svEPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-80-015b
January 1980
Experimental/
Engineering Support for
EPA's FBC Program:
Final Report - Volume II.
Particulate, Nitrogen Oxide,
and Trace Element Control
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Mention of trade names or commercial products does not con-
stitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-80-015b
January 1980
Experimental/Engineering Support
for EPA's FBC Program:
Final Report - Volume II.
Paniculate, Nitrogen Oxide,
and Trace Element Control
by
D.F. Ciliberti, M.M. Ahmed, N.H. Ulerich,
M.A. Alvin, and D.L Keairns
Westinghouse Research and Development Center
1310Beulah Road
Pittsburgh, Pennsylvania 15235
Contract No. 68-02-2132
Program Element No. INE825
EPA Project Officer: D. Bruce Henschel
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Westinghouse R&D Center is carrying out a program to provide
experimental and engineering support for the development of fluidized-
bed combustion systems under contract to the Industrial Environmental
Research Laboratory (IERL), U. S. Environmental Protection Agency (EPA),
at Research Triangle Park, NC. The contract scope includes atmospheric
(AFBC) and pressurized (PFBC) fluidized-bed combustion processes as they
may be applied for steam generation, electric power generation, or pro-
cess heat. Specific tasks include work on calcium-based sulfur removal
systems (e.g., sorption kinetics, regeneration, attrition, modeling),
alternative sulfur sorbents, nitrogen oxide (NOX) emissions, particulate
emissions and control, trace element emissions and control, spent sorbent
and ash disposal, and systems evaluation (e.g., impact of new source per-
formance standards (NSPS) on FBC system design and cost).
This report contains the results of work defined and completed
under the particulate, NOX, and trace element control tasks of the con-
tract. Work on these tasks was performed from January 1976 to January
1979 and is documented in the following EPA contract reports:
• The present report, which presents perspective on particu-
late profiles and control requirements for FBC systems,
construction of a high-pressure and -temperature particu-
late control test facility, perspective on available NOX
emission data and mechanisms of NO,, generation and reduc-
x
tion, projections of trace element fate in FBC systems,
and evaluation of available trace element emission data
• Report on the "Effect of SC-2 Emission Requirements on
Fluidized-Bed Combustion Systems: Preliminary Technical/
Economic Assessment," issued in August 1978 (EPA-600/7-78-
163, NTIS PB 286 871/7ST).1
iii
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• Report on "Evaluation of Trace Element Release from
Fluidized-Bed Combustion Systems," issued in March 1978
(EPA-600/7-78-050, NTIS PB 281 321).2
The final report also includes:
Volume 1: "Sulfur Oxide Control," EPA-600/7-80-15a
Volume 3: "Solid Residue Study," EPA-600/7-80-15c
Volume 4: "Engineering Studies," EPA-600/7-80-15d.
iv
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ABSTRACT
Particulate, nitrogen oxide, and trace element control are investi-
gated for atmospheric and pressurized fluidized-bed combustor AFBC and
PFBC systems. A detailed particle profile model was developed to permit
integrated analysis of particle size distributions, particle carry-over
rates, and control efficiency in these systems. An experimental high-
temperature/high-pressure particulate control test facility was con-
structed to permit investigation of alternative particulate control
equipment performance. Shakedown has been completed and the facility is
operational. Available data on NOX formation-decomposition are reviewed
to assess formation-decomposition mechanisms and to identify significant
operating parameters. These considerations provide the basis for per-
forming engineering assessments of NOX control. Thermodynamic projec-
tions of trace and minor element profiles for AFBC and PFBC operating
conditions are presented. These provide a first-level approximation for
the distribution of volatile and condensed phases present and a basis
for further work on potential toxicity and process constraints.
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TABLE OF CONTENTS
Page
1 INTRODUCTION 1
2 SUMMARY AND CONCLUSIONS 3
Particulate Control 3
Nitrogen Oxide Emissions 5
Trace Elements 7
3 RECOMMENDATIONS 9
Particulate Control 9
Nitrogen Oxide Emissions 9
Trace Elements 10
4 PARTICULATE CONTROL 12
Effect of Particulate Emission Requirements
on FBC Systems 12
Design and Operating Considerations for PFBC
Particulate Control Systems 14
High-Temperature, High-Pressure Gas-Cleaning
Particle Removal Equipment 39
Test Facility 41
Particulate Sampling 54
5 NITROGEN OXIDE EMISSIONS 60
Literature Review 60
Data Analysis 67
Assessment 75
6 TRACE ELEMENT RELEASE 78
Introduction 78
Thermodynamic Projections 89
Assessment 109
7 REFERENCES 114
vii
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TABLE OF CONTENTS (Continued)
Page
APPENDICES
A NITROGEN OXIDE EMISSIONS IN FLUID-BED COMBUSION
EXPERIMENTS
B LITERATURE SUMMARY OF NITROGEN OXIDE EMISSIONS IN
FLUIDIZED-BED COMBUSTION 141
C EFFECTS OF PRESSURE, EXCESS AIR, AND GASEOUS SULFUR
CONTENT ON VOLATILE TRACE AND MINOR SPECIES AT
EQUILIBRIUM IN FBC PROCESSES 149
D EQUILIBRIUM CALCULATIONS FOR FBC OPERATION AT 100
PERCENT EXCESS AIR, 90 PERCENT SULFUR REMOVAL,
AND 1013 kPa TOTAL PRESSURE 159
viii
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LIST OF FIGURES
Page
1. Schematic of Solids Flow Diagram 1
2. Fractional Efficiency of Cyclones 24
3. Grade Efficiency for Ambient Temperature and Pressure, 25
Laboratory-Scale Granular-Bed Filter
4. Baghouse Performance at Sunbury Steam Electric Station 26
5. Particle Size Distributions 28
6. Elutriation Correlation of Yagi and Aochi 28
7. Loading from Recycle Cyclone (Ash + Sorbent) , 31
8. Combined Sorbent and Ash Size Distributions from Final 31
Filter
9. Loading to Turbine as Function of Ca/S and Attrition for 33
Fabric-Filter Performance
10. Loading to Turbine as Function of Ca/S and Attrition for 33
Granular-Bed Performance
11. Incremental Cost of Electricity and Life of Turbine 37
Blades and Vanes as a Function of Particulate Loading and
Particle Erosivity
12. Schematic Diagram of Westinghouse Hot-Gas Cleanup 42
Facility
13. Particulate Control Test System and Support Facility 42
14. Centrifugal Compressor 43
15. Three-Stage Cooper Bessemer Compressor 44
16. Test Passage Air Preheaters 45
17. Fuel Blend Tanks and Facilities 46
IX
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LIST OF FIGURES (CONT'D)
Page
18. High-Temperature and -Pressure Partlculate Removal Test 47
Facility (Side Inlet)
19. High-Temperature and -Pressure Particulate Removal Test 47
Facility (Split Inlet)
20. High-Temperature and -Pressure Particulate Removal Test 48
Facility (Top Inlet)
21. High-Temperature and -Pressure Test Facility Pressure 49
Vessel
22. High-Temperature and -Pressure Test Facility Pressure 50
Vessel with Aerodyne Installed
23. High-Temperature and -Pressure Test Facility Pressure 51
Vessel Aerodyne Installation
24. High-Temperature and -Pressure Test Facility Control Room 52
25. High-Temperature and -Pressure Test Facility 53
26. Schematic of Sampling Train 56
27. Photograph of Particulate Sampling Train 57
28. Particulate Injection System 58
29. Effect of Fluidized-Bed Gombustor Size 70
30. Effect of Coal Nitrogen Content - AFBC 70
31. Effect of Coal Nitrogen Content - PFBC 70
32. Effect of Temperature and Excess Air - PFBC 71
33. Effect of Temperature and Excess Air - AFBC 71
34. Plot of Residuals - Statistical Analysis 73
35. Regression Fit NOX Projections 74
36. NO Decomposition Model - Pseudo-First-Order Rate Constants 76
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LIST OF TABLES
Page
1. Illustrative Factors Determining Particles Leaving 17
Fluidized-3ed Combustor
2. High -Temperature and -Pressure Test Facility 55
3. AFBC NO.,, Emission Data 68
A.
4. Fusion of Mineral Particles in a Coal Gas Flame - 80
Typifying Commercial Ash Products
5. Average Trace Element Content of Regional Coals throughout 81
the U. S.
6. Average Trace Element Content of Ash from U. S. Coals of 82
Various Ranks
7. Trace Elements in Coal and Sorbent Materials 83
8. Trace Element Concentration as a Function of Particle 86
Size as Reported by Lyon
9. Trace Element Concentration as a Function of Particle 87
Size as Reported by Cowherd
10. Trace Element Concentration as a Function of Particle 88
Size as Reported by Cato
11. Coal Composition 89
12. C-H-N-0-S-C1 Species Considered in Fluid-Bed Combustion 92
Reaction
13. Trace and Minor Species Considered in Fluid-Bed 93
Combustion Reactions
14. Partial Pressure of Gaseous Compounds and Moles of 105
Condensed Compounds in PFBC Processes at Combustion
Temperatures
15. Summary of Trace and Minor Element Reactions in. Fluidized- 107
Bed Combustion Systems
xi
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NOMENCLATURE
AFBC Atmospheric Fluidized-Bed Combustion
ANL Argonne National Laboratory
B&W Babcock and Wilcox
EPA U. S. Environmental Protection Agency
CTIU Component Test and Integration Unit
Conoco Consolidated Coal Company
FBC Fluidized-Bed Combustion
ICP Inductively Coupled Plasma Emission Spectroscopy
MIT Massachusetts Institute of Technology
NAA Neutron Activation Analysis
NCB National Coal Board, London, UK
PER Pope, Evans and Robbins
PFBC Pressurized Fluidized-Bed Combustion
SSMS Spark Source Mass Spectroscopy
PARTICULATE CONTROL
A rate constant in expression for shrinkage of solid particles,
-1
sec
A mass flow rate of attrited solids,g/s
D diameter of solids, microns
D smallest solids diameter, microns
m
D largest solids diameter, microns
F mass flow of solids in feed, g/s
F mass flow of solids in outflow, g/s
F mass flow of solids in carry-over, g/s
H height of unfluidized bed, cm
k rate constant in expression for shrinkage of solid particles,
-1
sec
K elutriation constant, sec
m mass of an individual solid particle, g
P pressure, atm
p size distribution of attrited solids, cm
3.
xii
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P^ size distribution of solids in bed, cm
p.. size distribution of solids in outflow, cm
1 -1
P? size distribution of solids in carry-over, cm
dD .
R=-: — rate of shrinkage of solid particles, cm/s
t t ime , s
T temperature, °C
UQ superficial velocity of fluidizing medium, cm/s
W total mass of solids in bed, g
z cumulative size distribution function, cm
z cumulative size distribution of the combined (A +F ) stream, cm"
A difference
H efficiency of solids removal device
2
p density of solids, g/cm
S
e bed porosity
summation
NITROGEN OXIDE CONTROL
h bed depth, m
k specific reaction rate constant, (hr)
p pressure, kpa
T temperature, °C
U superficial gas velocity, m/s
X percent excess air
TRACE ELEMENTS
G Gibbs free energy
H° standard state molar enthalpy
S° standard state molar entropy
Cp° standard state specific heat
M molar chemical potential
M° molar chemical potential at unit fugacity
n moles
R universal gas constant
xiii
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ACKNOWLEDGMENT
We want to express oar high regard for and acknowledge the contri-
bution of D. B. Henschel who served as the EPA. project officer.
P.P. Turner and R. P. Hangebrauck, Industrial Environmental Research
Laboratory, EPA, are acknowledged for their continuing contributions
through discussions and support of the program.
We gratefully acknowledge the contributions of A. Y. Ranadive for
his assistance in developing the particle profile model and computer
program and in performing FBC evaluations; of personnel at the Westing-
house Advanced Goal Conversion Department, who, under the supervision of
W. J. Havener, installed and operate the particulate control test facil-
ity; of E. A. DeZubay for his work on NOX emissions; of C. A. Hill in
developing an NOX emission data base; and of R. W. Liebermann who devel-
oped the free-energy minimization programs that form the basis of the
trace element analysis. The particle profile-turbine performance anal-
ysis is based on an extension of the evaluation presented in Volume IV
of the report. J. R. Hamm and R. W. Wolfe are acknowledged for their
coordination of the turbine analysis work. R. A. Wenglarz contributed
to the review of and subsequent extensions to the turbine tolerance
modeling.
xiv
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1. INTRODUCTION
The design of fluidized-bed combustion (FBC) systems for electric
power generation, industrial steam or process heat, or cogeneration
applications depends on an understanding of particle history, particu-
late control, and nitrogen oxide (NOX) emission and a perspective on the
fate of trace elements in order to achieve energy cost and environmental
objectives and requirements. Fluidized-bed combustion systems can offer
energy, cost, and environmental advantages over alternative processes if
the system design incorporates an understanding of the component/
subsystem performance, limitations, and available trade-offs as a func-
tion of operating and design parameters. Particulate carry-over and
control equipment performance, and NOX generation and reduction mechan-
isms represent two subjects that must be understood when design and
operating parameters that will achieve the process objectives and
environmental requirements at the lowest energy cost are selected. An
understanding of trace element history in FBC systems is important for
process considerations in pressurized fluidized-bed combustion (PFBC)
systems and for identifying any potential environmental concerns. The
results reported in this document extend our previous understanding of
these phenomena to provide a basis for FBC design and performance
evaluation.
An understanding of the particle loadings and size distributions of
particulate emissions and of the control of particulate emitted from FBC
processes is important for successfully meeting both environmental and
process constraints. The goal of the particulate work has been to
develop methods that give consistent and reliable estimates of particu-
late emissions for FBC processes. These, in turn, can be used to pro-
ject both the environmental and the economic consequences of FBC
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technology. Three areas of work are presented: the impact of emission
requirements and fluidized-bed combustor design and operating conditions
on FBC particulate control requirements and plant economics; the utili-
zation of a particle profile model to develop an understanding of the
critical fluidized-bed combustor and particulate control system design
parameters in order to meet turbine performance and emission require-
ments for FBC systems; and the construction of a high-temperature high-
pressure (HTHP) test facility to investigate particulate control equip-
ment performance and provide experimental data on new and conventional
devices.
An understanding of the mechanisms of NOX generation and destruc-
tion in FBC is required in order to define the design and operating
parameters necessary for minimizing NOX emissions and achieving environ-
mental standards. We have carried out work in two areas to develop such
an understanding: the statistical treatment of data presently available
that may present clues to the reaction mechanisms and the evolution of a
model to permit selection of design and operating criteria and to pro-
ject plant performance.
In assessing the environmental impact of FBC processes one must
determine the chemical fate of trace and minor elements to assess their
potential toxicity and their potential for corrosion or deposition in
process equipment. In previous work reported under this contract, West-
inghouse applied a thermodynamic model to project the chemical fate (and
emissions) of four trace elements in coal-fired FBC systems: lead (Pb),
beryllium (Be), mercury (Hg), and fluorine (F). This work has been
extended to project the chemical fate in the FBC system of eight addi-
tional metals by using the same thermodynamic model: aluminum (Al),
iron (Fe), titanium (Ti), cobalt (Co), chromium (Cr), manganese (Mn),
molybdenum (Mo), and nickel (Ni). An evaluation of available trace ele-
ment emission data from conventional boilers and FBC systems is
presented.
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2. SUMMARY AND CONCLUSIONS
Westinghouse has completed work that provides perspective on par-
ticulate control, NOX emissions, and the fate of trace elements in
fluidized-bed combustion systems.
PARTICULATE CONTROL
• A particle profile model for fluidized-bed combustion sys-
tems has been developed.
• The effect of the degree of gas cleaning on the cost of
electricity and turbine blade life for a FBC system was
developed by combining the particle profile model with an
existing turbine erosion model.
• The description and status of a high-temperature and
-pressure (HTHP) particulate control test facility is
discussed.
Particle Profile Model
Westinghouse has developed a particle profile model that is a
powerful tool for the parametric assessment of the effects on particle
emissions of such operating and design parameters as:
• Superficial velocity
• Attrition characteristics
• Bed depth
• Recycle cyclone design
• Calcium-to-sulfur (Ca/S) ratios
• Sorbent feed size distributions
• Elutriation characteristics.
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The model in its current state yields qualitative results. Its
greatest potential lies in its ability to give quick, consistent results
that indicate major effects and trends.
PFBC Particle Profile-Turbine Performance Analysis
The application of the model to a specific set of design and
operating conditions (described herein) using alternative particle
cleanup performance is used to illustrate the determination of turbine
blade life and electricity costs and to provide perspective on the
important design and operating parameters.
Some conclusions from the analysis are:
• Analytical tools are available to permit analyses that can
give perspective on trade-offs between FBC, gas cleaning,
and turbine design and operating parameters.
• Particle size distribution and materials erosion charac-
teristics are two important factors that determine turbine
life. Projections using particle size distributions from
filters with 5 to 20 percent >5 vim particles and nickel-
based turbine alloy erosion characteristics indicate load-
ings as low as 0.0046 g/m3 (0.002 gr/scf or 3.7 ppm) could
be required to achieve acceptable performance. Reducing
the >5 ym particle loading and erosion-resistant coatings
would increase this tolerance.
• Turbine tolerance requirements to achieve acceptable life
will control the selection of particle control equipment
for the specific case analyzed. Particulate control per-
formance to reduce the >5 urn particles and improved mate-
rial erosion characteristics could result in tolerance
requirements approaching 0.039 g/m3 (0.017 gr/scf or
30 ppm) which is the equivalent environmental limit for a
20 percent excess air PFBC design. Standards for fine
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particulates could also result in environmental require-
ments controlling the selection of particulate control
equipment.
• The filter design is of primary importance since the fil-
ter performance determines the particle size distribution
and loading presented to the turbine and emitted to the
environment.
• The selection of feed materials and the fluidized-bed cora-
bustor design will affect particle loading to the turbine
and the environment for a given filter performance. A
tenfold increase in attrition rate may increase mass load-
ing to the turbine and environment by a factor of 2.
• Ash particle size distribution, sorbent attrition rates,
and attrited sorbent size distributions are critical
parameters since they determine the bulk of material pre-
sented to the final filter.
• The design of the fluidized-bed combustor so as to mini-
mize the sorbent requirements and particle attrition is
important for minimizing particles in the turbine and the
environment.
Particulate Control Test Facility
A new HTHP particulate control test facility, along with such sub-
systems as the dust injection and hot, pressurized sampling systems, has
been constructed. The system described is one in which pilot-scale
experimentation can be undertaken at actual PFBC conditions without the
cost and complications of pilot plant runs. This flexible test facility
will play an important and unique role in the development of hot gas-
cleaning technology.
NITRIC OXIDE EMISSIONS
The objectives of this task have been to develop an understanding
of the nitrogen oxide (NOX) generation and destruction mechanisms in
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fluidized-bed combustion (FBC) systems. Information available in the
literature has been briefly reviewed to gain an insight into the
relationship between NOX formation and destruction reactions and the
fluidized-bed combustor design and operating parameters. We have
gathered the NOX emission data from PFBC and/or AFBC systems of Argonne
National Laboratory (ANL), Babcock and Wilcox (B&W), Combustion Power
Company, Consolidated Coal Company (Conoco), Exxon, National Coal Board
(NCB) and Pope, Evans and Robbins (PER); and from these, we have
attempted to develop a model for the selection of FBC design and operat-
ing criteria and to project plant performance. Among the various
sources there exist significant differences in FBC design and operating
conditions, coal and sorbents used, and NOX detection methods. Hence,
the conclusions drawn in this study should be used with caution.
The important observations reported In the literature are:
• In fluidized-bed combustion fuel-bound nitrogen is the
primary source of NOX emissions. The conversion of fuel-
bound nitrogen is less than 100 percent, suggesting the
decomposition of once-formed NO.
• Thermal fixation of molecular nitrogen is less favored
under fluidized-bed combustion conditions.
• The conversion of fuel-bound nitrogen to NO seems to
depend strongly on excess air level. Rapid production of
NO immediately above the distributor plate with substan-
tial reduction in NO concentration in the splash region
and in the freeboard have been observed.
• NOX emissions seem to exhibit a temperature maximum
between 750 to 800°C, suggesting that NO formation-
decomposition mechanisms and/or rate-determining steps
change with temperature.
• NOX emissions from PFBC operations seem to be less than
those from AFBC systems.
• Nitrogen-containing coal volatiles (NH3, amines, etc.),
CO, H2> and char have been observed to reduce NO to N2.
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• Staged combustion has the potential to further limit NOX
emissions.
• Precise kinetic information for NO formation and reduction
reactions in fluidized-bed combustion are lacking.
Some of the characteristic features of the data gathered from AFBC
and AFBC development units follow:
• NOX emissions from the relatively smaller units of ANL and
Exxon seem to be considerably greater than those from the
bigger units of PER, B&W, and NCB. This difference could
be due to the differences in the mixing pattern, local
stoichiometry, and mass transfer effects in the various
units.
• Data gathered from fluidized-bed combustion development
units indicate a similarity in temperature maximum,
reduced emissions at higher pressures, and increased emis-
sions with increased excess air with those previously
observed in the controlled laboratory-scale experiments.
• Data from relatively larger FBC development units suggest
that excess air levels of 15 to 20 percent in the proposed
commercial designs could result in NOX emissions of 129 to
301 ng N02/J (0.3-0.7 Ib N02/106 Btu).
• Regression analysis of the data from various FBC develop-
ment units resulted in a poor fit, possibly because scat-
ter and variations in the raw data from different sources
and/or the functional dependencies (first-order and
second-order terms) on pressure, temperature, excess air
level, and gas residence time chosen may not be represen-
tative of the NOX formation-decomposition reactions.
• Currently, there is no generalized model available for
a priori prediction of NOX emissions level in FBC,
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TRACE ELEMENTS
Theoretical projections at equilibrium were carried out to project
the quantity and the chemical form of the trace and minor elements from
coal and sorbent feed materials formed in both AFBC and PFBC systems.
Westinghouse has applied a therraodynamic model to project the chem-
ical fate of lead (Pb), beryllium (Be), mercury (Hg), and fluorine (F)
in coal-fired FBC systems. The previous thermodynamic analysis indi-
cated that essentially all the lead, beryllium, mercury, and fluorine
can be volatilized in the high-temperature zone in the fluidized-bed
combustor but did not attempt to demonstrate the reaction of the trace
species with either the clay or the carbonate constituents in the feed-
stock material. The areas selected for this study include:
• Further evaluation of available trace element emission
data from conventional boilers and FBC systems.
• Application of the thermodynamic model to project the
chemical fate in the FBC system of eight additional ele-
ments: aluminum (Al), iron (Fe), titanium (Ti), cobalt
(Co), chromium (Cr), manganese (Mn), molybdenum (Mo), and
nickel (Ni).
We conclude from the thermodynamic equilibrium model that the trace
and minor elements for AFBC and PFBC systems may be categorized as those
that yield:
• Potentially complete volatilization at 927°C: Mo (100%),
Pb (100%), Be (100%), Hg (100%), and F (100%)
• Partial volatilization at 927°C: Co (14%), Cr (79%), Mn
(^2%), and Ni (0,5%)
• Almost no volatilization at 927°C: Al (0.02%), Ti (0%),
and Fe (0%).
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3. RECOMMENDATIONS
PARTICULATE CONTROL
Particulate profile modeling should be extended to:
• Improve the modeling of sorbent attrition, including
breakage functions
• Obtain more experimental data to support attrition
models
• Develop a better understanding of such ash characteristics
as size distribution
• Develop reliable particulate control equipment operating
at the PFBC system temperature and pressure to achieve the
required particulate loading and size distributions for
economic turbine life. We recommend that alternative con-
cepts be tested in the dedicated HTHP test facility to
efficiently and economically screen candidate systems
prior to plant operation.
• Gain understanding of turbine performance through turbine
tolerance modeling which would include experimental deter-
mination of actual blade erosion damage as a function of
operating conditions in order to define particulate con-
trol requirements.
NITROGEN OXIDE EMISSIONS
The following recommendations are made for further work on NOX
emissions:
• Mechanistic and kinetic information for NOX reduction
reactions should be developed.
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• Comprehensive reporting of FBC development-unit data, such
as on reducing agents (NH3, H2, CO, char) concentrations
in the bed, is required for assessing the NOX formation-
reduction mechanisms proposed on the basis of controlled
laboratory experiments.
• NOX emission control options proposed should be assembled
on the basis of mechanisms that are identified and are at
least partially confirmed through the observation of data
trends.
• Continue the modeling work to provide a basis for project-
ing NOX emissions in FBC systems, and for the technical/
economic assessment of NOX control options necessary for
meeting EPA requirements.
TRACE ELEMENTS
Although the equilibrium model predicted the volatilization of lead
as lead tetrachloride (PbCl^), measurements to determine the fate of
lead in a cyclone-fed power plant indicated that 10 percent of the lead
was lost as an atmospheric discharge. The kinetics of conversion of
feedstock lead compounds to PbCl^ may be so intrinsically slow that
equilibrium within the combustor was not attained. Alternatively, there
may be more stable lead complexes, as silicates or borates, which may be
formed in the combustor^ Similarly, we projected molybdenum at equilib-
rium to volatilize completely at high combustion temperatures, but its
readsorption onto entrained fly ash particles may account for the
reduced emission percentages cited in the literature. The remaining
elements are partitioned in the solid fractions removed in the waste and
spent sorbent process, thus reducing the elemental concentration in the
stack gases. Relative agreement exists between the thermodynamic pro-
jections and the data obtained at the various coal-fired steam plants.
10
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We recommend continued investigation of additional trace and minor ele-
ment reactions, with emphasis on the potential chemical interactions in
the fluidized-bed combustor. Such an investigation would include:
• An expansion of the thermodynamic equilibrium model to
include an additional set of 25 trace and minor elements,
with parametric studies conducted to demonstrate the
interactions of the elements with the clay and carbonate
feedstock constituents for anticipated operating ranges of
various fluidized-bed combustor designs.
• A correlation of the equilibrium projections with in-field
data that would identify the elemental partitioning
between stack gas emissions and ash formations
• Modeling throughout the various AFBC and PFBC systems once
the chemical reactions and interactions of the trace and
minor elements are defined. Assessment of the potential
toxicity of the projected gaseous emissions should be
made, and control criteria for minimizing any potentially
toxic trace or minor element concentration in the stack
emissions should be advanced.
11
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4. PARTICULATE CONTROL
The understanding and control of participates emitted from FBC pro-
cesses is important for successfully meeting both environmental and pro-
cess constraints. To better understand the loadings and size distribu-
tions of emitted particulate, we must develop the basis for projecting
carry-over from the fluidized bed and the performance of various par-
ticulate control systems. The goal of this work has been to achieve
methods that give consistent and reliable estimates of particulate emis-
sions for FBC processes. These, in turn, can be used to make projec-
tions of both the environmental and the economic consequences of this
technology.
Work performed under this contract includes:
• Determining the impact of emission requirements and
fluidized-bed combustor design and operating conditions on
FBC particulate control requirements and plant economics
• Developing an understanding of the critical fluidized-bed
combustor and particulate control system design parameters
to meet turbine performance and emission requirements for
pressurized FBC systems
• Constructing a high-temperature high-pressure (HTHP) test
facility to investigate particulate control equipment per-
formance and to provide experimental data on new and con-
ventional devices.
EFFECT OF PARTICULATE EMISSION REQUIREMENTS ON FBC SYSTEMS
We evaluated the implications of more stringent degrees of particu-
late control on FBC plant design and cost. The previous particulate
12
-------
new source performance standard (NSPS) of 43.0 ng/J (0.1 Ib/MBtu) for
large coal-fired boilers and the newly-promulgated standard of 12.9 ng/J
(0.03 Ib/MBtu) for utility boilers were considered.
Particulate control in AFBC and in PFBC are quite different in
nature. Conventional technology exists for AFBC - hot electrostatic
precipitators (ESP) (~400°C) or fabric filter techniques (baghouses)
- that should, by suitable design, be capable of controlling particulate
emissions to the 12.9 ng/J (0.03 Ib/MBtu) level. Testing these control
options on operating fluidized-bed combustors, however, is necessary
before actual control performance and any operating problems can be
firmly defined. AFBC plants now under construction and initial opera-
tion will provide a basis for such an evaluation.
The protection of the gas turbine from erosion and deposition dam-
age for PFBC may require that particulate emissions be controlled to
levels lower than 12.9 ng/J (0.03 Ib/MBtu), depending on size distribu-
tion and composition. Granular bed filters, ceramic filters, and high-
temperature precipitators have been proposed for hot-gas cleaning but
have not yet been demonstrated.
Evaluation of the effects of the more stringent NSPS particulate
standards (12.9 to 107.5 ng/J) for both AFBC and PFBC systems is pre-
sented in a separate topical report. The total loading and particle
size distribution of particulates attrited and elutriated from a
fluidized-bed combustor are projected there using a Westinghouse model;
these projections are compared with the expected performance of particle
control equipment that might reasonably be employed. The projections
suggest that over the range of Ca/S ratios considered (up to 10), within
the variability of sorbent attrition performance expected and based on
the current data available, particulate emission levels of 12.9 ng/J
(0.03 Ib/MBtu) should be economically achievable for AFBC and PFBC.
13
-------
The major uncertainties with AFBC involve details of the equipment
specifications (filter materials, face velocities, etc.) and operating
and maintenance procedures (e.g., prevention of bag fires). Factors
such as resistivity of FBC ash and sorbent fines, and adhesion and flow
resistance properties of filter cake, are not yet well understood and can
significantly influence equipment design.
The level of particulate emissions standards may have little effect
on the development of PFBC since turbine life requirements may impose
more stringent requirements on expansion gas quality. Even encouraging
results with conventional cyclones that have resulted in particle size
distributions with only about 10 percent >5 to 6 urn particles do not meet
the standard.3 Fine material can arrive on the blades by turbulent and
molecular diffusion and can result in deposition and result in passage
choking problems. This may also require further cleaning, which may be
achieved on line.
Should it prove necessary we can develop more rugged turbines that
could accept higher particle loadings. This tactic, of course, will
trade off efficiency against capital costs and cleanup system costs.
As with sulfur removal, the combustor design and operating condi-
tions greatly effect the control of particulate emissions. With little
cost penalty we can design and operate the corabustor (e.g., at low veloc-
ities) to limit particle attrition and elutrlation, though very efficient
final-stage particulate control devices will still probably be required
for AFBC and PFBC systems. The coal sulfur content and the Ca/S ratio
have a far greater effect on the particulate control requirements for FBC
than do either coal ash control or coal heating value (i.e., sorbent feed
rate has the primary effect on particulate emissions).
DESIGN AND OPERATING CONSIDERATIONS FOR PFBC PARTICULATE CONTROL SYSTEMS
The commercial operation of coal-fired PFBC processes utilizing gas
turbine expanders depends on reliable operation of the gas turbine.
Reliable operation of the turbine, in turn, is related to the particulate
14
-------
and chemical composition of the gases that it expands. Erosion due to
micron-sized particles, deposition of submicron particles, and the for-
mation of corrosive deposits from alkali metal sulfates are of concern.
The scope of this assessmeat, however, is limited to the control of par-
ticulates and their effect on the erosion of turhine components. The
effects of alkali-induced corrosion and fine particle deposits were not
within the scope of this effort.
An understanding of the character of the particulates and the
development of appropriate methods for removing the particulates that
result from FBC processes is important in meeting environmental and pro-
cess constraints. Several aspects of the problem must be understood in
order to develop and specify both particulate control requirements and
equipment. These include an understanding of: particulate properties,
loadings, and size distributions from the fluidized-bed combustor; their
impact on gas turbine performance and life; and the environmental emis-
sion standards for concentration and size.
Perspective on the particulate control system requirements and con-
trol options have been previously presented. The present study extends
this earlier work to develop an understanding of the critical FBC and
particulate control system design parameters that effect the particu-
lates reaching the gas turbine and an understanding of the impact of
these parameters on turbine life and plant cost.
This study is based on the removal of particulates at the combustor
outlet temperature. Since the cost of particulate removal equipment is
a strong function of the operating temperature, the removal of particu-
lates at a reduced temperature was investigated and presented in a pre-
vious report.5 Two alternatives were investigated in the earlier study:
cooling the combustion gases by a convection-type boiler and removing
particulates at intermediate temperature, and cooling the combustion
gases with a recuperator, followed by a scrubber-cooler with subsequent
reheating of the gas. Results from the study show the low-temperature
15
-------
cleanup option may be competitive with a conventional plant with flue gas
desulfurization (FGD) but does not provide an economic or efficiency
margin for development. The present work is focused on high-temperature
particulate control.
Particle Profile Projections
Projections of the nature of the particles entering the turbine
expander must be developed in order to estimate the effect of particu-
late erosion on turbine life. To make these projections we have devel-
oped a particle profile model that incorporates the fluidized-bed com-
bustor and the particulate control subsystems. The computer model per-
mits rational, consistent estimates of particle loadings and size dis-
tributions throughout FBG systems. The model is used to perform para-
metric studies on the effect of different FBC design and operating con-
ditions on particulate emissions. The effect of the selection of FBC
design and operating conditions on particulate carry-over is discussed
along with a discussion of the model. Then the particulate control sys-
tem selected for this study is considered. The particulate that would
enter the turbine is then characterized for the parameters selected. The
objective is to provide perspective on important operating and design
choices.
Model for Fluidized-Bed Combustor Particulate Carry-over and Control
The FBC design and operating parameters, along with the coal and
sulfur sorbent characteristics, will determine the concentration, size,
physical character, and chemical composition of the particulate leaving
the combustor. A representative list of important factors is presented
in Table 1.
A particle profile model has been developed to project particle
loadings and size distributions in the carry-over from fluidized-bed com-
bustors and throughout any subsequent series of specified cleanup
devices. Westinghouse developed the early form of this model for ANL in
16
-------
Table 1
ILLUSTRATIVE FACTORS DETERMINING PARTICLES LEAVING
FLUIDIZED-BED COMBUSTOR
Feed Materials
Coal and sorbent (limestone or dolomite)
Chemical and physical properties, size reduction equipment
Design Parameters
Temperature control system design,
heat transfer surface, excess air
Carbon control system design,
recycle, carbon burnup cell, in-bed tempera'ture/bed
depth/excess air
Feed system design,
coal and sorbent feed introduction and location
Air distributor design
Combustor configuration,
bed configuration, freeboard design
Operating Parameters
Temperature
Pressure
Gas velocity
Bed depth
Environmental Regulations
Sulfur removal,
sorbent requirements
Nitrogen oxides
17
-------
support of their Component Integration and Test Unit (CTIQ) program.
The model is capable of analyzing FBC configurations that employ a
recycle cyclone for carbon utilizations as well as those that use a car-
bon burnup cell (CBC).
In the following, we present a brief review of the derivation of
the carry-over model. Details of the derivation and extensions of the
model are presented in Reference 6. A procedure for saving the
resulting performance equation is presented and a particulate control
performance model is incorporated.
The model employed to describe particle carry-over from the bed
(Figure 1) is based on a mass balance of particles in a certain size
range. The method used to estimate the rate at which particles are car-
ried out of the bed requires that a correlation for the elutriation rate
constant be available. This elutriation rate constant is defined by
A A
2 1' 2 2
1 '
PA.1,PA,2
Attrited
Feed
Fo,l'R0,2
Po,l,p0,2
Dwg.
F. ,. f
Elutricate
The first subscript identifies the stream
(eq. feed/draw-off etc.); the second sub-
script refers to the species - (One for
sorbent. two for ash)
Draw-Off
Figure 1 - Schematic of Solids Flow System
18
-------
asserting that the mass of particles of size D in the overhead is pro-
portional to the mass of particles of size D in Che bed, or that
F2p2(D)
K(D) = '
Many such correlations are available in the literature,^'6 but none
appears to be applicable to all systems.
The model treats attrition as if the surface of the large particles
is gradually abraded away so that the large particle slowly shrinks in
size according to some rate expression of the general form:
|£- R(D) (2)
The fines ground from the large particle are considered to pass out of
the system as if in the gas phase. The mass of these particles can be
calculated, but their size distribution must be assumed, and they are
not included in the recycle stream.
The general performance equation arises from a mass balance on
particles of size between D and D + AD. In unit time,
[Solids entering) _ /Solids leavingj _ /Solids leaving^ +
\ in feed / ~ \ in overflow / \in carry-over j
(Solids growing \ /Solids growing \ / Loss of mass \
into interval - out of interval + due to shrinking = 0 (3)
from larger size \to smaller size/ Within interval /
or
D + AD D + AD JD + AD
F2p2dD
f FoPodD - f FlPldD - f
"
AD
'D 'D
D + AD 3 WaRdD
/J W p, R.U.LJ
D = ° (4)
D
19
-------
Dividing by AD and taking limits as AD •*• 0, using equation (1) and
with the assumption of backmix flow, i.e., p^ = Pb> we obtain the fol-
lowing differential equation:
F0p0 - F1P1 - WKPl + W
d(p.R) 3 Wp R
dD
D
0 .
(5)
Further manipulation of this basic balance leads in the general perfor-
mance equation of the model which is given as
A
.. /^M D3I
W_ = /
FO J R
m
I(D,DM)
A
dD
(6)
where the I(D,DM) term is defined as
D I
I(D,DM) = exp
(7)
The final form of the performance equation is that of the triple inte-
gral expressed in equation (6). To include the effect of a cyclone
recycling coarse material to the bed, one need only modify the elutria-
tion rate constant K by multiplying it by the cyclone penetration (1-
efficiency) so that the K term of equation (7) is replaced by (K(l-n).
Use of this equation generally requires an iterative procedure,
since usually F0 and W are specified but F-^ is not. The solution
algorithm proceeds as follows:
1. For given F0 and W, pick F-L .
2. Calculate the triple integral of equation (6).
3. Compare the result with W/FO; if not sufficiently close, update
F value and iterate.
20
-------
4. Once convergence to F} is achieved PI can be calculated from
the expression:
5. Knowing pj one can calculate F2 as follows:
D.. D
/•M _M
/ F2p2dD = F2 = / W K(l-n)p1dD . (9)
D *D
m m
6. The size distribution of F2 can be obtained directly from the
elutriation rate expression
P2 = (W/F2)K(l-n)Pl . (10)
7. The mass of the attrited material A2 can be calculated by inte-
gration of the rate equation over the bed size distribution or,
more simply, by overall mass balance
A2 = Fo - Fl - F2 •
-------
given by pc(D) (i.e., pc(D) = dzc/dD (D), then the cumulative size dis-
tribution of the particles emerging from the the ith device is given by
D
z±(D) = I Pc(D)(i-n1) (i-n2)""(i-ni)dD . (13)
D
m
To include the effects of a second component, ash, in the
fluidized-bed segment of the model, we have assumed that the single com-
ponent particle balances on each species hold and the only coupling in
the two species extension occurs in the elutriation from the bed sur-
face. We presume this effect manifests itself by reducing the elutria-
tion rate of a species in proportion to the mass fraction of this spe-
cies in the bed. For example, if the bed were 0.80 sorbent and
0.20 ash, the single species elutriation rate calculated for the sorbent
would be reduced by multiplication by the factor of 0.8 sorbent and
0.20, since roughly these portions of the bed surface would be occupied
by the other species. In order to implement the approximation one must
use a trial-and-error procedure to determine the proper fractions of
each species in the bed. The basic algorithm used is as follows:
• Assume a fraction of sorbent.
• Calculate the withdrawal rates (F^) for both ash and sor-
bent independently with the exception that the elutriation
rate of each species is reduced as indicated above.
• Use F]_ (ash) and F^ (sorbent) to calculate the fraction of
each species in the bed and compare them with the assumed
values.
• Up-date the initial guess of the sorbent fraction and
iterate until convergence is achieved.
Having completed these calculations, one can carry out the remaining
computations independently, giving loadings and size distributions
throughout the system as well as the steady-state fractions of sorbent
and ash in the bed.
22
-------
Particulate Removal System
On the basis of a previous assessment^ Westinghouse has estimated
that a particle loading of 0.0046 g/m3 (0.002 gr/scf) with essentially
all particles smaller than 6 pm would be necessary to protect the gas
turbines from rapid choking and erosion. As discussed in Reference 2, a
ceramic filter or a granular-bed filter would probably be necessary in
order to meet this goal at elevated temperatures and pressures. We
believe these loadings and size constraints are conservative, however,
and the less stringent goals set by others in the field may prove to be
acceptable. Further discussion of the erosion analysis is presented in
Volume 4.
In accordance with the more stringent goals used in this study, the
particulate control train selected for this work consists of the follow-
ing: a relatively low-efficiency recycle cyclone, followed by a secon-
dary high-efficiency cyclone, followed by a granular-bed filter.
The recycle cyclone collection characteristics are shown in Fig-
ure 2. This grade efficiency was based on praliminary specifications
set by Steams-Roger for the "roughing" recycle cyclone in their plant
design for the ANL CTIU effort. This cyclone was purposely specified
as a low efficiency unit, to avoid the possibility of inordinately high
recycle rates of ash, and to operate at a total pressure of 1013 to
1216 kPa (10 to 12 atra) and at temperatures between 900 and 1000°C. The
total pressure drop across the cyclone was specified to be less than
13.8 kPa (2 psi).
The secondary cyclone grade efficiency curve also shown in Fig-
ure 2 is based on an estimate supplied by a commercial vendor for par-
ticles with a density of 2.5 g/cm3. The expected operating parameters
for this cyclone at 1013 kPa (10 atm) and 900°C are as follows:
• Inlet velocity 19.8 m/s
• 160 cm wg. pressure drop.
23
-------
Curve 713715-A
Primary
Recycle
Cyclone
1.0 10 100 1000
Particle Diameter, jam
Figure 2 - Fractional Efficiency of Cyclones
As is indicated by the grade efficiency curve, the proposed secondary
cyclone is a high-efficiency device and is intended to remove the bulk
of solids from the hot gas stream.
To achieve the desired final degree of removal, we have assumed
that a final stage of filtration will be required. Since actual commer-
cial filtering devices capable of operation at elevated temperatures and
pressures are not yet available, we made some assumptions about the
desired particle collection abilities of the filter. Two cases were
considered. For the first case the grade efficiency of the filter was
based on Westinghouse experimental data obtained from operation of a
small laboratory-scale granular-bed filter at ambient pressure and tem-
perature. During these runs a superficial velocity of 18 cm/s was used
through a 7.6 cm deep bed of Ottawa sand screened to be between 600 to
840 ym (20 to 30 mesh). The penetration vs. particle size curve deter-
mined by using cascade impactors is presented in Figure 3.
24
-------
Curve 687622-A
I
0.01
0.1
1
10
30
50
70
90
98
99
99.9 -
99.99
0.10
1.0
Particle Size, jam
10.0
Figure 3 - Grade Efficiency for Ambient Temperature and Pressure,
Laboratory-Scale Granular-Bed Filter
We obtained a second estimate of filter performance by assuming
that the likely upper limit on HTHP cleaning devices might be estimated
by using the grade efficiency of a conventional, low-temperature,
fabric-filter system. Since actual data of large-scale baghouse opera-
tions were available they were used. The assumed performance is pre-
sented in Figure 4 along with the pertinent operating parameters.
Particle Profile Calculations
The model described above was employed to estimate particulate
loadings and size distributions arriving at a gas turbine for chosen
sets of PFBC conditions. Calcium-to-sulfur ratios were varied from 0
to 5 and two sorbent attrition rates (0.2 and 2 %/hr) were examined.
The resultant loadings and size distributions escaping from the final
filter were then used in an erosion model to estimate the blade life and
25
-------
Curve 594489-A
w. ft
99.9
99
95
*s 90
51
.2
£ 50
c
o
$
S 10
5
1
0.1
0 01
1 i 1 1 1 ! 1 I 1 1 1 I | 1 1 I 1 | 1 1 [ 1 1 1 1 I
I ~_ 0-°-^
: *^" :
_
— —
_ _
_
-
__ —
_ _
_ —
Filtration Velocity 1 cm/s
T = 163°C
AP = 0.75 kPa
Reverse Air Cleaning
-
i i i i ii i 1 1 i i i i i i i > 1 i i i i i i i i
U. Ul
0.1
1
5
10
cf
o
50 2
Q>
S
CL.
90
95
99
99.9
QQ QQ
0.01 0.1 1.0 10.0
Particle Diameter;
Figure 4 - Baghouse Performance at Sunbury Steam
Electric Station
operating costs associated with different choices of operating param-
eters. This procedure allowed a consistent study of both the economic
and environmental consequences of PFBC.
Base operating parameters chosen for this study were as follows:
Temperature
Pressure
Superficial velocity
Bed height
Fines recycle
Coal
Excess air
900°C
1013 kPa (10 atm)
215 cm/s
260 cm
cyclone (Figure 2)
Illinois No. 6 (3% moist)
20%
26
-------
Ca/s 2:1; 5:1
Sorbent • dolomite
• minus 6350 ym
• single screened
• size distribution (Figure 5)
• attrition 0.2 - 2%/hr
• attrited size distribution
(Figure 5)
The sorbent feed size distribution was based on actual measurements
of a single-screened limestone. A standard sieve analysis was used for
the larger sizes. Both Coulter Counter and cascade impactor techniques
were used to establish the fines (44 to 0.5 urn) distributions.
The sorbent attrition used in this analysis is attributed to a con-
tinuous abrasion of the surface of particles. The fines abraded from
the surface are assumed to leave the bed immediately and penetrate the
recycle cylone. The mass of these fines can be calculated but, using
the model as is, not their size distributions. An assumed size distri-
bution must therefore be entered for these fines. Figure 5 presents the
distribution assumed for this work. This distribution was based on pre-
liminary experimental data obtained at Westinghouse with extrapolation
to the smaller than 10 ym sizes. The larger particles that abrade from
attrition and are elutriated from the bed are included in the model cal-
culations, and both loadings and size distributions escaping from the
recycle cyclone are calculated. Over the range of attrition rates st;id-
led, the size distribution of the particles elutriated (not attrLted)
did not change perceptably; it is presented In Figure 5.
Several models for elutriation have been offered in the litera-
ture** >^. For this work the correlation by Yagi and Aochi has been used
and is presented in Figure 6. While this correlation cannot be used as
a general prediction for particle carry-over, we have used it here for
Illustrative purposes.
27
-------
0.01
Elutriated Sorbent
(Recycle C"clone Exit)
Figure 5 - Particle Size Distributions
Curve 69674.-A
CSJ
=r 10
10
10
,-2
10 2 10"
1
dputpg/M
10 10
10,000
Figure 6 - Elutriation Correlatioa of Yagi and Aochi
28
-------
Since estimation of attrition parameters for ash is obviously dif-
ficult, we employed the following strategy. We matched the mass of ash
carry-over from the bed with NCB data10 by adjusting the attrition rate
constants and using the NCB emitted size distributions as the feed.
This same size distribution was used to typify the attrited ash frac-
tions. The result was thereby forced to give ash carry-over that was
similar in mass flow and size distributions to experimental data. Sub-
sequent calculations showed that the equilibrium bed fraction of ash was
relatively constant at about 2.5 to 5 percent, which seems generally
consistent with what we expected. The size distribuion of the ash cal-
culated to be escaping from the recyle cyclone is presented in
Figure 5.
The cleanup train consisted of the roughing recycle cyclone acid the
conventional high-efficiency cyclone, whose grade efficiency curves were
presented in Figure 2. The final stage of cleaning was accomplished by
using a granular-bed filter whose performance was assumed to be similar
either to the laboratory data presented in Figure 3 or to the
commercial-scale fabric filter data presented in Figure 4. Figure 5
can be used to present a summary of calculated size distributions of the
materials leaving the recycle cyclone. Since the ash size distribution
was essentially forced to agree with experimental data at this point, it
did not change with variations in either Ca/S or sorbent attrition.
Secondly, the sorbent size distribution tended to the "attrited" size
distribution for the high (2%/hr) attrition rates and approached the
"elutriated" size distribution for the low (0.2%/hr) attrition rates.
The recycle cyclone exit loadings as a function of Ca/S ratio and attri-
tion rates are presented in Figure 7. These loadings are generally in
the range of 11-20 g/m3 (5-10 gr/scf), which is in reasonable agreement
with typical findings available from the Exxon miniplant and the Curtiss
Wright test facilities.
These calculated loadings and the size distributions from the
recycle cyclone are then sent through the remainder of the cleanup train
29
-------
model consisting of the secondary cyclone and final filter. This pro-
cess has the effect of damping out differences in inlet distributions to
a large degree and results in combined ash and sorbent size distribu-
tions emitted to the turbine that are very similar. This point is
illustrated by Figure 8 where the combined size distributions for the
following range of conditions are presented:
A - fabric filter, 2.0%/hr, 5/1 Ca/S
n - fabric filter, 0.2%/hr, 2/1 Ca/S
o - Granular bed, 2.0%/hr, 5/1 Ca/S
x - Granular bed, 0.2%/hr, 2/1 Ca/S.
The calculations indicate that outlet size distributions from a
given final filter are virtually independent of the Ca/S ratio and
attrition rates. Additionally, the differences between outlet size dis-
tributions of the two different filters are relatively small, given the
approximations and assumptions incorporated in the model. The calcu-
lated differences can be explained by comparison of the two grade effi-
ciencies assumed (Figures 3 and 4). The baghouse performance curve is
based on a full-scale utility installation and indicates a slight
decline in efficiency around 8 to 10 pm, which explains why approxi-
mately 2% of the particles are larger than 10 urn for the fabric filter.
The granular-bed filter performance data were taken on a small bench-
scale rig where very high efficiencies for the >10 pm material were mea-
sured, thus explaining the absence of any material larger than 10 pm in
the filter effluent.
Although there are very small differences in size distributions of
the fabric filter and the granular-bed filter results, there is a large
difference in overall efficiency or penetration. Figures 9 and 10 dem-
onstrate this point by presenting a plot of total loading escaping the
final filter as a function of Ca/S ratio for 2 and 0.2%/hr attrition
rates. These figures indicate that there is almost an order of magni-
tude difference between the filters. For example, at Ca/S = 5 and a
30
-------
Curve 719996-A
10
*="
•a
to
o
Sorbent Attrition
2%/hr
Sorbent Attrition
0. 2%/hr
_L
22.90
20.61
18. 32
16.03
13.74
11.45
9. 16
6.87
4.58
Curve 7;9995-A
0 12 345
Ca/ S Ratio
Figure 7 - Loading from Recycle Cyclone
(Ash + Sorbent)
(%/hr)
Attrition
2.0
0.2
2.0
0.2
99
1.0
Particle Diameter,pro
Figure 8 - Combined Sorbent and Ash
Size Distributions from
Final Filter
10.0
-------
2%/hr attrition rate the fabric filter allows only about 0.006 g/m3
(4.6 ppm) of dust to penetrate, while the granular-bed filter penetra-
tion is projected to be on the order of 0.048 g/m3 (37 ppm).
General conclusions to be drawn from this example are as follows:
• A high-temperature/ -pressure filter device capable of
performance similar to that of a conventional fabric fil-
ter will probably be necessary if turbine inlet grain
loadings of 0.0046 g/m3 or 3.7 ppm (0.002 gr/scf) are
required.
• The filter design is of primary importance since the fil-
ter performance determines the particle size distribution
and loading presented to the turbine and emitted to the
environment.
• The selection of feed materials and the FBC design will
effect particle loading to the turbine and the environment
for a given filter performance. Figures 9 and 10 show
that a tenfold increase in attrition rate may increase
mass loading to the turbine and environment by a factor of
2.
• Ash particle size distribution, sorbent attrition rates,
and attrited sorbent size distributions are critical
parameters since they determine the bulk of material pre-
sented to the final filter.
• The design of the FBC to minimize sorbent requirements and
particle attrition is important since it also, thus, mini-
mizes particles in the turbine and the environment.
There are two factors that are of critical importance to be dis-
cussed when we consider these results. The first issue is that of pro-
jecting the performance of particulate collection devices in the smaller
than 10 urn range. Particulates in the 0.1 to 10 um range are very dif-
ficult to measure reliably, with the consequence that data on perfor-
mance in this range must be viewed carefully and judgments made as to
32
-------
Curve 713713-A
U)
a
E
o
TS
o
2 3 4
Calcium/Sulfur Ratio
0.00595
- 0.00550
Sorbent Attrition
0.2%/hr
- 0.00275
0.00229
.E
"D
S.
0.008
0.007
Curve 71371?-A
2345
Calcium/Sulfur Ratio
Figure 9 - Loading to Turbine as Function of
Ca/S and Attrition for Fabric/Filter
Performance
Figure 10 - Loading to Turbine as Function of
Ca/S and Attrition for Granular-Bed
Performance
-------
real operating situations. This is especially true for the final-filter
performance, since the upstream cyclones will probably have removed most
of the large material and essentially all of the particulate fed to the
final filter are in this <10 \m class. The second issue is similar in
nature: the actual distribution of the fines emitted from the bed to
the cleanup system are not well established. Typically, good data exist
down to ~44 um, and the distribution of the remainder of the material is
reached by log-normal extrapolation with some analytical support.
Although this <44 pm material may only represent a small fraction of the
feed to the system, it is virtually 100 percent of the feed to the
final-filter system. Small changes in this distribution, therefore, can
greatly affect the calculated emissions to the turbine and atmosphere.
Turbine Tolerance Projections
Projections of the turbine tolerance of particulates are made to
provide perspective on the requirements for environmental control. A
turbine tolerance model previously developed by Westinghouse is used to
provide guidance for the current study.^ Calculations of particle tra-
jectories through turbine blading have been carried out, including
impact damage, bounce angle, and subsequent impacts. Using related data
on the impact damage as a function of angle, velocity, and materials
properties, we have calculated actual metal recession rates due to ero-
sion that permit projection of turbine blade life for any given set of
conditions. We have also studied the effect of fine particles, since
these particles can arrive at blade surfaces by diffusion and can
deposit on the blades and eventually unbalance or choke the flow through
the blade passage. They can also serve as sites for corrosion to
begin.
A considerable amount of work remains to be done in this area with
respect to gathering impact damage data with actual PFBC ash and turbine
blade alloys at temperature and pressure. As with the particle profile
model, however, the turbine tolerance model provides perspective on
development requirements and needs.
34
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One must also recognize that the turbine tolerance will depend on
the turbine design. The results presented are based on a machine
designed to maximize the performance of a PFBC plant. Turbines operat-
ing at lower temperatures (e.g., <850°C) and with lower performance
(i.e., reduced particle-blade relative velocities) can have increased
particulate and chemical tolerances. Thus, an additional trade-off in
plant performance, cost, and reliability must be considered.
Using the Westinghouse turbine tolerance model, we can estimate the
erosion rate of the turbine blading as a function of particle size dis-
tribution, loading, and erosivity. The life of turbine blades is then
estimated on the basis of the allowable metal recession. Figure 11
shows the blade life plotted as a function of particulate loading and
erosivity. A constant particle size distribution is assumed for all
values of particulate loading. The particle size distribution assumed
is represented by the granular-bed-filter curve in Figure 8, which is
generally a log-normal distribution of sizes between 0.1 and 10 pm. We
do not feel that the accuracy of the carry-over and control model war-
rants differentiation between the curves presented in Figure 8. It is
important to note, however, that actual values will have an important
effect on turbine erosion, e.g., >10 ym particle loading.
The time between overhauls and the incremental cost of energy due
to the turbine blade and vane replacement have been calculated on the
basis of the following assumptions:
• The power plant is operated at full load whenever it is
operated.
• The operating time per year is 5000 hr (capacity factor
- 0.571).
• A spare rotor is normal practice with clean fuels.
• The power plant can be shut down for up to two weeks in
spring and fall (off-peak periods) without incurring a
penalty for not providing power to the grid.
35
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• The operating time is divided equally between winter and
summer periods.
• The penalty for replacing turbine parts in peak demand
periods is 20 mills/kWh.
• The capacity factor in the middle of winter or summer is
80 percent.
• The time required to replace bladed rotor and turbine
vanes is two weeks.
• The minimum practical overhaul period is three months.
• The effect of a boundary layer on erosion of turbine parts
is zero.
• Overhaul periods will be multiples of six months.
Figure 11 shows the relationship between particulate loading and
the incremental cost of electricity. For overhaul periods longer than
six months the increment cost varies in a series of steps of increasing
magnitude but on a constant slope base.. For overhaul periods of less
than six months, there is only one option (three months), and this is
assumed to be the minimum practical overhaul period. With the three-
month overhaul period, every other overhaul occurs in a peakload period
so the 20 mills/kWh penalty is applied. This changes the slope of the
step base at six months.
To use Figure 11 one enters through the particulate loading (for
example 10~2 g/m3). If one assumes the granular-bed filter size distri-
bution of Figure 8 and an erosivity of 1/25 silicon carbide (SiC), one
finds an incremental cost of electricity of about 1.2 mills/kWh over the
use of perfectly clean fuel. This loading corresponds to a life of
about 5000 hours and an overhaul schedule of about 12 months.
The maximum practical particulate loadings for the chosen size dis-
tribution is a function of erosivity. For an erosivity of 1/25 of SiC,
the maximum practical loading is 5*5 x 102 g/m3 (2.4 x 10" 2 gr/scf), and
for an erosivity of 1/50 of SiC it is 11 x 10~2 g/m3 (4.8 x 10~2
gr/scf). Thus, the maximum practical particulate loading is inversely
36
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106
10
1C
6
o
1 10°
I
-------
proportional to the particle erosivity. This finding indicates that
loadings in the range of r> x 10~2 to li x 10~2 g/m3 (0.02 - 0.05 gr/scf)
with the size distribution could be acceptable only if an incremental
cost of electricity of about 3 mil.ls/kWh could be justified along with a
three-month maintenance schedule. The specific performance and cost
results are dependent on the selected operating characteristics. The
purpose is to illustrate that tools are available to provide per-
spective on the important trade-offs that can result in choices leading
to a reliable FBC plant achieving environmental goals.
Assumptions incorporated in the turbine tolerance model that are of
importance are that:
• The estimates do not account for the appreciable slowing
of 1 to 3 urn particles in the blade boundary layers; on
this basis the erosion rate projections are high.
• The erosivity of the ash and spent sorbent is not well
known; two erosivitles are used in the projections which
are 1/25 and 1/50 the erosivity of SiC particles striking
a nickel alloy at room temperature.
Further discussion of the erosion analysis is presented in Vol-
ume TV of this report, EPA-600/7-80-015d. Estimates of gas turbine
blade life and system costs assuming different degrees of final-stage
filtrations were generated For PFBC systems using the carbon burn-up
cell concept. In this earlier study the basis for the erosion analysis
was similar to that presented here, but the methods used to project par-
ticle loadings and size distributions throughout the system were dif-
ferent and based on an earlier method for particle profile projection.
The ability to incorporate a recycle cyclone had not been built into the
carry-over model for that analysis. Westinghouse has carried out a sub-
sequent application of the combined particle profile/turbine erosion
model during 1979 under contract to EPRI (contract No. 1336-1). Results
from this study are generally consistent with the present study, indi-
cating that particulate loadings <~0.023 g/m3 (0.01 gr/scf) (or
38
-------
18 ppm) will be required for similar size distributions for 25,000-hr
life. This was based on the Exxon miniplant particle size distribution
~10% > 5ym) and loading (58 ppm) measured during turbine cascade tests
and on use of erosion-resistant turbine materials.
Environmental Requirements and Turbine Tolerance
The particulate control requirements for PFBG processes are deter-
mined by either environmental emission standards or turbine tolerance
requirements to achieve reliable and economic plant operation. Which of
these factors limits the design will depend on the PFBC concept, compo-
nent designs, component life criteria, and the emission standards.
The preliminary work, on turbine tolerance indicates that the ero-
sion and deposition on the blading will control the selection of partic-
ulate control equipment for PFBC processes; however, the inclusion of a
standard for fine particulates (e.g., <1 ym) could result in the envi-
ronmental requirements controlling the selection of particulate removal
equipment.
HIGH-TEMPERATURE, HIGH-PSESSURE GAS-CLEANING PARTICLE REMOVAL EQUIPMENT
TEST FACILITY
Background
Hot gas cleaning is required in a PFBC power plant. Cooling the
hot combustion gases, removing particles at low temperature by scrubbing
or filtration, and reheating the clean gases prior to their expansion
results in capital costs that are higher and operating efficiencies that
are lower than those for a conventional coal-fired plant.*> Westinghouse
studies indicate that hot gas cleaning is also desirable In a coal gasi-
fication combined-cycle plant for reducing costs and improving
efficiency.
A number of particle removal devices have been tested in previous
work at Westinghouse.
39
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• Cyclones. Both conventional and advanced rotary flow
units. Flow patterns have been measured, and grade effi-
cienty curves, presenting percent removal as a function of
particle size, have been determined. Bench- and pilot-
scale cyclones have been evaluated at 21 and 815°C (70 and
1500°F).
9 Moving wire impactors. A device based on a revolving
squirrel cage was devised, constructed, and evaluated as a
means of removing particles from gases passing from the
interior to the exterior of the cage. Fine particle
adherence and agglomeration on the moving wires was appar-
ently insufficient for effective operation of the device.
• Granular-bed filters. Filters involving the downward flow
of dirty gases through a stationary bed of particles sup-
ported on a perforated plate have been evaluated on both a
bench and pilot scale at both 21 and 760°C (70 and
1400°F). Grade efficiency curves have been determined.
Collected particles have been effectively removed from the
filter by briefly fuidizing the bed particles with a
reverse upward flow of gases.
• Porous ceramic filters. Filters involving the flow of
dirty gases through one of a stack of thin porous ceramic
membranes separated by ceramic corrugations have been
evaluated at both 21 and 760°C (70 and 1400°F). Collected
particles have been effectively removed from the filter by
a brief reverse flow of clean gases.
Other organizations have tested similar devices, such as fibrous ceramic
filters, hot, pressurized, electrostatic precipitators, granular-bed
filters, and cyclones of advanced and conventional design. It seems
likely that a successful hot-gas cleaning, particle removal system for a
PFBC or coal gasification combined-cycle power plant can be provided by
scaling up one or more of these devices.
40
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There Is a need to test, at high temperature and high pressure,
particle removal equipment large enough to permit extrapolation to the
design of utility-scale units. Westinghouse, with the support of both
EPA and DOE designed, constructed, and operated a test facility for
evaluating particle removal equipment using simulated flue gases at tem-
peratures up to 871°C (1600°F) and pressures up to 1520 k?a (15 atra).
Hot gas flows up to 5.44 kg/s (12 Ib/s), 42.5 m3/s (150 scf/s), can be
provided. Equipment up to 1.37 m (4.5 ft) diameter and 2.44 m (8 ft)
length can be mounted within an insulated pressure shell for testing.
The DOE has supplied funding for the pressure vessel, flow and
back-pressure valves, and bursting discs at a total cost on the order of
$40,000. The EPA funded the purchase of the piping and the installation
of that piping at the passage at a cost of about $85,000. Westinghouse
has supplied the remainder of the equipment in the system at a cost of
about $3,000,000.
TEST FACILITY
A functional schematic of the test passage is presented in Fig-
ure 12 and a floor plan of the entire test and development center In
Figure 13. The high-pressure air for the system is supplied by either
or both compressors available. A 1500 kW (2000 hp) centrifugal compres-
sor (Figure 14) can supply 3.4 kg/s (7.6 Ibm/sec) of air at 2026 kPa
(300 psig). A second three-stage 900 kW (1200 hp) reciprocating com-
pressor (Figure 15) can be run in parallel, providing flows up to
5.86 kg/s (12.9 Ibm/sec). This high-pressure air flows from the com-
pressor building to the laboratory where it can be heated to tempera-
tures up to 650°C by either of two propane or oil-fired air preheaters
(Figure 16).
The pressurized preheated air then flows through a corabustor where
enough No. 2 fuel is burned to raise the gases to the desired set
point. The combustor fuel is pumped from the fuel-blending building
(Figure 17) where several tanks are available for blending either corro-
sion inhibitors or promoters (combustible alkali organoraetallic
41
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Own. 7707A74
Operating Conditions
Pressure -Up to 1034 kPa< 150 psigK capability to 1517 kPa)
Temperature - 93 -871°C (200-1600°F)
Flow Rates -Up to 5. 44 kg/ s (12 Ib/ s)
Vessel -1..42 mDiax3. 19 m Length (56"Diax 110" Length)
Piping -0. 25 m( 10") Sh. 40 with 0.15 m(6") Inconel Liners
Air Compressors
Alkalis
Participate
Feeding
System
Rupture
Disc
Fuels
Blending
Tanks
Particulate
Sampling
By-Pass
CO-
Hot Gas
Cleaning
Pressure
Vessel
Particulate
-». Sampling
System
Muffler _
Chamber
Figure 12 - Schematic Diagram of Westinghouse Hot-Gas
Cleanup Facility
•fl
I !l) IO.OOO CAL H* I
. FUEL OIL TANKS
fS,OOO SAL.
. FUEL OIL TANKS - -r. / TOLUEHE TANK
2,000 GUI. r ir ~> /
*isre OIL r-^\ ii r"*i
l.H_,J I..J L-J
FUEL STORAGE AREA
COOLIHe TOWfRS
HEATWG 80IL£R
BOILER
SAL. Nf 6 FUEL OIL
•500 SAL. TOLVEHE
5fCO/VO FLOOR
HTHP Particulate Control
Test System
,., REV A 5-22-79
MADISON, PA.
2-2-78 SK-A-624-
Figure 13 - Particulate Control Test System and Support
Facility
42
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.£>
UJ
Figure 14 - Centrifugal Compressor
i
00
OJ
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Figure 15 - Three-Stage Cooper Bessemer Compressor
44
RM-76164
-------
Figure 16 - Test Passage Air Preheaters
00
Oi
-t-
-------
Figure 17 - Fuel Blend Tanks and Facilities
-------
Piping0.25 ml 10")
"itho. 15m If")
Inconel Liners
Pressure Vessel
871 °C 11600 °FI
1551 kPa (225 psig)
1.52m 15') Diax
2.44 m(8'l Long
Hot High-Pressure
Air up to
5. 44 kg/5(12 Ib/si
Figure 18 - High-Temperature and -Pressure Particulate Removal
Test Facility (Side Inlet)
Piping 0. 25 m 110") SS
•ithO. 15 m(6"l
Inconel Liners
Combustor
Pressure Vessel
871 "C( 1600 °F)
1551 kPa 1225 psig)
1.52m(5') Diax
2.44 ml8') Long
Hot High-Pressure
Air up to
5.44kg/s(12lb/s)
Figure 19 - High-Temperature and -Pressure Particulate Removal
Test Facility (Split Inlet)
47
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compounds). From the combustor the hot pressurized gases enter the test
passage piping. The passage piping and valving are fairly extensive, to
allow a great deal of flexibility in the manner in which the gases are
introduced to and exit from the pressure vessel, allowing virtually, any
device that will fit in the pressure vessel to be tested. Several
alternative flow paths are shown in Figures 18 through 20.
The pressure vessel used in this system is shown with dimensions in
Figure 21. Figures 22 and 23 are photographs showing how the internal
connections to a typical test device (an Aerodyne cyclone here) are made
within the vessel.
Overall control and operation of the passage is carried out from
the control room shown in Figure 24, although sampling and other opera-
tions must be carried out at the passage itself= Figure 25 shows a pho-
tograph of the passage pressure vessel and some of the piping.
Piping 0. 25mllO")SSwithO. 15m (6'
Inconel Liners
Combustor
Pressure Vessel
871«C (1600°F)
1551kPal225 psig
1. 52m(5') Diax
2. 44 m (8') Long
Hot High-Pressure
Air up to
5.44 kg/s (12 It/sec)
Figure 20 - High-Temperature -Pressure Particulate Removal
Test Facility (Top Inlet)
48
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Dv/p. 7681A02
5.1 cm
////x// ////
Figure 21 - High-Temperature and -Pressure Test Facility
Pressure Vessel
49
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Figure 22 - High-Temperature and -Pressure Test Facility Pressure
Vessel with Aerodyne Installed
50
RM-82546
-------
Figure 23 - High-Temperature and -Pressure Test Facility Pressure
Vessel Aerodyne Installation
51
RM-82547
-------
Ln
ro
Figure 24 - High-Temperature and -Pressure Test Facility
Control Room
8
Ul
.0-
00
-------
U)
Figure 25 - High-Temperature and -Pressure Test Facility
00
K>
Ul
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Pertinent facts about the Westinghouse HTHP Particulate Removal
Equipment Test Facility, its capabilities, and its operation are pre-
sented in Table 2. This facility provides the means for testing pilot-
scale apparatus under carefully controlled conditions at minimum cost.
The pressure vessel permits light construction of the particle removal
apparatus, since the device itself needs to withstand only its own pres-
sure drop.
PARTICULATE SAMPLING
Dust sampling parts have been included at several points in the
system. Figure 26 shows a schematic of the usual sampling train when
cascade impactors are used for mass loading and size distribution mea-
surements. As indicated in the schematic, this system allows the impac-
tor to be inserted directly into the passage piping for sampling. This
system minimizes the risk of altering the sample when extracting it from
the passage, conditioning it, and subsequently measuring its properties.
Figure 27 presents a photograph of the'sampling train used in the
system.
Containment Injection
In order to be able to suitably simulate PFBC flue gas conditions
provisions have been made for injection of solid particulate and gaseous
species.
Particulate Injection
The injection and subsequent dispersal of fine powders at elevated
pressures is a difficult task. Over a relatively long period a system
has evolved that appears to be adequate for metering and dispersing fine
test dusts. This system is shown schematically in Figure 28. The test
dust is placed in a pressurized pipe section containing a variable-speed
torque motor. The motor rotates a plate at the bottom of the dust hop-
per. This plate has a set number of through holes at a given radius,
54
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Table 2
HIGH-TEMPERATURE AND -PRESSURE TEST FACILITY
Vessel
Piping
Flow Conditions
Subsystems
Typical Test Devices
Manpower Requirements
2.79 m (110") Length 2.03 m (80") Straight Sides
1.42 m (56") Diameter
4 - 25.4 cm (10") Nozzles (2 Head, 1 Side, 1 Bottom)
2 - 7.6 cm (3") Nozzles (Head)
25.4 cm (10") Carbon Steel
15.0 cm (6") Inconel Liners
5.1 cm (2") Fiber Frax Insulation
Up to 5.44 kg/s (12 Ib/s)
Temperature, 93-871°C (200-1600°F)
Pressure, 0-1034 kPa (0-150 psig)
Oxidizing Atmosphere
Provisions for Injection of Virtually any Dust Type, Size, and Rate
Provisions for Sampling at All Vessel Inlet and Outlet Points
Provisions for Adding Sulfur and/or Alkali Metal Compounds in Fuel
Cyclones - Conventional and Rotary Flow Units
Granular Bed Filters
Ceramic Filters - Barrier or Bag Type
Electrostatic Precipitators
1 - Control Room Operator
1 - Auxiliary Equipment Monitor
1 - System Monitor
2 - Sampling Team
Electricity Fuel and Water Costs $75/hr (est.)
-------
Sampling System Take-off
762cm O.Hcm(l/4")RVl
(311 )Ss Ball Globe
Valve Valve p.
Sampling Train
Detached, Blind
FlangeF3IsBolted
on
Probe Align.
(Set Screw)
NV1
Fl BV1 /GV1
7. 62 cm (3") Gate Valve
CFM Totalizer
0.50-1.75
Rota meter
Figure 26 - Schematic of Sampling Train
which fiLl with the test dust upon rotation. A stationary plate is sup-
ported below the rotating disk. This plate has a single through hole
that is located so that the moving holes pass over the stationary hole.
As they do, the dust in the moving hole is "puffed" down through the
stationary hole by a high-pressure pulse from above. This action is
enhanced by the action of a straight "through" ejector which is fastened
to the bottom plate hole. This injector disperses and dilutes the
delivered "pellet" of dust and feeds it to a second, conventional,
orifice-type ejector where the dispersion is completed by a sonic flow
of motive air. The dispersed dust is then blown directly into the test
passage through connecting tubing.
56
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Figure 27 - Photograph of Particulate Sampling Train
i
00
-------
\J\
CO
Figure 28 - Particulate Injection System
-------
Gas Phase Contaminants
The introduction of gaseous species such as S02 is accomplished in
a straightforward manner by connecting a high-pressure tank of the gas
to an injection port and metering in the desired quantity.
Alkali metal contaminants can be injected into the system most eas-
ily by blending combustible organometallic compounds of the desired type
into the combustor fuel. This technique has a long, successful history
in combustion engineering research.
Test Facility Status
At this time the test facility construction is complete and opera-
tions for actually running the passage are shaken down and ready. To
date, the major problems have been associated with adequate control of
the dust injection rate and dispersion. The sampling system has been
tried at temperature and pressure and operates well.
Test Program Status
At this time, two test programs are scheduled for the test facil-
ity. The first is a DOE-sponsored program (Contract EF-77-C-01-2787)
to examine an advanced rotary flow cyclone's performance and compare it
with a conventional cyclone design.
The second program is an SRPI-sponsored program to test two ceramic
bag-filter concepts (Contract RP1336-1). The actual test program for
this contract is expected to begin late in 1979.
59
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5. NITROGEN OXIDE EMISSIONS
The objectives of this task are to develop an understanding of the
mechanisms of NOX generation and destruction in FBC so as to define the
design and operating parameters required to permit the minimization of
NOX emissions. We have chosen a dual approach to obtain such
understanding:
• The statistical treatment of data presently available that
may present clues to the reaction mechanisms
e The evolution of a model to permit selection of design and
operating criteria and to project plant performance.
LITERATURE REVIEW
Fluidized-bed combustion technology is being developed as an alter-
native to the conventional combustion techniques. The major emphasis is
on limiting sulfur oxide (SOX) emissions by using a suitable sorbent in
the bed. In this section information available in the literature is
reviewed briefly to offer insight into the NOX formation mechanisms and
into the effects of fluidized-bed design and operating parameters on NOX
emissions.
Mechanisms
In combustion processes nitric oxide (NO) can form by the thermal
fixation of molecular nitrogen in the combustion air and/or by the oxi-
dation of the chemically bound nitrogen in the fuel. The NO once formed
can be reduced to molecular nitrogen by homogeneous gas phase reactions
with carbon monoxide (GO), hydrogen, methane (€114), and S02, and/or by
the heterogeneous reaction with char.
60
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Source of NO
Thermal NO is believed to be formed largely through a relatively
slow and a very temperature-dependent reaction path commonly referred to
as the Zeldovich mechanism.^ These reactions describe the NO formation
in the postcombustion product gas stream, since there is no generally
accepted reaction mechanism for NO formation during the combustion pro-
cess. The relatively lower temperatures, less than 1000°C, encountered
in FBC seem to be unfavorable for thermal fixation of atmospheric nitro-
gen. Experiments conducted by several investigators1'4""1^ using air and
argon-oxygen mixtures as oxidizers have shown a general uniformity in
the NOX emissions from FBC that suggests fuel-bound nitrogen to be the
major source. Relatively little is known about the nature of nitrogen-
containing polynuclear structures present in coal and their conversion
to NO. During the initial phases of combustion, such as devolatiliza-
tion, some of the nitrogen in the coal can be released in the form of
hydrogen cyanide (HCN), ammonia (^3), nitrogen-containing organic bases
like pyridines, quinolines, and so on, while significant quantities of
nitrogen may remain in the char particle. As compared with molecular
nitrogen, these nitrogen-containing structures can be oxidized at lower
temperatures.
Relative Contribution of Volatile Matter and Char
Nitrogen in the coal has been observed to be distributed among the
volatiles and the fixed carbon (char).1' Pereira et al.1^ have shown
that at temperatures below 750°C most of the NOX is formed from the oxi-
dation of nitrogen left in the char* At higher temperatures, however,
800°C and above, the volatiles seem to be the major source of NOX emis-
sion. These observations suggest that nitrogen in the chars formed at
higher temperatures is less easily oxidized.
Coal Nitrogen Content
In the case of liquid and gaseous fuels, combustion experiments
conducted by doping the fuels with nitrogen compounds have shown
61
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decreased conversion of the total nitrogen present in the fuel mixture
to NO.18 Pereira et al.19 and Chronowski and Molayem20 have shown that
NO,, emissions under similar operating conditions increase with an
X
increase in the coal nitrogen content. Thus, there seems to be some
indirect evidence showing a similar decrease in the percent of conver-
sion of nitrogen in the coal to NO with an increase in the coal nitrogen
content.1^'18'19 This observation, however, is based on results from
burning different coals that may have significantly different combustion
characteristics .
NO Reduction Reactions
Less than 100 percent conversion of fuel-bound nitrogen to NO is
observed in FBC and can be explained by assuming the once-formed NO to
be reduced by, for example, CO, hydrogen, NH3, unburned hydrocarbons,
O 1
and char, which may be present in the combustion mixture. Pereira^ has
proposed that the homogeneous gas phase reducing reactions limits NOX
emissions at temperatures below 750 to ,800°C, while the heterogeneous
reaction between NO and char is accelerated above 800°C, resulting in
significantly decreased NOX emissions. Jonke et al. have shown that
the NO,, emissions decrease in FBC in the presence of limestone. Vogel
A
et al. reported that NOX emissions increase with an increase in the
Ca/S molar ratio. A close examination of their data, however, indicated
the possibility of increased emissions due to increased superficial gas
velocity rather than to the increased Ca/S ratio. Hammons and Skopp23
have shown that calcium sulfate (CaS04) can act as a catalyst during the
catalytic reduction of NO by CO or by
Effect of Fluidized-Bed Operating and Design Parameters
The NOX formation and reduction reactions in FBC can be signifi-
cantly influenced by the operating and design parameters. These influ-
ences are briefly described below.
62
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Pressure
Nitrogen oxide emissions were found to decrease substantially
between 101 and 304 to 405 kPa (1 and 3 to 4 atm) and then decrease less
rapidly with a further increase in pressure. 23 Pressurized beds are
usually deeper, providing increased gas residence times, and the fluid
dynamics in them favor relatively smaller bubbles. These factors can
have favorable influences on the interphase mass transfer steps involved
in the homogeneous NO reduction reactions and also on the adsorption-
desorption steps involved in the heterogeneous reduction of NO by char.
Temperature
A temperature maximum for NOX emissions was found by Pereira, Beer,
and Gibbs19 at 750 to 800°C. They observed NOX emissions to be substan-
tially less than those corresponding to 100 percent conversion of fuel-
bound nitrogen. They proposed that the relatively lower NOX emissions
at temperatures below 750°C can be due to the reducing action of CO,
hydrogen, and unburned hydrocarbons, while at higher temperatures the
decrease is caused by an accelerated reduction by char.
Excess Air
"" using air and argon-oxygen mixtures as oxidizers have
shown few differences in NOX emissions in FBG, suggesting the fuel-bound
nitrogen to be the major source of NOX emissions. The conversion of
fuel-bound nitrogen to NO has been observed to depend strongly on the
availability of oxygen and, hence, on the local stoichiometry. Furasawa
et al.1^ have shown the NO,, emissions to increase substantially between
A
0 and 40 to 50 percent excess air and then to increase less rapidly with
further increase in excess air. These observations suggest that the
interphase mass transfer and diffusional resistances govern the NOX for-
mation and destruction kinetics. Gibbs and Beer, * using a 30 cm
x 30 cm fluidized-bed combustor have shown rapid production of NO imme-
diately above the distributor plate, with substantial reduction in NO
63
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concentration in the splash region and in the freeboard. They showed
radial as well as axial concentration gradients for NO, indicating the
importance of fluid dynamics, which determines the local stoichiometry
of the combustion mixture. The NO concentration was observed to be
higher at the walls than at the cente* of the combustor, suggesting that
the NO formation takes place mainly in the particulate phase, where coal
particles are being burned.
Gas Residence Time
Pereira et al.15 have shown NOX emissions first to increase and
then to decrease with an increase in gas velocity at constant bed depth.
This observation suggests a reaction mechanism in which NO could be
treated as an intermediate product. For example:
+ fuel-bound + reducing
02 » NO *• N2 -
nitrogen agent
Particle Size
Gibbs et al. have shown increased NO reduction in NO-char systems
(in the absence of oxygen) with decreasing char particle size. This
reduction can be due to the minimization of diffusional resistances
involved in the heterogeneous NO-char reduction reactions. In
fluidized-bed combustors decreasing the coal feed particle size can have
an adverse affect on the combustion efficiency because of the possible
increase in the elutriation of unburned char from the bed.
Staged Combustion
Experiments carried out by Gibbs et al.2^ have shown that air stag-
ing can substantially reduce NOX emissions. In their study the primary
stage of the bed was operated at substoichiometric conditions, and sec-
ondary combustion air was injected into the freeboard for improved com-
bustion efficiency. Furusawa et al.^ have also observed considerably
lower NOX emissions in staged combustion. The relatively lower NOX
64
-------
emissions observed in staged firing can be due to the enhancement of NO
reduction reactions by CO, unburned hydrocarbons, and char in the
primary stage.
Models to Project NOX Emissions
Pereira and Beer have developed a model describing the formation
and destruction of NO in homogeneous reactions involving the coal
volatiles. The model consists of two parts - the homogeneous reaction
process of NO formation and destruction and the heterogeneous process of
NO formation and the NO-char reduction. Simulated results from
the theoretical model were observed to agree reasonably well witii
experimental data for temperatures between 600 and 800°C. .Above 800°C,
however, the discrepancies between model predictions and the
experimental results were attributed to the lack of information on the
fast reduction of NO by char. Recently, under the joint sponsorship of
the DOE Fluidized Combustion Modeling and the EPA NOX Emissions Control
contracts, work has commenced at MIT to develop a model describing NOX
emissions due to the oxidation of nitrogenous compounds evolved from the
devolatilized char.
The FBC NOX emission models proposed need additional refinements so
as to account for the release rate of nitrogen-containing volatiLes,
diffusion flames that may form during the rapid devolatilization
stage, more detailed models of the oxidation and reduction reactions of
coal nitrogen volatiles, and the catalytic and noncatalytic gas-solid
NOX formation and decomposition reactions involving the residual char.
The heterogeneous nature and the differences among the various coal
types can become a limiting factor for precise projections of NOX
emissions in FBC.
65
-------
Summary
The important observations made by the research workers looking
specifically at the NOX formation-decomposition mechanisms in FBC are:
• Nitric oxide formation from fuel-bound nitrogen is the
primary source of NOX emission in FBC.
• Thermal NO formation from atmospheric nitrogen and oxygen
is less favored under FBC conditions.
• Conversion of fuel-bound nitrogen is substantially less
than 100 percent in FBC, suggesting that the once-formed
NO is being decomposed, possibly by reducing agents such
as nitrogen-containing coal volatiles (NH3, amines, etc.),
CO, hydrogen, and char, which may be present in the com-
bustion mixture.
• Nitrogen oxide emissions from PFBC operation seem to be
less than those from AFBC.
• Conversion of fuel-bound nitrogen to NO seems to depend
strongly on the excess air level. Rapid production of NO
immediately above the distributor plate, with substantial
reduction in NO concentration in the splash region and in
the freeboard, has been observed.
• Nitrogen oxide emissions seem to exhibit a temperature
maximum around 750 to 800°C, suggesting that NO formation-
decomposition mechanisms and/or rate-determining steps
change with temperature.
• Nitrogen oxide emissions have been observed to show a gas
residence time maximum, indicating the occurrence of con-
secutive series-type (NO formation-decomposition)
reactions.
• The rate of NO-char reduction reaction seems to be influ-
enced by pore diffusional effects.
66
-------
• Staged combustion seems to reduce NO emissions
substantially.
• Precise kinetic information for NO formation and decompo-
sition reactions are lacking. The currently proposed NOX
emissions models also need additional refinements so as to
account for reactor dynamics (mixing pattern, interphase
and intraphase mass transfer effects), devolatilization
rate, catalytic effects of char (carbon loading in the
bed), etc.
DATA ANALYSIS
Pressurized and/or atmospheric pressure FI3C NOX emission data from
ANL, B&W, Combustion Power Company, Conoco, Exxon, NCB, and PER have
been gathered and are listed in Appendix A. These data consist of
average NOX emission values reported for batch combustor runs and the
NOX emissions observed at steady state from continuously operated
fluidized-bed coiabustors.
To gain insight into the NOX formation and destruction mechanisms,
the characteristic features of the NOX emission data collected are sum-
marized in Appendix B. Plots showing the NOX emissions from PFBC and
AFBC as a function of temperature with percent excess air as a parameter
are also included in Appendix A. Some of the observations that have
been made for AFBC, for example, are briefly summarized in Table 3,
which indicates an increase in NOX emissions with an increase in percent
excess air and/or temperature. In comparison with PFBC data, the NOX
emissions from AFBC units under similar operating temperatures and
excess air levels seem to be higher.
Effect of Fluidized-Bed Combustor Size
The NOX emission data reported by the various investigators for
AFBC operations with excess air in the range of 15 to 20 percent are
67
-------
Table 3
Dwg. 262X83
AFBC NOV EMISSION DATA
A.
Source
Unit Size
Superficial
Velocity, m/ s
Bed Depth, m
Coal Nitrogen Content, wt%
Exxon
0.07 mdia.
U. 6 - 1. 2
0. 15-0. 30
1.30
ANL
0. 15 m dia.
0. 84 - 2. 7
0.60
1, 11 - 1. 31
NCB
0. 68 m dia.
1. 80 - 3. 3
0.60
1.40
NCB
0. 91 m x 0. 45 m
0. 60 - 2. 45
0. 63 - 2. 10
1.40
Excess Air. Temperature, No. of
% °C Data
ng NO,/ J No. of ng NO,/ J No. of ng NO-/ J No. of ng NO,/ J
^ n-*~ ^ rw*-» ^ ni#a
Data
Data
PER B&W
0.45 mx 1.82 m 0.91 mx 0.91 m
3. 90 1. 31 - 3. 57
0. 32 - 0. 60 0. 28 - 0. 86
0. 99; 2. 55 0. 76; 0. 86
No. of ngNCL/J No. of ngNOJj
Data Data l
0-5.00
5. 01-10. 00
10. 01-15. 00
15. 01-20. 00
20.01-25.00
25.01-30.00
30.01-35.00
35. 01-41. 00
871
843
871
926
843
845
848
871
898
700
770-774
787
798
804
810
815
818, 819
826
829
838
843
845
848
850
854
857
860
865
871
894
898
904
915
926
932
937
948
965, 987
766
804
815
837
843
848
854
871
898
837
843
871
904
843
854
843
871
1
-
1
—
-
—
-
—
-
-
-
-
-
—
-
-
—
-
-
-
—
—
-
3
-
-
—
-
1
—
-
—
-
-
-
-
—
-
-
—
1
-
-
-
3
-
-
—
-
1
420
-
347
—
-
—
-
—
—
-
-
-
-
—
-
-
—
-
-
-
—
-
—
395-483
-
-
—
-
458
—
-
_
-
-
-
-
—
-
—
-
409
-
-
—
398-456
-
-
—
-
502
1
1
2
5
-
9
—
2
—
1
—
-
-
1
-
-
—
-
2
—
-
-
-
—
-
-
14
-
3
—
-
-
—
-
—
_
-
1
-
—
2
—
—
3
1
—
-
—
-
-
-
-
-
258
373
246-306
346-450
-
141-353
—
170; 182
—
187
—
-
-
247
—
-
—
-
162; 411
—
-
-
-
—
-
—
219-357
-
387-411
—
-
-
—
—
_
_
-
268
-
—
414-454
-
-
248-311
444
—
—
—
-
—
—
-
—
-
-
-
—
-
—
-
—
-
-
-
-
-
—
-
-
—
-
_
1
—
_
_
-
-
-
—
_
-
_
—
_
_
—
_
1
—
2
1
1
—
1
1
1
—
1
1
1
2
—
-
-
-
—
-
—
-
—
-
-
-
—
-
_
-
-
_
-
-
202
_
_
_
_
_
_
_
_
_
_
_
_
_
—
_
231
_
265-272
251
211
_
258
267
297
—
280
298
194
256; 290
-
203
121-204
9 125-286
224
-
-
1
-
3
1
_
1
—
2
—
_
4
—
3
—
3
—
1
1
1
2
1
2
-
—
162
-
97-159
123
_
147
—
146; 175
—
_
170-193
—
121-146
—
153
-
134
166
136
184,212
210
135; 152
1
1
-
2
—
—
•2
_
2
2
1
3
3
-
1
-
1
-
1
_
-
_
-
-
-
146
169
-
33; 181
_
-
144; 180
_
* 128;184
127; 129
176
143-167
114-185
-
194
-
120
-
201
_
-
_
-
-
-
229
188
68
-------
plotted as a function of temperature in Figure 29. The NOX emissions
from the relatively smaller units of ANL and Exxon seem to be
considerably higher than those from the bigger units of PER, B&W, and
NCB, possibly because of differences in the fluid dynamics (mixing
pattern), local stoichiometry, and mass transfer effects in the various
units.
Effect of Coal Type and Nitrogen Content
The NOX emission data from AFBC and PFBC units for excess air
levels in the range of 15 to 20 percent and for different coals are
plotted as a function of temperature in Figures 30 and 31, respectively.
Apparently, under the operating conditions investigated, the NOX emis-
sions are independent or a weak function of the coal type and nitrogen
content.
Effect of Fluidized-Bed Operating Conditions
Comparison of the NOX emission data plotted in Figures 30 and 31
show relatively lower NOX emissions from PFBC than from AFBC units.
Apparently, for both PFBC and AFBC, there is a temperature maximum
between 800 and 900°C. Additional data plotted in Figures 32 and 33
show increased NOX emission with increasing excess air levels. The
interpretation of the data to single out the effects of fluidizing
velocity, bed depth, coal particle size, S02 emissions, and so on is
difficult because of the accompanied variations in temperature and/or
excess air levels.
The above analysis suggests that the temperature, excess air, and
pressure are the most significant parameters. The trends observed
should be assessed with caution, however, because the more precise
effects may be concealed by variations in other operating parameters,
fluidized-bed design variables, and analytical techniques.
69
-------
473.011. 1)
387. 0 ( 0. 91
301. 0 ( 0. 71
2 215.0(0.5)
ll-
129.0(0.3)
Source
• NCB
o NCB
v B&W
D PER
• ANL
a Exxon
rurv° 719626-A
FBC Unit Size
0. 91m x 0.45m
0. 58m dia
0. 91mxO. 91m
0. 45m xl. 82m
0.15m
0.07m
Excess Air. % 15-20
Pressure.kPa 101
Gas Residence
Time, s 0. 12-0. 22
43.0(0. 1)
0
-
I
00 700 800 900 1000
Bed Temperature. "C
Figure 29 - Effect of Fluidized-Bed Combustor Size
430. 0 (1. 0
387. 0 (0. 91
344. 0 (0. 8)
301.0 (0. 7)
CM 3
S S 258. 0 10. 61
- *S
~ ~ 215. 0 (0. 5)
CSJ
% _, 172. 0 10. 41
CT>
C 129. 0 (0. 3)
86.0 (0.2)
43.0 (0.1)
_
o PER ( 2. 5 wt. Mil Cu"e 719626-"
» PERIO. 99 wt. %N)
o NCBll. 4wt. %NI
^ B&WIO. 76 wt. %N)
Pressure. kPa 101
Excess Air. % 15-20
Gas Residence
Time, s 0. 12-0. 17
6
So
°o *
o a a *
o
i i i i
600 700 800 900 1000
Bed Temperature, °C
Figure 30 - Effect of Coal Nitrogen Content - AF3C
t 344. 0 ( 0. 8)
D
^ 301.0(0.7)
§
2 258. 0 ( 0. 6)
215.0(0.5)
172.0(0.4)
129. 0 ( 0. 3)
86. 0 ( 0. 2)
43. 0 ( 0. 1)
0
Coal Nitrogen Content. wt% Expanded Bed Depth/ Superficial Velocity
<1 s > Is
5. 08 a o
1. 66 • ?
Excess Air 15-17.3%
Pressure - 810 kPa
~ m
-------
Curve 719621-''
Pressure, kPa
800-970
.a ;=;
JOI . U I U. 71
301. 0 ( 0. 7)
— -^
3
CO
*o 215. 0 ( 0. 5)
-'
129. 0 ( 0. 3)
43. 0 ( 0. 1)
n
Expanded Bed Depth,
• Superficial Velocity
Excess Air Level, %
o 5-10
• • v 35-40
o 65-70
Q • 100-120
D
a
v o
OS7
V
O Q
_ v
1 I l l
600 700 800 900 1000
Bed Temperature, °C
Figure 32 - Effect of Temperature and Excess Air - PFBC
Curv
CVJ
en
HI J. \J \ A. If
387. 0 ( 0. 9)
^301.0(0.7)
3
oa
^2
-^215.0(0.5)
-
129. 0 ( 0. 3)
43. 0 ( 0. 1)
n
Pressure, kPa 101
v
Expanded Bed Depth. s ~0. 66
^ Superficial Velocity
o ° Excess Air, %
o 0-5
° a 10-15
v v 20-25
9
^ o
a
a
a
-
1 I 1 1
600 700 800 900
Bed Temperature, °C
1000
Figure 33 - Effect of Temperature and Excess Air - AFBC
71
-------
Statistical Analysis
Assimilated data from both AFBC and PFBC tests have been subjected
to regression analysis to develop a simple equation for projecting NOX
emissions as a function of FBC operating conditions. Data from continu-
ously operated units have been used for regression fit because batch
runs reported average emission values for NOX that may not be represen-
tative of steady-state conditions. In the light of the discussions in
the preceding sections, fluidized-bed operating pressure, temperature,
percent excess air, and gas residence time have been chosen as the inde-
pendent variables. Regression analysis yielded the following empirical
equation describing the dependence of NOX emissions on these variables:
NOX = - (0.5775)(P) + (4.135 x 1CT4)(P)2 + (0.6598)(T)
- (4.238 x 1CT4)(T)2 + (1.1668)(X)
- (2.759 x 1CT3)(X)2 - (5-5066)(h/v)
where
NOX is expressed as ng NC^/J, and
P = pressure, kPa
T = temperature, °C
X = percent excess air
h = bed depth, m
v = superficial gas velocity, m/s.
The residual variance and the correlation coefficient for the regression
fit are 60 ng N02/J and 0.869, respectively. Such a low correlation
coefficient predicts poor fit, and, as shown in Figure 34, there is con-
siderable deviation in the experimentally observed values and in those
predicted by the regression fit. The NOX emissions predicted by the
empirical equation for various operating conditions are plotted in Fig-
ure 35. These results show the experimentally observed trends, such as
temperature maximum, increased NOX emissions with an increase in excess
air, and lower NOX emissions at higher pressures. Due to the poor
regression fit, however, an experimentally observed value of 43 ng NOo/J
72
-------
"-3
CO •"-.
S0"
* «
T3 C
0)
)-i «
> 4-1
1-1 •H
rH -H
CO P^i
4-1
C 0
0) O
•H W
!H CO
QJ 01
O, 1-1
X! M
W 0)
180
135 +
90 ;
45
-45
-90
-135
-180
"34
XX
+
X
X X
X
X
XX x
.
;
.
*
t
*
X A X
X A X
XX
v XX X
X v A X XX
* y x x x x xx
/AX xx x A x x YX
A
If X
X X
v X X
X X
* AXXX y v xxx x
^
+
XXXXXAAXXX X
XAXXVXX X A XV XXXX AX X
XXXA AXAVA*X A V X X
VX X Y
x x
y
xx*xxxxxxyxxx*>f y * * x x x x
, VXXX^X^AXXX^ x * x x
1
4
xxxx' x*xx xx
•' XA'X X XX X X
x v x x x
XA
XX
XXX X
xxx .x x x xxxxxx
AX X
x x XX
XX
XX
1 AX XXXX
+ XX XXX
.
+
•
X
X
X X
X
X
X
XX
X
X
68
202 136 170 204 238
Experimentally Observed NOX, ng N02/J
272
306
340
Figure 34 - Plot of Residuals - Statistical Analysis
-------
300 ,-
Curve 719622-P
Pressure, Temperature,
kPa °C
101
101
101
900
900
900
Gas Residence
Time = l s
A
B
C
D
E
F
800
600
1000
800
600
1000
20 40 60
Percent Excess Air
'80
Figure 35 - Regression Fit NOX Projections
could be predicted between 0 to 86 ng N(>2/J when the corresponding pres-
sure, temperature, excess air, and gas residence time values were
inserted in the above empirical equation. Similarly, an experimentally
observed value of 215 ng N02/J could be predicted between 0 and 430 ng
N02/J«
Data sets from different sources have been used in correlating the
data with regression analysis. Among the various sources there exist
significant variations in the fluidized-bed operating and design fac-
tors, the coal and sorbents used, and the NOX detection methods. These
differences result in an inherent scatter in the raw data used for
regression analysis and could possibly explain the resulting poor
74
-------
regression fit. Also, it is possible that the functional dependence of
NOX emissions on the operating variables (first-order and second-order
terms) chosen for regression fit are not representative of the NOX
formation-decomposition reaction mechanisms, reactor dynamics-like mix-
ing pattern, interphase and intraphase mass transfer effects, and so on.
Better regression correlations may be developed for each individual data
set, but these will have limited application, and the overall objectives
of the FBC technology assessment may not be fully served.
NOy Decomposition Model
Most of the researchers investigating NO emissions in FBC have
X
reported significantly higher concentrations of NO near the distributor
plate (air inlet to the bed) and a decrease in NO concentration as the
gas rises through the bed. NO-char reduction reactions at temperatures
of 750°C and higher have been suggested to be mainly responsible for the
decomposition of the once formed NO. In order to provide a preliminary
test of this mechanism, we calculated kinetic rate constants for NO
x
decomposition from available FBC data by assuming that all the nitrogen
in the coal is released at the base of the bed and that the NO then
x
decomposes according to first-order kinetics as it passes up through the
depth of the bed (to reach the concentrations measured in the flue gas).
The scatter in the first-order specific reaction rate constants plotted
in Figure 36 show the inadequacy of the first-order decomposition model.
These specific reaction rate constants, however, are within the range
reported by NO-char reduction studies at MIT.
ASSESSMENT
Data sets from different sources have been gathered. Among the
various sources there exist significant variations in the fluidized-bed
operating and design factors, the coal and sorbents used, and the NOX
detection methods. The NOX emission data from relatively larger
fluidized-bed combustors are similar in temperature maximum, reduced
emissions at higher pressures, and increased emissions with increased
75
-------
Curve 719627 A
o. u
7 fl
1 . U
6.0
5.0
4.0
3.0
~
• • | % wt% Nitrogen
** 1*** -Source
vvv • PER
v PER
? ° o NCB
oj> o BCW 0
a QQ Excess Air,
0°o o Pressure,
0
o
o
-
8
i i i
7.5 8.5 9.5 10.5
(~)^ lO^K)"1
in Coal
2.50
0.99
1.40
. 76-0. 86
% 15-20
kPa 101
L-Urv^ / i.'w-' '
Coal
Heating Value,
kJ/kg
28, 277
30, 238
35, 123
29, 263-29, 484
Figure 36 - NO Decomposition Model
Rate Constants
- Pseudo-First-Order
excess air to those previously observed in the controlled experiments in
laboratory-scale fluidized-bed combustors. Data from relatively larger
fluidized-bed combustors suggest that NOX emissions under certain
operating conditions could be less thanSOlag N02/J (0.7 Ib N02/
10^ Btu). The range of excess air levels anticipated for commercial
fluidized-bed combustor units is 15 to 20 percent. In this range the
data from larger fluidized-bed combustors suggest that the NOX emission
levels could be on the order of 129 to 301 ng N02/J (0.3-0.7 Ib N02/
10" Btu). With fluidized bed combustor design modifications such as
staged combustion the NOX emissions could possibly be limited even
further.
Currently, there is no generalized model available for a priori
prediction of NOX emissions in fluidized-bed combustion. Statistical
76
-------
analysis of the data gathered in this study resulted in poor regression
fit, possibly due to the scatter in the raw data. Also, the functional
dependence of NOX emissions on the operating variables chosen for
regression fit may not be representative of the NOX formation-
decomposition reaction mechanisms. Better regression correlations could
be developed for each individual data set, but these would have limited
application.
77
-------
6. TRACE ELEMENT RELEASE
INTRODUCTION
Pilot-scale tests of the fluidized-bed combustion of coal have
shown that air pollution from S02 and NOX emissions can be reduced in
order to meet EPA requirements. Coal contains many minor and trace ele-
ments in addition to carbon, hydrogen, nitrogen, oxygen, and sulfur,
that are chemically changed or are released during combustion. In
assessing the environmental impact of the FBC process, we must determine
the chemical fate of these trace and minor elements and assess their
potential toxicity.
f\
In previously reported work under this contract, Westinghouse
applied a thermodynamic model to project the chemical fate (and emis-
sions) of four trace elements in coal-fired FBC systems. These four
elements were: lead (Pb), beryllium (Be), mercury (Hg) and fluorine
(F). Since that earlier report was issued the trace element work has
been extended to include further evaluation of available trace element
emission data from conventional boilers and FBC systems and application
of the thermodynamic model to project the chemical fate in the FBC sys-
tem of eight additional elements: aluminum (Al), iron (Fe), titanium
(Ti), cobalt (Co), chromium (Cr), manganese (Mn), molybdenum (Mo), and
nickel (Ni).
This study emphasizes the chemical equilibrium reactions for the
eight metals in the PFBC and AFBC systems operating at 100 percent
excess air with 0, 90, and 99 sulfur removal efficiencies as a function
of temperature. Correlation of these reaction projections with 10 and
300 percent excess air combustion covers the range expected in the
alternative variations of the FBC process.
78
-------
Trace Elements in Coals
Numerous reports in the literature25-36 have Indicated that the
major mineral constituents of coal are silicon (Si), aluminum, titanium,
calcium (Ca), magnesium (Mg), iron, phosphorous (P), sulfur (S), sodium
(Na), and potassium (K). These mineral constituents exist either as
aluminosilicates (illites, kaolinites, mixed layers of illite, and mont-
morillonite), sulfides and sulfates (pyrites, marcasites), carbonates
(calcite, dolomite, siderite, ankerite), or as silica. At combustion
temperatures of 750°C the clay auminosilicates release lattice-bound
water and the sulflde fractions oxidize, releasing S02. The carbonate
fractions calcine, releasing C02; quartz (silica) remains as a stable
solid phase at high temperatures of combustion. Watt and Thorne-^
demonstrated that the ultimate fate of these constituents was princi-
pally associated with the final ash particle shape, color, and texture
and could be directly related to specific initial mineral phases in coal
that were present at the onset of combustion. By injecting powdered
specimens of shale, kaolin, sulfides, carbonates, and accessory minerals
into an air-coal gas or oxygen coal-gas flame (Table 4), they found that
fused particles that had formed appeared similar to the commercial ash
formed when pulverized coal is injected into boiler furnaces with suffi-
cient air to maintain combustion.
The trace elements lead, beryllium, mercury, fluorine, cobalt,
chromium, manganese, molybdenum, and nickel have the potential to exist
in more than one form in coal. The exact nature of the trace element's
occurrence in the coal particle may be an important factor in determin-
ing its behavior on combustion. Generally, the trace elements have been
reported to be associated with either the aluminosilicate minerals
(lithophilic) or the sulfide minerals (chalcophilic).-6 Miller et al.38
correlated the trace element association of fluorine with the clay alu-
minosilicate fraction, beryllium with the sulfide and sulfate fraction,
and mercury with both the clay and sulfur fractions. In addition to the
lithophilic and chalcophilic categories, Miller classified manganese
79
-------
Table 4
FUSION OF MINERAL PARTICLES IN A COAL GAS
FLAME - TYPIFYING COMMERCIAL ASH PRODUCTS37
MINERAL GROUP
SHALE
KAOLIN
CARBONATE
SULPHIDE
ACCESSORY
SILICATE
MINERALS
MINERAL SPECIES
MUSCOVITE
ILLITE
MONTMORILLONITE
KAOLIN I TE
ANKERITE
PYRI TE
QUARTZ
POTASSIUM FFLDSPAf
KYAN I TE
HORNBLENDE
TOURMALINE
8IOTITE
FLAME
COMPOSITION
AIR/COAL GAS
AIR/COAL GAS
AIR/COAL GAS
OXYGEN/COAL GAS
AIR/COAL GAS
OXYGEN/COAL GAS
OXY&EN/COAL GAS
OXYGEN/COAL GAS
OXYGEN/COAL GAS
APPEARANCt
SPONGY PARTICLES
GLASS SPHERES AND
CENOSPHfcKES
SPONGY PARTICLES
GLASS SPHERES
SPONGY PARTICLES
GLASS SPHtRES
SPONGY PARTICLES
GLASS SPHERES
OPAQUE NUN-MAGNETIC
SPHERrS
OPAQUE MAGNETIC SPHERES AND
HOUNDED PARTICLES" SOME SCO
HAEMATITE FkA&MENTS.
UNFUSED PAKTICES
GLASS SPHERES
GLASb SPHEKEb
LIGHT aRO*N ULASS SPHERES
BRONN GLASS SPHERES
BROWN OPAQUr GLASS SPHERES
and molybdenum as elements associated with the carbonate or the quartz
fraction in coal and chromium with quartz. The association of lead,
cobalt, and nickel with either the alumiriosilicate, sulfate, carbonate,
or quartz fraction was not identified.
The heterogeneous nature of coal when analyzed produces a range of
both trace and minor element concentrations that are the result of such
factors as geographical location (Table 5), coal rank (Table 6), and
location within the field or quarry. Illustrating the variation in
trace and minor elements contained in both coal and sorbent materials,
Table 7 presents a comprehensive listing of the elements and reported
concentrations considered in this study. Consistently throughout this
study only those values reported by Ruch and Gluskoter25 will be used.
Trace Element Behavior during Combustion
The fate of these elements during coal combustion depends not only
on the affinity, concentration, and distribution of each element with
the inorganic coal matrix, but also on process conditions such as tem-
perature, heating rate, exposure time at elevated temperatures,
80
-------
Table 5
AVERAGE TRACE ELEMENT CONTENT OF REGIONAL COALS
THROUGHOUT THE U.S, ppm29
\Region
Element: — ^
Be
F
Hg
Pb
Al
Co
Cr
Fe
Mn
Mo
Ni
Ti
West and
Southwest
1.1
4.6
13
3.1
14
250
Eastern
Interior
2.5
3.8
20
4.3
L5
450
Northern
Great Plains
1.5
2.7
7
1.7
7.2
591
Appalachian
Region
2.5
5.1
13
3.5
14
350
surrounding environment in either oxidizing or reducing conditions, type
of coal firing, and waste process removal systems. In a fluidized-bed
combustor, of course, some of these process conditions can be much
different from those that exist in a conventional boiler. For example,
the combustion temperature in a fluidized bed, 1100 to 1200 K, is much
lower than in a 1650 K conventional boiler. The mechanism and chemical
fate of the trace elements in fluidized-bed systems, however, has not
been delineated because of the limited data reported in the literature
and presently can only reflect an extension to low-temperature opera-
f\ s
tion data from the conventionally fired boiler systems. Lyon et al. ,
proposed the following mechanism for the behavior of the trace and minor
elements during combustion in conventional coal-fired boilers:
• Complex aluminosilicates do not decompose but melt and
coalesce to form slag or boiler bottom ash and fly ash.
81
-------
Table 6
AVERAGE TRACE ELEMENT CONTENT OF ASH FROM U.S.
COALS OF VARIOUS RANKS, ppm29
^\Rank
Element>\
Be
F
Hg
Pb
Al
Co
Cr
Fe
Mn
Mo
Ni
Ti
Anthracite
Coal
9
81
81
304
270
220
Bituminous Coals
Low
Volatility
16
189
172
221
280
141
Medium
Volatility
13
196
105
169
1432
263
High
Volatility
17
183
64
193
120
154
Lignite
6
60
45
54
688
129
During initial stages of combustion, a reducing environ-
ment probably exists within the coal particle and its
immediate vicinity. Under these conditions the chemical
bonding of metallic elements and sulfur in ,sulfide mineral
inclusions or between the elements and the organic matrix
may be broken, with the elements forming volatile species.
If the elements are dispersed in the coal organic matrix
they initially become dispersed in the gas stream when the
coal is burned.
Elements that initially are volatilized or dispersed in
the flue gas stream may then be oxidized to form less vol-
atile species that may then condense or be absorbed on the
fly ash as the temperature of the flue gas drops.
82
-------
Table 7
TRACE ELEMENTS IN COAL AND SORBENT MATERIALS (ppm)
COAL
ELFMf NT
RE
f
H(,
PB
AL
CO
CK
FE
MN
MO
MI
TI
FLFMEN r
HE
F
hb
PB
AL
CO
CK
FE
MN
MO
NI
TI
bLtlSKOTEH25 LYOM26 MASEt27 OS
1.61 0.64-3. 1
60.94 bO-160
n . 2 L) 1.122-99 U . 1 S
34.78 4.9-7.4 4-14
1 . 292 1 .08- 1.18
V.b7 2.9S-3.9bJ
13.75 18-22 2
1.928 1.18-1.68
49.40 33.8-S3 3
7.54 9-34
21.07 16
O.Q/S b(J6-55n 61
MURl HY*31
1.6
60.94
0.20
34.78
1 .80%*
0.57
13.75
2.328*
49.4
7.S4
21.07
U.098*
KAA< INEN32 UOUDBpRG3 MERKYM
3 2
<3
0.012 <2
2b <1
0.4V+0.03* 1.0« b«
b 10
100
0.37+O.G2Z l.Oa Nba
50 1 00
1+0.3 b 30
lb <10
SOU 500U
SORBENT
ELKMFMT rtElR30
K t -,.14-3.0
F 103-307
H (i <. . 0 1 - . 0 2
PB 1.3-26
AL
CO
CH .J . b 7 - 3 • 5
F£
MN 20.3-290
MO U,U4-lbO
N I 4 • 3-< 1 2
TI
MFHRYMAN 34 MURTHY 31
( A ) ( B )
<(J. DO&
^10
<0.3 U.2 0>2
j 0.2 B
0.18 0. 248 O.d7«**
0.3
b XZ 0 4.23
U.028 0.198 1,168**
1 0 U ^200 42
< J XI u 5
<2 XI 0 1
2 0.022 0.008Z**
OO OQ
NL WfcrtEKKA
2.2
190
17
J.U
12
U 38
3.1*
4 a9
14. a
21
Q U. 1 88
34 -35
AN CO AMEND
1 .b.2.44
121,62
1 .91 ,0.15
3.72,9.b
1 .45,4.8
15.4,24
2.38
3b,5U
14.8,15.0
385,695
*u«30
0. 16-2. 1
54-372
0. 131-U.322
U. 15-41
0.45-3.4
U.U-142.0
<0. 13-1 .3
2.3-51 . /
r T 36
CiTu
( A ) ( a i
1 • 1 0.7
117 61
<0,3 <0.3
8.b b. i
2.3 1.3
15 |4
l.b« 0 . 7 4 i
4b b/
H.6 <5o
790 720
(*) Pittsburgh No. 8 Coal
(A) #1359 Limestone
(B) Tymochtee Dolomite
(**) Reported as oxides
83
-------
• Since the slag is in contact with the flue gas for a short
time and at a high temperature, condensation of volatiles
on the slag is minimal.
Partitioning of the trace and minor elements in a conventional
boiler results, according to this mechanism, between the volatile stack-
gas emissions and the solid ash formation of either the slag or the fly
ash. Analysis of the ash and outlet gases by Lyon26 at the Allen Steam
Plant in Memphis, Tennessee indicates that the trace and minor elements
can be classified as:
• Elements that readily incorporate into slag forma-
tions: Al, Co, Cr, Fe, Mn, Ti, and possibly Ni. .These
elements do not volatilize in the combustion zone but form
a melt of rather uniform composition, divided almost
equally between the Ely ash entering the electrostatic
precipitator and the slag fraction. There is no apparent
tendency to concentrate these elements on ash particles
exiting from the electrostatic precipitator,
• Elements that concentrate in the inlet electrostatic pre-
cipitator fly ash instead of the slag,, and in the outlet
electrostatic precipitator fly ash instead of the inlet
electrostatic precipitator fly ash: Pb and possibly Mo.
These elements volatilize on combustion. With the removal
of the slag in the combustion zone, lead has no opportun-
ity to condense on the slag but condenses or becomes
adsorbed on the fly ash as the flue gas cools.
• Elements that remain completely in the gas phase: Hg.
O Q
Natusch et al., proposed a volatilization-condensation or adsorp-
tion mechanism that accounted for the relation between the trace element
concentration and the ash particle size. As the temperature of the flue
gas decreases, volatiles condense and chemically react with or are
absorbed onto the ash particle surface. Lyon*^, Cowherd^, and Cato^
have shown the concentration of the condensed element in a conventional
84
-------
boiler to be inversely proportional to the ash particle size as shown in
Tables 8 through 10. This finding would be expected since the surface
area increases as particle size decreases, thus increasing the concen-
tration of condensed volatile material per unit area.
The volatile trace and minor elements emitted in the stack gases
may be toxic. Cowherd et al.,-" however, indicated that the concentra-
tion of emissions from conventional utility boilers at ground-level is
less than the corresponding threshold limit value (TLV) for the various
inorganic trace and minor elements, with only the concentration of
beryllium approaching the level of potential concern. Limited informa-
tion is reported on potentially hazardous organic emissions. Polycyclic
organic material (POM) and polychlorinated biphenyls (PCB) could possi-
bly be formed within the corabustor prior to complete oxidation.
Although the exact chemical nature of the inorganic and organic
trace and minor elements in the Eluidized bed and stack gases is uncer-
tain, therraodynamic calculations at equilibrium allow a first-level
approximation for projecting the resulting product distribution in both
the condensed and the gas phases. The chemical reactions of the trace
and minor elements aluminum, cobalt, chromium, iron, molybdenum, manga-
nese, nickel, and titanium, in addition to chlorine, have been studied
for anticipated operating ranges of different fluidized-bed combustor
designs. The data will be discussed in light of available experimental
evidence or in-field data For the individual element reactions. A.n
investigation of the chemical interactions of these elements is not to
be presented in this report.
85
-------
Table 8
TRACE ELEMENT CONCENTRATION AS A FUNCTION OF PARTICLE SIZE AS
REPORTED BY LYON26
LOCATION: The Allen Plant, Memphis, Tennessee
DESCRIPTION: The boilers are fed with crushed coal via a cyclone
arrangement.
FUEL ANALYSIS: 9.5% moisture, 34% volatile matter, 43% fixed carbon,
approximately 13% ash, and 3.4% sulfur (as fired)
ASH COLLECTION: Approximately 60% goes through the slag tank, while
40% is collected by electrostatic precipitation.
Electrostatic Precipitator Inlet Fly Ash, ppm
Microns
Element
Be
F
Hg
Pb
Al
Co
Cr
Fe
Mn
Mo
Ni
Ti
>15
99600
56
433
181000
317
30
5860
14
97100
49
240
158000
294
51
6350
9
100000
45
250
140000
290
67
6670
6 I
t 3.5
1.4-0.5
80000 105000 95000 92100
50.6
320
67 65
83
420 490 634
140000 160000 156000 174000
320
110
6810
358 430
153 153
458
212
8280 9510 9630
Electrostatic Precipitator Outlet Fly Ash, ppm
Microns
Element
Be
F
Hg
Pb
Al
Co
Cr
Fe
Mn
Mo
Ni
Ti
11-2.9
57000
60
1100
143000
404
100
6670
2.0-1.3
99200
90
1300
170000
405
165
12000
0.9-0.6
86000
80
1000
77000
430
223
12600
86
-------
Table 9
TRACE ELEMENT CONCENTRATION AS A FUNCTION OF PARTICLE SIZE AS
REPORTED BY COWHERD35
LOCATION: Tennessee Valley Authority Widows Creek Steam Electric
Generating Station-Unit 5
DESCRIPTION:
The 125 MW utility boiler horizontally fired with pulver-
ized coal was equipped with a mechanical fly ash collec-
tor. Sampled streams included: pulverized coal, furnace
bottom ash, superheater ash, collection ash, and flue
gases at the inlet and outlet of the fly ash collection.
FUEL ANALYSIS: 1.42% moisture, 34.28% volatile matter, 48.46% fixed
carbon, 15.84% ash, and 3.47% sulfur (average weight
percent reported values for the Appalachian.coal)
ASH COLLECTION:
Two four-bank multiclone units used for fly ash col-
lection; V-type furnace bottom hoppers with water
sluice for bottom ash sampling
Dust Collector Inlet Sample, ppm
Microns
Element >3 .
Be
F '
Hg
Pb
Al
Co
Cr
96 2.35-3.96
5.2 8.7
14.5 15.5
26 30
251 458
Fe 145000 155000
Mn
Mo
Nl
Ti
149 274
460 840
1 1.61-2.35
4.7
29.5
28
1080
295000
189
690
0.87-1.61
5.4
12.1
58
3080
121000
569
2460
0.56-0.87
36.1
18.4
75
4510
184000
654
689
Dust Collector Outlet Sample, ppm
Microns
Element
Be /'
%£
Pb
Al
Co /
Cr/'
Fe
Mn
Mo
Ni -'
Ti
>2.87
12.6
10.5
55
347
105000
199
414
1.16-1.69
8.3
9.3
48
577
93000
288
319
0.61-1.16
3.5
6.8
67
709
68000
376
478
0.39-0.61
86
18.5
218
1790
185000
1560
512
87
-------
Table 10
TRACE ELEMENT CONCENTRATIONS AS A FUNCTION OF PARTICLE SIZE AS
REPORTED BY CATQ-36
LOCATION: Fremont, Nebraska
DESCRIPTION: Boiler Number 6 at the Fremont Plant was an Erie City Iron
Works water tube boiler with four Combustion Engineering
gas- and coal-type RO burners.
FUEL ANALYSIS: 6.85-7.65% moisture, 38.26-38.75% volatile matter,
43.07-43.58% fixed carbon, 10.18-10.79% ash, 1.03-1.28%
sulfur.
ASH COLLECTION: Dust collector was a mechanical cyclone type. Col-
lected materials include: bottom ash, dust collector
ash, flue gas collector inlet and outlet.
Inlet to Dust Collector, ppm
Microns
Element
Be
F
Hg
Pb
Al
Co
Cr
Fe
15 3.4
2.9 4.2
10 270
49 65
110 110
Mn 1100 900
Mo
Ni
330 47
Ti 7700 8400
Outlet from Dust
Collector, pptn
2.1
2.6
260
65
62
800
40
7000
1.4
3.6
570
78
170
1000
165
6100
0.69
9.1
300
69
83
1200
62
5400
0.34
<10
560
77
240
1300
260
<11000
Microns
Element
Be
F
Hg
Pb
Co
Cr
Fe
15 [ 3.44
4.3 3.3
200 360
63 66
92 58
Mn 1300 780
Mo
Ni
76 78
Ti 6900 6600.
2.06
3.5
360
62
62
1000
71
5700
1.38
6.3
400
57
55
1200
77
4800
0.69
<6.3
320
97
<140
1400
310
<14000
0.34
<15
410
1100
<360
1300
<340
<36000
88
-------
THERMODYNAMIC PROJECTIONS
In the previous Westinghouse study2 the effect that sulfur, chlo-
rine, and various fuel-to-air ratios have on the resulting partial pres-
sures of fluorine, beryllium, mercury, and lead complexes was investi-
gated in depth. The current study has extended this approach to pro-
jecting the reactions of aluminum, iron, titanium, cobalt, chromium,
manganese, molybdenum, and nickel in the fluidized bed, where chlorine
has the potential to act as an anionic carrier for each element.
The feedstock chosen in the fluidized-bed combustion study is a
model 3 to 4 percent sulfur coal with a mean composition for the U.S.
coals, as reported by Ruch and Gluskoter. 5 The calculated number of
moles for each key element fed into the fluidized bed per 100 grams of
coal burned is indicated in Table 11. Unlike the first Westinghouse
Table 11
COAL COMPOSITION25
Moles Fed to the
Fluid-Bed per 100 grams
Element Wt% of Coal Burned
C 70.28 5.8566
H 4.95 4^9107
N 1.30 0.0928
0 8.68 0.5425
S 3.27 0.1020
Cl 0.14 0.0039
Al 1.29 4.7811 x 10~2
Co 9.57 ppm 1.6239 x 10~5
Cr 13.75 ppm 2.6444 x 10~5
Fe 1.92 3.4380 x 10~2
Mn 49.40 ppm 8.9920 x 10~5
Mo 7.54 ppm 7.859 x 10~6
Ni 21.07 ppm 3.5889 x 10"5
Ti 0.07 1.4614 x 10~3
89
-------
study, in which the concentrations for beryllium, fluorine, mercury, and
lead were known for both coal and sorbent, in the present investigation
only the elemental coal concentrations are used. If sufficient data
were documented, reporting comprehensive elemental analyses for sorbent
materials, one would expect a negligible contribution of the sorbent's
trace or minor element concentration in the total (coal plus sorbent)
concentration and subsequent negligible impact on the calculated trace
element emission levels. Our approach has been to utilize one concen-
tration level for the trace and minor elements for the first-order emis-
sions estimate, emphasizing the potential chemical reactions and product
distribution at equilibrium for FBC systems operating at 100 percent
excess air with 0, 90, and 99 percent sulfur removal efficiencies as a
function of bed temperature. We have treated the effects of the vari-
able excess air ratios and system pressures as secondary in developing
the in-bed and above-bed chemical reactions- The expectation that only
minor variance in the partial pressure for the various volatile phases
would result in the PFBC as against the AFBC, or in the 10 percent
excess air as opposed to the 300 percent excess air system with 0 or
99 percent sulfur removal rather than the formation of additional
phases, is confirmed (See Appendix C). The detailed results of the
thermodynamic calculations at LOO percent excess air, 1013 kPa (10 atm)
total pressure for 90 percent sulfur removal efficiencies are given in
Appendix D.
Thermodynamic Equilibrium Calculation Basis
The equilibrium composition for trace element FBC conditions is
calculated by minimizing the Gibbs free energy of the polyphase system,
using the techniques of Geometric Programming,40 in addition to satisfy-
ing the mass conservation equations.
The Gibbs free energy (G) of a multicomponent system is represented
by a summation over the mixture chemical species; in other words
G =
(D
90
-------
where G^ = y^ is the molar chemical potential and n^ is the number of
moles of the lt11 species. The molar chemical potential is expressed as
U± = U° + 6 (RT In P±) , (2)
where for a gaseous species 5 = 1.0, and for a condensed species 6=0.
In the above equation P^ is the partial pressure of the gaseous species,
T is the gas temperature, R is the universal j
species's chemical potential at unit fugacity
T is the gas temperature, R is the universal gas constant, and \i is the
P° - H° - TS° . (3)
The molar enthalpy (H.) and molar entropy (S.) are the species's stan-
dard therraochemical properties which are functions of the species's
standard specific heat (C .) as shown in the following equations:
H° (T) = f C° dT + AH° (T ) (4)
Jn. ''
f
and
j
3±(T) = /
S.(T) = -* , (5)
The variable AH^ is the standard heat of formation for the compound at
the reference temperature (Tr) of 298.15 K.
The chemical equilibrium program determines the value of n-^ for
each species in all possible solid, liquid, or gaseous phases, given the
species's standard therraochemical data (as reported in the litera-
ture), 1~*9 the total gas pressure, and the mass constraints on the
91
-------
system. Tables 12 and 13 Illustrate the major combustion gas, minor,
and trace species for which thermocheraical data are available. The data
for each species have been reduced and used as input for the chemical
equilibrium calculations. It should be noted that this study considers
only the reactions of compounds for which therraodynamic data are avail-
able. It is reasonable to assume that other compounds may form in the
fluid-bed system, but data for such compounds have not been cited in the
literature, nor have estimates of their free energy, heats of formation,
or molecular constants been made in this study. We believe that com-
pounds not reported in the literature are less likely to form than are
those for which data are cited.
For each of the eight trace elements considered in the current
study, the system used in the thermodynaraic program was C-H-N-0-S-C1-X,
Table 12
C-H-N-0-S-C1 SPECIES CONSIDERED IN FLUID-BSD
COMBUSTION REACTIONS
GASES
C
CC1
CC12
CC120
CC13
CC14
CH
CHN
CHNO
CHO
GH2
CH20
CH3
CH4
CN
CHN
CN2
CO
C02
C2
C2C14
C2Clg
C2«
02H9
C2 H4
C2H40
C2N
C9N9
c2o"
C3
c3o2
C4
C4N2
cs
COS
Cl
C1HO
CIO
C102
C12
C120
H
HC1
UNO
HN03
HO
H02
US
H2
H20
a2s
H2S04
N
NH
NcI2
NH3
NO
N02
N03
MS
N2
N2H2
N9H4
N20
N203
N204
N205
0
°2'
°3
S
S2
S3
S3
SO
so?
so3
S20
SOLIDS/LIQUIDS
C
92
-------
Table 13
TRACE AND MINOR SPECIES CONSIDERED IN FLUID-BED COMBUSTION REACTIONS
GASES
Al
A1C1
A1C10
A1C12
A1C13
A1H
A1HO
A1H02
A1N
A10
A102
A1S
A19C12
Al2C16
A120
A1202
Co
CoCl
CoCl2
CoCl3
CoCl4
Cr
CrCl
CrCl2
CrCl3
CrCl4
CrN
CrO
Cr02
Cr02Cl2
Cr03
Cr02(OH)2
Cr02OH
CrS
Cr2
Fe
FeCl
FeCl2
FeCl3
Fe2Cl4
Fe2Cl6
FeH202
FeO
FeOCl
Mn
MnO
MnCl
MnCl?
Mo
MoO
MoO?
Mo03
Mo02Cl?
MoCl4
MoCl5
MoClg
Mo04H2
Ni
NiO
NiCl
NiCl 9
NiH
NiFe2Clg
Ni(C04)2
Ni(OH)2
Ti
TiS
TiO
Ti02
T1C1
TIC 10
T10C12
T1C13
TiCl4
SOLIDS/LIQUIDS
Al
A1C10
A1C13
A1(OH)3
A1N
A12°3
A1(S04)3
Co
CoCl2
CoO
CoS04
Co304
CoS0.89
Cr
Cr(CO)6
CrCl2
CrN
Cr02
Cr03
CrS3
Cr2(C03)3
Cr2N
Cr203
Cr2S3
Cr2(S03)3
Cr2(S04)3
Cr3C2
Cr4C
Cr7C3
Cr23C6
FeCl2
FeCl3
Fe
FeH202
FeH303
Fe°0.947
FeO
Fe2°3
FeS04
Fe2012S3
FeS
Fe304
Mn
MnC03
MnC2
MnO
MnO?
MnS"
MnS04
MnCl2
Mno03
Mn3C
Mn7C3
Mn304
Mo
MoSo
MoS3
MoO
MoO 9
Mo03
MoCl4
MoCl5
MoCl6
Mo(GO)6
Mo2C
Mo2N
Mo2S3
Mo3C2
Ni~
NiS
NiO
NiS04
N1C12
Ni3S2
Ti"
TiS2
TiO?
TiC2
TiCl3
TiCl4
Ti203
Ti305
Ti407
TiiI2
TIC
TiO
93
-------
where X is the specific trace or minor element involved. That is,
interactions between the trace and minor constituents were not consid-
ered in the current discussion.
Thermodynamic Equilibrium Reactions for Noninteractive Trace and Minor
Element Systems
Multiple reactions that occur in fluidized-bed combustors produce
numerous solids, liquids, or gaseous compounds that are dependent on the
pressure and temperature of the system. The final concentration of each
phase is a function of the relative concentration of speciific elements
or compounds introduced into the reaction as constituents from feedstock
materials. This study assumes 100 percent release of the feedstock ele-
mental concentrations and does not account for partial conversion of the
individual elements from one phase to another phase, the interaction
between the various trace and minor elements with either the clay or
carbonation fractions, or the kinetics of these reactions. The follow-
ing sections simply describe the chemical reactions of each trace or
minor element in fluidized-bed combustion systems.
Aluminum
The major chemical reaction of aluminum in FBC systems at equi-
librium is the formation of aluminum oxide, Al203
-------
At temperatures typical of the fluidized bed (815-900°C), there-
fore, the major chemical form of aluminum is that of the oxide rather
than the sulfate phase, as illustrated in the tables presented in Appen-
dix D. For 0 percent sulfur removal systems where the maximum sulfur
content has been released into the combustion stream, A1203 is no longer
projected to be present as a solid below 527°C because of the total con-
version of aluminum into the solid sulfate phase. The temperature of
the oxide — *• sulfate transition is a function of the total pressure of
the system and sulfur concentration.
No major volatile compounds are projected to form over the
(major phase)/Al2(SC>4)3 (potential minor phase) solids at f luidized-bed
operating temperatures. Insignificant traces of gaseous aluminum tri-
chloride (AlC^), aluminum oxycloride (A10C1), aluminum dichloride
(A1C12), aluminum dioxide (A102)> aluminum monoxyhydride (AlOH), alumi-
num monochloride (A1C1), aluminum monoxide (A10), and aluminum trichlo-
ride dimer (A^Clg) are thermodynamically projected to exist in equili-
brium with the solids at partial pressures of lO"-^ ^a (io~14 atni) ancj
below. The reaction of hydrogen chloride (HC1) with A^f^ influences
the formation of the volatile aluminum phases, as shown in reactions 7
and 8 .
Al203(s) + 6HCl(g) — *2AlCl3(g) + 3H20(g) (7)
Al203(s) + 2HCl(g)— «-2A10Cl(g) + H20(g) . (3)
In summary, the parametric calculations demonstrate that at fluid-
ization temperatures, aluminum released from the combustion of coal will
primarily exist as the solid oxide. The formation of an alternate
phase, the most probable of which is the sulfate, has the potential to
form from the reaction of aluminum with gaseous SOX if equilibrium is
attained locally within the bed where fluidization temperatures have
decreased to below 527°C. The major chemical composition of the fines
that are carried over from the bed into the cyclone are therefore pro-
jected as an oxide phase. Conversion of the fines, and subsequent stack
95
-------
gas emissions of the oxide to the sulfate, is not expected, nor has it
been demonstrated in the presented first-level equilibrium
calculations.
Iron
The principal reaction of iron in fluidized-bed combustion systems
is the formation of hematite, Fe303, and diiron trisulfate, Fe2(S04)3.
The relative concentration and stability of each compound is dependent
on the concentration of sulfur and the operating temperature of the sys-
tem. Hematite is the stable solid iron complex in fluidized-bed systems
operating at temperatures of 815 to 900°C; transition into magnetite,
Fe304, an alternate oxide structure as shown in reaction 9, would result
when combustion temperatures exceeded 1462°C.
6Fe203(s) —*4Fe304(s) + 02(g) . (9)
The reaction of iron with sulfur released from the combustion of .
coal produces Fe2(S04)3 at low temperatures in the fluidized bed:
or
Fe203(s) + 3S03(g)-*Fe2(S04)3(s) , (10)
Fe203(s) + 3H2S04(g)—«-Fe2(S04)3(s) + 3tI20(g) . (11)
For example, at equilibrium in fluidized-bed systems operating at
0 percent sulfur removal, solid Fe203 would be present until combustion
temperatures were reduced to below 627°C, whereupon 100 percent of the
iron released during combustion would react wiiih sulfur, forming solid
Fe2(S04)3. In the 90 percent sulfur removal systems considered in this
study, Fe203 is the stable major phase formed at fluidizing temperatures
and within cooler regimes, with Fe2(S04)3(s) present as a seondary phase
which is stable within the temperature range from 27 °C to between 527
96
-------
and 627°C.* Although FBC temperatures are well above 627 °C, this lower
temperature could be experienced by particulates carried out of the bed
into the cooler flue gas zones.
For a typical U.S. mean coal the major volatile compounds, iron
dihydroxide (Fe(OH2), iron dlchloride (FeCl2), iron trichloride (FeCl3),
formed pressures of 10~7 kPa (10~9 atm), as shown in Appendix D. These
volatile phases have the potential to escape as stack gas emissions, to
condense and deposit as iron oxide (Fe203) (Fe2(SC>4)3 if sufficient SOX
is present at equilibrium) on cooler metal surfaces, or to nucleate
along the surface of entrained flue gas ash particulates. The possible
series of reactions that could occur are illustrated below.
2Fe(OH)2(g) + 1/2 02(g) -*Fe203(s) + 2H20(g) (12)
(2Fe(OH)2(g) + 2 02(g) + 3S02(g) -* Fe2(S04)3(s) + 2H20(g))
2FeCl2(g) + 2H20(g) + 1/2 02(g) -* Fe203(s) + 4HCl(g) (13)
(2FeCl2(g) + 2H20(g) + 2 02(g) + 3S02(g) — *Fe2(S04)3(s) + 4HCl(g))
and
2FeCl3(g) + 3H20(g)-*-Fe203(s) + 6HCl(g) (14)
(2FeCl3(g) + 3H20(g) + 3S02(g)
+ 3/2 02(g)-»-Fe2(S04)3(s) + 6HCl(g)) .
Trace FeO, Fe2Cl4, FeCl, and (Fe2Cl3)2 could be thermodynamically formed
in addition to the major volatile compounds. These trace phases do not
exert partial pressures greater than 10"1-4 kPa (lO"1^ attn) at combustion
temperatures of 927 °C.
*Parametric calculations were performed in 100 degree increments.
Attempts at defining the specific transition or conversion temperature
as a function of pressure and combustion gas compositions x*ere not
made.
97
-------
Titanium
The projected equilibrium reaction of titanium in fluidized-bed
combustion systems is the formation of rutile, Ti02, as a stable solid
under the various temperature, pressure, excess oxygen, and sulfur
removal conditions. The major gaseous titanium compounds that could be
formed in equilibrium with rutile are titanium oxydichloride (TiOCl2).
titanium tetrachloride (TiCl4), and titanium dioxide (Ti02), as shown in
the following reactions:
t > 727°C
Ti02(s) + 2HCl(g) ^ -TiOCl2(g) + H20(g) (15)
t > 727°C
TiCl4(g) + 1/2 02(g)«« -TiOCl2(g) + 2Cl(g) (16)
t < 727°C
Ti02(s) + 4HCl(g) + *TiCl4(g) + 2H20(g) (17)
Ti02(s)*-*Ti02(g) . (IB)
As shown in Appendix D, the partial pressures of none of these projected
gaseous species exceed 10~*-> kPa (10"^' atm) and, hence, are not consid-
ered significant.
With variation in pressure at temperatures in excess of 727°C and
10 percent excess air, the partial pressure of TiOCl2 is projected to be
greater than TiCl4 and TiC>2, as shown in Appendix C. In systems operat-
ing at 100 percent excess air and 1013.6 to 1520.4 kPa (10-15 atm), the
partial pressures of the resulting gases should be similar to those of
the 10 percent excess air system (ppTiOC!2 > ppTiC!4 > ppTi02). If the
total system pressure were decreased to 101.3 - 1520.4 kPa (1-15 atm),
TiOCl2 would be the major gaseous phase, with the partial pressure of
Ti02 exceeding the partial pressure of TiCl4. Increasing the excess air
content to 300 percent favors the formation of TiOCl2 > Ti02 > TiCl4 at
all system pressures.
When the temperature of the fluidized-bed system is less than 727°C
the predominant gaseous phase is thermodynaraically projected to be
98
-------
TiCl4- These reactions apply for both 0 and 90 percent sulfur removal
systems. Variation in the sulfur content should not appreciably affect
the resulting partial pressure of each gas phase. The slight decrease
in the partial pressure of each compound at 90 percent sulfur removal,
if monitored, would not be detectably different from that of the 0 per-
cent sulfur removal system. Solid sulfur-titanium compounds are not
expected to form in the FBC system.
Data for titanium hydroxide (Ti(OH)x) compounds are not contained
in the present data file. Consideration may be given later to the pos-
sible formation of these compounds.
Similarity in the degree of volatilization of the minor elements
and solid formation has been projected for aluminum, iron, and titanium.
The principal volatile phases that are likely to form include the chlo-
ride complexes, exerting generally insignificant partial pressures over
the stable solid oxides.
Cobalt
Solid cobalt sulfate, CoS04, and cobalt oxides, CoO and Co304, are
formed in FBC systems operating at 10, 100, and 300 percent excess air.
The major chemical reactions include
3CoS04(s) + 1/2 02(g)—~Co304(s) + 3S03(g) (19)
CoS04(s) —-CoO(s) + S03(g) (20)
Co304(s) *3CoO(s) + 1/2 02(g) - (21)
The transition of CoS04 to CoO occurs in three successive decomposition
reactions as the temperature of the system is increased. Cobalt sulfate
releases S03, forming Co304 at temperatures of 727 to 827°C for 10 per-
cent excess air, 627 to 827°C for 100 percent excess air, and 627 to
727°C for 300 percent excess air for 0 percent sulfur removal condi-
tions. In 90 percent sulfur removal systems the temperature at which
CoS04 is stable is further reduced to between 627 and 727°C for 10 per-
cent and 100 percent excess air, and to between,527 to 627°C for
99
-------
300 percent excess air. Initially, the decomposition product is €0304,
followed by the formation of a mixture of €0304 and CoO, and finally
complete conversion to CoO as the temperature of the system is
increased.
The major gaseous phase formed in equilibrium with the 00804/003047
CoO solids is cobalt dichloride (C6C12), exerting a partial pressure of
lO"* kPa (10~6 atm) at fluidized-bed combustion bed temperatures.
Depending on the operating system temperature the following reactions
occur:
CoS04(s) + 2HCl(g) - *CoCl2(g) + H2S04(g) (22)
Co304(s) + 6HCl(g) - *3CoCl2(s) + 3H20(g) + 1/2 02(g) (23)
CoO(s) + Cl2(g)— *CoCl2(g) + 1/2 02(g) . (24)
Further reaction of CoCl2 with cloride yields cobalt trichloride
(CoCl3):
2CoCl2(g) + Cl2(g)*— ^2CoCl3(g) . (25)
Trace quantities of the cobalt dichloride dimer, Co2Cl4, are formed at
high combustion temperatures, in addition to cobalt monochloride, CoCl.
Data for cobalt hydroxides, oxychlorides, and oxide compounds are
not contained in the present data file. Consideration may later be
given to the possible formation of these compounds.
The concentration of cobalt released as a gas into the effluent
stream after combustion of U.S. mean coal for a typical pressurized
fluidized bed at 815 to 900° C, operating with 100 percent excess air
levels and 90 percent sulfur removal efficiencies is approximately
7.0 ppm. Although cobalt is projected to be more volatile than either
aluminum, iron or titanium, the projected trace emitted level is far
below the minimum acute toxicity effluent level^ of 100 ppm for cobalt
*Cl2(g) at low temperatures; 2Cl(g) at high temperatures.
100
-------
fume and 1600 ppm for CoCLj- Similar mechanisms of nucleation or con-
densation discussed for the preceding elements are applicable to the
gaseous cobalt phase. Solid emissions from the bed may contain
entrapped particles of either CoS04 » c°3°4 or Co°» depending on the sys-
tem's operating temperature.
Chromium
In an oxidizing environment, chromium oxide, Cr203 , forms as a
stable solid over the temperature range of 27 to 927°C. In the pres-
sence of sulfur, conversion to the sulfate by the reaction
Cr203(s) + 3S03(g) — *.Cr2(S04)3(s) (26)
is not projected at conditions existing in the fluidized bed. Ash
formed from combustion within the bed, therefore, and fines released
into the effluent gas stream are projected to contain chromium as
At temperatures greater than 121° C the major volatile phase pro-
jected to be formed in equilibrium with the oxide is dihydroxy-dioxy-
chromium VI (CrCICg)) as shown in reaction 27:
Cr203(s) + 2H20(g) + 02(g)— *>.2Cr04H2(g) . (27)
As the local temperature within the bed decreases below 727°C, however,
reaction with hydrogen chloride (HC1) and oxygen enhances the formation
of the oxychloride rather than the hydroxide complex (reaction 28):
Cr203(s) + 4HCl(g) + 02(g)— »2Cr02Cl2(g) + 2H20(g) . (28)
In addition to these major chromium volatiles, which exert maximum par-
tial pressures of approximately 10"^ kPa (10~^ atm), trace levels of
volatile chromium oxides and chlorides as Cr03 , Cr02, CrCl3, CrCl2,
CrCl4» and CrO are projected to form at partial pressures less than
10~6 kPa (10~8 atm) for a 927°C fluidized bed.
101
-------
Manganese
The thermochemical equilibrium reaction of manganese with FBC gases
containing sulfur and HC1 is the formation of solid manganese sulfate
(MnSC>4) and/or the manganese oxides Mn203, and Mn304 . At temperatures
below 627°C MnS04 is the stable solid form in both 0 and 90 percent sul-
fur removal conditions. As the temperature is increased to 827°C at
10 percent excess air, and 927°C at 100 percent and 300 percent excess
air, MnS04(s) is converted to Mn203(s) by the reaction
2MnS04(s) + 1/2 02(g) —»Mn203(s) + 2S03(g) . (29)
At temperatures greater than 927°C Mn203(s) releases oxygen, forming
solid Mn304:
3Mn203(s)—»2Mn304(s) + 1/2 02(g) . (30)
The likeliest manganese complex in the fluidized bed, therefore, is
Mn2°3» with the potential formation of MnS04 when the temperature of
equilibrated bed material is reduced to below 727°C.
The principal manganese gaseous compounds projected to be formed in
equilibrium with the manganese sulfate or oxide solid is manganese
dichloride (MnCl2). At 927°C operational temperatures the partial pres-
sure exerted by the innocuous volatile MnCl2 complex is approximately
10~* kPa (10~" atm). Additional gaseous phases of manganese chloride
(MnCl), manganese oxide (MnO), and manganese are present at trace levels
(10 kPa [
-------
therraodynamic calculations molybdenum trloxide, MoOg, is projected to
form as the stable solid equilibrium product between 27 and 327°C.
Volatilization of the compound should begin when the system temperature
exceeds 327°C and is enhanced in the presence of water vapor at high
temperatures, according to the reaction
Mo03(s) + H20(g) -*Mo02(OH)2(g) . (31)
In fluidized-bed combustion gases containing chloride, volatilization of
solid MoC>3 is complete, with a subsequent reaction of molybdenum with
chlorine, forming the dioxydichloride complex, Mo02Cl2, as shown in
reactions 32 and 33.
Mo03(s) + 2HCl(g) -*Mo02Cl2(g) + H20(g) (32)
Mo03(s) + Cl2(g) —-Mo02Cl2(g) + 1/2 02(g) . (33)
With the feedstock molybdenum concentration assumed for this study
(Table 11), the partial pressures of molybdenum dioxydihydroxide
(Mo02(OH)2) and Mo02Cl2 are thermodynamically projected to be as high as
10-13 and 10~16 kPa (10~15 and 10~18 atm) respectively, at the
fluidized-bed temperature.
Gas phases that are projected to be formed in addition to Mo02(OH)2
and Mo02Cl2 include Mo03, molybdenum dioxide (Mo02), molybdenum tetca-
chloride (MoCl^, molybdenum pentachlortde (MoClg), molybdenum monoxide
(MoO), and molybdenum hexachloride (MoClg) as shown in Appendix D.
In conclusion, the parametric calculations projected complete vola-
tilization of molybdenum contained in the feed stock material. The
ultimate fate of gaseous molybdenum complexes would appear to be
released as stack emissions. The possiblity of condensation of molybde-
num along cooled metal surfaces or nucleation by entrained ash particles
should be considered as potential mechanisms that minimize the concen-
tration of molybdenum in the stack gases. The current thermodynamic
103
-------
model has not taken into account potential removal sites in the process
design. No data are available documenting the toxicity of molybdenum
from industrial exposure.•**•
Nickel
The formation of stable nickel oxides and sulfate solids in the
fluidized bed is dependent on the system parameters of temperature,
pressure, excess air, and sulfur content. The major chemical reactions
of nickel in fluidized-bed gas that occur at equilibrium include
t > 827°C
NiO(s) •> NiO(g) (34)
t = 527 to 727°C
NiS04(s) »N10(s) + S03(g) (35)
NiS04(s) + 2HCl(g)—-NlCl2(g) + H2S04(g) (36)
NiO(s) + 2HCl(g)-—»NlCl2(g) + H20(g) (37)
NiS04(s) + H20(g)—*Ni(OH)2(g) + S03(g) (38)
NiO(s) + H20(g) —»Nl(OH)2(g) . (39)
With 0 percent sulfur removal, nickel sulfate (NiS04(s)) is pro-
jected to be present at temperatures between 727 and 827°C for pressures
of 506.5, 1013.6, and 1520.4 kPa (5, 10, and 15 atm) prior to the con-
version of the solid complex into nickel oxide, NiO (reaction 35) when
the operational temperature of the system is increased. The temperature
of the sulfate/oxide conversion, however, is between 627 and 727°C for
atmospheric, 0 percent sulfur removal systems. Similarly, Appendix D
illustrates a typical 90 percent sulfur removal PFBC system operating at
100 percent excess air levels where the sulfate/oxide transition occurs
between 627 and 727°C. Within the bed, therefore, the major chemical
phase of nickel at equilibrium should be that of the oxide.
The major volatile nickel species projected to form over NiS04(s)
or NiO(s) is nickel dichloride (NiCl2). The partial pressures exerted
104
-------
by the chloride are approximately 10~4 kPa (10~6 atm) at the fluidized-
bed temperature. Secondary gaseous phases that are projected to form
include nickel hydroxide (Ni(OH)2), nickel chloride (NiCl), NiO, nickel,
and nickel hydride (NiH). These gaseous phases are not considered
potentially toxic, even if the concentration in the stack gases were to
approach the level of 100 percent release of the content in the feed-
stock materials during combustion. Nickel carbonyl, Ni(CO)4, is consid-
ered most toxic of all the nickel compounds^ but is not projected to
form in the effluent combustion streams.
Summary of Reactions
Table 14 illustrates the resulting partial pressures of the gaseous
aluminum, cobalt, chromium, iron, manganese, molybdenum, nickel, and
titanium compounds and the number of moles of condensed phases if we
assume 100 percent combustion release of the individual elements in the
feedstock materials for a FBC system operating at 100 percent excess air
and 1013 kPa (10 atm) total pressure, with 90 percent sulfur removal
efficiencies. As indicated previously, these levels reflect combustion
of a U.S. mean coal within the fluidized bed and do not present the
reactions of interactions of carbonate (calcium and magnesium) and clay
(aluminum and silicon) with the trace and minor elements.
The levels of sulfur present in the various parametric calculations
were chosen to illustrate sulfur removal efficiencies (0, 90, and
99 percent removal) for systems in which the coal-to-sorbent feed ratios
is approximately 3.6.
A summary of the trace and minor element equilibrium calculations
indicating the principal condensed and volatile phases projected to be
formed and the volatilization percentage of each element from the feed-
stock material is presented in Table 15. Thermodynamically, the ele-
ments may be classified as those that have the potential to volatilize
completely at combustion temperatures within the fluidized bed (i.e.,
Mo), those that have the potential to volatilize partially (i.e., Co,
105
-------
Table 14
PARTIAL PRESSURE OF GASEOUS COMPOUNDS AND MOLES OF CONDENSED
COMPOUNDS IN PFBC PROCESSES AT COMBUSTION TEMPERATURES
Fluid Bed Combustion - Partial Pressure of Gaseous Compounds
100% Excess Air
90% Sulfur Removal
10 Atmospheres Total Pressure
Compound
Cr02OH
CoCl2
MnCl2
NiCl2
Ni(OH)2
Mo02Cl2
FeCl2
Fe(OH)2
CoCl3
FeCl3
Mo03
NiCl
Cr02
CoCl
MnCl
NiO
A1C13
TiOCl2
A10C1
CrCl4
FeO
MnO
Ni
TiCl4
Ti02
Fe2Cl4
Mn
FeCl
A102
927°C
(1700°F)
.3085-05
.1158-05
.4485-06
.3246-06
.2928-06
.2278-06
.3859-07
.3466-08
.1995-08
.1064-08
.3018-09
.3573-10
.2492-10
.1144-10
.4614-11
.1721-12
.1001-12
.5560-13
.1255-13
.1113-13
.1148-14
.8902-15
.3277-15
.7915-16
.7319-16
.5618-16
.2248-16
.1609-16
.1907-16
.5341-17
.3896-17
.7713-18
.5051-19
.4511-19
.1636-19
827°C
(1521°F)
.1395-05
.1143-05
.7081-07
.9051-07
.7825-07
.8949-07
.5283-08
.8095-08
.1805-09
.1820-09
.1704-10
.2421-10
.1523-10
.1352-11
.1513-12
.2221-14
.1650-14
.1803-13
.1644-15
.8044-16
.2712-15
.1881-15
.1174-16
.3890-17
.1183-17
.5141-16
.6581-19
.5125-19
.4735-19
.3147-17
.1318-19
.8209-19
,5707-22
.1696-21
.4495-22
727°C
(1341°F)
.5435-06
.1122-05
.7670-08
.1783-07
.1563-07 '
.2874-07
.4869-09
.2183-07
.9972-11
.2151-10
.5349-12
.1383-10
.8337-11
.1015-12
.2454-14
.1178-16
.1086-16
.3911-14
.8772-18
.2135-18
.4802-16
.2839-16
.2112-18
.1039-18
.8296-20
.4514-16
.5811-22
.5032-22
.3494-22
.1679-17
.1399-22
.5444-20
.1619-25
.2036-24
.3747-25
627°C
( ~\ 1 £ ~\ O T7\
i J_J_ D-L .r )
.1746-06
.1073-05
.5036-09
.1835-09
'.2956-09
.6712-09
.2511-11
.7003-07
.2854-12
.1489-11
.7691-14
.5198-12
.3715-11
.4091-14
.1485-17
.1908-19
.1749-20
.3424-17
.1981-21
.1430-22
.5485-17
.2706-17
.1505-20
.1188-20
.1878-22
.3700-16
.1031-25
.1448-26
.4908-27
.7312-18
.3160-26
.1769-21
.1023-30
.5202-28
.6367-29
106
-------
Table 14 (Cont'd)
T1C13
A1C12
CrO
Mo02
NiH
Fe
CrCl
(FeCl3)2
TiOCl
A10H
MoCl4
A1C1
T1C12
Cr
A10
TiO
MoCl5
A12C16
Mode
.6723-20
.4300-20
.3581-20
.9955-21
.3757-21
.3134-21
.1366-21
.8435-22
.4497-23
.5882-24
.2616-24
.1178-24
.3466-26
.3024-27
.1933-27
.8097-29
.5311-29
.1430-31
.6073-37
.4032-21
.5440-22
.4201-23
.5174-23
.4356-24
.1960-24
.2835-24
.1064-21
.1105-25
.5490-27
.1082-24
.1324-27
.1041-28
.5195-31
.4842-31
.1031-32
.4887-29
.2232-32
.6452-37
.1378-22
.2843-24
.1253-26
.9090-26
.1287-27
.2727-28
.1669-27
.1399-21
.8068-29
.1246-30
.3638-25
.3772-31
.9714-32
.1548-35
.2268-35'
<-35
.4302-29
.2447-33
.6775-37
.2105-24
.4405-27
.6004-31
.3688-29
.5905-33
.5076-33
.1819-31
.1732-21
.1143-22
.4298-35
.9093-26
.1687-35
.1832-35
<-35
<-35
<-35
.3504-29
.1507-34
.6880-37
Fluid Bed Combustion - Moles of Condensed Compounds
100% Excess Air
90% Sulfur Removal
10 Atmospheres Total Pressure
Compound
A1203
C0304
NiO
N1S04
927°C
(1700°F)
.2390-01
.4668-05
.0000
.2790-05
.1719-01
.4397-04
.0000
.3399-04
.0000
.1460-02
827°C
(1521°F)
.2390-01
.5201-05
.0000
.85.79-05
.1719-01
.4470-04
.0000
.3521-04
.0000
.1460-02
727°C
(1341°F)
.2390-01
.0000
.1610-04
.1306-04
.1719-01
.4491-04
.0000
.3562-04
.0000
.1460-02
627°C
(1161°F)
.2390-01
.0000
.1619-04
.1306-04
.1719-01
.0000
.8989-04
.0000
.3576-04
.1460-02
107
-------
o
oo
Dwg. 2624C84
Table 15
SUMMARY OF TRACE AND MINOR ELEMENT REACTIONS IN FLUIDIZED-BED COMBUSTION SYSTEMS
Element
Al
Co
Cr
Fe
Mn
Mo
Ti
Coal
Wt t/ppm
1.29%
9. 57 ppm
13. 75 ppm
1.92%
49. 40 ppm
7. 54 ppm
0.07%
Condensed
Phases
AI2Oj, AI2(S04>3
CoS04. Co3O..CoO
Cr203
Fe20j. Fe2(S04l,
MnS04. MruOj,
Mn304
MoOj
Ti02
Sulfate/Oxide Conversion Reactions
700-800 K
AI2IS04l3 Al?03(s) +3S03(g>
1000-1100 K
Co304lsl +3S03(g)
Cr203(sl
800-900 K
Fe^sl+SSOjfgl
800-900 K
Mn203lsH-2S03(g>
MoOjIs)
900-1000 K
Ti021200K
1000-1100 K
1000-1100 K
>1200K
looo- HOOK
400- 500 K
>1200K
Volatile
Phases"
AlClj. AIOCI.
AlClj, AIOH.
AICI. AIO.
CoClj. CoClj.
Co2CI4. CoCI
Cr04H2. CrOXL.
CrOjOH, CrOj.
Cr02. CrCI3.
CrCI2. CrCI4.
CrO.CrCI.Cr
FeClj. FelOHlj.
FeCL. FeO
ref\t FeCI.
IFeCI3)2. Fe
MnCU MnCI.
MnO, Mn
M004H2.M002CI2.
MoO,. MoO^
MOCI4. MoO.
Mod 5. MoCI6
NiCI. NiO. Ni,
NiH
FiOCI2. TiClj.
TICI2. TiCI.
TiCI4. TiOCI.
T^ TiO
Percent
olatilization at
27°C(1200IO"
aoz
13.76
7&6
0
2.2
100
0
'Major volatile phases are reported initially
"" Percent volatilization at 927°C for a FBC system operating at 1013 kPa, with 90% sulfur removal and 100% excess air
-------
Cr, Mn, Ni), and those that will remain in condensed ash phases with
almost no volatilization (i.e., Al, Ti, Fe). The elements that par-
tially or completely volatilize may condense along cooler metal surfaces
within the system or nucleate through either a physical adsorption mech-
anism or chemical reaction with entrained flue gas ash particles. In
the final particle control device (a fabric filter or electrostatic pre-
cipitator), for example, in an AFBC system operating between 150 and
375°C, condensation or nucleation reactions of the molybdenum, cobalt,
chromium, manganese, nickel gaseous complexes with the entrained ash may
occur, thus reducing the concentration of trace and minor elements in
the stack gases. In a PFBC system with hot gas and particulate clean-
ing, however, a higher concentration of volatile complexes is likely to
pass through the control device and escape as a stack gas emission pro-
duct.* Utilizing the thermodynamic calculations for the trace and minor
elemental product distribution in the fluidized bed as a first-level
approximation for projecting the ultimate fate and stack gas emission
concentration is therefore useful. With this basic understanding fur-
ther modeling which requires additional information concerning the pro-
cess design, the partitioning of gaseous phases with entrained ash
materials, and reaction kinetics will aid in ultimately determining the
fate of both innocuous and potentially toxic elements or complexes
within the FBC system.
ASSESSMENT
Gas phase measurements of the volatilized trace and minor elements
in the combustion zone of coal combustors and stack gas emission levels
have not been made as such. The extent to tfhich the trace and minor
elements partially or fully volatilize on combustion, however, can be
*The thermodynamic emission levels for the projected volatile Al, Co,
Cr, Fe, Mn, Mo, Ni, and Ti phases (without consideration given to the
potential reduction in concentration when particulate removal systems
are employed) are expected to be innocuous at equilibrium.
109
-------
estimated from reported data by determining the depletion of the speci-
fic element in the various slag or ash formations in the particular sys-
tems. The appearance of the specific element in, for example, the fly
ash fines, is not absolute evidence that volatilization is occurring.
The element may be present in that portion of the coal mineral matter
that is released as fly ash, without prior volatilization and reconden-
sation. Consistently higher concentrations in increasingly finer ash
particle fractions, however, certainly suggests that volatilization is a
candidate, initial mechanism. Our equilibrium projections on the vola-
tility percentages for specific trace and minor elements during coal
combustion agree relatively well with the experimental data reported by
Oak Ridge National Laboratory (ORNL) for a conventional coal-fired
steam plant- The following comparison results (Westinghouse PFBC pro-
jections of volatility in parentheses): aluminum ~0% (0.02%),
cobalt 33% (14%), nickel 43% (5%), and molybdenum 73% (100%). We pro-
ject cobalt and nickel to be thermodynamically less volatile than ORNL
observed. This difference may be attributed to either an external con-
tribution of the elements from process materials or alloys or, in part,
to the inaccuracies in experimental data for the molecular constants of
the various complexes used in this study. More practically, the higher
volatility of cobalt and nickel in the conventional boiler system may be
attributed to higher combustion temperatures.
Although at equilibrum 100 percent of the total molybdenum content
is projected to volatilize at PFBG temperatures, ORNL detects only
73 percent volatilization, even though the conventional furnace operates
at higher combustion temperature concentrate on the surface of entrained
ash particles. This result through either physical adsorption or chemi-
cal reaction of the gaseous oxyhydroxide or oxychloride molybdenum in
the effluent streams when efficient particulate removal systems are
employed. Similary, if particulate removal is not an integral part of
the plant, or if particulate removal occurs prior to the condensation/
adsorption reaction, emissions of molybdenum, possibly as Mo03 ^ume> niay
be increased.
110
-------
The sole exception to the relative agreement between the ORNL data
and our projections is chromium. The ORNL study found the fly ash to be
significantly enriched in chromium, even though the concentration in the
slag fraction was not depleted. The ORNL sampling indicated an enrich-
ment corresponding to between 24 and 40 percent of the original chromium
content of the feedstock coal, as opposed to the thermodynamic calcula-
tions which predict 79 percent volatilization for FBC operations using a
feedstock coal that contained a lower chromium content. The ORNL team
suggested that chromium removed from the boiler tubes may be respoasible
for the enrichment. If the thermodynamic calculations were repeated
using the ORNL's higher-chromium coal, the adjusted equilibrium value
would predict 47 percent volatilization.
Based on experimental work by Swift^ at ANL, where trace element
mass balances around a 6 in. bench-scale combustor were conducted, emis-
sion levels of 25 percent for chromium (77%),* 0 to 20 percent for
cobalt (14%), and 0 percent for iron (0%) and manganese (2.2%) x
-------
(Neutron Activation Analysis), and SSMS (Spark Source Mass Spectro-
scopy). Variations in the resulting percent ratios of the mass of ele-
ments in the flue gas to the total mass of each element in all input
streams were noted: Aluminum, 0.006-0.04 percent; cobalt, 0.20-
43.42 percent; chromium 7.57-9.84 percent; iron, 0.07-1.65 percent;
molybdenum, 15.02-18.26 percent; manganese 0.23-33.88 percent; nickel,
3.22-7.26 percent; and titanium 0.003-0.01 percent.* The thermodynamic
equilibrium projection for the trace and minor elements considered in
this study, with the exception of chromium and molybdenum, are within
the concentration ranges Exxon reported. When the potential stream
locations where partitioning of the elements occurs through gas/ash
interactions are. reviewed, it is evident that depletioa of the elements
froai the flue gas results particularly at the secondary cyclone. Tt is
at this location that gaseous chromium and molybdenum may be removed
from the effluent stream, thus lowering the projected therraodynamic
equilibrium volatilization percentage.
The current studies have only begun to determine the possible reac-
tions of trace elements throughout EBC processes. Although a complete
understanding of the process would require knowledge of the compounds in
which these elements are combined in the feedstock material and of the
resulting chemical phases and the kinetics of each reaction that occurs
during combustion, the thermodynamic projects at equilibrium provide a
first-level approximation of the possible distri-bution of the elements
or phases characteristic of the effluent and solid materials. Further
comparison of the Initial projections with future reported data from FBC
units and conventional power stations, and an inclusion of additional
*Exxon test conditions: 890°C bed temperature, 832°C secondary cyclone
temperature, 1.5 m3/rain superficial gas velocity, 3.3 m bed height,
40% excess air, 86.3 kg/hr coal feed rate, 13.2 kg/hr sorbent feed
rate, 900 kPa; feedstock materials: 2 percent sulfur Champion coal
and 0.6 percent sulfur Kentucky coal, and Pfizer No. 1337 dolomite.
112
-------
elements and their interactions with emphasis given to systems modeling
and partitioning mechanisms, will provide a more complete understanding
of the trace and minor element chemistry in the FBC process.
113
-------
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33. Bertine, K. K., and E. P. Goldberg, Fossil Fuel Combustion and the
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-------
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120
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APPENDIX A
NITROGEN OXIDE EMISSIONS IN FLUID-BED
COMBUSTION EXPERIMENTS
This appendix presents the data collection used for the NOX regres-
sion analyses. Reference numbers are the first entry, and these corre-
late with the reference list provided at the end of the data. In the
case of fluidized-bed combustor operating conditions, some investigators
have reported the expanded bed depth, whereas others have reported the
settled bed depth, and again some have differentiated between the ini-
tial and final settled bed depths. Thus, to identify the format in
which bed depth has been reported, we have assigned a bed depth code
(see Nomenclature at end of this appendix) as shown in the following
data collection. Some of these NOX emission data have been plotted in
figures as a function of temperature, with excess air level as param-
eter. These plots indicate that the NOX emissions increase with
increasing excess air and/or temperature.
121
-------
FILL SOURCi:
1 EXX (9/76)
2 EXX(9/76)
3 EXX(9/76)
4 EXX(9/76)
5 EXX(9/76)
6 EXX(9/76)
7 EXX(9/76)
8 EXX(9/76)
9 EXX(9/76)
10 EXX(9/76)
11 EXX(9/76)
12 EXX(9/76)
13 EXX(9/76)
14 EXX(9/76)
15 EXX(9/76)
16 EXX(9/76)
17 EXX(9/76)
18 EXX(9/76)
19 EXX(9/76)
20 EXX(9/76)
21 EXX(9/76)
22 EXX(9/76)
23 EXX(9/76)
24 EXX(9/76)
25 EXX(9/76)
26 EXX(9/76)
27 EXX(9/76)
23 EXX(9/76)
29 EXX(9/76)
30 EXX(9/76)
31 EXX(9/76)
32 EXX(9/76)
33 EXX(9/76)
34 EXX(9/76)
35 EXX(9/76)
36 EXX(9/76)
37 EXXC9/76)
38 EXX(9/76)
39 EXX(9/76)
40 EXX(9/76)
41 EXX(9/76)
42 EXX(9/76)
43 EXX(9/76)
44 EXX 9/76)
45 EXX 9/76)
46 EXX 9/76)
47 EXX 9/76)
48 EXX 9/76)
49 EXX(9/76)
50 EXX(9/76)
51 EXX(9/76)
52 EXX(9/76)
53 EXX(9/76)
54 EXX(9/76)
55 EXX(9/76)
56 EXX(9/76)
57 EXX(9/76)
58 EXX (9/76)
59 EXX(9/76)
60 EXX(9/76)
61 EXXC9/76)
62 EXX(9/76)
63 EXX(9/76)
64 EXX(9/76)
65 EXX(9/76)
66 EXX(9/76)
67 EXX(9/76)
68 EXX(9/76)
69 EXX(9/76)
70 EXX(9/76)
71 EXX(9/76)
72 EXX(9/76)
73 EXX(9/76)
74 EXX(9/76)
75 EXX(9/76)
76 EXX(9/76)
77 EXX(9/76)
73 EXX(9/761
79 EXX(9/76)
80 EXX(9/76)
81 EXX(9/76)
32 EXX(9/76)
83 EXX(9/76)
84 EXX(9/77)
85 EXX(9/77)
86 EXX(9/77)
87 EXX(9/77)
88 EXX(9/77)
89 EXX(9/77)
90 EXX(9/77)
RUN #
2.1
3.1A
3. IB
4.1
4.3
5.1
5.2
6.1
6.2
7.1
7.2
7.3
7.4
8.4
8.4A
9.1
10.1
10.2
10.3
11.1
11.2
12.1
12. 1A
12. IB
12. 1C
12. ID
12. IE
12. IF
12. 1G
12. 1H
12.11
12. U
12. IK
12. 1L
12.1M
12. IN
12.10
12. IP
12. 1Q
12.2
13.2
13. 2A
li.2B
13. 2C
13. 2D
13. 2E
13. 2F
14. 1A
14. IB
14.2
15. 1A
15. IB
15.2
15. 3A
15. 3B
15.4
16.1
16. 1A
16. IB
16. 1C
16. ID
16. IE
16. IF
16. 1G
6.3
17. 1A
17. IB
18.1
13.3
19.2
19. 2A
19. 2B
19. 2C
19. 2D
19. 2E
19. 2F
19. 2G
19. 2H
19.3
19. 3A
19. 3B
19. 3C
19. 3D
19.2
19.3
19.4
19.5
19. 6A
19. 6B
19. 7A
P(kPa)
395
395
395
1031
922
912
896
902
912
912
912
693
912
907
906
932
901
901
912
9 1.1)
912
922
922
922
922
922
922
922
922
922
922
922
922
922
922
922
922
922
922
912
912
912
912
912
912
912
912
902
912
912
907
902
912
921
902
912
821
821
821
821
821
821
821
826
932
906
913
935
958
922
922
922
922
922
922
922
92 ^
922
922
922
922
922
922
930
930
925
935
930
930
930
%EX AIR
27.50
11.80
-8.90
78.90
115.00
98.90
96.10
87.30
100.00
23.20
36.70
0.00
34.30
67.00
15.00
30.50
114.00
87.60
93.90
139.00
95.80
66. 5n
50.00
51.00
53. on
49.00
40.00
46.00
39.00
44.00
38.00
37.00
55.00
28.00
28.00
28.00
18.00
22.00
21.00
27.30
48.70
34.00
32.00
28.00
22.00
17.00
7.00
86.80
61.00
22.50
44.20
24.00
62.20
27.10
23.60
25.00
8.90
18.00
10.00
10.00
6.00
3.00
2.00
-3.10
31.00
16.70
35.30
57. 30
61.50
30.40
65.00
44.00
33.00
32.00
21.00
15.00
15.00
9.00
5.70
9.00
5.00
11.00
7.00
6.60
6.00
15.00
15.00
15.00
22.00
9.10
Ca/S
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
4.0
1.6
0.0
1.0
1.2
1.2
1.2
0.0
0.0
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
0.0
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
1.4
2.5
2.5
2.5
2.5
2.5
TEMP C
861.0
395.0
939.0
885.0
919.0
849.0
889.0
949.0
938.0
876.0
884.0
380.0
377.0
908.0
906.0
881.0
916.0
891.0
912.0
909. 0
915.0
903.0
901.0
903.0
901.0
903.0
901.0
903.0
901.0
903.0
903.0
903.0
903.0
903.0
903.0
903.0
903.0
903.0
903.0
896.0
910.0
910.0
910.0
910.0
910.0
910.0
910.0
909.0
916.0
934.0
910.0
902.0
916.0
889.0
901.0
905.0
882.0
882.0
882.0
382.0
882.0
882.0
382.0
875.0
893.0
898.0
863.0
899.0
910.0
874.0
874.0
874.0
874.0
874.0
874.0
874.0
874.0
874.0
879.0
879.0
879.0
879.0
879.0
872.0
871.0
880.0
892.0
884.0
825.0
879.0
SUP VEL
2.46
2.50
2.50
1.69
1.89
1.88
1.98
1.96
1.91
1.84
1.89
2.10
1.73
1.83
1.77
1.76
1.96
1.84
2.04
2.05
1.89
1.78
1.78
1.73
1.78
1.78
1.78
1.78
1.73
1.78
1.78
1.78
1.78
1.78
1.78
1.78
1.78
1.78
1.78
1.83
1.86
1.86
1.86
1.86
1.86
1.86
1.36
1.84
1.83
1.91
1.92
2.09
1.83
1.87
2.09
2.03
1.R3
1.83
1.81
1.83
1.83
1.83
1.83
1.84
2.05
2.13
2.03
1.71
1.86
1.81
1.81
1.81
1.81
1.81
1.81
1.81
1.81
1.81
1.89
1.89
1.89
1.89
1.89
1.90
1.90
1.99
2.00
2.02
1.94
1.98
B DEP
0.76
0.92
0.92
0.92
0.00
0.00
0.00
0.92
0.00
1.53
0.00
0.00
1.98
0.53
1.30
0.61
0.61
0.58
1.12
0.61
0.84
0.76
0.76
0. 76
0.76
0.76
0. 76
0.76
0.76
0.76
0.76
0.76
0.76
0. 76
0.76
0.76
0.76
0. 76
0.76
1.27
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.84
1.33
1.33
1.04
1.93
1.92
1.80
2.29
2.29
0.78
0.78
0.78
0.78
0.78
0.78
0.78
1.75
0.84
0.74
1.95
0.66
0.76
0.71
0.71
0.71
0.71
0. 71
0.71
0.71
0.71
0.71
1.45
1.45
1.45
1.45
1.45
0.71
1.45
1.58
1.98
1.58
1.60
1.96
CD
2
2
2
2
0
0
0
2
0
2
0
0
3
2
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
2
2
3
2
2
3
2
2
2
2
2
2
2
2
3
2
2
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
2
NOXppm
~
90
45
162
170
165
160
170
160
155
165
170
160
160
165
175
160
155
170
150
150
160
130
130
140
135
135
125
115
75
~
225
225
205
140
130
125
140
210
175
170
160
140
120
115
90
65
80
45
80
147
78
125
91
104
127
102
ZDESUL
o.no
0.00
0.00
0.00
o.oo
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
o.oo
n.oo
n.oo
o.oo
o.oo
n.oo
o.no
n.no
o.no
o.no
o.oo
o.no
o.on
o.oo
o.on
o.on
o.oo
o.oo
n.oo
n.oo
0'. 00
o.oo
o.oo
o.oo
o.oo
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.no
0.00
n.on
o.oo
0.00
n.oo
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0. 00
0.00
0. 00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
56.40
69.00
67.00
68.00
58.00
73.00
COAL
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ASKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWPICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGFT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
CHAMPION
CHAMPION
CHAMPION
CHAMP ION
CHAMP ION
CHAMPION
CHAMP ION
CHAMP ION
CHAMP I ON
CHAMP ION
CHAMPION
CHAMP TON
CHAMP I ON
CHAMP ION
CHAMFT ON
CHAMPT ON
CHAMP ION
CHAMP I OK
CHAMPION
CHAMPION
CHAMPION
CHAMP TON
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMP TON
CHAMP TON
CHAMP ION
CHAMP T0\
CHAMPION
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
1.50
50
50
50
50
50
1.50
1.50
50
50
50
50
50
50
50
50
10
1.10
.10
.10
.10
.10
.10
.10
.10
.11
.10
.10
.JO
1.10
1.10
1.10
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
1.60
1.60
60
60
60
60
1.60
1.60
1.60
1.60
1.60
1.61
1.61
1.
,61
,M
, (.< 1
1.61
122
-------
FILE SJURC.T
91 EXXT9/77)
92 EXX(<>/77)
93 EXX(9/77)
94 EXXC9/77)
95 EXX (9 /7 7)
96 EXX(9/77)
97 EXX(9/77)
98 EXX(9/77)
99 EXX(9/77)
100 EXX(9/77)
101 EXX(9/77)
102 EXX(9/77)
103 EXXC9/77)
10A EXX(9/77)
105 EXX(9/77)
106 EXX(9/77)
107 EXX(9/77)
108 EXX(9/77)
109 EXX(9/77)
110 EXX(9/77)
111 EXX(9/77)
112 EXX(9/77)
113 EXXC9/77)
114 EXX(9/77)
115 EXX(9/77)
116 EXX(9/771
117 EXX(9/77)
118 EXX(9/77)
119 EXX(9/77)
120 EXX{9/77)
121 EX;: 9/77)
122 EXX 9/77)
123 EXX 9/77)
124 EXX 9/77)
125 EXX 9/77)
126 EXX 9/77)
127 EXX 9/77)
128 EXX 9/77)
129 EXX(9/77)
130 EXX(9/77)
131 EXX(9/77)
132 EXX(9/77)
133 EXX(9/77)
134 EXX{9/77)
135 EXX 9/771
136 EXX 9/77)
137 EXX 9/77)
138 EXX 9/77)
139 EXX 9/77)
140 EXX(9/77)
141 EXX(9/77)
142 EXX(9/77)
143 EXX(9/77)
144 EXX(9/77)
145 EXX(9/77)
146 EXX(9/77)
147 EXX(9/77)
148 EXX(9/77)
149 EXX(9/77)
150 EXX(9/77)
151 EXXC9/77)
152 EXX(9/77)
153 EXX(9/77)
154 EXX(9/77)
157 EXX(5/78)
158 EXX(5/7S)
159 EXX(5/78)
160 EXX (5/73)
161 EXX(5/78)
162 EXX(5/78)
163 EXX(5/73)
164 EXX(5/73)
165 EXX(5/78)
166 EXXC5/73)
167 EXX(5/78)
168 EXX(5/78)
169 EXX(5/7S)
170 EXX(5/73)
171 EXX(5/78)
172 EXX (5/73)
173 EXX (5/73)
174 EXX(5/78)
175 EXX(5/73)
176 EXX(5/78)
177 EXX(5/78)
178 EXX (5/78)
179 EXX(5/78)
130 EXX(5/78)
131 EXX(5/73)
182 EXX(5/78)
183 EXX(5/73)
RUN #
19. 7B
19. 9A
19. 9B
20. 1A
20. IB
20. 1C
20. 2A
20. 2B
21
21B
22
23
25
26A
26B
27.1
27.2
27.3
27.4
27.5
27.6
27.7
27.3
27.9
27.10
27.11
27.12
27.13
27.14
27.15
27.16
27.17
27.13
27.19
27.20
27.21
28.1
28.2
28.3
28.4
28.5
29
30.1
30.2
10.3
30.4
31
32.1
32.2
32.3
33
34
35
36.1
36.2
37
38.1
33.2
33. 3
33.4
38.5
38.6
39.1
39.2
41.1
41.2
43.1
43.2
43.3
43.4
43.5
45.1
45.2
45.3
45.4
45.5
45.6
46.1
46.2
46.3
46.4
47
48
50. 1A
50. IB
50.2
50.3
50.4
50.5
51
52
P(kPa)
970
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
g T^
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
930
920
920
920
920
520
600
600
600
920
932
930
930
930
930
930
930
930
930
930
930
902
902
912
912
840
880
885
940
940
780
730
730
780
780
780
940
940
940
940
1075
930
910
915
900
900
900
900
932
930
%EX AIR
9.60
10.00
20.00
11.00
12.00
13.50
18.00
13.70
14.00
18.00
28.00
12.00
8.00
9.50
11.50
18.90
15.40
15. 30
20.50
12.10
14.50
12.40
12.60
13.10
7.80
11.00
23.00
13.50
14.60
8.20
10.40
13. HO
S.20
12.30
12.10
10.90
40.00
35.00
18.00
4.50
21.00
19.00
13.70
17.20
13.90
16.10
23.00
13.00
16.00
20.00
23.40
20.90
45.30
42.00
96.00
92.00
47.00
44.00
94.00
94.00
112.00
78.00
68.00
60.00
44.00
37.00
24.00
42.00
25.00
25.00
25.00
37.00
40.00
33.00
30.00
28.00
27.00
37.00
47.00
40.00
35.00
13.00
39.00
41.00
45.00
63.00
40.00
40.00
36.00
46.00
38.00
Ca/S
2.5
2.5
2. 5
3.3
3.3
3.3
1.5
3.3
3.3
3.3
0.0
1.3
1.3
3.7
3.7
0.5'
0.5
0.5
0.5
2.5
0.3
1.5
1.5
1.5
0.7
0.7
0.7
0.3
0.7
' .0
0.7
0.7
1.0
1.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
3.7
3.7
3.7
3.7
3.7
2.5
2.5
1.5
0.7
2. 5
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
1.5
1.5
1.5
2.5
2.5
0.8
0.8
1.2
0.7
0.7
1.2
0.5
0.7
0.7
1.3
1.0
0.0
0.0
2.5
2.5
2.5
1.5
1.5
1.4
1.2
1.2
1.2
1.2
1.2
1.2
1.4
1.2
TEMP C
937.0
870.0
926.0
870.0
827.0
927.0
927.0
927.0
870.0
930.0
870.0
885.0
970.0
927.0
885.0
880.0
927.0
902.0
329.0
829.0
321.0
835.0
878.0
922.0
883.0
931.0
334.0
888.0
892.0
389.0
341.0
891.0
909.0
907.0
895.0
846.0
840.0
870.0
920.0
920.0
930.0
875.0
885.0
929.0
885.0
835.0
838.0
950.0
947.0
836.0
918.0
900.0
905.0
900.0
913.0
902.0
891.0
894.0
762.0
762.0
690.0
684.0
750.0
674.0
889.0
875.0
940.0
845.0
940.0
940.0
945.0
880.0
385.0
890.0
870.0
875.0
875.0
920.0
865.0
760.0
865.0
885.0
875.0
890.0
390.0
805.0
890.0
890.0
895.0
871.0
890.0
SUP VEL
2.18
1.79
2.40
2.06
1.83
2.32
2.30
2.30
2.00
2.20
1.90
1.82
1.75
2.10
1.90
2.01
2.15
1.98
1.07
1. 72
1.72
1.72
1.83
2.09
1.87
2.23
1.94
2.02
2.04
1.88
1.74
1.97
2.09
2.08
2.03
1.67
2.13
2.16
2.13
1.40
2.65
2.16
2.15
2.50
2.10
1.90
1.96
2.20
2.10
1.50
1.56
1.50
1.54
1.40
3.00
2.96
2.08
2.09
1.85
1.84
1.9
1.30
1.52
1.40
1.60
1.50
1.70
1.80
1.80
1.70
1.70
1.40
1.40
1.40
1.40
1.40
1.40
1.30
1.20
1.00
1.40
2.20
1.50
1.20
1.20
1.20
1.30
1.30
1.40
1.50
1.50
B DEP
1.27
1.09
1.88
1.85
0.00
1. 32
1.22
1.65
1.60
2.11
2.11
1.19
1.37
1.12
2.28
4.00
4.00
3.00
0.00
6.00
5.00
6.00
7.00
5.00
5.00
7.00
7.00
6.00
6.00
5.00
5.00
6.00
7.00
7.00
7.00
5.00
1.02
0.00
0.00
0.00
9.70
0.80
1.60
0.00
0.00
2.26
1.60
1.40
0.00
0.90
0.76
2.29
2.26
1.40
1.70
1.68
1.14
0.00
0.00
0.00
0.00
2.26
1.22
0.00
2.30
2.00
1.40
2.10
1.60
1.60
2.20
2.30
0.00
0.00
0.00
0.00
2.20
1.80
2.30
2.30
2.00
2.10
1.50
1.60
0.00
0.00
3.20
3.30
2.20
1.90
1.70
CD NOXppm
3 141
2 135
3 105
2 117
0
3
2
3
2
3
2
2
2
2
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
3
2
2
0
0
3
2
2
0
3
2
2
2
2
3
2
2
0
0
0
0
3
2
0
2
3
2
3
2
2
3
2
0
0
0
0
3
2
3
2
3
2
2
2
0
0
0
0
0
2
2
95
157
200
195
195
210
110
125
185
180
207
199
176
200
189
143
135
12R
164
93
109
130
110
100
im
14
95
97
101
91
65
134
145
125
41
146
137
50
70
55
80
106
89
147
52
72
94
159
121
135
127
125
149
114
102
120
174
111
127
80
120
90
79
75
80
120
120
150
100
92
97
102
136
128
124
119
143
107
%nESUL
83.50
66.00
81.90
54.00
53.00
0.00
71.20
86.30
60.00
0.00
0.00
0.00
0.00
90.80
81.20
55.00
57.10
55.60
62.00
97.80
80.00
97.20
08.00
98.50
72.00
70.00
71.00
46. 0.0
64.00
71.00
87.00
72.00
84.50
90.00
11.00
14.00
10.00
13.50
9.00
1.60
3.60
55.70
49.70
89.10
64.50
32.10
66.00
76.40
60.00
66.00
0.00
0.00
61.60
65.60
75.60
46.00
40.00
45.00
48.00
71.00
76.00
82.00
0.00
0.60
68.00
100.00
93.00
60.00
63.00
96.00
44.00
65.00
92.00
84.00
82.00
56.00
62.00
90.00
86.00
55.00
64.00
2.70
58.00
69.00
70.00
86.00
95.00
96.00
29.00
71.00
0,00
COAL
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
ARKWRIGHT
ILLINOIS/^
ILLINOIS/'e
ILLINOIS^
ILLINOIS*' 6
ILLINOISC6
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMPION
CHAMP /KY
CHAMP /KY
CHAMP /KY
CHAMP /KY
CHAMP/KY
CHAMP /KY
CHAMP/KY
CHAMP/KY
WT% N
1.61
1.61
1.61
1.57
1.57
1.57
1.57
1.57
1.57
1.57
1.57
.57
1.57
1.57
1.57
1.57
1.57
1.57
1.57
1.62
1.62
1.62
1.62
1.62
1.62
1.62
62
60
60
60
1.60
60
60
60
60
60
60
1.60
60
60
60
60
60
60
60
60
60
60
60
1.60
.60
.60
.60
.40
.40
.40
.40
.40
.40
.40
.40
.40
.40
.40
.36
.07
1.17
1.17
1.17
1.17
1.17
.36
.36
. 36
.36
.36
.36
. 36
. 36
. 36
.36
. 36
.36
1.
1.
1.
1.
1.
1.
1.
1 ,
1 .
1.
1.
1.
1.50
1.50
1. 'SI
1.50
1.50
1.40
1.40
1.40
123
-------
FILE SOURCE
18 i EXX(5/73)
185 EXX(5/78)
186 EXX{5/78)
1S7 EXXC5/78)
138 EXX(5/78)
189 EXX(5/7b)
193 ANL(6/74)
191 ANL(6/74)
192 ANL(6/74)
193 ANL(6/74)
194 ANL(6/74)
195 ANL(6/74)
196 ANL(6/74)
197 ANL(6/74)
198 ANL(6/74)
199 ANL(G/74)
200 ANL(6/74)
201 NCB(9/71)
202 SCB (9/71)
203 NCB(9/71)
204 NCB(9/71)
205 NCB(9/71)
206 NCB(9/71)
207 NCB(9/71)
208 NCB(9/71)
209 NCB(9/71)
210 MCB(9/71)
211 NCB(9/71)
212 NCB(9/71)
213 NCB(9/71)
214 NCB(9/71)
215 NCB(9/71)
216 EXX11/73
217 EXX11/73
218 EXX10/75
219 EXX12/73
231 EXX8/75
232 EXX8/75
233 EXXil/7'i
234 EXX,3/7i
239 EXX9/75
240 EXX9/75
241 EXX9/75
242 EXX9/75
243 £XX(9/76)
244 EXX(9/76)
245 EXX2/74
246 EXX2/74
247 EXX2/74
248 EXX3/74
249 EXX3/74
250 EXX4/74
251 EXX11/74
252 EXX1/74
253 EXX1/74
254 EXX.1/74
255 EXX(9/76)
256 EXX(9/76)
257 EXX6/73
258 EXX6/73
259 EXX7/73
260 EXX11/73
261 EXX1/75
262 EXX1/75
263 EXX1/75
264 EXX3/75
265 EXX5/7ri
266 EXX6/7r>
267 EXXO/75
26S EXXC/71
269 EXX6//5
270 EXX6/7.5
271 EX.K7/75
273 ARG(10/74)
274 AKG(10/7<.)
RUN *
54
55
56
57
59.1
59.2
VAR 1
VAR 2
VAR 3
VAR 4
VAR 5
VAR 6
VAR 6
VAR 6
VAR 7
VAR 8
VAR 9
P(kPa)
595
570
800
810
891)
873
810
sin
81(1
810
810
810
810
810
sin
810
8ln
354
354
354
354
354
354
354
506
506
506
506
506
506
506
506
607
658
930
65!i
805
305
805
395
805
805
805
310
70»
800
65«
63(!
628
62U
6 2 a
840
S61
658
651!
65!)
810
800
820
820
871
65!!
800
800
800
800
800
800
Ell
800
800
800
800
blO
810
%EX AIR
29.00
13.00
34.00
14.00
33.00
26.00
15.00
15.00
15.00
15.00
15.00
15.00
15.00
15.00
15.00
15.00
15.00
25.00
28.04
32.07
29.62
16.66
27.27
30.43
42. 85
33. 75
32.07
38.15
33.75
20.68
22.09
33.75
97.00
77.00
9.10
88.00
21.00
37.00
62.00
61.00
12.00
16.00
17.00
33.00
44.00
15.00
56.00
61.00
27.00
58.00
43.00
43.00
0.00
45.00
26.00
110.00
46.00
5.00
209.00
203.00
130.00
8.00
30.00
42.00
58.00
0.00
32.00
31.00
14.00
24.00
25.00
17.00
22.00
16.66
16.66
Ca/S
0.0
0.0
0.6
0.7
0.7
0.0
2.9
2.9
1.1
1.9
1.0
2.0
2.1
2.0
2.2
1.2
i.O
0. 1
0.7
.1.9
0.9
1.4
1.8
1.9
1.8
1.6
1.8
1.5
2.0
1.8
f! • 1
1.0
t-.o
0.0
2 , 5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
o.o
0.0
0.0
0.0
0.0
0.0
0.0
2.9
2.9
TTMP C
910.0
930.0
815.0
935.0
956.0
949.0
785.0
852.0
857.0
899.0
795.0
852.0
349.0
SiTi.O
793.0
888.0
907.0
798. 8
798. 8
758.8
798.8
798.8
798.8
798.8
798.8
798. 8
798.8
798.8
798.8
798.8
793.8
798.8
737.7
926.6
879.4
998.8
870.0
865.0
893.8
875.0
913.8
925.0
887.2
902.7
875.0
850.0
871.1
943.3
910.0
946.1
737.7
848.8
860.0
1093.3
954.4
793.3
870.0
895.0
821.1
893.3
843.3
137 . 7
920.0
910.0
972.2
885.0
911.1
887.2
850.0
857.2
751.1
867.2
877.2
790.5
851.6
SUP VEL
1.90
2.10
1.40
1.40
1.60
1.70
0.63
1.44
0.63
0.69
3.40
1.08
1.08
1.05
1.26
1.08
1.47
0.60
0.60
n.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
1.80
1.98
1.95
1.95
1.10
1.41
1.05
1.41
1.14
1.14
1.17
1.83
1.53
1.23
1.50
1.86
1.86
1.86
1.56
1.74
1.35
2.43
2.07
1.86
1.08
1.55
1.68
1.83
1.14
1.89
1.23
1.26
1.20
1.57
1.12
1.38
1.41
1.44
1.08
1.92
1.08
0.63
1.44
B nr.P CD NOXppm
2.70
2.50
1.80
1.60
3.70
1.30
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
1.12
1.12
1.12
1.12
1.12
1.12
1. 12
1.12
1.12
1.12
1.12
1.12
1.12
1.12
1.12
0.12
0.30
1.57
0.60
0.75
0.75
0.75
0.45
0.75
0.75
i;.75
0. 36
0.49
0.42
0.60
0.60
0.60
0.60
0.60
0.60
0.50
0.60
0.36
0.60
0.45
0.86
0.60
0.60
0.60
0.37
0.50
0.50
0.26
0.80
0.45
0.75
0.75
0.75
0.75
0.75
0.54
0.90
0.90
0
0
2
3
0
3
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
2
4
4
2
2
4
2
2
1
4
1
1
1
1
1
1
1
1
4
1
4
1
4
4
1
1
2
2
4
2
2
7
2
4
2
2
2
0
0
110
104
35
7R
55
190
210
140
180
150
190
180
160
150
270
120
80
120
110
80
130
90
100
160
14o
190
90
90
140
310
300
102
365
190
1«9
191
220
175
151
231
208
160
205
335
370
240
250
230
220
170
470
610
300
380
340
410
330
160
201
176
153
166
217
160
198
190
210
1RESUL
31.00
30.00
93.00
87.00
88.00
66.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
19.00
57.00
89.00
85.00
SO. 00
1 6 . 0 0
96.00
95.00
95.00
95.00
94.00
98.00
66.00
77.00
85.00
8.00
34.00
73.00
72.00
6 8 , 5 L
62.00
69.00
69.50
82.60
70.50
(15.60
61.60
98.00
86.00
91.00
89.00
69.00
91.00
35.00
87.40
76.40
54.00
6.00
89.00
84.00
97.00
54.00
54.00
85.50
50.00
"7.30
99.70
84.00
n6.70
66.00
62.80
60.30
43. 70
67.90
60.80
85.40
94.78
94.35
COAL
CHA>fP/KY
CHAMP/KY
CHAMP /KY
CHAMP/KY
CHAMP/KY
CHAMP/KY
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKU'RICHT
ARKWRIGHT
ARKWRIGHT
WELBECK
WELBECK
WELBECK
WELBECK
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKKRITHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ASKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIHHT
ARKWRICHT
WYOMING
ILLINOIS
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRTGIIT
ARKWRIGHT
ARKWRIGHT
ARKWRIHHT
ARKWRT "T
ARKWRIGPT
ARKWRIGHT
ARKWRIGHT
ARKWRICKT
ARKWRIGHT
ARKWRIGHT
ARKWRTGHT
ARKWRICiii
ARKWRTGHT
WTJ; N
1.54
1.54
1.54
1.54
1.54
1.54
1.66
1.66
1.66
1.66
1.66
1.66
1.66
1.66
1.66
1.66
1.66
1.50
1.50
1.50
1.50
1.40
1.40
1.40
1.40
.40
1.40
1.40
1.40
1.40
1.40
1.40
1.49
1.49
1.49
1.49
U49
1. /i 9
1. .49
1.49
1.49
1.49
1.49
1.49
1.49
1.49
1.49
,49
,49
0.90
20
1.49
1.49
1.49
1.49
1.4°
1.49
1.49
1.49
1.49
1.4 9
1 .4°
] .49
1.49
1.40
1.49
1 . A °
1.41
1.4"
1.41
1.49
1.49
5.08
5.01
124
-------
FILE
275
276
277
273
279
230
231
232
233
284
235
236
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
SOUKCi: Ril!
ARG(l()/74)
ARG(10/74)
ARG(10/74)
ARG(lD/74)
ARG(10/74)
ARG(10/74)
ARG(10/74)
ARC (10/7 4)
ARG(10/74)
ARG(10/74)
ARG(10/74)
ARG(10/74)
ARG(10/74)
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG2/75
ARG10/74
ARG10/74
ARG10/74
ARG10/74
ARG11/74
ARG11/74
ARG1/75
ARG12/74
ARG12/74
ARG12/74
ARG12/74
ARG9/74
ARG11/75
ARG11/75
ARG11/75
ARG11/75
ARG11/75
ARG11/75
ARG11/75
ARG11/75
ARG12/75
ARG(4/76)
ARG(4/76)
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
EXX11/75
ARG(7/76)
ARG(7/76)
ARG(7/76)
ARG(7/76)
ARG(7/76)
ARG(7/76)
ARG(7/76)
ARG(7/76)
EXX(l/74)
EXX(l/74)
EXX(l/74)
EXXU/74)
EXX(l/74)
EXXd/74)
EXX1/7C
EXX1/76
EXX1/76
EXX5/76
EXX5/76
EXX5/76
EXX5/76
EXX5/75
EXX5/76
EXX5/76
EXX5/76
1 II F(kPa)
iilO
810
810
810
810
810
810
810
810
810
810
810
1013
810
810
Bin
sin
sin
810
810
810
sin
sin
810
810
810
810
810
810
810
810
810
sin
810
810
810
810
810
810
810
810
810
8in
820
810
810
825
633
851
810
820
810
320
861
810
810
310
310
810
810
810
810
sin
sin
815
400
815
815
314
810
310
810
810
810
810
sin
810
810
810
537
537
sin
810
320
820
820
810
321)
821)
820
820
820
820
820
:;EX AIR Ta/S TEMP C SUP VET.
16.66
16.66
16.66
16.66
16.66
16.66
16.66
16.66
16.66
16.66
16.66
16.66
23.52
17.31
17.00
44.00
44.00
44.00
44.00
75.00
75.00
75.00
75.00
16.66
15.38
16.02
15.38
16.66
40.93
-17.97
16.02
15.38
16.02
17.97
16.66
17.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
22.00
27.00
43.00
8.00
5.00
0.00
19.00
1.00
24.00
13.00
29.00
0.00
32.00
31.00
14.00
25.00
17.00
22.00
21.00
61.00
12.00
17.00
33.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
17.00
43.00
23.00
104.00
153.00
209.00
203.00
1.00
0.00
6.00
57.00
55.00
60.00
61.00
70.00
104.00
119.00
120.00
1.1
1.9
1.0
2.0
2.1
2.0
2.2
3.2
1.0
1.1
1.1
1.2
2.9
4.0
1.4
1.1
1.4
1.9
2.9
1.3
1.5
2.1
2.9
1.5
1.1
1.7
1.4
1.5
1.4
2.7
1.8
1.4
1.5
1.4
1.2
1.3
1.4
1.3
1.4
2.0
2.0
2.0
2.1
1.5
1.6
1.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.0
2.0
2.0
2.1
1.3
1.4
1.3
1.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
857.2
898.8
793.3
851.6
848.3
343.3
793.3
887.7
907.2
851.6
848.8
904.4
843.3
954.4
898.8
898.8
398.3
898. 8
898.8
398.8
898.8
89 8. 3
398.3
954.4
954.4
954.4
954.4
898.8
898.8
954.4
954.4
954.4
898.8
898.8
893.8
843. 3
843.3
843.3
843.3
843.3
843.3
343.3
843.3
840.0
900.0
900.0
870.0
900.0
880.0
690.0
850.0
350.0
920.0
860.0
827.2
855.0
340.0
885.0
911.1
887.2
850.0
751.1
867.2
877.2
870.0
875.0
913.8
887.2
902.7
840.0
840.0
840.0
840.0
340.0
840.0
340.0
840.0
804.4
904.4
804.4
843.8
821.1
893.3
875.0
380.0
850.0
850.0
830.0
850.0
902.2
882.2
882.7
837.7
825.0
0.63
l!o2
1.08
1.08
1.05
1.26
1.08
1.47
1.08
1.05
1.02
0..90
1.05
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1. 35
1.05
1.05
1,05
1.05
1.35
1.35
1.05
1.05
1.05
1.05
1.05
0.99
0.92
0.83
0.72
0.80
1.08
1.03
1.05
0.95
0.93
0.92
0.95
1.09
1.44
1.40
1.12
1.25
0.57
1.46
1.33
1.20
1.25
1.05
1.55
1.12
1.37
1.40
1.07
1.62
1.08
1.50
0.42
1.15
1.17
1.82
1.08
1.08
1.05
0.95
0.92
0.83
0.72
0.80
1.17
1.29
1.62
1.74
1.68
1.83
1.02
1.02
0.98
1.14
1.11
1.16
1.16
1.15
1.14
1.13
1.10
n DEP (
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
1.08
1.08
0.23
0.50
0.51
1.01
0.50
1.00
0.50
0.50
0.50
0.50
0.54
0.80
0.45
0.75
0.75
n.75
0.75
0.54
0.75
0.45
0.75
0.75
0.47
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.75
0.75
0.75
0.60
0.60
0.60
0.60
0.60
:n NOXnom
0
0
0
0
0
0
0
0
0
n
0
0
0
n
n
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
n
n
2
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
i
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
4
4
1
4
4
1
4
4
0
4
140
180
150
190
ISO
]60
150
270
120
150
130
150
200
150
160
211
132
215
245
180
266
190
135
130
84
110
180
225
130
84
110
95
93
130
160
170
180
210
190
180
160
135
150
300
120
240
220
220
180
170
150
170
180
170
201
176
153
217
160
198
190
220
175
231
208
190
180
160
135
160
170
ISO
210
310
290
340
450
380
340
140
112
122
201
210
230
239
240
251
241 •
299
JDESUL
S4.78
94.78
70.43
92.61
30.87
91.74
38.70
94.35
63.04
72.00
85.00'
RO.R7
13.91
35.00
83.00
76.00
71.00
86.00
93.00
86^00
93.00
12.00
16.00
87.00
68.00
57.00
81.00
71.00
77.00
72.00
63.00
62.00
56.00
82.00
90.00
92.00
93.00
89.00
92.60
10.90
11.70
92.60
39.10
36.00
R6.on
13.30
4i.no
60.00
99.no
93.00
99.00
99.00
64.00
98.00
99.99
35.00
93.00
51.00
49.00
42.00
34.00
41.00
54.00
68.50
69.50
82.60
85.60
61.60
92.60
90. 90
91.70
92.60
90.00
92.00
93.00
84^40
86.00
86.80
72.20
54.30
54.30
83.10
77.50
51.50
52.30
39.20
26.00
86.60
58.60
45.60
99.99
99.99
COAL
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
SAN JUAN
GLEHHAROl.n
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIOHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWPICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ARKWRICFT
ARKWRIGHT
ARKWRICHT
ARKWRIGHT
ARKWRIGHT
ARKWRIGHT
ARKWRICHT
ILLINOIS/' f,
ILLINOISfl6
ILLINOIS/>6
ILLINOIS/'S
ILLINOISf'6
ILLINOIS/'ft
WESTERN
WESTERN
KIT N
5.08
5.08
5.08
5.08
5.08
.08
.03
. OS
. OS
1.14
0.72
5.08
5. OR
5. OR
5. OR
5. OR
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
.03
.08
.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.08
5.03
5.08
5.OR
5.OR
5.OR
5.OR
5. OR
5. OR
1.49
1.49
1.49
.49
1.49
1.49
1.49
1.49
1.49
1.49
1.49
.49
.49
.49
.49
.49
.49
.49
1.49
1.49
1.49
1.49
1.41
1.41}
1.4°
! . 4T
1.40
1.49
1.4"
1.40
1.49
1.24
1.24
1.24
0.96
0.96
125
-------
402 EXX()/7fi
403 EXXU/7C)
4(14 PXYi,/7fi
415 CC( 1/70)
416 C C O / 7 il)
417 C C( 1 /7 0)
418 CCCJ/70)
19 CCO/70)
20 CCO/70)
CCO/70)
CCO/70)
CC(i/70)
C C ( j / 7 0)
25 CCO/70)
4Jh CP(10/75)
427 CPdO/75)
42.8 CP(10/73)
4J9 CP
430 CP
431 CP
432 CP
433 CP
10/75)
10/73)
10/75)
10/75)
10/75)
10/70)
10/70)
10/70)
10/70)
434 CP(9/75)
43* CP(9/75)
439 Cl'(9/73)
441 CP(9/75)
443 CP(9/75)
444 PERdO/70)
445 ?ER(10/70)
446 PER(10/70)
447 PER(10/70)
448 PERdO/70)
449 PER(10/70)
450 PER(10/70)
451 PER(10/70)
452 PERUO/70)
453 PERdO/70)
454 PER(10/70)
455 PERUO/70)
456 PERdO/70)
457 PERdO/70)
458 PERdO/70)
459 PERdO/70)
460 PERdO/70)
461 PERdO/70)
462 PERdO/70)
463 PERdO/70)
464 PER
465 PER
466 PER
467 PER
468 PERdO/70)
469 PERdO/70)
470 PERdO/70)
471 PERdO/70)
472 PERdO/70)
473 PERdO/70)
474 PEK(10/70)
475 PERdO/70)
476 PERdO/70)
477 PER(10/70)
478 PER(10/70)
479 PERdO/70)
480 PERdO/70)
481 PERdO/70)
482 PERdO/70)
483 PERd'J/70)
434 PCP.dP/70)
485 SCB
486 NCB
487 NCB
488 NCB
489 NCS(9/71)
490 SCBO/71)
491 NCB(9/71)
492 SCB(9/71)
493 NC3(9/71)
494 NCB(9/71)
495 NCBf9/71)
496 NCBO/71)
497 NCB(9/71)
498 SCB(9/71)
499 NCB(9/71)
500 SCB(9/71)
501 N'CB(9/71)
502 XCB(9/71)
503 NCB(9/71)
504 NCB(9/71)
505 NCB(9/71)
9/71)
9/71)
9/71)
9/71)
P ( k 1" a )
820
820
820
15b
156
156
156
156
15Ci
156
156
156
156
156
405
405
40 5
40~>
40 •">
403
405
40 ri
405
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
sr;x AIR
114.00
157.00
153.00
24.26
21.38
31. 25
24.26
-,2.91
28.83
25.74
23.52
28.83
28.04
25. 74
286.00
292.00
317.00
310.00
3.29.00
299.30
318.00
297.00
3h6.00
172.72
150.00
130.76
183. 7H
20.68
22.09
18.64
20.00
17.97
17.31
20.00
16.66
17.97
15.38
16.66
16.66
16.66
17.97
15. J8
16.02
16.66
16.66
16.66
14.13
15.38
16.66
16.66
16.02
16.66
17.07
16.66
17.97
16.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
23.52
27.27
25.74
22.09
24.26
22.09
26.50
21.38
36.36
11.11
12.90
14.13
11.70
12.29
17.31
17.31
17.31
12.29
11.70
1.44
14.13
Ca/S
0.0
0.0
0.0
7.3
7.9
8. 3
8.0
4 . °
2.0
4.0
1.8
1.4
0.9
3.6
1.5
3.4
1.4
3.3
1.4
3.3
1.6
1.5
1.4
1.2
1.3
n. ft
0.9
1.7
1.4
1.1
1.6
2.2
1.1
1.6
2.4
1.1
1.7
1.1
0.7
0.9
0.9
1.1
1.4
1 . ''<
1.3
1.3
1.4
2.4
2.4
2.2
2.2
1.7
1.7
1.7
1.9
2.0
2.4
2.2
1.7
2.0
2.0
1.4
1.8
1.3
1.6
1.6
1.8
1.8
2.9
1.8
1.8
0.6
0.6
1.7
0.6
4.7
5.5
2.4
1.9
1.1
2.2
3.2
O.S
0.8
0.8
1.8
2.9
0.8
1.8
TEMP C
850.0
850.0
842.7
926.6
982.2
982.2
1037. 7
982. 2
982.2
982.2
982.2
982.2
982.2
982.2
793.3
782.2
763.8
79S.8
7 <) 6 . 1
797.2
801.1
79H.8
785.0
915.5
371.1
112.7
912.7
871.1
837.7
948.8
937.7
937.7
854.4
854.4
854.4
804.4
804.4
804.4
860.0
860.0
810.0
987.7
965.5
932.2
915.5
871.1
898.8
843.3
871.1
871.1
871.1
843.3
826.6
904.4
860.0
854.4
871.1
871.1
871.1
882.2
882.2
882.2
882.2
882.2
882.2
876.6
876.6
876.6
776. S
771.1
837.7
848.8
915.5
915.5
776.6
898.8
843.3
848.8
843.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
sur VEL
1.13
1.12
1.13
0.45
0.45
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
2.07
2.07
1.92
1.95
1.92
1.98
2.01
1.98
2.01
1.84
1.80
1.83
1.83
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
3.90
.3.90
3.90
3.90
3.90
3.90
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
0.90
0.90
0.90
0.90
0.90
0.60
0.60
0.90
0.90
0.90
0.90
0.60
B DEP
0.60
0.60
0.60
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.6H
0.60
0.50
0.50
0.37
0.37
0.37
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.32
0.32
0.32
0.47
0.47
0.50
0.47
0.54
0.54
0.54
0.60
0.60
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
CD
4
4
4
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
NOXnpn
261
291
272
240
270
130
270
60
103
116
44
152
90
340
118
166
45
65
3fi
63
70
78
73
185
326
258
221
300
360
340
340
300
280
280
280
260
220
160
240
200
200
260
230
230
280
280
300
?.60
260
260
240
240
220
220
320
260
260
240
240
240
250
250
270
270
290
290
290
410
480
480
480
•'•TIER VI.
88.40
93.30
93.60
99.99
97.90
98.20
99.00
94.50
90.70
93.60
88.50
87.00
74.10
66.50
43.50
56.10
38.10
fi9.40
66.20
69.50
57.90
57.50
43.80
91.10
98.70
50.00
75.30
54.50
43.00
2.60
13.20
29.00
21.00
37.00
48.00
28.20
45.00
39.00
28.20
41.00
54.00
25.00
40.00
59.00
56.00
62.00
68.00
65.30
81.80
77.40
83.50
71.50
74.20
64.20
70.90
74.00
71.60
64.90
60.00
73.50
73.50
50.00
60.40
53.80
61.50
61.90
64.90
70.50
73.00
74.00
78.00
44.00
16.00
48.00
69.00
64.00
82.00
90.50
97.50
55.00
67.00
94.00
55.00
52.00
45.00
81.00
97.00
48.00
85.00
COAL
WESTERN
WESTERN
WESTERN
DISCO CHAR
DISCO CHAR
DISCO CHAR
DISCO CHAR
CRESAPCHAR
CRESAPCHAR
IRELAND
IRELAND
IRELAND
IRELAND
IRELAND
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS'
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
OHIO *S
OHIO /'R
OHIO »8
OHIO I'K
OHIO ftS
OHIO #8
OHIO #8
OHIO #8
OHIO #8
OHIO #8
OHIO #8
OHIO PR
OHIO #8
OHIO #8
OHIO #8 WA
OHIO tS WA
OHIO PS WA
OHIO #8 UA
OHIO l»8 WA
OHIO #8 WA
OHIO US UA
OHIO #8 UA
OHIO 08 UA
OHIO PS UA
OHIO #8
OHIO #8
OHIO fS
OHIO #8
OHIO PS
OHIO 08 If A
OHIO l>8 WA
OH 1 0 * 8
OHIO #8
OHIO 08
OHIO ^8 WA
OHIO US UA
OHIO #8 UA
OHIO #8 UA
OHIO #8 WA
OHIO #8 UA
OHIO #8 WA
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
ILLINOIS
ILLINOIS
ILLINOIS
WELBECK
WELBECK
WELBECK
WELBECK
WELBECK
WELBECK
WELBECK
wrr K
0^96
0.96
0.96
1.42
1.42
1.42
1.4?
1.55
1.55
1.37
1.37
1.37
1.37
1.37
1.36
1.36
1.16
1.36
1.36
1.36
1.36
1.36
I.. 36
1.36
1.36
1.36
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
2.50
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
2.50
2.SO
2.50
2.50
2.50
0.99
0.99
2.50
2.50
2.50
0.99
0.99
0.99
0.99
O.Q9
0.99
0.99
1.40
1.40
1.40
1.40
] .40
1.40
1.40
1.40
1.40
40
,40
,30
, 10
, 50
, 5P
, SO
, sn
5"
1.50
126
-------
FILE
506
507
508
509
510
511
512
513
514
515
516
517
513
519
520
521
522
523
524
525
526
527
528
529
530
531
532
533
534
535
536
537
538
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
537
533
590
591
592
593
594
595
596
597
598
599
SOURCE RUN
NCB(9/71)
NCB(9/71)
N'CB(9/71)
SCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB<9/71)
NCB(9/71)
NCB(9/71)
SCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB
NCB
NCB
NCB
9/71)
9/71)
9/71)
9/71)
SCB(9/71)
NCB(9/71)
SCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
SCB(9/71)
SCB(9/71)
MCB(9/71)
NCB(9/71)
NCB
NCB
NCB
NCB
9/71)
9/71)
9/71)
9/71)
NCBf9/7i)
NCB(9/71)
NCBC9/71)
SCB(9/71)
NCBC9/71)
NCBC9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB<9/71)
NCB(9/71)
NCB
NCB
NCB
NCB
NCB
9/71)
9/71)
9/71)
9/71)
9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71}
NCB
NCB
NCB
NCB
NCB
NCB
9/71)
9/71)
9/71)
9/71)
9/71)
9/71)
NCB(9/71)
HCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
NCB(9/71)
ARC (7/69)
ARG(7/69)
\RG(7/69)
ARG(7/69)
ARG(7/69)
ARG(7/69)
ARGC7/691
ARC
ARC
ARC
ARC
ARG
7/69)
7/69)
7/69)
7/69)
7/69)
7/69)
9 P(kPa)
101
101
103.
11)1
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
103.
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
ZEX AIR
13.51
10.52
21.38
20.00
15.38
22.80
20.00
22.09
22.80
22.09
25.00
56.71
19.31
20.68
20.68
20.68
22.09
23.52
21.38
32.91
32.07
40.93
26.50
20.68
26.50
25.74
22.09
19.31
25.00
17.31
18.64
14.13
16.66
16.02
16.02
16.02
13.51
17.97
14.13
17.97
17.97
12.90
15.38
16.66
11.11
13.51
10.52
12.90
11.70
12.90
15.38
14.13
16.02
14.75
12.90
14.75
14.13
12.90
13.51
13.51
11.70
12.29
11.11
13.51
14.13
16.66
21.38
16.02
22.09
15.38
17.31
16.66
18.64
19.31
14.75
16.66
16.66
19.31
19.31
18.64
17.31
200.00
200.00
60.00
60.00
130.00
130.00
130.00
56.00
56.00
56.00
20.00
22.50
11.00
:a/S TEMP C
1.3 798.8
2.7 798.8
1.5 815.5
0.4 821.1
3.0 832.2
1.8 848.8
0.8 854.4
2.4 843.3
0.7 843.3
2.4 854.4
1.6 851.1
1.4 846.6
1.0 848.8
2.3 843.3
3.8 848.8
0.6 843.3
2.4 848.8
1.9 815.5
2.6 832.2
2.6 854.4
2.R 843.1
2.6 841.3
2.6
2.6
1.7
2.2
2.2
2.2
1.3
2.2
3.3
1.2
2.2
3.3
1.1
2.3
2.9
i.n
1.0
1.7
1.6
1.9
5.7
6.0
1.1
2.6
0.8
1.0
2.1
3.1
1.5
2.2
3.3
1.1
2.2
1.1
2.1
1.1
3.6
0.9
1.7
2.6
0.9
0.9
1.9
3.1
2.6
2.7
2.7
2.2
1.6
2.5
5.4
5.3
5.2
5.0
1.8
2.1
2.8
2.8
3.0
3.5
5.1
1.4
2.8
2.0
2.9
4.0
1.5
2.1
2.6
2.5
A. 2
1.9
904.4
848.8
843.3
798.8
748.8
848.8
848.8
848.8
848.8
848.8
798.8
798.8
848.8
848.8
848.3
843.8
848. 3
848. 8
R48.8
848.8
843. 8
348.8
798.8
798.8
798. R
798.8
798.8
798.8
798.8
798.8
798.8
698.8
698.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
798.8
748.8
848.8
798.8
798.8
798.8
848.8
848.8
848.8
848.8
848.8
848.8
848.8
848.8
848.8
848.8
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
871.1
SUP VEL
0.90
0.90
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
2.40
1.80
3.30
2.10
3.30
2.40
1.80
2.40
1.20
1.20
1.20
1.20
i.2n
1.20
1.20
0.90
0.93
2.43
2.43
2.40
1.20
0.90
1.20
2.40
2.34
2.40
2.40
0.90
0.90
0.90
n.90
n.oo
n.90
n.90
n.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
1.20
1.23
1.14
1.20
0.63
0.66
2.40
2.40
2.43
2.40
2.40
2.40
2.40
2.37
2.40
1.23
0.93
0.93
0.96
0.96
1.38
1.38
1.38
1.38
1.38
1.38
0.90
0.90
0.90
B DEP CD NOXppm
0.60 1
0.60 1
0.60 1 430
0.60 1
0.60 1
0.60 1
0.60 1 380
0.60 1 490
0.60 1 500
0.60 1 390
0.60 1
0.60 1
0.60 1
0.6P 1
0.60 1
n.60 1
0.60 1
0.60 1
0.60 1
n.60 1 3.10
n.60 i sin
0.60 i 4in
0.60
0.60
0.60
0.66
0.66
n.66
n.66
n.63
n.66
n.63
0.69
0.63
0.63
0.63
0.63
0.63
0.60
0.63
0.66
1.05
1.08
1.08
0.60
0.60
0.60
0.60
0.60
0.60
0.60
n.60
n.60
0.60
0.60
0.9Q
0.90
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.63
n.63
0.63
0.63
1.11
1.14
0.81
0.81
1.20
2. in
1.65
0.63
0.63
0.66
1.14
0.69
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.37
0.60
1
1
1
1
1
1
1
i
I
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
4
0
0
0
4
4
0
4
4
0
0
0
500
470
530
470
515
445
560
400
234
244
360
392
39n
360
400
425
440
XDESUL
25.00
78.00
55.00
14.00
86.00
32.00
26.00
59.00
21.00
61.00
46.00
54.00
40.00
76.00
85.00
24.00
74.00
67.00
85. nn
77. nn
82. 00
77. on
58.no
Ri.no
fio.no
81.00
50.00
83. on
5R.OO
76. nn
01. on
60.00
84.0'0
9R.OO
34.00
56. 00
68.00
49.00
49.00
65.00
51.00
57.00
97.00
99.99
42.no
R4.00
50. nn
31.00
52.no
88. on
47.no
63.00
7R.OO
15.00
18.00
51.00
72. On
61.00
93.00
43.00
71.00
91.00
38.00
43.00
80.00
83.00
72.00
73.00
74.00
83. On
99. on
62.00
87.00
88.00
93.00
87.00
38. on
50.00
64. on
64. on
72.00
67. nn
74.00
42.00
75.00
61.00
74.00
87.00
29. on
51.00
60.00
72.00
86.00
68.00
COAL
PARK HILL
PARK HILL
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PARK HILL
PARK HILL
PARK HILL
PITTSBURGH
PITTSBURGH
PITTSBURGH
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
WELBECK
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBUPGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PTTT?BrRGU
PITTSBURGH
PITTSBURGH
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS
II.I ISOIS
ILL I NO 1 S
ILLINOIS
ILL TNI IF
I'.T T::HIS
ILLINOIS
ILLIM'IS
ILLINOIS
ILLINOIS
WTZ N
1.30
1.30
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.4(1
1.40
1.40
1.40
1,40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1. 30
1.30
1.30
1.40
l .in
] .40
1 . 10
1. 10
1. 10
1.30
1.30
1.30
1.30
1.30
1.30
1.40
1.40
1.40
1.40
1.40
1.50
1.40
1.40
1.40
1.40
1.40
1.40
1.40
1.40
i . 4 n
3.40
] * i 0
1.40
1.40
1.40
1.40
1 . /j 0
1 .11
3.31
1.31
1. 31
1.11
3.33
1.13
] . ^ 1
3.11
1. 1!
1. .1
1 . ?1
1. 11
127
-------
FILE
600
601
602
603
604
605
606
607
603
609
610
612
613
614
615
616
617
618
619
620
621
622
62 3
624
625
626
627
628
629
630
631
632
633
634
635
636
637
638
639
640
641
642
643
644
t / c
O 4 J
646
647
648
649
650
651
652
653
654
655
656
657
658
659
660
661
662
663
664
665
666
667
668
669
670
671
672
673
674
675
676
677
678
679
680
681
682
683
684
685
636
637
688
689
690
691
692
693
694
695
696
697
6 9 S
69 9
700
701
702
703
704
705
SOURCK
ARG (7/69)
ARC (7/69)
ARG(7/69)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARC(6/70)
ARG(6/70)
ARG(6/70)
\RG(6/70)
ARG(6/70)
ARC(fi/70)
ARG (6/70)
ARG (6/70)
ARC(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARC (6/70)
ARG (6/70)
ARG (6/70)
ARG(6/70)
ARG(6/7U)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG (6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARC (6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG (6/70)
ARG ( 6 / 7 0 ^
ARG(6/70)
ARG(6/70)
ARG 6/70)
ARG 6/70)
ARG 6/70)
ARG 6/70)
ARG(6/70)
ARG(6/70)
ARG (6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/70)
ARG(6/74)
ASG(6/74)
ARG(6/74)
ARG(6/74)
ARG(6/74)
ARG(6/74)
ARG(6/74)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
EXX(2/71)
BiW(3/77)
B .1 tf ( 3 / 7 7 )
B5,W(3/77)
BS,W(3/77)
B&WO/77)
B&W(3/77)
B4W(3/77)
B&WO/77)
BSW(3/77)
B4WO/77)
BiWO/77)
B&WO/77)
BiW(3/77)
B&W(3/77)
3&WO/77)
B&WO/77')
BAWO/77)
B&W(3/77)
BJ.WO/77)
BS.WO/77)
R'JN /' P(kPa)
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
10.1
101
101
101
101
101
101
• 101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
101
%EX AIR Ca
23.50 2.
15.00 2.
20.50 2.
17.97 2.
20.00 1.
7.69 1.
13.51 1.
16.66 3.
20.00 1.
18.64 1.
12.29 1.
20.00 1.
5.00 1.
13.51 2.
13.51 2.
7.69 2.
20.00 1.
20.63 2.
14.13 2.
22.09 4.
3.80 3.
16.66 1.
20.00. 2.
20.00 3.
21.38 3.
23.52 2.
23.52 0.
13.64 0.
16.02 0.
14.13 4.
14.13 1.
14.13 0.
14.13 2.
0.00 1.
0.00 2.
15.38 1.
16.66 1.
16.66 0.
17.97 1.
1. 1 . 7 0 1 .
13.51 2.
16.66 2 .
12.00 2.
20.00 2.
20.00 2.
23. 52 ?
23.52 2.
19.31 2.
16.66 2.
20.00 •>
19.31 2.
13.64 2.
17.97 •>.
20.00 i.
11.11 2.
19.31 1.
18.64 i.
17.97 i.
17.97 i.
16.66 i.
16.66 4.
16.66 11.
16.66 5.
16.66 6.
16.66 6.
5.00 4.
54.4113.
23.52m.
22.80 6.
20.68 6.
25.0017.
20.68 8.
22.8011.
11.70 3.
29.62 fi.
12.90 6.
27.27 7.
25.0010.
40.0010.
9.3711.
18.64 6.
22.80 5.
15.38 3.
17.97 6.
19.31 5.
14.75 2.
13.51 o.
16.66 1.
16. 6f 1.
17.33 i.
16.02 i.
16.66 i.
16.0 2.
19.31 2.
16.66 3.
18.64 i.
17.97 i.
16.66 2.
14.75 3 .
20.00 o.
14.75 2.
17. 31 2.
16.02 2.
16.66 2.
17.31 i.
16.66 i.
/S
4
6
2
9
7
2
7
0
3
7
6
0
0
4
4
4
5
0
0
2
4
5
6
0
0
4
8
6
8
0
7
6
4
2
0
6
5
6
2
5
1
6
3
5
3
2
2
5
5
5
5
5
5
5
1
S
8
6
4
6
1
9
4
0
0
0
S
4
6
4
4
8
9
7
2
2
3
6
0
9
3
4
8
5
6
7
5
5
4
5
8
7
1
2
5
1
1
4
4
8
0
1
3
1
8
6
TEMP C
871.1
871.1
871.1
871.1
371.1
871.1
871.1
871. 1
371.1
871.1
871.1
871.1
871. 1
871.1
871.1
871. 1
843. 3
34.3. 3
843.3
843.3
843. 3
893.8
898.8
898.8
898.8
898.8
898.8
898.3
898.8
843.3
843. 3
343.3
843. 3
871.1
871.1
871.1
871.1
871.1
871.1
871.1
371.1
871.1
871.1
371.1
371.1
871.1
304.4
760.0
787.7
315.5
843.3
871.1
760.0
871. 1
871.1
871.1
871.1
871.1
871.1
898.8
843.3
843. 3
843.3
787.7
898.8
787.7
887. 7
871.1
871.1
871.1
371.1
926.6
815.5
982.2
871.1
871.1
871.1
871.1
871.1
926.6
871.1
871.1
871.1
871.1
926.6
848.3
850.0
894.4
838.8
774.4
838.3
770.0
829.4
842.2
857.7
845.0
850.0
818.8
825.5
845.0
845.0
819.4
850.5
865.0
829.4
845.0
SUP VEL
0.90
0.90
0.90
0.90
0.90
0.90
n."o
0.90
2.70
2.70
2. 70
2.70
2.70
2.70
2.70
2.?n
o.9n
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
0.90
n.90
0.90
0.90
0.90
0.90
o.9n
0.90
0.90
0.90
0.85
0.85
0.3'5
0.35
O.S5
0.85
0.84
0.84
0.84
0.84
0.34
0.34
O.R4
0.84
0. 84
n. p. 4
0. 84
0.34
0.73
0.73
0.81
0.81
0.81
0.81
1.65
0.96
0.96
0.90
0.93
0.93
0.99
0.90
0.90
0.90
0.90
0.90
0.93
0.90
0.90 .
1.20
0.60
0.90
0.90
0.90
0.81
0.90
0.90
0.90
0.90
0.81
2.49
2.50
2.46
2.43
2.37
3.57
1.31
2.40
2.43
2.49
2.45
2.45
2.39
2.39
2.41
2.49
1.43
2.48
2.54
1.38
2.46
B DEP
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
n.fiO
0.60
0.60
0.60
0.60
0.60
0.6n
0.60
0.60
n.60
n.60
n.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.30
0.30
0.15
0.09
0.39
0.15
0.15
0.15
0.15
0.15
0.15
0.30
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.46
0.49
0.42
0.50
0.57
0.61
0.86
0.41
0.41
0.41
0.42
0.4?.
0.39
0.41
0.40
0.40
0.23
0.33
0.42
0.30
0.36
CD
0
0
0
0
0
4
4
4
0
4
0
0
0
4
4
4
n
4
4
4
4
0
4
4 '
4
0
4
4
4
0
4
4
4
0
4
0
0
0
4
0
4
0
4
4
4
/,
4
4
4
4
4
4
4
4
4
4
4
4
0
4
4
4
4
4
4
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
NOXppm
400
400
360
420
500
400
460
500
420
400
550
520
510
510
470
420
600
600
600
650
600
580
600
600
64n
530
550
690
530
500
550
350
395
365
4nn
3 SO
220
320
400
44n
330
25(1
230
360
430
430
270
75
60
75
75
100
100
135
110
140
150
140
130
190
600
600
700
700
700
750
6'50
650
750
800
750
285
212
334
215
300
213
56
213
285
322
233
303
238
269
246
296
190
199
313
265
%DERUL
53.00
52.00
87.00
79 .00
64.00
41.00
65.00
79.00
51.00
59.00
18.00
39.00
33.00
71.00
69.00
64.00
53.00
67.00
83.00
89.00
82.00
54.00
74.00
81.00
86.00
60.00
55.00
43.00
42.00
95.00
59.00
32.00
73.00
.13.00
65.00
87.00
78.00
45.00
69.00
66.00
83.00
79.00
83. on
7°. on
74.00
« i . n n
44.no
65.00
9i.no
11. on
86.00
53.00
99.00
92.00
95.00
95.00
90.00
84.00
16.00
60.00
90.00
88.00
78.00
66.00
68.00
80.00
80.00
80.00
80.00
80.00
80.00
80.00
ao. on
80.00
80.00
80.00
80.00
80.00
80.00
80.00
80.00
80.00
80.00
80.00
65.70
39.60
48.40
50.60
24.40
42.20
36.80
59.60
60.50
73.50
44.00
28.40
54.80
70.00
28.70
52.70
65.50
64.50
94.10
78.20
79.10
COAL
ILLINOIS
ILLINOIS
ILLINOIS
ILLINOIS/>6
ILL I NO IS/' 6
ILLINOIS/<6
ILLINOIS/'6
ILLINOIS/'6
ILLINOIS/16
ILLINOIS/16
ILLINOIS/'6
ILLINOIS/'6
ILLINOISy!fi
ILLINOIS'^
ILLINOIS'^
ILLINOIS/'6
IT,LINOIS/'6
ILLINOIS/!6
ILLINOIS/'6
ILLINOIS/'*
ILLINOIS/'6
ILLINOIS/<6
ILLINOIS/(6
ILLINOIS/'fi
ILLINOIS/<6
ILLINOIS/16
ILLINOIS/'6
ILLINOIS/'6
ILLINOISf>6
ILLINOIS#6
ILLINOIS/>6
ILLINOIS/<6
ILLINOIS/<6
ILLINOIS/-'6
ILLINOIS/.'6
ILLINOISl'6
ILLINCIIS/J6
ILLINOIS/'6
ILI,INOIS/;6
ILLINOI5/<6
ILLIKOIS/-'6
ILLINOIS/16
ILLINOIS/!6
ILLINOIS/^
ILLINOIS/'6
TLLIMOIS/'6
TLLINOIS/U
T LL INO T S/' 6
ILLINOIS/'^
IT.LINOIS/'S
ILLINOIS/1 f>
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
PITTSBURGH
WT? N
1.11
1.13
1.11
1.18
1.18
1.18
1.38
1.13
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.38
1.18
1. 18
1.18
1.18
1.18
1.18
1.13
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
18
18
18
18
1,
1.
1,
1.
1.18
1.18
1.18
1.18
1.18
1.18
ills'
3.18
.18
.18
1.18
n.on
n.oo
o.oo
o.on
n.oo
o.oo
o.no
o.oo
o.oo
n.oo
O.no
0.00
0.00
30
10
10
in
30
30
3n
30
30
30
3 .30
1.10
1.3"
1.10
1 .31
1.30
l.in
n. 86
0.86
O.R*
n.sf.
O.ff
0.76
0.76
0.76
0.76
0.76
ri.76
0.7*
0.7'
0. ,'l.
0. 76
(1.7*
0.7f
128
-------
to
vO
3
H
CQ
X
o
•=
H
E
pa
J
O
1.6 •
1.5
1.4
1.3
1.2
1.1
.9
.8
. 7
.6
. 5
. 4
.3
. 2
.1
0
PRESSURIZED DATA
0-10Z EXCESS AIR
.
t
"*l '
00 700 800 900 1000 llOO 1200
TEMPERATURE C
1 .6
1.5
1.4
1.3
1.2
1.1
1 ;
. 9 •
. 8 •
. 7 •
. 6 •
. 5
.4
. 3
. 2
. 1
0
PRESSURIZED DATA
10-20% EXCESS AIR
f •
•* .'* i
* •.&'•" J,"*'" !
1 1 1 ' 1 1 1
aOO 700 800 900 1000 llOO 1200
TEMPERATURE C
1.6
1.5
1.4
1.3
1.2
1.1
3 1
H *
jr .9
B "8
x .7
o
.0
.5
.3
.2
. 1
0
PRESSURIZED DATA
20-303; EXCESS AIR
.
* • *
• • *
' " "* I
$« * " • • * i
* i. *
60 700 800 900 1000 llOO 1200
TEMPERATURE C
1.6
1.5
1.4
1.3
1.2
1.1
0 1
H
E .9
•^
« ,8
XI -7
o
K .6
.5
.4
. 3
.2
. 1
0
PRESSURIZED DATA
30-40Z EXCESS AIR
•
: . i*
. !.•••!•'
• '
T-T 4— 1 1 1 1 1.
00
?00 800
TEMPERATURE C
LlOO
-------
1.6
1 . 5
1 .A
1 . 3
1. 2
1. 1
1
. q
. R
, 7
. 6
. 4
. 1
0
AOO
L. 6
I. 5
1. 4
. ft
on
PRESSURIZED DATA
40-50% EXCESS AIR
TOO
400
800
TEMPERATURE C
ioOO
100
1200
PRESSURIZED DAT A
50-60% EXCESS AIR
?oo
Son $00
TEMPERATURE C
looo
ioo
1200
;=>
H
fa
s:
Is
X
0
,8/MBTU
X
o
z
1.6 •
1.5
1.4
1 .3
1.2
1.1
1
.9
. R
. 7
. 6
. 5
.A
. 3
2
. 1
0
1.6 •
1.5-
1, 4 •
1.3
1.2 •
1.1
1
.9
.8
. 7
.6 ;
.5
,tt
• 3 .
. 2
. 1
0
PRESSURIZED DATA
60-70% EXCESS AIR
•
.
•
t
•
00 700 §00 §00 1000 llOO 1200
TrMPERATURE C
PRESSURIZED ATA
70-80% EXCESS AIR
^
.
1200
-------
1.6
1.5
1.4
1. 3
1.2
1.1
1
.1
. 8
. 6
. 5
. 3
. 1
0
PRESSURIZED TA
80-100% EXCESS AIR
>00
1.6
1.5
1.4
1.3
1.2
1. 1
1
. 9
. 8
. 7
. 6
. 5
. 2
. 1
0
00
800Tooiono
TEMPERATURE C
linn
-t2'
PRESSURIZED DATA
100-150T' excess air
,ori ^cio fei tcio looo iioo
TEMPERATURE C
H
CD
X
ca
X
o
a
c:
J^
-n
o
1.6
1.5
1.4
1.3
1.2
1.1
1
.9
.8
. 7
.6
. 5
'
.3
.2 :
.1
1. S •
1. 5
1.4
1.3
1.2
1 . 1
1
•^
. 3
, 7
. 6
. 5
. 2
. 1
ATMOSPHERIC DATA
EXCESS AIR RANGE ; 0-10Z
•
.
00 700 SOO $00 iOOO ilOO 1
TEMPERATURE C
ATMOSPHERIC DATA
10-20% EXCESS ATR RASOE
•
•
' " •
: j
-. i
, ; !
:•••••£' :.:'
. •
1 ! ! ! ! L
200
f20T
?00 800 $00
TEMPERATURE C
ion
-------
t-0
1.6 •
1.5 •
1.4
1.3
1.2
1.1
L
.9
.7
.6
. 5
.4
. 3
. 7.
• i
0
ATMOSPHERIC DATA
20-30% EXCESS AIR RANGE
• 1 ,
:
.
• .1
' * .
•
&oo loo Soo 4oo looo lino 1200
TEMPERATURE C
1.6
1.5
1.4
1.3
1.2
1.1
1
P q
H • *
pa
K .8
(3 7
Kj • '
g .6
K . 5
. 4
. 1
.2
. 1
0
ATMOSPHERIC DATA
30-40% EXCESS AIR RANGE
:
'
oo 700 Son 9oo iooo Urn i?oo
-------
REFERENCE LIST
File Numbers Reference, equipment
1-83 Hoke, R. C. et al., Studies of the Pressurized
Fluidized-bed Coal Combustion Process. Report to
U.S. EPA, Exxon Research and Engineering Company,
Linden, NJ, September 1976, EPA-600/7-76-011.
Exxon fluidized-bed combustion miniplant;. 12.5 in
internal diameter combustor.
84-156 Hoke, R. C. et al., Studies of the Pressurized
Fluidized-bed Coal Combustion Process. Report to
U.S. EPA, Exxon Research and Engineering Company,
Linden, NJ, September 1977, EPA-600/7-77-107.
Exxon fluidized-bed combustion miniplant; 12.5 in
internal diameter combustor.
157-189 Hoke, R. C. et al., Miniplant Studies of Pressurized
Fluidized-bed Coal Combustion. Third Annual Report
to U.S. EPA, Exxon Research and Engineering Company,
Linden, NJ, April 1978, EPA-600/7-78-069.
Exxon fluidized-bed combustion miniplant; 12.5 in
internal diameter combustor.
190-200 Vogel, G. J. et al., Reduction of Atmospheric
Pollution by the Application of Fluidized-bed Com-
bustion and Regeneration of Sulfur Containing
Additives, Annual Report. July 1973 - June 1974.
ANL/ES-CEN-1007 and EPA-650/2-74-104.
133
-------
File Numbers Reference, equipment
201-215 Reduction of Atmospheric Pollution. Report to EPA,
National Coal Board, London, UK, September 1971,
Reference No. DHB 060971.
24 in. x 48 in. continuous fluid-bed combustor
216-219 Hoke, R. C., et al., A Regenerative Process for
Fluidized Bed Coal Combustion and Desulfurization,
330-352 Monthly Reports prepared under contracts 68-02-0617,
, >r.. 68-02-1451, and 68-02-1312 to EPA, Esso Research and
402-404
Engineering Company, Linden, NJ .
216-218, 12/73; 4.5 in. diameter batch fluid-bed
combustor
219, 12/73; 4.5 in. diameter batch fluid-bed
combustor
231-234, 8/75; 4,5 in. diameter batch fluid-bed
combustor
239-242, 9/75; 4.5 in. diameter batch fluid-bed
combustor
243, 2^4, 4/73; 4.5 in. diameter batch fluid-bed
combustor
245-247, 2/74; 4.5 in. diameter batch fluid-bed
combustor
248, 249, 3/74; 4.5 in. diameter batch fluid-bed
combustor
250, 4/74; 4.5 in. diameter batch fluid-bed
combustor
251, 11/74; 4.5 in. diameter batch fluid-bed
combustor
252-254, 1/74; 4.5 in. diameter batch fluid-bed
combustor
255-258, 6/73; 4.5 in. diameter batch fluici-bed
combustor
134
-------
File Numbers Reference, equipment
259, 7/73; 4.5 in. diameter batch fluid-bed
combustor
260, 11/73; 4.5 in. diameter batch fluid-bed
combustor
261-263, 1/75; 4.5 in. diameter batch fluid-bed
combustor
264, 3/75; 4.5 in. diameter batch fluid-bed
combustor
265, 5/75; 4.5 in. diameter batch fluid-bed
combustor
266-270, 6/75; 4.5 in,, diameter batch fluid-bed
combustor
271, 7/75; 4.5 in. diameter batch fluid-bed
combustor
330-352, 11/75; 4.5 in. diameter batch fluid-bed
combustor
386-388, 1/76; 4.5 in. diameter batch fluid-bed
combustor
389-396, 5/76; 4.5 in. diameter batch fluid-bed
combustor
402-404, 6/76; 4.5 in. diameter batch fluid-bed
combustor
273-287 A Development Program on Pressurized Fluidized-Bed
Combustion. Interim Report No. 1 to Office of Coal
Research and EPA, Argonne National Laboratory, Argonne,
IL, October 1974, Contract No. 14-32-0001-1543.
6 in. diameter continuous fluid-bed combustor
288-318 Jonke, A. A., A Development Program on Pressurized
Fluidized-Bed Combustion, Monthly Progress Reports by
Argonne National Laboratory, Argonne, IL, Work
135
-------
File Numbers Reference, equipment
performed under an agreement between the U.S. Atomic
Energy Commission and the Office of Coal Research,
U.S. Department of Interior, Contract No. 14-32-0001-
1543.
6 in. diameter continuous fluid-bed combustor
288-297, 2/75
298-301, 10/74
302, 303, 11/74
304, 1/75
305-308, 12/74
309, 9/74
310-317, 11/75
318, 12/75
319-320 Jonke, A. A., A Development Program on Pressurized
Fluidized-Bed Combustion. Quarterly Report to ERDA
and EPA, Argonne National Laboratory, Argonne, IL,
April 1976, EPA Contract IAG-D5-E681.
6 in. diameter continuous fluid-bed combustor
372-379 Jonke, A. A., A Development Program on Pressurized
Fluidized-Bed Combustion. Annual Report to ERDA and
EPA, Argonne National Laboratory, Argonne, IL,
July 1976, EPA Contract IAG-D5-E681
6 in. diameter continuous fluid-bed combustor
380-385 Hoke, R. C., et al., A Regenerative Limestone Process
for Fluidized-Bed Coal Combustion and Desulfurization,
Esso Research and Engineering Company, Linden, NJ,
January 1974, NTIS PB 231 374.
4 in. diameter batch fluid-bed combustor
136
-------
File Numbers Reference, equipment
415-425 Zielke, C. W., H. E. Lebowitz, R. T. Struck, and
E. Gorin, Sulfur Removal During Combustion of Solid
Fuels in a Fluidized-Bed of Dolomite, J. of Air
Pollution Control Association, 20 (3): 164-69;
March 19790.
4 in. diameter continuous fluid-bed combustor
426-433 Energy Conversion from Coal Utilizing CPU-400 Tech-
nology. Annual Report to ERDA, Combustion Power
Company, Inc., Menlo Park, CA, October 1975,
No. 1 TR-75-10-123.
9-1/2 ft. diameter continuous fluid-bed combustor
434-443 Energy Conversion from Coal Utilizing CPU-400
Technology. Quarterly Report to ERDA, Combustion
Power Company, Inc., Menlo Park, CA, July-September
1975, No. 4 TR-75-126.
9-1/2 ft. diameter continuous fluid-bed combustor
137
-------
REFERENCE LIST - ATMOSPHERIC COMBUSTION
File Numbers Reference, equipment
444-484 Robinson, E. B., et al., Characterization and Control
of Gaseous Emissions from Coal-Fired Fluidized-bed
Boilers. Interim Report to NAPCA, Pope, Evans and
Robbins, Alexandria, VA, October 1970.
18 in. x 72 in. continuous fluid-bed combustor
485-586 Reduction of Atmospheric Pollution. Report to EPA,
National Coal Board, London, UK, Reference No.
DHB 060971, September 1971.
485-490, 508, 530; 27 in. diameter continuous
fluid-bed combustor
494, 495; 12 in. x 12 in. continuous fluid-bed
combustor
496-507; 6 in. diameter continuous fluid-bed
combustor
531-549; 36 in. x 18 in. continuous fluid-bed
combustor
587-602 Carls, E. L., et al., Reduction of Atmospheric
Pollution by the Application of Fluidized-Bed
Combustion. Report to NAPCA and U.S. Atomic Energy
Commission, Argonne National Laboratory, Argonne, IL,
July 1968 - July 1969, ANL/ES-CEN-1001.
6 in. diameter continuous fluid-bed combustor
138
-------
File Numbers Reference, equipment
603-658 Jonke, A. A., et al., Reduction of Atmospheric
Pollution by the Application of Fluidized-Bed
Combustion. Report to NAPCA, Argonne National
Laboratory, Argonne, IL, July 1969 - July 1970,
ANL/ES/CEN-1002,
6 in. diameter continuous fluid-bed combustor
659-665 Vogel, G. J., et al., Reduction of Atmospheric
Pollution by the Application of Fluidized-Bed
Combustion and Regeneration of Sulfur-Containing
Additives. Annual Report to EPA, Argonne National
Laboratory, Argonne, IL, July 1971 - June 1972,
ANL/ES-CEN-1005 and EPA-R2-73-253.
6 in. diameter continuous fluid-bed combustor
666-684 Hammons, G. A. and A. Skopp, A Regenerative Lime-
stone Process for Fluidized Bed Coal Combustion
and Desulfurization. Report to Air Pollution
Control Office, Esso Research and Engineering
Company, Linden, NJ, February 28, 1971, Contract
CPA 70-19.
3 in. diameter continuous fluid-bed combustor
685-705 Lange, H. B., et al., S02 Absorption in Fluidized-
Bed Combustion of Coal-Effect of Limestone Particle
Size, Final Report to EPRI, The Babcock and Wilcox
Company, Alliance, OH, January 1978, EPRI FP-667.
3 ft. x 3 ft. fluid-bed combustor
139
-------
NOMENCLATURE
Sup vel = Superficial velocity, m/s
B Dep = Bed depth, m
CD = Bed depth code
0 - Expanded bed depth
1 - Settled bed depth
2 - Initial settled bed depth
3 - Final settled bed depth
4 - Bed from previous run
140
-------
APPENDIX B
LITERATURE SUMMARY OF NITROGEN OXIDE
EMISSIONS IN FLUIDIZED-BED COMBUSTION
141
-------
Dwg. 2620CSO
Source Materials Used Type of Experimentation
1. Exxon Grove limestone Fluid-bed, batch combustor,
(2/71) Coal-Pittsburgh 3 in. dia. 870-980°C
bituminous 2.5 - 6* 02
atmospheric pressure
Direct Results
Mechanistic Studies Method of Determination
Conclusions
NOX emission is constant
in an inert bed
NOX emissions from a fluid
bed of lime at zero conversion
are higher than those from
an inert bed
NOX decreases as S02
increases in limestone beds
NOX reduced upon addition
of §02*0 a fluid bed of
partly sulfated stone
NOX emission not affected
by injection of S02 to an
inert bed ICaSO^ when N2
is transport gas but in air
NOX was reduced
MOX increased from 1100 to
1500 ppm as temperature
was raised from 670 - 980°C
(Note: These were not at
same S02 levels!
NOX not affected by varying
excess air
Simulated Gas Studies
- Ca S04 is not a NOX
decomposition catalyst
- NO and S02 react in
the presence of an
activated site
- S02 and NO do not
react at 888 °C in
1 second, only in
partly sulfated beds
- Gas temperature lowered
to 149°C, passed through
cyclone and fritted SS
fiiter.then air-cooled
condenser
-Whittaker polarographic
analyzer continuously
monitors NOX I full
response to NO, 80% to
N02)
- NOX reduction
mechanism proposed
I) CaO <-S02-CaS03
CaS03 + 2NO-CaS03-(NO)2
CaS03-(NO)2-CaS04<-N20
N20 - N2 + 1/2 02
21 Unidentified mechanism
for inert beds with
large excess 02 present
- Excess air has no effect on
NOX emission since oxidation
of fuel N2 occurs at bed
entrance where 02 level is
fairly independent of excess air
2. Exxon Grove limestone Fluid-bed batch combustor.
(12/711 Coal - Pittsburgh 3 in. diameter
bituminous Electrically heated fixed beds
670 - 980 °C,
2.5-6*02.
atmospheric pressure
- N02 emission negligible
- Increasing temperature from
816 to 927 °C
Doubles reduction of NO
in presence of steam
Littlp effect with no steam
Studies in fixed bed
• NO -S02
CaO t S02-CaS03
2CaSO,+2NO-
•NO -CO
2 CO
2NO-
2 CO,
Gas temperature lowered
to 149°C,passed through
cyclone, filter, air-
cooled and water-cooled
condensers
-Whittaker polarographic
NOX analyzer
- Beck man Model
ND 1R315B
NO analyzer
- Du Pont Model 461
NOX analyzer
• N02 -absorption
of visible light
•NO-oxidationto
IM02 under 414 kPa
0-. presence
- The NO -CO Reaction
1) Catalyzed by CaO more than
CaS04, more than Alundum
21 Second order in NO and CO
31 Ea=25-33fcJ/mole
(704 - 927 °C I
4) Decreasing temperature or
excess air increases CO there
by decreasing NO emissions
5) Addition of steam minimizes
the need for an active solid
su rface
The NO - S02 Reaction
II CaO necessary
21 order =0.5 in NO with no 02
31 Negative temperature depend-
ence (rate increases by a
factor of Sin reducing tem-
perature from 871 - 760°C,
decrease in rate coincides with
increase in CaS03 thermo-
dynamic stability)
- 2-Stage Combustor Proposed
II Phase one operating at
Stoichiometric conditions,
NO -CO reaction promoted
21 Add secondary air at a
higher point to complete
combustion and provide S02
for reaction with remaining NO
142
-------
Source Mal^riaK Used
3. ;v:
-------
Dwg. 2625C10
7. Argonne
(7/691
Limestones 1359. Bench-scale fluid-bed
1360, and
combustor. IScmdia.
Increasing 02 in flue gas
from 2.6 to 11.8* (14 to 128*
- NO values were higher N02- by gas ctiromatog -
than possiblyobtained raphy, unsuccessful
dolomite 1337
No limestone
used in Argon
substitution
experiments
Coal
Illinois, 4. 5% S
8. Argonne Tymochtee
1 6/70) dolomite
Illinois Seam
No. 6, 4. 5% S
9. Argonne Limestone 1359
16/731 Coal-Peabody.
4HS
10. Argonne Tymochtee
1 10/74) dolomite
coals -
Arkwright,
2.82% S
subbituminous.
0 78% 5
lignite. 0. 5*S
Atmospheres of N2/02
and Ar/02
atmospheric pressure
Bench -scale fluid -bed
combustor, 15cm dia.
SS pipe
870°C. 0.9 m/s
0.6 -2. 7m bed height
atmospheric pressure
Bench scale fluid-bed
combustor, 15cm dia.,
atmospheric pressure
Continuous, fluid -bed
combustor 15cm diameter
-788 -899°C
-Ca/Sof 1.2. and 3
-velocity of 0.6 -1.5 m/s
-pressure, 8-10atm
-0.9m bed height
- 15% excess air
excess air) increased NO
emission from 400-500 ppm.
Reduction in NO with S02
upon addition of limestone
-
1MU2 + bu2«- NU +• iU}
- Experiments with natural gas
had NO < 100 ppm as expected
in nitrogen fixation
equilibrium
- Initial NO of 600 ppm reduced
to 200 ppm in a flu id bed of
limestone
- NOX removal is inversely
proportional to Ca/S molar
ratio
- NOX removal is inversely
proportional to velocity of gas
- NO removal is proportional to
gas residence time
- NO emissions increased
with excess air ( 50-250%!
-NO emissions tended to be
lower at higher temperatures,
possibly because NO -CO
reaction increases with
temperature
- NO emissions were low
270 opm at Ca/S of 3. 2
888°C, 1.1 m ;
120 ppm at Ca/S of 1,
907°C, 1.5m
- Reduced Ca/S produced
higher S02 level sand lower
NO levels
by equilibrium
fluid-bed combustion
of coal
-Argon substitution for
N7 showed same NO in
flue aas
The reaction
N02 + S02^S03+NO
is not the mechanism
for NO removal with
502 since N02 levels
remain constant
Less than stoichio-
metric air was added
to a fluid bed When
air was added above
the bed NO emission
increased. Possible
reasons
11 NO & CO reduction
stopped
2) the excess air
oxidized, NH, etc.
to NO
Effect of Pressure
- Graatly increased NO
with decreased pres-
sur. in Alundumoed
( to 1600 opm at
101.3kPa)
- Smaller Increase in
NO with decreasing
pressure in coal and
dolomite bed
1 500 ppm at
101.3kPa)
Beckman infrared
analyzer
N02 -
11 phenoldisulfonic
acid procedure
2) mass spec NO/NOj
3) fast N02 analyzer
NO infrared analyzer
Sampling in 1.3 cm.
diameter SS tube.
Passed through sintered
nickel filter to remove
fines and a condenser
and refrigerator
Infrared analyzer
IR analyzer
Gas passed through
sintered SS filter
NO in flue gas comes from
reaction of solid nitrogeneous
material in coal
Injection of A^Oj and
Zrp2had noeffeclon
emissions
00304 increased NO emissions,
had no effect on SOg emissions
NO emission from a partly
su(fated lime bed was 20 -4K
lower than emission over an
inert bed
No dependence of NO
emission on temperature
or gas velocity
-NO levels at pressure are
significantly lower than at
101.3 kPa
-Temperature in range of
788 - 899°C has no effect
on NO emission
- Reduced Ca/Sgives lower
NO emissions
144
-------
2620C76
Source Materials Used Type o( Experimentation
1L Argonne
16/75)
Limestone 1359
and Tymochtee
dolomite
Bench-scale, fluid-bed
combustor, 15cm dia meter p
810 kPa pressure
Coal - Pittsburgh 954°C
bituminous,
2.82*5
Direct Results
NO increased with 02 in
flue gas
3% 03 - 160 opm NO
6% 02 - 200 ppm NO
9% 02 - 230 pom NO
Mechanistic Studies Method of Determination
Effect of precalcination Infrared analyzer
of sorbentonNO
emission
Conclusions
- Additive type does not effect
NO emission
- Precalcination of sorbent
does not effect NO emission
12. Argonne Grove limestone Continuously operated,
(12/75) andTymochtee fluid-bed combustor
dolomite 788-899^
Ca/S of 1 to 3,
gas velocity of
0.6-1.5m/s
810 kPa pressure, 0.9 m
fluidized-bed height.
Coals -
-Arkwright,
2.82*5
- San Juan,
0.78* S
- Glenharold,
0.53*5
3*0,
- NO levels were very low
(120 - 270 poml
- Increasing Ca/S.
increased NOX
- Coal & sorbent particle
size has no significant
effectonNOx
- Additive type has effect
on NOX
- NOX increases with 02
concentration
- Temperature variation
(788-899°CI has little
or no effect on flue gas
composition
- Increase in NO emission
occurs when pressure is
decreased
CO levels in flue gas
-In presence of
dolomite, increase
with decreasing
pressure
- Without sorbent-
CO level is minimum
at 405 kPa pressure
NOX infrared analyzers
Increasing NO emissions with
increasing Ca/S ratio - the
only independent variable with
a significant effect based on
regression analysis considering
temperature(788-8W°CI.
gas velocity (0.6- 1.5m/s)
and Ca/S 11-31
13. Argonne
(7/76)
Tymochtee
dolomite
(370 and
740 um)
Coal-
Arkwright,
2.8*5(150
and 640 um)
Continuously operated,
fluid-bed combustor
840°C, 810 kPa,
17* excess air. 1.07 m/s,
0.9 m bed height
-NO was low(120-150optn)
in all four runs
-NO, levels of 40-60 pom
were higher than the
expected 5 -10 ppm
Chemiiuminescence
analyzer
Particle size of coal and
sorbent have no effect on
NO emissions
Pope,
Evans
and
Robbins
(10/70)
limestone 1359 Continuously operated.
and fluid-bed combustor
dolomite 1337
Coals- 810-971°C
No. 8 Pittsburgh, 1.27 - 30 cm bed depth
4. 5* S 1.8 -4 m/s
Pike County, atmospheric pressure
low S and N
- NO varied from 320 opm (1%
02) to 440 Dom i 5% n2>
- N02 emission «as very low
-Useof sorbent had an un-
clear effector. MO emission,
in two cases 2 reduction in
NO was observed with
additive addition
A change from low to
high nitrogen coal
caused a small
increase in NO
emission
- Infrared absorption
- Total NOX by
p'henoldisulfonic acid
determination
-No consistent
correlation between
temperature and NO
emission at constant
02 concentration
-NO emission is
independent of bed
height
145
-------
D*9- 2620C78
Source Materials Used Type of Experimentation
direct Results
Mechanistic Studies Method of Determination
Conclusions
15. National U.K. limestone.
Coal Board limestone 1359.
(9/71) limestone 18.
U.K. dolomite.
and dolomite
1337
Coal
-Illinois,
4.4% S
- Pittsburgh,
2.8% S
- Park Hill,
2.5* S
- Welbeck,
1.5H S
16. NRDC/ U.K. limestone
BCURA and Dolomite
(7/74) 1337;
Coal-
Pittsburgh.
3*5 ; Illinois.
3.5%S
17. NRDC/ Dolomite 1337;
NCURL Coal-Illinois 6,
(9/77) 3* S
18. Pereira. No limestone
Beer, Bed material-
Gibbs inert
(4/76) silica -based
clinker
Coal -
1.7% Sand
1.4%N
Continuous fluitl-bed
combustor:
69cm diameter
91cmx 46cm
122 cm x 61 cm pressurized
749- 927 °C
0.46 -2.1 m bed height
0.61 -3.35m/s
101.3-506.5kPa
Continuous fluidized-bed
combustor, 0.11 mx0.61m;
584 kPa; 900-954° C;
14-20% excess air; 1.1- 1.4m
fluidized bed height
Continuous fluidized-bed
combustor, 0. 91 mx 0,61m ;
30 x 30 cm sectioned
continuous combustor
650 -850°C
-25 - +40% excess air
0.61 m bed depth
0. 9 m/s velocity
atmospheric oressure
7. 5 cm diameter batch
combustor
600-950°C
10 - 40 cm/s velocity
atmospheric oressi: re
- NO emissions were generally
in the range of 320 - 600 ppm
- in 91 cm combustor NOX
increased as SOj decreased
- NOX reduced to 100 ppm
when coal size was reduced
from '-. 3175 jm to
< 1680 urn
NOX emissions generally
86 ng NOj/J ( 150 ppml or
lower; however, in one test
high er values of 255 ng NOj/J
observed
NO emissions between 129-
215 ngNOj/JI 90-180 ppm);
higher emissions observed on
increasing the temperature
from 365to 902'C and super-
ficial velocity from 0. 8 to 2. 1
m/s
NO emissions increase
linearly with temperature
(650 -800"Ci at2.26ppm/°C
At temperatures above 800 °C,
the emissions levol off
Batch combustor NOX
emissions reach a
maximum at 750 °C
NO emissions ( mole/g of
coali increase with excess
air levels
Regression analysis gives
ram NO =-1093 +2. 26 T
-203N
• N = ratio of actua 1 to \
stoichiometric air
> T = "C
With higher concen-
trations of S02 in the
exhaust gas, relatively
lower NO emission
observed
Reduction of NO by
char
1) increased reaction
as temperature
raised above 800 °C
21 increased reduction
as particle size of
char is reduced
(Experiments in batch
combustor with no
oxyger '
90% reduction
NO emission at 930°C
with 100 Mm ^articles
Temperature maximum
for NO emissions
- Emissions increasing
uo to 750°Cdueto
decrease in reduction
by unburntCO, H2
and hydrocarbons
- Emissions decrease
at higher temperature
due to reduction by
char
Flue gas withdrawn
through silica probe
1 steel probe used for
pressurized combustor)
and bubbled through
water to remove
soluble gases
- About 5* NOX was
soluble and analyzed
by Saltzman's method
- Remaining NOX analyzed
two ways
11 Saltzman1 s method -
spectrophoto metric
21 BCURA NOX box.
NO oxidized to N02
and electrical
current measured
NO measured using
chemiluminsscence
monitor
Thermo Electron
Corporation
'chemiluminescence'
monitor
Continuous monitoring
of NO with chemi-
luminescent analyzer
- No correlation was found
between NOX emissions
and gas velocity, temperature,
Ca/S molar ratio or SOj
concentration
- In pressurized operation
NOX was lower, NO emission
increasing with decreasing
502
-Excess air is the primary
variable. Significant
increase in NO emissions
were observed for excess air
levels in the range of 0-6%.
- SO, may possibly inhibit
the formation or promote
the dissociation of NO inFBC
NO emissions increased
on decreasing the gas
residence time (increasing
superficial velocity) , and/or
increasing the temperature
- NO formation occurs
preferentially in regions
of high 02 concentration.
close to the distributor
and coal feed points
-NO reduction occurs in the
bed and freeboard. In the
freeboard, the reduction is
due to chemical reaction
rather than mixing
- NO is reduced by hot char
in the absence of oxygen..
The amount reduced in-
creases with temperature
and decreasing char particle
size
146
-------
REFERENCE FOR LITERATURE SUMMARY
1. Hammons, G. A., and A. Skopp, A Regenerative Limestone Process for
Fluidized Bed Coal Combustion and Desulfurization. Final report to
Air Pollution Control Office, Esso Research and Engineering Company,
Linden, NJ, February 28, 1971, Contract CPA 70-19.
2. Skopp, H., et al., Studies of the Fluidized Lime-Bed Coal Combustion
Desulfurization System, Part 2: Factors Affecting NO Formation and
X
Control in Fluidized Bed Combustion, Esao Research and Engineering
Company, Linden, NJ, December 31, 1971, NTIS PB 210 246.
3. Hoke, R. C., et al., A Regenerative Limestone Process for Fluidized-
Bed Coal Combustion and Desulfurization, Esso Research and Engineer-
ing Company, Linden, NJ, January 1974, NTIS PB 231 374.
4. Hoke, R. C., et al., Studies of the Pressurized Fluidized-Bed Coal
Combustion Process, Report to EPA, Exxon Research and Engineering
Co., Linden, NJ, September 1967, EPA-600/7-76-011.
5. Hoke, R. C., et al., Studies of the Pressurized Fluidized-Bed Coal
Combustion Process, Report to EPA, Exxon Research and Engineering
Co., Linden, NJ, September 1977, EPA-600/7-77-107.
6. Hoke, R. C., et al., Miniplant Studies of Pressurized Fluidized-Bed
Coal Combustion, Report to EPA, Exxon Research and Engineering Co.,
Linden, NJ, April 1978, EPA-600/7-78-069.
7. Carls, E. L., et al., Reduction of Atmospheric Pollution by the
Application of Fluidized Bed Combustion, Annual report to NAPCA and
U.S. Atomic Energy Commission, Argonne National Laboratory, Argonne,
IL, July 1968-July 1969, ANL/ES-CEN-1001.
8. Jonke, A. A., et al., Reduction of Atmospheric Pollution by the
Application of Fluidized-Bed Combustion, Annual report to NAPCA,
Argonne National Laboratory, Argonne, IL, July 1969-July 1970,
ANL/ES-CEN-1002.
9. Vogel, G. J., et al., Reduction of Atmospheric Pollution by the
Application of Fluidized-Bed Combustion and Regeneration of Sulfur-
Containing Additives, Report to EPA, Argonne National Laboratory,
Argonne, IL, June 1973, EPA-R2-73-253.
147
-------
10. A Development Program on Pressurized Fluidized-Bed Combustion.
Interim Report No. 1 to Office of Coal Research and EPA, Argonne
National Laboratory, Argonne, IL, October 1974, Contract No.
14-32-0001-1543.
11. Vogel, G. J., et al., A Development Program on Pressurized Fluidized-
Bed Combustion, Annual Report to ERDA, Argonne National Laboratory,
Argonne, IL, July 1975, ANL/ES-CEN-1011.
12. Vogel, G. J.., et al., Recent ANL Bench-Scale, Pressurized-Fluidized-
Bed Studies, Argonne National Laboratory, Argonne, IL, Proceedings of
the Fourth International Conference on Fluidized-Bed Combustion,
Washington, DC, December 9-11, 1975.
13. Jonke, A. A., A Development Program on Pressurized Fluidized-Bed
Combustion, Report to ERDA and EPA, Argonne National Laboratory,
Argonne, IL, July 1976.
14. Robinson, E. B., et al., Characterization and Control of Gaseous
Emmissions from Coal-Fired Fluidized-Bed Boilers, Interim Report
To NAPCA, Pope, Evans and Robbins, October 1970.
15. Reduction of Atmospheric Pollution, Report to EPA, National Coal
Board, London, UK, September 1971, Reference No. DHB 060971.
16. Pressurized Fluidized Bed Combustion, Report to Office of Coal
Research, National Research Development Corporation, London, UK,
July 1974, Contract No. 14-32-0001-1511, NTIS PB-234 591.
17. Roberts, A. G., et al., Pressurized Fluidized Bed Combustion, Report
to U. S. ERDA, Report No. 43, National Research Development Corporation,
London, UK, September 1977, FE-1511-43.
18. Pereira, F. J., J. M. Beer, and B. M. Gibbs, Nitric Oxide Emissions
from Fluidized Coal Combustion, the Combustion Institute, Central
States Section, Spring Meeting, April 5-6, 1976.
148
-------
APPENDIX C
EFFECTS OF PRESSURE, EXCESS AIR, AND GASEOUS SULFUR
CONTENT ON VOLATILE TRACE AND MINOR SPECIES AT
EQUILIBRIUM IN FBC PROCESSES*
*In this section PP stands for partial pressure,
149
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
ALUMINUM SPECIES AT EQUILIBRIUM
PHASE
PRESSURE*1520.«t-»101.3KpA
EXCESS AIRt
10 + 300-6
SULFUR RECCVALI
n -> 90*
Ul
o
ALCL3 INCREASED PPALCL3 AT
LOW TEMPERATURES
DECREASED PPALCL3 AT
HIGH TEMJvPEKAlURES
ALOCL INCREASED PPALUCL
ALCL2 INCREASED PPALCL2
ALC2 INCREASED FPALC2
ALOH INCREASED PPALOH
ALCL INCREASED FPALtL
ALO INCREASED PPALO
AL2CL6 DECREASED AL2CL6
DECREASED PHALCL3
INCREASED PPALOCL AT
LOU TEMPERATURES
DECREASED PPALOCL AT
HIGH TEMPERATURES
DECREASED PPALCL2
DECREASED PPAL02
DECREASED PPALOH
DECREASED PPALCL
DECREASED PPALU
DECREASED PPAL2CL*
INCREASED PPALCL3
AT LOW TEMPERATURES
INCREASED PPALOCL
AT LOU TEfFEKATUHES
INCREASED PPALCL2
INCREASED FFALC2
DECREASED PPALOH
DECREASED FFALCL
SLIGHTLY DECREASED
PPALO AT 1C* EXCESS
AIR
MO EFFECT
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
CHROMIUM SPECIES AT EQUILIBRIUM
GAS PRESSUKE»152f).4->101.3KPA
PHASE (15-MAT!*)
EXCESS AIRt
10 •» 300*
SULFUR REMOVAL*
0 -> 90S
CRC2CL2 DECREASED FPCH02CL2
CRC4H2
CECHtASEB PPChC4h2
CKC2CH PvO EFFECT
CR03 INCREASED PPCR03
CR02 INCREASED PPCR02
CRCL3 INCREASED FHCHCL3 AT
LUU TEMPERATURES
DECREASED PPCRCL3 AT
HIGH
CECHEASED PPCR02CL2
IWCHEASED
FOR 10« TO
EXCESS AJR
100*
DECREASED PPCR04H2
FOR 100% 10 300X
EXCESS AIR
INCREASED PPCR020H
INCREASED PPCR03
INCREASED HPCR02
CECKEASED PPCRCL3
IfoCREASED FPCRC2CL2
FOR 10* EXCESS AIR
INCREASED FFCRC4H2
ESPECIALLY FOR 10*
AND 100* EXCESS AIF
INCREASED FFCRC20H
ESPECIALLY FOR 10*
TO 100% EXCESS AIR
INCREASED PPCR03 AT
in* 10 ua* EXCESS
AIR Al 1 AND 5 ATft
INCREASED PPCR02 AT
10* TO ICG* EXCESS
AIR
DECREASED FFCRCL3 AT
100* EXCESS AIR AT
LOk TEMPERATURES
NO EFFECT AT HIGH
TEMPERATURES; AT
100% OR 300* EXCESS
AIR
CRCL2
INCREASED PPCRCL2
DECREASED PPCRCL?
NO EFFECT
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
CHROMIUM SPECIES AT EQUILIBRIUM (Cont)
CKCL4
DECREASED PPCKCL4
DECREASED PPCRCL4
Ui
Ni
CRC
CRCL
CR
INCREASED FFChC
CFCREASFD FHCRCL
INCREASED
DECREASED PPCKO
UEChEASED PPCRCL
CECHEASED PPCK
DECREASED FFCFCL1 AT
LOW TEMPERATUFi FOR
ITS; AND 100* EXCESS
AIR
INCREASED FPCRCL4 AT
HIGH TEMPERATURES FOR
10% ANC IOCS! EXCESS
AIR
NO EFFECT FOH 300*
EXCESS AIR
SLIGHILY DECREASED
PPCKO FOR HIGH
TEMPERATURES IK 10*
EXCESS AIR
SLIGHTLY DECREASED
PPCRCL AT 11* EXCESS
AIR AT HIGH
TEMPERATURES
DECREASED FFCR AT
100* EXCESS AIR
NO EFFECT FCR 100*
AND 300* EXCESS AIK
-------
EFFECT .OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
COBALT SPECIES AT EQUILIBRIUM
GAS PRESSUK£tl520.4-»101.3KPl
PHASE ll5-»lATl*i
EXCESS AIK»
10 •* 300%
SULFUK REMOVALt
o * sr*
COCL2
COCL3
CG2CL«
COCL
Ui
IfoCKEASED FPCCCL2
DECREASED PPCUCL3
INCREASED ppco2Ci_4
Al LOfc TERKFEFATDREi
DECREASED PPC02CLt
Al HIGH ^E^FEhAlLRES
INCREASED PPCOCL AT
LUU
INCREASED PPCOCL AT
HIGH TEWPEKAFURES FOrt
104 AMD 130* EXCESS
AlRt AND Q* AUD 9T«
SULFUH REMOVAL
DECREASED PPCOCL AT
HIGH 1FKPEHATLHES Fth
300* EXCESS AIR AND
0* AKD 90* SULFUR
REMOVAL
DECREASED PHCOCL2
DECHEASEJ3 PPCOCL3
DECREASED
DECREASED PPCOCL
INCREASED FPCOCL2
IWCKEASED PPCOCL3
AT LOU TEPFER/STUFES
WO EFFECT AT HIGH
TEfPEHATUhES
NO EFFECT AT HIGH
TEKI-ERATUHES
INCREASED PPCOCL
AT LOtv TEKFEHATUFES
WO EFFECT AT HIGH
TFHPEKATUHES
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
IRON SPECIES AT EQUILIBRIUM
GAS PRESSURE* 1520.t-*I01.3KPA
PHASE (15-HATM)
EXCESS AIR»
10 -> 3'30*
5=LLFLK REWCVALt
0 -» 90%
FE(OH)2 INCREASED PPFE(OH)2
FECL2
FECL3
FFO
FF.?CLt
INCREASED PPFECL2
Ii^REASED PPFECL3 AT
LOU TEMPERATURES
DECREASED PPFECL3 AT
HIGH TEFFEKATURES
INCREASED PPFEO
FOfc 03; SLLFUR
INCREASED PPFECL4 Al
LOU TEfiPERATUhES*
DECREASED PPFECL^t AT
HIGH TEfPEHATLRES
FCR 90% SLLFUf REfCVAL
DECREASED PPFECL4
OFCREASEO PPFE(OH)2
DECREASED PPFECL2
DECREASED PPFECL?
DECREASED PPFEO FOR
10*» 100*. 300*
EXCESS AIR FOR 9.)*
SULFUH REMOVAL
INCREASED PPFEO FOR
80TK IN 0* St'LFLH
REMOVALi DECREASED
PPFEO AT HIGHER
1EMPERATURES
TECFEASED PPFE2CL4
INCREASED PPFE2
AT LOU TE^FERAllJhES
INCREASED PPFECL2
AT LOU TEfFEKATUFES
INCREASED PPFECL3
AT LCU' TE^
IMCREASED PPFEO AT
LOU TEMPERATURES
FOR 1,'J* EXCESS AIR
CECREASEC PPFEC AT
HIGH TEMPERATURES
INCREASEC Pr-FE?CL«l
AT LOW TEMPERATURES
DECREASED PPFE2CL4
AT HIGP TEPPER/IIURE
FOR 10* EXCESS AIR
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
IRON SPECIES AT EQUILIBRIUM (Cont)
FECL
(FECL3)
Oi
Ui
FE
INCREASED
FuR 03 SULFUR REMOVAL:
INCHEASED PP
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
MANGANESE SPECIES AT EQUILIBRIUM
GAS t-hESSUKEt I520.t»->101.3KPA
PHASE (15->lATfi)
EXCESS AlRf
10 -» 300*
5ULFIR REMCVALi
0 -» 90*
MNCL2
MNCL
MNO
INCREASED pppn\icL2
INCREASED
PPMniO
Ii^CS?EASEO PPMiM
DECREASED PPHNCL2
DECREASED PPMNCL
INCREASED PPMNO AT
LOk TEHPEHATURES
DECREASED PPMNO AT
HIbh TEMPEKATLKES
DECREASED PPMN AT
HIPH TEMPERATLHES
INCREASED PPMNCL?
AT LOW TEPPERATUhES
NO EFFECT AT HIGH
INCREASED PPMNCL
AT LOU; 1ECFERATUHES
NO EFFECT AT HIGH
TEMPERATURES
INCREASED PPi-INO
AT LOU TEPFERATLKES
!MO EFFECT A I HIGH
TEKPERATUHES
INCREASED PPNN AT
LOU TEMPERATURES
SLIGHT DECREASE IN
PPKN AT UGH
TEMPERATURES FOR
10* EXCESS AIR
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
MOLYBDENUM SPECIES AT EQUILIBRIUM
GAS PRESSURE*1520.4-MQ 1. 3KPA
PHASE 115-tlATM
EXCESS AIR.
IP -> 300*
SULFUK REIOtfALt
0 -> 90%
MUC?(Ott)2 NO EFFECT
M002CL2
M003
MOCL4
I»OC
I"OCL5
INCREASED PPM002CL2
iVO EFFECT AT HIGH
TEF HEKATLhES
I'yJ EFFECT
INCREASED FPPLC2
SLIGHT INCREASE I'M
FPMCCL4 AT LCU
TEMPEKATUKES FOR
10* EXCESS AIH
INCREASE AT LUW
TEMPEIVATLKES FGH 1 0 (i
AND 300* EXCESS AIR
DECREASE IK
AT 1200K FCh 30»
AND 30f)* EXCESS AIR
M) EFFECT
DECREASED PPMCCL5
CECKEASED
PPM002(OH)2
DECREASED
IMO EFFECT
DECREASED PPM002
DECREASED
DECREASED PPMOO
CECHFASED PPMOCL5
SLIGHT INCREASE IN
PPMOO?(Ort)2 AT LOW
TEMPERATLKES
NO EFFECT AT HIGH
TEMPERATURES
SLIGHT DECREASE IN
PPMOC2CL2 AT LCU
TEMPERATURES FOR
EXCESS AJR
NO EFFECT AT HIGH
TEMPEKATLKES
NO EFFECT
SLIGHT DECREASE IK
PPilOO? FOR 10* EXCESS
AIR
DECREASE IN PPMOCL4
PARTICULARLY FOR
10* EXCESS AIR
DECREASE Ih PPMCC
AT 1 ATM FOR t«3*
EXCESS AIR; OTHERWISE*
WO EFFECT
DECREASED PFMCCL5 FOR
10* AND JLOQ* EXCESS
AIR
MOCL6
DECREASED PPI10CL6
DECREASED PPMOCL6
NO EFFECT
-------
EFFECT OF PRESSURE, EXCESS AIR AND SULFUR CONTENT ON VOLATILE
NICKEL SPECIES AT EQUILIBRIUM
GAS
PHASE
NICL2
PKESSUKE»1520..q-»lG1.3KPA
!\IKOH>2
NICL
Ul
oo
NIO
NI
NIH
UChEASED FPNICL2
LOW TEMPERATURES
1*0 CHANGE IN PPNICL2
AT T>100l)K
SLIGHTLY INCREASED
FFNKCH12 AT LOU
TEMPERATURES
fkO CHANGE AT TMOOQK
INChEASED FHMCL
ALL TEKPEKATURFS
PPHIIO AT
LUU TENFERATIKES
iiiO EFFECT AT T>10()r)K
INCREASED PP.«I AT
ALL 1EMPEHATURES
INCREASED PPnIH AI
>iiLL TEC'FEHA IUHES
EXCESS AIRt
10 -> 300 *
DECREASED HPNICL2
DECREASED PPNI(OH)2
LECKEASED PPNICL
INCREASED PPNIO AT
T<1000K
AT 1>iaOTK NO CHANGE
IS DETECTED
DECREASED
ilLFLK RE
0 -> 90*
SLIGHTLY CECREAbEC
PPNICL2 AT LOW
TEMPERATURES
IVU EFFECT AT T>100€K
'INCREASED PPNKOH)2 AT
LOU TEMFERATURES
&0 EFFECT AT
TEMPERATURES
ELEVATED
DECREASED FPMCL *T
600K FOR 1CU EXCESS
AIR
SLIGHT INCREASE i«
PPNICL AT LOU
TEMPERATURES FOR 100*
AND 300* E>CES£ AIR
NO EFFECT AT ELEVATED
TEMPERATURES
INCREASED PPIMIO AC
7QOK
NO EFFECT AT T>1f)90K
INCREASED PPNI AT
800K
SLIGHI DECREASE IN
PPNI AT T>100GK
INCREASED PPNIH AT
SOOK
SLIGHT DECREASE 1*
PPNIH AT ELEVATED
TEMPERATURES
-------
APPENDIX D
EQUILIBRIUM CALCULATIONS FOR FBC OPERATION AT 100 PERCENT
EXCESS AIR, 90 PERCENT SULFUR REMOVAL AND 1013 kPa
(10 atm) TOTAL PRESSURE
159
-------
ALUM1
NUM - FLUID BED COMBUSTION GAS
1004 EXCESS AIR
SULFUR REMOVAL
" "TB ATMOSPHERES TOTAL PRrsSURE
\
TEMP. \COMPOUND
(K) \ AL203 (0 AL2(S04)3 JC)
300 .OO'OO " .416^0-02
400 .19/5-01 .4100-02
500 .1975-01 .4160-02
fefifl .1975-01 .4158-02
TOO .1986-01 .4041-02
800 .2390-01 .OOOU
900 .2390-01 .0000
100U .239Q-Q1 .OOOU
1100 .2390-01 .OOUQ
1200 .239Q-01 .0000
\ . . _ .. . ....
TEMP. \COMPOUND
« ) \ AL02 (G ) ALOH < G )
300 .0000 .QOOU
400 .0000 .OOOU
500 .0000 .DOOQ
600 .0000 *UQUG
700 .0000 .0000
800 .1213-33 .OQOU
900 .6367-29 .4298-35
1000 .3747-25 .1246-30
1100 .4495-22 .5490-27
1200 . 1636-19 .5882-24
ALCL3 (G)
• oooo
.5612-32
. 1 128-25
..... .1.5171 -22
.9764-20
•3605-18
•5485-1 7
.4802-16
•2712-15
.1148-14
A L C L ( ti )
. u u u u
.auuu
.0000
.ouuo
.0000
• oouo
. 1637-35
.3772-31
• 13^4-27
. 1 1 78-24
ALOCL (UJ
• OOOO
.0000
.0000
.8027-36
.4755-30
.9121-26
. 1878-22
.8296-20
.1 183-17
.7319-16
ALO (G)
.OOUO
.OQOU
.OOUO
,0000
.0000
.0000
• UQUO
,2268-35
.4842-31
. 1933-27
IRON - FLUID BED COMBUSTION GAS
100% FXCESS AIR
90* SULFUR REMOVAL
10 ATMOSPHERES TOTAL
\
TEMP. \CQMPOUND
(K) \ FE203 (Sj F£2{S04)3
300 1303-01 .416U-02
400 t30"3-0l • 416.0-02
500 1303-01 .4160-02
600 1303-01 .4159-02
__Z GUI 1308-01 .4107-02
800 1576-01 .1426-02
900 1719-01 .0000
1UOO 1719-01 .0000
MOO 1719-01 .0000
1200 17 I 9-0" 1 .0000
\
TEMP. \COMPOUNO
. ..I.KJL _S E£0 ( ii FE2CL4 <
300 .0000 .0000
400 .0000 .0000
500 .0000 .2409-35
600 .0000 .1633-29
7013 .1627-36 .6833-26
800 .1999«.3D .2287-23
9QO .1031-25 .1769-21
1000 .5811-22 .5444-20
I TOO .ASBT-19 .8209-19
1200 .?248-l6 .7713-18
PRESSURE
(S) FE(OH)2 {Gl
• oaoa
• oooo
.9430*29
•3884-23
•3858-19
•3736-16
•7691-14
•5349-12
• 1704-10
•3018-09
• OQQO
• OOOO
• aouo
• oooo
• oooo
• 1602-32
•52Q2-28
•2036-24
• 1696-21
•451 i-19
) FECL2 (G,
.oooo
.1019-28
,7185-22
. 1 122-17
,5860-15
.5084-13
. 1489-1 1
,2151-10
. 1820-09
.1064-08
1FECL3)2
.1998-34
.4361-27
.3153-23
. 1076-21
.2246-21
.2173-21
. 1732-21
. 1399-21
• 1064-21
.8435-22
(C) moles
(G) atmospheres
ALCL2 (6
.OOOU
• OOOU
• OOOO
.GOOD
.3593-35
• 1326-30
.4405-27
.2843-24
.5440-22
•430G-2U
AL2CL6 H
.0000
.OUUU
.0000
• 0000
.0000
.4657-36
. 1507-34
• 2 4 4 7 - 3 3
• 1430-31
FECL3 {6!
.5063-26
•3794-19
•2561-15
•2669-13
• 2947-12
• 130B-1I
•3715-11
•8337-11
.1523-10
•2492-10
• Ooou
• 0000
• OOOO
• OOOO
• OOOO
.0000
•5076-33
.2727-28
• 1960-2H
•3134-21
160
-------
TITANIUM - FLUID 8En COMBUSTION GftS
100* EXCESS AIR
90s SULFUR REMOVAL
10 ATMOSPHERES TOTAL PRESSURE
\
TEMP. \COMPOUND
(K) \ TlQ2
300 146Q-Q2
*»00 1460-02
500 14AQ-02
600 146U-Q2
700 1460-02
800 1460-02
900 1H60-02
1000 146Q-02
1100 1460-02
1200 1460-02
\
TEMP. \COMPOUND
(K) \ TIOCL2 U I
300 .0000
400 .0000
500 .0000
600 .1361-30
700 .2945-2*
800 .H367-23
900 .1 188-20
1000 .1039-18
MOO .389Q-17
i200 =7915-16
TICL4 (G
.2294-34
. 1517-26
.3207-22
.5078-20
.57^7-19
.2577-18
.7312-18
. U79-17
.3147-17
.5341-17
TJOCL (ft
.OOOU
.OQOU
.OQUU
.ooou
.ouuo
.0000
. 1 143-22
.8Q68-29
. 1 105-25
.4497-23
COBALT - FLUID 8ED rOMbUSTIQN
1004 EXCESS AIR
90S SULFUR REMC
TO ATMOSPHERES
\
TEMP. \CQMPQUN0
(K) \ COS04 (S)
300" 1617-04
400 1618-04
500 IA18-04
600 1619-04
700 ~ 1619-04
800 1619-04
900 1619-04*
1000 1610-04
noo~ oooo
1200 0000
\
TEflP.VCOMPOUND
(K) \ C02CL4 (G)
300 .0000
400 .0000
500 .0000
600 .5150-31
700 .1873-25
800 .7798-21 . ...
900 .3424-17
10QU .3911-14
1100 .1803-13
1200 .5560-13
)VAL
> TOTAL
C0304 (S
• ooou
.OQUJ
,0000
• 0000
.0000
.0000
.0000
• 0000
.5201-05
.466^-05
COCL (Gl
.0000
.0000
,QOOU
.0000
.4245-31
•3827-25
• 1749-20
. 1086-16
. J650-1H
. 1001-12
) TICL3 (6)
.0000
.0000
.0000
.8916-34
. l 178-29
.1 119-26
•2105-24
. 1378-22
.4032-21
•6723-20
) TI02 (G)
• 0000
.0000
.0000
.0000
. 1081-36
.8480-31
.3160-26
. 1399-22
. 1318-19
.3896-17
GAS
PRESSURE
) COO (S)
• 0000
• 0000
• 0000
• 0000
.0000
• 0000
.0000
.ouoo
• QOUO
,0000
T10 (6)
.ooou
,000.0
.0000
.0000
.ooou
• OQUO
.0000
.OOOQ
.1031-3
.8097-2
COCL2 U)
.0000
.6780-31
,1952-23
.1Q86-18
.6S02-lb
.73S&-12
. I83b-09
,1783-07
,9051-07
.32H6-06
COCL3 ((a)
• ooou
.2M99-27
.8667-22
. 1743-18
.7353-16
* 1 058-13
.5198-12
•1383-1U
.2421-10
.3573-10
*1ASS CONSTRAINTS
CALCULATIONS
NOT
! ERROR OF 0.1-Q.4S RESULTED IN THE.
161
-------
UM -~FLUlD BED COMBUSTION GAS
100% EXCESS AIR
90S SULFUR REMOVAL
10 ATMOSPHERES TOTAL PRESSURE
TEMP.\
(K)
300
"TOO
5UO
600
7QQ
800
900
1000
1 100*
1 200*
\
COMPOUND
V CR203 f S )
• 13076-04
.r306-(54
•5686-05
•5791-05
•9060-05
• 1306-04
• 1306-04
• 1306-04
•8579-05
•279Q-05
CR02CL2 <&
.4154-07
•6644-06
.2169-05
•2138-05
• 1 176-..U5
•6264-06
•3618-Q6
.2338-06
. 160ii-06
* 1 158-06
TEMP,\CC)MPOUND
(M
300
400
500
600
700
800
... 900
1000
1 100*
1200*
\
\ CR02 (ti)
• OUOO
• oooa
• oaoo
. 1 678-33
. 1841-27
.6030-23
„ .1908-19
• 1 178-16
.2221-14
.1721-12
._
CRCL3 (&)
• 0000
.2930-33
. 1338-26
, 1 1 14-22
•2910-20
• 1433-18
.2706-17
.2839-16
•leai-is
.8902-15
TEMP. \CQMPOUNU
(K)
3_cm
400
500
600
700
euo
900
1000
UOQ*
1200*
\ CRCL (S)
t-OOOQ
.0000
.0000
.0000
• OQOO
. 1976-36
. 1819-31
•1669-27
•2835-24
•1366-21
CR (G)
.ooou
.OOOJ
* U 0 0 0
• ooou
• OQOU
.0000
.0000
• 1548-35
,5J95-31
,3024-27
•2029-12
•2608-10
.6795-09
•7lb9-06
.4270-07
•17H6-06
.5435-06
.J39b-05
.3085-05
CRCL2 (G)
• OUOO
. OUUO
• OUOO
. 1 660-31
.9871-27
•3088-23
•1505-20
• 21 12-18
. 1 174-16
•3277-15
CR020H (Q)
.3902-33
• 1395-18
.5544-15
.2016-12
.1652-10
.5036-09
,7670-06
,7081-07
,4465-06
CRCL4 (G)
.54/1-27
.2698-21
,2949-18
.6530-17
. 1882-16
.2927-16
•4514-16
.5141-16
.5618-16
CK03 (G)
,0000
.7476-32
.9271-25
•47U4-20
• 1044-16
.2854-12
.9972-1 1
• 1805-09
•1995-08
CRO (6)
.0000
• 0000
• 0000
• 0000
.0000
.2324-36
.6004-31
.1253-26
.4201-23
.3S&1-2U
•MASS CONSTRAINTS *F*t NOT
ERROK or 2« RESULTED
IN THE CALCULATIONS
162
-------
MANGANESE -
100*
90%
10
FLUID 8FO COMBUSTION r,AS
EXCESS AIR
SULFUR REMOVAL
ATMOSPHERES TqTAL PRESSURE
TEMP,\COMPQUND
(K) \ MKIS04 (Sj MN203 (S)
300 .8991-04 .0000
, Hfl 0 , ., B 9 9 3 rD *» • OQO Q
500 .8993-Q4 00000
400 .8988-04 tOQOU
700 .8989-04 .OQOU
800 .8989-Q4 .0000
' 900 .8989-04 «OOOU
1000 .0000 .4491-04
1100 •QOQQ .4470-04
1200 .QOUO .4397-04
MN3/4
.aoao
• OOUO
• ooao
.auuo
.0000
*oooo
*oauo
• OQOO
• OOUO
.aouu
(S)
.0000
.1273-23
.9795-19
,74Sb-15
^2956-09
. 1563-07
.7325-07
.2926-06
MNCL (6)
*ocoo
• uoou
• OOUO
• QOOU
. 1B91-32
•2661-26
.19B1-21
.8772-Jb
• 1 6 «H - 1 b
TEMP,\COMPOUNO
« ) \
300
500
600
700
8UO
900
1 100
1200
MNO (G)
• QOOQ
.OOUO
.0000
.0000
.0000
. 1478-32
. 1448-26
.5032-22
.5125-19
. 1609-16
H N ( 1 3 )
.0000
.0000
• OOUO
.0000
.oouu
.0000
. 1023-30
.5707-22
.5051-19
. FLUID RED COMBUSTION
1QOZ EXCESS AIR
90a SULFUR REMOVAL
10 ATMQSPHEHES TOTAL
VCOMPOUND
PRESSUKE
(K) \
300
400
500
600
700*
800
9r|JO
1000
1 100
1200
MOQ3 (S)
•7882-QS
.7868-05
,7784-05
.5462-05
.0000
• 0000
.0000
• oooo
• 0000
• oooo
H 2 M 0 0 4 1 G )
.3396-19
.2771-13
.9663-10
.2224-07
. 1 159-05
•8902-06
•1073-05
• 1 122-05
. 1 143-05
. 1 158-05
M002CL2 (G)
•3875-15
. 2b b 4 - 1 0
. 1231-07
.3314-06
•2008-05
.2^32-06
•7UU3-07
.2183-07
•8095-08
•3466-08
MOQ3 (G)
• oooo
.QOOO
.2001-2'*
,8422-23
.4602-18
.6263-16
.4Q91-14
. 1Q15-12
. 1352-1 1
. 1 144-1U
H002
-------
NICKEL - FLUID BED COMBUSTION
100* excess AIR
90$ SULFUR REMl
10 ATMOSPHERE^
"AL
TO
OfAL PRESSURE
TEMP.\COMPOUND
-V
400
500
600
700
800
900
1000
1 100
1200
\
TEMP.\COMPOUND
NJS04 _
.0000
,0000
« 2242 — «J 0
,5026-24
.7790-19
.1212-14
.2511-1 1
.4869-09
. 528 3 — 08
.3859-07
NJCL (fi)
• QOUU
• UUUU
• OOOO
•47/V-3&
.9219-28
.4858-22
• l46b-l?
•2454-14
. 1513-12
(K )
300
400
SOO
600
700
800
900
1000
1 100
1200
NIO (6)
• 0000
.0000
• 0000
.0000
• l728-3b
•2995-28
.1430-22
•2135-18
•8044-16
• 1 1 13-13
NJ (C,J
• oaou
• oooo
• OOOU
.OOOU
• 0000
* 1463-33
•4908-27
.3494-22
.473b-19
.1907-16
MIH (G)
• ooua
• aaua
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FLUORINE - FLUID BED COMBUSTION
1002 EXCESS AIR
90* SULFUR REMOVAL
10 ATMOSPHERES TOTAL PRESSURE
V
TEMP.
(K)
300
-
\COMPOUND
\ MF
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/7-80-015b
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE Experimental/Engineering Support for
EPA's FBC Program: Final Report--Volume 2. Parti-
culate, Nitrogen Oxide, and Trace Element Control
5. REPORT DATE
January 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
D.F.Ciliberti-, M.M.Ahmed, N.H.Ulerich,
M.A.Alvin, and D. L.Keairns
i. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Westinghouse Research and Development Center
1310 Beulah Road
Pittsburgh, Pennsylvania 15235
10. PROGRAM ELEMENT NO.
INE825
11. CONTRACT/GRANT NO.
68-02-2132
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13 TYPEOF REPORT AND PERIOD COVERED
Final; 12/75 - 12/78
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES J.ERL-RTP project officer is D. Bruce Henschel, Mail Drop 61,
919/541-2825. EPA-600/7-78-050 also relates to this work.
16. ABSTRACT
repOrf. gives results of an inves tigation of particulate, NOx, and
trace element control for atmospheric and pressurized fluidized-bed combustion
(FBC) systems used with coal. A model, developed previously to project the loading
and size distribution of particulate emissions from FBC systems, was used to per-
mit an integrated analysis of particle control options for FBC. An experimental 150
scf/sec high-temperature /-pressure particulate control test facility, treating simu-
lated flue gas , was constructed and shaken down to permit investigation of alternative
particulate control devices. Available data on NOx emissions from FBC, and on
NOx formation and decomposition, are reviewed to identify significant FBC operating
parameters affecting NOx emissions , and to assess formation/decomposition mech-
anisms that may be controlling in FBC. The previous thermodynamic projections
of trace element emissions from FBC were expanded to include aluminum, iron,
titanium, cobalt, chromium, manganese, molybdenum, and nickel. These projections
provide a first-level approximation of the distribution of volatile and condensed pha-
ses of compounds of these metals in FBC effluent streams.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution Metals
Combustion
Fluidized Bed Processing
Coal
Dust
Nitrogen Oxides
Pollution Control
Stationary Sources
Particulate
Trace Metals
13B
2 IB
13H,07A
21D
11G
07B
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport}
Unclassified
21. NO. OF PAGES
180
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
166
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