2004 Abstract Booklet Cover1

Twenty-First Annual International PITTSBURGH COAL CONFERENCE Coal – Energy and the Environment

ABSTRACTS

SESSIONS Page SESSIONS Page

Oral Sessions A Note to the Reader 34: International Coal Technology Co-Operation – 2 32 35: Environmental Control Technology – 6: Mercury 1: Combustion Technologies – 1: Modeling 1 33 2: Gasification – 1: Fundamentals 2 (2) 36: Coal Utilization Technologies in Steel industry – 3: Hydrogen in the Future – 1: General 3 34 4: Coal Utilization By-products – 1: Characterization 1: Keynote Lecture & Cokemaking process 4 37: Materials, Instrumentation & Controls – 1: USC & Use of Coal Utilization By-products 34 5: Environmental Control Technology – 1: Nitrogen Power Plants 4 Species and Organic Emissions 38: Gasification Application & Economics – 1 35 6: Coal Production & Preparation – 1 5 39: Low Rank Coal Utilization – 3 36 7: Combustion Technologies – 2: Co-combustion of 40: Synthesis of Liquid Fuels & Chemical from Coal 6 37 Coal & Alternative Fuels – 1: Fischer-Tropsch Synthesis 8: Gasification – 2: Fundamentals 7 41: Coal Production & Preparation – 2 38 9: Hydrogen in the Future – 2: Fundamentals of 42: Coal Utilization Technologies in Steel Industry – 8 39 Hydrogen Production from Coal 2: Coke Quality, Coal Characterization, Analysis 10: Coal Utilization By-products – 2: Coal Ash 43: Materials, Instrumentation & Controls – 2: 9 40 Utilization for Concrete & Materials Functional Materials 11: Environmental Control Technology – 2: 44: Gasification Applications & Economics – 2 41 10 Particulate Matter and Trace Elements (1) 45: Low Rank Coal Utilization – 4 42 46: Synthesis of Liquid Fuels & Chemicals from Coal 12: Coal Chemistry – 1 11 43 13: Combustion Technologies – 3: Experiences of – 2: Liquefaction & Natural Gas 12 47: Global Climate Change & Application of Large-Scale FBCs 44 14: Gasification – 3: Alternative Feedstocks 13 Industrial Ecology – 1 15: Hydrogen in the Future – 3: Hydrogen Production 48: Coal Utilization Technologies in Steel Industry – 14 45 Technologies (Direct & Indirect) 3: Coal Tar, Pitch, Co-Pyrolysis 16: Coal Utilization By-Products – 3: Coal Utilization 49: Materials, Instrumentation & Controls – 3: High 15 46 By-Products: Coal Ash Utilization Technologies Temperature Materials Issues 17: Environmental Control Technology – 3: 50: Gasification Applications & Economics – 3 47 16 Particulate Matter & Trace Elements (2) 51: Low Rank Coal Utilization – 5 48 52: Synthesis of Liquid Fuels & Chemicals from Coal 18: Coal Chemistry – 2 17 49 19: Combustion Technologies – 4: Behavior of – 3: Dimethyl Ether & Methanol 18 53: Global Climate Change & Application of Mineral Matter During Combustion 50 20: Advanced Energy Systems 19 Industrial Ecology – 2 21: Hydrogen in the Future – 4: Hydrogen Production 54: Coal Utilization Technologies in Steel Industry – 20 Technologies (Direct & Indirect) and Separation 4: Co-Pyrolysis, Coke Reactions in a Blast 51 22: Coal Utilization By-products – 4: Coal Ash Furnace 21 Utilization for Civil Engineering Materials

23: Environmental Control Technology – 4: Sulfur Poster Sessions 22 and PAH 24: Non-fuel Utilization of Coal – 1 23 1: Combustion Technologies 52 25: Combustion Technologies – 5: Emissions of 24 2: Gasification & Pyrolysis Technologies 53 Trace Elements & Particulate Matters 3: Coal Utilization By-Products 57 26: Gasification Advanced Technologies – 1: 4: Coal Utilization Technologies in the Steel Industry 57 Conventional & Advanced Synthesis Gas 25 5: Environmental Control Technologies for Sox, 58 Cleanup NOx, Particulates & Trace Elements 27: Low Rank Coal Utilization – 1 26 6: Synthesis of Liquid Fuels & Chemicals 60 28: International Coal Technology Co-Operation – 1 26 7: Coal Chemistry 61 29: Environmental Control Technology – 5: Mercury 27 8: Geosciences & Resources 62 (1) 9: Non-Fuel Utilization of Coal 63 30: Non-fuel Utilization of Coal – 2 28 10: Gas Turbines & Fuel Cell for Synthesis Gas & 63 31: Geosciences & Resources 29 Hydrogen Applications 32: Gasification Advanced Technologies – 2: 30 11: Low Rank Coal Utilization 64 Pyrolysis 12: Coal Production & Preparation 65 33: Low Rank Coal Utilization – 2 31 13: Other Topics 65

A NOTE TO THE READER

This Abstracts Booklet is prepared solely as a convenient reference for the Conference participants. Abstracts are arranged in the 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. P-3 (where ‘P’ designates a Poster Session) is the third paper to appear in the Coal Utilization By-Products Session.

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

On behalf of the Twenty-First Annual International Pittsburgh Coal Conference, we wish to express our sincere appreciation to Mr. Fan Shi and Ms. Crystal M. Jones for their assistance in preparing this Abstract Booklet.

Badie Morsi Executive Director International Pittsburgh Coal Conference University of Pittsburgh September 2004

different reduced models are used in a simulation, each reduced model being used only SESSION 1 under reaction conditions where it is representative of the full model. The AdapChem COMBUSTION TECHNOLOGIES 1: MODELING provides a method for avoiding the loss of efficiency while retaining chemical accuracy where it is required. The discrete-ordinates method was employed to 1-1 calculate the radiative heat transfer and incorporated in the AdapChem to show that Characteristics of Pulverized Coal Burner Using High Temperature Air AdapChem is feasible and accurate. Comparisons between the simulation results of Combustion Technology two axisymmetric laminar co-flowing partially premixed methane/air flames with and Toshiyuki Suda, Makoto Takafuji, Tetsuya Hirata and Jun’ichi Sato without radiation show that very similar topologic reacting structures can be obtained, Ishikawajima-Harima Heavy Industries, Co., Ltd., Japan but some differences in the size of the partitive zone and different chemical models for each flame exist. For the two cases studied, there is a reasonable temperature decrease High-Temperature Air Combustion Technology (HiCOT) is a new combustion with the radiation model incorporated. technology that achieves both high thermal efficiency and low NOx emission. In the previous study, HiCOT has been applied to pulverized coal combustion, and the 1-4 combustion behavior of pulverized coal in high temperature air has been investigated Dynamic Reactivity and Comminution Behaviour of Particles using a small scale regenerative furnace. In this study, pulverized coal burner using In CFBC HiCOT technology has been tested using a large scale furnace with thermal output of Jaakko Saastamoinen, Heidi Hasa, Juha Pitsink, Jouni Hamalainen and Antti Tourunen 1.2MWth. VTT Processes, Finland Furnace with 1.6 m width, 0.8 m height and 8.0 m length has been used in the Timo Hyppanen, Miro Loschkin and Toni Pikkarainen experiment, which has a pair of regenerative burner in each side of the furance. Foster Wheeler Energia, Finland Bituminous and anthracite coal whose average particle size is 40µm are fed into the furnace at the feed rate of 150kg/h by two pulverized coal burners. Combustion air is Steady state population balance modelling has widely been used to simulate the heated up to 1073K by the heat exchanger using thermal storage honeycombs. Inlet particle size distribution (PSD) of different material (fuel, ash, sand or sorbent port for pulverized coal is changed in order to clarify the effect of mixing with high particles) in fluidized bed (FBC) and circulating fluidized bed boilers (CFBC). The temperature air on ignition and NOx emission behavior. Excess air ratio is changed steady state approach cannot be used to study the effect of rapid changes in dynamic from 1.0 to 1.5. Flame behavior, exhaust gas composition and combustion efficiency conditions, where the fuel with different reactivity and PSD and the PSD of its ash are measured in the experiment. vary, but a dynamic model is more appropriate. Results show that NOx concentration in the exhaust gas is from 100 to 150 ppm Bench scale reactors can be applied to study basic comminution and reaction rate (6%O2) at the excess air ratio of 1.2, which seems to be smaller than that in behaviour of materials with a fuel batch input, which is more easily operated than conventional systems which uses much low temperature air. This is because the release reactor with a continuous feed. Then however, the dynamic population balance of volatile matter and fuel nitrogen by high temperature air are promoted and then the approach is required to interpret the results and extract model parameters from reduction zone is enhanced by rapid devolatilization. NOx emission is reduced by measurements. decreasing the oxygen concentration in the coal feeding air by mixing with recirculated The stability of combustion in FBC and CFBC depends much on the char inventory in exhaust gas. It is possible to maintain the stable flame by high temperature air even for the bed, which is affected by the size and reactivity of the fuel and the operational low volatile coal or low oxygen concentration condition. NOx concentration seems to conditions (temperature, oxygen level). Dynamic population model can be applied to decrease as the coal feeding point becomes far from high temperature air feeding duct. study the change of the char inventory due to changes in fuel or in operational Two types for heat regenrator (rotating heat regenerator and swithching type heat conditions. The effect the operational conditions (temperature and oxygen level) in a regenerator) have been tested. pilot scale reactor on the measured and calculated char PSD is studied. The steady state and the time required to approach steady can also be obtained with the 1-2 dynamic model. Numerical Investigation of the Impact of Air Distribution on the Performance A dynamic population balance model is applied to study reactivity and comminution of a 360MW W-fired Boiler behaviour of material. Tests are carried out in a pilot scale and bench scale fluidized H. Gao and E.H. Chui bed reactors. CANMET Energy Technology Centre, Canada 1-5 Combustion stability and coal burnout are important issues in using difficult-to-burn Development of China's First Training Simulator of a 135 MW CFB Boiler with coals in large utility boilers. For a given burner configuration, the secondary air Reheat distribution can greatly affect the performance of the unit. This study focuses on a Li Zheng, Cai Yi and Gao Qirui 360MW W-fired utility boiler firing anthracite. It is known that the flue gas Tsinghua University, P.R. China temperature and coal burnout can change dramatically under different secondary air Shangdong Zibo distributions. A computational fluid dynamical (CFD) tool was employed to provide CFB Power Plant, P.R. China insights for the field observations. Two simulations were performed with different secondary air distributions corresponding to the field tests. The model results Along with the successful development of 135 MW CFB boiler with reheat, about 30 correctly capture the significant change of flue gas temperature in the near burner CFB boilers has been or are going to be installed in Chinese power industry. More and region, as well as the variation of carbon-in-ash as observed in field trials over more operators who were familiar with pulverized coal boiler operation are expected to different secondary air operating conditions. The model results also show the grasp the skill of CFB boiler operation, which is different from their former sensitivity of anthracite combustion to surrounding airflow. This presentation will experiences. To meet this demand, under the support of Chinese Tenth-five year Plan, highlight the effects of secondary air flow on combustion stability, coal particle Tsinghua University developed a first-of-the-kind training simulator of a 135 MW trajectories, coal burnout, and the thermal characteristics of the boiler. In addition, CFB power plant with reheating in China. The simulator was successfully installed in an optimal secondary air distribution is uncovered for this specific unit based on the Shandong Zibo CFB power plant and was proved to be very helpful to educate and to numerical investigation. improve the operation technique of operators. Compared to the training simulator of conventional PC boiler power plant, the major 1-3 achievement of the new simulator lies in the development of real-time dynamic model Modeling of Complex Kinetics in Methane/Air Flames Using Adaptive Chemistry of CFB combustor. Our former experience in dynamic modeling of CFB combustor, Minghou Xu and Yu Qiao such as dynamic mass balance, dynamic carbon balance and dynamic energy balance, Huazhong University of Science and Technology, P.R. China were integrated into the new model. The newly developed model is robust in Viriato Semião responding the combined changes of different manipulation parameters, such as Instituto Superior Técnico, Portugal primary air, secondary air, coal feed and limestone feed and has the ability to reflect Pisi Lu the whole operation process from cold start to shut down. The distinguished features of Massachusetts Institute of Technology, USA the model lie in the ability to tell the difference of bottom temperature and outtake temperature of the combustor, the difference of carbon content of fly ash and bottom It is well known that the chemistry varies significantly in the different regions of a ash, and the different influence of primary air to secondary air ratio. flame. Using a single chemical kinetic model over the entire domain of a reacting flow About 60 operators have been trained on the simulator before they started their real simulation, which is commonly adopted by existing algorithms as the reduced operation on CFB power plant. Their feedback is really exciting. They felt great chemistry approach, does not describe the varying chemistry properly and may cause similarity between simulator training and real operation. The operation data of 8 discrepancies. Using very complex chemistry (the full chemistry approach) to compute months is now under analyzing and will be used to validate the accuracy of the model. all possible reactions and species everywhere in the computational domain for combustion and other reacting flows is computationally very demanding. In this paper, an Adaptive Chemistry (AdapChem) proposed by Green et al. was employed to simulate the complex kinetics in methane/air flames. In this approach, several 1

SESSION 2 2-3 GASIFICATION 1: FUNDAMENTALS CO2 Gasification Rate Analysis of Coal Char in Entrained Flow Coal Gasifier 2-1 Nobuyuki Suzuki Technology Options for Indian Coals and Optimization of IGCC Cycle Efficiency Electric Power Development Co., Ltd., Japan D.N. Reddy Shiro Kajitani, Masami Ashizawa and Saburo Hara Osmania University, India CRIEPI, Japan V.K. Sethi Rajiv Gandhi Technological University, India Power plants such as the Integrated Coal Gasification Combined Cycle (IGCC) are P. Rajesh being developed on the world to use coal more efficiently and cleanly. In Japan, 9 National Thermal Power Corporation Ltd., India electric power companies and EPDC (Electric Power Development Co., Ltd.) decided to start the project of a 250MWe air-blown two-stage entrained flow IGCC The Global concern for reduction in emission of green house gases (GHG) especially demonstration plant together. On the other hand, in the Europe and U.S., the oxygen- CO2 emissions are likely to put pressure on Indian Power Sector for adoption of blown gasifier has started commercial operation. Also in Japan, the pilot plant of the improved generation technologies. Although India does not have GHG reduction oxygen-blown gasifier which is named “the EAGLE project” aiming at the Integrated targets, it has actively taken steps to address the climate change issues. Mitigative Coal Gasification Fuel Cell (IGFC) combined cycle is operating. Hence, the oxygen- options for India for CO2 reduction, which have been taken up vigorously include, blown coal gasifier is one of the most interesting technology manufacturing materials GHG emission reduction in power sector through adoption of Co-generation, gas and clean fuel, such as hydrogen, DME (Dimethyl Ether) and GTL (Gas to Combined cycle, Clean Coal Technologies (CCTs) and Coal beneficiation. A major Liquid). thrust on CO2 reduction on long term and sustainable basis would however come It is necessary to acquire the gasification reaction rate of coal char under high through adoption of advanced technologies of power generation like temperature and pressure, in the optimal design and evaluation of a coal gasifier. Supercritical/Ultra-supercritical power cycles, Integrated Gasification Combined CRIEPI has developed the gasification reaction model in the air-blown gasifier. In Cycles (IGCC), Fluidized bed Combustion/Gasification Technologies using domestic oxygen-blown gasifier, the influence with high partial pressure of CO2 and CO prevent coal, which is the main stay of power generation in India. A beginning towards of the gasification reaction must be taken into consideration. Since the experiment is adoption of Supercritical Power Plants of 660 MW capacity has already been initiated. still more difficult, reaction model in oxygen-blown gasifier has not solved. Then, India is in favour of adopting in IGCC technology and the efforts are being made to put extension of a coal gasification reaction model applicable to oxygen-blown gasification this technology on the power technology map of India. is needed. IGCC has the inherent characteristic of lower emissions of CO2 and ash and negligible Two types of coal char were gasified with CO2 using a Pressurized Drop Tube Furnace emission of oxides of sulfur and nitrogen (SOx and NOx) achieved economically (PDTF) or a Pressurized Thermogravimetry (PTG) at high temperature and pressurized without additional control measures. The programs on carbon sequestration, hot gas condition, to simulate temperature and partial pressure of gasifying agent in an cleaning for desulfurisation and particulate control and advanced ash utilization oxygen-blown entrained flow coal gasifier. Chars were produced by rapid pyrolysis of could make IGCC a near zero emission power plant. The advanced gas turbines have pulverized bituminous coals using a DTF in a nitrogen gas flow at 1670 Kelvin. The greater potential to raise the efficiency of IGCC plants as high as 55%. Gas cleanup is conditions of gasification tests were following; temperature was from 1470K to one of the decision variables in the selection of gasification process. Hot gas cleanup, 1670K, pressure was from 0.5MPa to 1.0MPa, CO2 partial pressure was from 0.1MPa though contributes in attaining higher efficiencies, is yet to take-off commercially for to 0.7MPa in PDTF. And, temperature was from 1020K to 1370K, pressure was from want of resolving some front line issues particularly with high ash coals. Hot gas clean 0.1MPa to 1.0MPa, CO2 partial pressure was from 0.03MPa to 1.0MPa, CO partial up at high temperature (800-9000C) may be uneconomical due to need for high pressure was from 0MPa to 0.6MPa in PTG. temperature valves and special materials, which are very expensive to adopt at present. As a result, there was a difference between coal types on influence to the gasification Medium temperature particulate cleanup and medium temperature H2S removal has not reaction rate of CO2 partial pressure. And, prevention of CO2 gasification reaction by been fully demonstrated on continuous operation in a large-scale plant using high ash CO was observed. Hence, both nth order equation and Langmuir-Hinshelwood type coals. Further, in hot gas cleanup, a separate system is required to trap alkali vapors, equation was applied to char gasification reaction in random pore model. And, it which can cause high temperature corrosion in gas turbine. These systems are still in became clear that Langmuir-Hinshelwood type equation is suitable for the condition of developmental stage. An extensive study is undertaken with existing GT machine high CO2 and CO partial pressure in Oxygen-blown Entrained flow Gasifier. frames for IGCC cycle optimization using Indian coals with fluidized bed gasification technology. From the study it resolves that gas clean up temperature in the range of 2-4 500-550 0C is viable from the point of view of plant cost vis-à-vis efficiency gain Development and Applications of the Thermodynamic and Viscosity Models for achievable. Complex Coal Ash Slag Systems This paper manly focuses on optimizing the IGCC cycle efficiency by taking into E. Jak, A. Kondratiev, D. Saulov and P.C. Hayes consideration coal gas cleaning temperature and the bottoming cycle parameters for University of Queensland, Australia various topping cycle configurations. By improving the cycle parameters of topping & bottoming cycle gain in IGCC cycle efficiency is computed. In case of bottoming The complex behaviour of coal ash slags in slagging gasifiers (e.g. IGCC) is one of cycle, an optimum range can be achieved between IGCC cycle efficiency and design of the key issues in gasification industry. For successful prediction and modelling of the waste heat recovery boiler for varying process parameters. This approach in various processes taking place in slagging gasifiers (e.g. slag flow or slag adhesion) optimization of IGCC bottoming cycle process parameters compares well with the it is necessary to understand and evaluate such fundamental aspects of the chemistry experimental data available. and physico-chemical properties of coal ash slag systems as phase equilibria and viscosity. 2-2 In Pyrosearch Centre these and other fundamental characteristics of slag behaviour Gasification Behaviour of Australian Coals at High Temperature and Pressure are systematically investigated and analysed, and on such basis the general and D.J. Harris, D.G. Roberts and D.G. Henderson reliable thermodynamic and viscosity models have been developed. CSIRO Energy Technology, Australia The thermodynamic modelling has been carried out using the experimental results obtained in Pyrosearch Centre and the computer system FactSage, which is used for This paper presents gasification data generated for a suite of Australian coals reacting the calculation of multi-phase slag / solid / gas / matte / alloy / salt equilibria in at 20 bar pressure and at temperatures up to 1500°C, as part of a wider investigation multi-component systems of industrial interest. A modified quasi-chemical solution into the performance of Australian coals under gasification conditions. It builds on model is used for the liquid slag phase. The new thermodynamic database for the Al- previous work conducted at lower temperature (1100°C) whereby the effects of O:C Ca-Fe-K-Mg-Na-O-Si system has recently been developed. ratio, residence time and coal type on conversion levels and syngas quality were The experimental thermodynamic studies carrying out in Pyrosearch Centre include investigated. At the higher temperatures used here, coal conversion levels are, as the determination of phase equilibria and kinetics by using different techniques such expected, higher than those measured at 1100°C and product gas compositions reflect as equilibration, primary phase substrate, and levitation. the relevant gas phase equilibrium conditions. This increased conversion allows the Viscosity modelling in Pyrosearch Centre resulted in development of the modified contribution of coal-specific properties such as char structure and high temperature Urbain model for the Al-Ca-Fe-O-Si system and, recently, of the quasi-chemical reactivity to be investigated in more detail than previously possible. Furthermore, at viscosity model for the same slag system. The quasi-chemical viscosity model takes higher conversion levels the effects of coal type on product gas composition are more into account the complex internal structure of silicate slags evaluated from the quasi- apparent than at lower conversion levels. These high temperature, high pressure chemical solution model and therefore has more predictive capability than the gasification data have been reconciled with high pressure bench-scale pyrolysis and empirical viscosity models. The viscosity modelling has been carried out in char reactivity data, allowing the coal-specific effects of key gasification parameters on conjunction with the FactSage calculations to predict the viscosities of fully liquid as gasification behaviour to be investigated. This paper also presents new data from well as heterogeneous, partly crystallised slags. experiments conducted with steam in the reactant mix, demonstrating quantitatively Recently, an experimental set-up for high temperature viscosity measurements has the effects of steam addition on conversion levels and product gas composition. been developed in Pyrosearch Centre, which enables slag samples to be quenched after viscosity measurements and thereby allows to obtain direct information on the structure, phase assemblage and composition of heterogeneous slags. 2

Examples illustrating application of the thermodynamic and viscosity models to with low-pressure reformer has been developed for the hydrogen refueling station to complex industrial issues, such as coal ash slag deposit formation and ash adhesion, demonstrate their reliability and operability under New Energy and Technology will be presented in the paper. Development Organization (NEDO) Project. The second type with medium-pressure reformer (0.1-0.98MPaG) has been developed as a new series of compact hydrogen 2-5 production unit (HYSERVETM). The basic unit generates 30Nm3/h pure hydrogen Reactivity and Structure of Coal Char on Steam Gasification (99.999%), and all components are packaged on one skid. Recently, 100Nm3/h scale Yasushi Sekine, Kiyohiro Ishikawa, Eiichi Kikuchi and Masahiko Matsukata unit has been developed through improving efficiency based on medium-pressure Waseda University, Japan reformer. Our development effort realized to reduce 50% installation area, 50% capital Akimitsu Akimoto cost and 30% operating cost compared with the low-pressure type. CCUJ, Japan This paper describes the detail specifications of the new compact hydrogen production systems, and subsequently focuses on the performance test data of the new compact Steam gasification of various kinds of coal char was carried out with a fixed-bed hydrogen production unit for wide variety of applications. reactor. After the gasification, the reacted char was analyzed by LRS (Laser Raman Spectroscope) mapping system, CO2 adsorption, and SEM/EDX. We evaluated the 3-4 progress of graphitization of carbonaceous materials by several Raman parameters. GREENCAT™, an Environmentally Responsible Technology for Preparation Consequently we found the graphitization which was one of the factors reducing of Water Gas Shift Catalyst for Hydrogen Production reactivity progressed equably as conversion had become highly, presumed that the X.D. Hu, Jürgen Ladebeck and Yeping Cai progress of graphitization may be caused by the change of char morphology. Then in Süd-Chemie Inc., USA order to clarify the ash behavior affecting the char reactivity, characterizations of each char was carried out using SEM/EDX. From the results of SEM images and EDX- With world coal reserve of approximately 1000 billion tons and R/P ratio (reserve to mappings, we found the different behavior of elements and novel parallel analysis production) of 216, utilization of coal as a portable energy source is just a matter of between EDX-mapping and LRS-mapping was very effective for the comprehensive time. An integral approach of hydrogen production and electric power generation by evaluation of ash behavior and carbonaceous structure. Until the medium term of coal gasification/ oxidation shows promising. Since coal contains less hydrogen than gasification (that is around x=0.5), the reactivity of char was increased by the reason natural gas and crude oil (typically <5 wt% of hydrogen and >60 wt% of carbon), a that the catalytic activity of mineral elements is more dominant than the progress of shift reaction is essential to obtain maximum amount of hydrogen by reaction of carbonaceous graphitization. However in the latter term (that is around x=0.9), the H2O with the carbon containing compounds. The efficiency of the shift reaction has reactivity of char was decreased, because of graphitization that certain elements a large impact to the overall economics of the coal utilization. promoted and inhibition of gasification by subsumption of other elements. Traditional preparation method for making a shift catalyst is largely involved in acid- base reaction. During the catalyst making process, large amounts of waste effluent SESSION 3 containing halogen, alkaline, sulfur or nitrogen compounds are usually generated. HYDROGEN IN THE FUTURE 1: GENERAL For example, up to approximately 80 tons of wastewater containing 3 tons of nitrates 3-1 and 800 kg of NOx may be generated for production of one ton of oxide catalyst. In The U.S. Department of Energy Hydrogen, Fuel Cells and Infrastructure this presentation, an environmentally responsible process, GREENCAT™, is Technologies Program - Hydrogen Fuel Initiative Update introduced for preparation of the shift catalyst. This process is able to achieve zero Arlene Anderson and Steven Chalk wastewater discharge, zero nitrate discharge, very low or no NOx release, and US DOE, USA meantime substantially reduce the consumption of water and energy. The shift catalyst produced by GREENCAT™ process has suitable physical-chemical Clean forms of energy are under development that will support sustainable global properties. It has also been demonstrated high efficiency in the micro-reactor test as economic growth while mitigating greenhouse gas emissions and impacts on air well as in the life test. The key step in the GREENCAT™ process is the conversion quality. This paper provides an update of Program activities undertaken in response to of a low surface area solid metal or a low oxidation state material to a high surface the “Hydrogen Fuel Initiative” of February, 2003. To realize this vision, the U.S. is area metal oxide where a complete transition to the desirable oxide phase via a developing demonstrating advanced technologies for hydrogen production, delivery, colloidal intermediate can be achieved. The reaction of converting metal to oxide storage, conversion, and applications. proceeds as follows: One of the advantages of hydrogen is that it can utilize a variety of feedstocks and a variety of production technologies. Feedstock options include fossil resources such as Me (s) Mea+(col) coal, natural gas, and oil, and non-fossil resources such as biomass and water. Mea+(col) MeO (s) Hydrogen production and separations technologies selected under a DOE Hydrogen Production and Delivery Solicitation issued in 2003 will be reviewed. The near-term where Me is the starting material at lower oxidation state than the resulting catalyst focus on distributed hydrogen production from small-scale natural gas reforming, precursor. It is sown that the crystallite size and the phase can be tailored by electrolysis, and new concepts for hydrogen production systems will be emphasized. changing the reaction conditions. In contrast to the traditional processes, the The Hydrogen, Fuel Cells, and Infrastructure Technologies Program PEM fuel cell GREENCAT™ process is close-looped systems where the discharge of the mother RD&D will also be discussed as production of 99.999 % pure hydrogen for use in liquor is either eliminated or significantly reduced. This “green” technology is PEM fuel cells is a key technology focus of the Hydrogen Fuel Initiative. especially valuable in the coal rich regions where water source is scarce. The GREENCAT™ technology won 2003 USA Presidential Green Chemistry Challenge 3-2 award. A Strategic Scenario of Infrastructure Construction for FCV Masahiro Inui, Hiroyuki Iwabuchi and Kenzo Fukuda 3-5 The Institute of Applied Energy, Japan Design, Construction and Commissioning of a Coal to Fuel Cell Grade Hydrogen Technology Package Reducing carbon dioxide emissions is one of the most critical energy issues for Steve Pearce, Mark Boniface, Tony Clemens and Desmond Gong construction of future energy systems. The hydrogen energy system is widely CRL Energy Limited, New Zealand considered to be one of the most promising systems in the future for solving such an environmental problem. One of the most important questions when considering the development of a hydrogen Japanese Government has already decided the introduction targets of fuel cell vehicles infrastructure is: “where will the hydrogen come from?” It is up to each country to (FCVs), 50 thousand and 5 million vehicles in 2010 and 2020, respectively and develop the options best suited to its own particular mix of energy sources. New currently study is underway for expanding the timeframe to 2030 and for setting the Zealand has sufficient recoverable coal reserves to last for centuries and dwindling gas introduction target of FCV in 2030. supplies. It relies heavily on hydro-electricity but this option is struggling to keep up We propose a target value, 15 million FCV, for 2030 and made a tentative strategic with growing demand. scenario of the infrastructure construction for achieving the Government's and our Recognising the need for a wider range of supply options, the New Zealand proposed introduction targets of FCV. government has invested in a six-year research project “Hydrogen Energy for the Future of New Zealand” to create the technological platform required to allow New 3-3 Zealand to realise the benefits of moving to a hydrogen based energy economy and to New Compact Hydrogen Production Unit from Natural Gas demonstrate a small scale “coal to high purity hydrogen to electricity” distributed Takumi Tanaka, Takaaki Asakura, Toyokazu Tanaka and Takayuki Azuma generation package at the 50 kW scale. Osaka Gas Co., Ltd., Japan This new energy technology package is now built and commissioning work has begun. This paper describes some of the features of the gasifier and syn-gas clean-up Natural gas is expected to play an important role to produce hydrogen for hydrogen components of the technology package, some of the difficulties faced and means of refueling stations as well as industrial applications. Osaka Gas has developed two overcoming them. types of hydrogen production systems with different type of reformers. The first type 3

Consistent and well-defined properties of brake linings are important from the point of SESSION 4 view of transportation safety and environmental considerations. Among numerous COAL UTILIZATION BY-PRODUCTS 1: CHARACTERIZATION & other factors, the performance and properties of brake linings strongly depend on their USE OF COAL UTILIZATION BY-PRODUCTS formulation. One brake lining may contain up to 30 ingredients and more than 3,000 4-1 different materials were identified in formulations manufactured worldwide. Current State of Coal Ash Utilization in Japan Objective of this paper is to understand the role of fly ash additives on the frictional Yoshiaki Sakai, Akimitsu Akimoto and Kazuo Hara performance and properties of phenolic matrix brake linings. Three types of fly ash Center for Coal Utilization, Japan were used in this research. One US OE brake lining and one European OE brake lining, further modified by fly ash additives (up to 40 wt. %), were subjected to series In 2001, Japan imported approximately 152 million tons of coal comprising more than of friction tests and evaluation of their structural and physical properties. Friction 100 types from over 10 countries. Almost half of this amount was used for power- assessment and screening procedure and automotive dynamometer tests (Link sector and other industrial boilers as steaming coal. The consumption of coal in Japan Engineering, SAE J2430) were applied to 20 formulations. The analysis of materials is expected to escalate, mainly for the electric power sector, which makes the before and after friction testing involved light microscopy, X-Ray diffraction, FTIR, development of both clean-coal technology and coal-ash utilization technology gas chromatography, mass spectroscopy, scanning electron microscopy with increasingly important. In 2002, approximately 9.2 million tons of coal ash was microanalysis, swelling and growth test, termogravimetric analysis, hardness test, produced by coal combustion, 83.6% of which was effectively used and the rest compressibility test, shear test, profilometry and density measurements. disposed of. The ratio of coal ash utilization in the cement field, which is one of Detected frictional performance and wear characteristics of modified brake linings Japan’s major industries, is 78% of the total; public works is 9%; construction 5%; were ascribed to the formation of a complex friction layer. The friction layer was agriculture 2% and others 6%. detected on both the pad and cast iron disc surfaces and contained significant amounts The Center for Coal Utilization, Japan (CCUJ) has continuously promoted technology of fly ash, indicating its stability during frictional process. Wear of cast iron disc was for the smooth utilization of coal and coal ash. This paper introduces the current state higher when samples modified by fly ash were compared to OE materials. This was of effective coal ash utilization in Japan. related to abrasive effect of silica present in all types of fly ash. Ashes with higher content of carbon performed better in this respect. Improved thermal stability, 4-2 hardness, and strength of brake pads modified by fly ash additions were related to the The United States’ Combustion Byproducts Recycling Consortium inherent properties of ashes investigated. Tamara F. Vandivort and Paul F. Ziemkiewicz West Virginia University, USA 4-5 Tarunjit S. Butalia Properties of Zeolites Synthesized From Fly Ashes and Their Potential Ohio State University, USA Application to Co2 Removal from Flue Gas Izabela Majchrzak-Kucęba and Wojciech Nowak The Combustion Byproducts Recycling Consortium (CBRC) was initiated in the fall of Czestochowa University of Technology, Poland 1998 to provide national focus for development of beneficial uses for the products of coal combustion. CBRC promotes and supports the commercially viable and In recent years, much attention has been paid to the synthesis of zeolites from fly environmentally sound recycling of coal combustion byproducts for productive uses ashes. Among other issues, such situation results from the fact that the products through scientific research, development, and field testing. The CBRC is funded by obtained from fly ashes have a great potential for immobilization of environmental the U.S. Department of Energy—National Energy Technology Laboratory (DOE- pollutants like radioactive waste, removal of heavy metals and ammonium ions from NETL) and collaborating companies. Over the past five years, $3.65 million in U.S. industrial sludge and removal of gaseous pollutants as CO2 and SO2 from flue gases. DOE-NETL funds have been matched by $3.94 million industry dollars in 36 projects. Numerous potential applications of zeolites synthesized from fly ashes have not been Projects include: mine filling, pavement and structural applications, agricultural soil analysed yet. An example here may be removing CO2 from flue gases. It is of special amendments, construction products, ash-derived sorbents for CO2 and mercury importance due to the overall world tendency to restrict CO2 emissions, which are one control, and other uses of coal combustion byproducts. of the main causes of the greenhouse effect. Due to the above, the work examines the CBRC is managed by the West Virginia Water Research Institute at West Virginia adsorption capacity of carbon dioxide on the zeolites synthesized from fly ash, under University with regional management by Southern Illinois University, the University conditions typical of flue gases, at the same time describing possibilities of using them of North Dakota, and the University of Kentucky. Within each region, teams of in this respect. In order to obtain zeolites from fly ashes, alkaline, hydrothermal technical experts from industry and government have developed research priorities activation processes have been carried out. Samples of fly ash were obtained from the and, annually, rank proposals for funding. A national steering committee consisting of Turów Power Station in Poland (Circulating Fluidized Bed boiler of 235 MWe in senior Federal, State and Industry representatives provides program direction and capacity). Fly ashes were chemically analyzed and used to prepare the zeolitic project selection. material. The synthesis processes were run using the classic alkaline conversion and The objective of the CBRC is to develop and demonstrate technologies to address the method of fusion with sodium hydroxide prior to the hydrothermal reaction. In the issues related to the recycling of byproducts associated with coal combustion present work a chemical, physical, mineralogical and microstructural characterisation processes. A goal of the CBRC is that these technologies, by the year 2005, will lead of zeolites from fly ashes was presented. to a doubling of the 1998 rate of FGD byproducts use, a 10% increase in the overall X-ray diffraction pattern of the zeolite samples was obtained with CuKα radiation by national rate of byproduct use, and a 25% increase in the number of uses considered using a Feifert 3003 diffractometer. Particle morphology was observed by a JEOL “allowable” under state regulations. 5400 scanning electron microscope. The effect of temperature on zeolite samples and This paper describes how the CBRC is organized and managed, our research priorities dehydration kinetics of fly ash – based zeolites were studied by a Mettler TG/SDTA and funded projects. Twenty of the thirty-six funded projects have been completed and 851e thermobalance. The model – free kinetic method was applied to calculate the results of those completed projects are summarized. activation energy of the dehydration process of fly ash - based zeolites as a function of conversion and temperature. 4-3 To determine the surface area, specific volume, and mean pore radius, the samples 0 Alfa Foams - An Evaluation of Properties & Microstructure were first degassed at 350 C and then subjected to N2 adsorption with the use of the Y.Bhambri, J. Snider and V.Sikka BET method. The study was performed using a Sorptometer ASAP 2010 manufactured Oak Ridge National Laboratory, USA by Micromeritics. L.Boyd and R.Purgert Zeolites synthesized from fly ashes were tested in laboratory conditions, on a model Energy Industries of Ohio, USA stand. As a result of the tests carried out, adsorption capacity of carbon dioxide on the tested zeolites was determined, and impact of such parameters as: CO2 partial pressure, A new processing technique for producing aluminum based foam (Alfa foam) temperature, H2O and SO2 presence in flue gases on CO2 adsorption was evaluated. containing fly ash has been developed. The processing method for producing Alfa foam with different particulate aggregate sizes has been discussed. The foam is SESSION 5 characterized for mechanical properties as well as microstructure. Detailed image ENVIRONMENTAL CONTROL TECHNOLOGY 1: NITROGEN analysis reveals that difference in mechanical properties among foams of different SPECIES & ORGANIC EMISSIONS particulate sizes is due to variation in relative amount of constituent phases. Work is 5-1 continuing in altering the processing parameters in the production of Alfa foams to Formation of Nitrogenous Species during Coal Pyrolysis and Gasification meet the application demands of foam in acoustic damping and structural panels. Jian-ying Lin, Li-ping Chang, Jie Feng, Ke-Chang Xie Taiyuan University of Technology, P.R. China 4-4 Utilization of Coal Combustion Byproducts in Phenolic-Matrix Composite The formation rules of HCN, NH3 and NO during coal samples pyrolysis and Materials for Braking Applications gasification were investigated in this paper. And the distribution of nitrogen in the Peter Filip, Kok-Wai Hee, Samrat Mohanty and Y. Paul Chugh char, which obtained during pyrolysis, was also investigated. Eight different coal Southern Illinois University, USA samples were used in this work. All of them were sieved to size fraction 220-450µm 4

before use. Pyrolysis and gasification experiments were carried out in a programmed 5-4 mode at a heating rate of 10 /min with a fixed-bed quartz reactor at atmospheric A Numerical Simulation of a Pulverized Coal Combustion Field in a Test Furnace pressure. The gas flow rate is 600ml/min. About 1.0g dried sample was used in the with an Advanced Low NOx burner experiment. The amount of HCN and NH3 were quantified by ion chromatography. Hirofumi Tsuji, Ryoichi Kurose, and Hisao Makino And the amount of NO was quantified by Quintox flue gas analyzer. The nitrogen CRIEPI, Japan content in char was determined by element analyzer. The influence of coal rank on the formation rules of HCN, NH3 and NO was discussed. The results showed that the In pulverized coal combustion, the combustion conditions, the burner operating formation of HCN during pyrolysis mainly due to the thermal cracking of volatile. The conditions and coal properties affect the combustion characteristics. It is, therefore, content of volatile is the main factor that affected the HCN release. When volatile very difficult to experimentally optimize these conditions for each coals due to high content increased the amount of HCN also increased. The release of NH3 is expense, and the research and development on the combustion technology needs an complicated during pyrolysis. It not only relied on the volatile content but also relied exceedingly long term. In these days, the numerical simulation of a coal combustion on the coal geographic character. The results showed that more inertinite could field has become of major interest because the performance of computers is increasing increase the release of NH3. As for the formation rules of HCN during coal gasification rapidly and the models for coal combustion have improved. with CO2, it was just as the same as that during pyrolysis, and the release rules of NH3 In this study, a three-dimensional numerical simulation is applied to a pulverized coal during gasification had a little difference compared to that during pyrolysis. The higher combustion field in a test furnace equipped with an advanced low-NOx burner called volatile could increase the NH3 releasing amount during gasification. The formation CI- burner. The applicability of the numerical simulation to the prediction of NOx rules of NO during gasification were completely different compared with the formation concentration in exhaust gas and combustion efficiency for bituminous coals is rules of HCN and NH3. The formation of NO increases with volatile content increase investigated, and their results are compared with experimental results. The results and had a peak at 34% volatile content, then NO amount decrease with volatile content show that the present numerical simulation is generally applicable for the bituminous increase. coals. The accuracy of the numerical simulation is improved by faithfully duplicating the configuration of the burner, and by using this detailed model it can be verified that 5-2 a recirculation flow is formed in the high-gas-temperature region near CI- burner Development of Reduction Technology of Unburned Carbon Concentration in outlet, and this lengthens the residence time of coal particles in this high-temperature Fly Ash on Pulverized Coal Combustion region, promotes the evolution of volatile matter and the progress of char reaction, and Michitaka Ikeda, Masaru Saito, Yoshihiro Kishi and Hisao Makino produces an extremely low-O2 region for effective NOx reduction. CRIEPI, Japan 5-5 It is important to reduce both emissions of NOx and unburned carbon on pulverized Organic Emissions Control in Energy Generation, Process Modelling coal combustion. We have already developed the advanced low NOx burner. This Ana M. Mastral, Maria S. Callen, José M. López, Elvira Aylón and Maria T. de la burner with multi staged air injection method can reduce unburned carbon Cruz concentration in fly ash less than 3 % at 100 ppm of NOx concentration at the exit of Instituto de Carboquímica, CSIC, Spain furnace. In these days, ash utilization is problem and in order to utilize coal ash for valuable matter such as a cement mixture, unburned carbon concentration in fly ash Polycyclic Aromatic Hydrocarbons (PAH) are an important class of environmental has to reduce much more. This report describes the pulverized coal combustion pollutants that are generated during combustion processes. PAH emissions, due to their technologies to reduce unburned carbon concentration in fly ash less than 2.5 % at high volatility and reactivity, can be released, not only supported onto particulate 100 ppm of NOx concentration at the exit of furnace. Combustion tests were matter (PM) but also in the gas phase. While PAH supported on the PM can be trapped performed by firing three kinds of fuel ratio’s coal (0.8, 1.5 and 2.0), which were using the proper systems such as cyclones, electrostatic precipitators, etc; the used in Japanese power stations, on the pulverized coal combustion test furnace. The atmospheric PAH emission control becomes more difficult. Adsorption processes on main results are as follows. activated carbons and catalytic combustion seem to be a promising technology. When low fuel ratio coal (0.8) was fired, unburned carbon concentration in fly ash However, research effort, especially in the mathematical modeling of these processes, could be reduced less than 2.5 % at 100 ppm of NOx concentration at the exit of is still needed to implement these technologies at industrial scale. furnace. On the other hand, as fuel ratio was higher (1.5 and 2.0), unburned carbon In this communication, the modeling of breakthrough curves obtained in the adsorption concentration in fly ash increased more than 2.5 %. When A/C (Weight ratio of of Phenanthrene as model compound on a carbonaceous material is described. All the primary air to pulverized coal) decreased, pulverized coal stayed a long time in runs were performed in a fixed bed reactor with a process temperature of 150 ºC, combustion flame. We cleared that unburned carbon concentration in fly ash could similar to the observed in the flue gases of energy generation systems. This work is be reduced without the large increase of NOx concentration at the exit of furnace by mainly focused on the study of how adsorbent characteristics (surface area and decrease of A/C. When coals, which were higher fuel ratio, were fired, combustion micropore size distribution) influence the kinetics of the adsorption process. First, flame became narrow in the furnace, and could be diffused by increase of swirl vane equilibrium values are found from the breakthrough curves and they are satisfactory angle. Then, oxygen consumption is accelerated outer side in the furnace, and fitted to the well-known Freundlich isotherm. Using the obtained equilibrium values unburned carbon concentration in fly ash became lower. NOx reduction area at the together with the linear driving force model as kinetic expression, the breakthrough optimized air injection condition became wider than that at the conventional curve modeling is achieved. It was found that this model fits all the breakthrough condition. NOx was decomposed outer side in the furnace, and NOx concentration at curves and it is a useful tool for modeling purposes. Values for the Phenanthrene the exit of furnace decreased. surface and effective diffusion coefficients are calculated and reported, and a As a result, when air injection conditions were optimized for fuel ratio of bituminous relationship with the microporosity is found. As it was expected, it is observed that the coal, it was possible that unburned carbon concentration in fly ash reduced less than Phenanthrene molecule finds kinetic restrictions for the diffusion in those carbons with 2.5 % and NOx concentration at the exit of furnace also decreased less than 100 ppm. narrow microporosity, especially in those with a mean pore diameter close to the molecular size. 5-3 Low-Temperature Selective Catalytic Reduction of Nitric Oxide with Ammonia SESSION 6 Koichiro Shimizu, Caili Su and Eiji Sasaoka COAL PRODUCTION & PREPARATION: 1 Okayama University, Japan 6-1 Yuka Fujikawa Flotation of Coal and Sludge for Coal-Preparation Plant by New Reagents Okayama Prefectural Environmental Conservation Corporation Foundation, Japan Viktor I. Saranchuk and Leonid J. Galushko Md. Azhar Uddin National Academy of Science of Ukraine, Ukraine University of New South Wales, Australia In the last time in Ukraine the big attention is given a problem sludge pit on coal- Low Selective catalytic reduction of nitric oxide over TiO2, SiO2 and activated preparation plants as the sources of secondary raw material for power and by-product- carbon were studied using a conventional flow type packed bed reactor at 100oC coking industry. Design resources make about 25 million tons of coal and anthracite. under atmospheric pressure. The following results were obtained: Ash content of the sludge changes from 35 up to 75 %. Specially created installations (1) The presence of SO2, O2 and NH3 were indispensable for removal of NO over and the stationary equipment of coal-preparation plants use for enrichment sludge TiO2. One of ways of enrichment is flotation. This way is based on various wettability of a (2) The presence of SO2 contributed to oxidation of NO to NO2 over TiO2. surface of coal and mineral particles. Owing to a long finding in storehouses fine (3) If NO2 presented with NO in the reaction system, the presence of SO2 was not particles of coal are oxidized and get raised hydrophily. It demands the special indispensable for the removal of NO over TiO2. approach to a problem of flotation sludge. (4) It was clarified that the following tow reactions occurred over TiO2: NO + NO2 The carried out researches have shown, that existing technologies of flotation do not +2NH3 → 2N2 + 3H2O (a), 2NO2 + NH3 → N2 + NH4NO3 + H2O (b). provide reception of a commodity output from coal sludge with ash content more than Furthermore, it was suggested that the reaction of (b) occurred and the reaction of (a) 50 %. Two series of researches were carried out for development of technology of did not occur over SiO2 and activated carbon. flotation sludge: 1. Selection special flotator and technologies of enrichment for sludge; 5

2. Joint enrichment of a mix of ordinary coal with ash content about 25 % and country’s energy balance. The assumptions of Poland’s Energy Policy for years to 2-10 % sludge with ash content 45-65 %. come anticipate a gradual reduction of the coal share in the electricity production. Developed at the first stage flotator allow to receive a concentrate for the power However, coal will continue to play the leading role in the sector of electricity purposes appropriate to requirements, the concentrate for coking had raised ash production due to lower costs comparing to other energy carriers and due to the energy content. safety of the country. The experiences carried out at the second stage on flotation of a mix coals and sludge Run of mine coal is characterised by various qualitative parameters. The quality of the have shown, that the additive up to 10 % sludge does not influence for quality of a coal is not always in conformity with the standard conditions designed for the boiler. concentrate coke coals and in addition allows to take from sludge in a concentrate of The combustion of the coal of parameters considerably different than those designed coal of 200-500 kg from each ton sludge. Thus ash content a concentrate is 6-8 %, ash causes the deterioration of the boiler operation quality, thereby, lowering the content waste products is 85-95 %. The small increase of a degree of extraction of coal efficiency. In extreme cases, the boiler may even become damaged. In order for the from a mix is marked in comparison with ordinary coal. recipient of the coal to receive the product with parameters exactly reflecting those Optimization of process of flotation on structure and amount flotator is made. ordered the coal must be subject to preparation processes. The process that is most often used is coal preparation in dense media, in jigs, or in centrifugal separators. The 6-2 deeper the preparation is, the purer coal is obtained, of the better quality parameters. Development of Advanced Fine Coal Dewatering Technologies However, too deep preparation causes large amount of grains (organic substance) to R.-H. Yoon, J. Zhang, M. K. Eryadin and G. H. Luttrell transfer into the waste, thereby increasing the losses of chemical energy. Also the Virginia Polytechnic Institute & State University, USA quality of processing machines contributes to the amount of losses. The quality of preparation can be described by performance curves. These curves are prepared on the Dewatering processes are used in coal preparation plants to remove excess surface basis of densimetric analysis of tested coal. The boiler is another place where the moisture from the clean coal products. Coarser particles can be readily dewatered losses of chemical energy occur. The losses in the boiler are indicated through the using simple screening systems, while finer particles require costly unit operations boiler instrumentation systems, which allow drawing up the corresponding diagrams. such as centrifuges and filters. Moisture that is not removed by these processes reduces The relation between yield of coal in the preparation process and the losses in the the heating value and increases the cost of transporting the clean coal. Excess moisture boiler can be determined by a two step analysis. In the first step the relation between can also create unacceptable handling problems for both the coal producer and the densimetric fractions yield and the calorific value of prepared coal is found. In the downstream consumers by plugging chutes, bins, and rail cars. Coal handling can be second step the relation between the losses in the boiler and the calorific value of burnt particularly severe during winter months because of freezing. These problems typically coal is determined. The superposition of the two functions gives the relation between force U.S. coal producers to discard their fine coal (<0.15 mm), which reduces the yield of coal and losses in boiler. The relation in question allows setting such tonnage of saleable coal and creates a potential environmental hazard. In light of these preparation conditions at the preparation plant that the losses in the boiler during shortcomings, researchers at Virginia Tech have been developing a new suite of combustion are minimised. advanced technologies for fine coal dewatering. These include novel dewatering aids, hyperbaric filters and centrifuges, and other revolutionary processes that can eliminate 6-5 the need for thermal drying. In addition, innovative technologies have been developed Effect of Petrological Composition of Coal on Black Coal Flotation that offer near-term improvements in existing plant filters and centrifuges. This paper Peter Fecko, Iva Pectová, Pavla Ovcari, Vladimír Cablik and Barbara Tora provides an overview of test results obtained from recent laboratory, pilot-plant, and VSB - Technical University of Ostrava, Czech Republic field trials conducted using these advanced dewatering technologies. The paper deals with floatability of bituminous coal and examines how individual 6-3 maceral groups float in course of a fractional flotation. Flotation was tested on 4 Effects of Coal Characteristics on the Properties of Coal Water Slurry samples of bituminous coal from the localities of Jaworzno, Jankowice, Staszicz, Wei Yuchi, Baoqing Li, Wen Li, Haokan Chen Marcel (Poland) and 2 samples from the Dukla Mine (Czech Republic). The objective Chinese Academy of Sciences, P.R. China of this paper was to verify flotation of bituminous coal from localities in Poland and the Czech Republic; where the Montanol and Flotalex collector agents were tested as The effects of coal characteristics on the properties of coal water slurry (CWS) were well as their selectivity was evaluated from the petrologic point of view. systemically studied using 16 Chinese coals with different coal ranks from lignite to anthracite. Sodium naphthalene sulfonate formaldehyde condensate was selected as dispersant and the same conditions were used for the preparation of all CWS. The SESSION 7 correlationships of the CWS properties including slurryability (the concentration of COMBUSTION TECHNOLOGIES 2: CO-COMBUSTION OF COAL & slurry that apparent viscosity is 1200mPa.s at shear rate of 28.38s-1), rheological ALTERNATIVE FUELS behaviour (represent by flow index), and static stability (the days of formation soft 7-1 sediment) with coal properties including coal rank (Cdaf, Odaf), content of air Lafarge Cement Polska S.A. Experience Concerning Waste-Derived Alternative equilibrium moisture (Mad), maximum holding capacity of moisture (MHC), ash content, the surface properties, petrographic macerals, pore structure, adsorption Fuel Combustion characteristics of dispersants on coal surface and their corresponding electrochemical Alicja Uliasz-Bochenczyk Mineral and Energy Economy Research Institute, Poland properties of coal were investigated. Multiple regression analysis of different factors of Sarna Mieczyslaw coal properties indicated that: Lafarge Cement Polska S.A., Poland 1. The carbon content, content of air equilibrium moisture, grindability index (HGI), Cement industry belongs to the branch of industry that has been using waste-derived and surface area (SHg) by test of Autoscan 60 Mercury Porosimeter are main factors influencing the slurryability of CWS, which can be described by the following alternative fuel for over ten years. The alternative fuels use in that industry has been equation with correlation coefficient of 0.988. determined by many factors like conditions of conducted process (high temperature, proper kiln length, long time of input material residue in a kiln as well as basic C = 37.93 + 0.38[Cdaf] – 0.31[Mad] + 0.049[HGI] – 0.077[SHg] 2. The ash content, the content of soluble mineral matters in CWS (D ), pore volume environment allowing acid gas neutralization). Moreover it is a priceless advantage t that combustion inside a cement kiln is a wasteless process, as the combustion products (VHg), Zeta-potential properties (ξ)of coal surface mainly influence the rheological behaviour of CWS. The rheological behaviour can be described using the follow become an admixture during clinkerization operation. equation with correlation coefficient of 0.917. As mentioned above, waste derived alternative fuel combustion in cement plants constitutes a safe way of wastes utilization, environmentally safe and profitable both N = 0.86 - 0.098[Ad] – 0.0023[Dt] – 2.91[VHg] + 0.011[ξ] 3. The content of soluble mineral matters in CWS, inertinite content in petrographic for the plant and for society. macerals(I) are the main factors influencing the static stability of CWS, which can be Global economical growth causes the significant increase of both industrial and calculated by the following equation with correlation coefficient of 0.726. municipal wastes, the management of which becomes the challenge of XXI century. That is why many enterprises are gaining experience in both industrial and municipal W = 19.43 + 0.054[Dt] – 0.35[I] waste organic fraction utilization.Alternative fuel derived from such wastes as: tires, 6-4 fluid hydrocarbon waste products, industrial or/and municipal waste flammable Coal Preparation versus Losses of Chemical Energy in Combustion Processes fraction mixtures are used in many countries. Lidia Gawlik and Eugeniusz Mokrzycki Poland is the country of long cement production traditions. Nowadays fifteen cement Mineral and Energy Economy Research Institute, Poland plants run in Poland.Two cement plants belong to LAFARGE concern that possesses Tomasz Mirowski, Tadeusz Olkuski and Adam Szurlej strong background in alternative fuel application, dating back to 1982. Nowadays in AGH University of Science and Technology, Poland LAFARGE concern waste derived alternative fuel share in total fuel usage amounts to 7.7%.This paper focuses on hitherto achievements of the Lafarge Cement Polska S.A. Polish energy sector comprises nearly exclusively the conventional power plants, in the alternative fuel use. based on the domestic raw material, i.e. hard coal and brown coal. Coal is the basic source of energy, as well as the main factor providing the positive balance in the

7-2 The paper aims to present the results of combined combustion of coal and Meat and Co-Firing of Wood Chips In 10MW Grate Coal Boiler Bone Meal (MBM) the laboratory scale bubbling fluidised bed set located in the Marek Sciazko, Jerzy Rainczak Laboratory of Steam Boilers and Thermal Plants (LSBTP) of NTUA. Institute for Chemical Processing of Coal, Poland Through the MBM feeding ban for animals in the European Union, several millions tonnes of MBM have to be disposed yearly. MBM has been classified as biomass and "The strategy of the development of the renewable energy" is forcing Polish power can therefore be treated as a fuel substitute to coal. At the time, MBM combustion distributors and generators to increase the energy production from renewable sources seems the most adequate way of disposing MBM, since the level of temperature in the up to 7.5% by 2010 and to 14% in 2020. This is the reason for tasting undertaken on combustion chamber provides a significant potential of elimination of MBM while co-firing of coal and biomass in coal grate boiler of 10MWth capacity. The wood chips valorising its energetic potential. were produced from energy crops, specifically willow of type Salix. The energy The impact of combusting MBM with coal in fluidised beds is studied to study its efficiency effect and emission reduction was investigated in respect of biomass effect on the process, emissions and particularly the NOx and VOC. Furthermore the content. The results of the tests showed that there is observed reduction in emission of properties and particularities of the ashes produced are examined. In order to such gaseous components as sulfur dioxide, nitrogen oxides, and organic compounds. investigate the MBM co-combustion, a set of experiments for emission and ash- It was found that the addition of biomass in amount of 4-5% by mass cause increase of valorisation was carried out in a laboratory scale bubbling fluidised bed set up in boiler efficiency due to increased burn-out of carbon in the bottom ash. The results of NTUA. Fuel used was low risk greek MBM from local industries and greek coal co-firing were collected up to 35% v/v of biomass content in fuel mix. The main (lignite). attention was paid to the preparation of fuel mixture by applying double screw mixer Co-combustion tests investigate the effect of the operation conditions such as air and proper distribution of the fuel at the feeding point to the grate boiler. The preheat temperature, bed temperature, fuel supply, fluidisation air velocities and excess properties of coal and wood chips were investigated prior to co-combustion to make air levels on the quality of combustion of MBM with coal (gaseous emissions, air energy balance possible. During the boiler operation the basic technological pollutants, residual matter, auto combustion, ash agglomeration problems) in order to parameters were measured, particularly mass flow rates of fuel mix and air, determine the optimum MBM percentage in the fuel blend. taking into account. temperature of hot water produced, temperature of combustion gases at the outlet, and Furthermore, ash samples are collected and examined for their suitability for the content of combustible parts in bottom ash. The basic components of flue gases landfilling as well as other uses such as blending with cement. were investigated (CO2, CO, NO and SO2) as well as dust content. Additionally total The results of the tests will show whether the substitution of coal from biomass is organic carbon (TOC), polyaromatic hydrocarbons (PAH) including B( P were feasible and acceptable, conforming to the existing legislation. determined. The results of tests showed that significant reduction of the following components can be obtained in comparison to coal combustion: CO (53, 7%), CO2 SESSION 8 (27, 4%), SO2 (23, 5%) NO2 (8, 1%), TOC (17, 4%), PAH (17, 6%) and B( )P (47, GASIFICATION 2: FUNDAMENTALS 2%). The boiler efficiency at the wood chips content 35%v/v are smaller by 0.5% but 8-1 at 25%v/v higher by 0.3%. The results were confirmed in two repeated runs. High-temperature Interactions between Coal Char and Mixtures of Iron compounds, Quartz, and Kaolinite 7-3 Kayoko Morishita, Naoya Ichimura and Takayuki Takarada Possibilities of High Sulphur Content Coal Combustion with Biomass Gunma University, Japan Contribution Pavel Sedláček, Marcela Šafářová and Josef Valeš There is a scanty of knowledge about the thermal interactions between mineral matter Brown Coal Researche Institute, Czech Republic in coal and coal char, although it is important in the understanding of some coal conversion processes. We recently highlighted the reactions between mineral matter Combustion of solid fuels is controlled by valid legislation that determines emission and coal char. The carbothermal reactions of quartz and kaolinite started at 1200 C limits for combustion in facilities of different outputs. Lignite coal from the North under Ar atmospheres, releasing CO. In this study, the interaction between coal char Bohemian Lignite Field is characteristic for its high content of sulphur (up to 3.5 % and mixtures of iron compounds such as pyrite and iron oxide, quartz, aluminum and Std). During combustion of that coal, high emission concentrations are formed and that meta-kaolinite were investigated by heating to 1600 C under Ar. Pyrite was gradually coal becomes unsaleable. With regard to the long-term surface mining, there are land- reduced in the temperature ranging 800-1600 C and was changed to pyrrhotite at 800 C reclaimed mined out areas available, which can be used for growing energy biomass. and to troillite at 1000 C. Iron was detected above 1200 C and almost of all iron Grown biomass can be used for the production of a new product which contains, apart component became to iron at 1600 C. The mixtures of iron compounds and aluminum from hard saleable lignite coal with a high content of sulphur, a biomass compound and the mixtures of coal char and aluminum were quite stable and few interactions which, during combustion, decreases the value of emission concentrations and along were observed. In coexistence of coal char, aluminum and iron compounds, however, with an additive agent, which is another compound of the lignite coal pellets, ensures a interaction between iron compounds and aluminum was promoted with release of CO, decrease in emissions to a value which is determined for solid fuel combustion. For the and compound derived from Fe and Al was formed. It seems that carbon in coal char needs of burning tests, several samples of lignite coal pellets were prepared, which has removed oxygen in aluminum and Al obtained by reduction of aluminum and iron were burnt in a furnace designed for lignite coal combustion and the emission values compounds have been reacted. In addition, pyrite affected the reaction of carbon were compared with emission values which are reached during pure lignite coal /quartz and carbon/kaolinite and reduced the reaction initiated-temperature ca. 200 C at combustion. the case of quartz and ca.100 C at the case of kaolinite. As pyrite coexisted with SiO2 and coal char, pyrite was reduced to troillite at 1000-1200 C and reacted with SiO2 7-4 above 1400 C, forming Fe3Si. In the case of pyrite-kaolinite-coal char mixture, troillite Co-Combustion of Municipal Solid Waste and Thai Lignite was formed at 1000-1200 C as same as the case of SiO2 coexists. At 1400 C, however, In a Fluidised Bed three types of compounds were formed that was Fe1.34Si0.66, Fe3Si and Fe5Si3. In the Pornvipa Boonnuit, Kriengkrai Suksankraisorn, Suthum Patumsawad, Bundit sample heated at 1600 C, there were Fe3Si and SiC. On the other hand, Fe2O3-SiO2- Fungtummasan coal char mixture reacted at relatively lower temperature, Fe2SiO4 was formed and Fe King Mongkut’s Institute of Technology, Thailand at 1000 C. Above 1400 C, Fe1.34Si0.66, Fe3Si and Fe5Si3 was formed. In addition, crystallization of carbon was progressed with heat treatment temperature and graphite Experimental investigations on the co-combustion characteristics of high-moisture was clearly assigned at 1600 C. In the case of Fe2O3-kaolinite-coal char mixture, municipal solid waste (MSW) and high-sulphur Thai lignite were carried out using a hercynite was formed at 1000C and then changed to mullite with iron. And, SiC was laboratory scale fluidised-bed reactor. The objective is to study the effect of main observed at even 1400 C. operating parameters on the combustion characteristics and gas emissions. The results show that the co-combustion characteristics differ significantly from the combustion of 8-2 lignite alone. The co-combustion of MSW and lignite reduces the emission of SO2 A Model of Char Capture by Molten Slag Surface under High-Temperature while increasing NO and N2O slightly. It also results in a slight drop in combustion Gasification Conditions efficiency. The optimum condition for co-combustion of MSW with lignite, in view of Tadaaki Shimizu carbon combustion efficiency, emissions of CO, NO and N2O appears to be the Niigata University, Japan following: 20% MSW mass fraction, 40-60% excess air and 0.2 secondary to total air Hiroaki Tominaga ratio. However, this occurs at the expense of slightly smaller reduction in SO2 Idemitsu Kosan Co. Ltd., Japan emission, which could become insignificant with limestone addition in the bed. The synergistic effect of co-firing two fuels enhances the combustion reactivity and reduces A simple model was proposed for char capture by molten slag surface under high- NO, N2O and CO emissions. temperature gasification conditions. In this model, char particles were pneumatically carried to the molten slag surface. It was assumed that the char particles were captured 7-5 if they reach the molten slag surface whereas they were repelled if they reach the part Co-Combustion of Coal and Meat and Bone Meal (MBM) that is covered by the unreacted char particles. Thus the probability of char capture Emmanuel Kakaras, Kyriakos Panopoulos and Lydia Fryda was given by the balance of char feed rate per unit surface area of the slag and the rate National Technical University of Athens, Greece of char consumption by the gasification reaction. 7

Experiments were carried out to evaluate the probability of char capture by molten slag 8-5 surface at 1350 oC. A ceramic tube whose bottom was closed was vertically placed in Heat Transfer and Fluid Dynamics in CWS Preheater for Coal Gasifier an electric furnace. Mixture of coal ash and flux (limestone) was placed at the bottom Kosuke Aiuchi, Ryo Moriyama, Shohei Takeda, Shunji Kitada, of the reactor. The reactor was heated up to a temperature higher than the melting Masaki Onozaki and Yukuo Katayama point of the mixture of coal ash and flux, thus slag was formed at the bottom. Char The Institute of Applied Energy, Japan particles were conveyed by CO2 stream through a 4 mm i.d. nozzle from the top of the reactor to the molten slag surface. If the char particles were not captured at the reactor The authors have developed a preheating technology of coal water slurry (CWS) which bottom, they were immediately conveyed out of the reactor by the gas stream. CO was increases the efficiency of coal gasification with reduction of oxygen consumption.1) produced by gasification reaction in the presence of the molten slag at the bottom The objective of this paper is to describe a study on heat transfer and fluid dynamics in whereas only small amount of char was gasified in the absence of slag. Thus the the CWS preheater. In the experiment, 140 kg/h of CWS (50wt%, 1.7ton-coal/day) was presence of the slag surface was necessary to capture char particles at the bottom. The pumped up to 10MPa, and introduced into a single tube heat exchanger. After the fluid conversion of carbon to CO decreased with increasing char feed rate. The effect of was heated to 300 in the tube of 6 mm ID, the water in CWS was vaporized in a char properties such as particle size, density, and gasification rate, on the conversion of region where the diameter of the tube increased gradually (2-10 mm ID). This enables carbon to CO was evaluated. The theoretical results agreed well with the experimental the fluid velocity to be kept in a range that prevents both blockage and erosion. The results. water in CWS was completely vaporized, and the dried coal particles with steam were exhausted in the furnace. The total length of the tube was 120 m. The experiment 8-3 result was corresponding to the calculation result well. Release and Retention of Halogens during Pyrolysis and Gasification of Coals The temperature and pressure distributions of the fluid were calculated with empirical Akio Ueda and Makoto Takeda heat transfer and pressure drop correlations. The calculated results were well Babcock-Hitachi K.K., Japan corresponding to the experimental data measured in some test points. It is confirmed Noboru Suzuki that the position where the vaporization starts was in the 2 mm ID tube. The overall Utsunomiya University, Japan heat transfer coefficient is in a range of 200-900 Wm-2K-1 which is largely affected by Nakazato Yoshihiro, Naoto Tsubouchi and Yasuo Ohtsuka the outside heat transfer coefficient. Using the calculation model, a large scale Tohoku University, Japan apparatus (60wt% CWS, 300ton-coal/day) was designed in two approaches using -1 -1 molten salt (KNO3 + NaNO2 + NaNO3, =0.5 Wm K ) as a heating medium. In the The fate of halogen atoms in coal, mainly the chlorine (denoted as coal-Cl), during first approach, shell and multi-tube heat exchanger was used. In the second, a single pyrolysis and gasification is examined with fixed-bed and drop-tube reactors under tube heat exchanger was used for which the tube has a race track shape. These systems different conditions. Pyrolysis of several coals with C % of 73 – 92 wt%(daf) and Cl can be connected to boiler as well as gasifier. Slurries of other flammable substances % of 0.021 – 0.14 wt%(daf) at a slow heating rate of 2.5 – 400 K/min shows that the Cl such as paper sludge slurry and biomass slurry also can be treated. is released mostly as HCl and the rest is retained in pyrolyzed chars, the Cl distribution being almost independent of C %, Cl %, and heating rate. Since HCl yield up to 1073 SESSION 9 K tends to be higher at a larger content of Ca plus Na, coal-Cl may be present HYDROGEN IN THE FUTURE 2: FUNDAMENTALS OF HYDROGEN dominantly as the forms of these chlorides. When a sub-bituminous coal with C % of PRODUCTION FROM COAL 78 wt%(daf) is injected into an O2-blown, drop-tube gasifier at 0.9 – 2.6 MPa, char 9-1 conversion increases with increasing weight ration of O2/coal in the range of 0.66 – Overview of Hydrocarbon Processing Options and Proposed Concepts of 0.83, regardless of the pressure. The content of Cl or F in the char in the conversion Gasification for Hydrogen Production with Carbon Dioxide Capture level of 80 – 95 % is much larger than the corresponding value upon pyrolysis, that is, Chunshan Song at char conversion of zero. These observations mean that the halogens remain Pennsylvania State University, USA accumulated even at the latter part of gasification. Some model experiments and XPS measurements strongly suggest that such significant halogen retention originates from Hydrogen energy development is important for breaking the link between energy secondary reactions of HCl or HF once released with some minerals and carbon active utilization and emissions of pollutants and greenhouse gases. The research and sites in the char. development efforts using coal also provide a bridge to future hydrogen production using renewable resources. This paper discusses the processing options for hydrogen 8-4 production in conjunction with hydrogen utilization, fuel cells, and mitigation of CO2 Radiative Heat Transfer Properties of Coal Char and Ash Particles Cloud in emissions. By energy and atomic hydrogen sources, hydrogen can be produced from Gasification Processes coal (gasification, carbonization), natural gas and propane gas (steam reforming, Yoshinori Itaya, Naomi Nishio, Shigenobu Hatano, Nobusuke Kobayashi, Jun partial oxidation, autothermal reforming, plasma reforming), petroleum fractions Kobayashi and Shigekatsu Mori, Nagoya University, Japan (dehydrocyclization and aromatization, oxidative steam reforming, pyrolytic decomposition), biomass (gasification, steam reforming, biological conversion), and Coal gasification processes are operated at high temperature over 1700 K to effectively water (electrolysis, photocatalytic conversion, chemical and catalytic conversion). For produce gaseous fuels. In such a high temperature field, thermal radiation dominates fossil fuel-based H2 production in stationary plants such as coal gasification and the heat transfer in the furnace. The heat transfer problem in the furnace is a natural gas reforming, it would be desirable to develop new approaches that produce significantly important issue for precise design of the furnace and determination of hydrogen in a more economical and environmentally-friendly process that also factors such as the reaction rates of decomposition and gasification of coal, includes effective CO2 capture or CO2 utilization as an integral part of the system. A temperatures of char particles and gas phase, heat exchanger and wall cooling for concept called CO-enriched gasification (COEGas) with CO2 capture and partial protection to high temperature. Researches on radiative heat transfer in pulverized coal recycling of CO2 into the gasifier is proposed here for H2 production from gasification combustion and optical properties of coal and ash have been carried out previously. of coal (and biomass). CO2 reacts with carbon in a way similar to H2O but the reaction However, the most properties have been measured not for particles cloud but for a with CO2 at high temperature is more endothermic and produces more CO. The better block of samples. Those data may not be always available to the prediction of the use of high-temperature heat of gasification gas is important for improving gasifier radiative behavior of particles cloud in the furnace. It is quite difficult to apply their efficiency. The COEGas concept aims at better utilization of high-temperature heat model or data and to solve the problem with combining the gasification models in the with endothermic reactions that produce more CO, which in turn leads to more H2 furnace as well. through subsequent exothermic reactions that do not consume energy. It may help to In this study, the thermal radiation properties were determined for a cloud of coal char improve the overall energy efficiency for hydrogen production by minimizing the loss and ash particles. The monochromatic absorption of the sample particles dispersed in of energy, which includes both the quantity and quality of energy. For gasification- liquid paraffin wax was measured spectroscopically at an atmospheric state by using based H2 production, CO2 and H2O need to be separated from H2 in the product gas FT-IR. The effect of the particles number density in the cloud and the thickness of the mixture. The COEGas concept involves CO2 capture with more efficient adsorbent dispersion layer on the spectrum of absorption could be summarized by expressing in such as high-capacity nano-porous CO2 adsorbent based on MCM-41 modified with the form of the absorption efficiency. The spectral distribution of the absorption special polymers. Such adsorbents have been prepared in our laboratory, which have efficiency was dependent of wavelength in the region of 0.7 to 25 micrometers. The numerous CO2 affinity sites and do not require pre-separation of moisture from the gas absorption efficiency was influenced significantly so to overlap the optical property of stream. The presence of moisture further enhances CO2 capture on such adsorbents. the ash when the content of carbon in the char increased. The scattering of particles Therefore, it allows more efficient CO2 capture and easy recycling of CO2 for the was negligibly small except the forward direction. It results in that only the absorption proposed COEGas process. The CO2 capture and utilization must be designed such can be considered apparently for the radiative heat transfer. A parameter averaged over that the overall system is more efficient and will not result in more energy loss the wavelength was introduced to simply estimate the behavior of radiative heat compared to existing options that could lead to zero-CO2 emissions. The CO2 capture transfer. process should be more efficient than the existing processes based on liquid amines.

9-2 research areas. Potential candidate membranes that are suitable for the high Hydrogen from European Low Rank Coal: Reducing CO2 Emissions temperature and severe gasification environments will also be discussed. Roland Berger, Craig W. Hawthorne and Klaus R. G. Hein University of Stuttgart, Germany 9-5 Advanced Membranes for the Spontaneous Conversion of Coal to Hydrogen A process for hydrogen production from European low rank coal is being developed to Anthony F. Sammells, Michael V. Mundschau, Xiaobing (Brian) Xie, Carl R. Evenson meet European Union policy objectives of reducing CO2 emissions and decreasing Eltron Research Inc., USA dependency on energy imports. The driving principle of the process is the in situ removal of carbon dioxide by a sorbent (e.g. CaO) during steam gasification. This Oxygen transport membrane technology, under development at Eltron Research Inc., provides heat for endothermic gasification reactions with the added benefit of facilitates the exclusive mediation of oxygen from the atmosphere to a desired reaction increasing the equilibrium hydrogen concentration. High theoretical cold gas site. As a consequence, these membranes can be incorporated into Catalytic efficiencies are possible. Another key process is sorbent regeneration and reactivation: Membrane Reactors (CMRs) where exothermic coal partial oxidation chemistry can the carbonated sorbent is transferred to a regeneration unit that is capable of yielding a proceed while at the same time eliminating the need for a separate oxygen plant - a concentrated CO2 stream and a solid purge stream suitable for the cement industry. significant reduction in overall production costs compared to currently available The University of Stuttgart is coordinating two European projects examining technology. This leads to the spontaneous formation of synthesis gas, an equilibrium gasification with integrated CO2 capture and sorbent regeneration respectively. The mixture of hydrogen and carbon monoxide. Application of water-gas shift chemistry hydrogen product can be used to generate electricity in a combined cycle. leads to an increase in hydrogen fraction within the reformed feedstream prior to Experimental results from a 40 kW fluidized bed test facility for different European introduction into a hydrogen transport membrane. brown coals and locally available sorbents are presented. Hydrogen transport membranes compatible with the efficient separation of hydrogen from hydrogen containing feedstreams discussed above are also being developed 9-3 within our company. These dense hydrogen transport membranes possess hydrogen Continuous Experiment Regarding Hydrogen Production by Coal/CaO Reaction permeabilities one order of magnitude higher than palladium. Furthermore, these with Steam (HyPr-RING) membranes are far less expensive. Self-supporting wafers of these hydrogen transport Shi-Ying LIN, Michiaki Harada membranes have been successfully operated for thousand of hours at ambient pressure Center for Coal Utilization, Japan and for hundreds of hours under an applied pressure differential (450 psi) without Yoshizo Suzuki, Hiroyuki Hatano failure. Hydrogen fluxes across the membrane up to 360 ml/cm2/min have been National Institute of Advanced Industrial Science and Technology, Japan realized. The current status of these two complementary membrane technologies will be Hydrogen can be produced by integrating coal gasification and CO2 discussed. separation reactions in one reactor using a coal/CaO mixture that is continuously supplied to the reactor. In this study, the solid residues were sampled after the reaction SESSION 10 and analyzed. It was found that CaO first reacted with steam to form Ca(OH)2, which COAL UTILIZATION BY-PRODUCTS 2: COAL ASH UTILIZATION then absorbed the CO2 generated by coal gasification to form CaCO3. Hydration of FOR CONCRETE & MATERIALS CaO is expected to restore sorbent reactivity and supply heat for the coal gasification. 10-1 Most of the CO2 was fixed by Ca(OH)2 during the process. At 973 K, the particle size Lowering Foam Index in High-Carbon Fly Ashes for Concrete Applications of some of the solid materials increased by eutectic melting and these large particles Robert B. LaCount, Tiffany A. Leyda, Patrice J. Pique and Keith A. Giles blocked the reactor. However, at the relatively low temperature of 923 K, eutectic Waynesburg College, USA melting was not observed, and the experiment ran smoothly. Carbon conversions of John P. Baltrus and J. Rodney Diehl 60-80 % were obtained, and the calcium compounds crystallized and cohered into U.S. Department of Energy, NETL, USA small particles. Timothy L. Banfield Allegheny Energy Supply, USA 9-4 Douglas G. Kern Direct Extraction of Hydrogen from Coal Using a Membrane Reactor within a ViRoLac Industries, USA Gasifier Shain J. Doong, Estela Ong and Francis Lau Fly ash is often used commercially as a replacement for some of the Portland cement Gas Technology Institute, USA in concrete products. Air Entraining Admixtures (AEAs) are used in the concrete Arun C. Bose mixtures to improve the workability of the mixtures and the durability of the concrete Department of Energy, NETL, USA products to freeze-thaw cycles. Ron Carty Use of low-NOx burners in coal-fired boilers has resulted in variable increases in the Illinois Clean Coal Institute, USA unburned carbon content of fly ash. High-carbon fly ashes used in concrete often increase the amount of AEA required. The foam index (FI) test, which involves Gas Technology Institute is developing a novel concept of membrane reactor for clean, titration of a portion of the concrete mixture with an aqueous solution of surfactant efficient, and low cost production of hydrogen from coal. The concept incorporates a until a stable foam results, is used to determine the amount of AEA required in the hydrogen-selective membrane within a gasification reactor for direct extraction of concrete. hydrogen from coal synthesis gas. This concept has the potential of significantly This paper describes the results of research efforts directed towards developing a increasing the efficiency of producing hydrogen and simplifying the processing steps practical and economical thermal treatment for high-carbon fly ash that would reduce by reducing/eliminating the downstream shift reactor, separation and purification its FI without having to remove the carbon. Thermal treatments were carried out using operations for the conventional gasification technologies. In partnership with a controlled-atmosphere programmed-temperature oxidation (CAPTO) partial DOE/NETL, a GTI-led team with Illinois Clean Coal Institute (ICCI), and American oxidation or pyrolysis treatment. Temperature ramp, gas flow, and pressure were all Electric Power will determine the technical and economic feasibility of a coupled under software control. membrane reactor and hydrogen separator module in a coal gasifier to produce CAPTO thermal treatments were completed on fly ash obtained from pulverized coal-fired hydrogen from coal. The team will screen, test, and identify potential candidate utility boilers burning Pittsburgh seam bituminous coals under low-NOx conditions. membranes under high temperature and high pressure coal gasification conditions. The Oxidation and pyrolysis of the fly ash samples were accomplished by a linear increase in best performing membranes will be selected for preliminary reactor design and cost temperature accompanied by plug flow under either an oxidative or inert gas atmosphere. estimates. The overall economics of hydrogen production from this new process will The FI values of the treated samples were significantly lower compared to those for the be assessed and compared with other hydrogen production technologies from coal. untreated fly ashes, and were found to vary depending on the treatment parameters. In this paper, a modeling approach used to examine the performances of the membrane Selected untreated and treated samples were characterized using X-ray photoelectron reactor for hydrogen production from coal will be presented. Proton conducting dense spectroscopy, leachable-ion conductivity measurements and other methods in an ceramic materials of perovskite type have been identified as a good candidate attempt to correlate any changes in physical and chemical properties of the fly ashes membrane for hydrogen separation application in the gasifier. As hydrogen is removed with changes in FI brought about by the thermal treatments. Batch quantities of several directly from the gasifier, the gas phase reactions such as water gas shift and reforming fly ashes were treated to lower their FI values and then evaluated for use in preparing of methane and carbon dioxide are favored toward producing more hydrogen. A concrete test samples. These concrete samples containing untreated or thermally simplified model was developed to consider the H2 permeability of the membrane, the treated fly ash show approximately the same compressive strength test results. Air kinetics and the equilibriums of the gas phase reactions in the gasifier, the operating entrainment results may vary with the surfactant used. These test results and the conditions and the configurations of the membrane reactor. A fluidized bed gasifier CAPTO profiles will be discussed. was used for this modeling study. The results show that hydrogen production efficiency using the novel membrane gasification reactor concept can be increased by about 40% versus the conventional gasification process. The assumptions and limitations used in this preliminary analysis will be discussed in reference to the future 9

10-2 CCPs are a great chance for road constructions and road constructions are a great Performance Assessment of a Fly Ash Based Road Subbase in Illinois Using chance for CCPs utilization. Falling Weight Deflectometer Yoginder P. Chugh and Samrat Mohanty 10-4 Southern Illinois University, USA Demonstration Plant Operation for Development of the Coal Ash Granulated Calvin Hance Material to Civil Engineering Applications Morgan County Highway Department, USA Akira Ohnaka and Takashi Hongo Ube Industries, Ltd., Japan FWD is a nondestructive testing test that applies a dynamic load to a pavement by Yoshitsugu Izumo dropping a weight onto a circular loading plate, whose magnitude can be varied by Clean Japan Center, Japan changing the weight and drop height. Deflection transducers placed on the pavement surface measure the resulting pavement deflections. Backcalculation of pavement A coal ash granulated material Z-sand, which enables efficient use of environmentally moduli through FWD is widely used for pavement monitoring and evaluation. burdensome coal combustion by-product, is on the way to being demonstrated. Z-sand The post-construction performance and structural condition of a 2.1-mile industry is produced by putting ash from coal-fired power plants through a special process to access truck route were monitored twice over the past two years using FWD. The convert it into a non-pollutant and permeable artificial grain sand or soil as a pavement consists of 8 inch of asphalt concrete over a 6-inch granular base layer with geotechnical material and is expected to be in demand to civil engineering the untreated fly ash subbase thickness varying from 0 to 7 feet. The entire length of applications. the pavement was divided into three sections for the purpose of FWD studies, i.e. fly ash control section, non-fly ash asphalt concrete control sections AC1 and AC2. 10-5 For this research, deflection sensors were placed at 0, 8, 12, 18, 24, 36, 48, 60, and 72 The Promising New Market for Coal Ash Use inches from the load plate center. FWD results in conjunction with the pavement layer Ocean Fertilization by the Man-Made Sea-Mountains Made Of Coal Ash thicknesses were used to backcalculate the modulus of elasticity of the flyash layer. Tatsuo Suzuki These results were then compared to the road sections constructed without the flyash ASHCRETE Corporation, Japan subbase, as well as results obtained through correlations with Immediate Bearing Tsuneo Izutsu Values. In addition, the FWD data were used to backcalculate the effective structural Electric Power Development Co. Ltd., Japan number and structural capacity in terms of equivalent 18-kip single axle loads for the pavement sections. The first FWD survey, conducted two months after the road A possibility that food production will not fulfill demand is pointed out to the rapid construction, indicated lower overall deflections and higher subgrade modulus for the increase in world population. Especially a food self-sufficiency rate is very low as 40% fly ash section over the non-fly ash sections. The second FWD survey, conducted in in Japan. Since the food production in land is approaching to the limit, development of summer 2003, indicated the overall deflections and subgrade moduli for the fly ash the technology of producing food in the ocean is called for. In order to increase the section to be superior to control section AC2 and inferior to control section AC1. production of food in the ocean, it is necessary to make primary production increase. However, the subgrade moduli for both the flyash and non-fly ash sections were To make primary production increase in the ocean, it is necessary to add nutrient in the reasonable for backcalculated values of fine-grained soils. Additional FWD surveys euphotic zone. are planned over the next two years. Although 8 million-t coal ash is produced every year and the 80% is used effectively in Japan, improvement in the rate of effective use is desired. Although various effective 10-3 use technologies have been developed, expansion of a market which can use coal ash 250 000 Mg of bottom ash in Sochaczew project in large quantities is desired. Tomasz Szczygielski, Agnieszka Pawlowska and Jaroslaw Laskowski To generate an artificial upwelling and to add nutrient in the euphotic zone, a man- Ekotech, Poland made sea-mountain was considered. The sea-mountain was built from 1995 to the 2000 fiscal year to the seabed using coal ash, and the experiment which develops the fishing Polish power stations and heat and power stations produce about 15 million tons of ground of high productivity was conducted on the budget of 1,200 million yen. As for CCPs every year. Generally 70 % are utilized. The biggest chance for CCPs utilization this enterprise, Marino Forum 21 was performed in the Nagasaki offing in response to are large scale projects. the subsidy of the Fisheries Agency of Japan. Moreover, in this experiment, about Road construction in Sochaczew was one of the biggest applications of bottom ash in 20,000t coal ash were used, 5000 blocks of 1.6m cube were manufactured, and were road construction in Europe of year 2003. installed on the depth of 80m seabed. The technology of manufacturing a inexpensive In 2003, between April and August on route Warsaw – Poznań was utilized about 250 block with high strength, using coal ash in large quantities was developed, and the 000 Mg of silicate aggregate recovered from bottom ash. Bottom ash has been of mass production method was proved. With the development of the Super Fluidizing service as material for structure of road embankments in run of national road number Method, the cement ratio has been further reduced and the quality, manufacture-ability 2, section of a construction in km 6+900 to 9+000 and 4+046 to 4+600 bound up with and economy of this new material improved, resulting in a new product with clear construction of district of Sochaczew. advantages over normal concrete, especially for undersea applications. The Fisheries Thanks to engagement of three companies i.e. Elektrociepłowni Warszawskich S.A., Agency admits that this coal ashes hardening object has fully satisfied the safe Warszawskiego Przedsiębiorstwa Robót Drogowych S.A. and Ekotech Sp. z o.o., standard. The size of built sea-mountain is in the 12m peak, a length of 120m, and laboratory, project and administrative works have been started, which have caused width of 60m, and was built in the direction which interrupts the current. obtainment of essential decision permitting on utilization of silicate aggregate (mixture In the area of 20km 18km centering on a man-made sea-mountain, after the sea- of bottom ash) coming from landfill of waste near Myśliborska street in Warsaw, mountain was built, the fish catch by the fishing boat increased to 1500t, and increased competent to EWSA by construction of road embankments of district of Sochaczew. 6 times before construction. As for object sea area, the data of the artificial satellite of Ekotech, as a company possessing indispensables administrative decisions for a NASA showed that the concentration of Chlorophyll-a had increased 1.5 times transport of bottom ash mixture, has leaded supervision, co-ordination of recycling of compared with contrast area. Also the fixation of CO2 by propagation of aggregate from furnace waste and its transport on place of build in. phytoplankton and the relation with reduction of CO2 concentration in the atmosphere Transport proceeded by trucks. Every truck each time was precisely weighted by a is studying. self-service balance, before and after entrance on a landfill. At the beginning of April The man-made sea-mountain project was started at two places as public works from snowfall made difficult realization of a task, but the works were not held. As a the 2003 fiscal year; also many other prefectures show interest to this project. This regulator of a humidity was used a admixture of a low quantity FBC fly ash. project can use coal ash in large quantities in order to increase the production of food. Abutments were made of sand, however 90% of embankment was made of bottom ash. In order to use coal ash in large quantities, to create the new large-scale market which Sand was used only to strew of one abutment, to preserve it against dusting. There people need truly is desired. were places where an ash embankment was interbeded by a sand. Supplied mixture was currently built over by a spreading in layers of 0,3 m and compacting by tamping SESSION 11 rollers and plain-bodied rolls. At the landfill samples from a substance prepared to ENVIRONMENTAL CONTROL TECHNOLOGY 2: PARTICULATE load were currently collected in order to qualify it by a laboratory to build in an MATTER & TRACE ELEMENTS embankment. After preparing each layer, current research were performed, degree of 11-1 compaction of material were measured. Bearing capacity of each layer of embankment Removal of Major and Trace Inorganic Elements from Coal by Acid was continiuously monitored. Unloading proceeded simultaneously with spreading Pretreatment and Organic Solvent Extraction and compacting of bottom ash mixture. In some places bottom ash with a sand had to Chunqi Li, Kinya Sakanishi, Toshimasa Takanohashi, Ikuo Saito, Tetsuya Nakazato be mixed in order to increase a graining. Surface after correctly carried compacting by and Hiroaki Tao means of tamping roller and then plain-bodied roll. In May 2003 came sweltering Institute for Environmental Management Technology, AIST, Japan heat, what has forced additional pearling of delivered mixture in order to achieve optimal humidity to build in an embankment. In time of heat whole uncovered surface Thermal extraction with selected organic solvents is a very effective route for the was pearled in order to eliminate dusting. A body of embankment was strewed at the production of extremely low-ash coal (called HyperCoal) which is believed to be a scarps by sand. promising clean fuel for gas turbine. For this purpose, efforts are required to increase 10

the extraction yield in the one hand, and decrease the remaining amounts of inorganic Epidemiological studies have correlated adverse health impacts with ambient levels of

elements in the Hyper coal as greatly as possible on the other hand. Previous studies fine particulates with an aerodynamic diameter less than 10 µm (PM10) and less than have found that mild acid pretreatment can appreciably increase the yield of 2.5 µm (PM2.5). Legislation has been enacted both in Australia and overseas to set HyperCoal with a polar solvent N-methy-2-pyrrolidinone for some coals that are guidelines for ambient concentrations and to limit the emission of fine particles. enriched in ion-exchanged alkaline earth elements. In this study, we have revealed that Ash particles are formed during the combustion of coal in pf boilers. The main mild acid pretreatment is also effective for decreasing the concentrations of alkali and formation mechanisms of ash particles during coal combustion have been identified in alkaline earth elements in the resultant HyperCoal. This result is favorable for previous studies as (1) the coalescence of included mineral matter in the coal and the improving the qualities of the HyperCoal as a clean fuel. Moreover, inductively fragmentation of excluded minerals; (2) the fragmentation of char particles; and (3) the coupled plasma optical emission spectrometry (ICP-OES) and flow injection vaporization and condensation of inorganic material. Although these formation inductively coupled plasma mass spectrometry (FI-ICP-MS) have been used in this mechanisms have been identified, the contribution of each of the mechanisms to the study for examining the removal extents of a number of trace elements during the acid fine ash of legislative interest (PM10 and PM2.5) remains unclear. pretreatment and the organic solvent extraction. Environmentally concerned trace This study provides insight into the mechanisms and coal characteristics responsible elements such as Hg, Se, As, and Pb have found to be removed in both the acid for the formation of fine ash. Five well characterized Australian bituminous coals have treatment and the organic solvent extraction. been burned in a laminar flow drop tube furnace in two different oxygen environments to determine the amount and composition of the fine ash (PM10, PM2.5 and PM1) 11-2 formed. This paper describes the experimental setup, the analytical techniques and the Reasons of the Endemic Fluorosis in Western Guizhou Province, Southwest findings of this study. Coal characteristics have been identified that correlate with the China formation of fine ash during coal combustion. It was found that coal selection based on Shifeng Dai char characterization and on the ash fusion temperature can play an important role in China University of Mining and Technology, P.R. China the minimization of the fine ash formed. The implications of these findings for coal selection for use in pf-fired boilers are further discussed. The well-known endemic fluorosis in western Guizhou Province, southwest China is usually attributed to the high content fluorine in late Permian coals. This study found SESSION 12 that the average content of fluorine in fifty coal channel samples from western COAL CHEMISTRY: 1 Guizhou Province ranges form 16.6 µg/g to 500 µg/g, with an average of 83.1 µg/g, 12-1 which is close to the world average (80 µg/g) and that of most Chinese coals (82 µg/g). Formation of Carbon Stacking Structure in Coals with Different Expansion Additionally, the fluorine content of drinking water and fresh corn is too low to lead to Property during Rapid-Heating Process fluorosis in western Guizhou Province. However, the clay used as an additive for coal- Noriko Yoshizawa and Katsuhisa Maruyama burning and as a binder for briquette-making by local residents has a very high content National Institute of Advanced Industrial Science and Technology, Japan of fluorine, ranging from 100.8 µg/g to 2455.7 µg/g, with an average of 1027.6 µg/g. Akimitsu Akimoto The endemic fluorosis probably should be caused by the clay with a very high content Center of Coal Utilization, Japan of fluorine. Therefore, in areas where unscientific traditional coal burning habits and customs are kept, and furnaces without chimneys are used, the more clay used for a Three types of coals with different expanding property of their particles on a rapid coal-burning additive and as a binder for briquettes, the more serious the fluorosis pyrolysis were heat-treated below 1500 ˚C in a drop tube furnace to investigate their problem is. microstructure. The Fourier transformation of carbon 002 reflection peaks in their XRD patterns clarified that an average number of layers per stack (Nave) increased 11-3 according to the rise of temperature, except between 800-900 ˚C in which it showed a Release Behavior of As and Se during Coal Pyrolysis and Gasification sudden dip. Degrading of stacking structure around 800 ˚C like this has been Takahiro Kato, Katsuyasu Sugawara and Takuo Sugawara considered as a result of a coalescense of aromatic molecules, and therefore could be Akita University, Japan related to the chemical structure of original coals. On the other hand, Nave varied with temperature regardless of original particle sizes, although the balloning property was Release behavior of arsenic and selenium was followed during pyrolysis and sensitive to those sizes. It was accordingly implied that the original size of coal gasification of coals in nitrogen and carbon dioxide streams, respectively, up to particle could dominate the expantion property of the particle independent of the 1200 . Arsenic and selenium in coal and char were classified into three fractions by a chemical structure of that coal. We will discuss these XRD data more in detail with serial leaching method with HCl, HNO3 and H2SO4 solutions. Selenium forms in results by molecular adsorption measurements and observations with an electron coal, density-separated coal and char were analyzed by XAFS. Kinetic analysis was microscope. carried out for the release behavior of arsenic and selenium. The release behavior was successfully simulated by the determined kinetic parameters with the soluble. 12-2 Development of New Methodology for Determining Thermal Behavior of 11-4 Macromolecular Network Structure of Coal by Using Dielectric Property Effects of Coal Types on Trace Elements Emission in Pulverized Coal Fired Tetsuo Aida, Toyokazu Shinkai, Murakami Kiyonori and Daiki Kaji Process Kinki University, Japan Takashi Kuwabara Paul G. Aida Tokyo Electric Power Co., Inc., Japan The University of Tokyo, Japan Shinji Kambara and Hiroshi Moritomi Gifu University, Japan Nobel methodology for characterizing macromolecular network structure of coal by using the dielectric property has been developed. In this paper, we will present a In Japan, the consumption of steaming coal reached more than 65 millions tons/year detailed scheme of the instrumentation and discuss about the experimental data based and almost all coal is imported from overseas. More than 100 types of coal that has on thermal behaviors of the macromolecular network structure of Argonne Premium ranging from bituminous coal to sub-bituminous coal are consumed. Electricity Coals, such as initial softening (glass transition) temperature or fluidizing temperature, companies have developed a tool of coal evaluation system to choose low cost coals comparing those of synthetic model polymers including cellulose and lignin. and environmentally friendly coals. Recent year, fluorine, boron and selenium emission in wastewater from coal-fired 12-3 power plants are regulated in Japan. Therefore, we have to estimate behavior of such About Colloidal Structure and Peptization trace elements emission in coal power plants in advance. Of Coals with Melted Waste Plastics In this paper, we discussed boron emission behavior in pulverized coal fired process. A.V. Madatov Boron content in fly ash from various kinds of coal is investigated. Its recovery Ukrainian State University of Chemical Engineers, Ukraine showed wide range from 20% to 100%. It seemed that boron recovery was affected by G.A. Vlasov and G.G. Kleshnya coal types. Boron recovery in fry ash was correlated with content of Al2O3 in fly ash JSC, Ukraine and clay mineral in coal. And also, we investigated the functional forms of boron in V.D. Barsky coals to examine relation between the boron devolatilization and change of mineral Ukrainian State University of Chemical Engineers, Ukraine matters by using drop tube furnace. It is found that the boron emission is affected by the functional forms of boron in coal Some researchers consider coal as solid colloid structure. Thus, the main properties of and clay mineral content. coking coal, such as viscosity of plastic-coal mass, thickness of plastic layer, temperature interval of plastic state depend on disperse phase - dispersion medium 11-5 proportion, which is the function of coal metamorphism range. Coal Quality and Fine Ash Formation during Combustion Therefore, softening of coal at the time of coking is just transition of solid gel into Bart Buhre, Jim Hinkley, Raj Gupta, Peter Nelson and Terry Wall liquid sol (so called pyro-sol) by means of dispersion medium increase. When University of Newcastle, Australia temperature mounts to the end of temperature plastic state interval, growth of dispersed 11

phase at the expense of dispersion medium leads to conversion of sol into gel (semi- SESSION 13 coke) and further into coke crystal structure. COMBUSTION TECHNOLOGIES 3: EXPERIENCES OF LARGE- Peptization of colloid with appropriate solvent allows convert gel into sol at lower SCALE FBC’S temperature, therefore, broaden temperature plastic state interval at coking. Authors 13-1 peptized following coals: lignite, candle, gas, fat, coking, lean, anthracite with different Utilization of Alternative Fuels in the FCB Boilers solvents: ethyl, isopropyl, iso-butyl alcohols, acetone, mono- and dy-terpene, benzene, Václav Roubíček, Pavel Kolat, Miroslav Čech, Dagmar Juchelková, Zdeněk Kadlec toluene, pyridine and water at 20 C0, besides, with melted phenol, naphthalene, VŠB-Technical University Ostrava, Czech Republic paraffin, polyterpene, polyethylene, polystyrene, polyvinylchloride, polyethylene The energy utilization of the alternative fuels is one of the main topics for future terephtalat, polyamide at the temperature up to 350 C0. developments of recoverable sources in the European Union and in the Czech It was measured: swelling degree of the coals, optical density of residual solvent after Republic. The aim of research is combustion tests in the fluidized-bed boiler Foster peptization, angle of light leakage by colloidal particles in residual solvent, viscosity of Wheeler located at Štětí. residual solvent, viscosity of plastic-coal mass. The experiments are carried out for Czech brown coal, wood, sewage sludge and Correlation between swelling degree of the coals, viscosity of plastic-coal mass and wastes including analyses and recommendations for optimal thermal utilization and content of colloidal particles in residual solvent was discovered. Colloidal particles minimizing harmful emissions. The second steps are thermal analyses of coal, dimensions increase according to coal metamorphism range. Swelling degree of the alternative fuel- wood pellets and sewage sludge from treatment plant. coals depends on chemical nature of a solvent. Main goals may be outlined in the study of conditions for: Coals are peptized best: lignite one in alcohols, phenols, candle one in aldehydes, • Potential substitution of fuel with potential combustion of less valuable types of ketones, gas one in cycloalkanes, fat one in polycycloalkanes, resin acids, coking one coal simultaneously with the waste and bio-mass, sustainability of fluidised bed in aromatic hydrocarbons, lean one in polyaromatic hydrocarbons. Melted plastics give combustion. biggest swelling degree of the coals and decrease of viscosity of plastic-coal mass: • Chemical composition, crystallographic structures and mechanical properties of lignite one with acrylic resin, candle one with polyamide, gas one with polyethylene, combustion solid products ( ash, fly ash, deposits ). fat one with polyethylene terephtalat, coking one with polystyrene, lean one with • Analytical estabishment of sulphur forms in fuel and combustion products. resins. • Detailed study for mineralogical and chemical composition solid emission phase. Obtained results show, that colloidal structure of coal definite its coking plastic • Balance for volatile elements CL, S, Hg, Se, semi-volatile elements V, Ni, Co, As properties to a great extent and chemical nature of colloidal dispersion medium is and some non-volatile elements Cr and Sn. different in coal of different metamorphism range. • Leaching tests for combustion solid products. Melted waste plastics are very prospective kind of peptizing solvent for coking coals, • Long-term deposit formation on thermal exchangeŕ s walls. especially keeping in mind their huge amount and cheapness. From the results of experiments and thermal modelling it is clear that 15 % of

alternative fuels can be used in the large fluidized-bed boilers located in the Czech

Republic. The combined combustion will enable to fulfil the promise of the Czech 12-4 Republic to the European Commission concerning the development of renewable Some View on the Solubilities of Coals toward Solvents energy resources by 2010. Masakatsu Nomura and Koh Kidena

Osaka University, Japan 13-2 Satoru Murata Takaoka National College, Japan Deposit Measurements at Alholmens Kraft during Co-Firing A Case Study of the World’s Largest Biofuelled CFB

Patrik Yrjas, Bengt-Johan Skrifvars, Tor Laurén, Mikko Hupa According to the information concerning reactivity of coal model compounds the Åbo Akademi University, Finland authors did previously the methylene bridge bonds were believed to prevail in coal Juha Roppo structures. Ruthenium catalyzed oxidation reaction, however, indicated less abundance Kvaerner Power Oy, Finland of mono methylene bridge in all coals examined compared with dimethylene bridge, Marko Nylund this being judged due to the unstabilities of malonic acid (the product from Oy Alholmens Kraft Ab, Finland Monomethylene bridge) in the oxidation reaction conditions. This suggests strongly Pasi Vainikka the presence of the fission of alkyl side chains and recombination of the resulting VTT Processes, Finland active species in the coalification process. With this information and simulation study

of coal density based on the coal model structure in mind insolubility of coal organic The Alholmen power plant (550 MW ) started up in year 2001. The CFB power plant, materials in solvents can be explained due to a kind of entangled structure proposed by th which was supplied by Kvaerner Pulping Oy1, produces not only electricity (265 MW ) Cody et al and solubility of some coals can be also explained as well. e but also process steam for the nearby pulp factory and district heat for the inhabitants

of Jakobstad, Finland. Peat, coal, logging residues, and bark are the main fuels that are

used for the moment. 12-5 A research project started in 2002, with the goal to show the viability of the CFB Producing H and Coke from Coal 2 technology to maximise the use of biofuels at the Alhomen power plant. The project John W. Larsen and Harold Schobert lasts until the end of June, 2004 and is funded by the European Union. The project The Pennsylvania State University, USA consists of several parts of which one is to investigate the fouling tendencies of the

boiler. Coals react with sulfur to produce a carbonaceous product and H S. Hydrogen sulfide 2 Two deposit measurement campaigns have been done. One in May 2003 with fuel can be dissociated either thermally or catalytically to produce H and sulfur. If a 2 mixtures up to about 45% (energy based) biomass. A second campaign was performed commercially useful carbon can be produced in this process, it is a clean route to H . If 2 in August 2003 with even up to 100% biomass. The deposits were sampled with air- all of the hydrogen from the coal used to form metallurgical coke in the U.S. could be cooled probes with detachable rings. The deposits were sampled at two different captured as H , about 1.3 million tons of H could be produced annually. The 2 2 locations, one where the flue gas temperature was about 730°C (probe surface temp. abstraction of hydrogen from coals with the concomitant production of a commercially 540°C) and the second were the flue gas temperature was about 530°C (probe surface useful carbon product is a worthwhile goal. In this talk, we will concentrate on the temp. 350°) A total of 32 deposit measurements were done and from every deposit reactions of sulfur with coal. sample the rate of deposit build up (g/m2h) was determined. Furthermore, from every Sulfur is widely used to dehydrogenate alicyclic molecules to form aromatics. With deposit sample elemental analyses were done – one from the wind side, one from the coals, it first removes the alicyclic hydrogen. It is also capable of removing aromatic lee side, and one from an angle of about 50° from the wind side. The analyses were hydrogen and also does this when reacted with coals. This is a much slower process done with a SEM/EDX analyser and are compared to the compositions of the ESP and is probably responsible for the large decrease in reaction rate as hydrogen is ashes. increasingly removed from coals. The removal of aromatic hydrogen is accompanied Generally, the results showed that the rate of deposit build-up was low and in no case by some incorporation of sulfur into the coal. The reaction between sulfur and coal has the rate indicated severe deposit problems. The deposit compositions reflected the fuel been studied using solid sulfur, sulfur dissolved in a liquid, and sulfur vapor. In the mixtures that were used and in certain cases chlorine could be found in the deposits latter case, a coal was reacted with sulfur vapor at its devolatilization temperature. indicating possible corrosion risks. However, if the biomass part was kept below about About 75% of the hydrogen was removed and the carbonaceous product had physical 45% (energy based) no or only very small amounts of chlorine could be found. properties similar to the coke made from that coal.

13-3 in the reheater tube bundles, expansion slots were added to the upper convention cage). Biomass-Fired BFB Boiler at Ostroleka Power Station, Poland – Operating In spite of some problems, the CFB boilers have met all performance requirements Experiences confirming Turow’s decision to select FW technology for this re-powering project. Rafal Kobylecki, Robert Sekret, Wojciech Nowak, and Zbigniew Bis The fuel flexible, clean burning, efficient boilers have achieved the dynamic load Czestochowa University of Technology, Poland response required for modern grid systems and have extended the life of the power Rafal Psik station. Foster Wheeler Energy, Poland The paper presents the boiler design parameters, design arrangement and specific unique design features of CFB boilers. A particular concern with the CFB Operating experiences from a five day trial test of combustion of various types of boiler is the low rank brown coal and the large furnace which had to fit into the limited biomass and waste fuels in a bubbling fluidized bed (BFB) boiler at Ostroleka Power space of the existing plant. The processes and environmental performance of large- Station, Poland are presented in this paper. The boiler is a Foster Wheeler type BFB scale CFB boilers are demonstrated. Special emphasis is placed on operating and produces 11kg/s of steam at 4MPa and 4500C. Fluidization velocity in the bed is experience from the largest CFB boilers which have accumulated more than five years assumed as 1-1.5m/s, and height of the bed may vary from 0.5m up to 1.2m (at of operation. shutdown and full load, respectively). The boiler was originally designed to be fired with biomass (bark) from the neighboring areas. However, in order to maximize 13-5 economical benefits, it has been planned to ‘widen’ the types of fuels burned in the Design and Operation of a Large Scale CFB for IPP Use unit by choosing the proper one burnt depending on its actual market price. Kazuyoshi Ito The present study and test runs have focused on combustion and agglomeration Sumitomo Heavy Industries, Ltd., Japan characteristics of five fuels, assumed to be appropriate for combustion in that unit. The Song Wu reason for conducting the experiments was a serious agglomeration of the bed, that Foster Wheeler North America, USA occurred at some operating period in the past, when the fuel fed into the boiler was switched from bark to wood chips. Agglomeration of the bed in that time brought Sumitomo Heavy Industries, Ltd. designed, supplied and constructed a 149MW Coal about an immediate boiler shutdown. Fired Circulating Fluidized Bed (CFB) Boiler (largest size in Japan) Power plant During the five day test runs the boiler was fired with five fuel types (bark, wood of Taiheiyo Cement Itoigawa Power Station, located in Niigata Prefecture, that has be chips, paper mill sludge, and two types of biosludges, i.e. mixtures of sewage sludges en utilized as IPP for Tohoku Electric Power Co., Inc. with paper mill sludges). The fuel parameters varied within quite a wide range: ash The plant has started in commercial operation in July 2001 and experienced for more t 0.6-22%, inherent moisture 44-62%, volatiles 62-82%, sulfur 0.01-0.07%. Low heating han two years with stable and reliable operation. Since commencement of commercial value (LHV) of the fuels varied between 11-17MJ/kg. operation this plant has been operating at weekly start- During the test period no symptoms of agglomeration occurred and it was concluded stop mode and at daily swing load, which varies from 100% to 40% MCR depending o that all of the fuels could be safely burnt at the BFB unit. In order to achieve this, n the demand with full automatic start-up and shut- however, proper temperature, fuel feeding rate and mixing in the furnance had to be down as designed. It was confirmed that the CFB could be utilized for the utility powe maintained. Although results of laboratory tests, conducted at Czestochowa University r station through the commercial operation in Itoigawa Power Station. of Technology, showed no agglomeration of all fuels at temperatures of up to 10000C, The plant design, plant and boiler performance and operation results will be introduced for safe operation of the BFB unit at Ostroleka it had been recommended to maintain in the upcoming Conference. bed temperature below 9000C and adjust particle size distributions of fuel and the bed material depending on the hydrodynamic conditions in the boiler. It was also found out SESSION 14 that depending on fuel LHV, bed temperature had be regulated by changing air flow GASIFICATION 3: ALTERNATIVE FEEDSTOCKS and flue gas flow. 14-1 The main reason of bed agglomeration in the past was also given; it was found out that Experimental Results of a Two-Stage Gasifier Processing Waste Derived Fuels wrong adjustment of the fuel feed rate led to a rapid and uncontrolled increase of the H. Hasselbach, S. Weil, S. Hamel and W. Krumm bed temperature, and was directly responsible for agglomeration and defluidization of Universitat Siegen, Germany the bed. D. Lotter and C. Mertens Herhof-Umwelttechnik GmbH, Germany 13-4 Operation Experience of Large-Scale Circulating Fluidized Bed Boilers with The presented two-stage gasification process is especially developed for volatile Brown Coal component rich fuels. Due to the spatial separation of pyrolysis and gasification and Wojciech Nowak, Robert Sekret and Zbigniew Bis combustion unit – a two-stage double-line arrangement – the production of a Czestochowa University of Technology, Poland hydrogen-rich and undiluted synthesis gas with low tar content is demonstrated. Jerzy Laskawiec, Janusz Jablonski and Roman Walkowiak Fuel feeding into the first stage, the pyrolysis unit, leads immediately to fuel drying Power Plant Turow, Poland and pyrolysis due to contact with hot ash from the combustion unit. While pyrolysis gas, which contains higher hydrocarbons and tars, is leaving the first reactor, it has to The largest power plant adopting CFB technology is the Turow Power pass a hot layer of fluidized bed ash where steam input supports catalytic and thermal Plant, Poland. The Turow Power Plant is the world’s largest operating CFB boilers tar cracking. The remaining pyrolysis char and ash are fed into the second stage, a generating 965 MWe of electricity. Turow Plant is presently operating 3 CFB Foster fluidized bed combustion unit, where ash is heated up again by char combustion. So, Wheeler boilers each 235 MWe and one 260 MWe CFB Compact and has another 2 both reactors are connected by circulating ash to transport energy from the fluidized units under construction which include CFB Compact type boilers each 260 MWe in bed combustion unit to the pyrolysis unit. Due to the fact that product gas from the capacity. As the CFB technology is being constantly improved, a decision has been pyrolysis stage and flue gas from the fluidized bed stage are kept separate, nitrogen as made to construct new units with increased efficiency (91%) using the newest CFB a part of combustion air cannot dilute the produced pyrolysis gas. technology - the CFB Compact type. Capacity of three new units is increased to 260 At the University of Siegen a technical scale plant is operated according to this MWe each staying within the existing foot print. A unique features of these units are “Combined Pyrolysis and Combustion Process”. In this contribution a detailed the use a square separator instead of hot cyclones and an integrated heat exchanger description and a classification of this process will be given first, before experimental (Intrex) located in the lower part of the combustion chamber outside the main results from the gasification of mechanical-biological pretreated waste and wood are combustion area. presented and discussed. Furthermore operating experiences for example ash All performance tests on CFB boilers were met. The trial run performance test circulation and fuel feeding device are described. together confirmed that: • CFB boilers were in full compliance with UCPTE criteria, 14-2 • Turow CFB units were the first units on the Polish Power Grid to satisfy Modeling a Fixed Bed Gasifier for Decentral Biomass Utilization UCPTE, S. Weil, H. Hasselbach, S. Hamel and W. Krumm • guaranteed parameters were met in a wide range of load conditions, Universität Siegen, Germany • full capacity can be reached without any problems, • emission levels for gases and dust are met, Currently a considerable worldwide interest in lowering the CO2 emissions by using • the boiler is flexible in a wide range of loads. wood and other renewable energies for energy production can be notified. Today During commissioning and early operation of the plant it was determined that combustion technology is preferred for the commercial use of biomass. Due to the certain mechanical equipment required modification and optimization. Fan operational lower heating value of wood compared to other fuels like coal, crude oil or natural gas problem began in the early stages of commissioning. Temporary modifications of the and its small production-area ratio, short conveying distances are required. That means existing PA and SA fans have been successfully implemented in order to allow full that only small decentralized plants can be operated in an economical way, whereby load operation. The bottom ash coolers have not demonstrated their maximum design gasification technology is assumed to have higher potential for the thermal use of capacity when burning the high ash coal. The pressure parts required several minor biomass. Here development and technical use are focused on fixed bed and fluidized modifications (tube shields were installed on some tubes, spacer canes were installed bed reactors. For smaller operation units, fixed bed reactors are preferred. 13

Today, design and engineering of such reactors is carried out particularly empirical. In 14-5 order to use mathematical and physical design principles, numerous studies are carried Tar Evolution in Steam Gasification of Biomass out to understand the various steps of the gasification process, e.g. way and kinetics of Masahiro Suzuki, Yousuke Yamaguchi, Takeshi Furusawa, Atsushi Tsutsumi the chemical reactions. In addition to experimental work, development and use of The University of Tokyo, Japan mathematical models is another way to describe and to understand the process and various phenomenas going on during the gasification process. Steam gasification of biomass was studied using newly developed continuous cross- In this work a two-dimensional, transient description of a cylindrical reactor for flow moving bed type differential reactor. In the conventional methods such as pyrolysis, gasification, or combustion of organic material is presented. The various thermogravimetric analysis (TGA), drop tube reactor (DTR) and fixed and/or fluidized physical phenomena drying, chemical reaction, heat transfer and mass flow due to bed reactor (FB), it is impossible to investigate the time profile of tar evolution in biomass shrinkage are described by various models. In addition the thermal influence steam gasification of biomass with rapid heating in continuous feeding condition. of the different refractory materials and thickness on the gasification process is Thus, we have developed a continuous cross-flow moving bed type differential reactor. simulated. To describe the pyrolysis process and the further chemical reactions, a In this apparatus, a quartz glass half tube reactor is divided into six compartments hybrid method is used which combines kinetic approaches and equilibrium calculation whose gas flows were independent in order to collect gas and tar separately and using a Gibbs formulation. In this work different kinetic parameters using data found analyze their compositions in each compartment according to their residence time in literature are compared and faced to measured data. while biomass sample (cellulose, lignin) is continuously fed into the reactor. Steam The model is applicable to calculate the product gas composition, the temperature field with Ar carrier gas is fed into each of the compartment that is heated by an image and the outlet mass flow. The product gas composition and temperature field inside the furnace. Char is also collected at the end of the reactor. In this study, the time profile of reactor is calculated for different input materials and various operating conditions. tar evolution in gasification of biomass was investigated. It was found that there is an Furthermore changes of fuel feed and gasification agent on the gasification process are induction period for 15-20s before weight decrease of cellulose begins in steam shown and discussed. Problems relating the further use of the product gas are discussed gasification at 673 K, suggesting the existence of intermediate products. Produced tar in detail. was cellulose with low degree of original cellulose. The main comportments were levoglucosan, cellobiosan, and cellotriosan. We also analyzed producing tar in steam 14-3 gasification of lignin and biomass. Based on the results, we proposed a new Reforming of Wet Biomass to Reactive Feed Stock for Co-Gasification through mechanism of tar evolution in steam gasification of biomass. Hot Water Treatment with Ca(OH)2 and Dewatering in Oil Isao Hasegawa, Tatsuya Tsujiuchi, Hiroyuki Kono and Kazuhiro Mae SESSION 15 Kyoto University, Japan HYDROGEN IN THE FUTURE 3: HYDROGEN PRODUCTION TECHNOLOGIES (DIRECT & INDIRECT) Although a method for the effective utilization of biomass is keenly desired for saving 15-1 of CO2 emission, wet biomass such as food wastes are especially difficult to preserve Novel Technology of Efficient Storage and Transportation of Coal-Derived or convert because of high moisture, high oxygen content, and protein content. Since Hydrogen by Using Organic Hydrides such as Cyclohexane and Decalin the pretreatment of wet biomass consumes much energy in general, the biomass should Masaru Ichikawa be transformed into a valuable feed stock for co-utilization with other major energy Hokkaido University, Japan resources through this pretreatment. From this viewpoint, we proposed a new method in which wet biomass impregnated a few calcium compounds were treated with hot The novel technology of hydrogen storage and supply infrastructures using liquid water and dewatered in oil at 150 oC. In this study, we treated coffee beans (water organic hydrides such as cyclohexane and decalin recently emerge for 21st century content of 63.4 wt.%) at various combination of three above treatment and clarified its hydrogen eco-energy society connected with reliable PEM fuel cell society. Organic optimum condition. hydrides such as cyclohexane and decalin are appreciated as the feasible carrier Through the hot water treatment of coffee beans at 230 oC by utilizing beans’ own materials with the highest energy density for hydrogen storage and transportation in water, the oxygen content decreased but the gasification reactivity diminished by the terms of weight and volume among other techniques including carbon nano-tubes, cross-linking reaction. When Ca(OH)2 was physically mixed with coffee beans in metal alloys and even high pressured cylinders (250-350 atm). A new catalytic advance of the hot water treatment, the coffee bean was successfully reformed to converter of cyclohexane (or decalin) are developed with carbon-based Pt bimetallic reactive biomass with high gasification reactivity and low oxygen content. On the catalysts for efficient storage and supply of hydrogen at moderate conditions, 6 other hand, the water was almost removed from coffee beans in the vegetable oil m3H2/h at 150-250oC, 1-5 atm, and 20 m3/h H2 at 250-350oC, 1-2 atm, treatment at 150 oC. In addition, we performed the co-gasification of brown coal with respectively. An efficient and cyclic conversion of cyclohexane-benzene the pretreated biomass, and found a synergetic effect of the gasification rate. This was (methylcyclohexane-toluene or decalin-naphthalene) is conducted by the pulse-spray caused by the catalytic effect of the Ca(OH)2 impregnated biomass. Thus, the reactor to optimize the spray-size (ml/s), pulse interval (s) and reaction temperature proposed method was effective for reforming wet biomass into a valuable feed stock to achieve the stable catalytic performances and maximum rates of hydrogen storage for co-processing with coal. and supply. This technique is available for the hydrogen station for fuel cell cars, home electric generator and non-wiring (cable) transportation of electricity generated by solar cells, windmills and other renewable power sources. 14-4 This is the promising sustainable technology of zero CO2 emission and efficient Catalytic Hydrothermal Gasification of the Organic Compounds Dissolved In storage and transportation of large-scale hydrogen derived from coal, oil refinery and Waste Water from Coal Dewatering and Industrial Processes COG (coke oven gas) using organic hydrides such as cyclohexane and decalin which Hiroyuki Nakagawa and Kouichi Miura are economically and feasibly connected with the conventional infrastructures such Kyoto University, Japan as tank-lorry, railway and ship transportation systems. Atul Sharma Shiga Prefecture Industrial Support Plaza, Japan 15-2 Application of In-Situ CO2 Removal Gasification to Woody Biomass for Development of efficient dewatering and upgrading process for brown coal utilization Hydrogen Production is very necessary. However, some organic compounds are inevitably leached out in the Tomoaki Minowa, Toshiaki Hanaoka and Shinji Fujimoto water from the coal giving a significant amount of waste water containing organic National Institute of Advanced Industrial Science and Technology, Japan compounds in small concentration. Similarly, several industrial processes produce Kenji Kamei, Shi-Ying Lin and Michiaki Harada huge amounts of waste water that contain small concentrations of organic compounds. Center for Coal Utilization, Japan The treatment of waste water is a serious issue not only from environmental aspect but also due to loss of energy. A recently developed novel Ni/carbon catalyst is used to In-situ CO2 removal gasification has been developed for the hydrogen production from gasify organic compounds in the waste water from brown coal dewatering process and coal, named HyPr-RING in Japan. The overall reaction is as follows: industrial processes. The process removes the organic compounds by gasifying them Carbonaceous material + H2O + M Æ H2 + MCO2, at high temp. and high press. into caloric gases like methane and hydrogen. The investigations were focused on the Here, M is CO2 sorbent. We started the project to apply the in-situ CO2 removal efficiency of the Ni/carbon catalyst in terms of carbon conversion, catalyst deactivation gasification to produce hydrogen from woody biomass. due to sintering, nickel metal load of the carbon catalyst, effect of presence of alkali The powder of Japanese Oak was gasified into clean gas in the steam of 600 to 700 °C metals in the waste water. The preliminary results showed that up to 80 % carbon and 0.5 to 5 MPa using calcium hydroxide as a CO2 sorbent in a batch type autoclave, conversion can be achieved at 350 C, 20 MPa conditions. The sintering or deactivation and clean gas, mainly hydrogen, was obtained at the yield of 1.5 L/g-wood. The clean time was about 50 hrs under laboratory conditions and was mainly due to the increase gas contained 97 vol% of hydrogen, 3 vol% of methane and 0.1vol% of hydrocarbons. in the crystallite size of nickel particles. Various techniques such as XRD, TEM were No carbon dioxide and carbon monoxide was detected in the clean gas, and carbon used to investigate the sintering process and reaction mechanism. dioxide of 0.5 L/g-good was absorbed in the calcium. When hydrogen in the obtained methane was considered, the hydrogen yield was reached 89% on theoretical hydrogen amount.

After the batch test, a continuous bench-scale unit was constructed. The capacity was Hydrogen production technologies with high performance and low cost are highly 10 kg of wood a day, and the reactor was placed into a pressure vessel. We will requested to encourage hydrogen utilization. Coke oven gas so called COG containing present obtained results at the Conference. hydrogen of 50% is one of the high-potential resources of hydrogen because of abundant amounts in Japan. Hot COG with about 800 degree C produced from coke 15-3 ovens is cooled down by means of aqueous ammonia quenching and the pressurized Catalytic Steam Reforming of Coal-Tar Derived Oil cool COG is utilized as fuel or hydrogen source after tar contained in the gas is Atsushi Ishihara, Daisuke Yamada, Ida Nuryatin Finahari, I Putu Sutrisna, separated in iron works. Eika Weihua Qian and Toshiaki Kabe This paper introduces a new hydrogen production technology by means of partial Tokyo University of Agriculture & Technology, Japan oxidation and steam reforming of tar in the hot COG without catalyst. About twice the amount of H2 and CO in the original COG can be recovered by this technology. The One of the promising approaches to the production of hydrogen from coal is catalytic sensible heat of the hot gas is utilized for the reaction. Also, the sensible heat of the steam reforming of a liquid product (also known as coal-tar), which is generated from converted gas can be recovered. coal via carbonization. Generally, coal-tar is divided into light oil, middle oil, creosote The hot COG was produced from a test unit of coke, the capacity of which was 80 kg oil, anthracene oil and pitch by fractional distillation. The oils are predominantly a of coal, and was introduced into an experimental unit with the furnace where oxygen mixture of benzene from light oil, and phenol, cresol and naphthalene from middle and and steam were injected. Over 98 % of total carbon in the hot COG was partially creosote oil. However, the reforming of oils including aromatic ring would bring about oxidized and reformed with steam and converted to H2 and CO gases. About 1 a problem, which is the carbon deposition taking place preferentially on the catalyst. Nm3/h of hydrogen was continuously produced for five hours in this experiment. In Thus, the present study has concerned to investigate a series of catalysts having addition, the high-temperature steam produced by means of combustion of hydrogen reasonably high activity and stability for production of hydrogen from coal-tar and oxygen gases were used instead of oxygen and steam to convert tar to H2 and CO fractional distillation oils. In this study, a variety of research Ni, Ru, Ni-Ru catalysts gases. The feasibility study based on the experimental results showed that hydrogen is were prepared and their catalytic performance in the steam reforming of m-cresol produced by this technology with lower cost than separation from cool COG. derived from middle and creosote oil were tested. The precursor, including Ni, Ru, or combination of Ni-Ru, was supported to a mixture SESSION 16 of MgO, La2O3, and Al2O3. In the investigation of the effect of Ru loading added to the COAL UTILIZATION BY-PRODUCTS 3: COAL ASH UTILIZATION Ni catalyst, it was found that the presence of Ru strongly enhances the catalytic TECHNOLOGIES performance of the Ni-based catalyst when increasing Ru loading up to 2wt%. Effect 16-1 of Ni loading to the Ni/Ru/Al2O3(M1) catalyst system was further investigated to Use of Coal Combustion Product Grout to Construct a Grout Curtain Around an provide the optimal composition of Ni-Ru on the support that has an excellent catalytic Abandoned Coal-Mining Shaft to Reduce Ground Water Infiltration into the performance in the steam reforming of oxygenated compounds present in the bio-oil. It Mine Pool was found that Ru monometallic precursor (concentration of 2wt%) was not an active Gary R. Fuhrman species in the steam reforming of oxygenated compounds, and that addition of nickel Western Maryland Resource Conservation and Development Council, USA to the Ru/Al2O3 catalyst up to 15wt% enhanced significantly the catalytic activity of the catalyst. The stability of the Ru-Ni catalysts in the reforming of m-cresol was also The Kempton Man Shaft Project is one of several projects sponsored by the Maryland tested at 750oC. In agree with general observations of the use of Ni monometallic Department of Natural Resources Power Plant Research Program, and funded by the catalyst, the present study confirmed that deactivation of such catalyst due to the US Department of the Interior Office of Surface Mining, to demonstrate the carbon deposition reaction already occurred during the reforming of the oxygenated. replacement of concrete with coal combustion products (CCPs) from nearby coal-fired On the other hand, a reasonable high resistant on the carbon deposition for the power plants. The Kempton Mine complex was an active deep mine during the period reforming of m-cresol was given by the 2wt%Ru – 15wt%Ni catalyst system. An effort 1912 – 1950. The mine tunnels, varying in depths of 130 feet to 420 feet below grade, in improving the strength of the catalyst support with this catalyst system was also lie beneath an area of approximately 12 square miles spanning portions of West done, and the catalyst showed significant increasing in the stability of the reforming of Virginia and Maryland. Most of the tunnels are flooded by surface water intrusion or oxygenated aromatic compound. from local aquifers. The presence of residual coal in the tunnels acidifies the water and causes environmental damage when it discharges into nearby Laurel Run, a tributary of 15-4 the Potomac River. The Man Shaft, which lowered miners to the mine tunnel Production of Hydrogen and Other Value Added Products from Waste Tire entrances, is 420-feet below grade. Pyrolysis Exploratory boreholes drilled around the Man Shaft revealed horizontal fractures in Ana M. Mastral, Ramon Murillo, Maria S. Callen, José M. López, Elvira Aylón and siltstone bedrock at depths between 120 feet and 140 feet. The seepage of ground Maria T. de la Cruz water into the Man Shaft from these fractures is estimated to be 45,000 to 145,000 Instituto de Carboquímica, CSIC, Spain gallons per day. Ground water level measurements from monitoring wells installed in the boreholes indicate that the Man Shaft is a direct conduit for good quality ground Nowadays, more than 6 million tones per year of waste tire are being produced all water to flow into the mine pool. The project objective was to reduce the amount of around the world. This waste material generation produces a growing concern related ground water lost to the mine pool by installing a grout curtain to a depth of 160 feet to the economic and environmental problem associated with this non-biodegradable around the shaft using a cementitious grout prepared from coal combustion products residue. The most commonly used vulcanized tire rubber is a styrene-butadiene from nearby power plants. copolymer (SBR) or a mixture of natural rubber and SBR. In addition to these Because the available coal fly ash was a Class F ash (low Calcium) ash from a materials, carbon black is present in tires and used to strengthen the rubber and aid fluidized bed furnace, which mixes the coal with limestone prior to burning, was added abrasion resistance. In a typical tire composition, around 62% in weight would be to ensure proper hardening. rubber material and 30% in weight would be carbon black (2-5). The remaining 8% in Grout was injected into 28 6-inch holes, cased to 20 feet and filled to 150 – 160 feet weight would be comprised of ZnO, extender oils and fillers added during tyre using a tremie line. For most holes, good communication between adjacent holes was manufacturing. observed, indicating the flow of grout through the fractured siltstone was occurring. On the other side, hydrogen is a well-known fuel that in the future must be leading the Since completion of the grouting, a combination of potentiometric surface monitoring energy production sources because of its high calorific value without generating and dye tracing activities is being used to evaluate the effectiveness of the grout curtain pollutants or residues. Special efforts have been applied to the production of hydrogen in limiting the flow of ground water into the Man Shaft. In addition, core samples will from waste materials because in this way, not only a residue is eliminated but a clean be taken to evaluate the bonding integrity of the grout and rock. energy is obtained as well. Ultimate analysis of rubber tire shows that its hydrogen content is around 8%, a value 16-2 higher than the found in fossil fuels commonly used for hydrogen production via Application of Some Coal Treatment Products for Reclamation of Localities in gasification. In this communication, the recycling of waste tires through fast pyrolysis the North Bohemian Brown Coal Basin in a fluidized bed reactor is considered. During the fast pyrolysis process, and Michal Rehor and Marcela Safarova depending on the experimental conditions used, a gas with a remarkable content on Brown Coal Research Institute, Czech Republic hydrogen can be produced. In addition, oils are produced that can be used as Vratislav Ondracek transportation fuels or, because of their high hydrogen content (around 11 %), as raw Severoceske doly, Czech Republic material for additional hydrogen production through thermal cracking, partial oxidation or steam reforming. The importance of brown coal as raw material is nowadays given by rising energy needs of the Czech Republic. It is one more significant domestic fossil base material 15-5 without which the Czech Republic would become completely dependent on energy Hydrogen Production Technology by Partial Oxidation and Steam Reforming of source imports. Currently, more than 70% of brown coal deposits are mined in the Tar from Hot Coke Oven Gas North Bohemian Basin. Naturally, open brown coal mining has led to extensive M. Onozaki, K. Watanabe, T. Hashimoto, H. Saegusa and Y. Katayama damages on the landscape. Therefore, land reclamation works have grown on their The Institute of Applied Energy, Japan importance in the present times. 15

In majority, brown coal mining is carried out in four main localities that are completely constructions, the technology of stowing pond ash in the mines developed, different in terms of geological conditions and partly parameters of the extracted coal demonstrated and approved is finally here to be adapted. mass. This calls for various mining methods as well as different land reclamation methods. The difficulty in waste deposits land reclamation in the North Bohemian 16-4 Basin lies in extremely unfavourable properties of the loose-fill waste rock deposited Installation of Production and Transport of Ash and Water Dense Phase Slurry at on majority of the dump bodies. These are mainly waste rock of the overlying strata Patnow Power Station and brown-coal bed strata. Main loose-fill materials on the waste deposits are sands, Andrzej Kowalski kaolinitic clay sands and kaolinitic - illitic clays. The foreign matter in the loose-fill BSPiR Energoprojekt-Katowice SA, Poland waste rock are organic coal mass, siderite and pyrite. Those waste rocks are Tadeusz Zawacki and Marek Tymoszyk mechanically unstable against wind and water erosion, and due to on-going weathering Zespol Elektrowni Patnow-Adamow-Konin SA, Poland they get an unfavourable, acid (or phytotoxic) character. Marek Tymoszyk The coal mass on the surface of the land-reclaimed localities complicates both the Elektrownia Patnow, Poland technical as well as biological land reclamation. Some products of coal mass processing are successfully applied in improving land-reclamation utilization of the The paper presents the project consisting in construction of installation and production concerned localities. In the conditions of the North Bohemian Basin, these are mainly of dense phase ash and water slurry in Patnow Power Station, the slurry serving the oxyhumolites and power unit ashes. Acquired humitanes are very well utilizable for purpose of reclamation of brown coal abandoned workings. Basic conditions land reclamation both separately as well as in the mixture with other fertilizers. Power constituting a basis for creation of this project ware discussed, operation description unit ashes are experimentally applied as land reclamation additives in test areas along and parameters of installations and equipment are presented as well as assessment of with extremely heavy-grained overlying clays. The objective of the experiment is the operation and double ecological effect. improvement of the grain-distribution of the waste rock material. The submitted paper Presented are also the most important parameters of dense phase slurry upon its evaluates the application method of humitanes, power unit ashes and some other depositing in the abandoned workings with particular regard to the environment substances in connection with coal mining in the land-reclaimed areas of the North protection requirements. Bohemian Basin. The application success is illustrated by results of a long-term monitoring of physical, mineralogical and chemical – pedological parameters of the 16-5 waste rock from the individual test areas. Development of an Engineered Soil Using Coal Processing Waste and Combustion Byproducts 16-3 Yoginder P. Chugh and Greg Balk Pulverised Fuel Ash in Underground Minefills – A Successful Indian Endeavour Southern Illinois University, USA Vimal Kumar and Mukesh Mathur Technology Information Forecasting & Assessment Council, INDIA Very few studies have involved combining waste byproducts from both the coal and agriculture industries to develop an engineered soil without using a natural topsoil Indian underground coal mining industry, which has been riddled with problems of amendment. Such a soil would have applications in mine reclamation, landfill liners, less recovery of coal due to obsolete methods, equipments, machinery etc., is now etc. and would be highly cost effective. This research has developed an engineered soil facing another problem- this time, shortage of sand for mine-stowing. Sand reserves in based on fine coal (-100mesh x 0) processing waste (FCPW) from coal processing the river-beds are depleting and the mining industry is desperately looking for an plants, fluidized bed combustion (FBC) fly ash and animal waste (AW). The developed alternative material to river sand for filing into their voids. The laboratory test, trials soil is environmentally benign, and is a stabilized material suitable for reclamation and and field demonstrations have proved “Pond ash is a good substitute for sand for vegetation. Its commercial use will minimize environmental impacts associated with stowing into underground mines”. byproducts disposal as well as reduce ponds for FCPW, landfill space for CCBs Fly Ash Utilisation Programme (FAUP) of Technology Information, Forecasting & disposal, and a reduction of surface runoff of AW into surface and subsurface water. It Assessment Council (TIFAC), Department of Science & Technology (DST), can also provide the required topsoil (TS) for mine reclamation and other similar Government of India, adding to its credit of ‘firsts’, has successfully demonstrated applications according to regulatory agencies guidelines for chemical, elemental and stowing of pond ash in underground mines in India. About 10,000m3 of pond ash from contaminant concentration criteria. a captive Thermal Power Station of Heavy Water Plant (HWP), Manuguru (Andhra The developed soil contains FCPW (75-85%), FBC (3-12%), and AW (2-7%) from a Pradesh), was stowed in the underground mine of the Singreni Collieries Company mine and power plant in central Illinois, and AW from southern Illinois. The Ltd. (SCCL), Manuguru. The satisfaction expressed by the Directorate-General of performance of the engineered soil was demonstrated in the laboratory as well as in the Mine Safety (DGMS), Hyderabad, the regulating agency, over the demonstration field. Vegetation growth and yield for the ES was equal to or better than the top soil staged by the Central Mining Research Institute (CMRI), Dhanbad, at the site has (TS). It was also noticeably better than the combination of FCPW and FBC only paved the way to adopt the technology on a large scale and in its wake, take up the without the addition of AW. The FCPW alone showed poor growth and yield. major task of stowing 1.5 lakh m3 pond ash in the days ahead. Initial pH of ES was high with readings greater than 12.0 for ES involving FBC. The The demonstration came through a detailed laboratory programme and field work pH decreased rapidly to values below 8.0 in 3-4 weeks. taken up by the agencies mentioned earlier. Parameters under the scanner during the Leachate water showed no toxic levels of the heavy metals As, Cr, Cd, Pb or Hg. demonstration included load on the barricades, water filtration through these Concentrations of SO4, Ca, Na and Cl were high and slightly beyond Class II barricades, water percolation through pond ash bed, environmental impact of water groundwater standards for all ES treatments except for the TS. All other elements for draining from the barricades as also the chemical analysis of the pond ash, inlet water the developed ES were found to be within Class II groundwater standards. and discharge water collected through these barricades. The effect of pond ash Harvested vegetation was analyzed for plant essential nutrients and heavy metal stowing on neighbouring work places that of water draining from barricades on floor concentrations. The heavy metals assayed were As, Cr, Cd, Pb and Hg. coal of galleries and also that of main sump and pumps installed for pumping the All ES samples had large amounts of plant essential nutrients. discharge water were studied during the demonstration at Manuguru. The results were Cr, Cd, Pb and Hg were well below toxicity levels. However, all four ES treatments encouraging! showed values higher (up to three times) the standard limit. The effects of these on Persons could walk freely over the pond ash bed within half an hour of stowing. Water wildlife through ingestion of plant tissue are not certain. seepage through the barricades was found to be good as were the results of the Comparing pre-growth soil to post-growth soil, concentrations of Ca, S, B, Fe and Mn chemical analysis of water. It was observed that once the pond ash sealed to full were still high. The abundance of these elements was also found in the tissue and the height of the barricade, water percolation through the barricade reduced and started water except for boron, which was not abundant in the water. flowing through the level barricades. The water also drained off from the pond ash bed and the ash bed was found to have good consolidation. SESSION 17 Settlement of fine particles of ash and their discharge from the barricades was a matter ENVIRONMENTAL CONTROL TECHNOLOGY 3: PARTICULATE of concern during the initial stages of development of pond ash stowing technology. MATTER & TRACE ELEMENTS These issues were addressed with the use of an additive. The leachate was tested at 17-1 Central Fuel Research Institute (CFRI)-Dhanbad, and also at Nuclear Fuel Complex Release Behavior of Trace Elements from Coal during High Temperature (NFC), Hyderabad. No adverse impact was found and the additive had its way. Processing The demonstration of the technology and experience gained while its application, Yasushi Sekine, Kunihisa Sakajiri, Eiichi Kikuchi and Masahiko Matsukata buoyed-up the confidence of SCCL – the user agency, and DGMS – the regulatory Waseda University, Japan body. The confidence is also mirrored through replication of the technology at Western Coalfields Ltd. (WCL), Chandrapur, where pond ash from Chandrapur Super Power Coal includes so many kinds of trace elements with several 10 ppm concentrations. Thermal Power Station is being stowed in the Durgapur Raitwari Colliery, They volatilize at the combustion or gasification of coal, and would be released into Chandrapur. the atmosphere. In this study, we investigated how the reaction temperature and Considering the fact that the country today produces about 105 million tonnes of coal existence of the steam in the reaction atmosphere influence the releasing behavior of ash and there is also dearth of sand owing to its application in expanding civil the trace elements from coal. All experiments were conducted with DF system under the temperature range of 573~1573 K, and the contents of the trace elements in the 16

coal in each temperature was measured by ICP. As for Zn, Se, Sb, Hg and Pb, residual ppb range has been detected in real samples (KCl impinger solutions) prepared from ratios in coal changed with the rise of temperature. A change of residual ratio was not flue gas released by a pilot-scale coal fired combustion facility. A portable instrument observed about other elements. Residual ratios of Zn and Pb decreased at 1173 K or has also been used for the detection of mercury efficiently. BDD mounted in rotating more, irrespective of existence of steam. Even if it was in the presence of steam, disk electrode (RDE) system together with gold co-deposition has been demonstrated residual ratios of Zn and Pb were same as the case where it was in the absence of to detect mercury with higher sensitivity and reproducibility. steam. On the other hand, as for Se, Sb and Hg, the residual ratios in coal decreased greatly at low temperature (573~773 K). As for Se and Sb, residual ratios decreased in 17-5 the presence of steam. This is considered because it released from coal via a hydroxide Synthesis of Organic Calcium-Based Sorbent from the Biomass Pyroligneous form under low temperature region. However, residual ratios of Hg increased in the Acid and Its De-SO2 and De-Cl Capture Capabilities during the Combustion of presence of steam conversely. We considered that the existence form of elements in the High-sulfur Coals coal has correlation to the emission behavior. Yoshihiko Ninomiya and Lian Zhang Chubu University, Japan 17-2 Analysis of Arsenic, Boron and Some Other Elements in Coal Fly Ash by X-Ray This paper first aims to evaluate the possibility of synthesizing organic calcium Photoelectron Spectroscopy through the use of pyroligneous acid and raw limestone. The pyrolignous acid was the Akira Ohki, Yuka Sakaguchi, Tsunenori Nakajima and Hirokazu Takanashi byproduct produced by pyrolysis of woods at the temperature around 200oC. Kagoshima University, Japan Limestone has the particles as large as 500-1000 µm. The factors affecting this reaction were investigated including the pyroligneous acid type and the reaction conditions as Surface characterization of coal fly ash (CFA) was carried out by use of X-ray well. Secondly, two low-rank coals were impregnated with the calcium-enriched photoelectron spectroscopy (XPS), especially focusing on the occurrence of As and B. pyroligneous acid to evaluate the possibility of in situ desulfurization and capture of XPS spectra of CFA at 48.5 and 195 eV were assigned to As(3d) and B(1s), the vaporized trace elements in the combustion furnace. The experimental results respectively. The molar ratios of As and B as well as some other elements (Al, Ca, Fe, suggest the feasibility of reaction between pyroligneous acid and limestone under mild and S) normalized to Si were obtained from XPS analysis (MR-X) and bulk analysis conditions. The saturated solubility of calcium in the pyroligneous acid was obtained (MR-B). For a certified reference material of CFA (NIST-1633b), the MR-X/MR-B in 30 minutes at 50oC, which is mainly controlled by the acidity of the pyroligneous ratios for As and B were 24 and 55, respectively, suggesting that these elements are acids. The soluble calcium within pyroligneous acid is in form of calcium acetate highly enriched on the surface of CFA. Over 20 CFA samples were analyzed, and the having a low decomposition temperature around 400oC, far lower than that of raw MR-X/MR-B ratio for As varied from 13 to 274, while the ratio for B, from 6 to 55. limestone being about 700oC. Since of its solubility, calcium within pyroligneous acid The concentration depth profile of these elements in NIST-1633b was studied by using was loaded readily on the coals, forming the ultrafine particles in the impregnated coal Ar+ sputtering with the XPS. The MR-X/MR-B ratio for As gradually decreased when matrix. During coal combustion, the loaded calcium underwent quick decomposition the sputtering proceeded, and the ratio reached 10 after 10 min sputtering; the prior to char combustion, and subsequently, the formed ultrafine calcium oxide sputtering is presumed to give 10 nm depth profile. Also, the MR-X/MR-B ratio for B captured the evolved sulfur oxide and vaporized trace elements. after 10 min sputtering was 10. However, the sputtering provided almost no change in the ratio for Al. These results strongly support the enrichment of As and B on the SESSION 18 surface of CFA. COAL CHEMISTRY: 2 18-1 17-3 About Kinetics of Creation of Coal Coking Vapor-Gas By-Products Compositions and Leaching Behaviours of Combustion Residues Gennadiy Vlasov Nabajyoti Saikia, Yuji Sakaguchi, Shigeru Kato and Toshinori Kojima JSC, Ukraine Seikei University, Japan Vadim Barsky Ukrainian State University of Chemical Engineers, Ukraine Combustion residues collected from different incineration processes create a major environmental problem as these materials contain high amounts of toxic elements. Demand flow for chemical by-products of coal coking requires sufficiently quick These materials are generally used in land fillings or used as construction materials. reorganization onto preferred production of definite individual substances or in the best But before the use in construction purposes or in land fillings, some pretreatments are case, mixtures with preassigned composition. necessary in order to remove the soluble salts and to extract the toxic elements. In present work is explored gassing kinetics as major step of search, of directive effect Knowledge of the leaching behaviours of these wastes is very important for evaluation onto vapor-gas by-products of high-temperature coal charge pyrolysis. of such treatment methods. To study the leaching behaviours of three combustion As a result of process theoretical analysis mathematical expression for volume residues namely fly ash samples collected from coal combustion power plant (FA), outgassing rate during coking interval was found. municipality solid waste incineration plant (MSWI ash) and sewage sludge Function structure and parameters were verify according to laboratory and industrial incineration plant (SS ash), column leaching experiments at two different pH (pH = 6 data and used as base of kinetic description of direct coke-oven gas individual and 1) were conducted. The leachantes were analyzed for pH and the major elements: components. Ca, Al, Na, K, Mg and Fe. Analyses of leachants were also made for determination of minor elements: Pb, Cr, As, Cd, Se, B, Mo and Hg. Raw and treated samples were 18-2 characterized by XRD and SEM-EPMA techniques. From the results it was observed First Application of Al MQMAS NMR at 16.4 T to Inorganic Matter in Natural that the soluble salts content in the MSWI ash are higher than those in other two Coals residues and the halite and sylvite were the major soluble salts in MSWI ash. The Koji Saito and Koji Kanehashi alkalinities of the residues affect the pH of leachants and the order of alkalinities of Nippon Steel Corporation, JAPAN different residues was: FA>MSWI ash>SS ash. The alkalinities of the residues also affected the amount of leachants passing through the residues column. The Al multiple quantum magic angle spinning (MQMAS) technique at high magnetic field concentrations of major and minor elements present in the leachants fractions collected (16.4 T) averaging the second-order quadrupolar interaction that cause the spectral at different time intervals were compared with the total contents of the elements in the broadening and splitting was applied for the first time to the structural analysis of residues to determine the maximum leachable fractions. inorganic matter in natural coals. Resolution of 3QMAS spectra at 7.0 T was still insufficient to identification of inorganic matter in natural coals because the 17-4 cancellation of the second-order quadrupolar effect was not accomplished perfectly PPT Level Detection of Mercury using Diamond Rotating Disk Sensor Electrodes although 3QMAS spectra gave better resolution than conventional magic angle A. Manivannan and M. S. Seehra spinning (MAS) spectra. On the other hand, higher magnetic field, 16.4 T, greatly West Virginia University, USA improved 3QMAS spectral resolution compared with 7.0 T, hence it facilitated the E. Granite assignment of some minerals. Moreover, since 3QMAS at 16.4 T led to signal US DOE, NETL, USA enhancement by a factor of about 4 compared to at 7.0 T, it is very useful for the A. Fujishima analysis of inorganic matter in natural coals that have low concentration of aluminum Kanagawa Academy of Science & Technology, Japan (~ 2.0 mass %). 3QMAS and 5QMAS spectra at 16.4 T were also compared. As far as inorganic matter in natural coals is concerned, spectral resolution was almost We report determination of mercury ions at the ppb levels using highly boron doped unchanged between 3QMAS and 5QMAS although the excitation of 5 quantum diamond (BDD) films electrodes by differential pulse voltammetry (DPV). DPV coherences is less efficient than for 3 quantum coherences. It is concluded that the experiments were performed in nitrate, thiocyanate and chloride media. Investigation combination of MQMAS techniques with high magnetic field is a very effective for in chloride medium is important since practical samples always contain chloride characterization of inorganic matter in natural coals and especially well suited to the impurities. The formation of calomel in chloride medium is avoided on the BDD analysis of clay minerals that are low crystallinity in contrast to X-ray diffraction surface by the co-deposition of 3ppm of gold during DPV detection. Excellent linear (XRD). calibration plots have been obtained in all media for ppb ranges. Mercury in the 0.1-50 17

18-3 utilized during the experiment to simulate ash deposition condition inside the channel Geochemistry of Mercury in Indiana Coals and Their Fly Ash; Insights from a of gasifier. Several samples of pulverized coal are introduced at the top of DTF with Sequential Extraction Technique primary O2 and secondary N2 flow. The feed rate of coal sample is about 0.3g/min and Agnieszka Drobniak and Maria Mastalerz the reacted ash samples are collected on the funnel-shaped deposit probe at the bottom. Indiana University, USA After the experiment, weight analysis is carried out with deposit samples. Sample of Rosalice Buehrer and Gabriel Filippelli swage sludge is also experimented with DTF for the comparison of deposition IUPUI, USA behavior. Collected ash deposit layer was embedded in an epoxy resin for the SEM- EDX analysis to find the composition information of ash of every layer of deposition Coal from two of Indiana’s economically important Pennsylvanian coalbeds, the high- to define the chemical interaction between ash particles. sulfur Springfield Coal Member of the Petersburg Formation and the low-sulfur Danville Coal Member of the Dugger Formation, along with fly ashes were studied SESSION 19 with regard to mercury geochemistry. Both coals are of high-volatile bituminous rank; COMBUSTION TECHNOLOGIES 4: BEHAVIOR OF MINERAL mercury (Hg) content is 0.13 mg/kg in the Springfield and 0.03 mg/kg in the Danville. MATTER DURING COMBUSTION Study of the combustion products of these coals show relatively high Hg 19-1 concentrations in the low temperature fly ash, which is especially pronounced in the Emission of Particulate Matters from Coal Combustion and Its Danville coal (Mastalerz et al., in press). To better understand the fate of Hg during the Correlationship with Coal Mineral Properties combustion process, a sequential extraction procedure, adapted from Kolker and others Lian Zhang and Yoshihiko Ninomiya (2002), Bloom and others (2003) and Sladek and Gustin (2003) was used to evaluate Chubu University, Japan Hg affinity to four geochemically distinct fractions. In step I, ammonium acetate (CH3COONH4, or “AmmAcet”) was used to decompose some of the least resistant Emission of particulate matters (PM) was studied during combustion of four Chinese organic matter and some of the carbonates. In step II, the residue of step I was further coals. A laboratory-scaled drop tube furnace was used, and the following combustion leached with HCl, removing remaining carbonates, Fe oxides, sulfates, monosulfides, conditions were selected: coal feeding rate was about 0.2 g/min, air was used as the and certain chelated organic compounds (Kolker and others, 2002). In step III, HF gaseous atmosphere, which had the flow rate around 10.0 l/min, the reaction o dissolved the silicate minerals, and finally, in step IV, HNO3 was added to decompose temperature was 1200 C, and the residence time was 2.4 seconds in all runs. All the disulfides, especially pyrite, any remaining phosphates, and refractory organic matter. carbon was burnt completely under above conditions. The PM within the exit gas was Preliminary findings show that Hg content tends to be lowest in the HF residue and collected by a low-pressure-impactor (LPI) having thirteen stages, which automatically highest in the HNO3 residue, with variable amounts associated with the AmmAcet and size-segregated PM from 10.0 to 0.03µm. Each size of the collected PM was subjected HCl. This result suggests that most of the Hg is associated with disulfides, particularly to several techniques to quantify its characteristics: XRF was used for the elemental pyrite, and perhaps refractory organics, whereas negligible amounts of Hg appear to be composition; SEM-EDX was used for structure observation whereas computer- associated with silicates, including clays. Hg ranges from 0% to 57% Hg in mobile, controlled SEM (CCSEM) and XPS used identifying the chemical species within PM. water-soluble fractions, and from 0% to 42% Hg in carbonates, Fe oxides, Furthermore, the correlationship between coal mineral properties and PM formation monosulfides, and organic matter. Continuing work involves refining the sequential was studied to investigate the impact of raw fuel property. The results indicated a extraction analysis and comparing geochemical results between raw coal and fly ash to relatively strong linear relationship between the ash content in raw coal and PM elucidate the geochemical fractionation of Hg during combustion. concentration. About 0.5 to 2.5 wt% of the inherent minerals transformed into PM. The formed PM has a triple size distribution in the four studied cases. The largest mode 18-4 around 2.0µm was formed by the direct transferring of inherent minerals within coal, Determination of Trace Elements in Coal by Microwave Digestion with HNO3 which is rich in the refractory aluminosilicates. Combustion of the coal rich in Alone Followed by ICP-MS aluminosilicates led to the formation of much the largest PM. The smallest mode Jie Wang, Tetsuya Nakazato, Kinya Sakanishi, Osamu Yamada, Hiroaki Tao and Ikuo around 0.05µm was formed by the vaporization of trace elements, alkali and S/P/Cl. Its Saito amount was positively affected by the content of inherent sulfur within coals. In AIST, Japan addition, the medium mode around 0.2µm was formed containing both refractory and vaporized elements having the comparable contents, which should be caused by the Inductively coupled plasma mass spectrometry has a capability of simultaneous agglomeration between these two kinds of elements. Its formation was affected determination of multi-elements with excellent reliability and sensitivity, and it is complexly by the coal property. widely applied to the analysis of coal sample and coal derived materials. In this analysis, solubilization of solid samples is generally required. It is well known that 19-2 digestion with chloride-based acids and HF causes isobaric interference and corrosion Energy Utilization Biofuels Based On Sludge And Brown Coal problems in the following instrumental analysis. In this context, the present study is to Václav Roubíček, Pavel Kolat, Miroslav Čech, Dagmar Juchelková, develop a new microwave method with HNO3 alone compatible with ICP-MS analysis. Zdeněk Kadlec, Anna Cemerkova We found that the coal organic matrix and clay mineral were thoroughly decomposed by elevating the digestion temperature up to 240 °C and pressure to 7 MPa, and less VŠB-Technical University Ostrava, Czech RepublicEnergy utilization of the than 10% of carbon remained in the resultant transparent solution. Li, Be, V, Cr, Mn, alternative fuels is one of main tasks for development of recoverable sources in EU and Co, Ni, Zn, Ga, As, Sr, Cs, Ba, and Pb were determined by a common ICP-MS CR. The topics of the research consists of combustion tests in experimental pilot 300 analysis, and Cd, Se, and Hg were determined by flow injection (FI)-ICP-MS, since kW stand with atmospheric fluidized-bed located at the Technical University Dresden the latter three elements in coals were extremely low in the concentration and beyond Germany for the brown coal, sewage sludge and thermo-analytical studies of bio-fuels. the limits of quantification by the common ICP-MS. It was interestingly found that all Main goals may be outlined in the study of conditions for: these trace elements were extracted quantitatively with reference to three standard • Co-combustion of brown coal and biofuels pellets from sewage coals (SRM1632c, BCR180, and SARM19). sludge, waste and wood, sustainability of fluidized bed combustion.

• Evaluation of optimal combustion condition, creation of harmful 18-5 solid and flue gas emission. Ratio of coal and biofuel. Mineral Characteristics of the Fouling Deposit in the Entrained-Bed Gasifier • Balance of combustion elements choice. using DTF Won-Cheol Shin and Hyung-Taek Kim • Raw material input analysis and dependence of combustion solid Ajou University, Korea residues on raw material input. • Relating the experimental and mathematical model results IGCC (integrated gasification combined cycle) is recognized as second-generation • Chemical composition, crystallographic structures and power plant technology since firstly they can provide higher efficiency compared to mechanical properties of combustion solid products ( ash, fly ash, the conventional pulverized coal combustion facility, and secondly they produce only deposits ). minimal amounts of pollutants well below the current environmental regulations. • Detailed study for mineralogical and chemical composition solid Particularly, ash component of coal is discarded as slag form which is emission phase. environmentally-stable so that heavy metal elements in the coal ash can’t be reachable • Leaching tests for combustion solid products. into ground water. However, coal ash is bubbled inside gasifier during the high Comparing the results with EU standardsRecommendations for temperature operation of slagging condition and fly slag is carried with product gas suitability of thermal disposal of wastes in the atmospheric fluidized- through the heat exchanger section. So, the high temperature fouling is occurred bed are presented with minimizing the harmful emissions. It may be frequently at the section of flue exit-channel and heat exchanger. assumed from results that combustion with content of 15 % bio-fuels This paper presents an experimental approach to study the effect of mineral is applicable in the large fluidized-bed boilers installed in the Czech characteristics on ash deposition using a vertical DTF (drop tube furnace) in various Republic. The combined combustion will enable to fulfil the promise temperature conditions (500 ~900 ). Also, it aims to explain deposition of the Czech Republic to the European Commission concerning the characteristics according to the shape of deposit probe surface. A laminar DTF is development of renewable energy resources by 2010. 18

19-3 20-1 Direct Observation of Ash Deposition in Pulverized Coal Fired Boiler using CCD Construction of Sophisticated Environmental Controlled 600MW Pulverized Coal Camera and Model Development for Slagging Prediction Fired Tower Boiler for Urban Power Station Toru Yamashita and Katsuyuki Tachibana Toshirou Matsuda Idemitsu Kosan Co., Ltd., Japan Electric Power Development Co., Ltd., Japan Toshimitsu Asotani Shinobu Nakamura, Tetsuya Iwasaki, Yoshitomo Ohkuma and Kanya Muto Idemitsu Engineering Co., Ltd., Japan Ishikawajima-Harima Heavy industries Co., Ltd., Japan

A prediction, prompt detection and suitable control of ash deposition on heat transfer Replace project of 600MW coal fired unit at J-Power’s Isogo Thermal Power Station, surface are one of the most important factors for a stable and highly efficient operation Yokohama Japan, was carried out under operation of existing 265MW×2 units to be of pulverized coal fired boiler. In order to directly observe a clinker formation replaced. To adopt limited site area condition, IHI Tower Boiler is applied because of behavior, high temperature-resistant type CCD camera was installed at the 140t/h scale its compact layout and suitable erection procedure. By IHI’s Low NOx Combustion actual boiler. This observation was quite useful to determine the location and extent of technology, the highest steam condition in Japan and dry-type desulfurization system, clinker formation. A model that predicts deposit growth and exfoliation process was this unit contributes to reduce emission and increase power, giving a new solution for developed to simulate a possibility of clinker formation and its location for each coal replacing urban power station. type and operating condition. 20-2 Pricing Formulae for Hard Coal Sold To Power Plants and Chp Plants in Poland 19-4 Wieslaw Blaschke, Urszula Lorenz and Zbigniew Grudzinski Oxy-Fuel Combustion for Sequestration Ready Co2 – Technology Status, Mineral and Energy Economy Research Institute, Poland Assessment and Research Needs Terry Wall, Bart Buhre, Changdong Sheng, and Raj Gupta Hard coal prices are negotiated between producers and users. The price level results University of Newcastle, Australia from current economic and market conditions however, prices depend also on coal quality (mainly on net calorific value, ash, sulphur and moisture content). Other quality The awareness of the increase in the emission of greenhouse gases has resulted in the parameters like grindability, volatile matter, alkalies or phosphorus contents, etc. are development of new technologies with lower emissions and also technologies that can sometimes also determined in contracts. At the beginning, usually the basic price for “a accommodate capture and sequestration of carbon dioxide. Air fired combustion and standard (or reference) coal” is negotiated. This standard can be based on calorific gasification technologies require separation of CO2 from nitrogen after combustion. value only or on a number of selected parameters. Deviations from standard coal IGCC technology can only be used for new power generation plants. For existing quality result in price changes, and should reflect an economic value of coal, while plants there are two options for CO2 capture: removal of nitrogen from flue gases or assessing it from the user’s (buyer’s) point of view. removal of nitrogen from air before combustion so as to get a flue gas stream ready to In Polish practice, coal price variation being the result of the quality changes is be sequestered. This present report reviews the status of these options and, in determined using pricing formulae agreed during negotiations. Pricing formulae particular, the retrofit of existing plants. improve and simplify the conditions of bilateral settlements of coal deliveries. Traditionally, boilers use air for combustion where N2 from the air dilutes the CO2 This paper presents two proposals of new pricing formulae. The first one concerns concentration in the flue gas, which results in costly CO2 recovery using steam coal fines that are sold to domestic power plants (or combined heat and power monoethanolamine (MEA) scrubbers. An alternative is to reduce N2 using oxygen for stations). Price is connected with three main coal quality parameters: calorific value, firing instead of air. This technology recycles CO2 flue gas back into to the furnace to sulphur content and ash content. Coal price in the formula is proportional to the control temperature and make up the volume of the missing N2 to ensure there is calorific value. The valuation of the sulphur and ash impact on the price is done in enough gas to maintain the temperature and heat flux profiles in the boiler as far as accordance with the costs of obligatory fees (in Polish environmental regulations) for possible. This technology is known as Oxy-Fuel technology with Recycled Flue Gas the emissions of SO2 and PM, and for solid wastes (fly and bottom ashes) storage. (RFG). The second solution applies to the terms of sale of specific semi-products of coal like Studies on the application of this “oxyfuel” technology to pulverised coal combustion coking coal inter-layers and fine-grained flotation concentrates. The formula applies to power plants are presented in this review, including laboratory and pilot scale the usage of those semi-products for energetic purposes. Comparing to the typical experiments and full scale evaluations. steam coal fines burnt in domestic power plants they are relatively of higher calorific Recent research has given a comparative assessment of electricity production options, value and lower ash and sulphur contents. But their volatile matter content is lower and which includes oxyfiring with 95% CO2 capture for ultrasupercritical pf. The report caking properties are too high. These parameters decrease their value when used as a provides estimates of the cost of CO2 abatement, to conclude that CO2 capture for fuel for electricity generation in conventional power station. Moreover, flotation oxygen USC reduces the overall thermal efficiency by approximately 9%, due to the concentrates are fine-grained and are of high moisture content that worsens the flow parasitics for oxygen production and flue gas compression/liquefaction, CO2 capture properties. These semi-products can, however, be used as components for coal blends and compression reduces the sent out electricity by 18-20% for O2-USC, but that (in adequate proportions). To determine their market value (i.e. price) the new pricing currently and in the near future, oxyfiring would be the lowest cost technology for formula is proposed in the paper. carbon capture and storage. The most immediate application appears is for retrofit of existing pf units to generate 20-3 sequestration ready CO2, and would include a heat exchanger to increase the Coal Utilization Technology Development at NEDO convective exchange surface area and also a fabric filter for the high efficiency dust Sadao Wasaka, Takeshi Kobashi, Kazuo Kashima, Motoharu Yasumuro and Jyunichi removal required by the compressor. This technology is based on pilot-scale data on Ishihara emissions indicating that low NOx is formed in oxy-firing and that SO2 is removed in New Energy and Industrial Technology Development Organization (NEDO), Japan the first stage of the compressor/cooler. The review indicates that purpose built, retrofit ready and retrofitted plant can Recently, as global warming has become a chief issue, efforts to reduce CO2 emissions accommodate the technology, that the economics are favourable, and that the are increasingly being reflected in national energy policies. In Japan, the 3Es, “Energy technology provides a short-term option for near-zero emission coal technology for security”, “Environmental protection” and “Economic growth”, comprise the central power. From the information, the following aspects require research in order to pillars of the governmental energy policy. Given that Japan relies on imports for the evaluate and develop the technology. majority of her primary energy supply, “Energy security” is the most salient issue. The combustion of coal in an O2/CO2 atmosphere, including ignition, burn-out, and Under these circumstances, New Energy and Industrial Technology Development emissions. Flow sheet options and the gas cleaning required. The heat transfer Organization (NEDO), commissioned by Ministry of Economy, Trade and Industry of performance of new and retrofitted plant and the impact of oxygen feed concentration Japan (METI), is actively developing technologies for utilizing fossil fuels— and CO2 recycle ratio. Assessment of retrofits for electricity cost and cost of CO2 predominantly coal—to facilitate simultaneous achievement of the 3Es. avoided. The impact of the development of new, and less expensive, oxygen NEDO develops coal utilization technologies, such as clean coal technologies (CCT), generation technology. in addition to utilization technologies for other fossil fuels. Coal gasification technology and ash-free coal production technology are acknowledged as key technologies in CCT. Development of an innovative oxygen-blown, entrained-flow gasification technology (EAGLE) is carried out in a 150t/d pilot plant. This SESSION 20 gasification technology realizes high efficiency in syngas production and can be ADVANCED ENERGY SYSTEMS utilized widely in power generation and industrial applications. In addition to the gasification technology, a technology that decreases the amount of ash in coals to less than 200ppm is under development and the product, ash-free coal, is anticipated to be utilized as carbon material, as feedstock for pressurized fluidized bed combustors and gas turbines as well as for pulverized coal firing. This paper presents an outline of the projects carried out in NEDO. 19

20-4 SESSION 21 Advanced Pressurized Fluidized-Bed Combustion (A-PFBC) Technology HYDROGEN IN THE FUTURE 4: HYDROGEN PRODUCTION Hiroyuki Nakata TECHNOLOGIES & SEPARATION Electric Power Development Co., Ltd., Japan 21-1 Mutsuo Kato Reforming of Methanol in Supercritical Water for High-Pressure Hydrogen Center for Coal Utilization, Japan Production Keiji Usami Katsuaki Tadokoro, Nobuyuki Matsumoto and Takayuki Azuma Chubu Electric Power Co., Inc., Japan Osaka Gas Co., Ltd., Japan Yoshihiko Tsuchiyama Mitsubishi Heavy Industries, Ltd., Japan For the coming hydrogen energy age, it goes without saying that the fuel cell vehicle (FCV) is one of the most symbolic items consuming hydrogen fuel. In the process of The Advanced Pressurized Fluidized-Bed Combustion (A-PFBC) plant achieves higher the FCV technology development, the high-pressure hydrogen tank system is a efficiency with a technology that increases the gas turbine inlet temperature of the promising way to storage hydrogen in the FCV. However much work is required to pressurized fluidized-bed combined cycle (PFBC) system (from 850 deg. C to a level compress the produced hydrogen gas and much electricity is required to get the work. of 1,350 deg. C). The A-PFBC plant is a new combined cycle system that combines Aiming at more efficient method for producing high-pressure hydrogen, the steam three fluidized-bed furnaces with a gas and steam turbine. These three furnaces are a reforming of methanol in supercritical water was proposed as a novel system. The coal gasifier for the partial gasification of coal, a desulfurizer for the removal of sulfur system has a main advantage that the required compression work is quite little due to by limestone-gypsum process at high temperatures, and a combustor-oxidizer for the the low compressibility of the liquid fuel. combustion of the char residues from the coal gasifier and oxidization of the calcium The fundamental experiments on hydrogen production in supercritical water were sulfide discharged from the desulfurizer. The new advanced system holds promise of investigated in continuously operated tubular reactor made of stainless steel 316. The 46 % in net efficiency, which is roughly 10% improvement (relative value) compared metal catalyst supported by metal oxide is used for the gasification reaction. The metal with the PFBC. solid catalyst enables the gasification at the relatively low temperature, which has a In the A-PFBC project, the construction of a 15 ton/day coal throughput process great advantage for mechanical design of the high-pressure equipment. Hydrogen rich development unit (PDU) plant was completed on the site of Wakamatsu Research gas (72%) could be obtained from methanol for 1,000 hours operation stably at the Institute of J-Power in July 2001 and gasification trials of the PDU had been carried condition of 450 °C and 35 MPa. At that time, other components were the carbon out for a total of 1,201 hours, with a cumulative 18 test runs by March 2003. dioxide, carbon monoxide and methane. These contents were 26%, 1%, 1% The main purpose of these PDU trials was to verify the operating characteristics of the respectively. During the continuous operation almost complete gasification of three-furnace combined system and assess its gasification, desulfurization, and methanol could be achieved. Our catalyst has a good selectivity of hydrogen combustion-oxidation performance. The PDU plant experiments were conducted to production limiting the methanation reaction and a good durability under supercritical verify the system’s operating parameters and to yield essential data for scaling up to a condition of water. The composition has a good agreement with the equilibrium pilot plant and an industrial plant. composition without methane. This paper describes the outline of the A-PFBC system and the results of the PDU The effect of feed concentration of methanol and residence time on both methanol gasification trials. gasification rate and product gas composition was investigated. Also, the absorption process by water absorbent was experimentally investigated for 20-5 the purification of reformed gas. It was confirmed that most of the carbon dioxide in Technology and Resource Management of IGCC Power Plants in the Indian reformed gas could be removed by this method. Experimentally 93.7 % hydrogen was Context – A Case Study obtained at the pressure of 35 MPa. V.K. Sethi Rajiv Gandhi Technological University, India 21-2 D.N. Reddy Hydrogen Production from Biomass-Ethanol at Ambient Temperature with Novel Osmania University, India Diaphragm Reactor P. Rajesh Yasushi Sekine, Shinjiro Asai, Kouhei Urasaki, Eiichi Kikuchi and Masahiko National Thermal Power Corporation Ltd., India Matsukata Waseda University, Japan Integrated Gasification Combined Cycle (IGCC) is emerging as a highly efficient and Shigeru Kado environmentally benign technology for power generation from coal, refinery residue Tokyo Institute of Technology, Japan etc. IGCC, after adequate demonstration world wide, is now poised to compete with Fumihiro Haga the conventional power generation technologies and is the 21st century technology to Central Research Center, Nissan, Japan meet the stringent environmental regulations more efficiently and economically than the pulverized coal fired power generation, even for inferior fuels having high ash, We investigated novel liquid fuel reforming system with diaphragm and discharge high sulfur and low calorific values. hybrid apparatus. This process can be operated under ambient temperature and There is a very large potential for coal gasification application in Indian Power and atmospheric pressure. The target fuel was ethanol-water mixture (biomass-ethanol), Industrial heating sectors. Extensive tests have been carried out by Indian R&D and it has many advantages for future fuel candidate. The reactor was made of glass institutions on high pressure moving bed and high pressure fluidized bed systems using tube and thin diaphragm membrane was inserted in the middle of the reactor. Two high ash coals. Both technologies have been shown to be capable of accepting Indian electrodes were inserted from both end of the reactor, and high negative voltage about coals without much operational problems. The initial high cost of the gasification route 5 kV was applied with pulse form. Main product in the obtained gas was H2 and its for power and heating may be completely offset by the environmental benefits and concentration was about 70%. Energy consumption was rather low compare to other more extensive application through generation of value added products like Hydrogen, system because this process can be operated at ambient temperature and does not need Sulphur in Co-production mode etc. any heater or pump. Now we develop new small power supply and reaction system With regard to the potential for development of IGCC technology, some of the key which can apply to small fuel cell system or FCV. Up to now, the main problem is how issues that need to be addressed by developers include Technology as well as Fuel to remove CO from the products, because most of all carbon atoms in the fuel is related issues. The paper covers a methodology and strategy of Transfer of Technology converted to CO, not CO2. So we also try to apply new catalyst in the system which (TOT) from a developed economy to India for an IGCC plant based on high ash can play an important role in the ambient discharge system. Indian coals. Phasing out the need of import through a systematic transfer of technology is the basis of the approach. To phase out the need of import through 21-3 systematic transfer of technology, there is a need for standardization of product Development of Dense Cermet Membranes for Hydrogen Separation amongst various indigenous manufacturers, evaluation of foreign collaborations so that U. Balachandran, T. H. Lee, L. Chen, S. J. Song, J. J. Picciolo and S. E. Dorris viable industry (self reliant) structure is built over a reasonable period of time. Argonne National Laboratory, USA The methodology used for Transfer of Technology discussed in this paper consists of R. P. Killmeyer Jr. and B. Morreale breaking down each major component / sub system into constituent production US DOE, NETL, USA technology / production chain for an IGCC project firing high ash Indian coal / Pet coke. The time required to commercialize critical components of the two variants of Argonne National Laboratory (ANL) and the National Energy Technology Laboratory IGCC technology viz. Air Blown & Oxygen Blown Gasifiers through systematic (NETL) are developing dense ceramic membranes for separating hydrogen from mixed Transfer of Technology have been evaluated both at a normal pace and with gases, particularly product streams generated during coal gasification and/or methane accelerated pace. The model developed for evaluation of velocity of transfer of reforming. Hydrogen separation with these membranes is nongalvanic, i.e., it does not technology is generic in nature and can be updated for variety of applications and other use electrodes or an external power supply to drive the separation, and hydrogen Clean Coal Technologies like Supercritical, Ultra Supercritical and Fluidized Bed selectivity is nearly 100% because the membranes contain no interconnected porosity. Combustion based Power Generation. Novel cermet (i.e., ceramic-metal composite) membranes have been developed to separate hydrogen from gas mixtures at high temperature and pressure. The hydrogen 20

permeation rate, or flux, has been measured at atmospheric pressure in the temperature Further work to establish the chemical controls on element leachability, and the time- range of 500-900°C for cermet membranes with thickness of 22-210 m. The dependent aspects of the leaching process, are currently in progress. Preliminary hydrogen flux varied linearly with the inverse of membrane thickness, and reached ≈19 results of these investigations are incorporated in other papers to be presented at the cm3[STP]/min-cm2 for a membrane with a thickness of ≈22 m at 900°C with 100% conference. H2 as the feed gas. This relationship indicates that the hydrogen flux is controlled by bulk diffusion, and that it might be higher for a thinner (<22 m) membrane. Some of 22-2 the membranes were tested in a gas mixture containing high concentrations of CO and Leachability of Heavy Metals from Selected Australian Fly Ashes and Its CO2 for times approaching ≈200 h, and no performance degradation was observed; this Implications for Groundwater Contamination suggests that the membrane is chemically stable and may be suitable for long-term Jerzy Jankowski, Colin R. Ward and Sarah Groves operation. Hydrogen flux measurements in H2S-containing atmospheres show that the University of New South Wales, Australia

cermet membranes are stable in gases containing 200 ppm H2S for up to 500 h. The David French hydrogen flux of cermet membranes was measured at NETL at hydrogen pressures up CSIRO, Australia to 25 atm and temperature up to 900°C. The present status of membrane development at ANL/NETL will be presented in this talk. Batch leaching tests have been performed on fly ashes collected from four Australian power stations fuelled by chemically different coals. Two acidic and two alkaline fly 21-4 ashes were subjected to long-term (144 hour) leaching tests, and the behaviour of As, Effect of Intermetallic Diffusion Barrier on the Stability of Composite Pd/PSS Cd, Cu, Mo, Se and Pb was investigated to obtain data on their potential for Membranes at Higher Temperatures mobilisation during fly ash-water interactions. Leaching solutions with initial pH Federico Guazzone, M. Engin Ayturk and Yi Hua Ma values of 4, 7 and 10 were used to assess the influence of pH conditions on element Worcester Polytechnic Institute, USA mobility for each of the ash samples. The pH values developed during the leaching process appear to be related to the acidity Hydrogen separation technologies are of great importance due to the essential nature of and alkalinity of the original fly ashes. The acidic fly ashes produced acidic to neutral hydrogen as an alternate clean fuel and the increasing demand for hydrogen in various leachates with pH values independent of the pH of the initial solution, whereas the chemical and petrochemical industries. Pd and Pd/Alloy membranes supported on alkaline fly ashes produced alkaline leachates, all with pH values above 9.5, regardless porous stainless steel (PSS) are well-suited for high purity hydrogen production in of the pH of the initial leaching solution used. The percentages of each of these steam reforming reactors, as well as in hydrogen purification. However, the long-term elements leached from each of the different fly ashes show the following trends: for the stability of the produced composite membranes is limited by the intermetallic diffusion acidic fly ashes – Cd>Se>Mo>As>Cu and Se>Cd>As>Mo>Cu, and for the alkaline fly of support elements (i.e., Fe, Cr, Ni) into the dense membrane layer. In order to avoid ashes – Mo>Se>Cd>As>Cu. The highest proportions of key elements removed from intermetallic diffusion, the in-situ oxidation of PSS supports to produce a barrier layer the fly ashes by the leaching solutions, as a fraction of the total element concentration has been developed in our laboratory2. The objective of the current study was to in the original ash in each case, are: Cd (3 – 9%) and Se (1 – 6%) in the acidic fly investigate the high temperature stability of Pd membranes supported on oxidized PSS ashes and Mo (12 – 20%) in the alkaline fly ashes. The lowest proportion of element supports. on the list removed by leaching from all four fly ashes is that of Cu; a maximum of To thoroughly understand the effectiveness of the oxide layer as the intermetallic only 0.15% of the Cu in the ash was removed from the solid phase in either acidic or diffusion barrier, four composite Pd membranes were prepared using an un-oxidized alkaline leachates. PSS support and three supports oxidized at three different temperatures, 400oC, 500oC Several important conclusions can be drawn from these experiments concerning the and 600oC. Hydrogen permeation measurements for the electrolessly plated Pd behaviour of heavy metals in leachate solutions. The most important are that the pH of membranes with a thickness range from 20 to 35 m were carried out using a system final solution depends on the pH of the original fly ash, the mobility of heavy metals equipped with a data acquisition board to continuously log the hydrogen flux, shell- from fly ash is a very slow process, and only very small percentages of elements and-tube-side pressures and the temperature of the system. The accuracy of the present in the fly ashes are removed by leaching, even after a 144 hour batch test. The measurements was determined to be within 1%. concentrations of elements in the leachates are only slightly pH dependent, and there is Permeation results showed that the decline in hydrogen flux was significantly larger no clear difference in concentrations with changing pH values. for the membranes with an un-oxidized support and support oxidized at 400oC than the ones with higher oxidation temperatures (500-600oC). For the membrane with a 22-3 thickness of 33 m and an oxide barrier formed at 400oC, the initial hydrogen Environmental Monitoring of Full-Scale Coal Combustion Product (CCP) permeance of 7.5 m3/m2-h-atm0.5 decreased to 6.7 m3/m2-h-atm0.5 in 48 hours at 400oC Pavements during Accelerated Loading under hydrogen. The rate of permeance decline for the PSS supports with an Harold Walker, C.M. Cheng, Panuwat Taerakul, Tarunjit Butalia, and William Wolfe intermetallic diffusion barrier created at 500oC was significantly smaller and was The Ohio State University, USA negligible for the one that was oxidized at 600oC. The extent of the intermetallic diffusion was determined by SEM and EDX analysis and the results were consistent The goal of this study is to evaluate the environmental response of full-scale CCP with the hydrogen flux decline data. Finally, permeation results of membranes stable at pavement sections during accelerated loading. Six full-scale CCP pavement sections 500oC for over a thousand hours will be presented. were constructed and tested at the OSU/OU Accelerated Pavement Load Facility (APLF). Each pavement section consisted of a driving surface layer (asphalt or SESSION 22 Portland cement concrete), base layer(s), and subbase layer. Two different proportions COAL ASH UTILIZATION BY-PRODUCTS – 4: COAL ASH of fly ash to Portland Cement Concrete were utilized in making the concrete pavement UTILIZATION FOR CIVIL ENGINEERING MATERIALS layer. Additionally, a no fly ash control section was constructed. Different 22-1 combinations of CCPs (fly ash and bottom ash) and conventional materials (sand, fine Comparative Evaluation Leachability Test Methods and Element Mobility for and coarse aggregate) were used in base and subbase layers. The objectives of the Selected Australian Fly Ash Samples environmental portion of the study were (1) to characterize the chemical properties of Colin R. Ward and Jerzy Jankowski the materials used in the construction of the pavement sections; (2) to determine the University of New South Wales, Australia leaching potential of selected constituents in the laboratory; and (3) to monitor the David French water quality of surface runoff and groundwater infiltration at the APLF. CSIRO, Australia The chemical properties of pavement ingredients and mixes were determined by digestion (USEPA method 3052). The leaching potential of selected constituents was Comparative evaluations have been conducted of the proportions of major and trace determined using a modified Toxic Characteristics Leaching Procedure (TCLP) test elements mobilised from Australian fly ashes using four different types of leaching (USEPA SW-846). Leaching is examined with both the extraction fluid specified by tests. These included batch-leaching tests based on shaking with distilled water and a the TCLP test as well as modified extraction fluids at different ionic strength to synthetic groundwater, as well as the standard TCLP procedure and an extended-term simulate different roadway conditions. During the accelerated loading test, the column leaching test. pavement surface was periodically subjected to 1-hour rainfall events simulated The mobility of elements from the fly ashes tested was found to vary significantly through a rainfall simulation system, in which the rainfall intensity was accurately depending on the test procedure used. The column leach test provides similar results controlled. Simulated rain was prepared from deionized water by adding a for most elements to the simpler shake and SGLP test procedures. However, some sulfuric/nitric acid mixture to pH 4.2. Five 100-mL surface runoff samples were elements, such as sulphur, appear not to be released as readily from the column tests, collected periodically during each 1-hour rainfall event. Towards the end of the possibly because of re-precipitation in the lower parts of the leaching columns. TCLP accelerated loading test, the subgrade of the facility will be inundated with water testing tends to produce higher levels of leachability for many elements, especially through pipes beneath the subbase layer. Pore water samples from different base and from ashes that generate alkaline leachate solutions, than the other test procedures. subbase layers will be collected at regular intervals from preinstalled lysimeters. Inorganic elements including Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pd, K, Si, Na, Sr, S, and Zn in each sample were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Elements As and Se were determined by graphite furnace atomic absorption spectrometry (GFAAs). Hg was

analyzed by cold vapor atomic absorption spectrometry (CVAAs). These constituents Nevertheless, the method can not be applied for a long time, especially in the lower were chosen because many are typically found in CCPs and they are also of concern in parts of the dumping area, because of the danger of water contamination in the water evaluating highway runoff. reservoir that is planned in a final management of the open cast. Laboratory tests indicated that the leaching of inorganic elements from Portland In the nearest future it is planned to stop dumping the ashes and slugs at the special cement concrete pavement containing fly ash was similar to values observed for dumping area of power plant. All the wastes will be deposited at the internal dumping Portland cement concrete without fly ash. Increasing the ionic strength of the leaching areas of coal mine and in the final open cast of Belchatow Mine – where the huge solution, to simulate salt addition to the roadway, did not significantly increase the reservoir is to be arranged. amount of leaching of inorganic elements. Sampling and analysis of surface and Three methods of ashes deposition are considered, namely: in the form of mixture of subsurface water from the APLF is currently ongoing. Because this study is being ashes and overburden, using a hydraulic technology in sealed reservoirs and in the conducted in a well-controlled environment utilizing accelerated loading, the results form of emulsified ash that solidifies after deposition. obtained demonstrate how different CCP materials influence contaminant release from The research on the influence of the different methods of ashes deposition on full-scale pavement sections over time-scales equivalent to the life of the pavement environment, and especially on contamination of water in rock mass and in projected system. reservoir, are carried out. The results of the research will be decisive for the final choice of the method. 22-4 Trace Element Mobility from Selected Australian Fly Ashes SESSION 23 Jerzy Jankowski, Colin R. Ward and Sarah Groves ENVIRONMENTAL CONTROL TECHNOLOGY 4: SULFUR & PAH University of New South Wales, Australia 23-1 David French Sulphur Removal from Mae Moh Coal via Mixtures of Hydrogen Peroxide with CSIRO, Australia Formic Acid Rafedah Rakal, Khudzir Ismail and Mohd Azlan Mohd Ishak Batch leaching tests have been performed to determine the mobility of some key trace University Technology MARA, Malaysia elements, Co, Cr and Ni, on fly ashes collected from four Australian power stations. Mohd Asri Mohd Nawi These materials represent two acidic and two alkaline-generating fly ashes, each University Science Malaysia, Malaysia derived from chemically different coals. Three different solutions, with initial pH values of 4, 7 and 10 were used to assess the Desulphurisation of Mae Moh coal using mixture of hydrogen peroxide and formic mobility of these and other elements from the fly ashes under a range of chemical acid at leaching temperatures of 30, 50 and 70oC in ambient pressure was studied. conditions. The leaching solutions were made up from Milli-Q-Water of pH 7 and The results obtained indicated that pyrite, sulphate and organic sulphur removal adjusted to acidic conditions (pH 4) using HCl and to alkaline conditions (pH 10) using increased with increasing leaching temperature at various leaching time. The rate of NaOH. The liquid/solid ratio in each test was between 3.45 and 3.50. The mixtures of pyrite and sulphate sulphur removal is relatively high in the first hour of leaching time, fly ashes and leachant were shaken for up to 144 hours, to obtain information on the and subsided as the leaching time proceed. The reagent mixture at leaching long-term mobility of trace metals. temperatures of 30, 50 and 70 oC are capable of reducing ca 38, 49 and 47 % of total After 144 hours of laboratory leaching less than 0.05% of the Co had been removed sulphur content in the coal, respectively. Further, as much as sulphur removal being from the alkaline fly ashes. The proportion of the Co removed from the acidic fly achieved, a considerable amount of coal dissolution was also being observed and was ashes was between 0.2 and 0.8%, significantly higher than that removed from the estimated. Further, scanning electron microscopy with energy dispersive X-ray (SEM- alkaline fly ashes. Nickel shows a similar pattern; less than 0.02% of the Ni was EDX) on the leached coal sample showed some noticeable physical alteration due to removed from one alkaline fly ash and less than 0.2% from the second alkaline fly ash, the mild oxidative treatment, particularly at relatively high leaching temperature. This but between 0.3% and 0.5% of the Ni was removed from both acidic fly ashes. The observation was consistent with the slight decreased in the calorific values behaviour of Cr, however, was completely reversed, with less than 0.01% of the Cr performance of the leached coal and was within tolerable limit. being removed from the acidic fly ashes and between 0.3% and 3% from the alkaline fly ashes. Equilibrium between solid phase and solution was not reached in any of the 23-2 leaching experiments. The Selective Oxidation of H2S to Elemental Sulfur on Mechanically Mixed At the end of the 144-hour tests the leachate pH produced by the acidic fly ashes after X-V2O5 Zeolite Catalysts in IGCC System reaction with the different solutions was always relatively acidic. With an initial Jong-Dae Lee, No-Kuk Park, Jin Hyuk Jun, Si-Ok Ryu and Tae-Jin Lee solution of pH 4, for example, the final pH after reaction with the acidic fly ashes Yeungnam University, Korea increased only slightly to 5.0 – 5.5. After treatment with the alkaline solution (pH 10) it decreased to a pH of 8.5. Alkaline conditions were maintained, however, when the Due to the increasing standards of efficiency required by environmental protection, the alkaline fly ashes were leached by all three solutions (pH 4, 7 and 10), and indeed the direct sulfur recovery from the H2S-containing gases has become more and more pH of the leachates often increased up to a value of around 12. important. For this reason, we studied the selective catalytic oxidation of H2S to This experiment shows that acidic fly ashes leached by solutions with different pH elemental sulfur on the zeolite HX, NaX and KX. The basic zeolites such as zeolite values have the ability to produce large amounts of protons and maintain acidic NaX and KX showed good catalytic activity. The elemental sulfur yield was about conditions, whereas the alkaline fly ashes produce large amounts of hydroxyl ions 90% on zeolite NaX, KX after 4hr selective oxidation of H2S at 225 . On the other elevating and/or maintaining alkaline conditions in the leachates. The study has also hand, it was under 20% on zeolite HX after 4hr reaction at 225 . However, these shown that the mobilisation of trace metals from fly ashes is a very slow process, and zeolite NaX and KX were deactivated in presence of water vapour. This deactivation interaction with groundwater and surface water in fly ash dams will take a long time to was caused by the strong adsorption of water vapour on the zeolite catalysts. For remove trace metals from solid phase. Depending on the hydrogeochemical selective oxidation of H2S in presence of water vapour, V2O5 catalyst was selected. environment in which the ash is emplaced or used, this may give rise over long periods The reactivity of V2O5 catalyst was improved by adding X-type zeolites. The improved of time to potential contamination of associated groundwater and surface water reactivity was caused by the improvement of reduction property of V2O5. The yield of systems. elemental sulfur over the mechanically mixed zeolite NaX – V2O5 catalysts (9:1) was 88% at 200 in the presence of water vapour. Particularly, the reactivity in presence 22-5 of coal-derived synthetic gas was better than that of in presence of water vapour. It was Deposition of Wastes from Belchatow Power Plant In Connection With suggested that the reduction property of catalysts was vary important factor in selective Overburden Dumping and Final Management in Lignite Mine Belchatow oxidation of H2S and the reduction property of V2O5 catalyst could be improved by Zbigniew Kozlowski mechanically mixing X-type zeolites. Wroclaw Technical University, Poland Lidia Gawlik and Zbigniew Grudzinski 23-3 Polish Academy of Sciences, Poland Two-Stage Desulfurization Process for Hot Gas Ultra Cleanup in IGCC No-Kuk Park, Kyung Duck Choi, Dong-Hwal Lee, Jong Dae Lee, Jin Hyuk Jun, Tae Belchatow Power Plant of the current capacity of 4420 MW is the biggest heat and Jin Lee and Si Ok Ryu power plant in the world. It uses nearly 40 mln tonnes of lignite per year. Yeungnam University, Korea Burning of such a huge amount of lignite causes the problem with over 4 mln tonnes a Jae-Chang Kim year of wastes from furnaces. These are fly ashes and slugs that should be managed Kyungpook National University, Korea safely for environment. Chih Hung Chang In the first years of the power plant operation the power plant wastes were deposited Oregon State University, USA using a hydraulic method at a special dumping area. The method required big forest areas and was harmful for environment due to dusting and pollution of earth waters. In these days many developed countries make a great effort to develop the affordable So, when Belchatow Mine applied internal dumping system, a part of fly ashes from and sustainable energy technologies to resolve the environmental pollution issues from power plants has been dumped internally in the mine excavation in the form of specific fossil fuel consumption. Gasification technology represents an innovative electric proportion mixture of the ashes and overburden. power generation concept and it provides several advantages including high energy 22

efficiency, superior environmental performance and low cost electricity. In an integrated gasification combined cycle (IGCC), coal and other carbon-based fuels with Although coal is the largest domestic fossil hydrocarbon resource of the U.S., an oxidant are converted into a gaseous synthetic fuel after gas cleaning, and then it is estimated to last over 250 years at the present consumption rate, most of the premium forwarded to the combined cycle for electric power generation. Gasification utilizes the carbon products developed and manufactured in the US derive mainly from petroleum, low-grade fossil fuels including coal, residues from petroleum processes, petroleum thus creating a dependence on foreign imports to manufacture essential carbon coke, and other wastes to produce electricity, steam, syngas (CO and H2), ammonia, products for the domestic market. To ensure a sustainable development of the carbon and methanol. Syngas after an ultra gas cleaning process for further purification will be product market the inherent potential of the great abundance of coal in the U.S. must converted into the high value-added products, such as hydrogen for fuel cell and be pursued to supply and introduce environmentally benign and affordable premium chemicals (DME, DMC) for catalytic conversion processes in near future. carbon products to the general public. Accordingly, the development of premium In order to remove hydrogen sulfide from a synthetic gas produced in a gasifier, a two- carbon products from coal for commercial application has been pursued through the stage process for the ultra hot gas cleaning was set up in this study. In the first stage Consortium for Premium Carbon Products from Coal (CPCPC). The overall objective process the sulfur content of the gasified fuel gas was reduced from 10,000 parts per of CPCPC is to be a vehicle for industry-driven research on the promotion, million to several ppmv in a fluidized-bed reactor. A fixed-bed reactor was used to development, and transfer of innovative technology to the U.S. industry. A series of remove the small amount of residual hydrogen sulfide that remains less than 5 ppmv new advances in the development of premium carbon products from coal has been levels in the fuel gas in the second stage process. The suitable sorbents with high established, including: (i) Green Carbons from Coal, (ii) New Developments in sulfur-removing capacity and long-term durability for each stage were also developed Anthracite Research, (iii) Advances in Coal Extract, Tars and Binder Technology, and and their reactivity was investigated in the ultra hot gas desulfurization process (iv) Nano-Material and Novel Products from Coal, will be reported. incorporated with the two-stage process. Near-zero emission was achieved as a result of experiment in this study. 24-2 Modifed Protocols for Synthetic Feedstocks for Anodes 23-4 Peter G. Stansberry, Elliot B. Kennel and Nathan D. King Operation Results of IHI Flue Gas Desulfurization System for 700MW Reihoku West Virginia University, USA Power Station Unit 2 Daisuke Horiguchi, Tosihiro Abe, Shokichi Hirata and Yoshimitsu Tsumita New sources of feedstocks for anode-grade carbon are needed to augment diminishing Ishikawajima-Harima Heavy Industries Co., Ltd., Japan supplies of high quality pitches and anode-grade cokes available from petroleum refining and coal tar production. Previous work has shown that it is possible to No.2 unit of Reihoku Power station, which is the newest 700MW coal-fired produce high quality pitch and coke using coal feedstocks produced via solvent supercritical unit of Kyushu Electric Power Co., Inc, entered into commercial extraction techniques.i That is, coal is partially dissolved, and particulates are operation in June 2003. Ishikawajima-Harima Heavy Industries Co., Ltd. (IHI) removed via techniques such as hot filtration or centrifugation, thus producing a constructed the limestone-gypsum type flue gas desulfurization plant for this unit synthetic hydrocarbon which resembles pitch to an extent. In many cases, tetralin has which has the state-of-the-art technology achieved extremely low emission values, been used as a hydrogen donor solvent in order to increase the yield of soluble coal 25ppm of SOx and 0.8mg/Nm3 of dust concentration at the absorber outlet. To meet chemical. In addition, partial extractions without a donor solvent have been performed both demands for reducing construction cost and high performance in recent years, IHI using n-methyl pyrrolidone (NMP) as a solvent. Materials obtained in these processes adopted a single absorber for the mixed-ash process based on the simultaneous have been shown to meet specifications for anodes. However, a remaining issue is desulfurization method which combined a rectangular absorber with non-leakage Gas- whether economics are acceptable for introduction of such processes in industrial Gas Heater (GGH) and Low-Low temperature Electrostatic Precipitator (ESP). To settings. Two significant issues are solvent recovery and solvent costs. verify the performance of the rectangular absorber, the demonstration plant of 1/50 For these reasons, methods were sought to reduce solvent recovery requirements, to scale was constructed next to No.1 unit to utilize the real bypassed gas. The achieve lower material costs, and to incorporate more low-cost coal in order to produce demonstration test resulted in reduction in absorber volume by 50% for the real a synthetic binder pitch. This was accomplished using a low-cost petroleum refinery absorber for No.2 unit and reduction of the power consumption of the recycle pump by byproduct oil as a hydrogen donor solvent in place of methyl naphthalene or tetralin. It 20% compared with No.1 unit. This paper introduces the design characteristics of this was recognized that if the solvent has a lower cost than the intended product, it is advanced FGD system and satisfactory operation results derived from the permissible to retain the solvent in the product and not recover it. Accordingly, commissioning for 10 months. solvents with a materials cost less than about half the price of binder pitch were sought (that is, solvents with a cost less than $150 per ton). Several candidates were 23-5 identified. A mild hydrogenation step was used to break up chemical bonds in the coal PAHs Removal from Hot Gas by Porous Absorbents and to improve the coal solubility such that over 80% of the coal became soluble, and Zheng-Yue Ma, Hao-kan Chen, Wen Li, Bao-qing Li resulting in a solvent/coal ratio of 2.5:1. Additional thermochemical processing may Chinese Academic of Sciences, China result in acceptable pitch properties even with zero solvent separation and recovery, suggesting that solvent recovery costs can be reduced or eliminated. The aim of this paper is to investigate the abatement of polycyclic aromatic hydrocarbons (PAHs) model compounds including Napthalene (Nap), Fluorene (Flu) 24-3 and Phe- nanthrene (Phe) by using different porous materials as absorbents. The Applications of Carbon Foam Structures adsorption of these compounds was carried out at a laboratory scale in an experimental Felix D. Mallette and Craig Hannah rig designed for this purpose, where FID is used for detection. Experimental Quantex Materials Inc., Canada conditions, mainly in terms of adsorbing temperature and PAH concentration, close to Alfred H. Stiller and Lloyd J. Ford those observed in flue gases from energy generation systems were applied. The PAH West Virginia University, USA adsorption process was analyzed by means of experimentally obtained breakthrough curves. After the detection parameters had been optimized, the influence of the Carbon foam can be inexpensively produced using inexpensive coal-derived absorbents structures and SO2 CO2 in hot gas was studied. It is concluded that (1) The feedstocks such as coal tar pitch, coal extracts or even treated pulverized coal, using a BET surface area and micropore volume are determinant parameters for these PAHs controlled coking process. Among the attributes of carbon foam are its low density, removal when each variable is considered alone, and while these two variables are high energy absorption upon crushing, and excellent flame resistance. These considered together, the good partial-correlation and multi-correlation exist among the properties make carbon foam of interest for, among other applications, impact adsorption capacity, the BET surface area and micropore volume. Furthermore, no resistance, blast protection, fire protection, thermal insulation and structural relationship is found between PAHs adsorption capacity and mesopore volume; (2) reinforcement. Different reinforcement strategies can be considered for these The adsorption of three model compounds by absorbents from hot gas is inversely applications, including the use of material reinforcements such as carbon fiber to proportional to their volatility. The lower the PAH volatility is, the higher the increase strength and modulus, particularly in tensile and flexural modes. A second adsorption capacity is; (3) Adsorption isotherms show that adsorption behavior of AC- method to enhance the ability of carbon foam to act as a structural reinforcement is the 1 is suitable to Langmuir adsorption isotherm equation. (4) When the use of sheet reinforcements to create trilayers to distribute mechanical loads. Trilayers SO2(3000~5000ppm)/CO2(20~30% of carrier) was added into the reaction system, the can be fabricated using metals such as steel or aluminum, or fibrous materials such as adsorption capacities of absorbents was depressed considerably. fiberglass, Kevlar(R) or carbon cloth, depending on the intended application. Another key technology is the joining of carbon foam to dissimilar materials within the trilayer SESSION 24 itself, as well as joining the trilayered structures to other structures. For these purposes, NON-FUEL UTILIZATION OF COAL: 1 a variety of sealants and adhesives can be considered for joining the components of the 24-1 trilayer, including coal tar enamel. The result is a lightweight structural material with New Advances in the Development of Premium Carbon Products from Coal unique properties and attributes. John M. Andrésen Pennsylvania State University, USA John Stipanovich US DOE, NETL, USA 23

24-4 conductivity of dilution gas, and when the thermal conductivity of atmosphere gas Carbon Nanofiber Synthesis from High Sulfur Coal becomes low, ignition delay seems to increase. Takashi Yanagisawa GSI Creos Corporation, Japan 25-2 Max L. Lake Distribution of Trace Elements in Solid Emissions from AFB-FAR Combustion of Applied Sciences Inc., USA Lignite and Synthetic Fuel Sýkorová Ivana and Vašíček Michal Carbon nanofibers (CNF) are graphitic hollow filaments approximately 100 nm in Institute of Rock Structure and Mechanics AS CR, Czech Republic diameter consisting of nested graphene planes. CNF are the subject of much research Smolík Jiří, Schwarz Jaroslaw and Džumbová Lucie and development as an engineering material for the 21st century, for use in engineered Institute of Chemical Process Fundamentals AS CR, Czech Republic polymers, power components, and novel medical therapy. CNF are created by the Havránek Vladimír and Kučera Jan pyrolysis of hydrocarbon gases in the presence of a metallic catalyst. Coal derivatives Nuclear Physic Institute AC SR, Czech Republic are of particular interest in synthesizing carbon nanofibers for four main reasons. First, gasified coal results in the generation of hydrocarbon gas, which is conducive to In this work the influence of mineral matter on trace elements partitioning during nanofiber synthesis. Second, gasified coal is a less expensive source of carbon than Atmospheric Fluidized Bed Combustion with fly ash recirculation (AFB-FAR) of natural gas or other potential feedstocks. Third, gasified coal can be a supply of low- lignite containing 15.4 % of ash and synthetic solid fuel with 1.2 % Ad was cost catalysts in the form of hydrogen sulfide and organometallics. Fourth, coal investigated. Synthetic solid fuel (SF) was prepared from the soot CHEZACARB gasification can generate solid phase materials such as fly ash, which is traditionally (Chemopetrol Litvínov, Czech Republic) and bitumen emulsion KATEBIT T40 used as a reinforcement material. The concept of co-generation of power as well as (Paramo Pardubice, Czech Republic) was used as a binder. The fuel was enriched with reinforcement materials with coal derivatives becomes realistic for use of CNF in some trace elements at concentrations typical for the Czech lignites (Bouška and infrastructures. Prospects for gasification power plants to co-generate both electric Pešek, 1999). In addition, pure alumina, titania, silica, and limestone were used as power as well as carbon nanofibers at commodity prices are discussed. mineral admixtures. The experiments were performed using 100 kW AFCB boiler with sand as a material 24-5 of the bed. The samples of solid residues discharged from one experiment included Advanced Flue Gas Treatment by Novel DE-SOx Technology over Active Carbon bottom ash, coarse fly ash from cyclones, and fine fly ashes separated by BLPI Fibers impactor. The lignite sample and 5 types of granulated synthetic fuel (one without Masaaki Yoshikawa mineral admixtures and four with one of the mineral admixtures (CaCO3, SiO2, TiO2, Osaka Gas Co., Ltd., Japan Al2O3) were investigated. The solid output streams from the combustion experiments Akinori Yasutake were analyzed by fuel analysis methods, INAA, PIXE and AAS methods, and by Mitsubishi Heavy Industries, Ltd., Japan optical and scan electron methods. Isao Mochida The differences in chemical composition and morphology were observed between Kyushu University, Japan bottom ashes and fly ashes from combustion of both lignite and synthetic fuel. During combustion of lignite bottom ash enriched in Fe and Mn was produced. Chromium and There is worldwide and increasingly the discharge of the sulfur dioxide with the use of nickel was uniformly distributed between all ashes. In all cases the trace elements fossil fuel. Especially, the discharge in the Asia region has increased recently, but the were depleted in the bottom ash from combustion of synthetic fuel. The highest environment countermeasure has been retarded for the problem of economical concentrations of trace elements were found in fly ashes collected in cyclone and BLPI efficiency. Though in the advanced nation, the limestone gypsum method is mainly impactor. A substantial enrichment in fly ashes was observed for As, Co, Cu, Hg, Sb, used as flue gas de-SOx facilities, which cost very expensive in both initial and V, and Zn. The AAS analyses of input and output streams revealed that during the running. combustion experiments of lignite and synthetic solid fuel with CaCO3 about 95% of On the other hand, it becomes obvious that SOx in flue gas can be removed at room Hg left the system. The remaining Hg was distributed in fly ashes. The detailed temperature by using pitch-based Active Carbon Fibers (ACF) subjected to surface distribution of partially hazardous trace elements in solid output streams from AFB- treatment such as high temperature heat treatment. The flue gas treatment technology FAR of lignite and synthetic solid fuel is discussed. using ACF is a semidry oxidation type de-SOx method that is effective without regeneration of itself. In addition, this technology enables by-products such as sulfuric 25-3 acid and various sulfates to be recovered, and is applicable in the field of flue gas The Influence of Volatile Matter Content on Emisions of Coal treatment to which the conventional de-SOx method, such as the limestone gypsum G. Önal, M. Özer, F. Boylu and O. Kural method, could not be applied for economical reasons. Istanbul Technical University, Turkey I. Mustafaev SESSION 25 Azerbaijan Academy of Science, Turkey COMBUSTION TECHNOLOGIES: 5 25-1 In this study, the effect of volatile matter on emissions was investigated. Eight coal Mechanism of Ignition Delay in O2/CO2 Pulverized Coal Combustion samples with volatile matter contents ranged from 1.14 % to 46.36 % and laboratory Akio Yamamoto, Toshiyuki Suda and Ken Okazaki scale stove equipped with heat sensors on the smoke hole were used. Before the Tokyo Institute of Technology, Japan combustion tests, the moisture contents of the coals were reduced to their equilibrium moisture and the particle sizes of the coals were fixed to –13+4 mm for standard heat Coal combustion with O2/CO2 is promising because of its easy CO2 recovery, radiation. The fluid gas on out as point of the combustion test facility were directed to extremely low NOx emission and high desulphurization efficiency. However, it turns gas chromatography to analyze the emissions. According to the results of the study, the out that combustion behavior of coal becomes worse when this technique is applied volatile matter content has no effect on the fluid gas emissions and the fluid gas to a conventional pulverized coal burner. In this study, ignition delay of coal particle emissions are controlled by the properties of coals such as chemical structure, macerals is measured using the Drop Tube Furnace (DTF). Comparison for the ignition and geological age. But the volatile matter contents effected the particle emissions behavior has been made for different dilution gas, furnace temperature and coal type although there is no correlation between gas emission concentration and volatile to see the effect of physical properties of gas and volatile matter in the coal. matter. In conclusion, the coals with volatile matter contents lower than 20 % and In the experiment, an electrically heated DTF with 690 mm height and 35mm volatile mater contents higher than 30 % give low particle emissions on combustion. diameter has been used. A water-cooled probe with an ignition detector was inserted The volatile matter content between 20 - 30 % was found to be critical for particle and traversed from the lower part of DTF and was used to detect the ignition point. emissions. Ignition distance was judged from the rise of luminosity. Bituminous and anthracite coal whose average particle size is 40µm are fed into the top of furnace at the feed 25-4 rate of 0.1 g/min. Furnace was heated up to 1023, 1223, 1423 K. Air, O2-CO2 CCSEM Characterization on the Chemical Species in PM10 Emitted from Various mixtures and O2-rare gas mixtures have been used for the combustion gas. Combustion Sources Results show that ignition delay becomes shorter when oxygen concentration or Liang Zhang and Yoshihiko Ninomiya furnace temperature are high and with high volatilized coal. And from the results, it is Chubu University, Japan revealed that ignition delay in O2/CO2 gas is larger than that in O2/N2 gas (air). The difference of ignition behavior in CO2 dilution gas becomes clear when low volatile Particulate matters (PM), emitted from various combustion sources, were characterized coal is used. In order to clarify the effect of physical property of gas on ignition delay, by computer controlled SEM (CCSEM) to identify the chemical species within its He, Ar, N2, Kr and CO2 have been used as a dilution gas with fixed oxygen different sizes. Three cases, combustion of single coal, single sludge and their mixture concentration (20 %). It is clarified that large ignition delay in CO2 dilution gas is were studied. PM in the existing gas was first size-segregated by low-presssure- mainly due to the high heat capacity of CO2 gas. The difference of ignition delay can impactor (LPI). Secondly, three sizes of carbon plate-collected PM, 2.5, 0.33 and be arranged with the ratio of the heat capacity of coal particle and the thermal 0.06µm, were subjected to CCSEM analysis. The magnification of ×800 was used for PM of 2.5µm, whereas ×2000 was used for the latter two sizes. The analysis 24

preciseness of CCSEM was primarily examined by comparing its analysis result with almost identical; indicating that deactivation of the sorbent during the absorption- that of XRF analysis. The results indicate that, in the viewpoint of elemental regeneration cycles is negligible. The sorbents are considered to be satisfactorily used composition, CCSEM analysis on each size of PM is in fairly good consistence with for hot gas desulfurization process of the IGFC of next generation as well as advanced that of XRF analysis. In addition, both the elemental composition of PM and the IGCC plant equipped with high temperature gas turbine, based on the operation data of species within it vary greatly with its size and the fuel type. Aluminosilicate and its 200t/d IGCC pilot plant at Nakoso, Japan. An IGFC system of high thermal efficiency salts containing the refractory elements such as calcium and iron dominate the largest (53-55%, net, HHV) by use of a hot gas cleanup process has been conceptually particle of 2.5µm. With PM size down to 0.33µm, both the refractory and vaporized designed based on the data of this study and Nakoso pilot plant. alkali elements dominate it, and they have the comparable content in this size. The chemical forms are mainly of aluminosilicate salts containing calcium, iron and vaporized alkali elements. On the contrary, in the smallest PM of 0.06µm, the 26-3 compounds containing vaporized alkali/zinc/silica elements and Warm-Gas Desulfurization Process for ChevronTexaco Quench Gasifier Syngas sulfur/phosphate/chlorine dominate, whereas the aluminosilicate disappears. Co- Santosh Gangwal, Brian Turk, David Coker, Gary Howe and Raghubir Gupta combustion greatly affects the distribution of individual element and the species within Center for Energy Technology, USA differently sized PM. The results suggest the strong nteraction between the refractory Raj Kamarthi and Tom Leininger elements of two fuels and hence, the size of PM shifted to the greater value. ChevronTexaco, USA Furthermore, more the sludge combustion-derived vaporized alkali and trace elements Suresh Jain reacted with the coal combustion-derived evolved sulfur and chlorine to form the US DOE, USA gaseous species, which condensed into the ultrafine particulates smaller than 0.1µm. ChevronTexaco’s innovative high efficiency quench gasifier produces a medium SESSION 26 BTU syngas that is essentially free from all contaminants except sulfur gases (H2S GASIFICATION ADVANCED TECHNOLOGIES 1: CONVENTIONAL and COS), ammonia, and traces of mercury. Several modular gas cleanup processes & ADVANCED SYNTHESIS GAS CLEANUP are being developed to specifically target these contaminants by a research team including RTI, ChevronTexaco (CVX), KBR, SRI International, and Süd-Chemie, 26-1 Inc. This paper describes the progress with installation, commissioning and testing of Flex-Fuel Testing of the Ultra-Clean Process for the Control of Sulfur, Halide, RTI’s warm-gas desulfurization (WGD) process using a slipstream of syngas from and Mercury Compounds in Coal Gasification Gases CVX’s three ton coal per day research gasifier at Montebello, California. A transport Francis S. Lau, James Aderhold, Rachid B. Slimane, and Michael J. Roberts reactor system (16ft x 16ft x 80 ft) was installed and commissioned in March 2004 at Gas Technology Institute, USA Montebello. 300 lbs of RTI’s attrition resistant RTI-3 zinc oxide-based sorbent was Richard A. Newby and Harry Morehead loaded in the system for testing. The circulation of the sorbent was initially Siemens Westinghouse Power Corporation, USA established using nitrogen. The system consisted of two coupled circulating Suresh C. Jain fluidized-bed reactors for the desulfurizer and the regenerator. The sorbent was US DOE, NETL, USA circulated at about 1600 lb/h in the desulfurizer loop. Approximately 25% of the sorbent was transferred to the regenerator loop and back to the desulfurizer. Nitrogen The Siemens Westinghouse Power Corporation (SWPC) and the Gas Technology was replaced with syngas from the CVX gasifier containing about 8000 ppmv of Institute (GTI) are developing a novel “Ultra-Clean” process to control sulfur species, H2S and 200 ppmv of COS on a dry basis. The process was operated at 600 psig and halides, mercury, and particulates in syngases generated through gasification of 700oF with 10,000 scfh of syngas. The sorbent removed the gaseous sulfur carbonaceous feedstocks to meet very stringent cleaning requirements for chemical or compounds to 1 ppmv. Laboratory tests of sorbent after more than 50 hours of liquid fuel synthesis applications, or for fuel cell power generation. The Ultra-Clean circulation showed no decrease in its attrition resistance and its reactivity. CVX Process is a dry process in which fine sulfur, halide, and mercury sorbent particles are recently made a business decision to close down the Montebello facility. The testing injected into two stages of "barrier filter-reactors", coupling efficient particle capture was thus suspended in April 2004. RTI is actively pursuing the installation of the with an effective entrained and filter cake reaction environment. The process WGD process at another host site. The plan is to run several long-term tests (500 h) performance goal is to remove sulfur species to less than 60 ppbv, halides to less than to demonstrate the long-term performance of this process, including the dual loop 10 ppbv, mercury to less than 0.01 ppbv (or > 99% removal), and particulates to less circulating fluidized-bed system as well as RTI-3 sorbent. than 0.1 ppmw. Preferred operating conditions (temperature, sorbent materials, sorbent/contaminant ratios, etc.) have been estimated based on extensive laboratory work and conceptual performance evaluations. Extensive commercial process 26-4 evaluations have shown the technical feasibility and commercial merit for the Ultra- Investigations of Mercury Speciation under Gasification Conditions Clean Process compared to conventional, Rectisol-based syngas cleaning. Dennis Y. Lu, David L. Granatstein, Robin W. Hughes and Edward J. Anthony Based on the encouraging laboratory-scale test results as well as technical and CANMET Energy Technology Centre, Canada economic feasibility studies, SWPC/GTI are now conducting a bench-scale demonstration of the Ultra-Clean Process performance, using a newly constructed GTI Mercury (Hg) is the toxic trace metal of greatest concern in coal utilization because “FlexFuel” gasifier capable of handling 10 tons/day of coal. This paper describes the of its volatility, persistence, potential for bioaccumulation in the environment, and its test facility, scope and approach of testing activities, sampling and analytical high neurodevelopmental toxicity. The global atmospheric background level of measurement procedures, and the available experimental results. Test results will be mercury increases if the mercury is emitted in an elemental form whereas oxidized discussed in conjunction with commercial process evaluations. species will be deposited near their sources due to their high solubility in water and scrubbing by atmospheric processes. The identification and quantification of 26-2 individual physicochemical forms of Hg are, therefore, imperative in addressing Development of High Efficiency Hot-Gas Cleanup Technology for Integrated questions concerning atmospheric fate and emissions control. Unfortunately, there is Coal Gasification Fuel Cell Combined Cycle (IGFC) System a lack of information available on Hg emissions and speciation under gasification Michihiro Ishimori, Kouichiro Furusawa, Tetsuji Suzuki and Masafumi Katsuta conditions, which are substantially different from those seen from combustion. The Waseda University, Japan current authors investigated Hg speciation via gas-phase and heterogeneous reactions using simulated synthesis gas from coal gasification at varying temperatures. The In relation with recent global environment issues, development of the highly efficient results indicated that typical syngas constituents, including CO, CO2, HCl, Cl2, gas cleanup system for coal gasification is considered to be increasingly of importance. NH3, HCN, COS and H2S, do not promote Hg oxidation via gas-phase reactions and Integrated Coal Gasification Fuel Cell Combined Cycle (IGFC) system consisting of a that coal-Hg will be emitted in its elemental form under gasification conditions. gasifier, molten carbonate fuel cells (MCFC), gas turbine, and steam turbine has been Significant Hg oxidation was only observed in the presence of fly ash. This paper recognized as one of the most superior power technologies for next generation, also compares these results from the bench-scale tests with synthetic flue gases, with although development status of MCFC has not yet been satisfactory. In order to realize data obtained on mercury speciation chemistry using CANMET’s new pilot-scale the highly effective coal gasification power plants, development of hot-gas cleanup gasification plant. The entrained flow gasifier operates at pressures of 1.5 MPa and system, especially highly efficient desulfurization technology for hot coal gas is temperatures around 1400ºC and in these tests was used to gasifiy selected required. feedstocks of interest to the Canadian Clean Power Coalition (CCPC), including, In continuing our studies of zinc ferrite and related compounds as desulfurization eastern bituminous coals, western sub-bituminous coal, Saskatchewan lignite, and agents, we have found several excellent sorbents for hot reductive gas such as coal gas petroleum coke.

produced by an entrained-flow gasifier. The performance tests of the sorbents were carried out at a fixed-bed type bench-scale reactor, using simple reductive gas containing H2S and/or related gas. Some sorbents composed of zinc ferrite and transition metal oxides were found to show excellent desulfurization performance; concentration of H2S involved in the reductive gas was decreased from 1000 ppmv to less than 100-50 ppbv. Sorbent regeneration after sulfidation was carried out by oxidation. The feature of H2S breakthrough curves is that all breakthrough profiles are 25

26-5 27-3 A Sodium Speciation Model for Hot-Gas Cleanup Systems Demonstration of UBC Process in Indonesia – Upgrading of Low-Rank Coal Peter Gioko and Heng Ban Yasuo Otaka and Hajime Endo University of Alabama at Birmingham, USA JCOAL, Japan Tom Gale Tetsuya Deguchi and Takuo Shigehisa Southern Research Institute, USA Kobe Steel, Ltd., Japan

Advanced power system development relies heavily on successful development of hot- Half of the world’s coal resources are so-called low-rank coal such as lignite (brown gas cleanup systems. Advanced Integrated Gasification Combined Cycle (IGCC) coal), sub-bituminous coal. Such coal still remains to be local energy sources, because systems for example, require very sophisticated high-temperature filtering devices (i.e., it has low heat value and high propensity of spontaneous combustion. Some of low- ceramic candle filters) to remove particulate and other harmful gas species from the rank coals have advantages as clean coal; i.e. low ash and low sulfur content. syngas before feeding the high quality syngas to a gas turbine. However, there are still The UBC (Upgraded Brown Coal) process is a new technology to refine low-rank coal significant problems to resolve in the hot gas cleanup systems. Candle filter systems up to transportable solid fuel with high heat value and less spontaneous combustion for example, have a difficulty with bridging of between candles, which causes a propensity. This process removes coal moisture in the oil phase, so that heavy oil premature shutdown of the facility. Candle filters also suffer from candle breakage fraction is adsorbed on the internal surfaces of coal pores. This oil coating makes UBC problems, tar plugging problems, and leaks. There is another serious concern for these product not only stable but also re-wetting free. hot-gas cleanup systems. Thermodynamic predictions of all major metal species in Various coals, so as Australian and Indonesian low rank coal, were tested by syngas are predicted to condense prior to the particulate control device (PCD). Autoclave and Bench Scale Unit and the process application to Indonesian low rank However, even at the low temperatures that hot-gas filters currently operate, coal was proved to be most feasible. Demonstration plant with capacity of 5 tons/day is measurable metal and tar concentrations (sodium, various organics, and even iron) are now operated in Indonesia, expecting near future commercialization in order to utilize found well downstream of the PCD. These concentrations are often too large to allow abundant LRC of clean property. into the gas turbine, because they will quickly destroy the turbine blades. Of particular concern is sodium, which is in high concentration in gasifier fuels, is the most volatile 27-4 of major metal species in the syngas, and is highly corrosive. Upgrading by Kobe University Process and Control of Spontaneous Combustion The purpose of this project was to begin the development of a syngas speciation of Low Rank Coals model, capable of predicting the syngas composition at the PCD, based on the H. Usui complete syngas composition at the exit of the gasifier. Minor syngas components at Kobe University, Japan the gasifier exit were of significant interest, since these minor components may be Mahidin responsible for the trace sodium or other species passing the PCD. The initial Syiah University, Indonesia development of the speciation model was focused particularly on sodium, with D. F. Umar particular emphasis on determining why the sodium escapes the PCD in hot-gas DR&D Centre for Mineral and Coal Technology, Indonesia cleanup systems. Thermodynamic predictions of sodium speciation were made using CEA, a multi- The new upgrading method for low rank coals by a combined process of vacuum component thermochemical equilibrium code. This code along with the latest version drying and tar coating has been developed. A lignite coal from Indonesia has been of the thermodynamic library was used in this study. ChemKin, a software package treated. The raw and upgraded coals then subjected to several analyses for that contains the hundreds of auxiliary reaction equations needed to couple with the characterizing the properties, spontaneous combustion and combustion characteristics, desired syngas speciation model, was used as the frame work for the model and kinetic parameters of low-temperature oxidation. Based on those experimental development. The kinetic model used available data and was built to describe the results, it is finally concluded that this upgrading technique is promising to produce the change of gas composition across the temperature/time history to the front of the PCD. upgraded coals comparable to a bituminous coal and the surface of coals can be Thermodynamic predictions of the syngas composition ahead of the PCD were effectively coated in order to prevent the self-heating and spontaneous combustion. compared with the kinetic model predictions. For the purposes of the model, the conditions existing in Gas Technology Institute’s RENUGAS biomass gasifier should 27-5 be used to describe the parametric environment (i.e., temperatures, pressures, gas Lignite Water Characterization by Phase Transition – Differential Scanning compositions, residence times, etc.). Calorimetry Yi Fei, Alan Chaffee, Marc Marshall and W. Roy Jackson Monash University, Australia SESSION 27 LOW RANK COAL UTILIZATION: 1 We are investigating the nature of lignite-water interactions through the correlation of 27-1 water adsorption behaviour and measured features of their chemical and physical Strategic Planning Of Low Rank Coal Utilization In Indonesia structure. Wimpy S. Tjetjep It is postulated that the extent of the interaction with the most strongly bound water Ministry of Energy and Mineral Resources, Republic of Indonesia depends on the quantity and acid strength of carboxylic functional groups as well as the extent and nature of any cations exchanged at the sites of these functional group. Indonesia has proved herself to be a reliable and secure source of coal for the world To test this hypothesis, samples were chosen from the Latrobe Valley lignite seams to users. Coal resources are reported to be about 57.8 billion tonnes, of which measured include a range of lithotypes with varying cation content. Raw lignite samples were reserves amount to 6.98 billion tonnes. However, the majority of the coal (about washed with water or dilute acid and the three states of lignite (raw, water washed and 60%) is younger Tertiary in age and low in rank (LRC) with high moisture contents. acid washed) were provided for further investigation. Acid washed lignite samples This part of the resource basically is still under-utilized. Most of the coal currently were also subsequently exchanged with Na, Mg, Ca, Al and Fe to various levels. exploited is medium to high rank coals. However, future production will inevitably Equilibrium moisture contents were determined as a function of water partial pressure move towards the LRC, as resources of medium to high rank coals are depleted and through the use of dessicators and/or an automated dosing instrument known as the become more expensive to exploit. IGA (Intelligent Gravimetric Analyser). LRC should be used close to mine site due to its low calorific value, high moisture Results show that the concentration of carboxylic functional groups and the extent of content and low thermal efficiency. Upgrading LRC to products similar to high rank cation exchange do both significantly affect the amount of adsorbed water (in the coal (HRC) offers one of the best solutions of LRC utilization. The benefit of LRC partial pressure range 0.11-0.92). The relationship between equilibrium moisture upgrading includes increased value per tonne, both for export and domestic markets content and functional group/cation concentration can be used to help identify the type and stabilized coal quality feed for power generation and other industries. Indonesia of water (e.g., monolayer, multilayer, bulk water) in the lignite. under cooperation with JCOAL, Japan has successfully developed the UBC process to upgrade LRC into HRC of up to 6800 kcal/kg. Mine mouth power plant is the next SESSION 28 priority for the use of LRC, but this requires construction of long transportation lines INTERNATIONAL COAL TECHNOLOGY COOPERATION: 1 to transmit the energy generated to centers of demand. The conversion of LRC into 28-1 liquid and gaseous products is likely to become an important use for LRC in the Clean Coal Technology Development Strategy in Japan future. Michiaki Harada With the development of coal upgrading, mine mouth power plant and conversion Center for Coal Utilization, Japan technologies, LRC can be utilized in the future in a manner similar to current uses of HRC. Therefore, the utilization of LRC has to be encouraged in order to secure Coal has crucial importance as a primary energy resource in 21st century because coal national coal supply. Clean Coal Technology can be implemented in order to prevent is reserved enormously and distributed in worldwide. As Japan imports most of coal environmental pollution. and coal demand in Japan has increased in recent years, it is important to develop advanced CCT (Clean Coal Technology) in which coal is used more efficiently and environmental issues are few generated. In order to ensure more effective use of coal 26

while searching for solution to global environmental problems, various approaches of coal utilization in industry. Therefore, there will be a close mutual relationship should be tried. As desirable steps to accomplish these approaches, high-efficiency between the CTC and the industrial sector. coal use technology should be developed; nearly zero-emission from coal using systems should be realized. Although much effort has been made to achieve CCTs, 28-4 from now on we should take up a comprehensive theme where CO2 reduction takes the The U.S. Geological Survey’s International Coal Activities highest priority. The CCTs are required to ensure a wide-ranged reduction in CO2 Brenda Pierce, Susan Tewalt, Peter Warwick and Robert B. Finkelman emission. From the standpoint of considering global environment problems, the U.S. Geological Survey, USA development of CCT is urged in order to use coal 'effectively,' 'cleanly,' and 'carefully.' In other words, projects should emphasize developments of environment-conscious The U.S. Geological Survey (USGS) has long recognized the importance of coal utilization technologies and their worldwide promotion. This paper shows a international cooperation in coal science and technology. For the past several decades strategy for the first 30 years of the 21st century of CCT development for zero the USGS has engaged in a geographically and scientifically diverse program of emissions in Japan. Assuming that we will enter a hydrogen energy era in 2020-2030, international coal activities. These activities include the current World Coal Quality and taking into consideration the current development and diffusion of fuel cell power Inventory (WoCQI) a multinational cooperative effort to create the first unified global generation, fuel cell vehicles and coal quality database. To date, sixty countries have shared samples of coal and other hydrogen gas turbine combined cycle power generation, it is necessary to pursue such solid fuels, information, and digital maps. The USGS is providing coordination, a possibility which allows “CO2 free” energy power generation by means of coal comprehensive analyses of the samples, construction of an electronic database, and gasification, coal based CO2 recovery type hydrogen producing technology to become collaboration in making the information available to the public in print, digitally on melted into a new business category which could be called the Coal-based Energy & CDs, and on the Internet. Chemicals Integrated Center in combining power station, chemical industry, iron & Most of the USGS international activities are supported financially by third parties. steel industry and other business sectors. Among these activities are a proposed coal and environmental health research center in southern China. One of the primary objectives of the proposed center will be to 28-2 minimize or eliminate the heath problems caused by domestic use of mineralized coal Development Strategies for Clean Coal Technology in China that affects millions of people in the region. The USGS is also engaged in collaborative Yin Wu studies of health problems that may be caused by coal in Romania, the former National Development and Reform Commission, P.R. China Yugoslavia, and Bulgaria and on the mobilization of mercury and arsenic from coal Jerald J. Fletcher and Qingyun Sun use in Ukraine. USGS scientists have collaborated with scientists from other countries West Virginia University, USA including Chile, Hungary, and South Korea to evaluate coal bed methane potential and have conducted coal exploration and characterization projects in Pakistan, Poland, the China is now the world’s largest producer and consumer of coal. Economic growth former Yugoslavia, India, Armenia, Kyrgyzstan, and currently in Afghanistan. The demands more energy to fuel continued expansion. Although coal production reached a U.S. Department of State is supporting a USGS scientist to spend three months in historic high of 1.74 billion metric tons in 2003, many provinces experienced severe South Africa to work with the South African coal technology community and coal shortages of both coal and electric power. At the same time, pollution from coal education communities. The USGS and Russia have recently signed an agreement to mining and coal utilization has become a major topic of public concern. In an effort to cooperate on coal characterization and to evaluate Russian coal quality and assess its find a path toward sustainable development and solve the current energy shortage, technologic impacts, economic byproduct recovery potential and environmental and China is seeking to reform the structure of the coal industry, improve coal utilization health impacts. Education and training are important aspects of the USGS international efficiency, and enhance clean coal technology. Coal is the primary energy resource in coal activities. The USGS has offered workshops, short courses, and lectures on a wide China, so clean coal technology is a critical component of economic growth while range of coal science and technology in many of the world’s coal-producing countries. protecting environmental quality. This paper discusses possible alternatives that During the past several years, coal scientists from several countries have worked for China’s National Development and Reform Commission may use to increase several weeks to six months at USGS facilities in Reston and Denver conducting utilization of clean coal technology. A summary of current coal production and collaborative field and laboratory studies. The USGS welcomes inquiries concerning utilization is presented as well as potential scenarios for future development. mutually beneficial international coal cooperation.

28-3 28-5 Development of Coal Tecnology Centre Obstacles and Path for Wide Acceptance of CCT in Korea At Palimanan - Cirebon, West Jawa Indonesia Yongseung Yun Bukin Daulay Institute for Advanced Engineering, Korea R&D Centre for Mineral & Coal Technology, Indonesia Korea has a long-term plan to construct and operate CCT plants of 300 MW scale. The Coal has the potential to be a major future energy source in Indonesia due to it large plan in installing CCT plants has been rescheduled twice from three plants of 300 MW resource base, easy and low cost of exploitation, and the existence of transportation by 2007, 2013, 2014 to one CCT plant by 2009 according to the schedule published in facilities. Although more than 65% of identified reserves are of low rank coals, the 2002. Technological and economical obstacles should be cleared before wide quality is sufficient for a wide range of end uses. By contrast, oil reserves have been acceptance of CCT. Although many obstacles and uncertainties in economic and decreasing for a number of years, and historically, a large proportion of production has technical aspects are present, it appears imperative to utilize CCT in Korea because been exported to acquire foreign currency earnings. Korea imports 97% of energy and minimum 28-32% of electricity should come from Currently, domestic use of Indonesian coal is mainly limited to use by the power plant imported coal. With close cooperation on CCT among interest-sharing countries and and cement industries. Small amounts of coal are also used for some small scale private sector would enhance the possibility in actual CCT implementation of industries. In order to optimize the utilization of coal in terms both of efficient and commercial scale in Korea. appropriate uses, coal utilization technology should be fully mastered. Since 1980’s tekMIRA has conducted research on several coal utilization technologies on the SESSION 29 laboratory scale. However, before this technology is applied to commercial scale, the ENVIRONMENTAL CONTROL TECHNOLOGY 5: MERCURY research should be developed and scaled up to a pilot plant or demonstration scale. The 29-1 development of pilot plant or demonstration plant could be simulated closely to the Partitioning and Control of Trace Metals during Coal and Waste Combustion actual commercial scale operation. Through this activity, risks of failures can be Jost O.L. Wendt minimized in scaling up to commercial scale. University of Arizona, USA Based on the above considerations, tekMIRA wishes to establish a Coal Technology Centre (CTC) at Palimanan, Cirebon Indonesia. At this location, a demonstration plant This paper reviews recent work directed towards mechanisms of interaction between of biobriquette with 5 tonnes/hour capacity and a pilot plant of upgraded brown coal trace and toxic metals and alumino-silicates, calcium products and similarly based (UBC) of 5 tonnes/day capacity have been established. These two projects are substrates. Reactive scavenging processes such as these play dominant roles in developed under cooperation between the Government of Indonesia and Japan. Several determining the partitioning of trace metals during coal and biomass combustion, and pilot plants or demonstration plants are planned to be developed in this CTC, including in development of sorbents for the control of toxic metals (As, Se, Sb, Pb, Cd, Hg) coal gasifier, formed coke, recycling of waste lubricating oil using low rank coal as an during waste combustion. absorbent, coal combustion for small industries, coal liquefaction and activated carbon. Tests on a 17kW laboratory downfired combustor allowed partitioning mechanisms The establishment of the CTC at Palimanan, Indonesia should be fully supported by during coal combustion to be determined. A suite of six different coals was burned Indonesian Coal Stake Holder and overseas research and technology institutions under aerodynamically well defined, but practical conditions with no external heating. through technical cooperation agreements. Temperature histories, particle and gas concentrations were similar to those in coal- The function of the CTC is to become the central driving force for the introduction and fired boilers. Particles were extracted through an isokinetic, dilution probe, which innovation of coal utilization technology, and to be a seeding program facility in the delivered the samples to a Berner Low Pressure Impactor (LPI). The LPI allowed enhancing of coal utilization technology and demonstration in the field of coal particle segregation down to 0.03µm. Particles collected in the ultrafine particle size utilization technology. The establishment of CTC could speed up the implementation mode represented material that was vapor or had just nucleated at the sampling point. 27

Mechanisms between metals and other constituents were inferred from associations This paper reports work performed to investigate the feasibility of affecting mercury between elements in each particle size class. This was supported by special tests in emissions from coal-fired plants by manipulating boiler control settings. A theoretical which additives, such as Ca, Fe, S or even As were added to coals in which these model was developed to analyze the effect of thermo-chemical conditions, elements were low. Reactions between trace metals and sorbents were investigated by representative of coal-fire power plant exhaust gases, on the mercury fate, in relation to injecting aqueous or organic metal forms into a gas flame, with sorbent injection in the boiler control settings. Full-scale testing was performed at two units. One of the units, post flame region, and samples withdrawn above the metal dewpoint. equipped with a train than includes a rotative air preheater followed by two In coals, As and Se react with, and track, calcium, provided this is present in sufficient electrostatic precipitators in series. The other unit, equipped with hot and cold quantities. Otherwise, they react with Fe, unless much sulfur is present, in which case precipitators and a tubular air preheater. A strategy for mercury control by selectively the gaseous oxides are emitted. Sb can also form an oxy-ion and be bound on Ca and manipulating boiler control settings, if used in combination with other control Fe. Alternatively it is released as ultrafine particulate, or maybe gaseous, chloride, measures such as sorbent injection, will provide a relatively inexpensive option for depending on coal composition. Na, Pb, and Cs react rapidly with alumino-silicates, mercury control. but less rapidly on lime. Cd reacts very rapidly on lime and alumina, but less rapidly on alumino-silicates. These reactions were exploited to capture Na, Pb, Cs and Cd 29-5 from waste combustion, and the pertinent mechanisms of interaction with kaolinite are Review of Advanced FGD Technologies and Associated Co-Benefits now well understood, and have been quantified, for both single and multiple metals. Wojciech Jozewicz Finally, recent bench scale and pilot scale work on Hg sorption have shown that both ARCADIS, USA Hg0, and Hg++, can be chemisorbed at high temperatures on a sorbent containing both Scott M. Smouse kaolinite and calcium products, and derived from paper recycling wastes. US DOE, NETL, USA

29-3 This paper presents the review of advanced wet and dry flue gas desulfurization (FGD) Mercury Behavior in Flue Gas Control System with Sorbent technologies capable of providing control of pollutants other than SO2. Various Hiroshi Moritomi and Shinji Kambara technologies exist that have been designed to remove SO2 from flue gas produced by Gifu University, Japan electricity generating plants. However, more than 20 percent of coal-fired utility boiler Naoki Fujiwara, Yoshio Fujita and Katsumi Tomura capacity in the United States uses wet FGD systems to control SO2 emissions. Idemitsu Kosan Co. Ltd., Japan Therefore, wet FGD advances to increase the performance of existing once-through systems, enhance performance of new once-through wet FGD systems, and provide Toxic metals that are very harmful to health are also included in the coal combustion capability to control pollutants other than SO2, such as mercury and NOX, are of high flue gases and on ash particles that are discharged to the atmosphere. The mercury interest. In order to enhance the mercury capture by wet scrubbers, two different release behavior in bituminous coals, and the partitioning rate of mercury in solids and techniques could be considered: oxidation of elemental mercury prior to the wet FGD gaseous in flue gases have already measured. The rate of mercury partitioned into units and prevention of the reduction of dissolved oxidized mercury in the wet bottom ash in a bench-scale pulverized coal combustion furnace was a little and that scrubber solution. Wet FGD with upstream oxidation of NOX to higher oxides of into cyclone ash was low below 10%. The rest of the mercury was partitioned into nitrogen (such as in a LoTOx system) is capable of NOX control because these oxides mercury in gaseous form, but the rate partitioned into dust, oxidized mercury and are water soluble. elemental mercury varied slightly depending on the flue gas temperature and the type Dry FGD systems can also be designed to provide the co-benefit of mercury control. of coal. Therefore, in this study, the rate and behavior of the oxidized mercury and the Spray dryer systems, which are used on more than 10 percent of the total U.S. coal- elemental mercury were measured in the condition of adding sorbent as well as fired utility boiler capacity to control SO2 emissions, have demonstrated efficient different coal ashes. The kind of tested sorbent to capture the mercury were sixteen removal of oxidized mercury. Other dry FGD processes may also offer the co-benefit which were injected to make a thin bed on the filter. Experiments were carried out by of mercury removal. Advanced dry FGD has shown high mercury removal rates with using a small fixed bed of sorbent with mercury gas of 260 to 290µg/m3 to examine the lime sorbent. Other specialized sorbents offer the potential to capture more mercury. performance of mercury capture around 350 K and a flue gas duct of a bench-scale For example, testing of dry mineral sorbent in the Pahlman Process indicated above 99 pulverized coal combustion furnace of 42 mm ID and 1150 mm high to confirm the percent SO2, 93.6-96.6 percent NOX, and up to 67 percent mercury reduction in a performance to coal combustion gases around 450 K. In both experimental systems, a reactor, which operates at temperature between ambient and 160 oC. continuous mercury monitoring equipment was used. The concentrations of oxidized It is expected that this review will be useful to a broad audience, including individuals mercury and elemental mercury in gas and the total mercury in solid consisting of the responsible for developing and implementing SO2 control strategies at sources, persons sorbent and the coal ash were measured. involved in developing SO2 and other regulations, regulatory authorities implementing Consequently, activated carbon, fluidized bed combustion ash, wasted catalyst and SO2 control programs, and interested public at large. sorbents including sulfur or chlorine compound were effective to capture the mercury. However, the results by evaluating the partitioning of mercury in gas between oxidized SESSION 30 mercury and elemental mercury, showed that the element mercury captured by the NON-FUEL UTILIZATION OF COAL: 2 sorbent once was changed into the oxidized mercury though it depended on the kind of 30-1 sorbent and the gas condition. The capturing rate of oxidized mecury was signifcantly Overview of Chemicals and Materials from Coal and Coal-Derived Liquids lower than that of elemental mecury. It means that there is a trade-off relationship Chunshan Song, Harold H. Schobert and John M. Andresen between oxidized mercury and elemental mercury. Furthermore, to improve the Pennsylvania State University, USA performance of capturing mecury, it was very important to control the sorbent layer produced by filtering the fly ash and sorbent particulate. Chemicals and materials from coal have been recognized as an important area of continued research and development for future coal utilization. This review discusses 29-4 current status and future directions and presents an update from our first major review Impact of Boiler Operating Conditions on Mercury Emissions in Coal-Fired (C. Song and H. H. Schobert. Opportunities for Developing Specialty Chemicals and Utility Boilers Advanced Materials from Coals Fuel Processing Technol., 1993, 34 (2), 157-196). Carlos E. Romero, Nenad Sarunac, Edward K. Levy, Harun Bilirgen and Ying Li Coal has several positive attributes when considered as a feedstock for aromatic Lehigh University, USA chemicals, specialty chemicals, and carbon-based materials. The pathways and status of chemical processing of coal and coal-derived substances for making organic U.S. EPA’s studies have determined that mercury emissions from coal-fired power chemicals and carbon products in the future will be different from the past efforts plants pose significant hazards to public health and must be reduced. Coal-fired power during 1970s-1980s that could be characterized as coal-derived chemicals that are plants represent a significant fraction of the anthropogenic emissions of mercury into alternatives to petroleum-derived chemicals. Substantial progress in advanced polymer the atmosphere. Mercury emissions are impacted by factors such as coal type, boiler materials incorporating aromatic and polyaromatic units in their main chains has operation, fly ash characteristics and type of environmental control equipment installed created new opportunities for developing value-added or specialty organic chemicals on the unit. Field data show a wide variation in the fraction of mercury that is emitted from coal and tars from coal carbonization for coke-making. The decline of the coal in the gaseous phase, as elemental mercury and HgCl2 vapor, and as particulate-bound tar industry diminishes traditional sources of these chemicals. The new coal chemistry mercury. Oxidized mercury is a preferable species because is less volatile at stack for chemicals and materials from coal may involve direct and indirect coal conversion temperatures, water-soluble, and tends to interact with mineral matter and char, and strategies as well as co-production approach. High-value chemicals can be obtained by cold-end air pollution control devices. There is also evidence that boiler operating selective conversion of polycyclic hydrocarbons in coal and coal-derived liquids such conditions could be used to influence mercury behavior in the boiler, since they affect as naphthalene, biphenyl, and phenanthrene, over some zeolite catalysts. Examples the thermo-chemical conditions for mercury formation and reduction. However, include shape-selective alkylation of naphthalene into 2,6-dialkylnaphthalene, ring- operation of the boiler control settings, which result in mercury removal benefits, shift isomerization of sym-octahydrophenanthrene into sym-octahydroanthracene, should also consider the tradeoff between mercury reduction and other emissions shape-selective alkylation of biphenyl into 4,4’-dialkylbiphenyl, conformational (NOx, CO and SO2), the level of unburned carbon in the fly ash, unit efficiency and the isomerization of cis-decalin into trans-decalin, selective hydrogenation of naphthalene performance of particulate control equipment. into either cis- or trans-decalin, and regio-selective hydrogenation of heteroatom- containing aromatic compounds such as 1-naphthol. The products of such selective 28

reactions are specialty chemicals, monomers of advanced polymer materials such as of 10 nm. Fluorescence intensities and fluorescence lifetimes of trimethylsilyl- high-performance polyesters, advanced engineering plastics, and liquid crystalline substituted aromatic hydrocarbons were larger and longer than those of unsubstituted polymers, or components of advanced thermally stable aviation jet fuels for high-Mach ones, and they decreased in the order of Me3SiAr > Me3GeAr > Me3SnAr. aircraft. Needs for environmental-protection applications have also expanded market Fluorescence intensity of 1,3,6,8-tetrakis(trimethylsilyl)pyrene was largest among demand for carbon materials. Carbon-based materials such as activated carbons for those of a series of mono-, bis-, tris-, and tetrakis-(trimethylsilyl)pyrenes. gas-phase and liquid-phase applications are well known. Coal-based molecular sieving carbons are important for industrial gas separations. Coal-polymer composites have SESSION 31 also been shown to be promising materials with interesting thermal and electronic GEOSCIENCES & RESOURCES properties. Many items that we take for granted have some relation to carbon material, 31-1 including aluminum based products where anode carbon is used to reduce the Evaluation of Prospect Hole for Methane Mining In Czech Republic aluminum ore, steel from arc-furnaces using graphite electrodes, and even electric Zuzana Weishauptova and Jiri Medek contacts on the key-boards. However, the carbon we use is increasingly dependent on Institute of Rock Structure and Mechanics Academy of Sciences of the Czech the availability of petroleum-derived streams or other foreign sources. The decrease in Republic, Czech Republic domestic produced oil and the subsequent reliance on imported crude oil may have a Jaroslav Nemec serious impact on the future of carbon products and related materials in the US, since Eurogas, Czech Republic many carbon products are typically based on petroleum coke. Coal-derived carbon material can reduce the dependence on petroleum feedstock for carbon materials. In the Czech Republic, the Upper Silesian coal basin represents the largest potential Advances have been made recently in making carbon binders from coal-derived source of coal methane with the expected coal capacity for methane between 12 and 35 liquids, and graphite from high-rank coal (anthracite) based on pyrolytic conversion of m3 per ton according to published data. At present, large-scale prospecting of virgin coal. More recent work demonstrates that fullerenes and carbon nano-tubes can also be coal bearing areas is conducted, aimed at gas-bearing of given seams and possibility of produced from coal. economic exploitation of methane as a suitable energetic source. Regarding the regional type of the coal seams, complex analysis including a geological study and a 30-3 trial bore as well as large number of laboratory tests is always indispensable. Results Fractionation of Coal by Solvent Extraction at Different Temperatures below from the trial bore indicating in situ conditions are corroborated with analysis of coal 350°C characteristics directly related to gas-bearing properties, and are determinant for Kyosuke Nakagawa, Ryuichi Ashida, Hiroyuki Nakagawa and Kouichi Miura certain states and processes connected to degassing of coal methane. Kyoto University, Japan On the example of coal from a bore realized in the Čeladná-Krásná prospecting area in the southern part of the Upper Silesian basin covered with Beskydy nappes, evaluation We have presented a new coal solvent extraction method that realizes not only is documented of the textural character of the coal and the overlaying rocks from the demineralization of coal but also coal fractionation in terms of molecular mass. Firstly, viewpoint of gas-bearing and its correlation with gas permeability, and particularly 2 types of extracts were obtained by using a flowing stream of the solvent under with respect to predicating ability of the laboratory determined methane partial 10MPa at 350°C. One of them is the fraction soluble at 25°C (Frac-25) in non-polar volumes according to the mode of binding and bearing by comparing with gas yield solvent such as tetralin and the other is the fraction which precipitates as solid at 25°C found by a container test of the bore core. The method of analysis of the degassing from the extract obtained at 350°C (Frac+25-350). Then the Frac+25-350 was further curve has been applied as well in connection with the time effectiveness of the bore extracted stepwise at 150°C, 200°C, 250°C, 300°C, which could fractionate the coal degassing. into 7 fractions. Ultimate analysis and molecular mass measurement showed that the According to the laboratory tests, the coal from the Čeladná bore has textural fractions obtained at lower temperature consisted of smaller molecular mass conditions for economically exploitable gas-bearing. This has been confirmed by the compounds which were existent in the parent coal and have larger atomic H/C ratio. degassing tests of the bore cores from the coal seam horizons corresponding well with Furthermore, 6 fractions except Frac+350 were almost free from inorganic materials. the potential gas-bearing derived. Thermogravimetric and thermomechanical analyses of each fraction were performed to characterize it for the use of raw material of high performance carbon materials. The 31-2 melting and plastic behavior of Frac+25-150 was very close to that of naphthalene- Potentially Hazardous Trace Elements in Coals from the Czech Republic based pitch which was synthesized for producing high performance carbon materials. Ivana Sýkorová, Michal Vašíček and Ondřej Michna This result suggested a possibility of utilizing the fraction as a feedstock of high Institute of Rock Structure and Mechanics, Czech Republic performance carbon materials. Jiři Pešek and Karel Martínek Charles University Prague, Czech Republic 30-4 Robert Finkelman, John H. Bullock, Jr. and H. Ron Affolter The Effect of Coal-Based Acid on the Biological Activity of the Herbicide United States Geological Survey, USA Tribenuron-Methyl

Shanxiang Li, Baoqing Li and Wen Li Coal production and use have diverse impact on the surrounding land, atmosphere as Chinese Academy of Science, P.R. China well as hydrosphere. The enormous volumes of waste material which are the by Caifeng Zhang products of both underground and surface coal mining, are one of the main pollution Taiyuan Teachers’ College, P. R. China problems in addition to coal combustion in power plants in the Czech Republic. Some

of these problems could be reduced by the accurate and comprehensive coal quality Water-soluble coal-based humic acids (WSCA) obtained following oxidation of information in the database. Statistical processing of data of almost 31 000 coal Wuchuan weathered lignite (W-WSCA) or by extraction from the Jincheng weathered samples from Late Paleozoic and Tertiary basins of the Czech Republic in the database coal (J-WSCA), both enhanced the biological activity of tribenuron-methyl, a provided a survey of the quality of lignite, sub-bituminous coals, bituminous coals and herbicide. In the presence of the humic acid, the ED values for triberunon-methyl 90 anthracites including ash and sulfur contents, mineralogical composition and increased by a factor of 4.28 (W-WSCA) or 2.52 (J-WSCA). FTIR indicated that the distribution of potentially hazardous trace elements (As, B, Ba, Cd, Cl, Co, Cr, Cu, F, main interaction between WSCA and herbicide was via hydrogen bonds. NMR showed Hg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Th, U, Zn, Zr). that the humic acid had a lower concentration of condensed aromatics. Molecular d The database shows a broad spectrum of ash content A = 2.8 to 48 %, sulfur content dynamics simulation then established that this more open structure favoured interaction S d = 0.33 - 19.9 % in low rank coals, and sulfur content S d = 0.20 - 4.9 % in between the herbicide and additive. The strong interaction between herbicide and t t bituminous coals and anthracites. Great variation in distribution of trace elements in additive and consequent marked change in herbicide structure are probably related to relation to the age of geological units and basins was observed in Czech coal seams. the improved biological activity of the herbicide. The highest concentration of Ga, Ge, Mn, Sn, Th, Tl and Y was found in the samples from the Early Namurian coal seams of the Upper Silesian basin. In contrast, the 30-5 Middle to the Late Namurian seams of the same basin are enriched in B, Ba, Bi, Nb, Absorption and Fluorescence Properties of Silyl-Substituted Aromatic Sc, Se, Sr, Te, U and Zr. The highest content of Cs and Hg was determined in the Hydrocarbons Bolsovian coal seams of the Central Bohemian basins, whereas high concentration of Hajime Maeda and Kazuhiko Mizuno Be, Co, Cr, Mo, Ni and V was found in the Westphalian D coals of the same basins. Osaka Prefecture University, Japan Bituminous coals enriched in Ag, As, Cd, Cu, Mo, Pb and Zn occur in the Stephanian B coal seams of the Intra Sudetic and the Krkonoše Piedmont basins. Effects of trimethylsilyl, trimethylgermyl, and trimethylstannyl substituents attached to Extremely high concentration of As, Be, Cs, Hg and some heavy metals was found polyaromatic hydrocarbons such as pyrene, anthracene, phenanthrene, and naphthalene only in the Sokolov basin in the Oligocene coal seam rich in sulfides. For this reason were examined in respect of UV absorption and fluorescence properties. Absorption its exploitation was terminated in 1995. High content of As, Cd, Cu, Hg and Pb was maxima of trimethylsilyl-, trimethylgermyl-, trimethylstannyl-substituted aromatic observed in coal with high content of sulfides while Be, Co and Cr were possibly hydrocarbons shifted to longer wavelength than those of unsubstituted aromatic associated with clay minerals. Clay minerals, kaolinite and illite in particular, hydrocarbons. Absorption maxima of mono-, bis-, tris-, and pyrite/marcasite, quartz and carbonates (calcite, siderite and dolomite) represent the tetrakis(trimethylsilyl)pyrenes shifted to longer wavelength consecutively at intervals inorganic admixtures in all coals. Comparing with Krejci-Graf (1972), Czech lignites 29

show higher concentration of Cs, Nb and Rb. It is to be also noted that the content of varying thickness in the basin and drilling data in operation site of lignite, the oil shale Ag, Cs, Nb, Pb, Rb and Tl in Czech bituminous coals is in general much higher than reserve estimated to be 110 million tones. Samples collected from a number of 15 the highest values reported by Krejci-Graf (1972). Most of lignite and bituminous wells that cut oil shale were subjected to chemical analyses and mineralogic- coals from perspective deposits contain lower concentration of potentially hazardous petrographic examinations. trace elements. Based on the results of mineralogic-petrographic analyses and geochemical analyses, it was determined that overall quality and thickness of oil shales are not suitable to 31-3 produce synthetic oil. Therefore, a total of 150 tones oil shale and lignite sample Evaluate the Feasibility of Enhanced Coal Bed Methane Recovery in Kyushu collected from the operation site was subjected to burn tests in a 2 MW power plant Area with a circofluid fluidized bed combuster. Result of the tests yield that durable burn Kazunori Tamabayashi, Masayuki Sagisakaand Tadao Moro was obtained if a material consisting of 80 % lignite and 20 % oil shale and that oil Waseda University, Japan shales assisted desulfurization due to their carbonate content. If the mixing of oil shale and lignite is burned in new circofluid fluidized bed At COP3 held in Kyoto in 1997, the reduction target of greenhouse gas was set up combuster unit to be established in area, environmental impacts will be minimum. In for each developed country. Since Japan’s energy efficiency is at the world’s best addition, oil shales that have been so far disposed as overburden material will be cross level, it is critical to establish an effective way to make use of the sequestration economically consumed providing long life time for the coal to be used in thermal technology which can isolate CO2 in large quantities in a short period of time. power plant and other sectors. Enhanced Coal Bed Methane Recovery (ECBMR) particularly attracts attention, because it can achieve the recovery of methane and sequestration of CO2. SESSION 32 Conventional methods for the estimation of the Coal Bed Methane (CBM) GASIFICATION ADVANCED TECHNOLOGIES 2: PYROLYSIS production and CO2 sequestration quantity include many uncertainties, since these receive the various influences by geological feature, fluid property and injection 32-1 character. Therefore, the purpose of this study is to calculate the quantity more Development of Coal Partial Hydropyrolysis Process Hideaki Yabe, Takafumi Kawamura and Kohichiroh Gotoh accurately by using a new simulator in consideration of real geological feature, fluid Nippon Steel Corporation, Japan property and injection character. Moreover, I evaluate the feasibility of ECBMR in Akimitsu Akimoto Kyusyu area by analyzing the economic and environmental aspects. Center for Coal Utilization, Japan This study consists of two parts according to the objectives.

(1) The condition of well patterns and the CO2 injection quantity which optimize the Coal partial hydropyrolysis process aims at co-production of high yield of light oil potential of ECBMR. such as BTX and naphthalene and synthesis gas from a low rank coal under a mild (2）The possibility of ECBMR as an environmental business by analyzing Life hydropyrolysis condition. The characteristic of this process is in the hydropyrolysis Cycle CO2(LCCO2) and the cost. reactor composed of the reformer and gasifier. So far, in order to evaluate the process In section (1), I studied the variation of CBM production and CO2 sequestration concept a small-scale basic experiment and a 1t/day process development unit study quantity by varying the injection rate, pressure and the well spacing. In section (2), were carried out. The experimental results showed that coal volatiles were partially focusing on CO2 production and reduction, I performed LCA on the inventory date hydrogenated to increase the light oil and hydrocarbon gases at the condition of partial with regard to the ECBMR technology. In addition, I evaluated the revenue and the hydropyrolysis. This process has a possibility of producing efficiently and expenditure of the ECPM operation. economically liquid and gas products as chemicals and fuel for power generation. As a CBM is considered as an alternative energy source of LNG. It became clear by further development in the period of 2003 to 2008, a 20t/day pilot plant study is under LCCO2 analysis that the use of CBM as energy reduces 6.54g per 1MJ of life cycle planning to establish the process technologies for commercialization. CO2 emission in comparison to the case of LNG. Considering the quantity of CO2

sequestration, the reduction was even as high as 108g per 1MJ. In addition, it became clear that there was a break-even point in the economical analysis on 32-2 ECBMR project. It is clearly suggested that this technology might succeed both Coal Pyrolysis under Elevated Pressure Conditions technologically and economically. When I maximized the quantity of CO2 Yukihiko Okumura sequestration without taking out financial loss, it was made clear that the benefit was Maizuru National College of Technology, Japan 470 million yen in eight years and it can reduce about 0.8% of Japan’s yearly total Ken Okazaki CO2 as of 2000. It was concluded that ECBMR has a great potential in feasibility as Tokyo Institute of Technology, Japan an environmental project. A coal pyrolysis experiment using a pressurized thermobalance is carried out in 31-4 conditions changing from normal to high pressure (10.6 ata) and from low-rank Distribution of Ge and Ga in Lignite (73.1C%, daf) to high-rank coals (90.6C%, semi-anthracite). The pressure’s impact on Zdeněk Klika, Lenka Ambružova and Jana Seidlerová rapid pyrolysis is discussed. Essentially, the novel heating configuration in the VŠB-Technical University Ostrava, Czech Republic experiments almost eliminated the secondary pyrolosis chemistry of volatiles, so that Ivana Sýkorová the product distributions were especially well suited for calculating devolatilization Academy of Science, Czech Republic mechanisms. The consideration was developed by relating a gas release mechanism under elevated pressure conditions to the polymer reaction in the coal. Most procedures for calculation of elements affinity between organic and inorganic Pressure suppresses tar vapor formation. The amount by which the elevated pressure phases of coal are usually based on sink-float or other type technique of coal fractions reduces the amount of released volatile matter almost equals the suppressed tar yield. separation. For these procedures the assumption of constant concentration of element Calculations confirm also that the model, including the effect of vapor-liquid in organic parts of all coal fractions (no matter to their ash contents) is usually applied. equilibrium, is capable of quantitatively accounting for the actual weight loss of coal The assumption about constant coal concentration is not always valid for elements with under elevated pressure conditions. high affinity to organic matter (e.g. Ge and Ga). The distribution of both element In many types of coal, as pressure increases the CH4 gas yield increases and the CO, concentrations in coal fraction separated by sink-float technique is shown including CO2 gas yields increase slightly. The recombination reactions of the remaining their correlation with the lignite macerals. metaplasts (precursors of tar) are then activated, resulting in more intermediate chars and higher gas yields. 31-5 In many types of coals, the C2-C3 gas yields tend to decrease as pressure increases. Possibilities for Economic Utilization of the Seyitomer (Kutahya, Turkey) Lignites Under atmospheric pressure, released tar tends to be captured in liquid form. Under and Oil Shales elevated pressure, on the other hand, solid substances such as soot, which contains Ilker Senguler carbon, sulfur, and so on, tend to be captured instead of tar vapor. Mineral Research and Exploration of Turkey, Turkey The rate at which tar release is reduced by pressure, that is, (1.0 - the tar yield under

elevated pressure / tar yield under atmospheric pressure) increases as carbon content Although oil shales have many fields of use, the most commonly research is obtaining (C%, daf) increases. The pressure’s ability to suppress evolvable tar tends to increase of synthetic oil and its use as a solid fuel. In this study, the utilization of oil shales, as the coal rank increases. together with lignite in thermal power plant and oil extraction possibilities are The CO, CO2 gas yields decrease in proportion to carbon content under both investigated. The Seyitömer lignite and oil shale deposit is located in ENE-WSW atmospheric and elevated pressure conditions. On the other hand, in many types of oriented Neogene basin, NW of Kutahya, Western Turkey. The rock units exposed in coals the H2 gas yield doesn’t change in atmospheric or elevated pressure conditions. the investigated area from bottom to top are basement complex, lower conglomerate, The CH4 and C2H4 gas yields (wt%, daf) are higher than any other yields of green clay, main seam (lignite), yellow clay, upper seam (lignite), limestone-tuff and inflammable gases in many types of coals. upper conglomerate.

For this reason, area was geologically mapped in detail and a number of 18 wells was drilled in operation site of lignite. Considering economical grade oil shale zone with

32-3 determined by GC and GC-MS. The material balance between coal and products based Evolution of Sulfur Containing Gases During Coal Pyrolysis in Various on C, H and O was calculated. Initial stage of coal gasification including the secondary Atmospheres reactions subsequent to rapid pyrolysis of coal is discussed. Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu Dalian University of Technology, P. R. China SESSION 33 LOW RANK COAL UTILIZATION: 2 Coal is the main energy resource and consumption energy in China; meanwhile it is 33-1 also the main pollution contributor. Therefore, it is very urgent to make rational and Upgrading Low Rank Coals by Mechanical Thermal Expression (MTE) clean use of coal in China. And a better understanding of evolution of sulfur Yuli Artanto and Alan Chaffee containing gases in heat treatment is essential for effective and economical sulfur Monash University, Australia removal and consequently for environment protection. In this study, four Chinese coals, including Yanzhou (YZ), Datong (DT), Yima (YM) and Huolinhe (HLH) coal, Over recent years the Mechanical Thermal Expression (MTE) process has emerged as belongs to different rank and contains different sulfur content, were used to a highly prospective approach for dewatering/upgrading low rank coal. The process investigate the effect of pyrolysis under different atmospheres on the evolution of involves the use of moderate temperatures (150-220 °C), which can ‘soften’ the coal sulfur containing gases. The evolution rates of sulfur containing gases were measured and facilitate water removal via the application of mechanical pressure (3-12 MPa). by temperature-programmed pyrolysis of coals in an atmospheric pressure, vertical Some organic and inorganic components can also be removed with the water. The micro-fixed bed reactor. Compared with the evolution of sulfur containing gases in process is being evaluated at pilot scale in both Germany and Australia. N2, it indicated that CO promotes the decomposition of pyrite and sulfide and the This report compares the effectiveness of MTE for the beneficiation of a suite of low formation of COS. And most of the sulfide sulfur is converted into COS, only a little rank coals from Australia, Indonesia and India, as determined at laboratory scale. is converted into H2S; CO2 prohibits the evolution of sulfur-containing gases at We have observed that the percentage water removal decreases as the original water temperatures below 600oC, above this temperature it shows similar effect on sulfur content of the raw coal decreases such that, for the same MTE conditions, the data for containing compounds as CO does; CH4 prohibits the evolution of sulfur-containing all lignites we have examined fall close to a single trend line. The extent of water gases at temperatures below 600oC, and the extent is more pronounced than that of removal can still be significant in the sub-bituminous rank range, especially when CO2 does, but at temperatures above 800oC, CH4 promotes the formation of H2S; higher temperatures are used. H2 improves the formation of H2S and prohibits the formation of other sulfur- The removal of inorganics is variable depending on the mineralogy of the original coal. containing gases. The removal of organics increases with temperature. Other product characteristics, such as moisture holding capacity and shrinkage during 32-4 drying (at 105 °C) are principally affected by temperature. The helium density (true Transformation of Inorganic Species in Coal during Pyrolysis density) and elemental components (C, H, N ,O) of the coals are not affected within the Koichi Matsuoka, Akira Takaya and Akira Tomita limits of measurement error. Tohoku University, Japan 33-2 To avoid various ash-related problems during coal utilization technologies, it is Comparison of Physico-Chemical Properties for Various Lignites Treated by essential to understand the fundamental chemistry on the thermal behavior of inorganic Mechanical Thermal Expression species, such as inherent mineral matter and ion-exchanged metal species. In this Janine Hulston and Alan L. Chaffee study, we attempted to clarify the fate of these species during pyrolysis in a drop tube Monash University, Australia furnace (DTF) and in a fixed bed reactor (FBR) with different residence times. Christian Bergins and Karl Strauss Whiteoak bituminous coal and Berau subbituminous coal are used in this study. University of Dortmund, Germany First, we determined the amount and chemical form of inorganic species in raw coals using XRD, CCSEM, and ICP-AES analyses. It was found that main Ca-containing A significant proportion of the world’s energy reserves consist of lignites with high mineral matters in Whiteoak coal are calcite, dolomite, and ankerite. The total amount moisture contents of between 40 and 65 wt % (wb). When the raw lignite is burnt in of these species quantified by CCSEM was nearly equal to the Ca content determined conventional power stations, up to 20 % of the chemical energy of the lignite is lost by ICP-AES. This indicates the absence of ion-exchanged Ca. On the other hand, the due to the latent heat of vaporisation of water within the lignite structure. Relative to main Ca species in Berau coal were crandallite and ion-exchanged Ca. XRD pattern of black coal or gas-fired power stations, this results in larger boiler and equipment raw Berau coal showed only a weak quartz peak, while XRD of the low temperature requirements, reduced thermal efficiencies and, consequently, higher CO2 emissions ash revealed the presence of calcite and bassanite, which were derived from the per unit of electricity produced. interaction of ion-exchanged Ca with CO2 and SO2 evolved during ashing. The mechanical thermal expression (MTE) process is currently being investigated as a Carbonate minerals were converted to lime upon the pyrolysis of Whiteoak coal in means of reducing the moisture content of lignites prior to combustion or gasification. DTF at 1500 oC, while the interaction of carbonates with other mineral matters was This is achieved via mechanical expression (4 to 12 MPa) carried out at elevated hardly observed. In the case of pyrolysis of Berau coal in DTF, a considerable amount temperatures (< 200 C), whereby the water is removed in the liquid state. The MTE of crandallite disappeared and it was found that most of ion-exchanged Ca was process has been shown to be effective in reducing the moisture content of lignites and converted to very fine particles of oldhamite (CaS) that cannot be detected by CCSEM. thus has the potential to be retrofitted to existing power plants to improve their The interaction with other minerals was marginal due to the short residence time in efficiency, or be advantageously implemented in new, energetically optimised power DTF. When pyrolysis was carried out with a longer residence time in FBR, the size of plants. In addition, MTE products could potentially be considered for the export oldhamite increased enough to be detected by CCSEM. Furthermore, the interaction of market due to the significantly improved energy density, thus making it economically fine Ca species with aluminosilicate minerals became remarkable. more viable to transport. In conclusion, atomically dispersed Ca species in Berau raw coal was converted in This paper focuses on the effects of MTE processing conditions on the physico- DTF to very fine CaS, and upon longer exposure to 1500 oC it was subjected to chemical properties of various lignites after MTE processing and drying at ambient crystallite growth as well as interaction with aluminosilicates. conditions. Particular emphasis is placed on materials characteristics that are considered important for transportation, handling and storage. A range of properties 32-5 has been collated for MTE products prepared at laboratory scale. This includes Studies on the Secondary Reactions Subsequent to Rapid Pyrolysis of Coal moisture content after MTE processing, moisture content at ambient conditions, Osmau Yamada, Hajime Yasuda and Mamoru Kaiho shrinkage, porosity, apparent density, hardness, weathering, surface area and National Institute of Advanced Industrial Science and Technology, Japan spontaneous combustion behaviour. These properties will be compared with those of Aihua Zhang some typical lignite derived briquettes. California Stste University, USA 33-3 In order to evaluate an entrained flow gasification process, reaction occurred in rapid Upgraded Brown Coal (UBC) Mine Mouth Power Plant in Indonesia pyrolysis of coal under high temperature and high pressure should be well understood.. Environmentally Friendly Low CO2 Emission Lignite Based Power Plant Conventionally rapid pyrolysis of coal has been fundamentally studied by using a Eiichiro Makino Curie-point pyrolizer, a drop tube furnace, a wire mesh grid method and so on. Nissho Iwai Corporation, Japan Reaction conditions in these experiments, however, are thought to be considerably Yasuo Otaka different from that occurred in an actual gasifier. We have developed a special Japan Coal Energy Center, Japan apparatus that enable an investigation of a rapid pyrolysis of coal under Takuo Shigeshisa and T. Deguchi similar conditions in an actual entrained flow type gasifier. Coal was blown into the Kobe Steel, Ltd., Japan reaction chamber at 800 $B!n (B and 7.1MPa to complete pyrolysis for the duration Kazuo Miyama of 1 to 80 seconds, Gas generated in the reaction chamber was transferred to the gas Babcock-Hitachi K.K., Japan reservoir which was kept vacuum, after prescribed reaction time to quench pyrolysis of Masaaki Ebina coal. The volume and the composition of gas generated during pyrolysis were Nippon Koei Co., Ltd., Japan 31

Teddy Setiawan pretreatment can be effective for production of HyperCoals from low-rank coals. The PT. Triaryani, Indonesia mechanism of increment in the extraction yields by the pretreatment will be presented.

Life Cycle Assessment (LCA) is a useful tool to evaluate the environmental aspects SESSION 34 and potential impacts associated with a product throughout its life span. LCA method INTERNATIONAL COAL TECHNOLOGY COOPERATION: 2 is applied for the evaluation of CO2 emission to compare the Upgraded Brown Coal 34-1 IEA-China Power Plant Optimisation Study (UBCR) Fired Power Plant with the proven Low Rank Coal (LRC) Fired Power Plant Rupert Clarke at Mine Mouth in Indonesia. The UBC technology of which basic patent owned by Mitsui Babcock, UK Kobe Steel Ltd. Japan confirmed to be one of the ultimate solutions for the utilization Peter Nowak of lignite effectively judging from the environmental and economical point of view. Siemens, Germany Bert van Vliet 33-4 NOVEM, The Netherlands Application of the Hyper-Coal Process for Low Rank Coals Upgrading Leopold Zarowski and Jaroslaw Ciesielski Noriyuki Okuyama, Nobuyuki Komatsu and Takuo Shigehisa Alstom, Poland Kobe Steel, Ltd., Japan Peter Rozelle Takao Kaneko UD DOE, USA Mitsubishi Chemical Corporation, Japan Jack Cunningham and Keith Burnard AEA Technology, UK The low rank coals, such as sub-bituminous and brown coals, are characterized by the abundant reserves and the worldwide distribution. In spite of those, the market value of The power industry in China is rapidly expanding and, at the same time, undergoing the low rank coal is generally small, since it contains a large amount of moisture (20- significant institutional change. The installed power generation capacity of China is 60 %). In addition to that, the high transportation cost causes the small utilization, such the second largest in the world, next to the US. It is estimated that China will need to as a feedstock for the local power plant, in the present situation. On the other hand, a install 800GW of new capacity by 2030, much of which will be coal fired. Coal is the large part of the low rank coal contains a small amount of ash and/or sulfur. Therefore, main fuel for power generation in China; it fuels around 78% of the electricity the increasing in the low rank coal utilization will be an effective way to promote the generation mix and 95% of the fossil-fired electricity generation capacity. This clearly clean coal diffusion. has major implications for the environment. For sustainable development of the It can be said that the large moisture content is the principal reason to avoid the electric power industry, China must improve its energy conversion efficiency and diffusion of the low rank coal. When the low rank coal is simply air dried, a strong reduce its emissions. spontaneous combustionability will be appeared. Therefore, to realize the efficient One contribution to reducing these emissions is to improve the performance of existing upgrading for the low rank coal, the action to remove the moisture and to reduce the coal-fired plant. A project based on this approach was developed by the International spontaneous combustionability in the same time is needed. Energy Agency, China's Ministry of Science and Technology and two of China's newly Hyper-coal process, which has been developed since 1999, is an ash free coal formed power companies, the China Power Investment Corporation and the China manufacturing process by using the solvent de-ashing technology. Coal is extracted Datang Group. The project involved a team of Western power plant experts, brought into the coal-derivative two ring aromatics at 350-380 oC. The solution is separated together under the auspices of the International Energy Agency. Following audit of from the insoluble residue by the gravity settling and/or the filtration. Solvent is two typical coal-fired power plants in China, the team considered the potential to recovered and recycled in the process. Ash-free extracted coal (Hyper-coal, HPC) and improve efficiency and reduce emissions based on current best practice in ash-concentrated residue coal (RC) are obtained in this process. Usually, some industrialised countries. bituminous coals are found out to get a high yield of Hyper-coal (>60%). Led by the UK, the international team of experts spent one week at each of the two This paper focuses of the application of the Hyper-coal process for the low rank coal plants: Tongliao Power Plant, Tongliao, Inner Mongolia and Tianjia’an Power Plant, upgrading. Mulia coal, an Indonesian brown coal, 25 % of moisture content, 2 % of Huainan City, Anhui Province. Central to the success of the project was the close ash content and 0.2 % of sulfur content was used in this study. As the result of coal working relationship built up between the international team, the technical staff at the extraction test, the HPC yield from Mulia coal was only 30 % on daf, and RC yield plants and the staff member seconded to the team from China's Thermal Power was more than 50 %daf. Usually, such a yield structure cannot be accepted in Research Institute. Following the visit to China a summary visit report was produced, economy. On the other hand, looking at the RC properties, the obtained RC has only 5 in which preliminary findings were presented. Closer analysis of the data is currently % of ash, and the calorific value was increased from 5400 kcal/kg to 7300 kcal/kg, ongoing, some of which is presented in this paper. which was almost same level to the bituminous coal. Those improvements were The success of the project will be measured, first, against the extent to which the plants produced not only by the effect of dewatering, but also by the effect of removing the investigated will implement the measures identified by the IEA team and, second, oxygen-containing functional groups. It can be said that the Hyper-coal process may be against the broader take up of the measures at the numerous similar power plants an effective way to upgrade the low rank coal, which produces not only the ash-free throughout China. coal, but also the high value coal from a low rank coal. It was found that the spontaneous combustionability was also reduced by the effect of the removal of the 34-2 oxygen-containing functional groups. Analysis on Energy Production and Consumption of Recent Years in China Hailin Mu and Yasuhiko Kondou 33-5 AIST, Japan Effect of Pretreatment with CO2 Dissolved in Water on “HyperCoal” (ash-free Weisheng Zhou coal) Production from Low-Rank Coals Ritsumeikan University, Japan Kensuke Masaki, Nao Kashimura, Toshimasa Takanohashi, Shinya Sato, Yutaka Tonooka and Sakamoto Kazuhiko Akimitsu Matsumura and Ikuo Saito Saitama University, Japan National Institute of Advanced Industrial Science and Technology, Japan The energy consumption statistics indicate that China’s primary energy consumption “HyperCoal” (ash-free coal), which can be used as a feedstock for gas turbine to revealed a peak in 1996 and then began to fall year by year. It reached the minimum in achieve higher net power output as well as lower CO2 emission, is produced by thermal 1999 and fell by 6.35% compared with that in 1996, driven almost by declining the extractions with industrial organic solvents under inert atmosphere. Use of low-rank direct use of coal. Since 2000, China’s primary consumption has just expressed an coals as raw materials for HyperCoal production can be very advantageous with increasing trend and it exceeds that of 1996 until 2002. Because China’s economy still respect to production cost, and stable supply of low-rank coal resources. kept the higher economic growth rates of around 8%~8.5% in these years, this In this study, the effect of pretreatment with CO2 dissolved water (CO2/H2O) on the dramatic shift of primary energy consumption naturally cause a question for energy HyperCoal yields was investigated to produce HyperCoals from low-rank coals consumption statistics: may the reported statistics be seriously flawed or not? efficiently. Since China is the second largest country of CO2 emission in the world, it is very Coal and deionized water (with 10 wt% ethanol) were mixed in an autoclave under 1- important to clearly understand this shift and obtain the right energy consumption o 70 atm (Gauge pressure) with CO2 at 25 C for 24 h. Thermal extraction was conducted statistics, and thus to be able to estimate China’s CO2 emission reasonably. In this using a flow-type extractor at 200-360 ºC. Crude methylnaphthalene oil (CMNO) and paper, on the basis of analyzing the coal production situation, energy consumption crude quinoline (CQ), which are obtained from coal-tar distillation process, were used policies, environmental protection policies, changes of industrial structure and as extraction solvents. improvement of industrial technologies and equipments, we modify the China’s energy A remarkable positive effect was found even under lower treatment pressure (1 atm); consumption statistics of recent years. the thermal extraction yields at 360 oC were increased by 9-16 %, resulting in the high The original points of this study are as follows. extraction yields of about 55 % and 45 % for Wyodak subbituminous coal and Beulah- Through analyzing the statistic-investigation system and according to the import & zap lignite, respectively. In addition, CMNO extraction yields of pretreated Wyodak export amounts of petroleum products, the more reasonable energy consumption coal were significantly increased from 320 oC to 360 oC, and these increased extraction statistics are extracted from the two kinds of China’s energy consumption statistics: the yields were 5-13 % higher than those of raw ones. Therefore, the CO2/H2O whole country and sum by province; 32

According to the coal consumption and production policies, the improvement of coal Bringing up the experienced person in Asian area ranks (heat values) is estimated in recent years; Lecture at a university and/or a training institute by Japanese experts, and others The implementations of more and more serious energy-conservation and Joint development work environmental protection policies promote the improvement in energy use efficiency. Finding research project and CCT suited for each country, and others Meanwhile, the reported statistics may be made to reduce intentionally since the 3) Spread and enlightenment of CCT rewards and penalties of energy-conservation are considered to a company or the local Support to held CCT seminar, and others government. This part of reduced coal consumption amount is estimated in this paper. Expected results The China central government enacted that 20000 or more of coal mines, which are 1) Efficient coal utilization technology will spread in Asian regions. non-state ownership and whose scales are small and 30~40 state ownership coal mines 2) Utilization of Japanese CCT will be promoted. will be closed in order to improve the raw coal quality and reduce the coal production 3) R&D on coal utilization technology and bringing up of experienced person will be accidents. However, a part of them secretly carry out the production continuously or promoted. time and again. Therefore, this policy, on the one hand can enhance the quality of raw 4) CCT network in Asia will be built up. coal and reduce the output of raw coal to some extent; on the other hand, the coal consumption from the secretive production is omitted in the reported statistics. This SESSION 35 part of coal consumption is estimated in this paper. ENVIRONMENTAL CONTROL TECHNOLOGY 6: MERCURY 35-1 34-3 Catalytic Materials and Oxidation Condition for Mercury Oxidation in Effect on Coal Rank on Equipment and Performance of a Coal Fired Power Plant Combustion Flue Gas Nusyirwan Akimasa Yamaguchi, Yoshihisa Tochihara and Shigeo Ito PT Indonesia Power, Indonesia Central Research Institute of Electric Power Industry, Japan

All fossil fuel fired boilers are designed to burn a specific type of fuel. Furnace size When a fossil fuel or a refuge-derived fuel is burned, gaseous elemental mercury increases dramatically as heating values of fuels decrease. Heating surface are sized, (Hg0), gaseous oxidized mercury (Hg2+) and particles-bound mercury (Hgp) were positioned, and spaced according to the fuel and ash characteristics. Gas fired units are generated in the flue gas. The capture of Hg by flue gas cleaning devices is dependent smaller, since the cleanliness of gas allows for closer spacing of assemblies and the on Hg speciation. Hgp can be captured by electrostatic precipitators or fabric filters. higher heating value of the fuel means less fuel fired for the required heat release. Coal Hg0 is insoluble in water and cannot be captured in wet scrubbers. The predominant fired units must be larger to allow wider spacing of assemblies and greater volume for Hg2+ compounds in flue gas are weakly to strongly soluble, and more-soluble species burning more fuel for the same heat release. Coal quality has perhaps the greatest can be generally captured in wet scrubbers. Therefore, if insoluble Hg0 can be oxidized affect of all the factors on boiler efficiency and other plant equipment. Boilers are to soluble Hg2+, Hg emissions to the atmosphere can be controlled with wet scrubbers. designed to burn a given fuel within a specified optimum range of composition to meet In this study, the effects of temperature (363-573K), HCl concentration (1-100ppm), performance guarantees. Any variation from that composition will affect the operation and the presence of steam on the oxidation of Hg0 were evaluated. Some catalytic and performance, notably capacity, efficiency, reliability, availability and maintenance. materials were placed in simulated flue gases containing N2, CO2, O2, HCl, SO2, NO, Therefore it is very important to know its combustion characteristics and to determine and steam, and the conversion of Hg0 was examined. how the fuel switch will affect boiler performance and other plant equipment. This Some metallic oxides could convert Hg0 to Hg2+ at low HCl concentration (<5ppm) at report examines the experience of Suralaya coal fired power plant when firing out-of 423K. The conversion rate was affected by the presence of steam and temperature. The design coals. most efficient catalyst showed the conversion rate more than 90% at 2ppm of HCl and 363K. 34-4 Japanese Coal Preparation Technology Transfer to Developing Countries 35-2 Hajime Endo and Nobuhiro Koyanagi Behaviors of Mercury in Solid Fuels and Wastes during Combustion/Gasification JCOAL, Japan Processes Yasuo Kubo Hong Yao, Tamotsu Kameshima, Yohei Takigawa and Ichiro Naruse Nagata Seisakusyo Co., Ltd, Japan Toyohashi University of Technology, Japan

Japan Coal Energy Center (JCOAL) has been carrying out coal preparation technology Mercury emissions from combustion/gasification processes of solid fuels and wastes transfer to developing countries producing coal in Asia, entrusted by Japanese are greatly concerned in many industrialized countries. A variety of control strategies governmental fund since 1994. The paper will introduce the outline of the project, are now under intensive development. Usually, mercury exists as elemental mercury especially in China and Vietnam as a latest case study and the technology of VARI- and oxidized mercury such as Hg, HgCl2, HgS and so forth. The elemental mercury WAVE jig developed in Japan as a technical topic. The VARI-WAVE jig is an easily passes through particulate control devices since it is gaseous phase even at improved conventional jig and has been achieved excellent performance in Japanese ambient temperature. The oxidized mercury, however, is water-soluble, hence some coal preparation plants by using variable wave pattern. can be removed by wet desulfurization processes or wet scrubbers. Speciation of the Moreover, the importance and potentiality of coal preparation technology against mercury compounds in combustion/gasification processes is, therefore, a particularly environmental related issue in developing countries thinking about the matter in terms important issue to develop the appropriate mercury control strategies. of Clean Coal Technology will be emphasized in this paper. In this study, first, thermo-gravimetric (TG) experiments were carried out to understand fundamentals of mercury evolution behaviors under the combustion and 34-5 gasification conditions, using three types of coal and dried sewage sludge as the The Conception of the Information Sending Bases on Clean Coal Technology samples. Then, one sample was burnt in an electrically heated drop tube furnace to (CCT) in Asian Area study the evolution behavior of mercury in semi-practical combustion processes. Ikuo Saito Moreover, chemical equilibrium calculation predicted the tendency of mercury AIST, Japan evolution under the same experimental conditions. Meanwhile, the kinetic calculations Takayuki Takarada of mercury oxidation phenomena were also conducted to analyze the time evolution Gunma University, Japan behaviors of all mercury species concentrations, using CHEMKIN. The results Yoshikazu Ikai and Fumio Hiraguri obtained show that sulfur content in the fuels inhibits the evolution behaviors of Center for Coal Utilization, Japan mercury during sludge combustion. For coal, while, the fixed carbon content in the Yasuo Otaka coal plays an important role for the mercury evolution. Under the gasification JCOAL, Japan condition, however, the evolution of mercury becomes quickly because of the elemental mercury is easily produced. The calculation prediction also shows that the In Asian area, coal is very important energy resources and accounts for the major oxidation processes of mercury depend on some radicals, especially for Cl radical portion of primary energy supply now and future. To use CCT should be needed for produced. the solution to environmental issues which will be more and more severe without any countermeasures in the area. The objective of the project on “information sending 35-3 bases on CCT in Asian area” which is entrusted by NEDO (New Energy and Industrial Characteristics of the Removal of Mercury Vapor in Flue Gas by Activated Technology Development Organization) is to improve the energy and environmental Carbon Using H2S issues in those areas and to establish the CCT network in Asia. “Information sending Eiji Sasaoka, Takefumi Morimoto and Shengji Wu bases” are expected to help each country to develop CCT suited for the situation of Okayama University, Japan each country. For that purpose, Japan will help these activities to develop a foundation Md. Azhar Uddin of CCT by each country and to bring up the experienced person on CCT. Through the University of New South Wales, Australia following work program, the results will be expected to attain. Work program The major anthropogenic sources of mercury emission are coal combustion. However, 33

it is very difficult to remove the mercury compounds from the flue gas. Especially, historical context for coke reactivity, some progress in measuring and understanding Elemental mercury vapor is not effectively captured in typical air –pollution control it and predicting its extent that has been made in recent times, and the future device. requirements that will be placed on coke reactivity as blast furnace operators We had presented an Hg removal method using H2S and activated carbon. This method continually strive to have their furnaces become more efficient. based on the reaction of H2S and Hg over the adsorbents. It had been suggested in our previous report that Hg reacts with H2S to form HgS, but the reaction mechanism is not 36-3 well understood yet. Development of SCOPE21 Cokemaking process In this work, the characteristics of the Hg removal were studied. The following results Kunihiko Nishioka, Isao Sugiyama, Hironobu Oshima and Hideki Fujikawa were obtained: (1) the temperature range from 60 to 80oC was preferable for the Hg The Japan Iron and Steel Federation, Japan o removal. (2) At 150 C, the co-presences of H2S, SO2 and O2 were indispensable for the Kenji Kato o Hg removal. (3) The effect of the presence of H2O accelerated the removal at 80 C but Nippon Steel Corporation, Japan depressed it at 150oC. Development of the innovative cokemaking process, SCOPE21 (Super Coke Oven for 35-4 Productivity and Environmental enhancement toward the 21st century) has been Use of a Semi-Continuous Emissions Monitor for Measurement of In-Duct conducted by Japan Iron and Steel Federation (JISF) and Center for Coal Utilization Mercury Removals by Sorbent Injection Japan (CCUJ). It has been performed from 1994 to 2003 as a ten-year research Andrew Karash, Richard A. Harris and William J. O’Dowd program. Some technologies for SCOPE21 process have been developed to realize the US DOE, NETL, USA following concepts. • Effective use of coal resources A 500-lb/hr pulverized coal-fired combustion system at the National Energy • High productivity Technology Laboratory (NETL) was used to evaluate mercury sampling methods, as • Energy saving well as sorbent injection for mercury removal. Measurements characterized the • Environmental protection impact of duct temperature, residence time, and sorbent injection rate on mercury In 2002 the program was in the last stage of a pilot plant test to confirm the function of removal effectiveness of a commercially available activated carbon (Darco FGD, the SCOPE21 process and to collect the scale-up data for designing a commercial manufactured by Norit Americas Incorporated). A Powder River Basin (PRB) sub- plant. The pilot plant was successfully operated for about one year until March 2003. bituminous coal was used in the tests. In-duct removals were studied with the use of The concepts of the SCOPE21 process were verified and the engineering data for a Quicksilver Inertial Separation (QSIS) probe developed by Apogee Scientific. designing a commercial plant was collected at the same time. Mercury measurements were made using a PS Analytical semi-continuous emissions monitor (SCEM), EPA Method 101A, ASTM Method D6784-02 (Ontario-Hydro 36-5 method), and the Frontier Geosciences solid sorbent speciation method. Sampling Evaluation of a CO2 Reaction Mechanism of Coke using Microfocus X ray CT locations were upstream and downstream of the main baghouse on the 500-lb/hr unit Hidekazu Fujimoto, Izumi Shimoyama, Kiyoshi Fukada, Tetsuya Yamamoto and to determine in-duct removal, removal across the baghouse and material balances. A Shozo Itagaki summary of the mercury measurement and removal results is presented. In general, JFE Steel Corporation, Japan there was good agreement between the different measurement techniques employed. Baseline mercury speciation results and sorbent mercury removal performance were Improvement of coke strength against abrasion at the lower part of blast furnace is similar to values reported from full-scale testing at the We Energies Pleasant Prairie needed for a stable operation. Pore structure of coke is important for an improvement Power Plant firing the same coal. Sampling, operating, and maintenance procedures of coke abrasion strength, because its effect influences CO2 diffusion coefficient and which contribute to increased stability and precision of SCEM measurements are coke strength after CO2 reaction. In this study, production of coke samples having discussed. different pore structure was attempted by blending different size of slightly caking coal to coal blend. The effect of pore structure on CO2 reactivity and abrasion after CO2 35-5 reaction was investigated. Characteristics of the Removal of Mercury Vapor in Coal Derived Fuel Gas by In case that larger size (2-3 mm) slightly caking coal was added to coal blend and Iron Oxide carbonized, the pore size distribution of coke became wider and contained larger pore Shengji Wu and Eiji Sasaoka which had higher value of tortuosity than the coke produced by adding smaller size (1- Okayama University, Japan 2 mm) slightly caking coal particles. There were differences in the reactivity and Md.Azhar Uddin reactivity profiles in the coke lump analyzed by X-ray computerized tomography University of New South Wales, Australia between two kinds of coke. These differences are considered to be based on the fact that large pore enhances diffusion of CO2 into inner part of the coke, and that The major anthropogenic sources of mercury emission are coal combustion. concentration of shear stress easily occurs around large pores. Based on this However, it is very difficult to remove the mercury compounds from the fuel gas. knowledge, production technology of high strength coke against abrasion after CO2 Especially, Elemental mercury vapor is not effectively captured in typical air – reaction was developed by means of controlling coal particle size and it is applied to pollution control device. Furthermore, the coal gasification will be a main utilization industrial coke production. method of coal in near future. In this case, the Hg in the coal derived fuel gas has to be removed before use. SESSION 37 We had presented an Hg removal method using iron for the coal derived fuel gas. MATERIAL, INSTRUMENTATION & CONTROLS 1: USC POWER This method based on the reaction of H2S and Hg over the adsorbents. It had been PLANTS suggested in our previous report that Hg reacts with H2S to form HgS, but the 37-1 reaction mechanism is not well understood yet. Development of Creep and Type IV Resistant 9%Cr Steel Containing High Boron In this work, the characteristics of the Hg removal were studied. The following for USC Boilers results were obtained: Hiroyuki Semba, Masayuki Kondo, Masaaki Tabuchi and Fujio Abe (1) The presence of H2S was indispensable to the Hg removal for the coal derived National Institute for Materials Science (NIMS), Japan fuel gas. (2) The lower temperature in range from 60 to 150oC was more preferable for the Hg removal. (3) The effect of the presence of H2O suppressed the removal. Tungsten bearing 9-12% Cr ferritic heat resistant steels, such as P92 and P122 showing (4) At high temperature of 150oC, the absence of CO depressed the Hg removal. higher creep rupture strength than the conventional steel P91, have been developed for thick section components in ultra-supercritical (USC) boilers. However, their creep SESSION 36 strength is not sufficient for applying at the steam condition of 923K/35MPa or more, COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 1: which is a recent target condition in order to increase plant efficiency. Furthermore, KEYNOTE LECTURE & COKEMAKING PROCESS, COKE QUALITY Type IV failure in the heat affected zone (HAZ) of welded joints is a crucial problem 36-1 for these high-Cr ferritic steels, leading to shorter creep lives than those of base metals. 120 Years of Coke Reactivity The research and development project in NIMS on advanced ferritic steels which can Richard Sakurovs be applied at the steam condition of 923K/35MPa as boiler components with large CSIRO, Australia diameter and thick section has been carried out since 1997. In this project, it has been revealed that the addition of B more than 100ppm to the 0.08C-9Cr-3W-3Co-V,Nb- The study of the reaction of coke with carbon dioxide at high temperature has a long <0.003N steel remarkably improves creep strength. The highest creep rupture strength history. In 1884 it was studied to see if it could explain a perceived difference is obtained in the 0.08C-9Cr -3W-3Co-V,Nb-0.0139B-<0.003N steel, resulting in between the behaviour in blast furnaces of beehive-produced coke and the newly- excellent creep strength in comparison with that of P92 and P122. FE-AES analysis introduced by-product oven. Interest in coke reactivity has waxed and waned over clarified that the boron content in M23C6 carbides near prior-austenite grain boundaries the years, depending on how critical its measurement and prediction is felt to be by is higher than that inside the grains. This may suppress coarsening of M23C6 near blast furnace operators at the time. This Keynote presentation will provide a brief prior-austenite grain boundaries during creep deformation, leading to sufficient 34

microstructural stability and excellent creep strength. It has also been demonstrated carbon-free martensitic alloys and ferrite matrix 15Cr steel. This paper describes the that Type IV failure does not occur during creep tests at 923K performed on welded development of tempered martensitic advanced 9Cr steels for 650oC USC boilers. joints of these high-B containing steels even at the stresses in which P92 shows Type 9Cr-3W-3Co-VNb steels strengthened by boron and by nano-size MX nitride IV fracture. Retardation of M23C6 coarsening mentioned above and the HAZ dispersions are promising for application to thick section boiler components of USC microstructure consisting of relatively coarse grains, which is entirely different from power plant operating at 650oC. Carbon-free martensitic alloys, which are that in ordinary high-Cr ferritic steels, may contribute to superior creep rupture modification of low carbon Maraging steels, are promising for USC plant at 700oC and strength of these welded joins. Hence, it is concluded that this high-B bearing 9Cr- above. 3W-3Co-V,Nb steel is one of the promising candidate steels for thick section components in the advanced USC boilers. 37-5 Materials for Ultra-Supercritical Coal-Fired Power Plant Boilers 37-2 R. Viswanathan and Kent Coleman Mechanical Properties of Ultrasupercritical Steam Generator Materials EPRI, USA John P. Shingledecker, Robert W. Swindeman, R.L. Klueh and P.J. Maziasz Udaya Rao Oak Ridge National Laboratory, USA USDOE, NETL, USA

Higher steam temperatures and pressures are required to achieve increased efficiency The U.S. Department of Energy (DOE) and the Ohio Coal Development Office and decreased CO2 emissions in coal-fired boilers. A research program has been (OCDO) have recently initiated a project aimed at identifying, evaluating, and initiated for evaluating the mechanical properties of materials in an Ultrasupercritical qualifying the materials needed for the construction of the critical components of coal- (USC) Steam Generator operating with a main steam throttle condition of fired boilers capable of operating at much higher efficiencies than current generation of 720/760°C/35MPa. Current boiler materials, which typically operate below 600°C, supercritical plants. This increased efficiency is expected to be achieved principally cannot meet the high-temperature strength requirements of such a design, and thus through the use of ultra-supercritical steam conditions (USC). The project goal is to advanced materials must be utilized. A program at Oak Ridge National Laboratory is increase the main steam temperature initially to 760°C (1400°F), while attention also is generating the materials property data and performing materials analysis on a selection given to identifying the materials issues involved in service at temperatures up to of advanced materials. These materials include ferritics (SAVE12), austenitics (Super 870°C (1600°F) in the longer term. The project is intended to complement alloy 304H, HR6W), and superalloys (Haynes® 230, CCA617, INCONEL® 740). High- development and evaluation programs now being carried out in Europe and Japan. temperature mechanical properties research includes: creep/creep-rupture, fatigue, Those programs have identified ferritic steels capable of meeting the strength structural discontinuities (notches), weld evaluation, and weldment properties. The requirements of USC plants to approximately 620°C (1150°F) and nickel base alloys rationale for the selection of materials and test results, with over 8,000 hours of test suitable up to 732°C (1350°F). In this project, the maximum temperature capabilities data, will be discussed. of these and other available high-temperature alloys are being assessed to provide a basis for materials selection and application under a range of conditions prevailing in 37-3 the boiler, for 38.5 MPa/760°C (5500 psi/1400°F) main steam conditions. This paper Improvement of Steam Oxidation Resistance for USC Boiler Steels provides a status report on the progress to date achieved in this project. Hiroshi Haruyama, Hiroyuki Kutsumi, Seiji Kuroda and Fujio Abe National Institute for Materials Science, Japan SESSION 38 Considering recent global environmental problems, it seems to be an GASIFICATION APPLICATIONS & ECONOMICS: 1 important problem to restrain carbon dioxide discharged from thermal power plants which use fossil fuels such as coal and petroleum. Large-diameter tubes, as main steam 38-1 tubes for USC boilers, are required to withstand high temperatures of more than 873K FutureGen Zero Emission Power Plant of the Future over long periods. Targeted steam conditions have been increased up to 903K, 30MPa. Joseph Giove III, Jarad Daniels and Victor k. Der Thus, it is necessary to develop new steels whose creep strength and steam oxidation US DOE, USA resistance will be superior to those of the conventional high Cr ferritic steels. In order to make clear the effect of alloying elements, the authors have made a fundamental The United States is embarking on a future generation of coal plants based on a study on the oxidation behavior for a variety of heat resistant steels in steam. On the revolutionary concept of zero–emissions. The research towards this goal is culminated other hand, we have also tried to improve the steam oxidation resistance by forming a in a project called FutureGen. FutureGen will be the world’s first fully integrated coal protective Cr oxide layer. fired power plant that simultaneously produces hydrogen and electricity while Generally, as Cr concentration is high, steam oxidation resistance is better. And sequestering carbon dioxide. As a full-scale research facility, its aim is to prove out small amounts of Si are effective on the steam oxidation resistance. Our experimental the technical feasibility and potential economic viability for the zero emission result has suggested that trace amounts of S are suggested to have a certain technology option for coal. Its success would lead to future commercial contribution to oxidation resistance in steam at 923K. Although these effects of Cr, Si demonstrations and replication for the market place to address the global climate and S are considered, from a viewpoint of oxidation resistance, practical steel is not change concerns over carbon emissions from coal power plants. In this discussion, the developed yet above 923K. concept and strategy for the FutureGen plant is outlined in the context of the need for a On the other hand, we have also tried to improve the steam oxidation resistance zero-emission coal option. It is envisioned that FutureGen will be a cost-shared by forming a protective oxide layer. When surface strained high-Cr ferritic steels with partnership between the United States government and industry with potential small amounts of Pd was oxidized in steam at 923K, protective and thin Cr-rich oxide participation from international partners. layer was formed in the steel surface. In addition, pre-oxidation in argon flow over 923K to high-Cr ferritic steel without Pd was made to form similar protective oxide 38-2 layer. The steam oxidation resistance at 923K was dramatically improved by these Coal Gasification’s Environmental and Operational Capabilities Today protective oxide layers. In a steam temperature over 973K, austenitic steels are used David L. Denton from the viewpoint of creep strength. The protective oxide layer is formed on the Eastman Gasification Services Company, USA surface of austenitic steels by shot peening. Thus, austenitic steels treated by shot peening are in practical use. Although several coal gasification plants have been built in the past decade or more, those built for power production have primarily been demonstration plants and do not 37-4 fully represent the capabilities of gasification today. This presentation will address the o Ultra-Steel R & D in NIMS for USC Power Plant at 650 C and Above true environmental and operational capabilities of gasification from the perspective of Fujio Abe an experienced operator of the technology. Coal gasification, at appropriate economy National Institute for Materials Science (NIMS), Japan of scale and with an experienced and knowledgeable operator, can perform very reliably and very cleanly – better than any other clean coal technology. Eastman Since 1997, NIMS has been conducting the research and development project on Chemical Company was a pioneer in producing chemicals from coal via gasification. advanced ferritic steels for application to large diameter and thick section boiler Our coal gasification facility has been in continuous commercial use since 1983 and components such as main steam pipe and header of ultra-supercritical (USC) plant at has continued to set new standards of performance, including an average forced outage o o 650 C. Critical issues for the development of ferritic steels for 650 C USC boilers are rate of 1-2%. Eastman has practiced high sulfur removal (>99.9%), volatile mercury the improvement of oxidation resistance as well as long-term creep rupture strength. removal (>90-95%), and carbon dioxide capture for over twenty years. These proven The resistance to Type IV cracking strength loss in welded joints is also serious for capabilities and other experiences and innovations that represent the current construction of thick section boiler components. Furthermore, the thermal cycling capabilities of coal gasification will be described. capabilities of thick section components in USC plant would be severely restricted by fatigue damage. Our project involves the improvement of creep strength, oxidation resistance and creep-fatigue properties for ferritic steels, including welded joints. We have developed several kinds of ferritic steels, such as tempered martensitic 9Cr steels, 35

38-3 coal liquefaction project.In November 2001, Shell entered its first investment in coal Sasol’s Unique Position in Syngas Production from South African Coal Sources gasification through a 50/50 joint venture with its strategic alliance partner, China Using Sasol-Lurgi Fixed Bed Dry Bottom Gasifiers Petroleum and Chemical Corporation (Sinopec) in Yueyang, China. After going JC van Dyk, MJ Keyser and M Coertzen through the normal process of project development, the Board announced its “final Sasol Technology, South Africa investment decision” in June 2003. The gasifier, a 2000 tons coal per day unit, will replace the present naphtha reformer to supply syngas as feedstock to the existing Sasol has been operating the Sasol-Lurgi fixed bed coal gasification process for more downstream urea production units. Planned mechanical completion is end 2005. Two than fifty years, and with ninety seven units in operation still remains the world's other Sinopec projects, similar in size and application to the joint venture, have also largest commercial application of this technology. The combined operational and licensed Shell technology and their EPC development is following closely Yueyang’s engineering expertise vested in Sasol represents a formidable capability in the field of progress.Shell coal gasification technology’s commercialisation success has opened up coal and gasification science. Coal is a crucial feedstock for South Africa’s unique new options and volume in the SCGP critical equipment supply market to significantly synfuels and petrochemicals industry, and is used by Sasol as a feedstock to produce lower the costs. For example, spurred on by supply competition, recent projects have synthesis gas (CO and H2) via the Sasol-Lurgi fixed bed dry bottom gasification recorded around 20% cost reduction (against Buggenum level in money of the day process. terms) for the supply of the Shell gasifier, with its unique water-cooled inner South Africa, as well as many other countries in the world, will for many years to membrane wall and its syngas cooler. With increased commercialisation and supply come rely on its abundant coal resources for energy and specifically for the production options, the unit cost of syngas production using Shell coal gasification technology is of petrochemical products. Synthesis gas production through gasification is growing at expected to reduce further. a rate of approximately 10% per annum [1], indicating that gasification is definitely not a dying technology. The Sasol plants located in Secunda and Sasolburg (South Africa) 38-5 gasify >30 million tons per annum of bituminous coal to synthesis gas, which is Evaluation of Potential Applications for Coal Gasification in Taiwan converted to fuels and chemicals via the Fischer-Tropsch process. The production of Cheng-Hsien Shen, Heng-Wen Hsu, Ching-Lin Shieh, Wei-Chung Chin, Jui-Yen chemicals is currently the dominant application for synthesis gas, followed by power Cheng generation, Fischer-Tropsch synthesis and gaseous fuels. Clean Energy Technology Division, Energy & Resource Laboratories Industrial Sasol-Lurgi gasifiers are extremely robust devices, and coal from sources with widely Technology Research Institute, R.O.C varying properties (e.g. ash content <10% to as high as 35% or “brown coal” with moisture content of approximately 30%) can be gasified provided that certain In Taiwan, 98% of total energy resources must be imported. However, the price of operational changes are implemented. Other properties, like high caking propensity natural gas is very high and many arguments support de-emphasizing nuclear energy. for example, require blending to acceptable levels and /or mechanical modifications. The effectiveness of renewable energy is limited by the environment and climate, as Interpretation of coal characterization data gives an indication of expected gasifier well as the lack of economic incentives for its application. With an abundant supply performance and the suitability of a specific coal source for Sasol-Lurgi Fixed Bed and low cost, coal is the main source of energy in Taiwan. Hence, raising efficiency of Gasification process. It is therefore critically important to gain an accurate and coal utilization and converting coal to a clean, stable energy source is a very important fundamental understanding of the properties and expected behavior of the targeted coal issue in Taiwan. feedstock in order to (1) prepare a suitable conceptual flow scheme and (2) to Gasification technology has the advantages of feedstock flexibility, and syngas can be maximize the eventual probability of success in any proposed gasification venture and applied to produce multiple products, for example electricity, fuel, chemicals…etc. (3) to optimize the operation and profitability of existing plants and (4) effectively However, the capital cost of Integrated Gasification Combined Cycle (IGCC) is high address the environmental aspects. and IGCC’s availability, reliability, and economy is not as good as those of It is the view of the authors that fixed bed gasification technology has a bright future in supercritical pulverized coal boiler power generators. Therefore, it cannot be applied the areas mentioned above and that Sasol has a unique role in the future application in the near-term in Taiwan. However, it is possible for syngas of gasification to act as and commercialization of gasification technology globally. The unique skills of Sasol fuel, for example, if centralized gasification plants were to be set up in specific could however be complementary to those of other parties who share our view on the industrial parks and provide factories with syngas as fuel. The objective of this study future of gasification and related technologies. is to evaluate the potential for syngas application from coal gasification in industrial parks. The result of the study illustrates that the price of syngas was one-third of 38-4 natural gas and one-half of fuel oil per heating value in Taiwan. Consequently, it is Shell Coal Gasification Process and its commercial applications possible that syngas could economically substitute for natural gas and fuel oil. That Thomas Chhoa would be the main application direction for coal gasification technology in Taiwan. Shell Gas & Power, The Netherlands SESSION 39 The Shell Group developed the Shell Coal Gasification Process (SCGP) since the 70’s. LOW RANK COAL UTILIZATION: 3 Over the past 30 years, considerable R&D effort have gone into its development that is 39-1 now commercially proven and available. Today, Shell still continues to sponsor Liquefaction Studies of Low-Rank Malaysian Coal Using High-Pressure High- significant in-house R&D effort to strengthen and improve SCGP’s commercial Temperature Batch-Wise Reactor System applications.The Shell Coal Gasification Process is based on an entrained flow, oxygen Mohd Azlan Mohd Ishak, Khudzir Ismail and Mohd Fauzi Abdullah blown, slagging gasifier using a dry feed system, in which the pulverized coal is University Technology MARA, Malaysia pneumatically transported to the gasifier by nitrogen gas. The produced SCGP syngas Wan Hasiah Abdullah contains about 83% of the energy in the coal feed, known as the cold gas efficiency. A University Malaya, Malaysia wide range of coal feedstock and petroleum coke, including low-rank sub bituminous Mohd Kadir, Abdul Mohamed coal and lignite, can be used as the Shell process is relatively insensitive to coal Universiti Sains Malaysia, Malaysia properties, such as size, reactivity and caking tendency as well as sulphur and ash content. The development process of SCGP included the progressive sizing up of pilot Indirect liquefaction of low-rank Malaysian lignite namely Mukah Balingian (MB) was plants in different locations (Amsterdam, Hamburg, Houston), using various coal and successfully carried out with hydrogen donor solvent i.e. tetralin at temperatures of 360 lignite qualities. Its first commercial application is the NUON (previously called – 450°C and at pressures of 4 – 20 MPa in a 1-litre high-pressure high-temperature “Demkolec”) IGCC plant in Buggenum, The Netherlands, built in 1993. The project batch-wise reactor system. The results thus far indicated that, the percent conversion was conceived and owned by the Dutch government, with Shell supplying the obtained were in the range of 31 – 87%, optimizing at 450°C and 4 MPa with the oil, technology through a licensing arrangement. The NUON plant has a design coal asphaltene and preasphaltene of the coal extract were 89, 8 and 2%, respectively. gasification capacity of 2000 tons per day, and it delivers a net output of 253 MWe, Apparently, it was observed that heat plays an important role in comparison to pressure giving a net efficiency (LHV) of 43%. It started operation in 1994 and actual plant in contributing to high coal conversion and oil yield. Other parameters that were also performance met design conditions/requirements. Despite being one of the earliest being investigated in this study include reaction time (0 – 120 minutes), effect of world scale commercial IGCC plant, it is still one of the most efficient and best stirring rate, and effect of solvent to coal ratio and effect of reactor reaction capacity. environmental performers. In this NUON plant, process water, being considerably less Moreover, both temperature and pressure affect the elemental composition, thermal than wet feed systems, is treated and recycled so there is zero water discharge. Recent characteristics and calorific value of oil and coal liquefaction residue. availability - over 90% (between planned shut down) - is also amongst the best in class.Until 1997, with the exception of the Buggenum plant, SCGP was kept in-house. 39-2 Since then, SCGP is commercialised which has resulted in a number of licensed plants Effects of Hydrogen Transfer by the Exchanged Cobalt on the Liquefaction of currently in the EPC (Engineering, Procurement and Construction) stage. Although Low Rank Coal there are interests elsewhere, these plants are located in China, being the largest coal Motoyuki Sugano, Shin-ichi Ohura, Katsumi Hirano and Kiyoshi Mashimo producer and user in the world. All of them are for chemical feedstock applications and Nihon University, Japan the first of those plants is scheduled to start up in quarter one, 2005. In March 2004, Shell signed a license agreement with a subsidiary of the Shenhua Group – the It is well known that the low rank coals, such as brown and subbituminous coals, are country’s largest coal producer – to gasify coal to produce pure hydrogen for its direct highly oxygenated, much of which is present as carboxyl and phenolic hydroxyl 36

groups. During the cation exchange treatment of low rank coals, carboxyl groups in found by comparing pore size distributions for dried coal before and after the CWS coal structure are exchanged with desired cations. When the specific cation was production. These results imply that kneading of low-rank coal with high shear stress exchanged to coal, gasification and pyrolysis reaction of the coal were promoted. resulted in removing of water from the coal particles and in crashing fine pores in the On the hydrogenolysis of demineralized Adaro subbituminous coal with tetralin and coal. Water dissociated from coal stays in the continuous phase of water by the crush elemental sulfur at 420 , the upgrading, such as the decrease of acetone insoluble of fine pores in the coal. Product slurry was fed into a CWS pre-heater having yield and the increase of hexane soluble yield, was enhanced by exchanges of several processing ability of 150 L/h. Dried coal particles with steam were successfully kinds of cations (Co2+, Ni2+ and Fe2+) to coal [1]. On the hydrogenolysis of coal, it is exhausted from the outlet of the pre-heater. It was found that the water in the CWS was well known that several kinds of metals derived from metal carbonyls, which are completely vaporized in the pre-heater without blockage of feeding tube. Combination soluble in organic solvents, finely disperse to coal and enhance the hydrogenolysis of of these two processes will increase efficiency of a coal gasifier or a boiler. coal [2]. In comparison with the hydrogenolysis of the demineralized Adaro coal with oxide, sulfide or complex (metallocene or metal carbonyl) of cobalt, nickel or iron 39-4 (tetralin and elemental sulfur), the upgrading of coal was enhanced significantly on the Upgrading of Brown Coal for Production of Coal-Water-Mixture (CWM) reaction of cation (Co2+, Ni2+ and Fe2+) exchanged coal [3]. However, relation between Karin Laursen, Akihiro Kosuko, Masakazu Sakaguchi, Hiroyuki Nakagawa, Kouichi the upgrading of coal and the mechanism of hydrogen transfer from tetralin and Miura pressurized hydrogen gas has not been clarified. Kyoto University, Japan In this study, the hydrogenolysis of cobalt exchanged Adaro coal, which the hydrogen source was restricted either pressurized gas or solvent, was carried out. The effect of Coal-Water-Mixtures (CWM) with high solid-to-liquid fraction have successfully been hydrogen transfer from pressurized gas or solvent on the upgrading of coal was produced from high-rank coals, but so far no economically feasible methods have been discussed. Further, the catalytic effect of exchanged cobalt on the hydrogen transfer found for producing CWM from brown coal. The high moisture content, high porosity and the upgrading of the exchanged coal was discussed with the comparison of the and hydrophobic nature of brown coal makes it impossible to produce CWM from raw results after the hydrogenolysis of demineralized coal and demineralized coal plus brown coal, and some type of upgrading of the coal is required. Loy Yang brown coal complex [(C5H5)2Co or Co2(CO)8]. from Latrobe Valley, Victoria, Australia, was treated in a 20 ml stainless steel Compared with the hydrogenolyses of Co exchanged coal and the complex added coal autoclave at temperatures ranging from 200 to 350oC under steam drying and with tetralin and pressurized nitrogen gas, the upgrading of coal was enhanced on the hydrothermal dewatering conditions. Solid products from the upgrading processes hydrogenolyses with decalin and pressurized hydrogen gas. The amounts of were subjected to a range of analysis including proximate and ultimate analysis, transferred hydrogen on the hydrogenolyses with decalin and pressurized hydrogen gas mercury porosimetry, moisture holding capacity, XRD, FTIR and TEM, while gaseous were lower than that with tetralin and pressurized nitrogen gas. Therefore, the and liquid products were analyzed by GC and TOC, respectively. Based on upgrading of coal was considered to be enhanced because coal radicals were stabilized these chemical and structural information, this paper will discuss the transformations by the hydrogen radicals derived from the pressurized gas on the surface of Co. The taking place in the brown coal during upgrading. Finally, this paper will discuss the upgrading of coal occurred significantly on the hydrogenolysis with tetralin and effect different upgrading conditions will have on the potential for using the upgraded pressurized hydrogen gas, in particular, the yield of residue was only 0.3 % on the coal for CWM production. hydrogenolysis of Co exchanged coal. The amounts of transferred hydrogen on the hydrogenolyses of Co exchanged coal were almost equal on the hydrogenolyses of the 39-5 demineralized coal plus complex of Co. However, the upgrading of coal occurred Coal-Water Fuels from Chinese Low-Rank Coals significantly on the hydrogenolysis of Co exchanged coal in comparison with the Michael L. Swanson, Mark A. Musich and James E. Tibbetts hydrogenolysis of the demineralized coal plus complex of Co. University of North Dakota Energy & Environmental Research Center, USA Compared with the hydrogenolyses of Co exchanged coal and the Co2(CO)8 added coal with decalin and pressurized hydrogen gas, the yields of residue and ASHI was China, with its vast coal reserves, has become the world’s largest coal user, consuming decreased on the hydrogenolyses with naphthalene and pressurized hydrogen gas. On over a billion tons a year. Some of the largest reserves of low-sulfur coal could be used the hydrogenolyses with naphthalene and pressurized hydrogen gas, the yield of with minimal environmental impact are located in the northeastern and southwestern tetralin were 1.4, 3.8, 9.1 and 8.8% on the reaction of the demineralized coal, parts of China. These coals tend to be subbituminous or lignitic low-rank coals (LRCs) (C5H5)2Co added coal, Co2(CO)8 added coal and Co exchanged coal. Therefore, with high moisture contents. This property usually restricts their use to mine-mouth hydrogen shuttling through naphthalene was enhanced by Co derived from Co power generation. Conventional evaporative drying processes can be expensive and are exchanged coal and Co2(CO)8. Accordingly, the upgrading of coal on the generally only used when the dried coal can be utilized immediately to avoid handling hydrogenolyses of Co exchanged coal with pressurized hydrogen gas was observed problems such as moisture reabsorption, dust generation, and spontaneous combustion. significantly irrespective of the hydrogen donatability of solvent. It was reported that A nonevaporative process called hydrothermal treament (HTT) was developed by the complex of Co dispersed among the molecules of solvent and coal [2], Co in Co Energy & Environmental Research Center to convert high-moisture LRCs into an exchanged coal was attached to carboxyl group in coal macromolecules by the ion easily transported liquid fuel. HTT induces rapid coalification at moderate temperature exchange treatment [4]. Therefore, upgrading of Co exchanged coal was enhanced and pressure in the presence of liquid water and makes the LRCs hydrophobic with significantly because Co dispersed finely into the coal macromolecules with attached similar equilibrium moisture levels to bituminous coals. This process enables the carboxyl group irrespective of the size of coal molecules. production of additive-free LRC-water fuels (LRCWFs) with solids loadings comparable to those made from high-rank bituminous coals and energy densities 39-3 comparable to those of the raw coal. Upgrading of Low Rank Coal as Coal Water Slurry and its Utilization Several LRCs from northeast China were treated by the HTT process and made into Ryo Moriyama, Shohei Takeda, Masaki Onozaki, and Yukuo Katayama LRCWFs with energy densities greater than 14654 kJ/kg (6300 Btu/lb). These The Institute of Applied Energy, Japan LRCWFs compared favorably with LRCWFs made from American LRCs which have shown excellent combustions and emissions characteristics in pilot-scale combustion Low-rank coals are characterized by their high moisture content, which results in low tests. With lower LRCWF production costs in China, HTT could provide an efficiency of combustion or gasification because of latent heat of water evaporation. opportunity to develop low-cost pipeline transportation in China. This would enable The low-rank coals further have high ignitability after drying. This high moisture China’s enormous LRC reserves to be developed in an environmentally responsible content and ignitability have placed economic restrictions on transportation and have manner for widespread internal use and might lead to the development of a LRC export required the power plants to be situated directly adjacent to the opencast mines. market for these coals. Several drying technologies for the coals have been considered in recent years while these technologies have not been commercialized because of high cost of water SESSION 40 treatment and spontaneous ignition of dried coal. Effective reforming of the low-rank SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 1: coals has been required. FISCHER-TROPSCH SYNTHESIS This paper introduces two new processes for low-rank coal upgrading technology. One 40-1 is coal water slurry (CWS) production process from the coals proposed by KEM The Structure Change of Co/Zro2/Sio2 Catalyst during Fischer-Tropsch Reaction Corporation and the other is pre-heating feed process of the CWS developed by the Yuhan Sun, Wei Zhou, Jiangang Chen authors. CWS was produced with the special kneader developed by KEM and Chinese Academy of Sciences, P.R.China Corporation of Japan Systematization Laboratory. We received the indication of this brown coal upgrading technology from KEM. In this paper, we tested this technology Cobalt-based catalyst is a reasonable choice for F-T synthesis for its merits of high using Australian brown coal containing 62% of water and Indonesian brown coal activity, negligible WGS reaction and good selectivity [1~5]. However, the relative high containing 35% of water as samples. Sample with or without water was fed into the cost of cobalt requires the cobalt-containing catalyst with a long life. The study on the kneader and was heated with kneading. After a certain time of kneading, brown coal catalyst deactivation and structure change during the reaction is important. The [6~10] was converted into pumpable CWS without addition of surfactant. Properties of water Co/ZrO2/SiO2 catalyst has good F-T performance but the deactivation is hardly in the CWS were investigated based on its freezing properties. Water strongly understood. Thus a systemic study on the structure change of Co/ZrO2/SiO2 catalyst interacted with the coal having freezing point of < -50°C became free or bulk water during F-T reaction was carried out. having freezing point of about 0°C. Furthermore, crush of fine pores in the coal was 37

CO hydrogenation was performed at 463K, 2MPa and 500h-1 with stoichiometric wt. % Pd-supported beta catalyst with SiO2/Al2O3 ratios from 16.2 to 150 was syngas feeds (H2:CO=2:1) in a fixed bed reactor. A long-time running was carried out applied in the second reactor (down stream). Irrespective of the SiO2/Al2O3 ratios of and an apparent deactivation was observed (see Fig.1). According to the curve, the the beta zeolites, the products showed a sharp carbon number distribution in the course of the reaction could be divided into three periods (see Table 1 and 2). During range of C3-C6 and a high selectivity to iso-paraffins as shown in table 1. A the first period (24-168h), the catalyst deactivated partially. In the second period (168- significant change of selectivity to iso-paraffins was observed with the variation of 314h), the catalyst deactivated evidently. In the third period (314-411h), the catalyst the SiO2/Al2O3 ratios of the Pd/beta catalysts in the second reactor. Moreover, the kept a low activity. The catalyst deactivated entirely. Surprisingly, the CO2 selectivity stability of the Pd-supported beta catalyst was slightly influenced by the enhanced with time on stream. In order to investigate the catalyst deactivation, a SiO2/Al2O3 ratios. The effect of SiO2/Al2O3 ratios of the Pd/beta catalysts on the similar run was performed before the severe deactivation took place. Then the fresh selectivities to isomers at different stage of time on stream will be discussed in detail catalyst, the partial deactivated catalyst (time on stream 168h) and the total deactivated in this presentation. The reaction results can be correlated very well with the acidity catalyst (time on stream 411h) were sampled for characterization and named as F, P and crystallization of the beta zeolite. and T, respectively. In addition, some spent samples (P and T) were calcined at 773K for 4h in the air to remove the residual hydrocarbons and named as CP and CT. 40-4 A small broad peak appeared at 900~1100K as a function of time on stream from TPR A Study on the Fischer-Tropsch Synthesis in the n-Hexane/n-Decane Mixed profiles (see Fig.2). The peak was thought as the H2 consumption of the species of the Solvent cobalt silicates and/or hydrosilicates [11]. The areas of the total profile (390~1220K), of Wensheng Linghu, Xiaohong Li, Kenji Asami and Kaoru Fujimoto the former part (390~873K) and of the latter part (873~1220K) were integrated (see The University of Kitakyushu, Japan Table 3). From the TPR profiles and the quantitative results, the difference between CP and CT was larger than that between F and CP. It was concluded that the formation of Fischer-Tropsch synthesis (FTS) has regained interest during the last decade as an the cobalt silicates and/or hydrosilicates was responsible for the deactivation and the option for the production of clean fuels and chemicals from either coal or natural gas species was mainly produced in the course of the reaction. due to changes in fossil energy reserves and environmental demands [1-2]. BET surface area of the three samples decreased in the sequence of F>CP>CT, with The reaction performance of FTS in n-hexane/n-decane (n-C6/n-C10) mixed solvent in a average pore size increasing and pore volumes almost the same. This result suggested fixed bed reactor was studied in this work. Experimental apparatus and detailed analysis [12] that a particle growth course occur . Moreover, the dispersion of the catalysts were procedure has been reported in our earlier paper [3]. The catalyst used was a SiO2 shown in the same sequence of F>CP>CT. It also proved that the particles of the supported cobalt catalyst, which was prepared incipient wetness impregnation method. catalyst grew. In addition, the difference between F and CP was larger than that Composition of the catalyst was Co: 20 and SiO2: 80 by weight. A typical reaction o between CP and CT. It indicated that the particle growth was also a cause for the conditions were T=240 C, Ptotal=4.5 MPa, Psolvent =3.5 MPa and W/F = 5 g-cat.h/mol. deactivation and the course mainly occurred in the reduction or in the initial period of Argon was used as the internal standard in the feed gas. The results showed that CO the reaction. conversion in n-C6 was slightly higher than that in n-C6/n-C10 mixed solvents and in n- TG analysis was done on the extracted T catalyst (see Fig.3). The deposition of carbon C10 (Table 1). In general the composition of the solvent has not obvious influence on was proved and it was also one cause for the catalyst deactivation. The carbon was CH4 selectivity and CO2 selectivity. The composition of the solvent, however, has formed during the course of the reaction and might come from the Boudouard reaction. remarkable effect on the products distribution of the FTS under the reaction conditions + used in this study. The higher heavier products (C10 fractions) were obtained in the 40-2 mixed solvents and n-C10 than that in n-C6 solvent. The olefin content of the products at Chemical Effect and Spatial Effect of New Bimodal Catalysts for Fischer-Tropsch range of C2-C10 has not obvious change, however the olefin content of the heavier + Synthesis products (C10 fractions) increased with the increase of the n-C10 content in the mixed Yi Zhang, Yoshiharu Yoneyama and Noritatsu Tsubaki solvent. More data and detailed discussion will be presented at the meeting. Toyama University, Japan Table 1. The reaction performances of FT reaction in different solvents.

Run No. Solvent CO conv., % CH4 sel., % CO2 sel., % A catalyst support with both small pores and large pores, as well as a distinct bimodal A n-C6 46.86 8.54 1.45 pore structure, has excellent advantages in industrial solid-catalysis reaction because B 75%n-C6 /25%n- 42.58 9.51 1.16 the large pores provide pathways for rapid molecular transportation and the small pores C10 serve a large area of active surface. A simple preparation method of bimodal supports C 50%n-C6 /50%n- 44.02 8.77 1.55 was developed by introducing SiO2 or ZrO2 sol into large pores of SiO2 gel pellet C10 directly. The pores of the obtained bimodal supports distributed distinctly as two kinds D 25%n-C6 /75%n- 42.29 9.46 1.84 of main pores. On the other hand, the increased BET surface area and decreased pore C10 volume, compared to those of original silica gel, indicated that the obtained bimodal E n-C10 41.51 9.73 1.22 support formed according to the designed route. The obtained bimodal support loaded with cobalt was applied in slurry-phase Fischer-Tropsch synthesis (FTS). The bimodal 40-5 catalyst presented the best reaction performance in slurry-phase FTS as higher reaction A Comparison of Co and Fe Based Catalysts for Fischer-Tropsch Synthesis rate and lower methane selectivities, because the spatial promotional effect of bimodal Anton C. Vosloo, Philip Gibson and Peter J. van Berge structure and chemical effect of the porous zirconia were available inside the large Sasol Technology, South Africa pores of original silica gel. The properties of bimodal supports and catalysts were determined by BET, TGA. XRD, TEM, In-situ FT-IR, TPSR. The conversion of synthesis gas (CO and H2) to hydrocarbons by means of the Fischer- Tropsch (FT) process can be catalysed by a number of catalysts e.g. Fe, Co, Ni and Ru. 40-3 The only two catalysts that are currently of commercial importance are Co and Fe. Selective Production of Iso-paraffins from Synthesis Gas over Co/SiO2 and Although most of the proposed Gas-To-Liquids (GTL) plants in the world are based on Pd/beta Catalysts Co FT catalysis, Fe as a catalyst can still play a significant role in future synthetic fuel Zhong-Wen Liu, Xiaohong Li, Kenji Asami and Kaoru Fujimoto and chemicals plants. These two catalysts will in general terms be reviewed with The University of Kitakyushu, Japan regards to their preparation methods, kinetic and selectivity behaviour and areas of application. Some of Sasol’s recent developments with regards to both these types of The Fischer-Tropsch (FT) synthesis is an effective route to convert coal, natural gas, catalysts will also be discussed. or biomass derived synthesis gas (syngas, CO + H2) to liquid fuels and high-value added fine chemicals [1]. However, the FT products which are composed mainly SESSION 41 mixture of normal paraffins are nonselective and the product distribution is COAL PRODUCTION & PREPARATION: 2 controlled by the so-called Anderson-Schulz-Flory (ASF) polymerization kinetics 41-1 [1]. To selectively synthesize desired products such as diesel or high-octane gasoline, Commercially Viable Strategies for Enhancing Coal Quality it is essential to circumvent the ASF distribution. In our previous investigations [2,3], A. Patwardhan and Y. P. Chugh a fundamental concept by using physical mixture of a FT catalyst to synthesize long- Southern Illinois University at Carbondale, USA chain hydrocarbons and a Pd-supported solid acid catalyst to hydroconvert the FT products into iso-paraffins was developed and experimentally evaluated both in one The focus of this research is on coal quality enhancement which includes reduction in reactor and a consecutive dual reactor systems. The present investigation aims at the sulfur content and increase in heating value through innovative coal cleaning studying the effect of SiO2/Al2O3 ratios and crystallization of beta zeolite on the strategies involving fine coal cleaning and plant optimization. Preliminary evaluations performance of Pd-supported beta catalysts for the selective production of iso- on five mines in Illinois have indicated a potential to reduce the lbs SO2/mmBtu of paraffins in a dual reactor system. In the first reactor (up stream), a 20 wt.% Co/SiO2 these coals by up to 20% while increasing the product heating value by 300-450 catalyst was loaded for the production of FT hydrocarbons under the conditions of Btu/lb. In addition, the evaluations predict increases in coal yield by 2-6% depending 508 K, 0.1 MPa and W/F of 4.97 g.h/mol. To decompose the heavy hydrocarbons in on the mine evaluated. Based on the results of these evaluations a utility company has FT synthesis, a certain amount of beta zeolite was physically mixed with the cobalt independently estimated a cost reduction of $2.00/ton through the implementation of catalyst. 0.5 these concepts. 38

This research tools or strategies presented here can be used alone or in combinations to been tested in an operating coal preparation plant. Two different sets of mesh panels improve mine profitability through enhancement of coal quality. The strategies have been used to separately investigate the classification at d50 sizes of 150 micron include (i) SOx reduction primarily through ash reduction (increased BTUs) and and 45 micron, respectively. A head-to-head comparison has been made between the secondarily through pyritic sulfur reduction while maintaining clean coal performance of a Pansep screen and the bank of classifying cyclones operating in a characteristics for the entire product suitable for off-site power generation, (ii) SOx plant. Long-term tests over a period of one week have been conducted to investigate reduction through development of two products: 1) low ash- low sulfur content product the sensitivity of the performance of the Pansep screening technology. suitable for off-site power generation, and 2) high ash-high sulfur product suitable for Results of these studies will be discussed in this publication. on-site or near-mine site power generation or suitable for industrial markets, (iii) Application of partial coarse coal liberation for improving sulfur rejection and hence 41-5 lowering SOx, (iv) Application of advanced fine (-100 mesh) coal cleaning for Enhanced Gravity Floatation: A Novel Way of Cleaning Fine Coal increased coal recovery, and, (v) Overall plant optimization to operate the preparation M.K. Mohanty plant for production of product qualities driven by contractual requirements. Southern Illinois University at Carbondale, USA The strategies developed in this project are based on innovative applications of commercially available technologies while minimizing the capital investment A novel separation process namely, Enhanced Gravity (EG) Flotation has been requirements and requiring minimal changes to the current operation of the cleaning invented to treat the entire 1 mm x 0 coal fraction of a run-of-mine coal in a single plant. In addition, particular emphasis is on adherence to the coal quality requirements process. Unlike a conventional enhanced gravity concentrator which rotates to produce specified by the contracts of individual mines. Subject to these constraints, a centrifugal field, the EG Float Cell is fed with a tangential feed slurry, which spirals development of customized strategies is shown to achieve the goal of coal quality and around the outer section of the Cell. This rotary motion of the slurry generates a recovery enhancement. centrifugal field of sufficient magnitude to achieve an effective separation of coal pyrite particles, both coarse and fine as well as coarse refuse particles and their 41-2 concentration in the outermost section of the cell. A majority of the fine refuse Dewatering Ultr-Fine Clean Coal in a T.H. Filter Press particles is entrained with the clean coal slurry flowing towards the inner section of the A. Patwardhan and Y. P. Chugh Cell. By allowing this slurry to pass over a screen surface of a desired aperture size, the Southern Illinois University at Carbondale, USA coarser clean coal is separated and directed to the clean coal product launder, whereas B. J. Arnold the mixer of fine coal and refuse undergoes to a flotation step. This flotation step PrepTech Inc, USA achieves a separation of fine coal from the fine refuse particles. Thus, one feed stream N. Terblanche of 1 mm x 0 size coal results in three products after being processed by the EG Float PrepQuip (Pty.) Ltd, South Africa Cell: a combined coal pyrite and coarse refuse product, a fine refuse product and a clean coal product. The results obtained from this study will be the subject matter of Approximately 10% of the energy in mined coal lies in the –100 mesh particle size this publication. fractions. Primarily due to dewatering constraints, this valuable resource is discarded in ponds. Technological developments in the area of fine coal cleaning have provided SESSION 42 mine operators the ability to achieve near-perfect separations even in the ultrafine size COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 2: ranges. The adoption of these technologies by the industry, and thus, the ability to COKE QUALITY, COAL CHARACTERIZATION, ANALYSIS utilize the significant energy resource has been limited by the inability of existing 42-1 dewatering technologies to produce a low moisture content product with total particle Research on Coke-Making of Increasing a Ratio of High-Volatility Coal to the capture efficiency at a low cost. Coal Blend from Analysis of the High Temperature Property of the Metallurgy This results of the study reported here successfully demonstrates such a low-cost, high- Coke efficiency filter press technology for dewatering flotation clean coal products from two Bai Xi, Keliang Pang, Jianjun Yang and Guiying Xu coal mines. In-plant demonstration of this technology at these two locations provided Anshan University of Science and Technology, P.R.China stable, trouble free operation while achieving an excellent dewatering performance at high throughputs. At one location, filter cakes with residual total moisture contents in Through the carbon solution reaction of the coke under the condition of simulating the the 19-21% range were achieved. At the other location 25-27% residual total moisture blast furnace fusing zone, seeing about the high temperature property and the variety contents were achieved. optical texture of the coke, the study shows that the isotropic texture has anti-alkali Engineering economic evaluations have indicated that a fine coal product can be character, but isotropic texture is mainly produced by high-volatility coal, therefore, produced using column flotation and the filter press at the cost of $5.41/dry ton for one under the situation of not quite emphasizing the strength of cold stage in coke, we can mine. With appropriate blending strategies, profitability can be shown to increase by increase the gas coal appropriately. The degradation velocity of the coke does not show $900,000 per year for this 2 million tons per year mine. For the second 2.6 million the variety in the carbon solution loss because of the increment of the gas coal. tons per year mine, profitability was projected to increase by $2,000,000/year through Increasing the gas coal is reasonable that it can not only make the cost of the coal the application of the concepts presented here. blend lowered, the ash and the sulfur in coke reduced, but also make full use of the coal resources. 41-3 Reducing Moisture Content by Hot Water Drying Method 42-2 Datin Fatia Umar and Bukin Daulay Optimisation of Preparation of Coal Charge for Coke Making Research and Development Center for Mineral and Coal Technology, Indonesia L. Parthasarathy, N.K. Ghosh and M.K. Sharma Hiromoto Usui SAIL, India Kobe University, Japan R. Venugopal Indian School of Mines, India Experiments have been performed to measure the effects of residence time, processing temperature and coal particle size on the moisture content of upgraded low rank coal Coking coals used in SAIL plants are characterized by wide difference in their by hot water drying (HWD) method. A low rank coal from Berau, East Kalimantan properties in terms of ash content, caking/ coking properties, vitrinite content, rank and which is used in this study referred to sub-bituminous coal with moisture content of grindability index. Organic & inorganic inert content (about 50%) and middling & 18.92% and calorific value of 5477 kcal/kg in air dried basis. The results indicate that rejects (8-25%) in the indigenous coals, which constitute about 50% of the coal blend, the optimum condition of process reached at residence time of 60 minutes, processing are quite high. The imported coals used in the blend are characterized by temperature was 300°C and coal particle size was less than 0.5 cm. At this condition comparatively low ash (9-10%), higher vitrinite content (60-70%), high FSI values (7- the moisture content can be reduced to become 4.00% and calorific value increase up 8) and contain significant percentage (60-65%) of -3mm size fraction. Preparation of to 6755 kcal/kg in air died basis. coal charge from such a heterogeneous blend assumes important significance from the point of view of reducing the heterogeneity and preparing a coal charge that is 41-4 homogeneous in nature. In-Plant Testing of the Pansep Screen The present method of evaluating the level of coal charge preparation only by the Manoj K. Mohanty, Z. Wang, V. Gupta, S.K. Biswal, E. Bane Kroeger crushing level (% through 3 mm) is not adequate and does not take into account the Southern Illinois University, USA aspect of homogenization. For better evaluation, additional parameters, which J. Hirshi characterize the distribution of inert in the different size fractions, are also to be Illinois Clean Coal Institute, USA considered. Extensive pilot oven (250 kgs.) tests were carried out at R&D Centre, SAIL using the Past studies have indicated that the inefficiency in fine particle size classification in same coal blend but with different methods of coal charge preparation like, blend coal preparation plants results in significant loss of both quality and quantity of fine crushing, group wise crushing, group wise crushing with separation of fines and blend clean coal product. With an aim to improve upon the performance of fine particle size crushing with separation of fines. Though the coal blend composition was same in all 2 classification, a newly developed Pansep Screen having a floor space of 0.5 m has the tests, different coke quality parameters (M40, M10 and micro strength) could be 39

achieved due to the difference in coal charge preparation technique. The difference in Furthermore, the results indicate the necessity of an ample amount of Hm component coke quality in the above cases can be attributed to the difference in the distribution of which can exist stably in the softening temperature. pure coal substance and ash content in the different size fractions. From these tests, the following three parameters were identified which can better 42-5 evaluate the level of preparation of coal charge for coke making. The Study of Nanopores in Coal using Xe and Hyper-Polarized Xe NMR Content of coarse size fractions (+3 mm) in coal charge Spectroscopy Ratio of content of -1.4 specific gravity fraction in the coarser size fraction (+3 mm) Koji Saito and Koji Kanehashi and total coal charge Nippon Steel Corporation, Japan Coefficient of distribution of ash in the different size fractions of the coal charge Nanopores in coal are of great significance because of its influence on coal behavior With the help of the above new evaluation method, it would be possible to during mining, preparation and utilization processes. Recently, a new carbonization scientifically approach the problem of optimization of preparation of coal charge for process with high temperature preheating has been developed as Japan National coke making. Project (SCOPE 21). A mechanism which improved the results of coking test was examined with coal properties by solid state NMR. Though nanopore of coal is very 42-3 critical factor for carbonization reaction, there is no information between nanopore size Determination of Relations Connectiong Coking Coal Price with Selected Quality and its chemical composition of nanopore wall. It is well-known that Xe NMR is very Parameters powerful to estimate nanopore structures [1], at the same time there is a lack of Urszula Ozga-Blaschke and Stanislaw Blascke information for chemical composition of nanopores. In this paper, the nanopores Mineral and Energy Economy Research Institute, Poland structures of rapid preheat treated sample of Witbank coal in new carbonization process have been investigated using the combination between Xe and hyper-polarized The paper presents the method of coking coal valuation. The method comprises on Xe gas NMR spectroscopy [2]and its relaxation time. It has been clarified that the determination the dependence of coal price from quality parameters of coal. molecular structure of coal has been relaxed by the rapid preheating treatment and Technological value of coal depends on many different physical, chemical and there is a close relation in hydrogen bond and relaxation of molecular structure of coal. physico-chemical parameters. The choice of the set of parameters that were taken into Typical result of coal is shown (up-field peak; aliphatic regions, down-field peak; account was based on the criterion of coke yield and the quality of achieved aromatic regions). And then, as nanopores is increasing, reaction rate of carbonization metallurgical coke. The quality parameters of coal that influence the quality of coke becomes bigger. And also, these combination techniques showed the estimation of are: the indexes that characterise rank of coal (Vdaf, Ro), coke-making parameters average pore size for coals using our developed relation and also these chemical (caking properties, plasticity, and dilatation) as well as the content of ballast and compositions because the activity of hyper-polarized Xe gas is lost and relaxation time harmful components (moisture, ash, sulphur, phosphorus, alkalis). is short with the interaction of πelectron as soon as this gas puts into aromatic regions. The impact of each particular coal quality parameters on economics of coking process, on yield of coke and on coke quality was analysed. The correction coefficients were SESSION 43 evaluated that change the price of coal when chosen parameters deviates from the level MATERIAL, INSTRUMENTATION & CONTROLS 2: FUNCTIONAL assumed as the standard one. Two different variants of algorithms for coking coal MATERIALS valuation are proposed basing on selected quality characteristics. The variants differ by 43-1 the way of coal valuation regarding the coke-making parameters. Assuming that coal Development of Microporous Inorganic Membranes for Separation and price is a measure of use value of the coal, these algorithms can be used for forming Purification of Hydrogen the structure of coking coal pricing formulae. Roddie R. Judkins and Brian L. Bischoff Oak Ridge National Laboratory, USA 42-4 Change In The Aggregate Structure of Coal during Heat Treatment Activities are discussed concerning the development of microporous inorganic Haruo Kumagai membranes by Oak Ridge National Laboratory. These membranes have effective pore Hokkaido University, Japan diameters less than 2 nm. The International Union of Pure and Applied Chemistry Izumi Shimoyama designation for membranes of this pore size is microporous, although descriptively, JFE Steel Co., Japan they are nanoporous. Results of recent, i.e., from about January 2002 to the present, Yasuyuki Harada developments are discussed. Current development is directed to the fabrication of Mitsubishi Chemical Co., Japan tubular metal-supported ceramic membranes. The thin membranes are applied to the inner surface of the tubular supports, in part to prevent damage to the membranes Because of the importance of thermoplastic properties, which have definitive effects on during handling and installation into a separation system. Metal-supported membranes the properties of the resultant coke, much attention is being devoted to the also have advantages over ceramic-supported membranes with respect to integration thermoplastic characteristics of coking coal. The thermoplastic phenomenon is into gas separation units because they can be welded to the metal support structures believed to be related to the coal rank and is governed by the chemical and physical such as tubesheets. Characterization, flow, and separation performance data are structure, especially aggregate structure of the coal molecules. In this study, change in discussed. Separation factors for hydrogen, which are indicative of the selectivity of the aggregate structure of coal molecules induced by heating is investigated with in- the membranes for hydrogen in a binary gas mixture, are very high and are coupled situ pulse 1H-NMR. with very high permeances, or the volumetric flow per unit of surface area per unit of The variations of molecular mobility of coking and slightly-coking coal due to change transmembrane pressure difference. Performance data reported include permeance, in aggregate structure were monitored with pulse 1H-NMR employing a solid-echo ideal separation factors, and separation factors for actual gas mixtures. Physical pulse sequence. The echo signals obtained during heat treatment were deconvoluted properties of these membranes are also reported. This paper will also address the into a set of one Gaussian and three Lorentzian decay components which represent the status of classification and nonproliferation reviews, which are required prior to release immobile, intermediate, mobile and liquid-like component, respectively. The changes and use because of legacy classified technology issues. in the fractional intensity of mobile component (fHm) calculated from the signals during heat treatment under a flow of nitrogen at a heating rate of 3K/min well 43-2 corresponded to the softening and resolidification phenomena of coal. For both of Electrochemical Corrosion Rate Probes for High Temperature Energy coking and slightly-coking coal, apparent viscosity, a, determined by the needle Applications penetration method varies in agreement with the variation in the fHm, and the Bernard S. Covino, Jr., Sophie J. Bullard, Stephen D. Cramer, temperature of the minimum in the ha curve corresponds to the temperature at which Gordon R. Holcomb and Małgorzata Ziomek-Moroz fHm shows its maximum value. These results indicate that the deconvolution of the U.S. Department of Energy, USA signal into several components is appropriate for evaluating the thermoplastic Michael Cayard and David A. Eden phenomenon of coal upon heating, and also that the thermoplastic phenomenon is InterCorr International, USA closely related to the change of the Hm component. For both coking and slightly-coking coal, the spin-spin relaxation time,T2, for Hint and Corrosion occurs in the high temperature sections of energy production plants due to a Him, T2Hint and T2Him, display almost constant values during heat treatment. In case number of factors: ash deposition, coal composition, thermal gradients, and low NOx of coking coal, the T2 for Hm, T2Hm, maintains a stable value, representing the fact conditions, among others. High temperature electrochemical corrosion rate (ECR) that the Hm newly provided from dissociation of aggregate structure is homogeneous probes are rarely used at the present time, but if they were more fully understood, in terms of nuclear spin relaxation, and exists stably in the softening temperature corrosion could become a process variable at the control of plant operators. range. T2Hm for slightly-coking coal demonstrates a similar behavior, but the Research is being conducted to understand the effects of probe composition, ash temperature range in which Hm exists stably is narrower than that for coking coal. As composition, environment chemistry, and measurement technique on the accuracy, discussed above, the differences in the thermoplastic phenomenon between coking and response, and longevity of electrochemical corrosion rate probes. The primary goal is slightly-coking coal can be revealed with the variations of molecular mobility of coal. to understand when ECR probes accurately measure corrosion rates and when they are The results obtained from in-situ pulse 1H-NMR indicate that the thermoplasticity of simply qualitative indicators of changes in the corrosion processes. Research to date coal is affected by not only the quantity but also the quality of the Hm component. has resulted in moderate successes where the ECR probe corrosion rates and corrosion 40

rates from mass loss coupons agree within a factor of 2. This good agreement was hydrogen separations. Thus far, no perfect solution has been emerged. A different found to depend on the composition of the sensors, with the best results coming from material, carbon molecular sieve (CMS), has been pursued by us for this purpose. CMS more highly alloyed materials such as 316L stainless steel and poorer results from membranes, due to their unique porous and surface properties, have exhibited unique carbon steel sensors. Factors being considered to help explain the good or poor separation properties. By altering carbon precursor materials and pyrolysis conditions, agreement between mass loss and ECR probe corrosion rates are: values selected for membranes selective for H2, CO2, O2, or hydrocarbons can be prepared, as reported in the Stern-Geary constant, the effect of internal corrosion, and the presence of the literature. Further, the carbon surface is considered inert for most industrial gases; conductive corrosion scales and ash deposits. thus, unlike palladium-based membranes, it is resistant to attack by sulfur compounds. With a properly selected pore size, the CMS membrane delivers an excellent 43-3 permeance at intermediate temperatures, i.e., 100 to ~300ºC, for many industrially Preparation and Pore Size Control of Porous Carbon from Petroleum Coke significant gas separations, as opposed to the pervoskite based membrane, which Mingbo Wu, Yuzhen Zhang and Jieshan Qiu requires a much higher temperature to achieve a significant permeate flux. In addition, Dalian University of Technology, China our CMS membrane has demonstrated hydrothermal stability at this temperature range, Kouichi Miura in contrast to nanoporous metal oxide membranes. However, CMS membranes are Kyoto University, Japan susceptible to poisoning by various contaminants, particularly hydrophobic compounds, due to surface adsorption. An in-line regeneration process has been Porous carbons (PCs) were obtained from Daqing petroleum coke with potassium demonstrated for its effectiveness in the restoration of the permeance. Finally, to hydroxide (KOH) as active reagent by chemical activation method. Benzene was then become a commercially viable product, we have deposited this CMS membrane on our used as deposition agent in the following chemical vapor deposition (CVD) technique commercial ceramic membranes to retain the robust feature of the ceramic membranes. to control the pore size of the PCs prepared by KOH activation. Adsorptions of This membrane is currently being evaluated as a WGS membrane reactor for hydrogen nitrogen, benzene, methane (CH4) and carbon dioxide (CO2) have been used to production for coal gasification off-gas. characterize the pore size and adsorption ability of PCs. It has been found that the process parameters in chemical activation, such as weight ratio of KOH to the starting SESSION 44 material, activation temperature and activation time are crucial for preparing high GASIFICATION APPLICATIONS & ECONOMICS: 2 quality PCs. For CVD technique to control the pore size of PCs, the deposition 44-1 temperature is found to be one of the crucial factors. The results show that CVD Status of 250MW Air-blown IGCC Demonstration Project technique carried on PCs with benzene as deposition agent is an effect method to Yuso Oki, Shozo Kaneko, Jun Wada, Shuji Kameyama control the pore size of PCs and also can greatly enhance the separation ability of PCs Clean Coal R&D Co., Ltd., Japan over CO2 and CH4. A series of PCs with high surface area and in high yield were prepared in comparison to the traditional methods. As Japan has to import almost all of the energy sources, coal is one of the most valuable energy resources in terms of energy security, stability in price and supply. 43-4 However, coal emits more greenhouse gas than the other fossil fuels. To harmonize the A Novel Method of Joining Oxygen and Hydrogen Separation Membranes for reduction of greenhouse gas and coal utilization, there is an urgent need to develop a Advanced Coal Gasification Technology “break-through” high-efficiency power generation technology. K. Scott Weil, John S. Hardy and Jin Yong Kim IGCC (Integrated coal Gasification Combined Cycle) is one of the most promising Pacific Northwest National Laboratory, USA clean coal technologies. Japan has been aiming at developing a unique air-blown IGCC technology that realizes the highest net efficiency and environmental friendliness. An Coal is a potentially a very inexpensive source of clean hydrogen fuel for use in fuel experimental research with the IGCC pilot plant was completed successfully in 1996, cells, turbines, and various process applications. To realize its potential however, and a project of the 250MW IGCC demonstration plant has been started in 2001 by efficient, low-cost gas separation systems are needed to provide high purity oxygen to utility companies in Japan supported by METI (Ministry of Economy, Trade and enhance the coal gasification reaction and to extract hydrogen from the resulting gas Industry). Clean Coal Power R&D Co., Ltd. (CCP) was established in 2001 as the product stream. Several types of inorganic membranes are being developed for contractor of the project, funded by ten Japanese utility companies. hydrogen or oxygen separation, including porous alumina, transition metal oxide Initially CCP was located in central Tokyo to conduct preparatory activities including perovskites, and zirconia. One of the key challenges in developing solid-state plant design and Environmental Impact Assessments. membrane based gas separation systems is in hermetically joining the membrane to the During these three years the project has been successfully conducted on schedule. metallic body of the separation device. In an effort to begin addressing this issue, a Environmental Impact Assessments has been almost completed in accordance with new brazing concept has been developed. procedures. In April 2004, entire office of CCP was relocated next to the plant site, Referred to as air brazing, the technique differs from traditional ceramic-to-metal Nakoso, approximately 200 kilometers north of Tokyo. Construction is scheduled to brazing in two important ways: (1) it utilizes a liquid-phase oxide-noble metal melt as begin in September. the basis for joining and therefore exhibits high-temperature oxidation resistance and CCP has also been working on coal-slag recycle technology, which will be necessary (2) the process is conducted directly in air without the use of fluxes and/or inert cover when the operation tests of IGCC start in 2007. There have been no governmental gases. In fact, the strength of the bond formed during air brazing relies on the standards for the quality of coal gasifier slag. CCP conducted several field tests of formation of a thin, adherent oxide scale on the metal substrate. The technique slag-containing materials for roads or concrete-cast products, which showed high employs a molten oxide that is at least partially soluble in a noble metal solvent to pre- durability and no leaching. Govermental authorization for new standards of coal slag is wet the oxide faying surfaces, forming a new surface that the remaining molten filler expected soon, which will encourage and accelerate utilization of gasifier slag. material easily wets. Potentially, there are a number of metal oxide-noble metal systems that can be considered, including Ag-CuO, Ag-V2O5, and Pt-Nb2O5. Our 44-2 current interest is in investigating whether the Ag-CuO system is suitable for air Operation Experience of EAGLE Coal Gasification System brazing functional ceramic-to-metal joints such as those needed in practical Sadao Wasaka electrochemical devices. In a series of studies, the wetting behavior of the Ag-CuO New Energy and Industrial Technology Development Organization, Japan braze was investigated with respect to a number of ceramic membrane and heat Masao Sotooka and Hiroshi Yamashita resistant metal systems, including: alumina, (La0.6Sr0.4)(Co0.2Fe0.8)O3, (La0.8Sr0.2)FeO3, J-POWER/Electric Power Development Co., Ltd., Japan YSZ, fecralloy, and Crofer-22APU. Findings from these studies as well as from our work on joint strength and durability during high-temperature exposure testing will be One purpose of the EAGLE (coal Energy Application for Gas, Liquid and Electricity) discussed. Examples of where this brazing technique is being developed with project is to develop high efficient gasification system. commercial partners will also be presented. In the EAGLE pilot plant, we have adopted Oxygen-blow two-stage spiral flow gasifier with recycling char system. 43-5 The EAGLE gasifier consists of upper-stage and lower-stage coal-burners. At lower Carbon Molecular Sieve Hydrogen Selective Membranes and Their Use as stage char-burners and steam nozzles are placed. With the EAGLE gasifier, pulverized Membrane Reactor for Water Gas Shift Reaction coal is fed into the gasifier from the upper stage and the lower stage in a spiral flow. In Richard J. Ciora, Jr. addition, we can control the amount of oxygen fed into the lower stage and the upper Media and Process Technology Inc., USA stage independently. Because of the above EAGLE gasifier’s features, the lower stage Muhammad Sahimi and Theo T. Tsotsis is kept at relative high temperature to melt coal ash along with the efficient gasification University of Southern California, USA reaction at the upper stage through utilizing heat generated in the lower stage. And residence time of pulverized coal is long with a spiral flow in the gasifier. Therefore, The development of hydrogen selective membranes suitable for high temperature gas the EAGLE gasifier can keep the high gasification efficiency while stable slag separations has been the focus of significant research activity due to the growing discharge. We consider the EAGLE gasifier enables to apply wide range properties of interest in the production of clean fuel, i.e., hydrogen, from coal processing. Dense coals. membranes, such as palladium alloys and perovskites, and porous membranes, such as The pilot test has been continuing since March 2002 and planning to June 2006. Until metal oxides, have been identified as promising candidates for high temperature Jan 2004 we achieve total 1544 hours operation consuming 6789 tons of coal. This 41

paper describes the outline of the Gasification system of EAGLE pilot plant and our operational experience. SESSION 45 LOW RANK COAL UTILIZATION: 4 44-3 45-1 ® 5 MW Test Plant for High Pressure Partial Oxidation (HP POX ) Canadian Clean Power Coalition Project: The Evaluation of Options for CO2 Technology, Research, First Operating Experiences Extraction from Existing & New Coal-Fired Power Plants B. Meyer, P. Seifert, H. Heinzel and R. Zeißler Duke du Plessis Institute for Energy Process Engineering and Chemical Engineering, Germany Alberta Energy Research Institute and Alberta Economic Development, Canada H. Schlichting Robert Stobbs LURGI AG, Germany Canadian Clean Power Coalition, Canada Paul Clark Methanol is one of the most popular and important bulk intermediate product in the TranAlta Utilities Corp., Canada synthesis chemistry. It can easily be further converted to valuable products such as propylene, formaldehyde, olefins, synthetic fuels and acetic acid. Methanol is produced The Canadian Clean Power Coalition was created in 2000 to protect and enhance from synthesis gas, which is can be generated by reforming or partial oxidation of Canada’s vast coal and other carbon-based resource wealth and to ensure that liquid or gaseous hydrocarbons mainly natural gas and heavy residue oil. LURGI's Gas environmental public policy decisions recognized that these resources were a Canadian to Liquids technology focus on the economical conversion of natural gas to valuable asset, not an environmental liability. CCPC’s membership has been made up of seven products via the intermediate production of methanol. Canadian coal and coal-fired electricity producers: Atco, EPCOR, Luscar, Ontario The operating pressure of the present available reformer technology is below the Power Generation, Nova Scotia Power, SaskPower, TransAlta as well as the US methanol synthesis pressure. An energy intensive compression of the syngas is Electric Power Research Institute (EPRI) and the International Energy Agency (IEA). necessary as long as the reformer pressure cannot be increased. Support and additional research funding for Phase I has come from Natural Resources ® The new high pressure synthesis gas process HP POX represents a milestone in the Canada, Alberta Energy Research Institute (AERI) and Saskatchewan Industry & entrained flow gasification technology. The step forward to operating pressures up to Resources (SIR). 100 bar is done for the partial oxidation of hydrocarbons for the first time. LURGI Oel Phase I of the demonstration project was carried out over the past two years to evaluate • Gas • Chemie (Frankfurt a.M., Germany) and the Institute for Energy Process technologies for coal-fired power generation which reduce all emissions, including Engineering and Chemical Engineering (IEC) of the Technical University CO2, to levels below that of gas-fired plants. Technologies evaluated included Bergakademie Freiberg (Germany) are partners of this ambitious project. The project is gasification (IGCC), oxy-fuel combustion and amine scrubbing. These technologies supported by German federal and regional authorities. were evaluated with three coal types Eastern bituminous, Western subbituminous and The HP POX® test plant, which is built in Freiberg by LURGI, is the core of the lignite coals. Engineering studies determined the capital and operating costs, the cost project and an important step forward to an industrial scale plant. It is designed for an of electricity produced (with CO2 removed) and the cost per tonne of CO2 avoided. operating pressure up to 100 bar and a thermal capacity up to 5 MW. The plant is These studies also evaluated the potential utilization of CO2 generated in western unique with regard to its operating parameters and operating options: Gaseous as well Canada for Enhanced Oil Recovery and storage in depleted oil reservoirs or deep as liquid hydrocarbons can be used as reactor feedstock. Innovative burner saline aquifers. technologies allow autothermal catalytic or non-catalytic reforming for gaseous Phase 1 identified process optimization and technology enhancements to improve the feedstock and gasification of liquid feed streams such as heavy residue oil and competitiveness of gasification of low rank western Canadian coals. Phase II, started in chemical wastes. late 2003, will optimize the designs and develop business cases for one or more The plant was taken into the cold operation in November 2003. The hot operation is demonstration plants to be in place by 2012. Optimization will include site specific scheduled for spring 2004, the start for a detailed investigation program. The suitability demonstration plants producing clean power as well as steam and hydrogen for the for a wide range of gaseous and liquid feedstock has to be shown, the technological recovery and upgrading bitumen and utilization of CO2 for enhanced recovery of and energetic limits of the process have to be determined. conventional oil (polygeneration). The unique combination of feedstock and product The IEC scientific investigations focus on the theoretical description and the numerical options favour demonstration and commercialization of clean coal polygeneration calculation of the HP POX® process. Increased pressure, bigger reactor dimensions and plants in Western Canada. higher throughput change the conditions of flow and heat transfer in the reactor The paper will present the results of Phases 1 and 2 including comparative costs of the decisively. different technologies evaluated, optimized polygeneration process schemes and the Reaction mechanism and soot formation, formation of trace components as well as technology enhancements under investigation. investigatons of construction materials under gasification conditions have to be examined. There are extensive developments for coupled fluid dynamic and kinetic 45-2 models for the non-catalytic and catalytic autothermal process up to 100 bar. The Kinetics and Characteristics of the Pyrolysis of Zhaotong Lignite The presentation will give an overview of the plant, first operating experiences and Yaoling Chi and Shuyuan Li some fundamental results of the numerical calculations. University of Petroleum, China

44-4 The resources of lignite in Zhaotong, Yunnan Province are abundant. Because of large GE’s Coal Gasification Technology for Methanol/DME Applications moisture, low calorific value and high ash content, it has not been used as a fuel up to Francis Fong now. In this paper, the investigation of the Zhaotong lignite pyrolysis has been made to GE Gasification Technology Inc., USA find a rational method to use the lignite. Thomas O’Brien Zhaotong lignite contains the moisture of 60%. Therefore, the drying process becomes GE Energy, USA more important. The dryness at room temperature and in the oven was studied. Approximately 30% moisture can be removed and no cracking has been found during This paper describes the latest development of ChevronTexaco’s coal gasification room temperature drying. At the temperature of around 105 , however, the lignite technology for chemicals industries, with a particular focus on methanol & DME lump begins to crush into fine particles. In the tar, the sulfur content is 0.418% which (dimethyl ether) applications. The paper will present an update of ChevronTexaco’s is the lower than the requirement for fuel oil in China. So, the sulfur content is not the gasification successes in coal gasification, summarizes the latest commercial limitation to tar utilization. The diesel fraction is up to 60% of the tar. Therefore tar experience, in addition to a case study on methanol/DME production utilizing can be used to produce light diesel through distillation and upgrading. The gas with the ChevronTexaco’s coal gasification technology. calorific value of 18MJ/m3 can be directly used as civil gas and boiler fuel. Because of easy ignition and high calorific value (~20MJ/kg), semi-coke can become a clean fuel 44-5 for power generation or civil utilization. Lignite ash is the good raw material for the Westinghouse Plasma Gasification Technology – Commercial Projects Update production of cement and timbering. From mentioned above, it is concluded that S. V. Dighe and D. E. Lazzara comprehensive utilization of Zhaotong lignite has a good prospective. Westinghouse Plasma Corporation, USA The pyrolysis experiments on lignite were carried out using a thermogravimetric analyzer (TGA) at four different heating rates of 5, 10, 15 and 20 /min and with a This paper will provide update on the commercial operation of the WPC plasma final temperature of 600 . Because the calcium oxide in lignite ash has an effect on gasification commercial plants utilizing organic wastes such as municipal solid waste the pyrolysates, the samples were obtained by mixing lignite and ash mechanically (MSW), wastewater treatment sludge, plastic waste and other fuels. Brief discussion with different ratios. The mixture was pyrolysed using TGA with heating rates of on future projects under development will also be included. 15 /min to a final temperature of 600 . The kinetics model has been developed and the kinetic parameters were determined from TGA data.

45-3 Gasification of solid fuels such as coal, biomass and wastes is a major potential source Gasification of Low-Rank Coals in a Transport Reactor of hydrogen in the future hydrogen economy. This study investigates the significant Michael L. Swanson, Doug R. Hajicek, Michael E. Collings and Ann K. Henderson enhancement of hydrogen production during the gasification of Victorian brown coal University of North Dakota Energy & Environmental Research Center, USA with steam using iron as a catalyst. Iron was introduced into the acid-washed Loy Yang coal through impregnation using a The U.S. Department of Energy (DOE) National Energy Technology Laboratory ferric chloride aqueous solution. Gasification experiments were carried out using a (NETL) Office of Power Systems Product Management has as its mission to foster the fluidised-bed/fixed-bed reactor at a fast particle heating rate. The yield of char was development and deployment of advanced, clean, and affordable fossil (coal)-based determined by directly weighing the reactor before and after each experiment. Gases power systems. These advanced power systems include the development and were analysed using a GC with dual columns. The transformation of iron species demonstration of gasification-based advanced power systems which are an integral part loaded into the coal during the pyrolysis and gasification process was examined using of the Vision 21 Program being developed by DOE for the coproduction of power and XRD and other microscopic techniques. The results show that the loaded iron affects chemicals. DOE has also been developing advanced gasification systems that lower the both pyrolysis and gasification of brown coal. The overall gasification rate of a char capital and operating costs of producing syn gas for electricity and chemicals with steam increases significantly in the presence of iron. The gasification of iron- production. A transport reactor has shown potential to be a low-cost syn gas producer loaded coal samples gives much higher ratio of H2+CO2 to CO than that of the acid- compared to other gasification systems since its high throughput per unit cross- form coal under similar conditions. The novel configuration of our reactor system has sectional area reduces capital costs. This work directly supports the Power Systems allowed the feeding of the acid-form coal and iron-impregnated coal in different orders Development Facility (PSDF) utilizing the Kellogg Brown & Root (KBR) transport into the reactor, giving interesting results about the catalytic effects of iron loaded into reactor located at the Southern Company Services (SCS) Wilsonville, Alabama, site. the coal on the catalytic gasification of coal/char and water-gas shift reactions. The Over 2500 hours of operation on eleven different coals ranging from bituminous to effects of iron on the gasification rate and products distribution will be discussed lignite along with a petroleum coke have been completed to date in the pilot-scale together with the transformation of iron during pyrolysis and gasification. transport reactor development unit (TRDU) at the Energy & Environmental Research Center (EERC). The EERC has established an extensive database on the operation of SESSION 46 these various fuels in both air- and oxygen-blown modes utilizing a pilot-scale SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 2: transport reactor gasifier. This database has been useful in determining the LIQUEFACTION & NATURAL GAS effectiveness of design changes on an advanced transport reactor gasifier. 46-1 The effects of different fuel types on both gasifier performance and the operation of the Study for Coal to Liquid (CTL) hot-gas filter system have been determined. It has been demonstrated that corrected Hisanori Tanaka, Kyouichi Kougami and Masaki Sanemasa fuel gas heating values ranging from 105 to 130 Btu/scf have been achieved in air- Electric Power Development Co.Ltd, Japan blown mode while heating values up to 230 Btu/scf on a dry basis have been achieved in oxygen-blown mode. Carbon conversions up to 95% have also been obtained and Electric Power Development Co. (J-Power) is developing Coal gasification technology are highly dependent on the oxygen–coal ratio. Higher-reactivity (low-rank) coals for fuel cell. This technology product synthesis gas as CO and H2. appear to perform better in a transport reactor than the less reactive bituminous coals. Using FT synthesis technology it’s able to make FT synthesis oil from these CO and Factors that affect TRDU product gas quality appear to be coal type, temperature, and H2. oxygen–coal ratios. Testing with Australian brown coals and coal–wood biomass Then we just started to study about FT synthesis catalysts which are the key mixtures has recently been completed. Methods for the control of mercury under technology for CTL. warm-gas conditions are currently being investigated. 46-2 45-4 Catalytic Thermal Conversion of Kuzbass Liptobiolitic Coal To Liquid Products Processing Low Rank Coal to Obtain Chemical Products and Reducing Gas V.I. Sharypov, B.N. Kuznetsov, N.G. Beregovtsova, S.V. Baryshnikov Igor Shulga and Adolf Silka Institute of Chemistry and Chemical Technology Siberian Branch RAS, Russia Ukrainian State Research Institute for Carbochemistry, Ukraine N.U.Vasilieva Krasnoyarsk State University, Russia This new technology is intended to produce those products which are currently A.N. Startsev obtained mainly from petroleum and natural gas. The principle of the process lies in Institute of Catalysis Siberian Branch RAS, Russia heating a pretreated coal in the absence of the air to a temperature of 600-700 ºC, gasifying the solid material produced, separate removing and processing of vapour-gas The thermal conversion of liptobiolitic coal from Barzass coal-field of Kuzbass basin products formed at various stages of thermochemical conversion. The basic equipment (Siberia, Russia) was investigated at conditions of pyrolysis in hydrogen atmosphere of the process is a vertical furnace for heating coals, rotating drum furnace for and hydrogenation in the medium of petroleum residue (b.p.>350oC). The influence of gasification and apparatus for treatment of vapour-gas products. the mechanochemically activated iron-containing ore catalyst on the yield and The properties of the feed stock and related technological features of processing composition of liquids products was studied. Results of the study were compared with different types of coal has an impact on yields and quality of the final products. In data obtained with Kansk-Achinsk brown coal (Siberia, Russia) at the similar process particular, a solid material is produced in the process in the amount of 300-640 kg/t parameters. coal. It can be used as a substitute of coke if used beyond blast furnaces, as energy fuel It was found, that the liptobiolitic coal gives higher yield of liquid products as and a raw material for gasification. In the latter case, using air-steam blast, one tonne compared to the brown coal. They mainly consist of normal paraffinic hydrocarbons. of this material can give 3500-4500 m3 of gas having the calorific value 4-5 MJ/m3 for The total concentration of aromatic and oxygen containing substances in liquids from energy application. Using oxygen-steam- blast we can obtain 1600-2100 m3 of gas liptobiolitic coal was less then 20 mass%. (calorific value 10-11 MJ/m3) containing It was shown that the use of iron-ore catalyst in hydrogenation process allows to CO + H2 + CH4 over 80 % mainly for processes of chemical synthesis. Slag is also increase the degree of liptobiolitic coal conversion on 21-23%, and to produce liquid formed (80-120 kg/t coal) as a building material, raw stock for polymetallic alloys and products with the yield up to 58 mass%. The conversion degree reaches to 94-97 chemical fertilizer. mass% at 400-430оС in liptobiolitic coal hydrogenation process and to 78-80 mass%. One tonne of coal can also give a primary gas, 150-250 m3, calorific value 15-23 in pyrolysis in hydrogen atmosphere at 430-460оС. The further increase of a MJ/m3 (energy fuel, chemical stock), primary tar, 30-45 kg, and gas petrol, 16-40 kg temperature is accompanied by intensive formation of gaseous products and results in (chemical stock, component of motor fuel), phenols, 30-40 kg, ammonium sulphate, lower yield of liquids. 50-80 kg, sulphuric acid, 50-90 kg. The technology is realized in a continuous process in a chain of air-tight apparatus 46-3 allowing to eliminate scattering emissions into the atmosphere and to treat other Prospect of the Natural Gas Market in East Asia emissions to meet the existing requirements. The process has been investigated under Yutaka Shirakawa and Yutaka Kunigo laboratory conditions and tested on a pilot plant. Definition phase engineering has been Tokyo Gas Co., Ltd., Japan made for a semi-commercial introduction of the technology. Natural gas is the third primary energy in Asia and Pacific region after coal and oil, 45-5 which is different from the U.S. and Europe. Japan and South Korea highly depend on Enhancement of Hydrogen Production during the Gasification of Victorian oil imported from middle-East. Brown Coal with Steam Using Iron as the Catalyst The largest exporting country is Russia, followed by Canada and Norway. The largest Jianglong Yu, Lachlan J. McKenzie and Chun-zhu Li importing country is the US, followed by Germany and Japan, which is the largest CRC for Clean Power from Lignite, Monash University, Australia LNG importer. Following Japan, South Korea is the second largest LNG importer, and Fu-jun Tian and Mee Chin Chow these two countries and Taiwan imported almost 70% of the world’s LNG. Monash University, Australia LNG will continue to play an important role in natural gas supply in Asia and Pacific region. Japan, Korea and Taiwan, imported LNG from eight countries, have experienced low demand increase for the last several years due to the low economic 43

growth. However, gradual economic recovery and increasing concern on the global The paper presents short characteristic of the Polish power generation sector with a warming will increase a steady LNG demand. New markets, China and India, are special stress put on combined heat and power plants based on natural gas. Constrains planning to import LNG in the coming years. Potential demand in these two emerging that prevent from wider scale use of natural gas in the sector are described. The paper markets is expected to be large. In case, other importers in Philippines and West Coast demonstrates also the ecological and technical aspects of gas turbines use. It also of North America join the LNG market, the high LNG demand scenario in the region presents the comparison between structure of electricity production in Poland and in will be materialized. the European Union. On supply side, existing projects have exported 77 MMT of LNG in 2002. A number Finally, the paper shows the perspective of the development of energy sector and the of extensions and new grassroots projects are either under construction or planned. In role of the natural gas in future structure of primary energy mix for the purpose of addition to these LNG supplies, several pipeline projects are planned. However, the electricity production. share is much lower than oil trade due to massive capital investment for the long distance transportation of natural gas either by pipeline or LNG. SESSION 47 In view of the projected high increase in natural gas demand in the region, timely GLOBAL CLIMATE CHANGE & APPLICATION OF INDUSTRIAL development of natural gas infrastructures, LNG facilities and pipeline networks, is ECOLOGY: 1 essential. The infrastructure requires massive investments and it is important that 47-1 nations and economies in the region deliver a stable and consistent energy policy Future U.S. Greenhouse Gas Emission Reduction Scenarios Consistent With which provides an environment to facilitate investments. It is also important to create Atmospheric Stabilization the framework where the region shares that infrastructure as the viable solution to Vello A. Kuuskraa promote energy security, sustainable economic growth and environmental protection. Advanced Resources International, Inc., USA Natural gas in the US and European markets at relatively lower price has been Phil Dipietro competitive against other energy sources and maintaining high penetrations in these Energetics, Inc., USA markets. In Asia and Pacific region, downward trend of LNG prices has been observed Scott Klara and Sarah Forbes with cost reductions in LNG production and LNG and natural gas are expected to US DOE, NETL, USA become more competitive in pricing and flexible in utilization to meet the intensified competition caused by deregulation, which will promote natural gas to be a key The paper analyzes a scenario for reducing U.S. greenhouse gas (GHG) emissions that primary energy source in the 21st century in the region. is consistent, in the near term, with the President’s Global Climate Change Initiative (GCCI) and, in the longer term, atmospheric stabilization at 550 ppm. The purpose for 46-4 formulating and evaluating such a stabilization scenario is to define the role and Coal to Clean Fuel – The Shenhua Investment in Direct Coal Liquefaction expectations for performance of carbon sequestration technologies in a future, Qingyun SunRichard Bajura, and Jerald J. Fletcher speculative carbon-constrained world. The analysis shows that an integrated approach, West Virginia University, USA involving emphasis on energy efficiency, cost-effective renewables and availability of Yuzhuo Zhang and Xiangkun Ren advanced CO2 capture and storage technology, would be required for emissions Shenhua Group Corporation, P.R. China stabilization. Under this scenario, the carbon intensity of U.S. GDP is reduced by 18% in 2012 per the GCCI. From 2012 to 2050, GHG emissions intensity is further reduced Significant price increases and the associated potential for crude oil shortages have toward an absolute target of 1,250 MMmtC/year, representing a substantial U.S. once again brought energy security to the center stage. Countries with extensive coal contribution toward an atmospheric stabilization concentration of 550 ppm. This reserves may be led to reconsider technologies that transform coal into alternative analysis examines opportunities for reducing emissions (both CO2 and non-CO2 clean fuels. The successful operation of the Sasol indirect coal liquefaction (ICL) GHGs) in all sectors, including transportation, electricity supply, industrial, facilities and the development of the world’s first commercial direct coal liquefaction commercial and residential. The analysis quantifies the potential contribution of the (DCL) plant by the Shenhua Group Corporation provide case studies of commercial various GHG reduction options and shows that advanced lower-cost CO2 capture and coal liquefaction technologies. Without access to detailed information on the storage technology will need to play a key role in any future GHG emissions reduction processes, debate on the relative economic competitiveness that these processes can scenario. achieve continues. An increased understanding of these processes could affect the direction of future research and potential commercialization. 47-2 This paper presents a case study of the economics of DCL and ICL technologies using Employing Industrial Ecology Principles to Build Coal Power Plants information from the Sasol and Shenhua plants. The results indicate that the successful Mildred B. Perry and Udaya S. Rao development of a coal liquefaction project in any country depends on the resource US DOE, NETL, USA base, location, stage of economic development, and the policy environment. Focusing on the inputs and outputs of liquefaction facilities, the authors explore potential The U.S. DOE National Energy Technology Laboratory (NETL) located in Pittsburgh, complementarities of combining DCL and ICL technologies. Complementary fuel oil Pennsylvania, Morgantown, West Virginia, and Tulsa, Oklahoma is the implementing products and waste utilization that follow from integrating DCL and ICL processes field organization of the Office of Fossil Energy located in Washington DC. Among may cut inputs, reduce operational cost, and improve fuel oil quality. A case study of other responsibilities, NETL manages national programs in the United States to the Shenhua DCL and Sasol ICL projects will offer useful information for those demonstrate technologies to reduce cost, improve efficiency, and improve the countries rich in coal and dependent on oil imports that are considering coal environmental performance of coal-based electric power generation. While these liquefaction as a viable alternative to enhance energy security. demonstration programs have been effective, each project evaluates a first-of-a-kind concept; and, so far, the demonstrated technical advances have not been widely 46-5 adopted by industry. Nor has there been any systematic approach in the power Natural Gas As the Energy Carrier in Electricity Generation Sectors In Poland generation industry to undertake the integration of advanced technologies to and In the European Union Countries. The Present Situation and Perspectives demonstrate overall gains that are projected to be achievable in programs like Vision Lidia Gawlik and Tadeusz Olkuski 21 or the newly conceived FutureGen program. Here is an opportunity to begin to Mineral and Energy Economy Research Institute, Poland apply the principles of Industrial Ecology to minimize the impacts on resources and on Tomasz Mirowski, Eugeniusz Mokrzycki and Adam Szurlej the environment. This paper explores what may be needed to realize the benefits of AGH University of Science and Technology, Poland Industrial Ecology principles as applied to the construction and operation of coal-based power generation in the United States. Natural gas is widely used both as an energy carrier as well as important material for chemical industry. One of the most prospective directions of natural gas utilisation is 47-3 its usage for the purpose of electricity generation. The natural gas fired combined heat High-Capacity Nano-Porous Adsorbent Based on Polymer-Modified MCM-41 and power plants (CHP) characterise the high efficiency of chemical energy use. For Molecular Sieve for Effective CO2 Separation from Gas Mixtures Containing CO2 this reason natural gas has been recently more often used for electricity generation and H2O purposes. This is also why the role of natural gas will probably rise in future. Chunshan Song, Xiaochun Xu and Alan W. Scaroni Hard coal and lignite are dominant in Polish sector of electricity generation. The total Pennsylvania State University, USA electricity production in 2002 was 144,1 TW⋅h and the share of hard coal and lignite was about 96%. Practically the structure of Polish electricity generation has not Separation of CO2 from various gaseous streams is becoming increasingly important in changed for the recent 20 years. The only, but not very significant, change is that the field of sustainable energy development. Adsorption separation is one of the natural gas has just started to be used for co-generation of electricity and heat. It should promising methods. The key issue for adsorption separation is to prepare high- be mentioned, however, that the rate of electricity produced from natural in Poland is performance adsorbent for effective CO2 separation from CO2- and H2O-containing gas low – 2,1 TW⋅h (2002), i.e. only 1,5% of the total electricity generation. The biggest mixtures. In this work, adsorption separation of CO2 was investigated using a novel combined heat and power plant, that in spite of coal uses also natural gas is Lublin “molecular basket” adsorbent and simulated flue gas mixtures containing CO2, O2, N2 Wrotkow. with and without moisture. The CO2 “molecular basket” adsorbent was prepared by synthesizing mesoporous molecular sieve MCM-41 and loading it with a branched 44

polyethylenimine. Compared with the adsorption separation of CO2 from simulated at elevated temperatures and pressures. Changes in core porosity, secondary minerals, dry flue gas, both the CO2 breakthrough time and CO2 adsorption capacity increased and solution chemistry were measured. upon addition of the moisture into the simulated dry flue gas. This indicated that moisture has a promoting effect on the adsorption separation of CO2 from simulated SESSION 48 flue gas mixture by the novel “molecular basket”. When the feed concentration of COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 3: moisture was lower than that of CO2, CO2 adsorption capacity increased rapidly with COAL TAR, PITCH, CO-PYROLYSIS the increase of moisture concentration. When the feed concentration of moisture 48-1 became larger than that of CO2, the increase in CO2 adsorption capacity recessed. Study on the Emulsification Mechanism of Coal-tar Maximum promoting effect of moisture appears at moisture concentrations Shi Shizhuang approaching that of CO2 in the flue gas. The cyclic adsorption/desorption separation Wuhan University of Science and Technology, China results show that the novel “molecular basket” adsorbent is stable in the cyclic Liu Qibing operations of CO2 adsorption separation from moist flue gas. It should be noted that Wuhan Iron and Steel Co., China conventional adsorbents for CO2 require pre-removal of moisture and can only operate at low temperatures such as 25 °C. The new MCM-41-PEI adsorbents developed in In the paper, the causes why results in the increase of moisture in coal-tar, being our laboratory have numerous CO2 affinity sites, can operate at 75 °C, and do not difficult in dewater and in operation in coal-tar processing plant when the control of require pre-separation of moisture from the gas stream. In fact, the presence of coal charging emissions has been used in the WISCO (Wuhan Iron and Steel moisture further enhances CO2 capture on such adsorbents. Company) have been analyzed thoroughly and the conclusion has been drawn that the coal-tar took place emulsification. On the basis of above analysis, the samples of 47-4 WISCO have been taken and analyzed. And then, the emulsification mechanism of Characterization of Sodium-Based Sorbents for CO2 Capture from Flue Gas coal-tar and the factors on stability of coal-tar emulsions have been researched in Chong Kul Ryu, Joong Beom Lee, Tae Hyung Eom and Je Myung Oh laboratory simulating production condition and found that the coal-tar formed water- Korea Electric Power Research Institute, Korea in-oil (W/O) emulsions with the emulsifier of the solid carbonic powder (coke powder Chang Keun Yi and coal powder) drawing into coal-tar in the coal charging; the factors affecting on the Korea Institute of Energy Research, Korea stability of coal-tar emulsions include the consumption quantity of emulsifier, the composition of emulsifier (the proportion of coke powder to coal powder), the particle The purpose of this work is to identify potential materials for CO2 capture sorbent size of emulsifier, et al; and the more the emulsifier, the bigger the ratio of coal compositions and to make dry regenerable sorbents by spray drying technique to obtain powder, the finer the emulsifier, the more stable the coal-tar emulsions; and the more high mechanical strength and chemical reactivity. Much attention has been recently the emulsifier, the larger the viscosity of the emulsions and the more stable the coal-tar directed towards cost-effective and energy-efficient process - anthropogenic CO2 emulsions. sequestration techniques aimed at capturing CO2 released from fossil fuel–fired power plants. One of the advanced concepts for low-cost capturing CO2 is an absorption 48-2 process with dry regenerable sorbents. This report described mechanical strength and Co-Coking of Decant Oil and Coal: The Development of a Laboratory Delayed CO2 sorption capacity of spray-dried sodium-based CO2 sorbents applicable to the flue Coker, Product Distribution of Distillates and Isolated Carbon from the Process gas conditions. Leslie R. Rudnick, Omer Gul and Harold H. Schobert During the sorbent screening with Na2CO3 as active CO2 sorption components, the five The Pennsylvania State University, USA formulations containing 20-50wt% active component were spray-dried in the 2-16 kg scale based on solid raw materials. The TGA chemical reactivities of sorbents were We describe the development of a laboratory scale delayed coker and present results of also investigated along with pure Na2CO3 and NaHCO3 in the temperature range of 50- an investigation on the composition of recovered liquid from the coking of decant oil 70°C with simulated flue gas containing 10 vol% H2O and 14.4 vol% CO2. The CO2 and decant oil/coal mixtures. One of the major achievements of this coker design is sorption capacities of sorbents are 9-14 g CO2/100 g sorbent (or wt%) with the the ability to isolate coke artifacts essentially intact. The process of co-coking involves maximum sorbent utilization of 180%. The sorption capacity of some sorbents is the simultaneous co-carbonization of coal and petroleum resid under delayed coking comparable to or better than that of pure Na2CO3 and NaHCO3 sorbents. The chemical conditions. The co-coking process produces a solid “coke” by-product. Ideally this reactivity of sorbent is very sensitive to calcination temperature of green body, water coke should have a high market value and be suitable for use in products such as sorption capacity, and carbonation temperature. The sorbent calcined at 500°C showed anodes for the aluminum industry. the best chemical reactivity at 50°C. The attrition indices of some sorbents by ASTM The first part of this study addresses design features necessary to be able to isolate D 5757 reached below 60% and also depended on the calcination temperature. It is from the reactor the coke formed during the coking or co-coking process. We have concluded that dry regenerable spray-dried sodium-based sorbent could be a viable utilized two approaches to minimize these difficulties. Techniques were developed to option to capture CO2 from flue gas condition. isolate Kg quantities of intact coke from the reactor. This methodology provides material for detailed characterization and further processing. This provides the 47-5 opportunity to study the physical and chemical structure of the coke as a function of Ex-Situ and In-Situ Mineral Carbonation as a Means to Sequester Carbon reaction time, and other process parameters, and as a function of location within the Dioxide coking reactor. Liquids are obtained in suitable quantity for detailed chemical S.J. Gerdemann, D.C. Dahlin, W.K. O’Connor, L.R. Penner, and G.E. Rush characterization, recombination and distillation into refinery cuts for evaluation. Albany Research Center, U.S. Department of Energy, USA 48-3 The U. S. Department of Energy’s Albany Research Center is investigating mineral Conversion of Tar in Hot Coke Oven Gas by Pyrolysis carbonation as a method of sequestering CO2 from coal-fired-power plants. Motoaki Kawase, Tsunekata Kobata, Ingmar Gerlach, Hiroyuki Nakagawa, Kouichi Magnesium-silicate minerals such as serpentine [Mg3Si2O5(OH)4] and olivine Miura (Mg2SiO4) react with CO2 to produce magnesite (MgCO3), and the calcium-silicate Kyoto University, Japan mineral, wollastonite (CaSiO3), reacts to form calcite (CaCO3). It is possible to carry out these reactions either ex-situ (above ground in a traditional chemical processing The coke oven gas (COG) consists mainly of hydrogen and methane, the mole plant) or in-situ (storage underground and subsequent reaction with the host rock to fractions of which are ca. 50% and ca. 25%, respectively. The tar vapor is also trap CO2 as carbonate minerals). contained ca. 30 wt% in the COG. At the moment, tar is removed by condensating the For ex-situ mineral carbonation to be economically attractive, the reaction must vapor for preventing the deposition in the downstream processes. The enthalpy loss proceed quickly to near completion. The reaction rate is accelerated by raising the due to this operation greatly reduces the overall thermal efficiency. The utilization of activity of CO2 in solution, heat (but not too much), reducing the particle size, high the hot COG is becoming a key to improve the overall efficiency of the intensity grinding to disrupt the crystal structure, and, in the case of serpentine, heat- iron manufacture. In this study, possibility to convert the tar vapor to synthesis gas was treatment to remove the chemically bound water. All of these carry energy/economic investigated. Even only the removal of tar from the hot COG is profitable. In addition, penalties. An economic study illustrates the impact of mineral availability and process the reaction model of tar decomposition in COG was investigated taking into account parameters on the cost of ex-situ carbon sequestration. the effects of coexistent gases. In-situ carbonation offers economic advantages over any ex-situ process, because no Experiments of the pyrolysis of tar in helium and simulated COG atmospheres were chemical plant is required. Knowledge gained from the ex-situ work was applied to carried out. Since the COG contains carbon monoxide, carbon dioxide, steam as well long-term experiments designed to simulate in-situ CO2 storage conditions. The as methane and hydrogen, the tar pyrolysis experiments in these constituent gas Columbia River Basalt Group (CRBG), a multi-layered basaltic lava formation, has atmospheres were performed for investigating the effects of these gases. Tar, favorable mineralogy (up to 25% combined concentration of Ca, Fe2+, and Mg cations) CH0.65N0.010O0.022, condensed from an actual COG was used as the reactant. More for storage of CO2. However, more information about the interaction of CO2 with than 80% of tar could be decomposed in several seconds by pyrolysis at aquifers and the host rock is needed. Core samples from the CRBG, as well as samples temperature higher than 1000ºC. The coke yield reached 80% and the main gas of olivine, serpentine, and sandstone, were reacted in an autoclave for up to 2000 hours products were methane and hydrogen. The molecular weight of the product tar was higher than that of the reactant tar. The product tar contained 4–7-ring aromatics, 45

whereas the reactant tar contained 3–5-ring aromatics. Coke deposition was reduced in the CSRblast furnace coke values: if we consider the cokes with a value above 57 % to be of the presence of steam by steam gasification of coke. Carbon dioxide also caused the good quality and with the values 52 – 57 % to be acceptable, then it would only be gasification of coke but the reaction rate was lower than that by steam. No the coke from the mixture with 3 % rubber again that could not be used as a blast- apparent reaction of carbon dioxide or steam with tar was observed. When tar was furnace one but e.g. for heating. decomposed in the hydrogen atmosphere, the hydrogen yield decreased and the methane yield increased compared with those in helium. This indicates that SESSION 49 hydrocracking of tar took place. When tar vapor and methane were fed to the reactor, MATERIAL, INSTRUMENTATION & CONTROLS 3: HIGH the hydrogen yield and coke yield increased. The decrease in the methane yield, the TEMPERATURE MATERIALS ISSUES increase in the hydrogen yield, and the increase in the coke yield were approximately 49-1 1:2:1 on molar basis. This suggests that methane was pyrolyzed to form coke and Tests of an Oxide Dispersion-Strengthened High-Temperature Heat Exchanger hydrogen and no reaction of tar with methane took place. When tar was pyrolyzed in for Indirectly Fired Combined Cycles the simulated COG, coke deposition from methane in addition to the deposition from John P. Hurley and Greg F. Weber the tar was observed at high temperature. The reverse shift reaction forming carbon University of North Dakota, USA monoxide and steam also occurred during the tar pyrolysis in the simulated COG. Judged from the experimental results, the reaction model of the tar decomposition in Under the U.S. Department of Energy High-Performance Power System Program, a COG should consist of the tar pyrolysis to form hydrogen, methane, and coke, the pilotscale high-temperature heat exchanger (HTHX) was used to produce pressurized gasification of coke with steam and carbon dioxide, the methane pyrolysis to form air at up to 2000°F. An indirectly fired combined cycle (IFCC) power plant using this coke and hydrogen, and the shift conversion reaction. type of heat exchanger has the potential to reach efficiencies of 45% when firing coal and over 50% when a gas-fired duct burner is used to additionally heat the process air 48-4 entering the gas turbine. Because of its high efficiency, an IFCC system is the most Waste Plastics Recycling Technology Using Coke Ovens appropriate power concept for employing oxygen-enriched combustion in order to Kenji Kato, Seiji Nomura and Koichi Fukuda make carbon sequestration more economical. It has the added benefit of minimizing Nippon Steel Corporation, Japan water usage by dramatically reducing the amount of cooling and makeup water, since only half as much steam is produced as in a typical steam plant. By staging combustion At the advent of the 21st century, mankind is facing a global environmental problem, of the coal in such an oxygen-blown system, the need for flue gas recirculation and the industrial sector is required to take initiatives in the establishment of recycling to manage the flame temperature is reduced and the maximum amount of energy can society for efficient utilization of natural resources. The Japan Iron & Steel Federation, be channeled to the gas turbine, raising overall plant efficiency. In addition, reducing as a voluntary energy-saving action plan, proposed a 10 % energy reduction by 2010 the volume of flue gas would substantially reduce the required size of the baghouse or with 1990 as the basis. Furthermore, it has put forward an additional 1.5% energy electrostatic precipitator, flue gas desulfurization system, and induced- and forced- saving by the use of waste plastics as metallurgical raw materials. draft fans, thereby reducing both capital and operating costs. It would also permit the By laboratory and actual coke oven tests, it was found that waste plastics recycling most economical use of a condensing heat exchanger for reclaiming combustion water process using coke ovens is feasible to recover coke, tar, light oil and gas from general and thereby even further reducing the amount of outside water necessary for plant waste plastics mixed in coal by carbonization in coke ovens without deteriorating the operation. After water condensation, only carbon dioxide is left in the gas stream, qualities of coke. Waste plastics recycling process using coke ovens was started as a which can then be used industrially or sequestered. If the system is cofired with coal chemical recycling technology at Nippon Steel Nagoya and Kimitsu works in 2000. and biomass, sequestration of the carbon dioxide would lead to a net atmospheric Waste plastics recycling equipment with a total capacity of 120,000 t/y is in operating reduction of that gas. by Nippon Steel Corporation. In this paper, we describe results from recent oxygen-enriched and combined coal Using the life-cycle assessment (LCA) methodology, the waste plastics recycling and biomass-fired tests of an oxide dispersion-strengthened (ODS) heat exchanger process using coke ovens was estimated. And the process is thought to be effective to producing pressurized air at 1750°F (950°C). The tests were performed in a pilot-scale reduce CO2 emission significantly. slagging combustion system while firing coal in an oxygen-enriched configuration and while firing coal–biomass blends in air. In addition, results of laboratory tests of the 48-5 resistance of two actively cooled ODS alloys to corrosion by flowing coal and coal– Use of Waste Plastics and Rubber as Admixtures into Coking Charges biomass slags are presented, including scanning electron microscopy analyses of Pavel Straka elemental depletion versus depth. Academy of Science of the Czech Republic, Czech Republic 49-2 The coking of stamped charges with admixtures took place in the carbonizing High Temperature Erosion Testing In a Gasifier Environment equipment of the coking plant in Třinec Steel Works, Czech Rep., under simulated J. Tylczak, J. Rawers and T. Adler commercial conditions. This equipment – Karbotest – allows the determination and Albany Research Center, USA prediction of the yield of coke and its quality, and the yields of by-products. The content of plastics in charges was chosen to be 2–5 wt.-%, the content of rubber 2–3 The development of materials with the ability to operate in adverse conditions while wt.-%. These contents were chosen based on the conclusions from the preliminary resisting the effects of erosion and corrosion are key to the future success of high macrolaboratory experiments and taking into account the co-coking results in efficiency power plants. Many of the next generation coal power plants are envisioned Japanese works [1], which prefer small amounts of plastics admixtures in a charge. to be combined cycle, with gasifiers used to produce steam and syngas. The gasifier Three mixtures were examined as admixtures: a mixture of ABS polymer and rigid sections of these plants require materials of construction that are resistant to the effects polystyrene; a mixture of polyethylene, polypropylene, polystyrene and cellulose of erosion in a reducing atmosphere that contains sulfur and chloride compounds. The derivatives; and rubber. It was found that plastics admixtures affect the properties of Albany Research Center has developed a test apparatus designed to test the erosion- tar and improve the calorific value of the coking gas. The CSR and CRI parameters resistance of candidate materials under a range of conditions, including those found in of a blast-furnace coke were not substantially different, i.e., the waste plastics can gasifiers. This hostile atmosphere erosion wear test (HAET) has been used to examine economize on part of the coal used in a stamped charge. Additions of both light and a group of high alloy candidate materials such as iron aluminide and Haynes HR 160 heavy plastics can be used up to 5 % of a charge weight. On the other hand, a 3 %- and compare them to a conventional 310 stainless steel. These materials were erosion rubber addition influenced both parameters being considered. In the cokes obtained, tested using a 270µm silica abrasive, at temperatures up to 700%C, using typical the decisive parameters were observed using the standard method of Nippon Steel impact velocities of 20 m/sec. The effects of erosion under these conditions on the Comp.: reactivity (CRI) and coke strength after reaction (CSR). Also ash content, surface scales that form are described. The total loss rate, lost rate due to erosion and degasification and sulfur content in the cokes obtained were observed. It arises from corrosion for the test materials are compared. the results obtained that all of the cokes were well degassed, low-sulfur and low-ash. The measured values of CRI and CSR were statistically converted to values with 49-4 commercial applications based on long-term observations of the correlation Ash Monitoring System for Utility Boilers parameters of the cokes from the Karbotest tests and from commercial cokes from Richard Pomalis and Bruce Clements the same charges [2]. For the rectification of the parameters from the Karbotest tests CANMET Energy Technology Centre, Canada (CRIKarbotest and CSRKarbotest) to operational values (CRIblast furnace coke and CSRblast furnace coke), the linear equations were used after accumulation of a sufficient amount of data. Firing coal in utility obviates the need for sootblowing. Over time, heat exchange It follows from the operational values of both parameters that it is possible to obtain sections foul with ash deposits that have deleterious effects on heat transfer and boiler quality high-furnace cokes by co-coking with plastics, because the CRI and CSR efficiency. Knowing where and when to blow soot is of paramount importance if the values for the coke from a coal mixture and for the cokes from co-coking do not process is to be optimized. The CANMET Energy Technology Centre – Ottawa differ much. If we - based on experience - consider the blast-furnace coke with the (CETC-O) has developed and implemented a robust and customizable Ash Monitoring CRIblast furnace coke value below 36 % to be of good quality and those with the values 36 System (AMS) software for coal-fired boilers that assists operators during sootblowing – 40 % to be acceptable, then it would probably be only the coke from a mixture with operations. 3 % of rubber that would not be possible to use in a blast furnace. It is similar with 46

The AMS provides the operator on-line information about the state of cleanliness of 50-2 heat exchange sections. The information can be used to optimize sootblowing Succesful Continuous Injection of Solid Fuels into Gasification System Pressures - practices, which translates to significant cost savings. Specifically, optimized Doe Funded Program Results sootblowing results in the following benefits: lower steam consumption, reduced Derek Aldred and Timothy Saunders sootblower maintenance costs, less heat transfer equipment damage, lower NOx Stamet Inc., USA emissions, fewer ash related outages, increased boiler efficiencies, and assistance in Glenn Shirey decision-making regarding sootblowing events. CQ Inc., USA In addition, the AMS provides extensive performance data for the convective pass, economizers and air heaters. These data are supplied to a distributed control system The DOE, recognizing the need for a feeding solution for gasification systems, funded (DCS) in real time, allowing for performance tracking and system optimization. The a project to elevate operation of the unique Stamet “Posimetric Solids Pump” to such AMS program, written in Visual Basic, has menu driven access to performance data, system operating pressures. The ultimate objective is a mechanical rotary device for calibration and configuration utilities, distributed control system data, data acquisition continuously feeding coal into pressurized environments of at least 500 pounds per log (useful in determining when sensors fail), fouling factor trends, legends and online square inch. The “Posimetric” concept earlier achieved continuous feeding into gas help. pressures exceeding 200 PSI under an SBIR program grant, making it the first For the most part, the AMS is a physical model that uses flow, temperature and mechanically powered, continuous “pump” to achieve such pressure levels. pressure data from existing plant instrumentation. The AMS uses this information in The current DOE project comprises an initial phase for design and testing of a device various combustion, mass balance, heat load and pressure drop calculations to to feed coal into 300 PSI and a second Phase for feeding into 500 PSI. Phase 1 determine heat transfer section fouling factors as well as system performance data. included review, with advanced gasification and pressurized combustion system Using a multivariate approach, historical data are used to calibrate the AMS. Once operators, of current specifications and feed equipment to confirm the DOE identified calibrated, no additional training of the software is required. need. This review received strong positive response from gasification system The AMS has been successfully implemented at a major Canadian utility. It can be operators as to the feeding solution need. Additionally, study of coal properties easily installed and configured as an online add-on to an existing plant DCS using desirable for achieving the target pressure was undertaken by CQ Inc., a contributor to client/server software and minimum additional equipment. this paper, to ensure coal used is consistent with requirements of commercial systems. The Phase 1 feeder initial design and materials evaluation results were presented at this 49-5 conference in 2003. Optimization of Oxide Dispersion Strengthened FeCrAl and Fe3Al Alloys In December 2003, following a program of testing and modification, the Phase 1 Bimal Kad feeder achieved a record pressure for continuous injection of coal, 300 PSI, meeting University of California-San Diego, USA the Phase 1 objectives. Subsequently, in extended test runs undertaken at CQ’s facility Rod Judkins to confirm capability of the Phase 1 Pump for requested commercial test applications, Oak Ridge National Laboratory, USA the Phase 1 feeder achieved a pressure exceeding 330 PSI, another record. This Gaylord Smith experience is currently being applied to the Phase 2 design to ensure optimized Special Metals Corporation, USA performance at the 500-PSI target pressure level. Areas for optimization include lower power/torque requirements and enhanced gas sealing. Mechanically alloyed oxide dispersion strengthened (ODS) Fe-Cr-Al and Fe3Al alloy This paper will present a complete review and evaluation of the design and test results thin walled tubes and sheets, produced via powder consolidation methodologies, are of the successful Phase 1 feeder. The paper will present design optimizations for the promising materials for eventual use at temperatures up to 1200oC in the advanced Phase 2 feeder and results of initial Phase 2 testing completed by the date of the power generation systems, far above the temperature capabilities of conventional conference. alloys. Target end-uses range from gas turbine combustor liners to heat exchanger tubes. Grain boundary creep processes at service temperatures are the dominant failure 50-3 mechanisms for such components. The processed ODS alloy microstructure consists of Oxygen Transport Membranes for Future IGCC Power Plants elongated grains parallel to the tube axis, a result of dominant axial metal flow which Bart van Hassel, Ravi Prasad, Dante Bonaquist, Hancun Chen, Jack Chen, aligns the dispersoid particles and other impurities in the longitudinal direction. This Prasad Apte, Ry Drnevich, Joseph Corpus, Jonathan Lane, Eric Shreiber, John dispersion distribution is unaltered by recrystallization treatments and the high aspect Sirman,John Spero and Troy Raybold ratio grain shape typically obtained limits transverse grain spacing and consequently Praxair Inc., USA the hoop creep response. This represents a critical materials design and development challenge that must be overcome in order to fully exploit the potential of ODS alloys. In partnership with the U.S. Department of Energy’s National Energy Technology Fortunately, the material does exhibit requisite creep strength in the longitudinal Laboratory (NETL), a team led by Praxair is developing advanced Oxygen Transport direction and efforts to realign the underlying microstructure for hoop creep service are Membranes (OTM), which can be integrated with Integrated Gasification Combined of interest. We will describe our attempts to improving hoop creep in ODS-alloy Cycles (IGCC) power generation cycles to produce significantly lower-cost oxygen for components by manipulating the factors that dictate grain shape and control gasification. OTM technology, based on high-temperature, ceramic-mixed conductor recrystallization behavior. membranes, can be operated in a pressure-driven mode to separate oxygen with infinite selectivity and high flux, offering unique opportunities for synergistic integration. This paper will provide an overview of the OTM development program, and discuss the significant progress made in Phase 2. Novel schemes for OTM integration with SESSION 50 IGCC will be discussed, along with advances in membrane fabrication, element GASIFICATION APPLICATIONS & ECONOMICS: 3 performance, seal technology, and pilot plant tests. Results to date confirm the potential of OTM to achieve high performance and stability under high-pressure, high- 50-1 temperature operating conditions and to achieve step-change improvements in IGCC Preliminary Results from Field Testing an Improved Refractory Material For oxygen production. Slagging Coal Gasifiers James P. Bennett, Kyei-Sing Kwong and Cynthia Powell Doğan 50-4 USDOE-Albany Research Center, USA ITM Oxygen for Energy-Intensive Applications Phillip A. Armstrong and Hiromi Suzuki Slag attack of refractory materials used to line the hot face of slagging gasifiers limits Air Products Japan, Inc., USA their service life to between 3 and 24 months. These gasifiers use coal, petroleum E.P. (Ted) Foster, James C. Sorensen and VanEric E. Stein coke, or combinations of them as raw materials to produce chemicals, liquid fuel, Air Products and Chemicals, Inc., USA and/or electricity, with future consideration being given to the use of other abundant, low cost feedstock such as biomass. The ash from these materials generate liquid slags In partnership with the U.S. Department of Energy, an Air Products-led team is o during gasification temperatures between 1300 - 1600 C and pressures up to 1000 psi, developing a new air separation technology - Ion Transport Membrane Oxygen - based leading to severe slag attack of a vessel lining and causing unacceptable gasifier on ceramic membranes that selectively transport oxygen ions when operated at high reliability and on-line availability. To maximize refractory life and provide protection temperature. Under the influence of an oxygen partial-pressure driving force, the ITM of the gasifier metal shell, the best liners have contained a minimum of 60-70 pct Oxygen process achieves a high-purity, high-flux separation of oxygen from air. By chromia in combination with alumina, alumina/zirconia, or magnesia. The Albany integrating the energy-rich, vitiated, non-permeate stream with a gas turbine system, Research Center of DOE has developed a phosphate containing high chrome oxide the overall process co-produces high-purity oxygen, power, and steam if desired. As a refractory liner that indicates potential for increased service life over currently used result, the technology is ideally suited for advanced power generation processes that materials. This new liner has been produced commercially by a refractory company require oxygen as a feedstock for combustion, gas-conversion or gasification, as well and installed in a gasifier for performance evaluation. The properties of this material as for traditional industrial applications for oxygen. and preliminary results from the plant trial will be presented. During Phases I and II of a three-phase program, the ITM Oxygen team established the feasibility of the ceramic membrane approach and designed and built commercial-scale

membrane modules. A demonstration facility that will produce 5 tons-per-day of pyrolysis, AAEM species were volatilized into the gas phase to a substantial degree oxygen is in construction. Larger demonstrations are planned, with full while some portions remained in/on the char particles. Further experimental commercialization projected in the latter part of the decade. examinations were made on their catalytic roles in the steam reforming of the tar in the Pilot-scale demonstrations of ceramic processing steps and membrane performance gas phase and that over the char surface. Aiming to examine the catalytic roles of have confirmed the impressive economic benefits which are the basis for this AAEM (particularly, Na) in the gas phase, a novel two-stage drop-tube/tubular reactor development effort. This presentation will focus on the benefits that ITM Oxygen can (DTTR) was developed. Pulverized coal was and N2 carrier gas was fed into the drop- bring to a broad range of energy-intensive process applications. Specific examples of tube reactor of which bottom was equipped with SUS316 mesh for separating the ITM Oxygen applied to low-carbon-emission IGCC, oxygen-enriched combustion, and volatiles from the nascent char particles. The volatiles were then diluted with N2 or gas-to-liquid (GTL) plants will be discussed. steam-N2 and introduced into the second tubular reactor. The temperature of DTTR was fixed at 900 °C. The residence time of the volatiles within the tubular reactor was 50-5 about 10 s. The pyrolysis experiments were performed using three different samples: Development of Synthesis Gas Production Technology Using 3 T/D Scale Coal raw Loy Yang coal, a NaCl-loaded Loy Yang coal and an acid-washed (AAEM free) Gasification System Loy Yang coal. Under the conditions employed, 0.09 wt% and 0.80 wt% of Na (on dry Seok Woo Chung, Young Don Yoo and Yongseung Yun coal basis) were volatilized from the raw and NaCl-loaded coals, respectively. Institute for Advanced Engineering, Korea Volatilized Na was introduced into the second reactor together with the nascent volatiles. The distribution of the products from the nascent volatiles was substantially A synthesis gas producing facility that consists of pulverized coal influenced by the concentration of Na in the gas phase as well as the presence of feeding/gasification/hot gas clean-up system has been developed and tested for nine steam. The introduction of steam into the tubular reactor suppressed soot formation different coals, with the primary goal of providing coal selection guidelines for the from the tar converting the soot precursor into carbon oxides and H2 even in the future IGCC facilities in Korea. The coal gasifier of 3 ton/day (T/D) scale was absence of Na. The soot formation was further suppressed by increasing Na entrained-bed slagging type and was operated normally in the temperature range of concentration. On the other hand, introducing steam increased the residual tar yield in 2 2 1400~1450 , 8~10 kg/cm (max. 30 kg/cm ) pressure. The obtained composition of the absence of Na, while decreased the yield slightly even in the presence of Na. H2 or synthesis gas was 63~68% of CO, 20~25% of H2, 10~15% of CO2 in the dry, N2-free H radicals formed from the steam reforming of the soot precursor played a role of basis. The 95~99% of carbon of the suitable coal was converted to synthesis gas and “stabilizer” of the tar unless the Na concentration in the gas phase was sufficiently the ash was converted into non-leaching slag. high. Comparing the combined effects of steam and Na between the pyrolyses in DTR Through the more than five years of experimental study, many facilities were upgraded and DTTR, it was concluded that Na on the char surface was indispensable for in the areas such as the pulverized coal pneumatic feeding, synthetic gas production, simultaneous decrease in the yields of soot and residual tar, although Na in the gas and hot gas clean-up. For the reliability test of the coal gasification system, one month phase promoted the steam reforming of the soot precursor. continuous operation was proceeded while yielding the production of 120~200 Nm3/hr synthesis gas. This paper describes the coal gasification characteristics and the latest 51-3 operational results of the 3 T/D gasification facilities. Fates and Roles of Alkali and Alkaline Earth Metallic Species in Loy Yang Brown Coal during In-Situ Steam Gasification Bazardorj Bayarsaikhan, Taihei Shimada, Jun-ichiro Hayashi and Tadatoshi Chiba SESSION 51 Hokkaido University, Japan LOW RANK COAL UTILIZATION: 5 Chun-Zhu Li Monash University, Australia 51-1 Influence of Silicon Minerals on Gasification Kinetics during Gasification of Low- In-situ steam gasification of nascent char from the rapid pyrolysis of a Victorian brown Rank Coal coal, Loy Yang (LY), was investigated at temperature, total pressure and steam partial D.P.Ross pressure of 1173 K, 0.1 – 1.2 MPa and 0.053 – 0.6 MPa, respectively. Using a novel Tokyo University of Agriculture and Technology, BASE, Japan drop-tube/fixed-bed reactor enabled the minimized interaction among the char, the A. Kosminski and J.B. Agnew volatiles and gaseous products during the rapid pyrolysis of the coal and the Department of Chemical Engineering, Australia subsequent gasification of the nascent char. During the gasification, the conversion on a coal carbon basis rapidly increased within 100 s up to around 80 %, followed by The purpose of this study is to investigate the catalytic activity of Na as sodium further increase but much more slowly. The time dependent change in the conversion carboxylates (-COONa) or as NaCl in the presence of silica and kaolin during the was analyzed by assuming first order kinetics with respect to the amount of residual gasification of South Australian lignite coal. Coal from this region is characterised by carbon in the char. The instantaneous specific reactivity, defined by relative high sodium (1.0 wt% d.b.) and silica (5.0 wt% d.b.) contents. A set of Na- exchanged coal and a NaCl-loaded coal samples prepared from a Lochiel coal were  d()1−X  −  ()1−X (X: conversion of char on carbon basis), gasified in a fixed bed reactor with steam and carbon dioxide. The coal gasification dt rate at a given temperature was modelled by the “homogeneous” kinetic model and the   activation energy of coal determined. Both silica and kaolin significantly impact on the activation energy for both gasification reactions for coal containing carboxylate bound decreased by an order of magnitude within 100 s (first stage) and then became constant Na and to a lesser extent on coal containing NaCl. This is a result of the Na reacting (second stage). For in-situ gasification of the char from the acid-washed LY that with the silica or kaolin to form sodium silicates or sodium aluminosilicates, contained no alkali and alkaline earth metallic (AAEM) species, the specific reactivity preventing Na from becoming an active catalyst. Kaolin is a greater inhibitor of was constant over the entire range of the conversion, and moreover, in good agreement sodium catalytic effect than silica. The steam coal gasification reaction rate at 850oC with that during the second stage gasification of the char from LY. These results for coal containing carboxylate bound sodium was found to be three times faster than suggested that the conversion of the char from LY in the first stage and that in the for corresponding gasification in a carbon dioxide atmosphere. Controlling of the second stage were contributed mainly by the gasification catalyzed by inherent AAEM fouling and agglomeration propensity of coal for use in FBG by the addition of kaolin species and non-catalytic gasification, respectively. AAEM species underwent fast will have consequences on the catalytic char gasification rate. Both kinetic and volatilization in the first stage and much slower volatilization in the second stage, catalytic data obtained in this work compare well with data published in the literature while the concentration of the species (their amounts per that of residual carbon in the for gasification of other Australian lignites. char) rather increased. Thus, the decrease in the specific reactivity in the first stage gasification was explained by simultaneous progress of the loss of catalytic activities 51-2 of AAEM species due to their volatilization and intra-particle deactivation within 100 Catalytic Roles of Na in Homogeneous and Heterogeneous Steam Reforming of s. The intra-particle deactivation of AAEM species was also caused by heating the Tar from the Pyrolysis of a Brown Coal nascent char from LY at 1173 K for a long period or pyrolyzing the coal in the Eiji Ohtsubo, Jun-ichiro Hayashi, Nozomu Sonoyama and Tadatoshi Chiba presence of volatile-char interaction before the gasification. In such cases, the specific Hokkaido University, Japan reactivity of the resulting char agreed well with that of the char from the acid-washed Chun-Zhu Li LY over the full range of the char conversion. On the basis of the experimental Monash University, Australia findings, it was concluded that the specific reactivity of the char from LY was described as the sum of the intrinsic reactivity for the non-catalytic gasification and the When Victorian brown coal was pyrolyzed in an atmosphere containing steam in a reactivity for the gasification catalyzed by AAEM species, the latter of which was a drop-tube reactor (DTR) at 900 °C, nascent tar underwent steam reforming as well as function of concentration of “active” AAEM species. It was also demonstrated that the thermal cracking. Progress of the steam reforming resulted in the conversion of the non-catalytic gasification obeyed first order kinetics with respect to the residual initial tar as high as 95 – 99% with negligible soot formation. Such rapid steam amount of carbon in the char. reforming never occurred when alkali and alkaline earth metallic (AAEM) species were removed from the coal prior to the pyrolysis, and this was a direct indication of roles of AAEM species as inherent catalysts for the steam reforming. During the 48

51-4 the diesel vehicles, to SNG (substitute natural gas) and hydrogen for PEFC productions In-situ Gasification Reactivity of a Victorian Brown Coal in Steam: Catalysis and by reforming DME. Most of these technologies will be technically feasible thanks to Changes in Char Structure the vigorous efforts by the various Japanese organizations. Chun-Zhu Li, Xiaojiang Li In this paper, the outline and the main results of JOGMEC’s R&D on DME utilization Monash University, Australia technologies will be described. Jun-ichiro Hayashi Hokkaido University, Australia 52-3 In Situ ATR/FTIR Observation of Transformation of the Nickel Precursor in a The purpose of this study is to investigate the volatilisation of alkali and alkaline Catalytic System for Low-Temperature Methanol Synthesis in a Liquid Medium metallic species (AAEM) and the changes in char structure during the gasification of Seiichi Ohyama Loy Yang brown coal. The acid-washed (H-form), Na-exchanged (Na-form) and Ca- Central Research Institute of Electric Power Industry, Japan exchanged (Ca-form) Loy Yang brown coal samples were gasified in-situ in steam in a novel two-stage reactor at a range of temperatures from 700 to 900°C. The two-stage Low-temperature methanol synthesis from syngas rapidly proceeds in liquid media at reactor, which was a fluidised-bed/fixed-bed reactor in tandem with a combustor, was temperatures of approximately 373 K in the presence of catalysts composed of a Ni designed to monitor the release of carbon during the whole pyrolysis and gasification compound and an alkali alkoxide. Two catalysts, Ni(OCOCH3)2/CH3OK and process, allowing for the direct determination of specific reactivity of nascent char. Ni(CO)4/CH3OK, has been proposed for the reaction, in which methanol (MeOH) is The retention of AAEM species in char during pyrolysis and subsequent gasification considered to be formed through the carbonylation of MeOH to methyl formate (MF) was quantified. FT-IR/Raman spectroscopy was used to investigate the changes in char and the subsequent hydrogenation of MF to MeOH. However, the relation between the structure during gasification. The experimental results have provided insights into the two nickel precursors, Ni(OCOCH3)2 and Ni(CO)4, is not yet clarified and the active effects of AAEM species and char structural features on the char gasification reactivity species of Ni(OCOCH3)2/CH3OK still remains unknown. under a wide range of experimental conditions. An in situ ATR/FTIR technique was employed to probe transformation of the Ni precursor in Ni(OCOCH3)2/CH3OK. Ni(OCOCH3)2 was partially converted into - - 51-5 Ni(CO)4 and hydridocarbonylnickel anion ([HNi(CO)3] and/or [HNi2(CO)6] ) during Formation of NOx Precursors during the Gasification of Victorian Brown Coal in the reaction, the latter of which was responsible for the MF hydrogenation step in the Oxygen low-temperature methanol synthesis. It was also confirmed that carbonylation of Lachlan J. Mckenzie, Fu-Jun Tian, Jiang-Long Yu and Chun-Zhu Li methanol exclusively proceeded in the initial 10 min of the reaction and then Monash University, Australia hydrogenation of MF restricted the overall reaction rate in the latter period of the run. Assuming that the reaction rate obeys the first-order kinetics, a kinetic study was done The formation and subsequent release of nitrogen oxides (NOx) from coal-fired power with Ni(CO)4/CH3OK and Ni(OCOCH3)2/CH3OK. Each catalyst has two rate plants is a major environmental concern. A better understanding of the conversion of constants depending on the time. In the initial 10 min of the run, the rate constants for coal-n during gasification will contribute to the development of near zero-emission both catalysts were similar. In the other period of the run in which the hydrogenation -4 - power generation technologies using coal. This study aims to investigate the of MF was a rate determining step, the rate constant for Ni(CO)4/CH3OK (3.  sec 1 -5 -1 conversion of coal-n during the gasification of victorian brown coal with O2. A loy ) was four times larger than that for Ni(OCOCH3)2/CH3OK (8.0 10 sec ), which yang brown coal has been gasified in a novel fluidised-bed/fixed-bed reactor at low agreed with the ratio of the concentrations of the nickel anion which was observed with temperature and fast particle heating rates. The yields of main n-containing products, in situ FTIR. These findings indicate that the nickel anion promotes the hydrogenation including NO, NO2, HCN and NH3, have been quantified. of MF in both Ni(CO)4/CH3OK and Ni(OCOCH3)2/CH3OK in catalytic systems. High yields of HCN and NH3 have been observed from the gasification of the brown coal in O2-containing atmosphere. In addition to temperature and O2 concentration, 52-4 the coal feeding rate is an important factor influencing the release of coal-n during Catalyst Development for Methanol Synthesis by Design of Experiment and an gasification. These results provide evidence for the importance of volatile-char Artificial Neural Network interactions on the release of coal-n even at 500°C. Significant amounts of NO2 have Yuhsuke Watanabe, Tetsuo Umegaki, Masahiko Hashimoto, Sutarto, Kohji Omata and also been observed, probably as a result of complicated reactions involving active Muneyoshi Yamada radicals. Our experimental results will be discussed to provide some insights into the Tohoku University, Japan mechanisms for the conversion of coal-n during gasification in O2-containing atmosphere. Methanol and dimethyl ether attract much attention as high quality transportation fuels and hydrogen sources. Highly active catalyst for methanol synthesis at low pressure is SESSION 52 required in economic and compact process. Catalyst composition of Cu-Zn-Al-Cr-B- SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 3: Zr-Ga oxide catalyst for methanol synthesis was optimized for high activity. Catalysts DIMETHYL ETHER & METHANOL were designed by design of experiment (DOE) and prepared automatically. The 52-1 activities were measured in 96 well microplate reactor at high pressure. The results Direct Dimethyl Ether (DME) Synthesis from Natural Gas were analyzed by an artificial neural network. An active catalyst was discovered and Seiji Aoki, Takashi Ogawa, Norio Inoue, Tsutomu Shikada, Osamu Inokoshi, validated experimentally. Yotaro Ohno An orthogonal array of L18 by DOE was used to design 18 catalyst compositions. DME Development Co. Ltd., Japan Each composition (mol %) was selected from 3 levels as follows: Cu (40, 50 ,60); Zn (10, 20, 30); Al (0, 10, 20); Cr, B, Zr, Ga (0, 5, 10). The 18 catalysts were prepared by Dimethyl ether (DME) is a clean and economical alternative fuel, which can be ethanol-oxalic acid method. Ethanol solutions of metal salts were dispensed into a 96 produced from resources such as natural gas, coal or biomass. The properties of DME well microplate using automated liquid dispenser (Gilson, 222XL) according to the are very similar to those of LPG and its can be used for various fields; power L18 array. Ethanol solution of oxalic acid was then dispensed to each well to obtain generation, transportation, home fuel, etc. precipitate of mixed oxalate. After calcination the precursors were packed in Durham An innovative process of direct DME synthesis from synthesis gas has been developed. tubes (6 mm I.D., 40 mm length). The tubes were arrayed in a 96 well microplate made Five tons per day DME production pilot plant (5TPD) project had finished very of aluminum and the plate was placed at the bottom of an autoclave (15 cm I.D.). successfully in 2001 after two years process development. Based on the 5TPD results, Methanol synthesis was conducted in the autoclave at 225 °C, 1 MPa. Methanol from 100 tons per day DME production demonstration plant (100TPD) project started in each catalyst bed were transfered through capillary tube (0.1 mm I.D.) into water trap. 2003. The amount of methanol was determined by colorimetric reaction. The relation The first plant operation in December through January 2004 achieved 100 % load plant between the catalyst composition and catalytic activity was thus operation with DME product purity of more than 99.5 %. These projects are supported experimentally determined. by Japan’s Agency for Natural Resources and Energy under Ministry of Economy, For response surface modeling (RFM), an artificial neural network (ANN) was used. Trade and Industry (MITI). The relation between the catalyst composition and catalytic activity was used as training data of a variety of ANNs. Among them, a linear combination of ANNs gave 52-2 best fitting to test data and the ANN can predict catalytic activity as a function of Current Status of R&D for the DME Utilization Technologies in Japan any catalyst composition. In order to find the maximum activity of the ANN, activities Shinichi Suzuki of 230,230 combinations of 7 component catalyst with 5% step were predicted by the Japan Oil, Gas and Metals National Corporation, Japan ANN. Then minute predictions around the maximum were repeated with 1% step. The predicted most active catalyst gave a high activity for methanol synthesis. In the case In order to realize DME use as a fuel in the end of 2006, Japan Oil, Gas and Metals of 7 component, the number of possible combinations with 1% step is as large as National Corporation (JOGMEC) has been carrying out the R&D of DME utilization 1,705,904,746. It is impossible and unmeaningful to check the all combinations. The technologies with Japanese private companies from 2001. Since DME is recognized as tool composed of DOE, ANN and RSM as described above succeeded to discover the a clean versatile fuel, the theme of JOGMEC R&D varies ranging from the good result using only 18 data in such a huge search space and rapid catalyst turbine/boiler for power plants, the diesel engine/micro gas turbine for co-generations, development was achieved. 49

52-5 53-2 The Synthesis of Dimethyl Carbonate in a Slurry Reaction System with Cu+- Coal-Seq Project Update: Field Studies Of Ecbm Recovery/ Zeolite Catalyst Co2 Sequestration in Coalseams Zhong Li, Li Zhou, Li Yang Kechang Xie and Lihua Yin Vello A. Kuuskraa and Scott Reeves Taiyuan University of Technology, P.R. China Advanced Resources International, Inc., USA

In the past decade, dimethyl carbonate (DMC) has been drawing much attention as an In October 2000, a three-year government-industry project known as the Coal-Seq important green chemical feed stock all over the world because it can be used to project was launched in the United States. The project is studying the feasibility of replace environmentally unfriendly compounds in many commercial procedures and CO2 sequestration in deep, unmineable coalseams using enhanced coalbed recovery manufactured from coal. Now it has drawn more and more attention to research on the technology. The Coal-Seq project is specifically focused on understanding the results chemistry of the DMC synthesis processes because DMC has been considered as a of actual field experiments via reservoir modeling, with laboratory studies filling a promising chemical compound in view of the increasing world wide environmental supporting, not primary, role. The fields being studied are both in the San Juan basin. problem. The sites are the Allison Unit, operated by Burlington Resources and the Tiffany Unit, The traditional method for DMC synthesis is the reaction of methanol and phosgene. operated by BP America. These two sites are the only two in existence today, But it has being phased out due to the high toxicity of phosgene and the severe worldwide, where long-term, multi-well injection of CO2 or N2 is being performed. In corrosiveness of by-product HCl. Some non-phosgene syntheses of DMC have been addition to the field studies, supporting analytic work in the areas of multi-component developed since 1980s, such as transesterification of methanol with vinyl or propenyl sorption behavior, and coal swelling with CO2 adsorption, are being performed. carbonate, methyl nitrite method, direct synthesis from carbon dioxide and methanol, and oxidative carbonylation of methanol. 53-3 A number of investigations have been focused on the use of a supported copper Concept of the Zero-Emission Gas-Turbine Combined Power Plant System catalyst to synthesis DMC via liquid phase oxidative carbonylation of methanol in Yuji Ooka order to avoid the problems of using CuCl catalyst. King reported that the chloride is Kawasaki Heavy Industries, LTD., Japan not necessary for the copper catalysts to catalyze the gas phase oxidative carbonylation Paul Sims of methanol to DMC and developed a solid-state ion exchange method to prepare a CSIRO, Australia free-chlorine Cu+ catalyst on a zeolite support. This paper firstly reports the research results of the catalytic performance of Cu+ In response to global warming due to the increasing carbon dioxide gas in the zeolite catalysts in the liquid phase oxidative carbonylation of methanol to DMC. A atmosphere, investigation of carbon dioxide separation and capture technologies from series of CuCl-zeolite catalysts were prepared by solid-state ion exchange under exhaust gas of a thermal power plant and sequestration technologies have been flowing nitrogen. The condition of the catalyst preparation and the reaction were performed all over the world. investigated. For both DASY-CuCl catalyst and HZSM-CuCl catalyst, the space time In relation to geological sequestration technology, coal bed sequestration is regarded as yield (STY) of DMC firstly increase and then decreases with the rise of temperature, an economical choice and its technology is an extension of EOR. Importantly it also but the selectivity of DMC based on methanol (SDMC/MeOH) is almost no change. utilizes an undeveloped energy source in addition to carbon dioxide gas storage. HZSM-CuCl catalyst prepared at 350 for 4h had the best catalytic performance, Some research and development projects have been started to estimate and establish 0.56kg/kg·h STYDMC and 96.19% SDMC/MeOH. The morphological analysis by X-ray related technologies such as safety, monitoring, rock interactions etc. One of the newer powder diffraction shows at 250 the crystal phase of CuCl in the catalyst was technologies is to use a mixture of carbon dioxide and nitrogen for gas injection in remarkable, which indicates that most of copper on the zeolite surface existed in CuCl order to increase the recovery of coal seam methane. The recovery rate can be form. More CuCl exists in the catalyst, more micropore or channel of the zeolite are controlled by the mixing rate of two gases. However when nitrogen is used the energy blocked by solid CuCl crystal. In the result, the special area of the catalyst is reduced loses and economic disadvantages of using the gas must be considered. and reactant methanol is obstructed to pass through channel to be adsorbed on copper When a CO2/N2 mixture of a fixed ratio is not required, a CO2 recycle type gas species of the catalyst, which caused low activity and high corrosion to the autoclave. turbine can be used. Such a system, without using CO2 gas capture process has been With the rise of catalyst preparing temperature, the ion exchange reaction between classified as a Zero Emission Power Plant. In this concept, several disadvantages such CuCl and zeolite happened and Cu+ is dispersed in the cage of zeolite which had as an increase of power required due to nitrogen gas treatment and the associated catalytic active of oxidative carbonylation of methanol to DMC, and more CuCl was decrease of sequestrated carbon dioxide gas should be considered compared to other dispersed as a cluster in the surface of zeolite. When prepared at 650 , the catalyst did choices. not have any CuCl crystal to be observed by XRD. This highly dispersed Cu+ and Already in Japan as part of the development of clean electric power generation CuCl makes the catalyst have high catalytic active. But at high preparing temperature, technologies a carbon recovery type closed cycle gas turbine using oxygen combustor the catalyst would have less Cu+ loading due to the sublimation of CuCl phase and had been attempted in order to eliminate the capture process of carbon dioxide gas. decrease of the catalytic activity. And the corrosion of equipment caused by CuCl was Even in this concept, several technological hurdles including treating oxygen and cost reduced. The morphological analysis by X-ray powder diffraction (XRD), Scanning issues have to be addressed. electron microscope (SEM) and FTIR has shown that the catalyst has a clustering Both technologies, the coal bed sequestration and the oxygen combustor gas turbine, phenomena and the existence of copper chloride hydroxides (Cu(OH)3Cl) after mutually support the required mass flows and exhaust. At the start of the combined reaction. system, air is separated into nitrogen and oxygen. The coal bed sequestration need carbon dioxide and nitrogen; and the coal seam methane is obtained to drive the SESSION 53 oxygen combustor type gas turbine that exhausts pure carbon dioxide without the need GLOBAL CLIMATE CHANGE: 2 for capture. If an appropriate mass flow balance can be achieved in this system, it makes construction of perfect no emission power plant feasible; using methane from 53-1 unmineable as energy source and shares the air separation cost. The Proposition of CO2 Gas Disposal The purpose of this paper is to describe the estimated results of mass flow and cost of Maciej Mazurkiewicz, Zbigniew Piotrowski and Radoslaw Pomykala the combined system using existing commercial component’s characteristics and test AGH University of Science and Technology, Poland data of a coal bed sequestration project.

The idea of carbon dioxide reduction by underground storage with wastes is presented 53-4 in the paper. It was formed while searching a new method of underground fire fighting Co2 Adsorption by Australian Coals under Supercritical Conditions for the Polish coal mining. CO2 gas has been absorbed by fly ash suspension (in Stuart Day, Greg J. Duffy, Abou Saghafi and Richard Sakurovs water). The suspension has been commonly used in the majority of Polish underground CSIRO Energy Technology, Australia coal mines for backfilling of abandoned workings and cavings for over twenty years. The biggest advantage of this technology, apart from wastes utilization, is the CO2 sequestration is a technology that can, in principle, reduce CO2 emissions to the improvement of the mine ventilation system by filling and sealing of cavings in the atmosphere. Of the possibilities available for storage of CO2 in Australia the most longwall system. It helps fight with fire and methane hazard. For these reasons the prospective appear to be geological storage in saline aquifers or deep unmineable coal mining uses the big part of the Polish fly ash production. Annually it is a many seams. millions tons. It could give a change for carbon dioxide storage on a considerable A new gravimetric system has recently been constructed at CSIRO that allows CO2 scale. adsorption measurements of coal at the high pressures and temperatures characteristic Results of laboratory tests on a new installation are presented in the paper. The of deep coal seams, even in the presence of other gases such as water vapour, methane subjects of the tests were suspensions made with the use of fly ashes from traditional or nitrogen. Experiments are being carried out at pressures up to 17 MPa and and fluidized bed combustion, with or without desulphurization products. The o o temperatures up to 70 C, i.e. well above the critical pressure of CO2 (7.3 MPa, 31 C). influence of some factors on CO2 absorption such as temperature, pressure, amount of This gravimetric method avoids the problems associated with the volumetric methods water and blending conditions was analyzed. used in other studies where errors arise due to the lack of a reliable equation-of-state

for supercritical CO2, particularly when other gases are present.

The data from these experiments are being used in concurrent modelling studies including blend coal (BC), waste plastics (WP) and organic additive (OA), which from directed at developing new models to describe the sorptive behaviour of coals at high Shougang coking plant and municipal solid waste of Beijing city were used. The coke pressures and temperatures. strength indexes including M10, M40, CRI and CSR were analyzed. The results showed This paper will report the results of recent investigations that will form the basis for that the strength of coke from co-coking of coal and waste plastics is worse than that assessing the suitability of Australian coals as gas storage targets, and will outline from separately coking of blend coal. While, all the strength indexes of coke from co- some of the factors that will influence the rate of absorption and dispersal of carbon coking of coal and waste plastics by adding organic additive are better than that from dioxide in coal. separately coking of blend coal. This indicated that the coke strength can be enhanced in the process of co-coking of coal and waste plastics by adding a kind of organic 53-5 additive (OA). Experimental Study on Supercritical CO2 Adsorption on Coals in Relation to their Pore Structure 54-3 Sohei Shimada and Masaatsu Tamura Effect of Waste Wood Addition to Coal on Coke Quality The University of Tokyo, Japan Masaru Nishimura, Yuko Nishibata and Kanji Matsudaira The Kansai Coke & Chemicals Co., Ltd., Japan ECBMR (Enhanced Coalbed Methane Recovery) is one of the geologic carbon sequestration technologies and it is attractive from the viewpoint that it can recover As a part of recycling society promotion, waste plastics are used as a metallurgical raw CH4 besides sequestrate CO2. Coal seams are broadly distributed in the world. material in coke making plant. In Japan, Construction Materials Recycling Act was Therefore, this technology can be used in many countries. In order to perform a more enforced in 2002. Since it obliges us to recycle waste wood, new solution to recycle reliable gas production simulation, the basic data about CO2 and CH4 adsorption are waste wood is expected. So we have made a study to use waste wood as a coke making indispensable. Adsorption experiments of super-critical CO2 on coal were performed material. The 3mass% addition of raw waste wood into coal charge deteriorated coke 600 to find the relation between the pore structure and adsorption amount. qualities (I 9.5; measured with I-type drum tester). But preheating of waste wood at The experiments by using single gas of CO2 were conducted up to 11MPa and at 40 appropriate temperature improved the coke qualities. To get the reason, the gieseler degrees C by Constant Volume Method. Five samples were used for the experiments: maximum fluidity (MF) of coal blended with raw or preheated wood sample were Akabira coal, Taiheiyo coal, Yallourn coal, Maokhe coal and Actrivated carbon. measured, because the fluidity of coal has relation to coke strength. Raw waste wood Akabira coal and Taiheiyo coal are categorized to sub-bituminous coal, Yallourn coal addition to coal showed considerable decrease in MF. However pretreated wood is brown coal and Maokhe coal is anthracite. addition showed minor decrease in fluidity. Moreover we tested the fluidity of coal Activated carbon showed the highest amount of excess sorption. The adsorption blended with cellulose or lignin because cellulose and lignin are main constituent of isotherm of Mokhe coal was similar to that of Taiheiyo coal. The results suggest that wood, and confirmed cellulose and lignin caused the declination in fluidity. the coals having the similar pore distribution shows the similar adsorption isotherm shape. 54-4 CO2 adsorption experiment on the coals being treated by supercritical CO2 was Non-Fuel Use of Anthracite: Preparation of Activated Carbon and Adsorption performed for Taiheiyo coal and Akabira coal. The change of the adsorption amount Performance before and after treatment was observed. The cause might be a structural change of Jae Ho Kim inner surface of coal by contraction. Korea Coal Cooperation, Korea It is concluded that high rank coal with many micro pores is advantageous for Si Hyun Lee supercritical CO2 sequestration in coal. Korea Institute of Energy Research, Korea Sung Ho Kong SESSION 54 Hanyang University, Korea COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY: 4 54-1 Purpose of this study is to develop activated carbons from Korean anthracite. Low ash The Dissolution of Cokes in Molten Iron coals were separated by dense media technique to make raw materials for activation. S.Tsuey Cham and Veena Sahajwalla Activated carbons were produced with steam or CO2 from crushed and granular coals. The University of New South Wales, Australia Chemical pretreatment with alkali hydroxides (Na, K) were conducted to increase the Richard Sakurovs reactivity of anthracite for activation. Liquid and gas phase adsorption tests were CSIRO Energy Technology, Australia performed with organic compounds. Activated carbons having the surface area of 650m2/g from crushed coals and of 920m2/g from granular coals were produced. Blast furnace operators are facing increasing pressure to improve their efficiency and Chemical pretreatment have an effect on surface area increase from 650m2/g to increase their sustainability. One change that would improve efficiency that is now 840m2/g for the crushed coals, and on the increase of pore size and burn-off. It was being actively explored is reduction in operating temperature. However, for operating found that the activated carbons from crushed coals by chemical pretreatment and CO2 temperature to be reduced, feasibly, extensive understanding of the reactions that occur activation have well developed micro-porosity, and that the activated carbons from in the blast furnace and how their rates are controlled will be required. Central to blast granular coals by steam activation have wide ranges of porosity. They are suitable for furnace operations is coke. Coke in blast furnaces reacts with carbon dioxide and also gas phase and liquid phase adsorption respectively. dissolves in molten iron. While the former reaction has been well studied and is an important coke characterisation tool, the latter reaction has not been as well 54-5 investigated. Yet the rate of this reaction is important in determining how well the blast An Application of a Homogenization Method to Microstructure of Coke Using furnace operates and predicting how it would behave at lower temperature. We report Digital Image Processing here the findings of a study investigating the rate of dissolution of a number of cokes Kenta Ueoka, Tomoki Ogata, Yoshio Morozumi, Hideyuki Aoki and Takatoshi (with similar ash yields) in molten iron at 1550°C. We found that different cokes react Miura at very different rates with molten iron at this temperature; the rate can vary by over an Tohoku University, Japan order of magnitude depending on the coke. The reasons for these differences in reaction rate and their implications for coke selection and preparation will be A homogenization method is applied to the estimation of coke strength using discussed. digital image processing. Coke strength is the most important quality to retain the permeability in blast 54-2 furnaces. Since coke has complex microscopic geometry, it is difficult to analytically Enhancing the Strength of Coke from Co-Coking Of Coal and Waste Plastics by estimate the coke strength by considering microscopic pores. Recently, a Adding Additive homogenization method, which enables us to analyze macroscopic and microscopic Hong-qiang Liao, Peng Zhao, Ya-bin He, Kai Qian behavior simultaneously, has been applied to the understanding of the fracture Shougang Technical Research Institue, China mechanism in coke. In this study, the digital image analysis based on the Guang-wei Yu, Jiu-jv Cai homogenization method was used to solve two dimensional elastostatic problems Northeastern University, China considering the actual microstructure of two kinds of coke. One was coke made by Bao-qing Li caking coal, the other was coke made by a mixture of caking coal and slightly caking Institute of Coal Chemistry Chinese Academy of Sciences, China coal. The analyzed picture size was 100x100, 150x150 and 200x200 pixels. Calculated results of the homogenized elastic modulus distribution became narrow Waste plastics disposal by using traditional coking process was a viable way to with an increase in the analyzed picture size. The distribution of von Mises stress of overcome the white pollution coursed by waste plastics. However, there are many the coke made by caking coal was lower than that of the coke made by a mixture of researching work to do for enhancing the coke strength and increasing the ratio of caking coal and slightly caking coal. This is because that there were few microscopic adding waste plastics. This paper suggested a way to enhance the strength of coke from pores whose diameters were approximately 500 m and were relatively large in the co-coking of coal and waste plastics by adding additive. The experiment was carried coke made by caking coal. In addition, the matrices between microscopic pores in the out in a test coke-oven ,which can load 200 kg material. The experimental materials coke made by caking coal were thick. Consequently, the strength of the coke made 51 by caking coal was higher than that of the coke made by a mixture of caking coal and Moreover, the core of the process concerned consists of two nested columns that slightly caking coal. have a heat exchange interaction with each other on their entire lengths. The adiabatic rectification columns used commonly nowadays only have a partial heat exchange contact, respectively. Thus, the applied construction is both simple and POSTER SESSION 1 thermodynamically economical. Since the prevailing pressure is kept different on the COMBUSTION TECHNOLOGIES various sides of the main heat exchange surface, i.e. both the nested columns have P1-1 different pressures, the phase change of the produced fraction occurs at different Modern Technologies of Heat Production as the Opportunity for Coal temperatures in the various columns. Consequently, the main power source needed to Leon Kurczabiński and Roman Łój maintain the process in operation is a pump for decreasing the prevailing pressure in Coal Holding Katowice J.S.C., Poland the evaporation (inner) column. In this paper, the novel cryogenic method operating at normal pressure producing Since the beginning of the 90ties, Poland has been experiencing a gradual demand oxygen-enrichment is introduced. The theory behind the process as well as some decrease for coarse and medium stove coals used in houses and small and medium experimental and simulation results are studied. heat producing facilities. At the beginning of the 90ties the volume of coal used was about ___tons a year and P1-4 the end of the decade showed the decrease to the volume of about___. A Kinetic Study on Tin Oxidation This coal has high quality parameters: the heating value reaches 31 MJ / kg, the ash Ming-Hou Xu contents is up to 5 % and the sulphur contents is about 0,4 %. The decrease in this Huazhong University of Science and Technology, China coal use caused that the producers started to crash and add it into steam coal fines. Lai-Cai Li, An-Min Tian Coal has been gradually replaced by natural gas and furnace oil technologies. Sichuan Normal University, China However, the end of the 90ties showed certain change in the tendency when the Ning-Bew Wong market noticed new heating technologies based on coal and proposed for medium City University of Hong Kong, Hong Kong and small heat producing facilities (from 15 KW to 5 MW ). Their characteristic features are the efficiency up to 85%, small staff involvement, combustion conditions Ab initio MP2 method was performed to study the reaction mechanism and kinetics that significantly reduce toxic substances emission and also the heat production costs of stannic oxidation by oxidants (HOCl, HCl, ClO, ClO2 and NO3) during the even twice or three times lower than the costs of technologies based on natural gas or process of coal combustion. Nine reaction pathways listed below were found by furnace oil. calculations: (1) Sn + HOCl SnCl + OH, (2) Sn + HCl SnCl + H, This paper presents a short description of these technologies and the actions taken by (3)Sn+ClO SnO+Cl, (4) Sn+ClO2 SnO + ClO, (5) Sn + NO3 SnO + NO2, (6) Katowicki Holding Węglowy in order to implement them and to create new coal SnO + HCl SnCl + OH, (7) SnO+HOCl SnCl+HO2, (8) SnCl+HCl SnCl2+H, market which within recent 3 years has reached the level of 150 000 tons a year and (9) SnCl+HOCl SnCl2+OH. The geometric configurations of reactants, products, what is more, the tendency is increasing. intermediates and transition states were optimized (the metal element tin was computed using SDD basis sets, and other non-metallic elements were computed P1-2 using 6-311+G* basis sets). The energies of various compounds along the reaction Formation of NOx during Char Combustion in a Fixed Bed of Catalyst under pathways were derived at mutually the same computational level. The classical Reduced and Elevated Pressure Conditions transition state theory was used to calculate the reaction rate constants of the nine Tadaaki Shimizu, Toshiaki Takahashi, Masaru Tonsho, Makoto Inagaki reactions. Based on the above calculations, the microscopic mechanism and kinetics Niigata University, Japan of stannic oxidations by HOCl, HCl, OCl, ClOO and NO3, and of the further oxidation of SnO and SnCl by HOCl and HCl were studied. The results show that Sn The effect of catalyst on the conversion of char bound nitrogen to NOx during (3P0) may react with HCl, ClOO and NO3 to form SnO and SnCl; the product SnO combustion of one kind of coal char was evaluated using a fixed bed reactor at 1123 can be turned into SnCl by HOCl and HCl with difficulty; however, SnCl will be K. Petroleum coke ash was used as a catalyst that enhances NOx formation from further oxidized into the soluble compound SnCl2 by HOCl and HCl. Therefore, the volatile matter (NH3) but does not catalyze NOx reduction by CO. Different diluent toxic Sn (3P0) may be controlled by being turned into a soluble compound while the gases, He, Ne, Ar, and N2, were employed. The total pressure in the fixed bed was temperature is falling in coal combustion. varied from 0.2x105 to 3x105 Pa (absolute pressure). When He was used as the diluent, conversion of char-N to NOx increased by using the catalyst as bed material P1-5 instead of inert quartz sand under total pressures between 0.2x105 and 1x105 Pa but Decomposition of PFBC Bed Material Fired with Different Coals the increase was not remarkable when the total pressure was higher than 2x105 Pa. Miftahul Huda and Isao Mochida For Ar and Ne, the increase in NOx by employing catalyst bed was observed only Kyushu University, Japan when the total pressure was reduced to 0.2x105 Pa. For N2, no effect of catalyst on formation of NOx was observed even under reduced pressure conditions. The Agglomeration problems of bed materials were reported to take place in a large-scale present results indicate that nitrogen-containing fragments are released from char commercial PFBC boiler when Blair Athol (BA) coal was combusted. Sintered grain surface during char combustion and the fraction of the N-fragments oxidized on the of highly fused ash particles was formed at boiler load above 75% of designed neighboring catalysts is affected by the mean free path of the molecules. The capacity (360 MW). The formation of sintered grains reduced the bed density so estimated conversion of char-N to N-fragments was approximately 0.14. rapidly that the fluidization became poor to shut down within a few days due to slagging of bed materials. In contrast, the problems did not occur when Nanton (NT) P1-3 coal was combusted in the same PFBC. In this research Bed Material and fly ash Cryogenic Method Operating At Normal Pressure Enriching the Oxygen from the commercial PFBC were characterized, thermal behavior of coal ash as well Content in Air ash the combustion characteristic of the coal organic component was studied. Ilkka Saarenpää, Hanna Knuutila, Pauli Haukka Agglomerate in the bed material consists of gehlenite, lime and limestone suggesting Tampere University of Technology, Finland that decomposition of limestone was taking place on the PFBC despite of high partial pressure of CO2. Fly ash carried limestone, anhydrite, anorthite, gehlenite and Oxygen and oxygen-enrichment are produced from air generally by three methods: mullite. The very fine limestone was produced by attrition of bed material. Anhydrite cryogenic, adsorption and membrane separation. Various methods produce different was formed by reaction of sulphur dioxide with calcite or lime. High bed temperature purities and mass flows of oxygen. Again, the utilization of oxygen-enrichment, i.e. and short contact time of alumina silicate with bed material produced mullite. The not pure oxygen, is often sufficient in many combustion applications. combustion characteristics of Blair athol and Nanton coal were studied by TG-DTA. The process introduced in this paper is a novel cryogenic method producing oxygen- Blair Athol coal showed heterogeneous ignition even at its particle size of as large as enrichment more energy-efficiently than the methods used till now. The mass flow of +355 m while Nanton coal showed homogeneous ignition at the average particle the produced enrichment may vary with the number of parallel basic modules size over 75 m which was shifted to heterogenous one at finer particle size (- applied. Due to the low pressures used in the introduced process (at maximum 75 m). The heterogeneous ignition of Blair Athol coal yielded an intense DTA approximately 1.4 bar absolute pressure), the compression work needed is smaller peak, which may influence behavior of bed material of the PFBC. than e.g. in the Linde-Fränkl process (the maximum pressure about 6.5 bar absolute pressure), and the process approaches to reversible. Furthermore, the main fraction in P1-6 mass flow of air, i.e. the nitrogen-enriched fraction, is not liquefied which saves The Development of Coal Advisor Software for Intelligent Coal Purchase energy compared to the common cryogenic processes that liquefy this fraction. Quan Zhuang, Bruce Clements and Richard Pomalis Nevertheless, the achieved low temperature of the nitrogen-enriched fraction is CANMET Energy Technology Center, Canada efficiently utilized in the pre-cooling of the incoming process air. Since the process Dave Winship does not produce pure oxygen, the energy required to separate the last percents of Combustion and Thermal Power Consulting, Canada oxygen from nitrogen-enriched fraction is saved. This is noticeable because of the Doug Campbell and Roger Cormier last percents demand proportionately most separation energy. Nova Scotia Power Inc, Canada 52

made on real combustion units in the Czech Republic; the pilot units in the Germany The boilers of the Nova Scotia Power Inc (NSPI) were originally designed for and Austria were utilized to comparison. burning local specific high volatile bituminous coals. Due to the present situation with the local Nova Scotia coal mines, NSPI has been purchasing coals from various P1-10 sources including the eastern US and South America. The rank and properties of A Kinetic Study of CaSo4 Decomposition under Fluidized Bed Combustion coals, together with each boiler’s specific features, operating conditions and coal Conditions handling system, affect the boilers’ overall technical and economic performance. In Tadaaki Shimizu, Hideyuki Miura, Masaru Tonsho, Makoto Inagaki and Akira order to make informed coal purchasing decisions, the total cost including the hidden Okawa costs associated with using different types of coals in NSPI’s utility boilers must be Niigata University, Japan evaluated. These include assessing usage costs, in a specific boiler system, for each coal being considered for purchase on the basis of coal pulverization, combustion In fluidized bed combustors (FBCs), in-situ SO2 capture is conducted by feeding performance, slagging and fouling, emissions and waste disposals. All of these limestone (CaCO3) to the reactor as bed material. The limestone reacts with SO2 aspects will affect the economics of the power plant and therefore need to be after calcinaton in case of atmospheric FBCs (eqs. 1 and 2) or without calcinations in accounted for to ensure that the overall costs associated with a particular fuel for a case of pressurized FBCs (3). particular boiler are competitive. CaCO3 CaO + CO2 A Coal Advisor Program (CAP) has been developed for NSPI to carry out all of (1) these evaluations. The software was written in Visual Basic. The purpose of CAP is CaO + SO2 + 1/2O2 CaSO4 to enable NSPI to quickly evaluate bituminous coals as they become available on the (2) market. CaCO3 + SO2 + 1/2O2 CaSO4+ CO2 The CAP software is used interactively to examine and maintain a coal analysis (3) database. This system is multi-functional and has a huge potential to save money Pure CaSO4 is very stable under oxidizing conditions at FBC temperatures (1023 - and make intelligent coal purchasing decisions. 1173 K). However, the temperature of burning fuel particles or the temperature near fuel feed points where volatile matter combustion occurs are considered to be higher P1-7 than the average bed temperature. In addition, there exist coal ash around the Impact of a New Process for NOx Emissions Reduction on Reliability Operating sulfated limestone particles and it may affect the decomposition of CaSO4. The Performance in Circulating Atmospheric Fluidized Bed decomposition of CaSO4 with coal ash has not yet been fully understood, especially, Emmanuel Kakaras, Panagiotis Vourliotis, Platon Pallis and Stavros Spyrakis the rate of decomposition reaction is not known. National Technical University of Athens, Greece The objective of this work is to evaluate the decomposition rate of CaSO4 mixed with coal ash. The mixture was heated up from 1073 K to 1623 K in oxidizing The paper aims to present the results of different coal types combustion in the atmosphere and the SO2 emission was continuously measured. Pure CaSO4 was 100kWth Circulating Fluidized Bed Combustor (CFBC) facility, located in the found to be very stable and decomposition occurred only at higher temperatures than Laboratory of Steam Boilers and Thermal Plants (LSBTP) of NTUA. 1523 K. When coal ash is mixed with CaSO4, the decomposition started to occur at Three different types of brown coal (South African, Colombian and Greek) have relatively lower temperatures, for example1273 K. Rate expressions of SO2 been tested in the CFBC facility. The results reported in this paper include the evolution were obtained. determination of the operating conditions to achieve proper fuel burnout, the examination of the influence of the air staging on the temperature distribution inside P1-11 the reactor and the investigation of the combustion behavior of the particular fuel Utilization of Mechanical Activated Waste from Semi-Dry Desulphurisation type and emitted pollutants focusing mainly to the reduction of the NOx emissions. Installation in Fluidised Bed Boilers Many trials have been done using several air ratios and air distributions in different Arkadiusz Szymanek and Wojciech Nowak levels of the FBC reactor, so as to determine the influence of air staging in the University of Technology of Czêstochowa, Poland reduction of NOx emissions. As concerns the pollutant emissions, the CO2, CO, and Jacek Malanka NOx emissions are recorded during the several test cases, emphasizing in NOx Energomar-Nord. Sp.zoo. Warszawa, Poland emissions and their reduction. Several conclusions are drawn concerning the necessary modifications and The paper presents results of industrial utilisation of waste from the process of semi requirements of the plant layout when a large scale CFBC installation is designed to dry flue gas desulphurisation in a fluidised bed boiler. By products from the EC utilize these types of coal. Siekierki combined heat and power plant was mixed in 50 / 50 proportion with calcium carbonate, traditionally used in the flue gas desulphurisation process in the P1-8 CFB 450 boiler. The mixture was then mechanically activated and blew into the Effect of Biomass Co-Firing On the Emission in Pulverized Coal Cyclone boiler through a flue gas desulphurisation installation. The following results were Furnaces obtained: calcium sulphite was fully utilised and converted into sulphate and the flux Ju Soo Hyun, Si Hyun Lee, Young Jun Rhim, Young Ok Park, of sorbent applied was reduced by about 40%. Moreover, boiler efficiency increase Byung Moo Min and Jae Ek Son was observed as a result of incomplete and imperfect combustion loss decrease. Korea Institute of Energy Research, Korea Sung Chul Kim POSTER SESSION 2 Korea Electric Power Research Institute, Korea GASIFICATION & PYROLYSIS TECHNOLOGIES P2-1 Co-firing of biomass in existing coal-fired power plant offers a great potential. Effect Interpretation of Mineral Matter Transformation during Sasol-Lurgi Fixed Bed of co-firing of coal and biomass has been studied for a cyclonic combustion system Gasification By Means Of High Temperature X-Ray Diffraction originally designed for coal. The focus of the investigations in experimental was to JC van Dyk establish the impact of co-firing of biomass in coal fired systems with regard to Sasol Technology, South Africa combustion behavior and pollutant formation. The investigation reveals that biomass S Melzer addition has a positive effect on emission. Since biomass in most cases contain Corus Research, The Netherlands considerably less sulfur than coal, an increasing biomass share in the thermal output makes the SO2 emission decrease proportionally. Due to the high volatile contents of Coal is generally accepted to be the most heterogeneous natural resource and coal the biomass, low NOx emission can be achieved. In this investigation, fouling properties (chemical and physical) can vary extensively between geographical sites behavior of coal ash was studied using fouling probe, and it was found that the and even within the same regional location. Detail coal and feedstock characteristics blending of biomass have marginal impact on the fouling in furnace. are essential to predict gasification performance. One property that specifically gives more information on the suitability of a coal source for gasification purposes is the P1-9 ash fusion temperature (AFT). AFT analyses determine the average temperature at Criteria for Alternative Fuel Utilization in the FBC which the bulk mineral composition start to become soft and obtain liquid properties, Dagmar Juchelková, Helena Raclavska, Bohumir Cech, Pavel Kolat and Vaclav as well as an indication to what extent ash agglomeration / clinkering is likely to Roubíček occur within the gasifier. Ash clinkering inside the gasifier can cause channel VSB-Technical University of Ostrava, Czech Republic burning, pressure drop problems and unstable gasifier operation, resulting in cut back Franz Winter on gasifier load, which implies a direct loss in gas production. Technical University of Vienna, Austria Conventional AFT analyses (SABS/ISO methods) are currently used to predict slagging properties from mineral matter transformations of coal sources. Normal ash According to lot of completed tests will be the results presented. Special interest will fusion analyses give an average flow property and do not indicate exactly at what be given to the fuels, ash and others side products attribute. The measurement was temperature the first melt/sinter is occurring due to specific mineral matter transformations. Operating experience indicates that even when the gasifiers are 53 operated at temperatures above the flow temperature as given by an AFT analysis, a P2-4 percentage of slag (clinker) is formed. The principle aim of this paper is to interpret Research of the Thermal Characteristics during Coking mineral matter transformations during Sasol-Lurgi Fixed Bed Gasification by means V.I. Saranchuk, O.A. Yatsenko, G.A. Vlasov and V.V. Chuishchev of high temperature X-ray diffraction (HT-XRD). National Academy of Science of Ukraine, Ukraine HT-XRD results indicated that up to a temperature of 500oC the starting assemblage mainly composed kaolinite (Al2SiO5(OH)4), calcite (CaCO3) and dolomite One of the most important problems in by-product-coking industry is forecasting (CaMg(CO3)2), while quartz (SiO2) remained unchanged. Between 500oC and behavior coal charge during coking. Thus the role of laboratory coking sharply 700oC kaolonite decomposes first, followed by calcite and dolomite. Around grows. At laboratory coking modeling various conditions of coking is possible. 1000oC anorthite (CaAl2Si2O8) becomes stable probably due to partial melting of Laboratory installation for coking coal charge was designed on Avdeevka coke plant. the phase assemblage. Mullite decomposed at 1200oC, while quartz and anorthite The complex of gaugings of temperature coke column was made during all coking were observed up to 1350oC. Above 1350oC the whole phase assemblage of the period in different points and selection vapor gases products at different stages of coal was molten. HT-XRD supplies insight into specific mineral reactions and slag coking. formation, at temperatures below the average flow temperature obtained by Temperature conductivity for coals of different metamorphism stages were designed conventional AFT analyses. The findings are further supported with phase diagrams on the basis of the received experimental data. on the SiO2-CaO-Al2O3-MgO system. This could probably be an improved way to Dependence of temperature conductivity from time of coking and initial humidity of interpret flow properties of mineral matter in coal. Although the amount of melt was coal are investigated. Character of change of temperature conductivity is established fairly low at 1000oC, a percentage of melt is definitely present, which at this at change of a degree metamorphism. temperature is not reflected by conventional AFT analyses. Understanding phase The received results confirm, that course of process of coking in the designed transformations that occur during gasifiaction could possibly assist in quantifying laboratory installation is similar to course of process of coking in the industrial slag formation in gasifier operation at temperatures not reflected by AFT analyses. furnaces.

P2-2 P2-5 Development of Calcium Ferrite Prepared From Oyster Shell for H2s Effect of Hydrogen Pretreatment on Desulfurization of Coal during Coal Absorption Hydropyrolysis Michitaka Hamana, Yousuke Ohgaito, Na-Oki Ikenaga and Toshimitsu Suzuki Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu Kansai University, Japan Dalian University of Technology, P. R. China

Gases from coal gasifiers contain high levels of sulfur compounds. It is necessary to The effects of pretreatment of two Chinese coals, Datong and Yanzhou coal, under remove sulfur compounds, mainly H2S, from the coal gasification gas in the H2, N2, CO2 and saturation steam on desulfurization of coal during hydropyrolysis, temperature range of 500-800 oC, to utilize it for the high efficiency system, such as were studied in a 10g fixed-bed reactor. The pretreatments of H2, N2 and CO2 were integrated coal gasification combined cycle (IGCC) and integrated coal gasification carried out at temperature ranging from 200 to 400oC under 2Mpa and residence fuel cell (IGFC) technologies. Currently, desulfurization is carried out by wet time of 30min with gas flow rate of 1 L/min. The hydrothermal pretreatment was process, and loss of thermal energy is indispensable. Hot gas cleaning is a target of carried out in saturation steam in a batch unit at temperature ranging from 200- development. Development for an absorbent with high H2S removal efficiency, high 400oC and residence time of 15min. The succedent hydropyrolysis was run at sulfur absorption capacity, good regenerability and sufficient strength is still in under 650oC, 2Mpa and residence time of 20min with hydrogen flow rate of 1 L/min. It is way. Metal oxides and mixed metal oxides are proposed as an absorbent for H2S found that all the pretreatments show little effects on char yields, but pretreatments, removal. except N2 pretreatment, indeed have effects on desulfurization of coal during In order to develop a highly efficient and low cost absorbent, calcium ferrite was succedent hydropyrolysis. In direct hydyropyrolysis (650oC, 20min, 2Mpa), the prepared from oyster shell as calcium source in the presence of a low sulfur coal and sulfur content in char is 2.07 and 1.07wt% for Yanzhou and Datong coal, iron ion. Absorption behavior of the sorbent was observed using a fixed bed flow respectively. Under H2 pretreatment at temperature of 250oC for Yanzhou and reactor equipped with a quadrupole mass spectrometer. In the preparation of an 350oC for Datong coal, the sulfur content in the succedent hydropyrolysis char is absorbent from oyster shell with Yallourn coal, no diffraction peak ascribed to 1.93 and 0.55wt%, respectively. CaFe2O4 was observed after the calcinations in air at 500 oC. The calcium and iron mixed oxides exhibited surface area of 37 m2/g and more than 90% of the sample P2-6 contains mixed oxides. Desulfurization of Coal by Pyrolysis and Hydropyrolysis with Addition of Stoichiometry of H2S absorption is as follow: KOH/NaOH CaFe2O4 + 3H2S + H2 → CaS + 2FeS + 4H2O Haoquan Hu, Quanrun Liu, Shengwei Zhu and Qiang Zhou The performance of the absorbent was evaluated in term of the absorption capacity. Dalian University of Technology, P. R. China In the absorption tests, H2S concentration in the outlet gas was kept less than a few ppm before the breakthrough point. The absorption capacity of the absorbent There are many studies on coal pyrolysis as a means of thermal desulfurization to prepared from oyster shell and Yallourn coal was 90% at the absorption temperature produce a clean solid fuel from high sulfur coals. Unfortunately, sulfur removal of 500 oC. Surface area, oxide content, XRD patterns and the absorption capacity during pyrolysis at mild pyrolysis conditions is only between 15% to 40%, and the were quite similar to those of the absorbent prepared from pure calcium nitrate. sulfur content in char usually is higher than that of raw coal. To enhance the desulfurization efficiency of pyrolysis, other measures have to be taken. This paper P2-3 studies the effect of adding a certain amount of KOH into three high sulfur content Comparison of Syngas and Slag from Three Different Scale Gasifiers Using Chinese coals, YM, DT, and YZ, on desulfurization during pyrolysis and Australian Drayton Coal hydropyrolysis in a fixed-bed reactor. The experiments were carried out to measure Yongseung Yun, Gae Bong Lee and Young Don Yoo the contents of sulfur in coals and chars before and after the water washing; to Institute for Advanced Engineering, Korea investigate the effect of temperature of pyrolysis（450-650oC）, concentration of KOH (1-10wt%), reaction time (10~60 min)，atmosphere (H2 and N2) and pressure Comparison of syngas composition, conversion efficiencies in gasification, and slag on the desulfurization efficiency. The results showed that the most evidence factors characteristics was performed for data from three different gasification systems. Data that affect desulfurization yield are temperature and KOH concentration. With on syngas composition and conversion efficiencies from the 3 ton/day(T/D)-scale increase of temperature and KOH concentration, desulfurization efficiency increases. gasifier in Korea were compared with published data from the Shell gasification The desulfurization efficiency is not so closely related to atmosphere, pressure and systems of 150 T/D pilot plant as well as from the Shell commercial plant of 2,000 reaction time. At the temperature of 650oC and ambient pressure N2, the T/D scale. In addition, the shape and inner structure of slags obtained from the pilot desulfurization efficiency were enhanced by 37.6%(DT), 42.2%(YM) and 48.5% scale gasifier and from the commercial-scale gasifier for the same-seam coal was (YZ) respectively, and above 75% sulfur in raw coal was eliminated through addition compared to identify any gasifier-size effect. of 10% KOH combining with water-washing during pyrolysis. Moreover, after Cold gas efficiency showed a decreasing trend with smaller gasifier size from 79% to water-washing, sulfur content in chars was distinctly decreased, from 1.6% to 0.6% 71% while the carbon conversion was similarly more than 98% for all gasifier sizes. for DT, from 2.5% to 0.8 for YM and from 3.6 to 1.2% for YZ. As reported by some Optimal oxygen to coal weight ratio for the gasification also changed from 0.88 to other literatures, K2S formed during this process can be easily removed by water- 1.05 with decrease in gasifier size. Slags from gasifiers exhibited a similar size and washing and reused. In addition, the process has evident effect of demineralization, also the same indication of forming vesiculation inside the structure. Slags possessed about 70% mineral matter in coal can be removed. The transforms of S and K during normally less than 0.3% carbon content while showing no elutriation of heavy metals the process were analyzed by XRD patterns. The mechanism of desulfurization was by water. Inner structure of slags produced by gasification showed an amorphous discussed. By addition of KOH during coal pyrolysis combining with water-washing characteristics whereas combusted ash exhibited a clear indication of crystal nature is an attractive desulfurization method. by minerals, explaining that high temperature gasifier conditions of above 1400oC melted minerals to form intertwined slag structure with heavy metals.

P2-7 operating it in standalone conditions. Second sets of the simulation are made on Structure of the Coal Macerls and Their Pyrolysis integrated coal/biomass gasification, and the results show how the biomass gasification Jianming Zhou, Xuzhong Gong, Cao Min and Yonggang Wang can be integrated into the coal gasification effectively, giving the following options. China University of Mining and Technology, P.R. China The first option is to gasify the biomass with direct use of the thermal energy of the Wenhua Li product gas (involving H2O) from the coal gasifier, in other words, to integrate the China Coal Research Institute, P.R. China chemical energy of the biomass and the thermal energy into chemical energy of hydrogen-rich gas. Within a practical range of biomass/coal ratio of a carbon basis (< The structure of two kinds of Chinese coal macerals, Shenhua and Yanzhou 0.2), the biomass gasifier can produce 1.1 – 1.2 times of chemical energy compared bituminous coal, were studied by X-ray diffraction, XPS, FT-IR, respectively, and their with that of the biomass. The reduction of the gas temperature between the exits of the statistical constitution was analyzed. The results show that inertinite possessed the coal and biomass gasifiers is at most 200 °C. If integrated into IGCC, the biomass larger aromatic layers than the vintrinite, and vintrinite showed more functional groups gasifier can act as a chemical heat pump (thermochemical energy recuperator) in the than inertinite. The vintrinite has an obvious weight loss peak at 380~590 , and cycle. The second option is co-gasification of coal and biomass in the same gasifier, inertinite at 410~550 under Ar circumstances. The macro-molecule network of the which may bring about not thermodynamic but kinetic synergisms in the gasification. macerals tends to be tightened during pyrolysis. Alkali/alkaline-earth metallic species (particularly, K) abundant in the biomass can catalyze reactions of volatiles and char from the coal with steam and therefore make it P2-8 possible to lower the gasification temperature and reduce the O2 consumption thereby Investigation of Effect of Atmospheres on Sulfur Groups Changes in Coal increasing the cold gas efficiency. Both of the options need preheat treatment of the Pyrolysis with AP-TPR biomass (drying and chemical oxygen removal) utilizing thermal energy with Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu temperature lower than 300 °C, which is available downstream the gasifier(s). Dalian University of Technology, P.R. China P2-10 Yima coal was pyrolyzed followed by wet chemical analysis and atmospheric-pressure Estimation of Gasification Rate of Rapidly Pyrolyzed Coal Chars Using Pore temperature-programmed reduction (AP-TPR) to investigate the sulfur form changes Structure Parameters during pyrolysis in atmosphere of N2 and CO. Pyrolysis was carried out in an ambient Tatsuya Morimoto, Tetsuya Ochiai and Hirokazu Oda pressure, horizontal fixed-bed (i.d. 18mm) under the isothermal conditions of gas flow Kansai University, Japan rate 400ml/min, residence time 20min and temperature from 350oC to 900oC. And the AP-TPR experiments were performed in a vertical quartz micro-fixed bed (i.d.=4mm), Attempts were made to estimate a reaction rate of coal chars prepared under various about 100mg of fine sample (<100mesh) was placed into the reactor under a 10ml/min pyrolysis conditions using a random pore model (RPM). In order to determine the flow of pure hydrogen at atmospheric pressure and temperature from room temperature pore characteristic parameter ψ in the RPM, Pore structure of char was assessed in up to 1000oC at constant heating rate of 5K/min. The formed H2S was analyzed by terms of mercury porosimetry. The ψ value tended to decrease with higher pyrolysis GC with FPD detector on-line connected with the reactor system. From the wet temperatures and the reaction rate estimated with the ψ value was consistent with the analysis data of sulfur forms of chars obtained at different pyrolysis conditions, it can measured rate only in the initial stage of reaction. It was also suggested that there be seen that CO promotes the decomposition of pyrite and as a result, the formation of was a different ψ value in/after the middle stage of reaction from that in the initial. sulfide. The decomposition of pyrite is mainly occurred at temperature region of 350 ~550oC in CO and 450~650oC in N2, respectively. And it seems that CO prohibits the P2-11 transformation of pyrite to organic sulfur. From the AP-TPR results of raw coal and Effects of Pressure on Coal-nitrogen Conversion during the Pyrolysis and chars obtained at different pyrolysis temperature, it can be found that for YM raw coal, Gasification of Loy Yang Brown Coal two dominant, well-separated peaks, with two shoulders can be observed. The peaks at Fu-Jun Tian, Hongwei Wu, Jianglong Yu, Lachlan J. Mckenzie, Stelios Konstantinidis about 475 and 640oC are attributed to reduction of pyrite to troilite and subsequent and Chun-Zhu Li reduction of troilite to iron, respectively. The shoulder at lower temperatures (~400oC) Monash University, Australia corresponds to the reduction of thiols, dialkyl and aryl-alkyl sulfides etc, and the right CRC for Clean Power from lignite, Australia shoulder (~700oC) is caused by the reduction of thiophenes. And for both pyrolysis Jun-ichiro Hayashi and Tadatoshi Chiba atmospheres, with increasing prior pyrolysis temperature of coal, the starting reduction Hokkaido University, Japan temperature of the sulfur groups in char increases, and the shoulder at around 400oC gradually disappears, which indicates some organic sulfur groups with low thermal Gasification-based technologies are expected to greatly reduce the environmental stability, such as thiols, dialkyl etc, have decomposed in the previous pyrolysis. And impacts of power generation using coal. Gasification at elevated pressures is of special the shoulder in the higher temperature (>700oC) is more pronounced, which indicates interest. These gasification-based power generation technologies will have to meet the more stable organic sulfur presents in char. And the pyrite reduction peak becomes increasingly stringent standards in the future on the emission of NOx and their smaller and shifts to lower reduction temperature. The decrease of pyrite reduction precursors. Hence, understanding the conversion mechanism of coal-nitrogen (coal-N) peak is caused by the decomposition of pyrite in prior pyrolysis, and the shift is caused to NOx, HCN and NH3 during the gasification of coal will be essential for the choice of by the structure change during coal pyrolysis. Compared the AP-TPR profiles of chars optimum reaction conditions in the future gasifiers. However, the formation of NH3 obtained in the different pyrolysis atmospheres at the same temperature, it can be seen and HCN during pressurized gasification of coal is poorly understood. Hence, the aim that the significant differences is the pyrite reduction peak, i.e. the extent of the of this study is to investigate the effects of pressure on the formation NH3 and HCN decrease of pyrite reduction peak is more pronounced in CO than that in N2 with during the pyrolysis and gasification of Loy Yang brown coal in steam. increasing pyrolysis temperature. A pressurized drop-tube/fixed-bed reactor was used to carry out the pyrolysis and gasification of LY brown coal in steam. During pyrolysis, increases in pressure P2-9 resulted in increases in char yield, probably due to the char-volatile interaction. NH3 Thermodynamic Consideration on Integration of Biomass Conversion into Coal yield increased with increasing pressure during both pyrolysis and gasification, Gasification providing further evidence that the availability of H radicals (and also possibly OH Jun-ichiro Hayashi radicals) controls the hydrogenation of char-N into NH3. The corresponding HCN Hokkaido University, Japan yield appears much less sensitive to changes in pressure. Our experimental results will Kazuhiro Mae give some insights into the mechanisms of the coal-N converted into NH3 and HCN Kyoto University, Japan during the pyrolysis and gasification of coal with steam at elevated pressures.

Gasification is one of the attractive technologies to convert biomass resources into P2-12 gaseous fuel, while their particular natures such as substantially high contents of Operational Experience of Coal Gas Clean-up Technology Acceptable for Fuel moisture and alkali/alkaline-earth metallic species are responsible for problems Cells encountered in the gasification. This paper examines effectiveness of integrating Sadao Wasaka biomass conversion (including pretreatments and gasification) into coal gasification New Energy and Industrial Technology Development Organization, Japan mainly from a thermodynamic point of view. First sets of the numerical simulation are Masao Sotooka and Haruo Kanaboshi performed by assuming i) conversion of dry coal (sub-bituminous rank) alone or dry Electric Power Development Co., Ltd., Japan woody biomass alone, (ii) complete carbon conversion into gases using O2 and H2O as the oxidizing agents, (iii) adiabatic operation of the gasifier, (iv) chemical equilibrium It is proved that the Integrated coal Gasification Fuel Cell Combined cycle (IGFC) of product gases (H2, CO, CO2, CH4) and H2O at the gasifier exit with a temperature system which consists of a gasifier, fuel cells, gas turbine and steam turbine achieves of Texit. The results reveal that the biomass should be gasified with Texit lower by 150 higher efficiency than IGCC. °C or even more than that for the coal gasification for achieving equivalent cold gas The purpose of the EAGLE (coal Energy Application for Gas, Liquid and Electricity) efficiencies (i.e., the loss of chemical energy of the resource). Taken together with the project is to develop the technology to produce clean gas for fuel cells. above-described properties of biomass, it is inferred that integrating the biomass gasification into a high temperature chemical process is more reasonable than 55

The EAGLE project is subsidized by NEDO (New Energy and Industrial Technology The objective of the present work is to develop an effective approach to Development Organization) and METI (the Ministry of Economy, Trade and interpretation of the dynamic change in the char gasification rate with structure Industry). development of the char in the course of char gasification. A CO2 chemisorption In EAGLE pilot plant, coal gas from gasification unit is introduced to the gas clean- temperature-programmed desorption (TPD) method was used to determine the active up unit. This unit consists of water scrubbers, a COS converter, an MDEA (Methyl sites number of the char of different conversion levels at the same reactor with the Die Ethanol Amine) absorber and precise desulfurizer. gasification from 573 K up to the temperature as high as gasification temperature, In the first place, the syngas is cooled by gas-gas heater (GGH) and water scrubber. avoiding the deep cooling of the char. This paper presents the experimental results In the scrubber, impurities such as dust and halogen in the syngas are removed. In with different kind of chars at several temperatures and a model for char gasification order to desulfurize the gas, MDEA is used as solvent. Because of its low with this approach. absorptivity for carbonyl sulfide (COS), COS must be converted into H2S at a COS converter in advance. At last step, the clean syngas is further desulfurized by iron P2-15 oxides. And acid gas removed with the MDEA absorber is burned with air in a Viscous Behaviour of Australian CoalsAsh Slags with High Iron and Low furnace and the sulfur content is recovered as gypsum by the use of limestone. Silica/Alumna Ratio The pilot test has been continuing since March 2002 and planning to June 2006. This N.N. Kinaev and J.H. Patterson paper describes the outline of the gas clean-up unit of EAGLE pilot plant and our CSIRO Energy Technology, Australia operational experience. The flow behaviour of coal mineral matter at high temperatures is a critically P2-13 important criteria for coal use in entrained-flow gasification technologies. Hydrogenation by Partial Oxidation of Glucose in Supercritical Water As part of a broader program which consider the gasification performance of a wide Gasification range of Australian Coals, viscosities at temperatures from 1300°C to 1600°C and Yukihiko Matsumura, Takuya Yoshida, Masanori Shimamura, and Yoshihiro temperatures of critical viscosities (TCV) Have been measured of coal ash slags with Kikuchi iron levels between 15 and 25 wt% FeO (DAB) and Silica to Alumina (S/A) ratio Hiroshima University, Japan between 1.1 and 1.25. For slags with high iron content, an increase of S/A ratio decreased both viscosity and TCV. Addition of 5% of CaO in the slags with more Supercritical water gasification is expected to be a promising technology for set than 20 wt% FeO had a slight effect on the slag flow characteristics, while for slags biomass gasification. It treats biomass species in hot-compressed water so that with iron content less than 20 wt% the same increase of CaO significantly improved gasification takes place in water as a reaction medium. This fact enables treatment of the slag flow behaviour and decreased TCV. For slags with S/A ratio of 1.25 and wet biomass because drying pretreatment is not necessary. more than 10 wt% CaO, variation of iron concentration from 17.5 to 22.5 wt% had We have shown that partial oxidation is effective for achieving high gasification no significant effect of flow behaviour and TCV. At low CaO content for the same efficiency. While Adschiri et al. pointed out that partial oxidation in supercritical S/A ratio, an increase of iron improved flow characteristics and decreased TCV of water is effective for hydrogenation. They also suggested that formic acid, that is slags. For slags with low S/A ratio of 1.1 and low CaO content addition of iron did produced from carbon dioxide, that in turn is a product of partial oxidation is a good not show any significant effect on slag flow behaviour, and marginally decreased hydrogenation reagent from the experiment of coal extraction. Then, there is a TCV. possibility that high gasification efficiency with partial oxidation for biomass These measurements, combined with earlier slag viscosity data, covers almost the gasification in supercritical water is brought about with the help of this enhanced whole composition range of important Australian bituminous coals. These data can hydrogenation. be used to facilitate the initial assessment of suitability, and prediction of fluxing To investigate this possibility, we conducted hydrogenation of acetone in and/or blending strategies, for the use of Australian bituminous coals in entrained- supercritical water with partial oxidation of glucose. Glucose is a model compound flow slagging gasifiers from the slag flow point of view. The effects of minor of biomass, and expected to produce carbon monoxide through partial oxidation, then elements (K and Mg) on slag flow behaviour for slags with high iron and low to formic acid. Acetone is hydrogenated to produce 2-propanol. Both acetone and 2- silica/alumina ratio will also be discussed. propanol are rather stable in supercritical water, and thus suitable to investigate hydrogenation in this condition. P2-16

Experimental runs were conducted using a continuous flow-type reactor(3.17 mm ID Coal Char -CO2 Gasification Reaction Kinetics Models x 0.3 or 3 m) made of SS316 steel. The reactor was immersed into a molten salt bath Wang Yonggang, Gong Xuzhong and Zhou Jianming to control the temperature, and by changing the flow rate, residence time in the China University of Mining and Technology, China reactor was adjusted. Into the reactor were sent glucose (0.05-0.5 M at pump) and acetone (1 M at pump) aqueous solution and 10 times in flow rate of aqueous Three kinds of Chinese coal char (Yima, Yanzhou and Pingshuo bituminous coal of solution of hydrogen peroxide that was completely decomposed into oxygen before low rank)-CO2 gasification reactivities were studied by TGA. Their gasification mixing with glucose and acetone solution. reaction kinetics models were optimized, and kinetics parameters were calculated. The As was expected, formation of formic acid was observed, and hydrogenation of results show that Yima char gasification reaction adapts to Diffusion model and acetone to 2-propanol took place. However, surprisingly, the amount of formic acid Pingshuo char can be described by nucleation and growth model, and Yanzhou char did not affect the 2-propanol yield. This fact indicates hydrogenation takes place, but gasification can be described by Contracting geometry (spherical symmetry) at a lower not due to formic acid, but some compounds produced from glucose decomposition. heating rate and by Diffusion (1D) at higher heating rate. In addition, active energy A reaction rate equation was also derived. changes during reaction for the different coal rank were discussed.

P2-14 P2-17 An Effective Approach to Interpreting Reactivity Change of Coal Char with Variations in Chemistry of Macerals in Australian Coals Using Electron Structure Development of the Char in the Course of Char Gasification Microprobe Techniques Xiaoxun Ma and Hiroshi Nagaishi Colin R. Ward and Zhongsheng Li AIST, Japan University of New South Wales, Australia Lila W. Gurba Coal gasification modeling is fairly new, compared to that in coal combustion Co-operative Research Centre for Coal in Sustainable Development, Australia processes. In the case of gasification modeling, the relationship between gasification reactivity of coal char and the structure characteristics of the char as gasification The elemental composition of the individual macerals in a series of Australian coals, proceeds is of great importance. Most early investigations described the development ranging from sub-bituminous materials to anthracites, has been determined in-situ in of the total/active surface area as a function of carbon conversion. However, the polished sections using special light-element electron microprobe techniques. The measured surface area is always not the true surface area participating in the analyses of the individual macerals in a number of these coals have also been gasification reaction because the area is generally measured at a very low combined with conventional petrographic data to give a “theoretical” chemical temperature of 77 K (in the case of N2 adsorption) or 273 K (in the case of CO2 composition for the respective whole-coal samples, and this has been checked adsorption), far below the gasification temperature. This sometimes results in a low against the respective whole-coal ultimate analysis data. surface area due to activated diffusion effects. Furthermore, our recent investigation The composition of the different macerals in the coals was found to vary quite has shown, after cooled and exposed to air, both CO2 adsorption activity and significantly with rank advance. The inertinite macerals, for example, contain gasification reactivity of the char are somewhat degraded. significantly higher proportions of carbon, and lower proportions of oxygen, nitrogen In addition, at the most fundamental level, gasification reactivity of carbon in char and organic sulphur than the vitrinite macerals in the same coal samples. The depends greatly on fraction of active sites in carbon. Therefore, it should be an differences in carbon and oxygen between vitrinite and inertinite are greatest in the essential consideration to interpret the reactivity changes with carbon conversion lower rank coals of the sample suite, and decrease as the rank of the coals increases. based on the variations in the number of active sites. Some studies have been devoted The differences in N and S for the same macerals, however, appear to remain to the subject. Nevertheless, some problems remain to be unclear. relatively constant regardless of the rank level, although nitrogen in the organic

56 matter may decrease in some higher-rank coals with the development of ammonium of bottom ash as an aggregate in binary lightweight concrete, which contains in illite in the mineral matter. additional to the high volume of bottom ash also high volume of fly ash; (b) use of Small proportions of Ca, Al and Fe were also found as an inherent part of the bottom ash as part of the aggregate in ternary and quaternary concretes, which macerals (especially the vitrinites) in the lower-rank coals of the sample suite. contains in additional to bottom ash, high volume of fly ash, unprocessed crushed Provided acid-soluble minerals containing the same elements are not also present, the sand or unprocessed crushed sand and crushed rock, as an additional part of proportions of these elements appear to be consistent with the proportions of the aggregate, accordingly. The binary lightweight concrete was studied under laboratory same elements mobilised from the same coal samples by selective leaching and field conditions. The combined use of bottom ash and fly ash provides: (a) techniques. With the exception of some unusually high-sulphur coals from the forming of a dense matrix of hardened cement-fly ash paste; (b) possessing an Sydney and Cranky Corner Basins, these elements were not found in the macerals of optimum correlation between the desirable building properties (high thermal coals where the vitrinite reflectance is above 0.5% or where the carbon content of the insulating and sufficient strength) for such articles as masonry units, elements of telocollinite as indicated by the microprobe is higher than 75%. ceiling, etc. The combined use of bottom ash, fly ash and unprocessed crushed sand The elemental composition of individual macerals is of fundamental importance in and crushed rock, show promise for manufacturing the thermal insulating/structural coal utilisation, since it is the individual macerals that react, typically independently, and structural lightweight concretes. The developed technologies enable to produce when the coal is used in different applications. Electron microprobe analysis ecologically lightweight concretes containing bottom ash. provides the necessary data from points that consist only of the maceral required, without the admixture of other macerals or minerals that are typically included in the P3-2 analysis of maceral concentrates separated by physical means. The electron Dry Separation of Pulverized Fine Coal Using Novel Triboelectrostatic microprobe also provides a direct method for determining the organic sulphur and Separator the oxygen contents of the maceral components, parameters that are only determined Daniel Tao and Kelvin Jiang by indirect means in conventional coal analysis. Corrections for moisture or mineral University of Kentucky, USA matter, moreover, are not necessary when using the microprobe technique. Coal is the most abundant fossil fuel in the USA. More than 55% of electricity is P2-18 generated by burning coal. In general, coal is pulverized in dry state to a size of Fireside Corrosion of Alloys for Combustion Power Plants about 25 micron at power stations before it is sent to furnaces, which creates an K. Natesan excellent liberation between minerals and coal. However, it is not economically Argonne National Laboratory, USA feasible to employ any wet processes to process pulverized fine coal. Recently, a novel triboelectrostatic separator has been developed for dry fine particle separation. Conceptual designs of advanced combustion systems that utilize coal as feedstock An ash rejection rate of 41% was achieved for the pulverized coal furnace feed at the must include improved thermal efficiency and significant reduction in release of Dale power station while recovering greater than 88% of the combustibles. The sulfur oxides, nitrogen oxides, and carbon dioxide. Such systems require materials parameters affecting separation performance were also investigated. Significant and components that are capable of operating at much higher temperatures than those environmental and economical benefits might be achieved with the use of the novel found in current coal-fired power plants. Component reliability and long-term, triboelectrostatic separator between the pulverizer and furnace at power plants. trouble-free performance of structural materials for these systems necessitate development/evaluation of materials in simulated coal-combustion environments, for P3-3 application in steam superheaters and reheaters. Recently, the U.S. Department of Utilization of Coal Combustion Products in Europe – Valuable Raw Materials Energy has started to reevaluate coal-fired steam generation plants and, in particular, for the Construction Industry the designs based on supercritical and ultra-supercritical steam conditions. The Tomasz Szcygielski, Hans-Joachim Feuerbon, ECOBA, GERMANY ultimate goal of the staged development of power systems is to change steam pressure and temperature from the current values of 16.5-24 MPa (2400-3500 psig) In 2002, 63 million tonnes of coal combustion products (CCPs) were produced in and 540°C (1000°F), respectively, to 34.5 MPa (5000 psig) and 650°C (1200°F). Europe (EU 15). The CCPs include combustion residues such as boiler slag, bottom Development of a revolutionary boiler design for U.S. markets, based on ash and fly ash from different types of boilers as well as desulphurization products superheater/reheater temperatures >760°C, is also proposed. The higher steam like spray dry absorption product and FGD gypsum. Out of the total production of 63 temperature is expected to lead to another 2-3% increase in efficiency over a 700°C million tonnes of CCPs the amount of combustion residues produced was around 52 design, thus improving fuel usage and CO2 emissions. million tonnes while around 11 million tonnes are A program on fireside corrosion is being conducted at Argonne National Laboratory products obtained from flue gas desulphurization processes. The CCPs are mainly to evaluate the performance of several structural alloys in the presence of mixtures of utilized in the building material industry, in civil engineering, in road constructions, synthetic coal ash, alkali sulfates, and alkali chlorides. Experiments in the present for construction work in underground coal mining as well as for recultivation and program, which addresses the effects of deposit chemistry, temperature, and alloy restoration purposes in open cast mining. Most of the hard coal fly ashes are used in chemistry on the corrosion response of alloys, were conducted at temperatures concrete. In the majority of cases CCPs are used as a replacement for natural between 575-800°C for time periods up to ≈1850 h. Fe-base alloys selected for the materials and therefore offer environmental benefits by avoiding the need to quarry study included HR3C, 310TaN, HR120, SAVE 25, NF709, modified 800, 347HFG, or mine these resources. CCPs also help to reduce energy demand as well as and HCM12A. In addition, 800H clad with Alloy 671 was included in several of the emissions to atmosphere, for example CO2, which are exposures. Ni-base alloys selected for the study included 600, 601, 617, 690, 625, needed for - or result from the manufacturing process of the products which are 602CA, 214, 230, 45TM, HR 160, and 693. Data were obtained on weight change, replaced. Furhtermore, the majority of the CCPs are produced to meet certain scale thickness, internal penetration, microstructural characteristics of corrosion requirements of standards or other specifications with respect to utilization in certain products, mechanical integrity of the scales, and cracking of scales. Results showed areas. Due to different boundary conditions regarding climate, taxes and legislation that the relationship of corrosion rates to temperature followed a bell-shaped curve the utilization rate of CCPs is different across European countries. In order to face for Fe-base alloys, with peak rates at ≈725°C, but the rate itself was dependent on the the tasks resulting from legislation European power plant operators established alloy chemistry. Several Fe-base alloys showed acceptable rates in the sulfate- ECOBA the “European Coal Combustion Products Association” in 1990. In this containing coal-ash environment; but NaCl in the deposit led to catastrophic paper some information will be given on mission and work of ECOBA and on the corrosion at 650 and 800°C. Ni-base alloys generally exhibited less corrosion than present situation and perspectives of CCP production and utilization in Europe based the Fe-base alloys under similar exposure conditions; however, they were susceptible on the annual survey of ECOBA on production and utilization of CCPs in Europe to localized corrosion in the form of pits. (EU 15), on European regulations, political decisions of national authorities and on market needs in the construction industry in Europe.

POSTER SESSION 3 COAL UTILIZATIN BY-PRODUCTS POSTER SESSION 4 COAL UTILIZATION TECHNOLOGIES IN THE STEEL INDUSTRY P3-1 Utilization of Bottom Ash for Concrete Production Technology P4-1 Mark Nisnevich, Gregory Sirotin, Ya’akov Eshel Coal Pre-treating Technologies for Improving Coke Quality The Research Institute, College of Judea and Samaria, Israel Kenji Kato and Masaaki Naito Nippon Steel Corporation, Japan The bottom ash as a by-product of present power stations is characterized by low particle density (including pores) of 1.1 to 1.4 g/cm3 and a bulk density accordingly In Japan, improvement of coke quality and energy saving are strongly demanded. of 650 to 800 kg/m3. It is conducive to use bottom ash as an aggregate for production Improvement of the coke quality leads the increase of blending ratio of poorly- of lightweight concrete with low density. However, the possibility of using bottom coking coal in coal charge without deteriorating coke strength. So, the new ash is limited due to the low strength of its particles. In order to eliminate the above pretreatment technology for coal charge, called "DAPS", was developed and came on drawback, the following technological solutions were developed at The Research stream at Nippon Steel Corporation Oita works in 1992. In the process, the ratio of Institute of The College of Judea and Samaria (Ariel, Israel): (a) use of high volume fine coal agglomerated by the roll compactor is about 30 mass % of coal charge. The 57 agglomerated fine coal is added to the coarse coal over 0.3 mm size, and charged into methods including the Gieseler plastmetry and dilation tests. On the other hand, the coke ovens. By the application of this process to the coke-making plant, the ratio of coke forming process during the resolidification is poorly understood because of the non- or slightly-coking coal in coal charge is reported to increase by 20%. By difficulty of the analysis of the solid amorphous carbons, although it is recognized applying these coal pre-treatment processes, the heat consumption in coke ovens that the resolidification process affects significantly the strength of cokes produced. stood at 557 M cal/t-coal in 2000 and decreased by 51 M cal/t-coal (approximately 9 In this study, the resolidification process was examined from two aspects: one is the percent) on the basis of that in 1984. analysis of the hydrogen formation rate during the resolidification and the other is CMC process, CDQ facilities and automatic combustion control system (ACC) of direct observation of the solid carbon in the process of resolidification by the Laser coke oven batteries were among the energy saving technologies in the Japanese steel Raman spectroscopy. The hydrogen formation behavior is judged to be closely industry. And new coke-making process SCOPE21 is now under development. related to the growth of condensed aromatic rings, and the Laser Raman This paper describes the R&D of coal pre-treating technologies for improving coke spectroscopy is believed to be powerful to characterize amorphous carbons. quality. Various coals were heated at the rates of 5, 10, and 20 °C /min up to 900°C, and the formation rate of hydrogen was measured continuously by use of a mass P4-2 spectrometer. The measured formation rate of H2 was analyzed by using the so- The Effect of Added Plastic Size on Coal Carbonization Phenomena called distributed activation energy model (DAEM) to obtain the distribution of Seiji Nomura and Kenji Kato activation energy. It was found that the peak activation energy for the H2 formation Nippon Steel Corporation, Japan rate decreased with the increase of the caking property of coal, indicating that the formation of hydrogen is closely related to the caking property of coal. Raman The recycling process of waste plastics using coke ovens is now being studied. Coals spectra were measured for the coal sample heated up to a final temperature between and added plastics are carbonized and changed into coke, tar and oil and coke oven 600 and 900°C. The absolute intensity for the peak associated with the –CH2- or – gas in a coke oven chamber. It was thought that added plastics might affect the CH3 was found to decrease with the increase of the final temperature. The decrease quality of blast furnace coke. In this study, the effect of added plastic size on coke was well correlated with the amount of H2 produced up to the final temperature, was investigated. In the case of plastic addition rate of 2%, the coke strength showed indicating that the Raman spectrum reflects the proceeding of carbonization of coal. the minimum at the particle size of 10mm for polyethylene (PE) and 3mm for These results were also discussed with the XRD analysis from the viewpoint of the polystyrene (PS). The mechanism was well explained in connection with the weak progress of carbonization. coke structure formed on the interface between plastic and coal. Furthermore, it was shown that the addition of PE powder increased the coke strength and also increased P4-6 the coking pressure during carbonization. Reduction Behavior of Iron Ore with Various Carbon Sources Based on this fundamental study, we have determined that the size of waste plastic Risehiro Nonaka, Takuo Sugawara and Katsuyasu Sugawara used in a commercial-scale recycling process of waste plastics using coke ovens is Akita University, Japan over 20mm. Waste plastic recycling equipment with a total capacity of 80,000 tons per year started operation in 2000 at Nagoya and Kimitsu works. The equipment is The present study was carried out to obtain the fundamental data on the reduction of operating smoothly. iron-ore particles in solid and melting conditions using a model compound of coal tar and vacuum residue of heavy oils as carbon source. The reduction behavior of the P4-3 carbon-coated iron ore particles during rapid heating was studied using a drop tube Further Development of Aromatic Ring Size above 500oC in the Heat- reactor at temperatures from 973 K to 1773 K. Treatment of Coking Coals Higher reduction extent was obtained for the iron ore coated with vacuum residue of Koh Kidena, Koji Matsumoto, Satoru Murata and Masakatsu Nomura heavy oil rather than phenolphthalein–derived carbon. While sulfur contained in the Osaka University, Japan carbon source is one of the impeding elements in the iron ore reduction process, vacuum residue usually shows high sulfur content. Effects of sulfur and hydrogen in Because of the urgent needs for high-quality coke with lower cost in iron-making carbon source on reduction behavior were investigated. process, an application of lower rank coal to coke-making is desired earnestly. In order to achieve an expansion of the use of low rank coal, the chemical and physical POSTER SESSION 5 changes during coking process, which include plastic range, and carbonization, are ENVIRONMENTAL CONTROL TECHNOLOGIES FOR SOx, NOx, need to be clarified. The authors have been investigating the chemical structural PARTICULATES & TRACE ELEMENTS changes during plastic phenomena, but the following stage is unexploited. In this P5-1 paper, the authors focused on the structural changes of two types of coals after Carbon-Based Novel Sorbents for Removing Mercury in Flue Gases resolidification. The two coals are strongly and weakly coking coals, Goonyella and Si Hyun Lee, Young Jun Rhim, Sang Do Kim, Youngok Park, Jae Ek Son Enshu coals, respectively. Comparisons between semi-cokes derived from these two Korea Institute of Energy Research, Korea coals showed that semi-cokes from Goonyella coal tended to develop aromatic ring Jeom In Baek, Kyung Ryong Jang size. Korea Electric Power Research Institutes, Korea

P4-4 In present paper, the details of the development of functional activated carbon for Quantification of Mineral Matter in Coals and Their Cokes mercury removal in flue gases were described. To develop carbon-based sorbents to Richard Sakurovs and David French be used in gas-phase mercury removal, the performance of virgin activated carbons CSIRO Energy Technology, Australia (AC) and with that of chemically treated activated carbons were compared. According to the research result, virgin activated carbon with large oxygen The nature of mineral matter in coke helps is an important factor in determine functional groups was superior in mercury adsorption performance. Pre-oxidation of determining the behaviour of coke in the blast furnace. However, most studies on the activated carbons with acids were also investigated and adsorption performances relationships between coke reactivity and mineral matter have focussed on elemental were compared with. Injection of activated carbons has been investigated and the composition of the mineral matter, since it is relatively easy to obtain. When influential factors such as temperature, carbon dose (C/Hg ratio) were also discussed. predictions of the reactivity of coke based on elemental composition fail, the most In particular, when sulfur is impregnated, it is essential to select AC with large pore common reason given is that the form of the mineral matter and its distribution are as diameter. If the pore characteristics of AC are different, the AC capacities also differ important as elemental composition in determining the reactivity of a given coke. even if sulfur is impregnated. There are two types of sulfur impregnated into AC, one However, there have been few quantitative determinations of the types of mineral of which is desorbed at 250℃ and the other evaporates at 400℃. A condition under matter in coal and coke. Here we use a technique of quantitative X-ray diffraction – which highly reactive sulfur was selectively adsorbed was looked for. If the amount SIROQUANT ™ to determine the nature and quantity of mineral matter in twelve of sulfur that is strongly bonded to the carbon was large, the AC had a better mercury coals and their cokes, using samples used commercially around the world. We will adsorption performance. The developed sulfur-impregnated AC manufacturing describe the level of relationship between elemental composition and mineral matter process may be more economical than the existing sulfur impregnation method, and in coals and cokes and the transformation of minerals in coals to minerals in cokes. the result might be applied to the AC injection system of incinerators or power plants. P4-5 Examination of Coking Process of Coal by Use of Raman Spectroscopy and P5-2 Analysis of Hydrogen Formation Behavior Leaching of Organic Matters from Coal into Aqueous Media and Their Hiroyuki Nakagawa, Kenji Kumata and Kouichi Miura Ecotoxicities Kyoto University, Japan Tsunenori Nakajima, Takashi Fukuda, Hirokazu Takanashi and Akira Ohki Kagoshima University, Japan Caking coals, which are main raw materials of metallurgical cokes, are carbonized through softening, melting, and subsequent resolidification by the heat treatment A model study was carried out for the presence of organic matters in the wastewater above 400°C. Softening and melting characteristic can be estimated by several from coal piles. Finely powdered coal samples were extracted in a hot water 58 extraction (HWE) process. The determination of total organic carbon (TOC) in the Moreover, the enrichment mechanism of Na was elucidated by the size distribution aqueous phase was performed by a TOC analyzer. The ecotoxicities of organic of Na concentration in the fine particulates collected in each stage of the LPI. The matters extracted were examined by the Ames mutagenicity assay and the estrogen enrichment mechanisms also depended on the coal types. The reason for this receptor binding assay. The same investigation was made for the organic matters in difference was mainly due to the existence form of mineral particles in each of the the wastewater from hydrothermal treatment (HTT) upgrading process of low-rank raw coal. For the fine particulates produced, the enrichment phenomena were coals. For HWE process, the degree of TOC in the aqueous phase was found to controlled by a reaction of Na compounds vapor with the fine ash particulates or increase with elevating temperature. The degree of TOC varied with coal type, and homogeneous nucleation. For the relatively coarse particulates, on the other hand, the low-rank coals such as lignite and sub-bituminous coals tended to provide high TOC gas film diffusion controlled the enrichment of Na compounds into the ash particles degrees. The extracts of Loy Yang (LY) lignite gave an estrogenic activity, whereas with the chemical reactions of Na compounds vapor with those ash particles. no mutagenic activity was detected. For HTT process, the degree of TOC in the aqueous phase was increased when the reaction temperature was raised, and the P5-6 degree rapidly went up from 250 to 300 oC. The HTT extracts of LY lignite gave a Synthesis of ZnO Nano Wire Desulfurization Sorbents for Hot Gas Ultra higher estrogenic activity than that for the HWE extract. Cleanup No-Kuk Park, Dong-Hwal Lee, Jong Dae Lee, Jin Hyuk Jun, Si Ok Ryu and Tae Jin P5-3 Lee Determination of Major and Trace Elements in Coal Fly Ash by Microwave- Yeungnam University, Korea Assisted Acid-Digestion and ICP-AES Analysis Jae-Chang Kim Akira Iwashita, Tsunenori Nakajima, Hirokazu Takanashi, and Akira Ohki Kyungpook National University, Korea Kagoshima University, Japan Yoshio Fujita and Toru Yamashita The limited energy supply and the environmental pollutions have become an Idemitsu Kosan Co., Ltd., Japan international concern in energy related area. Therefore, many countries put a great effort to develop the economically acceptable and environmentally sustainable Microwave digestion and alkali fusion were investigated for the precise and easy technologies for utilization of fossil fuels. The integrated gasification combined cycle determination of major and trace elements in coal fly ash by ICP-AES. By use of (IGCC) is considered as the innovative clean and affordable energy system to certified reference materials, we evaluated the effectiveness of those methods for generate an electric power in the future. A variety of low-grade carbon-containing major elements (Al, Ca, Fe, Mg and P) as well as trace elements (Cd, Co, Cr, Cu, fuels including coal, heavy oil residue, petroleum coke, biomass, and wastes were Mn, Ni, Pb, and Zn). Coal fly ash samples were subjected to microwave digestion utilized to produce a synthetic gas from a gasifier. The produced synthetic gas after using the mixture of acids (HNO3+H2O2 or HNO3+H2O2+HF). We examined the hot gas cleanup process is converted into the marketable products, such as electricity, optimization of digestion method, especially focusing on the necessity of HF as well ammonia, and methanol. Further purification of syngas will produce the high value- as the removal methods of HF (H3BO3 addition and evaporation). The digestion added products, such as hydrogen for fuel cell and chemicals (DME, DMC) for without HF provided quite low recoveries of major and trace elements. For the catalytic conversion processes. digestion with the HF-H3BO3 addition system, the recoveries of major elements Hot gas desulfurization (HGD) is a very important process in the gas cleanup system were nearly 100 %, whereas trace elements in coal gave somewhat lower recoveries. and its main role is to remove harmful sulfur from the synthetic fuel gas. However, Although the HF-evaporation system provided quite low recoveries of Al, Ca and complete removal of sulfur content in a syngas is very difficult because a small Mg, good recoveries were obtained for the other elements. For alkali fusion with amount of sulfur compounds (e.g., H2S, SO2, and COS) are produced by the Na2CO3, the recoveries of major elements were nearly 100 %. However, the secondary reactions. Siemens reported that there was a thermodynamic limitation for determination of trace elements by ICP-AES gave quite low recoveries, which was zinc-based sorbents to reduce H2S to 5 ppmv and below in a fluidized-bed reactor improved by use of graphite furnace (GF) AAS. operated at high temperature. Zinc oxide nano wire as a sorbent having ability to overcome the secondary reactions by the reducing gases and high sulfur removing P5-4 capacity was developed for a ultra hot gas cleaning process in this study. Release Behavior of Mercury and Arsenic from Coal during Pyrolysis Characteristic behavior and optimum condition for the formation of the zinc oxide Shomei Tanamachi, Akira Iwashita, Tsunenori Nakajima, Hirokazu Takanashi and nano wire was investigated. Reactivity of sorbent during sulfidation/regeneration Akira Ohki process was also performed in this experiment. Kagoshima University, Japan P5-7 Seven brands of coals were subjected to pyrolysis (200-600ºC), and the release Development of Continuous Mercury Monitor with Dry Speciator Applied To behavior of Hg and As was examined. Powdery coal (0.5g) was placed in a alumina Combustion Flue Gases board and heated by a horizontal tubular furnace at a rate of 1 K/s up to 200-600ºC Naoki Noda and Shigeo Ito under N2 flow (100 ml/min) and the temperature was kept for a definite period. Then Central Research Institute of Electric Power Industry (CRIEPI), Japan Hg and As released from coal were trapped by KMnO4 solution, and the Koji Tanida concentrations of Hg and As in the solution were measured. For Hg, when the Nippon Instruments Corporation (NIC), Japan pyrolysis was performed at 300 and 400ºC, the % release was greatly varied with coal brands (20-80%). Above 500ºC, all of the coals gave high degree of % Hg Mercury emissions from anthropogenic sources occur in three main forms: release. According to a fractional determination of Hg by use of a sequential trap particulate mercury, gaseous oxidized mercury (Hg2+), and gaseous elemental (KCl solution trap and KMnO4 solution trap), it was found that the Hg species mercury (Hg0). The chemical forms of mercury affect the behavior in a combustion released from coal by the pyrolysis at 300ºC was mainly Hg0 (elemental mercury). process and come with a number of factors such as temperatures, etc. Therefore a For As, the % release for the 300ºC-pyrolysis was less than 20%, which was mercury speciator is necessary for correct understanding of the behavior in common for all coals. The % As release gradually increased as the pyrolysis combustion processes. temperature was elevated, and reached ca. 40% at 600ºC, which was also common CRIEPI and NIC developed a continuous mercury monitor which consists of a dry for all coals. The release mechanism for Hg and As will be discussed. speciater and an analyzer. The speciator separates mercury into Hg0 and total gaseous mercury (Hgtot) using an absorbent of Hg2+ to refine Hg0, and a reductant P5-5 to convert Hg2+ into Hg0 to measure Hgtot as Hg0. Each mercury is measured by Enrichment Behavior of Alkali Metal Compounds and Fine Particulate cold-vapor atomic absorption spectroscopy (CVAAS). The absorbent that captured Formation during Coal Combustion Hg2+ was regenerated by heating every 20 minutes and the reductant was self – Tsuyoshi Takuwa and Ichiro Naruse renewable in the presence of HCl. Therefore the monitor discharged little effluent Toyohashi University of Technology, Japan and needed little maintenance. Placing an acid gas remover for SO2, HCl, NOX from the sample gas before CVAAS, the system showed good accuracy of 5% within a Some trace metal compounds tend to be enriched in the fine particulates during the range from 0.1 to 100µg/m3N. coal combustion. In pressurized fluidized bed coal combustion systems, the fine particulates with the size of less than 1 m as well as hot metallic gases with alkali metal compounds cause erosive and corrosive effects. Therefore, it is necessary to understand behaviors and mechanisms of fine particulates formation with alkali metal compounds during coal combustion. In this study, coal combustion tests were conducted, using an electrically heated drop tube furnace. Two types of coal with different Na and K concentrations were burned as the samples. A low pressure impactor (LPI), which can separate particulates in the size range between 0.03 to 11 m, collected the burning particles along the furnace axis. As a result, formation characteristics of the particulates as well as the enrichment behavior of alkali metal compounds depended on the coal type. 59

P6-3 Improvements on Selective Conversion of Methanol/Dimethylether into POSTER SESSION 6 Liquefied Petroleum Gas over Zeolite Catalysts SYNTHESIS OF LIQUID FUELS & CHEMICALS Yingjie Jin, Sachio Asaoka, Xiaohong Li, Kenji Asami and Kaoru Fujimoto The University of Kitakyushu, Japan P6-1 The Chloromethylation of Polynuclear Aromatic Hydrocardbons Catalyzed by The synfuel process, based on the conversion of methanol to hydrocarbons over Rare Earth Metal Triflate zeolite catalysts, was the major development in production of alternative fuel from T. Kishida and T. Yamauchi coal or natural gas over the past several decades. This primarily concept was Nissei Kagaku Kogyosho, Japan extended from such as MTG process into indirect synthesis of Liquefied Petroleum Y. Kubota, K. Komura and Y. Sugi Gas (LPG), and a schematic flow chart of proposed process configuration was Gifu University, Japan already expatiated on several main operation units in our recent work.(Fuel Processing Technology; in press.) The chloromethylation of aromatic hydrocarbons is a promising key technology for This LPG route through methanol/dimethyl ether (DME) conversion to lower the functionalization of aromatic hydrocarbons. Zinc chloride is well known catalyst hydrocarbons is further demonstrated in terms of experimental argumentation in the for the purpose, however, it is necessary to use equivalent amounts to substrate current presentation. The significant improvements on the proposed LPG protocol because the reaction is usually carried out in hydrochloric acid solution1). Zinc are achieved both in catalytic reaction selectivity, which is mainly promoted by chloride has environmental burden because of the waste after the reaction. It is zeolite-modified materials as well as optimal conditions, and in whole LPG process important to find environmentally conscious catalysts for the chloromethylation. In selectivity, by a coupled reaction mode of recycled light olefinic byproducts with this paper, we report that some rare earth metal triflates are highly active for the methanol or its oxygenate feeds. Furthermore, available feeds are examined in details chloromethylation of many aromatic hydrocarbons. and the preferred zeolite catalysts are tested for active stability in methanol/ DME The catalytic activity of rare earth metal triflates for the chloromethylation of m- conversion. xylene (I) is shown in Fig. 1. They are highly active for the catalysis, and produced These deduced results may provide an experimental support to the process design for 1-chloromethyl-2,4-dimethylbenzene (II) in addition to small amounts of 1,3- highly selective and bulky domestic fuel production. bis(chloromethyl)-2,4-dimethylbenzene (III). Sc(OTf)3 has the highest activity for the formation of II, and decreased in the order: Sc(OTf)3 > Yb(OTf)3 > Sm(OTf)3. P6-4 Equivalent amount of zinc chloride against I gave the high yield of the Directive Synthesis of LPG from Syngas over Supported Palladium and Zeolite chloromethylated m-xylenes as known in the literature1). Qianwen Zhang, Xiaohong Li, Kenji Asami, Sachio Asaoka, Kaoru Fujimoto The chloromethylation using Sc(OTf)3 as a catalyst was enhanced by raising reaction The University of Kitakyushu, Japan temperature, the yield of II reached the maximum at 70 oC, and the yield decreased at higher temperature because of the decease of hydrogen chloride in the reaction The production of liquefied petroleum gas (LPG), a mixture of propane and butanes, mixture. The chloromethylation to yield II effectively with the ratio: trioxane/I=1.5, from syngas is an important technology of conversion of nature gas into higher- however, the excess of trioxane enhanced the formation of III. value-added product. LPG was directly synthesized from syngas over a hybrid Sc(OTf)3 also enhanced the chloromethylation of various aromatic hydrocarbons. catalyst composed of methanol synthesis catalyst and zeolite. Syngas was converted The chloromethylation occurred at ortho- and para-positions as known in the into hydrocarbon through methanol or DME as an intermediate in the reaction. classical zinc chloride method1). Biphenyl gave 4-chloromethylbiphenyl and 4,4’- Usually the temperature that was required for conversion of methanol into bis(chloromethyl) biphenyl in reasonable yield, however, the reaction also occurred hydrocarbons over zeolite was higher than 598K. The hybrid catalyst, composed of at 2-position to yield 2-chloromethylbiphenyl and 2,4’-bis(chloromethyl)biphenyl in Cu-Zn methanol synthesis catalyst and Y-type zeolite, showed a good initial activity small amount. 9,10-Dihydrophenanthrene afforded 2,7-bis(chloromethyl)-9,10- and selectivity for synthesis of LPG. But the stability of that catalyst remained to dihydrophenanthrene in high yield. improve, because the Cu-Zn catalyst deactivated with the time on stream when reaction temperature was higher than 573K. It was known that supported palladium P6-2 catalyst for methanol synthesis was more stable at high temperature. Experimental Large Pore One-Dimensional Zeolites. Catalysts for the Alkylation of Biphenyl results demonstrated that addition of palladium into Cr-Zn methanol catalyst Yoshihiro Sugi, Yoshihiro Kubota, Akira Ito, Hiroyoshi Maekawa, Ranjeet Kaur increased activity and selectivity of the hybrid catalyst for synthesis of LPG. Ahedi, Mahyua Bndyopadhyay, Seiji Watanabe, Ciharu Asaoka, Tomoko Shibata, Palladium supported on silica had a low activity for LPG synthesis, but the addition Daisuke Yamamoto, Yukio Hasegawa, and Suresh B. Wagmode of calcium promoted its activity. High dispersion of palladium metal benefited the Gifu University, Japan activity of hybrid catalyst. The hybrid catalyst based on palladium had lower initial H.S. Lee, Jong-Ho Kim and Gon Seo activity for LPG synthesis from syngas than that based on Cu-Zn. Increase of Chonnam National University, Korea reaction pressure will promoted the one through CO conversion. The characteristics of zeolite employed in hybrid catalyst played an important role in the distribution of The shape-selective alkylation of polynuclear hydrocarbons is the promising way to product hydrocarbons. Reaction temperature showed a great effect on the activity their funcionalization for advanced materials. We prevoiously found H-mordenite and selectivity of the catalyst. Low temperature benefited the formation of heavy (HM) is the excellent catalyst for shape-selective isopropylation of biphenyl and hydrocarbons, while high temperature increased the selectivity to methane. On other naphthalene1. In this paper, the selectivity for 4,4’-disopropylbiphenyl (4,4’-DIPB) hand, high temperature was unfavorable to equilibrium of methanol formation, that was compared in the isopropylation of biphenyl over large pore zeolites, CIT-5 and decreased the yield of hydrocarbons obviously. The appropriate reaction temperature UTD-1 for 14-membered ring zeolite and SSZ-31, HM, ZSM-12, and SSZ-42 for 12- for the hybrid catalyst consisted of (Pa-Ca/SiO2)/beta-zeolite was about 628K. That membered ring zeolite. We discuss also the reason why and where shape-selective catalyst showed one through CO conversion of 75% and selectivity of 75% for C3 ctalysis occurs. CIT-5 (0.75x0.72nm) enhanced the formation of 4,4’-DIPB at the and C4’s hydrocarbons at 628K and 5.1MPa. level of 50-60 % among DIPB isomers. Howevcer, selective formation of 4,4’-DIPB was not observed for UTD-1 (1.00x0.75nm): the level of the selectivity was around P6-5 20 %. These differences are due to their pore structures: the pore of CIT-5 restricts Hydrogenation of Carbon Monoxide Using Sulfide Catalysts Derived from sterically the transition states to yield selectively 4,4’-DIPB among DIPB isomers, Supperted Transition Metal Carbonyls however, the pore of UTD-1 is too loose to form 4,4’-DIPB preferentially. The Atsushi Ishihara, Makoto Ishii, Kazuo Hirabayashi, selective formation of 4,4’-DIPB was also observed at he level of 50-60 % over SSZ- Eika W. Qian and Toshiaki Kabe 31 (0.86x0.57nm), which has largest pore among 12-membered ring zeolites. The Tokyo University of Agriculture and Technology, Japan selectivity for 4,4’-DIPB was observed at the level of 80-90 % over HM (0.70x0.65nm), however, at the level of 60-70 % over ZSM-12 (0.62x0.55nm), A study of CO hydrogenation on catalysts derived from Ru carbonyl supported on although ZSM-12 has smaller pore than HM: the pores are too small for the Al2O3 or TiO2 was performed in a pressurized flow system. Ru carbonyl complex isopropylation of biphenyl inside the pore of ZSM-12. SSZ-42 (0.67x0.64nm) gave supported on Al2O3 (Ru/Al2O3) and supported on TiO2 (Ru/TiO2) were activated only 30 % selectivity for 4,4’-DIPB: this is due to the cages inside the pore. Form by H2S in H2 (sulfiding) or by H2 (reducing). Ru/Al2O3 catalyst gave high CO these results, it is concluded that the shapeselective formation of 4,4’-DIPB was due conversion and high selectivity for CH4 after reducing. When the catalyst was to the level of steric restriction of the transition state to form DIPB isomers by the activated by sulfiding, the conversion decreased remarkably. While over Ru/TiO2, size and structure of the pores. HM is the most efficient and versatile catalyst for the C2 - C6 paraffines and olefins were formed irrespective of the pretreatment shape-selective isopropylation of biphenyl among these zeolites. We also discuss the conditions. When Ru/TiO2 was modified by addition of K, a decrease in the CO application of large pore zeolites on the alkylation of naphthalene. conversion and a shift of the product distribution to higher hydrocarbons after sulfiding were observed. Hydrogenation of CO over Mo-based catalysts was also conducted. The CO conversion over Mo/Al2O3 or Mo/TiO2 catalysts after sulfiding was much higher than that after reducing regardless of the catalyst support. A product distribution shift to higher hydrocarbons was observed over both catalysts 60

after sulfiding. By addition of Ni or Co to Mo/Al2O3, the product distribution shifted The initial temperatures of SO2 evolution from different sulfur compounds were found to higher hydrocarbons over the catalyst after sulfiding while the CO conversion different, 170 C for aliphatic sulfur, 270 C for aromatic sulfur and 450 C for decreased slightly. Schulz-Flory plots showed a nearly linear behavior giving an α thiophenic sulfur, this order is consistent with that of bond energies of the sulfur value of 0.73 to 0.75 for Ru-based catalysts after sulfiding. structure, 62KJ/mol for C-Saliphatic, 361KJ/mol for C-Saromatic and 369KJ/mol for C-Sthiophene. During the oxidation of the sulfur structures, precursors of SO2 and P6-6 COS were found to react with the carbon support. This reaction seems to result in the Preparation of Novel Porous Acidic Oxide Catalysts from Metal-Containing formation of a small amount of CO2 at low temperatures and incorporation of sulfur Silsesquioxanes into the carbon matrix to form new sulfur-containing species, which may release in the Kenji Wada, Kiyohiko Tada, Naohiko Itayama, Koichi Yamada, form of SO2 and COS at a higher temperature stage. The sulfur in dibenzothiophene Teruyuki Kondo and Take-aki Mitsudo was found to release in the same temperature range as the oxidation of the carbon Kyoto University, Japan matrix, from 450 C to 550 C. It is clear that, in general, SO2 release temperature can not be directly correlated with the organic sulfur forms. Detailed information will be Preparation of novel porous acidic oxides is of great importance from the viewpoint given in the meeting. of the development of novel catalysts for the preparation of liquid fuels and chemicals from coals or coal-derived materials. The controlled calcination of newly- P6-9 synthesized metal-containing silsesquioxanes, such as Study on CO2 Reforming of Methane in the Presence of Ni-loaded Zeolite [HN(octyl)Me2]+{Al[(Me3SiO)(c-C5H9)7Si7O11]2}-, at around 823 K produces Catalysts porous oxides with high BET surface areas of 330 - 520 m2g-1 and uniformly- Satoru Murata controlled micropores of 5~6 Å diameter. Remarkably, from group 13 elements- Takaoka National College, Japan containing silsesquioxanes Brönsted acidic oxides are produced. Their acidic Nobuyuki Hatanaka, Koh Kidena and Masakatsu Nomura properties are greatly affected by the structure of silsesquioxane precursors, and Osaka University, Japan partly controlled by the selection of group 13 elements and counter cations. Differences in the dispersion of oxides of group 13 elements in silica matrixes, which CO2 reforming of methane is very attractive reaction, the reaction having several are closely related to the structure of precursors, are considered to be one of the advantages; (1) the reaction consumes greenhouse gases such as methane and carbon reasons of differences in their acidic characters. Among them, oxides prepared by dioxide, (2) it can convert less reactive gas, methane, to valuable syngas, and (3) low the calcination of aluminium-containing silsesquioxanes show excellent catalytic grade natural gas well containing lots of carbon dioxide can become available. activities towards the cumene cracking performed at around 573 K, whereas Therefore, many studies had been conducted. Nickel is a possible candidate for the commercial silica-alumina catalysts do not show significant activities under the catalyst of the reaction since it can be available at lower costs than noble metals and present conditions. Effects of the structure of silsesquioxane precursors on the pore has high activity at an initial stage of the reaction. However, nickel catalysts are structure of the resulting oxides will be also discussed in detail. usually deactivated by carbon deposition. In the previous study, we investigated the preparation of Ni-loaded zeolite catalysts and its applicability to the catalyst for CO2 P6-7 reforming of methane and found that the catalysts showed higher activity than Coal to Clean Fuel – The Shenhuya Investment in Direct Coal Liquefaction conventional Ni/Al2O3 catalyst, however, the activities of the catalysts degraded Qingyun Sun, Richard Bajura and Jerald J. Fletcher gradually. In the present study, we investigated the modification method of these West Virginia University, USA zeolite catalysts such as co-loading of alkali and alkaline-earth metals, co-loading of Yuzhuo Zhang and Xiangkun Ren secondary transition metals, and hybridization of zeolite with alumina or titania. Shenhua Group Corporation, China Modified catalysts showed higher resistivities toward deactivation by carbon deposition. These catalysts may become a possible candidate for commercial Significant price increases and the associated potential for crude oil shortages have catalysts of the reaction. once again brought energy security to the center stage. Countries with extensive coal reserves may be led to reconsider technologies that transform coal into alternative clean fuels. The successful operation of the Sasol indirect coal liquefaction (ICL) POSTER SESSION 7 facilities and the development of the world’s first commercial direct coal liquefaction COAL CHEMISTRY (DCL) plant by the Shenhua Group Corporation provide case studies of commercial P7-1 coal liquefaction technologies. Without access to detailed information on the Metamorphism and Dynamics of Solid Fuel Composition and Structure processes, debate on the relative economic competitiveness that these processes can Gennadiy Vlasov achieve continues. An increased understanding of these processes could affect the JSC, Ukraine direction of future research and potential commercialization. Vadim Barsky This paper presents a case study of the economics of DCL and ICL technologies using Ukrainian State University of Chemical Engineers, Ukraine information from the Sasol and Shenhua plants. The results indicate that the successful development of a coal liquefaction project in any country depends on the resource Quality of fossil fuel depends on its chemical composition and structure as a result of base, location, stage of economic development, and the policy environment. Focusing metamorphism, i.e. uninterrupted transformation of initial phytogenic material on the inputs and outputs of liquefaction facilities, the authors explore potential through peat to different “chemical age” coal-formations. This transformation complementarities of combining DCL and ICL technologies. Complementary fuel oil becomes apparent in change of coal element composition and ratio of molecular products and waste utilization that follow from integrating DCL and ICL processes structures with different chemical nature. may cut inputs, reduce operational cost, and improve fuel oil quality. A case study of Authors based themselves on hypothesis, that time determinates regular nature the Shenhua DCL and Sasol ICL projects will offer useful information for those process of transformation of fossil substances toward direction of their aggregate countries rich in coal and dependent on oil imports that are considering coal carbonization, whereas statistical background behind this regularity is formed by real liquefaction as a viable alternative to enhance energy security. multiformity of maternal phytogenic residues, their precipitation and decomposition conditions, temperature and pressure, oxidizing or reducing medium at different P6-8 territory zones. TPO-MS Study on Oxidation Behavior of Organic Sulfur Compounds Thermodynamic evaluation of possible carbonization reactions, evaluation of ratio Loaded on a Coke between aromatic and aliphatic compounds according to IR-spectroscopy of coal and Jinding Yan, Jianli Yang and Zhenyu Liu liquid pyrolysis by-products, allowed to produce metamorphism model. Chinese Academy of Sciences, PR China This model is used for evaluation of coal molecular structure dynamics and its calorific value during metamorphism. Temperature Programmed Oxidation (TPO) was used to study oxidation of various organic sulfur compounds loaded on a coke to simulate oxidation behavior of sulfur P7-2 structure in coal. Ideally, a sulfur functional group oxidizes in O2 to form SO2 at a Development of Measurement System for Continuous Monitoring of Gas specific temperature. However, SO2 release from coal during oxidation is very Generation Behavior during Coking Process complex and affected by many factors, such as the nature of the sulfur structure, Masayuki Nishifuji, Kenji Kato, Koji Saito and Yuji Fujioka properties of carbon matrix surrounding the sulfur structure, inorganic matters in the Advanced Technology Research Laboratories Nippon Steel Corporation, Japan coal and secondary reactions etc. It may be difficult to correlate a sulfur release temperature to a specific sulfur type in coal. Steel making process is based on many chemical reactions at high temperature more To simplify the above complexity, five organic sulfur compounds, Benzyl sulfide, than 1000℃ and is controlled with parameters on information of the characterization. Dibenzyl disulfide, p-Tolyl disulfide, 2-Naphthalenethiol and Dibenzothiophene, were For characterizing coking reaction, it can be important information to realize gas loaded on a coke and subjected to TPO in this study in pure oxygen. The gaseous generation behavior on pyrolysis of coal. products were analyzed continuously on line by a mass spectrometer (TPO-MS). In this study, a new monitoring system for gas generation behavior during coking reaction has been established. This system consists of three parts. There are the 61 carrier gas supplier part, the reaction part with a tube in an electric furnace for heating coal sample and the detector part of Fourier-transform infrared spectroscopic POSTER SESSION 8 analyzer (FT-IR) and a sensor for hydrogen which cannot be detected by FT-IR. GEOSCIENCES & RESOURCES Coal powder sample in nitrogen flow was heated with an electric furnace, and P8-1 generated gases were led to the detectors with nitrogen gas carrier continuously. This Water-Soluble Substances Present in Coals system has a good time-resolved of second order, so that a short time reaction of coal Leon Kurczabiński and Roman Łój pyrolysis can be monitored continuously. Katowicki Holding Węglowy S.A., Poland Using this system, different gas profiles of coking reaction of two coals, which have opposite characters on steel making process, could be obtained. This result was good The authors presented their conclusions drawn from the research carried out on the agreement with the reaction on the analogy of chemical structure characterized by water-soluble mineral substances present in coals. Nuclear Magnetic Resonance (NMR). As a result, it was revealed that chemical The research was carried on hard coals – steam and coke ones produced in the structures of coal should control gas generation of its pyrolysis. Upper-Silesian mines which are situated in the Southern part of Poland. Furthermore, this system is great effective in detailed characterization of coal The research shows that water-soluble mineral substances can make one of the main pyrolysis, because it is able to monitor continuously the reaction with in-situ to high sources of chlorine and alkalis in coals – and these substances are responsible for temperature (more than 600 °C). strong corrosion and erosion processes in the coal combustion and chemical processing. Any contact with water in the coal cleaning process may lead to these substances leaching. However, it depends on the conditions in which the process is performed. P7-3 The important arguments include the quality of water used in the cleaning process Effect of Polycyclic Aromatic Hydrocarbons on the Fluidity of Coal in the and they way in which the water-sludge circulation is effected in the mechanical Thermoplastic Phase processing plant. Yuji Fujioka, Koji Saito and Kenji Kato This paper refers to some of these problems. Nippon Steel Corporation, Japan P8-2

In the coke making process of steel making industry, coals in the coke oven soften at CO2 in Australian Coal Seams, Storage and Gas Diffusivity Properties at Low about 400˚C. And after the continuous thermoplastic phase, it re-solidifies to form Gas Pressure semi-coke around 500˚C. Basic carbon structure of coke forms during the A Saghafi and D. Roberts thermoplastic phase. Some properties of coal (e.g. maximum fluidity measured by CSIRO, Australia constant torque (Gieseler) plastometer, total dilatation measured with dilatometer, Many Australian coals contains significant amount of carbon dioxide. This has been etc.) in the thermoplastic phase have been used intensively so far as industrially the cause of numerous gas outbursts in coal mining in Australia in the last half a important factors for coking. In particular, the viscosity of coal in the thermoplastic century. phase has been investigated with the Gieseler plastmeter. In order to control the gas outburst, thresholds limits on CO2 content of coal have In this study, we investigated the effect of polycyclic aromatic hydrocarbons (PAHs), been set by coal mining industry. For instance in the coalfields of New South Wales nitrogen-contained aromatic hydrocarbons, and oxygen-contained aromatic in Australia, a limit of 5 m3 per tonne of coal had been set as statutory limit to hydrocarbons, on the fluidity of coal with the Gieseler plastmeter in the ensure safe mining operations. This CO2 content limit was based empirically on thermoplastic phase. The original coal samples we used were good-coking coal numerous outburst experiences concerning headings driven into geological (softening temperature: 386˚C, maximum fluidity temperature: 460˚C, re- discontinuities and so far this limit have proved to be adequate. solidification temperature: 490˚C, maximum fluidity (MF): 972 dial division per Studies have been undertaken to qualify and quantify the nature of outbursts and the minute (ddpm)). We added 1 mass % PAHs, nitrogen-contained aromatic role of gas type in the onset and the amount of energy released during such geo- hydrocarbons, and oxygen-contained aromatic hydrocarbons to each coal sample. mechanical events. The capacity of coal to store carbon dioxide together with its With the measurement of MF, we found the MF values of the sample with PAHs ability to release this gas is two factors among others which influence the (molecular weights 250-300) were improved from 972 ddpm to over 2000 ddpm. occurrences of gas outbursts. In order to accumulate enough energy to break Addition of nitrogen-contained aromatic hydrocarbons, or oxygen-contained mechanically the coal and rocks extensive volumes of free gas is required. Therefore aromatic hydrocarbons hardly contributed to the improvement of MF, especially for outburst to occur coal must have stored large amount of gas in adsorbed state and anthraquinone decreases MF to 269 ddpm. Boiling point of the sample with PAHs then coal should allow this gas to be released in a short time. The adsorption capacity (molecular weights 250-300) is presumed over 450˚C. As for the effect on the and diffusivity of coal for CO2 have therefore prominent roles in allowing the fluidity, PAHs in liquid phase decrease the viscosity in the thermoplastic phase. The occurrences of outburst. boiling point of anthraquinone is 380˚C, and is lower than softening temperature of In the last decade these two factors namely coal CO2 storage capacity and the coal. Therefore, anthraquinone might operate in lower temperature of softening point diffusivity of gas through coal were investigated by the authors. Numerous of coal, and its effect on coal is actualized in thermoplastic phase. measurements of coal adsorption isotherm on crushed coals and measurement of CO2 diffusivity through solid coals were undertaken. To measure the adsorption capacity of coal a gravimetric system was developed and used for Australian coal seams in-situ thermodynamic conditions up to 5000 kPa P7-4 pressure and below 50 °C temperature. A system for measurement of diffusivity was Ash Characteristics in Co-Combustion of Lignite with Wood, Sewage Sludge also built to measure the flux of gas through solid coal under constant concentration and Plastics gradient and at ambient temperature. Coefficients of diffusivity were determined for Zdeněk Klika, Jana Seidlerová, Martin Stach, Marta Valaskova, Bohumír Čech and coals for which CO2 adsorption isotherm were measured. Václav Roubíček This paper presents some of these measurements and discusses the results. The VŠB-Technical University Ostrava, Czech Republic results can be used in other areas were CO2 storage and flow are of interest such as in enhanced coalbed methane studies and CO2 sequestration. Co-combustion of lignite with limestone and with (a) wood and/or with (b) wood, sewage sludge, PTP (plastics, textile and paper) was performed in CFB. Inorganic P8-3 matter composition and properties of lignite, wood, bottom and fly ashes were Energy Analysis of CO2 Absorption Process with Various Amine Solutions characterized. For this, mineralogical, chemical and coal petrography analyses of Seok Kim and Hyung-Taek Kim solid samples as well as their leaching tests, unburned carbon, porosity, surface area Ajou University, Korea and other properties were determined. There are not striking differences in composition of bottom and fly ashes from both combustion regimes a) and b). In fly The CO2 absorption process in the flue gas widely utilizes alkanolamine solvents ash samples (regimes a and b) higher concentrations of Hg (about 2 ppm), As (about such as MEA, DEA, TEA and MDEA. In the present investigation, CO2 absorption 800 ppm) and chlorine (about 400 ppm) are present than they are in bottom ash process is simulated with AspenPlus™ and various amine solutions are applied in the (0.002 ppm Hg, 250 ppm As, and 220 ppm Cl). Also relating concentrations of above simulation to find out optimized operating condition for minimum energy usage. The elements determined in emissions are very similar for both combustion regimes main purpose of this study is to find the optimum condition of CO2 absorption and (about 0.010 mg.m-3 Hg, 0.027 mg.m-3 As and 24 mg.m-3 Cl). Contents of suggest the optimum operation condition to the actual bench-scale CO2 absorption unburned carbon are 1.7 and 1.0 wt.% in regime a) and b), respectively and the experimental set-up. For this purpose, bench-scale continuous CO2 absorber percentages of unburned organic in unburned carbon is about 35% in both regimes. (capacity =5 Nm3/hr) located in the Korea Institute of Energy Research is modeled and simulated as base case. Results of each simulation are compared with the experimental data of the bench-scale experiments such as CO2 absorption rates, liquid flow rates and the operation temperature. During the simulation, gas flow rates are typically varied from 35-85 l/min. and liquid flow rates from 1.0-3.0 l/min.

From the simulation results, the efficiency of absorption process is believed to be Adsorption of cooper ion from aqueous solutions on biologically activated brown mainly dependent on the mole ratio of amine solution and input CO2 concentration. coal was investigated. Four families of adsorbents were prepared from brown coal by The effects of the number of regenerator stage and reboiler heat duty variation on microorganisms activity. There were used microorganisms such as Aspergillus niger, CO2 separation rate is investigated as CO2 desorption increases with heat duty. Total Aspergillus clavatus, Penicillium glabrum and Trichoderma viride. Activated power requirement according as the flow rate variation of the flue gases and MEA samples of coal were characterised by the values of internal surface, the sorption solution are also investigated and results represent that power requirement is mainly isotherm has been constructed and the maximum capacity of the adsorbent has been depends on the variation of solution flow rate. Among the alkanoamine solvents used determined. in the study, MEA solution has relatively large CO2 separation activity. The effects of number of regenerator stage and reboiler heat duty variation on CO2 separation P9-2 rate are deduced. CO2 separation rate according to increment of number of stage Carbon Nanotube Production from Heavy Hydrocarbons does not vary over 3 stages. Other operation parameters which effect on CO2 Yuma Kamiyama, Koh Kidena and Masakatsu Nomura separation rate are analyzed through simulations. Exergy analysis to minimize power Osaka University, Japan requirement will be studied after analysis about operation parameters. Carbon nanotube is a material that has been attracting intensive interests. Several P8-4 methods for its production have been developed: for example, arc-discharge, laser Mercury Release Characteristics from Subbituminous Coal during Thermal ablation and vapor deposition. As one of the method for large-scale production, Upgrading catalytic chemical vapor deposition is promising. In this paper, the authors Zhenghe Xu, Guoqing Lu and On Yi Chan investigate the possibility for the production of carbon nanotube from heavy University of Alberta, Canada hydrocarbon resources such as natural asphalt or coal. At first, toluene was used as a substrate in order to organize the reaction system. With a ferrocene as catalyst, the Mercury emission from coal-fired power generation process has been considered as production of nanotube was confirmed on inner surface of quartz tube at 750-850 an environmental concern. As a mercury emission control option, mercury release deg-C. Then, asphaltene and/or maltene fraction from natural asphalt were tested to characteristics from a subbituminous coal during low temperature thermal upgrading obtain promising results. Under selected reaction conditions including the reaction is determined. Mercury was found to be enriched in fine size fractions which also temperature and the amount of catalyst, carbon natotube with a diameter of 30-60 nm show a higher mineral content. A rapid thermal upgrading at 673 K released was successfully found. approximately 70% of the mercury in the raw coals with a negligible total thermal energy loss. A corresponding increase in the calorific value of the upgraded coals POSTER SESSION 10 from about 21,000 to 26,000 kJ/kg was observed. A further increase in the upgrading GAS TURBINES & FUEL CELL FOR SYNTHESIS GAS & HYDROGEN temperature produced a minimal further increase in mercury removal with an APPLICATIONS obvious thermal energy loss. Mercury release characteristics were highly dependent P10-1 on the source of coal. Our laboratory tests demonstrated that thermal upgrading is a DOE FE Fuel Cell-Turbine Hybrid Development viable method for mercury emission control. Mark C. Williams, Richard A. Dennis, David Tucker and Norman Holcombe U.S. Department of Energy, NETL, USA P8-5 The Influence of Some Biogenous Factors on the Quality of Deposited Fly-Ashes The U.S. Department of Energy’s (DOE) Office of Fossil Energy’s (FE) National Maria Kusnierova, Andrea Slesarova and Maria Prascakova Energy Technology Laboratory (NETL), in partnership with private industries and Institute of Geotechnics of Slovak Academy of Sciences, Czech Republic others, is leading the development and demonstration of high efficiency solid oxide Peter Fecko fuel cells (SOFCs) and fuel cell/turbine hybrid power generation systems for near- VŠB-Technical University Ostrava, Czech Republic term distributed generation (DG) markets with emphasis on premium power and high reliability. NETL manages research under the Solid-State Energy Conversion The results of the study on qualitative changes in energy fly-ash deposited in situ for Alliance (SECA) initiative for the development and commercialization of modular, a different period of time (0, 5, 10 and 20 years) and laboratory model study of the low cost, and fuel flexible SOFC systems. The SECA initiative, through advanced influence of contamination of fly-ash by selected species of autochthonous materials, processing and system integration research and development (R&D) will Actinomycetaes have confirmed a positive influence of biogenous catalysis on the bring the fuel cell cost to $400 per kilowatt (kW) for stationary and auxiliary power mobility of studied macro elements: Al, Si, Fe and Ti. unit (APU) markets. Aggregation of these SOFC systems and integration with turbines will allow megawatt-scale efficiency of 60 to 75 percent depending on fuel. P8-6 Moreover, the President of the U.S. has launched us into exploring a new hydrogen The Utilization of the Gypsum Product from the Flue Gas Desulfurization for economy. The logic of a hydrogen economy is compelling. The movement to a the Sulfate-Reducing Bacteria Cultivation hydrogen economy would accomplish several strategic goals. The U.S. can use its Alena Luptakova, Maria Kusnierova, Maria Bezovska own domestic resources – solar, wind, hydro, and coal. The U.S. uses 20 percent of Institute of Geotechnics of Slovak Academy of Sciences, Slovak Republic world’s oil but has only 3 percent of resources. Also, the U.S. can reduce Peter Fecko greenhouse gas emissions. Clear Skies and Climate Change programs aim to reduce VŠB-Technical University Ostrava, Czech Republic carbon dioxide (CO2), nitrogen oxides (NOx), and sulfur dioxide (SO2) emissions. SOFCs have no emissions and hence figure significantly in these DOE strategies. In Industrial technologies for the desulfurization of combustion products produced addition, DG systems with SOFCs, reforming, and energy storage have significant during the generation of the electric energy by the combustion of fossil fuels use the benefit for enhanced security and reliability. The use of fuel cells is expected to limestone as an absorption agent. This process results in the formation of the gypsum bring about the hydrogen economy. However, commercialization of fuel cells is suspension which may be used as the source of sulphates for the sulphate-reducing expected to proceed first through portable and stationary applications. Like all fuel bacteria growth. The SRB represent a group of chemoorganotrophic and strictly cells, the SOFC will operate even better on hydrogen than conventional fuels. The anaerobic bacteria. They include genera like Desulfovibrio, Desulfomicrobium, SOFC hybrid may be a key part of the FutureGen plants. FutureGen is a major new Desulfobacter, Desulfosarcina, Desulfotomacullum, Thermodesulfobacterium, Presidential initiative to produce hydrogen from coal. The highly efficient SOFC Archaeoglobus, etc. The basic metabolic process of SRB is the anaerobic reduction hybrid plant will produce electric power and other parts of the plant could produce of sulphates in which organic substrate (lactate, malate, etc.) or gaseous hydrogen is hydrogen and sequester CO2. The hydrogen produced can be used in fuel cell cars the electron donor and sulphate is the electron acceptor. The bacterial sulphate and for SOFC DG applications. reduction has widespread environmental effects and this process has potential as a treatment process for acid mine drainage. P10-2 The aim of this work is to study of the utilization of gypsum product from flue gas Numerical Study on the Gas Turbine Combustor Burning Coal- or Heavy desulfurization for the sulfate-reducing bacteria cultivation, with the prospect of the Residue Oil-Derived Gas as Alternative Fuel hydrogen sulfide production and the heavy metals elimination from acid mine Chan Lee drainage. University of Suwon, Korea Je Young Seo POSTER SESSION 9 Kangrim Industries Co., Korea NON-FUEL UTILIZATION OF COAL Yongseung Yun P9-1 Institute for Advanced Engineering, Korea Application Of Biologically Activated Brown Coal In Cu(II) Sorption. Maria Prascakova and Maria Kusnierova A CFD (Computational Fluid Dynamics) research is conducted for the investigation Institute of Geotechnics of Slovak Academy of Sciences, Slovak Republic of the fuel alteration of MBTU (medium-Btu) gas in the IGCC gas turbine combustor Alexandra Simonovicova which is originally designed with natural gas. The computational analysis method of Comenius University, Slovak Republic the gas turbine combustor is constructed by incorporating MBTU gas reaction and 63 fuel NOx models into the CFD scheme of the commercial code, FLUENT, and then the decolorization of coal humic acid but for fungus FTN, AAO also might concern it is applied to a small annular-type gas turbine combustion chamber. With the use of somewhat the decolorization of coal humic acid. As for fungal strain WO-4, Lac the present analysis method, comparisons are made on the flow velocity, the activity appears in place of disappearance of MnP activity in the late incubation chemical species and the temperature distributions, and on the flame shape and period, it seems that both of MnP and Lac concern the decolorization of coal humic behavior of gas turbine combustors firing natural gas or MBTU gases (coal gas, acid. heavy residue oil gas). Furthermore, the NOx formation characteristics of the combustor are analyzed,. The computation results show that the MBTU-gas firing P11-2 cases give higher flame temperature and longer flame zone than the natural case. Upgrading of Solvent for “HyperCoal” (ash-free coal) Production Thermal and fuel NOx.emissions from the MBTU-gas firing combustor is more Nao Kashimura, Kensuke Masaki, Toshimasa Takanohashi, Shinya Sato, Akimitsu produced due to the higher temperature characteristics in the combustor. Based on Matsumura, Ikuo Saito the computed analysis results, the present study presents the directions for the National Institute of Advanced Industrial Science and Technology (AIST), Japan redeisgn and the design modification of IGCC gas turbine combustor firing MBTU gas as alternative fuel. HyperCoal power generation system is a highly efficient process, in which only ash- free portions of coal are extracted with industrial solvent at mild temperature and are P10-3 used as a feedstock for gas turbines. Process Analysis for Hydrogen Production by Reaction-Integrated Novel Preliminary work showed that crude methylnaphthalene oil (CMNO) gave higher Gasification (HyPr-RING) extraction yields at 360oC than light cycle oil (LCO). The former contains more Shi-Ying Lin and Michiaki Harada nitrogen-containing compounds than the latter. Furthermore, addition of nitrogen- Center for Coal Utilization, Japan containing compounds, such as N-methyl-2-pyrrolidinone, enhanced the extraction Yoshizo Suzuki and Hiroyuki Harano yields with LCO. National Institute of Advanced Industrial Science and Technology, Japan In this work, an attempt was made on searching a powerful solvent to produce HyperCoal more efficiently. Hydrogen production by the reaction-integrated novel gasification (HyPr-RING) Wyodak Anderson subbituminous coal was extracted at 360°C with flowing CMNO method was first proposed in 1999. This method involves the reactions of coal and or its derived materials. The original CMNO gave 42% of the extraction yield, while, CaO with H2O, that is, a combination of exothermic and endothermic, gas- the HCl solubles (AC-S) and methanol-water mixture solubles (MW-S) gave high production and gas-separation reactions, in a gasifier to produce H2. The equipment yields, 63 and 73%, respectively. GC-AED and GC-MS analyses of CMNO showed for the HyPr-RING process consists mainly of a gasifier, a sorbent regenerator, and that nitrogen-containing compounds in CMNO were mainly quinoline, isoquinoline, several heat exchangers. In this study, process components and the mass and energy indole and methylquinoline. MW-S was richer in indole than AC-S. When mixtures balances were analyzed by thermodynamic calculations. A fuel gas comprising an of 1-methylnaphthalene and quinoline were employed as extraction solvents, the equilibrium mixture of 91% H2 and 9 % CH4 can be obtained by gasification of coal extraction yields were in the range of 33 – 43%, while, a mixture of quinoline, 1- at 923 K and 3.0 MPa. The amount of the fuel gas produced was calculated to be methylnaphthalene and indole reached 53% of the yield. Thus, the containing of equivalent to 1.4 Nm3/kg-coal, giving a high cold-gas efficiency of 0.77. The indole gave rise to the difference in the extraction yield between AC-S and MW-C. equilibrium H2 and CH4 compositions are sensitive to the amount of steam The details of effect of additives will be presented. contained in the product gas. The energy contained in the coal is used in the gasifier and the regenerator in a ratio P11-3 of about 3/2. This gives a good energy balance, and a high cold gas efficiency for Pyrolysis and Kinetic Studies on Mixed Solvent Swelling of Malaysian Lignite the process. Using Thermogravimetric Analyzer Mohd Fauzi Abdullah, Khudzir Ismail and Mohd Azlan Mohd Ishak P10-4 University Technology MARA, Malaysia Investigation of Tetralin Dehydrogenation upon Transition-Metal Catalysts Pham Tien Dung, Tetsuya Satoh, Masahiro Miura and Masakatsu Nomura The volumetric swelling ratios of Mukah Balingian, Malaysian lignite have been Osaka University, Japan determined using various solvent mixed ratios of tetralin with H-bonding (i.e. pyridine, tetrahydrofuran, ethanol, methanol and acetone) and non-H-bonding (i.e. Dehydrogenation of tetralin was found to proceed smoothly at 220 – 300 oC by the benzene, cyclohexane and n-hexane) solvents at room temperature (30°C) and at use of supported transition-metal catalysts. Some palladium catalysts supported on ambient pressure. The results obtained thus far showed that the swelling ratios of activated carbon fibers showed particularly high activities. The reaction was tetralin mixed with H-bonding exhibit higher swelling ratios than with the non-H- conducted under various conditions to enhance its efficiency and elongate the bonding solvents. Moreover, the swelling ratios decreased with increased in the catalyst time. volume ratios of tetralin, especially with non-H-bonding solvents. This decrease is probably attributed to the less interaction of the coal reactive sites with the solvent due to its non-H-bonding characteristics. POSTER SESSION 11 The effect of mixed solvent pre-swelled coal towards thermal characteristics of both LOW RANK COAL UTILIZATION untreated and pre-swelled coal was investigated using the thermogravimetric P11-1 analyzer, whereby the activation energy and reaction rates were calculated and Decolorization of Coal Humic Acid for Hydrogen Production by Reaction- determined. Integrated Novel Gasification Yaeko Kabe and Takafumi Osawa P11-4 Tamagawa University, Japan Basic Study on Mineral Removal from Coal - The Influence of Mineral Atsushi Ishihara and Toshiaki Kabe Distribution and Size of Pulverized Coal on Characteristics of Mineral Removal Tokyo University of Agriculture & Technology, Japan Yoshiko Hiei, Hiromi Shirai and Hideki Kanda CRIEPI, Japan The objective of this work is to produce useful materials from coal humic acid contained abundantly in low-rank coal such as lignite and brown coal by the action From the viewpoint of the use of low grade coal that contain lots of minerals and to of fungal extracellular enzymes. We isolated several white-rot fungi able to decrease the amount of ash residue from coal fired power plants, it is imperative to decolorize and depolymerize coal humic acid. The last year, we isolated another two develop a simplified mineral removal method at the mine sites. The influence of excellent white-rot fungal strains, WO-4 and WT-5 from white-rotten wood. In this mineral distribution, mineral content and size of pulverized coal on characteristics of study, these two strains and white-rot fungal strain, FTN, which was isolated early in mineral removal from coal was investigated to develop an effective removal method our study and has high ability, were investigated on the decolorization of coal humic of mineral matter. The influence of the mineral distribution on removal ratio of acid. mineral matter from coal was evaluated by a specific gravity separation method. Four kinds of extracellular enzymes, laccase (Lac), aryl alcohol oxidase (AAO), It is found the mineral content in the raw coal affects that mineral removal ratio. The lignin peroxidase (LiP) and manganese peroxidase (MnP) have been known as decreasing particle size of minerals in the raw coal, removal ratio becomes smaller extracellular enzymes able to depolymerize macromolecules having complicated and smaller. On the other hand, the shape factor of the minerals does not affect the structures such as lignin and coal humic acid. The relation between these four removal ratio. In addition, mineral removal ratio is increasing with the decreased extracellular enzymes produced by above 3 kinds of white-rot fungi and the particle size of pulverized coal. These results showed that characteristics of mineral decolorization of coal humic acid were investigated. removal from coal are influenced by mineral content, particle size of minerals and As the results, the decolorization rate of fungal strain FTN was the highest and the particle size of pulverized coal. It is important to develop a pulverizing method, ratios of the decolorization were 50% for 7days and 73% for 21days. Those with which promotes a high effect while considered the influence of mineral content and fungal strain WO-4 were 42% for 7days and 65% for 21days and those with fungal size of mineral matter and size of crushed coal. strain WT-5 were 47% for 7days and 60% for 21days. As all of these strains have higher MnP activities of four enzymes, it was considered that MnP mainly concerns 64

POSTER SESSION 12 POSTER SESSION 13 COAL PRODUCTION & PREPARATION GENERAL TOPICS P12-1 P13-1 Solution of Environmental Policy in Okd, A.S., Mine Lazy,O.Z. Orlova Co-Production of Premium Coal Slurries as Alternatives to Diesel Oil and Horst Gondek, Lenka Landryova and Peter Fecko Heavy Fuel Oil VSB - Technical University of Ostrava, Czech Republic Fu Xiaoheng Wang Xinwen Wang Xinguo and Wang Zune China Univ. of Mining & Tech., P.R. China The paper gives review about solving of environmental politics on deep mine namely Mine Lazy, o.z. OKD a.s. It describes first steps of environment problems solving from Physical process developed for coal cleaning to give two premium products, the analysis of individual sources of pollution upon proper solution of problem. Total ultra- clean coal and conventional clean coal, and preparation of coal slurries thereof, solution is divided to organizational part as well as proper technical realisation. The including: - Ultra-fine grinding (usually £¼10¦Ìm) of coal for liberation of mineral improvement of the environment relates to both own mine and close surroundings. The matters finely disseminated in the organic matrix in parent coal; obtained results in mentioned mine including cost for their realization are shown in the - Selective coagulation of micronized pure coal particles, forming loose coal conclusion. aggregates of larger sizes; - By froth flotation, the high-ash constituents being firstly discarded and the rest P12-2 separated into the froth product, an ultra-clean coal, and the suspension product, a Research for Mining Optimization and Biogas Utilization with Minimizing its conventional clean coal; Escape into the Atmosphere - Dewatering of products and tailing separately by press filter; Horst Gondek, Lenka Landryova and Peter Fecko - Slurries preparation: with ultra-clean coal, the slurry as alternative to diesel oil, and VSB - Technical University of Ostrava, Czech Republic with conventional clean coal, the slurry as alternative to heavy fuel oil. Equipment specifically developed for the process: Directive of Council No. 91/156/EEC states the Strategy of the European Union (EU) - Ultra-fine grinding mill with low power consumption; for municipal waste management. According to this the member states must prohibit - Efficient facility for selective coagulation of ultra-fine coal in pulp; the negative impact of landfills on the environment. This policy has been worked into - Compact facility for preparing slurry from the sticky filtering cake. the standards of the Czech Republic from which ČSN 83 80 34 (Landfill Schematic diagram of the process and example of its material balance: Degasification) is the most important one. It is stated there, that municipal landfills - The process flowsheet; with more than 10 % of biodegradable content, a height of more than 2.5 m and - Material balance as an example. capacity larger than 10.000 m3, must have ensured, among others, that the rising gas Cost-effectiveness analysis: from them will be disposed. - Monetary input and output for slurry production; There about 160 landfills in the Czech Republic, but only about 50 of them can be, - Amount of oils substituted; regarding the concentration of methane gas, considered for the possibility of co- - Profitability related to oil price. generation of biogas (as researched within the framework of Granted Project No. 105/01/0311, 2001). The remaining (majority) of landfills have low concentration of P13-2 methane gas, but also these must have their biogas disposed of. Conversion and Operation of a Diesel Engine Fueled by Purified Coal Slurry This paper brings the newest findings and partly documents the experience gained Wang Xinwen Fu Xiaoheng Wang Xinguo Wang Zune from a research done on the mining optimization and biogas utilization. The latest China Univ. of Mining & Tech., P.R. China results coming from analyses done on degasification of landfills in Czech Republic as Zhang Bingjian Liu Ruihua well as at some selected landfills abroad are given. The sources for methane gas Xinya Industry Co. Ltd., P.R. China originating are mentioned. The activities leading to the utilisation of it are described for several types of landfills. Some of the cases of a successful minimisation of biogas Diesel engine conversion to adapt coal slurry fuel escape into the atmosphere are described in detail. Economic aspects are shown on real - Principal parts of the engine to be converted: the fuel injector and fuel pump, both examples. This contribution is supported by the granted project of GACR 105/04/1342 being of plunger-type; for the year 2004/2005. -The built-in high-pressure oil system and its functions: prevention of coal particles intruding into the micro-clearance and simultaneously realizing lubrication; - Performance of the high-pressure oil system. P12-3 The coal slurry fuel Desulfurization of Tabas Coal (C1 Seam) Based On Characterization Studies - The purified coal; E. Jorjani - Fuel composition and its characteristics. Azad University, Iran Test rig facility and apparatus - The small single-piston and high-speed diesel engine; The presence of huge reserves of coal in Tabas area is caused to be one of the - Schematic diagram of the test rig; promising coal mines in Iran. The average percentage of sulfur in different layers - The Eddy-Current Dynamometer; namely B1, B2, C1, C2, D has been reported 3.49, 1.35, 1.6, 1.11and 3.4 respectively. - The portable KM9000 gas analyzer; In order to identify the type and distribution of sulfur in coal , a representative sample - Procedure of test operation. from all effective working levels especially C1 layer has been taken and subjected to Operation experiment of the diesel engine characterization studies. Because of fine distribution of pyrite in organic matters and - Operation of the engine at different loading on high percentage of organic sulfur (46% Stotal), we predict that removal of sulfur is Coal slurry fuel, possible with chemical and microbial methods. Two new techniques (a) microwave Diesel oil; irradiation/Peroxyacetic acid (PAA) washing (b) PAA + Air oxidation / sodium - Fuel consumption and heat efficiency; butoxide leaching were used as chemical desulfurization. Microorganisms isolated - Emission measurement; from Zyrab coal washery plant tailing dump and Tehran refinery oily soils were used - Analysis of the operation data on coal slurry fuel vs diesel oil on microbial desulfurization. Desulfurization of microwaved sample with peroxyacetic Heat efficiency slightly lower; NOx emission much lower. acid at 50oC and 90 min removed about 62% of total sulfur with coal yield of 94 %. This process also seems to reduce the organic sulfur in the coal matrix to a significant P13-3 extent (35%). PAA in low temperature and time (at 45oC for 40 min) , also air A Research into the Compound Sulfur Fixing Additives in Coal-Water-Slurry oxidation for 1 hours at 100oC was used as pretreatment method for desulfurization Yang Qiaowen, Wu Lijun, Chu Zhuwei, Lizong Liu, Zuna Wang and Wu Huixiang with sodium butoxide. On optimized conditions (at 150oC for 90 min) about 60,74 China University of Mining and Technology, P.R. China and 44 % of total, pyritic and organic sulfur was removed respectively. On initial pH of 2, particle size less than 0.18 mm, pulp density of 5 %, temperature of 30 oC, In this thesis, investigations into sulfuric release pattern in Xinwen slurry-making shaking rate of 150 rpm, 50 mM of ferrous iron and leaching time of 10 days, mixed coal and the properties of compound sulfur-fixing additives were made, relying on culture isolated from coal washery plant tailing dump could remove pyritic and total above results, we discussed the effect of sulfur-fixing additives on the rheological sulfur 91.84 and 53.5 % respectively. Also, 36% of organic sulfur removed by behavior of coal-water-slurry and the mechanism of sulfur-fixing in coal-water- Rhodococcus Sp. P32C1 bacteria isolated from Tehran refinery oily soils. slurry. Through floatation experiment, we obtained clean coal for making slurry whose sulfur content was 2.39%, a typical double peak frame was showed in the online experiment of TGA-FTIR on sulfur release in coal, the temperature of release were 315℃ and 430℃. During the pyrolysis of calcium-based compound, the decompose temperature of Ca (OH)2 was close to those of sulfur in coal.

After the sulfur-fixing additives were added in coal-water-slurry, viscidity measure and static observation indicated that the changes of rheological behavior and stability of coal-water-slurry, which met the requirement for reserve and transportation of coal-water-slurry. The industrial simulate experiment on burning and sulfur-fixing using high-temperature tubal stove showed that when compound sulfur-fixing additives were added, the sulfur-fixing efficiency reached to 58.7% at 1000℃. Moreover, the effects of Ca/S, dosage of additives, temperature and burning time on sulfur-fixing efficiency were discussed. Through analysis of ash microstructure, we discussed the mechanism of accelerating sulfur-fixing additives, and drew some conclusions: a)MgO reacted to SO2 directly, and it，s activeness was higher than that of CaO, so more SO2 were left in ash. b) Adding of Al2O3 reduced the ratio of alkali to acid, increased the melting point of ash, and prevent the formation of 2CaOAl2O3SiO2, which was new matter in ash, and made more CaO useful. c) Adding of Fe2O3 promoted the transformation of SO2 into SO3, in other words, Fe2O3 acted as catalyst. Cooperation with MgO, Al2O3 and Fe2O3 greatly increased the sulfur-fixing efficiency. Based on the experiment results, the compound sulfur- fixing additives were practical during the burning of coal-water-slurry, in which Ca(OH)2 was primary sulfur-fixing agent and the compound oxides were assist sulfur-fixing additive, a ideal sulfur-fixing efficiency will be gained which only a little cost must be paid out.

P13-4 Advances in the Automated Measurement of Coal and Mineral Matter by QEMSCANTM Alan Butcher, Al Cropp and Paul Gottlieb Intellection Pty Ltd, Australia David French CSIRO Energy Technology, Australia Terry Wall and Rajender Gupta University of Newcastle, Australia

In order to improve the efficiency of coal utilisation and help reduce the environmental footprint, there is a requirement within the coal mining and utilisation industries to better characterise coal and coal utilisation by-products In response to this need, CSIRO and Intellection have developed, in collaboration with the CRC for Coal in Sustainable Development, a methodology whereby coal characteristics such as mineralogy, particle size distribution and mineral association can be measured automatically using a Scanning Electron Microscope (SEM). The system, known as QEMSCAN, builds on pioneering studies carried out by CSIRO in the 1980’s on the automated analysis of mineral matter in coal by QEM*SEM. Since launching the new technique in 2003, there have been significant improvements in QEMSCAN data collection, handling and visualisation. This paper reviews these improvements, illustrated with examples from case studies using coals from Australia and the United Kingdom. In particular, features such as quantitative mineralogical, textural and chemical analysis on a particle-by-particle basis, for both coal and mineral matter, will be presented.