulfurization (FGD), or mercury control systems. Many of these units, which collectively represent almost 60 GW of installed capacity, are difficult to retrofit for deep emission reductions because of space constraints and unfavorable economies of scale, making them increasingly vulnerable to retirement in the face of progressively more stringent environmental regulations. The Greenidge Multi-Pollutant Control Project is being conducted as part of the U.S. Department of Energys (DOE) Power Plant Improvement Initiative to demonstrate a solution for these units. The project seeks to establish the commercial readiness of a multi-pollutant control system that is designed to meet the needs of smaller coal-fired EGUs by offering deep emission reductions, low capital costs, small space requirements, and applicability to high-sulfur coals, mechanical simplicity, and operational flexibility. The system comprises an innovative combination of technologies including combustion modifications, a NOxOUT Cascade hybrid selective non-catalytic reduction (SNCR) / in-duct SCR system, and a Turbosorp circulating fluidized bed dry scrubbing system with baghouse ash recycling and activated carbon injection. These technologies were retrofitted to the 107-MW AES Greenidge Unit 4 by Babcock Power Environmental Inc. (BPEI) in 2006, with a total plant cost of ~ $340/kW and a footprint of < 0.5 acre. Extensive testing has been carried out through mid-2008 to evaluate the performance of the multi-pollutant control system during its first year-and-a-half of commercial operation. This paper summarizes performance and cost results from AES Greenidge Unit 4 and discusses commercial deployment of the demonstration technology. Guarantee tests conducted at AES Greenidge in 2007 proved that the multi-pollutant control system was capable of reducing NOx emissions to 0.10 lb/mmBtu, SO2 emissions by 96%, SO3 and HCl emissions by 97%, and mercury emissions by > 95% while the unit fired 2.43.2% sulfur eastern U.S. bituminous coal. Additional tests have since been conducted to characterize the performance of the system as a function of unit operating conditions; the results of these tests are presented. The predominant operating challenges encountered to-date have arisen from the combustion system and from accumulation of large particle ash (LPA) in the in-duct SCR catalyst; as a result, the unit has required several outages for catalyst cleaning and has routinely operated with NOx emissions slightly greater than 0.10 lb/mmBtu. The Turbosorp scrubber has operated commendably, routinely achieving > 95% SO2 removal efficiency while the unit is firing mid-to-high sulfur coals (e.g., containing 2.5-5.0 lb SO2 / mmBtu). Moreover, all tests performed to-date have demonstrated 93-99% mercury removal as a co-benefit of the hybrid NOx control and Turbosorp systems, without the need for any activated carbon injection.

As a result of the success at AES Greenidge, three additional retrofit applications of the Turbosorp system have been announced for small to moderate-sized coal-fired EGUs (i.e., 50-300 MW) in the United States. Additional announcements are anticipated. Key characteristics of these announced deployments, including unit and fuel characteristics and performance targets, are discussed.

SESSION 40 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 5

40-1 Mercury Capture by Bulgarian Fly Ashes: Evidence from Petrography and Surface Analysis James C. Hower, University of Kentucky; Maria Mastalerz, Indiana University, USA; Irena J. Kostova, Sofia University, BULGARIA Fly ash carbons from high volatile bituminous coals, such as the coals burned at most Kentucky power plants, consist primarily of neoformed carbons repolymerized from a vitrinite-derived thermoplastic fluid and inertinite derived, without substantial alteration, from the inertinite component of the feed coal. In contrast, carbons in fly ashes from low-rank coals, such as burned in Bulgarian power stations, consist of inertinite and a vitrinite-derived char. The latter has obviously not passed through a plastic state. In both cases, Hg capture by the fly ash is a function of the temperature at the collection point and the amount of fly ash carbon. The ashes differ in the lowrank-derived carbons having a greater ability to capture Hg, based on a Hg/C ratio, than high volatile bituminous-derived carbons. The Hg/C ratio decreases with the amount of C in the fly ash, perhaps a function of the blinding of interior C surfaces with thicker carbons. Increases in the BET and micropore surface areas correlate with increases in fly ash Hg. 40-2 Evaluation of Coal Preparation Plant Refuse Areas in Kentucky as a New Energy Resource Cortland F. Eble, Stephen F. Greb, James C. Hower, University of Kentucky, USA The demand for, and use of, coal in the United States is projected to increase as our energy consumption increases. In addition to conventional coal resources, unconventional resources, mainly in the form of preparation (or beneficiation) plant refuse, are beginning to be recognized and utilized, especially with the expansion of clean coal technologies. These newer technologies, which include gasification and fluidized bed combustion, can readily use preparation plant waste, especially the byproduct material from older (pre-1990) facilities. Older plants were not able to separate the coal from the non-coal (rock) fraction as efficiently as newer plants can, and hence the waste product ended up containing a relatively high percentage of coal (in some cases up to 40%). Kentucky has an abundance of abandoned preparation plant waste areas given the long history of coal mining in the Commonwealth. These areas represent an energy resource that requires further evaluation. The exploitation of older preparation plant refuse areas could significantly extend the amount of coal resources that remain in Kentucky. Re-mining of these areas could also be environmentally beneficial as preparation plant waste is often unsightly, and potentially damaging to streams and groundwater. Re-mining would also provide additional jobs in the mining and transportation sectors. 40-3 Development and Application of CCTM Model Shihua Ren, Guifeng Chen, Beijing Research Institute of Coal Chemistry, China Coal Research Institute, CHINA As one of the countries with largest coal production and consumption, China is introducing clean coal technologies. China Coal Research Institute (CCRI) developed Clean Coal Technology Model (CCTM) to meet the need of different clean coal technology options under different conditions. The model was derived from life cycle assessment, multiple indexes evaluation and input-output methodology, which has three functions including calculation and comparison of individual clean coal technologies, lifecycle assessment from coal mining to utilization, and prediction of energy demands. The model provides a convenient tool for evaluating clean coal technologies, and a perfect model for making decisions on clean coal technologies for enterprises, governments and research institutes. This paper finally gives an example to explain how to apply the model, which can evaluate the difference between the two lifecycle pathways (one is from coal, diesel, to diesel vehicles and another is from coal, DME to DME vehicles) in the aspects of technology, economy and environment separately and synthetically.

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40-4 Mineral Resources of Kuzbass Plants for Complex Deposits Developing in Innovation Technologies Realization of Deep Mineral Wealth and Mineral Waste Processing Boris F. Nifantov, Vadim P. Potapov, Coal and Coalchemistry Institute SB RAS, RUSSIA The natural potential of mineral resources in Kemerovo area includes different kinds of mineral wealth. The main of them are coal, iron ore, polimetal and others. Extracting and processing of mineral wealth, ore-dressing and burning are the industrial plants processes, which pollute the environment very much. Their gross data decreasing will be real in conditions of system program fulfilling of deep mineral wealth and waste processing, it will help in knowledge paradigm forming, in working out the technologies complex, completely covering all components of raw materials, extracting from the bowels.

Using a commercially-available, high-calcium hydrated lime, 90% CO2 and greater than 99% SO2 capture has been achieved on a once-through basis. With the success achieved on a once-through basis, the 20 pound per hour facility has been renovated for multicyclic studies. With the integration of a rotary kiln, a wider array of initial starting solid sorbents can be tested. Before the integration of the calciner, only calcium hyroxide and calcium oxide sorbents were available for testing. The calciner allows for carbonaceous materials to be tested, such as limestones and precipitated calcium carbonate. The presentation will focus on three areas. First, the construction of the 20 pound per hour facility and the results generated will be discussed. Second, process simulations for integrating the CCR process into an existing or new power plant will follow. Finally, conclusions and future work plans will be outlined. 41-3 Long-Term Operation for Carbon Dioxide Capture System Composed of Two Fluidized Bed Reactors Using a Potassium-Based Dry Sorbent Chang-Keun Yi, Young Cheol Park, Sung-Ho Jo, Ho-Jung Ryu, Seung-Yong Lee, Chong Kul Ryu, Korea Institute of Energy Research, KOREA Korea Institute of Energy Research (KIER) and Korea Electric Power Research Institute (KEPRI) have been developing a CO2 capture technology using dry sorbents. The CO2 removal in dry sorbent CO2 capture system consists of two reactors for carbonation and regeneration. We used dry sorbent manufactured by spray-drying method contains potassium carbonate, which was supplied by KEPRI in order to investigate the sorbent performance in continuous operation mode with solid circulation. In this study, we used the simulated flue gas containing 13% of CO2 for 2 Nm3/hr facility which is composed of a fast fluidized bed carbonator (5.4 m tall pipe of 0.025 m (i.d.)), the lower mixing zone (0.6 m tall pipe of 0.035 m (i.d.)) and a bubbling fluidized bed regenerator (1.28 m tall bed of 0.1 m (i.d.)). The dry sorbent consists of 35% K2CO3 as an active component and 65% support for mechanical strength and pore structure. The continuous operation was first executed during 54 hours and the next 50 h continuous operation was performed again using the same sorbent as the first operation. The average CO2 removal was 85% for 50 h continuous and smooth operation. This result indicates that CO2 capture process using potassium carbonate solid sorbent is applicable for CO2 capture in the flue gas. 41-4 Preparation of Composite Carbon Membranes from Waste Peanut Shells Petr evk, Ivan Koutnk, VB - Technical University of Ostrava; Vlastimil Fla, Institute of Chemical Technology Prague; Karel Titel, ZVU Engineering, CZECH REPUBLIC Porous carbon planar discs of cyclic crosscut were prepared by controlled carbonization of tablets made of peanut shells which were milled on powder of certain granularity and sequentially pressed in manual press. Tablets made of mixture of powder and binding pitch was also prepared in manual press. Structural parameters of obtained carbon planar discs were determined by mercury and helium porosimetry. Structural properties of these discs in dependence on press temperature and presence of binder were objectives of these experiments. Surfaces of these discs were visualized by scanning electron microscopy (SEM). By reason that results of analyses showed high porosity and narrow distribution of macropores were those discs used as a background for synthetic membrane layer based on titanosilicates. Temperature, pH and composition of synthesis solution along with the number of synthesis cycles were observed during the synthesis of deposition layer. Obtained synthetic layers on carbon supports were also visualized by SEM.

SESSION 41 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 4

41-1 The Dry Carbonate Process: Carbon Dioxide Recovery from Power Plant Flue Gas Thomas Nelson, David Green, Luke Coleman, Raghubir Gupta, RTI International; Jose Figueroa, DOE-NETL, USA The reversible reaction between sodium carbonate, carbon dioxide (CO2), and water vapor to form sodium bicarbonate can be used in a thermal-swing process to recover concentrated CO2 from power plant flue gas for sequestration or reuse. A process based on this reaction - RTIs Dry Carbonate Process - has been developed and is targeted as a retrofit CO2 capture technology for existing coal-fired power plants. This presentation will include the field testing of a prototype Dry Carbonate Process. Field test experiments were conducted using natural gas-derived and coal-derived flue gases from a combustor at the U.S. Environmental Protection Agencys research facility in Research Triangle Park, NC. The prototype unit was capable of achieving greater than 90% removal of CO2 during testing. Contaminants in the flue gas were shown to have no adverse effect on sorbent performance and the sorbent showed little or no physical attrition over hundreds of cycles. The unit was exposed to flue gas for over 230 hours and on-line experimentation lead to the identification of the most promising process conditions. An economic evaluation showed that the Dry Carbonate Process potentially has significant cost advantages over existing CO2 capture technologies. Currently, modifications to the process design are being made and additional R&D is being conducted leading up to the construction of a pilot-scale unit capable of capturing at least 1 ton of CO2 per day. This presentation will also include the results of the additional process design R&D and will highlight the activities being carried out in preparation for pilot-scale testing. This work was accomplished under a cooperative agreement with the U.S. Department of Energys National Energy Technology Laboratory (DOE/NETL). The project is part of DOE/NETLs Carbon Sequestration Program which seeks to develop technologies capable of 90% CO2 removal with a potential to limit the power generation impact to a less than 20% increase in cost of electricity. 41-2 Results from 20 Pound per Hour CO2 Capture Facility using Solid Sorbents William Wang, Liang-Shih Fan, Songgeng Li, Shwetha Ramkumar, Danny Wong, Mahesh Iyer, The Ohio State University; Robert M. Statnick, Clear Skies Consulting; Bartev Sakadjian, Babcock & Wilcox, USA A growing concern over anthropogenic carbon dioxide (CO2) emissions and its effect on global climate change has gained increasing attention. A significant portion, 39% of the worlds CO2 emissions, is derived from coal-combustion power plants. In an effort to curtail the negative effects of CO2 emissions on the environment, The Ohio State University has partnered with American Electric Power (AEP), Babcock & Wilcox, Clear Skies Consulting, CONSOL Energy, Duke Energy, and Specialty Minerals to further develop and test a novel process, known as the Carbonation-Calcination Reaction (CCR) process. The CCR process has the capability of removing CO2 from a coal-combustion flue gas stream. As an added benefit, the CCR process simultaneously removes sulfur dioxide. The CCR process utilizes a solid sorbent, in the form of an alkali metal oxide (CaO), in a high-temperature reaction to capture CO2 from a flue gas stream to produce a metal carbonate (CaCO3). The subsequent calcination reaction regenerates the metal carbonate into the metal oxide while also producing a pure stream of CO2, which is sequestrable. Several sources of calcium oxide have been tested from small-scale Thermogravimetric Analyzer experiments through sub-pilot scale experiments. At The Ohio State University, a 20 pound per hour stoker combusts bituminous, Ohio coal to generate the flue gas stream. Several sorbents have been tested in this unit.

SESSION 42 COAL UTILIZATION BY-PRODUCTS 1

42-1 Characterization of Fly-Ash Generated During Co-Firing of Lignite and Biomass for Use as Mineral Admixture with Ordinary Portland Cement Nabajyoti Saikia, Andrea Johnson, Stephen Kinrade, Lionel Catalan, Lakehead University, CANADA Fly-ash produced from the co-firing of coal and biomass (CBFA) was evaluated in comparison with conventional coal fly-ash (CFA) as a mineral admixture in ordinary Portland cement (OPC). CFA was obtained from combustion of pure lignite, and CBFA from mixtures of either 16:84 (mass ratio) sawmill waste-wood pellets and lignite or 5:95 grainscreening pellets and lignite. The properties assessed included: chemical and mineralogical composition; particle size distribution; hydration of CFA/CBFA-amended OPC; and compressive strength of amended mortars at different curing times. There was no significant difference in the chemical and mineralogical composition of CFA and CBFA (although CFA had a slightly higher proportion of fine particles). In addition to the dominant amorphous silicate phases, each contained quartz and a small amount of periclase. Both fly-ashes exhibited pozzolanic activity

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when added to OPC mortar (20 wt%), resulting in similar non-evaporable water content and compressive strength after 28 days hydration. Portlandite, calcium aluminate hydrate, calcite and/or calcium silicate hydrate and ettringite are the major early hydration products formed in cement pastes. Since the compressive strength of these amended mortars exceeded 75% that of ash-free control, both types of fly ash met ASTM requirement C 618 for mineral admixtures. 42-2 Strength Development, Durability, and Micromineralogical Analysis of Cement Mortar Samples Containing Fly-Ash from Co-Firing of Wood Pellets with Lignite Andrea Johnson, Nabajyoti Saikia, Lionel Catalan, Stephen Kinrade, Lakehead University, CANADA Co-firing coal with renewable/waste biomass for power generation has potential to mitigate atmospheric discharge of pollutants (e.g., SO2) and green-house gases. Widespread application of this technology is impeded, however, by current standards which prohibit coal-biomass fly-ash (CBFA) as a partial substitute for portland cement in concrete. We therefore undertook a study of compressive strength development and durability to freezing and thawing as well as to chemical attack of mortar containing portland cement, which was substituted up to 40 wt% with either conventional coal flyash (CFA) or CBFA obtained from combustion, respectively, of undiluted lignite or a 15:85 (mass ratio) wood pellet/lignite mixture at the Atikokan (Ontario) thermoelectric power station. Additionally, we investigated the micromineralogy (using scanning electron microscopy/energy dispersive spectrometry) of mortars produced with both types of fly-ash. 42-3 Utilization of Ultra Fine Fraction of Coal Combustion Fly Ash as Polymer Composites Zhe Lu, Tom Robl, Brock Marrs, Center for Applied Energy Research, University of Kentucky, USA Minerals are often used as a filler to form composites with polymer to improve physical characteristics and reduce raw material costs. Ultra-fine fly ash (UFA) with a mean particle size of less than 5 microns was obtained via the hydraulic classification of raw fly ash. The material was calcined to remove the residue carbon, and then added to a range of polyurethane foam densities (4 to 16 lb/ft3) in various loadings. The filled foam composites were tested for density, apparent porosity, and mechanical properties. The mechanical properties of the UFA urethane composites showed greatly increased modulus, compressive strength and toughness over unfilled foams. Compressive strength increased by up to a factor of almost 4. The modulus and compressive strength increased as a function of the UFA loading up to a level of 60 weight % ash and then decreased. The overall porosity of the composite was not greatly affected by the filler and was similar to the unfilled control. The increased strength and stiffness of the UFA urethane composites suggest that these materials may have applications where a combination of strength and light weight are desirable. 42-4 National Network of Research Studies to Promote Flue Gas Desulfurization (Fgd) Gypsum Use in Agriculture David Kost, Warren Dick, The Ohio State University, USA A national network of research sites has been established to investigate beneficial agricultural uses of flue gas desulfurization (FGD) products, especially FGD gypsum. This network was titled National Research and Demonstration Network of FGD Products in Agriculture and is hereafter referred to as the network. Field experiments in the network are supported by utilities that currently produce or will produce FGD gypsum and are interested in regional agricultural uses of the product. The experiments are designed according to a uniform protocol that includes a comparison of FGD gypsum with commercially-available gypsum, and involve at least two years of crop yield and other data collection. Environmental effects of gypsum applications are monitored by extensive chemical characterization of the gypsums, pre- and posttreatment soils, crop grain or other biomass, and shallow ground (vadose) water. The first research was begun in North Dakota in 2007. Additional studies are being established in 2008 in New Mexico, Indiana, Arkansas, Alabama, and Ohio. These studies are evaluating the use of gypsum to (1) ameliorate sodium-affected soils, (2) reduce soil crusting that affects seedling establishment, water runoff, and erosion, (3) reduce available phosphorus in surface soils receiving poultry litter amendment, and (4) ameliorate subsoil acidity. The data obtained from the various experiments are made available to all participants in the network to help promote sound agricultural and environmental use of FGD gypsum in the United States.

42-5 Fly Ash- Nonplastic Component for Production of the Composite Bricks Maria Kusnierova, Mria Prakov, Slovak Academy of Sciences, SLOVAKIA; Peter Fecko, VSB-Technical University of Ostrava, CZECH REPUBLIC The paper deals with the influence of added black-coal fly ash, slag and carbon black amounting to 5-15% on the compactness, bulk density, absorption capacity, capillarity and thermal resistance of newly made composite bricks. The results confirmed the potential utilization of certain power waste amounting up to 10% in the production of composite bricks with comparable and individually even better qualitative parameters.

SESSION 43 GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES 2

43-1 ITM Oxygen for the Real World: Pilot Scale Testing and Beyond Lori A. Vratsanos, Phillip A. Armstrong, Richard P. Underwood, VanEric E. Stein, E.P. (Ted) Foster, Air Products and Chemicals, Inc., USA A team led by Air Products and Chemicals in partnership with the U.S. Department of Energy is developing a novel air separation technology. The method uses high temperature ceramic membranes which selectively transport oxygen ions to produce high purity oxygen. A coproduct of the process is an energy-rich nonpermeate stream that can be used to produce power and steam. This technology is well suited for advanced power generation processes such as IGCC which require oxygen as a feedstock. Synergy with traditional energy intensive industrial processes which require oxygen and with CO2 capture applications is expected. ITM Oxygen technology has entered the final phase of a three-phase development effort. During Phases I and II, the ITM Oxygen team established the feasibility of the ceramic membrane approach and designed and built commercial-scale membrane modules. The team has demonstrated expected performance of commercial-scale modules in a prototype facility that produces up to 5 tons-per-day of oxygen. In Phase III, a membrane separator will be integrated with a turbine to produce power and up to 150 tons-per-day (TPD) of oxygen in the 2009-10 timeframe. Data from the 150-TPD plant test will provide the design basis for a much larger plant that could supply up to 2500 TPD scale. This paper will present an overview and update of the ITM Oxygen development effort, including testing of commercial-scale ceramic modules, developing integration schemes with gas turbines and energy-intensive industrial processes, and process economic analyses. A commercialization timeline will be discussed. 43-2 PWR Dry Feed System Development Status Kenneth M. Sprouse, David R. Matthews, Timothy Saunders, Pratt & Whitney Rocketdyne, Inc.; Greg F. Weber, University of North Dakota, USA Development of the Pratt & Whitney Rocketdyne (PWR) dry pump and feed system continues at PWR and the University of North Dakotas (UNDs) Energy & Environmental Research Center. This system is rated for 1,200-psia pump discharge gas pressures; 1,000-psia gasifier operating pressures; and 400-tons/day coal flow rates. Dry coal (pulverized to standard industrial grind) is fed throughout the pump and feed system under ultra-dense phase flow conditions -- i.e., void fractions below 55 vol% -- and delivered to the gasifier through a rapid-mix multi-element injector. The flow split non-uniformity from the multi-element injector was found to be a direct function of the injectors Bingham stress number. An assessment is provided for the effect of flow splitter non-uniformity on cold-gas and carbon-conversion efficiencies of a PWR entrained-flow compact gasifier. Preliminary design of the systems dry solids feed pump was completed in September 2007 followed by the start of a subscale test effort for key pump components at bulk solids stresses (compression and shear) in excess of 500-psi. These results will be incorporated into the pumps detail design currently scheduled for completion in CY2009. Pump testing at EERC is now scheduled to begin in CY2010. 43-3 Temperature Measurement in Gasification Processes Thomas Wolf, Emerson Process Management, GERMANY; Trent Riggs, Emerson Process Management, USA Globally gasification processes have gone through a renaissance, which is driven by rising crude oil prices, clean fuels Initiatives and other environmental drivers such as the capture of CO2. This evolving technology requires innovative instrumentation to meet the primary business drivers of process availability and safety. The enhanced design of high temperature thermocouples based on sapphire technology increased the runtime of the process by a factor of 4-5 and has significantly increased the safety due

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to triple seals. This has led to considerable operational savings in the maintenance and reduced process downtime. Problem/Challenges addressed Following Challenges have been defined: 1. Low Process Availability Contamination by poisoning gases of the high temperature thermocouple leads to failure of the temperature sensors after short time (up to 3 months) and leads to inability to control the gasification process. 2. Fugitive Emissions Current practice requires complicated and expensive purging to eliminate fugitive emissions. Solution: Use of gas tight ceramic material -in this case sapphire was chosen to protect the thermocouple wires from hydrogen contamination at process temperatures of up to 1800C. In order to practically eliminate the risk of fugitive emissions during operation due to the break of the temperature sensor, 2 pressure tight seals have been implemented. Primary seal being the pass through connection to the connection Head and secondary seal being the pass through to the connection terminals. Results/Benefits: Process availability was significantly increased as the life time of the high temperature thermocouple of approx. 15 month vs. approx. 4 month for a standard high temperature thermocouple. Risk for fugitive emissions due to thermocouple failure has been eliminated. 43-4 Extended Field Testing of an Acoustic Sensor for Gas Temperature Measurement in Coal Gasifiers Peter Ariessohn, Noel Fitzgerald, Enertechnix, Inc.; Kamalendu Das, DOENETL, USA Under contract DE-FC26-03NT41617 from the Department of Energy, and with assistance from ConocoPhillips and SG Solutions, Inc., Enertechnix, Inc. has developed a novel acoustic gas temperature sensor for use in coal gasifiers. This sensor has been tested successfully at the Wabash River coal gasification plant and an extended test is currently in progress. Since 1989 the U.S. Department of Energy has supported development of advanced coal gasification technology. However, a continuing challenge for entrained flow gasifiers is the tradeoff between achieving high carbon conversion which requires high internal gas temperatures, and degradation of the refractory which is exacerbated by those high temperatures. Reliably maintaining the optimum gas temperature is hindered by the lack of a reliable technology for measuring gas temperature. For this reason, the Department of Energy has funded several research projects to develop more robust and reliable temperature measurement approaches for use in coal gasifiers. Enertechnix has developed a line of acoustic gas temperature sensors for use in coalfired electric utility boilers, kraft recovery boilers, cement kilns and petrochemical process heaters. Acoustic pyrometry provides several significant advantages for gas temperature measurement in hostile process environments. First, it is non-intrusive so measurement component survival is not a serious problem. Second, it provides a lineof-sight average temperature rather than just a point measurement so the measured temperature is more representative of the process conditions than a thermocouple measurement. Third, unlike radiation pyrometers, the measured temperature is a linear average over the full path rather than a complicated function of gas temperature and the exponential Beers law. This permits tomographic reconstruction of the acoustic measurements on multiple paths to produce detailed 2-dimensional temperature maps. Therefore, acoustic pyrometry is an attractive choice for measuring gas temperature inside a coal gasifier. The objectives of this project are to adapt acoustic pyrometer technology for use inside a coal gasifier, to develop a prototype sensor, and to demonstrate its performance through testing in a commercial gasifier. During the course of this project, we have developed and tested a novel sound generation method suitable for use in a high pressure process. We evaluated the influence of gas composition variability, particle loading and slagging and developed methods to address these issues. A series of prototype sensors were fabricated and tested in the lab, and in 2006 a field prototype was fabricated and tested in the lab and at Wabash River. Those tests demonstrated the feasibility of the measurement technique in a commercial gasification plant and showed the ability of the sensor to make accurate gas temperature measurements inside the gasifier during normal operation. In 2007 upgrades to the hardware were implemented and in March, 2008 a long term test was initiated at the Wabash River plant and, once again, accurate gas temperature measurements were obtained. However, an incident early in the testing resulting from component failure combined with inadequate procedures caused a delay of several months. Following this incident, substantial improvements in the hardware, software, procedures, documentation and training were implemented and the unit was reinstalled on the gasifier in the late summer. Testing has now resumed and the sensor is operating properly. This paper reports on the theory and practical considerations affecting acoustic pyrometry in gasifiers, the operating characteristics of our prototype sensor, the lessons learned from the incident in March, and the results of testing to date at Wabash River.

43-5 Generic Process Design and Control Strategies Used to Develop a Dynamic Model and Training Software for an IGCC Plant with CO2 Sequestration Graham T. Provost, Herman P. Stone, Michael McClintock, Fossil Consulting Services, Inc.; Michael R. Erbes, Enginomix, LLC; Stephen E. Zitney, DOENETL; Richard Turton, West Virginia University; Jeffrey N. Phillips, Merrill Quintrell, Jose Marasigan, EPRI, USA To meet the growing demand for education and experience with the analysis, operation, and control of commercial-scale Integrated Gasification Combined Cycle (IGCC) plants, the Department of Energys (DOE) National Energy Technology Laboratory (NETL) is leading a collaborative R&D project with participants from government, academia, and industry. One of the goals of this project is to develop a generic, full-scope, real-time generic IGCC dynamic plant simulator for use in establishing a world-class research and training center, as well as to promote and demonstrate the technology to power industry personnel. The NETL IGCC dynamic plant simulator will combine for the first time a process/gasification simulator and a power/combined-cycle simulator together in a single dynamic simulation framework for use in training applications as well as engineering studies. As envisioned, the simulator will have the following features and capabilities: A high-fidelity, real-time, dynamic model of process-side (gasification and gas cleaning with CO2 capture) and power-block-side (combined cycle) for a generic IGCC plant fueled by coal and/or petroleum coke Full-scope training simulator capabilities including startup, shutdown, load following and shedding, response to fuel and ambient condition variations, control strategy analysis (turbine vs. gasifier lead, etc.), representative malfunctions/trips, alarms, scenarios, trending, snapshots, data historian, and trainee performance monitoring The ability to enhance and modify the plant model to facilitate studies of changes in plant configuration and equipment and to support future R&D efforts To support this effort, process descriptions and control strategies were developed for key sections of the plant as part of the detailed functional specification, which will form the basis of the simulator development. These plant sections include: Slurry Preparation Air Separation Unit Gasifiers Syngas Scrubbers Shift Reactors Gas Cooling, Medium Pressure (MP) and Low Pressure (LP) Steam Generation, and Knockout Sour Water Stripper Mercury Removal Selexol Acid Gas Removal System CO2 Compression Syngas Reheat and Expansion Claus Plant Hydrogenation Reactor and Gas Cooler Combustion Turbine (CT)-Generator Assemblies Heat Recovery Steam Generators (HRSGs) and Steam Turbine (ST)-Generator In this paper, process descriptions, control strategies, and Process & Instrumentation Diagram (P&ID) drawings for key sections of the generic IGCC plant are presented, along with discussions of some of the operating procedures and representative faults that the simulator will cover. Some of the intended future applications for the simulator are discussed, including plant operation and control demonstrations as well as education and training services such as IGCC familiarization courses.

SESSION 44 GASIFICATION TECHNOLOGIES: SYNTHESIS GAS CLEANING 2

44-1 Novel Method for Synthesis Gas Desulfurization Gregory Krumdick, Edward Daniels, Jianhong Yang, Argonne National Laboratory, USA; Boyd Davis, Alain Roy, Ian Glaw, Kingston Process Metallurgy, CANADA Research at Argonne National Laboratory and Kingston Process Metallurgy has demonstrated that a novel process incorporating molten copper to convert the H2S to SO2 while reforming contaminants such as ammonia and hydrocarbons to their elemental constituents is technically feasible and offers the potential for significant capital cost reduction and efficiency improvement relative to conventional gas cleanup technology. In this process, a series of conventional gas clean up unit operations are eliminated from the process including particulate scrubber, ammonia scrubber, amine stripper, amine regeneration, Claus plant and SCOT units. The H2 in the H2S contributes to the overall energy balance of the system, and the sulfur is removed from the system as SO2. In this system, the sulfur would be scrubbed using conventional flue gas desulfurization technology. This technology should be highly efficient

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because the SO2 is isolated from all other process gas streams upon regeneration of the molten copper; thus the SO2 stream is essentially 100% if using pure O2. Because the copper process offers the opportunity to completely change conventional gas-clean up from coal gasification, the capital cost reduction opportunity and efficiency improvement that results from this process for IGCC applications would also be directly applicable to any coal gasification process including indirect liquefaction for production of fuels and also for production of H2 from coal. 44-2 Metal-Based Adsorbents for Regenerable Deep Desulfurization of Warm Syngas Liyu Li, David L King, Jun Liu, Kake Zhu, Yong Wang, Pacific Northwest National Laboratory, USA Gasification of coal or biomass to syngas followed by catalytic synthesis of liquid hydrocarbons or oxygenates provides a feasible strategy to meet the increasing demand for transportation fuels. Syngas generated by the gasification of biomass or coal contains many impurities. Among the most important are the sulfur-containing molecules, as they are poisons for catalysts employed in subsequent conversion reactions. Solvent-based processes operated at ambient or lower temperature are currently employed to achieve the necessary sub-ppm sulfur levels. These processes are costly and energy intensive, since the syngas must be cooled to the solvent temperature and then reheated to the synthesis temperature. Removal of sulfur gases at temperatures greater than 250C will improve the energy efficiency and lower the process cost. Warm gas clean-up technologies have been developed, typically based on zinc oxide or modified zinc oxide, which can regenerably reduce sulfur gases to a few ppm level. However, such materials are inadequate for liquid fuel synthesis application, which requires sulfur concentrations in the syngas to be below 50 ppb to minimize the poisoning of synthesis catalysts. Catalyst poisoning by sulfur gases occurs through chemisorption of sulfur on the metal particle surfaces. The adverse effects of sulfur are well known in methanation, steam reforming, Fischer-Tropsch, and other syntheses reactions. This strong surface adsorption phenomenon has been exploited in the design of sacrificial metal-based guard beds, which can remove sulfur to the ppb levels. In order to develop regenerable adsorbents, however, several items need to be addressed. First, the metal needs to be finely divided to maximize the surface area, and therefore the adsorption capacity. The preparation method chosen must be simple and scalable. Second, the small metal particle size must be maintained--agglomeration and sintering must be avoided during both operation and regeneration. Third, the adsorbents must be regenerable using available gas streams and cost effective procedures. By trapping Ni and Ni-Cu alloy nanoparticles in three dimensional mesostructured silica SBA-16, we have developed a class of metal-based adsorbents that can remove sulfur from warm syngas to less than 50 ppb levels based on sulfur chemisorption. We have also discovered that a sequential oxidation-reduction treatment can effectively regenerate the sulfur-loaded adsorbent. Previously only sacrificial metal-based guard beds were available. For the first time, a sulfur-loaded metal-based adsorbent has been efficiently regenerated. This solid adsorbent-based approach may provide economic advantages compared with more conventional liquid adsorbents, which carry an economic penalty associated with cooling and reheating the syngas. With practical coal-based syngas that may contain several thousand ppm of sulfur, these adsorbents would need to used in combination with higher capacity adsorbents such as zinc oxide. The mesoporous-based adsorbents would provide the sub-ppm polishing capability that cannot be provided by zinc oxide alone. In addition to providing a practical approach to sulfur deep removal from warm syngas, the same concept may also find application for removal of other trace level contaminants in processes involving metal catalysts that are susceptible to poisoning. This work also provides new insights on the stability of nanoparticles within controlled mesostructures. Metal and metal oxide nanoparticles supported on high surface area materials are widely used in industry, but preventing particle agglomeration and sintering has remained a great challenge. Our study suggests that the stability and activity of nanoparticles may be substantially enhanced by judicial choice of the pore architecture that confines them. 44-3 Regenerable Multi-functional Sorbent Development for Sulfur and Chloride Removal from Coal-Derived Synthesis Gas Ranjani Siriwardane, Abbie Layne, DOE-NETL; Thomas Simonyi, Parsons, Inc., USA A large number of components in coal form corrosive and toxic compounds during coal gasification processes. DOEs NETL aims to reduce contaminants to parts per billion in order to utilize gasification gas streams in fuel cell applications. Even more stringent requirements are expected if the fuel is to be utilized in chemical production applications. Future emphasis of the NETL coal gasification/cleanup program is to develop multifunctional sorbents to remove multiple impurities in order to minimize the steps involved in the cleanup systems. To accomplish this goal, a regenerable sorbent capable of removing both HCl and H2S was developed. The results of the TGA tests

and bench scale fixed bed flow reactor tests conducted with the sorbent to evaluate the feasibility of both H2S and HCl sorption will be discussed in this paper. 44-4 Sorbents for Removing Trace Metal Contaminants from Coal-Derived Synthesis Gas Gokhan Alptekin, Margarita Dubovik, Bob Amalfitano, TDA Research, Inc., USA Gasifiers convert coal into synthesis gas feed streams that can be used in advanced power cycles to generate electricity and in the production of a wide variety of chemicals. However, the coal-derived synthesis gas contains a myriad of trace contaminants that cannot be released to the environment if the syngas is burned to generate power or may poison the catalysts used in the downstream chemical manufacturing processes. Therefore, removal of these contaminants is critical for the widespread and environmentally-friendly utilization of coal. TDA Research Inc. (TDA) is developing a sorbent-based system that can reduce the concentration of the trace metal contaminants (i.e., mercury, arsenic, selenium and cadmium) to less than parts per billion levels in the coal-derived synthesis gas at elevated temperatures (260C). Previously, in series bench-scale experiments, we first showed that the sorbent is capable of removing Hg, As and Se separately using simulated synthesis gas. The sorbent performance was also evaluated for combined removal of these contaminants. The impact of using syngas from different types of gasifiers (primarily the effect of steam partial pressure) and the presence of sulfur (as hydrogen sulfide and carbonyl sulfide) on sorbent performance were also evaluated. Based on the successful results, the performance of a sorbent-based multi-contaminant removal system was evaluated using actual coal-derived synthesis gas. The demonstration tests were carried out at the University of North Dakota Energy Environmental Research Center. This paper discusses the results of our sorbent development efforts and field test. 45-5 Palladium Sorbents for High Temperature Capture of Mercury, Arsenic, Selenium, and Phosphorus from Fuel Gas Evan J. Granite, Lindsay Bombalski, Christina R. Myers, Dennis P. Stanko, Henry W. Pennline, DOE-NETL; Wilson Chu, Johnson Matthey, USA; Hugh Hamilton, Liz Rowsell, Stephen Poulston, Andrew Smith, Thomas Ilkenhans, Johnson Matthey Technology Centre, UNITED KINGDOM In gasification for power generation, the removal of mercury by sorbents at elevated temperatures enhances the high thermal efficiency of the integrated gasification combined cycle system. Unfortunately, most sorbents will display poor capacity for elemental mercury at elevated temperatures. Previous experience with sorbents in flue gas has allowed for judicious selection of potential high temperature candidate sorbents. The capacities of many sorbents for elemental mercury from nitrogen, as well as from different simulated fuel gases at temperatures from 400F - 700F, were determined. The simulated fuel gas compositions contain varying concentrations of mercury, arsine, hydrogen selenide, phosphine, carbon monoxide, hydrogen, carbon dioxide, moisture, and hydrogen sulfide. Palladium is an attractive sorbent candidate for the removal of mercury from fuel gases at elevated temperatures. In addition, recent results suggest that palladium has excellent potential for arsenic, selenium, and phosphorus capture from fuel gases, making it capable of multi-pollutant capture. A license agreement has been signed by the United States Department of Energy and Johnson Matthey for further development of the sorbents. Current results and future sorbent development for trace metal capture from fuel gases will be discussed.

SESSION 45 ENVIRONMENTAL CONTROL TECHNOLOGIES: NOx/SOx CONTROL STRATEGIES

45-1 Metal Impregnation of Activated Carbon Fiber for Catalyzed Hydrogen Sulfide Oxidation Jason D. Monnell, Huixing Li, Radislav D. Vidic, University of Pittsburgh; Mary Anne Alvin, DOE-NETL, USA The contribution of metal centers, metal oxides, and catalyst supports to the catalytic breakdown of hydrogen sulfide at a process temperature ~140C suitable for low temperature clean-up of IGCC produced syngas was investigated. Materials were exposed to a typical IGCC syngas that contains 4000 ppm H2S in a down-flow packedbed reactor and the tail gas was analyzed via mass spectroscopy. Metal-free activated carbon fibers and high purity alumina samples were used as supports and as baseline H2S catalysts and H2S adsorbent materials. Catalytic metals (La, Ce, V, and Cu) were impregnated onto these supports via insipient wetness at approximately 5% w/w. Native alumina samples have very little catalytic or adsorptive capacity whereas activated carbon fibers have catalytic and adsorptive capacities that are comparable to

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some of the metal impregnated materials. The increased capacities for activated carbons are attributable to the increased surface area and reactive chemical functional groups that are present on carbon surface when compared to native alumina. While differences in surface area were directly correlated with increased retention of sulfur species, the chemical composition of the sulfur on the material was directly affected by the impregnated metal. Copper-impregnated alumina produced tail-gases rich in SO2 relative to COS whereas vanadium-impregnated alumina produced tail-gases rich in COS. The fact that different metal impregnates lead to dramatically different products is notable since COS is a more undesirable by-product than SO2. More importantly, there is a different mechanism for the interaction between the metal center and the H2S molecule. It must be noted that this effect is transient and the long-term balance results in a 1:1 ratio of COS to SO2 in the tail-gas. The return to a 1:1 ratio from a single product observation may indicate that the metal center becomes overwhelmed / poisoned and the breakdown of H2S into the products is performed on the support regardless of the metal impregnate. This may not be the case with Cu, because when Cu is used with activated carbon fibers to treat H2S, the off-gases observed are H2S, COS, and SO2 at a steady state ratio of 3:1:1. This may be due to a surface hand-off that occurs between copper and the carbon that does not happen with other metals. While it does not produce an ideal off-gas, these Cu-impregnated carbon catalysts are the most promising of these materials and are a step towards an economical means for H2S cleanup materials. 45-2 Low-Cost ESP Discharge Electrode Hajrudin Pasic, Ohio University, USA Discharge electrodes are critical components in electrostatic precipitators (ESP). Developments in discharge electrode technologies have fostered evolution in ESPs, such as rigid discharge electrodes to which many sharpened spikes are attached to maximize corona production for improved ESP performance. However, due to the harsh and corrosive service environment these electrodes typically have to be made from expensive materials such as stainless steel, adding substantially to the overall cost of the electrodes. Here we propose low-cost polymer electrode whose design results in drastic decrease of electrodes cost, due to reduction in the production and material cost. In addition, light-weight design will further reduce installation costs due to reduction in structural support requirements. 45-3 Advanced Equipment Development for Wet Lime Fgd System Use, i.e. in Accessing, Transport and Slaking of Pebble Lime Feed Kevin Furnary, LEEP Holdings, LLC; William Ellison, Ellison Consultants, USA Contacting pebble lime supply with water in a controlled fashion can ensure uniform wetting of all, newly exposed, lime particle surface, this being critical in gaining completion of CaO hydration and in maximizing the reactive surface area afforded in use of the calcium hydroxide, slaker output. This paper will review the design, operation and performance of an industrial dynamic mixer developed and commercially used in Australia that fulfills this objective. Avoiding all fugitive dust formation, the system design provides for enclosed pneumatic conveying of pebble lime feed to the slaker from silo storage, the latter equipped with novel, near-silosurface, fluid atomization. Uniquely generated fluid dynamic shearing achieved in this unique mixer breaks up any dry solids clumps while providing fullest mixing of the lime and water in straight-through flow in the pipe-like, cylindrical, slaker vessel. The paper will detail the design and performance of such an installation at the Lilydale Water Treatment Plant in Western Australia employing a three inch diameter, mixer flow-path, this with intensely high, mass transfer rate operation producing 88,000 lbs per day of slaked lime. 45-4 Ammonia Nitrogen Removal from Coking Wastewater by Chemical Precipitation and Repeated Use of MAP Shizhuang Shi, Yuan Yuan, Qixiang Li, Hui Wang, Wuhan University of Science and Technology; Shuangqing Zhou, Wuhan International Trade University; Hongbing Chang, Wuhan Iron and Steel Group Corporation, CHINA The paper introduces a technology to remove ammonia-nitrogen from coking wastewater by using MAP method. The ammonia-nitrogen removal efficiency under different rations of reagents, pH and operation conditions was studied. Under the suitable condition, purely crystal MAP were obtained, and the removal rate of ammonium-nitrogen is over 98%. The residues of magnesium ammonium phosphate (MAP) decomposed by heating under alkali conditions were repeatedly used as the only sources of phosphate and magnesium for the removal of high ammonium concentration from wastewater. Up to 93% of ammonium-nitrogen in wastewater could be removed by using residues decomposed under the following conditions: NH4+:OH- molar ratio= 1:1, temperature 100C, heating time 3 hrs. Chemical costs were greatly reduced and the ammonia in wastewaters was reclaimed.

SESSION 46 CHEMICALS, MATERIALS, AND OTHER NON-FUEL USES OF COAL 1

46-1 Optimization of Microwave-Assisted Extraction Shenfu Coal and Analysis of Extract and Residue Hong Chen, Jianwei Li, Hua Wang, Lingmei Ge, Xian University of Science and Technology, CHINA Coals consist of some simple molecules trapped in an organic matrix. Many of the simple compounds can be extracted by solvents. Soxhlet technique has been widely used for extracting organic compounds. How to decrease the harm to the environment when exploiting and utilizing coal, how to get clean resource or chemical products from such a traditional unclean resource, utilizing low-cost and an environmentfriendly microwave-assisted extraction technology becomes a new approach and field in comprehensive utilization of coal. In order to investigate extraction yields and chemical composition of extract, extraction with acetone was conducted for typical Chinese coal-Shenfu coal under microwave-assisted extraction (MAE) and acetoneextractable fraction was analyzed with GC/MS. The number of organic compounds (OCs) identified in acetone-extractable fraction was fifty-two. The organic compounds obtained by extraction contained normal alkanes, branched alkanes, cyclanes, nonsubstituted arenes, substituted arenes, organooxygens and organonitrogens. Carbon-13 nuclear magnetic resonance (NMR) spectra, which provide direct measurements of the chemical structure of organic matter, have been obtained for Shenfu coal (daf) and its residue of acetone extraction. Being converted into numerical parameters, the spectra show differences related to Shenfu coal(daf) and its residue of acetone extraction. Three NMR parametersfa,Ha,Xb are examined, which indicates the difference in macromolecule structure between Shenfu coal(daf) and its residue. 46-2 Extraction and Upgrading of Brown Coal through Treatment in Solvent at High Temperature Kouichi Miura, Ryuichi Ashida, Satoshi Umemoto, Akihiro Sakajo, Kyoto University; Koji Saito, Kenji Kato, Nippon Steel Corporation, JAPAN Treatment of brown coal in a solvent (1-methylnaphthalene) at temperatures lower than 350C is proposed as an effective method to fractionate brown coal into several upgraded fractions having different chemical compositions and structures. When an Australian brown coal, Loy Yang (C%=66.9, O%=27.7), was treated for 3 h at 350C in a batch extractor, it was converted into three upgraded fractions: the fraction soluble in solvent even at room temperature (Soluble; Yield:Y=0.218, average molecular weight: MW,a=330, C%=82.3, O%=9.8), the fraction soluble at 350C but insoluble at room temperature (Deposit; Y=0.105, MW,a=500, C%=77.0, O%=16.8), and the solvent insoluble fraction (UC; Y=0.527, MW,a=800, C%=79.6, O%=15.2). The rest of the brown coal was converted into either CO2 or H2O. This means that 80% of the brown coal was converted into high carbon and low oxygen content fractions having rather uniform molecular weight distribution under mild conversion. The fractions had properties significantly different from those of the raw coal, suggesting their application to various purposes. The proposed method will surely be one of novel and effective brown coal utilization methods. 46-3 Solvent Extracting Aromatic Hydrocarbons from Coal-Derived Oil Dexiang Zhang, Guolong Wang, Jue Huang, East China University of Science and Technology, CHINA Some solvents, including sulfolane, dimethyl sulfoxide and furfural, were used to extract aromatics from coal-derived oil. The coal-derived oil and solvent were put into extraction device according to different weight ratio and temperature. The group composition of the extracted oil was determined by column chromatography (Refer ASTM 2007, 2549-81). The results show that recovery efficiency and purity of aromatics are correlated to the kind of solvent, the weight ratio of solvent to oil and temperature. When the temperature and solvent/oil ratio are fixed, the selectivity coefficients of sulfolane and dimethyl sulfoxide are higher than that of the furfural while the furfural has the strongest dissolution ability. Contrasting to the other two solvents, furfural is preponderant in extracting aromatics from coal-derived oil. At 303 K for furfural, extraction recovery efficiency of aromatics increases with the increasing solvent/oil ratio. That is 50.64% and 97.29% when the weight ratio of solvent to oil equals to 1 and 9, respectively. But purity of extracted aromatics decreases with the rise of solvent/oil ratio. The purity of aromatics is 74.09% and 86.25% when the weight ratio of solvent to oil equals to 9 and 3, respectively. Considering both recovery efficiency and the purity, the best ratio of solvent to oil is 3. The effects of extracting temperature and water adding to solvent on aromatics extraction were investigated also.

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46-4 Co-Pyrolysis of Brown Coal Upgraded under Hydrothermal Condition and Plastic Wax Ryuichi Ashida, Monthicha Pattatapanusak, Kouichi Miura, Kyoto University; Koji Saito, Kenji Kato, Nippon Steel Corporation, JAPAN We have recently presented a co-pyrolysis process of hydrothermally upgraded brown coal and waxes prepared from plastics. This process intends to upgrade further the brown coal upgraded under hydrothermal condition utilizing interaction with waste plastics during the co-pyrolysis. Char and gas yields increased respectively by 13.2% and 6.0% for co-pyrolysis conducted at a rapid heating rate at 1040C when compared with the yields calculated assuming independent pyrolysis of the coal and the wax. Char and gas yields increased respectively by 15.0% and 6.7% even for co-pyrolysis conducted at a slow heating rate at 900C. Large increase in the yield of oxygencontaining inorganic gases suggested the further upgrading of the coal during the copyrolysis. On the other hand, no or little changes in the product yields were found when the raw coal was co-pyrolyzed with the wax. In this work co-pyrolysis behavior was examined using a residual coal obtained through high temperature solvent extraction of a bituminous coal as one of the ways of utilizing the residual coal. Significant increase in the char and gas yields was found for the co-pyrolysis of the residual coal and wax. To examine the co-pyrolysis mechanism, the wax supported on porous materials was pyrolyzed. Porous materials were used to eliminate chemical interactions between the wax and the coal leaving only physical effects. Rapid pyrolysis of wax in the pore of the porous materials produced more char and hydrocarbon gases than the rapid pyrolysis of wax in a bulk phase, indicating that physical effect might be involved in the rapid co-pyrolysis process as well as chemical interactions. For the slow pyrolysis, on the other hand, char was not formed at all for all the porous materials, suggesting that only chemical interaction might be involved for the slow co-pyrolysis, or that an attractive force between the wall of coals pores and the wax might be so strong that the attractive force could contribute to retaining the wax in the pore of the coal during the co-pyrolysis even under the slow heating and hence cause the chemical interactions.

flue gas in a well-mixed reactor. During the semi-batch tests, the solution was cycled between absorption and regeneration steps to measure the carrying capacity of the solution at various initial ammonia concentrations and temperatures. The continuous tests combined the absorption of carbon dioxide from a simulated gas and a thermal regeneration step to liberate a concentrated stream of carbon dioxide from the solution. Ammonia losses were measured and made up as an input to the absorber. The parameters that were studied included absorber temperature, regenerator temperature, initial NH3 concentration, simulated flue gas flow rate, liquid solvent inventory in the flow system, and height of the packed-bed absorber. Titrimetric methods were used to determine the amount of ammonium hydroxide, ammonium carbonate, and ammonium bicarbonate in the solution at appropriate locations and times. Results from the various testing systems will be discussed with respect to the implications that these results have on a scrubbing process scheme. 47-3 Novel Carbon Dioxide Separation Using High Temperature Direct FuelCell Technology for Carbon Sequestration Hossein Ghezel-Ayagh, Bob Sanderson, Dilip Patel, Sven Tobias Junker, Stephen Jolly, Carl Willman, FuelCell Energy, Inc., USA Given the United States heavy reliance on fossil fuel as an energy source, the reduction of carbon dioxide released to the environment poses both technical and economic challenges to the available sequestration technologies. In response to this growing environmental concern, FuelCell Energy (FCE) has developed novel system concepts for separation of carbon dioxide from greenhouse gas (GHG) emission sources using Direct FuelCell (DFC) technologies. For carbon dioxide separation, the DFC is modified to operate similar to an electrochemical membrane, whereas carbon dioxide is separated from GHG in the cathode and is transported to the CO2 enriched stream at the anode exhaust. The unique chemistry of carbonate fuel cell offers an innovative approach for separation of carbon dioxide from greenhouse gases (GHG). The carbonate fuel cell system also produces electric power at high efficiencies. The simultaneous generation of power and CO2 capture suggests an attractive scenario for re-powering the existing coal-fueled power plants. Development of this system is concurrent with emergence of DFC technology for generation of electric power from fossil fuels. DFC is based on carbonate fuel cell featuring internal reforming. This technology has been deployed in MW-scale power plants and is readily available as a manufactured product. Preliminary design studies have indicated that DFC based carbon dioxide separation systems are suitable for many types of coal-based power plants, from the existing PC to the future IGCC. The flue gases from PC and atmospheric circulating fluidized bed (ACFB) power plants are somewhat lean in oxygen, one of the reactants required at fuel cell cathode, for proper operation of DFC. Conditioning of the flue gas, therefore, included blending it with supplementary air before feed to the fuel cell. The basic system design has been based on the fuel cell performance measured in the laboratory scale testing that demonstrated the required minimum 90% CO2 separation. The tests were conducted using simulated clean flue gas from PC power plant. In one of the system concepts, CO2-containing flue gas from coal-fired, combustionbased power plants, such as the exhaust from a pulverized coal (PC) power plant, is utilized as oxidant for the DFC cathode. The concepts key feature is that the DFC utilizes the CO2 of the flue gas as a reactant for the electrochemical reaction to produce power, while synergistically transferring CO2 from the flue gas to the anode exhaust stream. In contrast to other carbon sequestration technologies, which consume power, the DFC-based system concept efficiently generates electricity as either a source of revenue or supply to the on-site power demand. The concept is suitable for capturing 90% or more of carbon dioxide from a wide-range of industrial CO2-containing streams as well as power plant flue gases. Basic system and economic analysis for the DFC-based CO2 separation system, estimating the increase in cost of electricity (COE) of a PC power plant retrofitted with the CO2 separation and capture system has indicated that the mature commercial DFC CO2 separation and capture systems have the potential for achieving the Carbon Sequestration Program goal for post-combustion CO2 capture (2012 goal of < 20% increase in COE). 47-4 Oxyfuel Combustion Using CFBC Some Early Lessons Ben Anthony, L. Jia, Y. Tan, CANMET Energy Technology Centre-Ottawa (CETC-O), Natural Resources Canada, CANADA Oxyfuel FBC has been examined in a 100 kW pilot plant operating with flue gas cooling. The results strongly support the view that this technology offers all of the advantages of air-fired FBC, with one possible exception. Emissions such as CO or NOx are lower or comparable to air firing, and it is possible to switch from air firing to oxy-firing easily, with oxygen concentrations as high as 60-70%, and flue gas recycle levels of 50-60%. Only sulphation is poorer, which is not in good agreement with other studies, and the reasons for this discrepancy need further exploration. However, longer tests have confirmed these findings with two coals and a petroleum coke. It also appears that changing from direct to indirect sulphation with the petroleum coke improves the sulphation, although a similar effect could not be confirmed with coal.

SESSION 47 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 5

47-1 Evaluating and Optimizing Post-Combustion CO2 Capture with AmmoniaBased Solvents Thomas J. Tarka, DOE-NETL, USA The growing threat and awareness of global climate change has intensified the need for viable post combustion capture technologies for use with the existing coal-fired fleet. If possible, this need has become even more acute as proposed power plants continue to be canceled or postponed, often due to escalating construction costs and regulatory uncertainty. Wet-scrubbing with chemical solvents such as amines remain the most likely post combustion capture technology available for deployment in the nearterm. One wet-scrubbing process which has garnered much attention in recent years is the use of ammonia-based solutions for CO2 capture. These technologies generally utilize the ammonium carbonate/ammonium bicarbonate absorption/desorption mechanism in order to achieve a less energy-intensive capture process, as compared to common amines. At least two large scale pilot projects have been initiated recently which examine these technologies. This paper utilizes AspenPlus and other modeling tools to determine the optimal operating conditions for a process utilizing the ammonium carbonate/ammonium bicarbonate CO2 capture mechanism. Both the economic and technical performance is evaluated. 47-2 Investigation of an Ammonia-Based Wet Scrubbing Process in a Continuous Flow System Kevin P. Resnik, RDS-Parsons; Henry W. Pennline, DOE-NETL, USA A preliminary analysis of an ammonia-based wet scrubbing system revealed significant advantages over the MEA process to capture carbon dioxide from flue gas from coalfired power plants in a conventional absorption/stripping system. The advantages included: a greater potential loading capacity to reduce sensible heating costs, a lower heat of reaction, a lower reagent cost, a lower equipment corrosion rate, a lack of irreversible degradation products, and the ability to be utilized as a multi-component carbon capture system with salable byproducts. Experimental research has been conducted to evaluate the performance of this ammonia-based system, focusing on the ability to remove carbon dioxide from flue gases. This paper discusses results from semibatch tests and details findings from the more recent continuous experiments. The semi-batch tests used a fixed amount of solution and a continuous stream of simulated

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47-5 Pressure Swing Adsorption Technology for Carbon Dioxide Capture James A. Ritter, Amol Mehrotra, Armin D. Ebner, University of South Carolina, USA There are many misconceptions about and misleading reports on the viability of pressure swing adsorption (PSA) cycles for CO2 capture from flue gas. These misconceptions and misleading reports stemmed largely from a 1994 International Energy Agency (IEA) report that evaluated CO2 separation and capture from flue gas using 13X zeolite in both PSA and temperature swing adsorption (TSA) processes. They concluded that PSA and TSA are too energy intensive for use with gas and coal fired power systems. This conclusion has led others to extrapolate their findings and further conclude that adsorption systems, in general, are not applicable for CO2 separation and capture from flue gas. This disturbing misinformation has perpetuated for nearly a decade with essentially the same misleading statements being made in a 2003 IEA report. However, it is strongly contended that those reports might have been factually inaccurate, that some grave errors might have been made in the evaluation of cyclic adsorption technologies for CO2 capture from flue gas, and that PSA might be very applicable to the capture of CO2 from flue gas. These claims are substantiated with evidence from works found in the literature and from some of the authors recent works. First and foremost, a recent report by Izumi from Mitsubishi Heavy Industry indicated that CO2 was being recovered from flue gas commercially using a layered PSA bed containing X and A type zeolites and activated carbon. Although, not much detail about the PSA cycle was provided, this news was exciting. The Japanese must have discovered something positive about using PSA for CO2 capture from flue gas that has been overlooked by investigators in the USA and apparently everyone else around the world! Second, the authors at USC have been exploring novel PSA cycles for the capture of CO2 from flue gas at high temperature using a K-promoted hydrotalcite like compound (HTlc) as the adsorbent. They revealed that a variety of vacuum swing adsorption (VSA) cycles could be used to concentrate CO2 to over 90 vol% at over 90% recovery from a feed stream containing 15 vol% CO2. The most effective cycles were based on the heavy reflux concept, a concept that has been largely missing from the PSA literature. What is really exciting about these high temperature heavy reflux PSA cycles is that they are completely applicable to ambient temperature adsorbents like zeolites and activated carbons. Moreover, they are still working on the problem and have discovered some better heavy reflux PSA cycles for CO2 capture from flue gas that will be discussed during this presentation. The authors also feel that the lack of information on and therefore the lack of understanding of the heavy reflux PSA concept for concentrating the heavy component from a feed stream might be the principle reason why the IEA reports were mistaken in their assessments of PSA for CO2 capture from flue gas. To this end, the heavy reflux concept will also be discussed during this presentation. Third, some very recent work by Webley and coworkers in Australia substantiated the claims made by the authors over the past few years on the economic viability of PSA cycles for CO2 capture from flue gas, especially VSA cycles. They proclaimed that the information about the cost of PSA provided in the 2003 IEA report was in error. They recalculated the cost of PSA to be around $67/tonne of CO2 produced compared to that in the IEA report of $97/tonne. This new cost for PSA, as verified through the IEA, compared much more favorably with amine scrubbing technology at $60/tonne. What is most exciting about this recent set of events is that the PSA cycles analyzed by the IEA were not designed for heavy component recovery, like CO2; instead, they were designed for light component recovery, like CH4 from a CH4/CO2 mixture. As alluded to above, there are significant differences between these two kinds of PSA cycles, i.e., between the ones designed for light component enrichment and recovery and those designed for heavy component enrichment and recovery, with understanding of the later lacking, even by some of the best PSA researchers in the field. To make matters worse, the design of a multi-bed PSA process with complex cycle sequencing, like that envisioned for CO2 capture from flue gas, is a non-trivial exercise. PSA beds are always coupled together, usually contain more than one layer of adsorbent, and operate sequentially with each undergoing cycle steps such as pressurization, feed, heavy reflux, equalization, depressurization, light reflux, and repressurization. As an added complication, each cycle step is not necessarily of the same duration. These features make the number of possible cycle configurations very large; and unfortunately, design strategies on how to best configure such a complex PSA cycle is more of an art than a science. To this end, this presentation will also introduce some VSA cycle sequences that might be applicable for CO2 capture from flue and stack gases. 48-1 Use of Lime-Activated Class F Fly Ash in the Full-Depth Reclamation of Asphalt Pavements: Environmental Aspects Harold Walker, Ryan Mackos, Tarunjit Butalia, William Wolfe, The Ohio State University, USA The goal of this study was to evaluate the environmental aspects associated with the use of lime-activated Class F fly ash in the full-depth reclamation (FDR) of asphalt pavements. FDR is a flexible pavement reclamation process in which the full pavement section (wearing surface, base / subbase, and a pre-determined portion of underlying soil) is uniformly pulverized, blended with chemical additives (e.g. cement, fly ash, lime, emulsion) and compacted to construct a new stabilized base. The silica and alumina in fly ash reacts with lime to increase the strength, stiffness, and durability of the stabilized base layer. Fly ash also acts as mineral filler to fill the voids in the granular pulverized pavement mix, thus reducing permeability of the FDR stabilized layer. Two field sites in Ohio, one in Warren Co. and the other in Delaware Co, were selected for examining the use of fly ash in FDR of pavements. The Warren Co. site consisted of two FDR test sections; a 6% fly ash section and a control. Six test sections were constructed in Delaware Co., two of which contained approximately 5-6% class F fly ash. Test sections were constructed and instrumented in the summer of 2006. The specific objectives of the environmental component of this study were (1) to determine the leaching potential of selected constituents for the various FDR mixes; and (2) to monitor the water quality in the FDR base layer at the field sites. The leaching potential of selected constituents was determined using TCLP and SPLP tests. Field sampling was carried out by installing lysimeters within the FDR base layer under each asphalt test section. Inorganic elements in leachate and field samples, including As, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pd, K, Se, Si, Na, Sr, S, and Zn were determined using standard methods. These constituents were chosen because many are typically found in CCPs and they are also of concern in evaluating highway runoff. Laboratory leaching tests indicated that the leaching of inorganic elements from FDR mixes was significantly below RCRA limits and Ohio non-toxic criteria, and similar or less than values observed for FDR mixes without fly ash. Leachate generated by the SPLP test generally had lower levels of inorganic elements than leachate from the TCLP test, with most elements analyzed being below the instrumental limits of detection. Analysis of groundwater in the FDR base was carried out on a monthly basis upon completion of construction in the summer of 2006. Water recovery from test sections containing fly ash has been significantly less than from non-fly ash-containing test sections. At Warren Co. only one water sample has been obtained from the fly ash test section, while water samples were obtained from the control section on five out of the twelve sampling trips. At Delaware Co. the fly ash test sections have been dry, while other test sections produce water. These data suggest that the incorporation of fly ash into the FDR mix reduces permeability of the base layer, which reduces the contact of groundwater and the generation of leachate. Chemical analysis of the water sample obtained from the fly ash test section at Warren Co. indicated that the levels of inorganic elements were below primary drinking water standards and were similar to levels observed in control sections. 48-2 Impact of Trona Injection on Ash Leaching Characteristics Jianmin Wang, Tingzhi Su, Missouri University of Science & Technology; Ken Ladwig, EPRI, USA Trona and other sodium-based alkaline sorbents are used to control SO2 and SO3 emissions from coal-fired power plants. The impact of trona injection on the leaching characteristics of trace elements from bituminous coal ashes is being investigated using fly ash samples from two power plants. One plant was testing trona for SO2 control, while the second was testing trona for SO3 control. Paired fly ash samples were collected from both plants, one sample during trona injection and one control sample when trona was not being injected. The samples were tested for total composition and detailed leaching characteristics, including varying pH and liquid/solid ratio. Preliminary results suggest that trona injection increases leaching of oxyanionic constituents (As, Se, Cr, V, Mo, and Sb). The increase was more pronounced for the sample pair where trona was used for SO2 control, due to the higher injection rates associated with this application. The increase appears to be related both to change in pH and to change in the way the trace constituents are sorbed to the ash. SESSION 48 COAL UTILIZATION BY-PRODUCTS 2

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48-3 Fly Ash as a Chemical Scrubber for Acidic Wastes Haim Cohen, Ithamar Pelly, Ariel University Center at Samaria; Eli Lederman, Ben-Gurion Univ of the Negev, ISRAEL; Mehmet Polat, IZTEK, TURKEY Israels annual coal consumption is 12.7 million tons in 4 power stations producing ~65% of the countrys electricity. The process produces 1.3 million tons per year of fly ash that must be utilized or disposed off properly in order to avoid environmental problems (the main concern is contamination of the underground aquifer by leaching of trace elements from the ash). At present ~50% of the ash is recycled as cement additive (10%w) to clinker and the rest as a construction material for embankments, road basements and in concrete production. The fly ash produced in Israel has a highly basic reaction when exposed to water. That is a result of the very low sulfur content allowed in coal imports due to strict environmental regulations. Thus, it is feasible to use the ash as a chemical scrubber for acidic wastes. In this study, coal fly ash has been examined as a scrubber for acidic sludge produced from the regeneration process of used motor car oil and the acidic wastes produced by the phosphate industry. The results show that the fly ash can be used as a very efficient scrubber for both wastes. Furthermore, the fixation of the trace elements and the organic components within the fly ash particles is highly efficient. It was also found that the fixation product can be used as a good aggregate in concrete production. Bricks produced using the aggregate as a sand substitute have proved to be strong enough according to the concrete standards. Furthermore the leaching of trace elements from the bricks is within environmental regulations. Thus using the two wastes (flyash + acidic waste) result in a green friendly product that do not need to be stored but can be recycled in the construction industry. The neutralization and fixation processes will be discussed in detail. 48-4 Kinetics and Mechanism of Cr (VI) from Aqueous Solution with Ultrafine Coal Fly Ash Liu Zhuan-nian, Xian University of Science and Technology, CHINA Coal fly ashes WSRA (collected from the Heat and Power Plant in the Western Suburb of Xian, Shaanxi province, China) and BQRA (collected from the Baqiao Thermal Power Plant, Xian, Shaanxi province, China) were used in this study. WSRA and BQRA were ball milled for 5 h and got the ultrafine coal fly ashes WSUA and BQUA, respectively. Batch kinetic, isotherm and pH effect on adsorption were studied to evaluate removal of Cr (VI) from aqueous solutions by ultrafine coal fly ashes and were compared with raw coal fly ashes. The kinetics of adsorption indicates the process to be intraparticle diffusion controlled and follows the Lagergren first-order kinetics for all coal fly ashes. The first-order rate constants (k1) of Cr (VI) adsorption onto WSRA, WSUA, BQRA and BQUA are 1.981 min-1, 1.497 min-1, 2.119 min-1 and 1.50010-2 min-1, respectively. The adsorption capacities of WSUA and BQUA are much better than that of WSRA and BQRA. Equilibrium adsorption data of all coal fly ashes well satisfy the Langmuir isotherm. The adsorbed amounts of Cr (VI) onto two kinds of ultrafine coal fly ashes decrease from pH 2 to pH 6 then increase up to pH 12. 48-5 Application of Color Measurements for Estimation of Composition Of Ash (FBC) Dagmar Juchelkova, Helena Raclavska, Konstantin Raclavsky, VSB-Technical University of Ostrava, CZECH REPUBLIC The relationships between color parameters and composition of combustion products (bottom ash and fly ash) were studied. Combustion tests were performed in the fluidized-bed boiler, Trinec, the Czech Republic. The measured color parameters according to CIE L*a*b* standard have significant relationships with mineral phases (magnetite, anhydrite, lime, amorphous phase) and with chemical components (MnO2, TiO2 and minor elements) of fly ash. Color measurements do not belong to the usual methods for the study of fly ash. A visual color assessment using Munsell color tables is the standard method for soils. Color measurements were used for the identification of iron oxides and hydroxysulfates in soils by Scheinost and Schwertmann (1999). This paper is devoted to the study of relationships between color parameters of fly ash and its chemical and mineral phase composition. The three combustion tests were performed at the power plant Energetika Trinec (fluidized-bed boiler K12) aiming at checking the possibility of combustion of waste sludge (oil residues) from Ostramo oil refinery in Ostrava in combination with bituminous coal. The town of Trinec is situated in northern Moravia (the north-eastern part of the Czech Republic), in the area of Ostrava-Karvina Industrial Region. It is the southern part of the Upper Silesian Coal Basin, the bigger part of which is situated in southern Poland. The first test was performed with bituminous coal from Poland, the second and third tests were performed with a mixture consisting of 10% of sludge and 90% of bituminous coal from Poland. The second test was performed at minimum output (102 t/h of steam), while the third test was performed at maximum output (141 t/h of steam). During the tests, the combustion temperature in fluidized-bed layer was comparable for both first and third test: the lower part 850C, the middle part 834C,

the up Results of these experiments are very interesting and can be used also on the other conditions.

SESSION 49 GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES 3

49-1 Interactions Between Slag and High Chrome Oxide Refractory Liners in Air Cooled Slagging Gasifiers James P. Bennett, Kyei-Sing Kwong, Arthur V. Petty, Hugh Thomas, Rick Krabbe, DOE-NETL, USA Gasification of carbon containing materials is used to produce CO and H2 for chemical and power production, including the production of liquid fuels. The generalized reaction that occurs in a gasifier at elevated temperatures, pressures, and in a reducing environment converts a carbon feedstock, water, and oxygen to primary products of carbon monoxide and hydrogen as follows: C (with impurities) + H2O + O2 H2 + CO + CO2 + H2S + minority gases + excess carbon as char + ash (from mineral impurities). A primary carbon feedstock used worldwide in gasification is coal; although coal and petcoke or mixtures of them with other carbon sources, such as biomass, can be used. The air cooled slagging gasifier typically operates between 1325 and 1575C, and at pressures between 400 and 1000 psi - conditions that depend on the specific gasifier design and the carbon feedstock. The reaction vessel where gasification occurs is lined with pre-fired refractory materials to protect the steel containment shell from the severe service environment. The major components of the refractory are chrome oxide (60-95 pct), alumina (2-40 pct), and zirconia (0-12 pt). Service life of these liner materials in the hot slagging environment can be as short as 3 months or as long as 24 months; and is directly dependent on slag chemistry, temperature of operation, feedstock throughput, and the gasifier cycling practices. The main causes of refractory failure are slag corrosion/dissolution of the refractory and spalling caused by slag penetration of the refractory. Slag originates from impurities in the carbon feedstock (ash) that liquefies at the elevated temperature of gasification; producing molten material high in oxides of Si, Fe, Al, and Ca. Other elements that may be present in the coal slags include S, K, Na, and Mg; with Ni and V present in petcoke slags. Discussions of how the slag interacts with the refractory liner and the compounds formed between them will be presented. These will include information on why hexavalent chrome oxide formation in gasifier slag/refractory interactions with current carbon feedstock (hexavalent chrome is not viewed as a problem), as well as a discussion on which carbon feedstock (and their slags) might be predicted to lead to its formation. In general, slags high in alkali or alkaline earth, such as biomass, could impact hexavalent chrome formation. Refractory/slag interactions, and the compounds formed, will be illustrated through post-mortem analyses of samples removed from commercial gasifiers. 49-2 Slag Penetration into Refractory Lining of Slagging Coal Gasifier Josef Maty, S. K. Sundaram, Carmen P. Rodriquez, Autumn B. Edmondson, Benjamin M. Arrigoni, Pacific Northwest National Laboratory, USA The impurities in coal are converted into molten slag typically containing SiO2, FeO, CaO, and Al2O3 when coal feedstock is burned in slagging gasifiers. The slag flows down the gasifier sidewalls, dissolves, and penetrates and reacts with the refractory lining that protects the stainless steel shell of the gasifier from elevated temperatures (13001600C). Refractories composed primarily of Cr2O3 have been found most resistant to slag corrosion, but they continue to fail performance requirements because of low resistance to spalling. Post-mortem analysis of high-chromia refractory bricks collected from commercial gasifiers suggests that the spalling is affected by the depth of slag penetration that is in turn affected by the wettability and interconnected porosity of the refractory as well as the slag viscosity. Laboratory tests were conducted to measure the viscosity of slags (Wyoming Powder River Basin [PRB], Pocahontas #3, and Pittsburgh #8), their contact angle on refractories (chromia-alumina [Aurex 75SR] and high-chromia [Serv 95 and Aurex 95P]), and the apparent porosity of selected refractories. In addition, the depth of slag penetration as a function of time and temperature was determined for various refractory-slag combinations. The results of laboratory tests were used to develop a refractory material that has high resistance to penetration by molten slag and thus has a potential to have a substantially longer service life than the materials currently being used.

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49-3 The Wettability of Coal and Petcoke Slags on 90 wt.% Cr2O3 - 10 wt.% Al2O3 Gasifier Refractory Liners Used in Gasification Jinichiro Nakano, Sridhar Seetharaman, Tyler Moss, Carnegie Mellon University; Kyei-Sing Kwong, James Bennett, DOE-NETL, USA By utilizing a Confocal Scanning Laser Microsope, the wettability as well as penetration behaviors of coal and petcoke slags on high chromia and alumina refractories have been investigated. The petcoke slag showed the lower initial deformation temperature and also lower melting temperature than the coal slag. The high chromia refractory, in general, returned better corrosion/erosion resistance against both slags with the exception that the alumina substrate outperformed in minimizing the slag penetration when the petcoke slag was interacted with a fined region of the refractory. The VOx-based phase was observed: as a layer of (V, Cr, Fe)Ox at the interface between the petcoke slag and the high chromia substrate; and as discrete particles of (V, Al, Si)Ox at the interface between the petcoke slag and the alumina refractory. In some cases, Ca- and Fe-rich VOx was also observed. For the coal slag, Ca-species penetrated most slowly through the fined regions of both refractories, whereas Fe-species was the fastest in any case. 49-4 Investigation of Heat Transfer and Gasification of Two Different Fuel Injectors in an Entrained Flow Gasifier Ting Wang, Armin Silaen, University of New Orleans, USA; Heng-Wen Hsu, Cheng-Hsien Shen, Industrial Technology Research Institute, TAIWAN One of the problems frequently encountered in a coal gasifier operation is fuel injector failure. Operating in extreme high pressure and high temperature, the typical fuel injector life span is 6 to 12 months. Numerical simulations are performed to study the flow and temperature fields in the vicinity of the injector tip and the metal temperature of two different fuel injector designs -- one with conical-nozzle tip and the other with a blunt tip -- in a dry-fed, entrained-flow coal gasifier. The complete 3-D Navier-Stokes equations are solved. The simulation models the gasification process with three global heterogeneous reactions and three homogeneous reactions, including volatile combustion. The results show the two different injectors give very different temperature and species distributions inside the gasifier. In the gasifier with the conical injector tip, the highest temperature inside the gasifier occurs at the center of the gasifier; whereas, in the gasifier with the blunt-tip injector, the highest temperature occurs near the wall. There is a potential of flash back combustion in the nozzle at the tip of the conical injector due to its premixing feature of fuel and oxidant in the nozzle. The highest temperatures on both injectors are the same, which is around 1600 K. However, the highest temperature on the conical-tip injector is concentrated at one location with an extended region of 30 mm between 1600 K and 1100 K; whereas on the blunt-tip injector hot spots scattered and the hot region (1600 K 1100 K) only extends about 3 mm. Experimental results support simulated results and has demonstrated a short life of the conical-tip fuel injector and much extended life for the blunt-tip fuel injector. 49-5 A Parametric Study to Design an Effective Spray Cooling Deployment in an Entrained-Flow Coal Gasifier Qiuwang Wang, Peiyao Liu, Xian Jiaotong University; Shisen Xu, Baomin Wang, Thermal Power Research Institute, CHINA; Ting Wang, University of New Orleans, USA Gasification is a clean technique that converts coal into syngas, which can be cleaned much more easily than the coal itself. The raw sysgas exiting the gasifier is usually at a very high temperature. To protect the rearward equipment, the raw syngas needs to be cooled to allow appropriate cleaning of particulates, ashes, and sulfur before it exits the gasifier. Cooling of the syngas can be performed by employing heat exchangers or direct spray cooling. This paper focuses on conducting a 3-D CFD parametric study to aid in the design of an effective water spray cooling deployment. The studied parameters include water droplet sizes (100~400 m) and water injection angles. The goal is to cool the syngas from 1550C to 800C using the shortest spray section. The gasifier is designed to produce methanol at a full load condition, so the amount of sprayed water is fixed to ensure the syngas composition meets the specifications for methanol production. The gasifier is steam-oxygen blown with dry coal feed using approximately 960 tons per day. The results reveal that smaller droplets are effective in reducing the cooling section length. Moreover, using three water injection angles show that inclining the spraying angle upward 45 degrees could shorten the effective cooling length. This study provides a guide for cutting the cost of manufacturing a gasifier cooling section. 50-1 Steam Hydrogasification of Coal-Wood Mixtures in a Batch Reactor Arun SK Raju, Chan S. Park, Joseph M. Norbeck, University of California, Riverside, USA Steam hydrogasification is a thermochemical process where a carbonaceous feedstock is gasified in the presence of hydrogen and steam. The product gas stream contains a significant amount of methane and has a high calorific value. The presence of steam during the traditional hydrogasification reaction significantly increases the rate of methane formation. The efficiency of the process and the product gas composition are governed by the feedstock composition (H2O/Feed and H2/C ratios), temperature, pressure and residence time. The product gas stream from a steam hydrogasifier can be reformed to generate synthesis gas (H2 and CO) that can be used in Gas to Liquid processes. Gasification of co-mingled coal-biomass feedstocks offers several advantages such as the reduction in the net CO2 emissions from the process. In this study, steam hydrogasification of coal-wood mixtures at various ratios have been performed in a batch reactor. Coal from the state of Utah and cedar wood have been used as the feedstock. The carbon conversions were measured at 700 and 800C at a H2O/Feed ratio of 2. Effects of water and hydrogen were also investigated. The results demonstrate that the carbon conversion depends on the reaction temperature and the ratio of coal to wood in the feed does not influence the conversion. The carbon conversion varies from 70-80% at 800C and 50-60% at 700C. The data also show that the relative composition of CH4, CO and CO2 vary with the coal to wood ratio. The results show that the percentage of CO in the outlet gas composition increases with the increase in the amount of wood in the feed. This paper presents the results of these experiments and also comparison of these data with simulation results. 50-2 Influence of Coal-Biomass Feed Mixtures on Gasification Products Bryan D. Morreale, George Richards, Todd Gardner, Yatish Shaw, Dirk Link, Paul Zandhuis, DOE-NETL, USA The United States Department of Energys National Energy Technology Laboratory (NETL) is aggressively pursuing research and development directed towards mitigating apprehensions over fuel independence, energy availability and reliability, and environmental issues, especially as related to global warming. The production of synthesis gas (syngas) from indigenous carbonaceous feedstocks has the potential to address some of these energy and environmental concerns. The abundance of coal in the US in conjunction with the flexibility of syngas, which can be converted to electricity, hydrogen and/or liquid fuels, is considered a promising near- to mid-term component in the transition to a renewable energy society. The addition of non-food oriented biomass to gasification feeds and carbon dioxide capture and sequestration can prolong national fossil energy resources while providing an energy conversion process with a negative carbon footprint. Although significant research and development has been conducted on the characterization of pure biomass- and fossil-based gasification systems, considerable technical challenges and uncertainties remain for co-feed systems. In this study, NETL researchers are focused on evaluating and reporting on the influence of various coal (Illinois#6, Wyodak, Pittsburgh River Basin, North Dakota Lignite and Texas Subbituminous) and biomass types (wheat straw, corn stover, switchgrass, mixed hardwood and distillers dried grains with corn fiber) on reaction rates and solid, liquid and gaseous products. 50-3 Fluidized-Bed Co-Gasification Process of Colombian Coal and Biomass Wastes Zulamita Zapata, Erika Arenas, Grupo de Energa y Termodinmica Universidad Pontificia Bolivariana; Farid Chejne, Universidad Nacional de Colombia - Sede Medelln, COLUMBIA Coffee husk, rice husk and sawdust are Colombian agroindustrial wastes which were mixed with fine coal from the Amag region (Antioquia). In some regions in Colombia, fine coal from coal mining is considering as a waste. Fine coal has little demand in Colombia because the most of the coal firing systems are stokers. One alternative for using this fine coal is fluidized beds due to fine coal has high ash and sulfur content, co-gasification with biomass is an option to decrease sulfur emissions. Those mixtures were gasified using air and steam as gasifying agents. In this study, the air-mixture ratio and steam-air ratio effects over conversion, temperature and carbon monoxide concentration were analyzed. Air-material ratio and steam-air ratio were changed obtaining conversion values between 76% and 86% and bed temperatures between 750C and 950C. The highest conversion and temperature values were obtained during sawdust-coal gasification, while rice-coal mixture gasification showed SESSION 50 GASIFICATION: CO-GASIFICATION

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the lowest carbon monoxide concentrations. Biomass-coal gasification showed better results than coal gasification. 50-4 Pyrolysis of Sawdust-Lignite Blends Preeti Aghalayam, Jeevan Baretto, Anuradda Ganesh, IIT Bombay, INDIA; Shehzaad Kauchali, University of Witwatersrand, SOUTH AFRICA Co-firing of biomass and coal has the dual benefits of increased efficiency and reduction in the overall CO2 emissions. India has considerable reserves of coals (nearly 250 billion tonnes). Many of the Indian coal seams consist of low grade lignites. The biomass potential of India is significant with volumes of agricultural waste. In the literature, it has been shown through thermal analysis that the reactivity of coalbiomass blends may be predicted based on knowledge of the individual reactivities, due to a lack of interaction between the two (Vuthaluru, 2004 & Folgueras et al., 2003). These articles use bituminous/sub-bituminous coals. Our literature search did not yield any articles on co-firing of particular interest to Indian coals, which are inherently of high ash or high moisture content. In this paper, we propose the use of sawdust as a blending material with lignite. Sawdust has been chosen as a representative biomass because of its abundant availability in India. Sawdust typically has low (<2%) ash content, and therefore, the results obtained can be thought of as independent of the effects of ash. Lignite from one of the Indian mines has been selected. This lignite is known to be of a low-grade (Sapru et al., 2007), with low sulphur content. We expect that the blending of sawdust with this lignite will have beneficial effects in co-fired boilers/gasifiers. An evaluation of the blends for co-firing applications has been done here by means of thermal analysis. Pyrolysis kinetics has been determined for various combinations of biomass & lignites (in terms of percentage amounts). The impact of the heating rate of the non-isothermal thermogravimetric analyser experiment, on the observed pyrolysis kinetics, has also been studied. Five blends have been used here with the compositions - 90:10,80:20,70:30,50:50 and 30:70 (lignite:sawdust, % by weight). The pure fuels have also been studied, for purpose of comparison. The thermal analysis for these seven cases has been performed at three heating rates 10 K/min, 20 K/min & 100 K/min. The obtained DTG curves indicate several interesting features. The sawdust demonstrates reactivity at a much lower temperatures (630 K) than the lignite (720 K). Furthermore, due to higher volatiles, the peak rate of reaction in case of sawdust is much greater than that for lignite, as expected. The DTG curves for the blends show two peaks in reactivity one each at the peak temperature for sawdust and lignite. Although the peak rate of reaction is consistently lower for the blends as compared with sawdust, it is to be noted that the range of temperatures over which good reactivity is demonstrated is much larger for blends than for either of the pure fuels. The results indicate that there is considerable interaction between the sawdust and the lignite, in the blends. Another clear demonstration of this interactive effect is the fact that, at 720 K, which is the lignite pyrolysis temperature, the reactivity of the blends is lower than that of the lignite. These conclusions are further confirmed by our analysis of the char yields obtained in each case, and are contrary to literature results (see for e.g. Vuthaluru, 2004; on sub-bituminous coals). We have further analysed the DTG data using the Coats and Redfern approximation (Sima-Ella et al., 2005) in order to determine the activation energies for the pyrolysis reaction. It is observed that the assumption of a single first order reaction is not valid over the entire range of temperatures. In general, the temperature range of 450-850 K wherein most of the interesting pyrolysis occurs, can be divided into two-three distinct regimes, each with its own activation energy. For the 10 K/min case, the activation energy in the lower temperature range (~450-625 K; where the sawdust has high reactivity), increases as the percentage of sawdust in the blend increases. This is in agreement with the observed peak reactivities in the DTG curves, in this temperature range. This trend is exactly reversed in the higher temperature range (~625-825 K), where the reactivity attributable to lignite is significant. In this study, a complete analysis of the effects of %biomass in the blends, in terms of pyrolysis kinetics, char yields, and heating rate dependencies will be undertaken. A comparison of the Coats and Redfern activation energies with those obtained from the use of a Distributed Activation Energy Model (Scott et al., 2005) will be made. Results of combustion and CO2 gasification studies of the pure fuels and the blends will also be reported. The work is expected to add valuable information pertaining to co-firing of biomass and coal, both for combustion and gasification, in the Indian context. References M. B. Folgueras, R. M. Diaz, J. Xiberta, I. Pinto, 2003, Fuel 82, pp. 2051-2055. R. K. Sapru, R. K. Sharma, A. A. Kuznetsov and V. K. Kapralov, 2007, Petrotech2007, January 15-19. S. A. Scott, J. S. Dennis, J. F. Davidson, and A. N. Hayhurst, 2006, Chem. Eng. Sci. 61, pp. 2339-2348. H. Sima-Ella, G. Yan, and T. Mays, 2005, Fuel 84, pp. 1920-1925. H. B. Vuthaluru, 2004, Bioresource Technology 92, pp. 187-195.

50-5 Study on the Co-Pyrolysis and Co-Gasification Characteristics of Coal and Biomass Wang Peng, Wen Fang, Bu Xuepeng, Beijing Research Institute of Coal Chemistry, CHINA The experiment results on the synergetic effects during co-prolysis and co-gasification of coal and biomass was given in this paper. The pyrolysis characteristics of three different samples -Dayan lignite, sawdust and the mixture of two samples were studied. Gasification kinetic behavior of the char from samples was studied using TGA. The primary research conclusions were obtained: (1) With the pyrolysis temperature increase, the yield of coal char was decreasing, the gas was increasing, and the tar increase at initial stage and then decrease in given temperature range. While, the H2 concentration in gas was increasing, CH4 decreasing, CO increasing obviously, and the LHV of gas was decreasing. (2) The sawdust pyrolysis result showed that the pyrolysis began from 100C and the pyrolysis reaction was most drastic at 300C- 400C. The final pyrolysis temperature would affect the yields and properties of gas and liquid products. The char yield would be stable when the final temperature over a certain value. (3) The synergetic effect was found during coal and biomass co-prolysis. The effect results was that the yield of char and gas decrease, the tar products increase and H2 and CH4 concentration were increase in gas composition. The affect extent of co-effect was relative with temperature, mixture rate, biomass kinds and etc. (4) Comparing the gasification activity, at the initial phase, the activity order of three char samples was coal char> sawdust char > the mixture char. The activity order would change to sawdust char>the mixture char> the coal char after some reaction time. (5) The modeling calculation result showed that the shrinking-core reaction model was better than the homogeneous reaction model. The activation energy of Dayan lignite char and the mixture char was adjacent, and the latter activation energy was smaller that indicated the coal char reaction activity would be increased by add the sawdust. (6) For sawdust char, the relation between the reaction conversion and the reaction time was linear because the higher reaction rate, lower ash content and negligible ash layer diffusion. The external diffusion control model can be used to describe the sawdust char gasification reaction properly, and the diffusion parameter was in proportional to temperature. 50-6 Characterization of Sawdust Gasified Tar from Air-Steam Atmosphere in the Fluidized Bed Yuhong Qin, Jie Fang, Wenying Li, Taiyuan University of Technology, CHINA The biomass air-steam gasification technology could produce hydro-rich gas and be a potential conversion technology for the further processing technology, such as fuel cell, synthesis of methanol and dimethyl ether. However, the large amounts of tar formation during the gasification cumber this technology becoming commercialized. Understanding tar chemical compositions and structure could help us adopt the suitable gasifier operation parameters and find the proper catalyst pointedly minimizing tar formation. The paper investigated the property of tar generating from sawdust airsteam gasified in the fluidized bed at atmospheric pressure. The different ratio of steam to biomass weight (S/B) was investigated. The tar molecular mass distribution and average molecular mass were measured by gel permeation chromatograph (GPC), also the UV character of tar in whole molecular mass range was analyzed by photodiode array detector (PDA). The GPC results indicated the molecular mass distributions had no difference with the increasing of S/B at 800C and 900C. Three distinct fractions were found at measuring range, that the fraction 1 (F1) was from 423u to 200u or so, fraction 2 (F2) was from 200u to 130u and fraction 3 (F3) was less than 130 u approximately. In addition, the F1 composed of long chain aliphatic acid or ester, paraffins and 4-9 rings aromatic compounds. The paraffins cracked intensified with the increment of S/B at 900C, and the aromatic character of F1 at 800C was stronger than at 900C. While the F2 had stronger aromatic character at 900C than at 800C, The 2~4 rings aromatic compounds were the major components in F2 at 900C, however, the major components in F2 at 800C were conjugated alkenes, unsaturated aldehyde and ketone. F3 showed same structure at 800C and 900C, it contained 1 ring aromatic compounds and heteroatom-contained compounds. Moreover, experiments results showed the tar yield decreased with the increasing amount of steam. The resulted showed with the increment of temperature, steam more easily acted on the high molecular mass compounds. At 800C, steam made 2-4 rings aromatic compounds almost cracked, and at 900C, steam acted on 4-9 rings high molecular mass compounds. The tar components gasified under air-steam atmosphere mainly composed of aromatic compounds, unsaturated conjugated bonds paffins and oxygen-containing compounds.

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SESSION 51 ENVIRNOMENTAL CONTROL TECHNOLOGIES: COMBUSTION BYPRODUCT APPLICATIONS, SOx

51-4 The Repac Process: Regeneration & Reuse of Pac from ACI Dale L. Nickels, Pittsburgh Mineral & Environmental Technology, Inc., USA The use of Activated Carbon Injection (ACI) for the removal of mercury from flue gas is a well established method that has been commercially implemented and requires the injection of Powdered Activated Carbon (PAC) into the flue gas stream. While this method successfully removes the mercury from the flue gas, it has inherent flaws. PAC is a costly reagent ($0.75/lb) that is consumed and ultimately landfilled, and the captured mercury is merely transferred from the air to the ground, not eliminated from the environment. PMET has developed a patented process (REPAC) that enables the regeneration and reuse of PAC after it has captured the mercury. This process is most effective when the ACI occurs after a fabric filter or electrostatic precipitator (ESP) and prior to a PAC collection device, such as a fabric filter. Once collected, the PAC is thermally treated in an inert atmosphere to desorb the contained mercury allowing the PAC to be returned to the injection system for reuse. The desorbed mercury is sequestered and thousandfold concentrated onto a specially formulated carbon that can subsequently be treated for mercury recovery as a salable metal, thus avoiding any disposal of potentially toxic waste streams. This step eliminates the environmental liability associated with the mercury for the generating entity. Compared to single-pass PAC that is injected once, collected and disposed of; REPAC offers significant operating cost savings, reduced PAC consumption to stretch the existing supply, and mercury emissions that are sequestered. PMET successfully demonstrated the ability to desorb mercury from PAC using a synthetically loaded carbon from Norit (DARCO FGD). After the mercury was desorbed, the regenerated PAC was found to have the same characteristics as virgin material. Using this test data, and the published data from US DOE, the REPAC process is capable of reducing the ACI operating costs by a factor of ten (10). These savings will allow high cost facilities with mercury emissions to comply with the upcoming regulations without a cap and trade sysetm. 51-5 Study of Thermodynamics and Kinetics of Flue Gas Desulphurization over Activated Coke from Taixi Anthracite Sun Zhongchao, Guo Zhi, Li Xuefei, Xiong Yinwu, Li Yanfang, Bu Xuepeng, Liang Daming, China Coal Research Institute, CHINA Thermodynamics and kinetics of flue gas desulphurization (FGD) over activated coke from Taixi anthracite were studied in a fixed bed reactor. The adsorption isotherm of SO2 in simulated flue gas over activated coke was investigated and modeled by Langmuir and Freundlich mechanism, while the Langmuir mechanism was proved to be more suitable for this system. When the temperature in the field of 403 ~ 463 K, intrinsic kinetics of desulphurization were investigated under the condition that internal diffusion and external diffusion were eliminated and the mathematical model was established. Results showed that the desulphurization process over activated coke was exothermic, and adsorption, desorption and reaction existed simultaneously on the surface but the adsorption process is dominant. There were 3 stages could be partitioned in the whole desulphurization process. SO2 conversion is 100% in the first stage, but which reduced rapidly in the second stage and keeped on a rather low value for a long period in the third stage. Most of the removed SO2 were absorbed on the surface of activated coke in the first and second stage and the process could be the expression of

51-1 Potential for Fly Ash to Mitigate Beach Erosion and Coastal Flooding Evan J. Granite, DOE-NETL, USA Much of the population in the United States resides in coastal regions. Coastal regions in the gulf and southeastern regions of the United States are routinely battered by tropical and hurricane force storms, resulting in loss of lives and billions of dollars in property damages. Approximately one billion tons of coal is burned annually in the United States, generating eighty million tons of fly ash. The coal is typically burned at 2500F, liberating the volatile matter, converting most of the carbon to carbon dioxide, and leaving behind mineral ash comprised mostly of silicon and aluminum oxides. Several studies have previously demonstrated the safety of coal-derived fly ashes. This material is potentially suitable for rebuilding (or nourishing) eroded coastal areas, thereby enhancing the safety of residents in flood prone regions, restoring the viability of tourist beach areas, and keeping enormous quantities of fly ash out of landfills. The use of fly ash for beach restoration would turn a waste product into a valuable resource. Approximately 650 million tons of sand has been used for beach nourishment in United States coastal regions over the past eighty years. The current state of the art for combating beach erosion is dredging sand from the ocean bottom, and transporting it to the shore. This is an expensive and temporary fix to a difficult problem. The dredging of sand can disturb local marine life. The use of fly ash in lieu of dredged sand has the advantages of reduced landfill usage, lower costs, and enhanced attractiveness of the rebuilt beaches. The potential uses of fly ash to mitigate beach erosion and flooding will be discussed. 51-2 Mercury Flux from Coal Utilization By-Product Samples Natalie Pekney, Donald Martello, Karl Schroeder, Evan Granite, DOE-NETL, USA Control technologies are being developed to achieve reduction of mercury emitted in the flue gas from coal-based power plants. As new mercury control technologies increasingly remove mercury from the flue gas, concentrations in coal utilization byproducts (CUBs), such as fly ash and flue gas desulfurization (FGD) products, are expected to increase. This increase has unknown effects on the stability of mercury in CUBs and therefore raises concerns about reemission. Effects of temperature, moisture content, and light exposure on mercury stability in CUBs are also unclear. To examine these effects, an environmental chamber was constructed to measure the mercury flux from CUB samples. A sensor monitored temperature and relative humidity in the chamber, and each sample was tested under both dark and lighted conditions and with or without the addition of water to the sample. Fly ash sample pairs were obtained from NETLs mercury control technology field testing program such that one sample was collected at a power plant before mercury control technology was installed, and its pair was collected after controls were in operation. Samples of FGD gypsum and the wallboard product made from it were also tested in the chamber. Results varied widely, with 7-day experiment averages ranging from 6.8 to 335 ng/m2-hr. Initial mercury content, fly ash type, and light exposure had no observable consistent effects on mercury flux. There did seem to be an observable effect from the presence of mercury control technology, however, for the fly ash samples. In all but one case the baseline samples released more or absorbed less mercury their corresponding after-controls samples. For three of the four pairs of FGD gypsum and wallboard samples, the wallboard sample actually released less (or absorbed more) mercury than the gypsum. Results from this study suggest that although there are some cases of high mercury release, especially for FGD materials, the mercury in CUBs is relatively stable. This technical effort was performed in support of the National Energy Technology Laboratorys on-going research in mercury control technology Under the RDS contract DE-AC26-04NT41817. 51-3 Intrinsic Kinetics of Flue Gas Denitration by Activated Coke Xuefei Li, Xuepeng Bu, Zhi Guo, Daming Liang, Beijing Research Institute of Coal Chemistry, China Coal Research Institute, CHINA TX activated coke was prepared by our method. Based on the elimination of internal and external diffusion, its denitration performance was determined in an isothermal integral tubular reactor. The intrinsic kinetic model was derived from Eley-Rideal model. The parameters in the model were also estimated based on experimental data. Analysis of statistic test indicated E-R model was preferable for denitration performance of TX activated coke, and the calculated values of NO conversion by E-R model were well agreed with the experimental data. The apparent activation energy of denitration was -23.6 kJ/mol.

q dq = k a c(qm q ) . To industrial applications, the first K dt

and second stage would be of more practical significance. 51-6 Sulphur Dioxide Capture under Pressurised Fluidised Bed Combustion Conditions using Dolomite and Coal-Ash as Sorbents Hein W.J.P. Neomagus, Raymond C. Everson, Steady Mukondiwa, North-West University, SOUTH AFRICA A study was carried out to investigate sulphur dioxide capture from coal combustion flue gas using South African mined dolomites, limestone and coal ash under atmospheric and pressurised fluidised bed coal combustion conditions using a thermogravimetric analyser. Temperatures between 750-900C were used, and a typical flue gas mixture composed of 2000 ppm SO2, 5.3% 02 and CO2 concentration of 10 and 20% for atmospheric and pressurised sulphation respectively and balance N2 was used. The performance of the sorbents was examined at atmospheric (0.875 bar) pressure where the active part of the sorbent was CaO and at 10 and 15 bar where the active part of the sorbent was CaCO3. Coal ash had a calcium content of 7% by weight, much lower than dolomite and limestone which had between 20-30% calcium by weight. The sorbents structural characterisation was done using nitrogen adsorption and mercury porosimetry. The raw dolomite and limestone had a small internal surface area, between 0.4-1.0 m2/g, increasing to between 10-15 m2/g on calcination. Coal ash

50

had a relatively high internal surface area of 11 m2/g comparable to the calcined sorbents. The porosity of raw sorbents increased from about 0.2 to 0.35 on calcination. Sulphation at atmospheric pressure showed calcium conversion between 22-44% for dolomites, 37-49% for limestone and 13-28% for coal ash after 180 minutes. At atmospheric pressure, dolomites and coal ash reactivity started off relatively fast followed by a sudden decline after 20% conversion, which was attributed to a change from reaction kinetic control to product layer diffusion control; limestone did not show a decline in reactivity. Under pressurised conditions the reaction initiated relatively slow and no signs of a sudden conversion decline were observed up to 180 minutes. Sulphation at 15 bar was higher than at 10 bar. At 15 bar dolomite calcium conversion ranged between 16-34% and limestone was between 18-36% and coal ash conversion was higher at 28-35% calcium conversion. The conversion results obtained compare well with results obtained by other researchers. A modified unreacted shrinking core model with variable effective diffusivity accounting for change in diffusion with growing product layer was successfully used to model results at both atmospheric and pressurised conditions.

52-4 Research on the Standard System to Evaluate the Quality of Coking Coal Gaifeng Xue, Ru Xiang, Peng Chen, Shangchao Liu, Research and Development Institute, Wuhan Iron and Steel Corp, CHINA Based on studying the match of coking coals with industrial indexes, process indexes, coal petrology indexes, the micro structure and thermo properties of coke coked from different provinces in China (Qinghai Province, Sichuan Province, Xinjiang Province, Henan Province, Shanxi Province), the paper presents a new standard system to evaluate the coking coal using volatile matter, caking index and micro structure (optical structure) of coke coked from unblended coal. This evaluating system can be used to reveal the nature of coking coal better than usual one used before. 52-5 Potential Utilization of Coal of an Energetically Lower Quality for the Preparation of Mixed Fuels Josef Vale, Jaroslav Kus, Monika Mdrov, Brown Coal Research Institute; Peter Feko, Milue Hlavat, VSB-Technical University of Ostrava, CZECH REPUBLIC The extraction of raw materials and industrial production have brought along a lot of ecological damage accompanied by the formation of various types of waste economically inexploitable at that time. Currently, former waste represents energetically utilizable materials. The objective of the research is the application of such materials with a significant energy potential to improve the use properties of lowcalorific types of brown coal, which often show higher sulphur contents. The qualitative characteristics of low-calorific types of brown coal with higher sulphur contents do not permit their direct energy utilization in the small consumers market or power-engineering. A suitable combination of components with substantial energy content, which is separately sold with difficulty or is not marketed at all, may produce so-called mixed, multi-component fuels. 52-6 Influence of Secondary Pyrolysis on Vapor Gases Viktor Saranchuk, Olga Chernova, Evgeniy Zbikovskiy, Donetsk National Tecnical University, UKRAINE For study of the process of the separation of the gas under pyrolysis two laboratory installations were used. In installation 1 processes secondary pyrolysis are vastly reduced to account of the small volume of the installation and quick removing vapor gases from underroof space. In installation 2 are imitated condition of the coking camera (exists the gradient of the temperature and simultaneous existence of the different layers). Got when undertaking the process pyrolysis charge gases has compared. The Results have shown that output and composition gas, got in different condition, differ. Leaving the gas from installation 1 on 24% more, than from installation 2. In given gas raised contents component with high heat of combustion and average heat of combustion given gas is 35,9 MDZH/m3 that comparable to heat of combustion of the natural gas and given gas can become the substitute of the natural gas in energy. Thereby, composition and amount of the gas pyrolysis, as well as quality of the other products pyrolysis possible control, using different ways pyrolysis, in which level of the secondary processes changes depending on way of the issue of the heat and from warm-up interval, in which is realized process pyrolysis. When undertaking the process pyrolysis in condition of the absence of the secondary processes can be received gas with heat of combustion above, than beside dry natural gas, since contents in him such, propane and butane forms before 20%. Such gas can be used in energy purpose, for syntheses of plastic, receptions propane-butane mixture and other integer. Increase degree secondary processes, running in coal loading and underroof space, brings about increase the output such component as CO and N2 that does the given gas by valuable raw material for undertaking chemical syntheses.

SESSION 52 CHEMICALS, MATERIALS, AND OTHER NON-FUEL USES OF COAL 2

52-1 Study on the Passivation of Coke and its Mechanism Shizhuang Shi, Wei Xu, Hui Wang, Feng Shi, Gang Shi, Cheng Zhang, Wuhan University of Science and Technology; Huiming Cui, Xinghong Lei, Coking Co. Ltd, Wuhan Iron and Steel Group Corporation, CHINA The coke passivation is to infuse coke in a boric acid solution, so that carbon solution loss reaction of coke can be decreased. In order to make clear the mechanism of the coke passivation, the surface of coke before and after passivation is observed separately by SEM. The result shows that the external pores of the coke passivated are jammed and, for the coke passivated, the carbon atoms surrounding the external crystal lattice form new chemical bonds after reaction with CO2. The two reasons result in the decreasing of the extent of carbon solution loss reaction coke. 52-2 Research on the Peculiarity of Coking Coal from Qinghai Province in China Gaifeng Xue, Shangchao Liu, Peng Chen, Ru Xiang, Research and Development Institute, Wuhan Iron and Steel Corp, CHINA Based on analyzing some indexes of coking coal from Qinghai Province in China, such as industrial analysis, coking properties, vitrinite reflectance distribution figure as well as thermal-properties and micro structure, the results showed that the industrial analysis indexes and coal petrology index have some limitation to evaluate coking coal quality, only microstructure (optical structure) of coke coked from single coal can reveal the nature of coking coal. 52-3 Research on the Micro Structure of Stamp-Charging Coking Coke and its Performance Gaifeng Xue, Peng Chen, Shangchao Liu, Zikui Song, Research and Development Institut of Wuhan Iron and Steel Corp, CHINA Stamp-charging coking technology has developed rapidly in recent years in China. By studying bulk density, porosity, micro structure, mechanical strength and thermoproperty of different stamp-charging coking coke samples from nearly 10 domestic coke plants as well as their blending coal quality, the following conclusions are obtained: After being stamp-charged, coke quality has been greatly improved with better mechanical strength (M40>88% even over 90%), higher bulk density and lower porosity. However thermo properties of coke fluctuated obviously. Coke reactivity indexes (CRI) were in a range of 28%~30 to 45-50%. And coke strength after reaction (CSR) of stamp-charged coke changed from 40% to 60%. The different of thermo properties of coke were resulted by the different micro structure that caused the blend ed coal mix of coking plants. This paper presents that the quantity of coking coal of low quality should have a limitation in the stamp-charging coking. This is due to the stamp-charging coking technology can improve the mechanical strength of coke, but the thermo properties of coke are determined by the micro structure of coke (i.e optical structure). Based on analyzing the relation between micro structure and thermo properties of coke, this paper gives give the rational micro structure of stamp-charging coke as well as the corresponding composition of blended coal mix to meet the demand of large-scale blast furnace.

SESSION 53 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND UTILIZATION 6

53-1 Coal Structure Rearrangement Caused by Sorption of CO2 Angela Goodman, DOE-NETL, USA Coals are glassy solids and the temperature at which they become rubbery (Tg) lies above their decomposition temperature. When swollen by a dissolved molecule, Tg decreases, coal properties change, and the coal may undergo a structural rearrangement. By creating additional free volume in the solid, they enable molecular motion and a rearrangement of the coal physical structure, even when present at low concentrations. The exposure of powdered and core unconfined coals to CO2 results in changes in the coals physical structures. Carbon dioxide seems to be an effective

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plasticizer of coals and it is important to understand why this is so. Coal structure change caused by carbon dioxide is explored using infrared spectroscopy to measure diffusion rates, scanning electron microscopy to examine changes in pores and surface area roughness, surface area measurements to examine the how carbon dioxide probes the coal interior, and differential scanning calorimetry to measure heat capacites of fresh and carbon dioxide exposed coals. 53-2 CO2 Reservoir Properties of Naturally Activated Australian Coals Abouna Saghafi, CSIRO Energy Technology, AUSTRALIA Australian coal seams have been subjected to numerous igneous intrusion events since their formation during the Permian period, with the latest major event to occur during the Tertiary, ~50 million years ago. These igneous intrusions have injected substantial volumes of carbon dioxide (CO2) into the coal seams and magmatic fluids heated and metamorphosed many coal systems. Considerable amounts of the magmatic CO2 has been adsorbed locally by the devolatilised coals, while the remaining gas eventually moved away from the intrusion sites and replaced the pre-existing methane (CH4) in unaffected coals away from the heat source. In recent years the CSIRO has been investigating the coal seams of the Sydney Basin for storage of CO2 from fossil fuel electricity generation. This research has been largely stimulated by the fact that the option of coal seams as reliable reservoirs for injecting the CO2, captured from nearby coal-fired power plants, is now seriously considered in Australia. A number of pilot projects (government and industry partnerships) are already planned and are scheduled to start within the next 2-3 years. This study was undertaken to evaluate the gas reservoir properties of CO2 naturally stored in coal seams and the effect of heating on the storage properties of these coals. The results of measurements show a significant enhancement in the storage capacity of coal to both CO2 and CH4 which is reversely proportional to the distance from the heat source (a dyke in this case). Furthermore, the diffusivity of gas in solid coal is enhanced for the devolatilised coals. This paper describes the methodology and result of measurements conducted on these coals, and discusses the impact of the findings on possible CO2 storage and CH4 recovery from heat affected coal seams. 53-3 Analysis of High-Temperature CO2 Capture Reactor Using Lithium Silicate Hideo Kitamura, Takeo Takahashi, Masahiro Kato, Toshihiro Imada, Yasuhiro Kato, Kenji Essaki, Toshiba Corporation, JAPAN Lithium silicate (Li4SiO4) can be used for high-temperature CO2 separator in thermal power stations such as pulverized coal-fired power plants or integrated gasification combined cycle power plants (IGCC). It absorbs CO2 effectively at temperatures between 450 to 650C and releases CO2 above 650C. Because the operation temperature of this sorbent is higher and lowering the gas temperature is not needed, the energy for CO2 separation can be reduced compared to that of conventional methods such as the amine method. In this paper, the numerical analysis of the reactor in which CO2 is captured from the flue gas of the thermal power station is studied. The analysis was based on onedimensional unsteady model assuming a pseudo plug flow, where heat transfer environment was also included. The reaction rate used in the computation was determined using the data of TG (thermogravimetry) profile of lithium silicate. As a result of the analysis in which a moving bed type reactor (500 m21.5 m) was installed in the 500 MW pulverized coal-fired power plant, the CO2 recovery coefficient was maximum when the inlet temperature of the flue gas was 450-500C. The CO2 recovery coefficient increased as the initial temperature of the sorbent decreased, and the CO2 recovery coefficient reached the highest value of 24% when the initial temperature was 650C. 53-4 Developments in Sequestering CO2 as a Carbonate Mineral: pH Control in a Biomimetic System for the Sequestration of CO2 as Calcium Carbonate Elizabeth C. Larkin, Gillian Bond, New Mexico Institute of Mining and Technology, USA Sequestration as a mineral carbonate offers the potential for safe long-term storage of CO2 without concerns of leakage or monitoring. Considerable progress has been made in the development of an aqueous biomimetic method to accomplish this end, the major remaining challenge prior to pilot-scale testing being that of economical pH control. Recent work has determined that a combination buffer of 200 mM NaOH and 200 mM NH4OH can be used as a buffer. This buffer contains inexpensive components, affords full utilization of calcium in waste brines, and offers the potential of value added to ammonia-rich agricultural waste.

53-5 The Second Generation of Nano-Porous Molecular-Basket Sorbents for CO2 Capture from Flue Gas Xiaoliang Ma, Xiaoxing Wang, Chunshan Song, The Pennsylvania State University, USA Carbon capture and sequestration (CCS) is considered as one of the key options for mitigating the emissions of CO2. However, the cost for CCS is greatly concerned and the cost of separation and capture of CO2 from the sources is estimated to be up to about two thirds of the total cost of CCS. Consequently, novel technologies with low cost for CO2 capture are therefore crucial for the commercial viability of this option to reduce CO2 emissions. Our previous study has shown that the Molecular-Basket Sorbent (MBS) by a polyethylenimine-modified molecular sieve MCM-41 is a promising sorbent for CO2 capture from flue gas. The present presentation will show our current approaches in development of the second generation of MBSs and integration of them in CO2 capture from flue gas, focusing on increasing capacity and sorption/desorption rate, decreasing MBS preparation cost, and solving the sorbent degradation problem. In comparison with the amine scrubbing process, our developing MBSs and process have shown some significant advantages: 1) high sorption capacity (~140 mg-CO2/g-S at 15 kPa of CO2); 2) no corrosion; 3) high sorption/desorption rate due to high gas-sorbent interface area (1-4107 m2/m3-MBS); 4) good regenerability and stability; 5) overcoming the degradation problem of MBS by using a physical MBS to remove SOx/NOx; 6) simple process and lower operational cost; and 7) flexible applications (fixed-bed, fluidized-bed or moving-bed). 53-6 Aminopropyl-Functionalized Mesoporous Silicas for the Adsorption of CO2 Xin Fu, Junping Li, Ning Zhao, Wei Wei, Yuhan Sun, Chinese Academy of Sciences, CHINA The gradual increase in the atmospheric concentration of carbon dioxide (CO2) due to fossil fuel combustion is becoming a serious environmental problem. Meanwhile, it is also one of the most important pollutants responsible for the green house effect. The Kyoto protocol (1997) points towards a reduction of CO2 and other greenhouse gases for more than 5% before 2012. Thus, the development of high-capacity adsorbent was becoming more important. One potential approach to preparing such an adsorbent is to graft CO2 adsorption sites on the high surface area support. Novel CO2 adsorbents were prepared by grafting aminopropyl on mesoporous silica MCM-41 and SBA-15. The NH2-functional group in APTMS could provide CO2 adsorption sites. The physical properties of these adsorbents were characterized by power X-ray diffraction (XRD) pattern, solid-state 29Si nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, and measurements of N2 adsorption and desorption isothermal, which confirmed that aminosilianes were grafted on the surface of the channels in the mesoporous materials. The amine-grafted MCM-41 materials adsorbed CO2 as carbonates and bicarbonates with a total capacity of 56.4 mg/g adsorbents at the room temperature. The experiment results indicate that the rate of CO2 adsorption on SBA-15 serial samples is more quickly than that on MCM-41 serial samples in beginning adsorption stage. However, the amounts of CO2 adsorption on MCM-41 series samples are higher than that on SBA-15 serial samples.

SESSION 54 COAL UTILIZATION BY-PRODUCTS 3

54-1 A Methodology for Environmental Impact Assessment Study for Back Filling of Coal Ash Generated from a Thermal Power Station in a Mine Filled With Acid Mine Drainage S.K. Dube, NTPC Limited, INDIA NTPC Limited, a prime power utility in India has an installed capacity of about 29,394 MW plus. Consequent to the usage of low-grade coal for power generation, enormous quantity of ash is generated. The land available for disposing such huge quantity of ash is gradually becoming scarcer. In addition, the Notification by the Regulatory Agencies for utilization of 100% ash over a period of 9 years invites exploration of other options. In view of the above limitation, back filling of abandoned mines appeared to be one of the most attractive proposals for large-scale ash utilization. However, the environmental impact of this option needs to be studied and documented for regulatory approval and final project implementation. The primary objective of this paper to present a suitable methodology for disposal of coal ash in safe and environmentally acceptable manner in any abandoned mine which is filed with acid mine drainage. If such a study is conducted then, it is expected to establish the existing environmental conditions and will help in predicting impacts, suggest appropriate mitigation measures and prepare Environmental Management Plan (EMP). The present paper covers the description of requirements of different tasks for conducting this type of study such as Environmental aspects including hydro-

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geological investigations and groundwater monitoring to establish baseline conditions, source, gradient, quantity, quality and characterization of hydrology regimes in the immediate vicinity of the mine site, Establishment of baseline environmental conditions such as Air, Noise etc.; Ash characterization and leachability, Ash and pit water characterization, Ash-mine pit water interaction and geo-chemical transport, Ash filling in the mine pits and requirement of evaluation of technologies, Environmental Impact Assessment (EIA) studies & mitigation measures. This document is expected to serve as a base document for conducting such studies to be taken for any Mine back filling project involving coal ash generated by a thermal power station. 54-2 Effects of Lignite Ash on Pyrolysis Kinetics of Lignite Yaoling Chi, Fuchen Ding, Hong Wang, Jieming Xiong, Beijing Institute of Petrochemical Technology; Shuyuan Li, State Key Lab of Heavy Oil Processing,University of Petroleum, CHINA The pyrolysis kinetics of Zhaotong lignite was studied using thermogravimetric analyzer at the heating rate of 15C/min. The effects of lignite ash on the pyrolysis process were investigated. The kinetic model of pyrolysis reaction was developed. The kinetic parameters were determined. The content of oil and gas produced by pyrolysis increased in the presence of lignite ash. The results showed that lignite ash has a catalytic effect on the lignite pyrolysis. The effect was closely related to temperature region. The corresponding activation energy decreased because of the effect of lignite ash. The pyrolysis process can be described by the two-step integral model. 54-3 Thermal Behaviour and Kinetics Investigations of Malaysian Oil Palm Biomass, Low rank Coal and their Blends during Pyrolysis via Thermogravimetric Analysis (TGA) Siti Shawalliah Idris, Khudzir Ismail, Norazah Abd Rahman, Azil Bahari Alias, Universiti Teknologi MARA Malaysia, MALAYSIA An experimental study on co-pyrolysis of Malaysian oil palm biomass (palm mesocarp fibre (PMF), empty fruit bunches (EFB), and palm kernel shell (PKS)) and low rank coal (Mukah Balingian) was performed via Thermogravimetry Analysis (TGA). All the tests were carried out in nitrogen atmosphere, under dynamic conditions at heating rates of 10, 20, 40, and 60C/min in temperature range from 25C to 900C. The Mukah Balingian/Oil palm biomass blends were prepared in the weight ratios of 100:0, 80:20, 60:40, 50:50 and 0:100. TGA results show that palm kernel shell has three thermal evolution profiles, while palm mesocarp fibre has two distinct peaks, and only one peak appeared in decomposition of empty fruit bunch. The thermal evolution profiles correspond to the disintegration of hemicellulose and cellulose at relatively low temperatures (ca. 300-350C), and lignin at much higher temperature (approximately 700C). Pyrolysis of coal/palm kernel shell revealed quart-modal derivative Thermogravimetric (TG) curve. In a similar manner, the coal/palm mesocarp fibre blends and coal/empty fruit bunch blends generate tri-modal and bimodal TG curves respectively. The thermal evolution profiles of coal/palm mesocarp fibre and coal/empty fruit bunch during pyrolysis, however, showed the domination of the biomass pyrolysis at lower temperature, with the coal pyrolysis (i.e. volatile matter released) occurred at much higher temperature. Unlike the fibre and empty fruit bunch coal blends, coal/palm kernel shell blends has additional peak appeared at temperature higher that that of coal pyrolysis. Apparently, no interactions were seen between the coal and biomass indicating lack of synergistic effects between these two solid fuels. First order equations were used to determine the biomass and coal component thermal decomposition kinetics. The lowest value of activation energy with respect to the coal volatile matter released is achieved in 80 wt% blend of MB/PMF with activation energy of 254 kJ/mol, while lowest value of activation energy of 257 kJ/mol and 265 kJ/mol achieved in 50 wt% blends of MB/PKS and MB/EFB, respectively. These findings will provide useful data for power generation industries for the development of co-firing options using coal/biomass blends.

In a first step, a fuel database is developed, including both the physico-chemical properties of coal but also its reactivity during pyrolysis (flammability) and combustion (emissions of pollutants, unburnt residues, etc.). The highly variable nature of the fuel and the variability of experiments carried out to obtain such data, represent a real difficulty for a reliable, comparative use of the obtained characteristics. In order to identify the parameters of interest, a previous work in collaboration with modelers has been performed to define precisely their needs (data interesting for the simulations, their precision, the impact of the test temperature on the simulations). In a second step, from these obtained experimental data, 3D simulations of the coal combustion behavior in PC boilers have been performed with the CFD software CodeSaturne. These simulations allowed us to obtain, at a lower cost, valuable information on some physical phenomena such as: the impact of the coal quality on its behavior in PC boilers under several conditions the impact on the pollutant emissions (NOx, SOx) Qualitative trend analysis (multi-criteria analysis) Simulation of alternative operating conditions Identification of risk-free low NOx operating conditions Prediction of unburnt carbon in ash Study of flame ignition and stability Analysis of corrosion risk Prediction of slagging and fouling The aim is therefore to characterize coals so to be, on one hand, representative of industrial operating conditions, and on a second hand in adequation with the 3D simulations needs in order to characterize the impact of the coal quality on its behaviour in PC boilers. P1-2 Study on the Fixing Sulfur Using Additives during Coal Combustion Qiaowen Yang, Liying Wang, Yanan Zhang, Ling Shi, Binbin Zhao, Xiaoyong Ma, Jian Chang, China University of Mining & Technology (Beijing), CHINA Middle high-sulfur coal of Xian was tested in this paper. Then the effect of selected sulfur-fixing additives on the sulfur-fixing capability of Ca(OH)2 was conducted. It was obtained that different additives produced different promoting effect on calcium carbide residue sulfur capture and the promoting effect and mechanism were dissimilar. For example, Al2O3 and Fe2O3 are more effective and lower-cost sulfurfixing additives. At last, three compositions additive were studied, and the sulfur-fixing efficiency of two composite additives, which were named CAM and NAM, was above 62%. P1-3 The Application of Multi-Sensor Data Fusion Technique Based on Parameter Estimation in Coal Spontaneous Combustion Experiment System Lian-hua Wang, Hua Wang, Baoxiang Cao, Qufu Normal University, CHINA The precise and credible measurement of temperature in coal spontaneous combustion (CSC) experiment is a most urgent technique problem should be solved recently. The paper puts forward a technique of CSC temperature data fusion on the basis of multisensor parameter estimation. In terms of data processing, first adopts the distribution diagram method to reject the negligent errors in the monitored data, and then fused the data by means of parameter estimation. Based on this, the temperature control system will control water temperature to track coal temperature automatically. Second, Uses the fused coal temperature data to simulate CSC under mine. The practical application demonstrates that the fused results possess higher precision and reliability. P1-4 Transformations of Trace Elements in Burning Coal Eugene Samujlov, Ludmila Pokrovskaja, Marina Faminskaja, Krzhizhanovsky Power Engineering Institute; Larisa Lebedeva, Fossil Fuels Institute, RUSSIA The model of processes of transformation of trace elements - zinc, cadmium, lead - is developed at burning Podmoskownij coal. The complex approach combining of geochemistry, chemical thermodynamics and physical and chemical kinetic is used. With the help of the literary data forms of a presence of trace elements in Podmoskownij coal are analysed. Thermodynamic researches of processes of their transformation are carried out at change of temperature. As a result of these researches the data on composition of the substances containing zinc, cadmium and lead are received at various temperatures. The data on temperatures of condensation of vapor the substances containing trace elements are received. Physical and chemical kinetic of transformations of the mentioned trace elements was investigated in the technological channel of boiler P-59 of the Rjazanskaja power plant. The problem was considered in one-dimensional approximation. Macroscopical parameters of a stream in the channel depending on time are known from the experimental data. The kinetic equation, describing processes of transformation the vapor substances containing zinc, cadmium, lead, is received and solved. Sedimentation of vapor substances, containing trace elements, on particles of fly ashes was taken into account. Calculations were carried out at restricted speed of an exit mentioned vapor from a mineral component of coal. The role of processes of volumetric condensation of vapor is appreciated.

POSTER SESSION 1 COMBUSTION TECHNOLOGIES

P1-1 A Complete Procedure from an Advanced Coal Characterization to Pollutants Emissions Prediction Anne-Lise Brasseur, Sandro Dal-Secco, EDF R&D, FRANCE Because of coal supplies diversification as well as the use of coal blends, a complete procedure from Coal Characterization to Pollutants emissions prediction has been developed in order to help the operator to control the impact of Fuel Flexibility on environmental issues (NOx, carbon in ash), but also on grinding, flame stability, slagging.

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Accommodation factors of vapor on a surface of particles of fly ashes were determined from the experimental data. As a result of calculations, mass fractions of trace elements not vaporization from mineral mass of coal are appreciated. Mass fractions of trace elements of zinc, cadmium, lead, not vaporization from the condensed phase at burning coal in boiler P-59, are accordingly equal 0.592; 0.398; 0.883. Initial concentration of zinc, cadmium, lead in the Podmoskownij coal burnt in boiler P-59, in g/t.coal accordingly are equal 160; 4,46; 33,1. Mass of Podmoskownij coal mentioned trace elements in vapors of the substances containing it elements, on an exit from the chimney are accordingly equal 45,1; 2,41; 3,47 g/t.coal. Mass of zinc, cadmium, lead condensed on microparticles of ashes on an exit from a chimney are accordingly equal 10,5; 0,316; 0,399. Mass product of burning is 4.749 kg./kg.coal. Work is executed at financial support (grants 05-08-01512 and 07-08-0082).

P2-3 Desulfurization of COS in Syngas with Iron-Based Sorbent Modified by Copper Dexiang Zhang, Changqing Hao, Hai Zhao, Tingting Wu, East China University of Science and Technology, CHINA In order to improve desulfurization properties of the iron-based (Fe2O3Al2O3) sorbent and increase the sulfur retention capacity and high H2S or/and COS adsorption rate, copper oxide promoters or some cerium are needed to modify the sorbent. The sorbents were prepared with iron trioxide hydrate (goethite) and copper monoxide by a novel preparation method like physical mixing in water. The results show that one of these sorbents is capable of reducing the H2S or/and COS content of coal-derived syngas from 10,000 10-6 to near 0.4 10-6 of each cycle prior to breakthrough simultaneously. There seems to be a temperature of 700 K for the optimum sulfur retention capacity reaching about 0.25 g S/g. No deactivation was observed after 10 successive adsorptionregeneration cycles. About 35% elemental sulfur of the sulfur retentated in sorbent was directly regenerated in the regeneration operation. The regeneration scheme was a two-stage process. Nitrogen gas mixed with 36% steam was introduced between 573 and 723 K in the first stage, and in the second stage, feeding with 1% oxygen was used when temperature reached above 723 K until 1023 K. Finally, the fresh, sulfurized and regenerated sorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy/energy dispersive-spectroscopy (SEM/EDS). Fourier transformed infrared spectroscopy (FTIR) and BET surface area analysis. P2-4 Desulfurization Performance of Fe-Mn-Ce Based Sorbents Prepared Using Different Precipitating Agents for COS Removal from Synthesis Gas Hai Zhao, Dexiang Zhang, Fangfang Wang, Tingting Wu, Changqing Hao, Jinsheng Gao, East China University of Science and Technology, CHINA Various Fe-Mn-Ce based sorbents were prepared by coprecipitation method with three kinds of precipitants, NaOH, NH4OH and Na2CO3, and the desulfurization performance of COS removal was studied. Test results showed that evident differences in bulk and surface phase exist among these sorbents prepared with different precipitation agent. The sample prepared with NH4OH coprecipitation show higher surface areas and larger sulfur capacity at low temperature. But the samples will sinter after high temperature treatment and its stability at high temperature is needed to be enhanced. The Na2CO3 precipitated sorbent represents higher surface area and better desulfurization behavior than the sorbents prepared by NH4OH and NaOH as the precipitants at high temperatures. The sorbent coprecipitated with NaOH shows lowest sulfur capacity and desulfurizatin efficiency compared with NH4OH and Na2CO3. The sorbents exhibited low desulfurization activity after higher calcination temperatures. The decrease of activity was mainly caused by the change of BET surface area due to the increase of the particle size at higher calcination temperature. P2-5

POSTER SESSION 2 GASIFICATION TECHNOLOGIES AND PNNL-CHINA

P2-1 Physical Properties and CO2 Gasification Characteristics of Liquid Phase Carbonization Coke at High Temperatures Jinsheng Gao, Shiyong Wu, Jing Gu, Ye Li, Youqing Wu, Zhenhua Qi, East China University of Science and Technology, CHINA In the study, the physical properties of liquid phase carbonization cokes (petroleum coke and pitch coke), including carbon crystalline structure and BET surface area, were measured at pyrolysis temperatures ranging from 950C to 1400C, respectively using the XRD and the pore structure analyzer, and their CO2 gasification characteristics were also performed isothermally in a thermo-gravimetric apparatus in the gasification temperature range of 950-1400C. The effects of pyrolysis temperature on carbon cryatlline structure, BET suface area and gasification activity of liquid phase carbonization cokes and their gasification processes were mainly investigated. Some significant findings were obtained. The increasing pyrolysis temperature resulted in the increase of BET surface area of liquid phase carbonization cokes, made their carbon crystalline structure more ordered, and more easily led to their graphitization in the higher temperature range. The high temperature pyrolysis, as a whole, was favorable for the gasification activity of calcinated cokes from liquid phase carbonization cokes, and the effects of BET surface area on the gasification activity of calcinated cokes form liquid phase carbonization cokes were stronger than the effects of their carbon crystalline structure. The gasification activity of liquid phase carbonization cokes was obviously lower than that of coal chars, and even lower than that of the natural graphite. Especially at high temperatures, the gas diffusion hardly affected the gasification process of liquid phase carbonization cokes. P2-2 High Performance of Limonite-Based Composite Catalysts in the Decomposition of Ammonia in a Simulated Syngas-Rich Fuel Gas Yasuo Ohtsuka, Naoto Tsubouchi, Hiroyuki Hashimoto, Tohoku University, JAPAN Catalytic decomposition of 2000 ppm NH3 with an Australian limonite ore, which is composed mostly of goethite (-FeOOH), has been studied from a viewpoint of hot gas cleanup with a fixed quartz reactor at ambient pressure under the high space velocity of 45000 1/h. It has already been reported that, when -FeOOH in the limonite is reduced with pure H2 at 500C, the transformation into nanoscale particles of metallic Fe takes place, and the catalyst achieves the almost complete NH3 decomposition in inert He at 500C. The limonite also exhibits such a high catalytic activity at 750C even without the H2 reduction or in the coexistence of 100 ppm H2S, whereas it is seriously deactivated by co-feeding syngas with NH3 because of carbon deposition from CO, and the extent of the deactivation is larger at a lower temperature and a higher syngas concentration. The strong XRD peaks of both iron carbides and crystallized carbon are observed on the used limonite after the reaction at 750C. On the other hand, the addition of small amounts of CO2 and H2O, which are always included in actual coalderived fuel gas, to a large concentration of syngas (50 vol.% CO/25 vol.% H2) can improve the activity of the limonite, and NH3 conversion to N2 at 750C is stable to be 6570% except for the initial decrease, though carbonaceous materials are still deposited significantly. When several limonite-based catalysts with alkali metal and alkaline earth metal cations are prepared by the impregnation method and used in the NH3 decomposition at 750C in 50% CO/25% H2/5% CO2/3% H2O, Mg cations work more effectively as the promoter, and the 3 mass % Mg-added limonite maintains the high and stable NH3 conversion of almost 100% for 50 h. In this case, no significant carbon deposition takes place, and metallic Fe is the only crystalline phase. It is probable that MgO with strong basicity suppresses the carbon formation from CO, and that the limonite-based composite catalyst thus shows the superior performance in the NH3 decomposition in syngas-rich gas that simulates raw fuel gas produced in O2blown coal gasification.

The Comparison of Fly Ash Carbon and Coal Char with Respect to the Physical and Chemical Properties and CO2 Gasification Reactivity Jinsheng Gao, Jing Gu, Shiyong Wu, Ye Li, Youqing Wu, East China University of Science and Technology, CHINA In this study, the fly ash carbon samples are collected from Texaco gasifier in Shanghai Coking Plant and Nanjing Chemical Plant, using Shenhua coal as the raw material and operating at different pressures. The physical and chemical properties and reactivity of two samples were studied and compared with rapid pyrolysis char of Shenhua coal, preparing at the temperature of 1673 K in a small-scale falling reactor, which regarded as reacted carbon in gasifier. The mineral matter fusion, degree of graphitization, pore structure and the CO2 gasification reaction characteristics of SCFA, NCFA and RPCC were investigated by SEM, XRD, N2 and CO2 adsorption method and isothermal thermo-gravimetric analysis. It was found that the fly ash samples exhibited lower carbon content and graphitization degree and higher specific surface area, as well as ash fusion degree. In general, the gasification reactivity of fly ash carbon was better than RPCC (Shenhua rapid pyrolysis char at temperature of 1400C) and the difference was obvious at higher temperature (~1373 K). P2-6 Influence of Superficial Velocity on Biomass Gasifier Design D. N. Reddy, K. Basu, Osmania University, INDIA Cleaner and cheaper tar heating downdraft gasifiers are generally used with low ash and low moisture wood for power generation. High gasification temperature enables devolatisation and gasification reactions to take place simultaneously. To maintain high temperature, oxygen supply could be higher than required for optimum gasification thereby reducing heating value of gas and lowering exergetic efficiency of gasification This study attempts to analyze the sensitivity of operating parameters on heating value of product gases and efficiency of gasification. Base parameters selected for comparison is Superficial Velocity, which is independent of gasifier configuration and related to gas flow. The analysis integrates devolatisation and gasification models

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enabling estimation of tar and char loss more accurately. Gasification energy optimization is through sensitivity analysis of preheated air and fuel. P2-7 Modeling Coal Gasifier Performance Using a Hybrid Finite Volume Finite Element Approach Vladimir Korolev, Ken Johnson, George Muntean, PNNL, USA Steady state and transient performance of a coal gasifier depends on macro-level process parameters such as operating temperature, coal feedstock and refractory type. However, predictive modeling of gasifier aging and plant economics is possible only through the explicit simulation of all the primary physical processes from the microlevel to the macro-level. Micro-level processes include the coal devolatilization, chemical kinetics, and the multi-component diffusion that occur within the gasifier flow stream. Macro-level processes include radiation heat transfer, heat transfer through the refractory walls, temperature induced deformations of the refractory, and other elements of the gasification plant. Refractory aging and degradation mechanisms under the aggressive chemical environment and temperature and pressure transients must also be considered in life assessment models. This paper describes a finite volume framework that was developed to predict gasifier performance using strongly coupled direct modeling of the coal devolatilization, coal, char and volatiles combustion chemical kinetics, volatiles multi-component diffusion, and slag and solid residual generation. This solution was then coupled with a finite element solver to simulate the heat transfer through the gasifier wall. The model results are compared with analytical models and experimental data. The ultimate goal is to provide a tool that will help optimize gasifier performance/life time/economics by calibrating the gasifier operative parameters for changing coal feedstock quality and feed rate. P2-8 Conversion of Lignite to Activated Carbon in Supercritical Water Jicheng Bi, Leming Cheng, Kezhong Li, Rong Zhang, Institute of Coal Chemistry, Chinese Academy of Sciences, CHINA For the aim of utilization of solid product for hydrogen production from lignite in supercritical water (SCW) as a cheap source of carbon adsorbents, conversion of lignite to active carbon was performed in SCW in the presence of CaO or KOH under the conditions of 600-650C, 25 MPa for 1 h. Comparative experiments of steam gasification under same temperature at ambient pressure were conducted to get a better understanding of the roles of SCW on gasification kinetics and pores structure development of the solid product. The result shows that a higher carbon gasification rate can be obtained at SCW and the obtained solid products displays higher adsorption capacity compared with those by steam under ambient pressure. In the case of catalysts added experiments, KOH shows a more significant promotion on the gasification rate and adsorption capacity of resulted residue than CaO. The BET surface of 10% KOH added sample can reach to 623 m2/g, compared to 330 m2/g of that without catalyst sample. The BET surface might be further increased when the pyrolysis condition in SCW is optimized to effectively remove tar adsorbed in carbon pore surface generated in pyrolysis reaction. Furthermore, the ash content of the KOH added sample can be reduced to about 3% after dilute HCl washing. Therefore, the solid product of SCW gasification of lignite can be used as active carbon, and this might be an economically viable option in conversion of low rank coal to hydrogen in SCW.

unburned carbon and HCl, Hg0 was captured and Hg2+ was later released. When the ash was exposed to the simulated combustion flue gas at temperatures between 120C and 210C, mercury oxidation improved at higher temperature. P3-2 Pilot Operation Production of Carbon from Waste Plastics for the Preparation of Carbonaceous Materials of Specific Properties Suitable for Industrial Applications Josef Vales, Jaroslav Kusy, Lukas Andel, Marcela Safarova, Brown Coal Research Institute, CZECH REPUBLIC A qualitatively various and difficultly recyclable group of plastics is a suitable source of pure carbon. The plastics are not decomposable by natural processes in most cases. The environment protection requires their liquidation by recycling processes with a subsequent material use of the products. The process of the total recycling of polyethyleneterephthalate (PET) by the pyrolysis is an efficient way to gain carbon. The thermal decomposition of waste PET in a pyrolysis unit without an air access under definite procession conditions is the base of the way. The charge is decomposed while a mixture of organic acids originates terephthalic and benzoic acid in 10:1 ratio and with yield about 78%. A carbonaceous rest with the high content of carbon and yield of 20% is the solid product of the decomposition. A pilot operation unit has been assembled in which all needed verifying tests were carried out, for the verification of the functions of running processes of thermal PET decomposition, specification of the process conditions, including acquisition of fundamental information of technical, technological, economical, and qualitative character. The research of carbonaceous materials with C content of 90-94% was carried out at modified activation processes at temperatures higher than 550C. The relations and dependencies were determined leading to the increase of specific surface and pores volume by using various activation agents and activation times. Technical and technological conditions were studied which can influence the size of created pores and their distribution occurrence. The modified processes of the reprocessing of solid carbon from PET decomposition enable to prepare the sorbents with demanded specific surface up to 1800 m2.g-1, pore volume up to c. 1.6 cm3.g-1, and with prevailing occurrence of micro-pores. The prepared sorbents of specific qualities were successfully tested for capture of various undesirable pollutants from both liquid and gaseous mediums. P3-3 Economical Energy Production and Environmental Protection Krzysztof Jesionek, Jzef Antoni Goliski, Wrocaw University of Technology, POLAND With reference to the article [1] of 1990 on the economical production of electricity, the authors supplement the remarks in regard to necessity of satisfying relevant restrictions as to the atmospheric pollutions. A kind of universal combined/cogeneration plant coupled to a high pressure coal-gas generator (Lurgi) has been proposed. For driving the power plant natural gas or coal gas is assumed. Compressed air and steam of 25 bar and 500C temperature, necessary for the gas generator, are extracted from the power plant system. Coal gas produced by a Lurgitype generator may be stored in a number of pressure tanks which may feed some other turbine systems. The coefficient of fuel utilization is quite high. The overall coefficient for the coupled system (the product of the fuel utilization coefficient and the chemical conversion efficiency) amounts to about 0.6. The authors believe that such a plant deserves some consideration in planning future development of energy systems. [1] Goliski J. A., Kilka sugestii dotyczcych ekonomicznego wytwarzania energii elektrycznej (in Polish) A few remarks concerning economical electrical energy production,Midzynarodowa konferencja Klimatyzacja i Ciepownictwo, Wrocaw Szklarska Porba, Prace Naukowe Instytutu Inynierii Chemicznej i Urzdze Cieplnych Politechniki Wrocawskiej, Seria: Konferencje, nr 12, 1990, s. 85-94. P3-4 Evaluation on Performance of a Novel Highly Effective Sulfur-Fixed Agent in Coal Burning Chen Hongbo, Jiang Yin, Shao Xun, Beijing Research Institute of Coal Chemistry, China Coal Research Institute, CHINA It is important to add some sulfur-fixed agents to coal in medium and small coal burning boilers in China because China has many such boilers. Performance of a novel highly effective sulfur-fixed agent in coal burning developed by a Chinese company was evaluated and studied in this paper, which is composed of special natural mineral ore and special catalyst, and has many characteristics such as rapid reaction, high calcium availability, low ratio of calcium to sulfur. Kulun sulfur determination apparatus was used to determine sulfur emission at different experiment conditions for five Chinese representative high sulfur content coal samples. Experiments were conducted to investigate the effect of combustion temperature and ratio of sulfur-fixed agent to coal on sulfur retention during coal combustion, sulfur retention was evaluated by comparing sulfur emission among different ratio of sulfur-fixed agent to coal. The

POSTER SESSION 3 ENVIRONMENTAL CONTROL TECHNOLOGIES

P3-1 Mercury Oxidation and Adsorption by Fly Ash in Coal Combustion Flue Gas Akimasa Yamaguchi, Naoki Noda, Hiroyuki Akiho, Shigeo Ito, Central Research Institute of Electric Power Industry; Kouichi Miura, Kyoto University, JAPAN Mercury capture by fly ash in coal combustion flue gas has been reported as adsorption on unburned carbon, but it is possible that mercury behavior depends on the gas composition, etc. and mercury oxidation is affected by the fly ash. In this study, mercury capture and oxidation caused by fly ash were investigated in the presence of SO2, HCl, and water vapor. Simulated coal combustion flue gas containing elemental mercury (Hg0) was fed to a thin flyash layer, with the following results. The captured mercury in the fly ash increased almost proportionally to the specific surface area of unburned carbon. HCl seemed to be necessary for mercury capture on the unburned carbon. The mercury capture capacity of the unburned carbon decreased in the presence of SO2 and water vapor. At higher SO2 conditions, the amount of captured mercury and the specific surface area decreased contrary to the increase in sulfur in the fly ash. This suggests that the sulfur compound accumulated in the fly ash inhibited mercury adsorption on the unburned carbon. Since the carbonfree ash did not oxidize mercury, oxidation was likely achieved by the unburned carbon. In the presence of

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results show that temperature is an important factor influencing sulfur retention, sulfur retention descends with the temperature rising. Ratio of sulfur-fixed agent to coal influences sulfur retention too, it increases with the addition ratio rising on certain temperature. At temperature of 900C, obvious effect is achieved when addition ratio is 4%, sulfur retentions of different samples are from 50% to 81%. At high temperature of 1150C, the effect is bad when addition ratio is less than 3%, but when addition ratio reach 10%, favorable effect is achieved, sulfur retention is above 30%, even up to 55%. This sulfur-fixed agent can also control arsenic emission during coal burning and reduce temperature of coal ash fusibility. It is possible to popularize this sulfur-fixed agent in China. P3-5 Evaporation of Wastewaters from Wet Gas Scrubbing Operations William A. Shaw, HPD, a Veolia Water Solutions & Technologies Company, USA In the EU and the USA, wet scrubbing for flue-gas desulfurization (FGD) is installed on more than 80% of coal-fired power plants and is considered to be best available technology (BAT). Similarly, coal gasification processes employ a wet scrubbing process for desulfurization of the syngas. Wet scrubbers typically require a continuous blowdown to limit the accumulation of corrosive salts, especially chlorides, and suspended solids washed from the gas stream. This purge stream usually cannot be discharged to the environment without some type of treatment. Evaporation plants can reduce the purge stream to a crystalline solid and recover high quality water for re-use in the power plant thereby achieving a true zero liquid discharge (ZLD) solution. A variety of evaporator types using various energy inputs can be applied to concentration of wet scrubber purge water. The major concerns when concentrating such a stream by evaporation are handling the high concentration of corrosive dissolved solids, handling the solids which precipitate, and selecting suitable materials of construction. This paper discusses various methods of configuring evaporator system components to achieve high availability and reliability treating wet scrubber purge water while minimizing capital and operating costs. This paper will present data from the operation of an evaporation/crystallization system installed to eliminate the liquid effluent from a wet limestone-gypsum FGD process retrofitted to two coalfired power generating units at a European site. The system is part of an overall effort by the power plant owner to reduce emissions and integrate environmentally-friendly processes and operational efficiency into the power station, which currently generates 336 MW of power from the use of coal as fuel.

P4-2 Distribution of Unminable Coals along the Eastern Margin of the Rome Trough in Central West Virginia with Considerations of Carbon Sequestration Potential and Risk Tom Wilson, Hema Siriwardane, West Virginia University, USA Successful carbon sequestration is gauged in terms of the likelihood of long term CO2 retention and the potential CO2 storage volume. Factors influencing long term reservoir integrity include coal seam continuity, coal seam depth, cap rock integrity, the presence of breaching faults and fracture zones, injection pressure and long term response of coal to CO2 injection. We selected an area in central West Virginia for detailed assessment of coal sequestration potential. The area lies near the border between the southern and northern coal regions where detailed maps of the deeper coals have not been compiled. The study area also lies along the eastern margin of the Rome trough, a failed rift that developed primarily during the Cambrian and Ordovician periods but continued to accommodate minor displacements during the later Paleozoic. The structural complexity of the area incorporates the potential for detached structures since the area lies along the western limit of detached structures observed in the Appalachian foreland. An associated issue addressed in this study is whether shallow structures observed in the coal bearing section are associated with syndepositional reactivation of margin structures or result from post-depositional detachment. The study incorporates interpretation of conventional vibroseis and higher resolution weight-drop seismic data. Geophysical logs from over 100 wells are used to develop structure and isopach maps of low density and low gamma zones that may represent individual coal seams. Interpreted low density intervals and potential coals in this area are believed to be confined largely to the Kanawha Formation. Isopach maps reveal that these zones generally have pod-like distribution and would, in todays terms, be considered unminable. The study also incorporates geomechanical simulations of surface displacements and pore pressure distributions resulting from hypothetical CO2 injection efforts along with estimates of injection volume as a function of permeability. Optimal high permeability injection scenarios suggest that the coals in the section do not represent a sufficient sink for commercial scale sequestration efforts. P4-3 Experimental Study on Sorption Mechanism of Gases in Coals Sohei Shimada, Naoto Sakimoto, The University of Tokyo; Mamoru Kaiho, Osamu Yamada, National Institute of Advanced Industrial Sciences and Technology (AIST), JAPAN For geological CO2 storage, not only in ECBMR, it is important to understand that sequestrated CO2 will be fixed for a long time. Generally, the storage mechanism of CO2, CH4 and N2 in coals are thought to be adsorption. The reasons behind this are coal is porous material, CO2, CH4 and N2 is nonpolar molecule and the Langmuir equation is applicable to the calculation of the adsorption amount for coal and CO2, CH4 and N2 system etc. However, some reports say that CO2 is not only adsorbed on coal but also dissolved in coal. Adsorption phenomenon between coal and gas was examined by measurement of heat of adsorption. The heat of adsorption was measured for Akabira coal (bituminous coal: Japan), Shenhua coal (bituminous coal: China) and Taiheiyo coal (sub-bituminous coal: Japan). Large differential heat of adsorption was measured at low pressure and it decreased with pressure. Compared with theoretical heat of adsorption, it was estimated that adsorbate was adsorbed on high affinity adsorption site in order and CO2 was dissolved in coal. P4-4 CO2 Sequestration Related to Shenhua Direct Liquefaction Plant Qingyun Sun, Jerald J. Fletcher, West Virginia University, USA The Shenhua direct coal liquefaction (DCL) plant, the first coal-to-liquids project in China, is expected to begin production in late 2008. With an initial investment of approximately $1.5 billion USD, the Shenhua DCL plant will produce the equivalent of about 24,000 barrels of oil per day in the form of liquid fuels (primarily diesel) while generating about 3.6 million metric tones of CO2 per year. Given growing concerns with CO2 emissions, carbon management is expected to become the biggest environmental and economic concern for future operation of the plant. To address this issue, West Virginia University (WVU) and the Shenhua Coal Liquefaction Research Center are cooperating on a joint research project to determine the feasibility of sequestering a significant proportion of the CO2 produced by the Shenhua DCL plant. This poster provides an overview of the WVU research activities related to the carbon sequestration prefeasibility study for the Shenhua DCL plant. Financial support for the WVU effort is provided by USDOE through a cooperative agreement with WVU. The activity is undertaken as part of the Annex II agreement between the US Department of Energy and Chinas National Development and Reform Commission (NDRC) under the US-China Clean Energy Protocol. The poster provides an overview of the CO2 sources including quantity and composition. Given currently available geological data, options for carbon storage and presented and compared. An initial assessment of the

POSTER SESSION 4 GLOBAL CLIMATE CHANGE

P4-1 Economical Evaluation of the Carbonation- Calcination System for Capturing CO2 Carmen Clemente, Julio Rodrigo Naharro, Etsiminas-UPM, SPAIN The cost of the CO2 capture using carbonation-calcination cycles as a technological option of the CO2 capture in post combustion is the sum of several terms: sorbent costs, capital costs related to the capture plant, the new operation and maintenance processes, the cost of the additional fuels necessary to compensate the penalty in the efficiency due to the capture, and the cost of the CO2 compression. The required conditions for the sorbents are that they have to be either very goods or very cheap. The cost of the sorbent flow cant be higher than 1-3 per separated CO2 ton. In the case of utilisation of CaCO3 as a sorbent, it has been calculated that the cost per separated CO2 ton is 2,5 . The problem of this sorbent is that its deactivation is quick, but this is compensated by its high abundance in the nature. Apart from this, it has to be into account other terms in order to obtain the global cost. It has supposed a generation plant of 360 MW with a fluidized bed reactor. It has been estimated that it can be reached a realistic capture up to 78% in the carbonator using CaO as a sorbent, as well as a 100% of the CO2 generated in the calcinator, resulting capture rates of 85% approximately. The assumptions for the operation and maintenance are that the carbonators require a molar relation Ca/C of 4 for an effective CO2 capture, a 30% of the fuel is burned in the calcinators and the rest in the combustor, the capacity of the CaO to capture CO2 decreases with the number of cycles, the recuperation rate of CaO is 92,5%, the global efficiency of the plant is 40,7%, the fuel is petroleum coke or anthracite. Furthermore, taking also into account the capital costs and the compression of the CO2, it has been calculated that the global cost is 15,5 for a life of 30 years of the plant. Therefore, a priori it seems to be a reasonable cost compared with the technological options of CO2 capture that are in operation nowadays, specially those which use amines.

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economics of the alternatives is included. Information on the Shenhua CO2 sequestration experience will help environmentalists, policy makers and industrial decision makers better understand the CO2 issues for CTL alternatives now under consideration in a number of countries around the world.

POSTER SESSION 5 SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL

P5-1 Studies on Mn Addition to Ru/Al2O3 Catalyst for Fischer-Tropsch Synthesis Mohammad Nurunnabi, Kazuhisa Murata, Kiyomi Okabe, Megumu Inaba, Isao Takahara, Biomass Technology Research Center, JAPAN The additive effect of Mn to Ru/Al2O3 catalyst was investigated on catalytic activity, selectivity and stability for FischerTropsch synthesis in a continuous stirred tank reactor (CSTR) under pressurized conditions. Without Mn modified Ru/Al2O3 catalyst showed low CO conversion and deactivation rate was clearly observed at low reaction temperature of 493 K, where small amount of Mn addition such as Mn/Al=1/19 on Ru/Mn/Al2O3 enhanced the CO conversion and C5+ selectivity for FischerTropsch synthesis. Under pressurized conditions, high catalytic activity and high resistance to catalyst deactivation with time on stream were observed under pressure of 60 bar, and equilibrium CO conversion was about 96%. From the characterization results of BET, XRD, TPR and XPS, the addition of Mn can be influenced to increase the number of Ru atoms on the catalyst surface by the removal of chloride from RuCl3, resulting to inhibit the catalyst deactivation. P5-2 Division of Macerals in Hydro-Liquefaction Based on Reflectance Chen Hongbo, Jiang Ying, Beijing Research Institute of Coal Chemistry, China Coal Research Institute, CHINA China is developing coal liquefaction for alternative fuels because of rich coal and poor oil. Shenhua Group Corporation, the largest coal producer in China, is constructing coal liquefaction plant, so 17 coal samples of different maceral compositions were selected from Shendong coal mining area, the inertinite contents of them are from 21.30% to 76.45%, and reflectance of all macerals were determined for every sample. Hydro-liquefaction behaviours of samples were achieved by Autoclave experiments at Optimal reaction temperatures, which rises with inertinite content increasing such as 470C for inertinite content above 70%, 465C for 60%~70%, 460C for 52%~60%, 455C for 45%~52%, 450C for below 45%. The results show that coals with high inertinite content can obtain relatively high oil yield if selecting appropriate reaction conditions, especially optimal temperature. But, if the inertinite content above 70%, the oil yield is relatively low. Macerals can be divided into active group, transition group and inert group based on reflectance, reaction temperature affects borderline, so division chart of macerals based on reflectance and temperature is achieved. Inertinite content of Shenhua coal is below 45% generally, reaction temperature of commercial plant is 450C or 455C. At the temperature of 450C, reflectance of transition group ranges from 0.90% to 1.15%, semifusinite has relatively high reactivity and belongs to transition group. P5-3 Thermocracking of Coal Wastes to Produce Gasification Fuel and Synthetic Crude Olufemi Anthony Olajide, Sreeja Madala, Elliot B. Kennel, West Virginia University; Richard A. Wolfe, Wolfe Engineering, USA A bench scale thermocracking process has been demo nstrated as a means to process coal wastes generated from prep plants and mining activities. The coal conversion process involves a thermocracking process, results in coproduction of three phases of valueadded products. First, a small amount of hydrocarbon gas is produced. Second, a liquid product is produced by condensing coal volatiles from the process stream. Third, a clean solid fuel is produced, potentially suitable for use in a coal gasification system such as FutureGen, the DOE zero emissions concept that uses coal gasification to co produce hydrogen and electrical power. The apparatus used to crack the waste coal, as well as the characteristics of each of the three phases are described. P5-4 Organic Modification Effects of Silica Support for Fischer-Tropsch Synthesis Catalysts Yuhan Sun, Lihong Shi, Bo Hou, Yao Xu, Debao Li, Jiangang Chen, State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, CHINA The catalytic activity and product selectivity of cobalt catalysts are strongly influenced by the surface properties of the support because they can change the interaction between cobalt and the support, resulting in different dispersion and reducibility of the

supported cobalt. There are plenty of silanols on the surface of SiO2, and the properties, concentration, and distribution of silanols on SiO2 surface can be modified by organic solvent pretreatment. However, there are few literature reports on the influence of SiO2 modified by different organic groups on the dispersion and reducibility of cobalt and its catalytic performance. In the present work, SiO2 was modified by organic silanes, such as methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES), chlorotrimethylsilane (TMCS), (3Aminopropyl)triethoxysilane (APTES) and N-[3-(Trimethoxysilyl)propyl] ethylenediamine (EDPTMS), to change the surface silanol concentration and property on the SiO2 support before the impregnation of cobalt an CH3-modified SiO2 (CH3SiO2) was prepared as follows. Ten grams of SiO2 was preheated at 200C for 12 h under vacuum to remove all adsorbed moisture but surface silanols, cooled to room temperature under vacuum, and then transferred into a 250 ml conical flask. After mixing with 40 ml toluene and 5 ml MTES, the mixture in the conical flask was put into an ultrasonic bath (operating frequency 50 kHz) for 2 h at ambient temperature. The sample was then obtained by extracting with toluene in a Soxhlet extractor for 24 h and drying at 50C for 20 h under vacuum. The same method was used for the preparation of (CH3)2-modified SiO2 ((CH3)2-SiO2), (CH3)3-modified SiO2 ((CH3)3SiO2), NH2-modified SiO2 (NH2-SiO2) and NH2(CH2)2NH-modified SiO2 (NH2(CH2)2NH-SiO2) using DMDES, TMCS, APTES and EDPTMS, respectively. (CH3-SiO2), (CH3)2-SiO2 and (CH3)3-SiO2 reduced the surface silanol (Si-OH) concentration of SiO2 support, suppressed the interaction between cobalt and silica, enhanced the reduction of the supported cobalt, and thus increased the catalytic activity of Co catalysts for Fischer Tropsch synthesis. However, coordination compounds were formed between NH2-SiO2 and Co2+ cation, and thus the interaction between cobalt and silica was enhanced, the catalytic activity of Co catalysts for Fischer Tropsch synthesis was decreased. Because chelated compounds were formed between NH2(CH2)2NHSiO2 and Co2+ cation the supported cobalt catalyst showed the worst performance in FT synthesis. These modified supports and the repective catalysts were characterized by BET, Si MAS NMR, FT-IR, XRD, Laman, TPR and XPS to understand how organicallymodified SiO2 influenced the properties of cobalt catalysts. These characterizations clearly showed the changes of morphology as well as chemical properties of the catalysts. The reducibility of these catalysts varied greatly and the organic modification remarkably influenced the catalytic properties of these cobalt catalysts. NH2-modified SiO2 and NH2(CH2)2NH-modified SiO2 had a negative effect on the catalytic properties of Co catalysts, whereas CH3, (CH3)2 and (CH3)3-modified SiO2 showed pronounced effects on the catalytic behaviors of Co catalysts. P5-5 Study on Deactivation of Co-Ru Catalyst for Fischer-Tropsch Synthesis Ajay Dalai, Ahamd Tavasoli, Reza Malek Abbaslou, University of Saskatchewan, CANADA Detailed activity study and the deactivation of Ru-Co/-Al2O3 catalyst for FischerTropsch (FT) synthesis over 1000 h was investigated considering different deactivation mechanisms. Morphology changes of the catalyst during FT synthesis were studied using XRD, TPR, BET, ICP, Carbon determination, H2 chemisorption and re-oxidation techniques. When the PH2O/(PH2+PCO) in the reactor is above 0.75 the deactivation rate is not dependent on the number of the catalyst active sites and is zero order to CO conversion. In this case the main deactivation mechanisms are: cobalt re-oxidation, metal support interactions and aluminates formation. The deactivation of Ru-Co/Al2O3 is related to cobalt cluster size. At lower amounts of PH2O/(PH2+PCO) deactivation can be simulated with a power law expression with a power order of 39.7 and the main deactivation is due to sintering. Regeneration of catalyst at 275C recovered the catalyst activity by 69.9% of total activity loss due to the reduction of oxidized cobalts. Catalyst regeneration at 400C recovered the activity by 21.9% of total activity loss due to the reduction of refractory forms of oxidized cobalt generated by cobalt-alumina interactions. 7.2% of total activity loss is irreversible and can be assigned to aluminates formation, sintering and coke deposition. P5-6 Investigation on Highly Dispersed Iron Catalyst for Direct Coal Liquefaction Zhou Jianming, Wang Naiji, Beijing Research Institute of Coal Chemistry, China Coal Research Institute; Gong Zhijian, Shandong University of Science and Technology; Wang Caihong, Wang Yonggang, China University of Mining and Technology, CHINA The highly dispersed FeOOH and FeOOH were prepared by sedimentation method, of which granularities, surface area, pore specific volume, average radius and character of thermal decomposition were analyzed by SEM, BET and TGA. The effects of catalysts, highly dispersed FeOOH and FeOOH, on the liquefaction of Shangwan coal were examined using a micro autoclave at same Fe moles, comparison with conventional Fe2O3. It was found that the granularities of FeOOH and FeOOH were between 20~80 nm, the FeOOH of spindle and the FeOOH of thread asymmetrical clew and batting, which gradually dehydrating covert into Fe2O3 and Fe2O3 at 250~300C. As a result, at 420C, the total conversion and oil yield order is: FeOOH > FeOOH > Fe2O3. The total conversion of FeOOH is 2.84% and

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11.33%, higher than that of FeOOH, and the Fe2O3, meanwhile the oil yield is 3.10% and 10.01%, higher than that of FeOOH, and the Fe2O3 at same adding Fe 3.00% (dried coal). With increasing the liquefaction temperature, the order of the liquefaction ability range of adding is: FeOOH < FeOOH < Fe2O3. It was shown that the FeOOH and FeOOH decreased the temperature for liquefaction reaction, because asphaltene and preasphaltene converted into small molecule gases and liquefaction products were promoted by FeOOH and FeOOH.

POSTER SESSION 6 CHEMICALS, MATERIALS, AND OTHER NON-FUEL USES OF COAL

P6-1 Carbon Prepared by Polyethyleneterephthalate (PET) Pyrolysis at Laboratory Conditions Lukas Andel, Jaroslav Kusy, Josef Vales, Marcela Safarova, Brown Coal Research Institute, CZECH REPUBLIC Waste plastics are the source of a carbon suitable for follow-up industrial applications. The way to obtain carbon is based on the thermal decomposition of unsorted polluted waste polyethyleneterephthalate (PET) at exactly defined process condition. The mixture of organic acids terephthalic and benzoic in 10:1 ratio and solid carbonaceous rest is the product of thermal decomposition. The mixture of organic acids is separated and purified in appropriated processes. Both acids can be further proceeded industrially. The running processes of the PET thermal decomposition were studied and verified by laboratory methods and its process condition were specified to optimise the semiproducts yield including acquisition of fundamental information of technical and technological character. The yield of organic acids about 78%, carbonaceous rest about 19%, and the rest of a loss in gaseous form can be expected from the pyrolysis of a crushed polluted and unseparated waste PET at optimised process conditions. The basic qualities of pyrolytic carbon were assessed and verified including the possibility of a further treatment. The solid carbonaceous rest is technically very pure. The content of carbon is 90 to 94% depending on the conditions of the decomposition. The relations and dependencies were looked for leading to the increase of specific surface and pores volume by using various activation agents and activation times. The test enabled to determine the dependencies of specific surface, pores volume, and the mass lost of the activate on the total activation time. The modified processes of the reprocessing of solid carbon from PET decomposition enable to prepare the sorbents with demanded specific surface up to 1250 m2.g-1, pore volume up to c. 0.65 cm3.g-1, and the carburisers of steel with low content of volatile combustibles, nitrogen, and sulphur at carbon content about 95% which show strongly favourable values of carburising grade and carbon utilisation than commonly used steel carburisers. P6-2 Catalytic Crystallization of Coal Chingiz Barnakov, Alexey Kozlov, Institute of Coal and Coal Chemistry SB RAS; Svetlana Seit-Ablaeva, Kemerovo Technological Institute of Food Industry; Zinfer Ismagilov, Boreskov Institute of Catalysis SB, RUSSIA The paper deals with a problem of coal catalytic crystallization. A mixture of coal (Gorlovskiy Basin anthracite, Western Siberia) and medium-temperature coal pitch was carbonized at the presence of 3D-metals salts (iron, cobalt, nickel). The influence of both composition and concentration of the salts and the process temperature on the degree of crystallization was shown. The degree of crystallization was studied by XRD analysis. P6-3 Power-Generating Fuel with Coal Preparation Waste Yevgen Zbykovskyy, Victor Saranchyk, Donetsk National Technical University; Aleksandr Gordienko, Mikhail Ilyshov, Donetsk Steel-Metallurgical Plant; Aleksandr Kolomiychenko, Makeevkoks; Victor Chalenko, Yasinovcky Koks and Camichal Plant, UKRAINE One of methods to solve energetic problems of Ukraine is the development of new kinds of artificial fuels, which would allow solving problems of energy conservation and environment protection. In this direction we have conducted wide research work under laboratory conditions, received pilot lots under industrial conditions and tested them on industrial installations. The main tasks solved in the paper are: to obtain the power-generating and domestic fuel with a low cost of the end product, which is competitive compared to coal patent fuel and traditional power-generating T and A mark coals; to ensure high ecology indices of clean power-generating (domestic) fuel (CPDF); to produce fuel with higher marketing properties; and to simplify the task of developing the non-waste technology for coal-breakers. The given tasks are solved via introduction of washed low-sulfurous low-rank gaseous coal and coal dressing waste into the initial mixture for fuel preparation. The initial mixture with these compositions has very low indices by fusibility and coking quality, namely, a low thickness of a

plastic layer (Y=8-10 mm), a high ash content (Ad=15-30%), and a high yield of volatiles (Vdaf=35-40%). Thats why the obtained initial mixture is thermally treated with the inert heat-carrier by high-speed heating up to given temperatures. At such heating of the initial mixture the warming-up to its transformation into plastic state in the course of the layer carbonization is accelerated; the duration of stay in the plastic state and the thickness of a plastic layer is increased; carrying out of thermal reductive processes is improved; and the gradient of temperature and shrinkage in a semi-coke layer is decreased. Increasing of the density of a heated mixture is not accompanied by temperature-conductivity decrease, and the process of carbonization is accelerated thanks to the heat content of a charge increased. Therefore, preliminary thermal treatment will allow producing lump fuel in traditional layer carbonization furnaces from a low-caking mixture. The carbonization of a thermally prepared initial mixture should be conducted at accelerated carbonization periods. Such obtained fuel CPDF has a whole range of advantages compared to other fuels. For instance, by data of dynamic investigations, burning of CPDF fuel pulverized particles in the air atmosphere at torch-furnace is advantageous as to the burn-out completeness and rate compared to power-generating coals T and A. The capability of planning CPDF quality indices depending on consumer requirements (ash content, volatiles yield), the price competitiveness compared to lean coals and anthracite, and the utilization of coal preparation waste ensure the economic expedience of CPDF use. The process and the formula of smokeless ecologically clean power-generating (domestic) fuel have been patented. The know-how owner Closed stock company Donetsksteel-metallurgical plant. For further cooperation, please contact us at address: Direction on innovations and diversification, 122, Ivana Tkachenko str., Donetsk, Ukraine, 83062. P6-4 A Comparative Study of Methane Explosion Inhibition with Inert Gases Hua Wang, Jun Deng, Xiaokun Chen, Lingmei Ge, Hu Wen, Xian University of Science and Technology, CHINA Based on experiment, the influence of container factors, CO2 and N2 on explosion limits and critical value of oxygen density in methane explosion are comparatively investigated. The experimental results show that the explosion limits of methane relates to many factors. Explosion range enlarges with increase of the expansibility of the container. CO2 and N2 inhibited in certain degree the methane explosion, while the inhibition effects of CO2 apparently are superior to N2. The results of the experiment are of great significance in preventing methane explosion in coal mines and conducting practice of branch-chain burning and branch-chain explosion. P6-5 Development of Coal Dry Beneficiation Technology in China Jin Lei, China University of Mining and Technology (Beijing), CHINA As more than two-thirds of available coal reserves in China are located in cold or arid areas, the dry beneficiation technology for coal cleaning is of great significance. A detailed survey of the current status of study and application of dry coal beneficiation technology is given in this paper. P6-6 Toxic Element Removal from Acid Mine Drainage using Zeolites Synthesized from Fly Ash Derivative V.R. Kumar Vadapalli, A.Ellendt, L.F.Petrik, N.Hendricks, W.Gitari, G. Balfour, University of the Western Cape; N.Misheer, Eskom Innovation and Research Department, SOUTH AFRICA South African Fly Ash (FA) was successfully used to treat and remove toxic elements from Acid Mine Drainage (AMD). As a result of the reaction between AMD and FA, insoluble precipitates deposit upon the FA particles at a neutral pH or higher. These solid residues (SR) are a suitable feedstock material for zeolite synthesis because of the Si and Al content. Zeolites are well known ion adsorbents which are often used in waste water treatment. In the current study it was shown that Zeolite Y and Zeolite P were synthesized by the hydrothermal treatment of SR at high (~600C) and low (~100C) temperatures respectively. The synthesized zeolites (Zeolite Y and Zeolite P) were investigated for their capacity to remove toxic elements from AMD. Their toxic element removal efficiencies were compared with commercial zeolite and ion exchange resins. A high percentage of toxic element removal from AMD was observed using both the zeolite types synthesized from SR. In some instances, the zeolites produced from SR performed better than the commercial zeolite or resins, indicating the high value of these low cost adsorbents. Thus the zeolite adsorbents prepared from waste SR can be effectively applied for decontamination of acidic waste waters.

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POSTER SESSION 7 COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES

P7-1 Effect of Technical Property of Coking Coal on Optical Texture of Coke Ru Xiang, Gaifeng Xue, Shangchao Liu, Wuhan Iron and Steel (Group) Corporation, CHINA The optical texture of coke is not only related with the metamorphism of coking coal, but also is related with the technical property of coking coal. In this paper, the effect of technical property of coking coal on optical texture of coke was studied, and the coke was coked by several kinds of coking coal with close rank but different technical property. The results showed that if the coking coal had high caking index and thickness of colloidal matter layer, it was easy to make the coke optical texture transform to higher aeolotropic degree, that was to say, the isotropic structure was easy to transform to the close grained or the close grained was easy to transform to the coarse grained; if the coking coal had low caking index and thickness of colloidal matter layer, the contents of isotropic and inert structure of its coke would become high. P7-2 Study on the Property of High Volatile 1/3 Coking Coal from Shandong Province in China Ru Xiang, Peng Chen, Gaifeng Xue, Wuhan Iron and Steel (Group) Corporation, CHINA By studying the technical indexes, the vitrinite reflectance, the measuring of colloidal matter layer, and the coke microstructure of gas coal and high volatile1/3 coking coal from Shandong Province and other regions, it was indicated the industry brand of high volatile 1/3 coking coal from Shandong Province belongs to the 1/3 coking coal, but the coal property of various mine was obvious different. The coal with high metamorphism and active ingredient still has the property of 1/3 coking coal, but the coal with low metamorphism and active ingredient leans to the property of gas coal. It should be blended rationally. P7-3 Rapid Method for Measuring Bulk Density of Coal Powders Amrit Boparai, Jack Demirgian, Kathryn Lawrence, GreatPoint Energy, USA At GreatPoint Energy, bulk density of powdered coal feed and processed coal streams is one of the parameters needed for characterization of the performance of the test reactors which are designed to convert coal and petroleum coke into methane. Typically, bulk density of coal powders is determined (ASTM Method D-4292/B-527) by pouring a weighed amount of powder into a graduated cylinder, vibrating or tapping the cylinder for several minutes and then using the graduations on the cylinder and a ruler to measure the volume. Bulk density is calculated by dividing the mass (g) of the sample by the volume (cm3) of the sample. Because of electrostatic interactions between the finely divided coal and glass, many samples do not form a clearly-level surface in the graduated cylinder. This causes uncertainty in determining the volume of the sample. Another potential error is in quantitatively transferring a pre-weighed sample of finely divided coal into a graduated cylinder. We developed a procedure that saves time by vibrating the sample as it is poured into a fixed volume vial and eliminates potential errors in measuring and recording weights and operator variability in measuring volume using a ruler. We interfaced a computer to the balance to enter the mass data directly into a spreadsheet to allow automatic calculation of bulk density. The procedure allows us to collect data for bulk density of a sample in less than 5 minutes. We will describe in detail how to assemble the proposed setup using commercially available material and discuss the standard deviation of measurements and comparison of bulk density values obtained by the proposed method and by using an ASTM Bulk Density Method. P7-4 Characteristics of the Roof and Floor of the Pittsburgh Coal Bed Main Bench Susan Tewalt, Leslie Ruppert, Kristin O. Dennen, U.S. Geological Survey, USA A three-dimensional model of the main bench of the Pittsburg coal bed, created in Earthvision1 using the U.S. Geological Surveys (USGS) 2000 National Coal Assessment stratigraphic dataset can be used to visualize mined and unmined areas at a regional scale, as well as previously known large-scale trends of bed thinning to the south and west. The predominant lithology of the two feet of overlying (roof) and underlying (floor) rock of the Pittsburgh main bench were extracted from the data and mapped in two dimensions for Maryland, Pennsylvania, West Virginia and Ohio. Coal is the predominant roof lithology where an overlying coaly zone is thickest in northern West Virginia and to the northeast in Pennsylvania. Predominant siltstone roof lithology occurs in sinuous belts (e.g. Monongalia County, West Virginia up

through Washington County, Pennsylvania; Belmont to Harrison Counties, Ohio) and coincides with occurrences of overlying fluvial sands. Floor lithologies are extensively described as fireclay and flintclay (flint), followed by fewer occurrences of claystone/mudstone. To a lesser degree, siltstone and coal also occur as floor material. Physical characteristics of overburden play a role in the rate of recharge and the quality of water that fills the mine void after coal removal. The roof and floor materials are exposed to air and water and contribute to the chemistry of the accumulating mine pool water. Roof collapse can play a role in mine water chemistry and the rate of vertical water infiltration may be affected by the competency of overlying rocks. Additional study of the physical characteristics of the entire sequence of Pittsburgh coal overburden, as well as chemical characterization of the immediate roof and floor, may be helpful in predicting environmental impacts as active mining decreases. P7-5 Viscosity Changes of Different Ranks of Coal-Anthracene Oil Slurry Under High Temperature-High Pressure During Preheating Jinsheng Gao, Yingjie Ren, Dexiang Zhang, East China University of Science and Technology, CHINA Coal-oil slurry preheating is an important step during coal direct liquefaction, and some physical and chemical changes will occur that will affect the viscosity of coal-oil slurry. The project is necessary for the building coal direct liquefacation demonstration plant and has a good application prospect. A rotary viscometer that can measure the viscosity of coal slurry at high pressure-high temperature was designed by self and manufactured in this project. Three kinds of crushed coal including Yanzhou Coal (middle rank and caking), Shenhua Coal (low rank and non-caking) and Shengli Coal (brown coal) were used, and anthracene oil was used as the hydrogen-donating solvent. The coal-oil slurry is prepared by mixing the anthracene oil with the coal powder (<200 mesh) according to a coal/solvent weight ratio equal to 2/3. The slurry was putted into the high temperature and high pressure viscometer and heated under 5 MPa initial hydrogen pressure at the rate of 5 K/min till the different setting temperature. At the same time the viscosity changes with increasing temperature of coal-oil slurry was investigated under atmosphere. The results show that both of Yanzhou Coal and Shenhua Coal display the viscosity peak with increasing temperature under atmosphere, but Shengli brown coal never displays the viscosity peak. Moreover, the viscosity peak of Yanzhou Coal shows earlier than that of Shenhua Coal. Yanzhou Coal has a higher viscosity peak, Shenhua Coal has a small viscosity peak but Shengli Coal has not viscosity peak under high pressure during the whole preheating. So the higher rank and more agglutinate the coal is, the easier the viscosity appearance is. In addition, the viscosity-temperature characteristics of preheated coal-oil slurry through different temperature are different. The viscosity of coal oil slurry with Yanzhou and Shenhua at the same measure temperature have a peak appearance with increasing preheating temperature, however, the viscosity of Shengli coal oil slurry always increases with increasing preheating temperature. P7-6 Abundances of Minerals in High-Alumina Fly Ashes from the Jungar Power Plant, Inner Mongolia, China Shifeng Dai, Lei Zhao, Yong Zhang, Dan Li, Yingying Sun, Yuwen Ma, Xibo Wang, China University of Mining and Technology, CHINA; Chen-Lin Chou, Illinois State Geological Survey, USA The fly ashes from the Jungar Power Plant, Inner Mongolia, China, are unique because they are highly enriched in alumina (Al2O3 > 50%). Samples of pristine fly ashes were collected from the economizer and the ash concentration units. Minerals in the fly ashes have been studied using X-ray diffraction analysis (XRD) and a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer (SEMEDX). The feed coal of the power plant is enriched in kaolinite and boehmite. The fly ashes mainly consist of amorphous glass, mullite, corundum, quartz, unburned carbon, and trace amounts of calcite, K-feldspar, and clay minerals. The mullite content in fly ashes is as high as 37.4% because of high boehmite and kaolinite contents in feed coal. Corundum is a characteristic mineral formed during the combustion of boehmite-rich coal. The amount of amorphous glass in the fly ashes decreases from the economizer to the wet ash collection units. Samples from the economizer were sieved into six size fractions (<120, 120-160, 160300, 300-360, 360-500 mesh, and > 500 mesh) for mineralogical analysis. The corundum content increases but amorphous glass decreases with decreasing particle size. The 300-360 mesh fraction is highest in mullite content. Fractions of small particle sizes are relatively high in mullite, probably because mullite was formed from fine clay mineral particles under high-temperature combustion condition. Similarly, fine corundum crystals formed in the boiler from boehmite in feed coal. Mineral matter in feed coal largely becomes amorphous glass during combustion.

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P7-7 Element Volatilisation During the Thermal Treatment of South African Bituminous Coals Monica Raghoo, Christien Strydom, North-West University; Henry Matjie, Sasol Technology (Pty) Ltd, SOUTH AFRICA; Harold Schobert, The Pennsylvania State University, USA The response of South African low-grade, medium rank C bituminous coals to sequential leaching with water, ammonium acetate, and hydrochloric acid has been investigated by the conventional chemical analysis of both the leached coals and the leachate solutions. The ammonium acetate treatment removed most of the Na, Ca, Mg and Mn suggestive of an organic association and occurrence as ions of carboxylate groups. Hydrochloric acid removed almost all the Ca and Fe from the coals. Close evaluation of the data suggests that some of the Al in the coals was also removed by the selective leaching process, primarily by the hydrochloric acid treatment. This may reflect a solution of organically-associated Al from the maceral components. The loss of fluxing elements (such as Ca and Mg) induced by the different leaching processes was also associated with increases in ash fusion temperatures. Samples from the sequential leaching process were demineralised and organicallyassociated elements were added to the samples. The original and demineralised samples were then analysed by a series of FT-IR Raman spectroscopic experiments, which included the thermal treatment of samples at various temperatures in an external lab-scale reactor. Vapour species were detected through ZnSe windows in the reactor. This is in contrast to conventional reactor techniques where volatile species are condensed and thereafter analysed via analytical methods. The poster will present observations and results from the experiments. P7-8 Effect of Trace Amount of Oxygen on Removal of Stable Sulfur in Coal Baoqing Li, Zongqing Bai, Wen Li, Fenrong Liu, Institute Of Coal Chemistry, Chinese Academy of Sciences, CHINA; Jan Yperman, Hasselt University, BELGIUM The stable organic sulfur forms in coal such as thiophenic and dibenzothiophenic sulfurs are very stable to be removed from coal during coal conversion processes, which leads to severe environmental problems. In this work, several typical organic sulfur model compounds including thiophenic and dibenzothiophenic sulfur were pyrolyzed under 1.0% O2/He and the sulfur forms released were detected by on-line mass spectroscopy in order to investigate the effect and the mechanism of trace amount of oxygen on the removal of the stable sulfurs in coal. Furthermore, the sulfur removal during pyrolysis of one Chinese Wujiaping coal (WJP) with high organic sulfur under oxidative atmosphere was also studied. The results show that the specific peak temperature of sulfur release is decreased during pyrolysis of the model compounds with stable thiophenic sulfur under trace amount of oxygen compared to that under inert atmosphere, which indicates that the trace amount of oxygen has positive effect on removal of the stable sulfur. When WJP coal is pyrolyzed under 1.0%O2/He, the peak temperature of SO2 is always lower than those of CO2 and CO, indicating that the oxidation of sulfur occurred before that of organic carbon frame of coal. The coal pyrolysis tests show that the trace amount of oxygen could increase the efficiency of sulfur removal without remarkable decrease in the char yield.

trace species with the SOFC anode requires prolonged effort due to the low concentrations of trace materials present in direct syngas. Test durations of at least 500-1000 hours are required for accurate prediction of long term degradation after operation at 40,000 hours. Additionally, the range of trace material forms available for testing in the laboratory is a small subset of the material forms existing in direct syngas. To enhance testing and accelerate collection of pertinent results, we have designed and deployed a mobile test skid capable of field testing SOFC button cells on direct coal syngas. The Multi-Cell Array (MCA) system simultaneously tests 12 SOFC button cells, fuelled in parallel and individually load controlled. Testing multiple specimens at once permits statistical comparison and accelerates testing compared to individual laboratory tests. The MCA system also supports an integrated GC-ICP/MS system that can provide analysis of the direct coal gas and can identify trace elements at a ppb level. The system requires a power source, and a source of coal gas, and bottled gas supplies and can operate outdoors and unattended for an indefinite period of time. Preliminary results were obtained from initial deployment of the SOFC MCA system at the Power Systems Development Facility (PSDF) gasifier in Wilsonville, AL. The 100 hour hydrogen test indicated successful operation of 5 cells over the entire duration. The success rate was greater than 40% for this initial deployment and further improvements to the test fixture will improve this rate. Further operation of the system at the PSDF on direct coal syngas is expected later in 2008. Results from the hydrogen baseline testing and testing on direct syngas will be described in this presentation. This technical effort was performed in support of the National Energy Technology Laboratory s on-going research in SOFC under the RDS contract DE-AC2604NT41817. P8-2 Novel Sulfur and Coke Resistant Anode Catalysts for Reduced Temperature Coal Gas Fed SOFC Systems Nandita Lakshminarayanan, Hyunkyu Choi, Umit. S. Ozkan, The Ohio State University, USA Solid Oxide Fuel Cells (SOFC) are the most desirable fuel cells for stationary power generation and as auxiliary power sources in transport applications. The fuel flexibility and higher efficiency of an SOFC make it a favorable choice. They can be used for a variety of applications including small-scale, remote co-generation purposes, uninterrupted power generation in hospitals as well as eventual incorporation into large-scale distributed power generation. The higher efficiencies that can be achieved in these systems make them ideal for coal gas fed power generation systems. However, despite the degree of hydrogen purification and sulfur removal after coal gasification, there remain traces of these impurities in the feed stream. The current Ni-YSZ anode catalysts exhibit very good catalytic activity towards hydrocarbon reforming and good compatibility with the rest of the SOFC system, however they are highly susceptible to poisoning due to sulfur in the fuel. Development of sulfur and coke resistant anodes will not only bring SOFCs closer to commercialization, it will also significantly reduce costs and eliminate material issues associated with gas clean-up and pre-treatment steps. The current work examines development, performance and resistance of new formulations to sulfur and coking. Bulk and surface specific characterization techniques, including X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD) and Vibrational Spectroscopy are used to understand the catalyst chemistry and nature of interactions. Anode performance is evaluated by testing activity for various fuel side reactions. P8-3 Continuum Degradation Model for SOFCs Anode Material under Coal Syngas and its Implementation in FEA to Predict Long-Term Structure Integrity Gulfam Iqbal, Huang Guo, Bruce Kang, West Virginia University, USA A degradation model is developed to predict long-term structural integrity of Solid Oxide Fuel Cell (SOFC) anode exposed to coal syngas. The model incorporates thermo-mechanical degradation and coal syngas contaminants effects on the anode microstructure. The proposed model is implemented into finite element analyses through user defined subroutine. The model is validated using a NexTech Probostat button cell test apparatus integrated with a Sagnac optical setup and infrared thermometer. This setup is capable of simultaneously measuring surface deformation, temperature and electrochemical performance. An analytical solution is also developed for button cell under uniform pressure to establish correlation between the degradation model and experimental measurements, as well as to determine the effective anode Youngs modulus due to thermal-mechanical and/or electrochemical degradation. P8-4 In-situ Surface Deformation and Temperature Measurement of Button Cell Under SOFC Operating Conditions Huang Guo, Gulfam Iqbal, Rajeev Dastane, Bruce Kang, West Virginia University, USA An experimental technique capable of simultaneously measuring in-situ surface deformation, temperature and electrochemical performance of solid oxide fuel cell

POSTER SESSION 8 GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND HYDROGEN APPLICATIONS

P8-1 Solid Oxide Fuel Cell Multi-Cell Array for Parallel Testing on Direct Coal Syngas Kirk Gerdes, Richard Pineault, Randall Gemmen, DOE-NETL; Greg Hackett, West Virginia University, USA Integration of solid oxide fuel cells (SOFC) and coal gasification systems is being pursued to improve energy production efficiency and enhance carbon capture capability. SOFCs are considered for integration owing to their high operating temperatures (in excess of 800C) and reduced cleanup requirements as compared to other fuel cell technologies. In addition to system efficiency, degradation performance must also be considered. The SOFC degradation target outlined by the U.S. Dept of Energy through the Solid State Energy Conversion Alliance (SECA) program is < 4% per 1000 hours for Phase I coal based systems. While this target has been met by SECA natural gas based systems, little system testing has been performed for SOFCs operating on direct coal syngas. Degradation due to fuelling with direct coal syngas must be considered since naturally occurring coal trace materials (Hg, Pb, Se, As, etc.) may have undesirable interaction with the SOFC anode. The long term SECA program goals target 40,000 hours of operation while maintaining good performance. However, determination of the interaction of coal

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(SOFC) button cell is developed. The experiment setup consists of a NexTech ProbostatTM SOFC button cell test apparatus integrated with a Sagnac interferometric optical setup and infrared (IR) thermometer. Preliminary results at room temperature and under hydrogen at 800C are presented. The results are validated with finite element analyses. P8-5 The Effect of Ph3 Impurity in Coal Syngas on SOFC Performance Oktay Demircan, Harry O. Finklea, John Zondlo, Chunchuan Xu, West Virginia University, USA The effect of impurities such as phosphorus on the stability and long term performance of solid oxide fuel cells is important to the development of power generation from coal syngas. Commercial solid oxide fuel cells were exposed to a synthetic coal syngas mixture (H2, H2O, CO, CO2) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In a pure syngas mixture, the decay of cell voltage did not exceed 0.1 mV/hour at current densities of 0.25 and 0.5 A/cm2. Phosphine (PH3) was introduced at concentrations of 10 ppm or 20 ppm and the cell operated for several hundred hours. In one test, after 50 hours of phosphine exposure at a current density of 0.5 A/cm2, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss exceeded 1 mV/hour. Removal of the phosphine from the coal syngas mixture did not result in a recovery of the original performance. In another test, the cell operated for over 200 hours at a current density of 0.25 A/cm2 in the presence of 20 ppm phosphine. The rate of voltage loss was 0.3 mV/hour, and changes in the series resistance and polarization resistance were small. Increasing the current density to 0.5 A/cm2 resulted in an accelerated degradation of the cell performance, including a rate of voltage loss of 3 mV/hour and significant increases in the polarization resistance. A partial recovery of cell performance (in polarization and impedance) was observed upon lowering the current density to 0.25 A/cm2 and then removal of the phosphine from the synthetic syngas mixture. SEM images of anode surface after phosphine exposure reveal changes in nickel particle size depending on the location. EDX chemical analysis supports the existence of phosphorus species at one point on the anode surface. No evidence for phosphorus-containing phases is observed in by Raman spectroscopy.

P9-2 Site Characterization Activities with a Focus on NETL MMV Efforts: Southwest Regional Partnership, San Juan Basin Pilot, New Mexico Tom Wilson, Henry Rauch, West Virginia University; Art Wells, Brian Strazisar, Rod Diehl, DOE-NETL, USA A variety of characterization activities have been undertaken on the Southwest Regional Carbon Sequestration Partnerships San Juan Basin pilot site to aid in the deployment and subsequent interpretation of the National Energy Technology Laboratory MMV tracer and soil gas monitoring efforts. In the San Juan Basin pilot test, approximately 75,000 tons of CO2 will be injected in the basal Fruitland coal at a depth of approximately 3500 feet. Site characterization efforts include field and satellite based fracture mapping, subsurface mapping of the region using geophysical logs, evaluation of interferrometric synthetic aperture radar (INSAR) measurements of ground movements at the site, detailed electromagnetic surveys, lineament analysis of radar and Landsat imagery, design of a near-surface ground water monitoring well program and the design of detailed logging and vertical seismic profiling (VSP) efforts in the injection well. Structure on the Fruitland coal across the pilot site is nearly flat and dips approximately 0.25NE toward the axis of the San Juan basin. The Fruitland Formation is about 175 feet thick in the area and contains three coals with net thickness of about 55 to 60 feet. The basal coal injection zone is about 28 feet thick. Subsurface mapping suggests that significant faults and fracture zones are not present at the site. Surface and satellite based fracture mapping reveal the presence of two systematic fracture sets with dominant NE and NW trends. Surface fracture trends are consistent with butt and face cleat trends observed in core through the Fruitland from a nearby well. The face cleat trend in the area is to the NE. Surface observations also included acquisition of 26 line-kilometers of EM data used to help locate potential near-surface fracture zones. We recommended placement of additional tracer and soil gas sample points, and shallow groundwater monitoring wells based on the history of fracture development and the near-surface distribution of low-conductivity features. Satellite based radar scenes of the site were collected multiple times over a three month interval to determine whether near-surface deformation was occurring in response to hydrocarbon production in the area. INSAR observations revealed strong coherence between images but no surface deformation. An attempt to examine longer term (2 year) production effects on surface subsidence failed due to poor coherence with an image of the area collected 2 years earlier. Detailed logging of the injection well is planned and includes the FMI log for detailed fracture characterization and the sonic scanner to obtain mechanical properties and measure sonic anisotropy. One zero offset and three offset VSPs will also be collected prior to and during injection to determine whether the presence of CO2 can be detected and its movements monitored. The VSP may also yield evidence of small scale faults and fracture zones and help the NETL MMV team interpret post-injection observations. The geophysical logging and VSP data will help other NETL and SWP researchers develop geomechanical and flow models.

POSTER SESSION 9 NETL-UNIVERSITY CONSORTIUM

P9-1 Comparative Thermodynamic Evaluation of Oxygen Carriers for Chemical Looping Combustion Rahul Solunke, Goetz Veser, University of Pittsburgh, USA Chemical looping combustion (CLC) is an emerging technology for clean energyproduction from fossil and renewable fuels. In CLC, an oxygen carrier (typically a metal) is first oxidized with air. The hot metal oxide is then reduced in contact with a fuel in a second reactor, thus combusting the fuel. Finally, the reduced metal is transferred back to the oxidizer, closing the materials loop. CLC is a green combustion technology since it allows for flame-less and completely NOx-free combustion without requiring expensive air separation. Furthermore, CLC produces sequestration-ready CO2-streams without significant energy penalty. Combined with sequestration, CLC thus enables high-efficiency, CO2 emissions-free combustion of fossil fuels, or combustion processes with negative CO2-footprint from biomassderived fuels. However, selection and synthesis of appropriate oxygen carrier materials is a crucial issue for CLC. We present a detailed thermodynamic study of a wide range of metals for use as oxygen carriers for CLC using the commercial software package FACTSAGE. The metals were evaluated for their suitability to chemical looping combustion of natural gas as well as coal-derived syngas streams. Maximum attainable fuel conversion, resistance to coking, and thermal stability were used as main comparison criteria in both cases. Additionally, selectivity towards total oxidation (vs partial oxidation) was evaluated for natural gas fed processes. Finally, a particular focus was put on sulfur resistance of the potential carrier materials since typical fossil fuel-derived streams contain significant amounts of S contaminants. In this context, the analysis was extended from metal-based carriers onto metal sulfide/sulfate carrier cycles. Overall, no single carrier was found to meet all possible requirements, and the choice of the carrier clearly depends on the process requirement. Different carrier choices will be discussed in detail in the presentation.

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