TWENTY - FIFTH ANNUAL INTERNATIONAL PITTSBURGH COAL CONFERENCE

COAL - ENERGY, ENVIRONMENT AND SUSTAINABLE DEVELOPMENT ABSTRACTS BOOKLET September 29 - October 2, 2008 The Westin Convention Center Pittsburgh, PA USA

The Westin Hotel and Convention Center Hosted By:

University of Pittsburgh Swanson School of Engineering

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 Page Oral Sessions Page

1: Gasification Technologies: General Session – 1...... 1 41: Global Climate Change: Science, 2: Special Symposium: NETL-University Consortium...... 1 Sequestration, and Utilization – 4...... 40 3: Combustion Technologies – 1...... 3 42: Coal Utilization By-Products – 1...... 40 4: Gas Turbines and Fuel Cells for Synthesis Gas and 43: Gasification Technologies: Hydrogen Applications – 1 ...... 3 Advanced Technologies – 2...... 41 5: Coal Production and Preparation – 1 ...... 4 44: Gasification Technologies: 6: Synthesis of Liquid Fuels: GTL, CTL and BTL – 1 ...... 5 Synthesis Gas Cleaning – 2 ...... 42 7: Gasification Technologies: General Session – 2...... 6 45: Environmental Control Technologies: 8: Hydrogen from Coal –1 ...... 7 NOx/SOx Control Strategies...... 43 9: Combustion Technologies – 2...... 8 46: Chemicals, Materials, and Other Non-Fuel 10: Gas Turbines and Fuel Cells for Synthesis Gas and Uses of Coal – 1...... 44 Hydrogen Applications – 2 ...... 9 47: Gloval Climate Change: Science, 11: Coal Production and Prepartion – 2 ...... 10 Sequestration, and Utilization – 5...... 45 12: Synthesis of Liquid Fuels: GTL, CTL, and BTL – 2 ...... 11 48: Coal Utilization By-Products – 2...... 46 13: Gasification Technologies: Substitute Natural Gas ...... 12 49: Gasification Technolgies: Advanced Technololgies – 3...... 47 14: Hydrogen from Coal – 2 ...... 13 15: Combustion Technologies – 3...... 14 50: Gasification Technologies: Co-Gasification...... 48 16: Coal Chemistry, Geosciences, and Resources – 1 ...... 15 51: Environmental Control Technologies: Combustion Byproduct Applications, SO ...... 50 17: Coal Production and Prepartion – 3 ...... 16 x 52: Chemicals, Materials, and Other Non-Fuel 18: Synthesis of Liquid Fuels: GTL, CTL, and BTL – 3 ...... 17 Uses of Coal – 2...... 51 19: Gasification Technologies: Fundamentals – 1 ...... 18 53: Global Climate Change: Science, 20: Underground Coal Gasification – 1 ...... 19 Sequestration, and Utilization – 6...... 51 21: Combustion Technologies – 4...... 20 54: Coal Utilization By-Products – 3...... 52 22: Coal Chemistry, Geosciences, and Resources – 2 ...... 21 23: Global Climate Change: Science, Sequestration, and Utilization – 1...... 22 24: Synthesis of Liquid Fuels: GTL, CTL, and BTL – 4 ...... 23 25: Gasification Technologies: Fundamentals – 2 ...... 23 26: Underground Coal Gasification – 2 ...... 24 Poster Sessions Page 27: Environmental Control Technologies: Mercury Capture, Noncarbon ...... 25 1: Combustion Technologies ...... 53 28: Coal Chemistry, Geosciences, and Resources – 3 ...... 26 2: Gasification Technologies and PNNL-China ...... 54 29: Global Climate Change: Science, 3: Environmental Control Technologies...... 55 Sequestration, and Utilization – 2...... 27 4: Global Climate Change...... 56 30: Synthesis of Liquid Fuels: GTL, CTL, and BTL – 5 ...... 28 5: Synthesis of Liquid Fuels: GTL, CTL, and BTL...... 57 31: GasificationTechnologies: Fundamentals – 3 ...... 29 6: Chemicals, Materials, and Other Non-Fuel 32: Underground Coal Gasification – 3 ...... 30 Uses of Coal...... 58 33: Environmental Control technologies: 7: Coal Chemistry, Geosciences, and Resources ...... 59 Mercury Capture, Carbon, NOx ...... 31 8: Gas Turbines and Fuel Cells for Synthesis Gas and 34: Coal Chemistry, Geosciences, and Resources – 4 ...... 32 Hydrogen Applications...... 60 35: Global Climate Change: Science, 9: NETL-University Consortium...... 61 Sequestration, and Utilization – 3...... 34 36: Gasification: PNNL-China...... 35 37: GasificationTechnologies: Advanced Technologies – 1...... 36 38: Gasification Technologies: Synthesis Gas Cleaning – 1...... 37 39: Environmental Control Technolgies: Multipollutant Control ...... 38 40: Coal Chemistry, Geosciences, and Resources – 5 ...... 39

analysis suggest that coal gasification with co-production projects could be competitive SESSION 1 and assured sources of transportation fuels, electricity, and other products over the long GASIFICATION TECHNOLOGIES: GENERAL SESSION – 1 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 1-1 construction and operation financially attractive. Compressing, transporting, and World’s Largest IGCC Celebrates 10th Anniversary permanently sequestering carbon dioxide could increase the cost of synthetic fuel by Wolfgang Schellberg, Uhde GmbH, GERMANY; Francisco Garcia Peña, approximately $10.00 per barrel, although revenues from enhanced oil recovery (EOR) ELCOGAS, S.A., SPAIN; Max Hooper, Uhde Corp. of America, USA 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 This paper describes the world’s largest IGCC based on solid feedstock, a mixture of and the credit rating agencies utilize a conservative long-term crude oil price petcoke and coal at ELCOGAS in Puertollano, Spain. Uhde’s PRENFLOTM process is expectation which reflects the likelihood that prices will fall, for periods of time, to used for the gasification of high-sulfur petcoke and high-ash coal. Operational results prices significantly below today’s energy prices. As a result, plants are likely to and lessons learnt in the last 10 years are described. require the support of a purchase agreement with a creditworthy counterparty and, in For more than 65 years Uhde (incorporated with Heinrich Koppers and Krupp some cases, government incentives to address a range of significant business risks, Koppers) is now active in the field of coal gasification technology, especially including price volatility in energy markets, high and escalating capital cost and entrained-flow gasification with dry coal dust feeding. operational uncertainties, and uncertainties about carbon policy. Thus, given the At the moment Uhde is involved in several projects in the United States based on country’s vast coal reserves, the cost advantage co-production plants are likely to have PRENFLO coal gasification, for the generation of electric power and the production of in sequestering carbon dioxide, and the demonstrated commercial track record of coal liquid fuels. gasification technologies, coal gasification with co-production affords the nation an In addition, the new PDQ process (PRENFLO with Direct Quench) will be presented. opportunity that is worthy of careful consideration. It is a total water quench mainly for chemical application. 1-5 1-2 Cleanly Unlocking the Value of Coal ZeroGen - Clean Coal Power Initiative with CCS Synthesis Energy Systems, J. Mathew Whitaker, USA Martin Oettinger, Zvonko Pregelj, Stanwell Corp., AUSTRALIA; Michael DeLallo, Jay White, WorleyParsons Group, Inc., USA; Rik van der Ploeg, Shell Synthesis Energy Systems, Inc. is a global industrial gasification company whose Global Solutions International, THE NETHERLANDS business is to build, own and operate coal gasification plants utilizing its proprietary U- GAS® fluidized bed gasification technology to convert low rank coal and coal wastes ZeroGen Pty Ltd, completed the initial phase of a multiple phase Feasibility Study (the into higher value energy products, such as transportation fuels. Its technology is the project) for the design of an Integrated Gasification Combined Cycle (IGCC) only commercial gasification technology that can process low rank and waste coals, incorporating carbon dioxide (CO2) capture and geosequestration. The project is which further advances project returns and unlocks extraordinary value from the coal located adjacent to the Stanwell Corporation thermal generation station in Queensland, resource. With its ability to process waste coal and the inherently friendly emissions Australia. The ZeroGen Project is a demonstration IGCC (Integrated Gasification profile of its facilities, SES is poised to make a positive impact on the overall Combined Cycle) Power Plant that will incorporate the capability to capture and environmental sustainability of coal conversion projects. And, with approximately sequester carbon dioxide (CO2) in geological formations. The primary objective of the fifty percent of the world’s coal falling into the low rank category, SES is positioned to facility s operational and demonstration program is to validate the application of CO2 facilitate resource owners in Cleanly Unlocking the Value of (their) Coal. 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 SESSION 2 confirmation of key process systems, the process design criteria and parameters for SPECIAL SYMPOSIUM: NETL-UNIVERSITY CONSORTIUM 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, 2-1 plant performance and emissions profiles, and characterized the carbon dioxide Robust and Efficient Oxygen Carriers for Chemical Looping Combustion geosequestration. Rahul Solunke, Tengfei Liu, Goetz Veser, University of Pittsburgh, USA 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. Chemical looping combustion (CLC) is an emerging technology for clean energy- production from fossil and renewable fuels. In CLC, an oxygen carrier (typically a 1-3 metal) is first oxidized with air. The hot metal oxide is then reduced in contact with a Developing Global Coal-Based Fuel, SNG & Chemical Projects fuel in a second reactor, thus combusting the fuel. Finally, the reduced metal is Tim Cornitius, Zeus Development Corporation, USA transferred back to the oxidizer, closing the materials “loop”. CLC is a ‘green’ combustion technology since it allows for flame-less and completely Sustained higher energy prices and growing demand are driving alternative fuel NOx-free combustion without requiring expensive air separation. Furthermore, CLC development. Large-scale 80,000-b/d CTL projects that have been in the study phase produces sequestration-ready CO2-streams without significant energy penalty. of development are now being pulled off the shelves in China, India, Australia and Combined with sequestration, CLC thus enables high-efficiency, CO2 emissions-free South Africa. China is quickly building a coal-to-methanol-based fuel/chemical combustion of fossil fuels, or combustion processes with negative CO2-footprint from infrastructure to supply the growing demand for DME cooking fuel/LPG substitute, biomass-derived fuels. However, CLC currently suffers from insufficient thermal synthetic diesel, ammonia fertilizers, olefins, acetic acid and other products. US stability of the oxygen carriers and slow re-oxidation kinetics. developers are focusing on coal/petcoke-based production of fuels, substitute natural We present a significant step towards overcoming these hurdles through the gas and power as well as using CO2 for enhanced oil recovery and other applications development of novel nanocomposite oxygen carriers. Nanostructured oxygen carriers rather than geological sequestration. were synthesized, characterized (via SEM, TEM, XRD, BET, and chemisorption), and evaluated for their performance in the chemical looping combustion of coal-derived 1-4 syngas streams via multi-cycle TGA experiments. The present contribution focuses on The Business Case for Coal Gasification with Co-Production Ni-based carriers, where nanoscaled Ni particles are embedded in a high-temperature David R. Berg; Brian Oakley, Scully Capital Services, Inc.; Andrew Paterson, stable ceramic matrix. Both high-temperature stabilized alumina and silica matrices Econergy, Inc., USA were synthesized and evaluated. Results are compared to that of conventional Ni- bentonite carrier. The nanocomposites show exceptional high temperature stability, “The Business Case for Coal Gasification with Co-Production” quantifies the highly reproducible oxidation-reduction cycles, and a significant acceleration of the re- economics of coal gasification with co-production, with and without carbon oxidation kinetics as compared to conventional carrier. The accelerated redox kinetics sequestration; examines the market, policy/regulatory, and technical risks associated can be traced back to the elimination of solid-state diffusion limitations in the NiO with developing large-scale early commercial U.S. co-production facilities; and overlayer, and the unusual stability of these materials is explained via a “nano-caging” evaluates the cost-effectiveness of incentives that could improve the financial effect. prospects of early commercial projects. The results of this unique multi-sponsor

1 Beyond the performance of these materials in the combustion of “clean” syngas currently in the process of evaluating the activity of these nanostructured catalysts in streams, we recently extended these studies onto the performance of these carrier WGS, as well as their stability in S-containing feed streams. 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 2-4 effect on structural stability of the materials as well as the reversibility of S-poisoning Exceptional Activity of Nanostructured Pt Catalysts in Low-Temperature was investigated. CO Oxidation Synthesis, characterization, and kinetic evaluation of the materials will be discussed in Yi Zhang, T. Sanders, G. Veser, University of Pittsburgh; S. Natesakhawat, C. detail in the presentation. Matranga, DOE-NETL, USA

2-2 Nanomaterials have found much attention in catalysis over the past decade due to the Synthesis and Characterization of Bimetallic Nanocatalysts for Fuel very high surface area, and sometimes even completely novel reactivity, observed in Processing Applications the “nanosize regime”. One of the major hurdles in studying and utilizing the potential Anmin Cao, Goetz Veser, University of Pittsburgh, USA of “nano-catalysts”, however, is their insufficient stability at realistic reaction conditions. We have recently been able to overcome this barrier by synthesizing Bimetallic nanoparticles (NPs), composed of two different metal elements, are of great highly active and sintering-resistant nanocomposite catalysts, in which metal interest from both scientific and technological perspective. The existence of a second nanoparticles are embedded into a high-temperature stabilized alumina matrix. These metal can introduce new properties and, in particular, lead to significant improvements materials thus combine the high reactivity of nano-sized noble metal particles with the of catalytic properties compared to the monometallic catalyst. As a result, bimetallic excellent high-temperature stability of barium hexa-aluminates (BHA). catalysts have been the topic of intense research for many decades, and recent Here, we present a study of CO oxidation at low-temperature conditions (T < 300 K) advances in the controlled synthesis of bimetallic nanoparticles have lead to a renewed over a 1 wt% Pt-BHA nanocomposite catalyst. CO oxidation is a key reaction in any interest in these systems. fuel processing scheme and has recently gained much attention in the context of Our investigation of bimetallic nanocatalysts for fuel processing applications builds preferential CO oxidation for the production of PEM-fuel cell ready hydrogen streams. onto our previous work on supported nanocatalyst. We had previously successfully At the same time, CO oxidation also serves as a relatively simple model reaction for demonstrated the synthesis of a series of monometallic nanoparticles embedded in a fundamental studies of size effects in nano-sized catalysts. nanostructured ceramic matrix, resulting in highly active and exceptionally stable Low-temperature CO oxidation was performed by saturating a Pt-BHA sample with nanocomposite catalysts. CO at 300 K followed by evacuation, cooling, and backfilling the chamber with O2 to In the present work, we are extending this approach by transforming this 0.5 Torr. The reaction progress was monitored in-situ via FTIR over a temperature nanocomposite into bimetallic catalysts via simple and efficient solution-based range of 200-300 K. We find an activation energy of ~ 9 kJ/mol for CO oxidation over synthesis routes, either through a polyol-mediated process or a galvanic replacement Pt-BHA, which is about three times lower than previously published values for route. In this approach, a monometallic nanocomposite such as Platinum - conventional supported Pt catalysts, indicating the exceptionally high reactivity of Bariumhexaaluminate (Pt-BHA) is first synthesized via a micro-emulsion based sol-gel these nanocomposite catalysts. These FTIR results are further supported by ambient- process and then “transformed” into different kinds of bimetallic catalysts as pressure kinetic studies which were conducted in parallel in a conventional fixed-bed PtM/BHA (M=Fe, Sn, Cu, Au etc.). The resulting materials were characterized by a reactor configuration. wide range of characterization techniques (SEM, TEM, XRD, BET, chemisorption, In order to gain deeper insights into this observation, we synthesized size-controlled and TPD). Pt-BHA with Pt particles sizes in the range of ~2.5-5 nm. These materials were further The results demonstrate that the transformation process does not affect the morphology studied via chemisorption and CO-TPD (temperature-programmed desorption). The of the nanocomposite. The bimetallic particles are well dispersed in the ceramic matrix TPD results shows a strong dependence of CO desorption energies on particle size, and retain the very high specific surface area of the monometallic precursor (>300 with an abrupt increase in CO bond energies by ~20 kJ/mol from particles with m2/g). However, their catalytic properties are fundamentally changed, as evidenced by diameters above 4 nm to particles with diameters below 3 nm. CO-TPD (temperature programmed desorption) experiments. A strong peak shift The results confirm that nano-sized metals could hold a large potential as “next occurs on both PtFe/BHA and PtSn/BHA while PtCu/BHA shows a linear generation” fuel processing catalysts, and that nanostructuring may be a viable way to superposition of the monometallic Pt-BHA and Cu-BHA equivalents. It is noteworthy harvest this potential at realistic process conditions. that the temperature decrease for CO desorption on PtSn/BHA is as high as 194°C, which corresponds to a reduction of the CO desorption energy by ~57.4 kJ/mol. 2-5 Overall, we see this work as a first step towards the synthesis of highly efficient and Analysis of Extracted Selenium from Coal-Combustion By-Products stable multicomponent catalysts for fuel processing applications. Lisa M. Horvath-Lohr, Dorothy J. Vesper, West Virginia University and DOE- NETL; Robert L. Thompson, DOE-NETL Site Support Contractor, Parsons; Karl 2-3 T. Schroeder, DOE-NETL, USA Nanostructured Water-Gas Shift Catalysts Yanan Wang, Shuang Liang, Goetz Veser, University of Pittsburgh, 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 The water gas shift reaction (WGS) is a key reaction in the production of liquid fuels toxicity and mobility are species dependent. Extractions mechanisms, such as column or hydrogen from fossil and renewable resources. It is widely used to adjust the CO:H2 leaching experiments, can predict the retention of selenium species in coal combustion ratio in synthesis gas for the production of chemicals and liquid fuels, and to reduce the by-products. Analysis of the supernatant for total selenium and speciated inorganic carbon monoxide content in order to produce hydrogen-rich streams for fuel cells. forms can show if all species are accounted for from the extracted fly ash samples. While WGS is at high temperatures limited only by thermodynamic equilibrium The NETL CUB group conducted column leaching experiments on fly ash samples. limitations, at lower temperatures (<400°C) the activity and stability of the catalysts is The procedure consisted of four fly ash samples being placed in columns and leached currently the limiting factor. Additionally, typical syngas-based feed streams contain with acetic acid, nitric acid and sodium carbonate, separately over a four-month time significant amounts of contaminants, in particular S-compounds, which adds further period. Supernatant samples were taken every two to three days throughout the four constraints on the lifetime of WGS catalysts. month period and analyzed for both total and speciated selenium along with other In recent years, Au has received much attention as a potentially highly active WGS major and trace elements. -2 -2 catalyst, in particular in combination with a CeO2-based support. Building onto these Speciation of the supernatant for oxyanions selenite (SeO3 ) and selenate (SeO4 , was reports, we are currently working on the synthesis of highly robust nanostructured conducted using a reverse-phase column coupled to a Perkin Elmer ICP-MS with DRC WGS catalysts in which noble metal nanoparticles are embedded into a nanostructured system. These ions have been reported as the most likely Se species associated with fly ceramic matrix. The work is an extension of our previous work in which we ash samples (Mattigod and Quinn, 2003). Separation of selenite and selenate is demonstrated the unusual stability of nanocomposite noble metal/alumina achieved within 2 minutes on a Brownlee C8 column using a 50 µL injection loop and nanocomposite materials for the production of synthesis gas via catalytic partial a flow rate of 1.0 mL/min at 25°C. The mobile phase consists of an acetic acid- oxidation of methane. The synthesis is based on a reverse microemulsion-templated ammonium acetate buffer plus tetrabutylammonium hydroxide for the ion-pairing sol-gel synthesis, in which the embedded metal nanoparticles are synthesized agent, and 5% methanol, resulting in a pH of 5.2. simultaneously with the ceramic matrix. Initial results show a large mass balance deficit between the total Se and the sum of the Based on this approach, we have been able to synthesize a range of CeO2- and La2O3- Se-species concentrations. This indicates that there is a loss of species during the based nanostructured ceramic supports with very high surface area and good thermal extraction or speciation, or there are other species present that are not accounted for stability over the relevant temperature range. Au, Ni, and Pt nanoparticles were using this method such as elemental selenium or organic phases, or instrument successfully embedded into these structures, and the resulting materials were interferences. The presence of a deficit has been reported by other researchers (EPRI, characterized via SEM, TEM, XRD, BET, and chemisorption. Main factors that affect 2006) although many studies have been focused on these species alone (Jackson and the pore structure will be discussed in the presentation. In particular, we will Miller, 1998; EPRI, 2006; NSMP, 2006). demonstrate that the Ce:La ratio in mixed Ce/La-oxides has a profound impact on the References: surface area and morphology of the resulting materials, and that the pore structure of EPRI (2006) Speciation and attenuation of Arsenic and Selenium at coal combustion the materials can be further tailored via changes in the water:alkoxide ratio. We are by-product management facilities. USDo Energy. 3: 69. 2 studies, weldability and fabricability evaluations, and review of applicable design Jackson BP, Miller WP (1998) “Arsenic and selenium speciation in coal fly ash codes and standards. These evaluations are nearly completed and are providing the extracts by ion chromatography-inductively coupled plasma mass spectrometry.” confidence that currently-available materials can meet the challenge. Key findings Journal of Analytical Atomic Spectrometry 13: 1107-1112. from the study will be presented.

Mattigod SV, Quinn TR (2003) Selenium content and oxidation states in flys ashes 3-4 from western U.S. coals, in KS Sajwan, ed., Chemistry of trace elements in fly ash: Post-Combustion CO2 Capture Technologies New York, Kluwer Academic/Plenum Publishers, p. 143-156. John Wheeldon, EPRI, USA

NSMP (2006) “A comparison of methods for measuring total selenium and selenium This paper provides a review of selected post-combustion CO2 capture technologies species in water.” Updated May 8, 2006, Retrieved 09/2007, from and processes under development. The majority of current efforts are focused on http://www.ocnsmp.com/pdf/Se_Speciation_Methods_Final%20Report_8May06.pdf. 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. SESSION 3 COMBUSTION TECHNOLOGIES – 1 3-5 DOE/NETL’s Mercury Control Technology R&D Program - Recent Results from Phase III Testing 3-1 Lynn A. Brickett, Thomas J. Feeley, III, B. Andrew O’Palko, DOE-NETL; Engineering and Economic Evaluation of a 1300°F Series Ultra- Andrew P. Jones, Science Applications International Corporation, USA Supercritical Pulverized Coal Plant John Wheeldon, EPRI, USA DOE/NETL has worked with industry, research organizations, and academia to develop advanced mercury control technology for coal-based power systems. Over the The strategy for lowering the cost of CO2 capture from coal-based power plants past seven years, this research has focused on the full-scale and slip-stream field includes raising generating efficiency. For pulverized coal (PC) plants this means testing of activated carbon injection (ACI) and flue gas desulfurization enhancements progressing to ultra-supercritical (USC) steam conditions, arbitrarily defined as having at nearly 50 U.S. coal-fired power plants. The goal of the field testing was to temperatures above 593°C (1100°F). Currently, USC steam temperatures are limited to demonstrate high levels (50-90%) of mercury capture over an extended period of approximately 627°C (1160°F) by the use of ferritic steels, the most advanced operation, while also reducing the cost of mercury removal. The field testing program commercially available steels. To go to higher temperatures, high-nickel alloys must has successfully met this goal. Due in large part to this success, coal-fired power plant be used, and these are still under development. operators have begun to install mercury control technology in response to state EPRI’s UltraGen Initiative is a proposed series of projects to advance regulations. As of April 2008, orders have been placed for over 44 gigawatts of ACI. commercialization of USC PC power plants with near-zero emissions of criteria This paper will provide an update on DOE/NETL’s mercury control technology R&D pollutants. One of these projects is UltraGen II, a 750-MW 1300°F Series plant design, program, including an assessment of the cost of capture. and this study was formulated to support its development. The objectives included establishing the plant’s 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 SESSION 4 that may be required before demonstrating the technology. Finally, design concepts GAS TURBINES AND FUEL CELLS that could potentially result in further increases in efficiency and decreases in FOR SYNTHESIS GAS AND HYDROGEN APPLICATIONS – 1 emissions are discussed.

3-2 4-1 Reducing CO2 Emissions by Improving the Efficiency of the Existing Coal- DOE’s SECA Program: Progress & Plans fired Power Plant Fleet Wayne A. Surdoval, DOE-NETL, USA Chris Nichols, Gregson Vaux, Connie Zaremsky, James Murphy, Massood Ramezan, DOE-NETL, USA Developing technology to ensure that the use of coal is an economic energy source while maintaining America’s ever tightening environmental and climate requirements In 2005, coal-fired power plants in the United States built before 1980 accounted for is of crucial U.S. national importance for solving today’s energy security concerns. 26% of total U.S. CO2 emissions. Analysis of GHG mitigation policies indicates that The U.S. Department of Energy’s (DOE) is sponsoring the research and development for CO2 taxes under 30-40 $/mtCO2 most of the existing coal-fired power plants will (R&D) of solid oxide fuel cells (SOFCs) under the Solid State Energy Conversion choose to operate as they are and “pay the tax.” If so, they will operate under a greatly Alliance (SECA). SECA is leading the way to low-cost, environmentally-friendly, enhanced economic incentive for efficiency improvements. The average efficiency of fuel-flexible SOFCs and coal-based SOFC power generation systems for stationary the pre-1980 sub-critical fleet is 31%, while the top 10% of this group achieves around markets. SECA is managed by the DOE’s National Energy Technology Laboratory 36%, showing that significant improvement is possible for older plants. This paper (NETL) Program Office, in partnership with private industry, educational institutions sets forth an estimate of the aggregate CO2 emissions reductions that could be achieved and national laboratories. through efficiency upgrades, taking into account the limitations at each plant. SECA has three major focus areas: Cost Reduction, Coal-Based Systems, and Core Individual power plants are grouped according to coal grade, boiler technology, Technology R&D. The SECA Cost Reduction goal is to reduce the manufactured cost pollution control equipment, altitude, water source, and other factors. The efficiency of SOFC power systems to $400 per kilowatt by 2010. Concurrently, Coal-Based improvement opportunity is estimated as the difference between the best performers in Systems is pursuing the scaling, aggregation and integration of the technology for use each group and the rest. in large Integrated Gasification Fuel Cell (IGFC) systems for central power generation applications in order to efficiently and cleanly utilize the nation’s large coal reserves. 3-3 The performance of IGFC systems will be consistent with Fossil Energy’s Advanced Materials for Advanced Ultra Supercritical Fossil Plant Power Systems goals, including over 45 percent efficiency (coal higher heating value R. Viswanathan, Electric Power Research Institute; Robert Purgert, Energy HHV to electricity) with 90 percent carbon capture. Megawatt-class proof-of-concept Industries of Ohio; Patricia Rawls, DOE-NETL, USA 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 One of the pathways for achieving the goal of utilizing the available large quantities of SECA Core Technology Program is providing vital R&D to further improve on the indigenous coal, at the same time reducing emissions, is by increasing the efficiency of substantial progress made through the SECA program. The first series of SOFC power plants by utilizing much higher steam conditions. The US Ultra-Supercritical system prototypes fielded by the SECA Industry Teams surpassed SECA’s Steam (USC) Project funded by US Department of Energy (DOE) and the Ohio Coal intermediate-targets for efficiency, reliability and production cost. Development Office (OCDO) promises to increase the efficiency of pulverized coal- Furthermore, NETL analyses show that an IGFC system with a pressurized SOFC and fired power plants by as much as nine percentage points, with an associated reduction catalytic gasification with recycle permits a high net efficiency approaching 60 percent of CO2 emissions by about 22% compared to current sub-critical steam power plants, HHV with carbon capture greater than 90 percent. Separate fuel and air streams to the by increasing the operating temperature and pressure to 760°C (1400°F) and 35 MPa SOFC substantially reduce the amount of water required to condense, recycle and (5000 psi), respectively. Preliminary analysis has shown such a plant to be reuse process water, and without a steam cycle, there is virtually no external water economically viable. The current project primarily focuses on developing the materials requirement. The high efficiency maintains an economic cost of electricity (COE) due technology needed to achieve these conditions in the boiler. The scope of the materials to less fuel per megawatt hour and a smaller plant. Meeting SECA goals result in the evaluation includes mechanical properties, steam-side oxidation and fireside corrosion lowest COE coal option with environmental regulation compliance and the ability to 3 capture greater than 90 percent of the carbon. This technology makes substantial 4-4 strides in permitting clean economic energy production from coal in any state in the System Tradeoffs and Sensitivities in an Integrated Gasification Fuel Cell U.S. Combined Cycle with Carbon Capture Eric Grol, DOE-NETL; Dale Keairns, Richard Newby, Science Applications 4-2 International Corporation (SAIC), USA Development of an Efficient Coal-Fueled Solid Oxide Fuel Cell Power System Concept Equipped for CO2 Separation The U.S. Department of Energy’s National Energy Technology Laboratory (NETL) Wayne L. Lundberg, Larry A. Shockling, Stephen E. Veyo, Eugene E. Smeltzer, conducts research of solid oxide fuel cells (SOFC) as part of an advanced power Gordon A. Israelson, Arun K. S. Iyengar, Siemens Power Generation, Inc., USA 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. A baseline, clean, coal-fueled, high-efficiency, fuel cell-based electric power system SOFC technology enables the use of advanced gasification technology to achieve concept has been developed as part of U.S. Department of Energy contract no. DE- system efficiencies targeted at 60% while capturing greater than 90% of carbon FC26-05NT42613. Key system design objectives were high electric efficiency with dioxide emissions. Solid oxide fuel cells can increase overall system performance with CO2 separation at a plant capacity greater than 100 MWe. The efficiency was to be significant methane content (e.g. 15-25%) in the fuel gas. An example is the use of greater than 50% (net AC/coal HHV) and it was required that at least 90% of the low temperature catalytic gasification technology, which has the potential to achieve carbon exiting the coal gasification system in syngas must be separated (in CO2 form), improved gasifier performance with methane concentrations that benefit the fuel cell ready for sequestration. The selected baseline power system cycle concept integrates system operation. System concepts are presented to achieve high efficiency electric pressurized SOFC generator modules with a gas turbine and a steam turbine bottoming power generation while capturing carbon dioxide. Material and energy balances for cycle. To maximize the system electric efficiency, a high degree of subsystem heat these systems are summarized. integration is employed. CO2 separation from syngas is accomplished prior to utilization by power generation components. The power system cycle concept is 4-5 described, major system components are identified and characterized, the component Micro-mixing Fuel Injection for Low Emission Combustion of Hydrogen for physical arrangement is discussed, and results of the system electric performance and Gas Turbine Applications conceptual-level cost evaluations are presented. A power system proof-of-concept Adel Mansour, Erlendur Steinthorsson, Brian Hollon, Parker Hannifin demonstration is planned at a capacity level of approximately 5 MWe. Corporation; Steven Hernandez, Qing Wang, Howard Lee, Vincent McDonell, University of California, Irvine, USA 4-3 Progress in Development of Coal-Based Solid Oxide Fuel Cell Power Plants The performance of a set of “micro-mixing” fuel injectors operating on hydrogen fuel Hossein Ghezel-Ayagh, Jody Doyan, Jim Walzak, Sven Tobias Junker, Dilip is investigated using experiments and computational fluid dynamics. A micro-mixing Patel, Allen Adriani, Peng Huang, FuelCell Energy, Inc; David Stauffer, fuel injector consists of multiple, small (thimble size) and closely spaced mixing cups, Vladimir Vaysman, WorleyParsons Group Inc.; Brian Borglum, Eric Tang, within which fuel and air mix rapidly at a small scale. The goal of the research is to Randy Petri, Versa Power Systems; Chakravarthy Sishtla, Gas Technology develop injectors capable of ultra-low NOx emissions-performance when operating on Institute, USA hydrogen and syngas fuels. In the present work, flame structure, flash-back performance and emissions results are presented for a number of mixing-cup FuelCell Energy (FCE) is involved in Phase I of a multiphase project for development configurations at various equivalence ratios and pressures up to 5 atm. The structure of of very efficient coal-to-electricity power plants with near-zero emissions. The project the hydrogen/air flame is captured using OH* chemiluminescence and emissions are is being carried out through a cooperative agreement with the Department of Energy’s measured using EPA certified approach. The results demonstrate that a number of Solid Energy Conversion Alliance (SECA) program. The primary objective of the configurations produce low single-digit NOx emissions for a range of adiabatic flame project is to develop an affordable, multi-MW-size SOFC-based power plant system temperatures, inlet temperatures and pressures while remaining robust relative to for utilization of synthesis gas (syngas) from a coal gasifier with near-zero emissions. flashback and lean blowout. Specifically, emissions in the range from 2 ppm to 5.5 Some of the key project objectives are the development of SOFC technologies, cell and ppm were demonstrated at adiabatic flame temperature of 1750 K and at pressures up stack size scale-up, SOFC performance optimization, increased stack manufacturing to 5 atm, without flashback on 100% hydrogen fuel. Based on the results obtained to capacity development and MW-class module engineering design. date, the micro-mixing approach appears promising relative to achieving low The project is organized in three phases: emissions while maximizing scalability and fuel flexibility. • 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 multi- MW SESSION 5 power plant systems will also be conducted. The Phase I deliverable will be test COAL PRODUCTION AND PREPARATION – 1 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 5-1 II of the project will focus on modularization of the Phase I stack building block units Future Impacts of Coal Distribution Constraints on Coal Costs into a MW-size module. Detailed design engineering and analysis for multi-MW David McCollum, Joan Ogden, University of California-Davis, USA 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 Coal consumption in the United States is projected to rise significantly over the next syngas. few decades. About two-thirds of all coal in the U.S. is transported via rail, but certain • Upon successful completion of Phase II and selection by DOE to continue, Phase coal-carrying rail corridors are already up against their capacity limits. Any future III of the project will focus on the design and fabrication of a proof-of-concept multi- increase in coal demand will probably necessitate significant capital investment by rail MW power plant. The Phase III deliverable will be tested for at least three years at a companies. This study seeks to identify existing capacity and potential constraints suitable SECA selected site. FCE utilizes the planar cell and stack technology of its within the U.S. coal distribution network and to estimate the costs of alleviating those SOFC provider, Versa Power Systems Inc (VPS) for all its SOFC development constraints under several scenarios of coal demand growth. We consider coal demand programs. VPS has well established processes, quality control procedures and both for electricity generation and production of hydrogen fuel for transportation equipment for the manufacture of small to intermediate size cells and stacks. This applications. Using a model of the U.S. rail network, we estimate the costs of adding serves as a solid basis for cell area and stack size scale-up. The other key objective is new rail capacity to meet growing coal demand. Total railroad capital investments implementation of an innovative system concept in design of a multi-MW power plant could be on the order of $1.5–$11.0 billion over the 2004–2050 timeframe, depending with anticipated coal-to-AC efficiencies approaching 60% on a coal HHV basis. on the particular scenario we model. While these infrastructure investments are Combined with existing carbon dioxide separation technologies, the power plant is substantial, it does not seem likely that the delivered cost of coal will necessarily expected to achieve ultra high efficiencies while emitting near-zero levels of emissions increase throughout the country as a result. Hence, on a cost basis our analysis shows of SOx, NOx, and greenhouse gases to the environment. that investment in coal distribution infrastructure should not be a barrier to a coal- The development of this technology will significantly advance the nation’s energy based “Hydrogen Economy”. security and independence interests, address pollution and greenhouse gases concerns, and help enhance the nation’s 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 5-2 oxygen content of 19%. The relative humidity of mixture of air and flue gas effect the A Rheological Study on the Pumpability of Co-Mingled Biomass and Coal rate of drying coal. In order to increase the rate of drying coal, the size of particle of Slurries coal is below 30 mm. Wei He, Chan S. Park, Joseph M. Norbeck, University of California, Riverside, Compared with other kind of drying coal process, the process of drying coal developed USA 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 There is considerable interest in the gasification and subsequent conversion of coal and larger quantities of low rank bituminous coal for use at the power plant. 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 SESSION 6 coal and biomass slurries in gasification processes is a critical issue that needs to be SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL – 1 more fully understood in order to maintain the high efficiencies of the technology. The pumpability is dependent on the slurry’s rheological properties (e.g. shear rate, shear stress and viscosity) which in turn are related to the slurry’s physical properties. 6-1 In this study, wood was initially hydrotreated to make a high solid content biomass The Most Effective Coal-To-Gasoline Conversion - Where Coal and Nuclear paste and then mixed in varying percentages with a coal-water slurry. The effect of Come Together solid particle size of the slurry, the initial coal and wood particle size distribution, and Heinz Termuehlen, USA; W. Jaeger, H.-J. Hamel, GERMANY 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 We can become independent of any oil import by producing gasoline from coal pumpability. The presence of a high percentage of biomass in solid form significantly utilizing nuclear energy. Because conventional coal combustion adversely effects the decreased slurry pumpability. The optimum solid/water ratio has been determined with environment, it is important to minimize this effect when using coal in the future. Coal various coal/biomass mixtures. The results of these experiments will be presented. 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 5-3 generated in nuclear power plants. This paper shows a way to most effectively Application of Flotation by Ecological Loads of the Cerny Prikop Stream combine the utilization of coal and nuclear fuel for the production of domestic Peter Fecko, Iva Janakova, Anna Kovalova, Monika Madrova, Lucia Kovalova, gasoline. VSB-Technical Univerzity of Ostrava, CZECH REPUBLIC 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 stream Cerny prikop is located in the Ostrava city districts of Marianske Hory, the highest gasoline production per specific coal consumption, leading to the lowest Moravska Ostrava and Privoz. This locality belongs among the most polluted areas in adverse effect on the environment. Ostrava as the locality is unbearably polluted by the Coking Plant of Jan Sverma, Integrated coal gasification combined cycle (IGCC) power plants are in operation for company BorsodChem MCHZ (the chemical plant), City Waste Water Treatment Plant power generation. In these plants coal is gasified for combustion in a gas turbine of a and a number of other companies in the given territory all the way to its mouth to the combined cycle power plant to generate power. An IGCC plant could also be designed Odra River. Moreover, the area is also affected by the construction of motorway D 47. for the production of methanol, which can be converted to gasoline. In such IGCC The sediments of Cerny prikop represent a significant ecological burden within the plants the coal gasification is an exothermic process demanding a large amount of heat Ostrava urban area. They are contaminated by a wide range of organic pollutants energy from the coal for this process. which have never been exactly identified. To minimizing the coal consumption for the production of a maximum of methanol The proposed project shall deal with the removal of selected organic pollutants, such as and then gasoline, the combination of a high temperature gas cooled reactor (HTGR) GRO, PCB´s and PAH´s by means of typical preparation method of flotation. The with a coal-to-gasoline conversion plant has been developed. This process features a basic research should bring minimization of the content of selected hazardous highly endothermic coal gasification process, which utilizes the high temperature gas substances from the Cerny prikop sediments. It is apparent from the laboratory discharge from the reactor in a steam reformer. A hydro-gasifier is utilized. This paper experiment results that after flotation test there is a cca 80% removal of PAH´s, 90% describes such combined plant. The capital and operating costs for this plant have been removal of PCB´s and 78% removal of GRO. 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 5-4 pollutants from the use of coal is minimized. Removal of Heavy Metals from Industrial Waste Water by Mineral Resources as Adsorbents 6-2 Nikolas Mucha, Vladimír Čablík, Kateřina Cechlová, Alena Sochorková, Iva Rentech’s Coal-To-Liquids Process: GHG Life-Cycle Inventory Relative to Janáková, VSB-Technical University of Ostrava, CZECH REPUBLIC Conventional Crude Oil Derived Distillate Fuels Robert L. Freerks, Rentech, Inc., USA 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 Rentech presented information at the 2007 International Pittsburgh Coal Conference on eliminate the influence of various inorganic and organic contaminants to the minimum, its initial assessment of the life-cycle greenhouse gas (GHG) emissions for a Coal-to- to clean up their effects or minimize them at least. One way to remove such substances Liquids (CTL) project in Natchez, MS. The Natchez project will process petroleum from water are adsorption technologies. These technologies of water purification are coke and/or coal and biomass in a modern CTL plant designed by Rentech based on a implemented especially in cases when biological treatment is unsuitable or insufficient. proprietary iron-based Fischer-Tropsch (FT) catalyst. The capture of CO2 is an Among the most tested adsorbents of heavy metals there are for example zeolites, integral part of the plant design. The CO2 will be sequestered in existing oil fields as carbonates, clays, peat, iron oxides, etc. part of planned enhanced oil recovery (EOR). This presentation updates the life-cycle With regard to the fact that currently recycling and waste minimization technologies inventory with emissions estimates for coal and petroleum coke processing into are being enforced, efforts are made to make the most efficient use of all materials. summer and winter-grade diesel fuel and kerosene-based jet fuel. Naphtha produced at Thus, earlier unused materials are becoming significant resources for today’s industry. the plant will be sold as an ethylene/propylene feedstock. Comparisons are made to Among those materials there are also waste rocks produced during brown coal typical crude oils and the average crude slate refined in the U.S. Gulf Coast region. extraction in the North Bohemian and Sokolov Basin, which can be used as adsorbents. Ranking of the various distillate fuel alternatives is dependent on how emissions are Their advantages are their natural origin, low price, high abundances and allocated for the various refined products and feedstocks being compared. Relative to improvements to economic effectiveness of mining. Moreover, as they are processed the marginal quality crude processed in the region, the GHG emissions for the CTL they need not be dumped and do not strain the environment. 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 5-5 superior quality of the FT naphtha, diesel and jet fuel. Studies on Reducing Low Rank Coal Moisture by Drying Wenhui Zhang, Huijun Xu, Shun Lu, Shunwei Gao, Xiaodian Wang, Xirong 6-3 Qiao, China Shenhua Energy Company LTD, CHINA Plants for Conversion of Coal to Heavy Crude Elliot B. Kennel, Mayuri Mukka, Alfred. H. Stiller, John W. Zondlo, West In order to reduce moisture of low rank coal produced by Shenhua, a process of drying Virginia University, USA; Gilbert Chalifoux, Quantex Energy Inc., CANADA 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 Conversion of coal feedstocks from the solid to liquid state generally involves adding mixture of air and flue gas is below 210°C which is below the ignition temperature of hydrogen and cracking molecules in the coal via different processes. Alternatively, low rank coal. The content of oxygen in mixture of air and flue gas is below 19%. The solvent extraction is one means by which this can be accomplished. A commodity explosion and combustion during coal drying do not take place below 210°C and solvent such as a coal tar distillation product or petrochemical dilutent is hydrogenated 5 to enhance its ability to digest coal. Crushed coal is then digested in the solvent - Improve the integration with downstream applications such as shift for chemical resulting in conversion of up to 90% of the dry, ash-free coal to the liquid state. Solids applications, water is added directly to the syngas, not via a saturator cycle in the are removed from the slurry via centrifugation. The centrifuged solids could be shift section. blended with other forms of coal or biomass, and would make up only a small - Allow power applications with integrated SCGP and downstream CO2 percentage of the total fuel feed. The resultant synthetic crude is to be distilled to sequestration produce a binder pitch. The overhead liquids can be recycled as a coal solvent, or - Allow gasification of high-fouling coals (with high alkaline contents and high alternatively, upgraded to produce value-added fuels and chemicals. The distillation chlorine), which cannot easily be processed with a syngas cooler. bottoms can be utilized as a binder pitch. Alternatively, a delayed coker can be used to - Allow the choice between keeping the ash dry to a large extent or go fully wet. thermocrack the heavy molecules to produce lighter liquids in addition to an anode Since the gasifier design is kept the same, the key advantages of SCGP are retained, grade coke residue. 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 6-4 multiple burners, which allow large single-unit capacities and an efficient slag Measurement of Coal Slurry Viscosities at High Temperature and High removal. Pressure Yan Wu, Zhi Guo, Ke-jian Li, Shi-dong Shi, Ping He, Beijing Research Institute 7-3 of Coal Chemistry, China Coal Research Institute, CHINA Co-Generation - Opportunities in the Integration of Chemicals Production and IGCC Power Production An apparatus for measuring coal slurry viscosity at high temperature and high pressure Esben Lauge Sørensen, Poul Erik Højlund-Nielsen, Martin Dan Palis Sørensen, were set-up. Two calculation methods named power number method (at Re < 300)and Jørgen Madsen, Haldor Topsøe A/S, DENMARK 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 Coal is becoming an increasingly important raw material for the power and chemicals reagents such as glycerin etc. The fundamental work provides viscosity data of coal production. Attractive synergies can be obtained by combining power generation with slurry at liquefaction conditions. Viscosity-temperature curves for a Chinese brown the production of chemicals. In an Integrated Gasification Combined Cycle (IGCC) coal slurry and a heavy coal liquefaction stream produced from hot separator bottom of plant, power is produced by burning the synthesis gas produced by gasification in a gas bench scale test unit under H2 pressure were obtained. The study results showed that turbine. This synthesis gas is also an excellent raw material for the production of the slurry viscosities are strongly affected by coal characteristics, heating rate and valuable chemicals such as methanol, hydrogen, high-grade DiMethyl Ether (DME) temperature. Curves of apparent viscosity versus temperature are suit for Vogel and ammonia, or fuels with practically no market saturation such as gasoline, fuel- equation. grade 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 SESSION 7 accommodate peak loads when the price of power is high. GASIFICATION TECHNOLOGIES: GENERAL SESSION – 2 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 7-1 however be carefully considered. Due to the concern for the possible effect of carbon Application of Siemens Fuel Gasification Technology for Different Types of dioxide (CO2) on the global climate, it is also necessary to analyse the effect of CO2 Coal capture on the integration schemes. Many studies have focused on the options for CO2 Frank Hannemann, Manfred Schingnitz, Joachim Lamp, Baoting Wu, Siemens sequestration from IGCC plants. Fuel Gasification Technology GmbH & Co. KG, GERMANY This paper presents examples of attractive systems obtained by a combination of power and chemicals production, as well as options for CO2 capture. The Siemens Fuel Gasification (SFG) technology can gasify a wide range of feedstocks including petcoke, hard coal, lignite, and low rank fuels like refinery 7-4 residuals and biomass. The technology has been selected for a number of projects in Effect of Gas-Turbine ASU Integration in Dynamics and Control of IGCC the last years. Applications range from chemicals & hydrogen production to IGCC. Power Plants Commissioning of Siemens’ first SFG-500 gasifiers is expected to start in 2009. This Priyadarshi Mahapatra, B. Wayne Bequette, Rensselaer Polytechnic Institute, paper will review the SFG technology and current projects. USA An extensive research and development program is underway to improve design features of Siemens gasification technology which in particular focuses on customer Gas turbines will certainly play a major role in future power generation and several requirements such as high availability and low maintenance. The paper will describe well justified concepts have been developed or are the subject of major feasibility Siemens’ approach to provide gasification solutions depending on rank of coal, ash studies. However, the combined cycle is now well established and offers superior composition and ash content. These particular parameters define operability and performance to any of the competing systems that are likely to be available in the applicability of entrained flow gasification systems which operate well above ash medium term for large scale power generation applications. In Integrated Gasification melting point. Slag characterization is essential for slag flowing behavior, Combined Cycle (IGCC) power plants, integration between gas-turbine and air agglomeration and leachability. Gasification test runs in combination with slag separation unit is determined by the percentage of total air separation unit (ASU) air viscosity analysis and determination of fusion temperature provide sufficient required coming from GT compressor which has a common shaft with the gas turbine. confidence to decide on optimal gasification temperature and potential addition of well This integration is a tradeoff among efficiency, investment cost, operational flexibility, selected flux material. power, and startup/shutdown times. Assuming a wide range of coal feedstock opportunities worldwide the Siemens Fuel In this study, a pressure-driven dynamic model for gas-turbine/gas-compressor (using Gasification test center in Freiberg represents a unique facility which offers a 5 MW ASPEN DYNAMICS) has been developed to investigate feasibility and applicability gasification pilot plant to investigate slag fusion and agglomeration behavior and in of integration with the ASU during varying load demands. The gas-turbine model addition two test rigs for slag viscosity analysis and high dense phase pulverized coal analysis incorporates internal surge-prevention controllers and inlet guide vanes conveyance. (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 7-2 column supplying the heat for the reboiler of the low pressure column. A Water Quench for the Shell Coal Gasification Process The process variables operating at different time scales are responsible for the Guillaume Fournier, Wouter Harteveld, Mark Prins, Thomas Von Kossak, Rob difficulties with commonly used PID-based control scheme with disturbances in Van den Berg, Shell Global Solutions International B.V., THE NETHERLANDS syngas and injected nitrogen feed pressure. In this paper we present a detailed operability analysis to better understand inherent control system performance The Shell Coal Gasification Process has been developed for a high efficiency and limitations. Further, we develop a model predictive control strategy that handles rate- minimum emissions to the environment and as part of integrated coal gasification of-change and multiple time-scale constraints imposed by the process design of the air combined cycle. The standard arrangement of the gasifier and syngas cooler internals separation and gas turbine/compressor units. Finally we close with a discussion of has been licensed many times in China and Europe. The syngas cooler is instrumental future work on the simulation and control of an entire IGCC power plant. 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

6 We combine a detailed engineering economic model of infrastructure components with SESSION 8 spatial data in a geographic information system (GIS) to optimize the design of HYDROGEN FROM COAL – 1 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 8-1 centers as hydrogen vehicle market penetration increases from 5% to 75% over a 30- Development of Membranes for Purifying Hydrogen Produced by Coal year period. The study region is defined by the jurisdiction of the Midwest Regional Gasification and/or Methane Reforming Carbon Sequestration Partnership (MRCSP), which includes Pennsylvania and several U. (Balu) Balachandran, T. H. Lee, Y. Lu, C. Y. Park, S. E. Dorris, Argonne neighboring states. National Laboratory, USA 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, the fuel of choice for both electric power and transportation sectors, can be hydrogen over pre-defined planning periods. In addition, cash flow analysis is used to produced from fossil and renewable resources by various technologies. Because it is identify the years in which the project might break even given different hydrogen produced in gas streams with numerous components, purification is a critical step in prices. The model is also used to examine the impact of various policy instruments on producing hydrogen. Argonne National Laboratory is developing dense cermet (i.e., the cost of hydrogen, including carbon taxes, tax credits, direct subsidies, and ceramic-metal composite) hydrogen transport membranes (HTMs) for separating depreciation schedules. This paper summarizes the results with an emphasis on the hydrogen from mixed gases, such as the product streams that are generated during coal estimated cost of hydrogen and the impacts of various policy instruments and gasification and/or methane reforming. Hydrogen separation with Argonne’s HTMs is technological improvements on these costs. We will also examine the sensitivity of nongalvanic (i.e., it does not use electrodes or an external power supply to drive the hydrogen costs to feedstock and construction cost escalation rates. separation), and it yields high purity hydrogen, thereby eliminating the need for post- separation purification steps. 8-4 HTMs were prepared by mixing ≈50 vol.% Pd with Y2O3-stabilized ZrO2. Using Hydrogen Production from Coal Direct Chemical Looping Process – several feed gas mixtures, we measured the nongalvanic hydrogen permeation rate, or Process Simulation flux, for the cermet membranes in the temperature range of 500-900°C. This rate L.-S. Fan, Liang Zeng, Fei Wang, Fanxing Li, Fu-Chen Yu, Andrew Tong, The varied linearly with the inverse of membrane thickness and reached ≈33 Ohio State University, USA cm3[STP]/min-cm2 at 900°C for an ≈15-μmthick membrane on a porous support structure when 100% H2 at ambient pressure was used as the feed gas. Because good The traditional hydrogen production from coal via a gasification and WGS process is chemical stability is critical for HTMs, due to the corrosive nature of product streams costly and relatively inefficient. This is especially the case when under a carbon from coal gasification and/or methane reforming, we evaluated the effect of various constrained scenario due to the energy consuming CO2 capture and compression steps. contaminants on the chemical stability of cermet membranes. Hydrogen sulfide (H2S), In this paper, a clean and efficient coal to hydrogen/electricity conversion scheme, a particularly corrosive contaminant, impedes hydrogen permeation through cermet known as the Coal Direct Chemical Looping (CDCL) process, is discussed. Utilizing membranes by reacting with them to form palladium sulfide (Pd4S). To evaluate the iron oxide as an oxygen carrier, the CDCL process produces hydrogen with in-situ CO2 chemical stability of membranes, the Pd/Pd4S phase boundary was determined in the capture under elevated pressure. Hence the carbon management cost of the coal temperature range ≈450-650°C in tests using various feed gases that contained 10-73% conversion process is drastically reduced. Novel thermodynamic models are developed H2 and ≈8-400 ppm H2S. Hydrogen flux measurements showed that at 900°C, the for analysis on individual CDCL reactor using ASPEN Plus®. Based on these results, cermet membranes are stable for up to 1200 h in gases that contain 400 ppm H2S. The process simulations are performed to further illustrate the energy management in the present status of HTM development at Argonne will be presented in this paper. CDCL process. The process simulation for the conventional gasification process for hydrogen production was also performed based on identical assumptions. The 8-2 simulation results show that ~ 78% HHV efficiency can be achieved with 100% CO2 Development and Testing of a Coal to Fuel Cell Grade Hydrogen capture. The high energy conversion efficiency of the CDCL process results from the Technology Package and a Pathway for Hydrogen Uptake in New Zealand process intensification coupled with the optimized energy management. Anthony H. Clemens, Tana Levi, Ruben Smit, CRL Energy Limited; Alister Gardiner, Industrial Research Limited; Jonathan Leaver, Unitec New Zealand, 8-5 NEW ZEALAND Co-Production of Pure Hydrogen and Electricity from Coal Syngas via the Steam-Iron Process Using Promoted Iron Based Catalysts The coal to fuel cell grade hydrogen technology development programme is entering Jason Trembly, Raghubir Gupta, Dharmesh Kumar, RTI International, USA 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 The reversible reaction between iron oxide, CO, and H2 to form metallic iron, CO2, and new technology, considers several issues that arose during its development and how H2O can be used in a redox cycle process with steam to produce pure high pressure these were addressed. hydrogen. A process based on this reversible reaction- RTI s Steam-Iron Process, has The paper also considers likely pathways whereby hydrogen may be taken up within been developed and is targeted as an addition to IGCC power plants for the co- the future New Zealand energy system. The methodology was similar to that used production of hydrogen and electricity. within the European Union as part of its HyWays project. A series of potential This presentation will detail the laboratory development of a fluidizable iron-based individual hydrogen supply chains were identified in consultation with energy material for the production of hydrogen from coal syngas. Fixed fluidized-bed bench- stakeholders from government and industry and the contributions of each chain in scale experiments were conducted at 500°C and 300 psig using simulated coal derived achieving future energy scenarios (out to 2050) were identified using a system syngas, including H2S, to determine optimal iron and promoter loadings for the -1 dynamics modeling package. The results of the individual chain selection process and catalyst. The catalysts were shown to be able to produce over 8.0 scc H2.gcat . the subsequent modeling are discussed along with their implications for the future Additionally the catalysts were shown to be able to sustain production for over 100 uptake of hydrogen in New Zealand. 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 8-3 Steam-Iron Process to be used for the co-production of H2 and electricity in an IGCC A Regional Model of Coal-Based Hydrogen power plant. Infrastructure Deployment with Carbon Capture and Storage (CCS) This work was accomplished under a cooperative agreement with the U.S. DOE. The Nils Johnson, Joan Ogden, Christopher Yang, University of California, Davis, project is part of DOE NETL s Hydrogen and Syngas Program which seeks to develop USA advanced energy technologies to facilitate the transition to the hydrogen economy though use of our nation’s vast reserves of coal. 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.

7 model with accurate results for heat transfer will provide verification of current boiler SESSION 9 design programs. COMBUSTION TECHNOLOGIES – 2 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. 9-1 Improvements required to produce better agreement with experimental values have Reactivity of Pulverised Coals in Simulated Air (O2/N2) and Oxy-Fuel been established. (O2/CO2) Atmospheres Renu Kumar Rathnam, Terry Wall, Behdad Moghtaderi, The University of 9-3 Newcastle, AUSTRALIA; Karin Eriksson, Lars Stromberg, Vattenfall Research Effect of Operating Parameters in Pressurized Mills on Coal Flow and Development AB, SWEDEN Distribution Between the Outlet Pipes Harun Bilirgen, Can Koroglu, Aly Elshabasy, Edward Levy, Lehigh University, The study of combustion characteristics of pulverised coals under oxy-fuel (O2/CO2) USA 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 Control of the pipe-to-pipe distribution of pulverized fuel (PF) has been difficult to pulverised coal in simulated air (O2/N2) and oxy-fuel (O2/CO2) conditions using a achieve in pulverizers with multiple outlet pipes connected directly to the discharge laboratory drop tube furnace (DTF) and a thermogravimetric analyser (TGA). In the turret at the top of the pulverizer. The current research has focused on understanding TGA, the fuel sample (~ 10 mg) was heated from 30 to 1100°C, at a heating rate of the flow behavior of coal and air mixtures in multiple-outlet pressurized pulverizers. 10°C/min, in various gas atmospheres that simulate pyrolysis (100% N2, 100% CO2) Experimental tests were performed with 1:7 scale pulverizer models with 4 and 6 and combustion conditions. Combustion conditions in air and oxy-fuel atmospheres outlet pipes. Each outlet pipe was connected to a separate cyclone to accurately were simulated by varying the O2 concentration in N2 and CO2 respectively. The mass measure the PF and air flows in each outlet pipe. loss rates measured in O2/CO2 conditions in the TGA were slightly lower at higher O2 Effects of primary air flow rate, classifier vane angle, and air-to-fuel ratio on the coal concentrations and lower temperatures. However, higher reactivity was observed at flow distributions between the outlet pipes were investigated. Moreover, the lower O2 concentrations and higher temperatures under O2/CO2 conditions in sensitivity of coal and primary air flow rates in each outlet pipes to orificing was comparison to O2/N2. The higher mass loss observed in O2/CO2 and not observed in studied in the 4 outlet pulverizer model. O2/N2 conditions is attributed to the reaction of the residual char with CO2. The The results indicate that coal flow in any outlet pipe varied as much as 30 percent as a apparent volatile yields measured in the DTF in 100% CO2 were found to be higher function of pulverizer operating parameters. Use of orifices was found to be an than the volatile yield measured in 100% N2 for Coal B and Coal C. The coal burnouts, ineffective method for adjusting coal flow distributions among the outlet pipes since measured at various O2 concentrations, in the DTF were also higher in O2/CO2 the primary air flow was much more sensitive to the orifices than the coal flow. 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 9-4 under O2/CO2 conditions could be higher in comparison to O2/N2 conditions probably Differences in Chars Formed from Coal Pyrolysis under N2 and CO2 due to the occurrence of the char-CO2 gasification reaction, especially at high Atmospheres temperatures and comparatively low O2 levels. Isothermal experiments at higher Dong Zeng, Shengteng Hu, Hamid Sarv, The Babcock & Wilcox Company temperatures are required to study the effect of the char-CO2 gasification reaction on Research Center, USA reactivity and confirm the mechanisms of coal combustion in oxy-fuel (O2/CO2) conditions. 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 9-2 carbon capture, oxy-combustion has gained considerable popularity and become the Assessment of Radiation Models in the Prediction of Heat Transfer in Coal subject of numerous bench and pilot-scale investigations. Replacement of N2 with CO2 Combustion and Oxy-Fuel Firing can affect coal devolatilization and char formation reactions. Detailed knowledge of Rachael Porter, Mohamed Pourkashanian, Alan Williams, L. Ma, University of char reactivity, swelling ratio, and pore structure is important to the accurate Leeds; Gerry Hesselmann, Norman Simpson, Brian Smith, David Smith, Doosan determination of char burnout and the development of efficient oxy-combustion Babcock, UNITED KINGDOM systems. However, despite the growing interest in oxy-combustion, fundamental research in this area has been sporadic. The accurate prediction of heat transfer in modern utility furnaces is a notoriously Babcock and Wilcox (B&W) used a newly-constructed entrained-flow reactor to study difficult problem to solve. Performance prediction methods for pf utility furnaces changes in physical properties and intrinsic reactivities of chars formed under oxy- developed over the years have tended to be based on plant experience and empirical combustion conditions. For comparison, pulverized samples of a lignite coal, a formulations. The accurate prediction of heat transfer involves the solution of the subbituminous coal, and an eastern high-volatile bituminous coal were devolatilized at Radiative Transfer Equation (RTE), a formidable task requiring considerable different temperatures in N2–entrained and CO2–entrained flows. Effects of pyrolysis computational resources. An exact solution of the RTE is not feasible except in the temperature and residence time were also investigated. Coal mass loss during pyrolysis very simplest cases and therefore a variety of different methods have been developed experiments was determined from ash analysis. Elemental char analysis was also to approximate the solution of the RTE. The difficulty of estimation of heat transfer carried out. Average swelling ratios were determined from the mass release and from pulverised coal flames increases because of the nature of the medium within the density measurements. Both BET and CO2 surface areas of the collected char samples furnace volume. The presence of fly-ash, char particles, soot and radiation from gases were measured. Char morphology was studied using a Scanning Electron Microscope. within the volume means that the medium is absorbing, emitting and scattering. The Reactivities of generated char samples were measured at isothermal and oxidizing problem is further complicated when the successful prediction of the heat transfer is conditions using a Thermo Gravimetric Analyzer. Intrinsic char oxidation rates were required for oxy-pf combustion. determined from the reactivity measurements. Measured and calculated changes in Current proposals for oxy-pf technologies involve recycling a portion of the flue gases char properties and reactivities due to switching from N2 to CO2 during coal and therefore the main component of the medium becomes carbon dioxide (CO2) devolatilization are discussed in the paper. 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 9-5 for heat transfer is a great challenge. Study of Coal Predrying and its Impact to Operational Parameter of 600 The increase in CO2 in oxy-pf means that the radiative properties of the medium will MW Coal Fired Power Plant be significantly changed. The heat capacity of CO2 is greater and the thermal Mochamad Choliq, Tonny Sarief, PT PLN (Persero) Research and Development, diffusivity lower. Crucially to the calculation of heat transfer, absorption and emission INDONESIA properties of the medium will be different. The interaction of molecules with the radiation must be considered because of the increased concentration. The radiative In general the preparation of coal prior to feeding to the boiler is reducing its size and properties of the medium are key in the solution of the RTE. Successful prediction of moisture content in the pulverizer. However, the air which is used for coal drying will these parameters in oxy-fuel firing is difficult because many emissivity models are be used as combustion air in the furnace. Whenever moisture content in the coal based on data for CO2 and H2O that apply to conventional combustion environments increase, the moisture content in the air also increase, as the result they will reduce the only. advantage of heat generated from combustion process and increasing the flue gas The accurate prediction of heat transfer during oxy-pf firing is important because of volume. The increasing flue gas volume affect the temperature and heat transfer retro-fitting oxy-pf combustion practices to existing power stations. For this to be distribution in the furnace that will reduce plant capability capacity, increasing successful the heat transfer to the steam side should be unchanged so that current pulverizer power consumption, reducing boiler efficiency, induced draft fan increase setups can be maintained or only marginally altered. For new plant builds, the nature of and finally increasing overall heat rate. The improvement of as mentioned condition it boiler design means that the methods used are often empirically based and hence there is needed by developing coal drying outside pulverizers by using flue gas as dryer is potential that heat transfer prediction in oxy-pf firing will be imprecise. A radiation agent prior to discharge to the environment.

8 Simulation result showing that by 10% reducing moisture content in coal using flue porous media which separates the fuel and tin. Fuel is introduced into a hot zone gas will reduce flue gas volume from combustion process and improve heat transfer surrounding the cell and is subject to a sort of internal gasification. This indirect efficiency around 4%, in addition the number pulverizer operation required reduced approach has been used for CellTech Gen 2 and Gen 3. Each approach may have from 6 to 5 pulverizer for 600 MW coal fired power plant. The flue gas required to application depending on factors such as plant size and impurity levels. 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. 10-3 The reducing moisture content prior to feeding to the pulverizers by using flue gas is Materials and Component Development for Advanced Turbine Systems possible to be implemented due to amount flue gas reasonably abundant and to reduce Mary Anne Alvin, DOE-NETL, USA the risk of implementation of as mentioned project in the power plant it is necessary to perform modeling in the laboratory scale. Hydrogen-fired and oxy-fueled land-based gas turbines are currently targeting inlet operating temperatures of ~1425-1760°C (~2600-3200°F). 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 SESSION 10 reviews recent technical accomplishments resulting from NETL’s bond coat GAS TURBINES AND FUEL CELLS development effort, and provides a comparative assessment of their high temperature, FOR SYNTHESIS GAS AND HYDROGEN APPLICATIONS – 2 cyclic oxidation, bench-scale performance to that of current state-of-the-art (SOTA) thermal barrier coatings (TBCs).

10-1 10-4 Effects of Coal Syngas Impurities on Anodes of Solid Oxide Fuel Cells: A Development of a Low-Swirl Burner for Syngasand H2 Gas Turbines Review Robert K. Cheng, David Littlejohn, Lawrence Berkeley National Laboratory; Fatma Cayan, Mingjia Zhi, Suryanarayana Pakalapati, Ismail Celik, Nianqiang Peter Strakey, Todd Sidwell, DOE-NETL; David R. Noble, Tim Lieuwen, Nick Wu, West Virginia University; Randall Gemmen, DOE-NETL, USA Georgia Institute of Technology, USA

A literature review is conducted to summarize the studies on the identification of The low-swirl injector (LSI) is an ultra-low NOx technology based on a novel lean impurities in coal syngas and their effects on the performance of Ni-yttria stabilized premixed combustion concept. It has been developed for gas turbines operating on zirconia (Ni-YSZ) anode of solid oxide fuel cells (SOFCs). Coal syngas typically natural gas and has the potential for adaptation to fuel-flexible gas turbines operating contains major species, CO, H2, CO2, H2O, CH4, N2, and H2S as well as trace on a variety of gaseous fuels. Under the sponsorship of the US Dept. of Energy (DOE) impurities. Thermodynamic equilibrium calculations have indicated that trace Clean Coal program, this technology is being developed for the gas turbines in impurities species such as Be, Cr, K, Na, and V in the coal syngas form condensed Integrated Gasification Combined Cycle (IGCC) coal power plants that burn syngases phases under warm gas cleanup conditions and can be effectively removed by the and/or fuels with very high H2 constituents when the IGCC plant is equipped with cleanup processes. For meaningful data comparison, a practical parameter is carbon capture and sequestration technologies. formulated to quantify the level of degradation normalized with respect to the relevant The LSI technology evolved from laboratory research and its operating principle has experimental parameters. Experimental results show that the existence of Hg, Si, Zn been characterized by laser-based diagnostics. The application of the fundamental and NH3 in the coal syngas does not significantly affect the performance of the Ni- knowledge has facilitated the transfer of this combustion method from the laboratory to YSZ anode. The presence of Cd and Se in the syngas impacts the SOFC anode the market place. To adapt LSI to the IGCC turbines, the first step is to gain an performance to some extent. Impurity species such as Cl, Sb, As, and P cause severe understanding of the effects of syngas and H2 on the flame behaviors. The experiments cell voltage degradation due to attack on the Ni-YSZ anode. Sb, As and P have the were conducted in three facilities. Open and enclosed laboratory flames at atmospheric potential to react with Ni to form secondary phases in the Ni-YSZ anode, which conditions were used to investigate the lean-blow off limits, global flame deteriorate the catalytic activity of the anode. characteristics, emissions, the flowfield structures and the turbulent flame speeds. Verification of syngas operation at elevated temperatures and pressures were 10-2 performed with a reduced scale LSI in a small pressurized combustion channel at Direct Coal Fuel Cell Georgia Institute of Technology. Verification of hydrogen operation at elevated Jeff Bentley, CellTech Power LLC, USA temperatures and pressures were performed with a full scale LSI in a research combustor at National Energy Technology Laboratory in West Virginia. These studies The Liquid Tin Anode (LTA) Fuel Cell can operate on gaseous, liquid and solid fuels show that the basic LSI design is amenable to burning syngases and pure hydrogen. containing hydrogen, carbon or hydrocarbon compounds. The current version of the The main effect of increasing H2 concentration in the fuel is an upstream shift in the LTA, called Gen 3.1 was developed specifically to generate electricity from liquid LSI flame position. This upstream shift is consistent with the prediction from a top hydrocarbon fuel. It has been shown to operate directly on military logistics fuel (JP- order analytical model for the coupling between the flowfield and the turbulent flame 8) for over 100 hours with peak efficiency greater than 40%. The LTA has also speed. The LSI also shows a higher resistance to H2 flame flashback than an idealized demonstrated the ability to operate in the presence of sulfur and under sooting high-swirl injector. However, prior to flashback, the high diffusivity and reactivity of conditions. the H2 fuel alter the LSI flame stabilization mechanism and thus the flame shape. The The LTA can also generate power directly from solid fuels. The power production in NOx emissions from syngas flames and from H2 flames show log-linear dependency on the LTA comes from the conversion of liquid tin to tin oxide: 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 Sn(l) + 2 O2- = SnO2 (s) + 4 e [1] gas turbine and the potential for meeting the DOE goal of operating at < 2 ppm NOx A solid fuel such as carbon can be used to reduce tin oxide back to tin via one of the (@15% O2) with high H2 fuels. following pathways. SnO2(s) + 2 C = 2 CO(g) + Sn [2] 10-5 Advanced Hydrogen Turbine Development Update SnO (s) + C = 2 CO (g) + Sn [3] 2 2 Joseph Fadok, Siemens Power Generation; Ihor Diakunchak, CDI Corp, USA

SnO2(s) + CO(g) = CO2(g) + Sn [4] Siemens Power Generation (SPG) has completed Phase 1 of the U.S. Department of CO2(g) + C = 2 CO(g) [5] Energy (DOE) Advanced Hydrogen Turbine Development Program and is currently in Equations [2] and [3] describe direct oxidation of carbon, which has been year one of Phase 2. The 3-phase (only Phases 1 and 2 have been awarded to date), demonstrated by CellTech Power. The Generation 3.1 cell incorporates a porous multi-year program goals are to develop an advanced syngas, hydrogen and natural gas ceramic which provides containment of the tin anode and allows only gaseous products fueled gas turbine fully integrated into coal-based Integrated Gasification Combined to interact with the tin. In this case, Eqs [4] and [5] describe the oxidation process. Cycle (IGCC) plants. The program objectives are to demonstrate by 2010 a 2 – 3 The LTA also makes power from hydrogen. The pathway in LTA for power percentage point efficiency improvement over the baseline, <2 ppm NOx @ 15% O2 on production from hydrogen, with water as the product is described elsewhere. syngas fuel and 20-30% reduction in combined cycle capital cost in $/kW. By 2015, Generation 2 LTA uses a porous separator to contain the tin anode. The equations the objectives of 3-5 percentage points efficiency improvement over the baseline, <2 superimposed on the micrograph show the location of reactions for a complex ppm NOx @ 15% O2 on H2 fuel, and CO2 sequestration readiness are to be hydrocarbon (in this case coal) utilizing indirect oxidation. demonstrated. This paper describes the Phase 1 accomplishments, Phase 2 first year’s CellTech is evaluating the use of LTA operating directly on carbon, coal, petroleum activities, and plans for the remainder of Phase 2. The two-year Phase 1 included coke, biomass and other carbonaceous feedstocks. For solid feedstocks, two identifying the advanced technologies required to achieve the program goals, novel or approaches are being evaluated. In one approach, a larger tin reservoir allows fuel and enhanced technologies development initiation and Research and Development tin to be directly mixed (fuel is introduced and mixed directly into the liquid tin Implementation Plan preparation. Phase 2 (5-year duration) will focus on advanced anode). This approach allows the direct reduction of tin oxide by carbon (Eq 3) or technologies development, downselection and validation, as well as the Hydrogen hydrogen and was used in CellTech s Gen 1 fuel cell. The second approach uses a Turbine conceptual design. In Phase 3, if awarded, the advanced gas turbine detailed 9 design will be completed, the prototype engine manufactured and installed into an water. This paper examines the application of dry beneficiation technology to the IGCC plant for validation testing to demonstrate the project’s commercial viability and separation of coal and mineral matter in a novel air-fluidized bed. that the DOE program goals have been achieved. The development effort so far has The Reflux Classifier (RC) is an innovative design that incorporates an inclined settler focused on cycle performance calculations, engine and plant cost estimates, gas above a conventional fluidized bed to achieve increased segregation rates and a higher turbine-IGCC plant integration studies, combustion concepts development, turbine throughput than separators with an equivalent footprint. The RC has been successfully aerodynamics/cooling concepts development, modular turbine component construction implemented as a water based system for processing -2+0.25 mm coal in Australia. In concepts evaluation, novel materials/coatings technologies development and engine this study, the effectiveness of magnetite and sand as dense media for the separation of system integration/flexibility considerations. coal in an air fluidized RC was evaluated. The effect of vibration on the separations In Phase 1, four combustion concepts (diffusion flame, catalytic, and two premix obtained using both these media was also examined. A vibrated fluidized bed has a systems) were investigated and down selected to two for further development in Phase lower minimum fluidization velocity and smaller bubbles resulting in a more 2 and eventual downselection to one successful candidate for incorporation into the consistent bed density. Hydrogen Turbine. This paper provides details on the combustion development testing, A single channel RC was used in this study in batch and semi-batch operation. It was test results and the downselection process. Considerable effort was devoted to established that multiple separations stages were required when using a magnetite identifying advanced turbine aerodynamic and airfoil cooling concepts for medium, but that a single stage semi-batch separation with sand medium and vibration development and incorporation into the advanced gas turbine. A study was carried out was demonstrated to out perform all magnetite separations. Vibration acts to on the performance benefits to be derived from a significant increase in the turbine significantly improve the separation efficiency in a sand system, but made no annulus height in excess of current state-of-the-art (SOTA), which was necessitated by improvement to the magnetite system. The effect of the direction and frequency of the the substantial increase in turbine mass flow resulting from the IGCC application. This vibration on the Ep and cut point of the separation are reported. study concluded that this concept is feasible from both mechanical integrity and On -8+1 mm coal using sand medium with vibration, the beneficiation achieved an ash manufacturability considerations. Substantial progress was made in advanced reduction from a feed of 30% ash coal to a 15% ash product corresponding to a yield bondcoat, thermal barrier coating and fabricated airfoil development. Conceptual of 76% and a combustibles recovery of 92%. This compares well with a water design reviews and risk analyses were conducted on the new gas turbine components. separation in the RC which has a product ash of about 13.5%. The separation Studies were carried out on the gas turbine-IGCC plant integration and different performance increased with increasing particle size with Ep values of 0.067 for - gasification and air separation technologies that should be considered and evaluated. 6.35+4 mm particles compared with 0.125 for the -2+1 mm fraction. The results of these studies and developments provided a firm basis for completing the The coal separation results are reported and compared with coal washability data. advanced Hydrogen Turbine technologies development in Phase 2. 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 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 11-1 significant amount of rocks are also transported along with coal. Also, in certain parts Coal Grinding & Drying for Coal Gasification Plants of USA due to the scarcity of water only selective mining is being done while Tobias Korz, Carsten Schoessow, Loesche GmbH, GERMANY 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 Since more than 100 years Loesche supplies pulverizers and complete grinding and processing will be economical as it will not utilize water and thus no dewatering or drying plants to the cement, steel and power industry. Loesche grinding plants utilise drying of the product will be required. energy and resources efficiently, and their quality and reliability are recognised The goal of this study was to evaluate a dry separation process for processing coal internationally. finer than 1/4 inch. High ash coal samples from two (Mine 1 and Mine 2) Western The modular structure of large roller grinding mills enables utilisation of the same Kentucky mines were selected for the present study. Statistical design experiments components in different mill sizes. Module components include grinding rollers, rocker were conducted to assess the effect of operating parameters of the dry separator on arms, pedestals and spring assemblies. The principle behind this structure was patented product yield for a given ash content. The tests showed that for Mine 1 coal, the air in1970 and is employed for coal grinding mills and mills in the cement and industrial table was able to reduce the ash from 27% to 10-12% ash with a clean yield of about minerals industry. 2, 3, 4 or even 6 grinding roller configurations for a single grinding 75-80%. The ash rejection was about 77-80% with a combustible recovery of about table can be realised. 95% indicating excellent separation efficiency. The pyritic sulfur was reduced from In 1990 Loesche supplied the first coal grinding plant for an IGCC power plant in 2.65% to about 1.5%. Processing of the combined -1/4” x 6 mesh coal reduced the ash Buggenum, Netherlands. With this experience Loesche is the first choice for the now content from 25.5% to 10.9%. The total sulfur was reduced from 4.05% to 3.35%. upcoming coal gasification projects all over the world. The heating value of the coal was increased from 10326 Btu/lb to 12623 Btu/lb. Our paper describes the technical features of the Loesche vertical roller mill for the For the Mine 2 coal, the clean coal yield was as high as 78% for 1/4” x 6 mesh size grinding and drying of coal, petcoke, anthracite or lignite. Within the next months fraction. The 6x14 mesh fraction provided a clean coal product contaning 9% ash at a Loesche will commission the biggest coal mill of the world, a LM 43.4 D with a name yield of 86%. The total sulfur was reduced from 3.36% to 3.05%. In summary, the air plate capacity of 210 t/h. Additionally, we will describe the function of our Loma hot table was effective in reducing ash by 65% and sulfur by about 25-35%. gas generator which produces the necessary heat to dry the coal. Furthermore, the safety of coal-grinding plants must be ensured in all operating 11-4 situations. Safety aspects are laid down in regulations and ordinances. Nowadays inert Rotating Coal Drying Kiln and pneumatically-operated grinding plants can be designed with incorporated Thomas A. Menditto, James R. Heitman, Energy Prep Inc., USA operational safety characteristics. Self-inert grinding plants that utilise recirculated gases occurring in the installation system itself. The required process heat is provided Energy Prep Inc is a coal preparation company offering services for intellectual license by a hot gas generator that is an intrinsic part of the grinding plant. to a process of a rotating coal drying kiln that will upgrade the quality of coal, and We will explain in detail the function of a so called self-inerted coal grinding plant therefore offer energy companies that use lower quality coal an opportunity to make a which enables safe and reliable operation under inert conditions. This includes the net profit of at least ten million a year. The incredible profits offered by our process necessary supervision of oxygen and CO contents, as well as the automatic control of are a direct result of our tested procedure, whose economic value is far superior to the plant in case of hazardous situations like emergency shut down or power failure. many other processes on the market. The IB-50 was in operation at the Wabash Valley The presentation will end with an outlook into the future where even bigger mills will Energy mine in 1983 by James R. Heitman. At that time James R. Heitman was the be used to reduce the investment costs of coal gasification plants. 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 11-2 capable of removing 10% to 20% of moisture from sub-bituminous coal at a rate of 50 The Effect of Vibration on Dry Coal Beneficiation in the Reflux Classifier tons per hour. Several samples of the Indiana coal were sent to labs for testing. Feed Siubhan Macpherson, Kevin Galvin, The University of Newcastle, AUSTRALIA 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. Coal preparation has traditionally involved separating coal and mineral matter particles On the same equipment feed rates were varied from 5 tons per hour to over 70 tons per using a variety of water based gravity beneficiation methods. As the reliability of water hour. It is the unique design of the apparatus that enables a product with low supplies decreases, new methods for the dry beneficiation of coal are being sought. A investments costs and great profit margins. dry beneficiated coal has the advantage of a reduced moisture content compared with Our process sufficiently dries the coal without causing combustion through the use of a conventionally processed coal. Further advantages include negligible process water digitally controlled rotating kiln drier. The most marketable part of our process is the requirements and less capital equipment for dewatering processes and the recovery of 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, beneficial to improve dispersing degree, catalysis activity and selectivity for C5 + during the testing it was determined that to achieve a 20% reduction in moisture less hydrocarbon. The CO conversition are 90.61% 97.81%, the selectivity for C5 than 5% of the product was consumed for fuel. The apparatus is small enough that hydrocarbon is 76.8% 84.7%, and the alkene/alkane rate in tail gas is close to zero at permits can be avoided, and therefore our initial start-up and maintenance cost are not the condition of temperature 240°C, pressure 2 MPa, and airspeed 500 h-1. more than $3/ton, which makes our process economically valuable on many levels. Energy Prep’s apparatus has many economic benefits that would interest energy 12-3 companies around the world. The upgraded fuel quality has been shown through tests The Liquefaction Reactivity of the Shangwan Parent Coal and its Lithotypes at Leigh University to increase boiler efficiency and decrease emission costs. from the ShenHua Coal Furthermore, the reduction in moisture content leads to weight reductions which Zhou Jianming, Wang Naiji, Beijing Research Institute of Coal Chemistry, China drastically reduce the rail costs. In addition, our apparatus is eligible for tax credits for Coal Research Institute; Wang Yonggang, Yang Zhengwei, Wang Caihong, providing an enhanced coal product. The summation of all these savings could lead to China University of Mining and Technology, CHINA 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 The hydro-liquefaction behaviors of Shangwan (Shenhua Coal) coal and its vitrain and within the coal and energy sector. fusain of lithotypes were investigated in a high pressure microautoclave at the different temperature (ranging from 400 to 450°C) and pressure (ranging from 7 to 11 MPa). 11-5 Results showed that with increasing in the temperature and initial hydrogen pressure, The Investigation of the Breakage Patterns of Coal Under Simulated Impact the total conversion and oil yield increased. At the 7 MPa initial hydrogen pressure, the and Attrition Breakage Conditions in Order to Predict Fines Generation temperature raising from 400°C up to 450°C, the total conversion were increased by During Transport and Handling 23.74%, 26.67% and 32.08%, respectively. At the same conditions, the liquefaction Q.P Campbell, North-West University; V. Claassens, Sasol Research and reactivity order of Shangwan coal and its lithotypes is: parent coal>vitrain>fusian. At Development, SOUTH AFRICA 450°C 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 This project was done to gather data and develop models to predict the breakage 27.68% respectively. The highest oil yield of vitrain was 48.12% at the temperature of characteristics of coal (and specifically fines generation) during the normal handling 440°C. The liquefaction reactivity of parent coal, which has higher ash content and and transport of freshly mined coal from the coal face to the end user. Two types of catalytic component, was higher than that of the vitrain. breakage events have been investigated: impact breakage (at transfer chutes, dropping into hoppers and silos, etc.) and attrition breakage (during transport on long conveyer 12-4 belts, railroad trucks, etc.). Freshly mined coal, from a number of different South Low Temperature Fischer-Tropsch Synthesis Using Iron-Based Catalysts in African sources, was used and subjected to single particle freefall tests where high Slurry Bubble Column Reactor speed video photography was used to characterize the breakage during impact. Hak-Joo Kim, Dong-Hyun Chun, Jung-Hoon Yang, Ho-Tae Lee, Heon Jung, Breakage product distributions were measured and related to a variety of factors, like Korea Institute of Energy Research, KOREA kinetic energy, coal type, and particle orientation during impact. Additionally, the attrition breakage due to motion during transport was simulated for extended times, Recently, the high oil price above 100$/barrel results in the deep interest of developing and results were correlated with some of the physical coal properties. These results are alternative technology for manufacturing clean and economic synthesis fuel for being used to establish a statistically based model to predict fines generation in an transportation. Coal-to-liquid (CTL) process can be one promising and effective route entire coal transportation system. 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 SESSION 12 conventional co-precipitation method with the addition of small amount of precious SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL – 2 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 12-1 diameter and 1.5 m of height. Catalyst was suspended in mineral oil and introduced to Effect of Pretreatment on the Activity, Selectivity and Life-time of Iron the reactor using high pressure pump. Catalyst slurry was bubbled with the synthesis Catalyst Supported on Carbon Nanotube for Fischer-Tropsch Synthesis gas purged from the gas distributor specially designed for proper control of bubble Ajay Dalai, Reza M. Malek Abbaslou, Ahmad Tavasoli, University of size. Precise flow control of reactants (H2/CO=2/1 molar ratio) was attained with the Saskatchewan, CANADA 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 This paper presents the effects of acid treatment on the activity, product selectivity and products were collected from the liquid collector prior equipped with a heat exchanger life span of iron Fischer-Tropsch (FT) catalysts supported on carbon nanotubes working with a cold liquid (0°C) circulating system. The volumetric flow rate of gas (CNTs). Two different types of CNTs with low surface area (~25 m2/g) and high phase product and unreacted feed gas was measured by the dry gas meter (Shinogawa, 2 surface area (~170 m /g) were prepared and treated with 35 wt% HNO3 at 25°C and 1 L/rev.). The gas was sampled with a gas-tight syringe in the sampling port located 110°C for 16 hours. Fe/CNTs were prepared using incipient wetness impregnation prior to the dry gas meter. Collected liquid products were analyzed with the aid of gas method with iron loading of 10 wt%. The CNT supports and catalysts were chromatographies. Addition of small amount of precious metal and transition metal characterized by nitrogen adsorption, ICP, TPR, XRD, SEM, TEM and Raman was effective for increasing the reducibility of iron-based catalysts at low temperature spectroscopy. The acid treatments at 25°C and 110°C increased the BET surface area of 220°C. In the reaction condition without mass transfer limitation, modified iron- by 18% and 31%. The results of Raman analysis revealed that the acid treatment based catalyst with enhanced reducibility was effective for producing higher waxy increased the number of defects which are considered as anchoring site for metal hydrocarbons. TPR profiles of the calcined catalysts showed two main peaks. Peak at particles. TEM analysis showed that the major parts of the iron particles were lower temperature was assigned to the reduction of Fe2O3 to Fe3O4, the higher homogenously distributed inside the acid treated nanotubes. According to the XRD temperature peak to the reduction of Fe3O4 to metallic Fe. Addition of precious metal analysis, the acid treatment on both families of CNTs resulted in decrease in metal and transition metal was effective for reducing the reduction temperature range. The particle sizes. The FT synthesis was carried out in a fixed-bed micro reactor (275°C, 2 chain growth probability of the modified iron-based catalysts, based on the A-S-F MPa, CO/H2 = 2) for 120 h. Among the catalysts studied, Fe catalyst supported on distribution, was higher than the conventional iron-based catalyst, showing high pretreated CNTs at 110°C was stable and active while, the other catalysts experienced potentials for catalyst design to produce longer chain length hydrocarbons. rapid deactivations. The Fe catalyst supported on CNTs low surface area and larger + diameter showed much lower CH4 and higher C5 selectivities. 12-5 Kinetic Modeling of a Fischer-Tropsch Reaction Over a Cobalt Catalyst in a 12-2 Slurry Bubble Column Reactor for Incorporation into a Computational Study on Eggshell Co/ZrO2/SiO2 Catalysts for the Fischer-Tropsch Multiphase Fluid Dynamics Model Synthesis Anastasia Gribik, Donna Guillen, Daniel Ginosar, Idaho National Laboratory, Cui-wei Xiao, Nai-ji Wang, Peng Miao, Ren-shan Ji, China Coal Research USA Institute, CHINA Currently multi-tubular fixed bed reactors, fluidized bed reactors, and slurry bubble Cobalt-based eggshell catalysts were prepared from support of formless SiO2. The column reactors (SBCRs) are used in commercial Fischer Tropsch (FT) synthesis. structure and reductionp roperty of the catalysts were characterized by SEM, EDS, and There are a number of advantages of the SBCR compared to fixed and fluidized bed Brunner-Enunett-Teller (BET) techniques. The results show that the catalysts’ reacting reactors. The main advantage of the SBCR is that temperature control and heat activity depend on available oxide cobalt amounts to a great extent, and lesser crystal recovery are more easily achieved. The SBCR is a multiphase chemical reactor where particle of cobalt is in favor of selectivity for liquid hydrocarbon. Additive of ZrO2 is a synthesis gas, comprised mainly of H2 and CO, is bubbled through a liquid 11 hydrocarbon wax containing solid catalyst particles to produce specialty chemicals, desired range of methane compositions for maximizing SNG production. The details lubricants, or fuels. The FT synthesis reaction is the polymerization of methylene are described in the body of the paper. groups [-(CH2)-] forming mainly linear alkanes and alkenes, ranging from methane to KBR has developed proprietary technologies around the core oxygen-blown TRIG high molecular weight waxes. gasifier to maximize water recovery and process heat utilization. The present The Idaho National Laboratory is developing a computational multiphase fluid configuration for SNG production incorporates these novel heat and water integration dynamics (CMFD) model of the FT process in a SBCR. This paper discusses the schemes, while minimizing the environmental footprint. Carbon dioxide is captured at incorporation of absorption and reaction kinetics into the current hydrodynamic model. a purity level suitable for enhanced oil recovery (EOR) and/or sequestration. A phased approach for incorporation of the reaction kinetics into a CMFD model is Robustness, enhanced flexibility, reduced energy and water consumption are key presented here. Initially, a simple kinetic model is coupled to the hydrodynamic model, features. with increasing levels of complexity added in stages. The first phase of the model includes incorporation of the absorption of gas species 13-3 from both large and small bubbles into the bulk liquid phase. The driving force for the Production of Bio-CNG by Gasification gas across the gas liquid interface into the bulk liquid is dependent upon the interfacial Christiaan van der Meijden, B.J. Vreugdenhil, A. van der Drift, R.W.R. Zwart, gas concentration in both small and large bubbles. However, because it is difficult to Energy Research Centre of the Netherlands (ECN); H.J. Veringa, University of measure the concentration at the gas-liquid interface, coefficients for convective mass Twente, THE NETHERLANDS 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 Compressed Natural Gas (CNG) is becoming more and more important as a transport effects from mass transfer of the gas phases to the bulk liquid phase, since there are fuel. The number of cars using CNG instead of liquid fuels is increasing rapidly (to 8 only small amounts of dissolved gas in the liquid phase. The product from the million in 2008). CNG is a relatively clean transport fuel. The emissions of CO2, incorporation of absorption is the steady state concentration profile of the absorbed gas particles and sulfur are significantly lower than for other conventional fossil fuels. species in the bulk liquid phase. Fossil CNG can easily be replaced by CNG produced from biomass (Bio-CNG), The second phase of the model incorporates a simplified macrokinetic model to the because the composition of the gas and the heating value are similar. Replacing CNG mass balance equation in the CMFD code. Initially, the model assumes that the catalyst by Bio-CNG will reduce fossil CO2 emissions to zero. Bio-CNG even has the potential particles are sufficiently small such that external and internal mass and heat transfer to become a CO2 negative transport fuel, as part of the carbon from the biomass is are not rate limiting. The model is developed utilizing the macrokinetic rate expression separated as pure CO2 from the fuel during the production of Bio-CNG. If this pure developed by Yates and Satterfield (1991). Initially, the model assumes that the only CO2 stream is sequestrated, Bio-CNG becomes CO2 negative. species formed other than water in the FT reaction is C27H56. Change in moles of the The production of Bio-CNG via digestion has been developed and is implemented reacting species and the resulting temperature of the catalyst and fluid phases is solved (mainly) in small-scale installations. The limited amount of suitable digestible feed simultaneously. The macrokinetic model is solved in conjunction with the species stock demands for development of a technology which can convert a wider range of transport equations in a separate module which is incorporated into the CMFD code. 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 Fischer- SESSION 13 Tropsch Diesel is significantly lower (below 50%). GASIFICATION TECHNOLOGIES: SUBSTITUTE NATURAL GAS 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 13-1 gasification gives the highest overall efficiency to Bio-CNG. The Case for Synthetic Natural Gas from Coal The Energy research Centre of the Netherlands (ECN) decided to continue the Gary Leatherman, Booz Allen Hamilton, USA development of an indirectly heated (allothermal) biomass gasification process (MILENA), because of its high overall efficiency to Bio-CNG. The foreseen scale for The production of pipeline quality synthetic natural gas (SNG) from coal is a a commercial Bio-CNG production facility is between 50 and 500 MWth or between 3 potentially attractive application of gasification technology. This paper examines the and 30 ton/h of Bio-CNG. The MILENA technology is suitable to be scaled up to this economics of SNG production using current state-of-the-art technology (entrained flow scale. ECN also develops and tests the required gas cleaning equipment. The gas from gasification and catalytic methanization) with and without carbon capture and storage. the final gas cleaning step can directly be upgraded into CH4 by conventional and The potential economic viability of this approach is then compared to a number of commercially available methanation catalysts. natural gas price scenarios. The potential of emerging gasification technologies to ECN has built and tested the Bio-CNG installation on a lab-scale of 6 kg/hour biomass create a step change in economics are also assessed. The paper then examines how input (30 kWth). A pilot scale gasification unit of 160 kg/hour (0.8 MWth) was built in SNG from coal with CCS can contribute to CO2 emission reductions. Details on the 2008. First tests in biomass combustion and gasification mode showed that the scale of market penetration required for significant CO2 impact are analyzed. installation is behaving as expected. The results from the lab-scale installation are promising. The gasifier and connected gas cleaning were operated successfully during 13-2 several 100 hour duration tests. Progress has been made in selecting the appropriate KBR’s Transport Gasifier (TRIG™) – An Advanced Gasification process conditions to obtain cleaned producer gas that can be sent to a commercial Technology for SNG Production from Low-Rank Coals methanation process. Siva Ariyapadi, Philip Shires, Manish Bhargava, David Ebbern, KBR, USA 13-4 The KBR Transport Gasifier (TRIG) operating in the oxygen-blown mode can provide Development of a Hydrogasification Process for Co-Production of Substitute clean, particulate-free synthesis gas (syngas) for a wide variety of coal-based Natural Gas (SNG), Biofuel and Electricity from Western Coal chemicals and fuels applications. This advanced gasification technology was jointly Raymond Hobbs, Xiaolei Sun, Fuyuki Noguchi, Arizona Public Service; Elaine developed by KBR and Southern Company Services, Inc. in an effort to offer a less Everitt, Chris Guenther, NETL/DOE, USA 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 The Advanced Hydrogasification Process (AHP) process is being developed by cracking (FCC) reactors and features dry feed injection/ dry ash handling systems. 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, An engineering-scale prototype of the Transport Gasifier has been in successful while also incorporating a renewable theme to address regulations in western states. A operation since the mid-1990s at the Power Systems Development Facility (PSDF) in fully integrated five-step process – Integrated Energy Strategy (IES) includes (1) Wilsonville, Alabama. A range of low-rank coals has been successfully tested in this Hydrogen production without CO2 emissions; (2) Substitute Natural Gas (SNG) facility under both air-blown and oxygen-blown modes. More recently, the TRIG generation by flash Hydrogasification of coal; (3) Oxy-combustion of coal/char to technology was selected for an advanced 600 MWe, two-gasifier IGCC facility for produce electricity, (4) Carbon recycling of CO2 emissions through biological Mississippi Power. The project is based on air-blown gasification of lignite and is processes, and (5) Biofuels production from carbon recycling. The combination of currently in the detailed engineering phase. these steps creates an integrated process that delivers energy and fuel in a long-term The focus of this article will be on oxygen-blown operation of TRIG to produce syngas sustainable fashion. During the current phase of this study, effort has been focused on suitable for Substitute Natural Gas (SNG) applications. The Transport Gasifier design and fabrication of a bench scale reactor system for generating data on operates at elevated pressures and moderate temperatures. The moderate temperature hydrogasification kinetics, coal conversion, product yield and composition. Extensive operation of TRIG is an important advantage for SNG production in comparison to the Computational Fluid Dynamic (CFD) simulations have been conducted to assist with various high temperature slagging gasifiers in particular, the specific-oxygen reactor design, especially hydrogen nozzle design. Test operations are expected to consumption is low, resulting in higher cold gas efficiencies. Moreover, by slight begin in late fall 2008. Investigation of a concept for using Algae as biological CO2 modifications in gasifier operating conditions, it is possible to provide syngas with a capture method is discussed.

12 13-5 while reducing pollutants in an indirect but highly effective manner, hence the cost for Overview of Viresco Energy’s Coal Pilot Plant Using Steam the hydrogen product is greatly reduced. Extensive demonstrations of the SCL process Hydrogasification Technology have been carried out under a fixed bed reactor using coal syngas as feedstock. Joseph M. Norbeck, Jim Guthrie, Viresco Energy LLC, USA 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. 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 14-2 advantages over current gasification technologies. It is an integrated system of three Effect of Reaction Temperature on the Performance of Thermal Swing different chemical processes. In the current configuration a steam hydrogasification Sorption Enhanced Reaction Process for Simultaneous Production of Fuel (SHR) step is followed by a steam methane reforming (SMR) step followed by a Cell Grade H2 and Compressed CO2 from Synthesis Gas Fischer-Tropsch reaction (FTR) step. This technology has been successfully Michael Beaver, Ki Bong Lee, Shivaji Sircar, Hugo Caram, Lehigh University, demonstrated at the process demonstration unit scale at the University of California USA 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. A novel cyclic thermal swing sorption enhanced reaction (TSSER) process concept The Department of Energy’s National Energy Technology Laboratory (NETL) has was recently proposed for simultaneous production of fuel-cell grade H2 and completed a detailed review of this technology, the results of which will be presented compressed CO2 from a synthesis gas containing CO and H2O [1, 2]. The process at the conference in another presentation. The next critical step in the carried out the catalytic water gas shift (WGS) reaction (CO + H2O ↔ CO2 + H2) with commercialization process is to design, construct and operate a pilot plant of the size simultaneous removal of CO2 from the reaction zone by a reversible, hydrophobic, CO2 of between fifteen to twenty tons/day. This facility will be constructed in Utah and use selective chemisorbent in order to circumvent the thermodynamic limitation of the a feed of Utah coal with the flexibility to use coal and biomass mixtures. A technical WGS reaction and enhance the rate of the forward reaction. The chemisorbent was team has been formed to lead in the commercialization that includes Viresco, the periodically regenerated using the principles of thermal swing adsorption by purging University of California, Riverside, Research Triangle Institute, Technip, and NETL. the sorber-reactor with super heated steam at different pressures and temperatures. This paper will present an overview of the technology, the anticipated design of the Several intermediate process steps were employed to produce a pure and compressed Utah facility, and details of the projected yield and capital cost of the pilot facility. CO2 by-product during the thermal desorption process. The present work reports (a) new experimental data demonstrating the concept of 13-6 sorption enhanced WGS reaction at different temperatures using a commercial WGS Co-Production of Substitute Natural Gas and Electricity via Catalytic Coal catalyst and Na2O promoted alumina as the CO2 chemisorbent, and (b) the effect of the Gasification sorption-reaction temperature on the TSSER process performance estimated by model Brian S. Turk, Raghubir Gupta, Andreas Weber, RTI International, USA simulation. Relatively slower kinetics of the sorption-enhanced WGS reaction imposes a lower bound (~ 200°C), while the thermal stability of the chemisorbent and the use of The convenience and clean-burning features associated with the use of natural gas has carbon steel sorber-reactors sets the upper bound (~ 550°C) of temperatures for allowed this fuel to become invaluable for industrial, commercial, and residential practical operation of the TSSER process. Simulated process performances (sorption- energy and heating needs. The challenge is that the domestic supply of this natural reaction at 200 and 400 C, and regeneration at 550°C) show that the operation of the resource is dwindling, which has driven up the cost of this resource. One approach for sorption-reaction step at 200 C increases the H2 and CO2 productivities of the process supplementing domestic resources of natural gas that is receiving considerable by, respectively, ~ 38% and 35% without changing the (a) moles of H2 produced per attention is the conversion of coal into a methane-rich gaseous product or substitute mole of CO in the feed gas, and (b) net CO2 recovery as a compressed by-product gas. natural gas (SNG), which meets current natural gas pipeline specifications. The main The total steam duty for the sorbent regeneration increases by ~ 14% for the lower advantage of this approach is that this SNG product can be added to the extensive sorption-reaction temperature operation. Another major benefit of the lower reaction network of existing natural gas pipelines increasing supply without any noticeable temperature operation was a very large increase in the pressure of the CO2 by- product effect by the end user. The technical challenge is to develop processes for converting (e.g. 40 and 21 bars at, respectively, 200 and 400°C) when the reactor feed gas coal into SNG that are thermally efficient, environmentally attractive and economically contained 20% CO + 80% H2O at a total pressure of 15 bar. competitive. With DOE/NETL funding, RTI has been exploring a novel process that converts low 14-3 ranked coals, like sub-bituminous coal and lignite, into a SNG product meeting Studies on the Reduction Mechanism of the Iron Oxide Based Composite pipeline specifications. Several key features of this process are the novel two-stage Particle in the Syngas Chemical Looping Process gasification approach that targets increasing carbon conversion with enhanced Liang-Shih Fan, Deepak Sridhar, Fanxing Li, Hyung Kim, Liang Zeng, Thomas selectivity for methane formation and use more effective warm syngas cleaning Yeh, The Ohio State University, USA 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 Syngas Chemical Looping (SCL) is a novel process developed to convert coal derived coal into a mixture of gas phase carbon species, H2 and solid char fines prior to the syngas into hydrogen of very high purity with integrated CO2 separation. The catalytic reactor. In a second catalytic reactor, the catalyst promotes the conversion of technology developed at the OSU revolves around the ability of the Iron based oxygen the gas phase carbon species and H2 into CH4. Because the ash is trapped in the solid carrier to perform the multiple tasks. char fines and the catalyst on a support, physical contact between the ash and catalyst There are three major reactors in the SCL process, namely, the Reducer, The Oxidizer is impossible eliminating the potential for reaction and deactivation of the catalyst. The and, the combustion train. The oxygen carrier passes through all three units mentioned product gas mixture from the catalytic reactor is cleaned using the hot gas above and gets involved in the critical reactions that enable the highly efficient desulfurization and CO2 capture technologies that have been developed at RTI. The process. product from the CO2 capture process is a high pressure sequestration ready CO2 The iron based composite particle synthesized at The Ohio State University maintains byproduct. With a final polishing methanation and gas cleaning process, an SNG high reactivity for more than 100 reduction-oxidation cycles and has strength that can product meeting pipeline specifications is produced. sustain commercial operations. These superior properties compared to commercial During Phase I of this project, RTI has focused on bench-scale testing of the technical Fe2O3 make the iron oxide composite particle an ideal choice to be adapted in the SCL feasibility of the different pieces of this coal conversion process. This presentation will process. describe the results from this bench-scale testing program for evaluating the technical In this paper, the reduction kinetics of the iron based composite particle using CO and and economic feasibility of the proposed process. 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 SESSION 14 make the SCL more efficient as well as economically attractive. HYDROGEN FROM COAL – 2 14-4 Calcium Looping Process for High Temperature High Pressure Hydrogen 14-1 Production with Insitu CO2 and Sulfur Capture Syngas Chemical Looping Process for Hydrogen Production Shwetha Ramkumar, L. S. Fan, Mahesh V. Iyer, The Ohio State University, USA L. -S. Fan, Fanxing Li, Deepak Sridhar, Hyung Kim, Liang Zeng, Fei Wang, 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 The Syngas Chemical Looping (SCL) process is a novel chemical looping process that year 2030. Currently, the United States is dependent on foreign oil for 56% of its can efficiently convert gaseous fuels such as syngas and hydrocarbons into hydrogen energy needs which is estimated to increase to 70% by 2025. This rising energy with in-situ CO2 capture. Through the assistance of a specially tailored Fe2O3 based demand coupled with the depleting global oil reserves and the dependence on foreign composite particle, the SCL process simplifies the overall fuel conversion scheme oil has brought processes which convert coal into hydrogen as well as cleaner, high 13 energy density fuels to the forefront. The United States has the world’s largest coal reserves and hence the development of an energy efficient coal to hydrogen, electricity SESSION 15 and liquid fuels technology is essential. COMBUSTION TECHNOLOGIES – 3 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 15-1 (WGS) reaction with in-situ carbon dioxide (CO2), sulfur and hydrogen halide remove CFD Modeling of Oxy-Fuel Combustion in a Utility Coal-Fired Boiler at high temperatures in a single reactor. Thus the integrated process combines several Zumao Chen, Alan Sayre, Rick Wessel, Denny K. McDonald, Babcock & unit operations, such as the WGS reactor, CO2 capture system, sulfur removal step, Wilcox, USA halide removal, and hydrogen purification in one process module thereby reducing the overall foot print of the process. Power generation from fossil fuel combustion results in the emissions of greenhouse In this process, the thermodynamic limitation of the WGSR is overcome by the in-situ gases, primarily carbon dioxide (CO2), which is generally believed to contribute to removal of CO2 by the calcium oxide sorbent obtained from the Ohio State University global climate change. Oxy-fuel combustion provides an approach in which CO2 in the patented Precipitated Calcium carbonate (PCC) sorbent. Besides, the calcium oxide flue gas may be concentrated to permit more efficient and economical capture and sorbent has also demonstrated superior performance in the removal of sulfur disposal. impurities. The morphological properties of the PCC sorbent can be tailored using Traditionally, air is used as the medium for combustion in coal-fired boilers. A large surface modifiers to form a mesoporous structure that results in superior performance amount of nitrogen from the air results in a low concentration of carbon dioxide in the over naturally occurring limestone and dolomite sorbents that are plagued by pore flue gas. The low concentration of carbon dioxide makes CO2 recovery or capture mouth closure leading to lower conversions. The PCC sorbent demonstrates a high more difficult and costly due to the large volume of flue gas that must be processed. In CO2 capture capacity of about 70% by weight while removing H2S impurities at high the case of oxy-fuel combustion, the oxygen in air is replaced by nearly pure oxygen temperatures to ppm levels and producing high purity hydrogen at elevated pressures from an air separation unit (ASU). The oxygen is then diluted by recycled flue gas, in the absence of a catalyst. Life cycle testing of the sorbent over multiple cycles of leading to a gas mixture with a lower oxygen concentration, to ensure that there is carbonation-calcination reactions shows that PCC sorbent attains a capture capacity of sufficient gas volume to control flame temperature and achieve the desired heat 40-36 wt% over 50-100 cycles, which is significantly higher than most of the high transfer within the boiler. The resulting flue gas leaving the boiler is a CO2-rich stream temperature sorbents reported in literature. Calcium carbonate which is formed in the ready for processing (compression and purification) and sequestration. process due to the reaction of calcium oxide with CO2 is separately calcined to yield a In this paper, the results of a computational fluid dynamics (CFD) modeling study are pure CO2 stream for its subsequent sequestration and the calcium oxide is recycled reported. In-house comprehensive software, COMOSM, is used to simulate pulverized back. Thus, the calcium looping scheme not only improves the hydrogen yield and coal combustion in a 520 gross MWe opposed-wall fired boiler. The combustion purity but also integrates a gas cleanup and CO2 management scheme in the hydrogen performance of the boiler is evaluated, and the heat transfer characteristics of the boiler production process. under oxy-firing conditions are discussed and compared with those under airfiring Process Evaluation and optimization of the calcium looping system for the production conditions. 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 15-2 of 99.999% pure hydrogen from coal is 63% (HHV) when compared to the state-of- Novel Air Separation Sorbents the-art, hydrogen from coal process which has an efficiency of 57% (HHV). The purity Gokhan Alptekin, Ambal Jayaraman, Margarita Dubovik, Lauren Brickner, TDA of hydrogen is increased by a large extent when the carbonation reaction is integrated Research, Inc., USA 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 Oxy-fuel combustion has the potential to dramatically decrease the environmental the process. In addition, the extent of H2S removal by the CaO sorbent is also enhanced impact of producing electrical power, especially because it can be retrofit to existing by operating at lower steam partial pressures. Experiments conducted in a bench scale pulverized coal power plants. In this technology, oxygen combustion replaces the system have revealed the superior performance of PCC sorbent for the production of traditional combustion environment of coal in air. This results in an off gas of steam H2. High purity hydrogen of 99.7% with less that 1 ppm sulfur impurity has been and pure CO2, which can be easily sequestered rather than released into the atmosphere obtained in a bench scale fixed bed reactor system. where it contributes to the green house effect. However, the technology is not yet used The calcium looping process results in the production of high purity H2 at high in spite of its promise, primarily because pure oxygen is currently too expensive. temperatures and pressures, simultaneous removal of CO2 as well as sulfur impurities, TDA Research, Inc. (TDA) is developing a low cost, high capacity sorbent for air production of a sequestrable CO2 stream by sorbent regeneration, reduction in excess separation to supply low cost oxygen for oxy-fuel combustion. The regenerable steam requirement and flexibility in carbon monoxide conversion to produce H2:CO sorbent can remove oxygen from air with very high capacity, and the sorbent maintains ratios of varying compositions suitable for fuels/chemical synthesis. its capacity for over 200 absorption/regeneration cycles under representative conditions. TDA’s oxygen sorbents also would find application in IGCC plants. 14-5 A Feasibility Study of Ni-Fe-Cr Based Metal Alloys as WGS Catalysts for 15-3 Catalytic Membrane Reactors at 700°C Oxy-Coal Combustion: Effects of PO2 on Coal Jet Stability in O2/CO2 San Shwe Hla, Greg Duffy, Jim Edwards, Alex Ilyushechkin, Leigh Morpeth, Environments Daniel Roberts, Dongchan Park, CSIRO Energy Technology, AUSTRALIA Jingwei Zhang, Eric G. Eddings, Jost O. L. Wendt, University of Utah, USA

Ni.Fe.Cr based metal alloys (Ni70Fe9Cr19, Ni64Fe1Cr21, and Ni10Fe69Cr19) in the form of The purpose of this research is to understand and predict the effects of the near burner fine powders have been examined for their water-gas-shift catalytic activity at zone environment on ignition characteristics of a turbulent axial pulverized coal jet. In significantly higher temperature (700°C) than can be achieved with conventional high oxy-coal combustion this environment consists of O2 and CO2 (instead of N2). temperature WGS catalysts. This study was performed in order to identify candidate Ultimately it is planned to provide data for subsequent simulation validation studies materials for the fabrication of high temperature catalytic membrane reactors for that can be used to predict how air fired combustors may be retrofitted to oxy-coal. hydrogen production from coal-derived syngases. It has been confirmed that the Ni– Specifically the objective is to explore effects of variations in the partial pressure of O2 Fe–Cr alloy powders tested promote CO conversion through the WGS catalytic and CO2 on coal jet ignition and flame stability. During the oxy coal jet ignition reaction to various extents and that this level of activity is to some extent dependent of process, the partial pressure of oxygen, PO2, in the transporting fluid, comprised one the type of pre-treatment applied to the powders. While it was observed that the bulk additional degree of freedom in controlling flame aerodynamics, and enhancing coal Ni–Fe–Cr powder remains phase-stable and chemically inert, surface chemistry ignition, flame attachment/detachment and modifying pollutant formation. The characterisation confirmed the enrichment of metal oxide layers on the surface of the experimental investigations are carried on in a 100 kW laboratory furnace outfitted powder as chromium oxides and iron oxides, which are believed to be the active with an axial burner and arrays of electrically-heated panels in the burner zone in order components for WGS reactions. 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.

14 15-4 signs of combustion or glowing, or the sample temperature rising 20 to 50°C above the Numerical Investigation of Oxy-Coal Combustion in Pilot Scale and the hot plate temperature. Challenges This study develops an experimental methodology to use the standard ASTM E2021 Maryam Gharebaghi, Lin Ma, Mohamad Pourkashanian, Alan Williams, test apparatus [2] to obtain thermal and kinetic parameters of Pittsburgh seam coal University of Leeds; Ben Goh, Power Technology Centre, UNITED KINGDOM subject to thermal ignition. Parameters include thermal conductivity, activation energy, coupled pre-exponential factor and heat of reaction term. These terms are required, but Sequestration as the process of capture and storage of carbon dioxide (CO2) is an rarely known, input values for modeling hot surface ignition of dust layers. Thermal alternative for decreasing the green house effect, producing mostly by coal-fired power conductivity was estimated by equating heat flux from the hot plate with heat loss on plants. If coal combustion is performed using oxygen instead of air, the product will be the boundaries at a low enough hot plate temperature where heat generation of dust rich in CO2 and therefore ready for sequestration and the process is known as Oxy-coal layer is negligible. Activation energy, and coupled pre-exponential factor and heat of combustion. Oxy-coal combustion could be applied to the conventional coal reaction term were obtained by a best fit temperature distribution of a 1D steady state, combustion plants that will require some modifications. In order to minimize the numerical model with experimental results. Numerically estimated values for thermal modification required to the plant, the use of Oxy-pulverized fuel (Oxy-PF) conductivity, activation energy, and coupled pre-exponential factor and heat of combustion combined with Recycled Flue Gas (RFG) is an alternative option. In this reaction term were 0.09 W/m-K, 73.2 kJ/mole, and 3.99×107 kJ/kg-s, respectively. study, to find out the extent of the modifications, by applying Computational Fluid These values are in good agreement with previous values reported in literature [3]. 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 References: concentration of CO2 in the combustion test facility, the flue gas temperature decreases 1. P. C. Bowes, Self-heating: Evaluating and Controlling the Hazards, ed. B.R. dramatically. Char combustion and particularly carbon in ash are influenced as well. It Establishment. 1984: Elsevier. has been found that the effect of C-CO2 and C-H2O reactions on char reactivity cannot 2. ASTM E 2021, Standard Test Method for Hot-Surface Ignition of Dust Layers, A. be disregarded. In order to improve the validity of the CFD code for the design International, Editor 2001. purposes, further modelling improvements for accurate predictions are addressed. 3. P.D. Reddy et al. Effect of Inerts on Layer Ignition Temperatures of coal dust, Combustion and flame 114 (1998) 41-53. 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 SESSION 16 University, CHINA COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES – 1

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 16-1 the environment. Among the general methods aiming at the removal of SO2 and NOx, Swelling of Coals in Different Gases at High Pressures reburning and dry sorbent injection technologies have the advantages of being simple Richard Sakurovs, Stuart Day, Robyn Fry, CSIRO Energy Technology, with less equipment, lower capital and operation costs, higher SO2 and NOx removal AUSTRALIA 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 If carbon dioxide can be sequestered in coal seams and it simultaneously results in injection temperature is about 1100°C ~ 1150°C. Calcium-based furnace sorbent (such enhanced coal bed methane (ECBM) production, some of the sequestration costs can as limestone) injection for SO2 removal is the most popular technology. be recovered in the generation of a useful gas. One potential difficulty with ECBM is Reburning is a mature NOx control technology that has been demonstrated on several that carbon dioxide is known to swell coal, which may reduce its permeability. Coals coal-fired boilers worldwide. Reburning is a three-step process, involving combustion also swell in other gases (St George and Barakat, 2001) though not to the same extent. of majority of the fuel under normal fuel-lean conditions, followed by injection of a However, the relationship between the degrees of swelling of coal in different gases reburning fuel to establish a fuel-rich zone in which nitrogen oxides formed in the has not been examined in any detail. Here we report on the swelling of a primary combustion zone are reduced to N2, and finally injection of over-fire air to subbituminous and bituminous coal in carbon dioxide, methane, nitrogen, argon and oxidize CO, H2, any remaining hydrocarbons and nitrogenous radicals (NHi, HCN, krypton. We find the maximum extent of swelling is proportional to the critical etc.) exiting in reburning zone. Natural gas, oil, pulverized coal and biomass can be temperature of the gas. This indicates that swelling of these coals by all of these gases effective reburn fuels. Biomass (such as wood, corn straw, rice husk, etc.) is a has a similar basic mechanism: carbon dioxide is only different in the extent to which regenerable energy. Because of biomass containing low nitrogen content and little it swells coal. sulfur content, high volatiles, relatively low ash contents and, and zero net CO2 emissions, biomass reburning technology to reduce NOx is more attractive. 16-2 As is well know NOx reduction reactions with solid fuels (coal, biomass) include Effects of Texture and Porosity on Diffusion and Sorption in Coal Lumps homogeneous mechanisms involving NOx reacting with volatiles and heterogeneous and Powder mechanisms involving NOx reacting with chars. In biomass reburning process, there Vyacheslav Romanov, Yee Soong, DOE-NETL, USA 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 Typically, the CO2 sorption measurements are conducted on crushed and pulverized activated biomass fly-ash. coal powder. The differences in texture and porosity between the powder and lumps The objective of this research was to study simultaneous removal of SO2 and NOx by may affect the transport and interaction of the sorbate fluids and coal. We address biomass reburning and furnace calcium-based sorbents (such as limestone) injection in macroscopic and mesoscopic structural differences between powdered and non- an entrained flow reactor (EFR). The effects of biomass type and particle size, powdered coals that influence the rates of the fluid sorption–desorption kinetics and temperature, residence time, Ca/S ratio, stoichiometric ratio (SR), and additives were the pressure dependence of the coal sorption capacity. In this work, experimental long- investigated. term 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 15-6 structure and interconnectivity. We propose a thermodynamic approach for modeling Estimation of Thermal and Kinetic Parameters to Model Coal Dust Ignition certain structural rearrangements of the macromolecular network of coal, which is tied Ali Rangwala, Haejun Park, Nicholas Dembsey, Kulbushan Joshi, Worcester to the fundamental molecular-scale CO2–coal interaction. Polytechnic Institute; Evan Granite, DOE-NETL, USA 16-3 The ignition temperature of a dust layer can depend on many parameters including: Differential Swelling of Coal thickness of layer, particle size, moisture content, and particle shape. Three separate Majewska Zofia, G.Ceglarska-Stefańska, S. Majewski, J. Ziętek, K. Czerw, models of dust ignition, based on different geometrical configurations have been AGH University of Science and Technology, POLAND 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 The aim of this study was to investigate the volumetric strain induced in coal by tests on samples: the constant temperature oven, the hot plate, and dust suspended in a sorption/desorption of carbon dioxide and methane. Rectangular specimens (40 mm x furnace within a wire mesh cube. Generally speaking, the data obtained by these 20 mm x 20 mm) were prepared from lumps of coal taken from the Budryk mine in the methods provide useful benchmark values, but do not provide the fundamental Upper Silesia Basin, Poland. The coal was a high volatile bituminous C coal. properties required for a broader understanding of dust thermal ignition theory. Most Specimens were cut with the long axis perpendicular to the bedding plane. of these tests are based on determining a reference minimum temperature necessary for Sorption/desorption measurements were carried out by the volumetric method, at 298 the ignition of a dust. This is normally performed by exposing a sample, with standard K, for gas pressures from 1.5 MPa to 4.0 MPa. dimensions and boundary conditions, to a fixed ambient temperature and observing During sorption/desorption tests expansion and contraction of the coal specimens were whether ignition occurs. Common criteria for ignition in hot plate tests are visible continuously monitored by four resistance-type strain gauges, attached to the sample 15 surface on opposite sides at mid-height, at right angles to one another, to pick up strain Besides this, taking into consideration our energy insurance, lignites in our country parallel and perpendicular to the bedding. The volumetric changes for the coal have a significant potential. spacimen were calculated from the measured strain. Studies conducted by General Directorate of MTA since 2005 facilitated the The major findings were as follows. Sorption kinetics indicated that the coal tested construction of Saray Coal Power Plant and hence it is considered that any plant showed comparable affinities for CH4 and CO2. None the less, sorption of CO2 led to construction could be made in other regions on same basin. swelling at least twice that induced by the sorption of CH4, even when considered with As were in foundation years, MTA has again undertaken a mission on energy supply, respect to the volume of the sorbed gas. The maximum volumetric strain varied from and this project, an important milestone for conversion of Thrace Basin to an Energy about 0.7 - 1.4% for CO2 and 0.3 - 0.45% for CH4. Basin, proceeds at present. 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 SESSION 17 in the volumetric strain occurred at the beginning of the test, swelling passed through a COAL PRODUCTION AND PREPARATION – 3 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 17-1 approached an apparent equilibrium level. However, during desorption, shrinkage of Burning Unprepared “Run Of Mine” Coal to Efficiently Fire a Stoker the coal matrix was approximately a linear function of the volume of gas desorbed. Boiler This was true for both sorbates used. These findings support the results of some other George Dumbaugh, Kinergy Corporation, USA studies, but contradict others. Swelling of the coal tested was additionally characterised by the time required to reach Mined coal can now be directly and efficiently used to fire a Stoker Boiler. This half of the maximum swelling (T1/2). For CO2 the values of T1/2 lay in the range of 0.4 - uncleaned, so-called “ROM” kind of 2” size stoker coal can have a high percentage of 1.0 hour, while for CH4 this was approximately 8 hours. fines. It can be wet and adhesive (sticky) and it can contain more than a normal amount The present study has demonstrated that differential swelling of coal matrix can take of non-combustible clays or other impurities. All that matters is the rate of coal being place and that the sorption-induced swelling is a non-linear function of the volume of fed has heat content needed by the Boiler. This very beneficial accomplishment is the sorbed gas. The results could have implications for the sequestration of CO2 in coal intended to make coal a more viable fuel. seams and CH4 recovery from coalbeds (ECBM). Swelling/shrinkage of the coal This timely progress is being achieved with a new Water Cooled Vibrating Grate. It matrix should be included in models used to predict coal permeability and gas flow uniquely has an enclosed, underside plenum that is used to receive the incoming air. In rates. 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 16-4 counterbalance to virtually eliminate transmitting any vibration to the exterior The Thermogravimetric Analysis of Chinese Coals with High Hydrogen structure. This Vibrating Grate can accommodate Boilers, because the vibratory forces Content are effectively spread across its width and along its length. The vibratory action is Shaoqing Wang, Harold H. Schobert, Gareth D. Mitchell, The Pennsylvania very “energy efficient”, which is why the Grate’s motor consumes very little power. State University, USA; Yuegang Tang, China University of Mining and By utilizing a simple method of electrical control, the fuel feed rate can be varied from Technology (Beijing), CHINA virtually zero to the maximum capacity wanted. This control also provides operating versatility. Selected Chinese coals, rich in barkinite, were studied by thermogravimetric analysis Flexible connections around the perimeter of the firng deck seal it with the Boiler in a nitrogen atmosphere at three heating rates (10, 15 and 25°C min-1). Proximate above. Because the ash is continually being discharged over one end of the firing deck, analysis, ultimate analysis and maceral composition were also measured according to collecting hoppers under the Grate are no longer needed. ASTM procedures. The values of hydrogen content and H/C atomic ratio of coal Since the vibratory action prompts the fuel to more thoroughly burn, it inherently samples studied are, separately >6 and 0.8. A good correlation between hydrogen and reduces the amount of ash particulant in the high temperature flue gas being passed to barkinite content was observed. When the coals are heated under an inert atmosphere, the scrubbers. In turn, the amount of pollutants such as CO, CO2, NOx are mass loss occurs in the region 300~550°C. The thermal profile shows a monotonic proportionally less. weight loss, however, the reaction is intense. In addition, two good linear relationships This kind of Vibrating Grate can be retrofitted to existing Stoker Boilers. While it was were found between H/C atomic ratio and the total mass loss as well as the maximum designed for burning coal, it can also be used to fire Boilers with the bio-mass fuels rate of mass loss. The results also showed that the TGA curves were not greatly such as shredded wood waste, cotton plants, palm trees, municipal solid waste, refuse influenced by heating rate employed, especially for those coal samples rich in barkinite derived fuel, and the like. Waste coals, which include culm, silt, and gob can also be content. burned. This remarkable power engineering feat is the result of the cooperative effort of the 16-5 Illinois Department of Energy (DOE), the Riley Power Group in Worcester, An Energy Basin in Turkey: Thrace Region Massachusetts, and Kinergy Corporation in Louisville, Kentucky. Ilker Senguler, Yusuf Ziya Cosar, General Directorate of Mineral Research and Exploration of Turkey, TURKEY 17-2 Evaluating the Achievable Benefits of Extending Technologies for Thrace Basin (Europen part of Turkey) is one of the most important basins because of Uneconomical Coal Resources in South Africa coal and hydrocarbon potential. Coal explorations have been conducted by General Mikolaj Zieleniewski, Sasol Synfuels; Alan Brent, University of Pretoria, Directorate of Mineral Research and Exploration (MTA), oil and natural gas SOUTH AFRICA explorations usually by Turkish Petroleum Corporation (TPAO). Coal formations in Thrace Basin of Tertiary are within Danismen Formation of As the South African economy relies heavily on its coal resources, these resources Oligocene. Danismen Formation has a lithology including gray-green claystone, should be utilised and managed in the best possible manner. Underground coal sandstone, conglomerate, tuff and lignite, and was named as lignitic sandstones in the gasification (UCG) is one of the leading technologies used where conventional mining region by first studies. techniques are uneconomical. UCG delivers gas suitable for synthesis, production of There are lignite occurrences on foothills of Istranca Mountains in N of Thrace Basin, fuels and electricity, or for home usage. The method is perceived as being and these are mentioned as Saray, Vize, Kirklareli and Demirhanli fields in general, environmentally friendly and safer than traditional mining. The study summarised in and Kesan, Malkara, Uzunkopru and Meric fields in the south. With drilled this paper was conducted so as to create a simple model that would allow for the explorations at significant depths from 1950 to 1980 performed by General Directorate evaluation of UCG process-related costs versus expected benefits in a wider context of Mineral Research and Exploration, about 400 million tons of lignite reserves were under different circumstances. The parameters of the model are: feasibility definition, estimated. i.e. maximum possible gas calorific value, based on geological surveys and gasification Lignites exposed at N and S of the basin gradually deepen toward center of the basin, agents; direct process derived from the expected capital and operational expenditures and reach to 10 000 meters of sedimentary sequence in central parts of the basin and and compared with the gas volume propensity; and assessment of externality costs. extend to depths below 600 meters. The externalities concept should encourage governmental agencies to consider Survey and drilling studies conducted in the region since 2005 by General Directorate investment in UCG technology as a vehicle for delivering, potentially, high savings in of Mineral Research and Exploration aim at exploring coal potential in deeper parts of terms of expenditure on national health and of the reduction in the costs of the basin. Lignite occurrences at depths between 300 and 500 m in the basin will environmental damage resulting from gaseous emissions into the atmosphere. 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. 16 17-3 The results of this study are critical for coal preparation as well as other minerals by Emissions Reduction and Plant Efficiency Improvement Using the using structured packing flotation column process. MagMill™ Robin R. Oder, Ron Hurst, Russell E. Jamison, MagMill Co. LLC, USA 17-5 Numerical Calculation and Determining Mechanizability of Coal Seams We will report recent results obtained with use of a commercial scale MagMill Using Fuzzy Logic demonstration unit located at the DTE Energy Services facility in Vicksburg, MS. The Mohammad Bitaraf, Islamic Azad University, IRAN 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 Mineral region of tabas is in east of central iran in yazd province. In this article to commercially by MagMill LLC, a joint venture between NALCO Mobotec and observe the mechanizability of coal seams located in this region and degree of EXPORTech Company, Inc. The demonstration unit is operated jointly by DTE improving level of mechanization, factors affecting on mechanizability are studied. Energy Services and MagMill LLC. Studies shows that thickness, dip, uniformity, roof and floor rock criteria and coal The MagMill is a dry method for cleaning coal at pulverized coal-fired power plants strength are important factors effect of mechanizability of one seam. So considering and other facilities such as direct injection steel furnaces. It consists of a pulverizer above factors a fuzzy model using fuzzy tech 5,12 software is made. In this model and a continuous dry magnetic separator operating together as one unit to clean coal. mechanizability of coal seams regarding effective factors is calculated as a numerical The technology removes hard to grind mineral impurities from the coal fed to the index without dimension. The range of index of mechanizability model changes pulverizer before they are ground to product specification of 70–80% passing 200 between 0-100. This comparative scientific suggestion categorize seams to low, mesh. Minerals such as iron pyrite – denser and harder to grind than the relatively soft medium and high, each one is espicific by limitations of certain numbers. As a case hydrocarbon component of coal – concentrate on the grinding table inside the study mechanizability of coal seams in tabas coal mine using this method has been pulverizer. They require more passes through the grinding zone to reach particle size analyzed. The study shows that the mechanizability of seam B1 is medium, seam C1 is specification; hence their concentration is higher on the table than it is in the incoming high, and seams C2, D is low. 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. 17-6 The separator rejects the mineral component and recovers clean carbon for return to Qualitative Analysis of Hanging Wall Caving in Longwall Mining; Case the mill for additional grinding. In addition to carrying sulfur and hazardous trace Study: Tabas Parvarde Coal Mine metals such as mercury and arsenic, these abrasive minerals limit the throughput of the Mehrshad Rostami, Islamic Azad University, IRAN 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 Longwall mining is one of the commonest underground mining methods in coal plant derating. mining worldwide. Longwall is a caving method and the caving process is one of the Pyrites and many of the other minerals found in coal are paramagnetic while the coal is most important parts of the extraction sequences. Therefore qualitative analysis of the diamagnetic, making continuous dry magnetic separation feasible. Magnetic caving can be a useful study to observe and predict the conditions of the hanging wall separation significantly lowers levels of ash, sulfur, and trace metals such as mercury behavior during the face advance and planning the extraction operation. In this study and arsenic before the pulverized coal is fed to the burner. In earlier measurements on first of all the parameters affecting on the caving has been classified in four groups. Eastern US bituminous coal employing a prototype MagMill, reductions in ash ranging These groups are: mechanical, geometrical, operational and geological parameters. up to 48% and total sulfur up to 54% were measured on a pounds per million Btu basis. Then the quality of caving according to these parameters and the factors resulting by Decreases up to 61% on a pound per tera BTU basis were observed in mercury. More them such as stability time, bulk factor, average particle size of the caved strata in the recently, direct measurements of dry magnetic separation of a 0.36 wt.% pyritic sulfur gob area and overhanging has been analyzed by using the Tabas Parvarde coal mine sub-bituminous coal from New Mexico showed decreases in ash of 30% and sulfur of conditions. Tabas Parvarde coal mine is located in Parvarde district, Yazd province in 8% on a pounds per million Btu basis and mercury reductions up to 70% on a pounds Iran. There are five coal seams in this area named B1, B2, C1 and C2. Now only the per Tera Btu basis. C2 is under the operation and the results of analysis on this seam show that caving This novel technology applicable to all coals and all types of coal pulverization has the quality in C2 is medium to low. 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 MW- Hr. output compared to the cost and time delay incurred when building a new coal- SESSION 18 fired plant. SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL – 3 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. 18-1 Effect of Changing Temperature and Inlet Gas Ratio on Water Gas Shift 17-4 Activity and Methane Selectivity in Fischer-Tropsch Synthesis Gas-Liquid Two-Phase Bubbly Flow in Structured Packing Column for Thierry Musanda, Diane Hildebrand, David Glasser, University of the Coal Preparation Witwatersrand, SOUTH AFRICA Chunjiang Liu, Jie Cheng, Tianjin University, CHINA; Fan Shi, University of Michigan, USA 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 Coal preparation or coal cleaning in froth flotation involves the selective separation of water gas shift activity is achieved then the H2 in the inlet gas can be supplemented by clean coal particles, which is naturally hydrophobic, from mineral matter, such as the production of more H2 from the conversion of water and CO to H2 and H2 and CO2. kaolinite, montmorillonite and illite, which are hydrophilic. In practice of flotation, The percentage approach to equilibrium is defined as the CO2 that is actually produced coal particles will attach to and rise with the froth after their collision, and then be divided by the amount that would be expected if equilibrium had been attained. recovered from the top of operating unit. The flotation separation relies on the Increasing the temperature increases the percentage approach to equilibrium. exploitation of the fundamental physics of multiple bubble-particle collisions. Methane is an undesired product in Fischer-Tropsch Synthesis because it has very little In this paper, bubble columns packed with structured packing (Mellapak 350Y use as a fuel or as a chemical feedstock and it is very expensive to be reformed. structured packing) present different hydrodynamic behavior from traditional empty Therefore, its production is preferred to be kept as lower as possible. An increase in bubble columns. Three-dimensional Laser Doppler Velocimetry (LDV) and temperature only has a marginal effect on the production of methane at the lower inlet computational fluid dynamic (CFD) method was used to simulate the liquid velocity gas ratio but the effect increases as the ratio increases. This is probably due to the fact distribution in structured packing bubble column. The influence of gas flow rate and that an increase in temperature probably increases the amount of dissociation of the geometry of inner packing on time-averaged velocity distribution is investigated. CO resulting in more active carbon on the catalyst surface which is then available for The results of 2D model indicated that rising bubbles oscillated and coalesced with direct hydrogenation to methane. increasing of gas inlet rate. The velocity of liquid surrounding the bubble increased and This paper will look at the impact of changing temperature and inlet gas ratio on water vortexes at different scales were observed. The velocity of single point in liquid gas shift activity and methane selectivity in Fischer-Tropsch synthesis. fluctuated more and more frequently as the gas inlet velocity increased. In three- Thermodynamic constraints, kinetics and graphical method will be used to understand dimensional unsteady simulation, the break-up of bubbles at crisscrossing section of this effect. 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. 17 18-2 Firstly, it was observed by in situ diffuse reflectance infrared spectroscopy (DRIFT) Syngas Conversion to Ethanol over La and/or V Oxide Promoted RhSiO2 that an acetyl intermediate was detected over CuFe catalyst. The existence of such Catalysts intermediate suggested the validity of adsorbed CO insertion into metal-alkyl (M-C) James J. Spivey, Nachal Subramanian, Louisiana State University; Jia Gao, bond, a mechanism popular for the Rh catalysts and CuCo clusters. Therefore, the Xunhua Mo, James G. Goodwin, Jr., Walter Torres, Clemson University, USA 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 In the last thirty years, much attention has been paid to synthesis of higher alcohols CuFe bimetallic system, by which Cu site was a center for adsorbing undissociated CO from coal-derived syngas due to their potential use as a fuel blend or alternative motor molecular and Fe site was acted as the roles in producing hydrocarbon and promoting fuel for the reduction of exhaust emissions [1]. Methanol is a common product the chain growth. produced from syngas conversion using copper/zinc based catalysts. However, higher Secondly, the results of N2 adsorption and XRD found that Cu and Fe phases highly alcohols may be more desirable products, due to their fuel and blending properties. In dispersed over CuFe catalyst, showing a surface area of 99.6 m2/g. The addition of zinc particular, ethanol is desirable because of the large market that has been created for its into CuFe catalyst led to a decease in surface area and the appearance of a new well- use as a fuel. Another interesting application is its potential use as a hydrogen carrier to resolved diffraction peak, characterizing as ZnFe2O4. However, the existence of supply fuel cells. By far the most widely studied catalysts for the hydrogenation of CO manganese in CuFe bimetallic system appears to be another picture: the higher to oxygenates are based on Rh [2]. Among supported metal catalysts, Rh appears to be dispersion of active phases after manganese introduction must be a contributor of the most active and selective for the synthesis of ethanol and higher alcohols from higher surface area. The zinc and manganese co-promoted CuFe catalyst did not syngas. Of particular interest are vanadium promoted Rh catalysts, which have been display other change apart from these mentioned above. In the process of H2-TPR, it reported to have a high selectivity (typically at low CO conversions) for the production was seen that over CuZnFe catalyst, the reduction peak position of CuO phase had of ethanol [3]. In this work, we have studied the effects of promoters on Rh/SiO2 been shifted to higher temperature related to CuFe catalyst as a result of the low catalysts under different reaction conditions. A series of La and/or V oxide promoted dispersion of Cu phase after zinc addition. In the case of Fe reduction, the manner of Rh/SiO2 catalysts were tested for CO hydrogenation to ethanol in a packed bed reactor. the H2-consumption peak changed into broader one, comparing with CuFe catalyst, due Of the catalysts tested, the doubly promoted La-V-Rh/SiO2 catalyst exhibits the highest to the appearance of a less re. Lastly, the catalytic performance for higher alcohols activity and selectivity towards ethanol at H2/CO: 2/1, 14 bar and 270°C -- CO synthesis over various CuFe catalysts, following the activation by syngas at 300°C for conversion was 7.5% and ethanol selectivity was 44%. Tests at two reaction 12 h, had been evaluated. It was found that alcohols and hydrocarbons were main temperatures (230°C and 270°C) indicate that both the ethanol selectivity and CO product over CuFe based catalysts, and the production of either alcohols or conversion are higher at 270°C whereas tests carried out by varying the H2/CO ratios hydrocarbons followed A-S-F distributions, and their parameters, being dependent on (2/1 and 4/1) suggest that H2/CO : 2/1 and 14 bar gives a higher selectivity towards the synergistic effect between copper and iron, were essentially different due to the ethanol relative to methane. impact of free carbon deposited on the surface of catalyst. The addition of zinc [1] Run Xu, Cheng Yang, Wei Wei, Wen-huai Li, Yu-han Sun, Tian-dou Hu, J. Molec. changed the catalytic behavior of CuFe catalyst markedly, i.e. increasing CO Catal. A, 221(2004) 51-58. conversion and alcohols yield. This finding must be due to the formation of ZnFe2O4, [2] James J. Spivey, Adefemi Egbebi, Chem. Soc. Rev., 36 (2007) 1-17. enhancing the activation ability of Fe towards CO molecular as detected by FT-IR. [3] G.van der lee, B. Schuller, H. Post, T. Favre, and V. Ponec, J.Catal., 98(1986) 522- However, the low dispersion of active phase after zinc addition weakened the 529. synergistic effect between Cu and Fe, leading to the lower parameter of alcohols synthesis. 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 SESSION 19 GASIFICATION TECHNOLOGIES: FUNDAMENTALS – 1 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. 19-1 In our previous work, alcohols can be synthesized over (promoted by) Fe-Cu based Gasification Kinetics: Model Development and Validation catalysts from syngas under temperate operation condition, which is made with low Vladimir Zamansky, Boris Eiteneer, GE Global Research, USA; JS Ravichandra, cost and shows high catalytic performance. In this work, based on original batch GE Global Research, INDIA; Cai Zeng, GE Global Research, CHINA; Thomas formula Fe-Cu catalyst, series of different amount cobalt were introduced by Fletcher, Brigham Young University, USA impregnation after the co-precipitation process. Catalytic evaluation were performed in a fixed bed high-pressure flow reactor under the conditions: T=350°C, P=6.0 MPa, GE Global Research is conducting an international R&D program on gasification -1 GHSV=10000 h , n(H2)/n(CO)=2.3. H2-TPR, H2-TPD, XRD characterization kinetics. The goal of the program is to develop and validate predictive models technique were applied to interpretive surface texture of catalysts. describing the chemical processes in the gasification and post-gasification zones of In this study, the effect of Fe-Cu catalysts with cobalt loaded was discussed in its practical gasification systems. In this program, the processes in the gasifier are activity performance over synthetic reaction of syngas. The experimental result shows modeled by detailed chemical reactions, which in turn are validated by experiments. that the cobalt loading can obviously enhance the selectivity of higher alcohols and We examined existing models of coal devolatilization, char gasification, soot yields of alcohol. Too little or too more cobalt was bad for its catalytic performance formation and growth, and homogeneous gas-phase interactions. After detailed -1 -1 over CO hydrogenation. A maximum alcohol yield (Yalcohol) is 0.98 g/mL ·h , and the analysis, several of these models were selected and adopted as the initial individual ethanol selectivity at the most is 34.13 w% and the C2+OH selectivity (SC2+OH) at the sub-models. The Chemical Percolation Devolatilization model and Char Burnout most is 59.00 w% when catalyst with 1.00 w% cobalt loaded at this reaction Kinetics model were adopted for the initial description of coal devolatilization and char conditions. conversion, respectively. A detailed mechanism of gasification and combustion of H2-TPR profiles show that when the catalyst is loaded with 1.00 w% cobalt, the benzene was selected to describe tar formation/conversion processes. The benzene reduction temperatures of both reduction peaks are lowest: the first reduction peak is at model was updated to include all reactions of gaseous products, including tar, and their the temperature of 266°C, and the second is at 400°C. H2-TPD shows that all catalysts conversion to soot precursors. The selected initial sub-models were integrated in have two active centers, and the second dehydrogenation peak of the catalyst modified Chemical Workbench kinetic code developed by Kintech in Russia. changes larger and moves to higher temperature. XRD spectrum declares 2θ=36.5° is The initial integrated gasification kinetic model will be first utilized for parametric diffraction peak of crystals of Cu2O, and its crystal is dispersion and thin. modeling of the gasification process and later for experimental validation and improvement of the individual sub-models. These improved sub-models will be 18-4 integrated in subsequent advanced versions of the gasification kinetic model. Higher Alcohols Synthesis from Syngas over Promoted Copper-Iron The experimental validation program has started. It will include testing of different Catalysts coal samples in bench-scale gasifier, high-pressure wire mesh reactor, high-pressure Yuhan Sun, Minggui Ling, Kegong Fang, Yao Xu, Debao Li, State Key thermogravimetric analyzer, and novel and unique entrained flow reactor, capable of Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy reaching hightemperature, high-pressure conditions of industrial gasifiers. of Sciences, CHINA 19-2 In the last 30 years, several catalytic systems have been developed for higher alcohols Modeling Entrained Flow Coal Gasifiers synthesis from syngas due to the potential application as a gasoline blend or alternative Mike Bockelie, Martin Denison, Dave Swensen, Connie Senior, Adel Sarofim, motor fuel for the reduction of exhaust emission. Recently, an efficient copper-iron Reaction Engineering International, USA 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 In this paper we describe a model for ash vaporization that is being implemented into reactor to study the promotional effect of zinc and manganese on the synergetic effect Computational Fluid Dynamic (CFD) models for entrained flow coal gasifiers that can between Cu and Fe. be used in studies to improve gasifier performance. The CFD models provide detailed 18 information about gasifier performance – including the gasifier flowfield, carbon thermodynamics analysis simulations were conduced in Hysys and GateCycle. conversion, slagging behavior, heat transfer, soot and tar formation, etc.. Ash Simulations in Hysys were carried out for different gasification technologies, kinetic vaporization has not been included in the model. Ash vaporization occurs in high reactions, gasifying agents and coal types. Syngas composition and lower heat values temperature regions of the gasifier and results in sub-micon aerosol formation that can were calculated for the all different conditions and had been loaded into GateCycle in re-condense and deposit on downstream equipment. The developed model is which Combined Cycle efficiency were studied for different environmental conditions. appropriate for evaluating the performance of one or two stage coal gasifier fired with Results show behavior for IGCC technologies at different places according to its either a slurry or dry feed. environmental and operational conditions, and coal rank.

19-3 Effect of Turbulence Models on Gasification Simulation Ting Wang, Armin Silaen, University of New Orleans, USA SESSION 20 UNDERGROUND COAL GASIFICATION – 1 Numerical simulations of coal gasification process inside a generic entrained-flow gasifier are carried out using the commercial CFD solver FLUENT. The Navier- Stokes equations and seven species transport equations are solved with three 20-1 heterogeneous global reactions and two homogeneous reactions. Finite rates are used The Future Prospects for Underground Coal Gasification for the heterogeneous solid-to-gas reactions, while eddy-breakup combustion model is Michael Green, UCG Partnership Ltd, UNITED KINGDOM adopted for homogeneous gas-to-gas reactions. Kobayashi’s two competing rates model is used for devolatilization process. Since the reactions are affected by the fluid Underground coal gasification is now an important option for coal exploitation and mechanics and the turbulence eddy dynamics, the effects of various turbulence models large-scale syngas production in most countries with substantial coal resources. UCG on the calculated results are investigated. Seven different turbulence models are offers the opportunity to exploit the natural coal reserves, which would otherwise be employed for comparison including Standard k-ε, Spalart-Allmaras, RNG (Re- left in the ground as uneconomic or physically unmineable coal. The alternatives for Normalized Group) k-ε, Realizable k-ε, Standard k-ω Model, Shear Stress Transport coal supply are conventional mining, often difficult in regions like the European (SST) k-ω Model, and Reynolds Stress Model (RSM). The flow and temperature Union, or the importing of coal at much increased prices from the major world fields and distributions of species concentrations are compared and analyzed. The suppliers. gasification performance is also compared including carbon conversion, fuel UCG has been the subject of intense research and field trials in many countries since conversion efficiency, syngas composition, and cold gasification efficiency. the Second World War, not least in the United States, where the development program in the 1970’s and 1980’s extended to 32 separate tests, and a supporting program in 19-4 National Government laboratories. The program led eventually to detailed proposals Quantification of Oxygen Capture in Mineral Structure During Gasification for commercial production of chemicals and SNG. Although technically proven, UCG Johan van Dyk, JHP van Heerden, Sasol Technology; Frans Waanders, North- could not compete with low price natural gas at the time and it was left to the West University, SOUTH AFRICA Europeans in the 1990’s and the Australians after 1999 to conduct further field trials in the coal fields relevant to these Regions. It has been observed that during the transformation of minerals at higher temperatures Increased gas prices and concerns about security of supply have produced a resurgence (>1000°C), mineral species are formed containing a high number of oxygen molecules, of interest in UCG in many countries. UCG offers an alternative to conventional coal i.e. gehlenite (Ca2Al2SiO7), mullite (Al6Si3O15), margarite (CaAl4Si2O10(OH)2) and mining, which is safer, more environmentally attractive and, like oil and gas extraction, almandine (Fe3Al2Si3O12). is more efficient in the use of production manpower. Furthermore, syngas is a flexible Results of the coal sources evaluated in this investigation indicated significant fuel and a potential feedstock for poly-generation plant supplying energy, fuel and differences in mineral elemental composition, i.e. the CaO content varied between 5 chemicals from the same complex. mass % and 10 mass %, the Fe2O3 content varied between 1.6 mass % to more than 5 The position today (2008) is that UCG feasibility studies and demonstrations are mass %, as well as differences in the TiO2, P2O5 and MgO content. The coal sources underway in countries as far apart as Mongolia, South Africa, Australia Latin America producing the highest concentration of Ca-Al-Si species (CaAl2Si2O8 anorthite and and the United States, and almost all the studies are in the hands of large mining or CaAl4Si2O10(OH)2 margarite), which crystallized from the slag-liquid phase during the power companies who are applying in–house or investor resources. Those companies combustion stage, also contained the highest amount of acidic components or highest are reporting that the unit energy cost for UCG is now substantially below the percentage of kaolinite. The highest concentration of mullite and free SiO2 after the alternatives of natural gas or surface gasification. Other studies suggest that world coal gasification reaction (before the combustion zone), also resulted in the highest reserves could be increased by more than two thirds when large scale concentration of Ca-Al-Si compounds forming during the oxidation phase. The free- commercialization of UCG becomes a reality. SiO2 in the mineral structure of the coal sources resulted then in the formation of Environmental issues for UCG tend to focus on the likely impact on ground water, and mineral structures with Mg, Na or Ca when present in the mineral structure, to form there is evidence from earlier trials that contamination can occur. However, UCG in new mineral compounds such as KAl3Si3O10(OH)2 (muscovite), Mg5Al2Si3O10(OH)8 deeper coal seams, combined with careful site selection, and the use of active pressure (clinochlore), or other high oxygen molecule-containing mineral compounds. Thus, if control of the cavity will minimize the underground environmental impact. Those free-SiO2 was not present after the gasification phase, and mostly taken up in the form already engaged with National or Regional regulators are confident that UCG under of anorthite (due to high or higher CaO contents or Fe-contents in high Fe-containing these conditions can meet the stringent ground water regulations now in place in coal sources), the concentration of Si-oxygen capture compounds are relatively low. Europe and most other developed regions of the world. An acceptable linear correlation between oxygen capture tendencies (increase in Low carbon emissions are another major consideration for fossil fuel usage. mineral matter content during the combustion phase) versus CaO-content was obtained Fortunately, UCG already compares well with other coal processes in terms of its with the South African coal sources evaluated. This confirmed the observations emissions per unit of electrical energy and the fact that UCG syngas can be used in obtained based on HT-XRD and FactSage modelling. It can be concluded that the combined cycle power generation. Moreover, the syngas is particularly well suited to linear model to predict oxygen capture behavior from CaO-content is acceptable and pre-combustion capture, because of the high pressure of the gases at surface and the can be used as a predictive tool. The SiO2 content, for example, has an inverse affect favorable partial pressure of the CO2. Partial CO2 capture and the production of on oxygen trends up to a specific concentration of CaO in the coal. However, this hydrogen- methane mixtures, with low carbon content are particularly attractive model is only valid for the coal types tested (South African Highveld coal sources), process options for UCG syngas. and additional test work will have to be conducted for other coal types, i.e. northern CO2 from the separation plant is compressed to pipeline pressure for transportation to hemisphere coal. 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 19-5 surrounding stressed areas is also potentially feasible under the right conditions. An Simulation of IGCC Technologies: Influence of Operational Conditions EU sponsored study to examine hydrogen production and low carbon emissions from (Environmental and Fuel Gas Production) UCG has commenced. The €3.2M project aims to investigate hydrogen production and César Nieto, Erika Arenas, Andrés Arrieta, Zulamita Zapata, Universidad CO2 capture and storage, which involves a variety of academic and research groups Pontificia Bolivariana; Carlos Londoño, Carlos Valdés, Farid Chejne, throughout Europe. The project is scheduled to last three years and if successful, field Universidad Nacional de Colombia - Sede Medellín, COLUMBIA 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 Integrated Gasification Combined Cycle (IGCC) is one of the most promising combination with CCS. 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 19 20-2 Underground Coal Gasification (UCG), which is a process of in-situ conversion of UCG & Surface Gasification Comparisons and Contrasts coal/lignite into Syngas, could allow exploitation of the un-mineable resource. UCG Eric Redman, HellerEhrman LLP, USA 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 Surface gasification, which is possible using several technologies, and underground particulate emission, lesser water requirement, no waste (ash) generation, no venting of coal gasification (UCG) represent different methods of achieving similar objectives. green house gases as in the mining, etc. However, there are environmental issues that These include creating new energy supplies, producing and capturing carbon dioxide arise from the process and can broadly be classified as surface and subsurface issues. for enhanced oil production or other sequestration, and producing valuable gases (e.g., Pollutants like phenols, tars, aromatic hydrocarbons etc. are co-produced along with synthetic natural gas, hydrogen, and argon), byproduct hydrocarbons, and other Syngas. If the pollutants escape from the underground reactor and find a pathway, they chemicals. Importantly, the objectives also include protecting the local and global could contaminate a nearby aquifer. If the un-treated surface water gets mixed with the environments through reduced air emissions of criteria pollutants, and through much- ground water, the latter can get polluted. The creation of void in the subsurface due to reduced net CO2 emissions when compared with power plants that burn coal. consumption of coal can lead to subsidence. In order to minimize these surface and Both forms of gasification – surface and underground – are technically suited to subsurface impacts, various parameters like geology and depth of coal seam, specific situations. Both can be conducted in an air-blown or oxygen-blown manner. overburden thickness and properties, hydrogeology of the coal seam and surrounding But the two gasification approaches are not complete alternatives to one another. For strata etc. are studied. The study of these parameters and selecting a suitable site is the example, UCG can be carried out only where suitable coal deposits exist (an easily most important step for minimization of impacts on the environment. Of course, an satisfied requirement, fortunately, in North America). Surface gasification can be overall appraisal including size and market of the resource decide the suitability of a conducted far from the nearest coal field, and close to load centers and needed site for the process of UCG. infrastructure, but requires significant coal mining, transport, and higher capital Whole suite of the parameters like proximate & ultimate analysis, depth of the deposit, investment than UCG. rank, seam dip, geology and lithology, hydrogeology, tectonics, permeability, Among developers of gasification projects, the Summit Power Group may be unique in geomechanical properties etc. were studied for a large number of coal / lignite fields developing both surface gasification projects (two types at two different scales) and spread across India. The aim of the study was to identify the site(s) that has sufficient power plants for UCG projects. This experience allows a “compare and contrast” look quantity of tectonically less disturbed resource and where the impact on the at UCG and surface gasification, and some conclusions about the comparative features environment due to the process of UCG is minimized. The screening process was a of each. This presentation will provide that look, with particular focus on cost, rigorous one and only one site out of several sites was identified as a suitable site for efficiency, reliability, scale, commercial readiness, related commercial and financing the process of UCG. Further, general geology showed isolation of the lignite seam in matters (such as warrantability), environmental impact, and – importantly – carbon the thick layer of clay and this envelope of clay shall act as an impervious layer management. preventing escape of pollutants from the underground gasifier. The hydrological data The author, an energy sector lawyer, serves as a business consultant to Laurus Energy showed absence of major aquifers. The unsuitable areas were either tectonically (a licensee of Ergo Exergy’s εUCG process) and as a leader of Summit’s gasification disturbed or indicated presence of major aquifers besides other unfavourable factors. group. Subsidence parameters have also been predicted. Various parameters shall be monitored through special wells drilled for the purpose. 20-3 The application of technology of UCG to a number of potential suitable sites could Hydrogen Oriented Underground Gasification of Coal open up a huge opportunity of exploiting the large un-mineable coal / lignite deposits Jan Rogut, GIG - Central Mining Institute, POLAND; Marc Steen, Institute for in India. Energy, Joint Research Centre, European Commission, THE NETHERLANDS 20-5 Underground coal gasification (UCG) is a technology with more than one century of Linking Underground Coal Gasification to CCS and the Downstream history. Recently, it has attracted renewed interest triggered by increasing global Opportunities energy security concerns and stringent environmental regulations on energy production Dermot Roddy, Newcastle University, UNITED KINGDOM 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 This paper starts by surveying the range of integration opportunities that have been clean coal technology R&D project in the European Union. HUGE raises high developed over a number of years in North East England for surface gasification of expectations because of the potential of its specific UCG concept to integrate large coal, linking into power generation, petrochemicals, synthetic fuels, fuel cells and scale in situ production of hydrogen-rich gases with on site geological storage of renewable energy production. It then draws on all of this to explore a range of ways in carbon dioxide. This would allow transferring underground generated low carbon and which an Underground Coal Gasification (UCG) project can be linked into similar partly purified hydrogen or synthesis gases to the surface as major product, while activities to create a range of value-adding opportunities. Conclusions are then drawn leaving behind the wastes generated during their conversion from coal. The project, about the scope for replication elsewhere. 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 SESSION 21 with heat and mass transfer phenomena taking place in geological multiphase systems COMBUSTION TECHNOLOGIES – 4 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 21-1 controlling the conversion processes. Hence, valuable expertise from in situ coal A Process for Clean Combustion or Hydrogen Production Using Coal gasification, from geological carbon dioxide storage, from geothermy and from Jinsheng Wang, Edward J. Anthony, Natural Resources Canada, CANADA 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 chemical looping process has been developed for combustion of gaseous fuel, the novel concept of geo-reactor, which stands for an underground, environmentally whereas clean combustion of solid fuels is of greater interest. Moreover, in chemical safe coal gasification plant intentionally integrated with geothermal heat exchange and looping combustion of gaseous fuel such as natural gas, large amount of water has to with carbon capture and storage, is investigated for exploitation of synergies between be separated from the CO2 product. The condensed water would potentially be various geological technologies. corrosive and thus add cost to the process. The oxy-fuel combustion is for solid fuels, but it requires large quantity of pure 20-4 oxygen. Moreover, the current approach of reducing combustion temperature with CO2 Environmental Issues of UCG-Study of Some of the Indian Coal / Lignite lowers the thermal efficiency. Deposits We propose a chemical looping process for clean combustion of coal, or hydrogen Rajinder Kumar Sapru, Rakesh Kumar Sharma, Dinesh Kumar Mathur, Oil & production from coal. The process is based on coal gasification with CO2 to produce Natural Gas Corporation Limited, INDIA 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 Indian economy is growing at more than 8% and presuming similar rate of growth till for disposal. The metal or lower oxide is sent to another reactor for oxidation. Heat or 2031, the requirement of primary energy shall increase by 3-4 times and that of power generation can be achieved through this highly exothermic reaction. The overall electricity supply by 5-7 times of today’s consumption. In order to meet the huge thermal effect is the same as the combustion of coal, but separation of CO2 is achieved. requirement, all the options of potential energy sources of India need to be explored Comparing with the chemical looping combustion of natural gas, very little water is and exploited. present in the CO2 product of the coal process. India is the fourth largest producer of coal in the world. Unfortunately, almost 75% of The gasification process can also be used for hydrogen production, via water gas shift the resource is at an un-mineable depth. Similarly, out of 38 billion tones of lignite, reaction of CO. A membrane reactor is evaluated, where the hydrogen product is only about 6 billion tones of lignite are mineable and the rest are un-mineable. 20 separated from CO, CO2, and steam. Existing fluidized bed technology is considered Utilizing today’s steam turbines in coal fired steam generating facilities requires a huge suitable for the proposed process. investment in natural resources and auxiliary equipment. Increasing efficiency in steam power plants will substantially reduce the need for coal, thereby reducing 21-2 emissions and extending fossil fuel resources well into the future. Thermoeconomic Comparison of Coal-Based Oxy-Fuel and Post- A way to achieve this objective is to replace steam turbines with more efficient prime Combustion CO2 Capture - Case Study for Polish Conditions movers through retrofit programs and construction of new power plants utilizing a Marcin Liszka, Andrzej Ziebik, Silesian University of Technology, POLAND 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” The carbon capture and storage (CCS) is perceived in many countries as mid-term developed by AAI, a typical 250 mw electric generator can be driven with (2020) reality. As CCS technology has not yet been implemented in full-scale plant the approximately 50% of the steam required by the typical steam turbine. This will comparison of different methods for CO2 removal would be helpful for forthcoming elevate the thermal efficiency of a coal fired steam plants to approach 60% thermal decision-making processes. efficiency. 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 21-5 on chemical CO2 absorption from the flue gas while another one applies oxy-fuel Clean Energy Systems’ Zero Emissions Oxy-Fuel Power Generation Process combustion. For both cases the same steam cycle parameters have been assumed. Scott MacAdam, Roger E. Anderson, Fermin Viteri, Keith L. Pronske, Clean Both CCS options have been evaluated from the point of view of cumulative energy Energy Systems, Inc., USA 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 by- Clean Energy Systems, Inc. (CES) has a developed a novel oxy-fuel power generation products generation. Applied cumulative calculus makes thus possible determination of concept that uses proven aerospace technology to enable zero-emissions power the primary energy consumption for electricity generation which is crucial for generation from fossil fuels. The core of the technology is a high-pressure oxy- thermodynamic comparison of both analyzed systems. combustor that burns gaseous fuels with oxygen in the presence of water to produce a The economic CCS aspects have been investigated taking discounted cash flow steam/CO2 working fluid for steam turbines or modified gas turbines. Carbon capture method as main tool. The cost of electricity production has been calculated assuming is achieved by separating CO2 from the turbine exhaust in a condenser, and delivering the value of modified internal rate of return (MIRR) for electricity producer equal to the conditioned, compressed CO2 to a storage site such as an enhanced oil recovery 10%. An other economic parameter included in this study is cost of CO2 avoidance (EOR) field, a depleted gas reservoir, or a saline aquifer. calculated for both CCS options in two versions: including cost of CO2 transport and CES has demonstrated the oxy-combustor for over 2,000 hours, mainly on natural gas, storage and neglecting this parameter. while supplying power to the grid at CES’s 20 MWth Kimberlina Power Plant outside The application of the presented system and economic approaches requires information Bakersfield, California. Under a $4.6 million award from the Department of Energy, on mass and energy fluxes passing the power units boundary. To calculate all CES is developing the oxy-combustion technology for coal-based power plants that necessary parameters, simulation models of both analyzed PC systems have been use synthesis gas as the fuel. It is closely associated with a DOE award to Siemens prepared. All models have been built on EES software. Most of them are composed of Power Generation to develop high-temperature turbines that would be powered by elementary components like heat exchangers, groups of turbine expansion stages, CO2 steam/CO2 working fluid from the CES oxy-fuel combustor. In Phase I of the project, compressors and coolers, etc. In case of CO2 chemical absorption unit and the cold box CES performed system studies of future oxy-syngas plants, and tested the existing for cryogenic air separation the literature-based index models have been applied. combustor at firing rates of up to 5 MWth on simulated syngas mixtures. In Phase II of The parameters of economic and technical environments have been assumed to values the project, CES is performing a detailed design of a 100 MWth syngas combustor, typical for southern Poland conditions. which will be fabricated and tested in Phase III. Obtained results indicate that the average increase of cumulative energy consumption CES has fabricated a commercial-scale 170 MWth natural gas combustor and plans to caused by CCS inclusion in PC power plant is equal to ca. 30% while the increase of test this unit with a modified GE J79 gas turbine at Kimberlina in mid-2008. These electricity cost amounts to 45% (post-combustion) and to 48% (oxy-fuel). The cost of components will be deployed in “first generation” CES power plants that would CO2 avoidance is equal respectively to 47 and 43 Euro/Mg CO2. 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 21-3 plants is the proposed site for the West Coast Regional Carbon Sequestration Chemical-Looping Combustion of Coal with Metal Oxide Oxygen Carriers Partnership (WESTCARB) “Phase III test” that would capture CO2 from the process Ranjani Siriwardane, George Richards, DOE-NETL; Thomas Simonyi, Hanjing and inject it into a deep saline aquifer. 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 SESSION 22 metal oxide) is first oxidized with air. The hot metal oxide is then reduced in contact COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES – 2 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 22-1 produces sequestration-ready CO2-streams without significant energy penalty. A Solid Element Affinity to Organic Part of Coal fuel such as coal is rarely used in CLC since the process with solid fuels faces many Zdeněk Klika, Lenka Ambružová, Ivan Kolomazník, Jana Seidlerová, Jiřina challenges. However, if we address these challenges CLC would be a very economical Vontorová, VŠB-Technical University Ostrava; Ivana Sýkorová, Institute of way for utilization of coal. Research work on feasibility of utilizing oxygen carriers for Rock Structure and Mechanics AS CR, CZECH REPUBLIC coal combustion will be presented in this paper Samples of coal mixed with bulk and supported metal oxides (NiO, CuO, MnOx, The organic element affinities (OEA) were studied on example of Ga and Ge in lignite. Co2O3) and metal sulfates were heated up to 1000°C in a Thermo Gravimetric Bulk sample of lignite was fractionated using sink-float technique and lignite fractions Analyzer equipped with a mass spectrometer. Three steps of weight losses were with different ash content were obtained. All lignite fractions were air-dried and observed: the moisture loss at about 100°C, coal partial pyrolysis at 400-500°C, and characterized by ash content (An) and the yield of the n-th fraction (fC,n), petrographic coal-combustion at 600-1000°C. The results strongly supported the feasibility of coal and chemical analyses. The data were processed by factor and regression analyses and combustion utilizing oxygen carriers. Multi cycle tests conducted with CuO as the very high correlation coefficients among some characteristics were obtained. oxygen carrier showed very promising results. Effect of CO2 and other additives were Correlation coefficients of Ga to organic part of coal to huminite and to ulminite are also investigated. Thermodynamic calculations to understand the feasibility of the 0.848, 0.803 and 0.833, respectively and correlation coefficients of Ge to organic part concept will also be presented. 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: 21-4 ccUcMA= . +⋅ Improving Thermal Efficiencies in Steam Power Plants by Replacing Steam Cin,, Ui , n MAi , n Turbines with New Generation Prime Mover where cC,i,n is the concentration of the i-th element in the n-th coal fraction, cU,i is the Jerry F. Willis, Admiral Air, Inc., USA concentration of the i-th element in the ulminite (U), Un - content of ulminite in the n- th coal fraction; cMA,i is the concentration of the i-th element in the mineral admixture Despite the fact that many believe that burning fossil fuels has a significant negative (MA), MAn is content of mineral admixture in the n-th coal fraction. impact on our environment, coal fired steam power plants continue to be the standard From the data for n lignite fraction the coefficients cU,i for Ga (18.2 ppm) and Ge (149 bearer for generating electric energy. With thermal efficiencies at approximately 35%, ppm) and coefficient cMA,i for Ga and Ge (10.0 ppm) were calculated. Using the Eq.(1) only 35 of every 100 railroad carloads of coal consumed generate electrical power. It is and relating data of each of n lignite fractions the organic element affinities OEA of Ga time to ask the question “Is the steam turbine still the best technology to drive electric and Ge have been calculated. The obtained results of OEA (77% for Ga and 97% for generators?” 21 Ge) are in good agreement with those ones calculated using former subroutine based successful financial mechanisms. Significant to understanding the challenges is to on different principle (Klika and Kolomazník, 2000). examine and discuss the lessons learned from similar deployments. Addressed are the major topics associated with CCS commercialization. To advance broad base 22-2 commercialization of carbon sequestration, projects need to consider the issues debated Occurrence and Distribution Patterns of Trace Elements in Black Rock by industry, the financial community, and the U.S. Congress. The topics addressed are Series of Yutangba, Hubei Province, P.R. China CCS Congressional Initiatives,, the governmental incentives to support the early Yuegang Tang, Sujuan Shi, Fenghua Zhaou, Shaoqing Wang, Weiwei Li, phases of CCS commercialization; Geologic Storage Regulatory Frameworks, the Huimin Hou, China University of Mining and Technology (Beijing), CHINA statutory and regulatory framework to support the injection of CO2; Environmental Financial Mechanisms, the funding mechanisms previously used to support energy and Mineralogy, geochemistry, and petrology of the selenium-rich black rocks in Yutangba environmental projects that may also be utilized to support CCS technologies; and of Enshi county, Hubei Province of southern China were studied using inductively Carbon Accounting, the process to verify and ensure the secure capture and storage of coupled plasma mass spectrometry, powder X-ray diffraction. The author researched carbon dioxide. Much can be learned from these lessons learned. patterns of distribution, modes of occurrence, character and mechanism of enrichment of Selenium in black rocks. Regularities of distribution and association of trace 23-3 element in bed succession of research area were discussed in detail by correlation. And Energy Project Risk Amidst Climate Change Regulatory Uncertainty it can be used to study cause of formation of Selenium. The results indicate that James Ekmann, Robert Dolence, Leonardo Technologies, Inc., USA 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 For anyone considering an energy-related project that emits greenhouse gases (GHG’s) profile section. or that offsets such emissions, the path forward is filled with uncertainty. Compare today’s development concerns with the 1970’s. In 1970 the primary uncertainties were 22-3 future electric demand, the cost of capital, and the return on investment granted by a Temperature Dependence of Lead (II) Adsorption from Aqueous Solutions public utility commission. In 2008, uncertainties include a global fuel market; resource on Subbituminous Coal depletion; future environmental policies, including traditional pollutants, GHG’s, and Boleslav Taraba, Roman Maršálek, Zuzana Kniezková, Ostrava University, issues that might appear over the long life of the project; rapidly escalating capital and CZECH REPUBLIC labor costs; unproven technology options; and geopolitical upheavals arising beyond energy and environment. Lawmakers and regulators are increasingly asked to ensure Adsorption behavior of lead (II) ions on subbituminous coal sample was investigated at clean, reliable and fairly-priced energy supply and energy security. How does one temperatures 30 and 60°C. Batch adsorption experiments were used to study the shape balance between the need to add new capacity while enhancing the sustainability of the of adsorption isotherms as well as the adsorption kinetics. SETARAM C80 calorimeter energy system? equipped with mixing vessel was then applied to determine heat effects accompanying The signatories to the Kyoto Protocol have entered the first budget period. The the interactions of lead (II) ions with coal surface. As a result, the most significant European Union Emission Trading System has been in operation since 2005. effect of temperature was ascertained for the kinetics of adsorption process. On the Experience from this trading system offers valuable lessons for emerging carbon other hand, practically no shift in adsorption capacity of coal to Pb(II) ions with markets. Discussions are underway to develop GHG reduction programs that might temperature was found. Simultaneously, enthalpy of adsorption was confirmed to be include the United States and the developing nations while the EU is moving ahead slightly exothermic with value of isosteric adsorption heat - 7 + 2 kJ/mol. with plans for reductions of 20 to 30% below 2005 levels. In the United States, regulation of GHG’s 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, SESSION 23 financial institutions are developing risk standards or investment policies to GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND incorporate risks arising from potential new GHG regulations or to the impact of UTILIZATION – 1 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 23-1 options essential to these strategies and their projected costs. The IPCC’s 4th Global Warming: The Electric Utility Challenge Assessment reports examined mitigation strategies under various scenarios. Frank Princiotta, USEPA, USA Assumptions underlay these analyses, assumptions that are often overlooked in discussions of policy, time lines for reductions, and metrics for success. These and The control of greenhouse gases presents a monumental challenge. Industrialization related assessments raise important questions about the efficacy of current efforts and and population growth provide strong drivers for accelerating emissions of greenhouse the pace of change. Can sound application of assessment tools improve the ability of gases, especially carbon dioxide. In light of the long lifetime of CO2, major reductions project developers to communicate with the spectrum of regulators and interested of emissions over time will be necessary to stabilize atmospheric concentrations at parties that routinely become involved in decision making? protective levels. The presentation quantifies the degree of emission control needed for Examination of key assessment studies argues that: several target CO2 global concentrations and warming increments. The paper then - Fossil fuels will be needed to meet societal needs for many years. focuses on electricity production and the technologies currently and potentially - Significant cuts in GHG emissions are essential for pragmatic reasons and must available to mitigate emissions from this source. Conventional coal boilers with CO2 start soon. capture and sequestration, integrated combined cycle gasification (IGCC) with capture - New technologies paired with enhanced performance of existing infrastructure and sequestration, solar, wind and nuclear options are compared. For these key can address both energy security and environmental concerns. technologies, the paper describes the state of development, current and projected costs, - Careful assessments of risks and of interactions amongst technologies are critical projected technology penetrations, and the projected ability to contribute to to ensure progress against both goals. quantifiable CO2 emission reductions in identifiable time frames. 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 23-2 studies that offer key insights, prevalent assumptions that underlie many major Policy and Financial Issues Surrounding Carbon Capture and Storage: assessments, and statistical gaps while summarizing policy and technology risks. Lessons Learned and the Path Forward Jesse E. Gandee, C. David Locke, Patrick R. Esposito, Augusta Systems, Inc., 23-4 USA Quantification of Mine Land Reclamation and Carbon Sequestration: New Technology for Non-Destructive, In-Situ Measurement In the 110th U.S. Congress, there have been more than 100 bills proposed that address Lucian Wielopolski, Brookhaven National Laboratory; Richard C. Stehouwer, Greenhouse Gases (GHG)s and Carbon Capture and Storage (CCS) technologies. The Penn State University, USA interest in these topics is reflective of the country’s motivation to resolve climate change issues. In fact, given the collection of GHG and CCS-related policy proposals, For the coal industry as a major energy source to remain viable and to grow, it must be the U.S. energy industries, such as coal and natural gas, could soon be functioning in a responsive to public concerns with; a) land disturbance from surface coal mining, and carbon constrained world. CCS is a viable option to reduce any hurdles associated with b) the massive emissions of CO2 and other greenhouse gasses from the combustion of GHG requirements but to do so effectively, it must be allowed to evolve in a coherent coal. While the industry has devoted considerable efforts toward both land reclamation legal and regulatory climate. Previous research reveals that a full-scale commercial and emissions control, the present need to mitigate atmospheric CO2 increases gives CCS industry will allow for coal companies to meet the energy needs of future mine soil restoration a new emphasis and importance. Based on 1992 NRI data land generations while simultaneously addressing any carbon constraints. Nevertheless, disturbed by mining was assessed at 4.4 Mha at United States alone. Implementation of there are several financial and project-cost factors that will influence the development reclamation strategies on these lands as well as on abandoned mined lands which focus of a commercial CCS industry, including government funding, market incentives, and on establishment of sustainable production of biomass and carbon sequestration would 22 be beneficial; a) to the mining industry in the eyes of the public, b) in supplementing and other contaminants that are detrimental to the steam reforming and Fischer- land needs for potential biofuels and crop production, c) to trading with carbon credits, Tropsch catalysts. and d) in sequestering some of the atmospheric CO2. 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 hydro- 23-5 treating units and hydrocracking units. The CTL facility produces approximately 5,488 Global Climate Change; The Challenge of Mitigating Three Trillion Tons of bbl/day of commercial-grade diesel liquid and 2,352 bbl/day of naphtha liquid, which CO2 could be shipped to a refinery for further upgrading into commercial-grade end Frank Princiotta, USEPA, USA 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 Anthropogenic emissions of greenhouse gases, especially carbon dioxide, CO2, have performed to explore a plant design that includes equipment to separate and compress led to increasing atmospheric concentrations which are the primary cause of the 0.8°C carbon dioxide for injection into a pipeline and potential sequestration. Facility with warming the earth has experienced since the industrial revolution. With industrial CO2 capture and sequestration off-site (65% capture) is included in this analysis. The activity and population expected to increase for the rest of the century, large increases overall plant thermal effective efficiency for the process configuration is 53.4 percent, in greenhouse gas emissions are projected, with additional and potentially substantial on an HHV basis. This paper presents the overview of the material & energy balances subsequent global warming predicted. While much literature exists on various aspects and the other results of the simulation. 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 24-3 that may be needed to constrain this warming, and the technologies needed to help Study of Co-liquefaction of Chinese Bituminous Coal and Lignin achieve the three trillion tons of CO2 mitigation that may be required. This paper uses Wang Zhi-hong, He Xu-wen, Xu De-ping, Wang Yong-gang, Guo Xiang-kun, available, transparent modeling tools and the most recent existing literature, to draw China University of Mining & Technology, CHINA broad conclusions about the challenge posed by climate change and potential technological remedies over the next century. The presentation provides an overview Co-liquefaction of Shenhua bituminous coal and lignin from black liquor of paper mill of the forces driving CO2 emissions, how different CO2 emission trajectories could was studied. In present work, tetralin was employed as hydrogen-donor solvent. The affect temperature this century, and a concise sector-by-sector summary of mitigation experiments were carried out in a 250 ml micro-autoclave. Effects of reaction options, and R&D priorities.The author will then quantify the emission reductions temperature, time, different initial pressure of hydrogen, lignin/Shenhua coal ratios on potentially available from two major and distinct categories in order to achieve such the conversion, liquid and yields, asphaltene and preasphaltene yields, hydrogen mitigation. The first involves the accelerated use of existing technologies, especially in consumption and effective hydrogen were investigated. The results show that the the building and transportation sectors. The second, and most important category, addition of lignin can promote the conversion of coal effectively compared with direct involves development and utilization of new energy production and end use coal liquefaction. The greatest extent promotion is in lignin/Shenhua of 2:8. technologies, with a focus on power generation and mobile sources. Key technologies Conversion and oil yield increase obviously when initial hydrogen pressure is less than will be characterized regarding their mitigation potential and developmental status. 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 440°C. Conversion and oil yield of co-liquefaction increases at first and then reduces with reaction time, and SESSION 24 reached maximum value of 82.66% and 51.49% at 60 min., respectively, under SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL – 4 optimum conditions of temperature 440°C, initial hydrogen pressure of 9 MPa, Lignin/bituminous coal of 2:8 and reaction time of 60 min.

24-1 Hydrogenation of Naphthalene using Nickel-Molybdenum Catalyst in a Trickle-Bed Reactor SESSION 25 Abhijit Bhagavatula, Elliot B. Kennel, Alfred H. Stiller, John W. Zondlo, West GASIFICATION TECHNOLOGIES: FUNDAMENTALS – 2 Virginia University, USA; Robert W. Svensson, Chalmers Lindholmen University College, SWEDEN 25-1 The hydrogenation of coal-tar distillates has been carried out in a Trickle Bed Reactor, Preventing Agglomeration Problems During Gasification of High-Sodium in which the liquid is allowed to flow through the catalyst bed in the presence of Lignite hydrogen. The purpose of these experiments is to reduce the residence time of the Robert S. Dahlin, Southern Research Institute; Johnny R. Dorminey, WanWang disitillates in the reactor, taking advantage of the geometry of the trickle-bed system. Peng, Roxann F. Leonard, Pannalal Vimalchand, Southern Company Services, Specifically, in trickle bed reactors, part of the catalyst surface is covered by gas and USA 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 Previous gasification studies have shown that sodium vapor released from high-sodium the liquid over the catalyst and higher liquid flow rates without flooding problems. Part lignites can react with silica to form sticky sodium silicates. These sticky sodium of the catalyst surface is simultaneously covered by gas and liquid. Hence, it is silicate compounds naturally tend to glue particles together leading to the formation of expected that the kinetics of the reaction would be much faster. Thus, the agglomerated deposits in the gasifier. Laboratory studies reported in our previous determination of the minimum practical residence time, order of the reaction and rate paper suggested that the formation of these sticky sodium silicates was responsible for of reaction for the desired catalytic hydrotreatment of coal tar distillates is the the agglomeration and deposition problems encountered during the use of high-sodium proposed topic of research. 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 24-2 by eliminating the sand bed material, reducing the gasifier operating temperature, and Baseline Technical and Economic Assessment of a Small Scale Steam introducing an inert particulate material (e.g., dolomite or limestone) to reduce the Hydrogasification Process with Fischer-Tropsch Liquids Facility contact between sticky particles. To take advantage of these observations, a Chan S. Park, Arun SK Raju, Joseph M. Norbeck, University of California, subsequent test run (TC16) was performed with the sand bed material eliminated, the Riverside; Larry Rath, Walter Shelton, DOE-NETL, USA gasifier operating temperature limited to about 930°C (1700°F), and with the addition of dolomite into the gasifier recycle loop. With these remedial steps in place, the high- A combination of Steam Hydro-gasification Reaction (SHR) and Steam Methane sodium lignite was successfully gasified without any signs of agglomeration or Reforming (SMR) can be used to produce synthesis gas (H2+CO) from carbonaceous deposition problems. After the successful gasification run in TC16, another run feedstock. This technology, developed at the University of California Riverside, Center (TC21) was attempted with the same lignite. In TC21, however, the sodium content of for Environmental Research and Technology (CE-CERT) operates at moderate the lignite was somewhat higher (about 8 to 9 wt% as Na2O in the ash versus about 6 temperatures and pressures when compared to other similar processes and can be used to 7 wt% in TC16). With the higher sodium content, the problems with agglomeration to produce Fischer-Tropsch liquids. The technical and economic feasibility of a and deposition recurred. commercial 4,000 metric ton per day Coal To Liquids (CTL) facility using this new To better understand the nature of the deposit formation in TC21, samples of the technology is being evaluated by CECERT and the National Energy Technology deposits taken from the lower mixing zone of the gasifier after TC21 were subjected to Laboratory (NETL). Detailed ASPEN Plus simulations have been performed for a various lab tests. First, the deposit chunks were pulverized and heated to various plant with a capability of 4000 tons/day coal feed. The simulations include a reactor temperatures to determine the minimum temperature required for reconsolidation. and a regenerator section for the SHR. The SHR is assumed to be a fluidized bed These tests showed that the deposits reconsolidated even at temperatures as low as reactor and the sand material is heated in the regenerator section to enable heat supply 540°C (1000°F). Given the relatively low temperatures at which reconsolidation was to the reactor. The simulation also has a gas cleanup system that will remove the sulfur 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, 23 because of the relatively large reconsolidation tendency of the TC21 deposit, it was 25-4 clear that any additives used to prevent agglomeration would need to be even more Preparation and Characterization of Sr(Mn1-xNix)O3 Solid Solution in effective than the dolomite used in TC16. With these factors in mind, a series of Relation to Their Use in Chemical Looping Oxygen Transfer experiments was conducted to evaluate various additives that might help minimize Ewelina Ksepko, Jan Figa, Institute for Chemical Processing of Coal; Ewa Talik, agglomeration and deposition problems. The additives tested included: dolomite, University of Silesia, POLAND amorphous silica fume, bauxite, vermiculite, kaolinite, waste-derived kaolinite, and meta-kaolin. Chemical looping (CL) using interconnected beds is a new promising combustion The laboratory tests showed that a coarse form of meta-kaolin (mean size 920 microns) technology for production of power with inherent separation of greenhouse gas CO2. could prevent reconsolidation of deposits at temperatures as high as 982˚C (1800˚F). The technique involves the use of metal oxide as an oxygen carrier which transfers SEM/EDX analysis confirmed that the metakaolin was able to capture sodium vapor oxygen from air to fuel. In the concept no extra energy is needed for CO2 separation. without consolidation. Based on these results, it was decided to conduct another The CL idea could be extended to the combustion of solid fuel and CO2 free H2 gasifier run with the high-sodium lignite, this time with the meta-kaolin used as an production. The important role in the mentioned process is played by simple solid additive. The successful gasification run (TC23) was started with PRB coal to replace oxygen carriers like: NiO, MnO2, Fe2O3. There are only few papers about complex any sand bed material with coarse coal ash. After the sand was eliminated from the potential CL material as perovskite-type La0.8Sr0.2Co0.2Fe0.8O3. system, the gasifier was transitioned to high-sodium lignite feed with the simultaneous New perovskite-type materials were obtained and characterized by means TG, SEM, addition of meta-kaolin. The meta-kaolin was added with the lignite at a rate roughly XRD, XPS measurements and melting points study. Solid state reaction of oxides was equivalent to the ash content of the lignite. During the run, the gasifier operating used for preparation. In order to investigate the oxidation/reduction of the materials conditions and solids samples were closely monitored to detect any signs of thermogravimetric measurements were performed. The mentioned perovskite material agglomeration or deposition. The monitoring included visual inspection of the change very quickly oxygen content with maintaining chemical properties during samples, examination of the samples under the optical microscope, and baking of the oxidized and reducing cycles. So it is believed to be suitable candidate for chemical samples in a laboratory muffle furnace to determine whether exposure to higher looping. XPS measurements were used to study electronic structure and chemical temperatures would cause sintering and agglomeration. No evidence of sintering or composition of the obtained perovskites. The obtained samples show deviations from agglomeration was found using any of these procedures. 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 25-2 observed during the thermal measurements of the SrMnO3 electronic structure in the Pilot Plant for Fluidised Bed Gasification of Carbon Products with the range of 20°C-700°C. Significant changes start above 350°C. XRD technique High-Temperature-Winkler (HTW) Gasifier at the Department of Ferrous measurements confirmed to be perovskite-type phase. The solid solution Sr(Mn1- Metallurgy xNix)O3 effected extremely high melting temperatures in reduction atmosphere, from Stephan Geimer, Dieter Senk, Thomas Baur, Department of Ferrous Metallurgy, 1370°C to 1590°C. Promising results obtained from reduction and oxidation RWTH Aachen University, GERMANY 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 Since several decades gasification of coal with HTW process is state of the art. The Combustion- Chemical Looping Gasification processes. increasing energy costs in connection with higher demand on energy lead to new developments for energy production. The good flexibility of the High-Temperature- 25-5 Winkler gasification process and the ability to use many different carbon and hydrogen Pressure Drop Predictions in a Fixed-Bed Coal Gasifier containing materials are some advantages. At the Department of Ferrous Metallurgy, Adam Luckos, John Bunt, Sasol Technology R&D, SOUTH AFRICA 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 In the Sasol Synfuels plant in Secunda, Sasol-Lurgi fixed-bed dry bottom gasifiers are 2007 the complete refractory and all control and measurement units have been used for the conversion of low-grade bituminous coals to synthesis gas (syngas). The revamped. All process units are now computer controlled and a continuous data gasifiers are fed with lump coal having a particle size in the range of 5 to 100 mm. acquisition enables to calculate the complete mass balance. Due to the size of the pilot Operating experience shows that the average particle size and particle size distribution plant a prediction for the coal consumption in industrial plants is possible. A wide (PSD) of fresh coal, char and ash influence the pressure drop across the bed and the range of different lignite coals, plastics and waste material in combination with gas-flow distribution within the bed. These hydrodynamic phenomena are responsible different reaction gas containing of oxygen, air and steam have been applied. A stable for stable gasifier operation and for the quality and production rate of the syngas. The operation for these products was archived to find optimum set of process parameters. counter-current operation produces four characteristic zones in the gasifier, namely, The production gas was online analysed to record its applicability for power plants but drying, devolatilization, reduction and combustion. The physical properties of the also for industrial application or ore reduction in the metallurgy. 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 25-3 (temperature, density and viscosity) and superficial velocity vary along the height of Gasification Reactivity of Solvent Extracted Ash Less Coals and Raw Coals the bed. The most popular equation used to estimate the pressure drop in packed beds with K2CO3 at 650°C Under Steam is that proposed by Ergun. The Ergun equation gives good predictions for non-reacting, Atul Sharma, Hiroyuki Kawashima, Ikuo Saito, Toshimasa Takanohashi, isothermal packed beds made of uniformly sized, spherical or nearly spherical National Institute of Advanced Industrial Science and Technology, JAPAN 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 HyperCoal is a clean coal with ash content <0.05 wt%.Oaky Creek [OC] (C=82%), the bed structure and gas flow vary significantly in the different reaction zones. In this and Pasir [PAS] (C= 68%) coals were subjected to solvent extraction method to study, the Ergun equation is applied to each reaction zone separately. The total prepare Oaky Creek HyperCoal [OCHPC], Pasir HyperCoal [PasHPC]. Experiments pressure drop across the bed is then calculated as the sum of pressure drops in all were carried out to compare the gasification reactivity of HyperCoals and parent raw zones. It is shown that the total pressure drop obtained this way agrees better with the coals with the 20, 40, 50 and 60% K2CO3 as a catalyst at 600 and 650°C with steam. measured one. 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 SESSION 26 gasification of HyperCoals was found to be chemical reaction controlled in the UNDERGROUND COAL GASIFICATION – 2 600~650°C 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 26-1 from coals and HyperCoals were similar. NMR results show no significant difference North America Prospects for UCG in a Carbon Constrained, Energy Secure between the chemical compositions of the chars. SEM images showed that chars from World HyperCoals are like porous zeolite while dense chars were observed for coals. The Samuel Friedmann, LLNL, USA difference in reactivity of HyperCoal and coal could be best explained by the macroscopic difference in chars from HyperCoals and coals. Underground coal gasification (UCG) has re-emerged as an energy technology of note. This is part is due to UCG’s 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.

24 Recent research suggests that the US can dramatically increase its domestic coal 26-4 reserves by gasifying unmineable coals at depth (300-1500 m). Cursory assessment of Underground Coal Gasification (UCG) Project Development in the major coal basins in North America (e.g., Powder River Basin, Illinois, Alberta Basin) Australasian Region suggests a conservative estimate of a four-fold increase in coal resource. These L.K.Walker, Cougar Energy Ltd., AUSTRALIA 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 Activity in UCG in Australia over the past 10 years has had a significant impact on the coincidence between North American coal resources and potential sites for carbon revitalization of the technology internationally. This paper summarizes the capture and sequestration (CCS). Initial estimates of sequestration resource published background to this work, including the gaining of environmental approvals for the by the DOE and others suggest >75% of previous UCG pilots lay within 50 km of successful Chinchilla project, significant commercial aspects of its operation, and its suitable saline aquifers, depleted oil and gas fields, and EOR possibilities. Case studies impact in the current climate of global warming concerns. The paper also describes in key basins demonstrate the potential pairing of conventional CCS with UCG the activities on a number of specific UCG projects in the region, which confirm the projects. The attractive, preliminary economic assessments for UCG suggest that it certainty behind the eventual commercialization of the technology. would be possible to fully or partially decarbonize many UCG product streams to deliver low-carbon coal energy to markets.

26-2 SESSION 27 Underground Coal Gasification Activities in China ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY Sohei Shimada, The University of Tokyo, JAPAN; Jie Liang, China University CAPTURE, NONCARBON of Mining and Technology, CHINA

UCG (Underground Coal Gasification) is an ultimate energy recovery method from 27-1 coal seam without exploiting coal. UCG has long history with different gasification Mercuric Chloride Based Catalysts for Oxidation of Mercury in Flue Gas scales from fundamental laboratory experiments and theoretical studies to pilot scale Evan J. Granite, John P. Baltrus, DOE-NETL, USA 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 A promising method for the removal of mercury involves catalytic oxidation or price. For the UCG is an unconventional way to recover the energy stored underground chlorination of elemental mercury. Elemental mercury is insoluble in water, whereas coal seam and it is rather expensive way to recover energy compared to other oxidized forms such as mercuric chloride are soluble. The catalytic oxidation of conventional energy resources. Incomplete technological maturity including elemental mercury to mercuric chloride, upstream of a wet scrubber, could be an environmental protection technology is one of the key factors in commercializing attractive strategy for the control of mercury emissions from coal-burning power UCG. plants. Many field tests were carried out in many countries in the world. China is one of the Many materials have been examined as potential catalysts for the oxidation of mercury advanced UCG country where UCG is commercialized and assigned one of the in flue gas [1-2]. These materials include: 1.) noble metals such as palladium, gold, national important technology development items. platinum, and iridium, 2.) activated carbons, 3.) fly ashes, and 4.) SCR catalysts. Many UCG technologies have been developed in China. The feature of the UCG There are significant differences in the performance of the catalysts in terms of active system in China is to use the used mine roadway as linking channel. Therefore, this is life in flue gas. However, the differences between the classes of catalysts, at least in called “Long and Large Tunnel Gasification Method”. Air and steam is usually used as terms of initial level of mercury oxidation achieved, are typically rather small. This an injection gas and in some cases underground water acts as hydrogen source. Recent suggests the possibility of a common reaction mechanism for the oxidation of mercury. technology target in UCG in China is to recover high concentration hydrogen for the One possibility is that gas phase HCl and/or Cl2 are highly reactive, readily adsorb on future hydrogen society. Two stage UCG method was developed to maintain high most surfaces, and thereby allow many materials to act as catalysts. gasification temperature. Air and steam is injected repeatedly for obtaining high It was recently found that the study of the homogeneous oxidation of elemental temperature distribution in coal seam with air injection and hydrogen production with mercury by the halogens is extremely difficult because of wall effects [3-5]. The walls steam injection. In steam injection stage the hydrogen with 50-60% concentration was of the reactor, even if chosen or coated to be especially inert, were found to readily produced. Recent technology challenge is oxygen-rich air injection. catalyze the oxidation of mercury. Medhekar has suggested that mercuric chloride China University of Mining and Technology established the UCG Research Center. deposits on the wall surfaces act as an active site for the oxidation of mercury, The Center has a large experimental apparatus with the dimension of 4.45 m (length) × rendering many different materials to behave as catalysts with similar levels of activity 1.17 m (width) × 1.57 m (height). This experimental apparatus enables the for the formation of mercuric chloride [3-5]. Schofield has suggested mercuric oxide measurement of gasification process and temperature distribution at combustion and or mercuric sulfate as a common active adsorbate in the catalytic oxidation of mercury gasification zone with time. The experiments in this apparatus make the reproduction [6-7]. of gasification process underground in more realistic situation. Mercuric chloride dispersed upon activated carbons is well-known and widely This paper summarizes the UCG technology development and present situation in employed catalysts for the hydrochlorination of acetylene [8-12]. Acetylene and practice and researches in China. 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 26-3 are usually around 120°C. The extensive literature on the mercuric chloride catalysts Application of the Exergy UCG Technology in International Industrial for hydrochlorination may provide useful insights on the oxidation of mercury in flue Projects: The Status Update gas. The structure of mercuric chloride adsorbed upon gold has also been previously M. Blinderman, A. Blinderman, G. Elliott, A. Metz, V. Pashenko, I. Saptikov, P. determined [13]. In addition, other metal chlorides have been employed as catalysts Bedi, Ergo Exergy Technologies, Inc., CANADA for the polymerization or selective chlorination of organic compounds [14-15], and this also may provide insight into the catalytic oxidation (chlorination) of elemental Underground Coal Gasification (UCG) is a gasification process carried on in non- mercury. The efficacy of mercuric chloride treated activated carbon, as well as other mined coal seams using injection and production wells drilled from the surface, chloride treated catalysts, will be determined, possibly through collaborative efforts. 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 Literature Cited Technologies is called the Exergy UCG Technology or εUCG™ Technology. 1. Presto, A.A.; Granite, E.J. Survey of Catalysts for Oxidation of Mercury in Flue The εUCG methods and techniques of environmental management are an effective tool Gas, Environmental Science & Technology 2006, 40(18), 5601-5609. to ensure environmental protection during an industrial application. A εUCG-IGCC 2. Presto, A.A.; Granite, E.J.; Karash, A.; Hargis, R.A.; O’Dowd, W.J.; Pennline, power plant will generate electricity at a much lower cost than existing or proposed H.W. A Kinetic Approach to the Catalytic Oxidation of Mercury in Flue Gas, fossil fuel power plants. CO2 emissions of the plant can be reduced to a level 55% less Energy & Fuels 2006, 20, 1941-1945. than those of a supercritical coal-fired plant and 25% less than the emissions of NG 3. Wang, J.; Anthony, E.J. An Analysis of the Reaction Rate for Mercury Vapor CC. and Chlorine, Chem. Eng. Technol. 2005, 28(5), 569-573. The εUCG technology is being applied in numerous power generation and chemical 4. Ariya, P.A.; Khalizov, A; Gidas, A. Reactions of Gaseous Mercury with Atomic projects worldwide. These include power projects in South Africa (1,200 MWe), India and Molecular Halogens: Kinetics, Product Studies, and Atmospheric (750 MWe), Pakistan, and Canada, as well as chemical projects in Australia and Implications, J. Phys. Chem. A 2002, 106, 7310-7320. Canada. A number of εUCG based industrial projects are now at a feasibility stage in 5. Medhekar, A.K.; Rokni, M.; Trainor, D.W.; Jacob, J.H. Surface Catalyzed New Zealand, USA, and Europe. This paper provides an update on current status of Reaction of Hg + Cl2, Chemical Physics Letters 1979, 65(3), 600-604. these projects, with primary focus on the Majuba UCG project in South Africa, SENZ 6. Schofield, K. Let them eat fish: Hold the mercury, Chem. Phys. Lett. 2004, 386, project in New Zealand, Two projects in India and the projects in North America 65. targeting power generation and provision of energy and raw materials for production 7. Schofield, K. Mercury emission chemistry: The similarities or are they and upgrading of petroleum products from tar sands in Western Canada. generalities of mercury and alkali combustion deposition processes? Proc. Comb. Inst. 2005, 30, 1263. 25 8. Ogunye, A.F; Ray, W.H. Optimization of a Vinyl Chloride Monomer Reactor, changes of outlet mercury concentration. Experimental results show that, mercury Ind. Eng. Chem. Process Des. Develop. 1970, 9(4), 619-624. adsorption in the surface of activated coke is physisorption process. And one makes an 9. Ghosh, A.K.; Agnew, J.B. Kinetics and Mechanism of the Catalytic in-depth research on thermodynamics and kinetics of Hg0 adsorption in active coke. Hydrochlorination of Acetylene to Vinyl Chloride by Use of a Transient Research shows that Hg0 adsorption is perfect to accord with Freundlich and Henry’s Response Technique, Ind. Eng. Chem. Process Des. Develop. 1985, 24(1), 152- law models in the original coke because of lower concentration, but results are poor 159. with using Langmuir adsorption model, that is, the initial stage can not be used to 10. Hutchings, G.J.; Grady, D.T. Hydrochlorination of Acetylene: The Effect of determine the whole adsorption isotherm. It’s not suitable for the prediction of mercury Mercuric Chloride Concentration on Catalyst Life, Applied Catalysis 1985, 17, adsorption capacity of high concentration. 155-160. Researching the mathematical model of mercury adsorption process, the mercury mass 11. Hutchings, G.J.; Grady, D.T. Effect of Drying Conditions on Carbon Supported ∂C ∂C 1−ε ∂q Mercuric Chloride Catalysts, Applied Catalysis 1985, 16, 411-415. balance reads + u + = 0 (1). Mass transfer includes 12. Dazhuang, L. The Loss Rate by Sublimation of Mercuric Chloride Adsorbed on ∂t ∂Z ε ∂t Activated Carbon, Carbon 1993, 8, 1237-1242. internal diffusion and external diffusion. The overall mass-transfer velocity can be 13. Laakso, A.; Lahtinen, J.; Levlin, M.; Hautojarui, P. Adsorption of HgCl2 on Au (111) surfaces studied by scanning tunneling microscopy, J. Chem. Phys. 2001, ∂q ∗ 115(8), 3763-3768. written as: = Ksav (q − q) (2).The rate of external diffusion and internal 14. Singh, A.P.; Kumar, S.B. Para selective chlorination of toluene with an L-zeolite ∂t catalyst, Applied Catalysis A: General 1995, 126, 27-38. ∂q 15. Cai, T.; Liu, S.; Qu, J.; Wong, S.; Song, Z.; He, M. Chlorinated alumina and its diffusion are simply given by γ = kg av ()c − ci (3) and catalytic behavior in selective polymerization of isobutene, Applied Catalysis A: ∂t General 1993, 97, 113-122. ∂q (4), respectively. Following the Henry’s law, surface 27-2 = ksav ()qi − q The Binding of Flue Gas Pollutants on Pd-Au Alloys and Monolayers ∂t Jennifer Wilcox, Erdem Sasmaz, Shela Aboud, Stanford University, USA adsorption process has the following equation: q = Kc (5). Finite difference

Density Functional Theory calculations have been performed to predict the binding method calculation for the eqs 1-5 is used to adjust mathematical simulation 0 parameters K and Ksav. The results show that, the smaller particle size and the more mechanism of flue gas pollutants such as SO2, Hg , HgCl2, HgO and SeO2 on pure Pd (001) and Au (001) and their binary alloys. The vast majority of the mercury released mesopore of adsorbent, the bigger mass transfer coefficient and physisorption from coal combustion is elemental (Hg0) and its binding on PdAu (111) has been capability. With the adsorption temperature increasing, the mass transfer coefficient is investigated. Additionally, the temperature effect on the binding mechanism of Hg0 larger, which accelerates the mass transfer process, but reduces the adsorption has been investigated on pure Pd (001). It has been found that the Pd surface is more capacity. reactive than the Au surface to the pollutants of coal combustion flue gas. A weak 0 27-5 interaction has been obtained for SO2 and HgCl2 molecules on Pd (001), whereas Hg , 0 Evaluation of Decomposition Characteristics of Mercury Compounds Using HgO and SeO2 bind strongly to the Pd (001) surface. Calculations for Hg binding on PdAu (111) have shown that small additions of Au to Pd increases the binding energy Mass Spectrometer by improving the surface reactivity of the alloy. Further studies showed that using a Md. Azhar Uddin, Saori Nagano, Masaki Ozaki, Eiji Sasaoka, Okayama monolayer of Pd overlayed on an Au substrate enhances binding compared to the University, JAPAN; Shengji Wu, Hangzhou Dianzi University, CHINA 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 Understanding the decomposition characteristics of mercury compounds is very composition uniformity and subsequent increased number of binding sites. 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 27-3 valuable data necessary for the design of solid sorbents. However, there are not enough data available on mercury compound’s stability in the flue or fuel gas conditions. The Development of Novel Catalyst for Mercury Oxidation under Post- Combustion Zone Conditions decomposition behavior of mercury compounds such as HgS, HgO, HgSO4, HgCl2, D Patanjali Varanasi, Sukh Sidhu, University of Dayton, USA Hg2Cl2 were investigated by TPDD (temperature programmed decomposition and desorption) technique using a mass spectrometer (TPD-Mass method). Especially, the The results of our previous mercury oxidation study conducted using six different Ohio stability and reactivity of mercury chloride (HgCl2) was mainly examined in coal coal fly ashes and model fly ashes show that the chemical composition of surfaces combustion flue gas and coal derived fuel gas conditions. plays an important role in mercury oxidation reactions. Mercury speciation depends on The mercury compounds were diluted with solids (diluents) such as SiO2, SiC, Al2O3, fly ash surface constituent like carbon, iron and calcium. It was also noted that fly ash TiO2 and activated carbon for TPD-Mass experiments. The following results were behavior for mercury adsorption/oxidation is based on its carbon content at lower obtained: (1) the order of the main peak temperature of mercury evolution from the temperature and on its metal content at higher temperature. The mercury should be decomposition of mercury compound in He flow was as follows: HgS (meta-cinnabar) present in its oxidized form for it to be effectively removed in the wet scrubbers. An = HgO < HgS (cinnabar) < HgSO4; (2) HgSO4 was hydrolyzed by H2O; (3) HgO was oxidation catalyst is needed to ensure oxidation of mercury before it enters the wet reduced by SO2 in the presence of H2O and O2; (3) HgCl2 and Hg2Cl2 were scrubber. The present study investigates the applicability of γ-iron oxide, copper oxide 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 and copper chloride as mercury oxidation catalyst. The mercury oxidation and mercury 0 adsorption/desorption capabilities of these catalyst were also examined in the presence could be converted to Hg over quartz wool, Pyrex wool, ceramics (SiO2-Al2O3) wool, of coal fly ash. In all experiments, the inlet concentration of Hg0(g) was maintained at carbon fiber and AC. 3 0 33 μg/m using a diffusion cell as the source of Hg (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 400°C. In each experiment the reactor effluent was sampled using modified Ontario-Hydro method. SESSION 28 After each experiment, fixed beds were also analyzed for mercury. The results show COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES – 3 that copper oxide and copper chloride were highly effective in oxidizing mercury. However the γ-iron oxide catalyst only showed high mercury adsorption and significant mercury oxidation was only observed after long exposure in the presence of 28-1 HCl. The Oxygen and its Influence on Coal Surface Roman Marsalek, Univerzity of Ostrava, CZECH REPUBLIC 27-4 Research on Kinetics of Mercury Capture with Active Coke Various types of oxidation of carbonaceous materials were evaluated. The zeta Yin-wu Xiong, Beijing Research Institute of Coal Chemistry; Ya-na Bai, potential of different kinds of carbonaceous materials was studied with respect to the CUMTB, CHINA 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 Active coke (AC) has eximious adsorption properties, which has maken great samples decreases to more negative values with increasing native amount of oxygen. development in flue gas purification. Active coke not only removal of major pollutants This trend was confirmed on samples of partially oxidized coal, for which the zeta 0 potential decreases with increasing temperature of oxidation and increasing amount of in flue gas such as SOx, NOx, but also removal of elemental mercury (Hg ). It is put in fixed-bed reactor, then mercury vapor from the Hg0 permeation tubes mixed with other chemisorbed oxygen. Similar relation was found for samples of graphite oxidized by simulated flue gas components pass through samples layer, at last, measure the nitric acid. A surface of carbonaceous materials was also modified by surfactant - SDS 26 (sodium dodecyl sulphate). We followed relationship between adsorbed amount of 28-5 SDS and changes of the zeta potential. Amount of oxygen in carbonaceous materials Maastrichtian Coals from Nigeria: Notes on the Origins of the Inertinite affects hydrophobicity of these samples. Decrease in oxygen content leads to increase Macerals, with Attention to Macrinite Formation as a Consequence of of adsorption of SDS. Fungal Degradation James C. Hower, University of Kentucky (CAER); Susan J. Tewalt, Harvey E. 28-2 Belkin, U.S. Geological Survey; Jennifer M.K. O’Keefe, Morehead State Study on the Properties of Huangling Coal and its Application in Coking University; J.D. Stucker, Allison R. Richardson, University of Kentucky, USA; Shizhuang Shi, Gang Shi, Feng Shi, Cheng Zhang, Wei Xu, Wuhan University Samson Adeleke Oke, Federal University of Technology, NIGERIA; Irena J. of Science and Technology; Yubao Guo, Shiqiang Ma, Huangling Ming Group Kostova, University of Sofia “St. Kliment Ohridski”, BULGARIA Corporation Ltd.; Jun Wang, Shangguo Liang, Xinhong Lei, Wuhan Iron and Steel Co. Ltd, CHINA 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, Huangling coal is a new kind of coal mined from a colliery with more than ten million Nigeria, were collected for the U.S. Geological Survey’s World Coal Quality tons per annum. In order to use it better, firstly, its properties are studied Inventory. Petrology was done at the University of Kentucky Center for Applied systematically, including preliminary analysis, ultimate analysis, ash component Energy Research. The coals show wide variation in the maceral percentages, from 34 analysis, maceral (petrographic) analysis, vitrinite reflectance analysis, technological to 82% huminite/vitrinite and 7.6 to 31% fusinite + semifusinite + inertodetrinite. property analysis, Hardgrove grindability analysis, coking property analysis, harmful The inertinite group contains not only relatively abundant fusinite and semifusinite, element analysis (e.g. phosphorus, arsenic, hydrargyrum, chromium, plumbum etc.) with lesser amounts of inertodetrinite; but also secretinite, micrinite, macrinite, and and so on. It is found that the huangling coal is a gas coal with low ash content, low funginite. The fusinite + semifusinite and each of the other maceral varieties can have sulfur content, medium phosphorus content, low arsenic content, low chromium distinct origins and it is misleading to consider all inertinites as having a more or less content, low plumbum content, medium hydrargyrum content according to Chinese common origin. In particular for this set of Cretaceous coals, macrinite, often a rare classification standard of coal. Then the huangling coal is used to blend and to coke. maceral, is present in amounts up to 3.8%. In these coals and in others we have The effect of the ratio and fineness of Huangling coal in blend on coke quality, examined, macrinite can be associated with funginite. Whether or not this is a causal including mechanical strength (M40, M10), thermal performance (CRI, CSR), micro- association is debatable, but it has been suggested by other researchers that there could strength (MSI), porosities, densities, optical texture etc., is studied systematically. be a genetic connection between the two macerals. Fungal degradation of woody and Experimental results show that the huangling coal possesses good coking property. other material is a plausible origin for the amorphous to (marginally) detrital structure When its proportion ranges from 2%-20% and under the conditions of different found in the associated macrinite. fineness, the various indexes of coke quality are stable basically.

28-3 Determination of Gieseler’s Plasticity Parameters of Coal Based on SESSION 29 Dielectric Property GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND Tetsuo Aida, Ken-ichi Fujita, Toyokazu Shinkai, Kinki University; Izumi UTILIZATION – 2 Shimoyama, JFE Steel Corporation, JAPAN

It has been developed a reliable methodology to determine the plasticity parameters of 29-1 coal, so-called, Gieseler s Initial Softening Temperature (ST), Maximum Fluidity Low-Cost, High-Efficiency CO2 Compressor Temperature (MFT), and Re-solidification Temperature (RT), based on the dielectric Peter Baldwin, Ramgen Power Systems, USA properties. The thermal behavior of dielectric property of coal was evaluated by using our instrumentation which has capability to determine a capacitance and electric Ramgen Power Systems, Inc. is developing a family of high performance CO2 conductivity with a function of temperature. Because of the physical definition of these compressors that combine many of the aspects of shock compression systems properties, the thermal mobility and polarizability of the macromolecular network commonly used in supersonic flight inlets, with turbo-machinery design practices structure of coal is thought to be more reasonably reflected on the plasticity of coal employed in conventional axial and centrifugal compressor design. Shock wave than viscosity. compression technology has the potential to develop very high compression ratio per A typical example of the measurement of the capacitance of the Argonne Premium stage and very high efficiency, simultaneously. This capability allows Ramgen to Illinois No.6 coal is demonstrated below, with the scheme determining ST- and MFT- configure a 2-stage CO2 compressor for a pressure ratio of 100:1, while conventional values, as 371°C and 410°C, of which Gieseler s determination were 367°C and technology will typically require 8-stages of compression. The input power to 417°C, respectively. Ramgen’s 2-stage compressor will be comparable to the 8-stage conventional The Re-solidification Temperature (RT) of Illinois No. 6 coal has also been determined approaches, but the individual compressor stage discharge temperature will be 450- by the same manor from the thermal behavior of electric conductivity of coal, as 500°F vs. the conventional 8-stage 200°F, allowing for cost effective heat recovery of 447°C, (cf. Gieseler s 444°C). 80% of the input Btu. The all-in capital cost is expected to be 1/3 of the conventional This paper will present details of the instrumentation, and discuss its potentiality in the approaches. Ramgen will present an update on its technical and commercial status. coal science with data of other Argonne Premium Coal Samples, comparing with Gieselers. 29-2 A Comparison of In-Line and Integrally-Geared Centrifugal CO2 28-4 Compressors The Definitions of Catalytic Index of Ash Component of Coking Coal and Kevin W. Kisor, MAN TURBO Inc., USA their Interrelations Shizhuang Shi, Cheng Zhang, Feng Shi, Wei Xu, Hui Wang, Wuhan University For gasification plants with carbon-capture capability, one of the problems that must of Science and Technology; Xinhong Lei, Coking Co. Ltd, Wuhan Iron and Steel be solved is how to compress the CO2 after it has been separated from the syngas Group Corporation, CHINA stream. Because the volume of gas is so large, a centrifugal compressor is the most realistic solution for that task. In order to comprehensively estimate the influence of ash component of coking coal on Whether injected into the aquifer or transported via pipeline to an enhanced oil catalysis of carbon solution loss reaction of coke, various catalytic indexes were recovery location, the CO2 must be compressed from approximately atmospheric defined and named by different researchers. The number of ash components used in the pressure at the separation unit up to pressures in the range of 2,000 – 3,000 psi. definition range from 4 to 10. In order to study the correlation among the various Traditional in-line centrifugal compressors could be used, and have a long history of definitions, firstly the ash component data of about 100 primary coking coals of China reliability in critical process and oilfiled services. Integrally-geared centrifugals have a were determined; and the catalytic indexes of each coal according to various lower capital cost and require less power, but have fewer references in this high definitions were calculated. Then the regression analyses between them were carried pressure range. Our presentation would describe the basic differences between the two out. The results show that there are very good correlativity between some catalytic compressor types in terms of design philosophy, construction details, and comparative indexes, for example, the correlation coefficient between the mineral catalytic index performance. We would finish with a case history of the CO2 pipeline compressors in MCIb of Baosteel Co. and Yang’s mineral catalytic index MCIy is 0.9996, the mineral operation at Dakota Gas Company in North Dakota. 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.

27 29-3 variable. Besides being affected by pressure variations and presence of cracks/ cleats, CO2 Sequestration in Unminable Coal Seams: Characterization, Modeling, permeability was strongly dependant on the CO2 exposure time. Coal “swelling” due to Assessment and Testing of Sinks in Central Appalachia the carbon dioxide sorption caused, at times, dramatic drops in permeability Michael Karmis, Nino Ripepi, I. Miskovic, Virginia Tech; J. Matthew Conrad, (sometimes by an order of magnitude). Often, the effects of carbon dioxide sorption Michael J. Miller, Chris Shea, Marshall Miller & Associates, Inc., USA were almost immediate; it would happen before the first carbon exposure test was completed. Over the time period of several days, permeability would sometimes This paper describes the work of the Central Appalachian Coal Seam Sequestration decrease by another order of magnitude. This phenomenon can significantly slow group of the Southeast Regional Carbon Sequestration Partnership (SECARB) on the down penetration of CO2 to the final sequestration target (coal matrix) and, thus, would characterization, modeling, assessment and testing of unminable coal seams in Central strongly affect the sequestration rates. 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 SESSION 30 Energy. SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL – 5 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 30-1 methane reserves by as much as 2.5 trillion cubic feet (Tcf). Since some of the Central Coal to Liquids vs. CO2 Management Appalachian coalbed methane fields are approaching maturity, CO2-enhanced coalbed Qingyun Sun, Jerald J. Fletcher, West Virginia University, USA methane recovery has the potential to add significant recoverable reserves and extend the life of these fields. High crude oil prices have again resulted in significant interest in coal-to-liquids (CTL) Based on geologic characterization results, a carbon dioxide injection site was selected technologies as an alternative source for liquid fuels in the US. While some concerns in Russell County, Virginia, where an existing CBM well was donated by CNX Gas. related to the technical feasibility and economical viability of CTL remain, CO2 Prior to injecting carbon dioxide, two monitor wells will be drilled in close proximity management has become a significant constraint to potential development. Current to the injection well to procure important geologic and engineering parameters CTL processes generate significant amounts of CO2. The ability to manage CO2 required for reservoir modeling. Core hole testing will include a thorough suite of emissions is expected to directly impact the financial and business decisions of geophysical logs, gas desorption tests, adsorption isotherms (carbon dioxide, methane investors and developers. and nitrogen), and petrographic analyses. As part of the field test, 1,000 tons of CO2 This paper discusses the quantity and quality of the CO2 generated during the will be injected into the CBM well in order to evaluate the ability of coal seams to liquefaction process and explores alternative CO2 management options for CTL sequester and adsorb CO2. projects. The CO2 streams generated by direct and indirect coal liquefaction This paper presents an overview of the characterization, modeling and assessment of technologies are compared both qualitatively and quantitatively. This assessment and the region and provides an update on testing protocols and procedures to further assure the related discussion will proved a better understanding of CO2 constraints and the success of coal seam sequestration with ECBM recovery in Central Appalachia. possible solutions relevant to future CTL development.

29-4 30-2 Profile of Mineral Characteristics for Geological Seals at Field Performance, Economics, and Greenhouse Gas Emissions from Coal and Demonstration Sites for Carbon Dioxide Sequestration in Saline Aquifers Biomass Synthetic Fuel Production Craig Griffith, Yee Soong, Sheila Hedges, DOE-NETL; Gregory Lowry, David Thomas J. Tarka, DOE-NETL; David Gray, Charles White, Noblis, Inc., USA Dzombak, Carnegie Mellon University, USA Record high oil prices and increasing concerns about energy security have prompted a In 2003, the U.S. Department of Energy initiated regional partnership programs to test renewed interest in the production of transportation fuels from alternative or promising carbon sequestration technologies and enable large scale implementation of unconventional sources. The fuels vary, as do their feedstocks, with consideration CO2 sequestration. Five of the seven partnerships are planning site demonstrations for being given to everything from hydrogen to cellulosic ethanol and natural gas-based CO2 sequestration in deep saline aquifers. A mineralogical profile of the seals liquids. Numerous studies are currently underway evaluating the economics, scale, overlying the target porous rock storage units across seven of the nine sites was and energy conversion efficiency of producing these fuels. Furthermore, the growing generated to identify minerals of interest with rock-brine-CO2 interactions that would awareness of global climate change has intensified the need for any fuel under be relevant in assessing seal integrity. The most abundant minerals present in these consideration to have life-cycle greenhouse gas (GHG) emissions which either match seal rocks, as reported in literature, include: Quartz, illite, dolomite, calcite, and or are reduced when compared to conventional petroleum fuels. glauconite along with significant levels of organic carbon. The types of formations in One potential pathway is the production of diesel fuel and naptha from coal and which these minerals occur, and their relative abundance will be discussed. In biomass. This pathway enables the use of a renewable, low-carbon fuel with an addition, initial studies of the extent and rate of reactivity of selected minerals with existing technology for liquid fuels production. The process looks economically CO2-saturated brine solutions under sequestration conditions will be described. attractive given the availability and cost of coal (as compared to oil) but has the drawback of increased GHG emissions compared to petroleum. 29-5 The National Energy Technology Laboratory (NETL) initiated a study in 2007 to Comparative Study of Bituminous and Lignite Coals in Application to CO2 better explore the potential for the production of these “unconventional” liquids, with Sequestration the goal of understanding the trade-offs between fuel cost, GHG footprint, and scale Igor V. Haljasmaa, Robert McLendon, Sinisha A. Jikich, Hema Siriwardane, Yee achievable. Over 16 different scenarios were examined, including the use of different Soong, Gino Irdi, DOE-NETL; Anastasia Dobroskok, EERC, University of plant configurations, various coal and biomass types, a representative selection of North Dakota, USA 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 Unmineable coal seams have been proposed for carbon dioxide sequestration. In order study. 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 30-3 permeability and the sorption capacity of the coal seam. In addition, if there are Fischer-Tropsch Fuels from Coal and Biomass interactions between the coal seam and the carbon dioxide, an estimate of the time Eric D. Larson, Guangjian Liu, Robert H. Williams, Thomas G. Kreutz, constant for such interactions is essential. Princeton University, USA Formation permeability is most accurately determined by well testing. Fluid flow through coal seams is primarily Darcy type flow through fractures, cleats, etc. We present results of detailed process design, simulation, and cost analysis of facilities However, carbon dioxide transport into the bulk of the coal matrix (to enable sorption) producing Fischer-Tropsch Liquid (FTL) fuels from biomass and coal, with capture is best determined in specialized equipment in controlled conditions in a laboratory and deep underground storage of by-product CO2. Biomass and coal are co-gasified in setting. The National Energy Technology Lab (NETL) has such equipment. A an oxygen-blown dry-feed entrained flow reactor, and following gas cleaning and modified Autolab 1500 unit (New England Research, Inc.) for handling very low conditioning, the resulting synthesis gas is fed to an iron-catalyzed FT reactor where it permeability cores and a CT scanner for measuring sorption rates of carbon dioxide in is converted into a raw “syncrude” that is refined to finished transportation fuels, coal cores were used to test bituminous and lignite cores. primarily diesel and gasoline substitutes. We present results for four process Times for sorption were determined at different confining and pore pressures. Profiles configurations, each with a different percentage of biomass in the biomass-plus-coal of sorption gradients were determined. Qualitatively, over certain range of confining feedstock. The percentage ranges from 0 to 100. We report energy and carbon and pore pressures, the sorption process in coal cores may require days to approach balances for each configuration, along with levelized FTL production costs as a equilibrium. Comparisons were made to powder studies for sorption isotherms function of assumed cost of carbon emissions. With the percentage of biomass in the (Langmuir or BET type 1). Measurements of permeability in coal cores were highly input feedstock equal to zero, there are net positive lifecycle carbon emissions 28 associated with the FTL product. With the biomass percentage at 100, there are net 31-3 negative lifecycle carbon emissions. An Improved Thermodynamic Factsage Simulation to Simulate Mineral Matter Transformation During a Fixed Bed Counter-Current Gasification 30-4 Process, Validated with Ht-Xrd Effect of Gasification Conditions on Fischer-Tropsch Liquid and Power JC van Dyk, Sasol Technology; Frans Waanders, North-West University, Production SOUTH AFRICA S. Srinivas, Anil Khadse, Preeti Aghalayam, Ranjan K. Malik, Sanjay M. Mahajani, IIT Bombay, INDIA 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 It is well-known that syngas composition from a gasification reactor depends on the during a fixed bed counter-current gasification process. It was concluded that the operating conditions and the feed stock. The aim is to compare the overall performance FactSage model developed, compared with HT-XRD experimental results and that the of a flowsheet consisting of the following blocks - a gasifier, an FT reactor and a FactSage thermodynamic modeling supplies insight into specific mineral reactions and power generator. Simulations are performed in Aspen Plus for a given set of operating slag formation. The specific value for Sasol in using FactSage, in combination with conditions (pressure and temperature) in different gasifiers and at different FT reactor HT-XRD is that it can be used to analyze equilibrium conditions for reactions temperatures by considering liquid yield from the FT process, power generation occurring between inorganic and organic materials together, as well as to provide potential from the reactor tail-gas and steam generation capability from the exothermic insight into mineral transformation and slag formation. The purpose of the present heat of the FT reactor. A simple equilibrium model is used to predict the syngas study was to improve the current FactSage modeling approach, by combining specific composition from different gasifiers. A detailed kinetic model reported in literature is zones in the gasification process. This can improve and speed-up the interpretation of used for the FT reactor simulations. The analysis of these simulation results and mineral matter transformations and flow properties of reacted mineral matter in coal observed trend between gasifier operating features and FT liquid yields/power and assist in identifying and quantifying slag formation in the gasifier operation at production is reported. 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 SESSION 31 indicated that feldspar formation (including anorthite) correlated with slag formation at GASIFICATION TECHNOLOGIES: FUNDAMENTALS – 3 temperatures around 1000°C 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 31-1 forms probably as a product between the SiO2, Al2O3 and Ca-containing species. In the A Simplified Phase Equilibrium Algorithm Used to Predict Ash/Slag gasification zone it was clear that slag-liquid formed at a temperature of 1000°C, with Behaviors in Slagging Gasifiers/Combustors a decrease in the feldspar content. Mullite formation was also observed in the base case Bing Liu, Humberto E. Garcia, Idaho National Laboratory; Larry L. Baxter, sample in the temperature range 1000°C and 1100°C. The decrease in the amount of Brigham Young University, USA SiO2 at 1100°C is related to the formation of mullite, but also that the slag-liquid phase also contains an amount of SiO2 in the molten form. 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 31-4 to serious ash deposition, which may lead to abnormal shutdown of the process; at Effect of Mineral Transformation on the Surface Tension, Viscosity, and sufficiently high temperatures, slag will dissolve refractory liners, possibly resulting in Size Fraction of Char Particles material corrosion problems. Knowledge of ash/slag phase equilibrium is needed to LaTosha Gibson, Narasimhan Soundarrajan, Sarma V. Pisupati, The keep normal operation of gasification processes and to estimate and possibly prolong Pennsylvania State University; Lawrence J. Shadle, DOE-NETL, USA 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 Controlling ash deposition and handling slag disposal in an entrained flow gasifier is a composition and the solubility of the refractory in slag at typical operating general concern. Excessive Ash/char deposition in the convective section is an issue temperatures. Melting points of several binary and ternary systems are used to test and since it can lead to unplanned shutdowns until the deposits are cleared. Excess amount verify the correctness and efficiency of the proposed algorithm. A CaO-Al2O3-SiO2 of char captured in the slag can render the slag useless for the cement industry. ternary system is used as an example to explore the solubility of Al2O3- and Cr2O3- Therefore, the behavior of coal must be analyzed from the stage of injection to its final based refractory materials. This algorithm has proven to be computationally efficient form (fly ash, component of slag, or bottom ash). To characterize this behavior of coal and can be used to predict ash/slag-related behaviors, such as ash melting points and within the entrained flow gasifier, the Discrete Phase Model will be used. The Discrete refractory corrosion rates in slagging gasifiers. 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 31-2 phase particles. As a requirement of the Discrete Phase Model, the boundary An Empirical Viscosity Model for Coal Slags conditions for the particle phase must be characterized through the coefficient of Josef Matyas, Scott Cooley, S.K. Sundaram, Carmen Rodriquez, Autumn restitution. The coefficient of restitution (COR) is defined as the ratio of the Edmondson, Benjamin Arrigoni, Pacific Northwest National Laboratory, USA rebounding velocity to the impacting velocity. However, in literature describing ash and particulate behavior, the impacting velocity is also known as the deposition Slags of low viscosity readily penetrate the refractory lining in slagging gasifiers, velocity. For an entrained flow gasifier, boundary conditions for the COR would have causing rapid and severe corrosion through spalling. In addition, a low-viscosity slag to be established for the refractory wall of a gasifier as well as the developing slag. that flows down the gasifier wall forms a relatively thin layer of slag on the refractory Through an extensive literature review of particle wall collision models, the surface surface, allowing the corrosive gases in the gasifier to participate in the chemical tension was found to be a main component that determines whether a particle adheres reactions between the refractory and the slag. In contrast, a slag viscosity of <25 Pa·s at or rebounds for a wall or substrate. The surface tension has often been used to 1400°C is necessary to minimize the possibility of plugging the slag tap. There is a determine the force of adhesion in particle-wall collision models. Once the surface need to predict and optimize slag viscosity so slagging gasifiers can operate tension, particle size fraction, and density of a particle are known, a force of energy continuously at temperatures ranging from 1300 to 1650°C. The approach adopted in balance is prescribed in determining the deposition velocity prior to impact. Surface this work was to statistically design and prepare simulated slags, measure the viscosity tension models developed by Hanoa and Tanaka on the basis of the Butler’s equation as a function of temperature under reducing conditions, and develop a model to predict for binary solutions could prove useful-if the molar fractions of the mineral slag viscosity based on slag composition and temperature. Statistical design software composition of the slag (and char particles) are known. was used to select compositions from a candidate set of all possible vertices that will The main challenge in employing this surface tension model and any one particle wall optimally represent the composition space for 10 main components. A total of 21 slag collision model (that includes the force of adhesion) within the entrained flow gasifier compositions were generated, including 5 actual coal slag compositions. The Arrhenius is the mineral transformation of the parent coal. Issues in quantitatively characterizing equation was applied to measured viscosity versus temperature data of 17 slags, and mineral transformations include describing surface reactions inclusive of mineral the Arrhenius coefficients (A and B in ln(vis) = A + B/T) were expressed as linear distribution at the surface, differentiating the behavior between extraneous and functions of the slag composition. The viscosity model was validated using 1) data inherent minerals, and incorporating the effects of the reducing environment in the splitting approach, and 2) viscosity/temperature data measured at Pacific Northwest gasifier on the transformation of minerals. Determining the reactions at the surface National Laboratory for four selected slag compositions from the literature. 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 29 carbon dioxide can lead to more reactive components for the mineral matter. Aside sharp decrease of the surface area of the char particle was a mark of char-slag from mineral reactions agglomeration, fragmentation, and coalescence also play a role. transition. The morphological change revealed by scanning electron microscope agreed Because the magnitude of forces determining the deposition velocity is dependent on well with this surface area change. Qualitative comparison with several pore models the particle size and gravity, these factors must also be addressed. This paper will showed that ash fusion effect should be considered for describing the porous structure discuss a method to determine an approximation for the surface tension, viscosity, and evolution during late stage of gasification at elevated temperatures. resulting size fraction over the expected residence time in an entrained flow gasifier. Agglomeration, fragmentation, and coalescence will also be discussed.

31-5 SESSION 32 High Temperature X-ray Diffraction Studies for Various Coal Sources in UNDERGROUND COAL GASIFICATION – 3 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 32-1 An NGO Perspective on Underground Coal Gasification Coal is generally accepted to be a heterogeneous resource where coal properties can Mike Fowler, Kurt Waltzer, Clean Air Task Force, USA vary extensively between geological sites or within a mine. Therefore detail coal characteristics are essential to predict the gasification performance of a particular coal. Recent studies suggests that underground coal gasification (UCG) with carbon capture Mineral matter transformations in coal with temperature and slag formation are and storage (CCS) may be able to provide low-carbon electricity at a cost comparable specific properties of a coal source that determine its suitability for combustion or to that for existing coal technologies without CCS, and therefore may be able to play a gasification processes, where ash flow temperature (AFT) is a parameter that meaningful role in reducing global greenhouse gas emissions. Recent studies also specifically gives information in this regard. suggest that environmental impacts of UCG, especially groundwater contamination, High temperature X-ray diffraction (HT-XRD) analysis for coal provides information can be reduced or eliminated by proper site selection, operational controls, and proper about mineral matter transformation in coal with temperature. HT-XRD can be used to site closure. A rational approach to deploying this potentially game-changing analyze reactions occurring between inorganic and organic matter in coal, as well as technology would include both early commercial characterization burns, co-located provide insight into mineral transformations and slag formation. This can improve the carbon dioxide capture and injection tests, and thorough real-time groundwater interpretation of flow properties of the reacted mineral matter in coal and assist in monitoring. An NGO perspective on these issues is advanced, and potential trade-offs identifying and quantifying slag formation in gasifier operation at temperatures not for UCG commercialization are discussed in the context of sound environmental reflected by normal AFT analysis. stewardship principals. In order to study mineral matter transformations in coal from various locations by HT- XRD, five non South-African, northern hemisphere coal samples with known detailed 32-2 characteristics and variability in properties, were selected for the present study. TEXYN’s “Santa Barbara” Mining System Detailed room temperature X-ray diffraction (RT-XRD) analysis revealed that the Tom Tillman, TEXYN, USA predominant phases present in original coal samples were quartz, kaolinite and muscovite, in various proportions. For calcium bearing minerals, in most cases calcite TEXYN is developing a new technology that will create low-cost hydrogen products but also dolomite were identified. Pyrite and siderite were present for iron bearing from ultra-deep coal, using a combined drilling/gasification method. The hardware is minerals. Traces of rutile, anatase, brushite and albite were also observed. an underground coal gasifier. We will turn the gasifier concept inside out, and then HT-XRD showed that decomposition of the minerals occurred according to expected bring the gasifier to the coal. The result is the lowest-cost path to industrial-scale routes. It was observed that the temperature sensitive pyrite decomposed first at 500- hydrogen production and to carbon-free electricity. The defining characteristics are 600°C, followed by kaolinite at 650-750°C and calcite at 750-850°C. Temperature (1) simplicity, (2) low capital costs, and (3) the most benign environmental profile resistant quartz, albite and anatase decomposed at much higher temperatures between of any fossil fuel. 1100-1450°C. TEXYN’s Technology It is commonly accepted that kaolinite decomposes to the intermediate amorphous TEXYN has developed two processes that complement each other: 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 1150-1500°C. 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 1200-1350°C. 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 1300-1450°C. Minerals which were formed in the samples in the intermediate temperature range were anhydrite and hematite. Anhydrite occurred in various samples between 400-1250°C probably as a result of decomposition of pyrite and calcite. Hematite was formed in number of samples in temperature range of 500-1350°C from decomposition of iron bearing minerals. In one sample traces of lime were observed between 800-1200°C. 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 The first process is a deep, electrically powered, underground coal gasifier that creates under atmospheric pressure. Coal particles were fed into the reactor for devolatilization its own steam and oxygen at the point of the reaction. This method provides at least a by a pure nitrogen flow or gasification by a premixed nitrogen-air flow under various 10X increase in reaction temperature, pressure, depth, flow-rate, cleanliness, etc, as heating temperatures. Specific carbon conversions were achieved by varying the compared to current Underground Coal Gasification (UCG) methods. residence time of coal particles in the reactor. Devolatilized and oxidized char particles Our target fuel source is an indigenous, “stranded”, and ubiquitous resource, which is were collected by a cyclone and a filter for further analysis. The carbon content and the beyond the physical reach of other extraction technologies. The zones in yellow and corresponding carbon conversion were determined by the loss-on-ignition test. The turquoise, in the map at left, indicate the location of such deep coal deposits. specific surface area and pore size distribution of the particles were determined by gas The gasification process works by deploying the tool into a horizontal bore in an adsorption analysis. The morphological changes of the particles were observed with a extremely deep (3000 to 8000 ft) coal seam. Water is injected at the surface in an scanning electron microscope. injection well. Power is provided by a high-voltage umbilical to the tool. The tool These analyses provide information concerning the influence of reaction temperature creates its own steam from the injected water. Much of this steam is reduced to on the char-slag transition of the coal particles during the gasification process. The oxygen and hydrogen by the extreme conditions created in the tool. Steam and oxygen 30 react with the coal to produce carbon monoxide and more hydrogen. The high- less expensive and easier option to determine UCG process performance at any given pressure product gasses are collected at a distant production well, for subsequent time. surface processing. The second process is a method to create and capture CO2 waste in the most 32-5 economical manner. This is a highly streamlined process as compared to the status Estimation of Chemical Reaction Occurred in Underground Coal quo. In order to achieve near-total CO2 capture, the method requires that the energy Gasification carrier be limited to hydrogen gas. However, that is not a negative, considering the Sohei Shimada, The University of Tokyo; Mamoru Kaiho, Osamu Yamada, low expected cost is projected for the hydrogen. AGR systems and gas compressors National Institute of Advanced Industrial Science and Technology, JAPAN are eliminated from the process. Energy Products National Institute of Advanced Industrial Science and Technology (AIST) has METRICS OVERVIEW ($/mmBTU) developed a method to determine the coefficients α to η in the chemical equation coal TEXYN-based Status-Quo gasification, CHmOn+αO2+ βH2O -> γH2+δCO+εCO2+ηCH4, based on the results of Technology Gasification ultimate analysis of coal and chemical analysis of gas composition (H2O and N2 free), Coal Cost $0.01 ~$0.50 - $2.00 in order to evaluate the process of reaction of actual coal gasification process. Gasification Cost ~$1.30 ~$2 - $3 Since the numerical expressions used to calculate α to η were derived based on the stoichiometry of the chemical equation without any arbitrary assumption and Raw Syngas Cost ~$1.30 ~$3 - $5 approximation, the method is thought to be applicable to the estimation of reactions of Hydrogen Cost ~$2 - $2.50 underground coal gasification (UCG). In the published results of gas composition The intermediate (well-head) product is a synthesis gas, is projected at ~$1.30 per produced by UCG, however, very few cases was found that comprised the data of mmBTU. This compares favorably to the cost of raw coal, delivered at approximately ultimate analysis of coal. 1 $1.80 , and to the cost of raw synthesis gas from a traditional surface gasifier at $3 to The result of UCG carried out in Fushin coal mine in China was investigated. Gasifier $5. The capital-burdened cost of hydrogen is projected at less than $2.50 per mmBTU. was constructed utilizing mining gallery and air was used as a gasifying agent. An important byproduct is 98% enriched carbon dioxide (CO2), used for Enhanced Oil Chemical equation was determined using the method above mentioned. Since the value Recovery (EOR) operations in underserved oil fields known to require vast amounts of of α in the formula and the amount of oxygen reacted were relatively small and β, CO2. The TEXYN process is not just “Carbon Capture Ready”; rather, it was set up amount of water reacted, was estimated to be positive, gasification reaction was expressly for the immediate low-tech capture of carbon at high pressure, for ultimate concluded to proceed in favorable conditions. Water may be decomposed by the sequestration. CO2 recovery is projected at greater than 99%. 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 1 http://www.netl.doe.gov/energy- ground water or moisture in coal seam. Chemical equation of UCG was compared with analyses/pubs/Bituminous%20Baseline_Final%20Report.pdf that of conventional fixed bed gasifier and characteristic of UCG gasification process was discussed. 32-3 Geomechanical Simulations Related to UCG Activities 32-6 Joseph Morris, Oleg Vorobiev, Tarabay Antoun, S. Julio Friedmann, Lawrence Development of a UCG Based Project in Canada Livermore National Laboratory, USA Simone Maev, Laurus Energy Inc., CANADA

This paper will present results from a recent investigation into a range of Underground Coal Gasification technology is getting significant attention around the geomechanical processes induced by UCG activities. The mechanical response of the globe as a new mining method to extract energy of stranded coal where other methods coal and host rockmass plays a role in every stage of UCG operations. For example, are not applicable. Laurus Energy is an exclusive Canadian licensee of the Exergy cavity collapse during the burn has significant effect upon the rate of the burn itself. In UCG. UCG technology provided by Ergo Exergy Technolgies Inc. from Montreal, the vicinity of the cavity, collapse and fracturing may result in enhanced hydraulic Canada. The UCG technology is being successfully applied in a number of conductivity of the rock matrix above the burn chamber. Even far from the cavity, commercial UCG projects around the world. Laurus Energy is developing its first stresses due to subsidence may be sufficient to induce new fractures linking previously commercial project based on UCG technology in North America. The project is isolated aquifers. These mechanical processes are key in understanding the risk of targeting power generation and supply of fuel and hydrogen for the local industrial unacceptable subsidence and the potential for groundwater contamination. These markets. mechanical processes are inherently non-linear, involving significant inelastic Laurus Energy has large coal holdings in Alberta, Canada and started execution of its response, especially in the region closest to the cavity. In addition, the response of the first Tomahawk I project development program, including regulatory and rock mass involves both continuum and discrete mechanical behavior. environmental approvals, Site Selection and Pre-Feasibilty and Site Characterization To better understand these effects, we have applied a suite of highly non-linear program. 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 SESSION 33 treatment for rock failure. Finally, we will present results of mechanical simulations ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY covering the range of a single burn up to multiple modules in a range of geologic CAPTURE, CARBON, NOx settings. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. 33-1 Understanding the Binding Mechanism of Mercury on Activated Carbon 32-4 Bihter Padak, Jennifer Wilcox, Stanford University, USA Compartment Modeling for Underground Coal Gasification Cavity Preeti Aghalayam, D. Sateesh, Ramesh Naidu, Sanjay Mahajani, Anuradda Coal combustion power plants constitute a significant amount of mercury released into Ganesh, IIT Bombay; R.K. Sapru, R.K. Sharma, UCG Group, IRS, INDIA the atmosphere. Oxidized mercury is captured by wet scrubbers, while gaseous elemental mercury passes through the scrubbers readily. Particulate matter such as fly Underground coal gasification (UCG) is the in-situ gasification process carried on in ash, unburned carbon and activated carbon can be used to capture elemental and un-mineable coal seams using injection and production wells drilled from the surface, oxidized mercury through adsorption processes. Activated carbon is currently used in which enables the coal to be converted into combustible gas. UCG process may many power plants effectively. Understanding the mechanism that mercury adsorbs on provide a secure energy supply and reduce green house gas emissions and is capable of activated carbon is crucial to develop better capture technologies for mercury. In this producing commercial quantities of gas to be used as a chemical feedstock or as fuel study we examine the possible binding mechanism of mercury on activated carbon, for power generation. As gasification proceeds, an underground cavity is formed. The performing ab initio energetics calculations using Gaussian03. Activated carbon volume of the cavity increases progressively with coal spalling from the roof and surface is modeled by a single graphene layer in which the edge atoms on the upper getting consumed. As underground coal gasification cavities are of irregular three- side are unsaturated in order to simulate the active sites. In some cases, chlorine atoms dimensional shapes, computational fluid dynamics studies (CFD) are essential in order are placed at the edge sites to see the effect of chlorine on mercury binding and to understand the complex flow patterns involved. The characterization of the non- investigate a possible surface reaction between mercury and chlorine. ideal 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 31 33-2 The results obtained in this study suggest that the presence of water, NO and HCl in Mercury Emission Control with Gas-Phase Brominated PAC Sorbents the flue gas facilitate oxidation of elemental mercury but their presence also leads to a Qunhui (Emma) Zhou, Sid Nelson Jr., Ron Landreth, Jon Miller, Arlen Overholt, decrease in the mercury uptake capacity. The presence of SO2 leads to a significant Xin Liu, Tang Zhong, Yinzhi Zhang, Sorbent Technologies Corporation; Lynn decrease in mercury uptake by the activated carbon sorbent. Increase in temperature Brickett, DOE-NETL, USA 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 B-PAC™, C-PAC™, and H-PAC™ compose the family of gas-phase brominated gases for optimal mercury removal by carbonaceous materials. powdered activated carbon sorbents specially developed for reducing mercury from flue gas of power plants with standard configurations, plants selling fly ash for 33-5 concrete use, and plants having hot-side electrostatic precipitators, respectively. This Effects of Hcl and SO2 Concentration on Mercury Removal by Activated series of sorbents has been proven cost-effective for mercury emission control at more Carbon Sorbents in Coal Derived Flue Gas than twenty coal power plant units and industrial boilers that burn different types of Ryota Ochiai, Md. Azhar Uddin, Eiji Sasaoka, Okayama University, JAPAN; coals and that are configured with different pollution control devices. For example, an Shengji Wu, Hangzhou Dianzi University, CHINA average of 91% of gas phase mercury was removed with 3 lbs/MMacf of B-PAC™ for 30-days at the Detroit Edison’s St. Clair power station, which burns a blend of In this study, the effect of presence of HCl and SO2 in the simulated coal combustion bituminous coal and subbituminous coal and has a cold-side ESP. Injecting 4.6 flue gas on the Hg0 removal by a commercial activated carbon (coconut shell AC) was lbs/MMacf of C-PAC™ upstream of a very small cold-side ESP (112 m2/kacf SCA) investigated in a laboratory scale fixed bed reactor in temperature range of 80 to achieved 81% of average mercury removal during a one-month full-scale tested trial at 200°C. The characteristics (thermal stability) of the mercury species formed on the the Midwest Generation Crawford Unit 7 and allowed the fly ash containing the C- sorbents under various adsorption conditions were investigated by temperature PAC™ to continue to be used in concrete as the substitute for cement. programmed decomposition desorption (TPDD) technique. It was found that the This paper will (1) briefly introduce the data from the full-scale mercury trials which presence of HCl and SO2 in the flue gas affected the mercury removal efficiency of the injected B-PAC™, C-PAC™, and H-PAC™ sorbents in flue gas of power plants, (2) sorbents as well as the characteristics of the mercury adsorption species. The mercury compare the efficiency of B-PAC™ family with that of other sorbents in comparative removal rate of AC increased with HCl concentration in the flue gas. In the presence of 0 0 trials, (3) discuss how the properties such as bromine species, particle size, and pore HCl and absence of SO2 during Hg adsorption by AC, a single Hg desorption peak at structure of these activated carbon-based sorbents influence mercury capture, and (4) around 300°C was observed in the TPDD spectra and intensity of this peak increased discuss how to optimize sorbent use to comply with strict mercury reduction with HCl concentration during mercury adsorption. The peak at around 300°C may be regulations. derived from the decomposition and desorption of mercury chloride species. The presence of SO2 during mercury adsorption had an adverse effect on the mercury 33-3 removal by AC in the presence of HCl. In the presence of both SO2 and HCl during Temperature Programmed Decomposition Desorption of Mercury Species Hg0 adsorption by AC, the major TPDD peaks temperatures changed drastically 0 over Activated Carbon Sorbents for Mercury Removal from Coal Derived depending on the concentration of HCl and SO2 in flue gas during Hg adsorption. Fuel Gas Md. Azhar Uddin, Masaki Ozaki, Eiji Sasaoka, Okayama University, JAPAN; 33-6 Shengji Wu, Hangzhou Dianzi University, CHINA Optimization of Scr System at Cayuga Unit 1 Carlos Romero, Zheng Yao, Fengqi Si, Eugenio Schuster, Lehigh University; Mercury (Hg0) removal process for coal derived fuel gas in the IGCC process will be Robert Morey, Jacob Peter, AES Cayuga, LLC; Barry N. Liebowitz, New York one of the important issues for the development of a clean and highly efficient coal State Energy Research and Development Authority, USA 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 AES Cayuga Unit 1 is a 160 MW unit, equipped with a low-NOx firing system and an the main impurity compounds in coal derived fuel gas, therefore H2S injection is not anhydrous ammonia (NH3), Selective Catalytic Reduction (SCR) system for NOx necessary in this system. HCl is also another impurity in coal derived fuel gas. In this emissions control. A combined boiler/SCR/air preheater (APH) optimization was study, the contribution of HCl to the mercury removal from coal derived fuel gas by a performed to minimize the cost of NOx emissions control. Boiler and low-NOx system commercial activated carbon (AC) was studied using a temperature programmed control settings, and SCR and air preheater (APH) operating conditions were included decomposition desorption (TPDD) technique. TPDD technique was applied to in a parametric test program. Information from a Breen Energy Solutions ammonium understand the decomposition character of the mercury species on the sorbents. The bisulfate (ABS) probe was also included for monitoring of ABS formation in real-time Hg0 removal experiments were carried out in a laboratory-scale fixed-bed reactor at and as a constraint to the SCR optimization. The parametric test data were used as the 80-300°C using a simulated fuel gas. The following results were obtained from this basis for the optimization that consisted of an approach that incorporates accurate on- study: 1) HCl contributed to the mercury removal from the coal derived fuel gas by the line support vector regression (AOSVR) modeling for adaptive learning, and genetic AC; 2) H2S suppressed the mercury removal with HCl by the AC; 3) The stability of algorithms for implementation of the multi-objective optimization. The results indicate the mercury surface species formed on the AC in the presence of H2S was different that optimal operating conditions can be achieved for a coordinated boiler/SCR/APH from that in the absence of H2S. operation, and minimal NH3 consumption, maximum SCR performance, and optimal net unit heat rate, subject to minimal impact on fly ash unburned carbon content, 33-4 mitigated ABS formation, and other operational and environmental constraints. The Impact of Acid Gases and Temperature on Mercury Oxidation and Uptake optimal conditions resulted in reduced NH3 usage of the order of 25 percent, with Catalyzed by Activated Carbon Surface improved APH fouling management. 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 SESSION 34 oxidation and uptake by novel carbon-based sorbent was evaluated. Carbonaceous COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES – 4 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 34-1 observed. However, the presence of carbon surface led to a significant (above 50%) Potential Respirable Quartz and Silica Dust Sources in Underground Coal increase in the oxidation of elemental mercury. The absence of water from the flue gas Mines Identified by Geochemical Analyses further increased mercury uptake capacity of the novel sorbent, but it also caused a Steven Schatzel, NIOSH, USA 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 Silicosis represents a significant health hazard to workers in US underground coal in the effluent gas for 24 hours. Absence of NO from the flue gas led to a significant mines. Prior research has suggested that the primary respirable silica dust source does decrease in the elemental mercury oxidation and faster breakthrough of mercury; not typically reside within the coal seam being mined. Mines which had a history of however an increase in the overall mercury uptake capacity was observed due to more high silica content in respirable dust samples (over 5% of the sample mass) were pronounced tailing effect. On the other hand, removal of NO2 led to no significant chosen for a new study which sought to identify the parent rock of respirable silica change in mercury uptake or in mercury oxidation. Removal of HCl reduced the dust material using geochemical methods. All of the coalbeds being mined at the study breakthrough time by a half, but it increased the overall mercury uptake capacity of the sites were found to have relatively low mineral matter contents. An experimental sorbent by nearly 70%. Moreover, removal of HCl also caused a significant decrease in methodology based on alkali and alkaline earth elemental concentrations in respirable elemental mercury oxidation. Upon increasing the fixed-bed temperature from 140°C dust samples was devised to distinguish mine roof from mine floor horizons in room to 240°C, an instant breakthrough of mercury was observed. Also, at 240°C, almost no and pillar mine sites. Some of the enrichment of these cation species in the roof units elemental mercury oxidation was observed, as compared to 50% oxidation at 140°C compared to immediate floor rock may be related to the percolation of fluids through under similar simulated flue gas condition. the overburden and the difficulty of fluids to migrate effectively through the coal or 32 coal precursor and into the floor units. It is recognized that in the application of these 34-4 techniques, some of the rock being characterized is removed as mined material and that New Achievements in the Field of Preventing the Spontaneous Combustions, the transportation of dust through the ventilation system is a complex process whereby Applied at the Level of the Pitcoal Mines in Jiu Valley – Romania all material is not conserved within a closed system. Aronel Matei, Ioel Veres, Adrian Zvanca, University of Petrosani; Lorand Toth, The calcium, magnesium, sodium and potassium concentrations from this study I.N.S.E.M.E.X. PETROSANI, ROMANIA 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 The coal is and will always be a main source of energy. The coal is integrated in the cassettes. Compositional comparisons between the silica in the respirable dust sample strategies that were conceived and implemented in the purpose of promoting the and the potential source rocks may indicate that modification during the mining development of sustainable energy in the CEE area and in the rest of world’s area. process may be responsible for the mineralogical proportions found in the respirable In our country, the field of energetic coal must function in the condition of dust fraction. The consequences of this process may be very pronounced in the silicate competitivity and reduction of the production costs. This thing was achieved by the mineral fraction. Quartz grains are denser and tend to form generally equant fragments reorganization and the modernization of the mining activity. The growth of the upon breakage where kaolinite and illite tend to form long or platy fragments and are extraction capacity at the viable mines was achieved by introducing the methods of of much lower density which could result in differing transport characteristics of the exploitation of high quality, such as the method of coal exploitation with undetermined mineral matter. The range of silicate mineral matter sources may not contribute sand bar. uniformly to the different particle size fractions. These findings may be significant This method amplifies some risk factors such as apparition of spontaneous since the potential severity of the silicosis risk to miners is strongly influenced by both combustions. the amount of quartz and the clay minerals in respirable dust. In order to reduce the risk factor that was mentioned above, after the study of the coal’s composition, the theories of the production of the spontaneous combustion and 34-2 the way to initiate the oxidation reaction, a series of substances were tested, substances Oxidative Decomposition of Formaldehyde to Carbon Dioxide and with an action of inhibitor during the process. Unlike the classical interpretation of Molecular Hydrogen Catalyzed by Bitunineous Coals prevention of the spontaneous combustions with the help of cold agents, the way of Haim Cohen, Uri Green, Ariel University Center at Samaria, ISRAEL 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 Self heating of large coal piles stored for long periods (1-6 months), due to diminution of the numbers of fires (spontaneous combustions) at the level of pit coal atmospheric oxidation (chemisorption\oxidation) raise a maintenance problem in the mines from Jiu Valley – Romania. storage sites near large power stations which use bitumineous coals as the fuel. Thus This work deals with the theoretical part and the laboratory experiments of the test of hot spots are formed resulting in reduction in calorific value of the coals and in the inhibitors in situ. extreme cases eruption of fires. The main gas released during the storage is carbon For the works that were done, as new ones, there were made documentations in order dioxide but also some carbon monoxide, low molecular weight organic molecules to obtain licenses. (C1-5) and water are produced. It has been established that moreover, bituminous coal exposed to mild oxidation conditions (temperature range 40-120°C in air atmosphere) 34-5 emit also molecular hydrogen as a side product. These reactions have been observed Molecular Hydrogen Formed via Low Temperature Oxidation of for a variety of bituminous coals worldwide. The amount of molecular hydrogen Bituminous Coals as the Source of Explosions in Underground Coal Mines formed (which is a reduction product) is surprisingly linear to the amount of oxygen Haim Cohen, Ariel University Center at Samaria, ISRAEL (oxidation reagent) consumed by the coal. It has been suggested that the low temperature oxidation produces some surface hydroperoxide groups which do oxidize Explosions in deep mines (or other confined spaces containing bituminous coals) are formaldehyde (which is also released by the self heating of the coal) to yield the usually attributed to methane gas concentrations above the LEL or accumulation of ustable cyclic intermediate dioxirane, CH2O2, which subsequently decomposes to fine coal dust which can undergo fast radical reactions. In order to avoid occurrence of molecular oxygen and carbon dioxide. The mechanism of reaction and the effect of such conditions in deep coal mines, methane detectors are installed and good water addition to inhibit molecular hydrogen production will be discussed in detail. ventilation is required. Coal piles stored for long periods at ambient temperatures might undergo autocatalytic 34-3 heating if the rate of heat dissipation from the pile is lower than the heat release due to Reconnaissance of Coal-Mine Fires in Perry County, Eastern Kentucky the chemisorption/oxidation of atmospheric oxygen inside the pores of the coal. Some James C. Hower, University of Kentucky Center for Applied Energy Research; (5-10%) of the reacting oxygen produces carbon dioxide but some carbon monoxide, Glenn B. Stracher, East Georgia College; John K. Hiett, Office of Mine Safety & low molecular weight organic molecules (C1-5) and water are also released. It has Licensing; Sarah M. Mardon, Kentucky Division of Water; Jennifer M.K. been established that bituminous coal exposed to mild oxidation conditions O’Keefe, Morehead State University; Paul A. Schroeder, University of Georgia; (temperature range 40-120°C in air atmosphere) emits also molecular hydrogen as a Donald R. Blake, University of California, Irvine; Stephen D. Emsbo-Mattingly, side product. These reactions have been observed for a variety of bituminous coals NewFields Environmental Forensics Practice, LLC, USA 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 Hundreds of underground and open pit coal-mine fires burning across the United States oxidative decomposition of formaldehyde groups with surface hydroperoxides and is are destroying a valuable natural resource while spewing noxious vapors and catalyzed by the coal surface. particulate matter into the atmosphere from gas vents and ground fissures, frequently Thus if there is an accumulation of hydrogen in a crack in the coal seam in a encrusted with the solid-by-products of combustion. These fires have destroyed faunal underground mine and the concentration increases to 4.1% (LEL in air) initiation of and floral habitats, poisoned and killed people, destroyed towns, metamorphosed and explosion by electrostatic charge or a spark is feasible. Indeed in the last decade melted rock adjacent to coal seams, and caused land subsidence. The fires usually several unexplained explosions have been reported in coal mines worldwide despite ignite by explosives and electrical work, the accidental ignition of methane and appropriate ventilation and no detection of methane had been observed. hydrogen during mining, surface fires, lightening strikes, and spontaneous combustion. We have checked if accumulation of hydrogen in a deep coal mine might reach the Numerous mine fires have been reported in the coalfields of Kentucky. During LEL of 4.1%. The results show that in extreme cases this is indeed the case and reconnaissance work in eastern Kentucky at the Ruth Mullins and Laura Campbell furthermore that during transportation of bituminous coal by sea hydrogen fires near Hazard, yellow-green smoke was observed to be billowing or continuously concentrations might reach levels of up to 10% in ship holds (which are also a exhaled from ground fissures and gas vents. In both cases, the fire is in abandoned confined space). underground and auger mines in the Pennsylvanian Breathitt Formation Hazard No. 7 These observations may indicate that molecular hydrogen accumulation in confined coalbed. Ignited by a forest fire in 2006, smoke from the Ruth Mullins fire, near the spaces might increase the risk to explosions and that appropriate measure should be town of Bulan, north of Hazard, was observed along the highwall in 2007. This fire is a taken in order to check this possibility. 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 385°C. 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.

33 35-3 SESSION 35 First U.S. Field Trial of Oxidation Technology for Coal Mine Ventilation GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND Air Methane UTILIZATION – 3 Deborah A. Kosmack, CONSOL Energy Inc.; Kenneth P. Zak, MEGTEC Systems, USA

35-1 CONSOL Energy Inc., in conjunction with MEGTEC Systems, Inc., the U.S. Application of Molecular Modeling for CO2 Sequestration in Coal Department of Energy, and the U.S. Environmental Protection Agency, designed, built, Tim Tambach, Frank van Bergen, TNO Built Environment and Geoscience, THE and operated a commercial-size thermal flow reversal reactor (TFRR) to evaluate its NETHERLANDS suitability to oxidize coal mine ventilation air methane (VAM). Coal mining, and particularly coal mine ventilation air, is a source of anthropogenic methane emissions, Underground storage of carbon dioxide (CO2) in deep coal beds is one of the options a greenhouse gas. The concentration of methane in the ventilation air is very small for reducing the CO2 emission to the atmosphere and the greenhouse effect. A (<1.5%) and flow rates can sometimes exceed 300,000 scfm for a single mine fan, so beneficial side effect of CO2 injection in the subsurface is the enhanced release of oxidation of this methane is difficult. This test program was conducted with simulated methane (CH4) which can then be produced as fuel. This technique is referred to as coal mine VAM in advance of deploying the technology on active coal mine CO2-enhanced coal bed methane (ECBM). The results of field and laboratory ventilation fans. The demonstration project team installed and operated a 30,000 scfm experiments are showing discrepancies with the current ideas on the interaction MEGTEC VOCSIDIZER oxidation system on an inactive coal mine in West Liberty, between CO2 and coal. Therefore, it is difficult to model these experiments with the WV. The performance of the unit was monitored and evaluated during months of present-day numerical reservoir models. The discrepancies can be partly attributed to unmanned operation at mostly constant conditions. The operating and maintenance the heterogenic character of coal and to the observed coal swelling, which both need history and how it impacts the implementation of the technology on mine fans will be further investigation. Additionally, the (Langmuir) adsorption model that is currently discussed. implemented in reservoir models is a clear simplification of the process, especially for Emission tests showed very low levels of all criteria pollutants at the stack. Parametric the supercritical CO2. For example, the (extended) Langmuir model implies sorption at studies showed that the equipment can successfully operate at the design specification a homogenous surface where preferential adsorption is solely determined by the partial limits. The results verified the ability of the TFRR to oxidize ≥95% of the low and pressures of the different gasses. variable concentration of methane in the ventilation air. For considering the effect of the heterogeneity of the coal surface we went down to the This technology provides new opportunities to reduce greenhouse gas emissions by the microscale level. Based on the literature we built a molecular model of coal using reduction of methane emissions from coal mine ventilation air. An economic Hyperchem (v7.51), which confirms the heterogeneity and complexity. We coupled the evaluation of the technology as applied to both methane oxidation and to energy software with our own in-house interface and computed the affinity of CO2 and CH4 recovery on a working coal mine will be discussed. A large commercial-size molecules for the coal surface. The idea is that the coal behaves as a solid phase with installation (180,000 scfm) on a single typical mine ventilation bleeder fan would the CO2 and CH4 molecules moving around it. The results show that the molecules can reduce methane emissions by 14,200 to 23,700 short ton per year (the equivalent of either be in the ‘free’ gas phase or adsorbed to the coal. One can understand that this 236,000 to 394,000 metric tonne carbon dioxide). 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 35-4 molecular density of is higher around the coal surface, but also adsorption is taking Carbon Dioxide Capture Technology Plan and Development in Taiwan place inside the micropores in the coal structure. The results further show that there is a Wan-Hsia Liu, Heng-Wen Hsu, Jyh-Feng Hang, Chin-Ming Huang, Hou-Chuan preference of CO2 adsorption, which is in agreement with experimental measurements. Wang, Industrial Technology Research Institute, TAIWAN 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, Taiwan is part of a group that suffers from highly dangerous Climate Changes as note the type of coal, and coal swelling. This will be helpful for developing relations in a U.N. report. In the past century Taiwan has experience a 1.3 increase in between pore size distributions and adsorption isotherms. Such relations can then be temperature, which is twice of the global average. The government of Taiwan, not a incorporated in reservoir models. signatory of the Kyoto Protocol, strives to comply with international treaties voluntarily. Taiwan also understands CO2 decrement is various countries’ common 35-2 responsibility. Related government agencies are already actively promoting various Geomechanical Simulations of CO2 Storage Integrity using the Livermore domestic reduction measures, including the Climate and Kyoto Protocol response Distinct Element Method working group, Greenhouse Gas Reduction Act (draft) in 2006, Greenhouse gas Joseph Morris, Scott Johnson, S. Julio Friedmann, Lawrence Livermore National reduction nationwide energy conference in 2005, education and other measures that are Laboratory, USA in the planning stages. This article will introduce the carbon dioxide (CO2) capture technology plan and Large-scale carbon capture and sequestration (CCS) projects involving annual carbon dioxide capture technologies research in Industrial Technology Research injections of millions of tons of CO2 are a key infrastructural element needed to Institute (ITRI) in Taiwan. According to the Bureau of Energy (BOE), Ministry of substantially reduce greenhouse gas emissions. The large rate and volume of injection Economic Affairs Statistic show CO2 emissions of 110 million metric tons and 265 will induce pressure and stress gradients within the formation that could activate million metric tons in 1990 and 2006 with an annual CO2 emission growth rate of existing fractures and faults, or drive new fractures through the caprock. We will 5.62% in Taiwan. present results of an ongoing investigation to identify conditions that will activate ITRI has surveyed Taiwan CO2 capture technologies development that show research existing fractures/faults or make new fractures within the caprock using the Livermore chiefly on absorption technology and adsorption technology and membrane diffusion Distinct Element Code (LDEC). LDEC is a multiphysics code, developed at LLNL, technology developed by academia. A gasification technology (2 tons of coal per day capable of simulating dynamic fracture of rock masses under a range of conditions. As of pressure entrained bed) is done on a pilot scale in ITRI (Kaohsiung). part of a recent project, LDEC has been extended to consider fault activation and In the future, power generation, petrochemical industry and steel and iron industries dynamic fracture of rock masses due to pressurization of the pore-space. We will are the first to be considered for reduction of CO2 emissions. Our goal is to establish a present several demonstrations of LDEC functionality and applications of LDEC to 1 to 3 MW (5 to 15 hundred tons CO2 every year) pilot plant in 2012, 10 to 30 MW (50 CO2 injection scenarios including injection into an extensively fractured rockmass. to 150 thousand tons CO2 every year) demonstration plant in 2020 and a commercial These examples highlight the advantages of explicitly including the geomechanical plant in 2027 for post-combustion capture. In addition, ITRI has to research and response of each interface within the rockmass. develop the CO2 capture technologies from flue gases including Gasification or We present results from our investigations of Teapot Dome using LDEC to study the Integrated Gasification Combined Cycle (IGCC), Carbonation and calcination recycle potential for fault activation during injection. Using this approach, we built finite (CCR) and innovative meso-porous nanomaterials for CO2 adsorption. 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 35-5 introduced and the area of fault activation was predicted as a function of injection rate. Dakota Gasification Company An International Energy Venture This work presents an approach where the interactions of all locations on the fault are Claudia Miller, Steve Pouliot, Dakota Gasification Company, USA 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 The Great Plains Synfuels Plant, located near Beulah, North Dakota, is the only this study are consistent with previous studies of Teapot Dome and indicate commercial-scale gasification plant operating in the United States that produces significantly elevated pore pressures are required to activate the bounding faults, given Synthetic Natural Gas (SNG) from coal. The plant is owned and operated by Dakota the assumed in situ stress state on the faults. 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 1970’s 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 34 throughout the Midwest via the Northern Border Pipeline. Numerous by-products and respectively. The results in the cold fluidized bed showed single biomass particles are co-products, including anhydrous ammonia, ammonium sulfate fertilizer, phenol, difficult to be fluidized, while a good fluidization can be gained with the addition of cresylic acid, krypton/xenon, naphtha and carbon dioxide (CO2) enhance the viability coal particles as long as the mass fraction of biomass particles was less than 50 wt%. of the facility. Similar trend was observed to the mixture of biomass char and coal char. A better The Great Plains Synfuels Plant has operated 14 Lurgi Mark IV gasifiers for over fluidization quality was gained when coal ash was added to the mixtures of coal char twenty years. On April 24, 1984 the gasification plant began producing an intermediate and biomass char, the minimum fluidization velocity of the mixtures of biomass char, raw gas. Subsequently, the first synthetic natural gas entered the nation’s interstate coal char and coal ash increased with the increase of mass fraction of coal ash. The pipeline network on July 28, 1984. While the facility had its challenges, it is a minimum fluidization velocities of two components and three components systems technical success story. Under current energy markets, it is an economic success as both could be predicted well by the empirical formulas. The thermal gravity results well. showed biomass char has higher reactivity than coal char. Co-gasification can be The idea for selling CO2 from the gasification plant arose well before the project was described by one order kinetics equation. In the self-heating fluidized bed, the effects being built in the early 1980’s. This became a reality in October of 2000 when Dakota of oxygen equivalence ratio, steam/carbon ratio, biomass/coal ratio and biomass type Gasification Company began exporting up to 95 million standard cubic feet per day on the gasification characteristics were studied in the temperature range of 850- high pressure CO2 from the Synfuels Plant. Today the plant has two Canadian 1050°C. The results showed a relatively lower oxygen equivalence ratio is customers and exports approximately 150 million standard cubic feet of CO2 per day. advantageous to gasification efficiency. There is an optical steam/carbon ratio for co- This paper discusses the original project and the expansion. A general overview of the gasification process. A rise of biomass ratio favors carbon conversion and gasification gasification process is included to define the steps required to concentrate the CO2 into efficiency. A stable operation can be obtained when the biomass ratio in mixtures is a usable product. 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.

SESSION 36 36-3 GASIFICATION: PNNL-CHINA Modeling Slag Penetration and Refractory Degradation Using the Finite Element Method Kenneth Johnson, Rick Williford, Josef Matyas, Siva Pilli, S.K. Sundaram, 36-1 Vladimir Korolev, Pacific Northwest National Laboratory, USA Design & Development of a Novel Research Gasifier George Muntean, Mike Dodson, Bob Robertus, Pacific Northwest National Refractory degradation due to slag penetration can significantly reduce the service life Laboratory, USA of gasifier refractory linings. This paper describes a modeling approach that was developed to predict refractory spalling as a function of operating temperature, coal The Pacific Northwest National Laboratory’s (PNNL) strategy is based on a feedstock and refractory type. The model simulates the coupled thermal, diffusion, and commitment to solve world-class problems by rapidly translating science into mechanical interactions of coal slag with refractory ceramics. The heat transfer and solutions. One of the primary laboratory mission statements guiding the execution of slag diffusion solutions are directly coupled through a temperature-dependent effective this strategy relates to our increasing domestic energy demands. The laboratory diffusivity for slag penetration. The effective diffusivity is defined from slag recognizes the critical need for the United States to effectively utilize its domestic penetration tests conducted in our laboratories on specific coal slag and refractory hydrocarbon resources in an environmentally benign manner. In support of this combinations. Chemically-induced swelling of the refractory and the buildup of mission, the laboratory has numerous ongoing research programs. Project examples mechanical stresses are functions of the slag penetration. The model results are include: compared with analytical spalling models and validated by experimental data in order • the use of millimeter-wave technology for corrosion, slag viscosity, and to develop an efficient refractory degradation model for implementation in a systems temperature measurements in gasifiers; level gasifier model. The ultimate goal of our research is to provide a tool that will • approaches to predict and control slag viscosity; help optimize gasifier performance by balancing conversion efficiency with refractory life. • 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 36-4 streams; Modeling of Time Varying Slag Flow in Coal Gasifiers • new Fisher-Tropsch catalysts and vessel configurations; Siva P. Pilli, Kenneth Johnson, Ralph Williford, S. K. Sundaram, Vladimir Korolev, Jarrod Crum, Battelle - PNNL, USA • CO capture using advanced solid sorbents, liquid solvents and membranes; 2 • advanced computer modeling of coal gasifiers; There is considerable interest within government agencies and the energy industries • development of a CO2/coal slurry pump for feeding gasifiers across the globe to further advance the clean and economical conversion of coal into While initial proof-of-concept tests for each of these projects can be performed at liquid fuels to reduce our dependency on imported oil. To date, advances in these areas small scales using simulated gases in pressurized bottles or other artificial conditions, have been largely based on experimental work. Although there are some detailed actual gasification gases are needed to prove that the processes will work satisfactorily systems level performance models, little work has been done on numerical modeling of in a commercial environment. Gaseous products from coal contain trace amounts of the component level processes. If accurate models are developed, then significant many impurities whose effects are unknown and not easily determined using synthetic R&D time might be saved, new insights into the process might be gained, and some bottled gases. In short, the mission as a whole and the individual projects within it good predictions of process or performance can be made. One such area is the require the credibility that comes with operating a real gasifier processing coal in a characterization of slag deposition and flow on the gasifier walls. Understanding slag high oxygen environment and testing new approaches in that realistic environment. rheology and slag-refractory interactions is critical to design and operation of gasifiers Ultimately, the scale-up of novel technologies requires testing at commercially with extended refractory lifetimes. Slag rheology and slag-refractory interactions is acceptable levels of demonstration such as the DOE-FE supported facilities at the also important to better control the operating parameters so that the overall gasifier PSDF (Power Systems Development Facility). We believe that efficient technology performance with extended service life can be optimized. In the present work, the development benefits from an additional, intermediate level of testing between bench literature on slag flow modeling was reviewed and a model similar to Seggiani’s was scale and commercial scale. To this end, PNNL has designed and procured a novel developed to simulate the time varying slag accumulation and flow on the walls of a and unique engineering-scale coal gasifier. The gasifier is a small entrained flow, Prenflo coal gasifier. This model was further extended and modified to simulate a slagging design. The gasifier will be capable of processing up to 100 lbs/hr of coal at refractory wall gasifier including heat transfer through the refractory wall with flowing pressures up to 500 psig and converting it into a suitable syngas test stream for the slag in contact with the refractory. The model was used to simulate temperature evaluation of novel separations and synthesis technologies. This talk will describe the dependent slag flow using rheology data from our experimental slag testing program. design and operation of this unique test bed including lessons learned and initial test These modeling results as well as experimental validation are presented. results. 36-5 36-2 Models for Refractory Spalling in Coal Gasifiers Process Development on Co-Gasification of Coal and Biomass in a Fluidized Rick Williford, Ken Johnson, S.K. Sundaram, Siva Pilli, Pacific Northwest Bed National Lab, USA Jicheng Bi, Rong Zhang, Kezhong Li, Institute of Coal Chemistry, Chinese Academy of Sciences, CHINA 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 Investigations on fluidization quality, gasification reactivity and operational are needed to help optimize gasifier performance by balancing conversion efficiency parameters optimization in coal and biomass co-gasification process were performed in with refractory life. Two predictive models for spalling are proposed in this paper. The a cold fluidized bed, a thermalgravity analyzer and a self-heating fluidized bed gasifier, two models treat spalling caused by volume expansion and by volume shrinkage, due 35 to chemical reactions of slag components with the porous refractory. Both models Furthermore, the tin (Sn) in the molten metal serves to capture sulfur as tin-sulfide gas express molten slag ingress into the porous refractory in terms of an effective that is subsequently roasted to tin-dioxide and reintroduced into the molten-metal bath, diffusivity, which is formulated in terms of the simultaneous transport of reactive therefore maintaining the tin composition integrity and operating temperature of the species by capillary action through the pores and by diffusive transport through the reactor. slag and the solid refractory material. The effective diffusivity depends on the total Several unique attributes of the HydroMax gasification technology result in significant pressure gradient across the refractory, the temperature and chemistry dependence of operational and economic benefits compared to existing gasification approaches, the slag viscosity, the refractory porosity, the pore tortuosity, and the average pore including: radius. The modeling results appear useful for large scale simulations to predict the - Capital cost reductions as a result of a simple and proven reactor design lifetimes of refractories in slagging coal gasifiers, and for determining whether an - Smaller gasification footprint due to the high thermal inertia of the molten-metal observed spall originates from tensile or compressive mechanisms. reactor - Flexibility to utilize any carbon feedstock due to the high thermal inertia 36-6 associated with a molten-metal bath Sensor Concepts and Development for Coal Gasification - Flexible and tailored outputs as a result of producing syngas and pure hydrogen S. K. Sundaram, J. V. Crum, Pacific Northwest National Laboratory; P. P. in separate streams Woskov, MIT, USA - Ability to accept high sulfur coals due to the unique sulfur removal approach via tin-sulfide Gasification or partial oxidation combines coal, oxygen and steam to produce synthesis Commercial and industrial HydroMax applications are numerous, including: utility- gas which will be further processed to get the final product. Several advancements are scale power generation, synthetic natural gas production, coal-to-liquid-fuels, and needed for cost-effective and environmentally-benign gasifier processes and operation, large-scale hydrogen production for oil refineries or the fertilizer industry. Currently, e.g., novel catalysts, membranes, and materials for advanced, lower cost separations of the HydroMax team is pursuing an initial market entry point focused on small hydrogen from carbon dioxide and other contaminants. In addition, improvements in industrial scale applications for converting coal and/or biomass into a fuel-gas for many technological areas will be needed, e.g., gasifier design, materials and feed process heating and drying applications used by a number of manufacturing systems, sensors, and advancements in carbon dioxide capture and sequestration companies. Diversified Energy is cooperating with two industrial firms, in different technology. An overview of sensor needs and challenges of coal gasification will be markets, to design a HydroMax gasification system to supply a natural gas substitute summarized. Additionally, progress made on sensors and capabilities development for for process heating and to explore the economic feasibility of incorporating HydroMax gasification under the Energy Conversion Initiative (ECI) at Pacific Northwest as a source for low-cost fuel gas. National Laboratory (PNNL) will be highlighted. It is shown that new millimeter-wave Previous laboratory and proof-of-concept tests have successfully demonstrated the technologies and methods can address many of the sensors needs for advancing coal fundamental science and approach of the HydroMax technology. Capital cost analysis gasification systems. 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 SESSION 37 feedstocks. Initial results from this model indicate that HydroMax performs better than GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES – 1 existing commercial gasifiers, particularly when using low-rank western coals or high- moisture content biomass as a feedstock. Also since 2007, HydroMax was selected by three different government organizations for development funding. The U.S. 37-1 Department of Energy is funding bench-scale HydroMax tests using PRB and Illinois The Potential Impact of Developing Technologies on the Economics and #6 coals. These tests will be completed in January 2008. The U.S. Department of Performance of Future IGCC Power Plants Defense is funding a HydroMax to liquid fuels feasibility study. This study will focus John Plunkett, David Gray, Charles White, Noblis, USA 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. This paper presents the results of a study funded by the National Energy Technology DEC will construct and install a HydroMax system at Evergreen Pulp to gasify waste Laboratory (NETL) to quantify the impacts of advanced technologies on the wood fines and provide syngas for process heating. performance and economics of future IGCC power plants. A reference IGCC power The HydroMax presentation will include: 1) A brief overview of the HydroMax coal plant that consists of currently available technology is used as the benchmark by which gasification technology 2) An introduction to the HydroMax development team 3) to measure the improvements provided by incorporating the advanced technologies. Previous test results and analyses including the January 2007 DOE funded tests 4) The advanced technologies that are analyzed in this study are: dry coal feed pumping Analyses conducted using models developed from AspenPlus® and a discussion of system to introduce the coal into the gasifiers and to replace water slurry feeding, HydroMax performance compared to commercially available gasifiers 5) Summary of warm gas cleaning to replace conventional acid gas and trace element removal, direct the industrial applications being pursued and evaluated 6) Progress status of DOD and sulfur recovery to replace the Claus unit, high temperature ionic membrane air State of California contracts 7) Future development plans and activities. separation to replace cryogenic air separation, advanced syngas gas turbines, and stationary solid oxide fuel cells. These technologies are under development within 37-3 NETL’s research and development (R&D) program. Aspen Plus simulations were ALSTOM’s Hybrid Combustion-Gasification Chemical Looping used to conceptualize the IGCC plants and estimate the performance improvement in Technology Development - Phase III terms of overall thermal efficiency, capital cost, and the levelized cost of electricity. Herbert Andrus, John Chiu, Paul Thibeault, ALSTOM Power Plant Laboratories; The novel technologies being developed through NETL’s R&D program will provide Ronald Breault, DOE-NETL, USA coal-based power plants for the future, which generate low-cost electricity with significantly improved efficiency and reduced environmental footprint. 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 37-2 for the global power market. This new power plant concept is based on a hybrid Progress on HydroMax – Breakthrough Molten-Metal Coal Gasification combustion-gasification process utilizing high temperature chemical and thermal Technology looping technology Phillip Brown, Jeff Hassannia, Steven Schenk, Diversified Energy Corporation, The chemical and thermal looping technology can be alternatively configured as 1) a USA combustion-based steam power plant with CO2 capture, 2) a hybrid combustion- gasification process producing a syngas for gas turbines or fuel cells or 3) an integrated HydroMax is a patented, breakthrough gasification technology that utilizes a unique hybrid combustion-gasification process producing hydrogen for gas turbines, fuel cells chemical pathway to produce syngas (CO + H2) and hydrogen (H2) in separate and or other hydrogen based applications while also producing a separate stream of CO2 for distinct streams, resulting in process and economic benefits. use or sequestration. Using two distinct steps, the HydroMax process begins with a molten Iron/Tin (FeSn) This paper covers the progress of recently completed Phase III Work with the US bath heated to 1300°C. In Step 1, steam is injected into the molten bath, which is then DOE. The objective for Phase III was to investigate the solids handling system for the thermo-chemically split (i.e. traditional steaming of iron) resulting in H2 gas (released) multiple solids streams, to develop an automatic control methodology for the process and oxidized Fe (FeO). After the Fe is oxidized, steam injection ceases and coal is components, and to generate enough information to design and build the prototype injected into the reactor (Step 2). Carbon, with its high affinity to oxygen, reduces the Chemical Looping system to be built in the next Phase of the program. These oxidized FeO to its pure form objectives were met. (Fe) and produces a CO-rich syngas, which is either used as a fuel gas or combined The main conclusion from Phase 1 and Phase 2 was that the PDU chemistry required with hydrogen from Step 1 to produce Fischer Tropsch fuels. Based on these for the chemical looping process has been validated. fundamental processes of steaming-iron and metal-bath-smelting, the oxidation and The main conclusion from Phase III is that it is possible to design an integrated reduction steps are then repeated in a cyclic fashion thus resulting in no molten-metal Chemical looping system with all of the components necessary for successful consumption. operation and it is also possible to design a control system to operate the multiple 36 solids transport loops. Economics were reevaluated based on the results of Phase I, II and III testing and were found to still be valid. SESSION 38 GASIFICATION TECHNOLOGIES: SYNTHESIS GAS CLEANING – 1 37-4 Coal Direct Chemical Looping Process for Hydrogen Production – Experimental Studies 38-1 Liang-Shih Fan, Hyung Kim, Fanxing Li, Deepak Sridhar, Liang Zeng, Fei 250 MW IGCC Demonstration Start Up – MHI Gas Clean-Up System Wang, The Ohio State University, USA Shintaro Honjo, Mitsubishi Heavy Industries America, Inc., USA; Makoto Susaki, Susumu Okino, Toshinobu Yasutake, Mitsubishi Heavy Industries, Ltd., The Coal Direct Chemical Looping (CDCL) process is a novel technology producing JAPAN 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 September 2007, 250 MW scale air-blown Integrated coal Gasification Combined coal to capture CO2 in the reducer. Then, these reduced particles are used in the second Cycle (IGCC) plant has successfully started up at Nakoso in Japan. This is first reactor to produce hydrogen through oxidation, as they react with high temperature Japanese commercial scale IGCC demonstration test to verify its performance and steam. The indirect combustion of coal with composite iron particles significantly reliability. All main components such as Gasifier, Turbine and Gas clean-up system are enhances the efficiency of the hydrogen production process. These composite iron designed and/or manufactured by Mitsubishi Heavy Industries, Ltd (MHI) for Japanese particles are uniquely synthesized by the Ohio State University to sustain the high Clean Coal Power R&D Co., Ltd (CCP). temperature reactions and transportation. The experimental results on the combustion Since the startup of September 2007, MHI confirmed this demonstration plant exceed of coal with iron particles show more than 90% conversion of coal and >95% CO2 are the entire performance target relate with pollution control (SOx, NOx and PMs). Plant achieved under optimized reaction conditions. In addition, effect of sulfur and ash on is now running continuous basis to proof its reliability. This paper describes on its the recyclability of the composite iron oxide particle was also studied. advanced cold gas clean-up process which also improves plant efficiency by 0.6% compared with conventional system. 37-5 The demonstration test will be continued till end of 2009. Retrofitting Existing Coal-Fired Power Plants with Plasma Gasification to Meet Clean Air Act Environmental Standards 38-2 Shyam Dighe, Tom Gdaniec, Westinghouse Plasma Corp.; Alan Sawyer, NRG UCSRP-HP - an Integrated Multi-Contaminant Removal Process for Energy, Inc., USA Treating Coal-Derived Syngas Howard S. Meyer, Diana Matonis, Timothy Tamale, Dennis Leppin, Gas Retrofitting existing coal power plants with plasma gasification results in modernized Technology Institute; Scott Lynn, University of California Berkeley, USA clean energy facilities. Plasma gasification technology offers an environmentally responsible solution for older power plants allowing old power plants to meet The University of California Sulfur Recovery Process-High Pressure (UCSRP-HP) increasingly stringent regulatory and environmental standards. Plasma Gasification testing program is developing an integrated, multi-contaminant removal process for technology converts coal / biomass into syngas, which is cleaned of impurities i.e. coal-derived syngas at 275°F to 300°F and at the given sour gas pressure. The process sulfur and mercury, and then combusted in the existing facility s steam electric will remove H2S, NH3, HCl and heavy metals, including Hg, As, Se and Cd, to parts- generating equipment (typically boilers). By retrofitting plasma gasification per-million (ppm) or in some cases parts-per-billion (ppb) levels in a single process. technology into the older power plants, much of the existing facility infrastructure is Contaminates, such as NH3, HCl and trace contaminants, are removed in the first retained and reused; thereby reducing repowering costs and the amount of air section of a compound reactor column. This is accomplished by a common solvent pollutants emitted is drastically reduced. As well, by replacing some of the coal with absorbing H2S, NH3, HCl and trace metals from the feed gas. NH3 and HCl form a renewable biomass feedstock, construction and demolition waste or municipal solid highly soluble NH4Cl salt and the absorbed heavy metals, As, Cd and Hg, precipitate waste, significant greenhouse gas reductions can also be attained. out as their very insoluble sulfides. The Se trace metal, present in the syngas as H2Se, Retrofitting coal fueled facilities using plasma gasification system is expected to forms a highly soluble (NH4)2Se under these conditions and remains dissolved in the reduce harmful air emissions below US environmental guidelines, with significant solvent. A slipstream of the solvent will be treated to remove the soluble and insoluble reductions of nitrogen oxides (NOx), mercury (Hg) and sulfur oxides (SOx). Reductions components. In the second section of the column, H2S is converted directly into in greenhouse gas emissions from retrofitted facilities are possible by combining elemental sulfur by reaction with sulfur dioxide in the liquid phase. The liquid sulfur biomass into the feedstock to displace the need for coal and further reduction may be formed rapidly separates from the solvent phase, allowing the Claus reaction to possible with the future add-on of carbon capture and sequestration technology. As continue without equilibrium limitations that controls gas-phase catalytic systems. The well, it enhances power generation on Brownfield sites in areas of high power demand. proposed process is tightly integrated and is expected to be significantly more Most importantly, it makes it unnecessary to abandon older power plants, the people economical both in terms of capital and operating costs because it replaces the sulfur who operate them, the vendors who sell goods and services to them, and the removal processes, acid-gas removal, Claus and SCOT, as well as the trace communities who benefit from them. As well, as it is a more time and cost efficient components removal processes used or proposed in conventional schemes by a single solution than building new facilities NRG Energy’s power plant in Somerset, MA unit. currently produces 110 megawatts (MW) with a pulverized coal combustion boiler and This paper will include an (i) investigation of long-term (i.e., 1000 hrs) solvent associated steam turbine. NRG has proposed and received required approvals from the stability by exposure of the solvent to a gas simulating synthesis gas from the Commonwealth of Massachusetts Department of Environmental Protection for the gasification of Illinois No. 6 coal containing all the contaminants that may be present design, construction, and operation of a plasma gasification system at Somerset and the in the feed to UCSRP reactor, (ii) investigation of metal corrosion related issues for refueling of the existing boiler from pulverized coal to clean syngas firing using the selecting suitable material of construction for UCSRP reactor, (iii) investigation of the plasma gasification technology developed by Westinghouse Plasma Corp (WPC). removal of the trace metal components from the syngas by the selected solvent, (iv) WPC is a wholly owned subsidiary of Alter Nrg. The approval also allows the use of investigation of the fate of COS in the system, (v) development of an Aspen-Plus up to 45% biomass, on a heat input basis to displace coal, thereby earning both based computer simulation model, and (vi) techno-economic evaluation of the process Renewable Energy Credits and significantly reducing the emissions of greenhouse gas applied to syngas cleanup. (GHG). There are close to 600 small to medium size coal-fired generation units in North 38-3 America that are nearing the end of their economic life because they can t meet new Development of a Warm Syngas Clean-Up Technology Platform for Power emissions standards. NRG Energy together with Alter NRG has identified more than and Chemicals Production 320 coal-fired units that are suitable for retrofitting using WPC plasma technology. Brian S. Turk, John R. Albritton, Jason Trembly, Raghubir Gupta, Lora Toy, NRG Energy s Somerset plant will be the world s first plasma gasification retrofit of a Paige Pressler-Jur, RTI International; Jerry Schlather, Jeremy Gibson, Joshua coal-fired power plant. Keller, Eastman Chemical Company, USA 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 is a proven commercial process for converting carbonaceous feedstocks, gasification of waste feed materials in commercial plants in Japan and India and the particularly low value and “dirty” feeds such as coal, lignite, petroleum coke and industry trends which are heightening interest in North America and around the world biomass into synthesis gas. The challenges for gasification are efficient utilization of for plasma gasification application for power generation. 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 37 decision factor in selecting gasification over other technologies in today’s carbon constrained world. SESSION 39 As the scope of syngas cleaning expands beyond sulfur, conventional commercial ENVIRONMENTAL CONTROL TECHNOLOGIES: MULTIPOLLUTANT technologies are challenged to achieve the environmental performance and high energy CONTROL 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 39-1 contaminants including sulfur, ammonia, mercury, arsenic, chlorine, alkali metals, and Assessment of the Alternative Oxidation-Reduction and Oxidation- even carbon dioxide. The primary focus for syngas cleaning is for the entire platform Absorption Chemical Process Modes in Integrated SO2, NOx and Hg to operate at temperatures >250°C. RTI and Eastman Chemical Company (Eastman) Removal have successfully demonstrated a transport reactor-based desulfurization technology William Ellison, Ellison Consultants, USA suitable for warm syngas. In addition, field testing of other syngas cleaning technologies have been completed this year. This paper will present new technical The presentation, after defining the two chemical processes, will review recent, early, development and feasibility analysis of this syngas cleaning technology platform, breakthrough commercial application of these principal, generic, chemical engineering along with commercialization plans. 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. 38-4 Details will be given of: CrystaSulf®-DO Process for Sulfur Removal from Warm Coal-Derived Gas - Principal system design challenges in engineering of a commercial, flue gas, Diana Matonis, Howard S. Meyer, Timothy Tamale, Dennis Leppin, Gas chemical pre-oxidation facility Technology Institute; David Seeger, CrystaTech Inc., USA - Key elements in achieving acceptable pre-oxidation system design and performance This paper presents the results of an on-going experimental study on the catalytic - Oxidation-reduction process design direct oxidation (DO) section of the CrystaSulf-DO process for the removal of sulfur - Advantages of use of oxidation reduction scrubbing chemistry compounds as elemental sulfur from syngas generated by the gasification of coal. This - Disadvantages in use of oxidation-reduction scrubbing chemistry hybrid process concept places the DO bed upstream of the CrystaSulf unit. This - Emphasis for this mode on merits of scrubber system design that achieves surface approach allows for 80-95% of the hydrogen sulfide in the inlet gas stream to be renewal, i.e. continuous, in-situ renewal of chemically active gas/liquid contact converted to elemental sulfur and removed before entering the CrystaSulf absorber. surface The primary benefit of this approach on the overall sulfur removal/recovery system is - Oxidation-absorption process design an 80% or greater reduction in the CrystaSulf unit’s circulation rate, and the size of the - Disadvantages in use of oxidation-absorption scrubbing chemistry. crystallizer, sulfur filter and associated equipment. Consequently, overall utilities and chemical consumption rates should be dramatically reduced. By tailoring the O2 to H2S 39-2 ratio in the DO process we can (1) minimize the loss of combustibles in the gas and (2) Cost-Effective Retrofitting of Fossil Fueled Power Plants with Raw Flue Gas control the amount of elemental sulfur versus SO2 in the exit. With this additional Pre-Oxidation in Meeting Nitrogen Oxides, Mercury and Sulfur Dioxide integration, the sulfur dioxide needed for the liquid phase reactions in CrystaSulf may Emission Limits be produced in the same catalyst bed, further simplifies the overall process and William A. Walsh, Jr., VGA Nozzle Company; William Ellison, Ellison lowering its cost. The CrystaSulf- DO approach could offer a significant cost Consultants, USA advantage over the amine/Claus/tail gas approach for syngas applications for coal feed rates up to 250 tons/day (tpd). Oxidizing of nitric oxide (NO), the principal flue-gas NOx component, to a higher Experiments were conducted to select a suitable catalyst; investigate the effect of oxide (NO2, N2O3 or N2O5) is a key step in gaining NOx emission control in major operating parameters, including water vapor content, on H2S removal efficiency; downstream dry and semi-dry scrubbing systems. The pre-oxidation step also determine optimum operating parameters; and ultimately develop a reactor design and simultaneously converts elemental mercury to an oxidized form and sulfur dioxide perform a preliminary economic analysis. (SO2) to sulfur trioxide (SO3) for their dry-mode removal. The proprietary Variable A bench-scale testing system at Gas Technology Institute (GTI) was used to measure Gas Atomization (VGA) nozzle-lance system described provides a cost-effective the performance of full-particle-size catalysts at pressures to 2.8 MPa (400 psi), and means of performing this pre-oxidation. It injects mixtures of chemicals, fed in-duct, temperatures primarily between 124–149°C (255 – 300°F). A blended gas stream, that interact to yield highly activated radical forms as they are being formed and which contains the primary components of syngas, is combined with oxygen (by air released. These further react with the non-dedusted, raw flue gas. Candidate oxidants addition) and passed over hot catalyst. From measured changes in composition of the include hydrogen peroxide (H2O2), yielding its reactive components as radicals, and syngas stream, the activity and selectivity of the catalyst are evaluated. Optimal sodium chlorate (NaClO3), yielding chlorine dioxide (ClO2). Oxidation may be process conditions are determined by varying the amount of oxygen added that reacts accomplished either in the raw-flue-gas duct directly upstream of scrubbing or, if selectively with hydrogen sulfide in the syngas minimizing the consumption of the higher reaction temperature is desired, upstream of the air pre-heater. It has valuable syngas components of carbon monoxide and hydrogen as will be shown. 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 38-5 scheduled for scrubber addition and for new power generating sources. Innovative Hot-Gas Cleanup Processes for Advanced IGCC Systems and for The paper will describe the processes and equipment to achieve in-situ formation of Hydrogen Production Processes the reactive chemical radicals effective in pre-oxidation. It will delineate the nozzle- Michihiro Ishimori, Yuya Mezaki, Seiji Terashita, Masafumi Katsuta, Waseda lance system design effectively utilized to achieve a uniform distribution of these University, JAPAN 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 Development of a hot-gas cleanup system, especially highly efficient desulfurization enable cost-effective emission control. technology has been studied to realize effective coal gasification plants such as advanced IGCC systems for electricity and advanced processes for high-grade 39-3 hydrogen production. We have explored innovative desulfurization agents composed Use of Advanced Process and Mechanical Engineering Means for Flue Gas of zinc ferrite, metal oxides and/or metal sulfides for hot-gas cleanup processes, using Treatment in SO2 and Hg Removal with an Optional Measure of Secondary simulated coal gas by an entrained-flow gasifier. It was shown that by use of the above Denox agents, hydrogen sulfide itself is almost completely removed and that sulfur atoms of Kevin Furnary, LEEP Holdings, LLC; William Ellison, Ellison Consultants, sulfuric substances such as COS involved in coal gas are also catalytically reduced to USA 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 Of Australian commercial origin, LEEP gas treatment technology to be detailed is (PFD/GC; 20 ppbv). The desulfurization agents can be satisfactorily used to realize based in part on international integration of commercially successful, American and advanced IGCC and IGFC plants having extremely high thermal efficiencies, and for overseas, mechanical and chemical engineering design technology. advanced processes of high-grade hydrogen production for PEFC. 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- 38 proven, generic, oxidation-reduction chemical process operation that achieves As a result of the success at AES Greenidge, three additional retrofit applications of ® simultaneous SO2, NOx, and Hgo removal. Examples are to be given of attractive the Turbosorp system have been announced for small to moderate-sized coal-fired chemical process and mechanical engineering design features utilized: EGUs (i.e., 50-300 MW) in the United States. Additional announcements are - Sub-atmospheric pressure scrubber operation arising from mechanical anticipated. Key characteristics of these announced deployments, including unit and engineering design devoid of booster fan use fuel characteristics and performance targets, are discussed. - 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 SESSION 40 disposal via construction of a structural landfill monolith COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES – 5 - 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 40-1 - Optional, high-velocity, existing, stack discharge of scrubbed, water saturated Mercury Capture by Bulgarian Fly Ashes: Evidence from Petrography and flue gas, that is hot by-pass gas reheated via advanced aerodynamic gas mixing Surface Analysis means James C. Hower, University of Kentucky; Maria Mastalerz, Indiana University, - Optional use of the alternative oxidation-absorption chemical process mode of USA; Irena J. Kostova, Sofia University, BULGARIA scrubber operation in applications in which NOx ppm reduction, as when augmenting SCR, is minimal. 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 39-4 vitrinite-derived thermoplastic fluid and inertinite derived, without substantial Regenerable “Molecular Basket” Sorbents for NO2 and SO2 Removal from alteration, from the inertinite component of the feed coal. In contrast, carbons in fly Flue Gas ashes from low-rank coals, such as burned in Bulgarian power stations, consist of Xiaoxing Wang, Xiaoliang Ma, Chunshan Song, Penn State University, USA 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 Molecular Basket Sorbent concept has been used to develop a new nanoporous the collection point and the amount of fly ash carbon. The ashes differ in the low- composite sorbent, which is able to remove NO2 and SO2 selectively from flue gas and rank-derived carbons having a greater ability to capture Hg, based on a Hg/C ratio, other gas streams at ambient conditions and can be regenerated easily. The present than high volatile bituminous-derived carbons. The Hg/C ratio decreases with the study may open a new window for development of the high performance of sorbents amount of C in the fly ash, perhaps a function of the blinding of interior C surfaces for gas separation. with thicker carbons. Increases in the BET and micropore surface areas correlate with increases in fly ash Hg. 39-5 The Greenidge Multi-Pollutant Control Project: Demonstration Results and 40-2 Deployment of Innovative Technology for Reducing Emissions from Smaller Evaluation of Coal Preparation Plant Refuse Areas in Kentucky as a New Coal-Fired Power Plants Energy Resource Dan Connell, CONSOL Energy Inc. R&D; Doug Roll, AES Greenidge LLC; Cortland F. Eble, Stephen F. Greb, James C. Hower, University of Kentucky, Rich Abrams, Roderick Beittel, Babcock Power Environmental Inc.; Wolfe USA Huber, DOE-NETL, USA The demand for, and use of, coal in the United States is projected to increase as our There are more than 420 coal-fired electric generating units (EGUs) in the United energy consumption increases. In addition to conventional coal resources, States with capacities of 50-300 MW that currently are not equipped with selective unconventional resources, mainly in the form of preparation (or beneficiation) plant catalytic reduction (SCR), flue gas desulfurization (FGD), or mercury control systems. refuse, are beginning to be recognized and utilized, especially with the expansion of Many of these units, which collectively represent almost 60 GW of installed capacity, clean coal technologies. These newer technologies, which include gasification and are difficult to retrofit for deep emission reductions because of space constraints and fluidized bed combustion, can readily use preparation plant waste, especially the unfavorable economies of scale, making them increasingly vulnerable to retirement in byproduct material from older (pre-1990) facilities. Older plants were not able to the face of progressively more stringent environmental regulations. separate the coal from the non-coal (rock) fraction as efficiently as newer plants can, The Greenidge Multi-Pollutant Control Project is being conducted as part of the U.S. and hence the waste product ended up containing a relatively high percentage of coal Department of Energy’s (DOE) Power Plant Improvement Initiative to demonstrate a (in some cases up to 40%). Kentucky has an abundance of abandoned preparation plant solution for these units. The project seeks to establish the commercial readiness of a waste areas given the long history of coal mining in the Commonwealth. These areas multi-pollutant control system that is designed to meet the needs of smaller coal-fired represent an energy resource that requires further evaluation. The exploitation of older EGUs by offering deep emission reductions, low capital costs, small space preparation plant refuse areas could significantly extend the amount of coal resources requirements, and applicability to high-sulfur coals, mechanical simplicity, and that remain in Kentucky. Re-mining of these areas could also be environmentally operational flexibility. The system comprises an innovative combination of beneficial as preparation plant waste is often unsightly, and potentially damaging to technologies including combustion modifications, a NOxOUT Cascade® hybrid streams and groundwater. Re-mining would also provide additional jobs in the mining selective non-catalytic reduction (SNCR) / in-duct SCR system, and a Turbosorp® and transportation sectors. circulating fluidized bed dry scrubbing system with baghouse ash recycling and activated carbon injection. These technologies were retrofitted to the 107-MW AES 40-3 Greenidge Unit 4 by Babcock Power Environmental Inc. (BPEI) in 2006, with a total Development and Application of CCTM Model plant cost of ~ $340/kW and a footprint of < 0.5 acre. Extensive testing has been Shihua Ren, Guifeng Chen, Beijing Research Institute of Coal Chemistry, China carried out through mid-2008 to evaluate the performance of the multi-pollutant Coal Research Institute, CHINA 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 As one of the countries with largest coal production and consumption, China is discusses commercial deployment of the demonstration technology. Guarantee tests introducing clean coal technologies. China Coal Research Institute (CCRI) developed conducted at AES Greenidge in 2007 proved that the multi-pollutant control system Clean Coal Technology Model (CCTM) to meet the need of different clean coal was capable of reducing NOx emissions to 0.10 lb/mmBtu, SO2 emissions by 96%, SO3 technology options under different conditions. The model was derived from life cycle and HCl emissions by 97%, and mercury emissions by > 95% while the unit fired 2.4- assessment, multiple indexes evaluation and input-output methodology, which has 3.2% sulfur eastern U.S. bituminous coal. Additional tests have since been conducted three functions including calculation and comparison of individual clean coal to characterize the performance of the system as a function of unit operating technologies, lifecycle assessment from coal mining to utilization, and prediction of conditions; the results of these tests are presented. The predominant operating energy demands. The model provides a convenient tool for evaluating clean coal challenges encountered to-date have arisen from the combustion system and from technologies, and a perfect model for making decisions on clean coal technologies for accumulation of large particle ash (LPA) in the in-duct SCR catalyst; as a result, the enterprises, governments and research institutes. This paper finally gives an example to unit has required several outages for catalyst cleaning and has routinely operated with explain how to apply the model, which can evaluate the difference between the two ® NOx emissions slightly greater than 0.10 lb/mmBtu. The Turbosorp scrubber has lifecycle pathways (one is from coal, diesel, to diesel vehicles and another is from coal, operated commendably, routinely achieving > 95% SO2 removal efficiency while the DME to DME vehicles) in the aspects of technology, economy and environment unit is firing mid-to-high sulfur coals (e.g., containing 2.5-5.0 lb SO2 / mmBtu). separately and synthetically. 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.

39 40-4 Using a commercially-available, high-calcium hydrated lime, 90% CO2 and greater Mineral Resources of Kuzbass Plants for Complex Deposits Developing in than 99% SO2 capture has been achieved on a once-through basis. With the success Innovation Technologies Realization of Deep Mineral Wealth and Mineral achieved on a once-through basis, the 20 pound per hour facility has been renovated Waste Processing for multicyclic studies. With the integration of a rotary kiln, a wider array of initial Boris F. Nifantov, Vadim P. Potapov, Coal and Coalchemistry Institute SB RAS, starting solid sorbents can be tested. Before the integration of the calciner, only RUSSIA calcium hyroxide and calcium oxide sorbents were available for testing. The calciner allows for carbonaceous materials to be tested, such as limestones and precipitated The natural potential of mineral resources in Kemerovo area includes different kinds of calcium carbonate. mineral wealth. The main of them are coal, iron ore, polimetal and others. Extracting The presentation will focus on three areas. First, the construction of the 20 pound per and processing of mineral wealth, ore-dressing and burning are the industrial plants hour facility and the results generated will be discussed. Second, process simulations processes, which pollute the environment very much. Their gross data decreasing will for integrating the CCR process into an existing or new power plant will follow. be real in conditions of system program fulfilling of deep mineral wealth and waste Finally, conclusions and future work plans will be outlined. processing, it will help in knowledge paradigm forming, in working out the technologies complex, completely covering all components of raw materials, 41-3 extracting from the bowels. 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 SESSION 41 GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND Korea Institute of Energy Research (KIER) and Korea Electric Power Research UTILIZATION – 4 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 41-1 method contains potassium carbonate, which was supplied by KEPRI in order to The Dry Carbonate Process: Carbon Dioxide Recovery from Power Plant investigate the sorbent performance in continuous operation mode with solid Flue Gas circulation. In this study, we used the simulated flue gas containing 13% of CO2 for 2 Thomas Nelson, David Green, Luke Coleman, Raghubir Gupta, RTI Nm3/hr facility which is composed of a fast fluidized bed carbonator (5.4 m tall pipe of International; Jose Figueroa, DOE-NETL, USA 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 The reversible reaction between sodium carbonate, carbon dioxide (CO2), and water 35% K2CO3 as an active component and 65% support for mechanical strength and pore vapor to form sodium bicarbonate can be used in a thermal-swing process to recover structure. The continuous operation was first executed during 54 hours and the next 50 concentrated CO2 from power plant flue gas for sequestration or reuse. A process h continuous operation was performed again using the same sorbent as the first based on this reaction - RTI’s Dry Carbonate Process - has been developed and is operation. The average CO2 removal was 85% for 50 h continuous and smooth targeted as a retrofit CO2 capture technology for existing coal-fired power plants. operation. This result indicates that CO2 capture process using potassium carbonate This presentation will include the field testing of a prototype Dry Carbonate Process. solid sorbent is applicable for CO2 capture in the flue gas. Field test experiments were conducted using natural gas-derived and coal-derived flue gases from a combustor at the U.S. Environmental Protection Agency’s research 41-4 facility in Research Triangle Park, NC. The prototype unit was capable of achieving Preparation of Composite Carbon Membranes from Waste Peanut – Shells greater than 90% removal of CO2 during testing. Contaminants in the flue gas were Petr Ševčík, Ivan Koutník, VŠB - Technical University of Ostrava; Vlastimil shown to have no adverse effect on sorbent performance and the sorbent showed little Fíla, Institute of Chemical Technology Prague; Karel Těšitel, ZVU Engineering, or no physical attrition over hundreds of cycles. The unit was exposed to flue gas for CZECH REPUBLIC 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 Porous carbon planar discs of cyclic crosscut were prepared by controlled Process potentially has significant cost advantages over existing CO2 capture carbonization of tablets made of peanut shells which were milled on powder of certain technologies. Currently, modifications to the process design are being made and granularity and sequentially pressed in manual press. Tablets made of mixture of additional R&D is being conducted leading up to the construction of a pilot-scale unit powder and binding pitch was also prepared in manual press. Structural parameters of capable of capturing at least 1 ton of CO2 per day. This presentation will also include obtained carbon planar discs were determined by mercury and helium porosimetry. the results of the additional process design R&D and will highlight the activities being Structural properties of these discs in dependence on press temperature and presence of carried out in preparation for pilot-scale testing. binder were objectives of these experiments. Surfaces of these discs were visualized by This work was accomplished under a cooperative agreement with the U.S. Department scanning electron microscopy (SEM). By reason that results of analyses showed high of Energy’s National Energy Technology Laboratory (DOE/NETL). The project is porosity and narrow distribution of macropores were those discs used as a background part of DOE/NETL’s Carbon Sequestration Program which seeks to develop for synthetic membrane layer based on titanosilicates. Temperature, pH and technologies capable of 90% CO2 removal with a potential to limit the power composition of synthesis solution along with the number of synthesis cycles were generation impact to a less than 20% increase in cost of electricity. observed during the synthesis of deposition layer. Obtained synthetic layers on carbon supports were also visualized by SEM. 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 SESSION 42 Consulting; Bartev Sakadjian, Babcock & Wilcox, USA COAL UTILIZATION BY-PRODUCTS – 1

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 42-1 the world’s CO2 emissions, is derived from coal-combustion power plants. In an effort Characterization of Fly-Ash Generated During Co-Firing of Lignite and to curtail the negative effects of CO2 emissions on the environment, The Ohio State Biomass for Use as Mineral Admixture with Ordinary Portland Cement University has partnered with American Electric Power (AEP), Babcock & Wilcox, Nabajyoti Saikia, Andrea Johnson, Stephen Kinrade, Lionel Catalan, Lakehead Clear Skies Consulting, CONSOL Energy, Duke Energy, and Specialty Minerals to University, CANADA 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 Fly-ash produced from the co-firing of coal and biomass (CBFA) was evaluated in coal-combustion flue gas stream. As an added benefit, the CCR process simultaneously comparison with conventional coal fly-ash (CFA) as a mineral admixture in ordinary removes sulfur dioxide. Portland cement (OPC). CFA was obtained from combustion of pure lignite, and The CCR process utilizes a solid sorbent, in the form of an alkali metal oxide (CaO), in CBFA from mixtures of either 16:84 (mass ratio) sawmill waste-wood pellets and a high-temperature reaction to capture CO2 from a flue gas stream to produce a metal lignite or 5:95 grainscreening pellets and lignite. The properties assessed included: carbonate (CaCO3). The subsequent calcination reaction regenerates the metal chemical and mineralogical composition; particle size distribution; hydration of carbonate into the metal oxide while also producing a pure stream of CO2, which is CFA/CBFA-amended OPC; and compressive strength of amended mortars at different sequestrable. Several sources of calcium oxide have been tested from small-scale curing times. There was no significant difference in the chemical and mineralogical Thermogravimetric Analyzer experiments through sub-pilot scale experiments. composition of CFA and CBFA (although CFA had a slightly higher proportion of fine At The Ohio State University, a 20 pound per hour stoker combusts bituminous, Ohio particles). In addition to the dominant amorphous silicate phases, each contained coal to generate the flue gas stream. Several sorbents have been tested in this unit. quartz and a small amount of periclase. Both fly-ashes exhibited pozzolanic activity 40 when added to OPC mortar (20 wt%), resulting in similar non-evaporable water 42-5 content and compressive strength after 28 days hydration. Portlandite, calcium Fly Ash- Nonplastic Component for Production of the Composite Bricks aluminate hydrate, calcite and/or calcium silicate hydrate and ettringite are the major Maria Kusnierova, Mária Praščáková, Slovak Academy of Sciences, early hydration products formed in cement pastes. Since the compressive strength of SLOVAKIA; Peter Fecko, VSB-Technical University of Ostrava, CZECH these amended mortars exceeded 75% that of ash-free control, both types of fly ash REPUBLIC met ASTM requirement C 618 for mineral admixtures. The paper deals with the influence of added black-coal fly ash, slag and carbon black 42-2 amounting to 5-15% on the compactness, bulk density, absorption capacity, capillarity Strength Development, Durability, and Micromineralogical Analysis of and thermal resistance of newly made composite bricks. The results confirmed the Cement Mortar Samples Containing Fly-Ash from Co-Firing of Wood potential utilization of certain power waste amounting up to 10% in the production of Pellets with Lignite composite bricks with comparable and individually even better qualitative parameters. Andrea Johnson, Nabajyoti Saikia, Lionel Catalan, Stephen Kinrade, Lakehead University, CANADA

Co-firing coal with renewable/waste biomass for power generation has potential to SESSION 43 mitigate atmospheric discharge of pollutants (e.g., SO2) and green-house gases. GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES – 2 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 43-1 durability to freezing and thawing as well as to chemical attack of mortar containing ITM Oxygen for the Real World: Pilot Scale Testing and Beyond portland cement, which was substituted up to 40 wt% with either conventional coal Lori A. Vratsanos, Phillip A. Armstrong, Richard P. Underwood, VanEric E. flyash (CFA) or CBFA obtained from combustion, respectively, of undiluted lignite or Stein, E.P. (Ted) Foster, Air Products and Chemicals, Inc., USA a 15:85 (mass ratio) wood pellet/lignite mixture at the Atikokan (Ontario) thermoelectric power station. Additionally, we investigated the micromineralogy A team led by Air Products and Chemicals in partnership with the U.S. Department of (using scanning electron microscopy/energy dispersive spectrometry) of mortars Energy is developing a novel air separation technology. The method uses high produced with both types of fly-ash. temperature ceramic membranes which selectively transport oxygen ions to produce high purity oxygen. A coproduct of the process is an energy-rich nonpermeate stream 42-3 that can be used to produce power and steam. This technology is well suited for Utilization of Ultra Fine Fraction of Coal Combustion Fly Ash as Polymer advanced power generation processes such as IGCC which require oxygen as a Composites feedstock. Synergy with traditional energy intensive industrial processes which require Zhe Lu, Tom Robl, Brock Marrs, Center for Applied Energy Research, oxygen and with CO2 capture applications is expected. University of Kentucky, USA 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 Minerals are often used as a filler to form composites with polymer to improve ceramic membrane approach and designed and built commercial-scale membrane physical characteristics and reduce raw material costs. Ultra-fine fly ash (UFA) with a modules. The team has demonstrated expected performance of commercial-scale mean particle size of less than 5 microns was obtained via the hydraulic classification modules in a prototype facility that produces up to 5 tons-per-day of oxygen. In Phase of raw fly ash. The material was calcined to remove the residue carbon, and then added III, a membrane separator will be integrated with a turbine to produce power and up to to a range of polyurethane foam densities (4 to 16 lb/ft3) in various loadings. The filled 150 tons-per-day (TPD) of oxygen in the 2009-10 timeframe. Data from the 150-TPD foam composites were tested for density, apparent porosity, and mechanical properties. plant test will provide the design basis for a much larger plant that could supply up to The mechanical properties of the UFA urethane composites showed greatly increased 2500 TPD scale. modulus, compressive strength and toughness over unfilled foams. Compressive This paper will present an overview and update of the ITM Oxygen development strength increased by up to a factor of almost 4. The modulus and compressive strength effort, including testing of commercial-scale ceramic modules, developing integration increased as a function of the UFA loading up to a level of 60 weight % ash and then schemes with gas turbines and energy-intensive industrial processes, and process decreased. The overall porosity of the composite was not greatly affected by the filler economic analyses. A commercialization timeline will be discussed. 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 43-2 combination of strength and light weight are desirable. PWR Dry Feed System Development Status Kenneth M. Sprouse, David R. Matthews, Timothy Saunders, Pratt & Whitney 42-4 Rocketdyne, Inc.; Greg F. Weber, University of North Dakota, USA National Network of Research Studies to Promote Flue Gas Desulfurization (Fgd) Gypsum Use in Agriculture Development of the Pratt & Whitney Rocketdyne (PWR) dry pump and feed system David Kost, Warren Dick, The Ohio State University, USA continues at PWR and the University of North Dakota’s (UND’s) Energy & Environmental Research Center. This system is rated for 1,200-psia pump discharge A national network of research sites has been established to investigate beneficial gas pressures; 1,000-psia gasifier operating pressures; and 400-tons/day coal flow agricultural uses of flue gas desulfurization (FGD) products, especially FGD gypsum. rates. Dry coal (pulverized to standard industrial grind) is fed throughout the pump and This network was titled “National Research and Demonstration Network of FGD feed system under ultra-dense phase flow conditions -- i.e., void fractions below 55 Products in Agriculture” and is hereafter referred to as the network. Field experiments vol% -- and delivered to the gasifier through a rapid-mix multi-element injector. The in the network are supported by utilities that currently produce or will produce FGD flow split non-uniformity from the multi-element injector was found to be a direct gypsum and are interested in regional agricultural uses of the product. The experiments function of the injector’s Bingham stress number. An assessment is provided for the are designed according to a uniform protocol that includes a comparison of FGD effect of flow splitter non-uniformity on cold-gas and carbon-conversion efficiencies gypsum with commercially-available gypsum, and involve at least two years of crop of a PWR entrained-flow compact gasifier. Preliminary design of the system’s dry yield and other data collection. Environmental effects of gypsum applications are solids feed pump was completed in September 2007 followed by the start of a sub- monitored by extensive chemical characterization of the gypsums, pre- and post- scale test effort for key pump components at bulk solids stresses (compression and treatment soils, crop grain or other biomass, and shallow ground (vadose) water. The shear) in excess of 500-psi. These results will be incorporated into the pump’s detail first research was begun in North Dakota in 2007. Additional studies are being design currently scheduled for completion in CY2009. Pump testing at EERC is now established in 2008 in New Mexico, Indiana, Arkansas, Alabama, and Ohio. These scheduled to begin in CY2010. 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) 43-3 reduce available phosphorus in surface soils receiving poultry litter amendment, and Temperature Measurement in Gasification Processes (4) ameliorate subsoil acidity. The data obtained from the various experiments are Thomas Wolf, Emerson Process Management, GERMANY; Trent Riggs, made available to all participants in the network to help promote sound agricultural Emerson Process Management, USA and environmental use of FGD gypsum in the United States. 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

41 to triple seals. This has led to considerable operational savings in the maintenance and 43-5 reduced process downtime. Generic Process Design and Control Strategies Used to Develop a Dynamic Problem/Challenges addressed Model and Training Software for an IGCC Plant with CO2 Sequestration Following Challenges have been defined: Graham T. Provost, Herman P. Stone, Michael McClintock, Fossil Consulting 1. Low Process Availability Services, Inc.; Michael R. Erbes, Enginomix, LLC; Stephen E. Zitney, DOE- Contamination by poisoning gases of the high temperature thermocouple leads to NETL; Richard Turton, West Virginia University; Jeffrey N. Phillips, Merrill failure of the temperature sensors after short time (up to 3 months) and leads to Quintrell, Jose Marasigan, EPRI, USA inability to control the gasification process. 2. Fugitive Emissions To meet the growing demand for education and experience with the analysis, Current practice requires complicated and expensive purging to eliminate fugitive operation, and control of commercial-scale Integrated Gasification Combined Cycle emissions. (IGCC) plants, the Department of Energy’s (DOE) National Energy Technology Solution: Laboratory (NETL) is leading a collaborative R&D project with participants from Use of gas tight ceramic material -in this case sapphire was chosen to protect the government, academia, and industry. One of the goals of this project is to develop a thermocouple wires from hydrogen contamination at process temperatures of up to generic, full-scope, real-time generic IGCC dynamic plant simulator for use in 1800°C. In order to practically eliminate the risk of fugitive emissions during operation establishing a world-class research and training center, as well as to promote and due to the break of the temperature sensor, 2 pressure tight seals have been demonstrate the technology to power industry personnel. The NETL IGCC dynamic implemented. Primary seal being the pass through connection to the connection Head plant simulator will combine for the first time a process/gasification simulator and a and secondary seal being the pass through to the connection terminals. power/combined-cycle simulator together in a single dynamic simulation framework Results/Benefits: for use in training applications as well as engineering studies. As envisioned, the Process availability was significantly increased as the life time of the high temperature simulator will have the following features and capabilities: thermocouple of approx. 15 month vs. approx. 4 month for a standard high temperature - A high-fidelity, real-time, dynamic model of process-side (gasification and gas thermocouple. Risk for fugitive emissions due to thermocouple failure has been cleaning with CO2 capture) and power-block-side (combined cycle) for a generic eliminated. IGCC plant fueled by coal and/or petroleum coke - Full-scope training simulator capabilities including startup, shutdown, load 43-4 following and shedding, response to fuel and ambient condition variations, Extended Field Testing of an Acoustic Sensor for Gas Temperature control strategy analysis (turbine vs. gasifier lead, etc.), representative Measurement in Coal Gasifiers malfunctions/trips, alarms, scenarios, trending, snapshots, data historian, and Peter Ariessohn, Noel Fitzgerald, Enertechnix, Inc.; Kamalendu Das, DOE- trainee performance monitoring NETL, USA - 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 Under contract DE-FC26-03NT41617 from the Department of Energy, and with To support this effort, process descriptions and control strategies were developed for assistance from ConocoPhillips and SG Solutions, Inc., Enertechnix, Inc. has key sections of the plant as part of the detailed functional specification, which will developed a novel acoustic gas temperature sensor for use in coal gasifiers. This sensor form the basis of the simulator development. These plant sections include: has been tested successfully at the Wabash River coal gasification plant and an - Slurry Preparation extended test is currently in progress. - Air Separation Unit Since 1989 the U.S. Department of Energy has supported development of advanced - Gasifiers coal gasification technology. However, a continuing challenge for entrained flow - Syngas Scrubbers gasifiers is the tradeoff between achieving high carbon conversion which requires high - Shift Reactors internal gas temperatures, and degradation of the refractory which is exacerbated by - Gas Cooling, Medium Pressure (MP) and Low Pressure (LP) Steam Generation, those high temperatures. Reliably maintaining the optimum gas temperature is and Knockout hindered by the lack of a reliable technology for measuring gas temperature. For this - Sour Water Stripper reason, the Department of Energy has funded several research projects to develop more - Mercury Removal robust and reliable temperature measurement approaches for use in coal gasifiers. - Selexol™ Acid Gas Removal System Enertechnix has developed a line of acoustic gas temperature sensors for use in coal- - CO2 Compression fired electric utility boilers, kraft recovery boilers, cement kilns and petrochemical - Syngas Reheat and Expansion process heaters. Acoustic pyrometry provides several significant advantages for gas - Claus Plant temperature measurement in hostile process environments. First, it is non-intrusive so - Hydrogenation Reactor and Gas Cooler measurement component survival is not a serious problem. Second, it provides a line- - Combustion Turbine (CT)-Generator Assemblies of-sight average temperature rather than just a point measurement so the measured - Heat Recovery Steam Generators (HRSGs) and Steam Turbine (ST)-Generator temperature is more representative of the process conditions than a thermocouple In this paper, process descriptions, control strategies, and Process & Instrumentation measurement. Third, unlike radiation pyrometers, the measured temperature is a linear Diagram (P&ID) drawings for key sections of the generic IGCC plant are presented, average over the full path rather than a complicated function of gas temperature and along with discussions of some of the operating procedures and representative faults the exponential Beer’s law. This permits tomographic reconstruction of the acoustic that the simulator will cover. Some of the intended future applications for the simulator measurements on multiple paths to produce detailed 2-dimensional temperature maps. are discussed, including plant operation and control demonstrations as well as Therefore, acoustic pyrometry is an attractive choice for measuring gas temperature education and training services such as IGCC familiarization courses. 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 SESSION 44 developed and tested a novel sound generation method suitable for use in a high GASIFICATION TECHNOLOGIES: SYNTHESIS GAS CLEANING – 2 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 44-1 was fabricated and tested in the lab and at Wabash River. Those tests demonstrated the Novel Method for Synthesis Gas Desulfurization feasibility of the measurement technique in a commercial gasification plant and Gregory Krumdick, Edward Daniels, Jianhong Yang, Argonne National showed the ability of the sensor to make accurate gas temperature measurements inside Laboratory, USA; Boyd Davis, Alain Roy, Ian Glaw, Kingston Process the gasifier during normal operation. Metallurgy, CANADA 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 Research at Argonne National Laboratory and Kingston Process Metallurgy has measurements were obtained. However, an incident early in the testing resulting from demonstrated that a novel process incorporating molten copper to convert the H2S to component failure combined with inadequate procedures caused a delay of several SO2 while reforming contaminants such as ammonia and hydrocarbons to their months. Following this incident, substantial improvements in the hardware, software, elemental constituents is technically feasible and offers the potential for significant procedures, documentation and training were implemented and the unit was re- capital cost reduction and efficiency improvement relative to conventional gas clean- installed on the gasifier in the late summer. Testing has now resumed and the sensor is up technology. In this process, a series of conventional gas clean up unit operations operating properly. are eliminated from the process including particulate scrubber, ammonia scrubber, This paper reports on the theory and practical considerations affecting acoustic amine stripper, amine regeneration, Claus plant and SCOT units. The H2 in the H2S pyrometry in gasifiers, the operating characteristics of our prototype sensor, the lessons contributes to the overall energy balance of the system, and the sulfur is removed from learned from the incident in March, and the results of testing to date at Wabash River. the system as SO2. In this system, the sulfur would be scrubbed using conventional flue gas desulfurization technology. This technology should be highly efficient 42 because the SO2 is isolated from all other process gas streams upon regeneration of the and bench scale fixed bed flow reactor tests conducted with the sorbent to evaluate the molten copper; thus the SO2 stream is essentially 100% if using pure O2. Because the feasibility of both H2S and HCl sorption will be discussed in this paper. copper process offers the opportunity to completely change conventional gas-clean up from coal gasification, the capital cost reduction opportunity and efficiency 44-4 improvement that results from this process for IGCC applications would also be Sorbents for Removing Trace Metal Contaminants from Coal-Derived Synthesis directly applicable to any coal gasification process including indirect liquefaction for Gas production of fuels and also for production of H2 from coal. Gokhan Alptekin, Margarita Dubovik, Bob Amalfitano, TDA Research, Inc., USA

44-2 Gasifiers convert coal into synthesis gas feed streams that can be used in advanced Metal-Based Adsorbents for Regenerable Deep Desulfurization of Warm power cycles to generate electricity and in the production of a wide variety of Syngas chemicals. However, the coal-derived synthesis gas contains a myriad of trace Liyu Li, David L King, Jun Liu, Kake Zhu, Yong Wang, Pacific Northwest contaminants that cannot be released to the environment if the syngas is burned to National Laboratory, USA generate power or may poison the catalysts used in the downstream chemical manufacturing processes. Therefore, removal of these contaminants is critical for the Gasification of coal or biomass to syngas followed by catalytic synthesis of liquid widespread and environmentally-friendly utilization of coal. hydrocarbons or oxygenates provides a feasible strategy to meet the increasing demand TDA Research Inc. (TDA) is developing a sorbent-based system that can reduce the for transportation fuels. Syngas generated by the gasification of biomass or coal concentration of the trace metal contaminants (i.e., mercury, arsenic, selenium and contains many impurities. Among the most important are the sulfur-containing cadmium) to less than parts per billion levels in the coal-derived synthesis gas at molecules, as they are poisons for catalysts employed in subsequent conversion elevated temperatures (260°C). Previously, in series bench-scale experiments, we first reactions. Solvent-based processes operated at ambient or lower temperature are showed that the sorbent is capable of removing Hg, As and Se separately using currently employed to achieve the necessary sub-ppm sulfur levels. These processes simulated synthesis gas. The sorbent performance was also evaluated for combined are costly and energy intensive, since the syngas must be cooled to the solvent removal of these contaminants. The impact of using syngas from different types of temperature and then reheated to the synthesis temperature. Removal of sulfur gases at gasifiers (primarily the effect of steam partial pressure) and the presence of sulfur (as temperatures greater than 250°C will improve the energy efficiency and lower the hydrogen sulfide and carbonyl sulfide) on sorbent performance were also evaluated. process cost. Warm gas clean-up technologies have been developed, typically based on Based on the successful results, the performance of a sorbent-based multi-contaminant zinc oxide or modified zinc oxide, which can regenerably reduce sulfur gases to a few removal system was evaluated using actual coal-derived synthesis gas. The ppm level. However, such materials are inadequate for liquid fuel synthesis demonstration tests were carried out at the University of North Dakota Energy application, which requires sulfur concentrations in the syngas to be below 50 ppb to Environmental Research Center. This paper discusses the results of our sorbent minimize the poisoning of synthesis catalysts. development efforts and field test. 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 45-5 reforming, Fischer-Tropsch, and other syntheses reactions. This strong surface Palladium Sorbents for High Temperature Capture of Mercury, Arsenic, adsorption phenomenon has been exploited in the design of sacrificial metal-based Selenium, and Phosphorus from Fuel Gas guard beds, which can remove sulfur to the ppb levels. In order to develop regenerable Evan J. Granite, Lindsay Bombalski, Christina R. Myers, Dennis P. Stanko, adsorbents, however, several items need to be addressed. First, the metal needs to be Henry W. Pennline, DOE-NETL; Wilson Chu, Johnson Matthey, USA; Hugh finely divided to maximize the surface area, and therefore the adsorption capacity. The Hamilton, Liz Rowsell, Stephen Poulston, Andrew Smith, Thomas Ilkenhans, preparation method chosen must be simple and scalable. Second, the small metal Johnson Matthey Technology Centre, UNITED KINGDOM particle size must be maintained--agglomeration and sintering must be avoided during both operation and regeneration. Third, the adsorbents must be regenerable using In gasification for power generation, the removal of mercury by sorbents at elevated available gas streams and cost effective procedures. temperatures enhances the high thermal efficiency of the integrated gasification By trapping Ni and Ni-Cu alloy nanoparticles in three dimensional mesostructured combined cycle system. Unfortunately, most sorbents will display poor capacity for silica SBA-16, we have developed a class of metal-based adsorbents that can remove elemental mercury at elevated temperatures. Previous experience with sorbents in flue sulfur from warm syngas to less than 50 ppb levels based on sulfur chemisorption. We gas has allowed for judicious selection of potential high temperature candidate have also discovered that a sequential oxidation-reduction treatment can effectively sorbents. The capacities of many sorbents for elemental mercury from nitrogen, as regenerate the sulfur-loaded adsorbent. Previously only sacrificial metal-based guard well as from different simulated fuel gases at temperatures from 400°F - 700°F, were beds were available. For the first time, a sulfur-loaded metal-based adsorbent has been determined. The simulated fuel gas compositions contain varying concentrations of efficiently regenerated. This solid adsorbent-based approach may provide economic mercury, arsine, hydrogen selenide, phosphine, carbon monoxide, hydrogen, carbon advantages compared with more conventional liquid adsorbents, which carry an dioxide, moisture, and hydrogen sulfide. economic penalty associated with cooling and reheating the syngas. With practical Palladium is an attractive sorbent candidate for the removal of mercury from fuel gases coal-based syngas that may contain several thousand ppm of sulfur, these adsorbents at elevated temperatures. In addition, recent results suggest that palladium has would need to used in combination with higher capacity adsorbents such as zinc oxide. excellent potential for arsenic, selenium, and phosphorus capture from fuel gases, The mesoporous-based adsorbents would provide the sub-ppm polishing capability that making it capable of multi-pollutant capture. A license agreement has been signed by cannot be provided by zinc oxide alone. the United States Department of Energy and Johnson Matthey for further development In addition to providing a practical approach to sulfur deep removal from warm of the sorbents. Current results and future sorbent development for trace metal capture syngas, the same concept may also find application for removal of other trace level from fuel gases will be discussed. 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 SESSION 45 sintering has remained a great challenge. Our study suggests that the stability and ENVIRONMENTAL CONTROL TECHNOLOGIES: NOx/SOx CONTROL activity of nanoparticles may be substantially enhanced by judicial choice of the pore STRATEGIES architecture that confines them.

44-3 45-1 Regenerable Multi-functional Sorbent Development for Sulfur and Chloride Metal Impregnation of Activated Carbon Fiber for Catalyzed Hydrogen Removal from Coal-Derived Synthesis Gas Sulfide Oxidation Ranjani Siriwardane, Abbie Layne, DOE-NETL; Thomas Simonyi, Parsons, Inc., Jason D. Monnell, Huixing Li, Radislav D. Vidic, University of Pittsburgh; Mary USA Anne Alvin, DOE-NETL, USA

A large number of components in coal form corrosive and toxic compounds during The contribution of metal centers, metal oxides, and catalyst supports to the catalytic coal gasification processes. DOE’s NETL aims to reduce contaminants to parts per breakdown of hydrogen sulfide at a process temperature ~140°C suitable for low billion in order to utilize gasification gas streams in fuel cell applications. Even more temperature clean-up of IGCC produced syngas was investigated. Materials were stringent requirements are expected if the fuel is to be utilized in chemical production exposed to a typical IGCC syngas that contains 4000 ppm H2S in a down-flow packed- applications. bed reactor and the tail gas was analyzed via mass spectroscopy. Metal-free activated Future emphasis of the NETL coal gasification/cleanup program is to develop multi- carbon fibers and high purity alumina samples were used as supports and as baseline functional sorbents to remove multiple impurities in order to minimize the steps H2S catalysts and H2S adsorbent materials. Catalytic metals (La, Ce, V, and Cu) were involved in the cleanup systems. To accomplish this goal, a regenerable sorbent impregnated onto these supports via insipient wetness at approximately 5% w/w. capable of removing both HCl and H2S was developed. The results of the TGA tests Native alumina samples have very little catalytic or adsorptive capacity whereas activated carbon fibers have catalytic and adsorptive capacities that are comparable to 43 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 SESSION 46 differences in surface area were directly correlated with increased retention of sulfur CHEMICALS, MATERIALS, species, the chemical composition of the sulfur on the material was directly affected by AND OTHER NON-FUEL USES OF COAL – 1 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 46-1 is notable since COS is a more undesirable by-product than SO2. More importantly, Optimization of Microwave-Assisted Extraction Shenfu Coal and Analysis there is a different mechanism for the interaction between the metal center and the H2S of Extract and Residue molecule. It must be noted that this effect is transient and the long-term balance results Hong Chen, Jianwei Li, Hua Wang, Lingmei Ge, Xi’an University of Science in a 1:1 ratio of COS to SO2 in the tail-gas. The return to a 1:1 ratio from a single and Technology, CHINA product observation may indicate that the metal center becomes overwhelmed / poisoned and the breakdown of H2S into the products is performed on the support Coals consist of some simple molecules trapped in an organic matrix. Many of the regardless of the metal impregnate. This may not be the case with Cu, because when simple compounds can be extracted by solvents. Soxhlet technique has been widely Cu is used with activated carbon fibers to treat H2S, the off-gases observed are H2S, used for extracting organic compounds. How to decrease the harm to the environment COS, and SO2 at a steady state ratio of 3:1:1. This may be due to a surface hand-off when exploiting and utilizing coal, how to get clean resource or chemical products that occurs between copper and the carbon that does not happen with other metals. from such a traditional unclean resource, utilizing low-cost and an environment- While it does not produce an ideal off-gas, these Cu-impregnated carbon catalysts are friendly microwave-assisted extraction technology becomes a new approach and field the most promising of these materials and are a step towards an economical means for in comprehensive utilization of coal. In order to investigate extraction yields and H2S cleanup materials. chemical composition of extract, extraction with acetone was conducted for typical Chinese coal-Shenfu coal under microwave-assisted extraction (MAE) and acetone- 45-2 extractable fraction was analyzed with GC/MS. The number of organic compounds Low-Cost ESP Discharge Electrode (OCs) identified in acetone-extractable fraction was fifty-two. The organic compounds Hajrudin Pasic, Ohio University, USA obtained by extraction contained normal alkanes, branched alkanes, cyclanes, non- substituted arenes, substituted arenes, organooxygens and organonitrogens. Discharge electrodes are critical components in electrostatic precipitators (ESP). Carbon-13 nuclear magnetic resonance (NMR) spectra, which provide direct Developments in discharge electrode technologies have fostered evolution in ESPs, measurements of the chemical structure of organic matter, have been obtained for such as rigid discharge electrodes to which many sharpened spikes are attached to Shenfu coal (daf) and its residue of acetone extraction. Being converted into numerical maximize corona production for improved ESP performance. However, due to the parameters, the spectra show differences related to Shenfu coal(daf) and its residue of harsh and corrosive service environment these electrodes typically have to be made acetone extraction. Three NMR parameters—fa,Ha,Xb are examined, which indicates from expensive materials such as stainless steel, adding substantially to the overall cost the difference in macromolecule structure between Shenfu coal(daf) and its residue. of the electrodes. Here we propose low-cost polymer electrode whose design results in drastic decrease 46-2 of electrode’s cost, due to reduction in the production and material cost. In addition, Extraction and Upgrading of Brown Coal through Treatment in Solvent at light-weight design will further reduce installation costs due to reduction in structural High Temperature support requirements. Kouichi Miura, Ryuichi Ashida, Satoshi Umemoto, Akihiro Sakajo, Kyoto University; Koji Saito, Kenji Kato, Nippon Steel Corporation, JAPAN 45-3 Advanced Equipment Development for Wet Lime Fgd System Use, i.e. in Treatment of brown coal in a solvent (1-methylnaphthalene) at temperatures lower Accessing, Transport and Slaking of Pebble Lime Feed than 350°C is proposed as an effective method to fractionate brown coal into several Kevin Furnary, LEEP Holdings, LLC; William Ellison, Ellison Consultants, upgraded fractions having different chemical compositions and structures. When an USA Australian brown coal, Loy Yang (C%=66.9, O%=27.7), was treated for 3 h at 350°C in a batch extractor, it was converted into three upgraded fractions: the fraction soluble Contacting pebble lime supply with water in a controlled fashion can ensure uniform in solvent even at room temperature (Soluble; Yield:Y=0.218, average molecular wetting of all, newly exposed, lime particle surface, this being critical in gaining weight: MW,a=330, C%=82.3, O%=9.8), the fraction soluble at 350°C but insoluble at completion of CaO hydration and in maximizing the reactive surface area afforded in room temperature (Deposit; Y=0.105, MW,a=500, C%=77.0, O%=16.8), and the use of the calcium hydroxide, slaker output. This paper will review the design, solvent insoluble fraction (UC; Y=0.527, MW,a=800, C%=79.6, O%=15.2). The rest operation and performance of an industrial dynamic mixer developed and of the brown coal was converted into either CO2 or H2O. This means that 80% of the commercially used in Australia that fulfills this objective. Avoiding all fugitive dust brown coal was converted into high carbon and low oxygen content fractions having formation, the system design provides for enclosed pneumatic conveying of pebble rather uniform molecular weight distribution under mild conversion. The fractions had lime feed to the slaker from silo storage, the latter equipped with novel, near-silo- properties significantly different from those of the raw coal, suggesting their surface, fluid atomization. Uniquely generated fluid dynamic shearing achieved in this application to various purposes. The proposed method will surely be one of novel and unique mixer breaks up any dry solids clumps while providing fullest mixing of the effective brown coal utilization methods. 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 46-3 Water Treatment Plant in Western Australia employing a three inch diameter, mixer Solvent Extracting Aromatic Hydrocarbons from Coal-Derived Oil flow-path, this with intensely high, mass transfer rate operation producing 88,000 lbs Dexiang Zhang, Guolong Wang, Jue Huang, East China University of Science per day of slaked lime. and Technology, CHINA

45-4 Some solvents, including sulfolane, dimethyl sulfoxide and furfural, were used to Ammonia Nitrogen Removal from Coking Wastewater by Chemical extract aromatics from coal-derived oil. The coal-derived oil and solvent were put into Precipitation and Repeated Use of MAP extraction device according to different weight ratio and temperature. The group Shizhuang Shi, Yuan Yuan, Qixiang Li, Hui Wang, Wuhan University of composition of the extracted oil was determined by column chromatography (Refer Science and Technology; Shuangqing Zhou, Wuhan International Trade ASTM 2007, 2549-81). The results show that recovery efficiency and purity of University; Hongbing Chang, Wuhan Iron and Steel Group Corporation, CHINA 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 The paper introduces a technology to remove ammonia-nitrogen from coking coefficients of sulfolane and dimethyl sulfoxide are higher than that of the furfural wastewater by using MAP method. The ammonia-nitrogen removal efficiency under while the furfural has the strongest dissolution ability. Contrasting to the other two different rations of reagents, pH and operation conditions was studied. Under the solvents, furfural is preponderant in extracting aromatics from coal-derived oil. At 303 suitable condition, purely crystal MAP were obtained, and the removal rate of K for furfural, extraction recovery efficiency of aromatics increases with the increasing ammonium-nitrogen is over 98%. The residues of magnesium ammonium phosphate solvent/oil ratio. That is 50.64% and 97.29% when the weight ratio of solvent to oil (MAP) decomposed by heating under alkali conditions were repeatedly used as the equals to 1 and 9, respectively. But purity of extracted aromatics decreases with the only sources of phosphate and magnesium for the removal of high ammonium rise of solvent/oil ratio. The purity of aromatics is 74.09% and 86.25% when the concentration from wastewater. Up to 93% of ammonium-nitrogen in wastewater weight ratio of solvent to oil equals to 9 and 3, respectively. Considering both recovery could be removed by using residues decomposed under the following conditions: efficiency and the purity, the best ratio of solvent to oil is 3. The effects of extracting + - NH4 :OH molar ratio= 1:1, temperature 100°C, heating time 3 hrs. Chemical costs temperature and water adding to solvent on aromatics extraction were investigated were greatly reduced and the ammonia in wastewaters was reclaimed. also.

44 46-4 flue gas in a well-mixed reactor. During the semi-batch tests, the solution was cycled Co-Pyrolysis of Brown Coal Upgraded under Hydrothermal Condition and between absorption and regeneration steps to measure the carrying capacity of the Plastic Wax solution at various initial ammonia concentrations and temperatures. The continuous Ryuichi Ashida, Monthicha Pattatapanusak, Kouichi Miura, Kyoto University; tests combined the absorption of carbon dioxide from a simulated gas and a thermal Koji Saito, Kenji Kato, Nippon Steel Corporation, JAPAN 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 We have recently presented a co-pyrolysis process of hydrothermally upgraded brown parameters that were studied included absorber temperature, regenerator temperature, coal and waxes prepared from plastics. This process intends to upgrade further the initial NH3 concentration, simulated flue gas flow rate, liquid solvent inventory in the brown coal upgraded under hydrothermal condition utilizing interaction with waste flow system, and height of the packed-bed absorber. Titrimetric methods were used to plastics during the co-pyrolysis. Char and gas yields increased respectively by 13.2% determine the amount of ammonium hydroxide, ammonium carbonate, and ammonium and 6.0% for co-pyrolysis conducted at a rapid heating rate at 1040°C when compared bicarbonate in the solution at appropriate locations and times. Results from the various with the yields calculated assuming independent pyrolysis of the coal and the wax. testing systems will be discussed with respect to the implications that these results Char and gas yields increased respectively by 15.0% and 6.7% even for co-pyrolysis have on a scrubbing process scheme. conducted at a slow heating rate at 900°C. Large increase in the yield of oxygen- containing inorganic gases suggested the further upgrading of the coal during the co- 47-3 pyrolysis. On the other hand, no or little changes in the product yields were found Novel Carbon Dioxide Separation Using High Temperature Direct when the raw coal was co-pyrolyzed with the wax. In this work co-pyrolysis behavior FuelCell® Technology for Carbon Sequestration was examined using a residual coal obtained through high temperature solvent Hossein Ghezel-Ayagh, Bob Sanderson, Dilip Patel, Sven Tobias Junker, extraction of a bituminous coal as one of the ways of utilizing the residual coal. Stephen Jolly, Carl Willman, FuelCell Energy, Inc., USA 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 Given the United States’ heavy reliance on fossil fuel as an energy source, the porous materials was pyrolyzed. Porous materials were used to eliminate chemical reduction of carbon dioxide released to the environment poses both technical and interactions between the wax and the coal leaving only physical effects. Rapid economic challenges to the available sequestration technologies. In response to this pyrolysis of wax in the pore of the porous materials produced more char and growing environmental concern, FuelCell Energy (FCE) has developed novel system hydrocarbon gases than the rapid pyrolysis of wax in a bulk phase, indicating that concepts for separation of carbon dioxide from greenhouse gas (GHG) emission physical effect might be involved in the rapid co-pyrolysis process as well as chemical sources using Direct FuelCell® (DFC®) technologies. For carbon dioxide separation, interactions. For the slow pyrolysis, on the other hand, char was not formed at all for the DFC is modified to operate similar to an electrochemical membrane, whereas all the porous materials, suggesting that only chemical interaction might be involved carbon dioxide is separated from GHG in the cathode and is transported to the CO2 for the slow co-pyrolysis, or that an attractive force between the wall of coal’s pores enriched stream at the anode exhaust. and the wax might be so strong that the attractive force could contribute to retaining The unique chemistry of carbonate fuel cell offers an innovative approach for the wax in the pore of the coal during the co-pyrolysis even under the slow heating and separation of carbon dioxide from greenhouse gases (GHG). The carbonate fuel cell hence cause the chemical interactions. 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 SESSION 47 carbonate fuel cell featuring internal reforming. This technology has been deployed in GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND MW-scale power plants and is readily available as a manufactured product. UTILIZATION – 5 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. 47-1 The flue gases from PC and atmospheric circulating fluidized bed (ACFB) power Evaluating and Optimizing Post-Combustion CO2 Capture with Ammonia- plants are somewhat lean in oxygen, one of the reactants required at fuel cell cathode, Based Solvents for proper operation of DFC. Conditioning of the flue gas, therefore, included blending Thomas J. Tarka, DOE-NETL, USA 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 The growing threat and awareness of global climate change has intensified the need for demonstrated the required minimum 90% CO2 separation. The tests were conducted viable post combustion capture technologies for use with the existing coal-fired fleet. using simulated clean flue gas from PC power plant. If possible, this need has become even more acute as proposed power plants continue In one of the system concepts, CO2-containing flue gas from coal-fired, combustion- to be canceled or postponed, often due to escalating construction costs and regulatory based power plants, such as the exhaust from a pulverized coal (PC) power plant, is uncertainty. Wet-scrubbing with chemical solvents such as amines remain the most utilized as oxidant for the DFC cathode. The concept’s key feature is that the DFC likely post combustion capture technology available for deployment in the “near- utilizes the CO2 of the flue gas as a reactant for the electrochemical reaction to produce term”. power, while synergistically transferring CO2 from the flue gas to the anode exhaust One wet-scrubbing process which has garnered much attention in recent years is the stream. In contrast to other carbon sequestration technologies, which consume power, use of ammonia-based solutions for CO2 capture. These technologies generally utilize the DFC-based system concept efficiently generates electricity as either a source of the ammonium carbonate/ammonium bicarbonate absorption/desorption mechanism in revenue or supply to the on-site power demand. The concept is suitable for capturing order to achieve a less energy-intensive capture process, as compared to common 90% or more of carbon dioxide from a wide-range of industrial CO2-containing amines. At least two large scale pilot projects have been initiated recently which streams as well as power plant flue gases. Basic system and economic analysis for the examine these technologies. DFC-based CO2 separation system, estimating the increase in cost of electricity (COE) This paper utilizes AspenPlus and other modeling tools to determine the optimal of a PC power plant retrofitted with the CO2 separation and capture system has operating conditions for a process utilizing the ammonium carbonate/ammonium indicated that the mature commercial DFC CO2 separation and capture systems have bicarbonate CO2 capture mechanism. Both the economic and technical performance is the potential for achieving the Carbon Sequestration Program goal for post-combustion evaluated. CO2 capture (2012 goal of < 20% increase in COE).

47-2 47-4 Investigation of an Ammonia-Based Wet Scrubbing Process in a Continuous Oxyfuel Combustion Using CFBC – Some Early Lessons Flow System Ben Anthony, L. Jia, Y. Tan, CANMET Energy Technology Centre-Ottawa Kevin P. Resnik, RDS-Parsons; Henry W. Pennline, DOE-NETL, USA (CETC-O), Natural Resources Canada, CANADA

A preliminary analysis of an ammonia-based wet scrubbing system revealed significant Oxyfuel FBC has been examined in a 100 kW pilot plant operating with flue gas advantages over the MEA process to capture carbon dioxide from flue gas from cooling. The results strongly support the view that this technology offers all of the coalfired power plants in a conventional absorption/stripping system. The advantages advantages of air-fired FBC, with one possible exception. Emissions such as CO or included: a greater potential loading capacity to reduce sensible heating costs, a lower NOx are lower or comparable to air firing, and it is possible to switch from air firing to heat of reaction, a lower reagent cost, a lower equipment corrosion rate, a lack of oxy-firing easily, with oxygen concentrations as high as 60-70%, and flue gas recycle irreversible degradation products, and the ability to be utilized as a multi-component levels of 50-60%. Only sulphation is poorer, which is not in good agreement with other carbon capture system with salable byproducts. Experimental research has been studies, and the reasons for this discrepancy need further exploration. However, longer conducted to evaluate the performance of this ammonia-based system, focusing on the tests have confirmed these findings with two coals and a petroleum coke. It also ability to remove carbon dioxide from flue gases. This paper discusses results from appears that changing from direct to indirect sulphation with the petroleum coke semibatch tests and details findings from the more recent continuous experiments. The improves the sulphation, although a similar effect could not be confirmed with coal. semi-batch tests used a fixed amount of solution and a continuous stream of simulated 45 47-5 Pressure Swing Adsorption Technology for Carbon Dioxide Capture SESSION 48 James A. Ritter, Amol Mehrotra, Armin D. Ebner, University of South Carolina, COAL UTILIZATION BY-PRODUCTS – 2 USA

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

46 48-3 the up Results of these experiments are very interesting and can be used also on the Fly Ash as a Chemical Scrubber for Acidic Wastes other conditions. Haim Cohen, Ithamar Pelly, Ariel University Center at Samaria; Eli Lederman, Ben-Gurion Univ of the Negev, ISRAEL; Mehmet Polat, IZTEK, TURKEY

Israel’s annual coal consumption is 12.7 million tons in 4 power stations producing SESSION 49 ~65% of the country’s electricity. The process produces 1.3 million tons per year of fly GASIFICATION TECHNOLOGIES: ADVANCED TECHNOLOGIES – 3 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 49-1 additive (10%w) to clinker and the rest as a construction material for embankments, Interactions Between Slag and High Chrome Oxide Refractory Liners in Air road basements and in concrete production. Cooled Slagging Gasifiers The fly ash produced in Israel has a highly basic reaction when exposed to water. That James P. Bennett, Kyei-Sing Kwong, Arthur V. Petty, Hugh Thomas, Rick is a result of the very low sulfur content allowed in coal imports due to strict Krabbe, DOE-NETL, USA 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 Gasification of carbon containing materials is used to produce CO and H2 for chemical sludge produced from the regeneration process of used motor car oil and the acidic and power production, including the production of liquid fuels. The generalized wastes produced by the phosphate industry. The results show that the fly ash can be reaction that occurs in a gasifier at elevated temperatures, pressures, and in a reducing used as a very efficient scrubber for both wastes. Furthermore, the fixation of the trace environment converts a carbon feedstock, water, and oxygen to primary products of elements and the organic components within the fly ash particles is highly efficient. It carbon monoxide and hydrogen as follows: C (with impurities) + H2O + O2 → H2 + was also found that the fixation product can be used as a good aggregate in concrete CO + CO2 + H2S + minority gases + excess carbon as char + ash (from mineral production. Bricks produced using the aggregate as a sand substitute have proved to be impurities). A primary carbon feedstock used worldwide in gasification is coal; strong enough according to the concrete standards. Furthermore the leaching of trace although coal and petcoke or mixtures of them with other carbon sources, such as elements from the bricks is within environmental regulations. Thus using the two biomass, can be used. wastes (flyash + acidic waste) result in a green friendly product that do not need to be The air cooled slagging gasifier typically operates between 1325 and 1575°C, and at stored but can be recycled in the construction industry. The neutralization and fixation pressures between 400 and 1000 psi - conditions that depend on the specific gasifier processes will be discussed in detail. 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 48-4 severe service environment. The major components of the refractory are chrome oxide Kinetics and Mechanism of Cr (VI) from Aqueous Solution with Ultrafine (60-95 pct), alumina (2-40 pct), and zirconia (0-12 pt). Service life of these liner Coal Fly Ash materials in the hot slagging environment can be as short as 3 months or as long as 24 Liu Zhuan-nian, Xi’an University of Science and Technology, CHINA months; and is directly dependent on slag chemistry, temperature of operation, feedstock throughput, and the gasifier cycling practices. The main causes of refractory Coal fly ashes WSRA (collected from the Heat and Power Plant in the Western Suburb failure are slag corrosion/dissolution of the refractory and spalling caused by slag of Xi’an, Shaanxi province, China) and BQRA (collected from the Baqiao Thermal penetration of the refractory. Slag originates from impurities in the carbon feedstock Power Plant, Xi’an, Shaanxi province, China) were used in this study. WSRA and (ash) that liquefies at the elevated temperature of gasification; producing molten BQRA were ball milled for 5 h and got the ultrafine coal fly ashes WSUA and BQUA, material high in oxides of Si, Fe, Al, and Ca. Other elements that may be present in the respectively. Batch kinetic, isotherm and pH effect on adsorption were studied to coal slags include S, K, Na, and Mg; with Ni and V present in petcoke slags. evaluate removal of Cr (VI) from aqueous solutions by ultrafine coal fly ashes and Discussions of how the slag interacts with the refractory liner and the compounds were compared with raw coal fly ashes. The kinetics of adsorption indicates the formed between them will be presented. These will include information on why process to be intraparticle diffusion controlled and follows the Lagergren first-order hexavalent chrome oxide formation in gasifier slag/refractory interactions with current kinetics for all coal fly ashes. The first-order rate constants (k1) of Cr (VI) adsorption carbon feedstock (hexavalent chrome is not viewed as a problem), as well as a onto WSRA, WSUA, BQRA and BQUA are 1.981 min-1, 1.497 min-1, 2.119 min-1 and discussion on which carbon feedstock (and their slags) might be predicted to lead to its 1.500×10-2 min-1, respectively. The adsorption capacities of WSUA and BQUA are formation. In general, slags high in alkali or alkaline earth, such as biomass, could much better than that of WSRA and BQRA. Equilibrium adsorption data of all coal fly impact hexavalent chrome formation. Refractory/slag interactions, and the compounds ashes well satisfy the Langmuir isotherm. The adsorbed amounts of Cr (VI) onto two formed, will be illustrated through post-mortem analyses of samples removed from kinds of ultrafine coal fly ashes decrease from pH 2 to pH 6 then increase up to pH 12. commercial gasifiers.

48-5 49-2 Application of Color Measurements for Estimation of Composition Of Ash Slag Penetration into Refractory Lining of Slagging Coal Gasifier (FBC) Josef Matyáš, S. K. Sundaram, Carmen P. Rodriquez, Autumn B. Edmondson, Dagmar Juchelkova, Helena Raclavska, Konstantin Raclavsky, VSB-Technical Benjamin M. Arrigoni, Pacific Northwest National Laboratory, USA University of Ostrava, CZECH REPUBLIC The impurities in coal are converted into molten slag typically containing SiO2, FeO, The relationships between color parameters and composition of combustion products CaO, and Al2O3 when coal feedstock is burned in slagging gasifiers. The slag flows (bottom ash and fly ash) were studied. Combustion tests were performed in the down the gasifier sidewalls, dissolves, and penetrates and reacts with the refractory fluidized-bed boiler, Trinec, the Czech Republic. The measured color parameters lining that protects the stainless steel shell of the gasifier from elevated temperatures according to CIE L*a*b* standard have significant relationships with mineral phases (1300–1600°C). Refractories composed primarily of Cr2O3 have been found most (magnetite, anhydrite, lime, amorphous phase) and with chemical components (MnO2, resistant to slag corrosion, but they continue to fail performance requirements because TiO2 and minor elements) of fly ash. of low resistance to spalling. Post-mortem analysis of high-chromia refractory bricks Color measurements do not belong to the usual methods for the study of fly ash. A collected from commercial gasifiers suggests that the spalling is affected by the depth visual color assessment using Munsell color tables is the standard method for soils. of slag penetration that is in turn affected by the wettability and interconnected Color measurements were used for the identification of iron oxides and porosity of the refractory as well as the slag viscosity. Laboratory tests were conducted hydroxysulfates in soils by Scheinost and Schwertmann (1999). This paper is devoted to measure the viscosity of slags (Wyoming Powder River Basin [PRB], Pocahontas to the study of relationships between color parameters of fly ash and its chemical and #3, and Pittsburgh #8), their contact angle on refractories (chromia-alumina [Aurex mineral phase composition. 75SR] and high-chromia [Serv 95 and Aurex 95P]), and the apparent porosity of The three combustion tests were performed at the power plant Energetika Trinec selected refractories. In addition, the depth of slag penetration as a function of time and (fluidized-bed boiler K12) aiming at checking the possibility of combustion of waste temperature was determined for various refractory-slag combinations. The results of sludge (oil residues) from Ostramo oil refinery in Ostrava in combination with laboratory tests were used to develop a refractory material that has high resistance to bituminous coal. The town of Trinec is situated in northern Moravia (the north-eastern penetration by molten slag and thus has a potential to have a substantially longer part of the Czech Republic), in the area of Ostrava-Karvina Industrial Region. It is the service life than the materials currently being used. 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 850°C, the middle part 834°C,

47 49-3 The Wettability of Coal and Petcoke Slags on 90 wt.% Cr2O3 - 10 wt.% SESSION 50 Al2O3 Gasifier Refractory Liners Used in Gasification GASIFICATION: CO-GASIFICATION Jinichiro Nakano, Sridhar Seetharaman, Tyler Moss, Carnegie Mellon University; Kyei-Sing Kwong, James Bennett, DOE-NETL, USA 50-1 By utilizing a Confocal Scanning Laser Microsope, the wettability as well as Steam Hydrogasification of Coal-Wood Mixtures in a Batch Reactor penetration behaviors of coal and petcoke slags on high chromia and alumina Arun SK Raju, Chan S. Park, Joseph M. Norbeck, University of California, refractories have been investigated. The petcoke slag showed the lower initial Riverside, USA deformation temperature and also lower melting temperature than the coal slag. The high chromia refractory, in general, returned better corrosion/erosion resistance against Steam hydrogasification is a thermochemical process where a carbonaceous feedstock both slags with the exception that the alumina substrate outperformed in minimizing is gasified in the presence of hydrogen and steam. The product gas stream contains a the slag penetration when the petcoke slag was interacted with a fined region of the significant amount of methane and has a high calorific value. The presence of steam refractory. The VOx-based phase was observed: as a layer of (V, Cr, Fe)Ox at the during the traditional hydrogasification reaction significantly increases the rate of interface between the petcoke slag and the high chromia substrate; and as discrete methane formation. The efficiency of the process and the product gas composition are particles of (V, Al, Si)Ox at the interface between the petcoke slag and the alumina governed by the feedstock composition (H2O/Feed and H2/C ratios), temperature, refractory. In some cases, Ca- and Fe-rich VOx was also observed. For the coal slag, pressure and residence time. The product gas stream from a steam hydrogasifier can be Ca-species penetrated most slowly through the fined regions of both refractories, reformed to generate synthesis gas (H2 and CO) that can be used in Gas to Liquid whereas Fe-species was the fastest in any case. processes. Gasification of co-mingled coal-biomass feedstocks offers several advantages such as 49-4 the reduction in the net CO2 emissions from the process. In this study, steam Investigation of Heat Transfer and Gasification of Two Different Fuel hydrogasification of coal-wood mixtures at various ratios have been performed in a Injectors in an Entrained Flow Gasifier batch reactor. Coal from the state of Utah and cedar wood have been used as the Ting Wang, Armin Silaen, University of New Orleans, USA; Heng-Wen Hsu, feedstock. The carbon conversions were measured at 700 and 800°C at a H2O/Feed Cheng-Hsien Shen, Industrial Technology Research Institute, TAIWAN ratio of 2. Effects of water and hydrogen were also investigated. The results demonstrate that the carbon conversion depends on the reaction One of the problems frequently encountered in a coal gasifier operation is fuel injector temperature and the ratio of coal to wood in the feed does not influence the conversion. failure. Operating in extreme high pressure and high temperature, the typical fuel The carbon conversion varies from 70-80% at 800°C and 50-60% at 700°C. The data injector life span is 6 to 12 months. Numerical simulations are performed to study the also show that the relative composition of CH4, CO and CO2 vary with the coal to flow and temperature fields in the vicinity of the injector tip and the metal temperature wood ratio. The results show that the percentage of CO in the outlet gas composition of two different fuel injector designs -- one with conical-nozzle tip and the other with a increases with the increase in the amount of wood in the feed. This paper presents the blunt tip -- in a dry-fed, entrained-flow coal gasifier. The complete 3-D Navier-Stokes results of these experiments and also comparison of these data with simulation results. equations are solved. The simulation models the gasification process with three global heterogeneous reactions and three homogeneous reactions, including volatile 50-2 combustion. The results show the two different injectors give very different Influence of Coal-Biomass Feed Mixtures on Gasification Products temperature and species distributions inside the gasifier. In the gasifier with the conical Bryan D. Morreale, George Richards, Todd Gardner, Yatish Shaw, Dirk Link, injector tip, the highest temperature inside the gasifier occurs at the center of the Paul Zandhuis, DOE-NETL, USA 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 The United States Department of Energy’s National Energy Technology Laboratory tip of the conical injector due to its premixing feature of fuel and oxidant in the nozzle. (NETL) is aggressively pursuing research and development directed towards The highest temperatures on both injectors are the same, which is around 1600 K. mitigating apprehensions over fuel independence, energy availability and reliability, However, the highest temperature on the conical-tip injector is concentrated at one and environmental issues, especially as related to global warming. The production of location with an extended region of 30 mm between 1600 K and 1100 K; whereas on “synthesis gas” (syngas) from indigenous carbonaceous feedstocks has the potential to the blunt-tip injector hot spots scattered and the hot region (1600 K – 1100 K) only address some of these energy and environmental concerns. The abundance of coal in extends about 3 mm. Experimental results support simulated results and has the US in conjunction with the flexibility of syngas, which can be converted to demonstrated a short life of the conical-tip fuel injector and much extended life for the electricity, hydrogen and/or liquid fuels, is considered a promising near- to mid-term blunt-tip fuel injector. 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 49-5 can prolong national fossil energy resources while providing an energy conversion A Parametric Study to Design an Effective Spray Cooling Deployment in an process with a “negative” carbon footprint. Entrained-Flow Coal Gasifier Although significant research and development has been conducted on the Qiuwang Wang, Peiyao Liu, Xi’an Jiaotong University; Shisen Xu, Baomin characterization of pure biomass- and fossil-based gasification systems, considerable Wang, Thermal Power Research Institute, CHINA; Ting Wang, University of technical challenges and uncertainties remain for co-feed systems. In this study, NETL New Orleans, USA researchers’ are focused on evaluating and reporting on the influence of various coal (Illinois#6, Wyodak, Pittsburgh River Basin, North Dakota Lignite and Texas Sub- Gasification is a clean technique that converts coal into syngas, which can be cleaned bituminous) and biomass types (wheat straw, corn stover, switchgrass, mixed much more easily than the coal itself. The raw sysgas exiting the gasifier is usually at a hardwood and distillers’ dried grains with corn fiber) on reaction rates and solid, liquid very high temperature. To protect the rearward equipment, the raw syngas needs to be and gaseous products. 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 50-3 direct spray cooling. This paper focuses on conducting a 3-D CFD parametric study to Fluidized-Bed Co-Gasification Process of Colombian Coal and Biomass aid in the design of an effective water spray cooling deployment. The studied Wastes parameters include water droplet sizes (100~400 μm) and water injection angles. The Zulamita Zapata, Erika Arenas, Grupo de Energía y Termodinámica - goal is to cool the syngas from 1550°C to 800°C using the shortest spray section. The Universidad Pontificia Bolivariana; Farid Chejne, Universidad Nacional de gasifier is designed to produce methanol at a full load condition, so the amount of Colombia - Sede Medellín, COLUMBIA 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 Coffee husk, rice husk and sawdust are Colombian agroindustrial wastes which were approximately 960 tons per day. The results reveal that smaller droplets are effective in mixed with fine coal from the Amagá region (Antioquia). In some regions in reducing the cooling section length. Moreover, using three water injection angles show Colombia, fine coal from coal mining is considering as a waste. Fine coal has little that inclining the spraying angle upward 45 degrees could shorten the effective cooling demand in Colombia because the most of the coal firing systems are stokers. One length. This study provides a guide for cutting the cost of manufacturing a gasifier alternative for using this fine coal is fluidized beds due to fine coal has high ash and cooling section. 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 750°C and 950°C. The highest conversion and temperature values were obtained during sawdust-coal gasification, while rice-coal mixture gasification showed

48 the lowest carbon monoxide concentrations. Biomass-coal gasification showed better 50-5 results than coal gasification. Study on the Co-Pyrolysis and Co-Gasification Characteristics of Coal and Biomass 50-4 Wang Peng, Wen Fang, Bu Xuepeng, Beijing Research Institute of Coal Pyrolysis of Sawdust-Lignite Blends Chemistry, CHINA Preeti Aghalayam, Jeevan Baretto, Anuradda Ganesh, IIT Bombay, INDIA; Shehzaad Kauchali, University of Witwatersrand, SOUTH AFRICA 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 Co-firing of biomass and coal has the dual benefits of increased efficiency and different samples -Dayan lignite, sawdust and the mixture of two samples were reduction in the overall CO2 emissions. India has considerable reserves of coals (nearly studied. Gasification kinetic behavior of the char from samples was studied using 250 billion tonnes). Many of the Indian coal seams consist of low grade lignites. The TGA. The primary research conclusions were obtained: biomass potential of India is significant with volumes of agricultural waste. In the (1) With the pyrolysis temperature increase, the yield of coal char was decreasing, the literature, it has been shown through thermal analysis that the reactivity of coal- gas was increasing, and the tar increase at initial stage and then decrease in given biomass blends may be predicted based on knowledge of the individual reactivities, temperature range. While, the H2 concentration in gas was increasing, CH4 decreasing, due to a lack of interaction between the two (Vuthaluru, 2004 & Folgueras et al., CO increasing obviously, and the LHV of gas was decreasing. 2003). These articles use bituminous/sub-bituminous coals. Our literature search did (2) The sawdust pyrolysis result showed that the pyrolysis began from 100°C and the not yield any articles on co-firing of particular interest to Indian coals, which are pyrolysis reaction was most drastic at 300°C- 400°C. The final pyrolysis temperature inherently of high ash or high moisture content. would affect the yields and properties of gas and liquid products. The char yield would In this paper, we propose the use of sawdust as a blending material with lignite. be stable when the final temperature over a certain value. Sawdust has been chosen as a representative biomass because of its abundant (3) The synergetic effect was found during coal and biomass co-prolysis. The effect availability in India. Sawdust typically has low (<2%) ash content, and therefore, the results was that the yield of char and gas decrease, the tar products increase and H2 and results obtained can be thought of as independent of the effects of ash. Lignite from CH4 concentration were increase in gas composition. The affect extent of co-effect was one of the Indian mines has been selected. This lignite is known to be of a low-grade relative with temperature, mixture rate, biomass kinds and etc. (Sapru et al., 2007), with low sulphur content. We expect that the blending of sawdust (4) Comparing the gasification activity, at the initial phase, the activity order of three with this lignite will have beneficial effects in co-fired boilers/gasifiers. char samples was coal char> sawdust char > the mixture char. The activity order would An evaluation of the blends for co-firing applications has been done here by means of change to sawdust char>the mixture char> the coal char after some reaction time. thermal analysis. Pyrolysis kinetics has been determined for various combinations of (5) The modeling calculation result showed that the shrinking-core reaction model was biomass & lignites (in terms of percentage amounts). The impact of the heating rate of better than the homogeneous reaction model. The activation energy of Dayan lignite the non-isothermal thermogravimetric analyser experiment, on the observed pyrolysis char and the mixture char was adjacent, and the latter activation energy was smaller kinetics, has also been studied. Five blends have been used here with the compositions that indicated the coal char reaction activity would be increased by add the sawdust. - 90:10,80:20,70:30,50:50 and 30:70 (lignite:sawdust, % by weight). The pure fuels (6) For sawdust char, the relation between the reaction conversion and the reaction have also been studied, for purpose of comparison. time was linear because the higher reaction rate, lower ash content and negligible ash The thermal analysis for these seven cases has been performed at three heating rates – layer diffusion. The external diffusion control model can be used to describe the 10 K/min, 20 K/min & 100 K/min. The obtained DTG curves indicate several sawdust char gasification reaction properly, and the diffusion parameter was in interesting features. The sawdust demonstrates reactivity at a much lower temperatures proportional to temperature. (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 50-6 curves for the blends show two peaks in reactivity – one each at the peak temperature Characterization of Sawdust Gasified Tar from Air-Steam Atmosphere in for sawdust and lignite. Although the peak rate of reaction is consistently lower for the the Fluidized Bed blends as compared with sawdust, it is to be noted that the range of temperatures over Yuhong Qin, Jie Fang, Wenying Li, Taiyuan University of Technology, CHINA which good reactivity is demonstrated is much larger for blends than for either of the pure fuels. The biomass air-steam gasification technology could produce hydro-rich gas and be a The results indicate that there is considerable interaction between the sawdust and the potential conversion technology for the further processing technology, such as fuel lignite, in the blends. Another clear demonstration of this interactive effect is the fact cell, synthesis of methanol and dimethyl ether. However, the large amounts of tar that, at 720 K, which is the lignite pyrolysis temperature, the reactivity of the blends is formation during the gasification cumber this technology becoming commercialized. lower than that of the lignite. These conclusions are further confirmed by our analysis Understanding tar chemical compositions and structure could help us adopt the suitable of the char yields obtained in each case, and are contrary to literature results (see for gasifier operation parameters and find the proper catalyst pointedly minimizing tar e.g. Vuthaluru, 2004; on sub-bituminous coals). formation. The paper investigated the property of tar generating from sawdust air- We have further analysed the DTG data using the Coats and Redfern approximation steam gasified in the fluidized bed at atmospheric pressure. The different ratio of steam (Sima-Ella et al., 2005) in order to determine the activation energies for the pyrolysis to biomass weight (S/B) was investigated. The tar molecular mass distribution and reaction. It is observed that the assumption of a single first order reaction is not valid average molecular mass were measured by gel permeation chromatograph (GPC), also over the entire range of temperatures. In general, the temperature range of 450-850 K the UV character of tar in whole molecular mass range was analyzed by photodiode wherein most of the interesting pyrolysis occurs, can be divided into two-three distinct array detector (PDA). The GPC results indicated the molecular mass distributions had regimes, each with its own activation energy. For the 10 K/min case, the activation no difference with the increasing of S/B at 800°C and 900°C. Three distinct fractions energy in the lower temperature range (~450-625 K; where the sawdust has high were found at measuring range, that the fraction 1 (F1) was from 423u to 200u or so, reactivity), increases as the percentage of sawdust in the blend increases. This is in fraction 2 (F2) was from 200u to 130u and fraction 3 (F3) was less than 130 u agreement with the observed peak reactivities in the DTG curves, in this temperature approximately. In addition, the F1 composed of long chain aliphatic acid or ester, range. This trend is exactly reversed in the higher temperature range (~625-825 K), paraffins and 4-9 rings aromatic compounds. The paraffins cracked intensified with the where the reactivity attributable to lignite is significant. increment of S/B at 900°C, and the aromatic character of F1 at 800°C was stronger In this study, a complete analysis of the effects of %biomass in the blends, in terms of than at 900°C. While the F2 had stronger aromatic character at 900°C than at 800°C, pyrolysis kinetics, char yields, and heating rate dependencies will be undertaken. A The 2~4 rings aromatic compounds were the major components in F2 at 900°C, comparison of the Coats and Redfern activation energies with those obtained from the however, the major components in F2 at 800°C were conjugated alkenes, unsaturated use of a Distributed Activation Energy Model (Scott et al., 2005) will be made. Results aldehyde and ketone. F3 showed same structure at 800°C and 900°C, it contained 1 of combustion and CO2 gasification studies of the pure fuels and the blends will also be ring aromatic compounds and heteroatom-contained compounds. Moreover, reported. The work is expected to add valuable information pertaining to co-firing of experiments results showed the tar yield decreased with the increasing amount of biomass and coal, both for combustion and gasification, in the Indian context. steam. The resulted showed with the increment of temperature, steam more easily acted on the high molecular mass compounds. At 800°C, steam made 2-4 rings References aromatic compounds almost cracked, and at 900°C, steam acted on 4-9 rings high M. B. Folgueras, R. M. Diaz, J. Xiberta, I. Pinto, 2003, Fuel 82, pp. 2051-2055. molecular mass compounds. The tar components gasified under air-steam atmosphere R. K. Sapru, R. K. Sharma, A. A. Kuznetsov and V. K. Kapralov, 2007, mainly composed of aromatic compounds, unsaturated conjugated bonds paffins and Petrotech2007, January 15-19. oxygen-containing compounds. 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.

49

SESSION 51 51-4 ENVIRNOMENTAL CONTROL TECHNOLOGIES: COMBUSTION The Repac Process: Regeneration & Reuse of Pac from ACI BYPRODUCT APPLICATIONS, SOx Dale L. Nickels, Pittsburgh Mineral & Environmental Technology, Inc., USA

The use of Activated Carbon Injection (ACI) for the removal of mercury from flue gas 51-1 is a well established method that has been commercially implemented and requires the Potential for Fly Ash to Mitigate Beach Erosion and Coastal Flooding injection of Powdered Activated Carbon (PAC) into the flue gas stream. While this Evan J. Granite, DOE-NETL, USA 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 Much of the population in the United States resides in coastal regions. Coastal regions captured mercury is merely transferred from the air to the ground, not eliminated from in the gulf and southeastern regions of the United States are routinely battered by the environment. tropical and hurricane force storms, resulting in loss of lives and billions of dollars in PMET has developed a patented process (REPAC) that enables the regeneration and property damages. Approximately one billion tons of coal is burned annually in the reuse of PAC after it has captured the mercury. This process is most effective when United States, generating eighty million tons of fly ash. The coal is typically burned at the ACI occurs after a fabric filter or electrostatic precipitator (ESP) and prior to a 2500°F, liberating the volatile matter, converting most of the carbon to carbon dioxide, PAC collection device, such as a fabric filter. Once collected, the PAC is thermally and leaving behind mineral ash comprised mostly of silicon and aluminum oxides. treated in an inert atmosphere to desorb the contained mercury allowing the PAC to be Several studies have previously demonstrated the safety of coal-derived fly ashes. returned to the injection system for reuse. The desorbed mercury is sequestered and This material is potentially suitable for rebuilding (or nourishing) eroded coastal areas, thousandfold concentrated onto a specially formulated carbon that can subsequently be thereby enhancing the safety of residents in flood prone regions, restoring the viability treated for mercury recovery as a salable metal, thus avoiding any disposal of of tourist beach areas, and keeping enormous quantities of fly ash out of landfills. The potentially toxic waste streams. This step eliminates the environmental liability use of fly ash for beach restoration would turn a waste product into a valuable associated with the mercury for the generating entity. resource. Approximately 650 million tons of sand has been used for beach nourishment in Compared to single-pass PAC that is injected once, collected and disposed of; REPAC United States coastal regions over the past eighty years. The current state of the art for offers significant operating cost savings, reduced PAC consumption to stretch the combating beach erosion is dredging sand from the ocean bottom, and transporting it to existing supply, and mercury emissions that are sequestered. the shore. This is an expensive and temporary fix to a difficult problem. The dredging PMET successfully demonstrated the ability to desorb mercury from PAC using a of sand can disturb local marine life. The use of fly ash in lieu of dredged sand has the synthetically loaded carbon from Norit (DARCO FGD). After the mercury was advantages of reduced landfill usage, lower costs, and enhanced attractiveness of the desorbed, the regenerated PAC was found to have the same characteristics as virgin rebuilt beaches. The potential uses of fly ash to mitigate beach erosion and flooding material. Using this test data, and the published data from US DOE, the REPAC will be discussed. 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 51-2 upcoming regulations without a cap and trade sysetm. Mercury Flux from Coal Utilization By-Product Samples Natalie Pekney, Donald Martello, Karl Schroeder, Evan Granite, DOE-NETL, 51-5 USA Study of Thermodynamics and Kinetics of Flue Gas Desulphurization over Activated Coke from Taixi Anthracite Control technologies are being developed to achieve reduction of mercury emitted in Sun Zhongchao, Guo Zhi, Li Xuefei, Xiong Yinwu, Li Yanfang, Bu Xuepeng, the flue gas from coal-based power plants. As new mercury control technologies Liang Daming, China Coal Research Institute, CHINA increasingly remove mercury from the flue gas, concentrations in coal utilization by- products (CUBs), such as fly ash and flue gas desulfurization (FGD) products, are Thermodynamics and kinetics of flue gas desulphurization (FGD) over activated coke expected to increase. This increase has unknown effects on the stability of mercury in from Taixi anthracite were studied in a fixed bed reactor. The adsorption isotherm of CUBs and therefore raises concerns about reemission. Effects of temperature, SO2 in simulated flue gas over activated coke was investigated and modeled by moisture content, and light exposure on mercury stability in CUBs are also unclear. To Langmuir and Freundlich mechanism, while the Langmuir mechanism was proved to examine these effects, an environmental chamber was constructed to measure the be more suitable for this system. When the temperature in the field of 403 ~ 463 K, mercury flux from CUB samples. A sensor monitored temperature and relative intrinsic kinetics of desulphurization were investigated under the condition that internal humidity in the chamber, and each sample was tested under both dark and lighted diffusion and external diffusion were eliminated and the mathematical model was conditions and with or without the addition of water to the sample. Fly ash sample established. Results showed that the desulphurization process over activated coke was pairs were obtained from NETL’s mercury control technology field testing program exothermic, and adsorption, desorption and reaction existed simultaneously on the such that one sample was collected at a power plant before mercury control technology surface but the adsorption process is dominant. There were 3 stages could be was installed, and its pair was collected after controls were in operation. Samples of partitioned in the whole desulphurization process. SO2 conversion is 100% in the first FGD gypsum and the wallboard product made from it were also tested in the chamber. stage, but which reduced rapidly in the second stage and keeped on a rather low value Results varied widely, with 7-day experiment averages ranging from –6.8 to 335 for a long period in the third stage. Most of the removed SO2 were absorbed on the ng/m2-hr. Initial mercury content, fly ash type, and light exposure had no observable surface of activated coke in the first and second stage and the process could be the consistent effects on mercury flux. There did seem to be an observable effect from the dq q presence of mercury control technology, however, for the fly ash samples. In all but ⎡ ⎤ expression of = ka c()qm − q − . To industrial applications, the first one case the baseline samples released more or absorbed less mercury their dt ⎣⎢ K ⎦⎥ 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) and second stage would be of more practical significance.

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 51-6 CUBs is relatively stable. Sulphur Dioxide Capture under Pressurised Fluidised Bed Combustion This technical effort was performed in support of the National Energy Technology Conditions using Dolomite and Coal-Ash as Sorbents Hein W.J.P. Neomagus, Raymond C. Everson, Steady Mukondiwa, North-West Laboratory’s on-going research in mercury control technology Under the RDS contract University, SOUTH AFRICA DE-AC26-04NT41817.

A study was carried out to investigate sulphur dioxide capture from coal combustion 51-3 flue gas using South African mined dolomites, limestone and coal ash under Intrinsic Kinetics of Flue Gas Denitration by Activated Coke Xuefei Li, Xuepeng Bu, Zhi Guo, Daming Liang, Beijing Research Institute of atmospheric and pressurised fluidised bed coal combustion conditions using a thermogravimetric analyser. Temperatures between 750-900°C were used, and a Coal Chemistry, China Coal Research Institute, CHINA typical flue gas mixture composed of 2000 ppm SO , 5.3% 0 and CO concentration 2 2 2 TX activated coke was prepared by our method. Based on the elimination of internal 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) and external diffusion, its denitration performance was determined in an isothermal pressure where the active part of the sorbent was CaO and at 10 and 15 bar where the 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. 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 Analysis of statistic test indicated E-R model was preferable for denitration weight. The sorbents’ structural characterisation was done using nitrogen adsorption 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 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 denitration was -23.6 kJ/mol. 50 had a relatively high internal surface area of 11 m2/g comparable to the calcined 52-4 sorbents. The porosity of raw sorbents increased from about 0.2 to 0.35 on calcination. Research on the Standard System to Evaluate the Quality of Coking Coal Sulphation at atmospheric pressure showed calcium conversion between 22-44% for Gaifeng Xue, Ru Xiang, Peng Chen, Shangchao Liu, Research and Development dolomites, 37-49% for limestone and 13-28% for coal ash after 180 minutes. At Institute, Wuhan Iron and Steel Corp, CHINA 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 Based on studying the match of coking coals with industrial indexes, process indexes, from reaction kinetic control to product layer diffusion control; limestone did not show coal petrology indexes, the micro structure and thermo properties of coke coked from a decline in reactivity. Under pressurised conditions the reaction initiated relatively different provinces in China (Qinghai Province, Sichuan Province, Xinjiang Province, slow and no signs of a sudden conversion decline were observed up to 180 minutes. Henan Province, Shanxi Province), the paper presents a new standard system to Sulphation at 15 bar was higher than at 10 bar. At 15 bar dolomite calcium conversion evaluate the coking coal using volatile matter, caking index and micro structure ranged between 16-34% and limestone was between 18-36% and coal ash conversion (optical structure) of coke coked from unblended coal. This evaluating system can be was higher at 28-35% calcium conversion. The conversion results obtained compare used to reveal the nature of coking coal better than usual one used before. well with results obtained by other researchers. A modified unreacted shrinking core model with variable effective diffusivity accounting for change in diffusion with 52-5 growing product layer was successfully used to model results at both atmospheric and Potential Utilization of Coal of an Energetically Lower Quality for the pressurised conditions. Preparation of Mixed Fuels Josef Valeš, Jaroslav Kusý, Monika Mádrová, Brown Coal Research Institute; Peter Fečko, Miluše Hlavatá, VSB-Technical University of Ostrava, CZECH REPUBLIC SESSION 52 CHEMICALS, MATERIALS, The extraction of raw materials and industrial production have brought along a lot of AND OTHER NON-FUEL USES OF COAL – 2 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 52-1 such materials with a significant energy potential to improve the use properties of low- Study on the Passivation of Coke and its Mechanism calorific types of brown coal, which often show higher sulphur contents. The Shizhuang Shi, Wei Xu, Hui Wang, Feng Shi, Gang Shi, Cheng Zhang, Wuhan qualitative characteristics of low-calorific types of brown coal with higher sulphur University of Science and Technology; Huiming Cui, Xinghong Lei, Coking Co. contents do not permit their direct energy utilization in the small consumers’ market or Ltd, Wuhan Iron and Steel Group Corporation, CHINA 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 The coke passivation is to infuse coke in a boric acid solution, so that carbon solution so-called mixed, multi-component fuels. 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 52-6 separately by SEM. The result shows that the external pores of the coke passivated are Influence of Secondary Pyrolysis on Vapor Gases jammed and, for the coke passivated, the carbon atoms surrounding the external crystal Viktor Saranchuk, Olga Chernova, Evgeniy Zbikovskiy, Donetsk National lattice form new chemical bonds after reaction with CO2. The two reasons result in the Tecnical University, UKRAINE decreasing of the extent of carbon solution loss reaction coke. For study of the process of the separation of the gas under pyrolysis two laboratory 52-2 installations were used. In installation 1 processes secondary pyrolysis are vastly Research on the Peculiarity of Coking Coal from Qinghai Province in China reduced to account of the small volume of the installation and quick removing vapor Gaifeng Xue, Shangchao Liu, Peng Chen, Ru Xiang, Research and Development gases from underroof space. In installation 2 are imitated condition of the coking Institute, Wuhan Iron and Steel Corp, CHINA camera (exists the gradient of the temperature and simultaneous existence of the different layers). Got when undertaking the process pyrolysis charge gases has Based on analyzing some indexes of coking coal from Qinghai Province in China, such compared. The Results have shown that output and composition gas, got in different as industrial analysis, coking properties, vitrinite reflectance distribution figure as well condition, differ. Leaving the gas from installation 1 on 24% more, than from as thermal-properties and micro structure, the results showed that the industrial installation 2. In given gas raised contents component with high heat of combustion analysis indexes and coal petrology index have some limitation to evaluate coking coal and average heat of combustion given gas is 35,9 MDZH/m3 that comparable to heat of quality, only microstructure (optical structure) of coke coked from single coal can combustion of the natural gas and given gas can become the substitute of the natural reveal the nature of coking coal. gas in energy. Thereby, composition and amount of the gas pyrolysis, as well as quality of the other 52-3 products pyrolysis possible control, using different ways pyrolysis, in which level of Research on the Micro Structure of Stamp-Charging Coking Coke and its the secondary processes changes depending on way of the issue of the heat and from Performance warm-up interval, in which is realized process pyrolysis. When undertaking the Gaifeng Xue, Peng Chen, Shangchao Liu, Zikui Song, Research and process pyrolysis in condition of the absence of the secondary processes can be Development Institut of Wuhan Iron and Steel Corp, CHINA 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 Stamp-charging coking technology has developed rapidly in recent years in China. By purpose, for syntheses of plastic, receptions propane-butane mixture and other integer. studying bulk density, porosity, micro structure, mechanical strength and thermo- Increase degree secondary processes, running in coal loading and underroof space, property of different stamp-charging coking coke samples from nearly 10 domestic brings about increase the output such component as CO and N2 that does the given gas coke plants as well as their blending coal quality, the following conclusions are by valuable raw material for undertaking chemical syntheses. 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 SESSION 53 (CSR) of stamp-charged coke changed from 40% to 60%. The different of thermo GLOBAL CLIMATE CHANGE: SCIENCE, SEQUESTRATION, AND properties of coke were resulted by the different micro structure that caused the blend UTILIZATION – 6 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 53-1 the thermo properties of coke are determined by the micro structure of coke (i.e optical Coal Structure Rearrangement Caused by Sorption of CO2 structure). Based on analyzing the relation between micro structure and thermo Angela Goodman, DOE-NETL, USA 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 Coals are glassy solids and the temperature at which they become rubbery (Tg) lies of large-scale blast furnace. 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 51 plasticizer of coals and it is important to understand why this is so. Coal structure 53-5 change caused by carbon dioxide is explored using infrared spectroscopy to measure The Second Generation of Nano-Porous “Molecular-Basket” Sorbents for diffusion rates, scanning electron microscopy to examine changes in pores and surface CO2 Capture from Flue Gas area roughness, surface area measurements to examine the how carbon dioxide probes Xiaoliang Ma, Xiaoxing Wang, Chunshan Song, The Pennsylvania State the coal interior, and differential scanning calorimetry to measure heat capacites of University, USA fresh and carbon dioxide exposed coals. Carbon capture and sequestration (CCS) is considered as one of the key options for 53-2 mitigating the emissions of CO2. However, the cost for CCS is greatly concerned and CO2 Reservoir Properties of Naturally Activated Australian Coals the cost of separation and capture of CO2 from the sources is estimated to be up to Abouna Saghafi, CSIRO Energy Technology, AUSTRALIA 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 Australian coal seams have been subjected to numerous igneous intrusion events since reduce CO2 emissions. Our previous study has shown that the “Molecular-Basket” their formation during the Permian period, with the latest major event to occur during Sorbent (MBS) by a polyethylenimine-modified molecular sieve MCM-41 is a the Tertiary, ~50 million years ago. These igneous intrusions have injected substantial promising sorbent for CO2 capture from flue gas. The present presentation will show volumes of carbon dioxide (CO2) into the coal seams and magmatic fluids heated and our current approaches in development of the second generation of MBSs and metamorphosed many coal systems. Considerable amounts of the magmatic CO2 has integration of them in CO2 capture from flue gas, focusing on increasing capacity and been adsorbed locally by the devolatilised coals, while the remaining gas eventually sorption/desorption rate, decreasing MBS preparation cost, and solving the sorbent moved away from the intrusion sites and replaced the pre-existing methane (CH4) in degradation problem. In comparison with the amine scrubbing process, our developing unaffected coals away from the heat source. In recent years the CSIRO has been MBSs and process have shown some significant advantages: 1) high sorption capacity investigating the coal seams of the Sydney Basin for storage of CO2 from fossil fuel (~140 mg-CO2/g-S at 15 kPa of CO2); 2) no corrosion; 3) high sorption/desorption rate electricity generation. This research has been largely stimulated by the fact that the due to high gas-sorbent interface area (1-4×107 m2/m3-MBS); 4) good regenerability option of coal seams as reliable reservoirs for injecting the CO2, captured from nearby and stability; 5) overcoming the degradation problem of MBS by using a physical coal-fired power plants, is now seriously considered in Australia. A number of pilot MBS to remove SOx/NOx; 6) simple process and lower operational cost; and 7) flexible projects (government and industry partnerships) are already planned and are scheduled applications (fixed-bed, fluidized-bed or moving-bed). to start within the next 2-3 years. This study was undertaken to evaluate the gas reservoir properties of CO2 naturally 53-6 stored in coal seams and the effect of heating on the storage properties of these coals. Aminopropyl-Functionalized Mesoporous Silicas for the Adsorption of CO2 The results of measurements show a significant enhancement in the storage capacity of Xin Fu, Junping Li, Ning Zhao, Wei Wei, Yuhan Sun, Chinese Academy of coal to both CO2 and CH4 which is reversely proportional to the distance from the heat Sciences, CHINA 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 The gradual increase in the atmospheric concentration of carbon dioxide (CO2) due to of measurements conducted on these coals, and discusses the impact of the findings on fossil fuel combustion is becoming a serious environmental problem. Meanwhile, it is possible CO2 storage and CH4 recovery from heat affected coal seams. 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 53-3 for more than 5% before 2012. Thus, the development of high-capacity adsorbent was Analysis of High-Temperature CO2 Capture Reactor Using Lithium Silicate becoming more important. One potential approach to preparing such an adsorbent is to Hideo Kitamura, Takeo Takahashi, Masahiro Kato, Toshihiro Imada, Yasuhiro graft CO2 adsorption sites on the high surface area support. Kato, Kenji Essaki, Toshiba Corporation, JAPAN 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 Lithium silicate (Li4SiO4) can be used for high-temperature CO2 separator in thermal adsorption sites. The physical properties of these adsorbents were characterized by power stations such as pulverized coal-fired power plants or integrated gasification power X-ray diffraction (XRD) pattern, solid-state 29Si nuclear magnetic resonance combined cycle power plants (IGCC). It absorbs CO2 effectively at temperatures (NMR), Fourier transform infrared (FTIR) spectra, and measurements of N2 adsorption between 450 to 650°C and releases CO2 above 650°C. Because the operation and desorption isothermal, which confirmed that aminosilianes were grafted on the temperature of this sorbent is higher and lowering the gas temperature is not needed, surface of the channels in the mesoporous materials. The amine-grafted MCM-41 the energy for CO2 separation can be reduced compared to that of conventional materials adsorbed CO2 as carbonates and bicarbonates with a total capacity of 56.4 methods such as the amine method. mg/g adsorbents at the room temperature. The experiment results indicate that the rate In this paper, the numerical analysis of the reactor in which CO2 is captured from the of CO2 adsorption on SBA-15 serial samples is more quickly than that on MCM-41 flue gas of the thermal power station is studied. The analysis was based on one- serial samples in beginning adsorption stage. However, the amounts of CO2 adsorption dimensional unsteady model assuming a pseudo plug flow, where heat transfer on MCM-41 series samples are higher than that on SBA-15 serial samples. 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 m2×1.5 m) was installed in the 500 MW pulverized coal-fired power plant, the CO2 recovery coefficient was SESSION 54 maximum when the inlet temperature of the flue gas was 450-500°C. The CO2 COAL UTILIZATION BY-PRODUCTS – 3 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 650°C. 54-1 A Methodology for Environmental Impact Assessment Study for Back 53-4 Filling of Coal Ash Generated from a Thermal Power Station in a Mine Developments in Sequestering CO2 as a Carbonate Mineral: pH Control in a Filled With Acid Mine Drainage Biomimetic System for the Sequestration of CO2 as Calcium Carbonate S.K. Dube, NTPC Limited, INDIA Elizabeth C. Larkin, Gillian Bond, New Mexico Institute of Mining and Technology, USA 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 Sequestration as a mineral carbonate offers the potential for safe long-term storage of quantity of ash is generated. The land available for disposing such huge quantity of CO2 without concerns of leakage or monitoring. Considerable progress has been made ash is gradually becoming scarcer. In addition, the Notification by the Regulatory in the development of an aqueous biomimetic method to accomplish this end, the Agencies for utilization of 100% ash over a period of 9 years invites exploration of major remaining challenge prior to pilot-scale testing being that of economical pH other options. In view of the above limitation, back filling of abandoned mines control. Recent work has determined that a combination buffer of 200 mM NaOH and appeared to be one of the most attractive proposals for large-scale ash utilization. 200 mM NH4OH can be used as a buffer. This buffer contains inexpensive However, the environmental impact of this option needs to be studied and documented components, affords full utilization of calcium in waste brines, and offers the potential for regulatory approval and final project implementation. of value added to ammonia-rich agricultural waste. 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- 52 geological investigations and groundwater monitoring to establish baseline conditions, In a first step, a fuel database is developed, including both the physico-chemical source, gradient, quantity, quality and characterization of hydrology regimes in the properties of coal but also its reactivity during pyrolysis (flammability) and immediate vicinity of the mine site, Establishment of baseline environmental combustion (emissions of pollutants, unburnt residues, etc.). The highly variable nature conditions such as Air, Noise etc.; Ash characterization and leachability, Ash and pit of the fuel and the variability of experiments carried out to obtain such data, represent water characterization, Ash-mine pit water interaction and geo-chemical transport, Ash a real difficulty for a reliable, comparative use of the obtained characteristics. In order filling in the mine pits and requirement of evaluation of technologies, Environmental to identify the parameters of interest, a previous work in collaboration with modelers Impact Assessment (EIA) studies & mitigation measures. has been performed to define precisely their needs (data interesting for the simulations, This document is expected to serve as a base document for conducting such studies to their precision, the impact of the test temperature on the simulations). be taken for any Mine back filling project involving coal ash generated by a thermal In a second step, from these obtained experimental data, 3D simulations of the coal power station. combustion behavior in PC boilers have been performed with the CFD software Code- Saturne. These simulations allowed us to obtain, at a lower cost, valuable information 54-2 on some physical phenomena such as: Effects of Lignite Ash on Pyrolysis Kinetics of Lignite - the impact of the coal quality on its behavior in PC boilers under several Yaoling Chi, Fuchen Ding, Hong Wang, Jieming Xiong, Beijing Institute of conditions Petrochemical Technology; Shuyuan Li, State Key Lab of Heavy Oil - the impact on the pollutant emissions (NOx, SOx) Processing,University of Petroleum, CHINA - Qualitative trend analysis (multi-criteria analysis) - Simulation of alternative operating conditions The pyrolysis kinetics of Zhaotong lignite was studied using thermogravimetric - Identification of « risk-free » low NOx operating conditions analyzer at the heating rate of 15°C/min. The effects of lignite ash on the pyrolysis - Prediction of unburnt carbon in ash process were investigated. The kinetic model of pyrolysis reaction was developed. The - Study of flame ignition and stability kinetic parameters were determined. The content of oil and gas produced by pyrolysis - Analysis of corrosion risk increased in the presence of lignite ash. The results showed that lignite ash has a - Prediction of slagging and fouling catalytic effect on the lignite pyrolysis. The effect was closely related to temperature The aim is therefore to characterize coals so to be, on one hand, representative of region. The corresponding activation energy decreased because of the effect of lignite industrial operating conditions, and on a second hand in adequation with the 3D ash. The pyrolysis process can be described by the two-step integral model. simulations needs in order to characterize the impact of the coal quality on its behaviour in PC boilers. 54-3 Thermal Behaviour and Kinetics Investigations of Malaysian Oil Palm P1-2 Biomass, Low rank Coal and their Blends during Pyrolysis via Study on the Fixing Sulfur Using Additives during Coal Combustion Thermogravimetric Analysis (TGA) Qiaowen Yang, Liying Wang, Yanan Zhang, Ling Shi, Binbin Zhao, Xiaoyong Siti Shawalliah Idris, Khudzir Ismail, Norazah Abd Rahman, Azil Bahari Alias, Ma, Jian Chang, China University of Mining & Technology (Beijing), CHINA Universiti Teknologi MARA Malaysia, MALAYSIA Middle high-sulfur coal of Xian was tested in this paper. Then the effect of selected An experimental study on co-pyrolysis of Malaysian oil palm biomass (palm mesocarp sulfur-fixing additives on the sulfur-fixing capability of Ca(OH)2 was conducted. It fibre (PMF), empty fruit bunches (EFB), and palm kernel shell (PKS)) and low rank was obtained that different additives produced different promoting effect on calcium coal (Mukah Balingian) was performed via Thermogravimetry Analysis (TGA). All carbide residue sulfur capture and the promoting effect and mechanism were the tests were carried out in nitrogen atmosphere, under dynamic conditions at heating dissimilar. For example, Al2O3 and Fe2O3 are more effective and lower-cost sulfur- rates of 10, 20, 40, and 60°C/min in temperature range from 25°C to 900°C. The fixing additives. At last, three compositions additive were studied, and the sulfur-fixing Mukah Balingian/Oil palm biomass blends were prepared in the weight ratios of 100:0, efficiency of two composite additives, which were named CAM and NAM, was above 80:20, 60:40, 50:50 and 0:100. TGA results show that palm kernel shell has three 62%. 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 P1-3 profiles correspond to the disintegration of hemicellulose and cellulose at relatively The Application of Multi-Sensor Data Fusion Technique Based on low temperatures (ca. 300-350°C), and lignin at much higher temperature Parameter Estimation in Coal Spontaneous Combustion Experiment System (approximately 700°C). Pyrolysis of coal/palm kernel shell revealed quart-modal Lian-hua Wang, Hua Wang, Baoxiang Cao, Qufu Normal University, CHINA derivative Thermogravimetric (TG) curve. In a similar manner, the coal/palm mesocarp fibre blends and coal/empty fruit bunch blends generate tri-modal and bi- The precise and credible measurement of temperature in coal spontaneous combustion modal TG curves respectively. The thermal evolution profiles of coal/palm mesocarp (CSC) experiment is a most urgent technique problem should be solved recently. The fibre and coal/empty fruit bunch during pyrolysis, however, showed the domination of paper puts forward a technique of CSC temperature data fusion on the basis of multi- the biomass pyrolysis at lower temperature, with the coal pyrolysis (i.e. volatile matter sensor parameter estimation. In terms of data processing, first adopts the distribution released) occurred at much higher temperature. Unlike the fibre and empty fruit bunch diagram method to reject the negligent errors in the monitored data, and then fused the coal blends, coal/palm kernel shell blends has additional peak appeared at temperature data by means of parameter estimation. Based on this, the temperature control system higher that that of coal pyrolysis. Apparently, no interactions were seen between the will control water temperature to track coal temperature automatically. Second, Uses coal and biomass indicating lack of synergistic effects between these two solid fuels. the fused coal temperature data to simulate CSC under mine. The practical application First order equations were used to determine the biomass and coal component thermal demonstrates that the fused results possess higher precision and reliability. 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 P1-4 energy of 254 kJ/mol, while lowest value of activation energy of 257 kJ/mol and 265 Transformations of Trace Elements in Burning Coal kJ/mol achieved in 50 wt% blends of MB/PKS and MB/EFB, respectively. These Eugene Samujlov, Ludmila Pokrovskaja, Marina Faminskaja, Krzhizhanovsky findings will provide useful data for power generation industries for the development Power Engineering Institute; Larisa Lebedeva, Fossil Fuels Institute, RUSSIA of co-firing options using coal/biomass blends. 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 POSTER SESSION 1 Podmoskownij coal are analysed. Thermodynamic researches of processes of their COMBUSTION TECHNOLOGIES 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 P1-1 the substances containing trace elements are received. Physical and chemical kinetic of A Complete Procedure from an Advanced Coal Characterization to transformations of the mentioned trace elements was investigated in the technological Pollutants Emissions Prediction channel of boiler P-59 of the Rjazanskaja power plant. The problem was considered in Anne-Lise Brasseur, Sandro Dal-Secco, EDF R&D, FRANCE one-dimensional approximation. Macroscopical parameters of a stream in the channel depending on time are known from the experimental data. The kinetic equation, Because of coal supplies diversification as well as the use of coal blends, a complete describing processes of transformation the vapor substances containing zinc, cadmium, procedure from Coal Characterization to Pollutants emissions prediction has been lead, is received and solved. Sedimentation of vapor substances, containing trace developed in order to help the operator to control the impact of Fuel Flexibility on elements, on particles of fly ashes was taken into account. Calculations were carried environmental issues (NOx, carbon in ash), but also on grinding, flame stability, out at restricted speed of an exit mentioned vapor from a mineral component of coal. slagging. The role of processes of volumetric condensation of vapor is appreciated. 53 Accommodation factors of vapor on a surface of particles of fly ashes were determined P2-3 from the experimental data. As a result of calculations, mass fractions of trace Desulfurization of COS in Syngas with Iron-Based Sorbent Modified by elements not vaporization from mineral mass of coal are appreciated. Mass fractions of Copper trace elements of zinc, cadmium, lead, not vaporization from the condensed phase at Dexiang Zhang, Changqing Hao, Hai Zhao, Tingting Wu, East China University burning coal in boiler P-59, are accordingly equal 0.592; 0.398; 0.883. Initial of Science and Technology, CHINA 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 In order to improve desulfurization properties of the iron-based (Fe2O3–Al2O3) sorbent trace elements in vapors of the substances containing it elements, on an exit from the and increase the sulfur retention capacity and high H2S or/and COS adsorption rate, chimney are accordingly equal 45,1; 2,41; 3,47 g/t.coal. Mass of zinc, cadmium, lead copper oxide promoters or some cerium are needed to modify the sorbent. The sorbents condensed on microparticles of ashes on an exit from a chimney are accordingly equal were prepared with iron trioxide hydrate (goethite) and copper monoxide by a novel 10,5; 0,316; 0,399. Mass product of burning is 4.749 kg./kg.coal. Work is executed at preparation method like physical mixing in water. The results show that one of these financial support РФФИ (grants 05-08-01512 and 07-08-0082). 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 POSTER SESSION 2 adsorption–regeneration cycles. About 35% elemental sulfur of the sulfur retentated in GASIFICATION TECHNOLOGIES AND PNNL-CHINA 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% P2-1 oxygen was used when temperature reached above 723 K until 1023 K. Finally, the Physical Properties and CO2 Gasification Characteristics of Liquid Phase fresh, sulfurized and regenerated sorbents were characterized by X-ray diffraction Carbonization Coke at High Temperatures (XRD), scanning electron microscopy/energy dispersive-spectroscopy (SEM/EDS). Jinsheng Gao, Shiyong Wu, Jing Gu, Ye Li, Youqing Wu, Zhenhua Qi, East Fourier transformed infrared spectroscopy (FTIR) and BET surface area analysis. China University of Science and Technology, CHINA P2-4 In the study, the physical properties of liquid phase carbonization cokes (petroleum Desulfurization Performance of Fe-Mn-Ce Based Sorbents Prepared Using coke and pitch coke), including carbon crystalline structure and BET surface area, Different Precipitating Agents for COS Removal from Synthesis Gas were measured at pyrolysis temperatures ranging from 950°C to 1400°C, respectively Hai Zhao, Dexiang Zhang, Fangfang Wang, Tingting Wu, Changqing Hao, using the XRD and the pore structure analyzer, and their CO2 gasification Jinsheng Gao, East China University of Science and Technology, CHINA characteristics were also performed isothermally in a thermo-gravimetric apparatus in the gasification temperature range of 950-1400°C. The effects of pyrolysis temperature Various Fe-Mn-Ce based sorbents were prepared by coprecipitation method with three on carbon cryatlline structure, BET suface area and gasification activity of liquid phase kinds of precipitants, NaOH, NH4OH and Na2CO3, and the desulfurization carbonization cokes and their gasification processes were mainly investigated. Some performance of COS removal was studied. Test results showed that evident differences significant findings were obtained. The increasing pyrolysis temperature resulted in the in bulk and surface phase exist among these sorbents prepared with different increase of BET surface area of liquid phase carbonization cokes, made their carbon precipitation agent. The sample prepared with NH4OH coprecipitation show higher crystalline structure more ordered, and more easily led to their graphitization in the surface areas and larger sulfur capacity at low temperature. But the samples will sinter higher temperature range. The high temperature pyrolysis, as a whole, was favorable after high temperature treatment and its stability at high temperature is needed to be for the gasification activity of calcinated cokes from liquid phase carbonization cokes, enhanced. The Na2CO3 precipitated sorbent represents higher surface area and better and the effects of BET surface area on the gasification activity of calcinated cokes desulfurization behavior than the sorbents prepared by NH4OH and NaOH as the form liquid phase carbonization cokes were stronger than the effects of their carbon precipitants at high temperatures. The sorbent coprecipitated with NaOH shows lowest crystalline structure. The gasification activity of liquid phase carbonization cokes was sulfur capacity and desulfurizatin efficiency compared with NH4OH and Na2CO3. The obviously lower than that of coal chars, and even lower than that of the natural sorbents exhibited low desulfurization activity after higher calcination temperatures. graphite. Especially at high temperatures, the gas diffusion hardly affected the The decrease of activity was mainly caused by the change of BET surface area due to gasification process of liquid phase carbonization cokes. the increase of the particle size at higher calcination temperature.

P2-2 P2-5 High Performance of Limonite-Based Composite Catalysts in the The Comparison of Fly Ash Carbon and Coal Char with Respect to the Decomposition of Ammonia in a Simulated Syngas-Rich Fuel Gas Physical and Chemical Properties and CO2 Gasification Reactivity Yasuo Ohtsuka, Naoto Tsubouchi, Hiroyuki Hashimoto, Tohoku University, Jinsheng Gao, Jing Gu, Shiyong Wu, Ye Li, Youqing Wu, East China University JAPAN of Science and Technology, CHINA

Catalytic decomposition of 2000 ppm NH3 with an Australian limonite ore, which is In this study, the fly ash carbon samples are collected from Texaco gasifier in composed mostly of goethite (α-FeOOH), has been studied from a viewpoint of hot gas Shanghai Coking Plant and Nanjing Chemical Plant, using Shenhua coal as the raw cleanup with a fixed quartz reactor at ambient pressure under the high space velocity of material and operating at different pressures. The physical and chemical properties and 45000 1/h. It has already been reported that, when α-FeOOH in the limonite is reduced reactivity of two samples were studied and compared with rapid pyrolysis char of with pure H2 at 500°C, the transformation into nanoscale particles of metallic Fe takes Shenhua coal, preparing at the temperature of 1673 K in a small-scale falling reactor, place, and the catalyst achieves the almost complete NH3 decomposition in inert He at which regarded as reacted carbon in gasifier. The mineral matter fusion, degree of 500°C. The limonite also exhibits such a high catalytic activity at 750°C even without graphitization, pore structure and the CO2 gasification reaction characteristics of the H2 reduction or in the coexistence of 100 ppm H2S, whereas it is seriously SCFA, NCFA and RPCC were investigated by SEM, XRD, N2 and CO2 adsorption deactivated by co-feeding syngas with NH3 because of carbon deposition from CO, and method and isothermal thermo-gravimetric analysis. It was found that the fly ash the extent of the deactivation is larger at a lower temperature and a higher syngas samples exhibited lower carbon content and graphitization degree and higher specific concentration. The strong XRD peaks of both iron carbides and crystallized carbon are surface area, as well as ash fusion degree. In general, the gasification reactivity of fly observed on the used limonite after the reaction at 750°C. On the other hand, the ash carbon was better than RPCC (Shenhua rapid pyrolysis char at temperature of addition of small amounts of CO2 and H2O, which are always included in actual coal- 1400°C) and the difference was obvious at higher temperature (~1373 K). derived 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 750°C is stable to be P2-6 65–70% except for the initial decrease, though carbonaceous materials are still Influence of Superficial Velocity on Biomass Gasifier Design deposited significantly. When several limonite-based catalysts with alkali metal and D. N. Reddy, K. Basu, Osmania University, INDIA alkaline earth metal cations are prepared by the impregnation method and used in the NH3 decomposition at 750°C in 50% CO/25% H2/5% CO2/3% H2O, Mg cations work Cleaner and cheaper tar heating downdraft gasifiers are generally used with low ash more effectively as the promoter, and the 3 mass % Mg-added limonite maintains the and low moisture wood for power generation. High gasification temperature enables high and stable NH3 conversion of almost 100% for 50 h. In this case, no significant devolatisation and gasification reactions to take place simultaneously. To maintain carbon deposition takes place, and metallic Fe is the only crystalline phase. It is high temperature, oxygen supply could be higher than required for optimum probable that MgO with strong basicity suppresses the carbon formation from CO, and gasification thereby reducing heating value of gas and lowering exergetic efficiency of that the limonite-based composite catalyst thus shows the superior performance in the gasification NH3 decomposition in syngas-rich gas that simulates raw fuel gas produced in O2- This study attempts to analyze the sensitivity of operating parameters on heating value blown coal gasification. 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 54 enabling estimation of tar and char loss more accurately. Gasification energy unburned carbon and HCl, Hg0 was captured and Hg2+ was later released. When the optimization is through sensitivity analysis of preheated air and fuel. ash was exposed to the simulated combustion flue gas at temperatures between 120°C and 210°C, mercury oxidation improved at higher temperature. P2-7 Modeling Coal Gasifier Performance Using a Hybrid Finite Volume Finite P3-2 Element Approach Pilot Operation Production of Carbon from Waste Plastics for the Vladimir Korolev, Ken Johnson, George Muntean, PNNL, USA Preparation of Carbonaceous Materials of Specific Properties Suitable for Industrial Applications Steady state and transient performance of a coal gasifier depends on macro-level Josef Vales, Jaroslav Kusy, Lukas Andel, Marcela Safarova, Brown Coal process parameters such as operating temperature, coal feedstock and refractory type. Research Institute, CZECH REPUBLIC However, predictive modeling of gasifier aging and plant economics is possible only through the explicit simulation of all the primary physical processes from the micro- A qualitatively various and difficultly recyclable group of plastics is a suitable source level to the macro-level. Micro-level processes include the coal devolatilization, of pure carbon. The plastics are not decomposable by natural processes in most cases. chemical kinetics, and the multi-component diffusion that occur within the gasifier The environment protection requires their liquidation by recycling processes with a flow stream. Macro-level processes include radiation heat transfer, heat transfer subsequent material use of the products. The process of the total recycling of through the refractory walls, temperature induced deformations of the refractory, and polyethyleneterephthalate (PET) by the pyrolysis is an efficient way to gain carbon. other elements of the gasification plant. Refractory aging and degradation mechanisms The thermal decomposition of waste PET in a pyrolysis unit without an air access under the aggressive chemical environment and temperature and pressure transients under definite procession conditions is the base of the way. The charge is decomposed must also be considered in life assessment models. This paper describes a finite while a mixture of organic acids originates terephthalic and benzoic acid in 10:1 ratio volume framework that was developed to predict gasifier performance using strongly and with yield about 78%. A carbonaceous rest with the high content of carbon and coupled direct modeling of the coal devolatilization, coal, char and volatiles yield of 20% is the solid product of the decomposition. combustion chemical kinetics, volatiles multi-component diffusion, and slag and solid A pilot operation unit has been assembled in which all needed verifying tests were residual generation. This solution was then coupled with a finite element solver to carried out, for the verification of the functions of running processes of thermal PET simulate the heat transfer through the gasifier wall. The model results are compared decomposition, specification of the process conditions, including acquisition of with analytical models and experimental data. The ultimate goal is to provide a tool fundamental information of technical, technological, economical, and qualitative that will help optimize gasifier performance/life time/economics by calibrating the character. gasifier operative parameters for changing coal feedstock quality and feed rate. The research of carbonaceous materials with C content of 90-94% was carried out at modified activation processes at temperatures higher than 550°C. The relations and P2-8 dependencies were determined leading to the increase of specific surface and pores Conversion of Lignite to Activated Carbon in Supercritical Water volume by using various activation agents and activation times. Technical and Jicheng Bi, Leming Cheng, Kezhong Li, Rong Zhang, Institute of Coal technological conditions were studied which can influence the size of created pores Chemistry, Chinese Academy of Sciences, CHINA and their distribution occurrence. The modified processes of the reprocessing of solid carbon from PET decomposition enable to prepare the sorbents with demanded For the aim of utilization of solid product for hydrogen production from lignite in specific surface up to 1800 m2.g-1, pore volume up to c. 1.6 cm3.g-1, and with prevailing supercritical water (SCW) as a cheap source of carbon adsorbents, conversion of occurrence of micro-pores. The prepared sorbents of specific qualities were lignite to active carbon was performed in SCW in the presence of CaO or KOH under successfully tested for capture of various undesirable pollutants from both liquid and the conditions of 600-650°C, 25 MPa for 1 h. Comparative experiments of steam gaseous mediums. 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 P3-3 development of the solid product. The result shows that a higher carbon gasification Economical Energy Production and Environmental Protection rate can be obtained at SCW and the obtained solid products displays higher adsorption Krzysztof Jesionek, Józef Antoni Goliński, Wrocław University of Technology, capacity compared with those by steam under ambient pressure. In the case of catalysts POLAND 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 With reference to the article [1] of 1990 on the economical production of electricity, added sample can reach to 623 m2/g, compared to 330 m2/g of that without catalyst the authors supplement the remarks in regard to necessity of satisfying relevant sample. The BET surface might be further increased when the pyrolysis condition in restrictions as to the atmospheric pollutions. A kind of universal SCW is optimized to effectively remove tar adsorbed in carbon pore surface generated combined/cogeneration plant coupled to a high pressure coal-gas generator (Lurgi) has in pyrolysis reaction. Furthermore, the ash content of the KOH added sample can be been proposed. For driving the power plant natural gas or coal gas is assumed. reduced to about 3% after dilute HCl washing. Therefore, the solid product of SCW Compressed air and steam of 25 bar and 500°C temperature, necessary for the gas gasification of lignite can be used as active carbon, and this might be an economically generator, are extracted from the power plant system. Coal gas produced by a Lurgi- viable option in conversion of low rank coal to hydrogen in SCW. type 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 POSTER SESSION 3 deserves some consideration in planning future development of energy systems. ENVIRONMENTAL CONTROL TECHNOLOGIES [1] Goliński J. A., “Kilka sugestii dotyczących ekonomicznego wytwarzania energii elektrycznej” (in Polish) “A few remarks concerning economical electrical energy P3-1 production”,Międzynarodowa konferencja “Klimatyzacja i Ciepłownictwo”, Wrocław Mercury Oxidation and Adsorption by Fly Ash in Coal Combustion Flue – Szklarska Poręba, Prace Naukowe Instytutu Inżynierii Chemicznej i Urządzeń Gas Cieplnych Politechniki Wrocławskiej, Seria: Konferencje, nr 12, 1990, s. 85-94. Akimasa Yamaguchi, Naoki Noda, Hiroyuki Akiho, Shigeo Ito, Central Research Institute of Electric Power Industry; Kouichi Miura, Kyoto University, P3-4 JAPAN Evaluation on Performance of a Novel Highly Effective Sulfur-Fixed Agent in Coal Burning Mercury capture by fly ash in coal combustion flue gas has been reported as adsorption Chen Hongbo, Jiang Yin, Shao Xun, Beijing Research Institute of Coal on unburned carbon, but it is possible that mercury behavior depends on the gas Chemistry, China Coal Research Institute, CHINA 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 It is important to add some sulfur-fixed agents to coal in medium and small coal SO2, HCl, and water vapor. Simulated coal combustion flue gas containing elemental burning boilers in China because China has many such boilers. Performance of a novel mercury (Hg0) was fed to a thin fly−ash layer, with the following results. The captured highly effective sulfur-fixed agent in coal burning developed by a Chinese company mercury in the fly ash increased almost proportionally to the specific surface area of was evaluated and studied in this paper, which is composed of special natural mineral unburned carbon. HCl seemed to be necessary for mercury capture on the unburned ore and special catalyst, and has many characteristics such as rapid reaction, high carbon. The mercury capture capacity of the unburned carbon decreased in the calcium availability, low ratio of calcium to sulfur. Kulun sulfur determination presence of SO2 and water vapor. At higher SO2 conditions, the amount of captured apparatus was used to determine sulfur emission at different experiment conditions for mercury and the specific surface area decreased contrary to the increase in sulfur in the five Chinese representative high sulfur content coal samples. Experiments were fly ash. This suggests that the sulfur compound accumulated in the fly ash inhibited conducted to investigate the effect of combustion temperature and ratio of sulfur-fixed mercury adsorption on the unburned carbon. Since the carbon−free ash did not oxidize agent to coal on sulfur retention during coal combustion, sulfur retention was evaluated mercury, oxidation was likely achieved by the unburned carbon. In the presence of by comparing sulfur emission among different ratio of sulfur-fixed agent to coal. The 55 results show that temperature is an important factor influencing sulfur retention, sulfur P4-2 retention descends with the temperature rising. Ratio of sulfur-fixed agent to coal Distribution of Unminable Coals along the Eastern Margin of the Rome influences sulfur retention too, it increases with the addition ratio rising on certain Trough in Central West Virginia with Considerations of Carbon temperature. At temperature of 900°C, obvious effect is achieved when addition ratio Sequestration Potential and Risk is 4%, sulfur retentions of different samples are from 50% to 81%. At high temperature Tom Wilson, Hema Siriwardane, West Virginia University, USA of 1150°C, 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 Successful carbon sequestration is gauged in terms of the likelihood of long term CO2 55%. This sulfur-fixed agent can also control arsenic emission during coal burning and retention and the potential CO2 storage volume. Factors influencing long term reservoir reduce temperature of coal ash fusibility. It is possible to popularize this sulfur-fixed integrity include coal seam continuity, coal seam depth, cap rock integrity, the agent in China. 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 P3-5 detailed assessment of coal sequestration potential. The area lies near the border Evaporation of Wastewaters from Wet Gas Scrubbing Operations between the southern and northern coal regions where detailed maps of the deeper William A. Shaw, HPD, a Veolia Water Solutions & Technologies Company, coals have not been compiled. The study area also lies along the eastern margin of the USA Rome trough, a failed rift that developed primarily during the Cambrian and Ordovician periods but continued to accommodate minor displacements during the In the EU and the USA, wet scrubbing for flue-gas desulfurization (FGD) is installed later Paleozoic. The structural complexity of the area incorporates the potential for on more than 80% of coal-fired power plants and is considered to be best available detached structures since the area lies along the western limit of detached structures technology (BAT). Similarly, coal gasification processes employ a wet scrubbing observed in the Appalachian foreland. An associated issue addressed in this study is process for desulfurization of the syngas. whether shallow structures observed in the coal bearing section are associated with Wet scrubbers typically require a continuous blowdown to limit the accumulation of syndepositional reactivation of margin structures or result from post-depositional corrosive salts, especially chlorides, and suspended solids washed from the gas stream. detachment. The study incorporates interpretation of conventional vibroseis and higher This purge stream usually cannot be discharged to the environment without some type resolution weight-drop seismic data. Geophysical logs from over 100 wells are used to of treatment. Evaporation plants can reduce the purge stream to a crystalline solid and develop structure and isopach maps of low density and low gamma zones that may recover high quality water for re-use in the power plant thereby achieving a true zero represent individual coal seams. Interpreted low density intervals and potential coals in liquid discharge (ZLD) solution. this area are believed to be confined largely to the Kanawha Formation. Isopach maps A variety of evaporator types using various energy inputs can be applied to reveal that these zones generally have pod-like distribution and would, in today’s concentration of wet scrubber purge water. The major concerns when concentrating terms, be considered unminable. The study also incorporates geomechanical such a stream by evaporation are handling the high concentration of corrosive simulations of surface displacements and pore pressure distributions resulting from dissolved solids, handling the solids which precipitate, and selecting suitable materials hypothetical CO2 injection efforts along with estimates of injection volume as a of construction. This paper discusses various methods of configuring evaporator function of permeability. Optimal high permeability injection scenarios suggest that system components to achieve high availability and reliability treating wet scrubber the coals in the section do not represent a sufficient sink for commercial scale purge water while minimizing capital and operating costs. sequestration efforts. 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 P4-3 process retrofitted to two coalfired power generating units at a European site. The Experimental Study on Sorption Mechanism of Gases in Coals system is part of an overall effort by the power plant owner to reduce emissions and Sohei Shimada, Naoto Sakimoto, The University of Tokyo; Mamoru Kaiho, integrate environmentally-friendly processes and operational efficiency into the power Osamu Yamada, National Institute of Advanced Industrial Sciences and station, which currently generates 336 MW of power from the use of coal as fuel. 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 POSTER SESSION 4 CO2, CH4 and N2 in coals are thought to be adsorption. The reasons behind this are GLOBAL CLIMATE CHANGE 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 P4-1 coal but also dissolved in coal. Economical Evaluation of the Carbonation- Calcination System for Adsorption phenomenon between coal and gas was examined by measurement of heat Capturing CO2 of adsorption. The heat of adsorption was measured for Akabira coal (bituminous coal: Carmen Clemente, Julio Rodrigo Naharro, Etsiminas-UPM, SPAIN Japan), Shenhua coal (bituminous coal: China) and Taiheiyo coal (sub-bituminous coal: Japan). The cost of the CO2 capture using carbonation-calcination cycles as a technological Large differential heat of adsorption was measured at low pressure and it decreased option of the CO2 capture in post combustion is the sum of several terms: sorbent with pressure. Compared with theoretical heat of adsorption, it was estimated that costs, capital costs related to the capture plant, the new operation and maintenance adsorbate was adsorbed on high affinity adsorption site in order and CO2 was dissolved processes, the cost of the additional fuels necessary to compensate the penalty in the in coal. 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 P4-4 very cheap. The cost of the sorbent flow can’t be higher than 1-3 € per separated CO2 CO2 Sequestration Related to Shenhua Direct Liquefaction Plant ton. In the case of utilisation of CaCO3 as a sorbent, it has been calculated that the cost Qingyun Sun, Jerald J. Fletcher, West Virginia University, USA 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 The Shenhua direct coal liquefaction (DCL) plant, the first coal-to-liquids project in has to be into account other terms in order to obtain the global cost. It has supposed a China, is expected to begin production in late 2008. With an initial investment of generation plant of 360 MW with a fluidized bed reactor. It has been estimated that it approximately $1.5 billion USD, the Shenhua DCL plant will produce the equivalent can be reached a realistic capture up to 78% in the carbonator using CaO as a sorbent, of about 24,000 barrels of oil per day in the form of liquid fuels (primarily diesel) as well as a 100% of the CO2 generated in the calcinator, resulting capture rates of 85% while generating about 3.6 million metric tones of CO2 per year. Given growing approximately. concerns with CO2 emissions, carbon management is expected to become the biggest The assumptions for the operation and maintenance are that the carbonators require a environmental and economic concern for future operation of the plant. To address this molar relation Ca/C of 4 for an effective CO2 capture, a 30% of the fuel is burned in issue, West Virginia University (WVU) and the Shenhua Coal Liquefaction Research the calcinators and the rest in the combustor, the capacity of the CaO to capture CO2 Center are cooperating on a joint research project to determine the feasibility of decreases with the number of cycles, the recuperation rate of CaO is 92,5%, the global sequestering a significant proportion of the CO2 produced by the Shenhua DCL plant. 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 This poster provides an overview of the WVU research activities related to the carbon calculated that the global cost is 15,5 € for a life of 30 years of the plant. sequestration prefeasibility study for the Shenhua DCL plant. Financial support for the Therefore, a priori it seems to be a reasonable cost compared with the technological WVU effort is provided by USDOE through a cooperative agreement with WVU. The options of CO2 capture that are in operation nowadays, specially those which use activity is undertaken as part of the Annex II agreement between the US Department of amines. Energy and China’s 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 56 economics of the alternatives is included. Information on the Shenhua CO2 supported cobalt. There are plenty of silanols on the surface of SiO2, and the sequestration experience will help environmentalists, policy makers and industrial properties, concentration, and distribution of silanols on SiO2 surface can be modified decision makers better understand the CO2 issues for CTL alternatives now under by organic solvent pretreatment. However, there are few literature reports on the consideration in a number of countries around the world. 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), (3- POSTER SESSION 5 Aminopropyl)triethoxysilane (APTES) and N-[3-(Trimethoxysilyl)propyl] SYNTHESIS OF LIQUID FUELS: GTL, CTL AND BTL ethylenediamine (EDPTMS), to change the surface silanol concentration and property on the SiO2 support before the impregnation of cobalt an CH3-modified SiO2 (CH3- SiO2) was prepared as follows. Ten grams of SiO2 was preheated at 200°C for 12 h P5-1 under vacuum to remove all adsorbed moisture but surface silanols, cooled to room Studies on Mn Addition to Ru/Al2O3 Catalyst for Fischer-Tropsch Synthesis temperature under vacuum, and then transferred into a 250 ml conical flask. After Mohammad Nurunnabi, Kazuhisa Murata, Kiyomi Okabe, Megumu Inaba, Isao mixing with 40 ml toluene and 5 ml MTES, the mixture in the conical flask was put Takahara, Biomass Technology Research Center, JAPAN 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 The additive effect of Mn to Ru/Al2O3 catalyst was investigated on catalytic activity, h and drying at 50°C for 20 h under vacuum. The same method was used for the selectivity and stability for Fischer–Tropsch synthesis in a continuous stirred tank preparation of (CH3)2-modified SiO2 ((CH3)2-SiO2), (CH3)3-modified SiO2 ((CH3)3- reactor (CSTR) under pressurized conditions. Without Mn modified Ru/Al2O3 catalyst SiO2), NH2-modified SiO2 (NH2-SiO2) and NH2(CH2)2NH-modified SiO2 showed low CO conversion and deactivation rate was clearly observed at low reaction (NH2(CH2)2NH-SiO2) using DMDES, TMCS, APTES and EDPTMS, respectively. temperature of 493 K, where small amount of Mn addition such as Mn/Al=1/19 on (CH3-SiO2), (CH3)2-SiO2 and (CH3)3-SiO2 reduced the surface silanol (Si-OH) Ru/Mn/Al2O3 enhanced the CO conversion and C5+ selectivity for Fischer–Tropsch concentration of SiO2 support, suppressed the interaction between cobalt and silica, synthesis. Under pressurized conditions, high catalytic activity and high resistance to enhanced the reduction of the supported cobalt, and thus increased the catalytic activity catalyst deactivation with time on stream were observed under pressure of 60 bar, and of Co catalysts for Fischer Tropsch synthesis. However, coordination compounds were 2+ equilibrium CO conversion was about 96%. From the characterization results of BET, formed between NH2-SiO2 and Co cation, and thus the interaction between cobalt and XRD, TPR and XPS, the addition of Mn can be influenced to increase the number of silica was enhanced, the catalytic activity of Co catalysts for Fischer Tropsch synthesis Ru atoms on the catalyst surface by the removal of chloride from RuCl3, resulting to was decreased. Because chelated compounds were formed between NH2(CH2)2NH- 2+ inhibit the catalyst deactivation. SiO2 and Co cation the supported cobalt catalyst showed the worst performance in F- T synthesis. P5-2 These modified supports and the repective catalysts were characterized by BET, Si Division of Macerals in Hydro-Liquefaction Based on Reflectance MAS NMR, FT-IR, XRD, Laman, TPR and XPS to understand how organically- Chen Hongbo, Jiang Ying, Beijing Research Institute of Coal Chemistry, China modified SiO2 influenced the properties of cobalt catalysts. These characterizations Coal Research Institute, CHINA 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 China is developing coal liquefaction for alternative fuels because of rich coal and remarkably influenced the catalytic properties of these cobalt catalysts. NH2-modified poor oil. Shenhua Group Corporation, the largest coal producer in China, is SiO2 and NH2(CH2)2NH-modified SiO2 had a negative effect on the catalytic properties constructing coal liquefaction plant, so 17 coal samples of different maceral of Co catalysts, whereas CH3, (CH3)2 and (CH3)3-modified SiO2 showed pronounced compositions were selected from Shendong coal mining area, the inertinite contents of effects on the catalytic behaviors of Co catalysts. 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 P5-5 experiments at Optimal reaction temperatures, which rises with inertinite content Study on Deactivation of Co-Ru Catalyst for Fischer-Tropsch Synthesis increasing such as 470°C for inertinite content above 70%, 465°C for 60%~70%, Ajay Dalai, Ahamd Tavasoli, Reza Malek Abbaslou, University of 460°C for 52%~60%, 455°C for 45%~52%, 450°C for below 45%. The results show Saskatchewan, CANADA that coals with high inertinite content can obtain relatively high oil yield if selecting appropriate reaction conditions, especially optimal temperature. But, if the inertinite Detailed activity study and the deactivation of Ru-Co/γ-Al2O3 catalyst for Fischer- content above 70%, the oil yield is relatively low. Macerals can be divided into active Tropsch (FT) synthesis over 1000 h was investigated considering different deactivation group, transition group and inert group based on reflectance, reaction temperature mechanisms. Morphology changes of the catalyst during FT synthesis were studied affects borderline, so division chart of macerals based on reflectance and temperature using XRD, TPR, BET, ICP, Carbon determination, H2 chemisorption and re-oxidation is achieved. Inertinite content of Shenhua coal is below 45% generally, reaction techniques. When the PH2O/(PH2+PCO) in the reactor is above 0.75 the deactivation temperature of commercial plant is 450°C or 455°C. At the temperature of 450°C, rate is not dependent on the number of the catalyst active sites and is zero order to CO reflectance of transition group ranges from 0.90% to 1.15%, semifusinite has relatively conversion. In this case the main deactivation mechanisms are: cobalt re-oxidation, high reactivity and belongs to transition group. metal support interactions and aluminates formation. The deactivation of Ru-Co/γ- Al2O3 is related to cobalt cluster size. At lower amounts of PH2O/(PH2+PCO) P5-3 deactivation can be simulated with a power law expression with a power order of 39.7 Thermocracking of Coal Wastes to Produce Gasification Fuel and Synthetic and the main deactivation is due to sintering. Regeneration of catalyst at 275°C Crude recovered the catalyst activity by 69.9% of total activity loss due to the reduction of Olufemi Anthony Olajide, Sreeja Madala, Elliot B. Kennel, West Virginia oxidized cobalts. Catalyst regeneration at 400°C recovered the activity by 21.9% of University; Richard A. Wolfe, Wolfe Engineering, USA 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 A bench scale thermocracking process has been demo nstrated as a means to process assigned to aluminates formation, sintering and coke deposition. coal wastes generated from prep plants and mining activities. The coal conversion process involves a thermocracking process, results in coproduction of three phases of P5-6 valueadded products. First, a small amount of hydrocarbon gas is produced. Second, a Investigation on Highly Dispersed Iron Catalyst for Direct Coal liquid product is produced by condensing coal volatiles from the process stream. Third, Liquefaction a clean solid fuel is produced, potentially suitable for use in a coal gasification system Zhou Jianming, Wang Naiji, Beijing Research Institute of Coal Chemistry, China such as FutureGen, the DOE zero emissions concept that uses coal gasification to co Coal Research Institute; Gong Zhijian, Shandong University of Science and produce hydrogen and electrical power. The apparatus used to crack the waste coal, as Technology; Wang Caihong, Wang Yonggang, China University of Mining and well as the characteristics of each of the three phases are described. Technology, CHINA

P5-4 The highly dispersed α–FeOOH and γ–FeOOH were prepared by sedimentation Organic Modification Effects of Silica Support for Fischer-Tropsch method, of which granularities, surface area, pore specific volume, average radius and Synthesis Catalysts character of thermal decomposition were analyzed by SEM, BET and TGA. The Yuhan Sun, Lihong Shi, Bo Hou, Yao Xu, Debao Li, Jiangang Chen, State Key effects of catalysts, highly dispersed α–FeOOH and γ–FeOOH, on the liquefaction of Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy Shangwan coal were examined using a micro autoclave at same Fe moles, comparison of Sciences, CHINA with conventional Fe2O3. It was found that the granularities of α–FeOOH and γ– FeOOH were between 20~80 nm, the α–FeOOH of spindle and the γ–FeOOH of thread The catalytic activity and product selectivity of cobalt catalysts are strongly influenced asymmetrical clew and batting, which gradually dehydrating covert into α–Fe2O3 and by the surface properties of the support because they can change the interaction γ–Fe2O3 at 250~300°C. As a result, at 420°C, the total conversion and oil yield order between cobalt and the support, resulting in different dispersion and reducibility of the is: α–FeOOH > γ–FeOOH > Fe2O3. The total conversion of α–FeOOH is 2.84% and 57 d 11.33%, higher than that of γ–FeOOH, and the Fe2O3, meanwhile the oil yield is 3.10% plastic layer (Y=8-10 mm), a high ash content (A =15-30%), and a high yield of daf and 10.01%, higher than that of γ–FeOOH, and the Fe2O3 at same adding Fe 3.00% volatiles (V =35-40%). That’s why the obtained initial mixture is thermally treated (dried coal). With increasing the liquefaction temperature, the order of the liquefaction with the inert heat-carrier by high-speed heating up to given temperatures. At such ability range of adding is: α–FeOOH < γ–FeOOH < Fe2O3. It was shown that the α– heating of the initial mixture the warming-up to its transformation into plastic state in FeOOH and γ–FeOOH decreased the temperature for liquefaction reaction, because the course of the layer carbonization is accelerated; the duration of stay in the plastic asphaltene and preasphaltene converted into small molecule gases and liquefaction state and the thickness of a plastic layer is increased; carrying out of thermal reductive products were promoted by α–FeOOH and γ–FeOOH. 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 POSTER SESSION 6 treatment will allow producing lump fuel in traditional layer carbonization furnaces CHEMICALS, MATERIALS, AND OTHER NON-FUEL USES OF COAL 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 P6-1 dynamic investigations, burning of CPDF fuel pulverized particles in the air Carbon Prepared by Polyethyleneterephthalate (PET) Pyrolysis at atmosphere at torch-furnace is advantageous as to the burn-out completeness and rate Laboratory Conditions compared to power-generating coals “T” and “A”. The capability of planning CPDF Lukas Andel, Jaroslav Kusy, Josef Vales, Marcela Safarova, Brown Coal quality indices depending on consumer requirements (ash content, volatiles yield), the Research Institute, CZECH REPUBLIC 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 Waste plastics are the source of a carbon suitable for follow-up industrial applications. formula of smokeless ecologically clean power-generating (domestic) fuel have been The way to obtain carbon is based on the thermal decomposition of unsorted polluted patented. The know-how owner – Closed stock company «Donetsksteel-metallurgical waste polyethyleneterephthalate (PET) at exactly defined process condition. The plant». For further cooperation, please contact us at address: Direction on innovations mixture of organic acids – terephthalic and benzoic in 10:1 ratio and solid and diversification, 122, Ivana Tkachenko str., Donetsk, Ukraine, 83062. 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 P6-4 proceeded industrially. A Comparative Study of Methane Explosion Inhibition with Inert Gases The running processes of the PET thermal decomposition were studied and verified by Hua Wang, Jun Deng, Xiaokun Chen, Lingmei Ge, Hu Wen, Xi’an University of laboratory methods and its process condition were specified to optimise the semi- Science and Technology, CHINA products yield including acquisition of fundamental information of technical and technological character. The yield of organic acids about 78%, carbonaceous rest about Based on experiment, the influence of container factors, CO2 and N2 on explosion 19%, and the rest of a loss in gaseous form can be expected from the pyrolysis of a limits and critical value of oxygen density in methane explosion are comparatively crushed polluted and unseparated waste PET at optimised process conditions. The investigated. The experimental results show that the explosion limits of methane basic qualities of pyrolytic carbon were assessed and verified including the possibility relates to many factors. Explosion range enlarges with increase of the expansibility of of a further treatment. The solid carbonaceous rest is technically very pure. The the container. CO2 and N2 inhibited in certain degree the methane explosion, while the content of carbon is 90 to 94% depending on the conditions of the decomposition. The inhibition effects of CO2 apparently are superior to N2. The results of the experiment relations and dependencies were looked for leading to the increase of specific surface are of great significance in preventing methane explosion in coal mines and conducting and pores volume by using various activation agents and activation times. The test practice of branch-chain burning and branch-chain explosion. 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 P6-5 reprocessing of solid carbon from PET decomposition enable to prepare the sorbents Development of Coal Dry Beneficiation Technology in China with demanded specific surface up to 1250 m2.g-1, pore volume up to c. 0.65 cm3.g-1, Jin Lei, China University of Mining and Technology (Beijing), CHINA 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 As more than two-thirds of available coal reserves in China are located in cold or arid carburising grade and carbon utilisation than commonly used steel carburisers. 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 P6-2 technology is given in this paper. Catalytic Crystallization of Coal Chingiz Barnakov, Alexey Kozlov, Institute of Coal and Coal Chemistry SB P6-6 RAS; Svetlana Seit-Ablaeva, Kemerovo Technological Institute of Food Toxic Element Removal from Acid Mine Drainage using Zeolites Industry; Zinfer Ismagilov, Boreskov Institute of Catalysis SB, RUSSIA Synthesized from Fly Ash Derivative V.R. Kumar Vadapalli, A.Ellendt, L.F.Petrik, N.Hendricks, W.Gitari, G. Balfour, The paper deals with a problem of coal catalytic crystallization. A mixture of coal University of the Western Cape; N.Misheer, Eskom Innovation and Research (Gorlovskiy Basin anthracite, Western Siberia) and medium-temperature coal pitch Department, SOUTH AFRICA 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 South African Fly Ash (FA) was successfully used to treat and remove toxic elements degree of crystallization was shown. The degree of crystallization was studied by XRD from Acid Mine Drainage (AMD). As a result of the reaction between AMD and FA, analysis. 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 P6-3 Si and Al content. Zeolites are well known ion adsorbents which are often used in Power-Generating Fuel with Coal Preparation Waste waste water treatment. In the current study it was shown that Zeolite Y and Zeolite P Yevgen Zbykovskyy, Victor Saranchyk, Donetsk National Technical University; were synthesized by the hydrothermal treatment of SR at high (~600°C) and low Aleksandr Gordienko, Mikhail Ilyshov, Donetsk Steel-Metallurgical Plant; (~100°C) temperatures respectively. The synthesized zeolites (Zeolite Y and Zeolite Aleksandr Kolomiychenko, Makeevkoks; Victor Chalenko, Yasinovcky Koks P) were investigated for their capacity to remove toxic elements from AMD. Their and Camichal Plant, UKRAINE toxic element removal efficiencies were compared with commercial zeolite and ion exchange resins. A high percentage of toxic element removal from AMD was observed One of methods to solve energetic problems of Ukraine is the development of new using both the zeolite types synthesized from SR. In some instances, the zeolites kinds of artificial fuels, which would allow solving problems of energy conservation produced from SR performed better than the commercial zeolite or resins, indicating and environment protection. In this direction we have conducted wide research work the high value of these low cost adsorbents. Thus the zeolite adsorbents prepared from under laboratory conditions, received pilot lots under industrial conditions and tested waste SR can be effectively applied for decontamination of acidic waste waters. 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 58 through Washington County, Pennsylvania; Belmont to Harrison Counties, Ohio) and POSTER SESSION 7 coincides with occurrences of overlying fluvial sands. Floor lithologies are extensively COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES 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 P7-1 of water that fills the mine void after coal removal. The roof and floor materials are Effect of Technical Property of Coking Coal on Optical Texture of Coke exposed to air and water and contribute to the chemistry of the accumulating mine pool Ru Xiang, Gaifeng Xue, Shangchao Liu, Wuhan Iron and Steel (Group) water. Roof collapse can play a role in mine water chemistry and the rate of vertical Corporation, CHINA water infiltration may be affected by the competency of overlying rocks. Additional study of the physical characteristics of the entire sequence of Pittsburgh coal The optical texture of coke is not only related with the metamorphism of coking coal, overburden, as well as chemical characterization of the immediate roof and floor, may but also is related with the technical property of coking coal. In this paper, the effect of be helpful in predicting environmental impacts as active mining decreases. 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 P7-5 property. The results showed that if the coking coal had high caking index and Viscosity Changes of Different Ranks of Coal-Anthracene Oil Slurry Under thickness of colloidal matter layer, it was easy to make the coke optical texture High Temperature-High Pressure During Preheating transform to higher aeolotropic degree, that was to say, the isotropic structure was easy Jinsheng Gao, Yingjie Ren, Dexiang Zhang, East China University of Science to transform to the close grained or the close grained was easy to transform to the and Technology, CHINA 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 Coal-oil slurry preheating is an important step during coal direct liquefaction, and high. 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 P7-2 plant and has a good application prospect. A rotary viscometer that can measure the Study on the Property of High Volatile 1/3 Coking Coal from Shandong viscosity of coal slurry at high pressure-high temperature was designed by self and Province in China manufactured in this project. Three kinds of crushed coal including Yanzhou Coal Ru Xiang, Peng Chen, Gaifeng Xue, Wuhan Iron and Steel (Group) Corporation, (middle rank and caking), Shenhua Coal (low rank and non-caking) and Shengli Coal CHINA (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 By studying the technical indexes, the vitrinite reflectance, the measuring of colloidal (<200 mesh) according to a coal/solvent weight ratio equal to 2/3. The slurry was matter layer, and the coke microstructure of gas coal and high volatile1/3 coking coal putted into the high temperature and high pressure viscometer and heated under 5 MPa from Shandong Province and other regions, it was indicated the industry brand of high initial hydrogen pressure at the rate of 5 K/min till the different setting temperature. At volatile 1/3 coking coal from Shandong Province belongs to the 1/3 coking coal, but the same time the viscosity changes with increasing temperature of coal-oil slurry was the coal property of various mine was obvious different. The coal with high investigated under atmosphere. The results show that both of Yanzhou Coal and metamorphism and active ingredient still has the property of 1/3 coking coal, but the Shenhua Coal display the viscosity peak with increasing temperature under coal with low metamorphism and active ingredient leans to the property of gas coal. It atmosphere, but Shengli brown coal never displays the viscosity peak. Moreover, the should be blended rationally. 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 P7-3 Coal has not viscosity peak under high pressure during the whole preheating. So the Rapid Method for Measuring Bulk Density of Coal Powders higher rank and more agglutinate the coal is, the easier the viscosity appearance is. In Amrit Boparai, Jack Demirgian, Kathryn Lawrence, GreatPoint Energy, USA addition, the viscosity-temperature characteristics of preheated coal-oil slurry through different temperature are different. The viscosity of coal oil slurry with Yanzhou and At GreatPoint Energy, bulk density of powdered coal feed and processed coal streams Shenhua at the same measure temperature have a peak appearance with increasing is one of the parameters needed for characterization of the performance of the test preheating temperature, however, the viscosity of Shengli coal oil slurry always reactors which are designed to convert coal and petroleum coke into methane. increases with increasing preheating temperature. 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 P7-6 the cylinder for several minutes and then using the graduations on the cylinder and a Abundances of Minerals in High-Alumina Fly Ashes from the Jungar Power ruler to measure the volume. Bulk density is calculated by dividing the mass (g) of the Plant, Inner Mongolia, China sample by the volume (cm3) of the sample. Because of electrostatic interactions Shifeng Dai, Lei Zhao, Yong Zhang, Dan Li, Yingying Sun, Yuwen Ma, Xibo between the finely divided coal and glass, many samples do not form a clearly-level Wang, China University of Mining and Technology, CHINA; Chen-Lin Chou, surface in the graduated cylinder. This causes uncertainty in determining the volume Illinois State Geological Survey, USA of the sample. Another potential error is in quantitatively transferring a pre-weighed sample of finely divided coal into a graduated cylinder. The fly ashes from the Jungar Power Plant, Inner Mongolia, China, are unique because We developed a procedure that saves time by vibrating the sample as it is poured into a they are highly enriched in alumina (Al2O3 > 50%). Samples of pristine fly ashes were fixed volume vial and eliminates potential errors in measuring and recording weights collected from the economizer and the ash concentration units. Minerals in the fly and operator variability in measuring volume using a ruler. We interfaced a computer ashes have been studied using X-ray diffraction analysis (XRD) and a scanning to the balance to enter the mass data directly into a spreadsheet to allow automatic electron microscope equipped with an energy-dispersive X-ray spectrometer (SEM- calculation of bulk density. The procedure allows us to collect data for bulk density of EDX). The feed coal of the power plant is enriched in kaolinite and boehmite. The fly a sample in less than 5 minutes. ashes mainly consist of amorphous glass, mullite, corundum, quartz, unburned carbon, We will describe in detail how to assemble the proposed setup using commercially and trace amounts of calcite, K-feldspar, and clay minerals. The mullite content in fly available material and discuss the standard deviation of measurements and comparison ashes is as high as 37.4% because of high boehmite and kaolinite contents in feed coal. of bulk density values obtained by the proposed method and by using an ASTM Bulk Corundum is a characteristic mineral formed during the combustion of boehmite-rich Density Method. coal. The amount of amorphous glass in the fly ashes decreases from the economizer to the wet ash collection units. P7-4 Samples from the economizer were sieved into six size fractions (<120, 120-160, 160- Characteristics of the Roof and Floor of the Pittsburgh Coal Bed Main 300, 300-360, 360-500 mesh, and > 500 mesh) for mineralogical analysis. The Bench corundum content increases but amorphous glass decreases with decreasing particle Susan Tewalt, Leslie Ruppert, Kristin O. Dennen, U.S. Geological Survey, USA 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 A three-dimensional model of the main bench of the Pittsburg coal bed, created in fine clay mineral particles under high-temperature combustion condition. Similarly, Earthvision™1 using the U.S. Geological Survey’s (USGS) 2000 National Coal fine corundum crystals formed in the boiler from boehmite in feed coal. Mineral matter Assessment stratigraphic dataset can be used to visualize mined and unmined areas at a in feed coal largely becomes amorphous glass during combustion. 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 59 P7-7 trace species with the SOFC anode requires prolonged effort due to the low Element Volatilisation During the Thermal Treatment of South African concentrations of trace materials present in direct syngas. Test durations of at least Bituminous Coals 500-1000 hours are required for accurate prediction of long term degradation after Monica Raghoo, Christien Strydom, North-West University; Henry Matjie, Sasol operation at 40,000 hours. Additionally, the range of trace material forms available for Technology (Pty) Ltd, SOUTH AFRICA; Harold Schobert, The Pennsylvania testing in the laboratory is a small subset of the material forms existing in direct State University, USA syngas. To enhance testing and accelerate collection of pertinent results, we have designed and The response of South African low-grade, medium rank C bituminous coals to deployed a mobile test skid capable of field testing SOFC button cells on direct coal sequential leaching with water, ammonium acetate, and hydrochloric acid has been syngas. The Multi-Cell Array (MCA) system simultaneously tests 12 SOFC button investigated by the conventional chemical analysis of both the leached coals and the cells, fuelled in parallel and individually load controlled. Testing multiple specimens leachate solutions. The ammonium acetate treatment removed most of the Na, Ca, Mg at once permits statistical comparison and accelerates testing compared to individual and Mn suggestive of an organic association and occurrence as ions of carboxylate laboratory tests. The MCA system also supports an integrated GC-ICP/MS system that groups. Hydrochloric acid removed almost all the Ca and Fe from the coals. Close can provide analysis of the direct coal gas and can identify trace elements at a ppb evaluation of the data suggests that some of the Al in the coals was also removed by level. The system requires a power source, and a source of coal gas, and bottled gas the selective leaching process, primarily by the hydrochloric acid treatment. This may supplies and can operate outdoors and unattended for an indefinite period of time. reflect a solution of organically-associated Al from the maceral components. The loss Preliminary results were obtained from initial deployment of the SOFC MCA system of fluxing elements (such as Ca and Mg) induced by the different leaching processes at the Power Systems Development Facility (PSDF) gasifier in Wilsonville, AL. The was also associated with increases in ash fusion temperatures. 100 hour hydrogen test indicated successful operation of 5 cells over the entire Samples from the sequential leaching process were demineralised and organically- duration. The success rate was greater than 40% for this initial deployment and further associated elements were added to the samples. The original and demineralised improvements to the test fixture will improve this rate. Further operation of the system samples were then analysed by a series of FT-IR Raman spectroscopic experiments, at the PSDF on direct coal syngas is expected later in 2008. Results from the hydrogen which included the thermal treatment of samples at various temperatures in an external baseline testing and testing on direct syngas will be described in this presentation. lab-scale reactor. Vapour species were detected through ZnSe windows in the reactor. This technical effort was performed in support of the National Energy Technology This is in contrast to conventional reactor techniques where volatile species are Laboratory s on-going research in SOFC under the RDS contract DE-AC26- condensed and thereafter analysed via analytical methods. The poster will present 04NT41817. observations and results from the experiments. P8-2 P7-8 Novel Sulfur and Coke Resistant Anode Catalysts for Reduced Temperature Effect of Trace Amount of Oxygen on Removal of Stable Sulfur in Coal Coal Gas Fed SOFC Systems Baoqing Li, Zongqing Bai, Wen Li, Fenrong Liu, Institute Of Coal Chemistry, Nandita Lakshminarayanan, Hyunkyu Choi, Umit. S. Ozkan, The Ohio State Chinese Academy of Sciences, CHINA; Jan Yperman, Hasselt University, University, USA BELGIUM Solid Oxide Fuel Cells (SOFC) are the most desirable fuel cells for stationary power The stable organic sulfur forms in coal such as thiophenic and dibenzothiophenic generation and as auxiliary power sources in transport applications. The fuel flexibility sulfurs are very stable to be removed from coal during coal conversion processes, and higher efficiency of an SOFC make it a favorable choice. They can be used for a which leads to severe environmental problems. In this work, several typical organic variety of applications including small-scale, remote co-generation purposes, sulfur model compounds including thiophenic and dibenzothiophenic sulfur were uninterrupted power generation in hospitals as well as eventual incorporation into pyrolyzed under 1.0% O2/He and the sulfur forms released were detected by on-line large-scale distributed power generation. The higher efficiencies that can be achieved mass spectroscopy in order to investigate the effect and the mechanism of trace amount in these systems make them ideal for coal gas fed power generation systems. However, of oxygen on the removal of the stable sulfurs in coal. Furthermore, the sulfur removal despite the degree of hydrogen purification and sulfur removal after coal gasification, during pyrolysis of one Chinese Wujiaping coal (WJP) with high organic sulfur under there remain traces of these impurities in the feed stream. The current Ni-YSZ anode oxidative atmosphere was also studied. The results show that the specific peak catalysts exhibit very good catalytic activity towards hydrocarbon reforming and good temperature of sulfur release is decreased during pyrolysis of the model compounds compatibility with the rest of the SOFC system, however they are highly susceptible to with stable thiophenic sulfur under trace amount of oxygen compared to that under poisoning due to sulfur in the fuel. Development of sulfur and coke resistant anodes inert atmosphere, which indicates that the trace amount of oxygen has positive effect will not only bring SOFCs closer to commercialization, it will also significantly reduce on removal of the stable sulfur. When WJP coal is pyrolyzed under 1.0%O2/He, the costs and eliminate material issues associated with gas clean-up and pre-treatment peak temperature of SO2 is always lower than those of CO2 and CO, indicating that the steps. The current work examines development, performance and resistance of new oxidation of sulfur occurred before that of organic carbon frame of coal. The coal formulations to sulfur and coking. Bulk and surface specific characterization pyrolysis tests show that the trace amount of oxygen could increase the efficiency of techniques, including X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction sulfur removal without remarkable decrease in the char yield. (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.

POSTER SESSION 8 P8-3 GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND Continuum Degradation Model for SOFCs Anode Material under Coal HYDROGEN APPLICATIONS Syngas and its Implementation in FEA to Predict Long-Term Structure Integrity Gulfam Iqbal, Huang Guo, Bruce Kang, West Virginia University, USA P8-1 Solid Oxide Fuel Cell Multi-Cell Array for Parallel Testing on Direct Coal A degradation model is developed to predict long-term structural integrity of Solid Syngas Oxide Fuel Cell (SOFC) anode exposed to coal syngas. The model incorporates Kirk Gerdes, Richard Pineault, Randall Gemmen, DOE-NETL; Greg Hackett, thermo-mechanical degradation and coal syngas contaminants effects on the anode West Virginia University, USA microstructure. The proposed model is implemented into finite element analyses through user defined subroutine. The model is validated using a NexTech Probostat™ Integration of solid oxide fuel cells (SOFC) and coal gasification systems is being button cell test apparatus integrated with a Sagnac optical setup and infrared pursued to improve energy production efficiency and enhance carbon capture thermometer. This setup is capable of simultaneously measuring surface deformation, capability. SOFCs are considered for integration owing to their high operating temperature and electrochemical performance. An analytical solution is also developed temperatures (in excess of 800°C) and reduced cleanup requirements as compared to for button cell under uniform pressure to establish correlation between the degradation other fuel cell technologies. model and experimental measurements, as well as to determine the effective anode In addition to system efficiency, degradation performance must also be considered. Young’s modulus due to thermal-mechanical and/or electrochemical degradation. 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 P8-4 coal based systems. While this target has been met by SECA natural gas based In-situ Surface Deformation and Temperature Measurement of Button Cell systems, little system testing has been performed for SOFCs operating on direct coal Under SOFC Operating Conditions syngas. Degradation due to fuelling with direct coal syngas must be considered since Huang Guo, Gulfam Iqbal, Rajeev Dastane, Bruce Kang, West Virginia naturally occurring coal trace materials (Hg, Pb, Se, As, etc.) may have undesirable University, USA interaction with the SOFC anode. The long term SECA program goals target 40,000 hours of operation while An experimental technique capable of simultaneously measuring in-situ surface maintaining good performance. However, determination of the interaction of coal deformation, temperature and electrochemical performance of solid oxide fuel cell 60 (SOFC) button cell is developed. The experiment setup consists of a NexTech P9-2 ProbostatTM SOFC button cell test apparatus integrated with a Sagnac interferometric Site Characterization Activities with a Focus on NETL MMV Efforts: optical setup and infrared (IR) thermometer. Preliminary results at room temperature Southwest Regional Partnership, San Juan Basin Pilot, New Mexico and under hydrogen at 800°C are presented. The results are validated with finite Tom Wilson, Henry Rauch, West Virginia University; Art Wells, Brian Strazisar, element analyses. Rod Diehl, DOE-NETL, USA

P8-5 A variety of characterization activities have been undertaken on the Southwest The Effect of Ph3 Impurity in Coal Syngas on SOFC Performance Regional Carbon Sequestration Partnership’s San Juan Basin pilot site to aid in the Oktay Demircan, Harry O. Finklea, John Zondlo, Chunchuan Xu, West Virginia deployment and subsequent interpretation of the National Energy Technology University, USA 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 The effect of impurities such as phosphorus on the stability and long term performance depth of approximately 3500 feet. Site characterization efforts include field and of solid oxide fuel cells is important to the development of power generation from coal satellite based fracture mapping, subsurface mapping of the region using geophysical syngas. Commercial solid oxide fuel cells were exposed to a synthetic coal syngas logs, evaluation of interferrometric synthetic aperture radar (INSAR) measurements of mixture (H2, H2O, CO, CO2) at a constant current and their performance evaluated ground movements at the site, detailed electromagnetic surveys, lineament analysis of periodically with electrochemical methods (cyclic voltammetry, impedance radar and Landsat imagery, design of a near-surface ground water monitoring well spectroscopy, and polarization curves). In a pure syngas mixture, the decay of cell program and the design of detailed logging and vertical seismic profiling (VSP) efforts voltage did not exceed 0.1 mV/hour at current densities of 0.25 and 0.5 A/cm2. in the injection well. Phosphine (PH3) was introduced at concentrations of 10 ppm or 20 ppm and the cell Structure on the Fruitland coal across the pilot site is nearly flat and dips operated for several hundred hours. In one test, after 50 hours of phosphine exposure at approximately 0.25°NE toward the axis of the San Juan basin. The Fruitland Formation a current density of 0.5 A/cm2, a significant degradation of cell performance (loss of is about 175 feet thick in the area and contains three coals with net thickness of about cell voltage, increase of series resistance and increase of polarization resistance) was 55 to 60 feet. The basal coal injection zone is about 28 feet thick. Subsurface mapping evident. The rate of voltage loss exceeded 1 mV/hour. Removal of the phosphine from suggests that significant faults and fracture zones are not present at the site. Surface the coal syngas mixture did not result in a recovery of the original performance. In and satellite based fracture mapping reveal the presence of two systematic fracture sets another test, the cell operated for over 200 hours at a current density of 0.25 A/cm2 in with dominant NE and NW trends. Surface fracture trends are consistent with butt and the presence of 20 ppm phosphine. The rate of voltage loss was 0.3 mV/hour, and face cleat trends observed in core through the Fruitland from a nearby well. The face changes in the series resistance and polarization resistance were small. Increasing the cleat trend in the area is to the NE. Surface observations also included acquisition of 26 current density to 0.5 A/cm2 resulted in an accelerated degradation of the cell line-kilometers of EM data used to help locate potential near-surface fracture zones. performance, including a rate of voltage loss of 3 mV/hour and significant increases in We recommended placement of additional tracer and soil gas sample points, and the polarization resistance. A partial recovery of cell performance (in polarization and shallow groundwater monitoring wells based on the history of fracture development impedance) was observed upon lowering the current density to 0.25 A/cm2 and then and the near-surface distribution of low-conductivity features. removal of the phosphine from the synthetic syngas mixture. SEM images of anode Satellite based radar scenes of the site were collected multiple times over a three month surface after phosphine exposure reveal changes in nickel particle size depending on interval to determine whether near-surface deformation was occurring in response to the location. EDX chemical analysis supports the existence of phosphorus species at hydrocarbon production in the area. INSAR observations revealed strong coherence one point on the anode surface. No evidence for phosphorus-containing phases is between images but no surface deformation. An attempt to examine longer term (2 observed in by Raman spectroscopy. 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 POSTER SESSION 9 measure sonic anisotropy. One zero offset and three offset VSPs will also be collected NETL-UNIVERSITY CONSORTIUM 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 P9-1 observations. The geophysical logging and VSP data will help other NETL and SWP Comparative Thermodynamic Evaluation of Oxygen Carriers for Chemical researchers develop geomechanical and flow models. Looping Combustion Rahul Solunke, Goetz Veser, University of Pittsburgh, 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) 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, 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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