Twenty-First Annual International

PITTSBURGH COAL CONFERENCE

Coal Energy and the Environment

ABSTRACTS

September 13-17, 2004

Grand Cube Osaka
(Osaka International Convention Center)
Osaka, Japan
PCC 2004
 TABLE OF CONTENTS

SESSIONS Page SESSIONS Page

Oral Sessions
A Note to the Reader 34: International Coal Technology Co-Operation 2 32
1: Combustion Technologies 1: Modeling 1 35: Environmental Control Technology 6: Mercury
33
2: Gasification 1: Fundamentals 2 (2)
3: Hydrogen in the Future 1: General 3 36: Coal Utilization Technologies in Steel industry
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 38: Gasification Application & Economics 1 35
Species and Organic Emissions
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 45: Low Rank Coal Utilization 4 42
Particulate Matter and Trace Elements (1)
12: Coal Chemistry 1 11 46: Synthesis of Liquid Fuels & Chemicals from Coal
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 51: Low Rank Coal Utilization 5 48
Particulate Matter & Trace Elements (2)
18: Coal Chemistry 2 17 52: Synthesis of Liquid Fuels & Chemicals from Coal
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 4: Co-Pyrolysis, Coke Reactions in a Blast 51
Technologies (Direct & Indirect) and Separation
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 2: Gasification & Pyrolysis Technologies 53
24
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,
Cleanup 58
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 8: Geosciences & Resources 62
27
(1) 9: Non-Fuel Utilization of Coal 63
30: Non-fuel Utilization of Coal 2 28 10: Gas Turbines & Fuel Cell for Synthesis Gas &
31: Geosciences & Resources 29 63
Hydrogen Applications
32: Gasification Advanced Technologies 2: 11: Low Rank Coal Utilization 64
30
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

Copyright 2004 Pittsburgh Coal Conference


SESSION 1
COMBUSTION TECHNOLOGIES 1: MODELING
1-1
Characteristics of Pulverized Coal Burner Using High Temperature Air
Combustion Technology
Toshiyuki Suda, Makoto Takafuji, Tetsuya Hirata and Junichi Sato
Ishikawajima-Harima Heavy Industries, Co., Ltd., Japan
High-Temperature Air Combustion Technology (HiCOT) is a new combustion
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
combustion behavior of pulverized coal in high temperature air has been investigated
using a small scale regenerative furnace. In this study, pulverized coal burner using
HiCOT technology has been tested using a large scale furnace with thermal output of
1.2MWth.
Furnace with 1.6 m width, 0.8 m height and 8.0 m length has been used in the
experiment, which has a pair of regenerative burner in each side of the furance.
Bituminous and anthracite coal whose average particle size is 40m are fed into the
furnace at the feed rate of 150kg/h by two pulverized coal burners. Combustion air is
heated up to 1073K by the heat exchanger using thermal storage honeycombs. Inlet
port for pulverized coal is changed in order to clarify the effect of mixing with high
temperature air on ignition and NOx emission behavior. Excess air ratio is changed
from 1.0 to 1.5. Flame behavior, exhaust gas composition and combustion efficiency
are measured in the experiment.
Results show that NOx concentration in the exhaust gas is from 100 to 150 ppm
(6%O2) at the excess air ratio of 1.2, which seems to be smaller than that in
conventional systems which uses much low temperature air. This is because the release
of volatile matter and fuel nitrogen by high temperature air are promoted and then the
reduction zone is enhanced by rapid devolatilization. NOx emission is reduced by
decreasing the oxygen concentration in the coal feeding air by mixing with recirculated
exhaust gas. It is possible to maintain the stable flame by high temperature air even for
low volatile coal or low oxygen concentration condition. NOx concentration seems to
decrease as the coal feeding point becomes far from high temperature air feeding duct.
Two types for heat regenrator (rotating heat regenerator and swithching type heat
regenerator) have been tested.
1-2
Numerical Investigation of the Impact of Air Distribution on the Performance
of a 360MW W-fired Boiler
H. Gao and E.H. Chui
CANMET Energy Technology Centre, Canada
Combustion stability and coal burnout are important issues in using difficult-to-burn
coals in large utility boilers. For a given burner configuration, the secondary air
distribution can greatly affect the performance of the unit. This study focuses on a
360MW W-fired utility boiler firing anthracite. It is known that the flue gas
temperature and coal burnout can change dramatically under different secondary air
distributions. A computational fluid dynamical (CFD) tool was employed to provide
insights for the field observations. Two simulations were performed with different
secondary air distributions corresponding to the field tests. The model results
correctly capture the significant change of flue gas temperature in the near burner
region, as well as the variation of carbon-in-ash as observed in field trials over
different secondary air operating conditions. The model results also show the
sensitivity of anthracite combustion to surrounding airflow. This presentation will
highlight the effects of secondary air flow on combustion stability, coal particle
trajectories, coal burnout, and the thermal characteristics of the boiler. In addition,
an optimal secondary air distribution is uncovered for this specific unit based on the
numerical investigation.
1-3
Modeling of Complex Kinetics in Methane/Air Flames Using Adaptive Chemistry
Minghou Xu and Yu Qiao
Huazhong University of Science and Technology, P.R. China
Viriato Semio
Instituto Superior Tcnico, Portugal
Pisi Lu
Massachusetts Institute of Technology, USA
It is well known that the chemistry varies significantly in the different regions of a
flame. Using a single chemical kinetic model over the entire domain of a reacting flow
simulation, which is commonly adopted by existing algorithms as the reduced
chemistry approach, does not describe the varying chemistry properly and may cause
discrepancies. Using very complex chemistry (the full chemistry approach) to compute
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
different reduced models are used in a simulation, each reduced model being used only
under reaction conditions where it is representative of the full model. The AdapChem
provides a method for avoiding the loss of efficiency while retaining chemical
accuracy where it is required. The discrete-ordinates method was employed to
calculate the radiative heat transfer and incorporated in the AdapChem to show that
AdapChem is feasible and accurate. Comparisons between the simulation results of
two axisymmetric laminar co-flowing partially premixed methane/air flames with and
without radiation show that very similar topologic reacting structures can be obtained,
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
with the radiation model incorporated.
1-4
Dynamic Reactivity and Comminution Behaviour of Particles
In CFBC
Jaakko Saastamoinen, Heidi Hasa, Juha Pitsink, Jouni Hamalainen and Antti Tourunen
VTT Processes, Finland
Timo Hyppanen, Miro Loschkin and Toni Pikkarainen
Foster Wheeler Energia, Finland
Steady state population balance modelling has widely been used to simulate the
particle size distribution (PSD) of different material (fuel, ash, sand or sorbent
particles) in fluidized bed (FBC) and circulating fluidized bed boilers (CFBC). The
steady state approach cannot be used to study the effect of rapid changes in dynamic
conditions, where the fuel with different reactivity and PSD and the PSD of its ash
vary, but a dynamic model is more appropriate.
Bench scale reactors can be applied to study basic comminution and reaction rate
behaviour of materials with a fuel batch input, which is more easily operated than
reactor with a continuous feed. Then however, the dynamic population balance
approach is required to interpret the results and extract model parameters from
measurements.
The stability of combustion in FBC and CFBC depends much on the char inventory in
the bed, which is affected by the size and reactivity of the fuel and the operational
conditions (temperature, oxygen level). Dynamic population model can be applied to
study the change of the char inventory due to changes in fuel or in operational
conditions. The effect the operational conditions (temperature and oxygen level) in a
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
dynamic model.
A dynamic population balance model is applied to study reactivity and comminution
behaviour of material. Tests are carried out in a pilot scale and bench scale fluidized
bed reactors.
1-5
Development of China's First Training Simulator of a 135 MW CFB Boiler with
Reheat
Li Zheng, Cai Yi and Gao Qirui
Tsinghua University, P.R. China
Shangdong Zibo
CFB Power Plant, P.R. China
Along with the successful development of 135 MW CFB boiler with reheat, about 30
CFB boilers has been or are going to be installed in Chinese power industry. More and
more operators who were familiar with pulverized coal boiler operation are expected to
grasp the skill of CFB boiler operation, which is different from their former
experiences. To meet this demand, under the support of Chinese Tenth-five year Plan,
Tsinghua University developed a first-of-the-kind training simulator of a 135 MW
CFB power plant with reheating in China. The simulator was successfully installed in
Shandong Zibo CFB power plant and was proved to be very helpful to educate and to
improve the operation technique of operators.
Compared to the training simulator of conventional PC boiler power plant, the major
achievement of the new simulator lies in the development of real-time dynamic model
of CFB combustor. Our former experience in dynamic modeling of CFB combustor,
such as dynamic mass balance, dynamic carbon balance and dynamic energy balance,
were integrated into the new model. The newly developed model is robust in
responding the combined changes of different manipulation parameters, such as
primary air, secondary air, coal feed and limestone feed and has the ability to reflect
the whole operation process from cold start to shut down. The distinguished features of
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
ash, and the different influence of primary air to secondary air ratio.
About 60 operators have been trained on the simulator before they started their real
operation on CFB power plant. Their feedback is really exciting. They felt great
similarity between simulator training and real operation. The operation data of 8
months is now under analyzing and will be used to validate the accuracy of the model.
 SESSION 2
GASIFICATION 1: FUNDAMENTALS
2-1
Technology Options for Indian Coals and Optimization of IGCC Cycle Efficiency
D.N. Reddy
Osmania University, India
V.K. Sethi
Rajiv Gandhi Technological University, India
P. Rajesh
National Thermal Power Corporation Ltd., India
The Global concern for reduction in emission of green house gases (GHG) especially
CO2 emissions are likely to put pressure on Indian Power Sector for adoption of
improved generation technologies. Although India does not have GHG reduction
targets, it has actively taken steps to address the climate change issues. Mitigative
options for India for CO2 reduction, which have been taken up vigorously include,
GHG emission reduction in power sector through adoption of Co-generation,
Combined cycle, Clean Coal Technologies (CCTs) and Coal beneficiation. A major
thrust on CO2 reduction on long term and sustainable basis would however come
through adoption of advanced technologies of power generation like
Supercritical/Ultra-supercritical power cycles, Integrated Gasification Combined
Cycles (IGCC), Fluidized bed Combustion/Gasification Technologies using domestic
coal, which is the main stay of power generation in India. A beginning towards
adoption of Supercritical Power Plants of 660 MW capacity has already been initiated.
India is in favour of adopting in IGCC technology and the efforts are being made to put
this technology on the power technology map of India.
IGCC has the inherent characteristic of lower emissions of CO2 and ash and negligible
emission of oxides of sulfur and nitrogen (SOx and NOx) achieved economically
without additional control measures. The programs on carbon sequestration, hot gas
cleaning for desulfurisation and particulate control and advanced ash utilization
could make IGCC a near zero emission power plant. The advanced gas turbines have
greater potential to raise the efficiency of IGCC plants as high as 55%. Gas cleanup is
one of the decision variables in the selection of gasification process. Hot gas cleanup,
though contributes in attaining higher efficiencies, is yet to take-off commercially for
want of resolving some front line issues particularly with high ash coals. Hot gas clean
up at high temperature (800-9000C) may be uneconomical due to need for high
temperature valves and special materials, which are very expensive to adopt at present.
Medium temperature particulate cleanup and medium temperature H2S removal has not
been fully demonstrated on continuous operation in a large-scale plant using high ash
coals. Further, in hot gas cleanup, a separate system is required to trap alkali vapors,
which can cause high temperature corrosion in gas turbine. These systems are still in
developmental stage. An extensive study is undertaken with existing GT machine
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
500-550 0C is viable from the point of view of plant cost vis--vis efficiency gain
achievable.
This paper manly focuses on optimizing the IGCC cycle efficiency by taking into
consideration coal gas cleaning temperature and the bottoming cycle parameters for
various topping cycle configurations. By improving the cycle parameters of topping &
bottoming cycle gain in IGCC cycle efficiency is computed. In case of bottoming
cycle, an optimum range can be achieved between IGCC cycle efficiency and design of
waste heat recovery boiler for varying process parameters. This approach in
optimization of IGCC bottoming cycle process parameters compares well with the
experimental data available.
2-2
Gasification Behaviour of Australian Coals at High Temperature and Pressure
D.J. Harris, D.G. Roberts and D.G. Henderson
CSIRO Energy Technology, Australia
This paper presents gasification data generated for a suite of Australian coals reacting
at 20 bar pressure and at temperatures up to 1500C, as part of a wider investigation
into the performance of Australian coals under gasification conditions. It builds on
previous work conducted at lower temperature (1100C) whereby the effects of O:C
ratio, residence time and coal type on conversion levels and syngas quality were
investigated. At the higher temperatures used here, coal conversion levels are, as
expected, higher than those measured at 1100C and product gas compositions reflect
the relevant gas phase equilibrium conditions. This increased conversion allows the
contribution of coal-specific properties such as char structure and high temperature
reactivity to be investigated in more detail than previously possible. Furthermore, at
higher conversion levels the effects of coal type on product gas composition are more
apparent than at lower conversion levels. These high temperature, high pressure
gasification data have been reconciled with high pressure bench-scale pyrolysis and
char reactivity data, allowing the coal-specific effects of key gasification parameters on
gasification behaviour to be investigated. This paper also presents new data from
experiments conducted with steam in the reactant mix, demonstrating quantitatively
the effects of steam addition on conversion levels and product gas composition.
2
2-3
CO2 Gasification Rate Analysis of Coal Char in Entrained Flow Coal Gasifier
Nobuyuki Suzuki
Electric Power Development Co., Ltd., Japan
Shiro Kajitani, Masami Ashizawa and Saburo Hara
CRIEPI, Japan
Power plants such as the Integrated Coal Gasification Combined Cycle (IGCC) are
being developed on the world to use coal more efficiently and cleanly. In Japan, 9
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
demonstration plant together. On the other hand, in the Europe and U.S., the oxygen-
blown gasifier has started commercial operation. Also in Japan, the pilot plant of the
oxygen-blown gasifier which is named the EAGLE project aiming at the Integrated
Coal Gasification Fuel Cell (IGFC) combined cycle is operating. Hence, the oxygen-
blown coal gasifier is one of the most interesting technology manufacturing materials
gas and clean fuel, such as hydrogen, DME (Dimethyl Ether) and GTL (Gas to
Liquid).
It is necessary to acquire the gasification reaction rate of coal char under high
temperature and pressure, in the optimal design and evaluation of a coal gasifier.
CRIEPI has developed the gasification reaction model in the air-blown gasifier. In
oxygen-blown gasifier, the influence with high partial pressure of CO2 and CO prevent
of the gasification reaction must be taken into consideration. Since the experiment is
still more difficult, reaction model in oxygen-blown gasifier has not solved. Then,
extension of a coal gasification reaction model applicable to oxygen-blown gasification
is needed.
Two types of coal char were gasified with CO2 using a Pressurized Drop Tube Furnace
(PDTF) or a Pressurized Thermogravimetry (PTG) at high temperature and pressurized
condition, to simulate temperature and partial pressure of gasifying agent in an
oxygen-blown entrained flow coal gasifier. Chars were produced by rapid pyrolysis of
pulverized bituminous coals using a DTF in a nitrogen gas flow at 1670 Kelvin. The
conditions of gasification tests were following; temperature was from 1470K to
1670K, pressure was from 0.5MPa to 1.0MPa, CO2 partial pressure was from 0.1MPa
to 0.7MPa in PDTF. And, temperature was from 1020K to 1370K, pressure was from
0.1MPa to 1.0MPa, CO2 partial pressure was from 0.03MPa to 1.0MPa, CO partial
pressure was from 0MPa to 0.6MPa in PTG.
As a result, there was a difference between coal types on influence to the gasification
reaction rate of CO2 partial pressure. And, prevention of CO2 gasification reaction by
CO was observed. Hence, both nth order equation and Langmuir-Hinshelwood type
equation was applied to char gasification reaction in random pore model. And, it
became clear that Langmuir-Hinshelwood type equation is suitable for the condition of
high CO2 and CO partial pressure in Oxygen-blown Entrained flow Gasifier.
2-4
Development and Applications of the Thermodynamic and Viscosity Models for
Complex Coal Ash Slag Systems
E. Jak, A. Kondratiev, D. Saulov and P.C. Hayes
University of Queensland, Australia
The complex behaviour of coal ash slags in slagging gasifiers (e.g. IGCC) is one of
the key issues in gasification industry. For successful prediction and modelling of the
various processes taking place in slagging gasifiers (e.g. slag flow or slag adhesion)
it is necessary to understand and evaluate such fundamental aspects of the chemistry
and physico-chemical properties of coal ash slag systems as phase equilibria and
viscosity.
In Pyrosearch Centre these and other fundamental characteristics of slag behaviour
are systematically investigated and analysed, and on such basis the general and
reliable thermodynamic and viscosity models have been developed.
The thermodynamic modelling has been carried out using the experimental results
obtained in Pyrosearch Centre and the computer system FactSage, which is used for
the calculation of multi-phase slag / solid / gas / matte / alloy / salt equilibria in
multi-component systems of industrial interest. A modified quasi-chemical solution
model is used for the liquid slag phase. The new thermodynamic database for the Al-
Ca-Fe-K-Mg-Na-O-Si system has recently been developed.
The experimental thermodynamic studies carrying out in Pyrosearch Centre include
the determination of phase equilibria and kinetics by using different techniques such
as equilibration, primary phase substrate, and levitation.
Viscosity modelling in Pyrosearch Centre resulted in development of the modified
Urbain model for the Al-Ca-Fe-O-Si system and, recently, of the quasi-chemical
viscosity model for the same slag system. The quasi-chemical viscosity model takes
into account the complex internal structure of silicate slags evaluated from the quasi-
chemical solution model and therefore has more predictive capability than the
empirical viscosity models. The viscosity modelling has been carried out in
conjunction with the FactSage calculations to predict the viscosities of fully liquid as
well as heterogeneous, partly crystallised slags.
Recently, an experimental set-up for high temperature viscosity measurements has
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.
Examples illustrating application of the thermodynamic and viscosity models to
complex industrial issues, such as coal ash slag deposit formation and ash adhesion,
will be presented in the paper.
2-5
Reactivity and Structure of Coal Char on Steam Gasification
Yasushi Sekine, Kiyohiro Ishikawa, Eiichi Kikuchi and Masahiko Matsukata
Waseda University, Japan
Akimitsu Akimoto
CCUJ, Japan
Steam gasification of various kinds of coal char was carried out with a fixed-bed
reactor. After the gasification, the reacted char was analyzed by LRS (Laser Raman
Spectroscope) mapping system, CO2 adsorption, and SEM/EDX. We evaluated the
progress of graphitization of carbonaceous materials by several Raman parameters.
Consequently we found the graphitization which was one of the factors reducing
reactivity progressed equably as conversion had become highly, presumed that the
progress of graphitization may be caused by the change of char morphology. Then in
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-
mappings, we found the different behavior of elements and novel parallel analysis
between EDX-mapping and LRS-mapping was very effective for the comprehensive
evaluation of ash behavior and carbonaceous structure. Until the medium term of
gasification (that is around x=0.5), the reactivity of char was increased by the reason
that the catalytic activity of mineral elements is more dominant than the progress of
carbonaceous graphitization. However in the latter term (that is around x=0.9), the
reactivity of char was decreased, because of graphitization that certain elements
promoted and inhibition of gasification by subsumption of other elements.
SESSION 3
HYDROGEN IN THE FUTURE 1: GENERAL
3-1
The U.S. Department of Energy Hydrogen, Fuel Cells and Infrastructure
Technologies Program - Hydrogen Fuel Initiative Update
Arlene Anderson and Steven Chalk
US DOE, USA
Clean forms of energy are under development that will support sustainable global
economic growth while mitigating greenhouse gas emissions and impacts on air
quality. This paper provides an update of Program activities undertaken in response to
the Hydrogen Fuel Initiative of February, 2003. To realize this vision, the U.S. is
developing demonstrating advanced technologies for hydrogen production, delivery,
storage, conversion, and applications.
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
coal, natural gas, and oil, and non-fossil resources such as biomass and water.
Hydrogen production and separations technologies selected under a DOE Hydrogen
Production and Delivery Solicitation issued in 2003 will be reviewed. The near-term
focus on distributed hydrogen production from small-scale natural gas reforming,
electrolysis, and new concepts for hydrogen production systems will be emphasized.
The Hydrogen, Fuel Cells, and Infrastructure Technologies Program PEM fuel cell
RD&D will also be discussed as production of 99.999 % pure hydrogen for use in
PEM fuel cells is a key technology focus of the Hydrogen Fuel Initiative.
3-2
A Strategic Scenario of Infrastructure Construction for FCV
Masahiro Inui, Hiroyuki Iwabuchi and Kenzo Fukuda
The Institute of Applied Energy, Japan
Reducing carbon dioxide emissions is one of the most critical energy issues for
construction of future energy systems. The hydrogen energy system is widely
considered to be one of the most promising systems in the future for solving such an
environmental problem.
Japanese Government has already decided the introduction targets of fuel cell vehicles
(FCVs), 50 thousand and 5 million vehicles in 2010 and 2020, respectively and
currently study is underway for expanding the timeframe to 2030 and for setting the
introduction target of FCV in 2030.
We propose a target value, 15 million FCV, for 2030 and made a tentative strategic
scenario of the infrastructure construction for achieving the Government's and our
proposed introduction targets of FCV.
3-3
New Compact Hydrogen Production Unit from Natural Gas
Takumi Tanaka, Takaaki Asakura, Toyokazu Tanaka and Takayuki Azuma
Osaka Gas Co., Ltd., Japan
Natural gas is expected to play an important role to produce hydrogen for hydrogen
refueling stations as well as industrial applications. Osaka Gas has developed two
types of hydrogen production systems with different type of reformers. The first type
3
with low-pressure reformer has been developed for the hydrogen refueling station to
demonstrate their reliability and operability under New Energy and Technology
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
production unit (HYSERVETM). The basic unit generates 30Nm3/h pure hydrogen
(99.999%), and all components are packaged on one skid. Recently, 100Nm3/h scale
unit has been developed through improving efficiency based on medium-pressure
reformer. Our development effort realized to reduce 50% installation area, 50% capital
cost and 30% operating cost compared with the low-pressure type.
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
hydrogen production unit for wide variety of applications.
3-4
GREENCAT, an Environmentally Responsible Technology for Preparation
of Water Gas Shift Catalyst for Hydrogen Production
X.D. Hu, Jrgen Ladebeck and Yeping Cai
Sd-Chemie Inc., USA
With world coal reserve of approximately 1000 billion tons and R/P ratio (reserve to
production) of 216, utilization of coal as a portable energy source is just a matter of
time. An integral approach of hydrogen production and electric power generation by
coal gasification/ oxidation shows promising. Since coal contains less hydrogen than
natural gas and crude oil (typically <5 wt% of hydrogen and >60 wt% of carbon), a
shift reaction is essential to obtain maximum amount of hydrogen by reaction of
H2O with the carbon containing compounds. The efficiency of the shift reaction has
a large impact to the overall economics of the coal utilization.
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
containing halogen, alkaline, sulfur or nitrogen compounds are usually generated.
For example, up to approximately 80 tons of wastewater containing 3 tons of nitrates
and 800 kg of NOx may be generated for production of one ton of oxide catalyst. In
this presentation, an environmentally responsible process, GREENCAT, is
introduced for preparation of the shift catalyst. This process is able to achieve zero
wastewater discharge, zero nitrate discharge, very low or no NOx release, and
meantime substantially reduce the consumption of water and energy. The shift
catalyst produced by GREENCAT process has suitable physical-chemical
properties. It has also been demonstrated high efficiency in the micro-reactor test as
well as in the life test. The key step in the GREENCAT process is the conversion
of a low surface area solid metal or a low oxidation state material to a high surface
area metal oxide where a complete transition to the desirable oxide phase via a
colloidal intermediate can be achieved. The reaction of converting metal to oxide
proceeds as follows:
Me (s) Mea+(col)
Mea+(col) MeO (s)
where Me is the starting material at lower oxidation state than the resulting catalyst
precursor. It is sown that the crystallite size and the phase can be tailored by
changing the reaction conditions. In contrast to the traditional processes, the
GREENCAT process is close-looped systems where the discharge of the mother
liquor is either eliminated or significantly reduced. This green technology is
especially valuable in the coal rich regions where water source is scarce. The
GREENCAT technology won 2003 USA Presidential Green Chemistry Challenge
award.
3-5
Design, Construction and Commissioning of a Coal to Fuel Cell Grade Hydrogen
Technology Package
Steve Pearce, Mark Boniface, Tony Clemens and Desmond Gong
CRL Energy Limited, New Zealand
One of the most important questions when considering the development of a hydrogen
infrastructure is: where will the hydrogen come from? It is up to each country to
develop the options best suited to its own particular mix of energy sources. New
Zealand has sufficient recoverable coal reserves to last for centuries and dwindling gas
supplies. It relies heavily on hydro-electricity but this option is struggling to keep up
with growing demand.
Recognising the need for a wider range of supply options, the New Zealand
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
Zealand to realise the benefits of moving to a hydrogen based energy economy and to
demonstrate a small scale coal to high purity hydrogen to electricity distributed
generation package at the 50 kW scale.
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
components of the technology package, some of the difficulties faced and means of
overcoming them.

SESSION 4
COAL UTILIZATION BY-PRODUCTS 1: CHARACTERIZATION &
USE OF COAL UTILIZATION BY-PRODUCTS
4-1
Current State of Coal Ash Utilization in Japan
Yoshiaki Sakai, Akimitsu Akimoto and Kazuo Hara
Center for Coal Utilization, Japan
In 2001, Japan imported approximately 152 million tons of coal comprising more than
100 types from over 10 countries. Almost half of this amount was used for power-
sector and other industrial boilers as steaming coal. The consumption of coal in Japan
is expected to escalate, mainly for the electric power sector, which makes the
development of both clean-coal technology and coal-ash utilization technology
increasingly important. In 2002, approximately 9.2 million tons of coal ash was
produced by coal combustion, 83.6% of which was effectively used and the rest
disposed of. The ratio of coal ash utilization in the cement field, which is one of
Japans major industries, is 78% of the total; public works is 9%; construction 5%;
agriculture 2% and others 6%.
The Center for Coal Utilization, Japan (CCUJ) has continuously promoted technology
for the smooth utilization of coal and coal ash. This paper introduces the current state
of effective coal ash utilization in Japan.
4-2
The United States Combustion Byproducts Recycling Consortium
Tamara F. Vandivort and Paul F. Ziemkiewicz
West Virginia University, USA
Tarunjit S. Butalia
Ohio State University, USA
The Combustion Byproducts Recycling Consortium (CBRC) was initiated in the fall of
1998 to provide national focus for development of beneficial uses for the products of
coal combustion. CBRC promotes and supports the commercially viable and
environmentally sound recycling of coal combustion byproducts for productive uses
through scientific research, development, and field testing. The CBRC is funded by
the U.S. Department of EnergyNational Energy Technology Laboratory (DOE-
NETL) and collaborating companies. Over the past five years, $3.65 million in U.S.
DOE-NETL funds have been matched by $3.94 million industry dollars in 36 projects.
Projects include: mine filling, pavement and structural applications, agricultural soil
amendments, construction products, ash-derived sorbents for CO2 and mercury
control, and other uses of coal combustion byproducts.
CBRC is managed by the West Virginia Water Research Institute at West Virginia
University with regional management by Southern Illinois University, the University
of North Dakota, and the University of Kentucky. Within each region, teams of
technical experts from industry and government have developed research priorities
and, annually, rank proposals for funding. A national steering committee consisting of
senior Federal, State and Industry representatives provides program direction and
project selection.
The objective of the CBRC is to develop and demonstrate technologies to address
issues related to the recycling of byproducts associated with coal combustion
processes. A goal of the CBRC is that these technologies, by the year 2005, will lead
to a doubling of the 1998 rate of FGD byproducts use, a 10% increase in the overall
national rate of byproduct use, and a 25% increase in the number of uses considered
allowable under state regulations.
This paper describes how the CBRC is organized and managed, our research priorities
and funded projects. Twenty of the thirty-six funded projects have been completed and
results of those completed projects are summarized.
4-3
Alfa Foams - An Evaluation of Properties & Microstructure
Y.Bhambri, J. Snider and V.Sikka
Oak Ridge National Laboratory, USA
L.Boyd and R.Purgert
Energy Industries of Ohio, USA
A new processing technique for producing aluminum based foam (Alfa foam)
containing fly ash has been developed. The processing method for producing Alfa
foam with different particulate aggregate sizes has been discussed. The foam is
characterized for mechanical properties as well as microstructure. Detailed image
analysis reveals that difference in mechanical properties among foams of different
particulate sizes is due to variation in relative amount of constituent phases. Work is
continuing in altering the processing parameters in the production of Alfa foams to
meet the application demands of foam in acoustic damping and structural panels.
4-4
Utilization of Coal Combustion Byproducts in Phenolic-Matrix Composite
Materials for Braking Applications
Peter Filip, Kok-Wai Hee, Samrat Mohanty and Y. Paul Chugh
Southern Illinois University, USA
4
Consistent and well-defined properties of brake linings are important from the point of
view of transportation safety and environmental considerations. Among numerous
other factors, the performance and properties of brake linings strongly depend on their
formulation. One brake lining may contain up to 30 ingredients and more than 3,000
different materials were identified in formulations manufactured worldwide.
Objective of this paper is to understand the role of fly ash additives on the frictional
performance and properties of phenolic matrix brake linings. Three types of fly ash
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
of friction tests and evaluation of their structural and physical properties. Friction
assessment and screening procedure and automotive dynamometer tests (Link
Engineering, SAE J2430) were applied to 20 formulations. The analysis of materials
before and after friction testing involved light microscopy, X-Ray diffraction, FTIR,
gas chromatography, mass spectroscopy, scanning electron microscopy with
microanalysis, swelling and growth test, termogravimetric analysis, hardness test,
compressibility test, shear test, profilometry and density measurements.
Detected frictional performance and wear characteristics of modified brake linings
were ascribed to the formation of a complex friction layer. The friction layer was
detected on both the pad and cast iron disc surfaces and contained significant amounts
of fly ash, indicating its stability during frictional process. Wear of cast iron disc was
higher when samples modified by fly ash were compared to OE materials. This was
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,
hardness, and strength of brake pads modified by fly ash additions were related to the
inherent properties of ashes investigated.
4-5
Properties of Zeolites Synthesized From Fly Ashes and Their Potential
Application to Co2 Removal from Flue Gas
Izabela Majchrzak-Kucba and Wojciech Nowak
Czestochowa University of Technology, Poland
In recent years, much attention has been paid to the synthesis of zeolites from fly
ashes. Among other issues, such situation results from the fact that the products
obtained from fly ashes have a great potential for immobilization of environmental
pollutants like radioactive waste, removal of heavy metals and ammonium ions from
industrial sludge and removal of gaseous pollutants as CO2 and SO2 from flue gases.
Numerous potential applications of zeolites synthesized from fly ashes have not been
analysed yet. An example here may be removing CO2 from flue gases. It is of special
importance due to the overall world tendency to restrict CO2 emissions, which are one
of the main causes of the greenhouse effect. Due to the above, the work examines the
adsorption capacity of carbon dioxide on the zeolites synthesized from fly ash, under
conditions typical of flue gases, at the same time describing possibilities of using them
in this respect. In order to obtain zeolites from fly ashes, alkaline, hydrothermal
activation processes have been carried out. Samples of fly ash were obtained from the
Turw Power Station in Poland (Circulating Fluidized Bed boiler of 235 MWe in
capacity). Fly ashes were chemically analyzed and used to prepare the zeolitic
material. The synthesis processes were run using the classic alkaline conversion and
the method of fusion with sodium hydroxide prior to the hydrothermal reaction. In the
present work a chemical, physical, mineralogical and microstructural characterisation
of zeolites from fly ashes was presented.
X-ray diffraction pattern of the zeolite samples was obtained with CuK radiation by
using a Feifert 3003 diffractometer. Particle morphology was observed by a JEOL
5400 scanning electron microscope. The effect of temperature on zeolite samples and
dehydration kinetics of fly ash based zeolites were studied by a Mettler TG/SDTA
851e thermobalance. The model free kinetic method was applied to calculate the
activation energy of the dehydration process of fly ash - based zeolites as a function of
conversion and temperature.
To determine the surface area, specific volume, and mean pore radius, the samples
were first degassed at 3500C and then subjected to N2 adsorption with the use of the
BET method. The study was performed using a Sorptometer ASAP 2010 manufactured
by Micromeritics.
Zeolites synthesized from fly ashes were tested in laboratory conditions, on a model
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,
temperature, H2O and SO2 presence in flue gases on CO2 adsorption was evaluated.
SESSION 5
ENVIRONMENTAL CONTROL TECHNOLOGY 1: NITROGEN
SPECIES & ORGANIC EMISSIONS
5-1
Formation of Nitrogenous Species during Coal Pyrolysis and Gasification
Jian-ying Lin, Li-ping Chang, Jie Feng, Ke-Chang Xie
Taiyuan University of Technology, P.R. China
The formation rules of HCN, NH3 and NO during coal samples pyrolysis and
gasification were investigated in this paper. And the distribution of nitrogen in the
char, which obtained during pyrolysis, was also investigated. Eight different coal
samples were used in this work. All of them were sieved to size fraction 220-450m
before use. Pyrolysis and gasification experiments were carried out in a programmed
mode at a heating rate of 10 /min with a fixed-bed quartz reactor at atmospheric
pressure. The gas flow rate is 600ml/min. About 1.0g dried sample was used in the
experiment. The amount of HCN and NH3 were quantified by ion chromatography.
And the amount of NO was quantified by Quintox flue gas analyzer. The nitrogen
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
formation of HCN during pyrolysis mainly due to the thermal cracking of volatile. The
content of volatile is the main factor that affected the HCN release. When volatile
content increased the amount of HCN also increased. The release of NH3 is
complicated during pyrolysis. It not only relied on the volatile content but also relied
on the coal geographic character. The results showed that more inertinite could
increase the release of NH3. As for the formation rules of HCN during coal gasification
with CO2, it was just as the same as that during pyrolysis, and the release rules of NH3
during gasification had a little difference compared to that during pyrolysis. The higher
volatile could increase the NH3 releasing amount during gasification. The formation
rules of NO during gasification were completely different compared with the formation
rules of HCN and NH3. The formation of NO increases with volatile content increase
and had a peak at 34% volatile content, then NO amount decrease with volatile content
increase.
5-2
Development of Reduction Technology of Unburned Carbon Concentration in
Fly Ash on Pulverized Coal Combustion
Michitaka Ikeda, Masaru Saito, Yoshihiro Kishi and Hisao Makino
CRIEPI, Japan
It is important to reduce both emissions of NOx and unburned carbon on pulverized
coal combustion. We have already developed the advanced low NOx burner. This
burner with multi staged air injection method can reduce unburned carbon
concentration in fly ash less than 3 % at 100 ppm of NOx concentration at the exit of
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
has to reduce much more. This report describes the pulverized coal combustion
technologies to reduce unburned carbon concentration in fly ash less than 2.5 % at
100 ppm of NOx concentration at the exit of furnace. Combustion tests were
performed by firing three kinds of fuel ratios coal (0.8, 1.5 and 2.0), which were
used in Japanese power stations, on the pulverized coal combustion test furnace. The
main results are as follows.
When low fuel ratio coal (0.8) was fired, unburned carbon concentration in fly ash
could be reduced less than 2.5 % at 100 ppm of NOx concentration at the exit of
furnace. On the other hand, as fuel ratio was higher (1.5 and 2.0), unburned carbon
concentration in fly ash increased more than 2.5 %. When A/C (Weight ratio of
primary air to pulverized coal) decreased, pulverized coal stayed a long time in
combustion flame. We cleared that unburned carbon concentration in fly ash could
be reduced without the large increase of NOx concentration at the exit of furnace by
decrease of A/C. When coals, which were higher fuel ratio, were fired, combustion
flame became narrow in the furnace, and could be diffused by increase of swirl vane
angle. Then, oxygen consumption is accelerated outer side in the furnace, and
unburned carbon concentration in fly ash became lower. NOx reduction area at the
optimized air injection condition became wider than that at the conventional
condition. NOx was decomposed outer side in the furnace, and NOx concentration at
the exit of furnace decreased.
As a result, when air injection conditions were optimized for fuel ratio of bituminous
coal, it was possible that unburned carbon concentration in fly ash reduced less than
2.5 % and NOx concentration at the exit of furnace also decreased less than 100 ppm.
5-3
Low-Temperature Selective Catalytic Reduction of Nitric Oxide with Ammonia
Koichiro Shimizu, Caili Su and Eiji Sasaoka
Okayama University, Japan
Yuka Fujikawa
Okayama Prefectural Environmental Conservation Corporation Foundation, Japan
Md. Azhar Uddin
University of New South Wales, Australia
Low Selective catalytic reduction of nitric oxide over TiO2, SiO2 and activated
carbon were studied using a conventional flow type packed bed reactor at 100oC
under atmospheric pressure. The following results were obtained:
(1) The presence of SO2, O2 and NH3 were indispensable for removal of NO over
TiO2.
(2) The presence of SO2 contributed to oxidation of NO to NO2 over TiO2.
(3) If NO2 presented with NO in the reaction system, the presence of SO2 was not
indispensable for the removal of NO over TiO2.
(4) It was clarified that the following tow reactions occurred over TiO2: NO + NO2
+2NH3 2N2 + 3H2O (a), 2NO2 + NH3 N2 + NH4NO3 + H2O (b).
Furthermore, it was suggested that the reaction of (b) occurred and the reaction of (a)
did not occur over SiO2 and activated carbon.
5
5-4
A Numerical Simulation of a Pulverized Coal Combustion Field in a Test Furnace
with an Advanced Low NOx burner
Hirofumi Tsuji, Ryoichi Kurose, and Hisao Makino
CRIEPI, Japan
In pulverized coal combustion, the combustion conditions, the burner operating
conditions and coal properties affect the combustion characteristics. It is, therefore,
very difficult to experimentally optimize these conditions for each coals due to high
expense, and the research and development on the combustion technology needs an
exceedingly long term. In these days, the numerical simulation of a coal combustion
field has become of major interest because the performance of computers is increasing
rapidly and the models for coal combustion have improved.
In this study, a three-dimensional numerical simulation is applied to a pulverized coal
combustion field in a test furnace equipped with an advanced low-NOx burner called
CI- burner. The applicability of the numerical simulation to the prediction of NOx
concentration in exhaust gas and combustion efficiency for bituminous coals is
investigated, and their results are compared with experimental results. The results
show that the present numerical simulation is generally applicable for the bituminous
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
a recirculation flow is formed in the high-gas-temperature region near CI- burner
outlet, and this lengthens the residence time of coal particles in this high-temperature
region, promotes the evolution of volatile matter and the progress of char reaction, and
produces an extremely low-O2 region for effective NOx reduction.
5-5
Organic Emissions Control in Energy Generation, Process Modelling
Ana M. Mastral, Maria S. Callen, Jos M. Lpez, Elvira Ayln and Maria T. de la
Cruz
Instituto de Carboqumica, CSIC, Spain
Polycyclic Aromatic Hydrocarbons (PAH) are an important class of environmental
pollutants that are generated during combustion processes. PAH emissions, due to their
high volatility and reactivity, can be released, not only supported onto particulate
matter (PM) but also in the gas phase. While PAH supported on the PM can be trapped
using the proper systems such as cyclones, electrostatic precipitators, etc; the
atmospheric PAH emission control becomes more difficult. Adsorption processes on
activated carbons and catalytic combustion seem to be a promising technology.
However, research effort, especially in the mathematical modeling of these processes,
is still needed to implement these technologies at industrial scale.
In this communication, the modeling of breakthrough curves obtained in the adsorption
of Phenanthrene as model compound on a carbonaceous material is described. All the
runs were performed in a fixed bed reactor with a process temperature of 150 C,
similar to the observed in the flue gases of energy generation systems. This work is
mainly focused on the study of how adsorbent characteristics (surface area and
micropore size distribution) influence the kinetics of the adsorption process. First,
equilibrium values are found from the breakthrough curves and they are satisfactory
fitted to the well-known Freundlich isotherm. Using the obtained equilibrium values
together with the linear driving force model as kinetic expression, the breakthrough
curve modeling is achieved. It was found that this model fits all the breakthrough
curves and it is a useful tool for modeling purposes. Values for the Phenanthrene
surface and effective diffusion coefficients are calculated and reported, and a
relationship with the microporosity is found. As it was expected, it is observed that the
Phenanthrene molecule finds kinetic restrictions for the diffusion in those carbons with
narrow microporosity, especially in those with a mean pore diameter close to the
molecular size.
SESSION 6
COAL PRODUCTION & PREPARATION: 1
6-1
Flotation of Coal and Sludge for Coal-Preparation Plant by New Reagents
Viktor I. Saranchuk and Leonid J. Galushko
National Academy of Science of Ukraine, Ukraine
In the last time in Ukraine the big attention is given a problem sludge pit on coal-
preparation plants as the sources of secondary raw material for power and by-product-
coking industry. Design resources make about 25 million tons of coal and anthracite.
Ash content of the sludge changes from 35 up to 75 %. Specially created installations
and the stationary equipment of coal-preparation plants use for enrichment sludge
One of ways of enrichment is flotation. This way is based on various wettability of a
surface of coal and mineral particles. Owing to a long finding in storehouses fine
particles of coal are oxidized and get raised hydrophily. It demands the special
approach to a problem of flotation sludge.
The carried out researches have shown, that existing technologies of flotation do not
provide reception of a commodity output from coal sludge with ash content more than
50 %. Two series of researches were carried out for development of technology of
flotation sludge:
1. Selection special flotator and technologies of enrichment for sludge;
2. Joint enrichment of a mix of ordinary coal with ash content about 25 % and
2-10 % sludge with ash content 45-65 %.
Developed at the first stage flotator allow to receive a concentrate for the power
purposes appropriate to requirements, the concentrate for coking had raised ash
content.
The experiences carried out at the second stage on flotation of a mix coals and sludge
have shown, that the additive up to 10 % sludge does not influence for quality of a
concentrate coke coals and in addition allows to take from sludge in a concentrate of
coal of 200-500 kg from each ton sludge. Thus ash content a concentrate is 6-8 %, ash
content waste products is 85-95 %. The small increase of a degree of extraction of coal
from a mix is marked in comparison with ordinary coal.
Optimization of process of flotation on structure and amount flotator is made.
6-2
Development of Advanced Fine Coal Dewatering Technologies
R.-H. Yoon, J. Zhang, M. K. Eryadin and G. H. Luttrell
Virginia Polytechnic Institute & State University, USA
Dewatering processes are used in coal preparation plants to remove excess surface
moisture from the clean coal products. Coarser particles can be readily dewatered
using simple screening systems, while finer particles require costly unit operations
such as centrifuges and filters. Moisture that is not removed by these processes reduces
the heating value and increases the cost of transporting the clean coal. Excess moisture
can also create unacceptable handling problems for both the coal producer and
downstream consumers by plugging chutes, bins, and rail cars. Coal handling can be
particularly severe during winter months because of freezing. These problems typically
force U.S. coal producers to discard their fine coal (<0.15 mm), which reduces the
tonnage of saleable coal and creates a potential environmental hazard. In light of these
shortcomings, researchers at Virginia Tech have been developing a new suite of
advanced technologies for fine coal dewatering. These include novel dewatering aids,
hyperbaric filters and centrifuges, and other revolutionary processes that can eliminate
the need for thermal drying. In addition, innovative technologies have been developed
that offer near-term improvements in existing plant filters and centrifuges. This paper
provides an overview of test results obtained from recent laboratory, pilot-plant, and
field trials conducted using these advanced dewatering technologies.
6-3
Effects of Coal Characteristics on the Properties of Coal Water Slurry
Wei Yuchi, Baoqing Li, Wen Li, Haokan Chen
Chinese Academy of Sciences, P.R. China
The effects of coal characteristics on the properties of coal water slurry (CWS) were
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
correlationships of the CWS properties including slurryability (the concentration of
slurry that apparent viscosity is 1200mPa.s at shear rate of 28.38s-1), rheological
behaviour (represent by flow index), and static stability (the days of formation soft
sediment) with coal properties including coal rank (Cdaf, Odaf), content of air
equilibrium moisture (Mad), maximum holding capacity of moisture (MHC), ash
content, the surface properties, petrographic macerals, pore structure, adsorption
characteristics of dispersants on coal surface and their corresponding electrochemical
properties of coal were investigated. Multiple regression analysis of different factors of
coal properties indicated that:
1. The carbon content, content of air equilibrium moisture, grindability index (HGI),
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
equation with correlation coefficient of 0.988.
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 (Dt), pore volume
(VHg), Zeta-potential properties ()of coal surface mainly influence the rheological
behaviour of CWS. The rheological behaviour can be described using the follow
equation with correlation coefficient of 0.917.
N = 0.86 - 0.098[Ad] 0.0023[Dt] 2.91[VHg] + 0.011[]
3. The content of soluble mineral matters in CWS, inertinite content in petrographic
macerals(I) are the main factors influencing the static stability of CWS, which can be
calculated by the following equation with correlation coefficient of 0.726.
W = 19.43 + 0.054[Dt] 0.35[I]
6-4
Coal Preparation versus Losses of Chemical Energy in Combustion Processes
Lidia Gawlik and Eugeniusz Mokrzycki
Mineral and Energy Economy Research Institute, Poland
Tomasz Mirowski, Tadeusz Olkuski and Adam Szurlej
AGH University of Science and Technology, Poland
Polish energy sector comprises nearly exclusively the conventional power plants,
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
6
countrys energy balance. The assumptions of Polands Energy Policy for years to
come anticipate a gradual reduction of the coal share in the electricity production.
However, coal will continue to play the leading role in the sector of electricity
production due to lower costs comparing to other energy carriers and due to the energy
safety of the country.
Run of mine coal is characterised by various qualitative parameters. The quality of the
coal is not always in conformity with the standard conditions designed for the boiler.
The combustion of the coal of parameters considerably different than those designed
causes the deterioration of the boiler operation quality, thereby, lowering the
efficiency. In extreme cases, the boiler may even become damaged. In order for the
recipient of the coal to receive the product with parameters exactly reflecting those
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
deeper the preparation is, the purer coal is obtained, of the better quality parameters.
However, too deep preparation causes large amount of grains (organic substance) to
transfer into the waste, thereby increasing the losses of chemical energy. Also the
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
basis of densimetric analysis of tested coal. The boiler is another place where the
losses of chemical energy occur. The losses in the boiler are indicated through the
boiler instrumentation systems, which allow drawing up the corresponding diagrams.
The relation between yield of coal in the preparation process and the losses in the
boiler can be determined by a two step analysis. In the first step the relation between
the densimetric fractions yield and the calorific value of prepared coal is found. In the
second step the relation between the losses in the boiler and the calorific value of burnt
coal is determined. The superposition of the two functions gives the relation between
yield of coal and losses in boiler. The relation in question allows setting such
preparation conditions at the preparation plant that the losses in the boiler during
combustion are minimised.
6-5
Effect of Petrological Composition of Coal on Black Coal Flotation
Peter Fecko, Iva Pectov, Pavla Ovcari, Vladimr Cablik and Barbara Tora
VSB - Technical University of Ostrava, Czech Republic
The paper deals with floatability of bituminous coal and examines how individual
maceral groups float in course of a fractional flotation. Flotation was tested on 4
samples of bituminous coal from the localities of Jaworzno, Jankowice, Staszicz,
Marcel (Poland) and 2 samples from the Dukla Mine (Czech Republic). The objective
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
well as their selectivity was evaluated from the petrologic point of view.
SESSION 7
COMBUSTION TECHNOLOGIES 2: CO-COMBUSTION OF COAL &
ALTERNATIVE FUELS
7-1
Lafarge Cement Polska S.A. Experience Concerning Waste-Derived Alternative
Fuel Combustion
Alicja Uliasz-Bochenczyk Mineral and Energy Economy Research Institute, Poland
Sarna Mieczyslaw
Lafarge Cement Polska S.A., Poland
Cement industry belongs to the branch of industry that has been using waste-derived
alternative fuel for over ten years. The alternative fuels use in that industry has been
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
environment allowing acid gas neutralization). Moreover it is a priceless advantage
that combustion inside a cement kiln is a wasteless process, as the combustion products
become an admixture during clinkerization operation.
As mentioned above, waste derived alternative fuel combustion in cement plants
constitutes a safe way of wastes utilization, environmentally safe and profitable both
for the plant and for society.
Global economical growth causes the significant increase of both industrial and
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
waste organic fraction utilization.Alternative fuel derived from such wastes as: tires,
fluid hydrocarbon waste products, industrial or/and municipal waste flammable
fraction mixtures are used in many countries.
Poland is the country of long cement production traditions. Nowadays fifteen cement
plants run in Poland.Two cement plants belong to LAFARGE concern that possesses
strong background in alternative fuel application, dating back to 1982. Nowadays in
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.
in the alternative fuel use.
 7-2
Co-Firing of Wood Chips In 10MW Grate Coal Boiler
Marek Sciazko, Jerzy Rainczak
Institute for Chemical Processing of Coal, Poland
"The strategy of the development of the renewable energy" is forcing Polish power
distributors and generators to increase the energy production from renewable sources
up to 7.5% by 2010 and to 14% in 2020. This is the reason for tasting undertaken on
co-firing of coal and biomass in coal grate boiler of 10MWth capacity. The wood chips
were produced from energy crops, specifically willow of type Salix. The energy
efficiency effect and emission reduction was investigated in respect of biomass
content. The results of the tests showed that there is observed reduction in emission of
such gaseous components as sulfur dioxide, nitrogen oxides, and organic compounds.
It was found that the addition of biomass in amount of 4-5% by mass cause increase of
boiler efficiency due to increased burn-out of carbon in the bottom ash. The results of
co-firing were collected up to 35% v/v of biomass content in fuel mix. The main
attention was paid to the preparation of fuel mixture by applying double screw mixer
and proper distribution of the fuel at the feeding point to the grate boiler. The
properties of coal and wood chips were investigated prior to co-combustion to make
energy balance possible. During the boiler operation the basic technological
parameters were measured, particularly mass flow rates of fuel mix and air,
temperature of hot water produced, temperature of combustion gases at the outlet, and
the content of combustible parts in bottom ash. The basic components of flue gases
were investigated (CO2, CO, NO and SO2) as well as dust content. Additionally total
organic carbon (TOC), polyaromatic hydrocarbons (PAH) including B( P were
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
(27, 4%), SO2 (23, 5%) NO2 (8, 1%), TOC (17, 4%), PAH (17, 6%) and B( )P (47,
2%). The boiler efficiency at the wood chips content 35%v/v are smaller by 0.5% but
at 25%v/v higher by 0.3%. The results were confirmed in two repeated runs.
7-3
Possibilities of High Sulphur Content Coal Combustion with Biomass
Contribution
Pavel Sedlek, Marcela afov and Josef Vale There is a scanty of knowledge about the thermal interactions between mineral matter
Brown Coal Researche Institute, Czech Republic
Combustion of solid fuels is controlled by valid legislation that determines emission
limits for combustion in facilities of different outputs. Lignite coal from the North
Bohemian Lignite Field is characteristic for its high content of sulphur (up to 3.5 %
Std). During combustion of that coal, high emission concentrations are formed and that
coal becomes unsaleable. With regard to the long-term surface mining, there are land-
reclaimed mined out areas available, which can be used for growing energy biomass.
Grown biomass can be used for the production of a new product which contains, apart
from hard saleable lignite coal with a high content of sulphur, a biomass compound
which, during combustion, decreases the value of emission concentrations and along
with an additive agent, which is another compound of the lignite coal pellets, ensures a
decrease in emissions to a value which is determined for solid fuel combustion. For the
needs of burning tests, several samples of lignite coal pellets were prepared, which
were burnt in a furnace designed for lignite coal combustion and the emission values
were compared with emission values which are reached during pure lignite coal
combustion.
7-4
Co-Combustion of Municipal Solid Waste and Thai Lignite
In a Fluidised Bed
Pornvipa Boonnuit, Kriengkrai Suksankraisorn, Suthum Patumsawad, Bundit
Fungtummasan
King Mongkuts Institute of Technology, Thailand
Experimental investigations on the co-combustion characteristics of high-moisture
municipal solid waste (MSW) and high-sulphur Thai lignite were carried out using a
laboratory scale fluidised-bed reactor. The objective is to study the effect of main
operating parameters on the combustion characteristics and gas emissions. The results
show that the co-combustion characteristics differ significantly from the combustion of
lignite alone. The co-combustion of MSW and lignite reduces the emission of SO2
while increasing NO and N2O slightly. It also results in a slight drop in combustion
efficiency. The optimum condition for co-combustion of MSW with lignite, in view of
carbon combustion efficiency, emissions of CO, NO and N2O appears to be the
following: 20% MSW mass fraction, 40-60% excess air and 0.2 secondary to total air
ratio. However, this occurs at the expense of slightly smaller reduction in SO2
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
NO, N2O and CO emissions.
7-5
Co-Combustion of Coal and Meat and Bone Meal (MBM)
Emmanuel Kakaras, Kyriakos Panopoulos and Lydia Fryda
National Technical University of Athens, Greece
7
The paper aims to present the results of combined combustion of coal and Meat and
Bone Meal (MBM) the laboratory scale bubbling fluidised bed set located in the
Laboratory of Steam Boilers and Thermal Plants (LSBTP) of NTUA.
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
can therefore be treated as a fuel substitute to coal. At the time, MBM combustion
seems the most adequate way of disposing MBM, since the level of temperature in the
combustion chamber provides a significant potential of elimination of MBM while
valorising its energetic potential.
The impact of combusting MBM with coal in fluidised beds is studied to study its
effect on the process, emissions and particularly the NOx and VOC. Furthermore the
properties and particularities of the ashes produced are examined. In order to
investigate the MBM co-combustion, a set of experiments for emission and ash-
valorisation was carried out in a laboratory scale bubbling fluidised bed set up in
NTUA. Fuel used was low risk greek MBM from local industries and greek coal
(lignite).
Co-combustion tests investigate the effect of the operation conditions such as air
preheat temperature, bed temperature, fuel supply, fluidisation air velocities and excess
air levels on the quality of combustion of MBM with coal (gaseous emissions, air
pollutants, residual matter, auto combustion, ash agglomeration problems) in order to
determine the optimum MBM percentage in the fuel blend. taking into account.
Furthermore, ash samples are collected and examined for their suitability for
landfilling as well as other uses such as blending with cement.
The results of the tests will show whether the substitution of coal from biomass is
feasible and acceptable, conforming to the existing legislation.
SESSION 8
GASIFICATION 2: FUNDAMENTALS
8-1
High-temperature Interactions between Coal Char and Mixtures of
Iron compounds, Quartz, and Kaolinite
Kayoko Morishita, Naoya Ichimura and Takayuki Takarada
Gunma University, Japan
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
and coal char. The carbothermal reactions of quartz and kaolinite started at 1200 C
under Ar atmospheres, releasing CO. In this study, the interaction between coal char
and mixtures of iron compounds such as pyrite and iron oxide, quartz, aluminum and
meta-kaolinite were investigated by heating to 1600 C under Ar. Pyrite was gradually
reduced in the temperature ranging 800-1600 C and was changed to pyrrhotite at 800 C
and to troillite at 1000 C. Iron was detected above 1200 C and almost of all iron
component became to iron at 1600 C. The mixtures of iron compounds and aluminum
and the mixtures of coal char and aluminum were quite stable and few interactions
were observed. In coexistence of coal char, aluminum and iron compounds, however,
interaction between iron compounds and aluminum was promoted with release of CO,
and compound derived from Fe and Al was formed. It seems that carbon in coal char
has removed oxygen in aluminum and Al obtained by reduction of aluminum and iron
compounds have been reacted. In addition, pyrite affected the reaction of carbon
/quartz and carbon/kaolinite and reduced the reaction initiated-temperature ca. 200 C at
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
above 1400 C, forming Fe3Si. In the case of pyrite-kaolinite-coal char mixture, troillite
was formed at 1000-1200 C as same as the case of SiO2 coexists. At 1400 C, however,
three types of compounds were formed that was Fe1.34Si0.66, Fe3Si and Fe5Si3. In the
sample heated at 1600 C, there were Fe3Si and SiC. On the other hand, Fe2O3-SiO2-
coal char mixture reacted at relatively lower temperature, Fe2SiO4 was formed and Fe
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
was clearly assigned at 1600 C. In the case of Fe2O3-kaolinite-coal char mixture,
hercynite was formed at 1000C and then changed to mullite with iron. And, SiC was
observed at even 1400 C.
8-2
A Model of Char Capture by Molten Slag Surface under High-Temperature
Gasification Conditions
Tadaaki Shimizu
Niigata University, Japan
Hiroaki Tominaga
Idemitsu Kosan Co. Ltd., Japan
A simple model was proposed for char capture by molten slag surface under high-
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
if they reach the molten slag surface whereas they were repelled if they reach the part
that is covered by the unreacted char particles. Thus the probability of char capture
was given by the balance of char feed rate per unit surface area of the slag and the rate
of char consumption by the gasification reaction.
Experiments were carried out to evaluate the probability of char capture by molten slag
surface at 1350 oC. A ceramic tube whose bottom was closed was vertically placed in
an electric furnace. Mixture of coal ash and flux (limestone) was placed at the bottom
of the reactor. The reactor was heated up to a temperature higher than the melting
point of the mixture of coal ash and flux, thus slag was formed at the bottom. Char
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
bottom, they were immediately conveyed out of the reactor by the gas stream. CO was
produced by gasification reaction in the presence of the molten slag at the bottom
whereas only small amount of char was gasified in the absence of slag. Thus the
presence of the slag surface was necessary to capture char particles at the bottom. The
conversion of carbon to CO decreased with increasing char feed rate. The effect of
char properties such as particle size, density, and gasification rate, on the conversion of
carbon to CO was evaluated. The theoretical results agreed well with the experimental
results.
8-3
Release and Retention of Halogens during Pyrolysis and Gasification of Coals
Akio Ueda and Makoto Takeda
Babcock-Hitachi K.K., Japan
Noboru Suzuki
Utsunomiya University, Japan
Nakazato Yoshihiro, Naoto Tsubouchi and Yasuo Ohtsuka
Tohoku University, Japan
The fate of halogen atoms in coal, mainly the chlorine (denoted as coal-Cl), during
pyrolysis and gasification is examined with fixed-bed and drop-tube reactors under
different conditions. Pyrolysis of several coals with C % of 73 92 wt%(daf) and Cl
% of 0.021 0.14 wt%(daf) at a slow heating rate of 2.5 400 K/min shows that the Cl
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
K tends to be higher at a larger content of Ca plus Na, coal-Cl may be present
dominantly as the forms of these chlorides. When a sub-bituminous coal with C % of
78 wt%(daf) is injected into an O2-blown, drop-tube gasifier at 0.9 2.6 MPa, char
conversion increases with increasing weight ration of O2/coal in the range of 0.66
0.83, regardless of the pressure. The content of Cl or F in the char in the conversion
level of 80 95 % is much larger than the corresponding value upon pyrolysis, that is,
at char conversion of zero. These observations mean that the halogens remain
accumulated even at the latter part of gasification. Some model experiments and XPS
measurements strongly suggest that such significant halogen retention originates from
secondary reactions of HCl or HF once released with some minerals and carbon active
sites in the char.
8-4
Radiative Heat Transfer Properties of Coal Char and Ash Particles Cloud in
Gasification Processes
Yoshinori Itaya, Naomi Nishio, Shigenobu Hatano, Nobusuke Kobayashi, Jun
Kobayashi and Shigekatsu Mori, Nagoya University, Japan
Coal gasification processes are operated at high temperature over 1700 K to effectively
produce gaseous fuels. In such a high temperature field, thermal radiation dominates
the heat transfer in the furnace. The heat transfer problem in the furnace is a
significantly important issue for precise design of the furnace and determination of
factors such as the reaction rates of decomposition and gasification of coal,
temperatures of char particles and gas phase, heat exchanger and wall cooling for
protection to high temperature. Researches on radiative heat transfer in pulverized coal
combustion and optical properties of coal and ash have been carried out previously.
However, the most properties have been measured not for particles cloud but for a
block of samples. Those data may not be always available to the prediction of the
radiative behavior of particles cloud in the furnace. It is quite difficult to apply their
model or data and to solve the problem with combining the gasification models in the
furnace as well.
In this study, the thermal radiation properties were determined for a cloud of coal char
and ash particles. The monochromatic absorption of the sample particles dispersed in
liquid paraffin wax was measured spectroscopically at an atmospheric state by using
FT-IR. The effect of the particles number density in the cloud and the thickness of the
dispersion layer on the spectrum of absorption could be summarized by expressing in
the form of the absorption efficiency. The spectral distribution of the absorption
efficiency was dependent of wavelength in the region of 0.7 to 25 micrometers. The
absorption efficiency was influenced significantly so to overlap the optical property of
the ash when the content of carbon in the char increased. The scattering of particles
was negligibly small except the forward direction. It results in that only the absorption
can be considered apparently for the radiative heat transfer. A parameter averaged over
the wavelength was introduced to simply estimate the behavior of radiative heat
transfer.
8
8-5
Heat Transfer and Fluid Dynamics in CWS Preheater for Coal Gasifier
Kosuke Aiuchi, Ryo Moriyama, Shohei Takeda, Shunji Kitada,
Masaki Onozaki and Yukuo Katayama
The Institute of Applied Energy, Japan
The authors have developed a preheating technology of coal water slurry (CWS) which
increases the efficiency of coal gasification with reduction of oxygen consumption.1)
The objective of this paper is to describe a study on heat transfer and fluid dynamics in
the CWS preheater. In the experiment, 140 kg/h of CWS (50wt%, 1.7ton-coal/day) was
pumped up to 10MPa, and introduced into a single tube heat exchanger. After the fluid
was heated to 300 in the tube of 6 mm ID, the water in CWS was vaporized in a
region where the diameter of the tube increased gradually (2-10 mm ID). This enables
the fluid velocity to be kept in a range that prevents both blockage and erosion. The
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
result was corresponding to the calculation result well.
The temperature and pressure distributions of the fluid were calculated with empirical
heat transfer and pressure drop correlations. The calculated results were well
corresponding to the experimental data measured in some test points. It is confirmed
that the position where the vaporization starts was in the 2 mm ID tube. The overall
heat transfer coefficient is in a range of 200-900 Wm-2K-1 which is largely affected by
the outside heat transfer coefficient. Using the calculation model, a large scale
apparatus (60wt% CWS, 300ton-coal/day) was designed in two approaches using
molten salt (KNO3 + NaNO2 + NaNO3, =0.5 Wm-1K-1) as a heating medium. In the
first approach, shell and multi-tube heat exchanger was used. In the second, a single
tube heat exchanger was used for which the tube has a race track shape. These systems
can be connected to boiler as well as gasifier. Slurries of other flammable substances
such as paper sludge slurry and biomass slurry also can be treated.
SESSION 9
HYDROGEN IN THE FUTURE 2: FUNDAMENTALS OF HYDROGEN
PRODUCTION FROM COAL
9-1
Overview of Hydrocarbon Processing Options and Proposed Concepts of
Gasification for Hydrogen Production with Carbon Dioxide Capture
Chunshan Song
Pennsylvania State University, USA
Hydrogen energy development is important for breaking the link between energy
utilization and emissions of pollutants and greenhouse gases. The research and
development efforts using coal also provide a bridge to future hydrogen production
using renewable resources. This paper discusses the processing options for hydrogen
production in conjunction with hydrogen utilization, fuel cells, and mitigation of CO2
emissions. By energy and atomic hydrogen sources, hydrogen can be produced from
coal (gasification, carbonization), natural gas and propane gas (steam reforming,
partial oxidation, autothermal reforming, plasma reforming), petroleum fractions
(dehydrocyclization and aromatization, oxidative steam reforming, pyrolytic
decomposition), biomass (gasification, steam reforming, biological conversion), and
water (electrolysis, photocatalytic conversion, chemical and catalytic conversion). For
fossil fuel-based H2 production in stationary plants such as coal gasification and
natural gas reforming, it would be desirable to develop new approaches that produce
hydrogen in a more economical and environmentally-friendly process that also
includes effective CO2 capture or CO2 utilization as an integral part of the system. A
concept called CO-enriched gasification (COEGas) with CO2 capture and partial
recycling of CO2 into the gasifier is proposed here for H2 production from gasification
of coal (and biomass). CO2 reacts with carbon in a way similar to H2O but the reaction
with CO2 at high temperature is more endothermic and produces more CO. The better
use of high-temperature heat of gasification gas is important for improving gasifier
efficiency. The COEGas concept aims at better utilization of high-temperature heat
with endothermic reactions that produce more CO, which in turn leads to more H2
through subsequent exothermic reactions that do not consume energy. It may help to
improve the overall energy efficiency for hydrogen production by minimizing the loss
of energy, which includes both the quantity and quality of energy. For gasification-
based H2 production, CO2 and H2O need to be separated from H2 in the product gas
mixture. The COEGas concept involves CO2 capture with more efficient adsorbent
such as high-capacity nano-porous CO2 adsorbent based on MCM-41 modified with
special polymers. Such adsorbents have been prepared in our laboratory, which have
numerous CO2 affinity sites and do not require pre-separation of moisture from the gas
stream. The presence of moisture further enhances CO2 capture on such adsorbents.
Therefore, it allows more efficient CO2 capture and easy recycling of CO2 for the
proposed COEGas process. The CO2 capture and utilization must be designed such
that the overall system is more efficient and will not result in more energy loss
compared to existing options that could lead to zero-CO2 emissions. The CO2 capture
process should be more efficient than the existing processes based on liquid amines.
 9-2
Hydrogen from European Low Rank Coal: Reducing CO2 Emissions
Roland Berger, Craig W. Hawthorne and Klaus R. G. Hein
University of Stuttgart, Germany
A process for hydrogen production from European low rank coal is being developed to
meet European Union policy objectives of reducing CO2 emissions and decreasing
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
provides heat for endothermic gasification reactions with the added benefit of
increasing the equilibrium hydrogen concentration. High theoretical cold gas
efficiencies are possible. Another key process is sorbent regeneration and reactivation:
the carbonated sorbent is transferred to a regeneration unit that is capable of yielding a
concentrated CO2 stream and a solid purge stream suitable for the cement industry.
The University of Stuttgart is coordinating two European projects examining
gasification with integrated CO2 capture and sorbent regeneration respectively. The
hydrogen product can be used to generate electricity in a combined cycle.
Experimental results from a 40 kW fluidized bed test facility for different European
brown coals and locally available sorbents are presented.
9-3
Continuous Experiment Regarding Hydrogen Production by Coal/CaO Reaction
with Steam (HyPr-RING)
Shi-Ying LIN, Michiaki Harada
Center for Coal Utilization, Japan
Yoshizo Suzuki, Hiroyuki Hatano
National Institute of Advanced Industrial Science and Technology, Japan
Hydrogen can be produced by integrating coal gasification and CO2
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
and analyzed. It was found that CaO first reacted with steam to form Ca(OH)2, which
then absorbed the CO2 generated by coal gasification to form CaCO3. Hydration of
CaO is expected to restore sorbent reactivity and supply heat for the coal gasification.
Most of the CO2 was fixed by Ca(OH)2 during the process. At 973 K, the particle size
of some of the solid materials increased by eutectic melting and these large particles
blocked the reactor. However, at the relatively low temperature of 923 K, eutectic
melting was not observed, and the experiment ran smoothly. Carbon conversions of
60-80 % were obtained, and the calcium compounds crystallized and cohered into
small particles.
9-4
Direct Extraction of Hydrogen from Coal Using a Membrane Reactor within a
Gasifier
Shain J. Doong, Estela Ong and Francis Lau
Gas Technology Institute, USA
Arun C. Bose
Department of Energy, NETL, USA
Ron Carty
Illinois Clean Coal Institute, USA
Gas Technology Institute is developing a novel concept of membrane reactor for clean,
efficient, and low cost production of hydrogen from coal. The concept incorporates a
hydrogen-selective membrane within a gasification reactor for direct extraction of
hydrogen from coal synthesis gas. This concept has the potential of significantly
increasing the efficiency of producing hydrogen and simplifying the processing steps
by reducing/eliminating the downstream shift reactor, separation and purification
operations for the conventional gasification technologies. In partnership with
DOE/NETL, a GTI-led team with Illinois Clean Coal Institute (ICCI), and American
Electric Power will determine the technical and economic feasibility of a coupled
membrane reactor and hydrogen separator module in a coal gasifier to produce
hydrogen from coal. The team will screen, test, and identify potential candidate
membranes under high temperature and high pressure coal gasification conditions. The
best performing membranes will be selected for preliminary reactor design and cost
estimates. The overall economics of hydrogen production from this new process will
be assessed and compared with other hydrogen production technologies from coal.
In this paper, a modeling approach used to examine the performances of the membrane
reactor for hydrogen production from coal will be presented. Proton conducting dense
ceramic materials of perovskite type have been identified as a good candidate
membrane for hydrogen separation application in the gasifier. As hydrogen is removed
directly from the gasifier, the gas phase reactions such as water gas shift and reforming
of methane and carbon dioxide are favored toward producing more hydrogen. A
simplified model was developed to consider the H2 permeability of the membrane, the
kinetics and the equilibriums of the gas phase reactions in the gasifier, the operating
conditions and the configurations of the membrane reactor. A fluidized bed gasifier
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
research areas. Potential candidate membranes that are suitable for the high
temperature and severe gasification environments will also be discussed.
9-5
Advanced Membranes for the Spontaneous Conversion of Coal to Hydrogen
Anthony F. Sammells, Michael V. Mundschau, Xiaobing (Brian) Xie, Carl R. Evenson
Eltron Research Inc., USA
Oxygen transport membrane technology, under development at Eltron Research Inc.,
facilitates the exclusive mediation of oxygen from the atmosphere to a desired reaction
site. As a consequence, these membranes can be incorporated into Catalytic
Membrane Reactors (CMRs) where exothermic coal partial oxidation chemistry can
proceed while at the same time eliminating the need for a separate oxygen plant - a
significant reduction in overall production costs compared to currently available
technology. This leads to the spontaneous formation of synthesis gas, an equilibrium
mixture of hydrogen and carbon monoxide. Application of water-gas shift chemistry
leads to an increase in hydrogen fraction within the reformed feedstream prior to
introduction into a hydrogen transport membrane.
Hydrogen transport membranes compatible with the efficient separation of hydrogen
from hydrogen containing feedstreams discussed above are also being developed
within our company. These dense hydrogen transport membranes possess hydrogen
permeabilities one order of magnitude higher than palladium. Furthermore, these
membranes are far less expensive. Self-supporting wafers of these hydrogen transport
membranes have been successfully operated for thousand of hours at ambient pressure
and for hundreds of hours under an applied pressure differential (450 psi) without
failure. Hydrogen fluxes across the membrane up to 360 ml/cm2/min have been
realized.
The current status of these two complementary membrane technologies will be
discussed.
SESSION 10
COAL UTILIZATION BY-PRODUCTS 2: COAL ASH UTILIZATION
FOR CONCRETE & MATERIALS
10-1
Lowering Foam Index in High-Carbon Fly Ashes for Concrete Applications
Robert B. LaCount, Tiffany A. Leyda, Patrice J. Pique and Keith A. Giles
Waynesburg College, USA
John P. Baltrus and J. Rodney Diehl
U.S. Department of Energy, NETL, USA
Timothy L. Banfield
Allegheny Energy Supply, USA
Douglas G. Kern
ViRoLac Industries, USA
Fly ash is often used commercially as a replacement for some of the Portland cement
in concrete products. Air Entraining Admixtures (AEAs) are used in the concrete
mixtures to improve the workability of the mixtures and the durability of the concrete
products to freeze-thaw cycles.
Use of low-NOx burners in coal-fired boilers has resulted in variable increases in the
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
titration of a portion of the concrete mixture with an aqueous solution of surfactant
until a stable foam results, is used to determine the amount of AEA required in the
concrete.
This paper describes the results of research efforts directed towards developing a
practical and economical thermal treatment for high-carbon fly ash that would reduce
its FI without having to remove the carbon. Thermal treatments were carried out using
a controlled-atmosphere programmed-temperature oxidation (CAPTO) partial
oxidation or pyrolysis treatment. Temperature ramp, gas flow, and pressure were all
under software control.
CAPTO thermal treatments were completed on fly ash obtained from pulverized coal-fired
utility boilers burning Pittsburgh seam bituminous coals under low-NOx conditions.
Oxidation and pyrolysis of the fly ash samples were accomplished by a linear increase in
temperature accompanied by plug flow under either an oxidative or inert gas atmosphere.
The FI values of the treated samples were significantly lower compared to those for the
untreated fly ashes, and were found to vary depending on the treatment parameters.
Selected untreated and treated samples were characterized using X-ray photoelectron
spectroscopy, leachable-ion conductivity measurements and other methods in an
attempt to correlate any changes in physical and chemical properties of the fly ashes
with changes in FI brought about by the thermal treatments. Batch quantities of several
fly ashes were treated to lower their FI values and then evaluated for use in preparing
concrete test samples. These concrete samples containing untreated or thermally
treated fly ash show approximately the same compressive strength test results. Air
entrainment results may vary with the surfactant used. These test results and the
CAPTO profiles will be discussed.
 10-2
Performance Assessment of a Fly Ash Based Road Subbase in Illinois Using
Falling Weight Deflectometer
Yoginder P. Chugh and Samrat Mohanty
Southern Illinois University, USA
Calvin Hance
Morgan County Highway Department, USA
FWD is a nondestructive testing test that applies a dynamic load to a pavement by
dropping a weight onto a circular loading plate, whose magnitude can be varied by
changing the weight and drop height. Deflection transducers placed on the pavement
surface measure the resulting pavement deflections. Backcalculation of pavement
moduli through FWD is widely used for pavement monitoring and evaluation.
The post-construction performance and structural condition of a 2.1-mile industry
access truck route were monitored twice over the past two years using FWD. The
pavement consists of 8 inch of asphalt concrete over a 6-inch granular base layer with
the untreated fly ash subbase thickness varying from 0 to 7 feet. The entire length of
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.
For this research, deflection sensors were placed at 0, 8, 12, 18, 24, 36, 48, 60, and 72
inches from the load plate center. FWD results in conjunction with the pavement layer
thicknesses were used to backcalculate the modulus of elasticity of the flyash layer.
These results were then compared to the road sections constructed without the flyash
subbase, as well as results obtained through correlations with Immediate Bearing
Values. In addition, the FWD data were used to backcalculate the effective structural
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
construction, indicated lower overall deflections and higher subgrade modulus for the
fly ash section over the non-fly ash sections. The second FWD survey, conducted in
summer 2003, indicated the overall deflections and subgrade moduli for the fly ash
section to be superior to control section AC2 and inferior to control section AC1.
However, the subgrade moduli for both the flyash and non-fly ash sections were
reasonable for backcalculated values of fine-grained soils. Additional FWD surveys
are planned over the next two years.
10-3
250 000 Mg of bottom ash in Sochaczew project
Tomasz Szczygielski, Agnieszka Pawlowska and Jaroslaw Laskowski
Ekotech, Poland
Polish power stations and heat and power stations produce about 15 million tons of
CCPs every year. Generally 70 % are utilized. The biggest chance for CCPs utilization
are large scale projects.
Road construction in Sochaczew was one of the biggest applications of bottom ash in
road construction in Europe of year 2003.
In 2003, between April and August on route Warsaw Pozna was utilized about 250
000 Mg of silicate aggregate recovered from bottom ash. Bottom ash has been of
service as material for structure of road embankments in run of national road number
2, section of a construction in km 6+900 to 9+000 and 4+046 to 4+600 bound up with
construction of district of Sochaczew.
Thanks to engagement of three companies i.e. Elektrociepowni Warszawskich S.A.,
Warszawskiego Przedsibiorstwa Robt Drogowych S.A. and Ekotech Sp. z o.o.,
laboratory, project and administrative works have been started, which have caused
obtainment of essential decision permitting on utilization of silicate aggregate (mixture
of bottom ash) coming from landfill of waste near Myliborska street in Warsaw,
competent to EWSA by construction of road embankments of district of Sochaczew.
Ekotech, as a company possessing indispensables administrative decisions for a
transport of bottom ash mixture, has leaded supervision, co-ordination of recycling of
aggregate from furnace waste and its transport on place of build in.
Transport proceeded by trucks. Every truck each time was precisely weighted by a
self-service balance, before and after entrance on a landfill. At the beginning of April
snowfall made difficult realization of a task, but the works were not held. As a
regulator of a humidity was used a admixture of a low quantity FBC fly ash.
Abutments were made of sand, however 90% of embankment was made of bottom ash.
Sand was used only to strew of one abutment, to preserve it against dusting. There
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
rollers and plain-bodied rolls. At the landfill samples from a substance prepared to
load were currently collected in order to qualify it by a laboratory to build in an
embankment. After preparing each layer, current research were performed, degree of
compaction of material were measured. Bearing capacity of each layer of embankment
was continiuously monitored. Unloading proceeded simultaneously with spreading
and compacting of bottom ash mixture. In some places bottom ash with a sand had to
be mixed in order to increase a graining. Surface after correctly carried compacting by
means of tamping roller and then plain-bodied roll. In May 2003 came sweltering
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
was pearled in order to eliminate dusting. A body of embankment was strewed at the
scarps by sand.
10
CCPs are a great chance for road constructions and road constructions are a great
chance for CCPs utilization.
10-4
Demonstration Plant Operation for Development of the Coal Ash Granulated
Material to Civil Engineering Applications
Akira Ohnaka and Takashi Hongo
Ube Industries, Ltd., Japan
Yoshitsugu Izumo
Clean Japan Center, Japan
A coal ash granulated material Z-sand, which enables efficient use of environmentally
burdensome coal combustion by-product, is on the way to being demonstrated. Z-sand
is produced by putting ash from coal-fired power plants through a special process to
convert it into a non-pollutant and permeable artificial grain sand or soil as a
geotechnical material and is expected to be in demand to civil engineering
applications.
10-5
The Promising New Market for Coal Ash Use
Ocean Fertilization by the Man-Made Sea-Mountains Made Of Coal Ash
Tatsuo Suzuki
ASHCRETE Corporation, Japan
Tsuneo Izutsu
Electric Power Development Co. Ltd., Japan
A possibility that food production will not fulfill demand is pointed out to the rapid
increase in world population. Especially a food self-sufficiency rate is very low as 40%
in Japan. Since the food production in land is approaching to the limit, development of
the technology of producing food in the ocean is called for. In order to increase the
production of food in the ocean, it is necessary to make primary production increase.
To make primary production increase in the ocean, it is necessary to add nutrient in the
euphotic zone.
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
use technologies have been developed, expansion of a market which can use coal ash
in large quantities is desired.
To generate an artificial upwelling and to add nutrient in the euphotic zone, a man-
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
ground of high productivity was conducted on the budget of 1,200 million yen. As for
this enterprise, Marino Forum 21 was performed in the Nagasaki offing in response to
the subsidy of the Fisheries Agency of Japan. Moreover, in this experiment, about
20,000t coal ash were used, 5000 blocks of 1.6m cube were manufactured, and were
installed on the depth of 80m seabed. The technology of manufacturing a inexpensive
block with high strength, using coal ash in large quantities was developed, and the
mass production method was proved. With the development of the Super Fluidizing
Method, the cement ratio has been further reduced and the quality, manufacture-ability
and economy of this new material improved, resulting in a new product with clear
advantages over normal concrete, especially for undersea applications. The Fisheries
Agency admits that this coal ashes hardening object has fully satisfied the safe
standard. The size of built sea-mountain is in the 12m peak, a length of 120m, and
width of 60m, and was built in the direction which interrupts the current.
In the area of 20km 18km centering on a man-made sea-mountain, after the sea-
mountain was built, the fish catch by the fishing boat increased to 1500t, and increased
6 times before construction. As for object sea area, the data of the artificial satellite of
NASA showed that the concentration of Chlorophyll-a had increased 1.5 times
compared with contrast area. Also the fixation of CO2 by propagation of
phytoplankton and the relation with reduction of CO2 concentration in the atmosphere
is studying.
The man-made sea-mountain project was started at two places as public works from
the 2003 fiscal year; also many other prefectures show interest to this project. This
project can use coal ash in large quantities in order to increase the production of food.
In order to use coal ash in large quantities, to create the new large-scale market which
people need truly is desired.
SESSION 11
ENVIRONMENTAL CONTROL TECHNOLOGY 2: PARTICULATE
MATTER & TRACE ELEMENTS
11-1
Removal of Major and Trace Inorganic Elements from Coal by Acid
Pretreatment and Organic Solvent Extraction
Chunqi Li, Kinya Sakanishi, Toshimasa Takanohashi, Ikuo Saito, Tetsuya Nakazato
and Hiroaki Tao
Institute for Environmental Management Technology, AIST, Japan
Thermal extraction with selected organic solvents is a very effective route for the
production of extremely low-ash coal (called HyperCoal) which is believed to be a
promising clean fuel for gas turbine. For this purpose, efforts are required to increase
the extraction yield in the one hand, and decrease the remaining amounts of inorganic
elements in the Hyper coal as greatly as possible on the other hand. Previous studies
have found that mild acid pretreatment can appreciably increase the yield of
HyperCoal with a polar solvent N-methy-2-pyrrolidinone for some coals that are
enriched in ion-exchanged alkaline earth elements. In this study, we have revealed that
mild acid pretreatment is also effective for decreasing the concentrations of alkali and
alkaline earth elements in the resultant HyperCoal. This result is favorable for
improving the qualities of the HyperCoal as a clean fuel. Moreover, inductively
coupled plasma optical emission spectrometry (ICP-OES) and flow injection
inductively coupled plasma mass spectrometry (FI-ICP-MS) have been used in this
study for examining the removal extents of a number of trace elements during the acid
pretreatment and the organic solvent extraction. Environmentally concerned trace
elements such as Hg, Se, As, and Pb have found to be removed in both the acid
treatment and the organic solvent extraction.
11-2
Reasons of the Endemic Fluorosis in Western Guizhou Province, Southwest
China
Shifeng Dai
China University of Mining and Technology, P.R. China
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
that the average content of fluorine in fifty coal channel samples from western
Guizhou Province ranges form 16.6 g/g to 500 g/g, with an average of 83.1 g/g,
which is close to the world average (80 g/g) and that of most Chinese coals (82 g/g).
Additionally, the fluorine content of drinking water and fresh corn is too low to lead to
fluorosis in western Guizhou Province. However, the clay used as an additive for coal-
burning and as a binder for briquette-making by local residents has a very high content
of fluorine, ranging from 100.8 g/g to 2455.7 g/g, with an average of 1027.6 g/g.
The endemic fluorosis probably should be caused by the clay with a very high content
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
coal-burning additive and as a binder for briquettes, the more serious the fluorosis
problem is.
11-3
Release Behavior of As and Se during Coal Pyrolysis and Gasification
Takahiro Kato, Katsuyasu Sugawara and Takuo Sugawara
Akita University, Japan
Release behavior of arsenic and selenium was followed during pyrolysis and
gasification of coals in nitrogen and carbon dioxide streams, respectively, up to
1200 . Arsenic and selenium in coal and char were classified into three fractions by a
serial leaching method with HCl, HNO3 and H2SO4 solutions. Selenium forms in
coal, density-separated coal and char were analyzed by XAFS. Kinetic analysis was
carried out for the release behavior of arsenic and selenium. The release behavior was
successfully simulated by the determined kinetic parameters with the soluble.
11-4
Effects of Coal Types on Trace Elements Emission in Pulverized Coal Fired
Process
Takashi Kuwabara
Tokyo Electric Power Co., Inc., Japan
Shinji Kambara and Hiroshi Moritomi
Gifu University, Japan
In Japan, the consumption of steaming coal reached more than 65 millions tons/year
and almost all coal is imported from overseas. More than 100 types of coal that has
ranging from bituminous coal to sub-bituminous coal are consumed. Electricity
companies have developed a tool of coal evaluation system to choose low cost coals
and environmentally friendly coals.
Recent year, fluorine, boron and selenium emission in wastewater from coal-fired
power plants are regulated in Japan. Therefore, we have to estimate behavior of such
trace elements emission in coal power plants in advance.
In this paper, we discussed boron emission behavior in pulverized coal fired process.
Boron content in fly ash from various kinds of coal is investigated. Its recovery
showed wide range from 20% to 100%. It seemed that boron recovery was affected by
coal types. Boron recovery in fry ash was correlated with content of Al2O3 in fly ash
and clay mineral in coal. And also, we investigated the functional forms of boron in
coals to examine relation between the boron devolatilization and change of mineral
matters by using drop tube furnace.
It is found that the boron emission is affected by the functional forms of boron in coal
and clay mineral content.
11-5
Coal Quality and Fine Ash Formation during Combustion
Bart Buhre, Jim Hinkley, Raj Gupta, Peter Nelson and Terry Wall
University of Newcastle, Australia
11
Epidemiological studies have correlated adverse health impacts with ambient levels of
fine particulates with an aerodynamic diameter less than 10 m (PM10) and less than
2.5 m (PM2.5). Legislation has been enacted both in Australia and overseas to set
guidelines for ambient concentrations and to limit the emission of fine particles.
Ash particles are formed during the combustion of coal in pf boilers. The main
formation mechanisms of ash particles during coal combustion have been identified in
previous studies as (1) the coalescence of included mineral matter in the coal and the
fragmentation of excluded minerals; (2) the fragmentation of char particles; and (3) the
vaporization and condensation of inorganic material. Although these formation
mechanisms have been identified, the contribution of each of the mechanisms to the
fine ash of legislative interest (PM10 and PM2.5) remains unclear.
This study provides insight into the mechanisms and coal characteristics responsible
for the formation of fine ash. Five well characterized Australian bituminous coals have
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)
formed. This paper describes the experimental setup, the analytical techniques and the
findings of this study. Coal characteristics have been identified that correlate with the
formation of fine ash during coal combustion. It was found that coal selection based on
char characterization and on the ash fusion temperature can play an important role in
the minimization of the fine ash formed. The implications of these findings for coal
selection for use in pf-fired boilers are further discussed.
SESSION 12
COAL CHEMISTRY: 1
12-1
Formation of Carbon Stacking Structure in Coals with Different Expansion
Property during Rapid-Heating Process
Noriko Yoshizawa and Katsuhisa Maruyama
National Institute of Advanced Industrial Science and Technology, Japan
Akimitsu Akimoto
Center of Coal Utilization, Japan
Three types of coals with different expanding property of their particles on a rapid
pyrolysis were heat-treated below 1500 C in a drop tube furnace to investigate their
microstructure. The Fourier transformation of carbon 002 reflection peaks in their
XRD patterns clarified that an average number of layers per stack (Nave) increased
according to the rise of temperature, except between 800-900 C in which it showed a
sudden dip. Degrading of stacking structure around 800 C like this has been
considered as a result of a coalescense of aromatic molecules, and therefore could be
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
sensitive to those sizes. It was accordingly implied that the original size of coal
particle could dominate the expantion property of the particle independent of the
chemical structure of that coal. We will discuss these XRD data more in detail with
results by molecular adsorption measurements and observations with an electron
microscope.
12-2
Development of New Methodology for Determining Thermal Behavior of
Macromolecular Network Structure of Coal by Using Dielectric Property
Tetsuo Aida, Toyokazu Shinkai, Murakami Kiyonori and Daiki Kaji
Kinki University, Japan
Paul G. Aida
The University of Tokyo, 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
detailed scheme of the instrumentation and discuss about the experimental data based
on thermal behaviors of the macromolecular network structure of Argonne Premium
Coals, such as initial softening (glass transition) temperature or fluidizing temperature,
comparing those of synthetic model polymers including cellulose and lignin.
12-3
About Colloidal Structure and Peptization
Of Coals with Melted Waste Plastics
A.V. Madatov
Ukrainian State University of Chemical Engineers, Ukraine
G.A. Vlasov and G.G. Kleshnya
JSC, Ukraine
V.D. Barsky
Ukrainian State University of Chemical Engineers, Ukraine
Some researchers consider coal as solid colloid structure. Thus, the main properties of
coking coal, such as viscosity of plastic-coal mass, thickness of plastic layer,
temperature interval of plastic state depend on disperse phase - dispersion medium
proportion, which is the function of coal metamorphism range.
Therefore, softening of coal at the time of coking is just transition of solid gel into
liquid sol (so called pyro-sol) by means of dispersion medium increase. When
temperature mounts to the end of temperature plastic state interval, growth of dispersed
phase at the expense of dispersion medium leads to conversion of sol into gel (semi-
coke) and further into coke crystal structure.
Peptization of colloid with appropriate solvent allows convert gel into sol at lower
temperature, therefore, broaden temperature plastic state interval at coking. Authors
peptized following coals: lignite, candle, gas, fat, coking, lean, anthracite with different
solvents: ethyl, isopropyl, iso-butyl alcohols, acetone, mono- and dy-terpene, benzene,
toluene, pyridine and water at 20 C0, besides, with melted phenol, naphthalene,
paraffin, polyterpene, polyethylene, polystyrene, polyvinylchloride, polyethylene
terephtalat, polyamide at the temperature up to 350 C0.
It was measured: swelling degree of the coals, optical density of residual solvent after
peptization, angle of light leakage by colloidal particles in residual solvent, viscosity of
residual solvent, viscosity of plastic-coal mass.
Correlation between swelling degree of the coals, viscosity of plastic-coal mass and
content of colloidal particles in residual solvent was discovered. Colloidal particles
dimensions increase according to coal metamorphism range. Swelling degree of the
coals depends on chemical nature of a solvent.
Coals are peptized best: lignite one in alcohols, phenols, candle one in aldehydes,
ketones, gas one in cycloalkanes, fat one in polycycloalkanes, resin acids, coking one
in aromatic hydrocarbons, lean one in polyaromatic hydrocarbons. Melted plastics give
biggest swelling degree of the coals and decrease of viscosity of plastic-coal mass:
lignite one with acrylic resin, candle one with polyamide, gas one with polyethylene,
fat one with polyethylene terephtalat, coking one with polystyrene, lean one with
resins.
Obtained results show, that colloidal structure of coal definite its coking plastic
properties to a great extent and chemical nature of colloidal dispersion medium is
different in coal of different metamorphism range.
Melted waste plastics are very prospective kind of peptizing solvent for coking coals,
especially keeping in mind their huge amount and cheapness.
12-4
Some View on the Solubilities of Coals toward Solvents
Masakatsu Nomura and Koh Kidena
Osaka University, Japan
Satoru Murata
Takaoka National College, Japan
According to the information concerning reactivity of coal model compounds the
authors did previously the methylene bridge bonds were believed to prevail in coal
structures. Ruthenium catalyzed oxidation reaction, however, indicated less abundance
of mono methylene bridge in all coals examined compared with dimethylene bridge,
this being judged due to the unstabilities of malonic acid (the product from
Monomethylene bridge) in the oxidation reaction conditions. This suggests strongly
the presence of the fission of alkyl side chains and recombination of the resulting
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
materials in solvents can be explained due to a kind of entangled structure proposed by
Cody et al and solubility of some coals can be also explained as well.
12-5
Producing H2 and Coke from Coal
John W. Larsen and Harold Schobert
The Pennsylvania State University, USA
Coals react with sulfur to produce a carbonaceous product and H2S. Hydrogen sulfide
can be dissociated either thermally or catalytically to produce H2 and sulfur. If a
commercially useful carbon can be produced in this process, it is a clean route to H2. If
all of the hydrogen from the coal used to form metallurgical coke in the U.S. could be
captured as H2, about 1.3 million tons of H2 could be produced annually. The
abstraction of hydrogen from coals with the concomitant production of a commercially
useful carbon product is a worthwhile goal. In this talk, we will concentrate on the
reactions of sulfur with coal.
Sulfur is widely used to dehydrogenate alicyclic molecules to form aromatics. With
coals, it first removes the alicyclic hydrogen. It is also capable of removing aromatic
hydrogen and also does this when reacted with coals. This is a much slower process
and is probably responsible for the large decrease in reaction rate as hydrogen is
increasingly removed from coals. The removal of aromatic hydrogen is accompanied
by some incorporation of sulfur into the coal. The reaction between sulfur and coal has
been studied using solid sulfur, sulfur dissolved in a liquid, and sulfur vapor. In the
latter case, a coal was reacted with sulfur vapor at its devolatilization temperature.
About 75% of the hydrogen was removed and the carbonaceous product had physical
properties similar to the coke made from that coal.
12
SESSION 13
COMBUSTION TECHNOLOGIES 3: EXPERIENCES OF LARGE-
SCALE FBCS
13-1
Utilization of Alternative Fuels in the FCB Boilers
Vclav Roubek, Pavel Kolat, Miroslav ech, Dagmar Juchelkov, Zdenk Kadlec
VB-Technical University Ostrava, Czech Republic
The energy utilization of the alternative fuels is one of the main topics for future
developments of recoverable sources in the European Union and in the Czech
Republic. The aim of research is combustion tests in the fluidized-bed boiler Foster
Wheeler located at tt.
The experiments are carried out for Czech brown coal, wood, sewage sludge and
wastes including analyses and recommendations for optimal thermal utilization and
minimizing harmful emissions. The second steps are thermal analyses of coal,
alternative fuel- wood pellets and sewage sludge from treatment plant.
Main goals may be outlined in the study of conditions for:
Potential substitution of fuel with potential combustion of less valuable types of
coal simultaneously with the waste and bio-mass, sustainability of fluidised bed
combustion.
Chemical composition, crystallographic structures and mechanical properties of
combustion solid products ( ash, fly ash, deposits ).
Analytical estabishment of sulphur forms in fuel and combustion products.
Detailed study for mineralogical and chemical composition solid emission phase.
Balance for volatile elements CL, S, Hg, Se, semi-volatile elements V, Ni, Co, As
and some non-volatile elements Cr and Sn.
Leaching tests for combustion solid products.
Long-term deposit formation on thermal exchange s walls.
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
Republic to the European Commission concerning the development of renewable
energy resources by 2010.
13-2
Deposit Measurements at Alholmens Kraft during Co-Firing
A Case Study of the Worlds Largest Biofuelled CFB
Patrik Yrjas, Bengt-Johan Skrifvars, Tor Laurn, Mikko Hupa
bo Akademi University, Finland
Juha Roppo
Kvaerner Power Oy, Finland
Marko Nylund
Oy Alholmens Kraft Ab, Finland
Pasi Vainikka
VTT Processes, Finland
The Alholmen power plant (550 MWth) started up in year 2001. The CFB power plant,
which was supplied by Kvaerner Pulping Oy1, produces not only electricity (265 MWe)
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.
A research project started in 2002, with the goal to show the viability of the CFB
technology to maximise the use of biofuels at the Alhomen power plant. The project
lasts until the end of June, 2004 and is funded by the European Union. The project
consists of several parts of which one is to investigate the fouling tendencies of the
boiler.
Two deposit measurement campaigns have been done. One in May 2003 with fuel
mixtures up to about 45% (energy based) biomass. A second campaign was performed
in August 2003 with even up to 100% biomass. The deposits were sampled with air-
cooled probes with detachable rings. The deposits were sampled at two different
locations, one where the flue gas temperature was about 730C (probe surface temp.
540C) and the second were the flue gas temperature was about 530C (probe surface
temp. 350) A total of 32 deposit measurements were done and from every deposit
sample the rate of deposit build up (g/m2h) was determined. Furthermore, from every
deposit sample elemental analyses were done one from the wind side, one from the
lee side, and one from an angle of about 50 from the wind side. The analyses were
done with a SEM/EDX analyser and are compared to the compositions of the ESP
ashes.
Generally, the results showed that the rate of deposit build-up was low and in no case
the rate indicated severe deposit problems. The deposit compositions reflected the fuel
mixtures that were used and in certain cases chlorine could be found in the deposits
indicating possible corrosion risks. However, if the biomass part was kept below about
45% (energy based) no or only very small amounts of chlorine could be found.
 13-3
Biomass-Fired BFB Boiler at Ostroleka Power Station, Poland Operating
Experiences
Rafal Kobylecki, Robert Sekret, Wojciech Nowak, and Zbigniew Bis
Czestochowa University of Technology, Poland
Rafal Psik
Foster Wheeler Energy, Poland
Operating experiences from a five day trial test of combustion of various types of
biomass and waste fuels in a bubbling fluidized bed (BFB) boiler at Ostroleka Power
Station, Poland are presented in this paper. The boiler is a Foster Wheeler type BFB
and produces 11kg/s of steam at 4MPa and 4500C. Fluidization velocity in the bed is
assumed as 1-1.5m/s, and height of the bed may vary from 0.5m up to 1.2m (at
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
economical benefits, it has been planned to widen the types of fuels burned in the
unit by choosing the proper one burnt depending on its actual market price.
The present study and test runs have focused on combustion and agglomeration
characteristics of five fuels, assumed to be appropriate for combustion in that unit. The
reason for conducting the experiments was a serious agglomeration of the bed, that
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
about an immediate boiler shutdown.
During the five day test runs the boiler was fired with five fuel types (bark, wood
chips, paper mill sludge, and two types of biosludges, i.e. mixtures of sewage sludges
with paper mill sludges). The fuel parameters varied within quite a wide range: ash
0.6-22%, inherent moisture 44-62%, volatiles 62-82%, sulfur 0.01-0.07%. Low heating
value (LHV) of the fuels varied between 11-17MJ/kg.
During the test period no symptoms of agglomeration occurred and it was concluded
that all of the fuels could be safely burnt at the BFB unit. In order to achieve this,
however, proper temperature, fuel feeding rate and mixing in the furnance had to be
maintained. Although results of laboratory tests, conducted at Czestochowa University
of Technology, showed no agglomeration of all fuels at temperatures of up to 10000C,
for safe operation of the BFB unit at Ostroleka it had been recommended to maintain
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
that depending on fuel LHV, bed temperature had be regulated by changing air flow
and flue gas flow.
The main reason of bed agglomeration in the past was also given; it was found out that
wrong adjustment of the fuel feed rate led to a rapid and uncontrolled increase of the
bed temperature, and was directly responsible for agglomeration and defluidization of
the bed.
13-4
Operation Experience of Large-Scale Circulating Fluidized Bed Boilers with
Brown Coal
Wojciech Nowak, Robert Sekret and Zbigniew Bis
Czestochowa University of Technology, Poland
Jerzy Laskawiec, Janusz Jablonski and Roman Walkowiak
Power Plant Turow, Poland
The largest power plant adopting CFB technology is the Turow Power
Plant, Poland. The Turow Power Plant is the worlds largest operating CFB boilers
generating 965 MWe of electricity. Turow Plant is presently operating 3 CFB Foster
Wheeler boilers each 235 MWe and one 260 MWe CFB Compact and has another 2
units under construction which include CFB Compact type boilers each 260 MWe in
capacity. As the CFB technology is being constantly improved, a decision has been
made to construct new units with increased efficiency (91%) using the newest CFB
technology - the CFB Compact type. Capacity of three new units is increased to 260
MWe each staying within the existing foot print. A unique features of these units are
the use a square separator instead of hot cyclones and an integrated heat exchanger
(Intrex) located in the lower part of the combustion chamber outside the main
combustion area.
All performance tests on CFB boilers were met. The trial run performance test
together confirmed that:
CFB boilers were in full compliance with UCPTE criteria,
Turow CFB units were the first units on the Polish Power Grid to satisfy
UCPTE,
guaranteed parameters were met in a wide range of load conditions,
full capacity can be reached without any problems,
emission levels for gases and dust are met,
the boiler is flexible in a wide range of loads.
During commissioning and early operation of the plant it was determined that
certain mechanical equipment required modification and optimization. Fan operational
problem began in the early stages of commissioning. Temporary modifications of the
existing PA and SA fans have been successfully implemented in order to allow full
load operation. The bottom ash coolers have not demonstrated their maximum design
capacity when burning the high ash coal. The pressure parts required several minor
modifications (tube shields were installed on some tubes, spacer canes were installed
13
in the reheater tube bundles, expansion slots were added to the upper convention cage).
In spite of some problems, the CFB boilers have met all performance requirements
confirming Turows decision to select FW technology for this re-powering project.
The fuel flexible, clean burning, efficient boilers have achieved the dynamic load
response required for modern grid systems and have extended the life of the power
station.
The paper presents the boiler design parameters, design arrangement and
specific unique design features of CFB boilers. A particular concern with the CFB
boiler is the low rank brown coal and the large furnace which had to fit into the limited
space of the existing plant. The processes and environmental performance of large-
scale CFB boilers are demonstrated. Special emphasis is placed on operating
experience from the largest CFB boilers which have accumulated more than five years
of operation.
13-5
Design and Operation of a Large Scale CFB for IPP Use
Kazuyoshi Ito
Sumitomo Heavy Industries, Ltd., Japan
Song Wu
Foster Wheeler North America, USA
Sumitomo Heavy Industries, Ltd. designed, supplied and constructed a 149MW Coal
Fired Circulating Fluidized Bed (CFB) Boiler (largest size in Japan) Power plant
of Taiheiyo Cement Itoigawa Power Station, located in Niigata Prefecture, that has be
en utilized as IPP for Tohoku Electric Power Co., Inc.
The plant has started in commercial operation in July 2001 and experienced for more t
han two years with stable and reliable operation. Since commencement of commercial
operation this plant has been operating at weekly start-
stop mode and at daily swing load, which varies from 100% to 40% MCR depending o
n the demand with full automatic start-up and shut-
down as designed. It was confirmed that the CFB could be utilized for the utility powe
r station through the commercial operation in Itoigawa Power Station.
The plant design, plant and boiler performance and operation results will be introduced
in the upcoming Conference.
SESSION 14
GASIFICATION 3: ALTERNATIVE FEEDSTOCKS
14-1
Experimental Results of a Two-Stage Gasifier Processing Waste Derived Fuels
H. Hasselbach, S. Weil, S. Hamel and W. Krumm
Universitat Siegen, Germany
D. Lotter and C. Mertens
Herhof-Umwelttechnik GmbH, Germany
The presented two-stage gasification process is especially developed for volatile
component rich fuels. Due to the spatial separation of pyrolysis and gasification and
combustion unit a two-stage double-line arrangement the production of a
hydrogen-rich and undiluted synthesis gas with low tar content is demonstrated.
Fuel feeding into the first stage, the pyrolysis unit, leads immediately to fuel drying
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
pass a hot layer of fluidized bed ash where steam input supports catalytic and thermal
tar cracking. The remaining pyrolysis char and ash are fed into the second stage, a
fluidized bed combustion unit, where ash is heated up again by char combustion. So,
both reactors are connected by circulating ash to transport energy from the fluidized
bed combustion unit to the pyrolysis unit. Due to the fact that product gas from the
pyrolysis stage and flue gas from the fluidized bed stage are kept separate, nitrogen as
a part of combustion air cannot dilute the produced pyrolysis gas.
At the University of Siegen a technical scale plant is operated according to this
Combined Pyrolysis and Combustion Process. In this contribution a detailed
description and a classification of this process will be given first, before experimental
results from the gasification of mechanical-biological pretreated waste and wood are
presented and discussed. Furthermore operating experiences for example ash
circulation and fuel feeding device are described.
14-2
Modeling a Fixed Bed Gasifier for Decentral Biomass Utilization
S. Weil, H. Hasselbach, S. Hamel and W. Krumm
Universitt Siegen, Germany
Currently a considerable worldwide interest in lowering the CO2 emissions by using
wood and other renewable energies for energy production can be notified. Today
combustion technology is preferred for the commercial use of biomass. Due to the
lower heating value of wood compared to other fuels like coal, crude oil or natural gas
and its small production-area ratio, short conveying distances are required. That means
that only small decentralized plants can be operated in an economical way, whereby
gasification technology is assumed to have higher potential for the thermal use of
biomass. Here development and technical use are focused on fixed bed and fluidized
bed reactors. For smaller operation units, fixed bed reactors are preferred.
Today, design and engineering of such reactors is carried out particularly empirical. In
order to use mathematical and physical design principles, numerous studies are carried
out to understand the various steps of the gasification process, e.g. way and kinetics of
the chemical reactions. In addition to experimental work, development and use of
mathematical models is another way to describe and to understand the process and
various phenomenas going on during the gasification process.
In this work a two-dimensional, transient description of a cylindrical reactor for
pyrolysis, gasification, or combustion of organic material is presented. The various
physical phenomena drying, chemical reaction, heat transfer and mass flow due to
biomass shrinkage are described by various models. In addition the thermal influence
of the different refractory materials and thickness on the gasification process is
simulated. To describe the pyrolysis process and the further chemical reactions, a
hybrid method is used which combines kinetic approaches and equilibrium calculation
using a Gibbs formulation. In this work different kinetic parameters using data found
in literature are compared and faced to measured data.
The model is applicable to calculate the product gas composition, the temperature field
and the outlet mass flow. The product gas composition and temperature field inside the
reactor is calculated for different input materials and various operating conditions.
Furthermore changes of fuel feed and gasification agent on the gasification process are
shown and discussed. Problems relating the further use of the product gas are discussed
in detail.
14-3
Reforming of Wet Biomass to Reactive Feed Stock for Co-Gasification through
Hot Water Treatment with Ca(OH)2 and Dewatering in Oil
Isao Hasegawa, Tatsuya Tsujiuchi, Hiroyuki Kono and Kazuhiro Mae
Kyoto University, Japan
Although a method for the effective utilization of biomass is keenly desired for saving
of CO2 emission, wet biomass such as food wastes are especially difficult to preserve
or convert because of high moisture, high oxygen content, and protein content. Since
the pretreatment of wet biomass consumes much energy in general, the biomass should
be transformed into a valuable feed stock for co-utilization with other major energy
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
water and dewatered in oil at 150 oC. In this study, we treated coffee beans (water
content of 63.4 wt.%) at various combination of three above treatment and clarified its
optimum condition.
Through the hot water treatment of coffee beans at 230 oC by utilizing beans own
water, the oxygen content decreased but the gasification reactivity diminished by the
cross-linking reaction. When Ca(OH)2 was physically mixed with coffee beans in
advance of the hot water treatment, the coffee bean was successfully reformed to
reactive biomass with high gasification reactivity and low oxygen content. On the
other hand, the water was almost removed from coffee beans in the vegetable oil
treatment at 150 oC. In addition, we performed the co-gasification of brown coal with
the pretreated biomass, and found a synergetic effect of the gasification rate. This was
caused by the catalytic effect of the Ca(OH)2 impregnated biomass. Thus, the
proposed method was effective for reforming wet biomass into a valuable feed stock
for co-processing with coal.
14-4
Catalytic Hydrothermal Gasification of the Organic Compounds Dissolved In
Waste Water from Coal Dewatering and Industrial Processes
Hiroyuki Nakagawa and Kouichi Miura
Kyoto University, Japan
Atul Sharma
Shiga Prefecture Industrial Support Plaza, Japan
Development of efficient dewatering and upgrading process for brown coal utilization
is very necessary. However, some organic compounds are inevitably leached out in the
water from the coal giving a significant amount of waste water containing organic
compounds in small concentration. Similarly, several industrial processes produce
huge amounts of waste water that contain small concentrations of organic compounds.
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
gasify organic compounds in the waste water from brown coal dewatering process and
industrial processes. The process removes the organic compounds by gasifying them
into caloric gases like methane and hydrogen. The investigations were focused on the
efficiency of the Ni/carbon catalyst in terms of carbon conversion, catalyst deactivation
due to sintering, nickel metal load of the carbon catalyst, effect of presence of alkali
metals in the waste water. The preliminary results showed that up to 80 % carbon
conversion can be achieved at 350 C, 20 MPa conditions. The sintering or deactivation
time was about 50 hrs under laboratory conditions and was mainly due to the increase
in the crystallite size of nickel particles. Various techniques such as XRD, TEM were
used to investigate the sintering process and reaction mechanism.
14
14-5
Tar Evolution in Steam Gasification of Biomass
Masahiro Suzuki, Yousuke Yamaguchi, Takeshi Furusawa, Atsushi Tsutsumi
The University of Tokyo, Japan
Steam gasification of biomass was studied using newly developed continuous cross-
flow moving bed type differential reactor. In the conventional methods such as
thermogravimetric analysis (TGA), drop tube reactor (DTR) and fixed and/or fluidized
bed reactor (FB), it is impossible to investigate the time profile of tar evolution in
steam gasification of biomass with rapid heating in continuous feeding condition.
Thus, we have developed a continuous cross-flow moving bed type differential reactor.
In this apparatus, a quartz glass half tube reactor is divided into six compartments
whose gas flows were independent in order to collect gas and tar separately and
analyze their compositions in each compartment according to their residence time
while biomass sample (cellulose, lignin) is continuously fed into the reactor. Steam
with Ar carrier gas is fed into each of the compartment that is heated by an image
furnace. Char is also collected at the end of the reactor. In this study, the time profile of
tar evolution in gasification of biomass was investigated. It was found that there is an
induction period for 15-20s before weight decrease of cellulose begins in steam
gasification at 673 K, suggesting the existence of intermediate products. Produced tar
was cellulose with low degree of original cellulose. The main comportments were
levoglucosan, cellobiosan, and cellotriosan. We also analyzed producing tar in steam
gasification of lignin and biomass. Based on the results, we proposed a new
mechanism of tar evolution in steam gasification of biomass.
SESSION 15
HYDROGEN IN THE FUTURE 3: HYDROGEN PRODUCTION
TECHNOLOGIES (DIRECT & INDIRECT)
15-1
Novel Technology of Efficient Storage and Transportation of Coal-Derived
Hydrogen by Using Organic Hydrides such as Cyclohexane and Decalin
Masaru Ichikawa
Hokkaido University, Japan
The novel technology of hydrogen storage and supply infrastructures using liquid
organic hydrides such as cyclohexane and decalin recently emerge for 21st century
hydrogen eco-energy society connected with reliable PEM fuel cell society. Organic
hydrides such as cyclohexane and decalin are appreciated as the feasible carrier
materials with the highest energy density for hydrogen storage and transportation in
terms of weight and volume among other techniques including carbon nano-tubes,
metal alloys and even high pressured cylinders (250-350 atm). A new catalytic
converter of cyclohexane (or decalin) are developed with carbon-based Pt bimetallic
catalysts for efficient storage and supply of hydrogen at moderate conditions, 6
m3H2/h at 150-250oC, 1-5 atm, and 20 m3/h H2 at 250-350oC, 1-2 atm,
respectively. An efficient and cyclic conversion of cyclohexane-benzene
(methylcyclohexane-toluene or decalin-naphthalene) is conducted by the pulse-spray
reactor to optimize the spray-size (ml/s), pulse interval (s) and reaction temperature
to achieve the stable catalytic performances and maximum rates of hydrogen storage
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.
This is the promising sustainable technology of zero CO2 emission and efficient
storage and transportation of large-scale hydrogen derived from coal, oil refinery and
COG (coke oven gas) using organic hydrides such as cyclohexane and decalin which
are economically and feasibly connected with the conventional infrastructures such
as tank-lorry, railway and ship transportation systems.
15-2
Application of In-Situ CO2 Removal Gasification to Woody Biomass for
Hydrogen Production
Tomoaki Minowa, Toshiaki Hanaoka and Shinji Fujimoto
National Institute of Advanced Industrial Science and Technology, Japan
Kenji Kamei, Shi-Ying Lin and Michiaki Harada
Center for Coal Utilization, Japan
In-situ CO2 removal gasification has been developed for the hydrogen production from
coal, named HyPr-RING in Japan. The overall reaction is as follows:
Carbonaceous material + H2O + M H2 + MCO2, at high temp. and high press.
Here, M is CO2 sorbent. We started the project to apply the in-situ CO2 removal
gasification to produce hydrogen from woody biomass.
The powder of Japanese Oak was gasified into clean gas in the steam of 600 to 700 C
and 0.5 to 5 MPa using calcium hydroxide as a CO2 sorbent in a batch type autoclave,
and clean gas, mainly hydrogen, was obtained at the yield of 1.5 L/g-wood. The clean
gas contained 97 vol% of hydrogen, 3 vol% of methane and 0.1vol% of hydrocarbons.
No carbon dioxide and carbon monoxide was detected in the clean gas, and carbon
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
10 kg of wood a day, and the reactor was placed into a pressure vessel. We will
present obtained results at the Conference.
15-3
Catalytic Steam Reforming of Coal-Tar Derived Oil
Atsushi Ishihara, Daisuke Yamada, Ida Nuryatin Finahari, I Putu Sutrisna,
Eika Weihua Qian and Toshiaki Kabe
Tokyo University of Agriculture & Technology, Japan
One of the promising approaches to the production of hydrogen from coal is catalytic
steam reforming of a liquid product (also known as coal-tar), which is generated from
coal via carbonization. Generally, coal-tar is divided into light oil, middle oil, creosote
oil, anthracene oil and pitch by fractional distillation. The oils are predominantly a
mixture of benzene from light oil, and phenol, cresol and naphthalene from middle and
creosote oil. However, the reforming of oils including aromatic ring would bring about
a problem, which is the carbon deposition taking place preferentially on the catalyst.
Thus, the present study has concerned to investigate a series of catalysts having
reasonably high activity and stability for production of hydrogen from coal-tar
fractional distillation oils. In this study, a variety of research Ni, Ru, Ni-Ru catalysts
were prepared and their catalytic performance in the steam reforming of m-cresol
derived from middle and creosote oil were tested.
The precursor, including Ni, Ru, or combination of Ni-Ru, was supported to a mixture
of MgO, La2O3, and Al2O3. In the investigation of the effect of Ru loading added to the
Ni catalyst, it was found that the presence of Ru strongly enhances the catalytic
performance of the Ni-based catalyst when increasing Ru loading up to 2wt%. Effect
of Ni loading to the Ni/Ru/Al2O3(M1) catalyst system was further investigated to
provide the optimal composition of Ni-Ru on the support that has an excellent catalytic
performance in the steam reforming of oxygenated compounds present in the bio-oil. It
was found that Ru monometallic precursor (concentration of 2wt%) was not an active
species in the steam reforming of oxygenated compounds, and that addition of nickel
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
tested at 750oC. In agree with general observations of the use of Ni monometallic
catalyst, the present study confirmed that deactivation of such catalyst due to the
carbon deposition reaction already occurred during the reforming of the oxygenated.
On the other hand, a reasonable high resistant on the carbon deposition for the
reforming of m-cresol was given by the 2wt%Ru 15wt%Ni catalyst system. An effort
in improving the strength of the catalyst support with this catalyst system was also
done, and the catalyst showed significant increasing in the stability of the reforming of
oxygenated aromatic compound.
15-4
Production of Hydrogen and Other Value Added Products from Waste Tire
Pyrolysis
Ana M. Mastral, Ramon Murillo, Maria S. Callen, Jos M. Lpez, Elvira Ayln and
Maria T. de la Cruz
Instituto de Carboqumica, CSIC, Spain
Nowadays, more than 6 million tones per year of waste tire are being produced all
around the world. This waste material generation produces a growing concern related
to the economic and environmental problem associated with this non-biodegradable
residue. The most commonly used vulcanized tire rubber is a styrene-butadiene
copolymer (SBR) or a mixture of natural rubber and SBR. In addition to these
materials, carbon black is present in tires and used to strengthen the rubber and aid
abrasion resistance. In a typical tire composition, around 62% in weight would be
rubber material and 30% in weight would be carbon black (2-5). The remaining 8% in
weight would be comprised of ZnO, extender oils and fillers added during tyre
manufacturing.
On the other side, hydrogen is a well-known fuel that in the future must be leading the
energy production sources because of its high calorific value without generating
pollutants or residues. Special efforts have been applied to the production of hydrogen
from waste materials because in this way, not only a residue is eliminated but a clean
energy is obtained as well.
Ultimate analysis of rubber tire shows that its hydrogen content is around 8%, a value
higher than the found in fossil fuels commonly used for hydrogen production via
gasification. In this communication, the recycling of waste tires through fast pyrolysis
in a fluidized bed reactor is considered. During the fast pyrolysis process, and
depending on the experimental conditions used, a gas with a remarkable content on
hydrogen can be produced. In addition, oils are produced that can be used as
transportation fuels or, because of their high hydrogen content (around 11 %), as raw
material for additional hydrogen production through thermal cracking, partial oxidation
or steam reforming.
15-5
Hydrogen Production Technology by Partial Oxidation and Steam Reforming of
Tar from Hot Coke Oven Gas
M. Onozaki, K. Watanabe, T. Hashimoto, H. Saegusa and Y. Katayama
The Institute of Applied Energy, Japan
15
Hydrogen production technologies with high performance and low cost are highly
requested to encourage hydrogen utilization. Coke oven gas so called COG containing
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
ovens is cooled down by means of aqueous ammonia quenching and the pressurized
cool COG is utilized as fuel or hydrogen source after tar contained in the gas is
separated in iron works.
This paper introduces a new hydrogen production technology by means of partial
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
sensible heat of the hot gas is utilized for the reaction. Also, the sensible heat of the
converted gas can be recovered.
The hot COG was produced from a test unit of coke, the capacity of which was 80 kg
of coal, and was introduced into an experimental unit with the furnace where oxygen
and steam were injected. Over 98 % of total carbon in the hot COG was partially
oxidized and reformed with steam and converted to H2 and CO gases. About 1
Nm3/h of hydrogen was continuously produced for five hours in this experiment. In
addition, the high-temperature steam produced by means of combustion of hydrogen
and oxygen gases were used instead of oxygen and steam to convert tar to H2 and CO
gases. The feasibility study based on the experimental results showed that hydrogen is
produced by this technology with lower cost than separation from cool COG.
SESSION 16
COAL UTILIZATION BY-PRODUCTS 3: COAL ASH UTILIZATION
TECHNOLOGIES
16-1
Use of Coal Combustion Product Grout to Construct a Grout Curtain Around an
Abandoned Coal-Mining Shaft to Reduce Ground Water Infiltration into the
Mine Pool
Gary R. Fuhrman
Western Maryland Resource Conservation and Development Council, USA
The Kempton Man Shaft Project is one of several projects sponsored by the Maryland
Department of Natural Resources Power Plant Research Program, and funded by the
US Department of the Interior Office of Surface Mining, to demonstrate the
replacement of concrete with coal combustion products (CCPs) from nearby coal-fired
power plants. The Kempton Mine complex was an active deep mine during the period
1912 1950. The mine tunnels, varying in depths of 130 feet to 420 feet below grade,
lie beneath an area of approximately 12 square miles spanning portions of West
Virginia and Maryland. Most of the tunnels are flooded by surface water intrusion or
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
the Potomac River. The Man Shaft, which lowered miners to the mine tunnel
entrances, is 420-feet below grade.
Exploratory boreholes drilled around the Man Shaft revealed horizontal fractures in
siltstone bedrock at depths between 120 feet and 140 feet. The seepage of ground
water into the Man Shaft from these fractures is estimated to be 45,000 to 145,000
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
water to flow into the mine pool. The project objective was to reduce the amount of
ground water lost to the mine pool by installing a grout curtain to a depth of 160 feet
around the shaft using a cementitious grout prepared from coal combustion products
from nearby power plants.
Because the available coal fly ash was a Class F ash (low Calcium) ash from a
fluidized bed furnace, which mixes the coal with limestone prior to burning, was added
to ensure proper hardening.
Grout was injected into 28 6-inch holes, cased to 20 feet and filled to 150 160 feet
using a tremie line. For most holes, good communication between adjacent holes was
observed, indicating the flow of grout through the fractured siltstone was occurring.
Since completion of the grouting, a combination of potentiometric surface monitoring
and dye tracing activities is being used to evaluate the effectiveness of the grout curtain
in limiting the flow of ground water into the Man Shaft. In addition, core samples will
be taken to evaluate the bonding integrity of the grout and rock.
16-2
Application of Some Coal Treatment Products for Reclamation of Localities in
the North Bohemian Brown Coal Basin
Michal Rehor and Marcela Safarova
Brown Coal Research Institute, Czech Republic
Vratislav Ondracek
Severoceske doly, Czech Republic
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
without which the Czech Republic would become completely dependent on energy
source imports. Currently, more than 70% of brown coal deposits are mined in the
North Bohemian Basin. Naturally, open brown coal mining has led to extensive
damages on the landscape. Therefore, land reclamation works have grown on their
importance in the present times.
In majority, brown coal mining is carried out in four main localities that are completely
different in terms of geological conditions and partly parameters of the extracted coal
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
Basin lies in extremely unfavourable properties of the loose-fill waste rock deposited
on majority of the dump bodies. These are mainly waste rock of the overlying strata
and brown-coal bed strata. Main loose-fill materials on the waste deposits are sands,
kaolinitic clay sands and kaolinitic - illitic clays. The foreign matter in the loose-fill
waste rock are organic coal mass, siderite and pyrite. Those waste rocks are
mechanically unstable against wind and water erosion, and due to on-going weathering
they get an unfavourable, acid (or phytotoxic) character.
The coal mass on the surface of the land-reclaimed localities complicates both the
technical as well as biological land reclamation. Some products of coal mass
processing are successfully applied in improving land-reclamation utilization of the
concerned localities. In the conditions of the North Bohemian Basin, these are mainly
oxyhumolites and power unit ashes. Acquired humitanes are very well utilizable for
land reclamation both separately as well as in the mixture with other fertilizers. Power
unit ashes are experimentally applied as land reclamation additives in test areas along
with extremely heavy-grained overlying clays. The objective of the experiment is
improvement of the grain-distribution of the waste rock material. The submitted paper
evaluates the application method of humitanes, power unit ashes and some other
substances in connection with coal mining in the land-reclaimed areas of the North
Bohemian Basin. The application success is illustrated by results of a long-term
monitoring of physical, mineralogical and chemical pedological parameters of the
waste rock from the individual test areas.
16-3
Pulverised Fuel Ash in Underground Minefills A Successful Indian Endeavour
Vimal Kumar and Mukesh Mathur
Technology Information Forecasting & Assessment Council, INDIA
Indian underground coal mining industry, which has been riddled with problems of
less recovery of coal due to obsolete methods, equipments, machinery etc., is now
facing another problem- this time, shortage of sand for mine-stowing. Sand reserves in
the river-beds are depleting and the mining industry is desperately looking for an
alternative material to river sand for filing into their voids. The laboratory test, trials
and field demonstrations have proved Pond ash is a good substitute for sand for
stowing into underground mines.
Fly Ash Utilisation Programme (FAUP) of Technology Information, Forecasting &
Assessment Council (TIFAC), Department of Science & Technology (DST),
Government of India, adding to its credit of firsts, has successfully demonstrated
stowing of pond ash in underground mines in India. About 10,000m3 of pond ash from
a captive Thermal Power Station of Heavy Water Plant (HWP), Manuguru (Andhra
Pradesh), was stowed in the underground mine of the Singreni Collieries Company
Ltd. (SCCL), Manuguru. The satisfaction expressed by the Directorate-General of
Mine Safety (DGMS), Hyderabad, the regulating agency, over the demonstration
staged by the Central Mining Research Institute (CMRI), Dhanbad, at the site has
paved the way to adopt the technology on a large scale and in its wake, take up the
major task of stowing 1.5 lakh m3 pond ash in the days ahead.
The demonstration came through a detailed laboratory programme and field work
taken up by the agencies mentioned earlier. Parameters under the scanner during the
demonstration included load on the barricades, water filtration through these
barricades, water percolation through pond ash bed, environmental impact of water
draining from the barricades as also the chemical analysis of the pond ash, inlet water
and discharge water collected through these barricades. The effect of pond ash
stowing on neighbouring work places that of water draining from barricades on floor
coal of galleries and also that of main sump and pumps installed for pumping the
discharge water were studied during the demonstration at Manuguru. The results were
encouraging!
Persons could walk freely over the pond ash bed within half an hour of stowing. Water
seepage through the barricades was found to be good as were the results of the
chemical analysis of water. It was observed that once the pond ash sealed to full
height of the barricade, water percolation through the barricade reduced and started
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.
Settlement of fine particles of ash and their discharge from the barricades was a matter
of concern during the initial stages of development of pond ash stowing technology.
These issues were addressed with the use of an additive. The leachate was tested at
Central Fuel Research Institute (CFRI)-Dhanbad, and also at Nuclear Fuel Complex
(NFC), Hyderabad. No adverse impact was found and the additive had its way.
The demonstration of the technology and experience gained while its application,
buoyed-up the confidence of SCCL the user agency, and DGMS the regulatory
body. The confidence is also mirrored through replication of the technology at Western
Coalfields Ltd. (WCL), Chandrapur, where pond ash from Chandrapur Super Power
Thermal Power Station is being stowed in the Durgapur Raitwari Colliery,
Chandrapur.
Considering the fact that the country today produces about 105 million tonnes of coal
ash and there is also dearth of sand owing to its application in expanding civil
16
constructions, the technology of stowing pond ash in the mines developed,
demonstrated and approved is finally here to be adapted.
16-4
Installation of Production and Transport of Ash and Water Dense Phase Slurry at
Patnow Power Station
Andrzej Kowalski
BSPiR Energoprojekt-Katowice SA, Poland
Tadeusz Zawacki and Marek Tymoszyk
Zespol Elektrowni Patnow-Adamow-Konin SA, Poland
Marek Tymoszyk
Elektrownia Patnow, Poland
The paper presents the project consisting in construction of installation and production
of dense phase ash and water slurry in Patnow Power Station, the slurry serving the
purpose of reclamation of brown coal abandoned workings. Basic conditions
constituting a basis for creation of this project ware discussed, operation description
and parameters of installations and equipment are presented as well as assessment of
the operation and double ecological effect.
Presented are also the most important parameters of dense phase slurry upon its
depositing in the abandoned workings with particular regard to the environment
protection requirements.
16-5
Development of an Engineered Soil Using Coal Processing Waste and Combustion
Byproducts
Yoginder P. Chugh and Greg Balk
Southern Illinois University, USA
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
amendment. Such a soil would have applications in mine reclamation, landfill liners,
etc. and would be highly cost effective. This research has developed an engineered soil
based on fine coal (-100mesh x 0) processing waste (FCPW) from coal processing
plants, fluidized bed combustion (FBC) fly ash and animal waste (AW). The developed
soil is environmentally benign, and is a stabilized material suitable for reclamation and
vegetation. Its commercial use will minimize environmental impacts associated with
byproducts disposal as well as reduce ponds for FCPW, landfill space for CCBs
disposal, and a reduction of surface runoff of AW into surface and subsurface water. It
can also provide the required topsoil (TS) for mine reclamation and other similar
applications according to regulatory agencies guidelines for chemical, elemental and
contaminant concentration criteria.
The developed soil contains FCPW (75-85%), FBC (3-12%), and AW (2-7%) from a
mine and power plant in central Illinois, and AW from southern Illinois. The
performance of the engineered soil was demonstrated in the laboratory as well as in the
field. Vegetation growth and yield for the ES was equal to or better than the top soil
(TS). It was also noticeably better than the combination of FCPW and FBC only
without the addition of AW. The FCPW alone showed poor growth and yield.
Initial pH of ES was high with readings greater than 12.0 for ES involving FBC. The
pH decreased rapidly to values below 8.0 in 3-4 weeks.
Leachate water showed no toxic levels of the heavy metals As, Cr, Cd, Pb or Hg.
Concentrations of SO4, Ca, Na and Cl were high and slightly beyond Class II
groundwater standards for all ES treatments except for the TS. All other elements for
the developed ES were found to be within Class II groundwater standards.
Harvested vegetation was analyzed for plant essential nutrients and heavy metal
concentrations. The heavy metals assayed were As, Cr, Cd, Pb and Hg.
All ES samples had large amounts of plant essential nutrients.
Cr, Cd, Pb and Hg were well below toxicity levels. However, all four ES treatments
showed values higher (up to three times) the standard limit. The effects of these on
wildlife through ingestion of plant tissue are not certain.
Comparing pre-growth soil to post-growth soil, concentrations of Ca, S, B, Fe and Mn
were still high. The abundance of these elements was also found in the tissue and the
water except for boron, which was not abundant in the water.
SESSION 17
ENVIRONMENTAL CONTROL TECHNOLOGY 3: PARTICULATE
MATTER & TRACE ELEMENTS
17-1
Release Behavior of Trace Elements from Coal during High Temperature
Processing
Yasushi Sekine, Kunihisa Sakajiri, Eiichi Kikuchi and Masahiko Matsukata
Waseda University, Japan
Coal includes so many kinds of trace elements with several 10 ppm concentrations.
They volatilize at the combustion or gasification of coal, and would be released into
the atmosphere. In this study, we investigated how the reaction temperature and
existence of the steam in the reaction atmosphere influence the releasing behavior of
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
coal in each temperature was measured by ICP. As for Zn, Se, Sb, Hg and Pb, residual
ratios in coal changed with the rise of temperature. A change of residual ratio was not
observed about other elements. Residual ratios of Zn and Pb decreased at 1173 K or
more, irrespective of existence of steam. Even if it was in the presence of steam,
residual ratios of Zn and Pb were same as the case where it was in the absence of
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
the presence of steam. This is considered because it released from coal via a hydroxide
form under low temperature region. However, residual ratios of Hg increased in the
presence of steam conversely. We considered that the existence form of elements in the
coal has correlation to the emission behavior.
17-2
Analysis of Arsenic, Boron and Some Other Elements in Coal Fly Ash by X-Ray
Photoelectron Spectroscopy
Akira Ohki, Yuka Sakaguchi, Tsunenori Nakajima and Hirokazu Takanashi
Kagoshima University, Japan
Surface characterization of coal fly ash (CFA) was carried out by use of X-ray
photoelectron spectroscopy (XPS), especially focusing on the occurrence of As and B.
XPS spectra of CFA at 48.5 and 195 eV were assigned to As(3d) and B(1s),
respectively. The molar ratios of As and B as well as some other elements (Al, Ca, Fe,
and S) normalized to Si were obtained from XPS analysis (MR-X) and bulk analysis
(MR-B). For a certified reference material of CFA (NIST-1633b), the MR-X/MR-B
ratios for As and B were 24 and 55, respectively, suggesting that these elements are
highly enriched on the surface of CFA. Over 20 CFA samples were analyzed, and the
MR-X/MR-B ratio for As varied from 13 to 274, while the ratio for B, from 6 to 55.
The concentration depth profile of these elements in NIST-1633b was studied by using
Ar+ sputtering with the XPS. The MR-X/MR-B ratio for As gradually decreased when
the sputtering proceeded, and the ratio reached 10 after 10 min sputtering; the
sputtering is presumed to give 10 nm depth profile. Also, the MR-X/MR-B ratio for B
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
surface of CFA.
17-3
Compositions and Leaching Behaviours of Combustion Residues
Nabajyoti Saikia, Yuji Sakaguchi, Shigeru Kato and Toshinori Kojima
Seikei University, Japan
Combustion residues collected from different incineration processes create a major
environmental problem as these materials contain high amounts of toxic elements.
These materials are generally used in land fillings or used as construction materials.
But before the use in construction purposes or in land fillings, some pretreatments are
necessary in order to remove the soluble salts and to extract the toxic elements.
Knowledge of the leaching behaviours of these wastes is very important for evaluation
of such treatment methods. To study the leaching behaviours of three combustion
residues namely fly ash samples collected from coal combustion power plant (FA),
municipality solid waste incineration plant (MSWI ash) and sewage sludge
incineration plant (SS ash), column leaching experiments at two different pH (pH = 6
and 1) were conducted. The leachantes were analyzed for pH and the major elements:
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
characterized by XRD and SEM-EPMA techniques. From the results it was observed
that the soluble salts content in the MSWI ash are higher than those in other two
residues and the halite and sylvite were the major soluble salts in MSWI ash. The
alkalinities of the residues affect the pH of leachants and the order of alkalinities of
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
concentrations of major and minor elements present in the leachants fractions collected
at different time intervals were compared with the total contents of the elements in the
residues to determine the maximum leachable fractions.
17-4
PPT Level Detection of Mercury using Diamond Rotating Disk Sensor Electrodes
A. Manivannan and M. S. Seehra
West Virginia University, USA
E. Granite
US DOE, NETL, USA
A. Fujishima
Kanagawa Academy of Science & Technology, Japan
We report determination of mercury ions at the ppb levels using highly boron doped
diamond (BDD) films electrodes by differential pulse voltammetry (DPV). DPV
experiments were performed in nitrate, thiocyanate and chloride media. Investigation
in chloride medium is important since practical samples always contain chloride
impurities. The formation of calomel in chloride medium is avoided on the BDD
surface by the co-deposition of 3ppm of gold during DPV detection. Excellent linear
calibration plots have been obtained in all media for ppb ranges. Mercury in the 0.1-50
17
ppb range has been detected in real samples (KCl impinger solutions) prepared from
flue gas released by a pilot-scale coal fired combustion facility. A portable instrument
has also been used for the detection of mercury efficiently. BDD mounted in rotating
disk electrode (RDE) system together with gold co-deposition has been demonstrated
to detect mercury with higher sensitivity and reproducibility.
17-5
Synthesis of Organic Calcium-Based Sorbent from the Biomass Pyroligneous
Acid and Its De-SO2 and De-Cl Capture Capabilities during the Combustion of
High-sulfur Coals
Yoshihiko Ninomiya and Lian Zhang
Chubu University, Japan
This paper first aims to evaluate the possibility of synthesizing organic calcium
through the use of pyroligneous acid and raw limestone. The pyrolignous acid was the
byproduct produced by pyrolysis of woods at the temperature around 200oC.
Limestone has the particles as large as 500-1000 m. The factors affecting this reaction
were investigated including the pyroligneous acid type and the reaction conditions as
well. Secondly, two low-rank coals were impregnated with the calcium-enriched
pyroligneous acid to evaluate the possibility of in situ desulfurization and capture of
the vaporized trace elements in the combustion furnace. The experimental results
suggest the feasibility of reaction between pyroligneous acid and limestone under mild
conditions. The saturated solubility of calcium in the pyroligneous acid was obtained
in 30 minutes at 50oC, which is mainly controlled by the acidity of the pyroligneous
acids. The soluble calcium within pyroligneous acid is in form of calcium acetate
having a low decomposition temperature around 400oC, far lower than that of raw
limestone being about 700oC. Since of its solubility, calcium within pyroligneous acid
was loaded readily on the coals, forming the ultrafine particles in the impregnated coal
matrix. During coal combustion, the loaded calcium underwent quick decomposition
prior to char combustion, and subsequently, the formed ultrafine calcium oxide
captured the evolved sulfur oxide and vaporized trace elements.
SESSION 18
COAL CHEMISTRY: 2
18-1
About Kinetics of Creation of Coal Coking Vapor-Gas By-Products
Gennadiy Vlasov
JSC, Ukraine
Vadim Barsky
Ukrainian State University of Chemical Engineers, Ukraine
Demand flow for chemical by-products of coal coking requires sufficiently quick
reorganization onto preferred production of definite individual substances or in the best
case, mixtures with preassigned composition.
In present work is explored gassing kinetics as major step of search, of directive effect
onto vapor-gas by-products of high-temperature coal charge pyrolysis.
As a result of process theoretical analysis mathematical expression for volume
outgassing rate during coking interval was found.
Function structure and parameters were verify according to laboratory and industrial
data and used as base of kinetic description of direct coke-oven gas individual
components.
18-2
First Application of Al MQMAS NMR at 16.4 T to Inorganic Matter in Natural
Coals
Koji Saito and Koji Kanehashi
Nippon Steel Corporation, JAPAN
Al multiple quantum magic angle spinning (MQMAS) technique at high magnetic field
(16.4 T) averaging the second-order quadrupolar interaction that cause the spectral
broadening and splitting was applied for the first time to the structural analysis of
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
cancellation of the second-order quadrupolar effect was not accomplished perfectly
although 3QMAS spectra gave better resolution than conventional magic angle
spinning (MAS) spectra. On the other hand, higher magnetic field, 16.4 T, greatly
improved 3QMAS spectral resolution compared with 7.0 T, hence it facilitated the
assignment of some minerals. Moreover, since 3QMAS at 16.4 T led to signal
enhancement by a factor of about 4 compared to at 7.0 T, it is very useful for the
analysis of inorganic matter in natural coals that have low concentration of aluminum
(~ 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
unchanged between 3QMAS and 5QMAS although the excitation of 5 quantum
coherences is less efficient than for 3 quantum coherences. It is concluded that the
combination of MQMAS techniques with high magnetic field is a very effective for
characterization of inorganic matter in natural coals and especially well suited to the
analysis of clay minerals that are low crystallinity in contrast to X-ray diffraction
(XRD).
 18-3
Geochemistry of Mercury in Indiana Coals and Their Fly Ash; Insights from a
Sequential Extraction Technique
Agnieszka Drobniak and Maria Mastalerz
Indiana University, USA
Rosalice Buehrer and Gabriel Filippelli
IUPUI, USA
Coal from two of Indianas economically important Pennsylvanian coalbeds, the high-
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
with regard to mercury geochemistry. Both coals are of high-volatile bituminous rank;
mercury (Hg) content is 0.13 mg/kg in the Springfield and 0.03 mg/kg in the Danville.
Study of the combustion products of these coals show relatively high Hg
concentrations in the low temperature fly ash, which is especially pronounced in the
Danville coal (Mastalerz et al., in press). To better understand the fate of Hg during the
combustion process, a sequential extraction procedure, adapted from Kolker and others
(2002), Bloom and others (2003) and Sladek and Gustin (2003) was used to evaluate
Hg affinity to four geochemically distinct fractions. In step I, ammonium acetate
(CH3COONH4, or AmmAcet) was used to decompose some of the least resistant
organic matter and some of the carbonates. In step II, the residue of step I was further
leached with HCl, removing remaining carbonates, Fe oxides, sulfates, monosulfides,
and certain chelated organic compounds (Kolker and others, 2002). In step III, HF
dissolved the silicate minerals, and finally, in step IV, HNO3 was added to decompose
disulfides, especially pyrite, any remaining phosphates, and refractory organic matter.
Preliminary findings show that Hg content tends to be lowest in the HF residue and
highest in the HNO3 residue, with variable amounts associated with the AmmAcet and
HCl. This result suggests that most of the Hg is associated with disulfides, particularly
pyrite, and perhaps refractory organics, whereas negligible amounts of Hg appear to be
associated with silicates, including clays. Hg ranges from 0% to 57% Hg in mobile,
water-soluble fractions, and from 0% to 42% Hg in carbonates, Fe oxides,
monosulfides, and organic matter. Continuing work involves refining the sequential
extraction analysis and comparing geochemical results between raw coal and fly ash to
elucidate the geochemical fractionation of Hg during combustion.
18-4
Determination of Trace Elements in Coal by Microwave Digestion with HNO3
Alone Followed by ICP-MS
Jie Wang, Tetsuya Nakazato, Kinya Sakanishi, Osamu Yamada, Hiroaki Tao and Ikuo
Saito
AIST, Japan
Inductively coupled plasma mass spectrometry has a capability of simultaneous
determination of multi-elements with excellent reliability and sensitivity, and it is
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
digestion with chloride-based acids and HF causes isobaric interference and corrosion
problems in the following instrumental analysis. In this context, the present study is to
develop a new microwave method with HNO3 alone compatible with ICP-MS analysis.
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
than 10% of carbon remained in the resultant transparent solution. Li, Be, V, Cr, Mn,
Co, Ni, Zn, Ga, As, Sr, Cs, Ba, and Pb were determined by a common ICP-MS
analysis, and Cd, Se, and Hg were determined by flow injection (FI)-ICP-MS, since
the latter three elements in coals were extremely low in the concentration and beyond
the limits of quantification by the common ICP-MS. It was interestingly found that all
these trace elements were extracted quantitatively with reference to three standard
coals (SRM1632c, BCR180, and SARM19).
18-5
Mineral Characteristics of the Fouling Deposit in the Entrained-Bed Gasifier
using DTF
Won-Cheol Shin and Hyung-Taek Kim
Ajou University, Korea
IGCC (integrated gasification combined cycle) is recognized as second-generation
power plant technology since firstly they can provide higher efficiency compared to
the conventional pulverized coal combustion facility, and secondly they produce only
minimal amounts of pollutants well below the current environmental regulations.
Particularly, ash component of coal is discarded as slag form which is
environmentally-stable so that heavy metal elements in the coal ash cant be reachable
into ground water. However, coal ash is bubbled inside gasifier during the high
temperature operation of slagging condition and fly slag is carried with product gas
through the heat exchanger section. So, the high temperature fouling is occurred
frequently at the section of flue exit-channel and heat exchanger.
This paper presents an experimental approach to study the effect of mineral
characteristics on ash deposition using a vertical DTF (drop tube furnace) in various
temperature conditions (500 ~900 ). Also, it aims to explain deposition
characteristics according to the shape of deposit probe surface. A laminar DTF is
18
utilized during the experiment to simulate ash deposition condition inside the channel
of gasifier. Several samples of pulverized coal are introduced at the top of DTF with
primary O2 and secondary N2 flow. The feed rate of coal sample is about 0.3g/min and
the reacted ash samples are collected on the funnel-shaped deposit probe at the bottom.
After the experiment, weight analysis is carried out with deposit samples. Sample of
swage sludge is also experimented with DTF for the comparison of deposition
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
to define the chemical interaction between ash particles.
SESSION 19
COMBUSTION TECHNOLOGIES 4: BEHAVIOR OF MINERAL
MATTER DURING COMBUSTION
19-1
Emission of Particulate Matters from Coal Combustion and Its
Correlationship with Coal Mineral Properties
Lian Zhang and Yoshihiko Ninomiya
Chubu University, Japan
Emission of particulate matters (PM) was studied during combustion of four Chinese
coals. A laboratory-scaled drop tube furnace was used, and the following combustion
conditions were selected: coal feeding rate was about 0.2 g/min, air was used as the
gaseous atmosphere, which had the flow rate around 10.0 l/min, the reaction
temperature was 1200oC, and the residence time was 2.4 seconds in all runs. All the
carbon was burnt completely under above conditions. The PM within the exit gas was
collected by a low-pressure-impactor (LPI) having thirteen stages, which automatically
size-segregated PM from 10.0 to 0.03m. Each size of the collected PM was subjected
to several techniques to quantify its characteristics: XRF was used for the elemental
composition; SEM-EDX was used for structure observation whereas computer-
controlled SEM (CCSEM) and XPS used identifying the chemical species within PM.
Furthermore, the correlationship between coal mineral properties and PM formation
was studied to investigate the impact of raw fuel property. The results indicated a
relatively strong linear relationship between the ash content in raw coal and PM
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
around 2.0m was formed by the direct transferring of inherent minerals within coal,
which is rich in the refractory aluminosilicates. Combustion of the coal rich in
aluminosilicates led to the formation of much the largest PM. The smallest mode
around 0.05m was formed by the vaporization of trace elements, alkali and S/P/Cl. Its
amount was positively affected by the content of inherent sulfur within coals. In
addition, the medium mode around 0.2m was formed containing both refractory and
vaporized elements having the comparable contents, which should be caused by the
agglomeration between these two kinds of elements. Its formation was affected
complexly by the coal property.
19-2
Energy Utilization Biofuels Based On Sludge And Brown Coal
Vclav Roubek, Pavel Kolat, Miroslav ech, Dagmar Juchelkov,
Zdenk Kadlec, Anna Cemerkova
VB-Technical University Ostrava, Czech RepublicEnergy utilization of the
alternative fuels is one of main tasks for development of recoverable sources in EU and
CR. The topics of the research consists of combustion tests in experimental pilot 300
kW stand with atmospheric fluidized-bed located at the Technical University Dresden
Germany for the brown coal, sewage sludge and thermo-analytical studies of bio-fuels.
Main goals may be outlined in the study of conditions for:
Co-combustion of brown coal and biofuels pellets from sewage
sludge, waste and wood, sustainability of fluidized bed combustion.
Evaluation of optimal combustion condition, creation of harmful
solid and flue gas emission. Ratio of coal and biofuel.
Balance of combustion elements choice.
Raw material input analysis and dependence of combustion solid
residues on raw material input.
Relating the experimental and mathematical model results
Chemical composition, crystallographic structures and
mechanical properties of combustion solid products ( ash, fly ash,
deposits ).
Detailed study for mineralogical and chemical composition solid
emission phase.
Leaching tests for combustion solid products.
Comparing the results with EU standardsRecommendations for
suitability of thermal disposal of wastes in the atmospheric fluidized-
bed are presented with minimizing the harmful emissions. It may be
assumed from results that combustion with content of 15 % bio-fuels
is applicable in the large fluidized-bed boilers installed in the Czech
Republic. The combined combustion will enable to fulfil the promise
of the Czech Republic to the European Commission concerning the
development of renewable energy resources by 2010.
 19-3
Direct Observation of Ash Deposition in Pulverized Coal Fired Boiler using CCD
Camera and Model Development for Slagging Prediction
Toru Yamashita and Katsuyuki Tachibana
Idemitsu Kosan Co., Ltd., Japan
Toshimitsu Asotani
Idemitsu Engineering Co., Ltd., Japan
A prediction, prompt detection and suitable control of ash deposition on heat transfer
surface are one of the most important factors for a stable and highly efficient operation
of pulverized coal fired boiler. In order to directly observe a clinker formation
behavior, high temperature-resistant type CCD camera was installed at the 140t/h scale
actual boiler. This observation was quite useful to determine the location and extent of
clinker formation. A model that predicts deposit growth and exfoliation process was
developed to simulate a possibility of clinker formation and its location for each coal
type and operating condition.
19-4
Oxy-Fuel Combustion for Sequestration Ready Co2 Technology Status,
Assessment and Research Needs
Terry Wall, Bart Buhre, Changdong Sheng, and Raj Gupta
University of Newcastle, Australia
The awareness of the increase in the emission of greenhouse gases has resulted in the
development of new technologies with lower emissions and also technologies that can
accommodate capture and sequestration of carbon dioxide. Air fired combustion and
gasification technologies require separation of CO2 from nitrogen after combustion.
IGCC technology can only be used for new power generation plants. For existing
plants there are two options for CO2 capture: removal of nitrogen from flue gases or
removal of nitrogen from air before combustion so as to get a flue gas stream ready to
be sequestered. This present report reviews the status of these options and, in
particular, the retrofit of existing plants.
Traditionally, boilers use air for combustion where N2 from the air dilutes the CO2
concentration in the flue gas, which results in costly CO2 recovery using
monoethanolamine (MEA) scrubbers. An alternative is to reduce N2 using oxygen for
firing instead of air. This technology recycles CO2 flue gas back into to the furnace to
control temperature and make up the volume of the missing N2 to ensure there is
enough gas to maintain the temperature and heat flux profiles in the boiler as far as
possible. This technology is known as Oxy-Fuel technology with Recycled Flue Gas
(RFG).
Studies on the application of this oxyfuel technology to pulverised coal combustion
power plants are presented in this review, including laboratory and pilot scale
experiments and full scale evaluations.
Recent research has given a comparative assessment of electricity production options,
which includes oxyfiring with 95% CO2 capture for ultrasupercritical pf. The report
provides estimates of the cost of CO2 abatement, to conclude that CO2 capture for
oxygen USC reduces the overall thermal efficiency by approximately 9%, due to the
parasitics for oxygen production and flue gas compression/liquefaction, CO2 capture
and compression reduces the sent out electricity by 18-20% for O2-USC, but that
currently and in the near future, oxyfiring would be the lowest cost technology for
carbon capture and storage.
The most immediate application appears is for retrofit of existing pf units to generate
sequestration ready CO2, and would include a heat exchanger to increase the
convective exchange surface area and also a fabric filter for the high efficiency dust
removal required by the compressor. This technology is based on pilot-scale data on
emissions indicating that low NOx is formed in oxy-firing and that SO2 is removed in
the first stage of the compressor/cooler.
The review indicates that purpose built, retrofit ready and retrofitted plant can
accommodate the technology, that the economics are favourable, and that the
technology provides a short-term option for near-zero emission coal technology for
power. From the information, the following aspects require research in order to
evaluate and develop the technology.
The combustion of coal in an O2/CO2 atmosphere, including ignition, burn-out, and
emissions. Flow sheet options and the gas cleaning required. The heat transfer
performance of new and retrofitted plant and the impact of oxygen feed concentration
and CO2 recycle ratio. Assessment of retrofits for electricity cost and cost of CO2
avoided. The impact of the development of new, and less expensive, oxygen
generation technology.
SESSION 20
ADVANCED ENERGY SYSTEMS
19
20-1
Construction of Sophisticated Environmental Controlled 600MW Pulverized Coal
Fired Tower Boiler for Urban Power Station
Toshirou Matsuda
Electric Power Development Co., Ltd., Japan
Shinobu Nakamura, Tetsuya Iwasaki, Yoshitomo Ohkuma and Kanya Muto
Ishikawajima-Harima Heavy industries Co., Ltd., Japan
Replace project of 600MW coal fired unit at J-Powers Isogo Thermal Power Station,
Yokohama Japan, was carried out under operation of existing 265MW2 units to be
replaced. To adopt limited site area condition, IHI Tower Boiler is applied because of
its compact layout and suitable erection procedure. By IHIs Low NOx Combustion
technology, the highest steam condition in Japan and dry-type desulfurization system,
this unit contributes to reduce emission and increase power, giving a new solution for
replacing urban power station.
20-2
Pricing Formulae for Hard Coal Sold To Power Plants and Chp Plants in Poland
Wieslaw Blaschke, Urszula Lorenz and Zbigniew Grudzinski
Mineral and Energy Economy Research Institute, Poland
Hard coal prices are negotiated between producers and users. The price level results
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
parameters like grindability, volatile matter, alkalies or phosphorus contents, etc. are
sometimes also determined in contracts. At the beginning, usually the basic price for a
standard (or reference) coal is negotiated. This standard can be based on calorific
value only or on a number of selected parameters. Deviations from standard coal
quality result in price changes, and should reflect an economic value of coal, while
assessing it from the users (buyers) point of view.
In Polish practice, coal price variation being the result of the quality changes is
determined using pricing formulae agreed during negotiations. Pricing formulae
improve and simplify the conditions of bilateral settlements of coal deliveries.
This paper presents two proposals of new pricing formulae. The first one concerns
steam coal fines that are sold to domestic power plants (or combined heat and power
stations). Price is connected with three main coal quality parameters: calorific value,
sulphur content and ash content. Coal price in the formula is proportional to the
calorific value. The valuation of the sulphur and ash impact on the price is done in
accordance with the costs of obligatory fees (in Polish environmental regulations) for
the emissions of SO2 and PM, and for solid wastes (fly and bottom ashes) storage.
The second solution applies to the terms of sale of specific semi-products of coal like
coking coal inter-layers and fine-grained flotation concentrates. The formula applies to
the usage of those semi-products for energetic purposes. Comparing to the typical
steam coal fines burnt in domestic power plants they are relatively of higher calorific
value and lower ash and sulphur contents. But their volatile matter content is lower and
caking properties are too high. These parameters decrease their value when used as a
fuel for electricity generation in conventional power station. Moreover, flotation
concentrates are fine-grained and are of high moisture content that worsens the flow
properties. These semi-products can, however, be used as components for coal blends
(in adequate proportions). To determine their market value (i.e. price) the new pricing
formula is proposed in the paper.
20-3
Coal Utilization Technology Development at NEDO
Sadao Wasaka, Takeshi Kobashi, Kazuo Kashima, Motoharu Yasumuro and Jyunichi
Ishihara
New Energy and Industrial Technology Development Organization (NEDO), Japan
Recently, as global warming has become a chief issue, efforts to reduce CO2 emissions
are increasingly being reflected in national energy policies. In Japan, the 3Es, Energy
security, Environmental protection and Economic growth, comprise the central
pillars of the governmental energy policy. Given that Japan relies on imports for the
majority of her primary energy supply, Energy security is the most salient issue.
Under these circumstances, New Energy and Industrial Technology Development
Organization (NEDO), commissioned by Ministry of Economy, Trade and Industry of
Japan (METI), is actively developing technologies for utilizing fossil fuels
predominantly coalto facilitate simultaneous achievement of the 3Es.
NEDO develops coal utilization technologies, such as clean coal technologies (CCT),
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
gasification technology realizes high efficiency in syngas production and can be
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.
 20-4
Advanced Pressurized Fluidized-Bed Combustion (A-PFBC) Technology
Hiroyuki Nakata
Electric Power Development Co., Ltd., Japan
Mutsuo Kato
Center for Coal Utilization, Japan
Keiji Usami
Chubu Electric Power Co., Inc., Japan
Yoshihiko Tsuchiyama
Mitsubishi Heavy Industries, Ltd., Japan
The Advanced Pressurized Fluidized-Bed Combustion (A-PFBC) plant achieves higher
efficiency with a technology that increases the gas turbine inlet temperature of the
pressurized fluidized-bed combined cycle (PFBC) system (from 850 deg. C to a level
of 1,350 deg. C). The A-PFBC plant is a new combined cycle system that combines
three fluidized-bed furnaces with a gas and steam turbine. These three furnaces are a
coal gasifier for the partial gasification of coal, a desulfurizer for the removal of sulfur
by limestone-gypsum process at high temperatures, and a combustor-oxidizer for the
combustion of the char residues from the coal gasifier and oxidization of the calcium
sulfide discharged from the desulfurizer. The new advanced system holds promise of
46 % in net efficiency, which is roughly 10% improvement (relative value) compared
with the PFBC.
In the A-PFBC project, the construction of a 15 ton/day coal throughput process
development unit (PDU) plant was completed on the site of Wakamatsu Research
Institute of J-Power in July 2001 and gasification trials of the PDU had been carried
out for a total of 1,201 hours, with a cumulative 18 test runs by March 2003.
The main purpose of these PDU trials was to verify the operating characteristics of the
three-furnace combined system and assess its gasification, desulfurization, and
combustion-oxidation performance. The PDU plant experiments were conducted to
verify the systems operating parameters and to yield essential data for scaling up to a
pilot plant and an industrial plant.
This paper describes the outline of the A-PFBC system and the results of the PDU
gasification trials.
20-5
Technology and Resource Management of IGCC Power Plants in the Indian
Context A Case Study
V.K. Sethi
Rajiv Gandhi Technological University, India
D.N. Reddy
Osmania University, India
P. Rajesh
National Thermal Power Corporation Ltd., India
Integrated Gasification Combined Cycle (IGCC) is emerging as a highly efficient and
environmentally benign technology for power generation from coal, refinery residue
etc. IGCC, after adequate demonstration world wide, is now poised to compete with
the conventional power generation technologies and is the 21st century technology to
meet the stringent environmental regulations more efficiently and economically than
the pulverized coal fired power generation, even for inferior fuels having high ash,
high sulfur and low calorific values.
There is a very large potential for coal gasification application in Indian Power and
Industrial heating sectors. Extensive tests have been carried out by Indian R&D
institutions on high pressure moving bed and high pressure fluidized bed systems using
high ash coals. Both technologies have been shown to be capable of accepting Indian
coals without much operational problems. The initial high cost of the gasification route
for power and heating may be completely offset by the environmental benefits and
more extensive application through generation of value added products like Hydrogen,
Sulphur in Co-production mode etc.
With regard to the potential for development of IGCC technology, some of the key
issues that need to be addressed by developers include Technology as well as Fuel
related issues. The paper covers a methodology and strategy of Transfer of Technology
(TOT) from a developed economy to India for an IGCC plant based on high ash
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
systematic transfer of technology, there is a need for standardization of product
amongst various indigenous manufacturers, evaluation of foreign collaborations so that
viable industry (self reliant) structure is built over a reasonable period of time.
The methodology used for Transfer of Technology discussed in this paper consists of
breaking down each major component / sub system into constituent production
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
IGCC technology viz. Air Blown & Oxygen Blown Gasifiers through systematic
Transfer of Technology have been evaluated both at a normal pace and with
accelerated pace. The model developed for evaluation of velocity of transfer of
technology is generic in nature and can be updated for variety of applications and other
Clean Coal Technologies like Supercritical, Ultra Supercritical and Fluidized Bed
Combustion based Power Generation.
20
SESSION 21
HYDROGEN IN THE FUTURE 4: HYDROGEN PRODUCTION
TECHNOLOGIES & SEPARATION
21-1
Reforming of Methanol in Supercritical Water for High-Pressure Hydrogen
Production
Katsuaki Tadokoro, Nobuyuki Matsumoto and Takayuki Azuma
Osaka Gas Co., 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 FCV technology development, the high-pressure hydrogen tank system is a
promising way to storage hydrogen in the FCV. However much work is required to
compress the produced hydrogen gas and much electricity is required to get the work.
Aiming at more efficient method for producing high-pressure hydrogen, the steam
reforming of methanol in supercritical water was proposed as a novel system. The
system has a main advantage that the required compression work is quite little due to
the low compressibility of the liquid fuel.
The fundamental experiments on hydrogen production in supercritical water were
investigated in continuously operated tubular reactor made of stainless steel 316. The
metal catalyst supported by metal oxide is used for the gasification reaction. The metal
solid catalyst enables the gasification at the relatively low temperature, which has a
great advantage for mechanical design of the high-pressure equipment. Hydrogen rich
gas (72%) could be obtained from methanol for 1,000 hours operation stably at the
condition of 450 C and 35 MPa. At that time, other components were the carbon
dioxide, carbon monoxide and methane. These contents were 26%, 1%, 1%
respectively. During the continuous operation almost complete gasification of
methanol could be achieved. Our catalyst has a good selectivity of hydrogen
production limiting the methanation reaction and a good durability under supercritical
condition of water. The composition has a good agreement with the equilibrium
composition without methane.
The effect of feed concentration of methanol and residence time on both methanol
gasification rate and product gas composition was investigated.
Also, the absorption process by water absorbent was experimentally investigated for
the purification of reformed gas. It was confirmed that most of the carbon dioxide in
reformed gas could be removed by this method. Experimentally 93.7 % hydrogen was
obtained at the pressure of 35 MPa.
21-2
Hydrogen Production from Biomass-Ethanol at Ambient Temperature with Novel
Diaphragm Reactor
Yasushi Sekine, Shinjiro Asai, Kouhei Urasaki, Eiichi Kikuchi and Masahiko
Matsukata
Waseda University, Japan
Shigeru Kado
Tokyo Institute of Technology, Japan
Fumihiro Haga
Central Research Center, Nissan, Japan
We investigated novel liquid fuel reforming system with diaphragm and discharge
hybrid apparatus. This process can be operated under ambient temperature and
atmospheric pressure. The target fuel was ethanol-water mixture (biomass-ethanol),
and it has many advantages for future fuel candidate. The reactor was made of glass
tube and thin diaphragm membrane was inserted in the middle of the reactor. Two
electrodes were inserted from both end of the reactor, and high negative voltage about
5 kV was applied with pulse form. Main product in the obtained gas was H2 and its
concentration was about 70%. Energy consumption was rather low compare to other
system because this process can be operated at ambient temperature and does not need
any heater or pump. Now we develop new small power supply and reaction system
which can apply to small fuel cell system or FCV. Up to now, the main problem is how
to remove CO from the products, because most of all carbon atoms in the fuel is
converted to CO, not CO2. So we also try to apply new catalyst in the system which
can play an important role in the ambient discharge system.
21-3
Development of Dense Cermet Membranes for Hydrogen Separation
U. Balachandran, T. H. Lee, L. Chen, S. J. Song, J. J. Picciolo and S. E. Dorris
Argonne National Laboratory, USA
R. P. Killmeyer Jr. and B. Morreale
US DOE, NETL, USA
Argonne National Laboratory (ANL) and the National Energy Technology Laboratory
(NETL) are developing dense ceramic membranes for separating hydrogen from mixed
gases, particularly product streams generated during coal gasification and/or methane
reforming. Hydrogen separation with these membranes is nongalvanic, i.e., it does not
use electrodes or an external power supply to drive the separation, and hydrogen
selectivity is nearly 100% because the membranes contain no interconnected porosity.
Novel cermet (i.e., ceramic-metal composite) membranes have been developed to
separate hydrogen from gas mixtures at high temperature and pressure. The hydrogen
permeation rate, or flux, has been measured at atmospheric pressure in the temperature
range of 500-900C for cermet membranes with thickness of 22-210 m. The
hydrogen flux varied linearly with the inverse of membrane thickness, and reached 19
cm3[STP]/min-cm2 for a membrane with a thickness of 22 m at 900C with 100%
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
the membranes were tested in a gas mixture containing high concentrations of CO and
CO2 for times approaching 200 h, and no performance degradation was observed; this
suggests that the membrane is chemically stable and may be suitable for long-term
operation. Hydrogen flux measurements in H2S-containing atmospheres show that the
cermet membranes are stable in gases containing 200 ppm H2S for up to 500 h. The
hydrogen flux of cermet membranes was measured at NETL at hydrogen pressures up
to 25 atm and temperature up to 900C. The present status of membrane development
at ANL/NETL will be presented in this talk.
21-4
Effect of Intermetallic Diffusion Barrier on the Stability of Composite Pd/PSS
Membranes at Higher Temperatures
Federico Guazzone, M. Engin Ayturk and Yi Hua Ma
Worcester Polytechnic Institute, USA
Hydrogen separation technologies are of great importance due to the essential nature of
hydrogen as an alternate clean fuel and the increasing demand for hydrogen in various
chemical and petrochemical industries. Pd and Pd/Alloy membranes supported on
porous stainless steel (PSS) are well-suited for high purity hydrogen production in
steam reforming reactors, as well as in hydrogen purification. However, the long-term
stability of the produced composite membranes is limited by the intermetallic diffusion
of support elements (i.e., Fe, Cr, Ni) into the dense membrane layer. In order to avoid
intermetallic diffusion, the in-situ oxidation of PSS supports to produce a barrier layer
has been developed in our laboratory2. The objective of the current study was to
investigate the high temperature stability of Pd membranes supported on oxidized PSS
supports.
To thoroughly understand the effectiveness of the oxide layer as the intermetallic
diffusion barrier, four composite Pd membranes were prepared using an un-oxidized
PSS support and three supports oxidized at three different temperatures, 400oC, 500oC
and 600oC. Hydrogen permeation measurements for the electrolessly plated Pd
membranes with a thickness range from 20 to 35 m were carried out using a system
equipped with a data acquisition board to continuously log the hydrogen flux, shell-
and-tube-side pressures and the temperature of the system. The accuracy of the
measurements was determined to be within 1%.
Permeation results showed that the decline in hydrogen flux was significantly larger
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
thickness of 33 m and an oxide barrier formed at 400oC, the initial hydrogen
permeance of 7.5 m3/m2-h-atm0.5 decreased to 6.7 m3/m2-h-atm0.5 in 48 hours at 400oC
under hydrogen. The rate of permeance decline for the PSS supports with an
intermetallic diffusion barrier created at 500oC was significantly smaller and was
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
with the hydrogen flux decline data. Finally, permeation results of membranes stable at
500oC for over a thousand hours will be presented.
SESSION 22
COAL ASH UTILIZATION BY-PRODUCTS 4: COAL ASH
UTILIZATION FOR CIVIL ENGINEERING MATERIALS
22-1
Comparative Evaluation Leachability Test Methods and Element Mobility for
Selected Australian Fly Ash Samples
Colin R. Ward and Jerzy Jankowski
University of New South Wales, Australia
David French
CSIRO, Australia
Comparative evaluations have been conducted of the proportions of major and trace
elements mobilised from Australian fly ashes using four different types of leaching
tests. These included batch-leaching tests based on shaking with distilled water and a
synthetic groundwater, as well as the standard TCLP procedure and an extended-term
column leaching test.
The mobility of elements from the fly ashes tested was found to vary significantly
depending on the test procedure used. The column leach test provides similar results
for most elements to the simpler shake and SGLP test procedures. However, some
elements, such as sulphur, appear not to be released as readily from the column tests,
possibly because of re-precipitation in the lower parts of the leaching columns. TCLP
testing tends to produce higher levels of leachability for many elements, especially
from ashes that generate alkaline leachate solutions, than the other test procedures.
21
Further work to establish the chemical controls on element leachability, and the time-
dependent aspects of the leaching process, are currently in progress. Preliminary
results of these investigations are incorporated in other papers to be presented at the
conference.
22-2
Leachability of Heavy Metals from Selected Australian Fly Ashes and Its
Implications for Groundwater Contamination
Jerzy Jankowski, Colin R. Ward and Sarah Groves
University of New South Wales, Australia
David French
CSIRO, Australia
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
ashes were subjected to long-term (144 hour) leaching tests, and the behaviour of As,
Cd, Cu, Mo, Se and Pb was investigated to obtain data on their potential for
mobilisation during fly ash-water interactions. Leaching solutions with initial pH
values of 4, 7 and 10 were used to assess the influence of pH conditions on element
mobility for each of the ash samples.
The pH values developed during the leaching process appear to be related to the acidity
and alkalinity of the original fly ashes. The acidic fly ashes produced acidic to neutral
leachates with pH values independent of the pH of the initial solution, whereas the
alkaline fly ashes produced alkaline leachates, all with pH values above 9.5, regardless
of the pH of the initial leaching solution used. The percentages of each of these
elements leached from each of the different fly ashes show the following trends: for the
acidic fly ashes Cd>Se>Mo>As>Cu and Se>Cd>As>Mo>Cu, and for the alkaline fly
ashes Mo>Se>Cd>As>Cu. The highest proportions of key elements removed from
the fly ashes by the leaching solutions, as a fraction of the total element concentration
in the original ash in each case, are: Cd (3 9%) and Se (1 6%) in the acidic fly
ashes and Mo (12 20%) in the alkaline fly ashes. The lowest proportion of element
on the list removed by leaching from all four fly ashes is that of Cu; a maximum of
only 0.15% of the Cu in the ash was removed from the solid phase in either acidic or
alkaline leachates.
Several important conclusions can be drawn from these experiments concerning the
behaviour of heavy metals in leachate solutions. The most important are that the pH of
final solution depends on the pH of the original fly ash, the mobility of heavy metals
from fly ash is a very slow process, and only very small percentages of elements
present in the fly ashes are removed by leaching, even after a 144 hour batch test. The
concentrations of elements in the leachates are only slightly pH dependent, and there is
no clear difference in concentrations with changing pH values.
22-3
Environmental Monitoring of Full-Scale Coal Combustion Product (CCP)
Pavements during Accelerated Loading
Harold Walker, C.M. Cheng, Panuwat Taerakul, Tarunjit Butalia, and William Wolfe
The Ohio State University, USA
The goal of this study is to evaluate the environmental response of full-scale CCP
pavement sections during accelerated loading. Six full-scale CCP pavement sections
were constructed and tested at the OSU/OU Accelerated Pavement Load Facility
(APLF). Each pavement section consisted of a driving surface layer (asphalt or
Portland cement concrete), base layer(s), and subbase layer. Two different proportions
of fly ash to Portland Cement Concrete were utilized in making the concrete pavement
layer. Additionally, a no fly ash control section was constructed. Different
combinations of CCPs (fly ash and bottom ash) and conventional materials (sand, fine
and coarse aggregate) were used in base and subbase layers. The objectives of the
environmental portion of the study were (1) to characterize the chemical properties of
the materials used in the construction of the pavement sections; (2) to determine the
leaching potential of selected constituents in the laboratory; and (3) to monitor the
water quality of surface runoff and groundwater infiltration at the APLF.
The chemical properties of pavement ingredients and mixes were determined by
digestion (USEPA method 3052). The leaching potential of selected constituents was
determined using a modified Toxic Characteristics Leaching Procedure (TCLP) test
(USEPA SW-846). Leaching is examined with both the extraction fluid specified by
the TCLP test as well as modified extraction fluids at different ionic strength to
simulate different roadway conditions. During the accelerated loading test, the
pavement surface was periodically subjected to 1-hour rainfall events simulated
through a rainfall simulation system, in which the rainfall intensity was accurately
controlled. Simulated rain was prepared from deionized water by adding a
sulfuric/nitric acid mixture to pH 4.2. Five 100-mL surface runoff samples were
collected periodically during each 1-hour rainfall event. Towards the end of the
accelerated loading test, the subgrade of the facility will be inundated with water
through pipes beneath the subbase layer. Pore water samples from different base and
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
were chosen because many are typically found in CCPs and they are also of concern in
evaluating highway runoff.
Laboratory tests indicated that the leaching of inorganic elements from Portland
cement concrete pavement containing fly ash was similar to values observed for
Portland cement concrete without fly ash. Increasing the ionic strength of the leaching
solution, to simulate salt addition to the roadway, did not significantly increase the
amount of leaching of inorganic elements. Sampling and analysis of surface and
subsurface water from the APLF is currently ongoing. Because this study is being
conducted in a well-controlled environment utilizing accelerated loading, the results
obtained demonstrate how different CCP materials influence contaminant release from
full-scale pavement sections over time-scales equivalent to the life of the pavement
system.
22-4
Trace Element Mobility from Selected Australian Fly Ashes
Jerzy Jankowski, Colin R. Ward and Sarah Groves
University of New South Wales, Australia
David French
CSIRO, Australia
Batch leaching tests have been performed to determine the mobility of some key trace
elements, Co, Cr and Ni, on fly ashes collected from four Australian power stations.
These materials represent two acidic and two alkaline-generating fly ashes, each
derived from chemically different coals.
Three different solutions, with initial pH values of 4, 7 and 10 were used to assess the
mobility of these and other elements from the fly ashes under a range of chemical
conditions. The leaching solutions were made up from Milli-Q-Water of pH 7 and
adjusted to acidic conditions (pH 4) using HCl and to alkaline conditions (pH 10) using
NaOH. The liquid/solid ratio in each test was between 3.45 and 3.50. The mixtures of
fly ashes and leachant were shaken for up to 144 hours, to obtain information on the
long-term mobility of trace metals.
After 144 hours of laboratory leaching less than 0.05% of the Co had been removed
from the alkaline fly ashes. The proportion of the Co removed from the acidic fly
ashes was between 0.2 and 0.8%, significantly higher than that removed from the
alkaline fly ashes. Nickel shows a similar pattern; less than 0.02% of the Ni was
removed from one alkaline fly ash and less than 0.2% from the second alkaline fly ash,
but between 0.3% and 0.5% of the Ni was removed from both acidic fly ashes. The
behaviour of Cr, however, was completely reversed, with less than 0.01% of the Cr
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
leaching experiments.
At the end of the 144-hour tests the leachate pH produced by the acidic fly ashes after
reaction with the different solutions was always relatively acidic. With an initial
solution of pH 4, for example, the final pH after reaction with the acidic fly ashes
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
alkaline fly ashes were leached by all three solutions (pH 4, 7 and 10), and indeed the
pH of the leachates often increased up to a value of around 12.
This experiment shows that acidic fly ashes leached by solutions with different pH
values have the ability to produce large amounts of protons and maintain acidic
conditions, whereas the alkaline fly ashes produce large amounts of hydroxyl ions
elevating and/or maintaining alkaline conditions in the leachates. The study has also
shown that the mobilisation of trace metals from fly ashes is a very slow process, and
interaction with groundwater and surface water in fly ash dams will take a long time to
remove trace metals from solid phase. Depending on the hydrogeochemical
environment in which the ash is emplaced or used, this may give rise over long periods
of time to potential contamination of associated groundwater and surface water
systems.
22-5
Deposition of Wastes from Belchatow Power Plant In Connection With
Overburden Dumping and Final Management in Lignite Mine Belchatow
Zbigniew Kozlowski
Wroclaw Technical University, Poland
Lidia Gawlik and Zbigniew Grudzinski
Polish Academy of Sciences, Poland
Belchatow Power Plant of the current capacity of 4420 MW is the biggest heat and
power plant in the world. It uses nearly 40 mln tonnes of lignite per year.
Burning of such a huge amount of lignite causes the problem with over 4 mln tonnes a
year of wastes from furnaces. These are fly ashes and slugs that should be managed
safely for environment.
In the first years of the power plant operation the power plant wastes were deposited
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.
So, when Belchatow Mine applied internal dumping system, a part of fly ashes from
power plants has been dumped internally in the mine excavation in the form of specific
proportion mixture of the ashes and overburden.
22
Nevertheless, the method can not be applied for a long time, especially in the lower
parts of the dumping area, because of the danger of water contamination in the water
reservoir that is planned in a final management of the open cast.
In the nearest future it is planned to stop dumping the ashes and slugs at the special
dumping area of power plant. All the wastes will be deposited at the internal dumping
areas of coal mine and in the final open cast of Belchatow Mine where the huge
reservoir is to be arranged.
Three methods of ashes deposition are considered, namely: in the form of mixture of
ashes and overburden, using a hydraulic technology in sealed reservoirs and in the
form of emulsified ash that solidifies after deposition.
The research on the influence of the different methods of ashes deposition on
environment, and especially on contamination of water in rock mass and in projected
reservoir, are carried out. The results of the research will be decisive for the final
choice of the method.
SESSION 23
ENVIRONMENTAL CONTROL TECHNOLOGY 4: SULFUR & PAH
23-1
Sulphur Removal from Mae Moh Coal via Mixtures of Hydrogen Peroxide with
Formic Acid
Rafedah Rakal, Khudzir Ismail and Mohd Azlan Mohd Ishak
University Technology MARA, Malaysia
Mohd Asri Mohd Nawi
University Science Malaysia, Malaysia
Desulphurisation of Mae Moh coal using mixture of hydrogen peroxide and formic
acid at leaching temperatures of 30, 50 and 70oC in ambient pressure was studied.
The results obtained indicated that pyrite, sulphate and organic sulphur removal
increased with increasing leaching temperature at various leaching time. The rate of
pyrite and sulphate sulphur removal is relatively high in the first hour of leaching time,
and subsided as the leaching time proceed. The reagent mixture at leaching
temperatures of 30, 50 and 70 oC are capable of reducing ca 38, 49 and 47 % of total
sulphur content in the coal, respectively. Further, as much as sulphur removal being
achieved, a considerable amount of coal dissolution was also being observed and was
estimated. Further, scanning electron microscopy with energy dispersive X-ray (SEM-
EDX) on the leached coal sample showed some noticeable physical alteration due to
the mild oxidative treatment, particularly at relatively high leaching temperature. This
observation was consistent with the slight decreased in the calorific values
performance of the leached coal and was within tolerable limit.
23-2
The Selective Oxidation of H2S to Elemental Sulfur on Mechanically Mixed
X-V2O5 Zeolite Catalysts in IGCC System
Jong-Dae Lee, No-Kuk Park, Jin Hyuk Jun, Si-Ok Ryu and Tae-Jin Lee
Yeungnam University, Korea
Due to the increasing standards of efficiency required by environmental protection, the
direct sulfur recovery from the H2S-containing gases has become more and more
important. For this reason, we studied the selective catalytic oxidation of H2S to
elemental sulfur on the zeolite HX, NaX and KX. The basic zeolites such as zeolite
NaX and KX showed good catalytic activity. The elemental sulfur yield was about
90% on zeolite NaX, KX after 4hr selective oxidation of H2S at 225 . On the other
hand, it was under 20% on zeolite HX after 4hr reaction at 225 . However, these
zeolite NaX and KX were deactivated in presence of water vapour. This deactivation
was caused by the strong adsorption of water vapour on the zeolite catalysts. For
selective oxidation of H2S in presence of water vapour, V2O5 catalyst was selected.
The reactivity of V2O5 catalyst was improved by adding X-type zeolites. The improved
reactivity was caused by the improvement of reduction property of V2O5. The yield of
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
of coal-derived synthetic gas was better than that of in presence of water vapour. It was
suggested that the reduction property of catalysts was vary important factor in selective
oxidation of H2S and the reduction property of V2O5 catalyst could be improved by
mechanically mixing X-type zeolites.
23-3
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
Jin Lee and Si Ok Ryu
Yeungnam University, Korea
Jae-Chang Kim
Kyungpook National University, Korea
Chih Hung Chang
Oregon State University, USA
In these days many developed countries make a great effort to develop the affordable
and sustainable energy technologies to resolve the environmental pollution issues from
fossil fuel consumption. Gasification technology represents an innovative electric
power generation concept and it provides several advantages including high energy
efficiency, superior environmental performance and low cost electricity. In an
integrated gasification combined cycle (IGCC), coal and other carbon-based fuels with
an oxidant are converted into a gaseous synthetic fuel after gas cleaning, and then it is
forwarded to the combined cycle for electric power generation. Gasification utilizes the
low-grade fossil fuels including coal, residues from petroleum processes, petroleum
coke, and other wastes to produce electricity, steam, syngas (CO and H2), ammonia,
and methanol. Syngas after an ultra gas cleaning process for further purification will be
converted into the high value-added products, such as hydrogen for fuel cell and
chemicals (DME, DMC) for catalytic conversion processes in near future.
In order to remove hydrogen sulfide from a synthetic gas produced in a gasifier, a two-
stage process for the ultra hot gas cleaning was set up in this study. In the first stage
process the sulfur content of the gasified fuel gas was reduced from 10,000 parts per
million to several ppmv in a fluidized-bed reactor. A fixed-bed reactor was used to
remove the small amount of residual hydrogen sulfide that remains less than 5 ppmv
levels in the fuel gas in the second stage process. The suitable sorbents with high
sulfur-removing capacity and long-term durability for each stage were also developed
and their reactivity was investigated in the ultra hot gas desulfurization process
incorporated with the two-stage process. Near-zero emission was achieved as a result
of experiment in this study.
23-4
Operation Results of IHI Flue Gas Desulfurization System for 700MW Reihoku
Power Station Unit 2
Daisuke Horiguchi, Tosihiro Abe, Shokichi Hirata and Yoshimitsu Tsumita
Ishikawajima-Harima Heavy Industries Co., Ltd., Japan
No.2 unit of Reihoku Power station, which is the newest 700MW coal-fired
supercritical unit of Kyushu Electric Power Co., Inc, entered into commercial
operation in June 2003. Ishikawajima-Harima Heavy Industries Co., Ltd. (IHI)
constructed the limestone-gypsum type flue gas desulfurization plant for this unit
which has the state-of-the-art technology achieved extremely low emission values,
25ppm of SOx and 0.8mg/Nm3 of dust concentration at the absorber outlet. To meet
both demands for reducing construction cost and high performance in recent years, IHI
adopted a single absorber for the mixed-ash process based on the simultaneous
desulfurization method which combined a rectangular absorber with non-leakage Gas-
Gas Heater (GGH) and Low-Low temperature Electrostatic Precipitator (ESP). To
verify the performance of the rectangular absorber, the demonstration plant of 1/50
scale was constructed next to No.1 unit to utilize the real bypassed gas. The
demonstration test resulted in reduction in absorber volume by 50% for the real
absorber for No.2 unit and reduction of the power consumption of the recycle pump by
20% compared with No.1 unit. This paper introduces the design characteristics of this
advanced FGD system and satisfactory operation results derived from the
commissioning for 10 months.
23-5
PAHs Removal from Hot Gas by Porous Absorbents
Zheng-Yue Ma, Hao-kan Chen, Wen Li, Bao-qing Li
Chinese Academic of Sciences, China
The aim of this paper is to investigate the abatement of polycyclic aromatic
hydrocarbons (PAHs) model compounds including Napthalene (Nap), Fluorene (Flu)
and Phe- nanthrene (Phe) by using different porous materials as absorbents. The
adsorption of these compounds was carried out at a laboratory scale in an experimental
rig designed for this purpose, where FID is used for detection. Experimental
conditions, mainly in terms of adsorbing temperature and PAH concentration, close to
those observed in flue gases from energy generation systems were applied. The PAH
adsorption process was analyzed by means of experimentally obtained breakthrough
curves. After the detection parameters had been optimized, the influence of the
absorbents structures and SO2 CO2 in hot gas was studied. It is concluded that (1) The
BET surface area and micropore volume are determinant parameters for these PAHs
removal when each variable is considered alone, and while these two variables are
considered together, the good partial-correlation and multi-correlation exist among the
adsorption capacity, the BET surface area and micropore volume. Furthermore, no
relationship is found between PAHs adsorption capacity and mesopore volume; (2)
The adsorption of three model compounds by absorbents from hot gas is inversely
proportional to their volatility. The lower the PAH volatility is, the higher the
adsorption capacity is; (3) Adsorption isotherms show that adsorption behavior of AC-
1 is suitable to Langmuir adsorption isotherm equation. (4) When the
SO2(3000~5000ppm)/CO2(20~30% of carrier) was added into the reaction system, the
adsorption capacities of absorbents was depressed considerably.
SESSION 24
NON-FUEL UTILIZATION OF COAL: 1
24-1
New Advances in the Development of Premium Carbon Products from Coal
John M. Andrsen
Pennsylvania State University, USA
John Stipanovich
US DOE, NETL, USA
23
Although coal is the largest domestic fossil hydrocarbon resource of the U.S.,
estimated to last over 250 years at the present consumption rate, most of the premium
carbon products developed and manufactured in the US derive mainly from petroleum,
thus creating a dependence on foreign imports to manufacture essential carbon
products for the domestic market. To ensure a sustainable development of the carbon
product market the inherent potential of the great abundance of coal in the U.S. must
be pursued to supply and introduce environmentally benign and affordable premium
carbon products to the general public. Accordingly, the development of premium
carbon products from coal for commercial application has been pursued through the
Consortium for Premium Carbon Products from Coal (CPCPC). The overall objective
of CPCPC is to be a vehicle for industry-driven research on the promotion,
development, and transfer of innovative technology to the U.S. industry. A series of
new advances in the development of premium carbon products from coal has been
established, including: (i) Green Carbons from Coal, (ii) New Developments in
Anthracite Research, (iii) Advances in Coal Extract, Tars and Binder Technology, and
(iv) Nano-Material and Novel Products from Coal, will be reported.
24-2
Modifed Protocols for Synthetic Feedstocks for Anodes
Peter G. Stansberry, Elliot B. Kennel and Nathan D. King
West Virginia University, USA
New sources of feedstocks for anode-grade carbon are needed to augment diminishing
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
produce high quality pitch and coke using coal feedstocks produced via solvent
extraction techniques.i That is, coal is partially dissolved, and particulates are
removed via techniques such as hot filtration or centrifugation, thus producing a
synthetic hydrocarbon which resembles pitch to an extent. In many cases, tetralin has
been used as a hydrogen donor solvent in order to increase the yield of soluble coal
chemical. In addition, partial extractions without a donor solvent have been performed
using n-methyl pyrrolidone (NMP) as a solvent. Materials obtained in these processes
have been shown to meet specifications for anodes. However, a remaining issue is
whether economics are acceptable for introduction of such processes in industrial
settings. Two significant issues are solvent recovery and solvent costs.
For these reasons, methods were sought to reduce solvent recovery requirements, to
achieve lower material costs, and to incorporate more low-cost coal in order to produce
a synthetic binder pitch. This was accomplished using a low-cost petroleum refinery
byproduct oil as a hydrogen donor solvent in place of methyl naphthalene or tetralin. It
was recognized that if the solvent has a lower cost than the intended product, it is
permissible to retain the solvent in the product and not recover it. Accordingly,
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
identified. A mild hydrogenation step was used to break up chemical bonds in the coal
and to improve the coal solubility such that over 80% of the coal became soluble, and
resulting in a solvent/coal ratio of 2.5:1. Additional thermochemical processing may
result in acceptable pitch properties even with zero solvent separation and recovery,
suggesting that solvent recovery costs can be reduced or eliminated.
24-3
Applications of Carbon Foam Structures
Felix D. Mallette and Craig Hannah
Quantex Materials Inc., Canada
Alfred H. Stiller and Lloyd J. Ford
West Virginia University, USA
Carbon foam can be inexpensively produced using inexpensive coal-derived
feedstocks such as coal tar pitch, coal extracts or even treated pulverized coal, using a
controlled coking process. Among the attributes of carbon foam are its low density,
high energy absorption upon crushing, and excellent flame resistance. These
properties make carbon foam of interest for, among other applications, impact
resistance, blast protection, fire protection, thermal insulation and structural
reinforcement. Different reinforcement strategies can be considered for these
applications, including the use of material reinforcements such as carbon fiber to
increase strength and modulus, particularly in tensile and flexural modes. A second
method to enhance the ability of carbon foam to act as a structural reinforcement is the
use of sheet reinforcements to create trilayers to distribute mechanical loads. Trilayers
can be fabricated using metals such as steel or aluminum, or fibrous materials such as
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
itself, as well as joining the trilayered structures to other structures. For these purposes,
a variety of sealants and adhesives can be considered for joining the components of the
trilayer, including coal tar enamel. The result is a lightweight structural material with
unique properties and attributes.
 24-4
Carbon Nanofiber Synthesis from High Sulfur Coal
Takashi Yanagisawa
GSI Creos Corporation, Japan
Max L. Lake
Applied Sciences Inc., USA
Carbon nanofibers (CNF) are graphitic hollow filaments approximately 100 nm in
diameter consisting of nested graphene planes. CNF are the subject of much research
and development as an engineering material for the 21st century, for use in engineered
polymers, power components, and novel medical therapy. CNF are created by the
pyrolysis of hydrocarbon gases in the presence of a metallic catalyst. Coal derivatives
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
nanofiber synthesis. Second, gasified coal is a less expensive source of carbon than
natural gas or other potential feedstocks. Third, gasified coal can be a supply of low-
cost catalysts in the form of hydrogen sulfide and organometallics. Fourth, coal
gasification can generate solid phase materials such as fly ash, which is traditionally
used as a reinforcement material. The concept of co-generation of power as well as
reinforcement materials with coal derivatives becomes realistic for use of CNF in
infrastructures. Prospects for gasification power plants to co-generate both electric
power as well as carbon nanofibers at commodity prices are discussed.
24-5
Advanced Flue Gas Treatment by Novel DE-SOx Technology over Active Carbon
Fibers
Masaaki Yoshikawa
Osaka Gas Co., Ltd., Japan
Akinori Yasutake
Mitsubishi Heavy Industries, Ltd., Japan
Isao Mochida
Kyushu University, Japan
There is worldwide and increasingly the discharge of the sulfur dioxide with the use of
fossil fuel. Especially, the discharge in the Asia region has increased recently, but the
environment countermeasure has been retarded for the problem of economical
efficiency. Though in the advanced nation, the limestone gypsum method is mainly
used as flue gas de-SOx facilities, which cost very expensive in both initial and
running.
On the other hand, it becomes obvious that SOx in flue gas can be removed at room
temperature by using pitch-based Active Carbon Fibers (ACF) subjected to surface
treatment such as high temperature heat treatment. The flue gas treatment technology
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
acid and various sulfates to be recovered, and is applicable in the field of flue gas
treatment to which the conventional de-SOx method, such as the limestone gypsum
method, could not be applied for economical reasons.
SESSION 25
COMBUSTION TECHNOLOGIES: 5
25-1
Mechanism of Ignition Delay in O2/CO2 Pulverized Coal Combustion
Akio Yamamoto, Toshiyuki Suda and Ken Okazaki
Tokyo Institute of Technology, Japan
Coal combustion with O2/CO2 is promising because of its easy CO2 recovery,
extremely low NOx emission and high desulphurization efficiency. However, it turns
out that combustion behavior of coal becomes worse when this technique is applied
to a conventional pulverized coal burner. In this study, ignition delay of coal particle
is measured using the Drop Tube Furnace (DTF). Comparison for the ignition
behavior has been made for different dilution gas, furnace temperature and coal type
to see the effect of physical properties of gas and volatile matter in the coal.
In the experiment, an electrically heated DTF with 690 mm height and 35mm
diameter has been used. A water-cooled probe with an ignition detector was inserted
and traversed from the lower part of DTF and was used to detect the ignition point.
Ignition distance was judged from the rise of luminosity. Bituminous and anthracite
coal whose average particle size is 40m are fed into the top of furnace at the feed
rate of 0.1 g/min. Furnace was heated up to 1023, 1223, 1423 K. Air, O2-CO2
mixtures and O2-rare gas mixtures have been used for the combustion gas.
Results show that ignition delay becomes shorter when oxygen concentration or
furnace temperature are high and with high volatilized coal. And from the results, it is
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
coal is used. In order to clarify the effect of physical property of gas on ignition delay,
He, Ar, N2, Kr and CO2 have been used as a dilution gas with fixed oxygen
concentration (20 %). It is clarified that large ignition delay in CO2 dilution gas is
mainly due to the high heat capacity of CO2 gas. The difference of ignition delay can
be arranged with the ratio of the heat capacity of coal particle and the thermal
24
conductivity of dilution gas, and when the thermal conductivity of atmosphere gas
becomes low, ignition delay seems to increase.
25-2
Distribution of Trace Elements in Solid Emissions from AFB-FAR Combustion of
Lignite and Synthetic Fuel
Skorov Ivana and Vaek Michal
Institute of Rock Structure and Mechanics AS CR, Czech Republic
Smolk Ji, Schwarz Jaroslaw and Dumbov Lucie
Institute of Chemical Process Fundamentals AS CR, Czech Republic
Havrnek Vladimr and Kuera Jan
Nuclear Physic Institute AC SR, Czech Republic
In this work the influence of mineral matter on trace elements partitioning during
Atmospheric Fluidized Bed Combustion with fly ash recirculation (AFB-FAR) of
lignite containing 15.4 % of ash and synthetic solid fuel with 1.2 % Ad was
investigated. Synthetic solid fuel (SF) was prepared from the soot CHEZACARB
(Chemopetrol Litvnov, Czech Republic) and bitumen emulsion KATEBIT T40
(Paramo Pardubice, Czech Republic) was used as a binder. The fuel was enriched with
some trace elements at concentrations typical for the Czech lignites (Bouka and
Peek, 1999). In addition, pure alumina, titania, silica, and limestone were used as
mineral admixtures.
The experiments were performed using 100 kW AFCB boiler with sand as a material
of the bed. The samples of solid residues discharged from one experiment included
bottom ash, coarse fly ash from cyclones, and fine fly ashes separated by BLPI
impactor. The lignite sample and 5 types of granulated synthetic fuel (one without
mineral admixtures and four with one of the mineral admixtures (CaCO3, SiO2, TiO2,
Al2O3) were investigated. The solid output streams from the combustion experiments
were analyzed by fuel analysis methods, INAA, PIXE and AAS methods, and by
optical and scan electron methods.
The differences in chemical composition and morphology were observed between
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
nickel was uniformly distributed between all ashes. In all cases the trace elements
were depleted in the bottom ash from combustion of synthetic fuel. The highest
concentrations of trace elements were found in fly ashes collected in cyclone and BLPI
impactor. A substantial enrichment in fly ashes was observed for As, Co, Cu, Hg, Sb,
V, and Zn. The AAS analyses of input and output streams revealed that during the
combustion experiments of lignite and synthetic solid fuel with CaCO3 about 95% of
Hg left the system. The remaining Hg was distributed in fly ashes. The detailed
distribution of partially hazardous trace elements in solid output streams from AFB-
FAR of lignite and synthetic solid fuel is discussed.
25-3
The Influence of Volatile Matter Content on Emisions of Coal
G. nal, M. zer, F. Boylu and O. Kural
Istanbul Technical University, Turkey
I. Mustafaev
Azerbaijan Academy of Science, Turkey
In this study, the effect of volatile matter on emissions was investigated. Eight coal
samples with volatile matter contents ranged from 1.14 % to 46.36 % and laboratory
scale stove equipped with heat sensors on the smoke hole were used. Before the
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
radiation. The fluid gas on out as point of the combustion test facility were directed to
gas chromatography to analyze the emissions. According to the results of the study, the
volatile matter content has no effect on the fluid gas emissions and the fluid gas
emissions are controlled by the properties of coals such as chemical structure, macerals
and geological age. But the volatile matter contents effected the particle emissions
although there is no correlation between gas emission concentration and volatile
matter. In conclusion, the coals with volatile matter contents lower than 20 % and
volatile mater contents higher than 30 % give low particle emissions on combustion.
The volatile matter content between 20 - 30 % was found to be critical for particle
emissions.
25-4
CCSEM Characterization on the Chemical Species in PM10 Emitted from Various
Combustion Sources
Liang Zhang and Yoshihiko Ninomiya
Chubu University, Japan
Particulate matters (PM), emitted from various combustion sources, were characterized
by computer controlled SEM (CCSEM) to identify the chemical species within its
different sizes. Three cases, combustion of single coal, single sludge and their mixture
were studied. PM in the existing gas was first size-segregated by low-presssure-
impactor (LPI). Secondly, three sizes of carbon plate-collected PM, 2.5, 0.33 and
0.06m, were subjected to CCSEM analysis. The magnification of 800 was used for
PM of 2.5m, whereas 2000 was used for the latter two sizes. The analysis
preciseness of CCSEM was primarily examined by comparing its analysis result with
that of XRF analysis. The results indicate that, in the viewpoint of elemental
composition, CCSEM analysis on each size of PM is in fairly good consistence with
that of XRF analysis. In addition, both the elemental composition of PM and the
species within it vary greatly with its size and the fuel type. Aluminosilicate and its
salts containing the refractory elements such as calcium and iron dominate the largest
particle of 2.5m. With PM size down to 0.33m, both the refractory and vaporized
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 0.06m, the
compounds containing vaporized alkali/zinc/silica elements and
sulfur/phosphate/chlorine dominate, whereas the aluminosilicate disappears. Co-
combustion greatly affects the distribution of individual element and the species within
differently sized PM. The results suggest the strong nteraction between the refractory
elements of two fuels and hence, the size of PM shifted to the greater value.
Furthermore, more the sludge combustion-derived vaporized alkali and trace elements
reacted with the coal combustion-derived evolved sulfur and chlorine to form the
gaseous species, which condensed into the ultrafine particulates smaller than 0.1m.
SESSION 26
GASIFICATION ADVANCED TECHNOLOGIES 1: CONVENTIONAL
& ADVANCED SYNTHESIS GAS CLEANUP
26-1
Flex-Fuel Testing of the Ultra-Clean Process for the Control of Sulfur, Halide,
and Mercury Compounds in Coal Gasification Gases
Francis S. Lau, James Aderhold, Rachid B. Slimane, and Michael J. Roberts
Gas Technology Institute, USA
Richard A. Newby and Harry Morehead
Siemens Westinghouse Power Corporation, USA
Suresh C. Jain
US DOE, NETL, USA
The Siemens Westinghouse Power Corporation (SWPC) and the Gas Technology
Institute (GTI) are developing a novel Ultra-Clean process to control sulfur species,
halides, mercury, and particulates in syngases generated through gasification of
carbonaceous feedstocks to meet very stringent cleaning requirements for chemical or
liquid fuel synthesis applications, or for fuel cell power generation. The Ultra-Clean
Process is a dry process in which fine sulfur, halide, and mercury sorbent particles are
injected into two stages of "barrier filter-reactors", coupling efficient particle capture
with an effective entrained and filter cake reaction environment. The process
performance goal is to remove sulfur species to less than 60 ppbv, halides to less than
10 ppbv, mercury to less than 0.01 ppbv (or > 99% removal), and particulates to less
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
evaluations have shown the technical feasibility and commercial merit for the Ultra-
Clean Process compared to conventional, Rectisol-based syngas cleaning.
Based on the encouraging laboratory-scale test results as well as technical and
economic feasibility studies, SWPC/GTI are now conducting a bench-scale
demonstration of the Ultra-Clean Process performance, using a newly constructed GTI
FlexFuel gasifier capable of handling 10 tons/day of coal. This paper describes the
test facility, scope and approach of testing activities, sampling and analytical
measurement procedures, and the available experimental results. Test results will be
discussed in conjunction with commercial process evaluations.
26-2
Development of High Efficiency Hot-Gas Cleanup Technology for Integrated
Coal Gasification Fuel Cell Combined Cycle (IGFC) System
Michihiro Ishimori, Kouichiro Furusawa, Tetsuji Suzuki and Masafumi Katsuta
Waseda University, Japan
In relation with recent global environment issues, development of the highly efficient
gas cleanup system for coal gasification is considered to be increasingly of importance.
Integrated Coal Gasification Fuel Cell Combined Cycle (IGFC) system consisting of a
gasifier, molten carbonate fuel cells (MCFC), gas turbine, and steam turbine has been
recognized as one of the most superior power technologies for next generation,
although development status of MCFC has not yet been satisfactory. In order to realize
the highly effective coal gasification power plants, development of hot-gas cleanup
system, especially highly efficient desulfurization technology for hot coal gas is
required.
In continuing our studies of zinc ferrite and related compounds as desulfurization
agents, we have found several excellent sorbents for hot reductive gas such as coal gas
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
almost identical; indicating that deactivation of the sorbent during the absorption-
regeneration cycles is negligible. The sorbents are considered to be satisfactorily used
for hot gas desulfurization process of the IGFC of next generation as well as advanced
IGCC plant equipped with high temperature gas turbine, based on the operation data of
200t/d IGCC pilot plant at Nakoso, Japan. An IGFC system of high thermal efficiency
(53-55%, net, HHV) by use of a hot gas cleanup process has been conceptually
designed based on the data of this study and Nakoso pilot plant.
26-3
Warm-Gas Desulfurization Process for ChevronTexaco Quench Gasifier Syngas
Santosh Gangwal, Brian Turk, David Coker, Gary Howe and Raghubir Gupta
Center for Energy Technology, USA
Raj Kamarthi and Tom Leininger
ChevronTexaco, USA
Suresh Jain
US DOE, USA
ChevronTexacos innovative high efficiency quench gasifier produces a medium
BTU syngas that is essentially free from all contaminants except sulfur gases (H2S
and COS), ammonia, and traces of mercury. Several modular gas cleanup processes
are being developed to specifically target these contaminants by a research team
including RTI, ChevronTexaco (CVX), KBR, SRI International, and Sd-Chemie,
Inc. This paper describes the progress with installation, commissioning and testing of
RTIs warm-gas desulfurization (WGD) process using a slipstream of syngas from
CVXs three ton coal per day research gasifier at Montebello, California. A transport
reactor system (16ft x 16ft x 80 ft) was installed and commissioned in March 2004 at
Montebello. 300 lbs of RTIs attrition resistant RTI-3 zinc oxide-based sorbent was
loaded in the system for testing. The circulation of the sorbent was initially
established using nitrogen. The system consisted of two coupled circulating
fluidized-bed reactors for the desulfurizer and the regenerator. The sorbent was
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
was replaced with syngas from the CVX gasifier containing about 8000 ppmv of
H2S and 200 ppmv of COS on a dry basis. The process was operated at 600 psig and
700oF with 10,000 scfh of syngas. The sorbent removed the gaseous sulfur
compounds to 1 ppmv. Laboratory tests of sorbent after more than 50 hours of
circulation showed no decrease in its attrition resistance and its reactivity. CVX
recently made a business decision to close down the Montebello facility. The testing
was thus suspended in April 2004. RTI is actively pursuing the installation of the
WGD process at another host site. The plan is to run several long-term tests (500 h)
to demonstrate the long-term performance of this process, including the dual loop
circulating fluidized-bed system as well as RTI-3 sorbent.
26-4
Investigations of Mercury Speciation under Gasification Conditions
Dennis Y. Lu, David L. Granatstein, Robin W. Hughes and Edward J. Anthony
CANMET Energy Technology Centre, Canada
Mercury (Hg) is the toxic trace metal of greatest concern in coal utilization because
of its volatility, persistence, potential for bioaccumulation in the environment, and its
high neurodevelopmental toxicity. The global atmospheric background level of
mercury increases if the mercury is emitted in an elemental form whereas oxidized
species will be deposited near their sources due to their high solubility in water and
scrubbing by atmospheric processes. The identification and quantification of
individual physicochemical forms of Hg are, therefore, imperative in addressing
questions concerning atmospheric fate and emissions control. Unfortunately, there is
a lack of information available on Hg emissions and speciation under gasification
conditions, which are substantially different from those seen from combustion. The
current authors investigated Hg speciation via gas-phase and heterogeneous reactions
using simulated synthesis gas from coal gasification at varying temperatures. The
results indicated that typical syngas constituents, including CO, CO2, HCl, Cl2,
NH3, HCN, COS and H2S, do not promote Hg oxidation via gas-phase reactions and
that coal-Hg will be emitted in its elemental form under gasification conditions.
Significant Hg oxidation was only observed in the presence of fly ash. This paper
also compares these results from the bench-scale tests with synthetic flue gases, with
data obtained on mercury speciation chemistry using CANMETs new pilot-scale
gasification plant. The entrained flow gasifier operates at pressures of 1.5 MPa and
temperatures around 1400C and in these tests was used to gasifiy selected
feedstocks of interest to the Canadian Clean Power Coalition (CCPC), including,
eastern bituminous coals, western sub-bituminous coal, Saskatchewan lignite, and
petroleum coke.
 26-5
A Sodium Speciation Model for Hot-Gas Cleanup Systems
Peter Gioko and Heng Ban
University of Alabama at Birmingham, USA
Tom Gale
Southern Research Institute, USA
Advanced power system development relies heavily on successful development of hot-
gas cleanup systems. Advanced Integrated Gasification Combined Cycle (IGCC)
systems for example, require very sophisticated high-temperature filtering devices (i.e.,
ceramic candle filters) to remove particulate and other harmful gas species from the
syngas before feeding the high quality syngas to a gas turbine. However, there are still
significant problems to resolve in the hot gas cleanup systems. Candle filter systems
for example, have a difficulty with bridging of between candles, which causes a
premature shutdown of the facility. Candle filters also suffer from candle breakage
problems, tar plugging problems, and leaks. There is another serious concern for these
hot-gas cleanup systems. Thermodynamic predictions of all major metal species in
syngas are predicted to condense prior to the particulate control device (PCD).
However, even at the low temperatures that hot-gas filters currently operate,
measurable metal and tar concentrations (sodium, various organics, and even iron) are
found well downstream of the PCD. These concentrations are often too large to allow
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
of major metal species in the syngas, and is highly corrosive.
The purpose of this project was to begin the development of a syngas speciation
model, capable of predicting the syngas composition at the PCD, based on the
complete syngas composition at the exit of the gasifier. Minor syngas components at
the gasifier exit were of significant interest, since these minor components may be
responsible for the trace sodium or other species passing the PCD. The initial
development of the speciation model was focused particularly on sodium, with
particular emphasis on determining why the sodium escapes the PCD in hot-gas
cleanup systems.
Thermodynamic predictions of sodium speciation were made using CEA, a multi-
component thermochemical equilibrium code. This code along with the latest version
of the thermodynamic library was used in this study. ChemKin, a software package
that contains the hundreds of auxiliary reaction equations needed to couple with the
desired syngas speciation model, was used as the frame work for the model
development. The kinetic model used available data and was built to describe the
change of gas composition across the temperature/time history to the front of the PCD.
Thermodynamic predictions of the syngas composition ahead of the PCD were
compared with the kinetic model predictions. For the purposes of the model, the
conditions existing in Gas Technology Institutes RENUGAS biomass gasifier should
be used to describe the parametric environment (i.e., temperatures, pressures, gas
compositions, residence times, etc.).
SESSION 27
LOW RANK COAL UTILIZATION: 1
27-1
Strategic Planning Of Low Rank Coal Utilization In Indonesia
Wimpy S. Tjetjep
Ministry of Energy and Mineral Resources, Republic of Indonesia
Indonesia has proved herself to be a reliable and secure source of coal for the world
users. Coal resources are reported to be about 57.8 billion tonnes, of which measured
reserves amount to 6.98 billion tonnes. However, the majority of the coal (about
60%) is younger Tertiary in age and low in rank (LRC) with high moisture contents.
This part of the resource basically is still under-utilized. Most of the coal currently
exploited is medium to high rank coals. However, future production will inevitably
move towards the LRC, as resources of medium to high rank coals are depleted and
become more expensive to exploit.
LRC should be used close to mine site due to its low calorific value, high moisture
content and low thermal efficiency. Upgrading LRC to products similar to high rank
coal (HRC) offers one of the best solutions of LRC utilization. The benefit of LRC
upgrading includes increased value per tonne, both for export and domestic markets
and stabilized coal quality feed for power generation and other industries. Indonesia
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
priority for the use of LRC, but this requires construction of long transportation lines
to transmit the energy generated to centers of demand. The conversion of LRC into
liquid and gaseous products is likely to become an important use for LRC in the
future.
With the development of coal upgrading, mine mouth power plant and conversion
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
national coal supply. Clean Coal Technology can be implemented in order to prevent
environmental pollution.
26
27-3
Demonstration of UBC Process in Indonesia Upgrading of Low-Rank Coal
Yasuo Otaka and Hajime Endo
JCOAL, Japan
Tetsuya Deguchi and Takuo Shigehisa
Kobe Steel, Ltd., Japan
Half of the worlds coal resources are so-called low-rank coal such as lignite (brown
coal), sub-bituminous coal. Such coal still remains to be local energy sources, because
it has low heat value and high propensity of spontaneous combustion. Some of low-
rank coals have advantages as clean coal; i.e. low ash and low sulfur content.
The UBC (Upgraded Brown Coal) process is a new technology to refine low-rank coal
up to transportable solid fuel with high heat value and less spontaneous combustion
propensity. This process removes coal moisture in the oil phase, so that heavy oil
fraction is adsorbed on the internal surfaces of coal pores. This oil coating makes UBC
product not only stable but also re-wetting free.
Various coals, so as Australian and Indonesian low rank coal, were tested by
Autoclave and Bench Scale Unit and the process application to Indonesian low rank
coal was proved to be most feasible. Demonstration plant with capacity of 5 tons/day is
now operated in Indonesia, expecting near future commercialization in order to utilize
abundant LRC of clean property.
27-4
Upgrading by Kobe University Process and Control of Spontaneous Combustion
of Low Rank Coals
H. Usui
Kobe University, Japan
Mahidin
Syiah University, Indonesia
D. F. Umar
DR&D Centre for Mineral and Coal Technology, Indonesia
The new upgrading method for low rank coals by a combined process of vacuum
drying and tar coating has been developed. A lignite coal from Indonesia has been
treated. The raw and upgraded coals then subjected to several analyses for
characterizing the properties, spontaneous combustion and combustion characteristics,
and kinetic parameters of low-temperature oxidation. Based on those experimental
results, it is finally concluded that this upgrading technique is promising to produce the
upgraded coals comparable to a bituminous coal and the surface of coals can be
effectively coated in order to prevent the self-heating and spontaneous combustion.
27-5
Lignite Water Characterization by Phase Transition Differential Scanning
Calorimetry
Yi Fei, Alan Chaffee, Marc Marshall and W. Roy Jackson
Monash University, Australia
We are investigating the nature of lignite-water interactions through the correlation of
water adsorption behaviour and measured features of their chemical and physical
structure.
It is postulated that the extent of the interaction with the most strongly bound water
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.
To test this hypothesis, samples were chosen from the Latrobe Valley lignite seams to
include a range of lithotypes with varying cation content. Raw lignite samples were
washed with water or dilute acid and the three states of lignite (raw, water washed and
acid washed) were provided for further investigation. Acid washed lignite samples
were also subsequently exchanged with Na, Mg, Ca, Al and Fe to various levels.
Equilibrium moisture contents were determined as a function of water partial pressure
through the use of dessicators and/or an automated dosing instrument known as the
IGA (Intelligent Gravimetric Analyser).
Results show that the concentration of carboxylic functional groups and the extent of
cation exchange do both significantly affect the amount of adsorbed water (in the
partial pressure range 0.11-0.92). The relationship between equilibrium moisture
content and functional group/cation concentration can be used to help identify the type
of water (e.g., monolayer, multilayer, bulk water) in the lignite.
SESSION 28
INTERNATIONAL COAL TECHNOLOGY COOPERATION: 1
28-1
Clean Coal Technology Development Strategy in Japan
Michiaki Harada
Center for Coal Utilization, Japan
Coal has crucial importance as a primary energy resource in 21st century because coal
is reserved enormously and distributed in worldwide. As Japan imports most of coal
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
while searching for solution to global environmental problems, various approaches
should be tried. As desirable steps to accomplish these approaches, high-efficiency
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,
from now on we should take up a comprehensive theme where CO2 reduction takes the
highest priority. The CCTs are required to ensure a wide-ranged reduction in CO2
emission. From the standpoint of considering global environment problems, the
development of CCT is urged in order to use coal 'effectively,' 'cleanly,' and 'carefully.'
In other words, projects should emphasize developments of environment-conscious
coal utilization technologies and their worldwide promotion. This paper shows a
strategy for the first 30 years of the 21st century of CCT development for zero
emissions in Japan. Assuming that we will enter a hydrogen energy era in 2020-2030,
and taking into consideration the current development and diffusion of fuel cell power
generation, fuel cell vehicles and
hydrogen gas turbine combined cycle power generation, it is necessary to pursue such
a possibility which allows CO2 free energy power generation by means of coal
gasification, coal based CO2 recovery type hydrogen producing technology to become
melted into a new business category which could be called the Coal-based Energy &
Chemicals Integrated Center in combining power station, chemical industry, iron &
steel industry and other business sectors.
28-2
Development Strategies for Clean Coal Technology in China
Yin Wu
National Development and Reform Commission, P.R. China
Jerald J. Fletcher and Qingyun Sun
West Virginia University, USA
China is now the worlds largest producer and consumer of coal. Economic growth
demands more energy to fuel continued expansion. Although coal production reached a
historic high of 1.74 billion metric tons in 2003, many provinces experienced severe
shortages of both coal and electric power. At the same time, pollution from coal
mining and coal utilization has become a major topic of public concern. In an effort to
find a path toward sustainable development and solve the current energy shortage,
China is seeking to reform the structure of the coal industry, improve coal utilization
efficiency, and enhance clean coal technology. Coal is the primary energy resource in
China, so clean coal technology is a critical component of economic growth while
protecting environmental quality. This paper discusses possible alternatives that
Chinas National Development and Reform Commission may use to increase
utilization of clean coal technology. A summary of current coal production and
utilization is presented as well as potential scenarios for future development.
28-3
Development of Coal Tecnology Centre
At Palimanan - Cirebon, West Jawa Indonesia
Bukin Daulay
R&D Centre for Mineral & Coal Technology, Indonesia
Coal has the potential to be a major future energy source in Indonesia due to it large
resource base, easy and low cost of exploitation, and the existence of transportation
facilities. Although more than 65% of identified reserves are of low rank coals, the
quality is sufficient for a wide range of end uses. By contrast, oil reserves have been
decreasing for a number of years, and historically, a large proportion of production has
been exported to acquire foreign currency earnings.
Currently, domestic use of Indonesian coal is mainly limited to use by the power plant
and cement industries. Small amounts of coal are also used for some small scale
industries. In order to optimize the utilization of coal in terms both of efficient and
appropriate uses, coal utilization technology should be fully mastered. Since 1980s
tekMIRA has conducted research on several coal utilization technologies on the
laboratory scale. However, before this technology is applied to commercial scale, the
research should be developed and scaled up to a pilot plant or demonstration scale. The
development of pilot plant or demonstration plant could be simulated closely to the
actual commercial scale operation. Through this activity, risks of failures can be
minimized in scaling up to commercial scale.
Based on the above considerations, tekMIRA wishes to establish a Coal Technology
Centre (CTC) at Palimanan, Cirebon Indonesia. At this location, a demonstration plant
of biobriquette with 5 tonnes/hour capacity and a pilot plant of upgraded brown coal
(UBC) of 5 tonnes/day capacity have been established. These two projects are
developed under cooperation between the Government of Indonesia and Japan. Several
pilot plants or demonstration plants are planned to be developed in this CTC, including
coal gasifier, formed coke, recycling of waste lubricating oil using low rank coal as an
absorbent, coal combustion for small industries, coal liquefaction and activated carbon.
The establishment of the CTC at Palimanan, Indonesia should be fully supported by
Indonesian Coal Stake Holder and overseas research and technology institutions
through technical cooperation agreements.
The function of the CTC is to become the central driving force for the introduction and
innovation of coal utilization technology, and to be a seeding program facility in the
enhancing of coal utilization technology and demonstration in the field of coal
utilization technology. The establishment of CTC could speed up the implementation
27
of coal utilization in industry. Therefore, there will be a close mutual relationship
between the CTC and the industrial sector.
28-4
The U.S. Geological Surveys International Coal Activities
Brenda Pierce, Susan Tewalt, Peter Warwick and Robert B. Finkelman
U.S. Geological Survey, USA
The U.S. Geological Survey (USGS) has long recognized the importance of
international cooperation in coal science and technology. For the past several decades
the USGS has engaged in a geographically and scientifically diverse program of
international coal activities. These activities include the current World Coal Quality
Inventory (WoCQI) a multinational cooperative effort to create the first unified global
coal quality database. To date, sixty countries have shared samples of coal and other
solid fuels, information, and digital maps. The USGS is providing coordination,
comprehensive analyses of the samples, construction of an electronic database, and
collaboration in making the information available to the public in print, digitally on
CDs, and on the Internet.
Most of the USGS international activities are supported financially by third parties.
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
minimize or eliminate the heath problems caused by domestic use of mineralized coal
that affects millions of people in the region. The USGS is also engaged in collaborative
studies of health problems that may be caused by coal in Romania, the former
Yugoslavia, and Bulgaria and on the mobilization of mercury and arsenic from coal
use in Ukraine. USGS scientists have collaborated with scientists from other countries
including Chile, Hungary, and South Korea to evaluate coal bed methane potential and
have conducted coal exploration and characterization projects in Pakistan, Poland, the
former Yugoslavia, India, Armenia, Kyrgyzstan, and currently in Afghanistan. The
U.S. Department of State is supporting a USGS scientist to spend three months in
South Africa to work with the South African coal technology community and coal
education communities. The USGS and Russia have recently signed an agreement to
cooperate on coal characterization and to evaluate Russian coal quality and assess its
technologic impacts, economic byproduct recovery potential and environmental and
health impacts. Education and training are important aspects of the USGS international
coal activities. The USGS has offered workshops, short courses, and lectures on a wide
range of coal science and technology in many of the worlds coal-producing countries.
During the past several years, coal scientists from several countries have worked for
several weeks to six months at USGS facilities in Reston and Denver conducting
collaborative field and laboratory studies. The USGS welcomes inquiries concerning
mutually beneficial international coal cooperation.
28-5
Obstacles and Path for Wide Acceptance of CCT in Korea
Yongseung Yun
Institute for Advanced Engineering, Korea
Korea has a long-term plan to construct and operate CCT plants of 300 MW scale. The
plan in installing CCT plants has been rescheduled twice from three plants of 300 MW
by 2007, 2013, 2014 to one CCT plant by 2009 according to the schedule published in
2002. Technological and economical obstacles should be cleared before wide
acceptance of CCT. Although many obstacles and uncertainties in economic and
technical aspects are present, it appears imperative to utilize CCT in Korea because
Korea imports 97% of energy and minimum 28-32% of electricity should come from
imported coal. With close cooperation on CCT among interest-sharing countries and
private sector would enhance the possibility in actual CCT implementation of
commercial scale in Korea.
SESSION 29
ENVIRONMENTAL CONTROL TECHNOLOGY 5: MERCURY
29-1
Partitioning and Control of Trace Metals during Coal and Waste Combustion
Jost O.L. Wendt
University of Arizona, USA
This paper reviews recent work directed towards mechanisms of interaction between
trace and toxic metals and alumino-silicates, calcium products and similarly based
substrates. Reactive scavenging processes such as these play dominant roles in
determining the partitioning of trace metals during coal and biomass combustion, and
in development of sorbents for the control of toxic metals (As, Se, Sb, Pb, Cd, Hg)
during waste combustion.
Tests on a 17kW laboratory downfired combustor allowed partitioning mechanisms
during coal combustion to be determined. A suite of six different coals was burned
under aerodynamically well defined, but practical conditions with no external heating.
Temperature histories, particle and gas concentrations were similar to those in coal-
fired boilers. Particles were extracted through an isokinetic, dilution probe, which
delivered the samples to a Berner Low Pressure Impactor (LPI). The LPI allowed
particle segregation down to 0.03m. Particles collected in the ultrafine particle size
mode represented material that was vapor or had just nucleated at the sampling point.
Mechanisms between metals and other constituents were inferred from associations
between elements in each particle size class. This was supported by special tests in
which additives, such as Ca, Fe, S or even As were added to coals in which these
elements were low. Reactions between trace metals and sorbents were investigated by
injecting aqueous or organic metal forms into a gas flame, with sorbent injection in the
post flame region, and samples withdrawn above the metal dewpoint.
In coals, As and Se react with, and track, calcium, provided this is present in sufficient
quantities. Otherwise, they react with Fe, unless much sulfur is present, in which case
the gaseous oxides are emitted. Sb can also form an oxy-ion and be bound on Ca and
Fe. Alternatively it is released as ultrafine particulate, or maybe gaseous, chloride,
depending on coal composition. Na, Pb, and Cs react rapidly with alumino-silicates,
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
from waste combustion, and the pertinent mechanisms of interaction with kaolinite are
now well understood, and have been quantified, for both single and multiple metals.
Finally, recent bench scale and pilot scale work on Hg sorption have shown that both
Hg0, and Hg++, can be chemisorbed at high temperatures on a sorbent containing both
kaolinite and calcium products, and derived from paper recycling wastes.
29-3
Mercury Behavior in Flue Gas Control System with Sorbent
Hiroshi Moritomi and Shinji Kambara
Gifu University, Japan
Naoki Fujiwara, Yoshio Fujita and Katsumi Tomura
Idemitsu Kosan Co. Ltd., Japan
Toxic metals that are very harmful to health are also included in the coal combustion
flue gases and on ash particles that are discharged to the atmosphere. The mercury
release behavior in bituminous coals, and the partitioning rate of mercury in solids and
gaseous in flue gases have already measured. The rate of mercury partitioned into
bottom ash in a bench-scale pulverized coal combustion furnace was a little and that
into cyclone ash was low below 10%. The rest of the mercury was partitioned into
mercury in gaseous form, but the rate partitioned into dust, oxidized mercury and
elemental mercury varied slightly depending on the flue gas temperature and the type
of coal. Therefore, in this study, the rate and behavior of the oxidized mercury and the
elemental mercury were measured in the condition of adding sorbent as well as
different coal ashes. The kind of tested sorbent to capture the mercury were sixteen
which were injected to make a thin bed on the filter. Experiments were carried out by
using a small fixed bed of sorbent with mercury gas of 260 to 290g/m3 to examine the
performance of mercury capture around 350 K and a flue gas duct of a bench-scale
pulverized coal combustion furnace of 42 mm ID and 1150 mm high to confirm the
performance to coal combustion gases around 450 K. In both experimental systems, a
continuous mercury monitoring equipment was used. The concentrations of oxidized
mercury and elemental mercury in gas and the total mercury in solid consisting of the
sorbent and the coal ash were measured.
Consequently, activated carbon, fluidized bed combustion ash, wasted catalyst and
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
mercury and elemental mercury, showed that the element mercury captured by the
sorbent once was changed into the oxidized mercury though it depended on the kind of
sorbent and the gas condition. The capturing rate of oxidized mecury was signifcantly
lower than that of elemental mecury. It means that there is a trade-off relationship
between oxidized mercury and elemental mercury. Furthermore, to improve the
performance of capturing mecury, it was very important to control the sorbent layer
produced by filtering the fly ash and sorbent particulate.
29-4
Impact of Boiler Operating Conditions on Mercury Emissions in Coal-Fired
Utility Boilers
Carlos E. Romero, Nenad Sarunac, Edward K. Levy, Harun Bilirgen and Ying Li
Lehigh University, USA
U.S. EPAs studies have determined that mercury emissions from coal-fired power
plants pose significant hazards to public health and must be reduced. Coal-fired power
plants represent a significant fraction of the anthropogenic emissions of mercury into
the atmosphere. Mercury emissions are impacted by factors such as coal type, boiler
operation, fly ash characteristics and type of environmental control equipment installed
on the unit. Field data show a wide variation in the fraction of mercury that is emitted
in the gaseous phase, as elemental mercury and HgCl2 vapor, and as particulate-bound
mercury. Oxidized mercury is a preferable species because is less volatile at stack
temperatures, water-soluble, and tends to interact with mineral matter and char, and
cold-end air pollution control devices. There is also evidence that boiler operating
conditions could be used to influence mercury behavior in the boiler, since they affect
the thermo-chemical conditions for mercury formation and reduction. However,
operation of the boiler control settings, which result in mercury removal benefits,
should also consider the tradeoff between mercury reduction and other emissions
(NOx, CO and SO2), the level of unburned carbon in the fly ash, unit efficiency and the
performance of particulate control equipment.
28
This paper reports work performed to investigate the feasibility of affecting mercury
emissions from coal-fired plants by manipulating boiler control settings. A theoretical
model was developed to analyze the effect of thermo-chemical conditions,
representative of coal-fire power plant exhaust gases, on the mercury fate, in relation to
boiler control settings. Full-scale testing was performed at two units. One of the units,
equipped with a train than includes a rotative air preheater followed by two
electrostatic precipitators in series. The other unit, equipped with hot and cold
precipitators and a tubular air preheater. A strategy for mercury control by selectively
manipulating boiler control settings, if used in combination with other control
measures such as sorbent injection, will provide a relatively inexpensive option for
mercury control.
29-5
Review of Advanced FGD Technologies and Associated Co-Benefits
Wojciech Jozewicz
ARCADIS, USA
Scott M. Smouse
US DOE, NETL, USA
This paper presents the review of advanced wet and dry flue gas desulfurization (FGD)
technologies capable of providing control of pollutants other than SO2. Various
technologies exist that have been designed to remove SO2 from flue gas produced by
electricity generating plants. However, more than 20 percent of coal-fired utility boiler
capacity in the United States uses wet FGD systems to control SO2 emissions.
Therefore, wet FGD advances to increase the performance of existing once-through
systems, enhance performance of new once-through wet FGD systems, and provide
capability to control pollutants other than SO2, such as mercury and NOX, are of high
interest. In order to enhance the mercury capture by wet scrubbers, two different
techniques could be considered: oxidation of elemental mercury prior to the wet FGD
units and prevention of the reduction of dissolved oxidized mercury in the wet
scrubber solution. Wet FGD with upstream oxidation of NOX to higher oxides of
nitrogen (such as in a LoTOx system) is capable of NOX control because these oxides
are water soluble.
Dry FGD systems can also be designed to provide the co-benefit of mercury control.
Spray dryer systems, which are used on more than 10 percent of the total U.S. coal-
fired utility boiler capacity to control SO2 emissions, have demonstrated efficient
removal of oxidized mercury. Other dry FGD processes may also offer the co-benefit
of mercury removal. Advanced dry FGD has shown high mercury removal rates with
lime sorbent. Other specialized sorbents offer the potential to capture more mercury.
For example, testing of dry mineral sorbent in the Pahlman Process indicated above 99
percent SO2, 93.6-96.6 percent NOX, and up to 67 percent mercury reduction in a
reactor, which operates at temperature between ambient and 160 oC.
It is expected that this review will be useful to a broad audience, including individuals
responsible for developing and implementing SO2 control strategies at sources, persons
involved in developing SO2 and other regulations, regulatory authorities implementing
SO2 control programs, and interested public at large.
SESSION 30
NON-FUEL UTILIZATION OF COAL: 2
30-1
Overview of Chemicals and Materials from Coal and Coal-Derived Liquids
Chunshan Song, Harold H. Schobert and John M. Andresen
Pennsylvania State University, USA
Chemicals and materials from coal have been recognized as an important area of
continued research and development for future coal utilization. This review discusses
current status and future directions and presents an update from our first major review
(C. Song and H. H. Schobert. Opportunities for Developing Specialty Chemicals and
Advanced Materials from Coals Fuel Processing Technol., 1993, 34 (2), 157-196).
Coal has several positive attributes when considered as a feedstock for aromatic
chemicals, specialty chemicals, and carbon-based materials. The pathways and status
of chemical processing of coal and coal-derived substances for making organic
chemicals and carbon products in the future will be different from the past efforts
during 1970s-1980s that could be characterized as coal-derived chemicals that are
alternatives to petroleum-derived chemicals. Substantial progress in advanced polymer
materials incorporating aromatic and polyaromatic units in their main chains has
created new opportunities for developing value-added or specialty organic chemicals
from coal and tars from coal carbonization for coke-making. The decline of the coal
tar industry diminishes traditional sources of these chemicals. The new coal chemistry
for chemicals and materials from coal may involve direct and indirect coal conversion
strategies as well as co-production approach. High-value chemicals can be obtained by
selective conversion of polycyclic hydrocarbons in coal and coal-derived liquids such
as naphthalene, biphenyl, and phenanthrene, over some zeolite catalysts. Examples
include shape-selective alkylation of naphthalene into 2,6-dialkylnaphthalene, ring-
shift isomerization of sym-octahydrophenanthrene into sym-octahydroanthracene,
shape-selective alkylation of biphenyl into 4,4-dialkylbiphenyl, conformational
isomerization of cis-decalin into trans-decalin, selective hydrogenation of naphthalene
into either cis- or trans-decalin, and regio-selective hydrogenation of heteroatom-
containing aromatic compounds such as 1-naphthol. The products of such selective
reactions are specialty chemicals, monomers of advanced polymer materials such as
high-performance polyesters, advanced engineering plastics, and liquid crystalline
polymers, or components of advanced thermally stable aviation jet fuels for high-Mach
aircraft. Needs for environmental-protection applications have also expanded market
demand for carbon materials. Carbon-based materials such as activated carbons for
gas-phase and liquid-phase applications are well known. Coal-based molecular sieving
carbons are important for industrial gas separations. Coal-polymer composites have
also been shown to be promising materials with interesting thermal and electronic
properties. Many items that we take for granted have some relation to carbon material,
including aluminum based products where anode carbon is used to reduce the
aluminum ore, steel from arc-furnaces using graphite electrodes, and even electric
contacts on the key-boards. However, the carbon we use is increasingly dependent on
the availability of petroleum-derived streams or other foreign sources. The decrease in
domestic produced oil and the subsequent reliance on imported crude oil may have a
serious impact on the future of carbon products and related materials in the US, since
many carbon products are typically based on petroleum coke. Coal-derived carbon
material can reduce the dependence on petroleum feedstock for carbon materials.
Advances have been made recently in making carbon binders from coal-derived
liquids, and graphite from high-rank coal (anthracite) based on pyrolytic conversion of
coal. More recent work demonstrates that fullerenes and carbon nano-tubes can also be
produced from coal.
30-3
Fractionation of Coal by Solvent Extraction at Different Temperatures below
350C
Kyosuke Nakagawa, Ryuichi Ashida, Hiroyuki Nakagawa and Kouichi Miura
Kyoto University, Japan
We have presented a new coal solvent extraction method that realizes not only
demineralization of coal but also coal fractionation in terms of molecular mass. Firstly,
2 types of extracts were obtained by using a flowing stream of the solvent under
10MPa at 350C. One of them is the fraction soluble at 25C (Frac-25) in non-polar
solvent such as tetralin and the other is the fraction which precipitates as solid at 25C
from the extract obtained at 350C (Frac+25-350). Then the Frac+25-350 was further
extracted stepwise at 150C, 200C, 250C, 300C, which could fractionate the coal
into 7 fractions. Ultimate analysis and molecular mass measurement showed that the
fractions obtained at lower temperature consisted of smaller molecular mass
compounds which were existent in the parent coal and have larger atomic H/C ratio.
Furthermore, 6 fractions except Frac+350 were almost free from inorganic materials.
Thermogravimetric and thermomechanical analyses of each fraction were performed to
characterize it for the use of raw material of high performance carbon materials. The
melting and plastic behavior of Frac+25-150 was very close to that of naphthalene-
based pitch which was synthesized for producing high performance carbon materials.
This result suggested a possibility of utilizing the fraction as a feedstock of high
performance carbon materials.
30-4
The Effect of Coal-Based Acid on the Biological Activity of the Herbicide
Tribenuron-Methyl
Shanxiang Li, Baoqing Li and Wen Li
Chinese Academy of Science, P.R. China
Caifeng Zhang
Taiyuan Teachers College, P. R. China
Water-soluble coal-based humic acids (WSCA) obtained following oxidation of
Wuchuan weathered lignite (W-WSCA) or by extraction from the Jincheng weathered
coal (J-WSCA), both enhanced the biological activity of tribenuron-methyl, a
herbicide. In the presence of the humic acid, the ED90 values for triberunon-methyl
increased by a factor of 4.28 (W-WSCA) or 2.52 (J-WSCA). FTIR indicated that the
main interaction between WSCA and herbicide was via hydrogen bonds. NMR showed
that the humic acid had a lower concentration of condensed aromatics. Molecular
dynamics simulation then established that this more open structure favoured interaction
between the herbicide and additive. The strong interaction between herbicide and
additive and consequent marked change in herbicide structure are probably related to
the improved biological activity of the herbicide.
30-5
Absorption and Fluorescence Properties of Silyl-Substituted Aromatic
Hydrocarbons
Hajime Maeda and Kazuhiko Mizuno
Osaka Prefecture University, Japan
Effects of trimethylsilyl, trimethylgermyl, and trimethylstannyl substituents attached to
polyaromatic hydrocarbons such as pyrene, anthracene, phenanthrene, and naphthalene
were examined in respect of UV absorption and fluorescence properties. Absorption
maxima of trimethylsilyl-, trimethylgermyl-, trimethylstannyl-substituted aromatic
hydrocarbons shifted to longer wavelength than those of unsubstituted aromatic
hydrocarbons. Absorption maxima of mono-, bis-, tris-, and
tetrakis(trimethylsilyl)pyrenes shifted to longer wavelength consecutively at intervals
29
of 10 nm. Fluorescence intensities and fluorescence lifetimes of trimethylsilyl-
substituted aromatic hydrocarbons were larger and longer than those of unsubstituted
ones, and they decreased in the order of Me3SiAr > Me3GeAr > Me3SnAr.
Fluorescence intensity of 1,3,6,8-tetrakis(trimethylsilyl)pyrene was largest among
those of a series of mono-, bis-, tris-, and tetrakis-(trimethylsilyl)pyrenes.
SESSION 31
GEOSCIENCES & RESOURCES
31-1
Evaluation of Prospect Hole for Methane Mining In Czech Republic
Zuzana Weishauptova and Jiri Medek
Institute of Rock Structure and Mechanics Academy of Sciences of the Czech
Republic, Czech Republic
Jaroslav Nemec
Eurogas, Czech Republic
In the Czech Republic, the Upper Silesian coal basin represents the largest potential
source of coal methane with the expected coal capacity for methane between 12 and 35
m3 per ton according to published data. At present, large-scale prospecting of virgin
coal bearing areas is conducted, aimed at gas-bearing of given seams and possibility of
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
trial bore as well as large number of laboratory tests is always indispensable. Results
from the trial bore indicating in situ conditions are corroborated with analysis of coal
characteristics directly related to gas-bearing properties, and are determinant for
certain states and processes connected to degassing of coal methane.
On the example of coal from a bore realized in the eladn-Krsn prospecting area in
the southern part of the Upper Silesian basin covered with Beskydy nappes, evaluation
is documented of the textural character of the coal and the overlaying rocks from the
viewpoint of gas-bearing and its correlation with gas permeability, and particularly
with respect to predicating ability of the laboratory determined methane partial
volumes according to the mode of binding and bearing by comparing with gas yield
found by a container test of the bore core. The method of analysis of the degassing
curve has been applied as well in connection with the time effectiveness of the bore
degassing.
According to the laboratory tests, the coal from the eladn bore has textural
conditions for economically exploitable gas-bearing. This has been confirmed by the
degassing tests of the bore cores from the coal seam horizons corresponding well with
the potential gas-bearing derived.
31-2
Potentially Hazardous Trace Elements in Coals from the Czech Republic
Ivana Skorov, Michal Vaek and Ondej Michna
Institute of Rock Structure and Mechanics, Czech Republic
Jii Peek and Karel Martnek
Charles University Prague, Czech Republic
Robert Finkelman, John H. Bullock, Jr. and H. Ron Affolter
United States Geological Survey, USA
Coal production and use have diverse impact on the surrounding land, atmosphere as
well as hydrosphere. The enormous volumes of waste material which are the by
products of both underground and surface coal mining, are one of the main pollution
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
information in the database. Statistical processing of data of almost 31 000 coal
samples from Late Paleozoic and Tertiary basins of the Czech Republic in the database
provided a survey of the quality of lignite, sub-bituminous coals, bituminous coals and
anthracites including ash and sulfur contents, mineralogical composition and
distribution of potentially hazardous trace elements (As, B, Ba, Cd, Cl, Co, Cr, Cu, F,
Hg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Th, U, Zn, Zr).
The database shows a broad spectrum of ash content Ad = 2.8 to 48 %, sulfur content
Std = 0.33 - 19.9 % in low rank coals, and sulfur content Std = 0.20 - 4.9 % in
bituminous coals and anthracites. Great variation in distribution of trace elements in
relation to the age of geological units and basins was observed in Czech coal seams.
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
Middle to the Late Namurian seams of the same basin are enriched in B, Ba, Bi, Nb,
Sc, Se, Sr, Te, U and Zr. The highest content of Cs and Hg was determined in the
Bolsovian coal seams of the Central Bohemian basins, whereas high concentration of
Be, Co, Cr, Mo, Ni and V was found in the Westphalian D coals of the same basins.
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 Krkonoe Piedmont basins.
Extremely high concentration of As, Be, Cs, Hg and some heavy metals was found
only in the Sokolov basin in the Oligocene coal seam rich in sulfides. For this reason
its exploitation was terminated in 1995. High content of As, Cd, Cu, Hg and Pb was
observed in coal with high content of sulfides while Be, Co and Cr were possibly
associated with clay minerals. Clay minerals, kaolinite and illite in particular,
pyrite/marcasite, quartz and carbonates (calcite, siderite and dolomite) represent the
inorganic admixtures in all coals. Comparing with Krejci-Graf (1972), Czech lignites
show higher concentration of Cs, Nb and Rb. It is to be also noted that the content of
Ag, Cs, Nb, Pb, Rb and Tl in Czech bituminous coals is in general much higher than
the highest values reported by Krejci-Graf (1972). Most of lignite and bituminous
coals from perspective deposits contain lower concentration of potentially hazardous
trace elements.
31-3
Evaluate the Feasibility of Enhanced Coal Bed Methane Recovery in Kyushu
Area
Kazunori Tamabayashi, Masayuki Sagisakaand Tadao Moro
Waseda University, Japan
At COP3 held in Kyoto in 1997, the reduction target of greenhouse gas was set up
for each developed country. Since Japans energy efficiency is at the worlds best
cross level, it is critical to establish an effective way to make use of the sequestration
technology which can isolate CO2 in large quantities in a short period of time.
Enhanced Coal Bed Methane Recovery (ECBMR) particularly attracts attention,
because it can achieve the recovery of methane and sequestration of CO2.
Conventional methods for the estimation of the Coal Bed Methane (CBM)
production and CO2 sequestration quantity include many uncertainties, since these
receive the various influences by geological feature, fluid property and injection
character. Therefore, the purpose of this study is to calculate the quantity more
accurately by using a new simulator in consideration of real geological feature, fluid
property and injection character. Moreover, I evaluate the feasibility of ECBMR in
Kyusyu area by analyzing the economic and environmental aspects.
This study consists of two parts according to the objectives.
(1) The condition of well patterns and the CO2 injection quantity which optimize the
potential of ECBMR.
(2The possibility of ECBMR as an environmental business by analyzing Life
Cycle CO2(LCCO2) and the cost.
In section (1), I studied the variation of CBM production and CO2 sequestration
quantity by varying the injection rate, pressure and the well spacing. In section (2),
focusing on CO2 production and reduction, I performed LCA on the inventory date
with regard to the ECBMR technology. In addition, I evaluated the revenue and the
expenditure of the ECPM operation.
CBM is considered as an alternative energy source of LNG. It became clear by
LCCO2 analysis that the use of CBM as energy reduces 6.54g per 1MJ of life cycle
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
ECBMR project. It is clearly suggested that this technology might succeed both
technologically and economically. When I maximized the quantity of CO2
sequestration without taking out financial loss, it was made clear that the benefit was
470 million yen in eight years and it can reduce about 0.8% of Japans yearly total
CO2 as of 2000. It was concluded that ECBMR has a great potential in feasibility as
an environmental project.
31-4
Distribution of Ge and Ga in Lignite
Zdenk Klika, Lenka Ambruova and Jana Seidlerov
VB-Technical University Ostrava, Czech Republic
Ivana Skorov
Academy of Science, Czech Republic
Most procedures for calculation of elements affinity between organic and inorganic
phases of coal are usually based on sink-float or other type technique of coal fractions
separation. For these procedures the assumption of constant concentration of element
in organic parts of all coal fractions (no matter to their ash contents) is usually applied.
The assumption about constant coal concentration is not always valid for elements with
high affinity to organic matter (e.g. Ge and Ga). The distribution of both element
concentrations in coal fraction separated by sink-float technique is shown including
their correlation with the lignite macerals.
31-5
Possibilities for Economic Utilization of the Seyitomer (Kutahya, Turkey) Lignites
and Oil Shales
Ilker Senguler
Mineral Research and Exploration of Turkey, Turkey
Although oil shales have many fields of use, the most commonly research is obtaining
of synthetic oil and its use as a solid fuel. In this study, the utilization of oil shales,
together with lignite in thermal power plant and oil extraction possibilities are
investigated. The Seyitmer lignite and oil shale deposit is located in ENE-WSW
oriented Neogene basin, NW of Kutahya, Western Turkey. The rock units exposed in
the investigated area from bottom to top are basement complex, lower conglomerate,
green clay, main seam (lignite), yellow clay, upper seam (lignite), limestone-tuff and
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
30
varying thickness in the basin and drilling data in operation site of lignite, the oil shale
reserve estimated to be 110 million tones. Samples collected from a number of 15
wells that cut oil shale were subjected to chemical analyses and mineralogic-
petrographic examinations.
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
produce synthetic oil. Therefore, a total of 150 tones oil shale and lignite sample
collected from the operation site was subjected to burn tests in a 2 MW power plant
with a circofluid fluidized bed combuster. Result of the tests yield that durable burn
was obtained if a material consisting of 80 % lignite and 20 % oil shale and that oil
shales assisted desulfurization due to their carbonate content.
If the mixing of oil shale and lignite is burned in new circofluid fluidized bed
combuster unit to be established in area, environmental impacts will be minimum. In
addition, oil shales that have been so far disposed as overburden material will be
economically consumed providing long life time for the coal to be used in thermal
power plant and other sectors.
SESSION 32
GASIFICATION ADVANCED TECHNOLOGIES 2: PYROLYSIS
32-1
Development of Coal Partial Hydropyrolysis Process
Hideaki Yabe, Takafumi Kawamura and Kohichiroh Gotoh
Nippon Steel Corporation, Japan
Akimitsu Akimoto
Center for Coal Utilization, Japan
Coal partial hydropyrolysis process aims at co-production of high yield of light oil
such as BTX and naphthalene and synthesis gas from a low rank coal under a mild
hydropyrolysis condition. The characteristic of this process is in the hydropyrolysis
reactor composed of the reformer and gasifier. So far, in order to evaluate the process
concept a small-scale basic experiment and a 1t/day process development unit study
were carried out. The experimental results showed that coal volatiles were partially
hydrogenated to increase the light oil and hydrocarbon gases at the condition of partial
hydropyrolysis. This process has a possibility of producing efficiently and
economically liquid and gas products as chemicals and fuel for power generation. As a
further development in the period of 2003 to 2008, a 20t/day pilot plant study is under
planning to establish the process technologies for commercialization.
32-2
Coal Pyrolysis under Elevated Pressure Conditions
Yukihiko Okumura
Maizuru National College of Technology, Japan
Ken Okazaki
Tokyo Institute of Technology, Japan
A coal pyrolysis experiment using a pressurized thermobalance is carried out in
conditions changing from normal to high pressure (10.6 ata) and from low-rank
(73.1C%, daf) to high-rank coals (90.6C%, semi-anthracite). The pressures impact on
rapid pyrolysis is discussed. Essentially, the novel heating configuration in the
experiments almost eliminated the secondary pyrolosis chemistry of volatiles, so that
the product distributions were especially well suited for calculating devolatilization
mechanisms. The consideration was developed by relating a gas release mechanism
under elevated pressure conditions to the polymer reaction in the coal.
Pressure suppresses tar vapor formation. The amount by which the elevated pressure
reduces the amount of released volatile matter almost equals the suppressed tar yield.
Calculations confirm also that the model, including the effect of vapor-liquid
equilibrium, is capable of quantitatively accounting for the actual weight loss of coal
under elevated pressure conditions.
In many types of coal, as pressure increases the CH4 gas yield increases and the CO,
CO2 gas yields increase slightly. The recombination reactions of the remaining
metaplasts (precursors of tar) are then activated, resulting in more intermediate chars
and higher gas yields.
In many types of coals, the C2-C3 gas yields tend to decrease as pressure increases.
Under atmospheric pressure, released tar tends to be captured in liquid form. Under
elevated pressure, on the other hand, solid substances such as soot, which contains
carbon, sulfur, and so on, tend to be captured instead of tar vapor.
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
(C%, daf) increases. The pressures ability to suppress evolvable tar tends to increase
as the coal rank increases.
The CO, CO2 gas yields decrease in proportion to carbon content under both
atmospheric and elevated pressure conditions. On the other hand, in many types of
coals the H2 gas yield doesnt change in atmospheric or elevated pressure conditions.
The CH4 and C2H4 gas yields (wt%, daf) are higher than any other yields of
inflammable gases in many types of coals.
 32-3
Evolution of Sulfur Containing Gases During Coal Pyrolysis in Various
Atmospheres
Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu
Dalian University of Technology, P. R. China
Coal is the main energy resource and consumption energy in China; meanwhile it is
also the main pollution contributor. Therefore, it is very urgent to make rational and
clean use of coal in China. And a better understanding of evolution of sulfur
containing gases in heat treatment is essential for effective and economical sulfur
removal and consequently for environment protection. In this study, four Chinese
coals, including Yanzhou (YZ), Datong (DT), Yima (YM) and Huolinhe (HLH) coal,
belongs to different rank and contains different sulfur content, were used to
investigate the effect of pyrolysis under different atmospheres on the evolution of
sulfur containing gases. The evolution rates of sulfur containing gases were measured
by temperature-programmed pyrolysis of coals in an atmospheric pressure, vertical
micro-fixed bed reactor. Compared with the evolution of sulfur containing gases in
N2, it indicated that CO promotes the decomposition of pyrite and sulfide and the
formation of COS. And most of the sulfide sulfur is converted into COS, only a little
is converted into H2S; CO2 prohibits the evolution of sulfur-containing gases at
temperatures below 600oC, above this temperature it shows similar effect on sulfur
containing compounds as CO does; CH4 prohibits the evolution of sulfur-containing
gases at temperatures below 600oC, and the extent is more pronounced than that of
CO2 does, but at temperatures above 800oC, CH4 promotes the formation of H2S;
H2 improves the formation of H2S and prohibits the formation of other sulfur-
containing gases.
32-4
Transformation of Inorganic Species in Coal during Pyrolysis
Koichi Matsuoka, Akira Takaya and Akira Tomita
Tohoku University, Japan
To avoid various ash-related problems during coal utilization technologies, it is
essential to understand the fundamental chemistry on the thermal behavior of inorganic
species, such as inherent mineral matter and ion-exchanged metal species. In this
study, we attempted to clarify the fate of these species during pyrolysis in a drop tube
furnace (DTF) and in a fixed bed reactor (FBR) with different residence times.
Whiteoak bituminous coal and Berau subbituminous coal are used in this study.
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
mineral matters in Whiteoak coal are calcite, dolomite, and ankerite. The total amount
of these species quantified by CCSEM was nearly equal to the Ca content determined
by ICP-AES. This indicates the absence of ion-exchanged Ca. On the other hand, the
main Ca species in Berau coal were crandallite and ion-exchanged Ca. XRD pattern of
raw Berau coal showed only a weak quartz peak, while XRD of the low temperature
ash revealed the presence of calcite and bassanite, which were derived from the
interaction of ion-exchanged Ca with CO2 and SO2 evolved during ashing.
Carbonate minerals were converted to lime upon the pyrolysis of Whiteoak coal in
DTF at 1500 oC, while the interaction of carbonates with other mineral matters was
hardly observed. In the case of pyrolysis of Berau coal in DTF, a considerable amount
of crandallite disappeared and it was found that most of ion-exchanged Ca was
converted to very fine particles of oldhamite (CaS) that cannot be detected by CCSEM.
The interaction with other minerals was marginal due to the short residence time in
DTF. When pyrolysis was carried out with a longer residence time in FBR, the size of
oldhamite increased enough to be detected by CCSEM. Furthermore, the interaction of
fine Ca species with aluminosilicate minerals became remarkable.
In conclusion, atomically dispersed Ca species in Berau raw coal was converted in
DTF to very fine CaS, and upon longer exposure to 1500 oC it was subjected to
crystallite growth as well as interaction with aluminosilicates.
32-5
Studies on the Secondary Reactions Subsequent to Rapid Pyrolysis of Coal
Osmau Yamada, Hajime Yasuda and Mamoru Kaiho
National Institute of Advanced Industrial Science and Technology, Japan
Aihua Zhang
California Stste University, USA
In order to evaluate an entrained flow gasification process, reaction occurred in rapid
pyrolysis of coal under high temperature and high pressure should be well understood..
Conventionally rapid pyrolysis of coal has been fundamentally studied by using a
Curie-point pyrolizer, a drop tube furnace, a wire mesh grid method and so on.
Reaction conditions in these experiments, however, are thought to be considerably
different from that occurred in an actual gasifier. We have developed a special
apparatus that enable an investigation of a rapid pyrolysis of coal under
similar conditions in an actual entrained flow type gasifier. Coal was blown into the
reaction chamber at 800 $B!n (B and 7.1MPa to complete pyrolysis for the duration
of 1 to 80 seconds, Gas generated in the reaction chamber was transferred to the gas
reservoir which was kept vacuum, after prescribed reaction time to quench pyrolysis of
coal. The volume and the composition of gas generated during pyrolysis were
31
determined by GC and GC-MS. The material balance between coal and products based
on C, H and O was calculated. Initial stage of coal gasification including the secondary
reactions subsequent to rapid pyrolysis of coal is discussed.
SESSION 33
LOW RANK COAL UTILIZATION: 2
33-1
Upgrading Low Rank Coals by Mechanical Thermal Expression (MTE)
Yuli Artanto and Alan Chaffee
Monash University, Australia
Over recent years the Mechanical Thermal Expression (MTE) process has emerged as
a highly prospective approach for dewatering/upgrading low rank coal. The process
involves the use of moderate temperatures (150-220 C), which can soften the coal
and facilitate water removal via the application of mechanical pressure (3-12 MPa).
Some organic and inorganic components can also be removed with the water. The
process is being evaluated at pilot scale in both Germany and Australia.
This report compares the effectiveness of MTE for the beneficiation of a suite of low
rank coals from Australia, Indonesia and India, as determined at laboratory scale.
We have observed that the percentage water removal decreases as the original water
content of the raw coal decreases such that, for the same MTE conditions, the data for
all lignites we have examined fall close to a single trend line. The extent of water
removal can still be significant in the sub-bituminous rank range, especially when
higher temperatures are used.
The removal of inorganics is variable depending on the mineralogy of the original coal.
The removal of organics increases with temperature.
Other product characteristics, such as moisture holding capacity and shrinkage during
drying (at 105 C) are principally affected by temperature. The helium density (true
density) and elemental components (C, H, N ,O) of the coals are not affected within the
limits of measurement error.
33-2
Comparison of Physico-Chemical Properties for Various Lignites Treated by
Mechanical Thermal Expression
Janine Hulston and Alan L. Chaffee
Monash University, Australia
Christian Bergins and Karl Strauss
University of Dortmund, Germany
A significant proportion of the worlds energy reserves consist of lignites with high
moisture contents of between 40 and 65 wt % (wb). When the raw lignite is burnt in
conventional power stations, up to 20 % of the chemical energy of the lignite is lost
due to the latent heat of vaporisation of water within the lignite structure. Relative to
black coal or gas-fired power stations, this results in larger boiler and equipment
requirements, reduced thermal efficiencies and, consequently, higher CO2 emissions
per unit of electricity produced.
The mechanical thermal expression (MTE) process is currently being investigated as a
means of reducing the moisture content of lignites prior to combustion or gasification.
This is achieved via mechanical expression (4 to 12 MPa) carried out at elevated
temperatures (< 200 C), whereby the water is removed in the liquid state. The MTE
process has been shown to be effective in reducing the moisture content of lignites and
thus has the potential to be retrofitted to existing power plants to improve their
efficiency, or be advantageously implemented in new, energetically optimised power
plants. In addition, MTE products could potentially be considered for the export
market due to the significantly improved energy density, thus making it economically
more viable to transport.
This paper focuses on the effects of MTE processing conditions on the physico-
chemical properties of various lignites after MTE processing and drying at ambient
conditions. Particular emphasis is placed on materials characteristics that are
considered important for transportation, handling and storage. A range of properties
has been collated for MTE products prepared at laboratory scale. This includes
moisture content after MTE processing, moisture content at ambient conditions,
shrinkage, porosity, apparent density, hardness, weathering, surface area and
spontaneous combustion behaviour. These properties will be compared with those of
some typical lignite derived briquettes.
33-3
Upgraded Brown Coal (UBC) Mine Mouth Power Plant in Indonesia
Environmentally Friendly Low CO2 Emission Lignite Based Power Plant
Eiichiro Makino
Nissho Iwai Corporation, Japan
Yasuo Otaka
Japan Coal Energy Center, Japan
Takuo Shigeshisa and T. Deguchi
Kobe Steel, Ltd., Japan
Kazuo Miyama
Babcock-Hitachi K.K., Japan
Masaaki Ebina
Nippon Koei Co., Ltd., Japan
 Teddy Setiawan
PT. Triaryani, Indonesia
Life Cycle Assessment (LCA) is a useful tool to evaluate the environmental aspects
and potential impacts associated with a product throughout its life span. LCA method
is applied for the evaluation of CO2 emission to compare the Upgraded Brown Coal
(UBCR) Fired Power Plant with the proven Low Rank Coal (LRC) Fired Power Plant
at Mine Mouth in Indonesia. The UBC technology of which basic patent owned by
Kobe Steel Ltd. Japan confirmed to be one of the ultimate solutions for the utilization
of lignite effectively judging from the environmental and economical point of view.
33-4
Application of the Hyper-Coal Process for Low Rank Coals Upgrading
Noriyuki Okuyama, Nobuyuki Komatsu and Takuo Shigehisa
Kobe Steel, Ltd., Japan
Takao Kaneko
Mitsubishi Chemical Corporation, Japan
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 low rank coal is generally small, since it contains a large amount of moisture (20-
60 %). In addition to that, the high transportation cost causes the small utilization, such
as a feedstock for the local power plant, in the present situation. On the other hand, a
large part of the low rank coal contains a small amount of ash and/or sulfur. Therefore,
the increasing in the low rank coal utilization will be an effective way to promote the
clean coal diffusion.
It can be said that the large moisture content is the principal reason to avoid the
diffusion of the low rank coal. When the low rank coal is simply air dried, a strong
spontaneous combustionability will be appeared. Therefore, to realize the efficient
upgrading for the low rank coal, the action to remove the moisture and to reduce the
spontaneous combustionability in the same time is needed.
Hyper-coal process, which has been developed since 1999, is an ash free coal
manufacturing process by using the solvent de-ashing technology. Coal is extracted
into the coal-derivative two ring aromatics at 350-380 oC. The solution is separated
from the insoluble residue by the gravity settling and/or the filtration. Solvent is
recovered and recycled in the process. Ash-free extracted coal (Hyper-coal, HPC) and
ash-concentrated residue coal (RC) are obtained in this process. Usually, some
bituminous coals are found out to get a high yield of Hyper-coal (>60%).
This paper focuses of the application of the Hyper-coal process for the low rank coal
upgrading. Mulia coal, an Indonesian brown coal, 25 % of moisture content, 2 % of
ash content and 0.2 % of sulfur content was used in this study. As the result of coal
extraction test, the HPC yield from Mulia coal was only 30 % on daf, and RC yield
was more than 50 %daf. Usually, such a yield structure cannot be accepted in
economy. On the other hand, looking at the RC properties, the obtained RC has only 5
% of ash, and the calorific value was increased from 5400 kcal/kg to 7300 kcal/kg,
which was almost same level to the bituminous coal. Those improvements were
produced not only by the effect of dewatering, but also by the effect of removing the
oxygen-containing functional groups. It can be said that the Hyper-coal process may be
an effective way to upgrade the low rank coal, which produces not only the ash-free
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
oxygen-containing functional groups.
33-5
Effect of Pretreatment with CO2 Dissolved in Water on HyperCoal (ash-free
coal) Production from Low-Rank Coals
Kensuke Masaki, Nao Kashimura, Toshimasa Takanohashi, Shinya Sato,
Akimitsu Matsumura and Ikuo Saito
National Institute of Advanced Industrial Science and Technology, Japan
HyperCoal (ash-free coal), which can be used as a feedstock for gas turbine to
achieve higher net power output as well as lower CO2 emission, is produced by thermal
extractions with industrial organic solvents under inert atmosphere. Use of low-rank
coals as raw materials for HyperCoal production can be very advantageous with
respect to production cost, and stable supply of low-rank coal resources.
In this study, the effect of pretreatment with CO2 dissolved water (CO2/H2O) on the
HyperCoal yields was investigated to produce HyperCoals from low-rank coals
efficiently.
Coal and deionized water (with 10 wt% ethanol) were mixed in an autoclave under 1-
70 atm (Gauge pressure) with CO2 at 25 oC for 24 h. Thermal extraction was conducted
using a flow-type extractor at 200-360 C. Crude methylnaphthalene oil (CMNO) and
crude quinoline (CQ), which are obtained from coal-tar distillation process, were used
as extraction solvents.
A remarkable positive effect was found even under lower treatment pressure (1 atm);
the thermal extraction yields at 360 oC were increased by 9-16 %, resulting in the high
extraction yields of about 55 % and 45 % for Wyodak subbituminous coal and Beulah-
zap lignite, respectively. In addition, CMNO extraction yields of pretreated Wyodak
coal were significantly increased from 320 oC to 360 oC, and these increased extraction
yields were 5-13 % higher than those of raw ones. Therefore, the CO2/H2O
32
pretreatment can be effective for production of HyperCoals from low-rank coals. The
mechanism of increment in the extraction yields by the pretreatment will be presented.
SESSION 34
INTERNATIONAL COAL TECHNOLOGY COOPERATION: 2
34-1 IEA-China Power Plant Optimisation Study
Rupert Clarke
Mitsui Babcock, UK
Peter Nowak
Siemens, Germany
Bert van Vliet
NOVEM, The Netherlands
Leopold Zarowski and Jaroslaw Ciesielski
Alstom, Poland
Peter Rozelle
UD DOE, USA
Jack Cunningham and Keith Burnard
AEA Technology, UK
The power industry in China is rapidly expanding and, at the same time, undergoing
significant institutional change. The installed power generation capacity of China is
the second largest in the world, next to the US. It is estimated that China will need to
install 800GW of new capacity by 2030, much of which will be coal fired. Coal is the
main fuel for power generation in China; it fuels around 78% of the electricity
generation mix and 95% of the fossil-fired electricity generation capacity. This clearly
has major implications for the environment. For sustainable development of the
electric power industry, China must improve its energy conversion efficiency and
reduce its emissions.
One contribution to reducing these emissions is to improve the performance of existing
coal-fired plant. A project based on this approach was developed by the International
Energy Agency, China's Ministry of Science and Technology and two of China's newly
formed power companies, the China Power Investment Corporation and the China
Datang Group. The project involved a team of Western power plant experts, brought
together under the auspices of the International Energy Agency. Following audit of
two typical coal-fired power plants in China, the team considered the potential to
improve efficiency and reduce emissions based on current best practice in
industrialised countries.
Led by the UK, the international team of experts spent one week at each of the two
plants: Tongliao Power Plant, Tongliao, Inner Mongolia and Tianjiaan Power Plant,
Huainan City, Anhui Province. Central to the success of the project was the close
working relationship built up between the international team, the technical staff at the
plants and the staff member seconded to the team from China's Thermal Power
Research Institute. Following the visit to China a summary visit report was produced,
in which preliminary findings were presented. Closer analysis of the data is currently
ongoing, some of which is presented in this paper.
The success of the project will be measured, first, against the extent to which the plants
investigated will implement the measures identified by the IEA team and, second,
against the broader take up of the measures at the numerous similar power plants
throughout China.
34-2
Analysis on Energy Production and Consumption of Recent Years in China
Hailin Mu and Yasuhiko Kondou
AIST, Japan
Weisheng Zhou
Ritsumeikan University, Japan
Yutaka Tonooka and Sakamoto Kazuhiko
Saitama University, Japan
The energy consumption statistics indicate that Chinas primary energy consumption
revealed a peak in 1996 and then began to fall year by year. It reached the minimum in
1999 and fell by 6.35% compared with that in 1996, driven almost by declining the
direct use of coal. Since 2000, Chinas primary consumption has just expressed an
increasing trend and it exceeds that of 1996 until 2002. Because Chinas economy still
kept the higher economic growth rates of around 8%~8.5% in these years, this
dramatic shift of primary energy consumption naturally cause a question for energy
consumption statistics: may the reported statistics be seriously flawed or not?
Since China is the second largest country of CO2 emission in the world, it is very
important to clearly understand this shift and obtain the right energy consumption
statistics, and thus to be able to estimate Chinas CO2 emission reasonably. In this
paper, on the basis of analyzing the coal production situation, energy consumption
policies, environmental protection policies, changes of industrial structure and
improvement of industrial technologies and equipments, we modify the Chinas energy
consumption statistics of recent years.
The original points of this study are as follows.
Through analyzing the statistic-investigation system and according to the import &
export amounts of petroleum products, the more reasonable energy consumption
statistics are extracted from the two kinds of Chinas energy consumption statistics: the
whole country and sum by province;
According to the coal consumption and production policies, the improvement of coal
ranks (heat values) is estimated in recent years;
The implementations of more and more serious energy-conservation and
environmental protection policies promote the improvement in energy use efficiency.
Meanwhile, the reported statistics may be made to reduce intentionally since the
rewards and penalties of energy-conservation are considered to a company or the local
government. This part of reduced coal consumption amount is estimated in this paper.
The China central government enacted that 20000 or more of coal mines, which are
non-state ownership and whose scales are small and 30~40 state ownership coal mines
will be closed in order to improve the raw coal quality and reduce the coal production
accidents. However, a part of them secretly carry out the production continuously or
time and again. Therefore, this policy, on the one hand can enhance the quality of raw
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
part of coal consumption is estimated in this paper.
34-3
Effect on Coal Rank on Equipment and Performance of a Coal Fired Power Plant
Nusyirwan
PT Indonesia Power, Indonesia
All fossil fuel fired boilers are designed to burn a specific type of fuel. Furnace size
increases dramatically as heating values of fuels decrease. Heating surface are sized,
positioned, and spaced according to the fuel and ash characteristics. Gas fired units are
smaller, since the cleanliness of gas allows for closer spacing of assemblies and the
higher heating value of the fuel means less fuel fired for the required heat release. Coal
fired units must be larger to allow wider spacing of assemblies and greater volume for
burning more fuel for the same heat release. Coal quality has perhaps the greatest
affect of all the factors on boiler efficiency and other plant equipment. Boilers are
designed to burn a given fuel within a specified optimum range of composition to meet
performance guarantees. Any variation from that composition will affect the operation
and performance, notably capacity, efficiency, reliability, availability and maintenance.
Therefore it is very important to know its combustion characteristics and to determine
how the fuel switch will affect boiler performance and other plant equipment. This
report examines the experience of Suralaya coal fired power plant when firing out-of
design coals.
34-4
Japanese Coal Preparation Technology Transfer to Developing Countries
Hajime Endo and Nobuhiro Koyanagi
JCOAL, Japan
Yasuo Kubo
Nagata Seisakusyo Co., Ltd, Japan
Japan Coal Energy Center (JCOAL) has been carrying out coal preparation technology
transfer to developing countries producing coal in Asia, entrusted by Japanese
governmental fund since 1994. The paper will introduce the outline of the project,
especially in China and Vietnam as a latest case study and the technology of VARI-
WAVE jig developed in Japan as a technical topic. The VARI-WAVE jig is an
improved conventional jig and has been achieved excellent performance in Japanese
coal preparation plants by using variable wave pattern.
Moreover, the importance and potentiality of coal preparation technology against
environmental related issue in developing countries thinking about the matter in terms
of Clean Coal Technology will be emphasized in this paper.
34-5
The Conception of the Information Sending Bases on Clean Coal Technology
(CCT) in Asian Area
Ikuo Saito
AIST, Japan
Takayuki Takarada
Gunma University, Japan
Yoshikazu Ikai and Fumio Hiraguri
Center for Coal Utilization, Japan
Yasuo Otaka
JCOAL, Japan
In Asian area, coal is very important energy resources and accounts for the major
portion of primary energy supply now and future. To use CCT should be needed for
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
bases on CCT in Asian area which is entrusted by NEDO (New Energy and Industrial
Technology Development Organization) is to improve the energy and environmental
issues in those areas and to establish the CCT network in Asia. Information sending
bases are expected to help each country to develop CCT suited for the situation of
each country. For that purpose, Japan will help these activities to develop a foundation
of CCT by each country and to bring up the experienced person on CCT. Through the
following work program, the results will be expected to attain.
Work program
33
Bringing up the experienced person in Asian area
Lecture at a university and/or a training institute by Japanese experts, and others
Joint development work
Finding research project and CCT suited for each country, and others
3) Spread and enlightenment of CCT
Support to held CCT seminar, and others
Expected results
1) Efficient coal utilization technology will spread in Asian regions.
2) Utilization of Japanese CCT will be promoted.
3) R&D on coal utilization technology and bringing up of experienced person will be
promoted.
4) CCT network in Asia will be built up.
SESSION 35
ENVIRONMENTAL CONTROL TECHNOLOGY 6: MERCURY
35-1
Catalytic Materials and Oxidation Condition for Mercury Oxidation in
Combustion Flue Gas
Akimasa Yamaguchi, Yoshihisa Tochihara and Shigeo Ito
Central Research Institute of Electric Power Industry, Japan
When a fossil fuel or a refuge-derived fuel is burned, gaseous elemental mercury
(Hg0), gaseous oxidized mercury (Hg2+) and particles-bound mercury (Hgp) were
generated in the flue gas. The capture of Hg by flue gas cleaning devices is dependent
on Hg speciation. Hgp can be captured by electrostatic precipitators or fabric filters.
Hg0 is insoluble in water and cannot be captured in wet scrubbers. The predominant
Hg2+ compounds in flue gas are weakly to strongly soluble, and more-soluble species
can be generally captured in wet scrubbers. Therefore, if insoluble Hg0 can be oxidized
to soluble Hg2+, Hg emissions to the atmosphere can be controlled with wet scrubbers.
In this study, the effects of temperature (363-573K), HCl concentration (1-100ppm),
and the presence of steam on the oxidation of Hg0 were evaluated. Some catalytic
materials were placed in simulated flue gases containing N2, CO2, O2, HCl, SO2, NO,
and steam, and the conversion of Hg0 was examined.
Some metallic oxides could convert Hg0 to Hg2+ at low HCl concentration (<5ppm) at
423K. The conversion rate was affected by the presence of steam and temperature. The
most efficient catalyst showed the conversion rate more than 90% at 2ppm of HCl and
363K.
35-2
Behaviors of Mercury in Solid Fuels and Wastes during Combustion/Gasification
Processes
Hong Yao, Tamotsu Kameshima, Yohei Takigawa and Ichiro Naruse
Toyohashi University of Technology, Japan
Mercury emissions from combustion/gasification processes of solid fuels and wastes
are greatly concerned in many industrialized countries. A variety of control strategies
are now under intensive development. Usually, mercury exists as elemental mercury
and oxidized mercury such as Hg, HgCl2, HgS and so forth. The elemental mercury
easily passes through particulate control devices since it is gaseous phase even at
ambient temperature. The oxidized mercury, however, is water-soluble, hence some
can be removed by wet desulfurization processes or wet scrubbers. Speciation of the
mercury compounds in combustion/gasification processes is, therefore, a particularly
important issue to develop the appropriate mercury control strategies.
In this study, first, thermo-gravimetric (TG) experiments were carried out to
understand fundamentals of mercury evolution behaviors under the combustion and
gasification conditions, using three types of coal and dried sewage sludge as the
samples. Then, one sample was burnt in an electrically heated drop tube furnace to
study the evolution behavior of mercury in semi-practical combustion processes.
Moreover, chemical equilibrium calculation predicted the tendency of mercury
evolution under the same experimental conditions. Meanwhile, the kinetic calculations
of mercury oxidation phenomena were also conducted to analyze the time evolution
behaviors of all mercury species concentrations, using CHEMKIN. The results
obtained show that sulfur content in the fuels inhibits the evolution behaviors of
mercury during sludge combustion. For coal, while, the fixed carbon content in the
coal plays an important role for the mercury evolution. Under the gasification
condition, however, the evolution of mercury becomes quickly because of the
elemental mercury is easily produced. The calculation prediction also shows that the
oxidation processes of mercury depend on some radicals, especially for Cl radical
produced.
35-3
Characteristics of the Removal of Mercury Vapor in Flue Gas by Activated
Carbon Using H2S
Eiji Sasaoka, Takefumi Morimoto and Shengji Wu
Okayama University, Japan
Md. Azhar Uddin
University of New South Wales, Australia
The major anthropogenic sources of mercury emission are coal combustion. However,
it is very difficult to remove the mercury compounds from the flue gas. Especially,
Elemental mercury vapor is not effectively captured in typical air pollution control
device.
We had presented an Hg removal method using H2S and activated carbon. This method
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
well understood yet.
In this work, the characteristics of the Hg removal were studied. The following results
were obtained: (1) the temperature range from 60 to 80oC was preferable for the Hg
removal. (2) At 150oC, the co-presences of H2S, SO2 and O2 were indispensable for the
Hg removal. (3) The effect of the presence of H2O accelerated the removal at 80oC but
depressed it at 150oC.
35-4
Use of a Semi-Continuous Emissions Monitor for Measurement of In-Duct
Mercury Removals by Sorbent Injection
Andrew Karash, Richard A. Harris and William J. ODowd
US DOE, NETL, USA
A 500-lb/hr pulverized coal-fired combustion system at the National Energy
Technology Laboratory (NETL) was used to evaluate mercury sampling methods, as
well as sorbent injection for mercury removal. Measurements characterized the
impact of duct temperature, residence time, and sorbent injection rate on mercury
removal effectiveness of a commercially available activated carbon (Darco FGD,
manufactured by Norit Americas Incorporated). A Powder River Basin (PRB) sub-
bituminous coal was used in the tests. In-duct removals were studied with the use of
a Quicksilver Inertial Separation (QSIS) probe developed by Apogee Scientific.
Mercury measurements were made using a PS Analytical semi-continuous emissions
monitor (SCEM), EPA Method 101A, ASTM Method D6784-02 (Ontario-Hydro
method), and the Frontier Geosciences solid sorbent speciation method. Sampling
locations were upstream and downstream of the main baghouse on the 500-lb/hr unit
to determine in-duct removal, removal across the baghouse and material balances. A
summary of the mercury measurement and removal results is presented. In general,
there was good agreement between the different measurement techniques employed.
Baseline mercury speciation results and sorbent mercury removal performance were
similar to values reported from full-scale testing at the We Energies Pleasant Prairie
Power Plant firing the same coal. Sampling, operating, and maintenance procedures
which contribute to increased stability and precision of SCEM measurements are
discussed.
35-5
Characteristics of the Removal of Mercury Vapor in Coal Derived Fuel Gas by
Iron Oxide
Shengji Wu and Eiji Sasaoka
Okayama University, Japan
Md.Azhar Uddin
University of New South Wales, Australia
The major anthropogenic sources of mercury emission are coal combustion.
However, it is very difficult to remove the mercury compounds from the fuel gas.
Especially, Elemental mercury vapor is not effectively captured in typical air
pollution control device. Furthermore, the coal gasification will be a main utilization
method of coal in near future. In this case, the Hg in the coal derived fuel gas has to
be removed before use.
We had presented an Hg removal method using iron for the coal derived fuel gas.
This method 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 well understood yet.
In this work, the characteristics of the Hg removal were studied. The following
results were obtained:
(1) The presence of H2S was indispensable to the Hg removal for the coal derived
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.
(4) At high temperature of 150oC, the absence of CO depressed the Hg removal.
SESSION 36
COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 1:
KEYNOTE LECTURE & COKEMAKING PROCESS, COKE QUALITY
36-1
120 Years of Coke Reactivity
Richard Sakurovs
CSIRO, Australia
The study of the reaction of coke with carbon dioxide at high temperature has a long
history. In 1884 it was studied to see if it could explain a perceived difference
between the behaviour in blast furnaces of beehive-produced coke and the newly-
introduced by-product oven. Interest in coke reactivity has waxed and waned over
the years, depending on how critical its measurement and prediction is felt to be by
blast furnace operators at the time. This Keynote presentation will provide a brief
34
historical context for coke reactivity, some progress in measuring and understanding
it and predicting its extent that has been made in recent times, and the future
requirements that will be placed on coke reactivity as blast furnace operators
continually strive to have their furnaces become more efficient.
36-3
Development of SCOPE21 Cokemaking process
Kunihiko Nishioka, Isao Sugiyama, Hironobu Oshima and Hideki Fujikawa
The Japan Iron and Steel Federation, Japan
Kenji Kato
Nippon Steel Corporation, Japan
Development of the innovative cokemaking process, SCOPE21 (Super Coke Oven for
Productivity and Environmental enhancement toward the 21st century) has been
conducted by Japan Iron and Steel Federation (JISF) and Center for Coal Utilization
Japan (CCUJ). It has been performed from 1994 to 2003 as a ten-year research
program. Some technologies for SCOPE21 process have been developed to realize the
following concepts.
Effective use of coal resources
High productivity
Energy saving
Environmental protection
In 2002 the program was in the last stage of a pilot plant test to confirm the function of
the SCOPE21 process and to collect the scale-up data for designing a commercial
plant. The pilot plant was successfully operated for about one year until March 2003.
The concepts of the SCOPE21 process were verified and the engineering data for
designing a commercial plant was collected at the same time.
36-5
Evaluation of a CO2 Reaction Mechanism of Coke using Microfocus X ray CT
Hidekazu Fujimoto, Izumi Shimoyama, Kiyoshi Fukada, Tetsuya Yamamoto and
Shozo Itagaki
JFE Steel Corporation, Japan
Improvement of coke strength against abrasion at the lower part of blast furnace is
needed for a stable operation. Pore structure of coke is important for an improvement
of coke abrasion strength, because its effect influences CO2 diffusion coefficient and
coke strength after CO2 reaction. In this study, production of coke samples having
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
reaction was investigated.
In case that larger size (2-3 mm) slightly caking coal was added to coal blend and
carbonized, the pore size distribution of coke became wider and contained larger pore
which had higher value of tortuosity than the coke produced by adding smaller size (1-
2 mm) slightly caking coal particles. There were differences in the reactivity and
reactivity profiles in the coke lump analyzed by X-ray computerized tomography
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
concentration of shear stress easily occurs around large pores. Based on this
knowledge, production technology of high strength coke against abrasion after CO2
reaction was developed by means of controlling coal particle size and it is applied to
industrial coke production.
SESSION 37
MATERIAL, INSTRUMENTATION & CONTROLS 1: USC POWER
PLANTS
37-1
Development of Creep and Type IV Resistant 9%Cr Steel Containing High Boron
for USC Boilers
Hiroyuki Semba, Masayuki Kondo, Masaaki Tabuchi and Fujio Abe
National Institute for Materials Science (NIMS), Japan
Tungsten bearing 9-12% Cr ferritic heat resistant steels, such as P92 and P122 showing
higher creep rupture strength than the conventional steel P91, have been developed for
thick section components in ultra-supercritical (USC) boilers. However, their creep
strength is not sufficient for applying at the steam condition of 923K/35MPa or more,
which is a recent target condition in order to increase plant efficiency. Furthermore,
Type IV failure in the heat affected zone (HAZ) of welded joints is a crucial problem
for these high-Cr ferritic steels, leading to shorter creep lives than those of base metals.
The research and development project in NIMS on advanced ferritic steels which can
be applied at the steam condition of 923K/35MPa as boiler components with large
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-
<0.003N steel remarkably improves creep strength. The highest creep rupture strength
is obtained in the 0.08C-9Cr -3W-3Co-V,Nb-0.0139B-<0.003N steel, resulting in
excellent creep strength in comparison with that of P92 and P122. FE-AES analysis
clarified that the boron content in M23C6 carbides near prior-austenite grain boundaries
is higher than that inside the grains. This may suppress coarsening of M23C6 near
prior-austenite grain boundaries during creep deformation, leading to sufficient
microstructural stability and excellent creep strength. It has also been demonstrated
that Type IV failure does not occur during creep tests at 923K performed on welded
joints of these high-B containing steels even at the stresses in which P92 shows Type
IV fracture. Retardation of M23C6 coarsening mentioned above and the HAZ
microstructure consisting of relatively coarse grains, which is entirely different from
that in ordinary high-Cr ferritic steels, may contribute to superior creep rupture
strength of these welded joins. Hence, it is concluded that this high-B bearing 9Cr-
3W-3Co-V,Nb steel is one of the promising candidate steels for thick section
components in the advanced USC boilers.
37-2
Mechanical Properties of Ultrasupercritical Steam Generator Materials
John P. Shingledecker, Robert W. Swindeman, R.L. Klueh and P.J. Maziasz
Oak Ridge National Laboratory, USA
Higher steam temperatures and pressures are required to achieve increased efficiency
and decreased CO2 emissions in coal-fired boilers. A research program has been
initiated for evaluating the mechanical properties of materials in an Ultrasupercritical
(USC) Steam Generator operating with a main steam throttle condition of
720/760C/35MPa. Current boiler materials, which typically operate below 600C,
cannot meet the high-temperature strength requirements of such a design, and thus
advanced materials must be utilized. A program at Oak Ridge National Laboratory is
generating the materials property data and performing materials analysis on a selection
of advanced materials. These materials include ferritics (SAVE12), austenitics (Super
304H, HR6W), and superalloys (Haynes 230, CCA617, INCONEL 740). High-
temperature mechanical properties research includes: creep/creep-rupture, fatigue,
structural discontinuities (notches), weld evaluation, and weldment properties. The
rationale for the selection of materials and test results, with over 8,000 hours of test
data, will be discussed.
37-3
Improvement of Steam Oxidation Resistance for USC Boiler Steels
Hiroshi Haruyama, Hiroyuki Kutsumi, Seiji Kuroda and Fujio Abe
National Institute for Materials Science, Japan
Considering recent global environmental problems, it seems to be an
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
tubes for USC boilers, are required to withstand high temperatures of more than 873K
over long periods. Targeted steam conditions have been increased up to 903K, 30MPa.
Thus, it is necessary to develop new steels whose creep strength and steam oxidation
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
study on the oxidation behavior for a variety of heat resistant steels in steam. On the
other hand, we have also tried to improve the steam oxidation resistance by forming a
protective Cr oxide layer.
Generally, as Cr concentration is high, steam oxidation resistance is better. And
small amounts of Si are effective on the steam oxidation resistance. Our experimental
result has suggested that trace amounts of S are suggested to have a certain
contribution to oxidation resistance in steam at 923K. Although these effects of Cr, Si
and S are considered, from a viewpoint of oxidation resistance, practical steel is not
developed yet above 923K.
On the other hand, we have also tried to improve the steam oxidation resistance
by forming a protective oxide layer. When surface strained high-Cr ferritic steels with
small amounts of Pd was oxidized in steam at 923K, protective and thin Cr-rich oxide
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
layer. The steam oxidation resistance at 923K was dramatically improved by these
protective oxide layers. In a steam temperature over 973K, austenitic steels are used
from the viewpoint of creep strength. The protective oxide layer is formed on the
surface of austenitic steels by shot peening. Thus, austenitic steels treated by shot
peening are in practical use.
37-4
Ultra-Steel R & D in NIMS for USC Power Plant at 650oC and Above
Fujio Abe
National Institute for Materials Science (NIMS), Japan
Since 1997, NIMS has been conducting the research and development project on
advanced ferritic steels for application to large diameter and thick section boiler
components such as main steam pipe and header of ultra-supercritical (USC) plant at
650 oC. Critical issues for the development of ferritic steels for 650 oC USC boilers are
the improvement of oxidation resistance as well as long-term creep rupture strength.
The resistance to Type IV cracking strength loss in welded joints is also serious for
construction of thick section boiler components. Furthermore, the thermal cycling
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
carbon-free martensitic alloys and ferrite matrix 15Cr steel. This paper describes the
development of tempered martensitic advanced 9Cr steels for 650oC USC boilers.
9Cr-3W-3Co-VNb steels strengthened by boron and by nano-size MX nitride
dispersions are promising for application to thick section boiler components of USC
power plant operating at 650oC. Carbon-free martensitic alloys, which are
modification of low carbon Maraging steels, are promising for USC plant at 700oC and
above.
37-5
Materials for Ultra-Supercritical Coal-Fired Power Plant Boilers
R. Viswanathan and Kent Coleman
EPRI, USA
Udaya Rao
USDOE, NETL, USA
The U.S. Department of Energy (DOE) and the Ohio Coal Development Office
(OCDO) have recently initiated a project aimed at identifying, evaluating, and
qualifying the materials needed for the construction of the critical components of coal-
fired boilers capable of operating at much higher efficiencies than current generation of
supercritical plants. This increased efficiency is expected to be achieved principally
through the use of ultra-supercritical steam conditions (USC). The project goal is to
increase the main steam temperature initially to 760C (1400F), while attention also is
given to identifying the materials issues involved in service at temperatures up to
870C (1600F) in the longer term. The project is intended to complement alloy
development and evaluation programs now being carried out in Europe and Japan.
Those programs have identified ferritic steels capable of meeting the strength
requirements of USC plants to approximately 620C (1150F) and nickel base alloys
suitable up to 732C (1350F). In this project, the maximum temperature capabilities
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
the boiler, for 38.5 MPa/760C (5500 psi/1400F) main steam conditions. This paper
provides a status report on the progress to date achieved in this project.
SESSION 38
GASIFICATION APPLICATIONS & ECONOMICS: 1
38-1
FutureGen Zero Emission Power Plant of the Future
Joseph Giove III, Jarad Daniels and Victor k. Der
US DOE, USA
The United States is embarking on a future generation of coal plants based on a
revolutionary concept of zeroemissions. The research towards this goal is culminated
in a project called FutureGen. FutureGen will be the worlds first fully integrated coal
fired power plant that simultaneously produces hydrogen and electricity while
sequestering carbon dioxide. As a full-scale research facility, its aim is to prove out
the technical feasibility and potential economic viability for the zero emission
technology option for coal. Its success would lead to future commercial
demonstrations and replication for the market place to address the global climate
change concerns over carbon emissions from coal power plants. In this discussion, the
concept and strategy for the FutureGen plant is outlined in the context of the need for a
zero-emission coal option. It is envisioned that FutureGen will be a cost-shared
partnership between the United States government and industry with potential
participation from international partners.
38-2
Coal Gasifications Environmental and Operational Capabilities Today
David L. Denton
Eastman Gasification Services Company, USA
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
fully represent the capabilities of gasification today. This presentation will address the
true environmental and operational capabilities of gasification from the perspective of
an experienced operator of the technology. Coal gasification, at appropriate economy
of scale and with an experienced and knowledgeable operator, can perform very
reliably and very cleanly better than any other clean coal technology. Eastman
Chemical Company was a pioneer in producing chemicals from coal via gasification.
Our coal gasification facility has been in continuous commercial use since 1983 and
has continued to set new standards of performance, including an average forced outage
rate of 1-2%. Eastman has practiced high sulfur removal (>99.9%), volatile mercury
removal (>90-95%), and carbon dioxide capture for over twenty years. These proven
capabilities and other experiences and innovations that represent the current
capabilities of coal gasification will be described.
 38-3
Sasols Unique Position in Syngas Production from South African Coal Sources
Using Sasol-Lurgi Fixed Bed Dry Bottom Gasifiers
JC van Dyk, MJ Keyser and M Coertzen
Sasol Technology, South Africa
Sasol has been operating the Sasol-Lurgi fixed bed coal gasification process for more
than fifty years, and with ninety seven units in operation still remains the world's
largest commercial application of this technology. The combined operational and
engineering expertise vested in Sasol represents a formidable capability in the field of
coal and gasification science. Coal is a crucial feedstock for South Africas unique
synfuels and petrochemicals industry, and is used by Sasol as a feedstock to produce
synthesis gas (CO and H2) via the Sasol-Lurgi fixed bed dry bottom gasification
process.
South Africa, as well as many other countries in the world, will for many years to
come rely on its abundant coal resources for energy and specifically for the production
of petrochemical products. Synthesis gas production through gasification is growing at
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)
gasify >30 million tons per annum of bituminous coal to synthesis gas, which is
converted to fuels and chemicals via the Fischer-Tropsch process. The production of
chemicals is currently the dominant application for synthesis gas, followed by power
generation, Fischer-Tropsch synthesis and gaseous fuels.
Sasol-Lurgi gasifiers are extremely robust devices, and coal from sources with widely
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
operational changes are implemented. Other properties, like high caking propensity
for example, require blending to acceptable levels and /or mechanical modifications.
Interpretation of coal characterization data gives an indication of expected gasifier
performance and the suitability of a specific coal source for Sasol-Lurgi Fixed Bed
Gasification process. It is therefore critically important to gain an accurate and
fundamental understanding of the properties and expected behavior of the targeted coal
feedstock in order to (1) prepare a suitable conceptual flow scheme and (2) to
maximize the eventual probability of success in any proposed gasification venture and
(3) to optimize the operation and profitability of existing plants and (4) effectively
address the environmental aspects.
It is the view of the authors that fixed bed gasification technology has a bright future in
the areas mentioned above and that Sasol has a unique role in the future application
and commercialization of gasification technology globally. The unique skills of Sasol
could however be complementary to those of other parties who share our view on the
future of gasification and related technologies.
38-4
Shell Coal Gasification Process and its commercial applications
Thomas Chhoa
Shell Gas & Power, The Netherlands
The Shell Group developed the Shell Coal Gasification Process (SCGP) since the 70s.
Over the past 30 years, considerable R&D effort have gone into its development that is
now commercially proven and available. Today, Shell still continues to sponsor
significant in-house R&D effort to strengthen and improve SCGPs commercial
applications.The Shell Coal Gasification Process is based on an entrained flow, oxygen
blown, slagging gasifier using a dry feed system, in which the pulverized coal is
pneumatically transported to the gasifier by nitrogen gas. The produced SCGP syngas
contains about 83% of the energy in the coal feed, known as the cold gas efficiency. A
wide range of coal feedstock and petroleum coke, including low-rank sub bituminous
coal and lignite, can be used as the Shell process is relatively insensitive to coal
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
plants in different locations (Amsterdam, Hamburg, Houston), using various coal and
lignite qualities. Its first commercial application is the NUON (previously called
Demkolec) IGCC plant in Buggenum, The Netherlands, built in 1993. The project
was conceived and owned by the Dutch government, with Shell supplying the
technology through a licensing arrangement. The NUON plant has a design coal
gasification capacity of 2000 tons per day, and it delivers a net output of 253 MWe,
giving a net efficiency (LHV) of 43%. It started operation in 1994 and actual plant
performance met design conditions/requirements. Despite being one of the earliest
world scale commercial IGCC plant, it is still one of the most efficient and best
environmental performers. In this NUON plant, process water, being considerably less
than wet feed systems, is treated and recycled so there is zero water discharge. Recent
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.
Since then, SCGP is commercialised which has resulted in a number of licensed plants
currently in the EPC (Engineering, Procurement and Construction) stage. Although
there are interests elsewhere, these plants are located in China, being the largest coal
producer and user in the world. All of them are for chemical feedstock applications and
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
countrys largest coal producer to gasify coal to produce pure hydrogen for its direct
36
coal liquefaction project.In November 2001, Shell entered its first investment in coal
gasification through a 50/50 joint venture with its strategic alliance partner, China
Petroleum and Chemical Corporation (Sinopec) in Yueyang, China. After going
through the normal process of project development, the Board announced its final
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
downstream urea production units. Planned mechanical completion is end 2005. Two
other Sinopec projects, similar in size and application to the joint venture, have also
licensed Shell technology and their EPC development is following closely Yueyangs
progress.Shell coal gasification technologys commercialisation success has opened up
new options and volume in the SCGP critical equipment supply market to significantly
lower the costs. For example, spurred on by supply competition, recent projects have
recorded around 20% cost reduction (against Buggenum level in money of the day
terms) for the supply of the Shell gasifier, with its unique water-cooled inner
membrane wall and its syngas cooler. With increased commercialisation and supply
options, the unit cost of syngas production using Shell coal gasification technology is
expected to reduce further.
38-5
Evaluation of Potential Applications for Coal Gasification in Taiwan
Cheng-Hsien Shen, Heng-Wen Hsu, Ching-Lin Shieh, Wei-Chung Chin, Jui-Yen
Cheng
Clean Energy Technology Division, Energy & Resource Laboratories Industrial
Technology Research Institute, R.O.C
In Taiwan, 98% of total energy resources must be imported. However, the price of
natural gas is very high and many arguments support de-emphasizing nuclear energy.
The effectiveness of renewable energy is limited by the environment and climate, as
well as the lack of economic incentives for its application. With an abundant supply
and low cost, coal is the main source of energy in Taiwan. Hence, raising efficiency of
coal utilization and converting coal to a clean, stable energy source is a very important
issue in Taiwan.
Gasification technology has the advantages of feedstock flexibility, and syngas can be
applied to produce multiple products, for example electricity, fuel, chemicalsetc.
However, the capital cost of Integrated Gasification Combined Cycle (IGCC) is high
and IGCCs availability, reliability, and economy is not as good as those of
supercritical pulverized coal boiler power generators. Therefore, it cannot be applied
in the near-term in Taiwan. However, it is possible for syngas of gasification to act as
fuel, for example, if centralized gasification plants were to be set up in specific
industrial parks and provide factories with syngas as fuel. The objective of this study
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
natural gas and one-half of fuel oil per heating value in Taiwan. Consequently, it is
possible that syngas could economically substitute for natural gas and fuel oil. That
would be the main application direction for coal gasification technology in Taiwan.
SESSION 39
LOW RANK COAL UTILIZATION: 3
39-1
Liquefaction Studies of Low-Rank Malaysian Coal Using High-Pressure High-
Temperature Batch-Wise Reactor System
Mohd Azlan Mohd Ishak, Khudzir Ismail and Mohd Fauzi Abdullah
University Technology MARA, Malaysia
Wan Hasiah Abdullah
University Malaya, Malaysia
Mohd Kadir, Abdul Mohamed
Universiti Sains Malaysia, Malaysia
Indirect liquefaction of low-rank Malaysian lignite namely Mukah Balingian (MB) was
successfully carried out with hydrogen donor solvent i.e. tetralin at temperatures of 360
450C and at pressures of 4 20 MPa in a 1-litre high-pressure high-temperature
batch-wise reactor system. The results thus far indicated that, the percent conversion
obtained were in the range of 31 87%, optimizing at 450C and 4 MPa with the oil,
asphaltene and preasphaltene of the coal extract were 89, 8 and 2%, respectively.
Apparently, it was observed that heat plays an important role in comparison to pressure
in contributing to high coal conversion and oil yield. Other parameters that were also
being investigated in this study include reaction time (0 120 minutes), effect of
stirring rate, and effect of solvent to coal ratio and effect of reactor reaction capacity.
Moreover, both temperature and pressure affect the elemental composition, thermal
characteristics and calorific value of oil and coal liquefaction residue.
39-2
Effects of Hydrogen Transfer by the Exchanged Cobalt on the Liquefaction of
Low Rank Coal
Motoyuki Sugano, Shin-ichi Ohura, Katsumi Hirano and Kiyoshi Mashimo
Nihon University, Japan
It is well known that the low rank coals, such as brown and subbituminous coals, are
highly oxygenated, much of which is present as carboxyl and phenolic hydroxyl
groups. During the cation exchange treatment of low rank coals, carboxyl groups in
coal structure are exchanged with desired cations. When the specific cation was
exchanged to coal, gasification and pyrolysis reaction of the coal were promoted.
On the hydrogenolysis of demineralized Adaro subbituminous coal with tetralin and
elemental sulfur at 420 , the upgrading, such as the decrease of acetone insoluble
yield and the increase of hexane soluble yield, was enhanced by exchanges of several
kinds of cations (Co2+, Ni2+ and Fe2+) to coal [1]. On the hydrogenolysis of coal, it is
well known that several kinds of metals derived from metal carbonyls, which are
soluble in organic solvents, finely disperse to coal and enhance the hydrogenolysis of
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
(tetralin and elemental sulfur), the upgrading of coal was enhanced significantly on the
reaction of cation (Co2+, Ni2+ and Fe2+) exchanged coal [3]. However, relation between
the upgrading of coal and the mechanism of hydrogen transfer from tetralin and
pressurized hydrogen gas has not been clarified.
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
hydrogen transfer from pressurized gas or solvent on the upgrading of coal was
discussed. Further, the catalytic effect of exchanged cobalt on the hydrogen transfer
and the upgrading of the exchanged coal was discussed with the comparison of the
results after the hydrogenolysis of demineralized coal and demineralized coal plus
complex [(C5H5)2Co or Co2(CO)8].
Compared with the hydrogenolyses of Co exchanged coal and the complex added coal
with tetralin and pressurized nitrogen gas, the upgrading of coal was enhanced on the
hydrogenolyses with decalin and pressurized hydrogen gas. The amounts of
transferred hydrogen on the hydrogenolyses with decalin and pressurized hydrogen gas
were lower than that with tetralin and pressurized nitrogen gas. Therefore, the
upgrading of coal was considered to be enhanced because coal radicals were stabilized
by the hydrogen radicals derived from the pressurized gas on the surface of Co. The
upgrading of coal occurred significantly on the hydrogenolysis with tetralin and
pressurized hydrogen gas, in particular, the yield of residue was only 0.3 % on the
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
demineralized coal plus complex of Co. However, the upgrading of coal occurred
significantly on the hydrogenolysis of Co exchanged coal in comparison with the
hydrogenolysis of the demineralized coal plus complex of Co.
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
decreased on the hydrogenolyses with naphthalene and pressurized hydrogen gas. On
the hydrogenolyses with naphthalene and pressurized hydrogen gas, the yield of
tetralin were 1.4, 3.8, 9.1 and 8.8% on the reaction of the demineralized coal,
(C5H5)2Co added coal, Co2(CO)8 added coal and Co exchanged coal. Therefore,
hydrogen shuttling through naphthalene was enhanced by Co derived from Co
exchanged coal and Co2(CO)8. Accordingly, the upgrading of coal on the
hydrogenolyses of Co exchanged coal with pressurized hydrogen gas was observed
significantly irrespective of the hydrogen donatability of solvent. It was reported that
complex of Co dispersed among the molecules of solvent and coal [2], Co in Co
exchanged coal was attached to carboxyl group in coal macromolecules by the ion
exchange treatment [4]. Therefore, upgrading of Co exchanged coal was enhanced
significantly because Co dispersed finely into the coal macromolecules with attached
carboxyl group irrespective of the size of coal molecules.
39-3
Upgrading of Low Rank Coal as Coal Water Slurry and its Utilization
Ryo Moriyama, Shohei Takeda, Masaki Onozaki, and Yukuo Katayama
The Institute of Applied Energy, Japan
Low-rank coals are characterized by their high moisture content, which results in low
efficiency of combustion or gasification because of latent heat of water evaporation.
The low-rank coals further have high ignitability after drying. This high moisture
content and ignitability have placed economic restrictions on transportation and have
required the power plants to be situated directly adjacent to the opencast mines.
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
treatment and spontaneous ignition of dried coal. Effective reforming of the low-rank
coals has been required.
This paper introduces two new processes for low-rank coal upgrading technology. One
is coal water slurry (CWS) production process from the coals proposed by KEM
Corporation and the other is pre-heating feed process of the CWS developed by the
authors. CWS was produced with the special kneader developed by KEM and
Corporation of Japan Systematization Laboratory. We received the indication of this
brown coal upgrading technology from KEM. In this paper, we tested this technology
using Australian brown coal containing 62% of water and Indonesian brown coal
containing 35% of water as samples. Sample with or without water was fed into the
kneader and was heated with kneading. After a certain time of kneading, brown coal
was converted into pumpable CWS without addition of surfactant. Properties of water
in the CWS were investigated based on its freezing properties. Water strongly
interacted with the coal having freezing point of < -50C became free or bulk water
having freezing point of about 0C. Furthermore, crush of fine pores in the coal was
37
found by comparing pore size distributions for dried coal before and after the CWS
production. These results imply that kneading of low-rank coal with high shear stress
resulted in removing of water from the coal particles and in crashing fine pores in the
coal. Water dissociated from coal stays in the continuous phase of water by the crush
of fine pores in the coal. Product slurry was fed into a CWS pre-heater having
processing ability of 150 L/h. Dried coal particles with steam were successfully
exhausted from the outlet of the pre-heater. It was found that the water in the CWS was
completely vaporized in the pre-heater without blockage of feeding tube. Combination
of these two processes will increase efficiency of a coal gasifier or a boiler.
39-4
Upgrading of Brown Coal for Production of Coal-Water-Mixture (CWM)
Karin Laursen, Akihiro Kosuko, Masakazu Sakaguchi, Hiroyuki Nakagawa, Kouichi
Miura
Kyoto University, Japan
Coal-Water-Mixtures (CWM) with high solid-to-liquid fraction have successfully been
produced from high-rank coals, but so far no economically feasible methods have been
found for producing CWM from brown coal. The high moisture content, high porosity
and hydrophobic nature of brown coal makes it impossible to produce CWM from raw
brown coal, and some type of upgrading of the coal is required. Loy Yang brown coal
from Latrobe Valley, Victoria, Australia, was treated in a 20 ml stainless steel
autoclave at temperatures ranging from 200 to 350oC under steam drying and
hydrothermal dewatering conditions. Solid products from the upgrading processes
were subjected to a range of analysis including proximate and ultimate analysis,
mercury porosimetry, moisture holding capacity, XRD, FTIR and TEM, while gaseous
and liquid products were analyzed by GC and TOC, respectively. Based on
these chemical and structural information, this paper will discuss the transformations
taking place in the brown coal during upgrading. Finally, this paper will discuss the
effect different upgrading conditions will have on the potential for using the upgraded
coal for CWM production.
39-5
Coal-Water Fuels from Chinese Low-Rank Coals
Michael L. Swanson, Mark A. Musich and James E. Tibbetts
University of North Dakota Energy & Environmental Research Center, USA
China, with its vast coal reserves, has become the worlds largest coal user, consuming
over a billion tons a year. Some of the largest reserves of low-sulfur coal could be used
with minimal environmental impact are located in the northeastern and southwestern
parts of China. These coals tend to be subbituminous or lignitic low-rank coals (LRCs)
with high moisture contents. This property usually restricts their use to mine-mouth
power generation. Conventional evaporative drying processes can be expensive and are
generally only used when the dried coal can be utilized immediately to avoid handling
problems such as moisture reabsorption, dust generation, and spontaneous combustion.
A nonevaporative process called hydrothermal treament (HTT) was developed by the
Energy & Environmental Research Center to convert high-moisture LRCs into an
easily transported liquid fuel. HTT induces rapid coalification at moderate temperature
and pressure in the presence of liquid water and makes the LRCs hydrophobic with
similar equilibrium moisture levels to bituminous coals. This process enables the
production of additive-free LRC-water fuels (LRCWFs) with solids loadings
comparable to those made from high-rank bituminous coals and energy densities
comparable to those of the raw coal.
Several LRCs from northeast China were treated by the HTT process and made into
LRCWFs with energy densities greater than 14654 kJ/kg (6300 Btu/lb). These
LRCWFs compared favorably with LRCWFs made from American LRCs which have
shown excellent combustions and emissions characteristics in pilot-scale combustion
tests. With lower LRCWF production costs in China, HTT could provide an
opportunity to develop low-cost pipeline transportation in China. This would enable
Chinas enormous LRC reserves to be developed in an environmentally responsible
manner for widespread internal use and might lead to the development of a LRC export
market for these coals.
SESSION 40
SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 1:
FISCHER-TROPSCH SYNTHESIS
40-1
The Structure Change of Co/Zro2/Sio2 Catalyst during Fischer-Tropsch Reaction
Yuhan Sun, Wei Zhou, Jiangang Chen
Chinese Academy of Sciences, P.R.China
Cobalt-based catalyst is a reasonable choice for F-T synthesis for its merits of high
activity, negligible WGS reaction and good selectivity [1~5]. However, the relative high
cost of cobalt requires the cobalt-containing catalyst with a long life. The study on the
catalyst deactivation and structure change during the reaction is important. The
Co/ZrO2/SiO2 catalyst has good F-T performance [6~10] but the deactivation is hardly
understood. Thus a systemic study on the structure change of Co/ZrO2/SiO2 catalyst
during F-T reaction was carried out.
CO hydrogenation was performed at 463K, 2MPa and 500h-1 with stoichiometric
syngas feeds (H2:CO=2:1) in a fixed bed reactor. A long-time running was carried out
and an apparent deactivation was observed (see Fig.1). According to the curve, the
course of the reaction could be divided into three periods (see Table 1 and 2). During
the first period (24-168h), the catalyst deactivated partially. In the second period (168-
314h), the catalyst deactivated evidently. In the third period (314-411h), the catalyst
kept a low activity. The catalyst deactivated entirely. Surprisingly, the CO2 selectivity
enhanced with time on stream. In order to investigate the catalyst deactivation, a
similar run was performed before the severe deactivation took place. Then the fresh
catalyst, the partial deactivated catalyst (time on stream 168h) and the total deactivated
catalyst (time on stream 411h) were sampled for characterization and named as F, P
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.
A small broad peak appeared at 900~1100K as a function of time on stream from TPR
profiles (see Fig.2). The peak was thought as the H2 consumption of the species of the
cobalt silicates and/or hydrosilicates [11]. The areas of the total profile (390~1220K), of
the former part (390~873K) and of the latter part (873~1220K) were integrated (see
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
the cobalt silicates and/or hydrosilicates was responsible for the deactivation and the
species was mainly produced in the course of the reaction.
BET surface area of the three samples decreased in the sequence of F>CP>CT, with
average pore size increasing and pore volumes almost the same. This result suggested
that a particle growth course occur [12]. Moreover, the dispersion of the catalysts were
shown in the same sequence of F>CP>CT. It also proved that the particles of the
catalyst grew. In addition, the difference between F and CP was larger than that
between CP and CT. It indicated that the particle growth was also a cause for the
deactivation and the course mainly occurred in the reduction or in the initial period of
the reaction.
TG analysis was done on the extracted T catalyst (see Fig.3). The deposition of carbon
was proved and it was also one cause for the catalyst deactivation. The carbon was
formed during the course of the reaction and might come from the Boudouard reaction.
40-2
Chemical Effect and Spatial Effect of New Bimodal Catalysts for Fischer-Tropsch
Synthesis
Yi Zhang, Yoshiharu Yoneyama and Noritatsu Tsubaki
Toyama University, Japan
A catalyst support with both small pores and large pores, as well as a distinct bimodal
pore structure, has excellent advantages in industrial solid-catalysis reaction because
the large pores provide pathways for rapid molecular transportation and the small pores
serve a large area of active surface. A simple preparation method of bimodal supports
was developed by introducing SiO2 or ZrO2 sol into large pores of SiO2 gel pellet
directly. The pores of the obtained bimodal supports distributed distinctly as two kinds
of main pores. On the other hand, the increased BET surface area and decreased pore
volume, compared to those of original silica gel, indicated that the obtained bimodal
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
catalyst presented the best reaction performance in slurry-phase FTS as higher reaction
rate and lower methane selectivities, because the spatial promotional effect of bimodal
structure and chemical effect of the porous zirconia were available inside the large
pores of original silica gel. The properties of bimodal supports and catalysts were
determined by BET, TGA. XRD, TEM, In-situ FT-IR, TPSR.
40-3
Selective Production of Iso-paraffins from Synthesis Gas over Co/SiO2 and
Pd/beta Catalysts
Zhong-Wen Liu, Xiaohong Li, Kenji Asami and Kaoru Fujimoto
The University of Kitakyushu, Japan
The Fischer-Tropsch (FT) synthesis is an effective route to convert coal, natural gas,
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
mixture of normal paraffins are nonselective and the product distribution is
controlled by the so-called Anderson-Schulz-Flory (ASF) polymerization kinetics
[1]. To selectively synthesize desired products such as diesel or high-octane gasoline,
it is essential to circumvent the ASF distribution. In our previous investigations [2,3],
a fundamental concept by using physical mixture of a FT catalyst to synthesize long-
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
reactor and a consecutive dual reactor systems. The present investigation aims at
studying the effect of SiO2/Al2O3 ratios and crystallization of beta zeolite on the
performance of Pd-supported beta catalysts for the selective production of iso-
paraffins in a dual reactor system. In the first reactor (up stream), a 20 wt.% Co/SiO2
catalyst was loaded for the production of FT hydrocarbons under the conditions of
508 K, 0.1 MPa and W/F of 4.97 g.h/mol. To decompose the heavy hydrocarbons in
FT synthesis, a certain amount of beta zeolite was physically mixed with the cobalt
catalyst. 0.5
38
wt. % Pd-supported beta catalyst with SiO2/Al2O3 ratios from 16.2 to 150 was
applied in the second reactor (down stream). Irrespective of the SiO2/Al2O3 ratios of
the beta zeolites, the products showed a sharp carbon number distribution in the
range of C3-C6 and a high selectivity to iso-paraffins as shown in table 1. A
significant change of selectivity to iso-paraffins was observed with the variation of
the SiO2/Al2O3 ratios of the Pd/beta catalysts in the second reactor. Moreover, the
stability of the Pd-supported beta catalyst was slightly influenced by the
SiO2/Al2O3 ratios. The effect of SiO2/Al2O3 ratios of the Pd/beta catalysts on the
selectivities to isomers at different stage of time on stream will be discussed in detail
in this presentation. The reaction results can be correlated very well with the acidity
and crystallization of the beta zeolite.
40-4
A Study on the Fischer-Tropsch Synthesis in the n-Hexane/n-Decane Mixed
Solvent
Wensheng Linghu, Xiaohong Li, Kenji Asami and Kaoru Fujimoto
The University of Kitakyushu, Japan
Fischer-Tropsch synthesis (FTS) has regained interest during the last decade as an
option for the production of clean fuels and chemicals from either coal or natural gas
due to changes in fossil energy reserves and environmental demands [1-2].
The reaction performance of FTS in n-hexane/n-decane (n-C6/n-C10) mixed solvent in a
fixed bed reactor was studied in this work. Experimental apparatus and detailed analysis
procedure has been reported in our earlier paper [3]. The catalyst used was a SiO2
supported cobalt catalyst, which was prepared incipient wetness impregnation method.
Composition of the catalyst was Co: 20 and SiO2: 80 by weight. A typical reaction
conditions were T=240 oC, Ptotal=4.5 MPa, Psolvent =3.5 MPa and W/F = 5 g-cat.h/mol.
Argon was used as the internal standard in the feed gas. The results showed that CO
conversion in n-C6 was slightly higher than that in n-C6/n-C10 mixed solvents and in n-
C10 (Table 1). In general the composition of the solvent has not obvious influence on
CH4 selectivity and CO2 selectivity. The composition of the solvent, however, has
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
mixed solvents and n-C10 than that in n-C6 solvent. The olefin content of the products at
range of C2-C10 has not obvious change, however the olefin content of the heavier
products (C10+ fractions) increased with the increase of the n-C10 content in the mixed
solvent. More data and detailed discussion will be presented at the meeting.
Table 1. The reaction performances of FT reaction in different solvents.
Run No. Solvent CO conv., % CH4 sel., % CO2 sel., %
A n-C6 46.86 8.54 1.45
B 75%n-C6 /25%n- 42.58 9.51 1.16
C10
C 50%n-C6 /50%n- 44.02 8.77 1.55
C10
D 25%n-C6 /75%n- 42.29 9.46 1.84
C10
E n-C10 41.51 9.73 1.22
40-5
A Comparison of Co and Fe Based Catalysts for Fischer-Tropsch Synthesis
Anton C. Vosloo, Philip Gibson and Peter J. van Berge
Sasol Technology, South Africa
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.
The only two catalysts that are currently of commercial importance are Co and Fe.
Although most of the proposed Gas-To-Liquids (GTL) plants in the world are based on
Co FT catalysis, Fe as a catalyst can still play a significant role in future synthetic fuel
and chemicals plants. These two catalysts will in general terms be reviewed with
regards to their preparation methods, kinetic and selectivity behaviour and areas of
application. Some of Sasols recent developments with regards to both these types of
catalysts will also be discussed.
SESSION 41
COAL PRODUCTION & PREPARATION: 2
41-1
Commercially Viable Strategies for Enhancing Coal Quality
A. Patwardhan and Y. P. Chugh
Southern Illinois University at Carbondale, USA
The focus of this research is on coal quality enhancement which includes reduction in
the sulfur content and increase in heating value through innovative coal cleaning
strategies involving fine coal cleaning and plant optimization. Preliminary evaluations
on five mines in Illinois have indicated a potential to reduce the lbs SO2/mmBtu of
these coals by up to 20% while increasing the product heating value by 300-450
Btu/lb. In addition, the evaluations predict increases in coal yield by 2-6% depending
on the mine evaluated. Based on the results of these evaluations a utility company has
independently estimated a cost reduction of $2.00/ton through the implementation of
these concepts.
This research tools or strategies presented here can be used alone or in combinations to
improve mine profitability through enhancement of coal quality. The strategies
include (i) SOx reduction primarily through ash reduction (increased BTUs) and
secondarily through pyritic sulfur reduction while maintaining clean coal
characteristics for the entire product suitable for off-site power generation, (ii) SOx
reduction through development of two products: 1) low ash- low sulfur content product
suitable for off-site power generation, and 2) high ash-high sulfur product suitable for
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
lowering SOx, (iv) Application of advanced fine (-100 mesh) coal cleaning for
increased coal recovery, and, (v) Overall plant optimization to operate the preparation
plant for production of product qualities driven by contractual requirements.
The strategies developed in this project are based on innovative applications of
commercially available technologies while minimizing the capital investment
requirements and requiring minimal changes to the current operation of the cleaning
plant. In addition, particular emphasis is on adherence to the coal quality requirements
specified by the contracts of individual mines. Subject to these constraints,
development of customized strategies is shown to achieve the goal of coal quality and
recovery enhancement.
41-2
Dewatering Ultr-Fine Clean Coal in a T.H. Filter Press
A. Patwardhan and Y. P. Chugh
Southern Illinois University at Carbondale, USA
B. J. Arnold
PrepTech Inc, USA
N. Terblanche
PrepQuip (Pty.) Ltd, South Africa
Approximately 10% of the energy in mined coal lies in the 100 mesh particle size
fractions. Primarily due to dewatering constraints, this valuable resource is discarded
in ponds. Technological developments in the area of fine coal cleaning have provided
mine operators the ability to achieve near-perfect separations even in the ultrafine size
ranges. The adoption of these technologies by the industry, and thus, the ability to
utilize the significant energy resource has been limited by the inability of existing
dewatering technologies to produce a low moisture content product with total particle
capture efficiency at a low cost.
This results of the study reported here successfully demonstrates such a low-cost, high-
efficiency filter press technology for dewatering flotation clean coal products from two
coal mines. In-plant demonstration of this technology at these two locations provided
stable, trouble free operation while achieving an excellent dewatering performance at
high throughputs. At one location, filter cakes with residual total moisture contents in
the 19-21% range were achieved. At the other location 25-27% residual total moisture
contents were achieved.
Engineering economic evaluations have indicated that a fine coal product can be
produced using column flotation and the filter press at the cost of $5.41/dry ton for one
mine. With appropriate blending strategies, profitability can be shown to increase by
$900,000 per year for this 2 million tons per year mine. For the second 2.6 million
tons per year mine, profitability was projected to increase by $2,000,000/year through
the application of the concepts presented here.
41-3
Reducing Moisture Content by Hot Water Drying Method
Datin Fatia Umar and Bukin Daulay
Research and Development Center for Mineral and Coal Technology, Indonesia
Hiromoto Usui
Kobe University, Japan
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
by hot water drying (HWD) method. A low rank coal from Berau, East Kalimantan
which is used in this study referred to sub-bituminous coal with moisture content of
18.92% and calorific value of 5477 kcal/kg in air dried basis. The results indicate that
the optimum condition of process reached at residence time of 60 minutes, processing
temperature was 300C and coal particle size was less than 0.5 cm. At this condition
the moisture content can be reduced to become 4.00% and calorific value increase up
to 6755 kcal/kg in air died basis.
41-4
In-Plant Testing of the Pansep Screen
Manoj K. Mohanty, Z. Wang, V. Gupta, S.K. Biswal, E. Bane Kroeger
Southern Illinois University, USA
J. Hirshi
Illinois Clean Coal Institute, USA
Past studies have indicated that the inefficiency in fine particle size classification in
coal preparation plants results in significant loss of both quality and quantity of fine
clean coal product. With an aim to improve upon the performance of fine particle size
classification, a newly developed Pansep Screen having a floor space of 0.5 m2 has
39
been tested in an operating coal preparation plant. Two different sets of mesh panels
have been used to separately investigate the classification at d50 sizes of 150 micron
and 45 micron, respectively. A head-to-head comparison has been made between the
performance of a Pansep screen and the bank of classifying cyclones operating in a
plant. Long-term tests over a period of one week have been conducted to investigate
the sensitivity of the performance of the Pansep screening technology.
Results of these studies will be discussed in this publication.
41-5
Enhanced Gravity Floatation: A Novel Way of Cleaning Fine Coal
M.K. Mohanty
Southern Illinois University at Carbondale, USA
A novel separation process namely, Enhanced Gravity (EG) Flotation has been
invented to treat the entire 1 mm x 0 coal fraction of a run-of-mine coal in a single
process. Unlike a conventional enhanced gravity concentrator which rotates to produce
a centrifugal field, the EG Float Cell is fed with a tangential feed slurry, which spirals
around the outer section of the Cell. This rotary motion of the slurry generates a
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
concentration in the outermost section of the cell. A majority of the fine refuse
particles is entrained with the clean coal slurry flowing towards the inner section of the
Cell. By allowing this slurry to pass over a screen surface of a desired aperture size, the
coarser clean coal is separated and directed to the clean coal product launder, whereas
the mixer of fine coal and refuse undergoes to a flotation step. This flotation step
achieves a separation of fine coal from the fine refuse particles. Thus, one feed stream
of 1 mm x 0 size coal results in three products after being processed by the EG Float
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
this publication.
SESSION 42
COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 2:
COKE QUALITY, COAL CHARACTERIZATION, ANALYSIS
42-1
Research on Coke-Making of Increasing a Ratio of High-Volatility Coal to the
Coal Blend from Analysis of the High Temperature Property of the Metallurgy
Coke
Bai Xi, Keliang Pang, Jianjun Yang and Guiying Xu
Anshan University of Science and Technology, P.R.China
Through the carbon solution reaction of the coke under the condition of simulating the
blast furnace fusing zone, seeing about the high temperature property and the variety
optical texture of the coke, the study shows that the isotropic texture has anti-alkali
character, but isotropic texture is mainly produced by high-volatility coal, therefore,
under the situation of not quite emphasizing the strength of cold stage in coke, we can
increase the gas coal appropriately. The degradation velocity of the coke does not show
the variety in the carbon solution loss because of the increment of the gas coal.
Increasing the gas coal is reasonable that it can not only make the cost of the coal
blend lowered, the ash and the sulfur in coke reduced, but also make full use of the
coal resources.
42-2
Optimisation of Preparation of Coal Charge for Coke Making
L. Parthasarathy, N.K. Ghosh and M.K. Sharma
SAIL, India
R. Venugopal
Indian School of Mines, India
Coking coals used in SAIL plants are characterized by wide difference in their
properties in terms of ash content, caking/ coking properties, vitrinite content, rank and
grindability index. Organic & inorganic inert content (about 50%) and middling &
rejects (8-25%) in the indigenous coals, which constitute about 50% of the coal blend,
are quite high. The imported coals used in the blend are characterized by
comparatively low ash (9-10%), higher vitrinite content (60-70%), high FSI values (7-
8) and contain significant percentage (60-65%) of -3mm size fraction. Preparation of
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
homogeneous in nature.
The present method of evaluating the level of coal charge preparation only by the
crushing level (% through 3 mm) is not adequate and does not take into account the
aspect of homogenization. For better evaluation, additional parameters, which
characterize the distribution of inert in the different size fractions, are also to be
considered.
Extensive pilot oven (250 kgs.) tests were carried out at R&D Centre, SAIL using the
same coal blend but with different methods of coal charge preparation like, blend
crushing, group wise crushing, group wise crushing with separation of fines and blend
crushing with separation of fines. Though the coal blend composition was same in all
the tests, different coke quality parameters (M40, M10 and micro strength) could be
achieved due to the difference in coal charge preparation technique. The difference in
coke quality in the above cases can be attributed to the difference in the distribution of
pure coal substance and ash content in the different size fractions.
From these tests, the following three parameters were identified which can better
evaluate the level of preparation of coal charge for coke making.
Content of coarse size fractions (+3 mm) in coal charge
Ratio of content of -1.4 specific gravity fraction in the coarser size fraction (+3 mm)
and total coal charge
Coefficient of distribution of ash in the different size fractions of the coal charge
With the help of the above new evaluation method, it would be possible to
scientifically approach the problem of optimization of preparation of coal charge for
coke making.
42-3
Determination of Relations Connectiong Coking Coal Price with Selected Quality
Parameters
Urszula Ozga-Blaschke and Stanislaw Blascke
Mineral and Energy Economy Research Institute, Poland
The paper presents the method of coking coal valuation. The method comprises on
determination the dependence of coal price from quality parameters of coal.
Technological value of coal depends on many different physical, chemical and
physico-chemical parameters. The choice of the set of parameters that were taken into
account was based on the criterion of coke yield and the quality of achieved
metallurgical coke. The quality parameters of coal that influence the quality of coke
are: the indexes that characterise rank of coal (Vdaf, Ro), coke-making parameters
(caking properties, plasticity, and dilatation) as well as the content of ballast and
harmful components (moisture, ash, sulphur, phosphorus, alkalis).
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
evaluated that change the price of coal when chosen parameters deviates from the level
assumed as the standard one. Two different variants of algorithms for coking coal
valuation are proposed basing on selected quality characteristics. The variants differ by
the way of coal valuation regarding the coke-making parameters. Assuming that coal
price is a measure of use value of the coal, these algorithms can be used for forming
the structure of coking coal pricing formulae.
42-4
Change In The Aggregate Structure of Coal during Heat Treatment
Haruo Kumagai
Hokkaido University, Japan
Izumi Shimoyama
JFE Steel Co., Japan
Yasuyuki Harada
Mitsubishi Chemical Co., Japan
Because of the importance of thermoplastic properties, which have definitive effects on
the properties of the resultant coke, much attention is being devoted to the
thermoplastic characteristics of coking coal. The thermoplastic phenomenon is
believed to be related to the coal rank and is governed by the chemical and physical
structure, especially aggregate structure of the coal molecules. In this study, change in
the aggregate structure of coal molecules induced by heating is investigated with in-
situ pulse 1H-NMR.
The variations of molecular mobility of coking and slightly-coking coal due to change
in aggregate structure were monitored with pulse 1H-NMR employing a solid-echo
pulse sequence. The echo signals obtained during heat treatment were deconvoluted
into a set of one Gaussian and three Lorentzian decay components which represent the
immobile, intermediate, mobile and liquid-like component, respectively. The changes
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
corresponded to the softening and resolidification phenomena of coal. For both of
coking and slightly-coking coal, apparent viscosity, a, determined by the needle
penetration method varies in agreement with the variation in the fHm, and the
temperature of the minimum in the ha curve corresponds to the temperature at which
fHm shows its maximum value. These results indicate that the deconvolution of the
signal into several components is appropriate for evaluating the thermoplastic
phenomenon of coal upon heating, and also that the thermoplastic phenomenon is
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
Him, T2Hint and T2Him, display almost constant values during heat treatment. In case
of coking coal, the T2 for Hm, T2Hm, maintains a stable value, representing the fact
that the Hm newly provided from dissociation of aggregate structure is homogeneous
in terms of nuclear spin relaxation, and exists stably in the softening temperature
range. T2Hm for slightly-coking coal demonstrates a similar behavior, but the
temperature range in which Hm exists stably is narrower than that for coking coal. As
discussed above, the differences in the thermoplastic phenomenon between coking and
slightly-coking coal can be revealed with the variations of molecular mobility of coal.
The results obtained from in-situ pulse 1H-NMR indicate that the thermoplasticity of
coal is affected by not only the quantity but also the quality of the Hm component.
40
Furthermore, the results indicate the necessity of an ample amount of Hm component
which can exist stably in the softening temperature.
42-5
The Study of Nanopores in Coal using Xe and Hyper-Polarized Xe NMR
Spectroscopy
Koji Saito and Koji Kanehashi
Nippon Steel Corporation, Japan
Nanopores in coal are of great significance because of its influence on coal behavior
during mining, preparation and utilization processes. Recently, a new carbonization
process with high temperature preheating has been developed as Japan National
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
critical factor for carbonization reaction, there is no information between nanopore size
and its chemical composition of nanopore wall. It is well-known that Xe NMR is very
powerful to estimate nanopore structures [1], at the same time there is a lack of
information for chemical composition of nanopores. In this paper, the nanopores
structures of rapid preheat treated sample of Witbank coal in new carbonization
process have been investigated using the combination between Xe and hyper-polarized
Xe gas NMR spectroscopy [2]and its relaxation time. It has been clarified that the
molecular structure of coal has been relaxed by the rapid preheating treatment and
there is a close relation in hydrogen bond and relaxation of molecular structure of coal.
Typical result of coal is shown (up-field peak; aliphatic regions, down-field peak;
aromatic regions). And then, as nanopores is increasing, reaction rate of carbonization
becomes bigger. And also, these combination techniques showed the estimation of
average pore size for coals using our developed relation and also these chemical
compositions because the activity of hyper-polarized Xe gas is lost and relaxation time
is short with the interaction of electron as soon as this gas puts into aromatic regions.
SESSION 43
MATERIAL, INSTRUMENTATION & CONTROLS 2: FUNCTIONAL
MATERIALS
43-1
Development of Microporous Inorganic Membranes for Separation and
Purification of Hydrogen
Roddie R. Judkins and Brian L. Bischoff
Oak Ridge National Laboratory, USA
Activities are discussed concerning the development of microporous inorganic
membranes by Oak Ridge National Laboratory. These membranes have effective pore
diameters less than 2 nm. The International Union of Pure and Applied Chemistry
designation for membranes of this pore size is microporous, although descriptively,
they are nanoporous. Results of recent, i.e., from about January 2002 to the present,
developments are discussed. Current development is directed to the fabrication of
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
during handling and installation into a separation system. Metal-supported membranes
also have advantages over ceramic-supported membranes with respect to integration
into gas separation units because they can be welded to the metal support structures
such as tubesheets. Characterization, flow, and separation performance data are
discussed. Separation factors for hydrogen, which are indicative of the selectivity of
the membranes for hydrogen in a binary gas mixture, are very high and are coupled
with very high permeances, or the volumetric flow per unit of surface area per unit of
transmembrane pressure difference. Performance data reported include permeance,
ideal separation factors, and separation factors for actual gas mixtures. Physical
properties of these membranes are also reported. This paper will also address the
status of classification and nonproliferation reviews, which are required prior to release
and use because of legacy classified technology issues.
43-2
Electrochemical Corrosion Rate Probes for High Temperature Energy
Applications
Bernard S. Covino, Jr., Sophie J. Bullard, Stephen D. Cramer,
Gordon R. Holcomb and Magorzata Ziomek-Moroz
U.S. Department of Energy, USA
Michael Cayard and David A. Eden
InterCorr International, USA
Corrosion occurs in the high temperature sections of energy production plants due to a
number of factors: ash deposition, coal composition, thermal gradients, and low NOx
conditions, among others. High temperature electrochemical corrosion rate (ECR)
probes are rarely used at the present time, but if they were more fully understood,
corrosion could become a process variable at the control of plant operators.
Research is being conducted to understand the effects of probe composition, ash
composition, environment chemistry, and measurement technique on the accuracy,
response, and longevity of electrochemical corrosion rate probes. The primary goal is
to understand when ECR probes accurately measure corrosion rates and when they are
simply qualitative indicators of changes in the corrosion processes. Research to date
has resulted in moderate successes where the ECR probe corrosion rates and corrosion
rates from mass loss coupons agree within a factor of 2. This good agreement was
found to depend on the composition of the sensors, with the best results coming from
more highly alloyed materials such as 316L stainless steel and poorer results from
carbon steel sensors. Factors being considered to help explain the good or poor
agreement between mass loss and ECR probe corrosion rates are: values selected for
the Stern-Geary constant, the effect of internal corrosion, and the presence of
conductive corrosion scales and ash deposits.
43-3
Preparation and Pore Size Control of Porous Carbon from Petroleum Coke
Mingbo Wu, Yuzhen Zhang and Jieshan Qiu
Dalian University of Technology, China
Kouichi Miura
Kyoto University, Japan
Porous carbons (PCs) were obtained from Daqing petroleum coke with potassium
hydroxide (KOH) as active reagent by chemical activation method. Benzene was then
used as deposition agent in the following chemical vapor deposition (CVD) technique
to control the pore size of the PCs prepared by KOH activation. Adsorptions of
nitrogen, benzene, methane (CH4) and carbon dioxide (CO2) have been used to
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
material, activation temperature and activation time are crucial for preparing high
quality PCs. For CVD technique to control the pore size of PCs, the deposition
temperature is found to be one of the crucial factors. The results show that CVD
technique carried on PCs with benzene as deposition agent is an effect method to
control the pore size of PCs and also can greatly enhance the separation ability of PCs
over CO2 and CH4. A series of PCs with high surface area and in high yield were
prepared in comparison to the traditional methods.
43-4
A Novel Method of Joining Oxygen and Hydrogen Separation Membranes for
Advanced Coal Gasification Technology
K. Scott Weil, John S. Hardy and Jin Yong Kim
Pacific Northwest National Laboratory, USA
Coal is a potentially a very inexpensive source of clean hydrogen fuel for use in fuel
cells, turbines, and various process applications. To realize its potential however,
efficient, low-cost gas separation systems are needed to provide high purity oxygen to
enhance the coal gasification reaction and to extract hydrogen from the resulting gas
product stream. Several types of inorganic membranes are being developed for
hydrogen or oxygen separation, including porous alumina, transition metal oxide
perovskites, and zirconia. One of the key challenges in developing solid-state
membrane based gas separation systems is in hermetically joining the membrane to the
metallic body of the separation device. In an effort to begin addressing this issue, a
new brazing concept has been developed.
Referred to as air brazing, the technique differs from traditional ceramic-to-metal
brazing in two important ways: (1) it utilizes a liquid-phase oxide-noble metal melt as
the basis for joining and therefore exhibits high-temperature oxidation resistance and
(2) the process is conducted directly in air without the use of fluxes and/or inert cover
gases. In fact, the strength of the bond formed during air brazing relies on the
formation of a thin, adherent oxide scale on the metal substrate. The technique
employs a molten oxide that is at least partially soluble in a noble metal solvent to pre-
wet the oxide faying surfaces, forming a new surface that the remaining molten filler
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
current interest is in investigating whether the Ag-CuO system is suitable for air
brazing functional ceramic-to-metal joints such as those needed in practical
electrochemical devices. In a series of studies, the wetting behavior of the Ag-CuO
braze was investigated with respect to a number of ceramic membrane and heat
resistant metal systems, including: alumina, (La0.6Sr0.4)(Co0.2Fe0.8)O3, (La0.8Sr0.2)FeO3,
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
discussed. Examples of where this brazing technique is being developed with
commercial partners will also be presented.
43-5
Carbon Molecular Sieve Hydrogen Selective Membranes and Their Use as
Membrane Reactor for Water Gas Shift Reaction
Richard J. Ciora, Jr.
Media and Process Technology Inc., USA
Muhammad Sahimi and Theo T. Tsotsis
University of Southern California, USA
The development of hydrogen selective membranes suitable for high temperature gas
separations has been the focus of significant research activity due to the growing
interest in the production of clean fuel, i.e., hydrogen, from coal processing. Dense
membranes, such as palladium alloys and perovskites, and porous membranes, such as
metal oxides, have been identified as promising candidates for high temperature
41
hydrogen separations. Thus far, no perfect solution has been emerged. A different
material, carbon molecular sieve (CMS), has been pursued by us for this purpose. CMS
membranes, due to their unique porous and surface properties, have exhibited unique
separation properties. By altering carbon precursor materials and pyrolysis conditions,
membranes selective for H2, CO2, O2, or hydrocarbons can be prepared, as reported in
the literature. Further, the carbon surface is considered inert for most industrial gases;
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
permeance at intermediate temperatures, i.e., 100 to ~300C, for many industrially
significant gas separations, as opposed to the pervoskite based membrane, which
requires a much higher temperature to achieve a significant permeate flux. In addition,
our CMS membrane has demonstrated hydrothermal stability at this temperature range,
in contrast to nanoporous metal oxide membranes. However, CMS membranes are
susceptible to poisoning by various contaminants, particularly hydrophobic
compounds, due to surface adsorption. An in-line regeneration process has been
demonstrated for its effectiveness in the restoration of the permeance. Finally, to
become a commercially viable product, we have deposited this CMS membrane on our
commercial ceramic membranes to retain the robust feature of the ceramic membranes.
This membrane is currently being evaluated as a WGS membrane reactor for hydrogen
production for coal gasification off-gas.
SESSION 44
GASIFICATION APPLICATIONS & ECONOMICS: 2
44-1
Status of 250MW Air-blown IGCC Demonstration Project
Yuso Oki, Shozo Kaneko, Jun Wada, Shuji Kameyama
Clean Coal R&D Co., Ltd., Japan
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.
However, coal emits more greenhouse gas than the other fossil fuels. To harmonize the
reduction of greenhouse gas and coal utilization, there is an urgent need to develop a
break-through high-efficiency power generation technology.
IGCC (Integrated coal Gasification Combined Cycle) is one of the most promising
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
experimental research with the IGCC pilot plant was completed successfully in 1996,
and a project of the 250MW IGCC demonstration plant has been started in 2001 by
utility companies in Japan supported by METI (Ministry of Economy, Trade and
Industry). Clean Coal Power R&D Co., Ltd. (CCP) was established in 2001 as the
contractor of the project, funded by ten Japanese utility companies.
Initially CCP was located in central Tokyo to conduct preparatory activities including
plant design and Environmental Impact Assessments.
During these three years the project has been successfully conducted on schedule.
Environmental Impact Assessments has been almost completed in accordance with
procedures. In April 2004, entire office of CCP was relocated next to the plant site,
Nakoso, approximately 200 kilometers north of Tokyo. Construction is scheduled to
begin in September.
CCP has also been working on coal-slag recycle technology, which will be necessary
when the operation tests of IGCC start in 2007. There have been no governmental
standards for the quality of coal gasifier slag. CCP conducted several field tests of
slag-containing materials for roads or concrete-cast products, which showed high
durability and no leaching. Govermental authorization for new standards of coal slag is
expected soon, which will encourage and accelerate utilization of gasifier slag.
44-2
Operation Experience of EAGLE Coal Gasification System
Sadao Wasaka
New Energy and Industrial Technology Development Organization, Japan
Masao Sotooka and Hiroshi Yamashita
J-POWER/Electric Power Development Co., Ltd., Japan
One purpose of the EAGLE (coal Energy Application for Gas, Liquid and Electricity)
project is to develop high efficient gasification system.
In the EAGLE pilot plant, we have adopted Oxygen-blow two-stage spiral flow
gasifier with recycling char system.
The EAGLE gasifier consists of upper-stage and lower-stage coal-burners. At lower
stage char-burners and steam nozzles are placed. With the EAGLE gasifier, pulverized
coal is fed into the gasifier from the upper stage and the lower stage in a spiral flow. In
addition, we can control the amount of oxygen fed into the lower stage and the upper
stage independently. Because of the above EAGLE gasifiers features, the lower stage
is kept at relative high temperature to melt coal ash along with the efficient gasification
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 EAGLE gasifier can keep the high gasification efficiency while stable slag
discharge. We consider the EAGLE gasifier enables to apply wide range properties of
coals.
The pilot test has been continuing since March 2002 and planning to June 2006. Until
Jan 2004 we achieve total 1544 hours operation consuming 6789 tons of coal. This
paper describes the outline of the Gasification system of EAGLE pilot plant and our
operational experience.
44-3
5 MW Test Plant for High Pressure Partial Oxidation (HP POX)
Technology, Research, First Operating Experiences
B. Meyer, P. Seifert, H. Heinzel and R. Zeiler
Institute for Energy Process Engineering and Chemical Engineering, Germany
H. Schlichting
LURGI AG, Germany
Methanol is one of the most popular and important bulk intermediate product in the
synthesis chemistry. It can easily be further converted to valuable products such as
propylene, formaldehyde, olefins, synthetic fuels and acetic acid. Methanol is produced
from synthesis gas, which is can be generated by reforming or partial oxidation of
liquid or gaseous hydrocarbons mainly natural gas and heavy residue oil. LURGI's Gas
to Liquids technology focus on the economical conversion of natural gas to valuable
products via the intermediate production of methanol.
The operating pressure of the present available reformer technology is below the
methanol synthesis pressure. An energy intensive compression of the syngas is
necessary as long as the reformer pressure cannot be increased.
The new high pressure synthesis gas process HP POX represents a milestone in the
entrained flow gasification technology. The step forward to operating pressures up to
100 bar is done for the partial oxidation of hydrocarbons for the first time. LURGI Oel
Gas Chemie (Frankfurt a.M., Germany) and the Institute for Energy Process
Engineering and Chemical Engineering (IEC) of the Technical University
Bergakademie Freiberg (Germany) are partners of this ambitious project. The project is
supported by German federal and regional authorities.
The HP POX test plant, which is built in Freiberg by LURGI, is the core of the
project and an important step forward to an industrial scale plant. It is designed for an
operating pressure up to 100 bar and a thermal capacity up to 5 MW. The plant is
unique with regard to its operating parameters and operating options: Gaseous as well
as liquid hydrocarbons can be used as reactor feedstock. Innovative burner
technologies allow autothermal catalytic or non-catalytic reforming for gaseous
feedstock and gasification of liquid feed streams such as heavy residue oil and
chemical wastes.
The plant was taken into the cold operation in November 2003. The hot operation is
scheduled for spring 2004, the start for a detailed investigation program. The suitability
for a wide range of gaseous and liquid feedstock has to be shown, the technological
and energetic limits of the process have to be determined.
The IEC scientific investigations focus on the theoretical description and the numerical
calculation of the HP POX process. Increased pressure, bigger reactor dimensions and
higher throughput change the conditions of flow and heat transfer in the reactor
decisively.
Reaction mechanism and soot formation, formation of trace components as well as
investigatons of construction materials under gasification conditions have to be
examined. There are extensive developments for coupled fluid dynamic and kinetic
models for the non-catalytic and catalytic autothermal process up to 100 bar.
The presentation will give an overview of the plant, first operating experiences and
some fundamental results of the numerical calculations.
44-4
GEs Coal Gasification Technology for Methanol/DME Applications
Francis Fong
GE Gasification Technology Inc., USA
Thomas OBrien
GE Energy, USA
This paper describes the latest development of ChevronTexacos coal gasification
technology for chemicals industries, with a particular focus on methanol & DME
(dimethyl ether) applications. The paper will present an update of ChevronTexacos
gasification successes in coal gasification, summarizes the latest commercial
experience, in addition to a case study on methanol/DME production utilizing
ChevronTexacos coal gasification technology.
44-5
Westinghouse Plasma Gasification Technology Commercial Projects Update
S. V. Dighe and D. E. Lazzara
Westinghouse Plasma Corporation, USA
This paper will provide update on the commercial operation of the WPC plasma
gasification commercial plants utilizing organic wastes such as municipal solid waste
(MSW), wastewater treatment sludge, plastic waste and other fuels. Brief discussion
on future projects under development will also be included.
42
SESSION 45
LOW RANK COAL UTILIZATION: 4
45-1
Canadian Clean Power Coalition Project: The Evaluation of Options for CO2
Extraction from Existing & New Coal-Fired Power Plants
Duke du Plessis
Alberta Energy Research Institute and Alberta Economic Development, Canada
Robert Stobbs
Canadian Clean Power Coalition, Canada
Paul Clark
TranAlta Utilities Corp., Canada
The Canadian Clean Power Coalition was created in 2000 to protect and enhance
Canadas vast coal and other carbon-based resource wealth and to ensure that
environmental public policy decisions recognized that these resources were a Canadian
asset, not an environmental liability. CCPCs membership has been made up of seven
Canadian coal and coal-fired electricity producers: Atco, EPCOR, Luscar, Ontario
Power Generation, Nova Scotia Power, SaskPower, TransAlta as well as the US
Electric Power Research Institute (EPRI) and the International Energy Agency (IEA).
Support and additional research funding for Phase I has come from Natural Resources
Canada, Alberta Energy Research Institute (AERI) and Saskatchewan Industry &
Resources (SIR).
Phase I of the demonstration project was carried out over the past two years to evaluate
technologies for coal-fired power generation which reduce all emissions, including
CO2, to levels below that of gas-fired plants. Technologies evaluated included
gasification (IGCC), oxy-fuel combustion and amine scrubbing. These technologies
were evaluated with three coal types Eastern bituminous, Western subbituminous and
lignite coals. Engineering studies determined the capital and operating costs, the cost
of electricity produced (with CO2 removed) and the cost per tonne of CO2 avoided.
These studies also evaluated the potential utilization of CO2 generated in western
Canada for Enhanced Oil Recovery and storage in depleted oil reservoirs or deep
saline aquifers.
Phase 1 identified process optimization and technology enhancements to improve the
competitiveness of gasification of low rank western Canadian coals. Phase II, started in
late 2003, will optimize the designs and develop business cases for one or more
demonstration plants to be in place by 2012. Optimization will include site specific
demonstration plants producing clean power as well as steam and hydrogen for the
recovery and upgrading bitumen and utilization of CO2 for enhanced recovery of
conventional oil (polygeneration). The unique combination of feedstock and product
options favour demonstration and commercialization of clean coal polygeneration
plants in Western Canada.
The paper will present the results of Phases 1 and 2 including comparative costs of the
different technologies evaluated, optimized polygeneration process schemes and the
technology enhancements under investigation.
45-2
The Kinetics and Characteristics of the Pyrolysis of Zhaotong Lignite
Yaoling Chi and Shuyuan Li
University of Petroleum, China
The resources of lignite in Zhaotong, Yunnan Province are abundant. Because of large
moisture, low calorific value and high ash content, it has not been used as a fuel up to
now. In this paper, the investigation of the Zhaotong lignite pyrolysis has been made to
find a rational method to use the lignite.
Zhaotong lignite contains the moisture of 60%. Therefore, the drying process becomes
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
room temperature drying. At the temperature of around 105 , however, the lignite
lump begins to crush into fine particles. In the tar, the sulfur content is 0.418% which
is the lower than the requirement for fuel oil in China. So, the sulfur content is not the
limitation to tar utilization. The diesel fraction is up to 60% of the tar. Therefore tar
can be used to produce light diesel through distillation and upgrading. The gas with the
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
for power generation or civil utilization. Lignite ash is the good raw material for the
production of cement and timbering. From mentioned above, it is concluded that
comprehensive utilization of Zhaotong lignite has a good prospective.
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
final temperature of 600 . Because the calcium oxide in lignite ash has an effect on
the pyrolysates, the samples were obtained by mixing lignite and ash mechanically
with different ratios. The mixture was pyrolysed using TGA with heating rates of
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 Low-Rank Coals in a Transport Reactor
Michael L. Swanson, Doug R. Hajicek, Michael E. Collings and Ann K. Henderson
University of North Dakota Energy & Environmental Research Center, USA
The U.S. Department of Energy (DOE) National Energy Technology Laboratory
(NETL) Office of Power Systems Product Management has as its mission to foster the
development and deployment of advanced, clean, and affordable fossil (coal)-based
power systems. These advanced power systems include the development and
demonstration of gasification-based advanced power systems which are an integral part
of the Vision 21 Program being developed by DOE for the coproduction of power and
chemicals. DOE has also been developing advanced gasification systems that lower the
capital and operating costs of producing syn gas for electricity and chemicals
production. A transport reactor has shown potential to be a low-cost syn gas producer
compared to other gasification systems since its high throughput per unit cross-
sectional area reduces capital costs. This work directly supports the Power Systems
Development Facility (PSDF) utilizing the Kellogg Brown & Root (KBR) transport
reactor located at the Southern Company Services (SCS) Wilsonville, Alabama, site.
Over 2500 hours of operation on eleven different coals ranging from bituminous to
lignite along with a petroleum coke have been completed to date in the pilot-scale
transport reactor development unit (TRDU) at the Energy & Environmental Research
Center (EERC). The EERC has established an extensive database on the operation of
these various fuels in both air- and oxygen-blown modes utilizing a pilot-scale
transport reactor gasifier. This database has been useful in determining the
effectiveness of design changes on an advanced transport reactor gasifier.
The effects of different fuel types on both gasifier performance and the operation of the
hot-gas filter system have been determined. It has been demonstrated that corrected
fuel gas heating values ranging from 105 to 130 Btu/scf have been achieved in air-
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
are highly dependent on the oxygencoal ratio. Higher-reactivity (low-rank) coals
appear to perform better in a transport reactor than the less reactive bituminous coals.
Factors that affect TRDU product gas quality appear to be coal type, temperature, and
oxygencoal ratios. Testing with Australian brown coals and coalwood biomass
mixtures has recently been completed. Methods for the control of mercury under
warm-gas conditions are currently being investigated.
45-4
Processing Low Rank Coal to Obtain Chemical Products and Reducing Gas
Igor Shulga and Adolf Silka
Ukrainian State Research Institute for Carbochemistry, Ukraine
This new technology is intended to produce those products which are currently
obtained mainly from petroleum and natural gas. The principle of the process lies in
heating a pretreated coal in the absence of the air to a temperature of 600-700 C,
gasifying the solid material produced, separate removing and processing of vapour-gas
products formed at various stages of thermochemical conversion. The basic equipment
of the process is a vertical furnace for heating coals, rotating drum furnace for
gasification and apparatus for treatment of vapour-gas products.
The properties of the feed stock and related technological features of processing
different types of coal has an impact on yields and quality of the final products. In
particular, a solid material is produced in the process in the amount of 300-640 kg/t
coal. It can be used as a substitute of coke if used beyond blast furnaces, as energy fuel
and a raw material for gasification. In the latter case, using air-steam blast, one tonne
of this material can give 3500-4500 m3 of gas having the calorific value 4-5 MJ/m3 for
energy application. Using oxygen-steam- blast we can obtain 1600-2100 m3 of gas
(calorific value 10-11 MJ/m3) containing
CO + H2 + CH4 over 80 % mainly for processes of chemical synthesis. Slag is also
formed (80-120 kg/t coal) as a building material, raw stock for polymetallic alloys and
chemical fertilizer.
One tonne of coal can also give a primary gas, 150-250 m3, calorific value 15-23
MJ/m3 (energy fuel, chemical stock), primary tar, 30-45 kg, and gas petrol, 16-40 kg
(chemical stock, component of motor fuel), phenols, 30-40 kg, ammonium sulphate,
50-80 kg, sulphuric acid, 50-90 kg.
The technology is realized in a continuous process in a chain of air-tight apparatus
allowing to eliminate scattering emissions into the atmosphere and to treat other
emissions to meet the existing requirements. The process has been investigated under
laboratory conditions and tested on a pilot plant. Definition phase engineering has been
made for a semi-commercial introduction of the technology.
45-5
Enhancement of Hydrogen Production during the Gasification of Victorian
Brown Coal with Steam Using Iron as the Catalyst
Jianglong Yu, Lachlan J. McKenzie and Chun-zhu Li
CRC for Clean Power from Lignite, Monash University, Australia
Fu-jun Tian and Mee Chin Chow
Monash University, Australia
43
Gasification of solid fuels such as coal, biomass and wastes is a major potential source
of hydrogen in the future hydrogen economy. This study investigates the significant
enhancement of hydrogen production during the gasification of Victorian brown coal
with steam using iron as a catalyst.
Iron was introduced into the acid-washed Loy Yang coal through impregnation using a
ferric chloride aqueous solution. Gasification experiments were carried out using a
fluidised-bed/fixed-bed reactor at a fast particle heating rate. The yield of char was
determined by directly weighing the reactor before and after each experiment. Gases
were analysed using a GC with dual columns. The transformation of iron species
loaded into the coal during the pyrolysis and gasification process was examined using
XRD and other microscopic techniques. The results show that the loaded iron affects
both pyrolysis and gasification of brown coal. The overall gasification rate of a char
with steam increases significantly in the presence of iron. The gasification of iron-
loaded coal samples gives much higher ratio of H2+CO2 to CO than that of the acid-
form coal under similar conditions. The novel configuration of our reactor system has
allowed the feeding of the acid-form coal and iron-impregnated coal in different orders
into the reactor, giving interesting results about the catalytic effects of iron loaded into
the coal on the catalytic gasification of coal/char and water-gas shift reactions. The
effects of iron on the gasification rate and products distribution will be discussed
together with the transformation of iron during pyrolysis and gasification.
SESSION 46
SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 2:
LIQUEFACTION & NATURAL GAS
46-1
Study for Coal to Liquid (CTL)
Hisanori Tanaka, Kyouichi Kougami and Masaki Sanemasa
Electric Power Development Co.Ltd, Japan
Electric Power Development Co. (J-Power) is developing Coal gasification technology
for fuel cell. This technology product synthesis gas as CO and H2.
Using FT synthesis technology its able to make FT synthesis oil from these CO and
H2.
Then we just started to study about FT synthesis catalysts which are the key
technology for CTL.
46-2
Catalytic Thermal Conversion of Kuzbass Liptobiolitic Coal To Liquid Products
V.I. Sharypov, B.N. Kuznetsov, N.G. Beregovtsova, S.V. Baryshnikov
Institute of Chemistry and Chemical Technology Siberian Branch RAS, Russia
N.U.Vasilieva
Krasnoyarsk State University, Russia
A.N. Startsev
Institute of Catalysis Siberian Branch RAS, Russia
The thermal conversion of liptobiolitic coal from Barzass coal-field of Kuzbass basin
(Siberia, Russia) was investigated at conditions of pyrolysis in hydrogen atmosphere
and hydrogenation in the medium of petroleum residue (b.p.>350oC). The influence of
the mechanochemically activated iron-containing ore catalyst on the yield and
composition of liquids products was studied. Results of the study were compared with
data obtained with Kansk-Achinsk brown coal (Siberia, Russia) at the similar process
parameters.
It was found, that the liptobiolitic coal gives higher yield of liquid products as
compared to the brown coal. They mainly consist of normal paraffinic hydrocarbons.
The total concentration of aromatic and oxygen containing substances in liquids from
liptobiolitic coal was less then 20 mass%.
It was shown that the use of iron-ore catalyst in hydrogenation process allows to
increase the degree of liptobiolitic coal conversion on 21-23%, and to produce liquid
products with the yield up to 58 mass%. The conversion degree reaches to 94-97
mass% at 400-430 in liptobiolitic coal hydrogenation process and to 78-80 mass%.
in pyrolysis in hydrogen atmosphere at 430-460. The further increase of a
temperature is accompanied by intensive formation of gaseous products and results in
lower yield of liquids.
46-3
Prospect of the Natural Gas Market in East Asia
Yutaka Shirakawa and Yutaka Kunigo
Tokyo Gas Co., Ltd., Japan
Natural gas is the third primary energy in Asia and Pacific region after coal and oil,
which is different from the U.S. and Europe. Japan and South Korea highly depend on
oil imported from middle-East.
The largest exporting country is Russia, followed by Canada and Norway. The largest
importing country is the US, followed by Germany and Japan, which is the largest
LNG importer. Following Japan, South Korea is the second largest LNG importer, and
these two countries and Taiwan imported almost 70% of the worlds LNG.
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
growth. However, gradual economic recovery and increasing concern on the global
warming will increase a steady LNG demand. New markets, China and India, are
planning to import LNG in the coming years. Potential demand in these two emerging
markets is expected to be large. In case, other importers in Philippines and West Coast
of North America join the LNG market, the high LNG demand scenario in the region
will be materialized.
On supply side, existing projects have exported 77 MMT of LNG in 2002. A number
of extensions and new grassroots projects are either under construction or planned. In
addition to these LNG supplies, several pipeline projects are planned. However, the
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.
In view of the projected high increase in natural gas demand in the region, timely
development of natural gas infrastructures, LNG facilities and pipeline networks, is
essential. The infrastructure requires massive investments and it is important that
nations and economies in the region deliver a stable and consistent energy policy
which provides an environment to facilitate investments. It is also important to create
the framework where the region shares that infrastructure as the viable solution to
promote energy security, sustainable economic growth and environmental protection.
Natural gas in the US and European markets at relatively lower price has been
competitive against other energy sources and maintaining high penetrations in these
markets. In Asia and Pacific region, downward trend of LNG prices has been observed
with cost reductions in LNG production and LNG and natural gas are expected to
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
primary energy source in the 21st century in the region.
46-4
Coal to Clean Fuel The Shenhua Investment in Direct Coal Liquefaction
Qingyun SunRichard Bajura, and Jerald J. Fletcher
West Virginia University, USA
Yuzhuo Zhang and Xiangkun Ren
Shenhua Group Corporation, P.R. China
Significant price increases and the associated potential for crude oil shortages have
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)
facilities and the development of the worlds first commercial direct coal liquefaction
(DCL) plant by the Shenhua Group Corporation provide case studies of commercial
coal liquefaction technologies. Without access to detailed information on the
processes, debate on the relative economic competitiveness that these processes can
achieve continues. An increased understanding of these processes could affect the
direction of future research and potential commercialization.
This paper presents a case study of the economics of DCL and ICL technologies using
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
base, location, stage of economic development, and the policy environment. Focusing
on the inputs and outputs of liquefaction facilities, the authors explore potential
complementarities of combining DCL and ICL technologies. Complementary fuel oil
products and waste utilization that follow from integrating DCL and ICL processes
may cut inputs, reduce operational cost, and improve fuel oil quality. A case study of
the Shenhua DCL and Sasol ICL projects will offer useful information for those
countries rich in coal and dependent on oil imports that are considering coal
liquefaction as a viable alternative to enhance energy security.
46-5
Natural Gas As the Energy Carrier in Electricity Generation Sectors In Poland
and In the European Union Countries. The Present Situation and Perspectives
Lidia Gawlik and Tadeusz Olkuski
Mineral and Energy Economy Research Institute, Poland
Tomasz Mirowski, Eugeniusz Mokrzycki and Adam Szurlej
AGH University of Science and Technology, Poland
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
its usage for the purpose of electricity generation. The natural gas fired combined heat
and power plants (CHP) characterise the high efficiency of chemical energy use. For
this reason natural gas has been recently more often used for electricity generation
purposes. This is also why the role of natural gas will probably rise in future.
Hard coal and lignite are dominant in Polish sector of electricity generation. The total
electricity production in 2002 was 144,1 TWh and the share of hard coal and lignite
was about 96%. Practically the structure of Polish electricity generation has not
changed for the recent 20 years. The only, but not very significant, change is that
natural gas has just started to be used for co-generation of electricity and heat. It should
be mentioned, however, that the rate of electricity produced from natural in Poland is
low 2,1 TWh (2002), i.e. only 1,5% of the total electricity generation. The biggest
combined heat and power plant, that in spite of coal uses also natural gas is Lublin
Wrotkow.
44
The paper presents short characteristic of the Polish power generation sector with a
special stress put on combined heat and power plants based on natural gas. Constrains
that prevent from wider scale use of natural gas in the sector are described. The paper
demonstrates also the ecological and technical aspects of gas turbines use. It also
presents the comparison between structure of electricity production in Poland and in
the European Union.
Finally, the paper shows the perspective of the development of energy sector and the
role of the natural gas in future structure of primary energy mix for the purpose of
electricity production.
SESSION 47
GLOBAL CLIMATE CHANGE & APPLICATION OF INDUSTRIAL
ECOLOGY: 1
47-1
Future U.S. Greenhouse Gas Emission Reduction Scenarios Consistent With
Atmospheric Stabilization
Vello A. Kuuskraa
Advanced Resources International, Inc., USA
Phil Dipietro
Energetics, Inc., USA
Scott Klara and Sarah Forbes
US DOE, NETL, USA
The paper analyzes a scenario for reducing U.S. greenhouse gas (GHG) emissions that
is consistent, in the near term, with the Presidents Global Climate Change Initiative
(GCCI) and, in the longer term, atmospheric stabilization at 550 ppm. The purpose for
formulating and evaluating such a stabilization scenario is to define the role and
expectations for performance of carbon sequestration technologies in a future,
speculative carbon-constrained world. The analysis shows that an integrated approach,
involving emphasis on energy efficiency, cost-effective renewables and availability of
advanced CO2 capture and storage technology, would be required for emissions
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
toward an absolute target of 1,250 MMmtC/year, representing a substantial U.S.
contribution toward an atmospheric stabilization concentration of 550 ppm. This
analysis examines opportunities for reducing emissions (both CO2 and non-CO2
GHGs) in all sectors, including transportation, electricity supply, industrial,
commercial and residential. The analysis quantifies the potential contribution of the
various GHG reduction options and shows that advanced lower-cost CO2 capture and
storage technology will need to play a key role in any future GHG emissions reduction
scenario.
47-2
Employing Industrial Ecology Principles to Build Coal Power Plants
Mildred B. Perry and Udaya S. Rao
US DOE, NETL, USA
The U.S. DOE National Energy Technology Laboratory (NETL) located in Pittsburgh,
Pennsylvania, Morgantown, West Virginia, and Tulsa, Oklahoma is the implementing
field organization of the Office of Fossil Energy located in Washington DC. Among
other responsibilities, NETL manages national programs in the United States to
demonstrate technologies to reduce cost, improve efficiency, and improve the
environmental performance of coal-based electric power generation. While these
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
adopted by industry. Nor has there been any systematic approach in the power
generation industry to undertake the integration of advanced technologies to
demonstrate overall gains that are projected to be achievable in programs like Vision
21 or the newly conceived FutureGen program. Here is an opportunity to begin to
apply the principles of Industrial Ecology to minimize the impacts on resources and on
the environment. This paper explores what may be needed to realize the benefits of
Industrial Ecology principles as applied to the construction and operation of coal-based
power generation in the United States.
47-3
High-Capacity Nano-Porous Adsorbent Based on Polymer-Modified MCM-41
Molecular Sieve for Effective CO2 Separation from Gas Mixtures Containing CO2
and H2O
Chunshan Song, Xiaochun Xu and Alan W. Scaroni
Pennsylvania State University, USA
Separation of CO2 from various gaseous streams is becoming increasingly important in
the field of sustainable energy development. Adsorption separation is one of the
promising methods. The key issue for adsorption separation is to prepare high-
performance adsorbent for effective CO2 separation from CO2- and H2O-containing gas
mixtures. In this work, adsorption separation of CO2 was investigated using a novel
molecular basket adsorbent and simulated flue gas mixtures containing CO2, O2, N2
with and without moisture. The CO2 molecular basket adsorbent was prepared by
synthesizing mesoporous molecular sieve MCM-41 and loading it with a branched
polyethylenimine. Compared with the adsorption separation of CO2 from simulated
dry flue gas, both the CO2 breakthrough time and CO2 adsorption capacity increased
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
flue gas mixture by the novel molecular basket. When the feed concentration of
moisture was lower than that of CO2, CO2 adsorption capacity increased rapidly with
the increase of moisture concentration. When the feed concentration of moisture
became larger than that of CO2, the increase in CO2 adsorption capacity recessed.
Maximum promoting effect of moisture appears at moisture concentrations
approaching that of CO2 in the flue gas. The cyclic adsorption/desorption separation
results show that the novel molecular basket adsorbent is stable in the cyclic
operations of CO2 adsorption separation from moist flue gas. It should be noted that
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
our laboratory have numerous CO2 affinity sites, can operate at 75 C, and do not
require pre-separation of moisture from the gas stream. In fact, the presence of
moisture further enhances CO2 capture on such adsorbents.
47-4
Characterization of Sodium-Based Sorbents for CO2 Capture from Flue Gas
Chong Kul Ryu, Joong Beom Lee, Tae Hyung Eom and Je Myung Oh
Korea Electric Power Research Institute, Korea
Chang Keun Yi
Korea Institute of Energy Research, Korea
The purpose of this work is to identify potential materials for CO2 capture sorbent
compositions and to make dry regenerable sorbents by spray drying technique to obtain
high mechanical strength and chemical reactivity. Much attention has been recently
directed towards cost-effective and energy-efficient process - anthropogenic CO2
sequestration techniques aimed at capturing CO2 released from fossil fuelfired power
plants. One of the advanced concepts for low-cost capturing CO2 is an absorption
process with dry regenerable sorbents. This report described mechanical strength and
CO2 sorption capacity of spray-dried sodium-based CO2 sorbents applicable to the flue
gas conditions.
During the sorbent screening with Na2CO3 as active CO2 sorption components, the five
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
also investigated along with pure Na2CO3 and NaHCO3 in the temperature range of 50-
70C with simulated flue gas containing 10 vol% H2O and 14.4 vol% CO2. The CO2
sorption capacities of sorbents are 9-14 g CO2/100 g sorbent (or wt%) with the
maximum sorbent utilization of 180%. The sorption capacity of some sorbents is
comparable to or better than that of pure Na2CO3 and NaHCO3 sorbents. The chemical
reactivity of sorbent is very sensitive to calcination temperature of green body, water
sorption capacity, and carbonation temperature. The sorbent calcined at 500C showed
the best chemical reactivity at 50C. The attrition indices of some sorbents by ASTM
D 5757 reached below 60% and also depended on the calcination temperature. It is
concluded that dry regenerable spray-dried sodium-based sorbent could be a viable
option to capture CO2 from flue gas condition.
47-5
Ex-Situ and In-Situ Mineral Carbonation as a Means to Sequester Carbon
Dioxide
S.J. Gerdemann, D.C. Dahlin, W.K. OConnor, L.R. Penner, and G.E. Rush
Albany Research Center, U.S. Department of Energy, USA
The U. S. Department of Energys Albany Research Center is investigating mineral
carbonation as a method of sequestering CO2 from coal-fired-power plants.
Magnesium-silicate minerals such as serpentine [Mg3Si2O5(OH)4] and olivine
(Mg2SiO4) react with CO2 to produce magnesite (MgCO3), and the calcium-silicate
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
plant) or in-situ (storage underground and subsequent reaction with the host rock to
trap CO2 as carbonate minerals).
For ex-situ mineral carbonation to be economically attractive, the reaction must
proceed quickly to near completion. The reaction rate is accelerated by raising the
activity of CO2 in solution, heat (but not too much), reducing the particle size, high
intensity grinding to disrupt the crystal structure, and, in the case of serpentine, heat-
treatment to remove the chemically bound water. All of these carry energy/economic
penalties. An economic study illustrates the impact of mineral availability and process
parameters on the cost of ex-situ carbon sequestration.
In-situ carbonation offers economic advantages over any ex-situ process, because no
chemical plant is required. Knowledge gained from the ex-situ work was applied to
long-term experiments designed to simulate in-situ CO2 storage conditions. The
Columbia River Basalt Group (CRBG), a multi-layered basaltic lava formation, has
favorable mineralogy (up to 25% combined concentration of Ca, Fe2+, and Mg cations)
for storage of CO2. However, more information about the interaction of CO2 with
aquifers and the host rock is needed. Core samples from the CRBG, as well as samples
of olivine, serpentine, and sandstone, were reacted in an autoclave for up to 2000 hours
45
at elevated temperatures and pressures. Changes in core porosity, secondary minerals,
and solution chemistry were measured.
SESSION 48
COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY 3:
COAL TAR, PITCH, CO-PYROLYSIS
48-1
Study on the Emulsification Mechanism of Coal-tar
Shi Shizhuang
Wuhan University of Science and Technology, China
Liu Qibing
Wuhan Iron and Steel Co., China
In the paper, the causes why results in the increase of moisture in coal-tar, being
difficult in dewater and in operation in coal-tar processing plant when the control of
coal charging emissions has been used in the WISCO (Wuhan Iron and Steel
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
WISCO have been taken and analyzed. And then, the emulsification mechanism of
coal-tar and the factors on stability of coal-tar emulsions have been researched in
laboratory simulating production condition and found that the coal-tar formed water-
in-oil (W/O) emulsions with the emulsifier of the solid carbonic powder (coke powder
and coal powder) drawing into coal-tar in the coal charging; the factors affecting on the
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
size of emulsifier, et al; and the more the emulsifier, the bigger the ratio of coal
powder, the finer the emulsifier, the more stable the coal-tar emulsions; and the more
the emulsifier, the larger the viscosity of the emulsions and the more stable the coal-tar
emulsions.
48-2
Co-Coking of Decant Oil and Coal: The Development of a Laboratory Delayed
Coker, Product Distribution of Distillates and Isolated Carbon from the Process
Leslie R. Rudnick, Omer Gul and Harold H. Schobert
The Pennsylvania State University, USA
We describe the development of a laboratory scale delayed coker and present results of
an investigation on the composition of recovered liquid from the coking of decant oil
and decant oil/coal mixtures. One of the major achievements of this coker design is
the ability to isolate coke artifacts essentially intact. The process of co-coking involves
the simultaneous co-carbonization of coal and petroleum resid under delayed coking
conditions. The co-coking process produces a solid coke by-product. Ideally this
coke should have a high market value and be suitable for use in products such as
anodes for the aluminum industry.
The first part of this study addresses design features necessary to be able to isolate
from the reactor the coke formed during the coking or co-coking process. We have
utilized two approaches to minimize these difficulties. Techniques were developed to
isolate Kg quantities of intact coke from the reactor. This methodology provides
material for detailed characterization and further processing. This provides the
opportunity to study the physical and chemical structure of the coke as a function of
reaction time, and other process parameters, and as a function of location within the
coking reactor. Liquids are obtained in suitable quantity for detailed chemical
characterization, recombination and distillation into refinery cuts for evaluation.
48-3
Conversion of Tar in Hot Coke Oven Gas by Pyrolysis
Motoaki Kawase, Tsunekata Kobata, Ingmar Gerlach, Hiroyuki Nakagawa, Kouichi
Miura
Kyoto University, Japan
The coke oven gas (COG) consists mainly of hydrogen and methane, the mole
fractions of which are ca. 50% and ca. 25%, respectively. The tar vapor is also
contained ca. 30 wt% in the COG. At the moment, tar is removed by condensating the
vapor for preventing the deposition in the downstream processes. The enthalpy loss
due to this operation greatly reduces the overall thermal efficiency. The utilization of
the hot COG is becoming a key to improve the overall efficiency of the
iron manufacture. In this study, possibility to convert the tar vapor to synthesis gas was
investigated. Even only the removal of tar from the hot COG is profitable. In addition,
the reaction model of tar decomposition in COG was investigated taking into account
the effects of coexistent gases.
Experiments of the pyrolysis of tar in helium and simulated COG atmospheres were
carried out. Since the COG contains carbon monoxide, carbon dioxide, steam as well
as methane and hydrogen, the tar pyrolysis experiments in these constituent gas
atmospheres were performed for investigating the effects of these gases. Tar,
CH0.65N0.010O0.022, condensed from an actual COG was used as the reactant. More
than 80% of tar could be decomposed in several seconds by pyrolysis at
temperature higher than 1000C. The coke yield reached 80% and the main gas
products were methane and hydrogen. The molecular weight of the product tar was
higher than that of the reactant tar. The product tar contained 47-ring aromatics,
whereas the reactant tar contained 35-ring aromatics. Coke deposition was reduced in
the presence of steam by steam gasification of coke. Carbon dioxide also caused the
gasification of coke but the reaction rate was lower than that by steam. No
apparent reaction of carbon dioxide or steam with tar was observed. When tar was
decomposed in the hydrogen atmosphere, the hydrogen yield decreased and the
methane yield increased compared with those in helium. This indicates that
hydrocracking of tar took place. When tar vapor and methane were fed to the reactor,
the hydrogen yield and coke yield increased. The decrease in the methane yield, the
increase in the hydrogen yield, and the increase in the coke yield were approximately
1:2:1 on molar basis. This suggests that methane was pyrolyzed to form coke and
hydrogen and no reaction of tar with methane took place. When tar was pyrolyzed in
the simulated COG, coke deposition from methane in addition to the deposition from
the tar was observed at high temperature. The reverse shift reaction forming carbon
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
COG should consist of the tar pyrolysis to form hydrogen, methane, and coke, the
gasification of coke with steam and carbon dioxide, the methane pyrolysis to form
coke and hydrogen, and the shift conversion reaction.
48-4
Waste Plastics Recycling Technology Using Coke Ovens
Kenji Kato, Seiji Nomura and Koichi Fukuda
Nippon Steel Corporation, Japan
At the advent of the 21st century, mankind is facing a global environmental problem,
and the industrial sector is required to take initiatives in the establishment of recycling
society for efficient utilization of natural resources. The Japan Iron & Steel Federation,
as a voluntary energy-saving action plan, proposed a 10 % energy reduction by 2010
with 1990 as the basis. Furthermore, it has put forward an additional 1.5% energy
saving by the use of waste plastics as metallurgical raw materials.
By laboratory and actual coke oven tests, it was found that waste plastics recycling
process using coke ovens is feasible to recover coke, tar, light oil and gas from general
waste plastics mixed in coal by carbonization in coke ovens without deteriorating the
qualities of coke. Waste plastics recycling process using coke ovens was started as a
chemical recycling technology at Nippon Steel Nagoya and Kimitsu works in 2000.
Waste plastics recycling equipment with a total capacity of 120,000 t/y is in operating
by Nippon Steel Corporation.
Using the life-cycle assessment (LCA) methodology, the waste plastics recycling
process using coke ovens was estimated. And the process is thought to be effective to
reduce CO2 emission significantly.
48-5
Use of Waste Plastics and Rubber as Admixtures into Coking Charges
Pavel Straka
Academy of Science of the Czech Republic, Czech Republic
The coking of stamped charges with admixtures took place in the carbonizing
equipment of the coking plant in Tinec Steel Works, Czech Rep., under simulated
commercial conditions. This equipment Karbotest allows the determination and
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 25 wt.-%, the content of rubber 23
wt.-%. These contents were chosen based on the conclusions from the preliminary
macrolaboratory experiments and taking into account the co-coking results in
Japanese works [1], which prefer small amounts of plastics admixtures in a charge.
Three mixtures were examined as admixtures: a mixture of ABS polymer and rigid
polystyrene; a mixture of polyethylene, polypropylene, polystyrene and cellulose
derivatives; and rubber. It was found that plastics admixtures affect the properties of
tar and improve the calorific value of the coking gas. The CSR and CRI parameters
of a blast-furnace coke were not substantially different, i.e., the waste plastics can
economize on part of the coal used in a stamped charge. Additions of both light and
heavy plastics can be used up to 5 % of a charge weight. On the other hand, a 3 %-
rubber addition influenced both parameters being considered. In the cokes obtained,
the decisive parameters were observed using the standard method of Nippon Steel
Comp.: reactivity (CRI) and coke strength after reaction (CSR). Also ash content,
degasification and sulfur content in the cokes obtained were observed. It arises from
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
commercial applications based on long-term observations of the correlation
parameters of the cokes from the Karbotest tests and from commercial cokes from
the same charges [2]. For the rectification of the parameters from the Karbotest tests
(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.
It follows from the operational values of both parameters that it is possible to obtain
quality high-furnace cokes by co-coking with plastics, because the CRI and CSR
values for the coke from a coal mixture and for the cokes from co-coking do not
differ much. If we - based on experience - consider the blast-furnace coke with the
CRIblast furnace coke value below 36 % to be of good quality and those with the values 36
40 % to be acceptable, then it would probably be only the coke from a mixture with
3 % of rubber that would not be possible to use in a blast furnace. It is similar with
46
the CSRblast furnace coke values: if we consider the cokes with a value above 57 % to be of
good quality and with the values 52 57 % to be acceptable, then it would only be
the coke from the mixture with 3 % rubber again that could not be used as a blast-
furnace one but e.g. for heating.
SESSION 49
MATERIAL, INSTRUMENTATION & CONTROLS 3: HIGH
TEMPERATURE MATERIALS ISSUES
49-1
Tests of an Oxide Dispersion-Strengthened High-Temperature Heat Exchanger
for Indirectly Fired Combined Cycles
John P. Hurley and Greg F. Weber
University of North Dakota, USA
Under the U.S. Department of Energy High-Performance Power System Program, a
pilotscale high-temperature heat exchanger (HTHX) was used to produce pressurized
air at up to 2000F. An indirectly fired combined cycle (IFCC) power plant using this
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
entering the gas turbine. Because of its high efficiency, an IFCC system is the most
appropriate power concept for employing oxygen-enriched combustion in order to
make carbon sequestration more economical. It has the added benefit of minimizing
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
of the coal in such an oxygen-blown system, the need for flue gas recirculation
to manage the flame temperature is reduced and the maximum amount of energy can
be channeled to the gas turbine, raising overall plant efficiency. In addition, reducing
the volume of flue gas would substantially reduce the required size of the baghouse or
electrostatic precipitator, flue gas desulfurization system, and induced- and forced-
draft fans, thereby reducing both capital and operating costs. It would also permit the
most economical use of a condensing heat exchanger for reclaiming combustion water
and thereby even further reducing the amount of outside water necessary for plant
operation. After water condensation, only carbon dioxide is left in the gas stream,
which can then be used industrially or sequestered. If the system is cofired with coal
and biomass, sequestration of the carbon dioxide would lead to a net atmospheric
reduction of that gas.
In this paper, we describe results from recent oxygen-enriched and combined coal
and biomass-fired tests of an oxide dispersion-strengthened (ODS) heat exchanger
producing pressurized air at 1750F (950C). The tests were performed in a pilot-scale
slagging combustion system while firing coal in an oxygen-enriched configuration and
while firing coalbiomass blends in air. In addition, results of laboratory tests of the
resistance of two actively cooled ODS alloys to corrosion by flowing coal and coal
biomass slags are presented, including scanning electron microscopy analyses of
elemental depletion versus depth.
49-2
High Temperature Erosion Testing In a Gasifier Environment
J. Tylczak, J. Rawers and T. Adler
Albany Research Center, USA
The development of materials with the ability to operate in adverse conditions while
resisting the effects of erosion and corrosion are key to the future success of high
efficiency power plants. Many of the next generation coal power plants are envisioned
to be combined cycle, with gasifiers used to produce steam and syngas. The gasifier
sections of these plants require materials of construction that are resistant to the effects
of erosion in a reducing atmosphere that contains sulfur and chloride compounds. The
Albany Research Center has developed a test apparatus designed to test the erosion-
resistance of candidate materials under a range of conditions, including those found in
gasifiers. This hostile atmosphere erosion wear test (HAET) has been used to examine
a group of high alloy candidate materials such as iron aluminide and Haynes HR 160
and compare them to a conventional 310 stainless steel. These materials were erosion
tested using a 270m silica abrasive, at temperatures up to 700%C, using typical
impact velocities of 20 m/sec. The effects of erosion under these conditions on the
surface scales that form are described. The total loss rate, lost rate due to erosion and
corrosion for the test materials are compared.
49-4
Ash Monitoring System for Utility Boilers
Richard Pomalis and Bruce Clements
CANMET Energy Technology Centre, Canada
Firing coal in utility obviates the need for sootblowing. Over time, heat exchange
sections foul with ash deposits that have deleterious effects on heat transfer and boiler
efficiency. Knowing where and when to blow soot is of paramount importance if the
process is to be optimized. The CANMET Energy Technology Centre Ottawa
(CETC-O) has developed and implemented a robust and customizable Ash Monitoring
System (AMS) software for coal-fired boilers that assists operators during sootblowing
operations.
The AMS provides the operator on-line information about the state of cleanliness of
heat exchange sections. The information can be used to optimize sootblowing
practices, which translates to significant cost savings. Specifically, optimized
sootblowing results in the following benefits: lower steam consumption, reduced
sootblower maintenance costs, less heat transfer equipment damage, lower NOx
emissions, fewer ash related outages, increased boiler efficiencies, and assistance in
decision-making regarding sootblowing events.
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
(DCS) in real time, allowing for performance tracking and system optimization. The
AMS program, written in Visual Basic, has menu driven access to performance data,
calibration and configuration utilities, distributed control system data, data acquisition
log (useful in determining when sensors fail), fouling factor trends, legends and online
help.
For the most part, the AMS is a physical model that uses flow, temperature and
pressure data from existing plant instrumentation. The AMS uses this information in
various combustion, mass balance, heat load and pressure drop calculations to
determine heat transfer section fouling factors as well as system performance data.
Using a multivariate approach, historical data are used to calibrate the AMS. Once
calibrated, no additional training of the software is required.
The AMS has been successfully implemented at a major Canadian utility. It can be
easily installed and configured as an online add-on to an existing plant DCS using
client/server software and minimum additional equipment.
49-5
Optimization of Oxide Dispersion Strengthened FeCrAl and Fe3Al Alloys
Bimal Kad
University of California-San Diego, USA
Rod Judkins
Oak Ridge National Laboratory, USA
Gaylord Smith
Special Metals Corporation, USA
Mechanically alloyed oxide dispersion strengthened (ODS) Fe-Cr-Al and Fe3Al alloy
thin walled tubes and sheets, produced via powder consolidation methodologies, are
promising materials for eventual use at temperatures up to 1200oC in the advanced
power generation systems, far above the temperature capabilities of conventional
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
mechanisms for such components. The processed ODS alloy microstructure consists of
elongated grains parallel to the tube axis, a result of dominant axial metal flow which
aligns the dispersoid particles and other impurities in the longitudinal direction. This
dispersion distribution is unaltered by recrystallization treatments and the high aspect
ratio grain shape typically obtained limits transverse grain spacing and consequently
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.
Fortunately, the material does exhibit requisite creep strength in the longitudinal
direction and efforts to realign the underlying microstructure for hoop creep service are
of interest. We will describe our attempts to improving hoop creep in ODS-alloy
components by manipulating the factors that dictate grain shape and control
recrystallization behavior.
SESSION 50
GASIFICATION APPLICATIONS & ECONOMICS: 3
50-1
Preliminary Results from Field Testing an Improved Refractory Material For
Slagging Coal Gasifiers
James P. Bennett, Kyei-Sing Kwong and Cynthia Powell Doan
USDOE-Albany Research Center, USA
Slag attack of refractory materials used to line the hot face of slagging gasifiers limits
their service life to between 3 and 24 months. These gasifiers use coal, petroleum
coke, or combinations of them as raw materials to produce chemicals, liquid fuel,
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
during gasification temperatures between 1300 - 1600oC and pressures up to 1000 psi,
leading to severe slag attack of a vessel lining and causing unacceptable gasifier
reliability and on-line availability. To maximize refractory life and provide protection
of the gasifier metal shell, the best liners have contained a minimum of 60-70 pct
chromia in combination with alumina, alumina/zirconia, or magnesia. The Albany
Research Center of DOE has developed a phosphate containing high chrome oxide
refractory liner that indicates potential for increased service life over currently used
materials. This new liner has been produced commercially by a refractory company
and installed in a gasifier for performance evaluation. The properties of this material
and preliminary results from the plant trial will be presented.
47
50-2
Succesful Continuous Injection of Solid Fuels into Gasification System Pressures -
Doe Funded Program Results
Derek Aldred and Timothy Saunders
Stamet Inc., USA
Glenn Shirey
CQ Inc., USA
The DOE, recognizing the need for a feeding solution for gasification systems, funded
a project to elevate operation of the unique Stamet Posimetric Solids Pump to such
system operating pressures. The ultimate objective is a mechanical rotary device for
continuously feeding coal into pressurized environments of at least 500 pounds per
square inch. The Posimetric concept earlier achieved continuous feeding into gas
pressures exceeding 200 PSI under an SBIR program grant, making it the first
mechanically powered, continuous pump to achieve such pressure levels.
The current DOE project comprises an initial phase for design and testing of a device
to feed coal into 300 PSI and a second Phase for feeding into 500 PSI. Phase 1
included review, with advanced gasification and pressurized combustion system
operators, of current specifications and feed equipment to confirm the DOE identified
need. This review received strong positive response from gasification system
operators as to the feeding solution need. Additionally, study of coal properties
desirable for achieving the target pressure was undertaken by CQ Inc., a contributor to
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
conference in 2003.
In December 2003, following a program of testing and modification, the Phase 1
feeder achieved a record pressure for continuous injection of coal, 300 PSI, meeting
the Phase 1 objectives. Subsequently, in extended test runs undertaken at CQs facility
to confirm capability of the Phase 1 Pump for requested commercial test applications,
the Phase 1 feeder achieved a pressure exceeding 330 PSI, another record. This
experience is currently being applied to the Phase 2 design to ensure optimized
performance at the 500-PSI target pressure level. Areas for optimization include lower
power/torque requirements and enhanced gas sealing.
This paper will present a complete review and evaluation of the design and test results
of the successful Phase 1 feeder. The paper will present design optimizations for the
Phase 2 feeder and results of initial Phase 2 testing completed by the date of the
conference.
50-3
Oxygen Transport Membranes for Future IGCC Power Plants
Bart van Hassel, Ravi Prasad, Dante Bonaquist, Hancun Chen, Jack Chen,
Prasad Apte, Ry Drnevich, Joseph Corpus, Jonathan Lane, Eric Shreiber, John
Sirman,John Spero and Troy Raybold
Praxair Inc., USA
In partnership with the U.S. Department of Energys National Energy Technology
Laboratory (NETL), a team led by Praxair is developing advanced Oxygen Transport
Membranes (OTM), which can be integrated with Integrated Gasification Combined
Cycles (IGCC) power generation cycles to produce significantly lower-cost oxygen for
gasification. OTM technology, based on high-temperature, ceramic-mixed conductor
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
IGCC will be discussed, along with advances in membrane fabrication, element
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-
temperature operating conditions and to achieve step-change improvements in IGCC
oxygen production.
50-4
ITM Oxygen for Energy-Intensive Applications
Phillip A. Armstrong and Hiromi Suzuki
Air Products Japan, Inc., USA
E.P. (Ted) Foster, James C. Sorensen and VanEric E. Stein
Air Products and Chemicals, Inc., USA
In partnership with the U.S. Department of Energy, an Air Products-led team is
developing a new air separation technology - Ion Transport Membrane Oxygen - based
on ceramic membranes that selectively transport oxygen ions when operated at high
temperature. Under the influence of an oxygen partial-pressure driving force, the ITM
Oxygen process achieves a high-purity, high-flux separation of oxygen from air. By
integrating the energy-rich, vitiated, non-permeate stream with a gas turbine system,
the overall process co-produces high-purity oxygen, power, and steam if desired. As a
result, the technology is ideally suited for advanced power generation processes that
require oxygen as a feedstock for combustion, gas-conversion or gasification, as well
as for traditional industrial applications for oxygen.
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
oxygen is in construction. Larger demonstrations are planned, with full
commercialization projected in the latter part of the decade.
Pilot-scale demonstrations of ceramic processing steps and membrane performance
have confirmed the impressive economic benefits which are the basis for this
development effort. This presentation will focus on the benefits that ITM Oxygen can
bring to a broad range of energy-intensive process applications. Specific examples of
ITM Oxygen applied to low-carbon-emission IGCC, oxygen-enriched combustion, and
gas-to-liquid (GTL) plants will be discussed.
50-5
Development of Synthesis Gas Production Technology Using 3 T/D Scale Coal
Gasification System
Seok Woo Chung, Young Don Yoo and Yongseung Yun
Institute for Advanced Engineering, Korea
A synthesis gas producing facility that consists of pulverized coal
feeding/gasification/hot gas clean-up system has been developed and tested for nine
different coals, with the primary goal of providing coal selection guidelines for the
future IGCC facilities in Korea. The coal gasifier of 3 ton/day (T/D) scale was
entrained-bed slagging type and was operated normally in the temperature range of
1400~1450 , 8~10 kg/cm2 (max. 30 kg/cm2) pressure. The obtained composition of
synthesis gas was 63~68% of CO, 20~25% of H2, 10~15% of CO2 in the dry, N2-free
basis. The 95~99% of carbon of the suitable coal was converted to synthesis gas and
the ash was converted into non-leaching slag.
Through the more than five years of experimental study, many facilities were upgraded
in the areas such as the pulverized coal pneumatic feeding, synthetic gas production,
and hot gas clean-up. For the reliability test of the coal gasification system, one month
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
operational results of the 3 T/D gasification facilities.
SESSION 51
LOW RANK COAL UTILIZATION: 5
51-1
Influence of Silicon Minerals on Gasification Kinetics during Gasification of Low-
Rank Coal
D.P.Ross
Tokyo University of Agriculture and Technology, BASE, Japan
A. Kosminski and J.B. Agnew
Department of Chemical Engineering, Australia
The purpose of this study is to investigate the catalytic activity of Na as sodium
carboxylates (-COONa) or as NaCl in the presence of silica and kaolin during the
gasification of South Australian lignite coal. Coal from this region is characterised 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
gasified in a fixed bed reactor with steam and carbon dioxide. The coal gasification
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
Na and to a lesser extent on coal containing NaCl. This is a result of the Na reacting
with the silica or kaolin to form sodium silicates or sodium aluminosilicates,
preventing Na from becoming an active catalyst. Kaolin is a greater inhibitor of
sodium catalytic effect than silica. The steam coal gasification reaction rate at 850oC
for coal containing carboxylate bound sodium was found to be three times faster than
for corresponding gasification in a carbon dioxide atmosphere. Controlling of the
fouling and agglomeration propensity of coal for use in FBG by the addition of kaolin
will have consequences on the catalytic char gasification rate. Both kinetic and
catalytic data obtained in this work compare well with data published in the literature
for gasification of other Australian lignites.
51-2
Catalytic Roles of Na in Homogeneous and Heterogeneous Steam Reforming of
Tar from the Pyrolysis of a Brown Coal
Eiji Ohtsubo, Jun-ichiro Hayashi, Nozomu Sonoyama and Tadatoshi Chiba
Hokkaido University, Japan
Chun-Zhu Li
Monash University, Australia
When Victorian brown coal was pyrolyzed in an atmosphere containing steam in a
drop-tube reactor (DTR) at 900 C, nascent tar underwent steam reforming as well as
thermal cracking. Progress of the steam reforming resulted in the conversion of the
initial tar as high as 95 99% with negligible soot formation. Such rapid steam
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
pyrolysis, AAEM species were volatilized into the gas phase to a substantial degree
while some portions remained in/on the char particles. Further experimental
examinations were made on their catalytic roles in the steam reforming of the tar in the
gas phase and that over the char surface. Aiming to examine the catalytic roles of
AAEM (particularly, Na) in the gas phase, a novel two-stage drop-tube/tubular reactor
(DTTR) was developed. Pulverized coal was and N2 carrier gas was fed into the drop-
tube reactor of which bottom was equipped with SUS316 mesh for separating the
volatiles from the nascent char particles. The volatiles were then diluted with N2 or
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
about 10 s. The pyrolysis experiments were performed using three different samples:
raw Loy Yang coal, a NaCl-loaded Loy Yang coal and an acid-washed (AAEM free)
Loy Yang coal. Under the conditions employed, 0.09 wt% and 0.80 wt% of Na (on dry
coal basis) were volatilized from the raw and NaCl-loaded coals, respectively.
Volatilized Na was introduced into the second reactor together with the nascent
volatiles. The distribution of the products from the nascent volatiles was substantially
influenced by the concentration of Na in the gas phase as well as the presence of
steam. The introduction of steam into the tubular reactor suppressed soot formation
from the tar converting the soot precursor into carbon oxides and H2 even in the
absence of Na. The soot formation was further suppressed by increasing Na
concentration. On the other hand, introducing steam increased the residual tar yield in
the absence of Na, while decreased the yield slightly even in the presence of Na. H2 or
H radicals formed from the steam reforming of the soot precursor played a role of
stabilizer of the tar unless the Na concentration in the gas phase was sufficiently
high. Comparing the combined effects of steam and Na between the pyrolyses in DTR
and DTTR, it was concluded that Na on the char surface was indispensable for
simultaneous decrease in the yields of soot and residual tar, although Na in the gas
phase promoted the steam reforming of the soot precursor.
51-3
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
Hokkaido University, Japan
Chun-Zhu Li
Monash University, Australia
In-situ steam gasification of nascent char from the rapid pyrolysis of a Victorian brown
coal, Loy Yang (LY), was investigated at temperature, total pressure and steam partial
pressure of 1173 K, 0.1 1.2 MPa and 0.053 0.6 MPa, respectively. Using a novel
drop-tube/fixed-bed reactor enabled the minimized interaction among the char, the
volatiles and gaseous products during the rapid pyrolysis of the coal and the
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
further increase but much more slowly. The time dependent change in the conversion
was analyzed by assuming first order kinetics with respect to the amount of residual
carbon in the char. The instantaneous specific reactivity, defined by
d(1 X)
(1 X) (X: conversion of char on carbon basis),
dt
decreased by an order of magnitude within 100 s (first stage) and then became constant
(second stage). For in-situ gasification of the char from the acid-washed LY that
contained no alkali and alkaline earth metallic (AAEM) species, the specific reactivity
was constant over the entire range of the conversion, and moreover, in good agreement
with that during the second stage gasification of the char from LY. These results
suggested that the conversion of the char from LY in the first stage and that in the
second stage were contributed mainly by the gasification catalyzed by inherent AAEM
species and non-catalytic gasification, respectively. AAEM species underwent fast
volatilization in the first stage and much slower volatilization in the second stage,
while the concentration of the species (their amounts per that of residual carbon in the
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
of AAEM species due to their volatilization and intra-particle deactivation within 100
s. The intra-particle deactivation of AAEM species was also caused by heating the
nascent char from LY at 1173 K for a long period or pyrolyzing the coal in the
presence of volatile-char interaction before the gasification. In such cases, the specific
reactivity of the resulting char agreed well with that of the char from the acid-washed
LY over the full range of the char conversion. On the basis of the experimental
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
reactivity for the gasification catalyzed by AAEM species, the latter of which was a
function of concentration of active AAEM species. It was also demonstrated that the
non-catalytic gasification obeyed first order kinetics with respect to the residual
amount of carbon in the char.
 51-4
In-situ Gasification Reactivity of a Victorian Brown Coal in Steam: Catalysis and
Changes in Char Structure
Chun-Zhu Li, Xiaojiang Li
Monash University, Australia
Jun-ichiro Hayashi
Hokkaido University, Australia
The purpose of this study is to investigate the volatilisation of alkali and alkaline
metallic species (AAEM) and the changes in char structure during the gasification of
Loy Yang brown coal. The acid-washed (H-form), Na-exchanged (Na-form) and Ca-
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 900C. The two-stage
reactor, which was a fluidised-bed/fixed-bed reactor in tandem with a combustor, was
designed to monitor the release of carbon during the whole pyrolysis and gasification
process, allowing for the direct determination of specific reactivity of nascent char.
The retention of AAEM species in char during pyrolysis and subsequent gasification
was quantified. FT-IR/Raman spectroscopy was used to investigate the changes in char
structure during gasification. The experimental results have provided insights into the
effects of AAEM species and char structural features on the char gasification reactivity
under a wide range of experimental conditions.
51-5
Formation of NOx Precursors during the Gasification of Victorian Brown Coal in
Oxygen
Lachlan J. Mckenzie, Fu-Jun Tian, Jiang-Long Yu and Chun-Zhu Li
Monash University, Australia
The formation and subsequent release of nitrogen oxides (NOx) from coal-fired power
plants is a major environmental concern. A better understanding of the conversion of
coal-n during gasification will contribute to the development of near zero-emission
power generation technologies using coal. This study aims to investigate the
conversion of coal-n during the gasification of victorian brown coal with O2. A loy
yang brown coal has been gasified in a novel fluidised-bed/fixed-bed reactor at low
temperature and fast particle heating rates. The yields of main n-containing products,
including NO, NO2, HCN and NH3, have been quantified.
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,
the coal feeding rate is an important factor influencing the release of coal-n during
gasification. These results provide evidence for the importance of volatile-char
interactions on the release of coal-n even at 500C. Significant amounts of NO2 have
also been observed, probably as a result of complicated reactions involving active
radicals. Our experimental results will be discussed to provide some insights into the
mechanisms for the conversion of coal-n during gasification in O2-containing
atmosphere.
SESSION 52
SYNTHESIS OF LIQUID FUELS & CHEMICALS FROM COAL 3:
DIMETHYL ETHER & METHANOL
52-1
Direct Dimethyl Ether (DME) Synthesis from Natural Gas
Seiji Aoki, Takashi Ogawa, Norio Inoue, Tsutomu Shikada, Osamu Inokoshi,
Yotaro Ohno
DME Development Co. Ltd., Japan
Dimethyl ether (DME) is a clean and economical alternative fuel, which can be
produced from resources such as natural gas, coal or biomass. The properties of DME
are very similar to those of LPG and its can be used for various fields; power
generation, transportation, home fuel, etc.
An innovative process of direct DME synthesis from synthesis gas has been developed.
Five tons per day DME production pilot plant (5TPD) project had finished very
successfully in 2001 after two years process development. Based on the 5TPD results,
100 tons per day DME production demonstration plant (100TPD) project started in
2003.
The first plant operation in December through January 2004 achieved 100 % load plant
operation with DME product purity of more than 99.5 %. These projects are supported
by Japans Agency for Natural Resources and Energy under Ministry of Economy,
Trade and Industry (MITI).
52-2
Current Status of R&D for the DME Utilization Technologies in Japan
Shinichi Suzuki
Japan Oil, Gas and Metals National Corporation, Japan
In order to realize DME use as a fuel in the end of 2006, Japan Oil, Gas and Metals
National Corporation (JOGMEC) has been carrying out the R&D of DME utilization
technologies with Japanese private companies from 2001. Since DME is recognized as
a clean versatile fuel, the theme of JOGMEC R&D varies ranging from the
turbine/boiler for power plants, the diesel engine/micro gas turbine for co-generations,
49
the diesel vehicles, to SNG (substitute natural gas) and hydrogen for PEFC productions
by reforming DME. Most of these technologies will be technically feasible thanks to
the vigorous efforts by the various Japanese organizations.
In this paper, the outline and the main results of JOGMECs R&D on DME utilization
technologies will be described.
52-3
In Situ ATR/FTIR Observation of Transformation of the Nickel Precursor in a
Catalytic System for Low-Temperature Methanol Synthesis in a Liquid Medium
Seiichi Ohyama
Central Research Institute of Electric Power Industry, Japan
Low-temperature methanol synthesis from syngas rapidly proceeds in liquid media at
temperatures of approximately 373 K in the presence of catalysts composed of a Ni
compound and an alkali alkoxide. Two catalysts, Ni(OCOCH3)2/CH3OK and
Ni(CO)4/CH3OK, has been proposed for the reaction, in which methanol (MeOH) is
considered to be formed through the carbonylation of MeOH to methyl formate (MF)
and the subsequent hydrogenation of MF to MeOH. However, the relation between the
two nickel precursors, Ni(OCOCH3)2 and Ni(CO)4, is not yet clarified and the active
species of Ni(OCOCH3)2/CH3OK still remains unknown.
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
Ni(CO)4 and hydridocarbonylnickel anion ([HNi(CO)3]- and/or [HNi2(CO)6]-) during
the reaction, the latter of which was responsible for the MF hydrogenation step in the
low-temperature methanol synthesis. It was also confirmed that carbonylation of
methanol exclusively proceeded in the initial 10 min of the reaction and then
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
with Ni(CO)4/CH3OK and Ni(OCOCH3)2/CH3OK. Each catalyst has two rate
constants depending on the time. In the initial 10 min of the run, the rate constants for
both catalysts were similar. In the other period of the run in which the hydrogenation
of MF was a rate determining step, the rate constant for Ni(CO)4/CH3OK (3. -4 sec-
1
) was four times larger than that for Ni(OCOCH3)2/CH3OK (8.0 10-5 sec-1), which
agreed with the ratio of the concentrations of the nickel anion which was observed with
in situ FTIR. These findings indicate that the nickel anion promotes the hydrogenation
of MF in both Ni(CO)4/CH3OK and Ni(OCOCH3)2/CH3OK in catalytic systems.
52-4
Catalyst Development for Methanol Synthesis by Design of Experiment and an
Artificial Neural Network
Yuhsuke Watanabe, Tetsuo Umegaki, Masahiko Hashimoto, Sutarto, Kohji Omata and
Muneyoshi Yamada
Tohoku University, Japan
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
required in economic and compact process. Catalyst composition of Cu-Zn-Al-Cr-B-
Zr-Ga oxide catalyst for methanol synthesis was optimized for high activity. Catalysts
were designed by design of experiment (DOE) and prepared automatically. The
activities were measured in 96 well microplate reactor at high pressure. The results
were analyzed by an artificial neural network. An active catalyst was discovered and
validated experimentally.
An orthogonal array of L18 by DOE was used to design 18 catalyst compositions.
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
ethanol-oxalic acid method. Ethanol solutions of metal salts were dispensed into a 96
well microplate using automated liquid dispenser (Gilson, 222XL) according to the
L18 array. Ethanol solution of oxalic acid was then dispensed to each well to obtain
precipitate of mixed oxalate. After calcination the precursors were packed in Durham
tubes (6 mm I.D., 40 mm length). The tubes were arrayed in a 96 well microplate made
of aluminum and the plate was placed at the bottom of an autoclave (15 cm I.D.).
Methanol synthesis was conducted in the autoclave at 225 C, 1 MPa. Methanol from
each catalyst bed were transfered through capillary tube (0.1 mm I.D.) into water trap.
The amount of methanol was determined by colorimetric reaction. The relation
between the catalyst composition and catalytic activity was thus
experimentally determined.
For response surface modeling (RFM), an artificial neural network (ANN) was used.
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
best fitting to test data and the ANN can predict catalytic activity as a function of
any catalyst composition. In order to find the maximum activity of the ANN, activities
of 230,230 combinations of 7 component catalyst with 5% step were predicted by the
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
of 7 component, the number of possible combinations with 1% step is as large as
1,705,904,746. It is impossible and unmeaningful to check the all combinations. The
tool composed of DOE, ANN and RSM as described above succeeded to discover the
good result using only 18 data in such a huge search space and rapid catalyst
development was achieved.
 52-5
The Synthesis of Dimethyl Carbonate in a Slurry Reaction System with Cu+-
Zeolite Catalyst
Zhong Li, Li Zhou, Li Yang Kechang Xie and Lihua Yin
Taiyuan University of Technology, P.R. China
In the past decade, dimethyl carbonate (DMC) has been drawing much attention as an
important green chemical feed stock all over the world because it can be used to
replace environmentally unfriendly compounds in many commercial procedures and
manufactured from coal. Now it has drawn more and more attention to research on the
chemistry of the DMC synthesis processes because DMC has been considered as a
promising chemical compound in view of the increasing world wide environmental
problem.
The traditional method for DMC synthesis is the reaction of methanol and phosgene.
But it has being phased out due to the high toxicity of phosgene and the severe
corrosiveness of by-product HCl. Some non-phosgene syntheses of DMC have been
developed since 1980s, such as transesterification of methanol with vinyl or propenyl
carbonate, methyl nitrite method, direct synthesis from carbon dioxide and methanol,
and oxidative carbonylation of methanol.
A number of investigations have been focused on the use of a supported copper
catalyst to synthesis DMC via liquid phase oxidative carbonylation of methanol in
order to avoid the problems of using CuCl catalyst. King reported that the chloride is
not necessary for the copper catalysts to catalyze the gas phase oxidative carbonylation
of methanol to DMC and developed a solid-state ion exchange method to prepare a
free-chlorine Cu+ catalyst on a zeolite support.
This paper firstly reports the research results of the catalytic performance of Cu+
zeolite catalysts in the liquid phase oxidative carbonylation of methanol to DMC. A
series of CuCl-zeolite catalysts were prepared by solid-state ion exchange under
flowing nitrogen. The condition of the catalyst preparation and the reaction were
investigated. For both DASY-CuCl catalyst and HZSM-CuCl catalyst, the space time
yield (STY) of DMC firstly increase and then decreases with the rise of temperature,
but the selectivity of DMC based on methanol (SDMC/MeOH) is almost no change.
HZSM-CuCl catalyst prepared at 350 for 4h had the best catalytic performance,
0.56kg/kgh STYDMC and 96.19% SDMC/MeOH. The morphological analysis by X-ray
powder diffraction shows at 250 the crystal phase of CuCl in the catalyst was
remarkable, which indicates that most of copper on the zeolite surface existed in CuCl
form. More CuCl exists in the catalyst, more micropore or channel of the zeolite are
blocked by solid CuCl crystal. In the result, the special area of the catalyst is reduced
and reactant methanol is obstructed to pass through channel to be adsorbed on copper
species of the catalyst, which caused low activity and high corrosion to the autoclave.
With the rise of catalyst preparing temperature, the ion exchange reaction between
CuCl and zeolite happened and Cu+ is dispersed in the cage of zeolite which had
catalytic active of oxidative carbonylation of methanol to DMC, and more CuCl was
dispersed as a cluster in the surface of zeolite. When prepared at 650 , the catalyst did
not have any CuCl crystal to be observed by XRD. This highly dispersed Cu+ and
CuCl makes the catalyst have high catalytic active. But at high preparing temperature,
the catalyst would have less Cu+ loading due to the sublimation of CuCl phase and
decrease of the catalytic activity. And the corrosion of equipment caused by CuCl was
reduced. The morphological analysis by X-ray powder diffraction (XRD), Scanning
electron microscope (SEM) and FTIR has shown that the catalyst has a clustering
phenomena and the existence of copper chloride hydroxides (Cu(OH)3Cl) after
reaction.
SESSION 53
GLOBAL CLIMATE CHANGE: 2
53-1
The Proposition of CO2 Gas Disposal
Maciej Mazurkiewicz, Zbigniew Piotrowski and Radoslaw Pomykala
AGH University of Science and Technology, Poland
The idea of carbon dioxide reduction by underground storage with wastes is presented
in the paper. It was formed while searching a new method of underground fire fighting
for the Polish coal mining. CO2 gas has been absorbed by fly ash suspension (in
water). The suspension has been commonly used in the majority of Polish underground
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
improvement of the mine ventilation system by filling and sealing of cavings in the
longwall system. It helps fight with fire and methane hazard. For these reasons the
mining uses the big part of the Polish fly ash production. Annually it is a many
millions tons. It could give a change for carbon dioxide storage on a considerable
scale.
Results of laboratory tests on a new installation are presented in the paper. The
subjects of the tests were suspensions made with the use of fly ashes from traditional
and fluidized bed combustion, with or without desulphurization products. The
influence of some factors on CO2 absorption such as temperature, pressure, amount of
water and blending conditions was analyzed.
50
53-2
Coal-Seq Project Update: Field Studies Of Ecbm Recovery/
Co2 Sequestration in Coalseams
Vello A. Kuuskraa and Scott Reeves
Advanced Resources International, Inc., USA
In October 2000, a three-year government-industry project known as the Coal-Seq
project was launched in the United States. The project is studying the feasibility of
CO2 sequestration in deep, unmineable coalseams using enhanced coalbed recovery
technology. The Coal-Seq project is specifically focused on understanding the results
of actual field experiments via reservoir modeling, with laboratory studies filling a
supporting, not primary, role. The fields being studied are both in the San Juan basin.
The sites are the Allison Unit, operated by Burlington Resources and the Tiffany Unit,
operated by BP America. These two sites are the only two in existence today,
worldwide, where long-term, multi-well injection of CO2 or N2 is being performed. In
addition to the field studies, supporting analytic work in the areas of multi-component
sorption behavior, and coal swelling with CO2 adsorption, are being performed.
53-3
Concept of the Zero-Emission Gas-Turbine Combined Power Plant System
Yuji Ooka
Kawasaki Heavy Industries, LTD., Japan
Paul Sims
CSIRO, Australia
In response to global warming due to the increasing carbon dioxide gas in the
atmosphere, investigation of carbon dioxide separation and capture technologies from
exhaust gas of a thermal power plant and sequestration technologies have been
performed all over the world.
In relation to geological sequestration technology, coal bed sequestration is regarded as
an economical choice and its technology is an extension of EOR. Importantly it also
utilizes an undeveloped energy source in addition to carbon dioxide gas storage.
Some research and development projects have been started to estimate and establish
related technologies such as safety, monitoring, rock interactions etc. One of the newer
technologies is to use a mixture of carbon dioxide and nitrogen for gas injection in
order to increase the recovery of coal seam methane. The recovery rate can be
controlled by the mixing rate of two gases. However when nitrogen is used the energy
loses and economic disadvantages of using the gas must be considered.
When a CO2/N2 mixture of a fixed ratio is not required, a CO2 recycle type gas
turbine can be used. Such a system, without using CO2 gas capture process has been
classified as a Zero Emission Power Plant. In this concept, several disadvantages such
as an increase of power required due to nitrogen gas treatment and the associated
decrease of sequestrated carbon dioxide gas should be considered compared to other
choices.
Already in Japan as part of the development of clean electric power generation
technologies a carbon recovery type closed cycle gas turbine using oxygen combustor
had been attempted in order to eliminate the capture process of carbon dioxide gas.
Even in this concept, several technological hurdles including treating oxygen and cost
issues have to be addressed.
Both technologies, the coal bed sequestration and the oxygen combustor gas turbine,
mutually support the required mass flows and exhaust. At the start of the combined
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
oxygen combustor type gas turbine that exhausts pure carbon dioxide without the need
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
unmineable as energy source and shares the air separation cost.
The purpose of this paper is to describe the estimated results of mass flow and cost of
the combined system using existing commercial components characteristics and test
data of a coal bed sequestration project.
53-4
Co2 Adsorption by Australian Coals under Supercritical Conditions
Stuart Day, Greg J. Duffy, Abou Saghafi and Richard Sakurovs
CSIRO Energy Technology, Australia
CO2 sequestration is a technology that can, in principle, reduce CO2 emissions to the
atmosphere. Of the possibilities available for storage of CO2 in Australia the most
prospective appear to be geological storage in saline aquifers or deep unmineable coal
seams.
A new gravimetric system has recently been constructed at CSIRO that allows CO2
adsorption measurements of coal at the high pressures and temperatures characteristic
of deep coal seams, even in the presence of other gases such as water vapour, methane
or nitrogen. Experiments are being carried out at pressures up to 17 MPa and
temperatures up to 70oC, i.e. well above the critical pressure of CO2 (7.3 MPa, 31oC).
This gravimetric method avoids the problems associated with the volumetric methods
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
directed at developing new models to describe the sorptive behaviour of coals at high
pressures and temperatures.
This paper will report the results of recent investigations that will form the basis for
assessing the suitability of Australian coals as gas storage targets, and will outline
some of the factors that will influence the rate of absorption and dispersal of carbon
dioxide in coal.
53-5
Experimental Study on Supercritical CO2 Adsorption on Coals in Relation to
their Pore Structure
Sohei Shimada and Masaatsu Tamura
The University of Tokyo, 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
CH4 besides sequestrate CO2. Coal seams are broadly distributed in the world.
Therefore, this technology can be used in many countries. In order to perform a more
reliable gas production simulation, the basic data about CO2 and CH4 adsorption are
indispensable. Adsorption experiments of super-critical CO2 on coal were performed
to find the relation between the pore structure and adsorption amount.
The experiments by using single gas of CO2 were conducted up to 11MPa and at 40
degrees C by Constant Volume Method. Five samples were used for the experiments:
Akabira coal, Taiheiyo coal, Yallourn coal, Maokhe coal and Actrivated carbon.
Akabira coal and Taiheiyo coal are categorized to sub-bituminous coal, Yallourn coal
is brown coal and Maokhe coal is anthracite.
Activated carbon showed the highest amount of excess sorption. The adsorption
isotherm of Mokhe coal was similar to that of Taiheiyo coal. The results suggest that
the coals having the similar pore distribution shows the similar adsorption isotherm
shape.
CO2 adsorption experiment on the coals being treated by supercritical CO2 was
performed for Taiheiyo coal and Akabira coal. The change of the adsorption amount
before and after treatment was observed. The cause might be a structural change of
inner surface of coal by contraction.
It is concluded that high rank coal with many micro pores is advantageous for
supercritical CO2 sequestration in coal.
SESSION 54
COAL UTILIZATION TECHNOLOGIES IN STEEL INDUSTRY: 4
54-1
The Dissolution of Cokes in Molten Iron
S.Tsuey Cham and Veena Sahajwalla
The University of New South Wales, Australia
Richard Sakurovs
CSIRO Energy Technology, Australia
Blast furnace operators are facing increasing pressure to improve their efficiency and
increase their sustainability. One change that would improve efficiency that is now
being actively explored is reduction in operating temperature. However, for operating
temperature to be reduced, feasibly, extensive understanding of the reactions that occur
in the blast furnace and how their rates are controlled will be required. Central to blast
furnace operations is coke. Coke in blast furnaces reacts with carbon dioxide and also
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
investigated. Yet the rate of this reaction is important in determining how well the blast
furnace operates and predicting how it would behave at lower temperature. We report
here the findings of a study investigating the rate of dissolution of a number of cokes
(with similar ash yields) in molten iron at 1550C. We found that different cokes react
at very different rates with molten iron at this temperature; the rate can vary by over an
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
discussed.
54-2
Enhancing the Strength of Coke from Co-Coking Of Coal and Waste Plastics by
Adding Additive
Hong-qiang Liao, Peng Zhao, Ya-bin He, Kai Qian
Shougang Technical Research Institue, China
Guang-wei Yu, Jiu-jv Cai
Northeastern University, China
Bao-qing Li
Institute of Coal Chemistry Chinese Academy of Sciences, China
Waste plastics disposal by using traditional coking process was a viable way to
overcome the white pollution coursed by waste plastics. However, there are many
researching work to do for enhancing the coke strength and increasing the ratio of
adding waste plastics. This paper suggested a way to enhance the strength of coke from
co-coking of coal and waste plastics by adding additive. The experiment was carried
out in a test coke-oven ,which can load 200 kg material. The experimental materials
51
including blend coal (BC), waste plastics (WP) and organic additive (OA), which from
Shougang coking plant and municipal solid waste of Beijing city were used. The coke
strength indexes including M10, M40, CRI and CSR were analyzed. The results showed
that the strength of coke from co-coking of coal and waste plastics is worse than that
from separately coking of blend coal. While, all the strength indexes of coke from co-
coking of coal and waste plastics by adding organic additive are better than that from
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
additive (OA).
54-3
Effect of Waste Wood Addition to Coal on Coke Quality
Masaru Nishimura, Yuko Nishibata and Kanji Matsudaira
The Kansai Coke & Chemicals Co., Ltd., Japan
As a part of recycling society promotion, waste plastics are used as a metallurgical raw
material in coke making plant. In Japan, Construction Materials Recycling Act was
enforced in 2002. Since it obliges us to recycle waste wood, new solution to recycle
waste wood is expected. So we have made a study to use waste wood as a coke making
material. The 3mass% addition of raw waste wood into coal charge deteriorated coke
qualities (I6009.5; measured with I-type drum tester). But preheating of waste wood at
appropriate temperature improved the coke qualities. To get the reason, the gieseler
maximum fluidity (MF) of coal blended with raw or preheated wood sample were
measured, because the fluidity of coal has relation to coke strength. Raw waste wood
addition to coal showed considerable decrease in MF. However pretreated wood
addition showed minor decrease in fluidity. Moreover we tested the fluidity of coal
blended with cellulose or lignin because cellulose and lignin are main constituent of
wood, and confirmed cellulose and lignin caused the declination in fluidity.
54-4
Non-Fuel Use of Anthracite: Preparation of Activated Carbon and Adsorption
Performance
Jae Ho Kim
Korea Coal Cooperation, Korea
Si Hyun Lee
Korea Institute of Energy Research, Korea
Sung Ho Kong
Hanyang University, Korea
Purpose of this study is to develop activated carbons from Korean anthracite. Low ash
coals were separated by dense media technique to make raw materials for activation.
Activated carbons were produced with steam or CO2 from crushed and granular coals.
Chemical pretreatment with alkali hydroxides (Na, K) were conducted to increase the
reactivity of anthracite for activation. Liquid and gas phase adsorption tests were
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.
Chemical pretreatment have an effect on surface area increase from 650m2/g to
840m2/g for the crushed coals, and on the increase of pore size and burn-off. It was
found that the activated carbons from crushed coals by chemical pretreatment and CO2
activation have well developed micro-porosity, and that the activated carbons from
granular coals by steam activation have wide ranges of porosity. They are suitable for
gas phase and liquid phase adsorption respectively.
54-5
An Application of a Homogenization Method to Microstructure of Coke Using
Digital Image Processing
Kenta Ueoka, Tomoki Ogata, Yoshio Morozumi, Hideyuki Aoki and Takatoshi
Miura
Tohoku University, Japan
A homogenization method is applied to the estimation of coke strength using
digital image processing.
Coke strength is the most important quality to retain the permeability in blast
furnaces. Since coke has complex microscopic geometry, it is difficult to analytically
estimate the coke strength by considering microscopic pores. Recently, a
homogenization method, which enables us to analyze macroscopic and microscopic
behavior simultaneously, has been applied to the understanding of the fracture
mechanism in coke. In this study, the digital image analysis based on the
homogenization method was used to solve two dimensional elastostatic problems
considering the actual microstructure of two kinds of coke. One was coke made by
caking coal, the other was coke made by a mixture of caking coal and slightly caking
coal. The analyzed picture size was 100x100, 150x150 and 200x200 pixels.
Calculated results of the homogenized elastic modulus distribution became narrow
with an increase in the analyzed picture size. The distribution of von Mises stress of
the coke made by caking coal was lower than that of the coke made by a mixture of
caking coal and slightly caking coal. This is because that there were few microscopic
pores whose diameters were approximately 500 m and were relatively large in the
coke made by caking coal. In addition, the matrices between microscopic pores in the
coke made by caking coal were thick. Consequently, the strength of the coke made
by caking coal was higher than that of the coke made by a mixture of caking coal and
slightly caking coal.
POSTER SESSION 1
COMBUSTION TECHNOLOGIES
P1-1
Modern Technologies of Heat Production as the Opportunity for Coal
Leon Kurczabiski and Roman j maintain the process in operation is a pump for decreasing the prevailing pressure in
Coal Holding Katowice J.S.C., Poland
Since the beginning of the 90ties, Poland has been experiencing a gradual demand
decrease for coarse and medium stove coals used in houses and small and medium
heat producing facilities.
At the beginning of the 90ties the volume of coal used was about ___tons a year and
the end of the decade showed the decrease to the volume of about___.
This coal has high quality parameters: the heating value reaches 31 MJ / kg, the ash
contents is up to 5 % and the sulphur contents is about 0,4 %. The decrease in this
coal use caused that the producers started to crash and add it into steam coal fines.
Coal has been gradually replaced by natural gas and furnace oil technologies.
However, the end of the 90ties showed certain change in the tendency when the
market noticed new heating technologies based on coal and proposed for medium
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
that significantly reduce toxic substances emission and also the heat production costs
even twice or three times lower than the costs of technologies based on natural gas or
furnace oil.
This paper presents a short description of these technologies and the actions taken by
Katowicki Holding Wglowy in order to implement them and to create new coal
market which within recent 3 years has reached the level of 150 000 tons a year and
what is more, the tendency is increasing.
P1-2
Formation of NOx during Char Combustion in a Fixed Bed of Catalyst under
Reduced and Elevated Pressure Conditions
Tadaaki Shimizu, Toshiaki Takahashi, Masaru Tonsho, Makoto Inagaki
Niigata University, Japan
The effect of catalyst on the conversion of char bound nitrogen to NOx during
combustion of one kind of coal char was evaluated using a fixed bed reactor at 1123
K. Petroleum coke ash was used as a catalyst that enhances NOx formation from
volatile matter (NH3) but does not catalyze NOx reduction by CO. Different diluent
gases, He, Ne, Ar, and N2, were employed. The total pressure in the fixed bed was
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
instead of inert quartz sand under total pressures between 0.2x105 and 1x105 Pa but
the increase was not remarkable when the total pressure was higher than 2x105 Pa.
For Ar and Ne, the increase in NOx by employing catalyst bed was observed only
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
present results indicate that nitrogen-containing fragments are released from char
surface during char combustion and the fraction of the N-fragments oxidized on the
neighboring catalysts is affected by the mean free path of the molecules. The
estimated conversion of char-N to N-fragments was approximately 0.14.
P1-3
Cryogenic Method Operating At Normal Pressure Enriching the Oxygen
Content in Air
Ilkka Saarenp, Hanna Knuutila, Pauli Haukka
Tampere University of Technology, Finland
Oxygen and oxygen-enrichment are produced from air generally by three methods:
cryogenic, adsorption and membrane separation. Various methods produce different
purities and mass flows of oxygen. Again, the utilization of oxygen-enrichment, i.e.
not pure oxygen, is often sufficient in many combustion applications.
The process introduced in this paper is a novel cryogenic method producing oxygen-
enrichment more energy-efficiently than the methods used till now. The mass flow of
the produced enrichment may vary with the number of parallel basic modules
applied. Due to the low pressures used in the introduced process (at maximum
approximately 1.4 bar absolute pressure), the compression work needed is smaller
than e.g. in the Linde-Frnkl process (the maximum pressure about 6.5 bar absolute
pressure), and the process approaches to reversible. Furthermore, the main fraction in
mass flow of air, i.e. the nitrogen-enriched fraction, is not liquefied which saves
energy compared to the common cryogenic processes that liquefy this fraction.
Nevertheless, the achieved low temperature of the nitrogen-enriched fraction is
efficiently utilized in the pre-cooling of the incoming process air. Since the process
does not produce pure oxygen, the energy required to separate the last percents of
oxygen from nitrogen-enriched fraction is saved. This is noticeable because of the
last percents demand proportionately most separation energy.
52
Moreover, the core of the process concerned consists of two nested columns that
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
thermodynamically economical. Since the prevailing pressure is kept different on the
various sides of the main heat exchange surface, i.e. both the nested columns have
different pressures, the phase change of the produced fraction occurs at different
temperatures in the various columns. Consequently, the main power source needed to
the evaporation (inner) column.
In this paper, the novel cryogenic method operating at normal pressure producing
oxygen-enrichment is introduced. The theory behind the process as well as some
experimental and simulation results are studied.
P1-4
A Kinetic Study on Tin Oxidation
Ming-Hou Xu
Huazhong University of Science and Technology, China
Lai-Cai Li, An-Min Tian
Sichuan Normal University, China
Ning-Bew Wong
City University of Hong Kong, Hong Kong
Ab initio MP2 method was performed to study the reaction mechanism and kinetics
of stannic oxidation by oxidants (HOCl, HCl, ClO, ClO2 and NO3) during the
process of coal combustion. Nine reaction pathways listed below were found by
calculations: (1) Sn + HOCl SnCl + OH, (2) Sn + HCl SnCl + H,
(3)Sn+ClO SnO+Cl, (4) Sn+ClO2 SnO + ClO, (5) Sn + NO3 SnO + NO2, (6)
SnO + HCl SnCl + OH, (7) SnO+HOCl SnCl+HO2, (8) SnCl+HCl SnCl2+H,
(9) SnCl+HOCl SnCl2+OH. The geometric configurations of reactants, products,
intermediates and transition states were optimized (the metal element tin was
computed using SDD basis sets, and other non-metallic elements were computed
using 6-311+G* basis sets). The energies of various compounds along the reaction
pathways were derived at mutually the same computational level. The classical
transition state theory was used to calculate the reaction rate constants of the nine
reactions. Based on the above calculations, the microscopic mechanism and kinetics
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
(3P0) may react with HCl, ClOO and NO3 to form SnO and SnCl; the product SnO
can be turned into SnCl by HOCl and HCl with difficulty; however, SnCl will be
further oxidized into the soluble compound SnCl2 by HOCl and HCl. Therefore, the
toxic Sn (3P0) may be controlled by being turned into a soluble compound while the
temperature is falling in coal combustion.
P1-5
Decomposition of PFBC Bed Material Fired with Different Coals
Miftahul Huda and Isao Mochida
Kyushu University, Japan
Agglomeration problems of bed materials were reported to take place in a large-scale
commercial PFBC boiler when Blair Athol (BA) coal was combusted. Sintered grain
of highly fused ash particles was formed at boiler load above 75% of designed
capacity (360 MW). The formation of sintered grains reduced the bed density so
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)
coal was combusted in the same PFBC. In this research Bed Material and fly ash
from the commercial PFBC were characterized, thermal behavior of coal ash as well
ash the combustion characteristic of the coal organic component was studied.
Agglomerate in the bed material consists of gehlenite, lime and limestone suggesting
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
mullite. The very fine limestone was produced by attrition of bed material. Anhydrite
was formed by reaction of sulphur dioxide with calcite or lime. High bed temperature
and short contact time of alumina silicate with bed material produced mullite. The
combustion characteristics of Blair athol and Nanton coal were studied by TG-DTA.
Blair Athol coal showed heterogeneous ignition even at its particle size of as large as
+355 m while Nanton coal showed homogeneous ignition at the average particle
size over 75 m which was shifted to heterogenous one at finer particle size (-
75 m). The heterogeneous ignition of Blair Athol coal yielded an intense DTA
peak, which may influence behavior of bed material of the PFBC.
P1-6
The Development of Coal Advisor Software for Intelligent Coal Purchase
Quan Zhuang, Bruce Clements and Richard Pomalis
CANMET Energy Technology Center, Canada
Dave Winship
Combustion and Thermal Power Consulting, Canada
Doug Campbell and Roger Cormier
Nova Scotia Power Inc, Canada

The boilers of the Nova Scotia Power Inc (NSPI) were originally designed for
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
sources including the eastern US and South America. The rank and properties of
coals, together with each boilers specific features, operating conditions and coal
handling system, affect the boilers overall technical and economic performance. In
order to make informed coal purchasing decisions, the total cost including the hidden
costs associated with using different types of coals in NSPIs utility boilers must be
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
performance, slagging and fouling, emissions and waste disposals. All of these
aspects will affect the economics of the power plant and therefore need to be
accounted for to ensure that the overall costs associated with a particular fuel for a
particular boiler are competitive.
A Coal Advisor Program (CAP) has been developed for NSPI to carry out all of
these evaluations. The software was written in Visual Basic. The purpose of CAP is
to enable NSPI to quickly evaluate bituminous coals as they become available on the
market.
The CAP software is used interactively to examine and maintain a coal analysis
database. This system is multi-functional and has a huge potential to save money
and make intelligent coal purchasing decisions.
P1-7
Impact of a New Process for NOx Emissions Reduction on Reliability Operating
Performance in Circulating Atmospheric Fluidized Bed
Emmanuel Kakaras, Panagiotis Vourliotis, Platon Pallis and Stavros Spyrakis
National Technical University of Athens, Greece
The paper aims to present the results of different coal types combustion in the
100kWth Circulating Fluidized Bed Combustor (CFBC) facility, located in the
Laboratory of Steam Boilers and Thermal Plants (LSBTP) of NTUA.
Three different types of brown coal (South African, Colombian and Greek) have
been tested in the CFBC facility. The results reported in this paper include the
determination of the operating conditions to achieve proper fuel burnout, the
examination of the influence of the air staging on the temperature distribution inside
the reactor and the investigation of the combustion behavior of the particular fuel
type and emitted pollutants focusing mainly to the reduction of the NOx emissions.
Many trials have been done using several air ratios and air distributions in different
levels of the FBC reactor, so as to determine the influence of air staging in the
reduction of NOx emissions. As concerns the pollutant emissions, the CO2, CO, and
NOx emissions are recorded during the several test cases, emphasizing in NOx
emissions and their reduction.
Several conclusions are drawn concerning the necessary modifications and
requirements of the plant layout when a large scale CFBC installation is designed to
utilize these types of coal.
P1-8
Effect of Biomass Co-Firing On the Emission in Pulverized Coal Cyclone
Furnaces
Ju Soo Hyun, Si Hyun Lee, Young Jun Rhim, Young Ok Park,
Byung Moo Min and Jae Ek Son
Korea Institute of Energy Research, Korea
Sung Chul Kim
Korea Electric Power Research Institute, Korea
Co-firing of biomass in existing coal-fired power plant offers a great potential. Effect
of co-firing of coal and biomass has been studied for a cyclonic combustion system
originally designed for coal. The focus of the investigations in experimental was to
establish the impact of co-firing of biomass in coal fired systems with regard to
combustion behavior and pollutant formation. The investigation reveals that biomass
addition has a positive effect on emission. Since biomass in most cases contain
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
the biomass, low NOx emission can be achieved. In this investigation, fouling
behavior of coal ash was studied using fouling probe, and it was found that the
blending of biomass have marginal impact on the fouling in furnace.
P1-9
Criteria for Alternative Fuel Utilization in the FBC
Dagmar Juchelkov, Helena Raclavska, Bohumir Cech, Pavel Kolat and Vaclav
Roubek
VSB-Technical University of Ostrava, Czech Republic
Franz Winter
Technical University of Vienna, Austria
According to lot of completed tests will be the results presented. Special interest will
be given to the fuels, ash and others side products attribute. The measurement was
53
made on real combustion units in the Czech Republic; the pilot units in the Germany
and Austria were utilized to comparison.
P1-10
A Kinetic Study of CaSo4 Decomposition under Fluidized Bed Combustion
Conditions
Tadaaki Shimizu, Hideyuki Miura, Masaru Tonsho, Makoto Inagaki and Akira
Okawa
Niigata University, Japan
In fluidized bed combustors (FBCs), in-situ SO2 capture is conducted by feeding
limestone (CaCO3) to the reactor as bed material. The limestone reacts with SO2
after calcinaton in case of atmospheric FBCs (eqs. 1 and 2) or without calcinations in
case of pressurized FBCs (3).
CaCO3 CaO + CO2
(1)
CaO + SO2 + 1/2O2 CaSO4
(2)
CaCO3 + SO2 + 1/2O2 CaSO4+ CO2
(3)
Pure CaSO4 is very stable under oxidizing conditions at FBC temperatures (1023 -
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
than the average bed temperature. In addition, there exist coal ash around the
sulfated limestone particles and it may affect the decomposition of CaSO4. The
decomposition of CaSO4 with coal ash has not yet been fully understood, especially,
the rate of decomposition reaction is not known.
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
atmosphere and the SO2 emission was continuously measured. Pure CaSO4 was
found to be very stable and decomposition occurred only at higher temperatures than
1523 K. When coal ash is mixed with CaSO4, the decomposition started to occur at
relatively lower temperatures, for example1273 K. Rate expressions of SO2
evolution were obtained.
P1-11
Utilization of Mechanical Activated Waste from Semi-Dry Desulphurisation
Installation in Fluidised Bed Boilers
Arkadiusz Szymanek and Wojciech Nowak
University of Technology of Czstochowa, Poland
Jacek Malanka
Energomar-Nord. Sp.zoo. Warszawa, Poland
The paper presents results of industrial utilisation of waste from the process of semi
dry flue gas desulphurisation in a fluidised bed boiler. By products from the EC
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
CFB 450 boiler. The mixture was then mechanically activated and blew into the
boiler through a flue gas desulphurisation installation. The following results were
obtained: calcium sulphite was fully utilised and converted into sulphate and the flux
of sorbent applied was reduced by about 40%. Moreover, boiler efficiency increase
was observed as a result of incomplete and imperfect combustion loss decrease.
POSTER SESSION 2
GASIFICATION & PYROLYSIS TECHNOLOGIES
P2-1
Interpretation of Mineral Matter Transformation during Sasol-Lurgi Fixed Bed
Gasification By Means Of High Temperature X-Ray Diffraction
JC van Dyk
Sasol Technology, South Africa
S Melzer
Corus Research, The Netherlands
Coal is generally accepted to be the most heterogeneous natural resource and coal
properties (chemical and physical) can vary extensively between geographical sites
and even within the same regional location. Detail coal and feedstock characteristics
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
ash fusion temperature (AFT). AFT analyses determine the average temperature at
which the bulk mineral composition start to become soft and obtain liquid properties,
as well as an indication to what extent ash agglomeration / clinkering is likely to
occur within the gasifier. Ash clinkering inside the gasifier can cause channel
burning, pressure drop problems and unstable gasifier operation, resulting in cut back
on gasifier load, which implies a direct loss in gas production.
Conventional AFT analyses (SABS/ISO methods) are currently used to predict
slagging properties from mineral matter transformations of coal sources. Normal ash
fusion analyses give an average flow property and do not indicate exactly at what
temperature the first melt/sinter is occurring due to specific mineral matter
transformations. Operating experience indicates that even when the gasifiers are
operated at temperatures above the flow temperature as given by an AFT analysis, a
percentage of slag (clinker) is formed. The principle aim of this paper is to interpret
mineral matter transformations during Sasol-Lurgi Fixed Bed Gasification by means
of high temperature X-ray diffraction (HT-XRD).
HT-XRD results indicated that up to a temperature of 500oC the starting assemblage
mainly composed kaolinite (Al2SiO5(OH)4), calcite (CaCO3) and dolomite
(CaMg(CO3)2), while quartz (SiO2) remained unchanged. Between 500oC and
700oC kaolonite decomposes first, followed by calcite and dolomite. Around
1000oC anorthite (CaAl2Si2O8) becomes stable probably due to partial melting of
the phase assemblage. Mullite decomposed at 1200oC, while quartz and anorthite
were observed up to 1350oC. Above 1350oC the whole phase assemblage of the
coal was molten. HT-XRD supplies insight into specific mineral reactions and slag
formation, at temperatures below the average flow temperature obtained by
conventional AFT analyses. The findings are further supported with phase diagrams
on the SiO2-CaO-Al2O3-MgO system. This could probably be an improved way to
interpret flow properties of mineral matter in coal. Although the amount of melt was
fairly low at 1000oC, a percentage of melt is definitely present, which at this
temperature is not reflected by conventional AFT analyses. Understanding phase
transformations that occur during gasifiaction could possibly assist in quantifying
slag formation in gasifier operation at temperatures not reflected by AFT analyses.
P2-2
Development of Calcium Ferrite Prepared From Oyster Shell for H2s
Absorption
Michitaka Hamana, Yousuke Ohgaito, Na-Oki Ikenaga and Toshimitsu Suzuki
Kansai University, Japan
Gases from coal gasifiers contain high levels of sulfur compounds. It is necessary to
remove sulfur compounds, mainly H2S, from the coal gasification gas in the
temperature range of 500-800 oC, to utilize it for the high efficiency system, such as
integrated coal gasification combined cycle (IGCC) and integrated coal gasification
fuel cell (IGFC) technologies. Currently, desulfurization is carried out by wet
process, and loss of thermal energy is indispensable. Hot gas cleaning is a target of
development. Development for an absorbent with high H2S removal efficiency, high
sulfur absorption capacity, good regenerability and sufficient strength is still in under
way. Metal oxides and mixed metal oxides are proposed as an absorbent for H2S
removal.
In order to develop a highly efficient and low cost absorbent, calcium ferrite was
prepared from oyster shell as calcium source in the presence of a low sulfur coal and
iron ion. Absorption behavior of the sorbent was observed using a fixed bed flow
reactor equipped with a quadrupole mass spectrometer. In the preparation of an
absorbent from oyster shell with Yallourn coal, no diffraction peak ascribed to
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
contains mixed oxides.
Stoichiometry of H2S absorption is as follow:
CaFe2O4 + 3H2S + H2 CaS + 2FeS + 4H2O
The performance of the absorbent was evaluated in term of the absorption capacity.
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
prepared from oyster shell and Yallourn coal was 90% at the absorption temperature
of 500 oC. Surface area, oxide content, XRD patterns and the absorption capacity
were quite similar to those of the absorbent prepared from pure calcium nitrate.
P2-3
Comparison of Syngas and Slag from Three Different Scale Gasifiers Using
Australian Drayton Coal
Yongseung Yun, Gae Bong Lee and Young Don Yoo
Institute for Advanced Engineering, Korea
Comparison of syngas composition, conversion efficiencies in gasification, and slag
characteristics was performed for data from three different gasification systems. Data
on syngas composition and conversion efficiencies from the 3 ton/day(T/D)-scale
gasifier in Korea were compared with published data from the Shell gasification
systems of 150 T/D pilot plant as well as from the Shell commercial plant of 2,000
T/D scale. In addition, the shape and inner structure of slags obtained from the pilot
scale gasifier and from the commercial-scale gasifier for the same-seam coal was
compared to identify any gasifier-size effect.
Cold gas efficiency showed a decreasing trend with smaller gasifier size from 79% to
71% while the carbon conversion was similarly more than 98% for all gasifier sizes.
Optimal oxygen to coal weight ratio for the gasification also changed from 0.88 to
1.05 with decrease in gasifier size. Slags from gasifiers exhibited a similar size and
also the same indication of forming vesiculation inside the structure. Slags possessed
normally less than 0.3% carbon content while showing no elutriation of heavy metals
by water. Inner structure of slags produced by gasification showed an amorphous
characteristics whereas combusted ash exhibited a clear indication of crystal nature
by minerals, explaining that high temperature gasifier conditions of above 1400oC
melted minerals to form intertwined slag structure with heavy metals.
54
P2-4
Research of the Thermal Characteristics during Coking
V.I. Saranchuk, O.A. Yatsenko, G.A. Vlasov and V.V. Chuishchev
National Academy of Science of Ukraine, Ukraine
One of the most important problems in by-product-coking industry is forecasting
behavior coal charge during coking. Thus the role of laboratory coking sharply
grows. At laboratory coking modeling various conditions of coking is possible.
Laboratory installation for coking coal charge was designed on Avdeevka coke plant.
The complex of gaugings of temperature coke column was made during all coking
period in different points and selection vapor gases products at different stages of
coking.
Temperature conductivity for coals of different metamorphism stages were designed
on the basis of the received experimental data.
Dependence of temperature conductivity from time of coking and initial humidity of
coal are investigated. Character of change of temperature conductivity is established
at change of a degree metamorphism.
The received results confirm, that course of process of coking in the designed
laboratory installation is similar to course of process of coking in the industrial
furnaces.
P2-5
Effect of Hydrogen Pretreatment on Desulfurization of Coal during Coal
Hydropyrolysis
Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu
Dalian University of Technology, P. R. China
The effects of pretreatment of two Chinese coals, Datong and Yanzhou coal, under
H2, N2, CO2 and saturation steam on desulfurization of coal during hydropyrolysis,
were studied in a 10g fixed-bed reactor. The pretreatments of H2, N2 and CO2 were
carried out at temperature ranging from 200 to 400oC under 2Mpa and residence
time of 30min with gas flow rate of 1 L/min. The hydrothermal pretreatment was
carried out in saturation steam in a batch unit at temperature ranging from 200-
400oC and residence time of 15min. The succedent hydropyrolysis was run at
650oC, 2Mpa and residence time of 20min with hydrogen flow rate of 1 L/min. It is
found that all the pretreatments show little effects on char yields, but pretreatments,
except N2 pretreatment, indeed have effects on desulfurization of coal during
succedent hydropyrolysis. In direct hydyropyrolysis (650oC, 20min, 2Mpa), the
sulfur content in char is 2.07 and 1.07wt% for Yanzhou and Datong coal,
respectively. Under H2 pretreatment at temperature of 250oC for Yanzhou and
350oC for Datong coal, the sulfur content in the succedent hydropyrolysis char is
1.93 and 0.55wt%, respectively.
P2-6
Desulfurization of Coal by Pyrolysis and Hydropyrolysis with Addition of
KOH/NaOH
Haoquan Hu, Quanrun Liu, Shengwei Zhu and Qiang Zhou
Dalian University of Technology, P. R. China
There are many studies on coal pyrolysis as a means of thermal desulfurization to
produce a clean solid fuel from high sulfur coals. Unfortunately, sulfur removal
during pyrolysis at mild pyrolysis conditions is only between 15% to 40%, and the
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
studies the effect of adding a certain amount of KOH into three high sulfur content
Chinese coals, YM, DT, and YZ, on desulfurization during pyrolysis and
hydropyrolysis in a fixed-bed reactor. The experiments were carried out to measure
the contents of sulfur in coals and chars before and after the water washing; to
investigate the effect of temperature of pyrolysis450-650oC, concentration of
KOH (1-10wt%), reaction time (10~60 min)atmosphere (H2 and N2) and pressure
on the desulfurization efficiency. The results showed that the most evidence factors
that affect desulfurization yield are temperature and KOH concentration. With
increase of temperature and KOH concentration, desulfurization efficiency increases.
The desulfurization efficiency is not so closely related to atmosphere, pressure and
reaction time. At the temperature of 650oC and ambient pressure N2, the
desulfurization efficiency were enhanced by 37.6%(DT), 42.2%(YM) and 48.5%
(YZ) respectively, and above 75% sulfur in raw coal was eliminated through addition
of 10% KOH combining with water-washing during pyrolysis. Moreover, after
water-washing, sulfur content in chars was distinctly decreased, from 1.6% to 0.6%
for DT, from 2.5% to 0.8 for YM and from 3.6 to 1.2% for YZ. As reported by some
other literatures, K2S formed during this process can be easily removed by water-
washing and reused. In addition, the process has evident effect of demineralization,
about 70% mineral matter in coal can be removed. The transforms of S and K during
the process were analyzed by XRD patterns. The mechanism of desulfurization was
discussed. By addition of KOH during coal pyrolysis combining with water-washing
is an attractive desulfurization method.
P2-7
Structure of the Coal Macerls and Their Pyrolysis
Jianming Zhou, Xuzhong Gong, Cao Min and Yonggang Wang
China University of Mining and Technology, P.R. China
Wenhua Li
China Coal Research Institute, P.R. China
The structure of two kinds of Chinese coal macerals, Shenhua and Yanzhou
bituminous coal, were studied by X-ray diffraction, XPS, FT-IR, respectively, and their
statistical constitution was analyzed. The results show that inertinite possessed the
larger aromatic layers than the vintrinite, and vintrinite showed more functional groups
than inertinite. The vintrinite has an obvious weight loss peak at 380~590 , and
inertinite at 410~550 under Ar circumstances. The macro-molecule network of the
macerals tends to be tightened during pyrolysis.
P2-8
Investigation of Effect of Atmospheres on Sulfur Groups Changes in Coal
Pyrolysis with AP-TPR
Haoquan Hu, Qiang Zhou, Quanren Liu and Shengwei Zhu
Dalian University of Technology, P.R. China
Yima coal was pyrolyzed followed by wet chemical analysis and atmospheric-pressure
temperature-programmed reduction (AP-TPR) to investigate the sulfur form changes
during pyrolysis in atmosphere of N2 and CO. Pyrolysis was carried out in an ambient
pressure, horizontal fixed-bed (i.d. 18mm) under the isothermal conditions of gas flow
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),
about 100mg of fine sample (<100mesh) was placed into the reactor under a 10ml/min
flow of pure hydrogen at atmospheric pressure and temperature from room temperature
up to 1000oC at constant heating rate of 5K/min. The formed H2S was analyzed by
GC with FPD detector on-line connected with the reactor system. From the wet
analysis data of sulfur forms of chars obtained at different pyrolysis conditions, it can
be seen that CO promotes the decomposition of pyrite and as a result, the formation of
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
transformation of pyrite to organic sulfur. From the AP-TPR results of raw coal and
chars obtained at different pyrolysis temperature, it can be found that for YM raw coal,
two dominant, well-separated peaks, with two shoulders can be observed. The peaks at
about 475 and 640oC are attributed to reduction of pyrite to troilite and subsequent
reduction of troilite to iron, respectively. The shoulder at lower temperatures (~400oC)
corresponds to the reduction of thiols, dialkyl and aryl-alkyl sulfides etc, and the right
shoulder (~700oC) is caused by the reduction of thiophenes. And for both pyrolysis
atmospheres, with increasing prior pyrolysis temperature of coal, the starting reduction
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
stability, such as thiols, dialkyl etc, have decomposed in the previous pyrolysis. And
the shoulder in the higher temperature (>700oC) is more pronounced, which indicates
more stable organic sulfur presents in char. And the pyrite reduction peak becomes
smaller and shifts to lower reduction temperature. The decrease of pyrite reduction
peak is caused by the decomposition of pyrite in prior pyrolysis, and the shift is caused
by the structure change during coal pyrolysis. Compared the AP-TPR profiles of chars
obtained in the different pyrolysis atmospheres at the same temperature, it can be seen
that the significant differences is the pyrite reduction peak, i.e. the extent of the
decrease of pyrite reduction peak is more pronounced in CO than that in N2 with
increasing pyrolysis temperature.
P2-9
Thermodynamic Consideration on Integration of Biomass Conversion into Coal
Gasification
Jun-ichiro Hayashi
Hokkaido University, Japan
Kazuhiro Mae
Kyoto University, Japan
Gasification is one of the attractive technologies to convert biomass resources into
gaseous fuel, while their particular natures such as substantially high contents of
moisture and alkali/alkaline-earth metallic species are responsible for problems
encountered in the gasification. This paper examines effectiveness of integrating
biomass conversion (including pretreatments and gasification) into coal gasification
mainly from a thermodynamic point of view. First sets of the numerical simulation are
performed by assuming i) conversion of dry coal (sub-bituminous rank) alone or dry
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
of product gases (H2, CO, CO2, CH4) and H2O at the gasifier exit with a temperature
of Texit. The results reveal that the biomass should be gasified with Texit lower by 150
C or even more than that for the coal gasification for achieving equivalent cold gas
efficiencies (i.e., the loss of chemical energy of the resource). Taken together with the
above-described properties of biomass, it is inferred that integrating the biomass
gasification into a high temperature chemical process is more reasonable than
55
operating it in standalone conditions. Second sets of the simulation are made on
integrated coal/biomass gasification, and the results show how the biomass gasification
can be integrated into the coal gasification effectively, giving the following options.
The first option is to gasify the biomass with direct use of the thermal energy of the
product gas (involving H2O) from the coal gasifier, in other words, to integrate the
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 (<
0.2), the biomass gasifier can produce 1.1 1.2 times of chemical energy compared
with that of the biomass. The reduction of the gas temperature between the exits of the
coal and biomass gasifiers is at most 200 C. If integrated into IGCC, the biomass
gasifier can act as a chemical heat pump (thermochemical energy recuperator) in the
cycle. The second option is co-gasification of coal and biomass in the same gasifier,
which may bring about not thermodynamic but kinetic synergisms in the gasification.
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
possible to lower the gasification temperature and reduce the O2 consumption thereby
increasing the cold gas efficiency. Both of the options need preheat treatment of the
biomass (drying and chemical oxygen removal) utilizing thermal energy with
temperature lower than 300 C, which is available downstream the gasifier(s).
P2-10
Estimation of Gasification Rate of Rapidly Pyrolyzed Coal Chars Using Pore
Structure Parameters
Tatsuya Morimoto, Tetsuya Ochiai and Hirokazu Oda
Kansai University, Japan
Attempts were made to estimate a reaction rate of coal chars prepared under various
pyrolysis conditions using a random pore model (RPM). In order to determine the
pore characteristic parameter in the RPM, Pore structure of char was assessed in
terms of mercury porosimetry. The value tended to decrease with higher pyrolysis
temperatures and the reaction rate estimated with the value was consistent with the
measured rate only in the initial stage of reaction. It was also suggested that there
was a different value in/after the middle stage of reaction from that in the initial.
P2-11
Effects of Pressure on Coal-nitrogen Conversion during the Pyrolysis and
Gasification of Loy Yang Brown Coal
Fu-Jun Tian, Hongwei Wu, Jianglong Yu, Lachlan J. Mckenzie, Stelios Konstantinidis
and Chun-Zhu Li
Monash University, Australia
CRC for Clean Power from lignite, Australia
Jun-ichiro Hayashi and Tadatoshi Chiba
Hokkaido University, Japan
Gasification-based technologies are expected to greatly reduce the environmental
impacts of power generation using coal. Gasification at elevated pressures is of special
interest. These gasification-based power generation technologies will have to meet the
increasingly stringent standards in the future on the emission of NOx and their
precursors. Hence, understanding the conversion mechanism of coal-nitrogen (coal-N)
to NOx, HCN and NH3 during the gasification of coal will be essential for the choice of
optimum reaction conditions in the future gasifiers. However, the formation of NH3
and HCN during pressurized gasification of coal is poorly understood. Hence, the aim
of this study is to investigate the effects of pressure on the formation NH3 and HCN
during the pyrolysis and gasification of Loy Yang brown coal in steam.
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
resulted in increases in char yield, probably due to the char-volatile interaction. NH3
yield increased with increasing pressure during both pyrolysis and gasification,
providing further evidence that the availability of H radicals (and also possibly OH
radicals) controls the hydrogenation of char-N into NH3. The corresponding HCN
yield appears much less sensitive to changes in pressure. Our experimental results will
give some insights into the mechanisms of the coal-N converted into NH3 and HCN
during the pyrolysis and gasification of coal with steam at elevated pressures.
P2-12
Operational Experience of Coal Gas Clean-up Technology Acceptable for Fuel
Cells
Sadao Wasaka
New Energy and Industrial Technology Development Organization, Japan
Masao Sotooka and Haruo Kanaboshi
Electric Power Development Co., Ltd., Japan
It is proved that the Integrated coal Gasification Fuel Cell Combined cycle (IGFC)
system which consists of a gasifier, fuel cells, gas turbine and steam turbine achieves
higher efficiency than IGCC.
The purpose of the EAGLE (coal Energy Application for Gas, Liquid and Electricity)
project is to develop the technology to produce clean gas for fuel cells.
The EAGLE project is subsidized by NEDO (New Energy and Industrial Technology
Development Organization) and METI (the Ministry of Economy, Trade and
Industry).
In EAGLE pilot plant, coal gas from gasification unit is introduced to the gas clean-
up unit. This unit consists of water scrubbers, a COS converter, an MDEA (Methyl
Die Ethanol Amine) absorber and precise desulfurizer.
In the first place, the syngas is cooled by gas-gas heater (GGH) and water scrubber.
In the scrubber, impurities such as dust and halogen in the syngas are removed. In
order to desulfurize the gas, MDEA is used as solvent. Because of its low
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
oxides. And acid gas removed with the MDEA absorber is burned with air in a
furnace and the sulfur content is recovered as gypsum by the use of limestone.
The pilot test has been continuing since March 2002 and planning to June 2006. This
paper describes the outline of the gas clean-up unit of EAGLE pilot plant and our
operational experience.
P2-13
Hydrogenation by Partial Oxidation of Glucose in Supercritical Water
Gasification
Yukihiko Matsumura, Takuya Yoshida, Masanori Shimamura, and Yoshihiro
Kikuchi
Hiroshima University, Japan
Supercritical water gasification is expected to be a promising technology for set
biomass gasification. It treats biomass species in hot-compressed water so that
gasification takes place in water as a reaction medium. This fact enables treatment of
wet biomass because drying pretreatment is not necessary.
We have shown that partial oxidation is effective for achieving high gasification
efficiency. While Adschiri et al. pointed out that partial oxidation in supercritical
water is effective for hydrogenation. They also suggested that formic acid, that is
produced from carbon dioxide, that in turn is a product of partial oxidation is a good
hydrogenation reagent from the experiment of coal extraction. Then, there is a
possibility that high gasification efficiency with partial oxidation for biomass
gasification in supercritical water is brought about with the help of this enhanced
hydrogenation.
To investigate this possibility, we conducted hydrogenation of acetone in
supercritical water with partial oxidation of glucose. Glucose is a model compound
of biomass, and expected to produce carbon monoxide through partial oxidation, then
to formic acid. Acetone is hydrogenated to produce 2-propanol. Both acetone and 2-
propanol are rather stable in supercritical water, and thus suitable to investigate
hydrogenation in this condition.
Experimental runs were conducted using a continuous flow-type reactor(3.17 mm ID
x 0.3 or 3 m) made of SS316 steel. The reactor was immersed into a molten salt bath
to control the temperature, and by changing the flow rate, residence time in the
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
solution of hydrogen peroxide that was completely decomposed into oxygen before
mixing with glucose and acetone solution.
As was expected, formation of formic acid was observed, and hydrogenation of
acetone to 2-propanol took place. However, surprisingly, the amount of formic acid
did not affect the 2-propanol yield. This fact indicates hydrogenation takes place, but
not due to formic acid, but some compounds produced from glucose decomposition.
A reaction rate equation was also derived.
P2-14
An Effective Approach to Interpreting Reactivity Change of Coal Char with
Structure Development of the Char in the Course of Char Gasification
Xiaoxun Ma and Hiroshi Nagaishi
AIST, Japan
Coal gasification modeling is fairly new, compared to that in coal combustion
processes. In the case of gasification modeling, the relationship between gasification
reactivity of coal char and the structure characteristics of the char as gasification
proceeds is of great importance. Most early investigations described the development
of the total/active surface area as a function of carbon conversion. However, the
measured surface area is always not the true surface area participating in the
gasification reaction because the area is generally measured at a very low
temperature of 77 K (in the case of N2 adsorption) or 273 K (in the case of CO2
adsorption), far below the gasification temperature. This sometimes results in a low
surface area due to activated diffusion effects. Furthermore, our recent investigation
has shown, after cooled and exposed to air, both CO2 adsorption activity and
gasification reactivity of the char are somewhat degraded.
In addition, at the most fundamental level, gasification reactivity of carbon in char
depends greatly on fraction of active sites in carbon. Therefore, it should be an
essential consideration to interpret the reactivity changes with carbon conversion
based on the variations in the number of active sites. Some studies have been devoted
to the subject. Nevertheless, some problems remain to be unclear.
56
The objective of the present work is to develop an effective approach to
interpretation of the dynamic change in the char gasification rate with structure
development of the char in the course of char gasification. A CO2 chemisorption
temperature-programmed desorption (TPD) method was used to determine the active
sites number of the char of different conversion levels at the same reactor with the
gasification from 573 K up to the temperature as high as gasification temperature,
avoiding the deep cooling of the char. This paper presents the experimental results
with different kind of chars at several temperatures and a model for char gasification
with this approach.
P2-15
Viscous Behaviour of Australian CoalsAsh Slags with High Iron and Low
Silica/Alumna Ratio
N.N. Kinaev and J.H. Patterson
CSIRO Energy Technology, Australia
The flow behaviour of coal mineral matter at high temperatures is a critically
important criteria for coal use in entrained-flow gasification technologies.
As part of a broader program which consider the gasification performance of a wide
range of Australian Coals, viscosities at temperatures from 1300C to 1600C and
temperatures of critical viscosities (TCV) Have been measured of coal ash slags with
iron levels between 15 and 25 wt% FeO (DAB) and Silica to Alumina (S/A) ratio
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
than 20 wt% FeO had a slight effect on the slag flow characteristics, while for slags
with iron content less than 20 wt% the same increase of CaO significantly improved
the slag flow behaviour and decreased TCV. For slags with S/A ratio of 1.25 and
more than 10 wt% CaO, variation of iron concentration from 17.5 to 22.5 wt% had
no significant effect of flow behaviour and TCV. At low CaO content for the same
S/A ratio, an increase of iron improved flow characteristics and decreased TCV of
slags. For slags with low S/A ratio of 1.1 and low CaO content addition of iron did
not show any significant effect on slag flow behaviour, and marginally decreased
TCV.
These measurements, combined with earlier slag viscosity data, covers almost the
whole composition range of important Australian bituminous coals. These data can
be used to facilitate the initial assessment of suitability, and prediction of fluxing
and/or blending strategies, for the use of Australian bituminous coals in entrained-
flow slagging gasifiers from the slag flow point of view. The effects of minor
elements (K and Mg) on slag flow behaviour for slags with high iron and low
silica/alumina ratio will also be discussed.
P2-16
Coal Char -CO2 Gasification Reaction Kinetics Models
Wang Yonggang, Gong Xuzhong and Zhou Jianming
China University of Mining and Technology, China
Three kinds of Chinese coal char (Yima, Yanzhou and Pingshuo bituminous coal of
low rank)-CO2 gasification reactivities were studied by TGA. Their gasification
reaction kinetics models were optimized, and kinetics parameters were calculated. The
results show that Yima char gasification reaction adapts to Diffusion model and
Pingshuo char can be described by nucleation and growth model, and Yanzhou char
gasification can be described by Contracting geometry (spherical symmetry) at a lower
heating rate and by Diffusion (1D) at higher heating rate. In addition, active energy
changes during reaction for the different coal rank were discussed.
P2-17
Variations in Chemistry of Macerals in Australian Coals Using Electron
Microprobe Techniques
Colin R. Ward and Zhongsheng Li
University of New South Wales, Australia
Lila W. Gurba
Co-operative Research Centre for Coal in Sustainable Development, Australia
The elemental composition of the individual macerals in a series of Australian coals,
ranging from sub-bituminous materials to anthracites, has been determined in-situ in
polished sections using special light-element electron microprobe techniques. The
analyses of the individual macerals in a number of these coals have also been
combined with conventional petrographic data to give a theoretical chemical
composition for the respective whole-coal samples, and this has been checked
against the respective whole-coal ultimate analysis data.
The composition of the different macerals in the coals was found to vary quite
significantly with rank advance. The inertinite macerals, for example, contain
significantly higher proportions of carbon, and lower proportions of oxygen, nitrogen
and organic sulphur than the vitrinite macerals in the same coal samples. The
differences in carbon and oxygen between vitrinite and inertinite are greatest in the
lower rank coals of the sample suite, and decrease as the rank of the coals increases.
The differences in N and S for the same macerals, however, appear to remain
relatively constant regardless of the rank level, although nitrogen in the organic
matter may decrease in some higher-rank coals with the development of ammonium
illite in the mineral matter.
Small proportions of Ca, Al and Fe were also found as an inherent part of the
macerals (especially the vitrinites) in the lower-rank coals of the sample suite.
Provided acid-soluble minerals containing the same elements are not also present, the
proportions of these elements appear to be consistent with the proportions of the
same elements mobilised from the same coal samples by selective leaching
techniques. With the exception of some unusually high-sulphur coals from the
Sydney and Cranky Corner Basins, these elements were not found in the macerals of
coals where the vitrinite reflectance is above 0.5% or where the carbon content of the
telocollinite as indicated by the microprobe is higher than 75%.
The elemental composition of individual macerals is of fundamental importance in
coal utilisation, since it is the individual macerals that react, typically independently,
when the coal is used in different applications. Electron microprobe analysis
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
analysis of maceral concentrates separated by physical means. The electron
microprobe also provides a direct method for determining the organic sulphur and
the oxygen contents of the maceral components, parameters that are only determined
by indirect means in conventional coal analysis. Corrections for moisture or mineral
matter, moreover, are not necessary when using the microprobe technique.
P2-18
Fireside Corrosion of Alloys for Combustion Power Plants
K. Natesan
Argonne National Laboratory, USA
Conceptual designs of advanced combustion systems that utilize coal as feedstock
must include improved thermal efficiency and significant reduction in release of
sulfur oxides, nitrogen oxides, and carbon dioxide. Such systems require materials
and components that are capable of operating at much higher temperatures than those
found in current coal-fired power plants. Component reliability and long-term,
trouble-free performance of structural materials for these systems necessitate
development/evaluation of materials in simulated coal-combustion environments, for
application in steam superheaters and reheaters. Recently, the U.S. Department of
Energy has started to reevaluate coal-fired steam generation plants and, in particular,
the designs based on supercritical and ultra-supercritical steam conditions. The
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)
and 540C (1000F), respectively, to 34.5 MPa (5000 psig) and 650C (1200F).
Development of a revolutionary boiler design for U.S. markets, based on
superheater/reheater temperatures >760C, is also proposed. The higher steam
temperature is expected to lead to another 2-3% increase in efficiency over a 700C
design, thus improving fuel usage and CO2 emissions.
A program on fireside corrosion is being conducted at Argonne National Laboratory
to evaluate the performance of several structural alloys in the presence of mixtures of
synthetic coal ash, alkali sulfates, and alkali chlorides. Experiments in the present
program, which addresses the effects of deposit chemistry, temperature, and alloy
chemistry on the corrosion response of alloys, were conducted at temperatures
between 575-800C for time periods up to 1850 h. Fe-base alloys selected for the
study included HR3C, 310TaN, HR120, SAVE 25, NF709, modified 800, 347HFG,
and HCM12A. In addition, 800H clad with Alloy 671 was included in several of the
exposures. Ni-base alloys selected for the study included 600, 601, 617, 690, 625,
602CA, 214, 230, 45TM, HR 160, and 693. Data were obtained on weight change,
scale thickness, internal penetration, microstructural characteristics of corrosion
products, mechanical integrity of the scales, and cracking of scales. Results showed
that the relationship of corrosion rates to temperature followed a bell-shaped curve
for Fe-base alloys, with peak rates at 725C, but the rate itself was dependent on the
alloy chemistry. Several Fe-base alloys showed acceptable rates in the sulfate-
containing coal-ash environment; but NaCl in the deposit led to catastrophic
corrosion at 650 and 800C. Ni-base alloys generally exhibited less corrosion than
the Fe-base alloys under similar exposure conditions; however, they were susceptible
to localized corrosion in the form of pits.
POSTER SESSION 3
COAL UTILIZATIN BY-PRODUCTS
P3-1
Utilization of Bottom Ash for Concrete Production Technology
Mark Nisnevich, Gregory Sirotin, Yaakov Eshel
The Research Institute, College of Judea and Samaria, Israel
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
of 650 to 800 kg/m3. It is conducive to use bottom ash as an aggregate for production
of lightweight concrete with low density. However, the possibility of using bottom
ash is limited due to the low strength of its particles. In order to eliminate the above
drawback, the following technological solutions were developed at The Research
Institute of The College of Judea and Samaria (Ariel, Israel): (a) use of high volume
57
of bottom ash as an aggregate in binary lightweight concrete, which contains in
additional to the high volume of bottom ash also high volume of fly ash; (b) use of
bottom ash as part of the aggregate in ternary and quaternary concretes, which
contains in additional to bottom ash, high volume of fly ash, unprocessed crushed
sand or unprocessed crushed sand and crushed rock, as an additional part of
aggregate, accordingly. The binary lightweight concrete was studied under laboratory
and field conditions. The combined use of bottom ash and fly ash provides: (a)
forming of a dense matrix of hardened cement-fly ash paste; (b) possessing an
optimum correlation between the desirable building properties (high thermal
insulating and sufficient strength) for such articles as masonry units, elements of
ceiling, etc. The combined use of bottom ash, fly ash and unprocessed crushed sand
and crushed rock, show promise for manufacturing the thermal insulating/structural
and structural lightweight concretes. The developed technologies enable to produce
ecologically lightweight concretes containing bottom ash.
P3-2
Dry Separation of Pulverized Fine Coal Using Novel Triboelectrostatic
Separator
Daniel Tao and Kelvin Jiang
University of Kentucky, USA
Coal is the most abundant fossil fuel in the USA. More than 55% of electricity is
generated by burning coal. In general, coal is pulverized in dry state to a size of
about 25 micron at power stations before it is sent to furnaces, which creates an
excellent liberation between minerals and coal. However, it is not economically
feasible to employ any wet processes to process pulverized fine coal. Recently, a
novel triboelectrostatic separator has been developed for dry fine particle separation.
An ash rejection rate of 41% was achieved for the pulverized coal furnace feed at the
Dale power station while recovering greater than 88% of the combustibles. The
parameters affecting separation performance were also investigated. Significant
environmental and economical benefits might be achieved with the use of the novel
triboelectrostatic separator between the pulverizer and furnace at power plants.
P3-3
Utilization of Coal Combustion Products in Europe Valuable Raw Materials
for the Construction Industry
Tomasz Szcygielski, Hans-Joachim Feuerbon, ECOBA, GERMANY
In 2002, 63 million tonnes of coal combustion products (CCPs) were produced in
Europe (EU 15). The CCPs include combustion residues such as boiler slag, bottom
ash and fly ash from different types of boilers as well as desulphurization products
like spray dry absorption product and FGD gypsum. Out of the total production of 63
million tonnes of CCPs the amount of combustion residues produced was around 52
million tonnes while around 11 million tonnes are
products obtained from flue gas desulphurization processes. The CCPs are mainly
utilized in the building material industry, in civil engineering, in road constructions,
for construction work in underground coal mining as well as for recultivation and
restoration purposes in open cast mining. Most of the hard coal fly ashes are used in
concrete. In the majority of cases CCPs are used as a replacement for natural
materials and therefore offer environmental benefits by avoiding the need to quarry
or mine these resources. CCPs also help to reduce energy demand as well as
emissions to atmosphere, for example CO2, which are
needed for - or result from the manufacturing process of the products which are
replaced. Furhtermore, the majority of the CCPs are produced to meet certain
requirements of standards or other specifications with respect to utilization in certain
areas. Due to different boundary conditions regarding climate, taxes and legislation
the utilization rate of CCPs is different across European countries. In order to face
the tasks resulting from legislation European power plant operators established
ECOBA the European Coal Combustion Products Association in 1990. In this
paper some information will be given on mission and work of ECOBA and on the
present situation and perspectives of CCP production and utilization in Europe based
on the annual survey of ECOBA on production and utilization of CCPs in Europe
(EU 15), on European regulations, political decisions of national authorities and on
market needs in the construction industry in Europe.
POSTER SESSION 4
COAL UTILIZATION TECHNOLOGIES IN THE STEEL INDUSTRY
P4-1
Coal Pre-treating Technologies for Improving Coke Quality
Kenji Kato and Masaaki Naito
Nippon Steel Corporation, Japan
In Japan, improvement of coke quality and energy saving are strongly demanded.
Improvement of the coke quality leads the increase of blending ratio of poorly-
coking coal in coal charge without deteriorating coke strength. So, the new
pretreatment technology for coal charge, called "DAPS", was developed and came on
stream at Nippon Steel Corporation Oita works in 1992. In the process, the ratio of
fine coal agglomerated by the roll compactor is about 30 mass % of coal charge. The
agglomerated fine coal is added to the coarse coal over 0.3 mm size, and charged into
coke ovens. By the application of this process to the coke-making plant, the ratio of
non- or slightly-coking coal in coal charge is reported to increase by 20%. By
applying these coal pre-treatment processes, the heat consumption in coke ovens
stood at 557 M cal/t-coal in 2000 and decreased by 51 M cal/t-coal (approximately 9
percent) on the basis of that in 1984.
CMC process, CDQ facilities and automatic combustion control system (ACC) of
coke oven batteries were among the energy saving technologies in the Japanese steel
industry. And new coke-making process SCOPE21 is now under development.
This paper describes the R&D of coal pre-treating technologies for improving coke
quality.
P4-2
The Effect of Added Plastic Size on Coal Carbonization Phenomena
Seiji Nomura and Kenji Kato
Nippon Steel Corporation, Japan
The recycling process of waste plastics using coke ovens is now being studied. Coals
and added plastics are carbonized and changed into coke, tar and oil and coke oven
gas in a coke oven chamber. It was thought that added plastics might affect the
quality of blast furnace coke. In this study, the effect of added plastic size on coke
was investigated. In the case of plastic addition rate of 2%, the coke strength showed
the minimum at the particle size of 10mm for polyethylene (PE) and 3mm for
polystyrene (PS). The mechanism was well explained in connection with the weak
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
the coking pressure during carbonization.
Based on this fundamental study, we have determined that the size of waste plastic
used in a commercial-scale recycling process of waste plastics using coke ovens is
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
operating smoothly.
P4-3
Further Development of Aromatic Ring Size above 500oC in the Heat-
Treatment of Coking Coals
Koh Kidena, Koji Matsumoto, Satoru Murata and Masakatsu Nomura
Osaka University, Japan
Because of the urgent needs for high-quality coke with lower cost in iron-making
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
changes during coking process, which include plastic range, and carbonization, are
need to be clarified. The authors have been investigating the chemical structural
changes during plastic phenomena, but the following stage is unexploited. In this
paper, the authors focused on the structural changes of two types of coals after
resolidification. The two coals are strongly and weakly coking coals, Goonyella and
Enshu coals, respectively. Comparisons between semi-cokes derived from these two
coals showed that semi-cokes from Goonyella coal tended to develop aromatic ring
size.
P4-4
Quantification of Mineral Matter in Coals and Their Cokes
Richard Sakurovs and David French
CSIRO Energy Technology, Australia
The nature of mineral matter in coke helps is an important factor in determine
determining the behaviour of coke in the blast furnace. However, most studies on the
relationships between coke reactivity and mineral matter have focussed on elemental
composition of the mineral matter, since it is relatively easy to obtain. When
predictions of the reactivity of coke based on elemental composition fail, the most
common reason given is that the form of the mineral matter and its distribution are as
important as elemental composition in determining the reactivity of a given coke.
However, there have been few quantitative determinations of the types of mineral
matter in coal and coke. Here we use a technique of quantitative X-ray diffraction
SIROQUANT to determine the nature and quantity of mineral matter in twelve
coals and their cokes, using samples used commercially around the world. We will
describe the level of relationship between elemental composition and mineral matter
in coals and cokes and the transformation of minerals in coals to minerals in cokes.
P4-5
Examination of Coking Process of Coal by Use of Raman Spectroscopy and
Analysis of Hydrogen Formation Behavior
Hiroyuki Nakagawa, Kenji Kumata and Kouichi Miura
Kyoto University, Japan
Caking coals, which are main raw materials of metallurgical cokes, are carbonized
through softening, melting, and subsequent resolidification by the heat treatment
above 400C. Softening and melting characteristic can be estimated by several
58
methods including the Gieseler plastmetry and dilation tests. On the other hand, the
coke forming process during the resolidification is poorly understood because of the
difficulty of the analysis of the solid amorphous carbons, although it is recognized
that the resolidification process affects significantly the strength of cokes produced.
In this study, the resolidification process was examined from two aspects: one is the
analysis of the hydrogen formation rate during the resolidification and the other is
direct observation of the solid carbon in the process of resolidification by the Laser
Raman spectroscopy. The hydrogen formation behavior is judged to be closely
related to the growth of condensed aromatic rings, and the Laser Raman
spectroscopy is believed to be powerful to characterize amorphous carbons.
Various coals were heated at the rates of 5, 10, and 20 C /min up to 900C, and the
formation rate of hydrogen was measured continuously by use of a mass
spectrometer. The measured formation rate of H2 was analyzed by using the so-
called distributed activation energy model (DAEM) to obtain the distribution of
activation energy. It was found that the peak activation energy for the H2 formation
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
spectra were measured for the coal sample heated up to a final temperature between
600 and 900C. The absolute intensity for the peak associated with the CH2- or
CH3 was found to decrease with the increase of the final temperature. The decrease
was well correlated with the amount of H2 produced up to the final temperature,
indicating that the Raman spectrum reflects the proceeding of carbonization of coal.
These results were also discussed with the XRD analysis from the viewpoint of the
progress of carbonization.
P4-6
Reduction Behavior of Iron Ore with Various Carbon Sources
Risehiro Nonaka, Takuo Sugawara and Katsuyasu Sugawara
Akita University, Japan
The present study was carried out to obtain the fundamental data on the reduction of
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
carbon-coated iron ore particles during rapid heating was studied using a drop tube
reactor at temperatures from 973 K to 1773 K.
Higher reduction extent was obtained for the iron ore coated with vacuum residue of
heavy oil rather than phenolphthaleinderived carbon. While sulfur contained in the
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
carbon source on reduction behavior were investigated.
POSTER SESSION 5
ENVIRONMENTAL CONTROL TECHNOLOGIES FOR SOx, NOx,
PARTICULATES & TRACE ELEMENTS
P5-1
Carbon-Based Novel Sorbents for Removing Mercury in Flue Gases
Si Hyun Lee, Young Jun Rhim, Sang Do Kim, Youngok Park, Jae Ek Son
Korea Institute of Energy Research, Korea
Jeom In Baek, Kyung Ryong Jang
Korea Electric Power Research Institutes, Korea
In present paper, the details of the development of functional activated carbon for
mercury removal in flue gases were described. To develop carbon-based sorbents to
be used in gas-phase mercury removal, the performance of virgin activated carbons
(AC) and with that of chemically treated activated carbons were compared.
According to the research result, virgin activated carbon with large oxygen
functional groups was superior in mercury adsorption performance. Pre-oxidation of
activated carbons with acids were also investigated and adsorption performances
were compared with. Injection of activated carbons has been investigated and the
influential factors such as temperature, carbon dose (C/Hg ratio) were also discussed.
In particular, when sulfur is impregnated, it is essential to select AC with large pore
diameter. If the pore characteristics of AC are different, the AC capacities also differ
even if sulfur is impregnated. There are two types of sulfur impregnated into AC, one
of which is desorbed at 250 and the other evaporates at 400. A condition under
which highly reactive sulfur was selectively adsorbed was looked for. If the amount
of sulfur that is strongly bonded to the carbon was large, the AC had a better mercury
adsorption performance. The developed sulfur-impregnated AC manufacturing
process may be more economical than the existing sulfur impregnation method, and
the result might be applied to the AC injection system of incinerators or power
plants.
P5-2
Leaching of Organic Matters from Coal into Aqueous Media and Their
Ecotoxicities
Tsunenori Nakajima, Takashi Fukuda, Hirokazu Takanashi and Akira Ohki
Kagoshima University, Japan
A model study was carried out for the presence of organic matters in the wastewater
from coal piles. Finely powdered coal samples were extracted in a hot water
extraction (HWE) process. The determination of total organic carbon (TOC) in the
aqueous phase was performed by a TOC analyzer. The ecotoxicities of organic
matters extracted were examined by the Ames mutagenicity assay and the estrogen
receptor binding assay. The same investigation was made for the organic matters in
the wastewater from hydrothermal treatment (HTT) upgrading process of low-rank
coals. For HWE process, the degree of TOC in the aqueous phase was found to
increase with elevating temperature. The degree of TOC varied with coal type, and
low-rank coals such as lignite and sub-bituminous coals tended to provide high TOC
degrees. The extracts of Loy Yang (LY) lignite gave an estrogenic activity, whereas
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
degree rapidly went up from 250 to 300 oC. The HTT extracts of LY lignite gave a
higher estrogenic activity than that for the HWE extract.
P5-3
Determination of Major and Trace Elements in Coal Fly Ash by Microwave-
Assisted Acid-Digestion and ICP-AES Analysis
Akira Iwashita, Tsunenori Nakajima, Hirokazu Takanashi, and Akira Ohki
Kagoshima University, Japan
Yoshio Fujita and Toru Yamashita
Idemitsu Kosan Co., Ltd., Japan
Microwave digestion and alkali fusion were investigated for the precise and easy
determination of major and trace elements in coal fly ash by ICP-AES. By use of
certified reference materials, we evaluated the effectiveness of those methods for
major elements (Al, Ca, Fe, Mg and P) as well as trace elements (Cd, Co, Cr, Cu,
Mn, Ni, Pb, and Zn). Coal fly ash samples were subjected to microwave digestion
using the mixture of acids (HNO3+H2O2 or HNO3+H2O2+HF). We examined the
optimization of digestion method, especially focusing on the necessity of HF as well
as the removal methods of HF (H3BO3 addition and evaporation). The digestion
without HF provided quite low recoveries of major and trace elements. For the
digestion with the HF-H3BO3 addition system, the recoveries of major elements
were nearly 100 %, whereas trace elements in coal gave somewhat lower recoveries.
Although the HF-evaporation system provided quite low recoveries of Al, Ca and
Mg, good recoveries were obtained for the other elements. For alkali fusion with
Na2CO3, the recoveries of major elements were nearly 100 %. However, the
determination of trace elements by ICP-AES gave quite low recoveries, which was
improved by use of graphite furnace (GF) AAS.
P5-4
Release Behavior of Mercury and Arsenic from Coal during Pyrolysis
Shomei Tanamachi, Akira Iwashita, Tsunenori Nakajima, Hirokazu Takanashi and
Akira Ohki
Kagoshima University, Japan
Seven brands of coals were subjected to pyrolysis (200-600C), and the release
behavior of Hg and As was examined. Powdery coal (0.5g) was placed in a alumina
board and heated by a horizontal tubular furnace at a rate of 1 K/s up to 200-600C
under N2 flow (100 ml/min) and the temperature was kept for a definite period. Then
Hg and As released from coal were trapped by KMnO4 solution, and the
concentrations of Hg and As in the solution were measured. For Hg, when the
pyrolysis was performed at 300 and 400C, the % release was greatly varied with
coal brands (20-80%). Above 500C, all of the coals gave high degree of % Hg
release. According to a fractional determination of Hg by use of a sequential trap
(KCl solution trap and KMnO4 solution trap), it was found that the Hg species
released from coal by the pyrolysis at 300C was mainly Hg0 (elemental mercury).
For As, the % release for the 300C-pyrolysis was less than 20%, which was
common for all coals. The % As release gradually increased as the pyrolysis
temperature was elevated, and reached ca. 40% at 600C, which was also common
for all coals. The release mechanism for Hg and As will be discussed.
P5-5
Enrichment Behavior of Alkali Metal Compounds and Fine Particulate
Formation during Coal Combustion
Tsuyoshi Takuwa and Ichiro Naruse
Toyohashi University of Technology, Japan
Some trace metal compounds tend to be enriched in the fine particulates during the
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
Moreover, the enrichment mechanism of Na was elucidated by the size distribution
of Na concentration in the fine particulates collected in each stage of the LPI. The
enrichment mechanisms also depended on the coal types. The reason for this
difference was mainly due to the existence form of mineral particles in each of the
raw coal. For the fine particulates produced, the enrichment phenomena were
controlled by a reaction of Na compounds vapor with the fine ash particulates or
homogeneous nucleation. For the relatively coarse particulates, on the other hand, the
gas film diffusion controlled the enrichment of Na compounds into the ash particles
with the chemical reactions of Na compounds vapor with those ash particles.
P5-6
Synthesis of ZnO Nano Wire Desulfurization Sorbents for Hot Gas Ultra
Cleanup
No-Kuk Park, Dong-Hwal Lee, Jong Dae Lee, Jin Hyuk Jun, Si Ok Ryu and Tae Jin
Lee
Yeungnam University, Korea
Jae-Chang Kim
Kyungpook National University, Korea
The limited energy supply and the environmental pollutions have become an
international concern in energy related area. Therefore, many countries put a great
effort to develop the economically acceptable and environmentally sustainable
technologies for utilization of fossil fuels. The integrated gasification combined cycle
(IGCC) is considered as the innovative clean and affordable energy system to
generate an electric power in the future. A variety of low-grade carbon-containing
fuels including coal, heavy oil residue, petroleum coke, biomass, and wastes were
utilized to produce a synthetic gas from a gasifier. The produced synthetic gas after
hot gas cleanup process is converted into the marketable products, such as electricity,
ammonia, and methanol. Further purification of syngas will produce the high value-
added products, such as hydrogen for fuel cell and chemicals (DME, DMC) for
catalytic conversion processes.
Hot gas desulfurization (HGD) is a very important process in the gas cleanup system
and its main role is to remove harmful sulfur from the synthetic fuel gas. However,
complete removal of sulfur content in a syngas is very difficult because a small
amount of sulfur compounds (e.g., H2S, SO2, and COS) are produced by the
secondary reactions. Siemens reported that there was a thermodynamic limitation for
zinc-based sorbents to reduce H2S to 5 ppmv and below in a fluidized-bed reactor
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
capacity was developed for a ultra hot gas cleaning process in this study.
Characteristic behavior and optimum condition for the formation of the zinc oxide
nano wire was investigated. Reactivity of sorbent during sulfidation/regeneration
process was also performed in this experiment.
P5-7
Development of Continuous Mercury Monitor with Dry Speciator Applied To
Combustion Flue Gases
Naoki Noda and Shigeo Ito
Central Research Institute of Electric Power Industry (CRIEPI), Japan
Koji Tanida
Nippon Instruments Corporation (NIC), Japan
Mercury emissions from anthropogenic sources occur in three main forms:
particulate mercury, gaseous oxidized mercury (Hg2+), and gaseous elemental
mercury (Hg0). The chemical forms of mercury affect the behavior in a combustion
process and come with a number of factors such as temperatures, etc. Therefore a
mercury speciator is necessary for correct understanding of the behavior in
combustion processes.
CRIEPI and NIC developed a continuous mercury monitor which consists of a dry
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
to convert Hg2+ into Hg0 to measure Hgtot as Hg0. Each mercury is measured by
cold-vapor atomic absorption spectroscopy (CVAAS). The absorbent that captured
Hg2+ was regenerated by heating every 20 minutes and the reductant was self
renewable in the presence of HCl. Therefore the monitor discharged little effluent
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
range from 0.1 to 100g/m3N.

POSTER SESSION 6
SYNTHESIS OF LIQUID FUELS & CHEMICALS
P6-1
The Chloromethylation of Polynuclear Aromatic Hydrocardbons Catalyzed by
Rare Earth Metal Triflate
T. Kishida and T. Yamauchi
Nissei Kagaku Kogyosho, Japan
Y. Kubota, K. Komura and Y. Sugi
Gifu University, Japan
The chloromethylation of aromatic hydrocarbons is a promising key technology for
the functionalization of aromatic hydrocarbons. Zinc chloride is well known catalyst
for the purpose, however, it is necessary to use equivalent amounts to substrate
because the reaction is usually carried out in hydrochloric acid solution1). Zinc
chloride has environmental burden because of the waste after the reaction. It is
important to find environmentally conscious catalysts for the chloromethylation. In
this paper, we report that some rare earth metal triflates are highly active for the
chloromethylation of many aromatic hydrocarbons.
The catalytic activity of rare earth metal triflates for the chloromethylation of m-
xylene (I) is shown in Fig. 1. They are highly active for the catalysis, and produced
1-chloromethyl-2,4-dimethylbenzene (II) in addition to small amounts of 1,3-
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.
Equivalent amount of zinc chloride against I gave the high yield of the
chloromethylated m-xylenes as known in the literature1).
The chloromethylation using Sc(OTf)3 as a catalyst was enhanced by raising reaction
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
mixture. The chloromethylation to yield II effectively with the ratio: trioxane/I=1.5,
however, the excess of trioxane enhanced the formation of III.
Sc(OTf)3 also enhanced the chloromethylation of various aromatic hydrocarbons.
The chloromethylation occurred at ortho- and para-positions as known in the
classical zinc chloride method1). Biphenyl gave 4-chloromethylbiphenyl and 4,4-
bis(chloromethyl) biphenyl in reasonable yield, however, the reaction also occurred
at 2-position to yield 2-chloromethylbiphenyl and 2,4-bis(chloromethyl)biphenyl in
small amount. 9,10-Dihydrophenanthrene afforded 2,7-bis(chloromethyl)-9,10-
dihydrophenanthrene in high yield.
P6-2
Large Pore One-Dimensional Zeolites. Catalysts for the Alkylation of Biphenyl
Yoshihiro Sugi, Yoshihiro Kubota, Akira Ito, Hiroyoshi Maekawa, Ranjeet Kaur
Ahedi, Mahyua Bndyopadhyay, Seiji Watanabe, Ciharu Asaoka, Tomoko Shibata,
Daisuke Yamamoto, Yukio Hasegawa, and Suresh B. Wagmode
Gifu University, Japan
H.S. Lee, Jong-Ho Kim and Gon Seo
Chonnam National University, Korea
The shape-selective alkylation of polynuclear hydrocarbons is the promising way to
their funcionalization for advanced materials. We prevoiously found H-mordenite
(HM) is the excellent catalyst for shape-selective isopropylation of biphenyl and
naphthalene1. In this paper, the selectivity for 4,4-disopropylbiphenyl (4,4-DIPB)
was compared in the isopropylation of biphenyl over large pore zeolites, CIT-5 and
UTD-1 for 14-membered ring zeolite and SSZ-31, HM, ZSM-12, and SSZ-42 for 12-
membered ring zeolite. We discuss also the reason why and where shape-selective
ctalysis occurs. CIT-5 (0.75x0.72nm) enhanced the formation of 4,4-DIPB at the
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
20 %. These differences are due to their pore structures: the pore of CIT-5 restricts
sterically the transition states to yield selectively 4,4-DIPB among DIPB isomers,
however, the pore of UTD-1 is too loose to form 4,4-DIPB preferentially. The
selective formation of 4,4-DIPB was also observed at he level of 50-60 % over SSZ-
31 (0.86x0.57nm), which has largest pore among 12-membered ring zeolites. The
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),
although ZSM-12 has smaller pore than HM: the pores are too small for the
isopropylation of biphenyl inside the pore of ZSM-12. SSZ-42 (0.67x0.64nm) gave
only 30 % selectivity for 4,4-DIPB: this is due to the cages inside the pore. Form
these results, it is concluded that the shapeselective formation of 4,4-DIPB was due
to the level of steric restriction of the transition state to form DIPB isomers by the
size and structure of the pores. HM is the most efficient and versatile catalyst for the
shape-selective isopropylation of biphenyl among these zeolites. We also discuss the
application of large pore zeolites on the alkylation of naphthalene.
60
P6-3
Improvements on Selective Conversion of Methanol/Dimethylether into
Liquefied Petroleum Gas over Zeolite Catalysts
Yingjie Jin, Sachio Asaoka, Xiaohong Li, Kenji Asami and Kaoru Fujimoto
The University of Kitakyushu, Japan
The synfuel process, based on the conversion of methanol to hydrocarbons over
zeolite catalysts, was the major development in production of alternative fuel from
coal or natural gas over the past several decades. This primarily concept was
extended from such as MTG process into indirect synthesis of Liquefied Petroleum
Gas (LPG), and a schematic flow chart of proposed process configuration was
already expatiated on several main operation units in our recent work.(Fuel
Processing Technology; in press.)
This LPG route through methanol/dimethyl ether (DME) conversion to lower
hydrocarbons is further demonstrated in terms of experimental argumentation in the
current presentation. The significant improvements on the proposed LPG protocol
are achieved both in catalytic reaction selectivity, which is mainly promoted by
zeolite-modified materials as well as optimal conditions, and in whole LPG process
selectivity, by a coupled reaction mode of recycled light olefinic byproducts with
methanol or its oxygenate feeds. Furthermore, available feeds are examined in details
and the preferred zeolite catalysts are tested for active stability in methanol/ DME
conversion.
These deduced results may provide an experimental support to the process design for
highly selective and bulky domestic fuel production.
P6-4
Directive Synthesis of LPG from Syngas over Supported Palladium and Zeolite
Qianwen Zhang, Xiaohong Li, Kenji Asami, Sachio Asaoka, Kaoru Fujimoto
The University of Kitakyushu, Japan
The production of liquefied petroleum gas (LPG), a mixture of propane and butanes,
from syngas is an important technology of conversion of nature gas into higher-
value-added product. LPG was directly synthesized from syngas over a hybrid
catalyst composed of methanol synthesis catalyst and zeolite. Syngas was converted
into hydrocarbon through methanol or DME as an intermediate in the reaction.
Usually the temperature that was required for conversion of methanol into
hydrocarbons over zeolite was higher than 598K. The hybrid catalyst, composed of
Cu-Zn methanol synthesis catalyst and Y-type zeolite, showed a good initial activity
and selectivity for synthesis of LPG. But the stability of that catalyst remained to
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
catalyst for methanol synthesis was more stable at high temperature. Experimental
results demonstrated that addition of palladium into Cr-Zn methanol catalyst
increased activity and selectivity of the hybrid catalyst for synthesis of LPG.
Palladium supported on silica had a low activity for LPG synthesis, but the addition
of calcium promoted its activity. High dispersion of palladium metal benefited the
activity of hybrid catalyst. The hybrid catalyst based on palladium had lower initial
activity for LPG synthesis from syngas than that based on Cu-Zn. Increase of
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
product hydrocarbons. Reaction temperature showed a great effect on the activity
and selectivity of the catalyst. Low temperature benefited the formation of heavy
hydrocarbons, while high temperature increased the selectivity to methane. On other
hand, high temperature was unfavorable to equilibrium of methanol formation, that
decreased the yield of hydrocarbons obviously. The appropriate reaction temperature
for the hybrid catalyst consisted of (Pa-Ca/SiO2)/beta-zeolite was about 628K. That
catalyst showed one through CO conversion of 75% and selectivity of 75% for C3
and C4s hydrocarbons at 628K and 5.1MPa.
P6-5
Hydrogenation of Carbon Monoxide Using Sulfide Catalysts Derived from
Supperted Transition Metal Carbonyls
Atsushi Ishihara, Makoto Ishii, Kazuo Hirabayashi,
Eika W. Qian and Toshiaki Kabe
Tokyo University of Agriculture and Technology, Japan
A study of CO hydrogenation on catalysts derived from Ru carbonyl supported on
Al2O3 or TiO2 was performed in a pressurized flow system. Ru carbonyl complex
supported on Al2O3 (Ru/Al2O3) and supported on TiO2 (Ru/TiO2) were activated
by H2S in H2 (sulfiding) or by H2 (reducing). Ru/Al2O3 catalyst gave high CO
conversion and high selectivity for CH4 after reducing. When the catalyst was
activated by sulfiding, the conversion decreased remarkably. While over Ru/TiO2,
C2 - C6 paraffines and olefins were formed irrespective of the pretreatment
conditions. When Ru/TiO2 was modified by addition of K, a decrease in the CO
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
 after sulfiding. By addition of Ni or Co to Mo/Al2O3, the product distribution shifted
to higher hydrocarbons over the catalyst after sulfiding while the CO conversion
decreased slightly. Schulz-Flory plots showed a nearly linear behavior giving an
value of 0.73 to 0.75 for Ru-based catalysts after sulfiding.
P6-6
Preparation of Novel Porous Acidic Oxide Catalysts from Metal-Containing
Silsesquioxanes
Kenji Wada, Kiyohiko Tada, Naohiko Itayama, Koichi Yamada,
Teruyuki Kondo and Take-aki Mitsudo
Kyoto University, Japan
Preparation of novel porous acidic oxides is of great importance from the viewpoint
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-
synthesized metal-containing silsesquioxanes, such as
[HN(octyl)Me2]+{Al[(Me3SiO)(c-C5H9)7Si7O11]2}-, at around 823 K produces
porous oxides with high BET surface areas of 330 - 520 m2g-1 and uniformly-
controlled micropores of 5~6 diameter. Remarkably, from group 13 elements-
containing silsesquioxanes Brnsted acidic oxides are produced. Their acidic
properties are greatly affected by the structure of silsesquioxane precursors, and
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
are closely related to the structure of precursors, are considered to be one of the
reasons of differences in their acidic characters. Among them, oxides prepared by
the calcination of aluminium-containing silsesquioxanes show excellent catalytic
activities towards the cumene cracking performed at around 573 K, whereas
commercial silica-alumina catalysts do not show significant activities under the
present conditions. Effects of the structure of silsesquioxane precursors on the pore
structure of the resulting oxides will be also discussed in detail.
P6-7
Coal to Clean Fuel The Shenhuya Investment in Direct Coal Liquefaction
Qingyun Sun, Richard Bajura and Jerald J. Fletcher
West Virginia University, USA
Yuzhuo Zhang and Xiangkun Ren
Shenhua Group Corporation, China
Significant price increases and the associated potential for crude oil shortages have
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)
facilities and the development of the worlds first commercial direct coal liquefaction
(DCL) plant by the Shenhua Group Corporation provide case studies of commercial
coal liquefaction technologies. Without access to detailed information on the
processes, debate on the relative economic competitiveness that these processes can
achieve continues. An increased understanding of these processes could affect the
direction of future research and potential commercialization.
This paper presents a case study of the economics of DCL and ICL technologies using
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
base, location, stage of economic development, and the policy environment. Focusing
on the inputs and outputs of liquefaction facilities, the authors explore potential
complementarities of combining DCL and ICL technologies. Complementary fuel oil
products and waste utilization that follow from integrating DCL and ICL processes
may cut inputs, reduce operational cost, and improve fuel oil quality. A case study of
the Shenhua DCL and Sasol ICL projects will offer useful information for those
countries rich in coal and dependent on oil imports that are considering coal
liquefaction as a viable alternative to enhance energy security.
P6-8
TPO-MS Study on Oxidation Behavior of Organic Sulfur Compounds
Loaded on a Coke
Jinding Yan, Jianli Yang and Zhenyu Liu
Chinese Academy of Sciences, PR China
Temperature Programmed Oxidation (TPO) was used to study oxidation of various
organic sulfur compounds loaded on a coke to simulate oxidation behavior of sulfur
structure in coal. Ideally, a sulfur functional group oxidizes in O2 to form SO2 at a
specific temperature. However, SO2 release from coal during oxidation is very
complex and affected by many factors, such as the nature of the sulfur structure,
properties of carbon matrix surrounding the sulfur structure, inorganic matters in the
coal and secondary reactions etc. It may be difficult to correlate a sulfur release
temperature to a specific sulfur type in coal.
To simplify the above complexity, five organic sulfur compounds, Benzyl sulfide,
Dibenzyl disulfide, p-Tolyl disulfide, 2-Naphthalenethiol and Dibenzothiophene, were
loaded on a coke and subjected to TPO in this study in pure oxygen. The gaseous
products were analyzed continuously on line by a mass spectrometer (TPO-MS).
61
The initial temperatures of SO2 evolution from different sulfur compounds were found
different, 170 C for aliphatic sulfur, 270 C for aromatic sulfur and 450 C for
thiophenic sulfur, this order is consistent with that of bond energies of the sulfur
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
COS were found to react with the carbon support. This reaction seems to result in the
formation of a small amount of CO2 at low temperatures and incorporation of sulfur
into the carbon matrix to form new sulfur-containing species, which may release in the
form of SO2 and COS at a higher temperature stage. The sulfur in dibenzothiophene
was found to release in the same temperature range as the oxidation of the carbon
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
given in the meeting.
P6-9
Study on CO2 Reforming of Methane in the Presence of Ni-loaded Zeolite
Catalysts
Satoru Murata
Takaoka National College, Japan
Nobuyuki Hatanaka, Koh Kidena and Masakatsu Nomura
Osaka University, Japan
CO2 reforming of methane is very attractive reaction, the reaction having several
advantages; (1) the reaction consumes greenhouse gases such as methane and carbon
dioxide, (2) it can convert less reactive gas, methane, to valuable syngas, and (3) low
grade natural gas well containing lots of carbon dioxide can become available.
Therefore, many studies had been conducted. Nickel is a possible candidate for the
catalyst of the reaction since it can be available at lower costs than noble metals and
has high activity at an initial stage of the reaction. However, nickel catalysts are
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
reforming of methane and found that the catalysts showed higher activity than
conventional Ni/Al2O3 catalyst, however, the activities of the catalysts degraded
gradually. In the present study, we investigated the modification method of these
zeolite catalysts such as co-loading of alkali and alkaline-earth metals, co-loading of
secondary transition metals, and hybridization of zeolite with alumina or titania.
Modified catalysts showed higher resistivities toward deactivation by carbon
deposition. These catalysts may become a possible candidate for commercial
catalysts of the reaction.
POSTER SESSION 7
COAL CHEMISTRY
P7-1
Metamorphism and Dynamics of Solid Fuel Composition and Structure
Gennadiy Vlasov
JSC, Ukraine
Vadim Barsky
Ukrainian State University of Chemical Engineers, Ukraine
Quality of fossil fuel depends on its chemical composition and structure as a result of
metamorphism, i.e. uninterrupted transformation of initial phytogenic material
through peat to different chemical age coal-formations. This transformation
becomes apparent in change of coal element composition and ratio of molecular
structures with different chemical nature.
Authors based themselves on hypothesis, that time determinates regular nature
process of transformation of fossil substances toward direction of their aggregate
carbonization, whereas statistical background behind this regularity is formed by real
multiformity of maternal phytogenic residues, their precipitation and decomposition
conditions, temperature and pressure, oxidizing or reducing medium at different
territory zones.
Thermodynamic evaluation of possible carbonization reactions, evaluation of ratio
between aromatic and aliphatic compounds according to IR-spectroscopy of coal and
liquid pyrolysis by-products, allowed to produce metamorphism model.
This model is used for evaluation of coal molecular structure dynamics and its
calorific value during metamorphism.
P7-2
Development of Measurement System for Continuous Monitoring of Gas
Generation Behavior during Coking Process
Masayuki Nishifuji, Kenji Kato, Koji Saito and Yuji Fujioka
Advanced Technology Research Laboratories Nippon Steel Corporation, Japan
Steel making process is based on many chemical reactions at high temperature more
than 1000 and is controlled with parameters on information of the characterization.
For characterizing coking reaction, it can be important information to realize gas
generation behavior on pyrolysis of coal.
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
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
analyzer (FT-IR) and a sensor for hydrogen which cannot be detected by FT-IR.
Coal powder sample in nitrogen flow was heated with an electric furnace, and
generated gases were led to the detectors with nitrogen gas carrier continuously. This
system has a good time-resolved of second order, so that a short time reaction of coal
pyrolysis can be monitored continuously.
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
agreement with the reaction on the analogy of chemical structure characterized by
Nuclear Magnetic Resonance (NMR). As a result, it was revealed that chemical
structures of coal should control gas generation of its pyrolysis.
Furthermore, this system is great effective in detailed characterization of coal
pyrolysis, because it is able to monitor continuously the reaction with in-situ to high
temperature (more than 600 C).
P7-3
Effect of Polycyclic Aromatic Hydrocarbons on the Fluidity of Coal in the
Thermoplastic Phase
Yuji Fujioka, Koji Saito and Kenji Kato
Nippon Steel Corporation, Japan
In the coke making process of steel making industry, coals in the coke oven soften at
about 400C. And after the continuous thermoplastic phase, it re-solidifies to form
semi-coke around 500C. Basic carbon structure of coke forms during the
thermoplastic phase. Some properties of coal (e.g. maximum fluidity measured by
constant torque (Gieseler) plastometer, total dilatation measured with dilatometer,
etc.) in the thermoplastic phase have been used intensively so far as industrially
important factors for coking. In particular, the viscosity of coal in the thermoplastic
phase has been investigated with the Gieseler plastmeter.
In this study, we investigated the effect of polycyclic aromatic hydrocarbons (PAHs),
nitrogen-contained aromatic hydrocarbons, and oxygen-contained aromatic
hydrocarbons, on the fluidity of coal with the Gieseler plastmeter in the
thermoplastic phase. The original coal samples we used were good-coking coal
(softening temperature: 386C, maximum fluidity temperature: 460C, re-
solidification temperature: 490C, maximum fluidity (MF): 972 dial division per
minute (ddpm)). We added 1 mass % PAHs, nitrogen-contained aromatic
hydrocarbons, and oxygen-contained aromatic hydrocarbons to each coal sample.
With the measurement of MF, we found the MF values of the sample with PAHs
(molecular weights 250-300) were improved from 972 ddpm to over 2000 ddpm.
Addition of nitrogen-contained aromatic hydrocarbons, or oxygen-contained
aromatic hydrocarbons hardly contributed to the improvement of MF, especially
anthraquinone decreases MF to 269 ddpm. Boiling point of the sample with PAHs
(molecular weights 250-300) is presumed over 450C. As for the effect on the
fluidity, PAHs in liquid phase decrease the viscosity in the thermoplastic phase. The
boiling point of anthraquinone is 380C, and is lower than softening temperature of
coal. Therefore, anthraquinone might operate in lower temperature of softening point
of coal, and its effect on coal is actualized in thermoplastic phase.
P7-4
Ash Characteristics in Co-Combustion of Lignite with Wood, Sewage Sludge
and Plastics
Zdenk Klika, Jana Seidlerov, Martin Stach, Marta Valaskova, Bohumr ech and coals for which CO2 adsorption isotherm were measured.
Vclav Roubek This paper presents some of these measurements and discusses the results. The
VB-Technical University Ostrava, Czech Republic
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
matter composition and properties of lignite, wood, bottom and fly ashes were
characterized. For this, mineralogical, chemical and coal petrography analyses of
solid samples as well as their leaching tests, unburned carbon, porosity, surface area
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
ash samples (regimes a and b) higher concentrations of Hg (about 2 ppm), As (about
800 ppm) and chlorine (about 400 ppm) are present than they are in bottom ash
(0.002 ppm Hg, 250 ppm As, and 220 ppm Cl). Also relating concentrations of above
elements determined in emissions are very similar for both combustion regimes
(about 0.010 mg.m-3 Hg, 0.027 mg.m-3 As and 24 mg.m-3 Cl). Contents of
unburned carbon are 1.7 and 1.0 wt.% in regime a) and b), respectively and the
percentages of unburned organic in unburned carbon is about 35% in both regimes.
62
POSTER SESSION 8
GEOSCIENCES & RESOURCES
P8-1
Water-Soluble Substances Present in Coals
Leon Kurczabiski and Roman j
Katowicki Holding Wglowy S.A., Poland
The authors presented their conclusions drawn from the research carried out on the
water-soluble mineral substances present in coals.
The research was carried on hard coals steam and coke ones produced in the
Upper-Silesian mines which are situated in the Southern part of Poland.
The research shows that water-soluble mineral substances can make one of the main
sources of chlorine and alkalis in coals and these substances are responsible for
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.
The important arguments include the quality of water used in the cleaning process
and they way in which the water-sludge circulation is effected in the mechanical
processing plant.
This paper refers to some of these problems.
P8-2
CO2 in Australian Coal Seams, Storage and Gas Diffusivity Properties at Low
Gas Pressure
A Saghafi and D. Roberts
CSIRO, Australia
Many Australian coals contains significant amount of carbon dioxide. This has been
the cause of numerous gas outbursts in coal mining in Australia in the last half a
century.
In order to control the gas outburst, thresholds limits on CO2 content of coal have
been set by coal mining industry. For instance in the coalfields of New South Wales
in Australia, a limit of 5 m3 per tonne of coal had been set as statutory limit to
ensure safe mining operations. This CO2 content limit was based empirically on
numerous outburst experiences concerning headings driven into geological
discontinuities and so far this limit have proved to be adequate.
Studies have been undertaken to qualify and quantify the nature of outbursts and the
role of gas type in the onset and the amount of energy released during such geo-
mechanical events. The capacity of coal to store carbon dioxide together with its
ability to release this gas is two factors among others which influence the
occurrences of gas outbursts. In order to accumulate enough energy to break
mechanically the coal and rocks extensive volumes of free gas is required. Therefore
for outburst to occur coal must have stored large amount of gas in adsorbed state and
then coal should allow this gas to be released in a short time. The adsorption capacity
and diffusivity of coal for CO2 have therefore prominent roles in allowing the
occurrences of outburst.
In the last decade these two factors namely coal CO2 storage capacity and the
diffusivity of gas through coal were investigated by the authors. Numerous
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
pressure and below 50 C temperature. A system for measurement of diffusivity was
also built to measure the flux of gas through solid coal under constant concentration
gradient and at ambient temperature. Coefficients of diffusivity were determined for
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.
P8-3
Energy Analysis of CO2 Absorption Process with Various Amine Solutions
Seok Kim and Hyung-Taek Kim
Ajou University, Korea
The CO2 absorption process in the flue gas widely utilizes alkanolamine solvents
such as MEA, DEA, TEA and MDEA. In the present investigation, CO2 absorption
process is simulated with AspenPlus and various amine solutions are applied in the
simulation to find out optimized operating condition for minimum energy usage. The
main purpose of this study is to find the optimum condition of CO2 absorption and
suggest the optimum operation condition to the actual bench-scale CO2 absorption
experimental set-up. For this purpose, bench-scale continuous CO2 absorber
(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
mainly dependent on the mole ratio of amine solution and input CO2 concentration.
The effects of the number of regenerator stage and reboiler heat duty variation on
CO2 separation rate is investigated as CO2 desorption increases with heat duty. Total
power requirement according as the flow rate variation of the flue gases and MEA
solution are also investigated and results represent that power requirement is mainly
depends on the variation of solution flow rate. Among the alkanoamine solvents used
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
rate are deduced. CO2 separation rate according to increment of number of stage
does not vary over 3 stages. Other operation parameters which effect on CO2
separation rate are analyzed through simulations. Exergy analysis to minimize power
requirement will be studied after analysis about operation parameters.
P8-4
Mercury Release Characteristics from Subbituminous Coal during Thermal
Upgrading
Zhenghe Xu, Guoqing Lu and On Yi Chan
University of Alberta, Canada
Mercury emission from coal-fired power generation process has been considered as
an environmental concern. As a mercury emission control option, mercury release
characteristics from a subbituminous coal during low temperature thermal upgrading
is determined. Mercury was found to be enriched in fine size fractions which also
show a higher mineral content. A rapid thermal upgrading at 673 K released
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
from about 21,000 to 26,000 kJ/kg was observed. A further increase in the upgrading
temperature produced a minimal further increase in mercury removal with an
obvious thermal energy loss. Mercury release characteristics were highly dependent
on the source of coal. Our laboratory tests demonstrated that thermal upgrading is a
viable method for mercury emission control.
P8-5
The Influence of Some Biogenous Factors on the Quality of Deposited Fly-Ashes
Maria Kusnierova, Andrea Slesarova and Maria Prascakova
Institute of Geotechnics of Slovak Academy of Sciences, Czech Republic
Peter Fecko
VB-Technical University Ostrava, Czech Republic
The results of the study on qualitative changes in energy fly-ash deposited in situ for
a different period of time (0, 5, 10 and 20 years) and laboratory model study of the
influence of contamination of fly-ash by selected species of autochthonous
Actinomycetaes have confirmed a positive influence of biogenous catalysis on the
mobility of studied macro elements: Al, Si, Fe and Ti.
P8-6
The Utilization of the Gypsum Product from the Flue Gas Desulfurization for
the Sulfate-Reducing Bacteria Cultivation
Alena Luptakova, Maria Kusnierova, Maria Bezovska
Institute of Geotechnics of Slovak Academy of Sciences, Slovak Republic
Peter Fecko
VB-Technical University Ostrava, Czech Republic
Industrial technologies for the desulfurization of combustion products produced
during the generation of the electric energy by the combustion of fossil fuels use the
limestone as an absorption agent. This process results in the formation of the gypsum
suspension which may be used as the source of sulphates for the sulphate-reducing
bacteria growth. The SRB represent a group of chemoorganotrophic and strictly
anaerobic bacteria. They include genera like Desulfovibrio, Desulfomicrobium,
Desulfobacter, Desulfosarcina, Desulfotomacullum, Thermodesulfobacterium,
Archaeoglobus, etc. The basic metabolic process of SRB is the anaerobic reduction
of sulphates in which organic substrate (lactate, malate, etc.) or gaseous hydrogen is
the electron donor and sulphate is the electron acceptor. The bacterial sulphate
reduction has widespread environmental effects and this process has potential as a
treatment process for acid mine drainage.
The aim of this work is to study of the utilization of gypsum product from flue gas
desulfurization for the sulfate-reducing bacteria cultivation, with the prospect of the
hydrogen sulfide production and the heavy metals elimination from acid mine
drainage.
POSTER SESSION 9
NON-FUEL UTILIZATION OF COAL
P9-1
Application Of Biologically Activated Brown Coal In Cu(II) Sorption.
Maria Prascakova and Maria Kusnierova
Institute of Geotechnics of Slovak Academy of Sciences, Slovak Republic
Alexandra Simonovicova
Comenius University, Slovak Republic
63
Adsorption of cooper ion from aqueous solutions on biologically activated brown
coal was investigated. Four families of adsorbents were prepared from brown coal by
microorganisms activity. There were used microorganisms such as Aspergillus niger,
Aspergillus clavatus, Penicillium glabrum and Trichoderma viride. Activated
samples of coal were characterised by the values of internal surface, the sorption
isotherm has been constructed and the maximum capacity of the adsorbent has been
determined.
P9-2
Carbon Nanotube Production from Heavy Hydrocarbons
Yuma Kamiyama, Koh Kidena and Masakatsu Nomura
Osaka University, Japan
Carbon nanotube is a material that has been attracting intensive interests. Several
methods for its production have been developed: for example, arc-discharge, laser
ablation and vapor deposition. As one of the method for large-scale production,
catalytic chemical vapor deposition is promising. In this paper, the authors
investigate the possibility for the production of carbon nanotube from heavy
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
production of nanotube was confirmed on inner surface of quartz tube at 750-850
deg-C. Then, asphaltene and/or maltene fraction from natural asphalt were tested to
obtain promising results. Under selected reaction conditions including the reaction
temperature and the amount of catalyst, carbon natotube with a diameter of 30-60 nm
was successfully found.
POSTER SESSION 10
GAS TURBINES & FUEL CELL FOR SYNTHESIS GAS & HYDROGEN
APPLICATIONS
P10-1
DOE FE Fuel Cell-Turbine Hybrid Development
Mark C. Williams, Richard A. Dennis, David Tucker and Norman Holcombe
U.S. Department of Energy, NETL, USA
The U.S. Department of Energys (DOE) Office of Fossil Energys (FE) National
Energy Technology Laboratory (NETL), in partnership with private industries and
others, is leading the development and demonstration of high efficiency solid oxide
fuel cells (SOFCs) and fuel cell/turbine hybrid power generation systems for near-
term distributed generation (DG) markets with emphasis on premium power and high
reliability. NETL manages research under the Solid-State Energy Conversion
Alliance (SECA) initiative for the development and commercialization of modular,
low cost, and fuel flexible SOFC systems. The SECA initiative, through advanced
materials, processing and system integration research and development (R&D) will
bring the fuel cell cost to $400 per kilowatt (kW) for stationary and auxiliary power
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.
Moreover, the President of the U.S. has launched us into exploring a new hydrogen
economy. The logic of a hydrogen economy is compelling. The movement to a
hydrogen economy would accomplish several strategic goals. The U.S. can use its
own domestic resources solar, wind, hydro, and coal. The U.S. uses 20 percent of
worlds oil but has only 3 percent of resources. Also, the U.S. can reduce
greenhouse gas emissions. Clear Skies and Climate Change programs aim to reduce
carbon dioxide (CO2), nitrogen oxides (NOx), and sulfur dioxide (SO2) emissions.
SOFCs have no emissions and hence figure significantly in these DOE strategies. In
addition, DG systems with SOFCs, reforming, and energy storage have significant
benefit for enhanced security and reliability. The use of fuel cells is expected to
bring about the hydrogen economy. However, commercialization of fuel cells is
expected to proceed first through portable and stationary applications. Like all fuel
cells, the SOFC will operate even better on hydrogen than conventional fuels. The
SOFC hybrid may be a key part of the FutureGen plants. FutureGen is a major new
Presidential initiative to produce hydrogen from coal. The highly efficient SOFC
hybrid plant will produce electric power and other parts of the plant could produce
hydrogen and sequester CO2. The hydrogen produced can be used in fuel cell cars
and for SOFC DG applications.
P10-2
Numerical Study on the Gas Turbine Combustor Burning Coal- or Heavy
Residue Oil-Derived Gas as Alternative Fuel
Chan Lee
University of Suwon, Korea
Je Young Seo
Kangrim Industries Co., Korea
Yongseung Yun
Institute for Advanced Engineering, Korea
A CFD (Computational Fluid Dynamics) research is conducted for the investigation
of the fuel alteration of MBTU (medium-Btu) gas in the IGCC gas turbine combustor
which is originally designed with natural gas. The computational analysis method of
the gas turbine combustor is constructed by incorporating MBTU gas reaction and
fuel NOx models into the CFD scheme of the commercial code, FLUENT, and then
it is applied to a small annular-type gas turbine combustion chamber. With the use of
the present analysis method, comparisons are made on the flow velocity, the
chemical species and the temperature distributions, and on the flame shape and
behavior of gas turbine combustors firing natural gas or MBTU gases (coal gas,
heavy residue oil gas). Furthermore, the NOx formation characteristics of the
combustor are analyzed,. The computation results show that the MBTU-gas firing
cases give higher flame temperature and longer flame zone than the natural case.
Thermal and fuel NOx.emissions from the MBTU-gas firing combustor is more
produced due to the higher temperature characteristics in the combustor. Based on
the computed analysis results, the present study presents the directions for the
redeisgn and the design modification of IGCC gas turbine combustor firing MBTU
gas as alternative fuel.
P10-3
Process Analysis for Hydrogen Production by Reaction-Integrated Novel
Gasification (HyPr-RING)
Shi-Ying Lin and Michiaki Harada
Center for Coal Utilization, Japan
Yoshizo Suzuki and Hiroyuki Harano
National Institute of Advanced Industrial Science and Technology, Japan
Hydrogen production by the reaction-integrated novel gasification (HyPr-RING)
method was first proposed in 1999. This method involves the reactions of coal and
CaO with H2O, that is, a combination of exothermic and endothermic, gas-
production and gas-separation reactions, in a gasifier to produce H2. The equipment
for the HyPr-RING process consists mainly of a gasifier, a sorbent regenerator, and
several heat exchangers. In this study, process components and the mass and energy
balances were analyzed by thermodynamic calculations. A fuel gas comprising an
equilibrium mixture of 91% H2 and 9 % CH4 can be obtained by gasification of coal
at 923 K and 3.0 MPa. The amount of the fuel gas produced was calculated to be
equivalent to 1.4 Nm3/kg-coal, giving a high cold-gas efficiency of 0.77. The
equilibrium H2 and CH4 compositions are sensitive to the amount of steam
contained in the product gas.
The energy contained in the coal is used in the gasifier and the regenerator in a ratio
of about 3/2. This gives a good energy balance, and a high cold gas efficiency for
the process.
P10-4
Investigation of Tetralin Dehydrogenation upon Transition-Metal Catalysts
Pham Tien Dung, Tetsuya Satoh, Masahiro Miura and Masakatsu Nomura
Osaka University, Japan
Dehydrogenation of tetralin was found to proceed smoothly at 220 300 oC by the
use of supported transition-metal catalysts. Some palladium catalysts supported on
activated carbon fibers showed particularly high activities. The reaction was
conducted under various conditions to enhance its efficiency and elongate the
catalyst time.
POSTER SESSION 11
LOW RANK COAL UTILIZATION
P11-1
Decolorization of Coal Humic Acid for Hydrogen Production by Reaction-
Integrated Novel Gasification
Yaeko Kabe and Takafumi Osawa
Tamagawa University, Japan
Atsushi Ishihara and Toshiaki Kabe
Tokyo University of Agriculture & Technology, 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
of fungal extracellular enzymes. We isolated several white-rot fungi able to
decolorize and depolymerize coal humic acid. The last year, we isolated another two
excellent white-rot fungal strains, WO-4 and WT-5 from white-rotten wood. In this
study, these two strains and white-rot fungal strain, FTN, which was isolated early in
our study and has high ability, were investigated on the decolorization of coal humic
acid.
Four kinds of extracellular enzymes, laccase (Lac), aryl alcohol oxidase (AAO),
lignin peroxidase (LiP) and manganese peroxidase (MnP) have been known as
extracellular enzymes able to depolymerize macromolecules having complicated
structures such as lignin and coal humic acid. The relation between these four
extracellular enzymes produced by above 3 kinds of white-rot fungi and the
decolorization of coal humic acid were investigated.
As the results, the decolorization rate of fungal strain FTN was the highest and the
ratios of the decolorization were 50% for 7days and 73% for 21days. Those with
fungal strain WO-4 were 42% for 7days and 65% for 21days and those with fungal
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
the decolorization of coal humic acid but for fungus FTN, AAO also might concern
somewhat the decolorization of coal humic acid. As for fungal strain WO-4, Lac
activity appears in place of disappearance of MnP activity in the late incubation
period, it seems that both of MnP and Lac concern the decolorization of coal humic
acid.
P11-2
Upgrading of Solvent for HyperCoal (ash-free coal) Production
Nao Kashimura, Kensuke Masaki, Toshimasa Takanohashi, Shinya Sato, Akimitsu
Matsumura, Ikuo Saito
National Institute of Advanced Industrial Science and Technology (AIST), Japan
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
used as a feedstock for gas turbines.
Preliminary work showed that crude methylnaphthalene oil (CMNO) gave higher
extraction yields at 360oC than light cycle oil (LCO). The former contains more
nitrogen-containing compounds than the latter. Furthermore, addition of nitrogen-
containing compounds, such as N-methyl-2-pyrrolidinone, enhanced the extraction
yields with LCO.
In this work, an attempt was made on searching a powerful solvent to produce
HyperCoal more efficiently.
Wyodak Anderson subbituminous coal was extracted at 360C with flowing CMNO
or its derived materials. The original CMNO gave 42% of the extraction yield, while,
the HCl solubles (AC-S) and methanol-water mixture solubles (MW-S) gave high
yields, 63 and 73%, respectively. GC-AED and GC-MS analyses of CMNO showed
that nitrogen-containing compounds in CMNO were mainly quinoline, isoquinoline,
indole and methylquinoline. MW-S was richer in indole than AC-S. When mixtures
of 1-methylnaphthalene and quinoline were employed as extraction solvents, the
extraction yields were in the range of 33 43%, while, a mixture of quinoline, 1-
methylnaphthalene and indole reached 53% of the yield. Thus, the containing of
indole gave rise to the difference in the extraction yield between AC-S and MW-C.
The details of effect of additives will be presented.
P11-3
Pyrolysis and Kinetic Studies on Mixed Solvent Swelling of Malaysian Lignite
Using Thermogravimetric Analyzer
Mohd Fauzi Abdullah, Khudzir Ismail and Mohd Azlan Mohd Ishak
University Technology MARA, Malaysia
The volumetric swelling ratios of Mukah Balingian, Malaysian lignite have been
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.
benzene, cyclohexane and n-hexane) solvents at room temperature (30C) and at
ambient pressure. The results obtained thus far showed that the swelling ratios of
tetralin mixed with H-bonding exhibit higher swelling ratios than with the non-H-
bonding solvents. Moreover, the swelling ratios decreased with increased in the
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.
The effect of mixed solvent pre-swelled coal towards thermal characteristics of both
untreated and pre-swelled coal was investigated using the thermogravimetric
analyzer, whereby the activation energy and reaction rates were calculated and
determined.
P11-4
Basic Study on Mineral Removal from Coal - The Influence of Mineral
Distribution and Size of Pulverized Coal on Characteristics of Mineral Removal
Yoshiko Hiei, Hiromi Shirai and Hideki Kanda
CRIEPI, Japan
From the viewpoint of the use of low grade coal that contain lots of minerals and to
decrease the amount of ash residue from coal fired power plants, it is imperative to
develop a simplified mineral removal method at the mine sites. The influence of
mineral distribution, mineral content and size of pulverized coal on characteristics of
mineral removal from coal was investigated to develop an effective removal method
of mineral matter. The influence of the mineral distribution on removal ratio of
mineral matter from coal was evaluated by a specific gravity separation method.
It is found the mineral content in the raw coal affects that mineral removal ratio. The
decreasing particle size of minerals in the raw coal, removal ratio becomes smaller
and smaller. On the other hand, the shape factor of the minerals does not affect the
removal ratio. In addition, mineral removal ratio is increasing with the decreased
particle size of pulverized coal. These results showed that characteristics of mineral
removal from coal are influenced by mineral content, particle size of minerals and
particle size of pulverized coal. It is important to develop a pulverizing method,
which promotes a high effect while considered the influence of mineral content and
size of mineral matter and size of crushed coal.
 POSTER SESSION 12
COAL PRODUCTION & PREPARATION
P12-1
Solution of Environmental Policy in Okd, A.S., Mine Lazy,O.Z. Orlova
Horst Gondek, Lenka Landryova and Peter Fecko
VSB - Technical University of Ostrava, Czech Republic
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
analysis of individual sources of pollution upon proper solution of problem. Total
solution is divided to organizational part as well as proper technical realisation. The
improvement of the environment relates to both own mine and close surroundings. The
obtained results in mentioned mine including cost for their realization are shown in the
conclusion.
P12-2
Research for Mining Optimization and Biogas Utilization with Minimizing its
Escape into the Atmosphere
Horst Gondek, Lenka Landryova and Peter Fecko
VSB - Technical University of Ostrava, Czech Republic
Directive of Council No. 91/156/EEC states the Strategy of the European Union (EU)
for municipal waste management. According to this the member states must prohibit
the negative impact of landfills on the environment. This policy has been worked into
the standards of the Czech Republic from which SN 83 80 34 (Landfill
Degasification) is the most important one. It is stated there, that municipal landfills
with more than 10 % of biodegradable content, a height of more than 2.5 m and
capacity larger than 10.000 m3, must have ensured, among others, that the rising gas
from them will be disposed.
There about 160 landfills in the Czech Republic, but only about 50 of them can be,
regarding the concentration of methane gas, considered for the possibility of co-
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
methane gas, but also these must have their biogas disposed of.
This paper brings the newest findings and partly documents the experience gained
from a research done on the mining optimization and biogas utilization. The latest
results coming from analyses done on degasification of landfills in Czech Republic as
well as at some selected landfills abroad are given. The sources for methane gas
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
escape into the atmosphere are described in detail. Economic aspects are shown on real
examples. This contribution is supported by the granted project of GACR 105/04/1342
for the year 2004/2005.
P12-3
Desulfurization of Tabas Coal (C1 Seam) Based On Characterization Studies
E. Jorjani
Azad University, Iran
The presence of huge reserves of coal in Tabas area is caused to be one of the
promising coal mines in Iran. The average percentage of sulfur in different layers
namely B1, B2, C1, C2, D has been reported 3.49, 1.35, 1.6, 1.11and 3.4 respectively.
In order to identify the type and distribution of sulfur in coal , a representative sample
from all effective working levels especially C1 layer has been taken and subjected to
characterization studies. Because of fine distribution of pyrite in organic matters and
high percentage of organic sulfur (46% Stotal), we predict that removal of sulfur is
possible with chemical and microbial methods. Two new techniques (a) microwave
irradiation/Peroxyacetic acid (PAA) washing (b) PAA + Air oxidation / sodium
butoxide leaching were used as chemical desulfurization. Microorganisms isolated
from Zyrab coal washery plant tailing dump and Tehran refinery oily soils were used
on microbial desulfurization. Desulfurization of microwaved sample with peroxyacetic
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
extent (35%). PAA in low temperature and time (at 45oC for 40 min) , also air
oxidation for 1 hours at 100oC was used as pretreatment method for desulfurization
with sodium butoxide. On optimized conditions (at 150oC for 90 min) about 60,74
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,
shaking rate of 150 rpm, 50 mM of ferrous iron and leaching time of 10 days, mixed
culture isolated from coal washery plant tailing dump could remove pyritic and total
sulfur 91.84 and 53.5 % respectively. Also, 36% of organic sulfur removed by
Rhodococcus Sp. P32C1 bacteria isolated from Tehran refinery oily soils.
65
POSTER SESSION 13
GENERAL TOPICS
P13-1
Co-Production of Premium Coal Slurries as Alternatives to Diesel Oil and
Heavy Fuel Oil
Fu Xiaoheng Wang Xinwen Wang Xinguo and Wang Zune
China Univ. of Mining & Tech., P.R. China
Physical process developed for coal cleaning to give two premium products, the
ultra- clean coal and conventional clean coal, and preparation of coal slurries thereof,
including: - Ultra-fine grinding (usually 10m) of coal for liberation of mineral
matters finely disseminated in the organic matrix in parent coal;
- Selective coagulation of micronized pure coal particles, forming loose coal
aggregates of larger sizes;
- By froth flotation, the high-ash constituents being firstly discarded and the rest
separated into the froth product, an ultra-clean coal, and the suspension product, a
conventional clean coal;
- Dewatering of products and tailing separately by press filter;
- Slurries preparation: with ultra-clean coal, the slurry as alternative to diesel oil, and
with conventional clean coal, the slurry as alternative to heavy fuel oil.
Equipment specifically developed for the process:
- Ultra-fine grinding mill with low power consumption;
- Efficient facility for selective coagulation of ultra-fine coal in pulp;
- Compact facility for preparing slurry from the sticky filtering cake.
Schematic diagram of the process and example of its material balance:
- The process flowsheet;
- Material balance as an example.
Cost-effectiveness analysis:
- Monetary input and output for slurry production;
- Amount of oils substituted;
- Profitability related to oil price.
P13-2
Conversion and Operation of a Diesel Engine Fueled by Purified Coal Slurry
Wang Xinwen Fu Xiaoheng Wang Xinguo Wang Zune
China Univ. of Mining & Tech., P.R. China
Zhang Bingjian Liu Ruihua
Xinya Industry Co. Ltd., P.R. China
Diesel engine conversion to adapt coal slurry fuel
- Principal parts of the engine to be converted: the fuel injector and fuel pump, both
being of plunger-type;
-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.
The coal slurry fuel
- The purified coal;
- Fuel composition and its characteristics.
Test rig facility and apparatus
- The small single-piston and high-speed diesel engine;
- Schematic diagram of the test rig;
- The Eddy-Current Dynamometer;
- The portable KM9000 gas analyzer;
- Procedure of test operation.
Operation experiment of the diesel engine
- Operation of the engine at different loading on
Coal slurry fuel,
Diesel oil;
- Fuel consumption and heat efficiency;
- Emission measurement;
- Analysis of the operation data on coal slurry fuel vs diesel oil
Heat efficiency slightly lower; NOx emission much lower.
P13-3
A Research into the Compound Sulfur Fixing Additives in Coal-Water-Slurry
Yang Qiaowen, Wu Lijun, Chu Zhuwei, Lizong Liu, Zuna Wang and Wu Huixiang
China University of Mining and Technology, P.R. China
In this thesis, investigations into sulfuric release pattern in Xinwen slurry-making
coal and the properties of compound sulfur-fixing additives were made, relying on
above results, we discussed the effect of sulfur-fixing additives on the rheological
behavior of coal-water-slurry and the mechanism of sulfur-fixing in coal-water-
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 its 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 1980s 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.

66