CD A U.S. Environmental Protection Agency Industrial Environmental Research EPA-600/7-"]
•— • •» Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711 MdfCh 1978
EVALUATION OF TRACE ELEMENT
RELEASE FROM FLUIDIZED-9E*
COMBUSTION SYSTEMS
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports pf the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
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tems. The goal of the Program is to assure the rapid development of domestic
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essary environmental data and control technology. Investigations include analy-
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-050
March 1978
EVALUATION OF TRACE ELEMENT
RELEASE FROM FLUIDIZED-BED
COMBUSTION SYSTEMS
by
M. A. Alvin, E. P. O'Neill, L N. Yannopoulos,
and D. L. Keairns
Westinghouse Research and Development Center
1310 Beulah Road
Pittsburgh, Pennsylvania 15235
Contract No. 68-02-2132
Program Element No. EHE623A
EPA Project Officer: D. Bruce Henschel
Industrial Environmental Research Laboratory
Office of Energy, Minerals and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 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, U.S. Environmental Protection Agency (EPA), at
Research Triangle Park, NC. The contract scope includes atmospheric
and pressurized fluidized-bed combustion processes as they may be
applied for steam generation, electric power generation, or process
heat. Specific tasks include work on calcium-based sulfur removal
system studies (e.g. sorption kinetics, regeneration, attrition,
modeling), alternative sulfur sorbents, nitrogen oxide emissions,
particulate emissions and control, trace element emissions and control,
spent sorbent and ash disposal, and systems evaluation (e.g. impact of
new source performance standards on fluidized-bed combustion system
design and cost).
This document contains the results of work defined and completed
under the trace element task from December 1975 to January 1977. Results
from work carried out by Westinghouse or reported by other investigators
after January 1977 are not assimilated into this task report. The work
reported represents an extension of prior work completed by Westinghouse
under contract to EPA. Results from this prior work on fluidized-bed
combustion include:
• 'Assimilation of available data on fluidized-bed combustion,
including sulfur dioxide removal, sorbent regeneration,
sorbent attrition, nitrogen oxide minimization, combustion
efficiency, heat transfer, particle carry-over, boiler tube
corrosion/erosion fouling, and gas-turbine erosion/corrosion
deposition
iii
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• Assessment of markets for industrial boilers and utility
power systems
e Development of designs for fluidized-bed industrial boilers
• Development of designs for fluidized-bed combustion utility
power systems: atmospheric-pressure fluidized-bed combustion
boiler-combined cycle power systems, adiabatic fluidized-bed
combustion-combined cycle power systems—including first-
and second-generation concepts
• Preparation of a preliminary design and cost estimate for
a 30 MW (equivalent) pressurized fluidized-bed combustion
boiler development plant
• Assessment of the sensitivity of operating and design para-
meters selected for the base power plant design on plant
economics
• Collection of experimental data on sulfur removal and sorbent
regeneration using limestone and dolomites
• Preparation of cost and performance estimates for once-through
and regenerative sulfur removal systems
• Evaluation of alternative sulfur sorbents
• Collection and analysis of data on spent sorbent disposal—
utilization and environmental impact of disposal
• Projection and analysis of trace emissions from fluidized-bed
combustion systems
• Analysis of particulate removal requirements and development
of a particulate control system for high-temperature, high-
pressure fluidized-bed combustion systems
• Construction of a high-pressure/temperature particulate control
test facility
• Development of plant operation and control procedures
• Construction of a corrosion/erosion test facility for
the 0.63 MW Exxon miniplant
• Continued assessment of fluidized-bed combustion power plant
cycles and component designs to evaluate environmental impact.
iv
-------
The results of these surveys, designs, evaluations, and exper-
imental programs provide the basis for the work being carried out under
the current contract. Seven reports are available which document the prior
contract work (see references 30-32). Other reports published under
the current contract include "Alternatives to Calcium-Based Sorbents
( 33)
for Fluidized-Bed Combustion: Conceptual Evaluation, "Calcium-Based
(34)
Sorbent Regeneration for Fluidized-Bed Combustion," and "Disposal
of Solid Residue from Fluidized-Bed Combustion: Engineering and Labora-
tory Studies."(35)
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ABSTRACT
The chemical fate of minor and trace elements is important in
assessing the environmental impact of the fluidized-bed combustion (FBC)
process and, for certain elements, in determining the potential for
deposits or corrosion in process equipment. Four trace elements of
environmental concern are investigated: lead, beryllium, mercury, and
fluorine. Equilibrium product distributions for these elements at opera-
ting conditions corresponding to atmospheric and pressurized fluidized-
bed combustion systems are projected on the basis of thermodynamic
calculations. The results show which elements are likely to be vola-
tilized in the high-temperature zone of the combustor and which are
likely to condense on cooling the gases. The projections are compared
with available experimental plant data. Alternatives for continuously
monitoring the release of the four toxic trace elements in the labora-
tory were also investigated.
The thermodynamic analysis shows that essentially all the lead,
mercury, fluorine, and beryllium can be volatilized in the fluidized-bed
combustor. Partial beryllium and fluorine condensation in the form of
clay and alkali compounds will occur. Lead condensation is affected by
the chlorine available. These thermodynamic projections provide a basis
for experimental and monitoring studies. Initial plant data generally
confirm the projections.
vii
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CONTENTS
1. INTRODUCTION. 1
2. CONCLUSIONS 3
3. RECOMMENDATIONS 4
4. FEEDSTOCK TRACE ELEMENTS 5
Coal 5
Limestones and Dolomites 7
5. THERMODYNAMIC PROJECTIONS 11
Approach 11
Thermodynamlc Calculation Basis 11
Equilibrium Calculations 12
Thermodynamic Stability of the Trace Element
Species 21
Fluorine 21
Beryllium 24
Mercury 32
Lead 38
Fluorine, Beryllium, Mercury, Lead Systems 39
Parametric FBC Equilibrium Concentrations 39
Assessment 44
Extension of Thermodynamic Projections to Other
Elements Present in Coal - Using Element Volatility
as a Criterion 45
6. EXPERIMENTAL DETERMINATION 48
Approach 48
Flame Emission Spectrophotometry 49
Apparatus Modifications 51
Results and Discussion 55
7. REFERENCES 59
APPENDICES
A. CALCULATED PARTIAL PRESSURES OF GASEOUS TRACE COM-
POUNDS AND MOLES OF TRACE-SOLIDS PRODUCED AT
EQUILIBRIUM FOR HIGH COAL-HIGH DOLOMITE SYSTEMS
AT 90 PERCENT SULFUR REMOVAL IN 0, 100, AND
300 PERCENT EXCESS AIR 63
ix
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CONTENTS (Cont'd)
B. PARTIAL PRESSURES OF GASEOUS TRACE COMPOUNDS
PRODUCED AT 1200 K FOR HIGH COAL-HIGH DOLOMITE
AND MEAN COAL-LOW DOLOMITE SYSTEMS OPERATING AT
100 PERCENT EXCESS AIR WITH 90 PERCENT SULFUR
REMOVAL 79
C. THERMOCHEMICAL PROPERTIES OF FLUID-BED COMBUSTION
GASES CONTAINING TRACE COMPOUNDS 85
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FIGURES
Number page
1 Reaction Pathways in the Trace Element System 19
2 Major Trace Element Reactions for High Coal-High
Dolomite Systems at 10 Atmospheres Total Pressure
as a Function of Temperature 20
3 Number of Moles of Solid MgF as a Function of
Temperature and Pressure 25
4 Number of Moles of Solid CaF_ as a Function of
Temperature and Pressure 26
5 Partial Pressure of Gaseous HF as a Function of
Temperature and Pressure 27
6 Partial Pressure of Gaseous NaF as a Function of
Temperature and Pressure 28
7 Partial Pressure of Gaseous KF as a Function of Tem-
perature and Pressure 29
8 Chemical Equilibrium Reactions of Beryllium with
Clay Constituents of Coal 31
9 Partial Pressure of Gaseous Be(OH)2 as a Function
of Temperature and Pressure. Interaction between
Beryllium and Aluminum Produces a Solid Complex of
BeO«Al203 at Low Temperatures. Production of Gaseous
Be(OH)2 Is Dependent on the Volatilization of
Beryllium from This Complex 33
10 Number of Moles of Solid BeO«Al203 as a Function
of Temperature and Pressure Produced When Aluminum
Is Presented at Ten Times the Beryllium Level for
U. S. Mean Coal Systems 34
11 Partial Pressure of Gaseous Be(OH)2 as a Function
of Temperature and Pressure without Be/Al-Si Inter-
action: Production of Gaseous Be(OH)2 Is Dependent
on the Volatilization of Solid BeSO^, 35
xi
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FIGURES (Cont'd)
Kucber Page
12 Number of Moles of Solid BeSCty as a Function of
Temperature and Pressure without Be/Al-Si
Interaction 36
13 Apparatus for the Flame Spectrescopic Determination
of Alkali Release from Feed Materials in the
Fluidized-Bed Combustors 50
14 Flame Emission Intensity-Time Curve Illustrating the
Release of Potassium Vapor Impurity from 300 mg of
Tymochtee Dolomite at 875°C in Flowing Fuel Gas
(22.1% H2/19.4% CO/18.2% C02/40.3% NZ at 75 cc/min) 52
15 Release of Na from Geneva Dolomite (Sample Weight
100 mg, Particle Size 35-40 Mesh) 53
16 Total Signal Output of the Flame Emission Spectrum
of Pb from 0.200 mg of PbO (i.e., ^185.6 yg of Pb)
(Resonance Lines: 4059°A; Oxidizing Carrier Gas
(19.8% C02/2.2% 02//N2 at 75 cc/min) 56
xii
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TABLES
Number Page
1 Trace Elements In Coal 8
2 Analysis by Emission Spectroscopy of Trace
Impurities in Selected U. S. Limestones and
Dolomites 10
3 Coal and Sorbent Composition 12
4 Concentration of Fluid-Bed Combustion Elements
Used in Parametric Studies 13
5 C-HhN-0-S-Cl-K-Na Species Considered in Fluid-Bed
Combustion Reactions 16
6 Trace Species Considered in Fluid-Bed Combustion
Reactions 17
7 Chemical Equilibrium Computer Programs 18
8 Distribution of Trace Elements in High Coal-High
Dolomite Systems for 10% Excess Air - 90%
Sulfur Removal 40
9 Distribution of Trace Elements in High Coal-High
Dolomite Systems for 100% Excess Air - 90%
Sulfur Removal 41
10 Distribution of Trace Elements in High Coal-High
Dolomite Systems for 300% Excess Air - 90%
Sulfur Removal 42
11 Trace Elements in Coal 46
Al HF 64
A2 KF 65
A3 NaF 66
A4 S02F2 6?
xiii
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TABLES (Cont'd)
Number Page
68
69
70
71
72
73
74
75
76
77
78
80
81
82
83
ies of Fluid-Bed Combustion
Gases Containing Trace Compounds 86
A5
A6
A7
A8
A9
A10
All
A12
A13
A1A
A15
Bl
B2
B3
B4
Cl
Beso4
Be (OH) 2
HgCl2
Hg
HgO
Hg2
HgCl
PbCl4
Pbci2
PbO
PbCl
Fluorine Compounds
Beryllium Compounds
Mercury Compounds
Lead Compounds
Thermo chemical Prop
xiv
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ACKNOWLEDGMENT
We want to express our high regard for and acknowledge the contribu-
tion of Mr. D. B. Henschel who served as the EPA project officer.
Mr. P. P. Turner and Mr. R. P. Hangebrauck, Industrial Environmental
Research Laboratory, EPA, are acknowledged for their continuing contribu-
tions through discussions and support of the program.
The program consultation and continued support of Dr. D. H. Archer,
manager, Chemical Engineering Research, at Westinghouse are acknowledged.
Acknowledgments are also extended to R. W. Liebermann for the development
of and guidance in using the equilibrium model and to S. L. Anderson for
his work on the experimental program.
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SECTION 1
INTRODUCTION
Conventional steam-turbine cycles and combined steam- and gas-
turbine cycles are being utilized with fluidized-bed coal combustion
techniques, (e.g., atmospheric-pressure fluidized-bed boilers, super-
charged fluidized-bed boilers, and adiabatic combustors) to develop
power generation systems having superior environmental control and
economics. Current development programs primarily emphasize the use
of calcium-based sorbents (limestones and dolomites) to provide in situ
control of SO in the combustor.
x
Pilot-scale tests of fluidized-bed combustion of coal have shown
that air pollution from S0~ and NO emissions can be reduced to
£* 3t
meet EPA requirements. Coal, however, contains many minor and trace
elements in addition to the combustible carbon (C), hydrogen (H), and
sulfur (S). In assessing the environmental impact of the fluidized-bed
combustion process, it is important to determine the chemical fate of
these trace elements, some of which have toxic forms at certain
concentrations.
Ideally, a complete model of the process would include a knowledge
of the compounds in which these elements are combined in the process
feedstock. Kinetic models of the reactions that occur during coal com-
bustion would then be used to calculate the product distribution of
chemical species as a function of the process operating conditions.
This would permit quantification of the concentration and type of chemi-
cal compound emitted in the solid or gaseous effluents from the plant.
Although the ranges of concentrations of many elements of interest
in U.S. coals have been determined, the chemical form of each element is
not always known and may vary significantly in different coals. The
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kinetics of the chemical reactions occurring are not known. It is pos-
sible, hox*ever, to fall back on a common assumption used in high-
temperature chemistry and assume, as a first level of approximation, that
thermodynaraic equilibrium will be reached in the bed and that the
equilibrium product distribution will be characteristic of the process
effluent.
Four trace elements of environmental concern - lead, beryllium,
mercury, and fluorine - are studied. The equilibrium product distribution
has been investigated for the anticipated operating ranges of different
designs of fluidized-bed combustors. The data are then discussed in the
light of available experimental evidence.
Of those elements known to be present in coal, lead and mercury are
also among the most toxic, persistent, and abundant of the heavy metals
in the environment. Coal combustion contributed 920 tons of lead
(0.5 percent of total emissions) in 1968, but since the major source
(gasoline combustion - 94.8 percent) has declined recently, the relative
importance of potential lead emissions from the anticipated increase in
coal burning has greatly increased. Inorganic mercury is readily con-
verted to methyl mercury by microorganisms, and this compound easily
enters the human food chain. Beryllium is a notoriously toxic element
in all of its common inorganic forms (oxides, chlorides, sulfates), and
3
the original air pollution limits proposed (0.01 yg/m ) reflected this
concern. Later work has shown that high-temperature-fired oxide is far
less toxic. Fluorine is of concern because the ultimate product of
release, fluoride salts, is readily ingested by both animals and humans,
and fluorine has been responsible for serious air pollution in localized
areas where emissions are high.
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SECTION 2
CONCLUSIONS
Conclusions from the initial phase of the study on trace element
emissions are reported. Lead, beryllium, mercury, and fluorine, four
trace elements of environmental concern, were investigated.
The thermodynamic analysis shows that essentially all the fluorine,
beryllium, mercury, and lead can be volatilized in the high-temperature
zone of the fluid-bed combustion process. For the beryllium and
fluorine species, some condensation will occur on cooling the gases.
The gaseous mercury released is stable to ambient temperatures. The
fate of lead is more complex and depends heavily on both the feedstock
material and the operating conditions of the process. At atmospheric
pressure, or for low-chlorine coals, lead is largely volatilized as
lead oxide, which will condense on particulate matter on passing through
the cooler parts of the system. At high pressures and with high-
chlorine coals, there is a tendency for lead tetrachloride to form in
the gas phase.
Continuous monitoring of the toxic trace element release from the
feed materials cannot be accomplished using the flame emission spectro-
photometric apparatus. To achieve this objective, alternative methods
and high-temperature sampling techniques have to be developed. A
reasonable approach may be the determination of the total trace element
release (vapor and entrained particulates) through an analysis of con-
densates collected at selected time intervals, using spark source mass
spectroscopic and neutron activation techniques.
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SECTION 3
RECOMMENDATIONS
Thermodynamic projections have resulted in three results that
correlate very well with experience (those concerning the emis-
sion of volatile PbO, Hg, and HF), one result for which there
is some evidence (volatile loss of Be), and one result that
is surprising - loss of lead as PbCl, in pressurized
fluidized-bed comb us tors. This last finding should be tested
by analyzing solid effluents from the Exxon miniplant to see if
depletion of lead is observed at high pressures. In addition,
laboratory experiments on the effect of partial pressure on
retention of lead in fluidized-bed coal combustor ash at pres-
sure and temperature (10 atm, 43 K) should be carried out.
A comparison should be made of the results of thermodynamic
projections using the Westinghouse programs and those available
from other sources, to search for inconsistencies and for a
firmer data base.
The projections will be extended to include other potentially
volatile elements present in coal - e.g., vanadium - and other
elements that may act as getters for volatile elements, such
as boron, or aluminosilicates.
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SECTION 4
FEEDSTOCK TRACE ELEMENTS
COAL
Intensive efforts, largely sponsored by EPA, have been directed at
determining the trace element composition of U.S. coals. Work in this
area has been reviewed by Magee, and the available data show a con-
sensus of the expected concentrations of elements of interest. The con-
centrations of the four elements chosen for study are shown in Table 1.
There has been much dispute about the level of mercury, Hg, in coal and
its emission from coal-fired power plants.
Concern about mercury in coals has been exaggerated by two facts.
(2)
Joensuu concluded that 3000 Mg of mercury were released annually,
worldwide, from coal combustion, an amount comparable to that resulting
from industrial use of mercury, 10,000 Mg. Second, apparently high
values for mercury in coal were published by Headlee and Hunter, of
the West Virginia Geological Survey.
According to Magee, however, Joensuusfs 3000 Mg estimate is based
on an assumed value of 1 ppm mercury in coal: the true value of
0.18 ppm yields 540 Mg total release, more than an order of magnitude
less than the industrial pollution value. In addition, the Headlee and
Hunter high values are reputed to be the result of a typographical
error.
Two sets of analyses confirm the level of mercury in coal to be as
stated by Magee: Gluskoter found 0.20 ± 0.20 ppm mercury in
102 U.S. coals; Page/ et al. found 0.11 ± 0.06 ppm mercury in
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TABLE 1. TRACE ELEMENTS IN COAL
Westinghouse (1973) 24 Samples
Western Coals(•>) (ppm)
0.11 ± 0.06
61.25 ± 31.99
1.43 ± 2.13
24.2 ± 13.5
Magee (1973)
[Review of Literature]
Hg 0.18
F 50-160
Be 0.64-3.1
Pb 4-14
(2)
Oluskoter (1973)
101 SampleaW (ppm)
0.20 ± 0.2
60.94 ± 20.99
1.61 ± 0.82
34.8 ± 43.7
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western coals; the U.S.G.S. found 0.06 ppm for the same area. The
values reported by Gluskoter for fluorine, F, beryllium, Be, mercury
and lead, Pb, were used in the calculations reported here.
It has been noted that the low concentration of fluorine in coal
shows it to be depleted, relative to its concentration in the earth's
crust, by one order of magnitude; agreement on its concentration in
U.S. coals by different schools of analysts is relatively good. For
beryllium, agreement among the analysts is excellent. Gluskoter's
values for lead are higher than those reported in the other studies.
In order to carry out thermodynamic projections of trace element
release, it was necessary to include in the analyses other elements,
such as chlorine, Cl, which can act as an anion carrier for metals.
These values are all taken from Gluskoter's work(see Table 3).
LIMESTONES AND DOLOMITES
There is no recent study of trace element concentrations and their
distribution in limestone and dolomite. Estimates of the maximum likely
concentrations are made possible for some elements by atomic emission
data (within a factor of three) and from neutron activation analysis
data obtained by Exxon and Argonne National Laboratories (ANL).
Several of the Westinghouse limestone or dolomite analyses are shown in
Table 2. It should be noted that these techniques do not determine the
fluorine or mercury content of a given sample.
Upper limits to the concentrations of two elements were obtained
/Q\
from an unpublished study by the Ohio State Geological Survey on the
concentration of trace elements in dolomites from that state. Analysis
(9)
of nine typical U.S. limestones and dolomites reported by Harvey were
found at the conclusion of this work: they show a mean value for mercury
of 0.07 ppm ± 0.07, indicating that the choice of 0.16 ppm mercury in
the sorbent was conservatively high.
The trace element concentrations in the sorbent (a dolomite)
assumed for this study are shown in Table 3. The number of dolomites
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TABLE 2. ANALYSIS BY EMISSION SPECTROSCOPY OF TRACE IMPURITIES
IN SELECTED U. S. LIMESTONES AND DOLOMITES, WT %
Al
Ag
B
Ba
Be
Bi
Cd
Co
Cr
Cu
Fe
K*
Li
Mn
Mo
Na*
Nb
Ni
P
Pb
Sb
Si
Sn
Sr
Ti
V
Zn
Zr
No. 10 Glasshouse 1337
(Ohio: Dolomite) (1°)
0.1
<0.0001
<0.0004
—
—
<0.0004
<0.04
<0.004
<0.004
<0.0004
0.04
0.0250
—
0.004
<0.004
0.0180
<0.004
<0.0004
MM MM
<0.004
<0.004
0.3
<0.002
—
0.002
<0.004
0.02
<0.02
Tymochtee riQ.
(Ohio: Dolomite)^ {Texas:
>0.4
<0.0001
0.008
—
—
<0.0004
<0.04
<0.004
<0.004
0.001
0.1
0.3700
__
0.004
<0.002
0.0329
<0.004
<0.0004
._
<0.004
<0.004
2.
<0.002
—
0.008
<0.004
<0.02
<0.004
CP&L ,-r
Limestone) U '
0.4
<0.0004
<0.004
0.0004
<0.0004
<0.0004
<0.04
<0.0004
<0.004
0.008
0.2
0.116
<0.0004
0.04
<0.004
0.014
<0.004
<0.004
<0.004
<0.0004
<0.004
«v2.
<0.004
0.08
0.04
<0.004
<0.004
<0.004
*Atomic absorption
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TABLE 3. COAL AND SORBENT COMPOSITION
Coal Composition
Element
C
H
N
0
S
Cl
K
Na
F*
Be*
Hg*
Pb*
for Fluid-Bed Combustor(4)
wt%
70.28
4.95
1.30
8.68
3.27
0.14
0.16
0.05
60.94
1.61
0.20
34.78
Sorbent (Dolomite) Composition for Fluid-Bed
C
H
N
0
S
Cl*
K*
Na*
F*
Be*
Hg*
Pb*
Ca
Mg
13.031
—
__
52.06
__
2000, 806, 200
4000, 300, 100
300, 150, 50
10
4
0.16
18.5
21.70
13.19
2a wt%
0.28
0.22
0.09
81.93
2.43
0.40
78.47
Combufltor(1°'12)
*Value in ppm
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for which minor and trace element data are available is small, and it
is not possible to represent the spread of the likely values, as in
the Gluskoter study, on coal. Therefore, values representing the
highest and lowest alkali and chlorine content were selected.
10
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SECTION 5
THERMODYNAMIC PROJECTIONS
APPROACH
Thermodynamic Calculation Basis
The feedstock chosen in the trace element fluid-bed combustor study
is a model coal that has the mean composition of U.S. coals found by
Gluskoter (Table 3). The minor (chlorine, sodium, Na, potassium, K,)
and trace (fluorine, beryllium, mercury, lead) element constituents of
the coal are varied as:
1. The mean value (referred to as the "mean coal" or "mean
sorbent")
2. The mean value + (2 a) (referred to as the "high or low
coal", or "high or low sorbent")
where a = standard deviation of the concentration determined by Glus-
koter for 101 U.S. coals.
^-
The impact of the desulfurizing sorbent is projected by using
three levels of chlorine, three levels of alkali (sodium and potassium),
and the four trace elements at their mean values (Table 3).
Each projection is calculated at equilibrium in 10, 100, and
300 percent excess air, from 1 to 15 atmospheres, and from 300 to
1200 K. The excess air values and the system pressures were selected
to cover the range expected in the alternative variations of the
fluidized-bed combustion process. The temperatures were selected to
cover the range that would be seen by the combustion gases, from the
combustion zone of the furnace through the ducting to the exhaust stack.
11
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Each projection is carried out for a 4 percent sulfur coal with a
steady-state SO value in the effluent corresponding to 0, 90, and
2E
99 percent sulfur removal.
Table 4 indicates the moles of each key element fed into the bed
per 100 g of coal burned, based upon the composition indicated in
Table 3.
Equilibrium Calculations
The equilibrium composition for trace element fluid-bed combustion
(12)
conditions is calculated by minimizing the Gibbs free energy of the
(13)
polyphase system, using the techniques of Geometric Programming, in
addition to satisfying the mass conservation equations.
The Gibbs free energy (G) of a multicomponent system is represented
by a summation over the mixture chemical species, i.e.,
G =
1
where G. = \i. is the molar chemical potential and n. is the number of
th
moles of the i species. The molar chemical potential is expressed as
y± = yj + 6 (RT In P.) , (2)
where for a gaseous species 6 - 1.0, and for a condensed species 6=0.
In the above equation P. Is the partial pressure of the gaseous species,
'I
T is the gas temperature, R is the universal gas constant, and y° is the
species* chemical potential at unit fugacity,
V. = H. - TS. , (3)
12
-------
TABLE 4. MOLES OF KEY ELEMENTS FED TO THE FLUID-BED PER
lOOg OF COAL BURNED
Element
C
H
N
0
S
Cl
K
Na
F
Be
Hg
Pb
(a)
(b)
(0
(a)
(b)
(c)
(d)
(e)
(f)
High Coal-
High Sorbent
6.1563 moles
4.9107
57.41855
104.39774
208.79473
16.70376
29.1919
56.9430
0.124800
0.012480
0.001248
9.455E-3
8.4505E-3
4.3108E-3
4.4572E-4
3.921E-5
2.016E-7
4.033E-5
System
Mean Coal-
Mean Sorbent
6.1563 moles
4.9107
57.41855
104.39774
208.79473
16.70376
29.1919
56.9430
0.124800
0.012480
0.001248
4.5765E-3
4.3038E-3
2.578E-3
3.3526E-4
3.012E-5
1.019E-7
1.92505E-5
Mean Coal-
Low Sorbent
6.1563 moles
4.9107
57.41855
104.39774
208.79473
16.70376
29.1919
56.9430
0.124800
0.012480
0.001248
4.1047E-3
4.1627E-3
2.234926E-3
3.3526E-4
3.012E-5
1.019E-7
1.92505E-5
NOTE: Excess air = 10%(a), 100%(b), 300%(c). Sulfur removal for
dolomite in this study uses a Ca/S ratio of 1.25/1 for 0% removal
(d), 90% removal (e), and 99% removal (f). The impact of Ca/S
ratio on the trace metals fed via the dolomite has not been
considered.
13
-------
where H° (molar enthalpy) and S. (molar entropy) are the species' standard
thermochemical properties, which are functions of the species standard
specific heat, C , i.e.,
*» *•
T
o
H° (T) = f C°^± dT + AH° (Tr) (4)
and
T
r
C° - dT
S±(T) = / -£«£ , (5)
where AH_ is the standard heat of formation for the compound at the ref-
erence temperature (T ) 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* standard thermochemical data (as reported in the litera-
(15—23)
ture), the total gas pressure, and the mass constraints on the
system. Tables 5 and 6 illustrate the species for which thermochemical
data are presently available for use in the current computer study.
The data for each species have been reduced (see Program *FJANAF) and
used as input for the chemical equilibrium calculations. The reaction
of fluorine with combustion gases, for example, uses compounds formed
from carbon, C; hydrogen, H; nitrogen, N; oxygen, 0; sulfur, S; chlorine,
and fluorine. The interaction of alkali with fluorine additionally
requires specification of those compounds containing those same
elements and associated alkali compounds. Table 7 lists the computer
programs used in calculating the equilibrium composition and thermo-
chemical properties of the fluid-bed combustion mixture at defined
parameters of pressure and temperature for a given system defined by
the considered elements. Additional CALCOMP routines are available
for visually displaying the data as either profile or isometric plots.
Multiple reactions that occur in fluid-bed combustors produce
numerous solids, liquids, or gaseous compounds that are dependent on the
14
-------
TABLE 5. C-H-N-0-S-Cl-K-Na SPECIES CONSIDERED IN FLUID-BED
COMBUSTION REACTIONS
Gases
C
CC1
CC12
CC120
CC13
CC14
CH
CHN
CHNO
CHO
CH2
CH20
CH3
CH4
CN
CHN
CN2
CO*
C02*
C2
C2C14
C2C16
C2H
C2H2
C2H4
C2H40
C2N
C2N2
C20
C3
C302
C4
C4N2
CS
COS
Cl*
C1HO*
CIO*
C102
C12*
C120
H
HC1*
HK
HNO
HN03*
HO*
H02
HS
H2*
H20*
H2S
H2S04*
K*
KC1*
KCN
KO
KOH*
K2
K2Cl2*
K2C2N2
K202H2*
K2S04*
N
NH
NH2
NH3
NO*
N02*
N03
NS
N2*
N2H2
N2H4
N20*
N203
N204
N205
Na*
NaCl*
NaCN
NaH
NaO
NaOH*
Na2
Na2Cl2*
Na2C2N2
Na202^2*
Na2S04*
0*
02*
03
S
S2
S3
S8
SO
S02*
503*
S20
Solids/Liquids
C
K
KC1
K2C03
KCN
KH
KOH
K02
K2C12
K202H2
K20
K202
K2S04*
Na
NaCl
NaC03
NaCN
NaH
NaOH
NaO
Na2Cl2
Na202H2
Na2S
Na2S04*
*Species resulting in fluid-bed combustion conditions for C-H-N-0-S-Cl-K-Na
Systems as projected by the CHEMEQ *INITAL program.
15
-------
TABLE 6. TRACE SPECIES CONSIDERED IN FLUID-BED COMBUSTION REACTIONS
Gases
Solids/Liquids
CF
CFO
CFN
CF2
CF20
CF3
CF4
CF40
CHC1F2
CHC12F
CHFO
CHF3
CH2C1F
CH2F2
C2F3N
C2HF
CC1FO
CC1F3
CCl2F2
fT**i *si?
LAjX^J:
F
FC1
FHO
FK*
FNa*
FN
FNO
FN02
FN03
FO
F02
F2
F2K2
F2N
F2N2
F2Na2
F20
F2OS
F202S*
F3C1
F3N
F3NO
F4N2
F5C1
HF*
SF
SF2
SF3
SF4
SFs
SF6
Hg*
Hg2*
ffgGl*
HgCl2*
HgH*
HgO*
Pb
Pb2
PbCl*
PbCl2*
PbCl4*
PbH
PbO*
BeC2
BeCl
BeCl2
Be2Cl4
BeH
BeH2
BeN
BeO
Be (OH) 2*
Be20
Be202
FHg
F2Hg
PbF
PbF2
PbF4
FK
FNa
F2HK
Hg
HgCl
HgCl2
Hg2Cl2
HgO
Pb
PbC03
PbCl
PbO
Pb02
Pb304
PbS
PbS04
PbO-PbS04
2PbO-PbS04
4PbO-PbS04
Be
BeCl2
BeO
BeS04*
Be2C
BesN2
F2Hg
F2Hg2
PbF2
*Trace species found to result at fluid-bed combustion conditions,
based upon the thermodynamic projection model.
16
-------
TABLE 7. CHEMICAL EQUILIBRIUM COMPUTER PROGRAMS
(13)
CHEMEQ* FJANAF
CHEMEQ* INITAL
CHEMEQ* GASF
CHEMEQ* THERMO
Program designed to curve-fit the therraochemical data
, 298 je, ^200 ,c) of compounds as a function of
Cp for solids and liquids, and in terms of the molecu-
lar constants for gases.
Program designed to select the specific (active)
compounds that are involved in the reactions at
equilibrium. For example, 175 compounds are included
in the INITAL calculation that are considered as
possible candidate species for the reaction. The
results of INITAL indicate that only 48 react as
either major or trace constituents. The reduction
in the number of compounds involved in the equilibrium
reaction is now within the limits of the CHEMEQ* GASF
program.
Program designed to calculate the number of moles, mole
fraction, pressure, part/cc, density, and mass of the
compounds contained in the mixture at equilibrium as a
function of pressure and temperature for specified
element concentrations. Modifications to GASF include
the options for the creation of the CQFILE, which enables
the user to plot the partial pressure of the gas and the
number of moles of solid/liquid formed as a function of
temperature. CQFILE can be expanded to include a series
of calculations at various pressures, from which isometric
plots may be generated.
Program designed to calculate the thermo chemical
properties of the equilibrium mixture at defined pres-
sures and temperatures.
17
-------
pressure and temperature of the system. The final concentration of each
phase is a function of the relative concentration of specific elements
or compounds introduced into the reaction as constituents of coal
and/or sulfur sorbents. For example, the sulfur concentration of coal
defines the level at which SO , S0_, and alkali sulfates are formed.
With the addition of the calcium-based sorbents, the initial sulfur
levels are reduced. Furthermore, a high level of chlorine has been
shown to suppress the formation of liquid/solid alkali sulfates to lower
temperatures. Chlorine present in fluid-bed gases reacts with the trace
elements of coal or sorbent that are released into the effluent gases,
producing gaseous trace chlorides. Silicon, Si, and aluminum, Al, the
major clay constituents of coal, react with alkali and trace elements,
forming complex structures that are removed as solids in the waste and
spent sorbent process. A composite diagram (Figure 1) illustrates those
reactions that are projected to result, according to the thermodynamic
calculations, when trace elements are present in fluid-bed combustion
gases.
In order to illustrate the projected major reactions of the trace
elements, the partial pressure of the gaseous trace compounds and the
number of moles of trace solids produced at 10 atmospheres are plotted
in Figure 2 as a function of temperature for fluid-bed operating
conditions at 10 percent excess air with 90 percent sulfur removal and
with the highest anticipated trace concentrations (high coal-high dolo-
mite) . The calculated equilibrium partial pressures for the phase dia-
gram are tabulated in Appendix A. Reference to this section provides
useful information about the modification required on the phase diagram
for systems operating at pressures other than 10 atm. At fluid-bed
combustion temperatures only gaseous trace compounds are projected to
form. Trace solids are predicted to be thertnochemically unstable at
elevated operating temperatures. As shown in Figure 2, the solid BeSO,
is projected to form at temperatures below 600 K for fluid-bed systems
containing carbon, hydrogen, nitrogen, oxygen, sulfur, chlorine, fluorine,
beryllium, mercury, and lead. The thermodynamic calculations, however,
18
-------
Dwg. 1687B79
VO
NaOH H,0 KOH
MgSOjTi
MgS *l
MgO f
MgCO J
BeO-ALO. "f
23 ^^ Be(OH) +AI 0
Clay - Complexes
Figure 1. Possible Reaction Pathways in the Trace Element System.
-------
Ctirn M90X-C
10
.-3
10
' I ' I ' I ' I
High Coal - High Dolomite
90% Sulfur Removal
10* Excess Air
10 Atmospheres
300 400 500 600 700 800 900 1000 1100 1200 1300
Temperature. °K
Figure 2. Major Trace Element Reactions for High Coal-High
Dolomite Systems at 10 Atmospheres Total Pres-
sure as a Function of Temperature.
20
-------
assumed that all the elements in coal and sorbent were "matrix free."
If some elements in the feed materials were instead "matrix bound," the
elements would be less capable of reactions, and the concentrations of
gaseous products would be lower than those projected here.* Fluorine
and beryllium, for example, may exist as calcium or magnesium fluoride,
CaF2 and MgF2, and as beryllium aluminate, BeO • A1-0-, in the feed
material. Unless total combustion of the coal and dolomite has occurred,
the projected levels of both volatile and condensed phases should be
regarded as the maximum trace concentrations at any location in the
system.
It should be noted that this study considers only the reactions
of compounds for which thermodynamic data are available. It is reason-
able to assume that other compounds may form in the fluid-bed system.
Data for such compounds have not been cited in the literature, however,
nor have estimates of their free energy, heats of formation, or
molecular constants been made. It is the opinion of the authors that
compounds not reported in the literature are less likely to form than
are those for which data are cited.
THERMODYNAMIC STABILITY OF THE TRACE ELEMENT SPECIES
Fluorine
At the highest temperatures, in the range of 1100 to 1200 K,
fluorine is projected to be released to the gas phase as NaF(g), sodium
fluoride; KF(g), potassium fluoride; and HF(g), hydrogen fluoride, the
preponderant fluorine species. As the temperature falls toward 800 K,
the HF recombines with the excess calcium oxide to form solid CaF_
*• >
and at lower temperatures (below 700 K) solid MgF2 is the stable
compound. At low temperatures, 300 to 500 K, sulfuryl difluoride,
S09F9, is the equilibrium gaseous product, even with 90 percent sulfur
*Matrix bound - Element entrapped with a solid structure not permitted
to react further with surrounding gases.
Matrix free - Element reactive with a solid structure capable of
reacting simultaneously with the surrounding gases.
21
-------
removal. In systems that consider the formation of calcium and magnesium
fluorides, the formation of gaseous sulfuryl difluoride is suppressed.
As the concentration of sulfur in the fluidized-bed combustor efflu-
ent gas is decreased, the production of gaseous SCLF.. is reduced. At
the lower gas phase sulfur concentrations fluorine that remains in the
gas phase combines instead with either hydrogen, sodium, or potassium,
forming gaseous HF or alkali fluorides instead of SO^Fy.
In the presence of HC1 formed in the combustion gases, SO-F- is
converted to HF, as shown by the following reaction:
S02F2(g) + HCl(g)^=S02(g) + Cl2(g) + HF(g) . (6)
This reaction is governed not only by the level at which fluorine, sulfur,
and chlorine are present, but is a function of the temperature and pres-
sure of the reaction. At low temperatures (300 to 500 K) the major com-
pound formed is SO-F~; as the temperature increases, the reaction is
pushed to the right, favoring the formation of gaseous HF.
Reducing the sulfur concentration to levels present in 99 percent
sulfur removal conditions no longer produces gaseous SO»F,, but, between
300 and 800 K, solid NaF. Since fluorine is bound in the form of NaF(s)
at low temperatures, the projected level of HF in the gas is lowered in
systems that favor total sulfur removal. At elevated temperatures HC1,
formed in the combustion process, reacts with NaF, converting the alkali
fluoride into the stable NaCl solid plus gaseous HF. Thus,
NaF(s) + HCl(gK - ^NaCl(s) + HF(g) . (7)
The production of gaseous alkali fluorides occurs in both 0 and
90 percent sulfur removal systems. Lowering the concentration of sulfur
increases the level of fluorine that reacts with the alkalis present
in the gas phase. Equilibrium calculations indicate significant differ-
ences in the partial pressures of the alkali fluorides at low tempera-
tures. For example, the partial pressure of NaF»(g) at 600 K is
—25
0% S removal - 2.19 x 10 atm
99% S removal - 5.39 x 10~17 atm
22
-------
when the total pressure of the system is 15 atmospheres. This effect is
also demonstrated by the partial pressure of KF_ gas.
Dimeric forms of the alkali fluoride (K2F_t Na2F.) result when the
concentration of sulfur is further reduced to 99 percent sulfur removal
conditions. The concentrations of the dimers are below those of the
2
resulting alkali fluorides by a factor of 10 at 1200 K. Tables 1
through 4 of Appendix A show the partial pressures calculated at
equilibrium for the most significant trace-fluorine compounds as a
function of pressure and temperature. Parameters for the high coal-
high dolomite system include 10, 100, and 300 percent levels of excess
air at 90 percent sulfur removal conditions.
The previous discussion illustrates the reactions that occur when
fluorine reacts with fluid-bed combustor gases. Consideration must
be given, however, to reactions that are likely to result when lime-
stone (CaCCO or dolomite (CaCO, • MgCO_) is present in the equilibrium
system. The major reaction of fluorine with calcium and magnesium is
the initial formation of solid MgF_, which is converted to solid
CaF_, between 660 and 680 K. Calcium fluoride remains stable until
900 to 920 K but is removed at elevated temperatures, permitting the
formation of HF in the gas phase. The difference between the two
reaction systems may be written as:
Without carbonates
S02F2(g) + 2HCl(g) <7°° » S02(g) + Cl2(g) + 2HF(g) (8)
With carbonates
CaF2(s) + H20(g) <90°-920 £ CaO(s) + 2 HF(g) . (9)
Introduction of the carbonate material diminishes the production of
gaseous SO_F9 at equilibrium conditions, with fluorine re-forming as
part of the CaF«-sorbent that is removed in the spent sorbent waste
process.
23
-------
The major fraction of the remaining fluorine is found in the gaseous
phase as HF. Both reactions 8 and 9 favor the production of HF at ele-
vated temperatures and are unaffected by the level of sulfur present at
1000 to 1300 K. Figures 3 through 7 illustrate, for the reactions in a
C-H-N-0-S-Cl-K-Na-Ca-Mg-F system, the effect pressure and temperature
have on the formation of solid and gaseous fluorine compounds
resulting from U.S. mean coal-mean dolomite in 90 percent sulfur
removal/100 percent excess air systems.
Beryllium
As shown in Figure 2, the major gaseous beryllium species formed
at high temperature is beryllium hydroxide, Be(OH)~. The major gaseous
sulfur species in fluid-bed combustion systems at low temperatures is
H SO,. As temperature increases, the H.SO, vapor dissociates, forming
gaseous sulfur trioxide, S0g, and H_0. Sufficient sulfur is present in
both 0 and 90 percent sulfur removal systems to produce solid beryllium
sulfate, BeSO, , at temperatures of 300 to 500 K, and pressures between
1 and 15 atmospheres:
Be(s) +1/2 02(g) + S03(g) - » BeS04(s) . (10)
At temperatures greater than 500 K BeSO, (s) dissociates forming solid
beryllium oxide, BeO, and gaseous SO :
BeS04(s) (5°°-600 *> BeO(s) + S0(g) . (11)
The highly volatile beryllia in the fluid-bed combustion systems then
react with water vapor, forming the stable gaseous Be(OH)2 phase at
higher temperatures:
BeO(s) + H20(g) - ». Be(OH)2(g) . (12)
Thermodynamic calculations do not project the presence of BeO when proc-
esses are operated at 0 to 90 percent sulfur removal because of the
H20(g)
simultaneous conversion of the BeSO.(s) - + Be(OH)_(g).
24
-------
System: C-H-N-0-S-Cl-K-Na-Ca-Mg-F
Species Name
TEMF. ( K)
.3000+03
.4000*03
.50LO+CI3
.6000*03
.70GO+03
.8000*03
.9000+03
.1000*01
.1100+04
.1200*04
Number of Moles
, 1500+02 atm
.2228-03
.2229-03
.2228-03
.2221-03
.ocou
.oouo
.OGLO
.0000
.0001'
.0000
.1000*02 atm
.222S-C3
.2223-03
.2228-L3
. CJOUU
.0000
.couo
.0000
.LOGO
.0000
,5000+01 atm
.2229-03
.222i»-03
.2228-03
.2216-03
.0000
.uooo
.ooou
.0000
.OOOu
.0000
.1000*01 atm
.2229-03
.2229-03
.2228-03
.2200-03
.0000
.0000
.0000
.0000
.0000
.0000
oo
rO
O)
-------
System: C-H-N-0-S-Cl-K-Na-Ca-Mg-F
Species Name CaF£: Number of Moles
TEMP. ( K)
.30004-03
.5000*03
.6000+03
.7000*03
. 80Cti*03
.9000*03
.1000-»U<«
. 1100*014
• 150OL2 atm
.0000
. OCUU
.0000
. UDLO
.2069-03
.1681-03
.7981-01
. ccon
.GOOD
.CiCLO
.1000+02 atm
.0000
.COC.U
.COOO
.LOOO
.2U69-U J
.1681-C3
.7980-04
.CLOU
.0000
.GOliU
.5UOL+L1 atm
.0000
. UCJOD
.0000
.0000
.20b9-CU
.1661-03
.7377-0^
. UCUU
.0000
.LDOO
.lOOr+Dlatm
.0000
.0000
.OUQU
.0000
.2069-U3
.1681-03
.7967-01
.0000
.OUCO
.OOOD
00
CM
d
« o
+•
-------
System: C-H-N-0-S-Cl-K-Na-Ca-Mg-F
Species Name HF: Partial Pressure
TEMP. ( K)
,3000*03
, <*OGU-»03
,5000*03
.60GO03
, 7UOO*G3
.80CG+03
,9000*03
1100*0'*
,1200+Ot
15 tit* 02 atm
.1<*78-11
.6312-09
.2136-07
.7U30-05
.2<*26-0«*
.6338-0<*
,9870-0<*
.9938-OU
.971P-0<*
1GLO-K 2 atm
.^350-12
.4925-12
.162<«-07
.2faa8-Le
.1*720-03
.1617-L4
.4225-U4
.6572-LU
.6548-0^4
,o'»2fa-L'.
.dlld-08
.1908-1,6
.^'360-05
.3C67-U3
.2113-0'*
.3287-OU
.J257-n<»
.31E7-LJU
1000*01 atm
.9673-13
.lo23-L3
.8331-07
.<»720-06
.1618-05
.««228-05
.6538-05
.6<»2<»-05
.6169-05
(O
6
Kl CM
•f- —
00
o
d
oo
o
ID
0.0
in
in
9>
_q
.50
O
O
U.S. Mean Coal/Mean Dolomite
90% Sulfur Removal
100% Excess Air
300 400 500 600 700 800
TEMPERATURE, K
15 atm
10 atm
5 atm
900
1000
I atm
1100
Figure 5. Partial Pressure of Gaseous HF as a Function
of Temperature and Pressure.
27
-------
System: C-H-N-0-S-Cl-K-Na-Ca-Mg-F
Species Name NaF: Partial Pressure
TEMP. ( *0
.300G*U3
.4000*03
.5000*03
,600C*03
.7000*03
.80tiCi+03
.3000*03
.1000*04
.1100*04
.1200*04
,150L+Ij2 atm
.0000
.25U8-31
.1358-23
.2991-16
.2C76-11
.2299-OS
.6927-08
.7593-07
.3253-06
. 1&OU + U2 atm
.UQUU
.25US-31
.1358-23
.3664-18
.4624-m
.2U7b-ll
.2300-03
.6S2fo-C8
.7581-07
.5317-L6
,5UOL*Ul atm
.UOQO
.1353-23
.5181-18
,«*b24-l'4
.23CO-09
.b92U-08
.595«*-Q7
.10UO*01 atu
.QUQU
.25U8-31
.1858-23
.1159-17
.4624-14
,2Ci76-ll
.2300-09
.6138-08
.5303-07
.1288-06
O
CD
O
f>-
6
O
(0
6
oo
*
atm
1 atm
900
1000
1100
Figure 6. Partial Pressure of Gaseous NaF as a Function
of Temperature and Pressure.
28
-------
System: C-H-N-0-S-Cl-K-Na-Ca-Mg-F
Species Name KF: Partial Pressure
TEMP. ( K)
.3000*113
, 1000*03
,5000*03
,6000*03
.7000*03
,8000*03
.9000*03
,1000*04
.1100*04
,1200*04
,1500*02 atm
.CCUD
.4550-30
.1715-22
.2048-17
.2695-13
.1072-10
.1021-08
.2678-07
.2633-06
.1095-05
.1000*02 atm
. COLO
.4550-3U
.1715-^.2
.2503-17
.26S5-1J
.1072-10
.1021-08
.2677-07
.2b2S-L6
.8378-Ob
5UOO*Uiatm
. UOOU
.-4550-30
.1715-22
.3547-17
.2655-13
.1072-10
.1021-08
.2675-07
.2065-Ofc
.o226-0b
.10UO*01 atm
.OUQD
.4550-30
.1715-22
.7530-17
.2b95-13
.1072-10
.1021-08
.2373-07
.9105-07
.2655-06
CM
rO
00
CM
CM
CD
00
CD
o
Q.
O
U.S. Mean Coal/Mean Dolomite
90% Sulfur Removal
100% Excess Air
10, 15 atm
atn
atm
300 400 500 600 700 800 900 1000 1100
TEMPERATURE, K
Figure 7. Partial Pressure of Gaseous KF as a Function
of Temperature and Pressure.
29
-------
Reduction of the sulfur concentration to the levels present at
99 percent removal no longer produces solid BeSO, but BeO(s):
Be(s) + 1/2 02(g) ^BeO(s) , (13)
which reacts with water vapor to form gaseous Be(OH)_. Therefore, the
production of Be(OH)_(g) is enhanced at lowered temperatures when the
sulfur level is reduced. Tables 5 and 6 of Appendix A list the partial
pressure of Be(OH), and the number of moles of solid BeSO, projected to
result at equilibrium for fluid-bed combustor systems operating at 10,
100, and 300 percent levels of excess air and at 90 percent sulfur
removal conditions. It is to be noted that these projections assume
that beryllium is present in the coal and sorbent feed in a matrix-free
form. If beryllium is instead present in some complex form, the fate
of beryllium in the fluid-bed combustion systems could be different from
that projected here. One aspect of this possibility is discussed below.
Consideration must be given to the reaction of beryllium with alumi-
num and silicon, the major clay constituents of coal. Calculations
indicate that in the presence of excess aluminum, the stable form
of solid BeO • 3 A120« is produced. Introduction of magnesium and
silicon to the system alters the reaction in such a manner that
aluminum does not stoichiometrically re-form in the 6:1 ratio (forming
BeO • 3 A1203), but forms the stable BeO • Al_03(s) in addition to
magnesium aluminate, MgO • Al_03(s); magnesium silicate, MgO • SiO_(s);
silicon dioxide, SiO_(s); aluminum silicate, A120_ • SiO_(s); and
aluminum hydroxide, Al(OH)_(s). Figure 8 illustrates the reactions of
beryllium, as a trace element, with the clay constituents of coal.
In order to illustrate the effect aluminum has on the production of
gaseous beryllium hydroxide, profile plots of the BeO • Al20»/Be(OH)2
30
-------
Dwa. 6403A73
Si00(s)
MgO-AI203(s)
x-MgO(s)
• SKUs)
AI203-Si02(s)
AI2°3(S)
AI2°3(S)
Be(OH)
Figure 8.
Chemical Equilibrium Reactions of Beryllium with
Clay Constituents of Coal.
31
-------
system are presented in Figures 9 and 10 for comparison with those of
the BeSO, /Be (OH) £ equilibrium system (Figures 11 and 12). The following
have been noted:
• In the BeO • Al203/Be(OH)2 system
1. BeSO.(s) is not stable, even at low temperatures
2. Be(OH)_(g) is produced as the major beryllium compound at
temperatures greater than 400 K, indicative of BeO • Al.O-Cs)
removal.
• In the BeSO , /Be (OH) _ system
1. Be (OH) (g) is produced at temperatures greater than 600 K
at concentrations comparable to those produced in the
BeO • Al90,/Be(OH)_ system at elevated temperatures.
*L .3 £,
2. Tables 5 and 6 of Appendix A should be consulted for the
partial pressure of Be(OH)_(g) and number of moles of
BeSO, (s) formed at 90 percent sulfur removal for 10, 100
and 300 percent excess air for high coal-high dolomite.
Mercury
The reaction of mercury with fluid-bed combustion gases produces
volatile species of mercury II chloride (HgCl2(g)), mercury monoxide
(HgO(g)), and monoatomic mercury (Hg(g)), in systems containing 100 and
300 percent excess air. Fluid-bed combustion systems operating at
10 percent excess air additionally form diatomic mercury (Hg^) , mercury
chloride (HgCl) , mercurous chloride (Hg-Clp , and mercury mono-
hydride (HgH).
Mercury II chloride is the favored trace chlorine compound that
forms at low temperatures. Mercury II chloride gas is stable below
900 K; above this temperature HC1 is released from the complex with the
production of gaseous mercury and further oxidation of mercury to HgO:
EgCl2(g) - *Hg(g) + Cl2(g) (14)
Hg(g) + 1/2 02(g) - *HgO(g) . (15)
32
-------
System: C-H-N-0-S-Cl-K-Mg-Al-Si-Be
BE (OH) i (,as: Partial Pressure
temp ( K)
3UU.O
HuU.U
bUU.U
6UU.U
/UU.O
8uU. 0
9UU.U
1 UUU. (J
1 1UU.U
1.0 atm
3.bJ9u-l2
b.6H 1U-U7
b.786U-07
5, 7«^U-U7
5. 78HU-U7
b. /a^u-u;
b. 78SJ-07
b. 7VIU-U7
b. 7B3U-U7
5.0 atm
1 .fa03u-lU
3.773U-07
2 .893J-U6
2.692U-U6
2.8V2U-06
2.892U-06
2.8920-06
2 • 896U-G6
2.69MU-06
10.0 atm
2.M270-U9
3. 1 720-07
S. 7870-U6
5. /81CJ-06
b. 78^0-06
b. 78MU-06
b.78HU-06
b. 791U-06
b. 7870-06
<0
6"
(O
10
"
o
¥ *
00'
CM
ro
X
o
(DO
to
U.S. Mean Coal/Mean Dolomite
90% Sulfur Removal
100% Excess Mr
[Al] = [Si] = 10 [Be]
_0
o
o
o.
o
o
-10 atm
.5 atm
atm
300
400
500
900
1000
Figure 9,
600 700 800
TEMPERATURE, K
Partial Pressure of Gaseous Be(OH)2 as a Function of
Temperature and Pressure. Interaction between
Beryllium and Aluminum Produces a Solid Complex of
BeO»Al203 at Low Temperatures. Production of
Gaseous Be(OH)2 Is Dependent on the Volatilization
of Be from This Complex.
1100
33
-------
System: C-H-N-0-S-Cl-K-Mg-Al-Si-Be
tcnp ( K)
3uU.U
HUU.U
bUU.O
6QU.U
/UU.U
euu.u
9uU.ii
1UUU.U
1 1 UU. U
1. 0 atm
3.V21U-U5
1 . 0220-06
.OOUU
. OUUU
.UUOO
.UUUU
. 13 U U U
.UOUU
. OUOU
5.0 atm
J. V 1 6u-Ub
3.
-------
System: C-H-N-0-S-Cl-K-Be
Bt(OH)
_o
o
Q.
O
q
d.
U.S. Mean Coal/Mean Dolomite
90% Sulfur Removal
100% Excess Air
atm
10 atm
atm
ntm
300
400
500
900
1000
1100
Figure 11.
600 700 800
TEMPERATURE, K
Partial Pressure of Gaseous Be(OH)2 as a Function of
Temperature and Pressure without Be/Al-Si Inter-
action. Production of Gaseous Be(OH)2 Is Dependent
on the Volatilization of Solid BeS04.
35
-------
System: C-H-N-0-S-Cl-K-Be
temp ( K) i.o amp 5.0 atm
10.0 atm
15.0 atm
3uU.U
MUO. U
bJU. U
6UL). 0
7uU.U
buu.u
9UU.O
1 UUU.U
1 1JU.U
3.91 8u-Ub
3.91 8U-Ob
3.9190-Ob
. OUOU
.OOUU
.OUOU
. uuou
.UUOU
.uuou
3.91 Uu-Ub
3.918J-Ub
3.9 19U-05
. UUUu
. UOOU
• UOUU
. UUOu
.UUUu
. UUUJ
3.918U-U&
3. V 16U-U5
3.9180-05
. JUUO
.UUUU
.UOOU
.OUUU
.UUUU
.ouou
3 . 9 1 Bu-05
3.918U-05
3.91 8U-U5
3.83MU-05
. OOOu
• UOUU
.UOUU
.OOOU
.UOOU
15 atm
U.S. Mean Coal/Mean Dolomite
90% Sulfur Removal
100% Excess Air
300
600 700 800
TEMPERATURE, K
900
1000
1100'
Figure 12. Nunfrer of Moles of Solid BeS04 as a Function of Tempera-
ture and Pressure 'without Be/Al-Si Interaction.
36
-------
At reduced pressures and elevated temperatures removal of HgCl-
from the gas phase is enhanced. Similarly, reduction of the sulfur con-
centration in fluid-bed gases further reduces the partial pressure of
the HgCl2 due to the increased oxygen partial pressure in the system,
favoring reaction 15. This is illustrated by comparison of the
partial pressure of HgCl_ at 1200 K:
Sulfur Removal, %
SYSTEM TOTAL PRESSURE
15 atm
0 3.753 x 10"10atm
99 1.119 x 10~13atm
1 atm
2.053 x 10"13 atm
8.191 x 10""17 atm
The trace level of mercury used in the equilibrium calculations for
all fluid-bed combustion systems is on the order of 10~ moles (see
Table 4). Relative concentrations of this magnitude are sufficiently
low to produce a l-to-4 percent mass constraint error. This error is
significant for the trace level of mercury, so caution must therefore
be exercised when comparing results quantitatively for the mercury
compounds.
12
Trace levels (<10 atm) of Hg2(g) and HgCl(g) are projected to
form in fluid-bed gases. Reduction in the concentration of sulfur to
99 percent removal produces a greater partial pressure of Hg2 and
of HgCl at low temperatures than in the O-to-90 percent sulfur removal
systems. .Equivalence in the partial pressure exerted by Hg2(g) for the
O-to-90 and 99 percent removal systems, is reached at elevated tempera-
tures. Gaseous HgCl is not detected in systems containing 300 percent
excess air.
Tables 7 through 11 of Appendix A illustrate the partial pressures
for the gaseous mercury compounds formed in fluid-bed combustor gases.
The results are determined for the high coal-high dolomite system with
90 percent sulfur removal. Solids and sulfate compounds of mercury
37
-------
are not projected to form stable phases under any fluid-bed condition.
Mercury released as a gas should not condense in the cooling stages of
the process. Complete volatilization of mercury in the coal or sorbent
is projected with emission from the stack in the form of oxides and
chlorides that are capable of entrainment on the surface of particu-
lates in the gas stream.
Lead
The volatile compounds lead tetrachloride, PbCl,; lead dichloride,
PbCl,,; lead chloride, PbCl; and lead oxide, PbO, are projected to be
formed when lead is present in fluid-bed combustion gases. Over the
temperature range of 300 to 1200 K, lead tetrachloride is the pre-
dominant gaseous trace compound. Formation of PbCl, results from the
reaction of PbO with HC1 as shown by the reaction:
PbO(g) + 4 HCl(g) + 1/2 02 - *PbCl4(g) + 2 H20(g) . (16)
Reducing the sulfur level (i.e., 99 percent sulfur removal) increases
the partial oxygen pressure and limits the formation of gaseous PbCl,
at low pressures when the temperature is greater than 1000 K (reverse
of reaction 16). Between 1000 and 1100 K. PbCl. releases chlorine,
' 4 »
reducing the concentration of the PbCl, while increasing the PbCl2
(reaction 17) :
PbCl4(g) - ^PbCl2(g) + 2 Cl(g) . (17)
Reduction of the pressures at elevated temperatures causes a further
transition of the PbCl2 phase. Chlorine is removed from PbCl2,
forming gaseous PbCl:
PbCl2(g) - », PbCl(g) + Cl(g) . (18)
Reducing the sulfur level from 90 to 99 percent produces a dramatic
increase in the partial pressure of PbO. Only a light change is
38
-------
detected, however, between the 0 to 90 percent systems. At 1200 K and
15 atmospheres the partial pressures of PbO for the 10 and 100 percent
excess air cases are as follows:
Excess Air
Sulfur Removal, %
10%
100%
0 1.273 x 10"9 atm 1.056 x 10"9 atm
90 1.376 x 10"9 atm 1.265 x 10~9 atm
99 1.559 x 10"5 atm 8.899 x 10~6 atm
Tables 12 through 15 of Appendix A illustrate the partial pressures
for volatile lead compounds produced by fluid-bed combustion systems
with 90 percent sulfur removal.
Fluorine, Beryllium, Mercury, Lead System
The equilibrium reactions of fluid-bed combustion gases do not
project the interaction of trace elements. For example, fluorine and
mercury do not form stable phases of mercurous fluoride, FHg and F.Hg-,
or mercuric fluoride, F2Hg, as either solids, liquids, or gases.
Similarly, fluorine does not react with lead-forming trace complexes
of lead mono-, di-, or tetrafluorides, (FPb, F2?b, or F^Pb). Oxy-
fluorides and fluorides do not combine with beryllium, nor do chlorides
of beryllium-fluorine result (i.e., BeCIF).
PARAMETRIC FBC EQUILIBRIUM CONCENTRATIONS
The reactions of the trace elements in fluid-bed combustors act as
individual systems, producing the chlorides, sulfates, and oxides of the
particular element. Tables 8, 9, and 10 summarize the distribution of
the trace elements in various gaseous and solid phases for 90 percent
sulfur removal conditions in 10, 100, and 300 percent excess air for
high coal-high dolomite systems. It is evident that temperature influ-
ences the form in which the trace element is most stable, as well as
the variations in the distribution of the element with total system
pressure.
39
-------
TABLE 8. DISTRIBUTION OF TRACE ELEMENTS IN HIGH COAL-HIGH DOLOMITE
SYSTEMS FOR 10% EXCESS AIR - 90% SULFUR REMOVAL
FRACTIONAL DISTRIBUTION OF THE TRACE ELEMENTS AMONG THEIR
PRINCIPAL COMPOUNDS - (GASEOUS UNLESS OTHERWISE NOTED)
Trace
Compound
HF
KF
NaF
S02F2
BeS04(s)
Be(OH)2
Hg
HgO
HgCl2
PbCl4
PbCl2
PbCl
PbO
NaCl
NaOH
Na2S04
Na2S04(s)
KC1
KOH
K2S04
K2S04(s)
1200
15 atm |
0.99
4.64 x 10 ^
1.38 x 10"^
_ 7
2.79 x 10
1.00
0.96
3.70 x 10"^
4.53 x 10
0.99
3.31 x 10";:
1.21 x 10"^
8.71 x 10"5
2.93 x 10"^
8.83 x 10";?
8.33 x 10" ^
0.97
3.63 x 10"^
2.14 x 10",
2.73 x 10" J
0.96
K
1 atm
0.99
1.11 x 10"^
3.29 x 10~Z
— Q
7.30 x 10 *
1.00
0.99
9.90 x 10"^
1.93 x 10" ^
0.31
0.25
1.44 x 10"^
0.42
0.34
2.11 x 10";?
1.25 x 10" J
0.65
0.42
5.11 x 10",
4.09 x 10"2
0.54
300
15 atm |
1.70 x 10~3
—
__
0.99
0.99 .,
3.95 x 10 *
-29
9.34 x 10 :,
1.39 x 10~/
0.97
0.99
—
—
—
„
__
_—
1.00
4.16 x 10" •"
__
— —
1.00
K
1 atm
1.70 x 10"3
,^,_
0.99
0.99
7.71 x 10
-97
1.41 x 10 ,'
5.40 x 10~/7
0.97
0.99
—
__
—
mrm^m
»**
_ —
1.00
—34
3.16 x 10 M
.«.
_— .
1.00
SYSTEM: C-H-N-0-S-Cl-K-Na-F-Be-Hg-Pb.
40
-------
TABLE 9. DISTRIBUTION OF TRACE ELEMENTS IN HIGH COAL-HIGH DOLOMITE
SYSTEMS FOR 100% EXCESS AIR - 90% SULFUR REMOVAL
FRACTIONAL DISTRIBUTION OF THE TRACE ELEMENTS AMONG THEIR
PRINCIPAL COMPOUNDS - (GASEOUS UNLESS OTHERWISE NOTED)
Trace
Compound
HF
KF
NaF
Be (OH) 2
Hg
HgO
HgCl2
PbCl2
PbCl
PbO
NaCl
NaOH
Na2S04
Na2S04(s)
KC1
KOH
K2S04
1200
15 atm 1
0.99
6.11 x 10" ;!
1.82 x 10"^
2.86 x 10"'
1.00
0.98
7.79 x io~:f
5.20 x 10" J
0.99
3.00 x 10";:
1.01 x 10~£
1.42 x 10~*
3.80 x 10"^
1.16 x 10"?
1.48 x 10"*
0.96 „
4.70 x 10"^
2.82 x 10,
4.85 x 10" J
0.95
K
1 atm
0.99
1.38 x 10";?
4.09 x ID"*
8.37 x 10~y
1.00
0.93
1.92 x 10~;f
1.65 x 10"5
0.19
0.17
1.01 x 10"z
0.63
0.38
2.63 x 10",
2.22 x 10" J
0.62
°-*7 -4
6.36 x 10 I
7.27 x 10"Z
0.46
300
15 atm 1
1.70 x 10~3
0.99
0.99 .,
7.57 x 10"16
1.36 x 10" _
4.17 x 10"2/
0.79
1.00
—
—
—
1.00
lju M
1.00
K
1 atm
1.70 x 10~3
0.99
1.49 x 10"15
2.56 x 10""
2.03 x 10~^°
0.99
1.00
—
—
—
1.00
2.94 x 10" 34
1.0
SYSTEM: C-H-N-0-S-Cl-K-Na-F-Be-Hg-Pb.
41
-------
TABLE 10. DISTRIBUTION OF TRACE ELEMENTS IN HIGH COAL-HIGH DOLOMITE
SYSTEMS FOR 300% EXCESS AIR - 90% SULFUR REMOVAL
FRACTIONAL DISTRIBUTION OF THE TRACE ELEMENTS AMONG THEIR
PRINCIPAL COMPOUNDS - (GASEOUS UNLESS OTHERWISE NOTED)
Trace
Compound
HF
KF
NaF
S°2F2
BeS04(s)
Be(OH)2
Hg
HgO
HgCl2
PbCl2
PbCl
PbO
NaCl
NaOH
Na2S04
Na2S04 (s)
KC1
KOH
K2S04
K SO (s)
1200
15 atm |
0.99 .
1.10 x 10"*
3.28 x 10"^
1.73 x 10"'
__
0.99
0.97 .
9.40 x 10",
2.89 x 10~J
0.99
5.25 x 10";:
2.41 x 10~l
5.51 x 10~*
6.53 x 10",
2.10 x 10"?
2.92 x 10~4
0.93
8.09 x 10"^
5.08 x 10",
9.55 x 10" J
0.91
K
1 atm
0.99
2.40 x 10"?
mmtft
7.11 X 10 Q
5.42 x 10" y
—
0.99
0.93
2.34 x 10" £
4.96 x 10~°
2.02 x 10"*
6.00 x 10",
6.53 x 10" J
0.91
0.48
4.58 x 10",
4.38 x 10" J
0.53
0.57
1.11 x 10" J
0.14
0.29
300 K
15 atm
1.70 x 10~-
—
0.99
0.99
1.17 x 10"1
3.76 x 10"S
1.41 x 10""
1.11
0.99
-—
—
— —
__
1.00
„_
__
—
1.00
I 1 atm
» -3
5 1.70 x 10
—
0.99
L5 °-" -15
2.31 x 10 ^
\l 5.16 x 10:^
5.00 x 10 i
1.02
0.99
__
—
__
__
1.00
^ 9^^
__
__
1.00
SYSTEM: G-H-N-0-S-Cl-K-Na-F-Be-Hg-Pb.
42
-------
In order to demonstrate that the trace compounds formed in high
coal-high dolomite systems are produced in fluid-bed combustion systems
that use various grades of coals and sulfur sorbents, the equilibrium
composition was calculated for mean coal-mean dolomite conditions and
mean coal-low dolomite conditions. Parametrically, these conditions
define the upper, middle, and lower limits of the trace element concen-
trations. In varying the level of each constituent, no change in
chemical form is observed in the final trace products. The active com-
pounds for mean coal-low dolomite are identical with those that result
in high coal-high dolomite systems. The only change that should be
noted when using an alternative system is that the level of the gaseous
trace compound reflects the initial trace concentration in the coal and
sorbent feedstock. Tables 1 through 4 of Appendix B indicate the partial
pressures of the gaseous trace compounds produced at 1200 K for operating
conditions of 100 percent excess air, with 90 percent sulfur removal for
high coal-high dolomite and mean coal-low dolomite systems. Note the
difference in the partial pressures of each compound when the initial
levels of the trace constituents are varied (see Table 4 of Section 4
for initial concentrations).
The partial pressures of the trace compounds that result in high
coal-high dolomite systems have been calculated as a function of the
excess air content. For all sulfur removal systems operating between
1 and 15 atmospheres at temperatures of 1200 K, the partial pressures
of the trace compounds HF, KF, NaF, Be(OH>2, HgCl^ HgCl, HgO, PbCl4,
and PbCl7 are shown to be suppressed as more air is supplied to the
combustion process. This is simply a dilution effect. The partial
pressures of PbO and PbCl are projected to slightly increase in
300 percent excess air for O-to-90 percent sulfur removal conditions
at high system pressures.
The thermochemical properties of the trace fluid-bed combustion
system were calculated (as part of the computer program subroutine)
(Appendix C). Variations between trace systems as compared with pure
43
-------
fluid-bed gases exist only within the sixth decimal position. The
properties for systems with and without trace elements are virtually
the same.
ASSESSMENT
The thennodynamic analysis performed shows that essentially all of
the beryllium, lead, mercury, and fluorine can be volatilized at the
normal operating temperatures, pressures, and sulfur dioxide levels in
fluidized-bed combustion. These projections assume that all of these
trace metals are present in the coal and sorbent feedstocks in a
matrix-free form, available for the reactions considered. For
beryllium and fluorine species, some condensation will occur on cool-
ing the gases through reactions of the trace element phases with the
carbonate and clay fractions of the coal and sorbent. The gaseous
species of lead and mercury when formed do not condense at ambient
temperatures. No significant interaction between these trace elements
is projected, and no significant differences between pressurized and
atmospheric-pressure operation were noted, except for lead, as dis-
cussed below.
These projections may be compared with the mass balances performed
by Argonne National Laboratories (ANL) around a pressurized fluidized-
bed combustion system. In their experiments, ANL found that of the
four elements mentioned above, good retention (£lOO percent) of lead
was noted in the solids phase, but the average retention of the other
elements was only 42 percent, despite the relatively low temperature
(600-800°F) at which overhead samples were collected. This power
retention in the solid phases is in agreement with the projections
reported in this study, although this study reports even poorer reten-
tion than that which Argonne observed. It is significant to note that
the retention of fluorine in the ANL experiments was much higher
(56-62 percent) with a calcium sorbent than with a sorbent-free bed
(5-23 percent), agreeing further with the projections made in this
44
-------
study. The projections shown here indicate that cooling the gas
with excess CaO, as normally present in fines, leads to retrapment
of the liberated fluorine.
It is surprising that lead retention is predicted thermodynam-
ically to be poor in pressurized systems. ' In the Argonne experi-
ments both lead and beryllium were concentrated in the finer
particles (indicating redeposition on cooling). In measurements to
determine the fate of elements in a cyclone-fed power plant,
Fulkerson et al. (Oak Ridge)^ ' found that 10 percent of the lead
was lost as an atmospheric discharge. This makes the predicted
volatilization of lead as PbCl, unlikely, and several reasons can
be advanced. The kinetics of conversion of the other lead compounds
to PbCl, may be intrinsically slow, or the lead may be bound up in
the mineral matter in a form that is not very accessible to the HC1
content of the gas. Alternatively, there may be more stable com-
pounds of lead - silicates or berates - than those considered here. In
addition, conversion of lead to PbCl, is initially dependent on the
concentration of HC1 in the gas. If the HC1 level falls to 50 per-
cent of its assumed value, then PbCl, falls to 6 percent of its
previous value. This can be seen by examining the mean coal-low
dolomite case in Table 4 of Appendix B, where for the atmospheric pres-
sure case, PbO(g) is the predominant lead compound. In this case, lead
will quickly condense on particulate matter on cooling. The circum-
stances that favor PbO are, therefore, low-pressure operation and low
HC1 release, which would occur with a low-chlorine coal or when alkali
release is high enough to lower the free HC1 content of the gas.
EXTENSION OF THERMODYNAMIC PROJECTIONS TO OTHER ELEMENTS PRESENT IN
COAL, USING ELEMENT VOLATILITY AS A CRITERION
Consideration was given to choosing a representative selection
of additional elements based upon the classification of trace ele-
ments and upon the concentration of the element in coal. (Refer to
-------
Table 11.) The selection of four trace elements (bromine, molyb-
denum, antimony, and vanadium) resulted from reported volatile loss
in high- and low-temperature ashing processes. Thermodynamic data
available for these four elements were reviewed from the work of
JANAF and Barin and Khache:
• Br - data for complexes forming Cl-H-N-0-K-Na-Pb-Hg-Mg, etc.
• Mo - data for Cl-O-F-H readily available
• Sb - not reported in JANAF
• V - oxides and nitrides - limited.
On the basis of available data bromine and molybdenum are good
choices; and antimony and vanadium would take an additional litera-
ture review and estimates to fit reported data. Substitution may
be made, with phosphorus and boron both showing reasonable data in
JANAF, and both can be used to demonstrate interaction with the
previous Be-F-Hg-Pb study. Toxicity data, which is included in
Table 11, should not be used as a major deciding factor since the
levels are listed for compounds found in NIOSH and may not include
pertinent species that form in the fluid-bed system.
46
-------
TABLE 11. TRACE ELEMENTS IN COAL
Trace
Element
Classification
Comment
TWAa
As Mineral matter
Concentration
Data Bank
Organic affinity
Clean coal
15 mg/m 102 ppm
Boron complexes with
Br, 0, Cl, F, H, Li, K,
Be, F, Pb, K, Mg
Be
Completed
Br
Volatiles lost Br, - 0.1 ppm 15.42 ppm Bromium complexes Cl, F,
in LTAb -\.100Z H, N, Hg, K, Mg, N, Na,
P, Pb
Cd
Co
Cr
Cu
F
Ga
Mineral matter
Combination
Combination
Combination
Completed — — —
Organic and
inorganic affinity
Ge
Organic affinity
clean coal
Hg
Mn
Mo
_
Mineral matter
Mineral matter
Completed — —
Lost in HTA° MnO, - 7.5 mg/m3 7.54 ppm
-V-33Z
—
Oxide complexes
Ni
P
Combination
Organic and
Inorganic affinity
PbCl, - 0.5 pn
71.1 ppm Oxide, chloride and
sulfide complexes
Pb
Sb
Completed
Organic and
inorganic
Volatiles lost
In LTA ~5Z
1.26 ppm
Not reported
Se
U
V
Combination
Inorganic
Organic and
Inorganic
Lost in HTA Va05 -
•\,25Z /8hrs (TCLo)d
32.71 ppm
Oxides
nitrides
Zn
Zr
Mineral matter
Mineral matter
fTWA - Time Weighted Average
LTA - Low-Temperature Ashing
*JHTA - High-Temperature Ashing
TCLo - Lowest Published Toxic Concentration
47
-------
SECTION 6
EXPERIMENTAL DETERMINATION
APPROACH
The thennodynamic projections reported indicate potential path-
ways for the release of trace elements into the gaseous effluent from
the fluidized-bed combustion system. On the other hand, a limited
number of experimental studies have been carried out to analyze the
effluent streams and characterize their actual trace element content.
These studies are of immense value, but they do not cover the ranges
of proposed operating conditions or possible design applications.
Since our major objective is to attempt to characterize and evaluate
emissions before development of full-scale systems, an intermediate
experimental study is required, in which the kinetics of trace ele-
ment release are studied over a range of simulated fluidized-bed
combustor operating conditions.
Previous experimental studies at Westinghouse on the release of
trace elements from fluidized-bed combustion feedstock materials have
concentrated on the principal elements that induce corrosion on
boiler tubes and turbine metal surfaces - namely, sodium and potassium.
A custom-built flame-emission spectroscopic apparatus was used to
monitor continuously the release of these elements from coal ash and
dolomite sorbents and to study the use of getter materials to suppress
alkali release. Because this apparatus can be used to simulate the
effect of a number of important operating variables - temperature, gas
composition, particle size, coal type, and sorbent type - it was thought
worthwhile to assess its use in an extended program to measure the
kinetics of release of potentially volatile trace metals such as lead
-------
and mercury under fluidized-bed combustor operating conditions. The
experimental program was limited to ascertaining the utility of the
existing apparatus for this purpose, and only minor modifications were
considered.
FLAME EMISSION SPECTROPHOTOMETRY
The flame emission spectroscopic technique, used for the continu-
ous monitoring of sodium- and potassium-bearing vapors that are
released from heated samples of dolomite stones, is shown by the sche-
matic drawing of Figure 13. A known quantity of sample matter is
filled into a nickel boat and placed inside a nickel tube that serves
as a heating susceptor for the RF radiation. The sample temperature
is monitored with an Inconel-sheathed thermocouple, the hot junction
of which is near the sample bucket. A controlled flow of a synthetic
gas mixture is passed through the tubular nickel crucible. Volatile
material given off the sample is carried with the gas without appreci-
able cooling through a reduced opening into a hydrogen/oxygen flame.
Hydrogen and oxygen are piped through annular tubes to the burner
nozzle. A laminar flow of nitrogen keeps the outer quartz tubing
free from deposits and protects it from overheating in the area
around the flame.
A uniform section of the diffusion flame is focused on the inlet
slit of a Jarrel-Ash spectrometer. A portion of the spectrum is picked
up by an image intensifier tube. The signals are digitized and dis-
played on a TV tube. Hollow cathode light sources are used to preset
the optical and recording system and maximize the signal output.
O
The maximum characteristic line intensity (5896 A for sodium and
7665 A for potassium) is plotted out on a strip chart recorder,
although digital data handling and reduction would be preferable.
In order to quantify the emission signal from sodium and potassium
radiation, known amounts of NaCl and KC1 are completely vaporized into
the gas stream. The signal-time integral of the known standard is
applied as a unit measure to quantify the accumulated signal of an
unknown sample.
49
-------
Dwq. 1663B68
H
II
TT
-Hollow Cathode Lamp
T.C.
Wl
o
Thermo-
couple
Oxidizing N2 02 H2 N2
Carrier Gas
RF - Coil
O\O O O O O
— H
o-
e
t
.
r
t
t
^
t
/
/
/•
o o/o o o o
Lens
Sample
Ni-Crucible Filter
Grating
Spectrometer
-Quartz Glass
Flame
•Vent
Optical
Multichannel
Analyzer
Intensifier Detector Head
Mirror •
Figure 13. Apparatus for the Flame Spectrescopic Determination of Alkali Release from
Feed Materials in the Fluidized-Bed Combustors.
-------
A typical emission intensity-versus-time output curve plotted on
a strip chart recorder is shown in Figure 14. The shaded area covers
the width of intensity fluctuations that may be caused by local vari-
ations of the release of alkali vapors. The magnitude of the recorded
signal and the shape of the curve depend on the temperature, the geo-
logical origin of the dolomite, and the total alkali impurity content.
Generally, the characteristic alkali signal reaches a maximum quickly,
as soon as the desired final temperature is attained. The signal drops
off, at first abruptly, and then more gradually, falling to a very low
quasi-steady value. The intensity charts were graphically integrated
and quantified by comparison with intensity curves from known KC1 or
NaCl standards. The results of the calculation are alkali release
curves that give the accumulated amount of released alkali in yg as a
function of time, as shown in Figure 15.
In order to obtain reproducible results, parameters such as the
hydrogen, oxygen, and synthetic combusted gas flow rates must be
accurately controlled. The shape of the corabustor nozzle and the
effusion hole of the susceptor can appreciably affect the emission
signal. Calibration runs have to be periodically repeated, particu-
larly after replacing the combustor or nickel susceptor, in order to
take small uncontrollable changes of the calibration factor into
account. Care must also be taken that the alkali vapor density in
the flame does not exceed an upper level, above which linearity
between emission signal and concentration is impaired. If the emis-
sion signal becomes too high, the sample size has to be appropriately
reduced.
Apparatus Modifications
Any changes required to test the signal output of the flame emis-
sion spectrum of the toxic elements (lead, mercury, etc.) were made in
the spectroscopic and detector components of the apparatus. In order
to gain an insight into the difficulties that may be encountered in
using this technique for the continuous monitoring of the toxic trace
51
-------
Curve 683903-A
I
if
NJ
.._ . •.-••-•:••*•
110 100
90
80
70
60 50
Time (min)
40
30
20
10
•
o
so"
CD
0
Figure 14. Flame Emission Intensity-Time Curve Illustrating the Release of Potassium
Vapor Impurity from 300 mg of Tymochtee Dolomite at 875°C in Flowing Fuel
Gas (22.1% H2/19.4% CO/18.2% O>2/40.3% N2 at 75 cc/min)
-------
Curve 685032-B
u>
0
: Synthetic Fuel Carrier Gas N2II 22.1% H2/19.4% CO/18.2% COJ
10
20
30
40
Time(Min.
50
60
70
80
Figure 15. Release of Na from Geneva Dolomite. (Sample Weight 100 mg;
Particle Size, 35-40 Mesh - ASTM; Carrier Oas: 19.fi%
C02/2.2% 02//N2 at 75 cc/min.; Na Concentration in
Sample: 204 + 13 ppm)
-------
element release, the total content of these traces in the coal feed
materials as well as their spectrochemical properties must be con-
sidered. In the case of coal ash samples that have been prepared at
temperatures below 700°C, the total lead content can be as high as
50 ppm.(25)
For 100 mg of such a sample (the maximum capacity of the nickel
sample holder), the absolute total amount of lead will be about 5 pg.
Only 1 to 10 percent (i.e., 0.05 to 0.5 yg) of this lead is expected to
be released at coal combustion temperatures. The strong resonance
o
line for lead (4059 A) yields an emission signal a factor of ^100 less
o
intense than that of the K-line (7665 A). Taking these latter two
facts in conjunction, the magnitude of the difficulties becomes rather
obvious. Furthermore, even if the optimum position of the per-
missible hydrogen/oxygen flame in this apparatus is employed, the
spectral response may be even less than the above quoted factor of 100.
Mercury probably will be more difficult to monitor than lead,
since mercury is expected to be less sensitive than lead in the flame
emission mode by a factor of ^20, and its total content in the same
materials is expected to be less than that of lead by a factor of
-100/25'
A Westinghouse commercial hollow cathode lamp was always used to
preset the emission signal output. The entrance straight slit to the
Jarrel Ash spectrometer (Model No. 82-000) was 100 pm. The optimum
flame emission volume was found to be close to the beginning of the
outer zone of the diffusion flame. In the case of lead, in addi-
tion to the previously used Silicon Intensified Target (SIT) detector
( 26^
with the Optical Multichannel Analyzer (OMA), a photomultiplier
tube (RCA P28) was used. In this case the signal was transferred to
a microamplifier unit. In both of the above cases, the output was
monitored on a strip chart recorder. In the first combination, the
SIT detector had a photocathode stage prior to its silicon target; a
fiber optic faceplate (scintillator) was attached to this photo-
o
cathode. This extends the response of the detector below 3000 A and
54
-------
close to the UV range (i.e., covers the Hg-resonance line of 2536 A).
This response was tested with the mercury hollow cathode lamp. The
advantages of the SIT detector are the measurement of intensities at
closely spaced wavelengths, i.e., line and background, and a substantial
increase in the number of wavelengths that can be monitored. The dis-
o
persion of this Jarrel Ash monochromator is 16 A/mm, and the width of
the target on the detector is 12.7 mm. At the proper operating frame
o
voltage (9 kV), a spectral range of ^203 A is covered on the oscillo-
scope screen. The sensitivity of a photomultiplier is normally higher
than that of this detector. In the case of the photomultiplier, how-
ever, the signal-to-noise ratio is lower than with the SIT detector-OMA
system. This SIT-OMA combination allows accumulation of the signal in
the DMA unit (signal averaging technique) and results in a high signal-
to-noise ratio.
In addition to the calibrant type of materials (i.e., lead, PbO,
Hgl,,) tested in this apparatus, a coal ash sample was also examined
for any lead release. The experimental procedure in conducting a
typical run or calibration was similar to that described for the alkali
metal release studies.
RESULTS AND DISCUSSION
Among the combinations mentioned in the previous section, the largest
calibration signal output for lead was obtained using the SIT detector-OMA
unit. Such a calibration signal output illustrates the extent of the lead
detection by this apparatus, as shown in Figure 16. The background level
of this signal is obviously far from ideal. A similar signal was obtained
when lead was used instead of PbO as the calibrant material, and also when
the carrier gas was reducing (i.e., 22.1% H2/19.4% CO/18.2% O>2//N2)
instead of oxidizing, as illustrated in Figure 16.
The total amount of equivalent lead (185.6 vg) used for the
2
calibration and the measured area (52.4 cm ) under the resulting
2
curve above the base line give a factor of 3.54 yg of Pb/cm . The area
7 2
of 1 cm is shown to scale on Figure 16. This area of 1 cm corresponds
55
-------
Curve 685770-A
O
15
•5
CM
*4/l
C
CD
•s
1cm
I i j I
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (Min.)
Figure 16. Total Signal Output of the Flame Emission Spectrum of
Pb from 0.200 mg of PbO (i.e; M.85.6 yg of Pb)
(Resonance Line: 4059°A; Oxidizing Carrier Gas
(19.8% C02/2.2% 02//N2 at 75 cc/min)
56
-------
to 0.0155 division on the planimeter that was used for the area measure-
ments. This is barely measurable with the planimeter. The observed
fluctuations in the ordinate (intensity), however, do not justify more
accurate means for the measurement of the area of the signal. In order
to cover the low predicted range of the total lead release (i.e.,
0.05-0.5 yg) from the sample volume that can be accommodated inside the
nickel boat, the total area under the curve of Figure 16 should represent
approximately less than 0.262 yg of lead; that is, an improvement by a
factor of at least 708 (185.6/0.262) in the signal output is required.
This allows a factor of M.O over the limit of detectability (i.e., twice
the maximum variation of the background intensity). In practice, this
expected minimum release (M).05 yg) will be the cumulative amount over
a period of time; thus, another factor of approximately 10 may be needed
for the accuracy required to establish the cumulative lead release curves,
This total improvement will yield a signal output comparable to that
of sodium. The expected improvement in the best of the presently attain-
able signal outputs (Figure 16) from any changes in the monochromator
(i.e., grating, slit width, etc.) will be minimal. The complete absence
of any signal for lead when 100 mg of coal ash sample were slowly heated
to 1323 K confirmed the result of Figure 16. The total amount of lead
in this sample was 6.5 yg.* Hence, even in the unlikely situation of
total lead release, this amount could have gone undetected.
Mercury was tested using Hgl as the calibrant material; the
2. 0 o
intensity of two mercury lines (2536 A and 3650 A) was followed as a
function of" time and flame position. The vapors of mercury were
slowly generated at low temperatures (323-473 K) from samples of
solid Hgl . In no case was a calibration emission spectrum observed.
The performance of the optical and detection systems was tested with
the mercury hollow cathode lamp and was found satisfactory. The
absence of any mercury flame emission spectrum during calibration
*Atomic absorption analysis of digested solution of the coal ash sample.
57
-------
and the aforementioned lower flame emission sensitivity for mercury
than lead did not justify any additional tests for the toxic mercury
trace release. A total improvement by a factor of ^10 in the
signal output of Figure 16 is estimated to be needed in order to be
able to monitor continuously the release of mercury from the feed materials
of the fluidized-bed combustor. Similarly, beryllium was not examined
because its total content in the coals is reported as low as its optical
emission spectroscopic detection limit.
In conclusion, the results of the tests and the available informa-
tion in the literature show that the original objective - that is, the
continuous monitoring of the toxic trace element release from the feed
materials of the coal combustor process - cannot be accomplished using
the flame emission spectrophotometrie apparatus.
To achieve this objective, alternative methods and high-
temperature sampling techniques must be developed. The use of atomic
absorption, microwave excitation emission, and X-ray fluorescence
techniques will not be adequate to monitor continuously the small
releasable portion of the trace elements under the conditions of the
coal combustor. Some recent determinations of the metallic elemental
concentrations of heated (613-1523 K) coal ash samples in oxidizing
atmospheres reveal, indeed, that any release would have been within
(2.7 28}
the estimated precision of these techniques. 'A reasonable
approach may be the determination of a total trace element release
(vapors and entrained particulates) through an analysis of condensates
collected at selected time intervals. This analysis may be performed
using the spark source mass spectrometric technique. Neutron activa-
tion analysis will be suitable for mercury if its constituents in the
deposits are volatile under the spark source mass spectrometric con-
ditions. The reported sensitivity in the nuclear reaction
202. 203, —4
ng (n,Y) tig is 1 x 10 yg, as defined for 1000 disintegrations/
14
minute of activation product after irradiation in a flux of 10
2 (29)
neutrons/cm /s to saturation.
58
-------
SECTION 7
REFERENCES
1. Magee, E. M., H. J. Hall, and G. M. Varga, Jr., "Potential Pollutants
in Fossil Fuels," Report to EPA, ESSO R&E Co., June 1973, Contract
68-02-0629, NTIS PB 225 039.
2. Joensuu, 0. I., "Fossil Fuels'as a Source of Mercury Pollution,"
Science 172, 1972, 1027-28.
3. Headlee, A. J. W., and R. G. Hunter, "The Inorganic Elements in the
Coals," West Virginia Geological Survey, Vol. XIIIA, Morgantown,
1955.
4. Ruch, R. R., H. J. Gluskoter, and N. F. Shimp, "Occurrence and
Distribution of Potentially Volatile Trace Elements in Coal,"
Report to EPA, Illinois State Geological Survey, July 1974,
EPA 650/2-74-054, NTIS PB 238 091.
5. Page, C. L., et al., "Analysis of Coal and Overburden at Four Corners,1
Westinghouse Research and Development Center, December 13, 1973,
Research Memo 73-7P4-ACHEJ-M2.
6. Hoke, R., "Emissions from Pressurized Fluidized Bed Combustion,"
Exxon R&E, Proceedings of the Fourth International Conference on
Fluidized Bed Combustion. The Mitre Corporation, McLean, Virginia
December 1975.
7. Swift, W. M., G. J. Vogel, A. F. Panek, and A. A. Jonke, "Trace
Element Mass Balances around a Bench-Scale Combustor," Argonne
National Laboratories., Proceedings of the Fourth International
Conference on Fluidized Bed Combustion, The Mitre Corporation,
McLean, Virginia, December 1975.
59
-------
8. Knapp, N., Personal Communication, 1976.
9. Harvey, R. D., "Petrographic and Mineralogical Characteristics of
Carbonate Rocks Related to Sulfur Dioxide Sorption in Flue Gases,"
Report to EPA, Illionois Geological Survey, July 1971, Contract
CPA 22-69-65.
10. Unpublished Westinghouse Data.
11. OfNeill, E. P., D. L. Keairns, and M. A. Alvin, "Sorbent Selection
for the CAFB Residual Oil Gasification Demonstration Plants,"
Westinghouse Research Laboratory, March 1977, EPA 600/7-77-029.
12. Private Communication, U. S. Geological Survey, Columbus, Ohio.
13. Liebermann, R. W., "Equilibrium and Thermodynamic Properties of
Complex Chemical Mixtures," Westinghouse Research and Development
Center, Pittsburgh, Pa., 1970.
14. Duffin, R. J., E. L. Peterson, and C. Zener, GeometricProgramming,
New York: John Wiley and Sons, 1967.
15. Chase, M. W., J. L. Curnutt, H. Prophet, R. A. McDonald, and
A. N. Syverud, JANAF Thermochemical Tables. Journal of Physical
and Chemical Reference Data, National Bureau of Standards, 2nd
edition, and 1974-1975 supplements.
16. Hertzberg, G., Molecular Spectra and Molecular Structure I, II, III,
New York: D. Van Nostrand Co., Inc., 1966.
17. Glassner, A., The Thermochemical Properties of the Oxides,
Fluorides and Chlorides to 2500 K, Argonne National Laboratory,
Argonne, Illinois, 1957, ANL-5750.
18. Barin, J. and 0. Knacke, Thermochemical Properties of Inorganic
Substances, Berlin: Springer-Verlag, 1973.
19. Oppermann, Von H., Fur Anorzanische und Allgemeine Chemie, Band
359, _52_, 1968.
60
-------
20. Krasnor, K. S., Handbook: Molecular Constants of Inorganic Com-
pound, Khimiya, 1968.
21. National Bureau of Standards, Selected Values of Chemical Thermo-
dynamic Properties. 1968, NBS TN 270-3.
22. Feber, R. C., Heats of Dissociation of Gaseous Halide, Los
Alamos Scientific Laboratory, N. M., 1965, LA-3164, TSC-4,
Chemistry TID-4500 (40th ed.).
23. Shick, H. L., Thermodynamics of Certain Refractory Compounds
New York Academic Press, 1966.
24. Klein, D. H., W. Fulkerson, et al., "Pathways of Thirty-seven
Trace Elements through a Coal-Fired Power Plant," Env. Sci.
Technol. _9, 1975, p. 973.
25. Babu, S. P., Ed., "Trace Elements in Fuel," Advances in Chemistry
Series, 141 (1975), p. 40, 45, 51.
26. Yannopoulos, L. N., et al., "Experimental Determination of Alkali
Impurity Release from Various Dolomites," Combustion and Flame,
30, 1977, p. 61-69.
27. Vogel, G. J. et al., "A Development Program on Pressurized
Fluidized Bed Combustion," Report to ERDA, EPA, Argonne National
Laboratory, Argonne, Illinois, October-December, 1975,
ANL/ES-CEN-1014.
28. Vogel, G. J., et al., "A Development Program on Pressurized
Fluidized Bed Combustion," Report to ERDA, EPA, Argonne
National Laboratory, Argonne, Illinois, January-March,
1976, ANL/ES-CEN-1015.
29. Meinke W. and B. Scribner Eds., Symposium on Trace Characteriza-
tion, NBS Monograph 100, National Bureau of Standards, Washington,
D. C., 1966.
-------
30. Archer, D. H., et al., "Evaluation of the Fluidized-Bed
Combustion Process," Vols. I-III, Report to EPA, Westinghouse
Research and Development Center, Pittsburgh, Pa., November,
1971, Contract 76-9, NTIS PB 211-494, 212-960, 213-152.
31. Keairns, D. L., et al., "Evaluation of the Pressurized
Fluidized-Bed Combustion Process - Pressurized Fluidized-Bed
Combustion Process Development and Evaluation," Vols. I and II;
"Pressurized Fluidized-Bed Boiler Development Plant Design,"
Vol. Ill, Report to EPA, Westinghouse Research and Development
Center, Pittsburgh, Pa., December 1973, EPA 650/2-73-048 a, b,
and c, NTIS Numbers 231-162, 231-163, 232-433.
32. Keairns, D. L., et al., "Pressurized Fluidized-Bed Coal Combus-
tion Development," Report to EPA, Westinghouse Research and
Development Center, Pittsburgh, Pa., September 1975, EPA
650/2-75-027c, NTIS PB 246-116.
33. Newby, R. A., and D. L. Keairns, "Alternatives to
Calcium-Based SO- Sorbents for Fluidized-Bed Combus-
tion: Conceptual Evaluation," Report to EPA, Westing-
house Research and Development Center, Pittsburgh, Pa.,
January 1978, EPA-600/7-78-005.
34. Newby, R. A., S. Katta, and D. L. Keairns, "Calcium-Based
Sorbent Regeneration for Fluidized-Bed Combustion: Engineer-
ing Evaluation," Report to EPA, Westinghouse Research and
Development Center, Pittsburgh, Pa., March 1978, EPA-600/
7-78-039.
35. Sun, C. C., et al., Disposal of Solid Residue from Fluidized-
Bed Combustion: Engineering and Laboratory Studies, Report
to EPA, Westinghouse Research and Development Center,
Pittsburgh, Pa., March 1978, EPA 600/7-78-049.
62
-------
APPENDIX A
CALCULATED PARTIAL PRESSURES OF GASEOUS TRACE COMPOUNDS AND
MOLES OF TRACE-SOLIDS PRODUCED AT EQUILIBRIUM FOR HIGH
COAL-HIGH DOLOMITE SYSTEMS AT 90 PERCENT SULFUR
REMOVAL IN 0, 100, AND 300 PERCENT EXCESS AIR.
63
-------
TABLE Al. HF
90% S Removal
10% Excess Air
Species Name HF
TIM?
K
.3000*03
.4UO(J*03
.5000»C3
.70CO*L3
.9000*03
.10t'U*C4
.1100*04
.12DD+04
.15CL+L2 ATM
.2365-06
.5553-05
.3060-04
.8502-04
.1557-03
.1737-03
.1746-03
.1746-U3
.1746-03
.1746-03
TRESSLRES
.1UOO+L2 ATM
.1976-06
.3702-05
.2041-04
.57b5-U4
.1065-U3
.1160-0:.
.1164-U3
.1164-03
.1164-03
.5oou*uiATM
.^832-07
.1851-05
.1022-04
.3017-04
.b519-04
.581U-D4
.5821-04
.5821-04
.5821-04
.5818-04
.1000*01 A™
.1376-07
.3628-06
.2065-05
.7H36-U5
.1150-04
.1164-04
.1164-L4
.1164-04
.1164-04
.1162-04
100% Excess Air
Species Name
TEMP. K
HF
3CCC+C
FCCC+C3
SCCC*C3
7CCC*C3
3G32+D3
9CCC+C3
120C*C4
.3125-C5
.1724-C4
.491C-C4
.SC77-C4
.373G-C4
.9S22-C4
.3323-34
.9829-04
.3329-C4
.1112-C6
.2^83-25
.115C-C4
.27S3-34
.6176-C4
.5533-34
.6E53-C4
.3553-24
.6553-C4
.5553-24
.S561-C7
1042-CE
.57E4-CE
1793-C4
317C-C4
3?73-C4
3276-04
3^75-04
327E-C4
3275-24
.icoc+ni
•1112-C7
.2087-06
.1174-CE
.4513-05
.65Cf-CE
.7?8G-C5
.6557-C5
.6553-05
.6557-05
.5538-05
300% Excess Air
Species Name Hf
.3LOO+13
.40CO+C3
.6000*03
,70CO*C3
.8000*03
.9CPC*C3
.1000*04
.1100+04
.1200*04
.1500*02
.8462-07
.1535-U5
.8758-05
.2617-04
.4755-04
.4377-L4
.4SEF-P4
.4386-04
.4968-04
.4986-04
,10Uli*D2
.5b4i-LJ7
.1U57-05
.5847-L5
.1821-04
.3214-U4
.332U-U4
.3324-L4
.3324-04
.3324-U4
.3324-U4
5UUO*Ul
.5284-06
./19J7-05
.1U01-G4
.1662-04
.1662-04
.1662-04
.16fc2-04
.1661-04
.1000*01
,5b42-L8
.1057-06
.6082-06
.2617-05
.3312-05
.3324-05
.3324-L5
.3324-05
.3324-U5
.3312-05
System: C-H-N-0-S-Cl-K-Na-F
64
-------
TABLE A2. KF
90% S Removal
10% Excess Air
Species Name KF
TEMP. K
.30011*1)3
.4000+03
.5000+03
.6000+03
.7000+03
.8000+03
.9000+03
.1000+04
.1100+04
.1200+04
150C+02 ATM
.0000
.3319-36
.789h-28
.2380-22
.2590-18
.3191-15
.8018-13
.7287-11
.3270-09
.8099-08
.1000+02 ATM
.COOO
.3118-36
.6452-28
.2026-22
.2510-18
.3184-15
.8173-13
.7661-11
18762-03
.5000+01 ATM
.0000
.2205-36
.4574-23
.1603-22
.2441-13
.3193-15
.8546-13
.8445-11
.4026-03
.9955-08
,1000+01 ATM
.0000
.9881-37
.2091-28
.1259-22
.2412-18
.3324-15
.9973-13
.1116-10
.5560-09
.1288-07
100% Excess Air
Species Name
TEMF. K
.3QCO+C3
.4CCC+C3
.500C+C3
.6CCC+C3
.7COC+C3
.BCCC+C3
.9DCO+C3
.10CT+C4
•11CC+C4
.12CC+C4
KF
.28cE-36
.5931-28
.19C4-Z2
.2432-18
.5126-15
.7595-13
.6333-11
.2531-29
.6CC7-C8
1CCC+C2
.ccco
.4351-23
.1C63-22
.2443-13
.3113-15
.7575-13
.G548-11
.2744-29
.6417-CB
.5CCC+C1
.CGOG
.1654-3E
.3447-28
.1397-22
.2411-18
.3136-15
.7355-13
.E9S9-11
.3CS3-C9
.7153-C8
.10CC+C1
.ocor
.7398-37
.1502-23
.1272-22
.2394-13
.3449-15
.854C-13
.8E4C-11
.4C22-C3
.9C19-C3
300% Excess Air
Species Name
TEMP. K
.3000+03
.4000+03
.5000+03
.6000+03
.7UOU+U3
.8000+03
.9000+03
.1000+04
.1100+04
.1200+04
KF
1500+02
. LOOC
.2041-3fe
.4238-28
.1537-22
.2423-18
.3107-15
.7512-13
.6162-11
.2454-09
,54S8-['S
System: C-H-N-0-S-Cl-K-Na-F
, iuL'O + t 2
. UOOu
. ADC b- 3b
.3472-23
.14UU-22
.24U8-13
.31U3-15
.7582-13
.2584-U3
.5816-06
.5LOU+01
.LJOQQ
.1178-36
.2473-2d
.1277-22
.2395-18
.3108-15
.7742-13
.fa7k,i-ll
.^343-09
.b374-Ua
.1000+01
.OOOb
.5269-37
.1193-28
.1331-22
.2385-18
.3158-15
.8394-13
.8126-11
.3b24-09
.7960-L8
65
-------
TABLE A3. NaF
90Z S Removal
10% Excess Air
Species Name
TEMP. K
.3000*03
.4000+03
.500Q«-03
.6000+03
.7000+03
.80CC+03
.9000+03
.1000+04
.1100+01
.1200+04
NaF
.1500+02 A™
.0000
.0000
.8556-29
.3478-23
.4443-19
.6181-16
.1806-13
.1865-11
.9429-10
.2405-08
PRESSURES
,1000+C2 ATM
.0000
.0000
.6991-29
.2362-23
.4307-19
.6169-lfc
.1842-13
.1982-11
.1Q15-U9
.2602-08
.5000+01 ATM
.0000
.0000
.4956-29
.2348-23
.4189-19
.6194-16
.1925-13
.2185-11
.1161-09
.2956-08
.1000+01 ATM
.0000
.0000
.2265-29
.1840-23
.4138-19
.6440-16
.2246-13
.2886-11
.1603-09
.3826-08
100% Excess Air
Species Name
TEMP. K
.1COC+C3
.4-000+03
.500C+C3
.6000+03
.7CQC+03
.3000+03
.9COC+C3
.1000+04
.11CC+04
.1200+04
NaF
,15CC+':2
.cccc
.DOOC
.E427-29
.2781-23
.4258-19
.EC56-1S
.171D-13
.1540-11
PRESSURES
.1789-C8
.ococ
.ccac
.5256-29
.243C-23
.4192-19
•6C43-1S
.1729-13
.1G34-11
.7913-1C
•1305-23
•5CCO+01
.OCCC
..ccoa
.3735-22
.2CT41-23
.4135-19
.5C56-1S
.1771-1?
.1811-11
.8B17-1C
.2124-08
,1000+01
.OCCC
.0000
.1736-23
.1858-23
.6S81-16
.1946-13
.2235-11
.1160-09
.2679-08
300% Excess Air
Species Name
TEMP. K
.3000+03
.4000+03
.5000+03
.6000+03
.7000+03
.8000+03
.9000+03
.1000+04
.1100+04
.1200+04
NaF
.1500+02
.OUUO
.0000
.4592-29
.2245-23
.4157-19
.6019-16
.1692-13
.1594-11
.7075-10
.1633-08
PSCSSORES
.1UUIJ+02
• CUOL
.uooo
.3762-29
.2045-24
.4131-19
.6011-lb
.1707-13
.1640-11
.7451-10
.1727-08
,5000+01
.0000
.0000
.2686-29
.1866-23
.4108-19
.6022-16
.1743-13
.1739-11
.8212-10
.1893-08
.1000+01
.0000
.0000
.1293-29
.1944-23
.4092-19
.6118-16
.1890-13
.2102-11
.1045-09
.2364-08
System: C-H-N-0-S-Cl-K-Na-F
66
-------
TABLE M. SO F
90% S Removal
10% Excess Air
Species Name
7EKP. K
.30PO+l'3
.4COG+03
.50C'0+[,3
.600G+03
.7000+03
.8000*03
.9000+03
.1000 + 0*4
.110U*U4
.1200+04
, 1500+02 ATM
.6715-04
.8458-04
.7204-04
. 44S2-04
.948C'-05
.4906-Ofa
.2833-07
.2243-08
.2055-Oi
.2440-10
.1000+02 ATM
.5813-04
.5637-04
.4802-04
.2933-04
.4968-G5
.2205-Oe
.1253-07
.3042-03
.7374-10
.9255-11
.5000+01 ATM
.2906-04
.2919-04
.2400-U4
.1402-04
.1514-05
.5503-07
.2872-08
.1860-09
.1506-10
.1791-11
,1000+OlATM
.5813-05
.5641-05
.4790-05
.2104-05
.7301-07
.2C51-U3
.8435-10
.4263-11
.3158-12
.4248-13
100% Excess Air
Species Name
TEMP. K
.3C3C+C3
.4GOC+C3
.50CC+C3
.6CCC+C3
.70C003
.8CCO+CZ
.903C+D3
.1CCC+C4
.110C+C4
,12CC-»G4
P-'ZSSURE:
.49C5-C4
.47?9-C4
.4D53-C4
.24PC-C4
.3763-35
.1EZ4-CE
.1D33-C7
.9417-C9
.12T7-C3
.14CE-1C
1CCC+C2
.3271-C4
.3172-C4
.27^1-24
.1E35-C4
.1375-C5
.7232-C7
.4?H2-C3
.3222-C2
.41C3-10
.5472-11
.5CCC+C1
.1535-04
.1E8E-C4
.1353-C4
.7392-C5
.5379-CS
.1831-C7
-1C74-D8
.8581-1C
.8273-11
.1C99-11
.1CCO+C1
.3271-05
.3173-05
.2S9C-C5
.9E7C-OS
.2390-07
.8271-CS
.35S1-1C
.2252-11
.1912-12
.2741-13
300% Excess Air
Species Name
TEMP. K
.3000+03
.4000*03
.5000+03
.6000+03
.70004-03
.8000*03
.9000*03
. 10UO+CI4
.1100*04
.1200*04
SO.F,
151HJ+L2
.2483-04
.2414-04
.2055-04
.1164-U4
.1153-05
.42bfi-l-7
.2726-L3
.2975-10
.4315-11
,lbtib-U4
.1J7U-04
.7517-L5
.5494-Ub
.1315-L!7
.112U-03
.1U77-US
.1142-10
5UOL+01
.329o-0l3
.ttD46-Ci5
.0842-05
.i478-0b
.4 7fcl-L'6
.2353-0*
.2393-1L-
.2453-11
.3557-12
.1000+01
.1659-05
.1609-05
.1358-L5
.3537-06
.6224-03
.1834-09
.9707-11
.6551-12
.6059-13
.9005-14
System: C-H-N-0-S-Cl-K-Na-F
67
-------
TABLE A5. BeSO,
902 S Removal
10% Excess Air
Species Name
TEMP. K
.JUUO+U3
•100U*03
.bU(JO + U3
.6000*03
.7UUO*OJ
•UOOO+U3
.9000+03
.1000*01
• 1100*01
.1200*01
BeS0
.3916-jl
.3916-ul
.3918-01
.3686-ul
.0000
.0000
.0000
.0000
.0000
.OOuO
Moles
, 1000 + 02 ATM
.3915-01
.3V16-U1
.3917-U1
.0000
.0000
.0000
.0000
.0000
.0000
.0000
.bOOU + 01 A™
.391b-01
.39lb-01
. J917-01
.OOOO
.0000
.OOOu
.OOOu
.0000
.0000
.0000
, 1 U 0 U * u I A™
.3916-ul
,J916-01
. J916-U1
.0000
.OOUO
.0000
.0000
.0000
.0000
.0000
Species Name
TEMP. K
.3000*03
.4000*03
.5000*03
.6000*03
.7000*03
.8000*03
.3000*03
.1000*04
.1100*04
.1200*04
100% Excess Air
BeS04 (s) Moles
,1500*02
.3918-04
.3918-04
.3918-04
.3834-04
.OOUO
.0000
.0000
.0000
.0000
.0000
.1000*02
.3918-04
.3918-04
.3918-04
.0000
.0000
.0000
.0000
.0000
.0000
.0000
.5000*01
.3918-04
.3913-04
.391S-U4
.0000
.bOOU
.UOOQ
.0000
.0000
.UDOU
.0000
.1000*01
.3918-04
.3918-C4
.3919-114
.0000
.0000
.0000
.OOOU
.0000
.OOOU
.0000
300% Excess Air
Species Name BeSO^ (s)
. 7CCO+1 ?
. 3i;uu+i ^
.&i ru+L?
. iuoo*ri"
.nro*i"*
- ^. I -u-
"^ 7 J i -1,
I I t I
t 'j '„ C
[ I '..I
L'UuL
I !. Ml
Moles
; L--+L i.
: - . L - L •
. . L I . I
till
. l."L-
i I Pi.
I '•! t
I I '. L
System: C-H-N-0-S-Cl-K-Na-Be
.LL-Lio
. f I: 01
.LLOU
.(•i.UC
.LoOU
1UOL*01
.38^1-04
.39^1-04
.25C3-04
.L.CL-0
.OCCO
.LULO
.0000
.LOtiO
.DOOO
68
-------
TABLE A6. Be (OH),
90% S Removal
Excess Air
Species Name Be(OH)0
.3UOO*U3
.4000*03
.50C.-0*03
.6UCO*03
. 70DO*li3
.8000*03
.9UPO+1'3
.10CO*G4
.11DO*04
.1200*04
1500*02 ATM
.60f. 8-2U
.1297-12
.3188-06
.2964-05
.1536-04
.153fi-04
.1536-04
.1535-04
.1536-04
.1536-04
.1UOO*C2 ATM
.4477-20
.957U-13
.2354-Oc
.23L1-US
.1024-L4
.1024-04
.10^4-L4
.1024-04
.1U24-04
.1024-04
.5UOO*01 ATM
.2662-2U
.5690-13
.1403-U6
.157U-05
.5121-05
.5120-05
.5113-05
.5119-05
.5119-D5
.5122-05
.10UO*OlATM
.7961-21
.1711-13
.42S4-U9
.9502-05
.11)24-05
.1024-C5
.1024-05
.1024-05
.1024-U5
.1024-05
100% Excess Air
Species Name
TEMP. K
.3CCC+C3
.50COC2
• 6QOOC3
.7CCOC3
.8023*03
.9CCC*C3
.10C3*34
.12C3+C4
Be(OH)2
.15CO*?2
.E547-2C
.1399-12
.862«»-C5
.3S21-C5
.8632-05
. 3S«»3-C5
.3S51-CE
PRESSURES
•1C32-12
.25«»E-C8
.27S3-C5
.E75C-C5
.573C-Q5
.57E6-C5
.5?55-"5
57G5-C5
267Z-2C
6139-13
1E21-C8
2C23-CE
2875-CT
2383-05
3877-CE
2333-25
.1000»01
.8589-21
.1836-13
.«>736-D9
.575C-06
.575C-eg
.600S-OE
.5765-06
.5765-06
.5755-06
.5766-06
300% Excess Air
Species Name Be(OH)2
150t;*l'2
.3000*03
.4000*03
.soro*t3
. 6000*03
.7DPO*03
.8000*03
.90t'0*03
.1000*04
.11PO*04
.1200*04
.5146-2U
.1100-12
.2717-U8
.3159-05
,43t3-D5
.4379-CJ5
.4383-U5
.4384-C5
.4365-05
.4385-05
iUJU + t.2
,37i7-/:ti
.8113-13
.^Uil-hS
.2ob4-uo
.2S23-L5
.2923-U5
.2923-L'S
.292 J-u-5
System: C-H-N-0-S-Cl-K-Na-Be
>5uGU*Ul
.2257-2U
.4327-13
.12L'ci-(J8
.1462-1)3
.1454-U5
.14bl-05
.14fal-C'5
.1462-U5
.1462-05
.1457-05
>10UO*U1
.6754-21
.1444-13
.3S04-L9
.2919-U6
.2922-U6
.2923-06
.2923-U6
.2923-Ub
.2916-06
69
-------
TABLE A7. HgCl,
90% S Removal
10% Excess Air
Species Name
T-MF. K
30CU+L3
10(10+0.5
50Cn*03
601 U+1,'3
70GG+&3
8ULL-HJ3
9DOO+C3
11GL+C1
12UO+OU
HgCl,
,15bU-»-L2 ATM
. 7536-07
. 7b3f.-07
.7535-07
.8D*» 11-07
.7167-07
. 71E1-L7
.7457-07
.1171-08
.3581-OS
TRLSSLPES
,1000-H 2 ATM
.50 90- 07
.5U9L-U7
.5U3U-U7
. «* a 7 a- o 7
.1557-U8
.1238-U9
.Z5H5-U7
.25«*5-U7
.2545-U7
.ZESU-U7
.2183-07
.2333-07
.2795-OS
.1855-10
.1UOD*U1 ATM
.509L-C3
.5090-08
.5U9C-03
.4978-L-3
.U67S-08
.2U25-L.3
.9177-10
.1052-12
100% Excess Air
Species Name
TEMP. K
.3DCC+C2
HgCl,
ECCC+CT
5CCC*C3
7CCC4C?
8CCD*C3
9CCC+C7
.3529-C7
.3532-C7
.I7CC-C7
2Z53-C7
2332-C7
.4237-C7
.ISI't-C?
.22'59-C7
.2«»9r-C8
.2311-09
275C-D7
277C-T7
27oC-:7
2781-07
1C35-C7
933C-C9
733^-lC
5CCC*01
.1177-C7
.119f-C7
.1EC1-C7
.1383-C7
.1387-C7
.1U27-C7
.1283-C7
• 253«t-C3
.1B13-CS
.8872-11
.2911-08
.2955-C3
•298B-C8
.27S3-C3
.278C-C8
.2372-08
.1135-08
.2A77-11
.1*831-13
300% Excess Air
Species Name
TEtfP. K
.3UC-P+03
HgCl,
.5UOD-»L3
.6000*03
.7UCD+C'3
,3000*C3
.9000+CJ3
. 1000*0«»
.11DO*0<(
.1200*0<*
.150U+L2
.251t-.-L7
•251R-07
.251f.-07
.231H-1.7
.251 i-C'7
.2U23-U7
.2P25-L7
.1U23-07
Ib77-07
1H35-U7
1«»S7-U7
1J20-U7
13«*c-L'7
13«fti-U7
2123-1U
System: C-H-N-0-S-Cl-K-Na-Hg
SuOUi-01
.8385-08
.7177-08
.7feSl-U8
.o7<4b-03
.b62b-lO
.2663-11
.lOUQi-01
.152b-08
.1528-08
.1535-U8
.1348-08
.13H8-08
.1350-08
.H89D-U9
.192H-10
.73^2-12
70
-------
90% S Removal
TABLE A8. Hg
10% Excess Air
Species Name
TEMP. K
.30CC+03
.HCCC+03
.5CCC+C3
.60CP+C3
.70CC+03
.8COO+C3
.90CC+C3
.10CC+C4
.11GC+C4
.12CC+C4
PRESSURES
.7369-35
.8925-26
.4162-2C
.6375-16
.9310-13
.26C8-1C
.2133-08
.3575-C7
•7294-C7
.75E9-C7
.1CCC+LI ATM
.7375-35
.2C51-26
.4483-2C
.7473-16
.1128-12
.3188-1C
.2609-08
.3438-07
.5C2C-07
.EC8E-C7
.5CCC+C1 ATM
.7336-35
.93C4-26
.5172-2C
.994C-16
.1575-12
.4488-1C
.3459-08
.2239-C7
.2586-C7
.2576-07
.1CCC+01 ATM
.7«»22-35
.1C14-25
.7837-20
.1671-15
.9778-10
.33««2-Oa
.5197-C8
.5C<»1-C8
.5<»12-08
100% Excess Air
Species Name
TEMP. K
PRESSURE:
.«»DCC+C3
.50DC*C3
.6CCC+C3
.70DC+C3
.8CCC+C3
.9D3C*C3
,1CCO-»C«»
,15DO-»C2
.5038-35
.7122-26
.2335-2:
.327C-16
.1315-1C
.9S51-C3
.1891-C7
.37S8-C7
.4339-07
.1CCC+C2
.SC42-35
.72C1-26
.3C54-2C
.3297-16
.5753-13
.1E79-1C
.12S2-D3
.1S71-C7
.2E22-27
.2939-C7
5COC+C1
.60f9-35
.5111-16
.79E9-13
.2239-1C
.1124-C7
.1303-07
.1156-07
.1CCC*01
.7586-35
.9665-26
.5592-20
.9752-16
.1585-12
.4868-1C
.1701-C8
.2779-08
.2695-08
.2759-08
Species Name
TEMP. K
.30004-03
.4000+03
.5000*03
.6UOO+03
.7000*U3
.8000+03
.9UOO+U3
.1000+04
.1100+04
.1200+04
300% Excess Air
Hg
15LL+U2
.8483-35
.9814-2fa
.3583-20
,34L8-lb
.4743-13
.8141-03
.1397-07
.2095-U7
.2175-D7
.8437-35
.846:1-^6
.3457-2U
.4577-13
.1^-47- IP
.1096-U3
.!Ub3-U7
.1447-U7
.1473-L7
.U495-35
.8621-26
.39U5-20
.7747-13
.174U-1U
.13^3-08
.7D6U-08
.7571-U8
,7384-Ua
.1000+01
.7752-35
.9688-26
.5191-20
.7977-16
.1332-12
.3883-10
.1128-08
.153S-U8
.1525-08
.1404-08
System: C-H-N-0-S-Cl-K-Na-Hg
71
-------
90Z S Removal
Species Name HgO
Tr*r.
.51 f
. oUn
. 71 ( I.-+1 '-
. 3i:ilOt-(.'3
.90CO+C ?
.1200+1, «
TABLE A9. HgO
10% Excess Air
A™
11 - ' — ' 7
I 1 -/". J-^
• i r 5*-- £ •
.i;7:-:-
. 11• i. - A .1
.2771-^1
.Ic2i-u!-
. 2-1 7c-ij -.
i S 3 i. 3 «.
li'tj-Zb
ii.li)-*:!
I753-lc
Ib3b-t:8
lilic-Uc
A™
1121-25
75113-09
Si51-U9
57H9-09
100U*D1ATM
.5*»b5-26
.12^)1-21'
.2682-11
.7797-1U
.bQbO-lU
.5«4U«*-ll-
Species Name
. K
100% Excess Air
HgO :
.30DD*C3
15003*03
I7C02*C3
-8CCOC3
IlCCC*t4
.1852-33
.3C74-IS
".1S24-1E
.1643-13
.2S79-11
.152C-C9
.2271-C8
.3621-C3
.1513-33
.2T38-25
.3237-20
tl534-13
.2323-11
.isi7-:a
.1E3E-C8
.2C57-C8
.131E-T8
.1C71-33
.18I3-2E:
.31T5-2C
.17E3-1E
.155:-13
.2831-11
.1437-09
.7781-C2
.7212-09
.5322-C9
.1COO«C1
.6C09-3«»
.1C77-2E
.15CC-16
.2759-11
.S83B-1C
.S68T-10
.5683-10
Species Name HgO
TEMP. K
.30004-03
,«»OCO-»D3
.5000*03
.6CPP+03
.7000*03
.9000*03
.1100*04
.1200+U4
300% Excess Air
C
.3171-33
.5163-25
,59<27-2U
.1913-13
.2876-11
.1553-03
,20*»2-D8
.2453-08
.2119-08
.2581-i.i
.1535-13
.27^'4-ii
.1713-Ui
.1.533-U3
.1174-L8
System: C-H-N-0-S-Cl-K-Na-Hg
5UOL+U1
.183<4-33
..S624-2U
.1752-16
.1836-14
.Z6£b-ll
,5974-Oa
.5114-09
1000*U1
.7<485-31
.2154-20
.1495-lb
.1412-13
.2681-11
.5570-10
.580i)-llJ
.4611-10
.J524-10
72
-------
90% S Removal
Species Name
TEMP. K
.3CCC*C3
.1CCC*03
.5CCC*C3
.sncc+03
.7CCC*C3
.8CCC*03
.9CCC*C3
.100C*0«I
.1200*01
TABLE A10. Hg
10% Excess Air
PRESSURE:
I5oc+r2 ATM
.cccc
• OOCC
.cccc
.3675-31
.EC93-28
.2371-23
.1177-19
.3316-17
.1161-16
.1072-16
.1COO+C2 A™
.CCCC
.OOOC
.CCCC
.5C5C-31
.7179-28
.1293-23
.221C-19
.3C91-17
.5513-17
.1853-17
.5CCC*G1 ATM
.CCCC
.ccoc
.cccc
.8935-31
.1159-27
.85C5-23
.3885-19
.1313-17
.1163-17
.1215-17
.10CC-»C1
.cccc
.ccoc
.ccoc
.2525-33
.6975-27
-4C22-22
.3E27-19
.7073-19
.5558-19
.5*97-19
ATM
Species Name
100% Excess Air
.3CCC+CI
.1000+C3
.600C+D3
.70CC*C3
.8DDD*C3
.9CCC+C3
.1000*01
.11CC+C1
.120D+C1
.cere
.0000
.core
- 9135-35
.11C6-28
.7237-21
.3C17-2C
.9331-18
.31C7-17
.3533-17
.cccc
• OCDC
.cccc
.1115-31
.1S1S-28
.1C53-23
.517C-20
.7329-18
.1501-17
.1521-17
.5C3OC1
.CCCC
.cocc
.cccc
.2353-31
.3732-28
.2113-23
.87I7-2C
.3307-18
.3697-18
.2505-18
,1QOO«-C1
.COCC
.CCDO
.OCCC
.86C1-31
.1669-27
.10C1-22
.9398-2C
.2C22-13
.1589-19
.1128-19
300% Excess Air
Species Name
TEMP. K
.3000*03
.1000*03
.5000*03
.6000*03
.7000*03
.8000*03
.9000*03
.1000*01
.1100*01
.1200*01
Hg,
.1500+C2
. DOOC
.0000
.0000
.1050-31
.1322-28
.1386-21
.2152-20
.5111-18
.9600-18
.8913-18
. UUUU
.UOUQ
.UCGC
.9339-35
.1231-28
.6570-21
.3S03-2C
.2961-18
.1579-18
.1105-13
500U+01
.UUUU
.UOOO
.UOCU
.1580-31
.3525-28
.1278-23
.6355-20
.1312-18
.1251-18
.1023-13
.1000*01
.OOOC
.0000
.0000
.5755-31
.1012-27
.6368-23
.1128-20
.6201-20
.5087-20
.3638-20
System: C-H-N-0-S-Cl-K-Na-Hg
73
-------
TABLE All. HgCl
90% S Removal
10% Excess Air
Species Name HgCl
TZun- K
TRESSLPES
.30CC*U3
.4ULC. + L>3
.5000+03
.7000+03
.8liUD+03
.9000+1)3
.1000+0"*
. 1100*0-4
.1200*0'*
. 15L-L+U2 ATM
.0000
. fa445-31
.3084-25
.12E9-ZL.
.1446-17
.3151-15
.2087-13
.2935-12
.5165-12
1CUU + II2
.OOUO
.6544-31
.635U-25
.1122-^C.
.130U-17
.2845-15
.1385-13
.2086-12
.2517-12
.2182-12
ATM
,5bOb+Ul ATM .1000+01 ATM
.0000 .QUQL
.4978-31 .2324-31
.5202-25 .2864-25
.!sl5u-21 .4813-21
.1086-17 .7179-18
.2387-15 .1557-15
.1487-13 .4302-14
.8P78-13 .5593-14
.7353-13 .4303-14
.60LS-13 .2074-14
100% Excess Air
Species Name
TEMP. K
.3CCCI+C3
HgCl
PRESSURES
5CCS+C3
6CCC*CI
7D30*D3
8CCC+C3
900D+C3
1CDC+C4
113C+C4
12CC+C4
.4585-25
.B2I1-21
.7341-13
.1624-15
.1313-13
.1E7E-12
.2353-12
.1CCC + C2
.CCDD
.4237-71
.3942-25
.5388-21
.5925-18
.1437-15
.9737-14
.1C31-12
.1453-12
.1323-12
.5CCC+C1
• CCC3
•IC31-31
I47C8-21
.5715-13
.127E-15
.7535-14
.4354-13
.4287-13
.2784-13
.10CC+C1
-ODOC
.1729-31
.1854-25
.291C-21
.3754-18
.844^-15
.2358-14
.321E-14
.2419-14
.1CC9-14
System: C-H-N-0-S-Cl-K-Na-Hg
74
-------
TABLE A12. PbCl,
90% S Removal
Species Name
TEMP. K
.30CO-«-03
.40Lt,*£)3
.50CO*03
. 7000*03
.80&OG3
.9000+03
.HCiO*U4
.1200*04
10% Excess Air
PbCl,
.1500+l> 2 A™
.1581-014
.1581-04
.1581-04
.1581-04
.1580-0'*
.158C-04
.1580-04
.1580-04
.1581-04
.1575-04
PRESSURES
100U+G2 ATM
.1054-04
.1U54-C4
.1U54-04
.1U54-U4
.1U54-04
.1053-L4
.1053-04
.1U54-U4
.1054-04
.1U47-Q4
5LOL*01 ATM
.5270-05
.b270-05
.5269-05
.527LJ-05
.5266-05
.526b-05
.5263-05
.52b9-05
.5143-05
.1000*01 ATM
.105<»-U5
.1U54-U5
.1054-U5
.1U53-U5
.1054-U5
.1U54-05
.1U54-U5
.1054-05
.1019-05
.3294-06
Species Name
TEMP. K
,3DOD*C3
.HOGC+C2
.50DC3*C3
.6CCC+C2
.7QOC*C3
.80CC*C3
.9000+G3
.ICCO + C'J
.11DC*C'»
100% Excess Air
A G
3837-05
8897-CE
3337-C5
889C-CE
3392-C5
889Z-C5
3393-C5
8897-C5
3897-C5
8867-CE
PRESSURES
.1CCC+C2
.5931-05
.5931-CE
.5931-r£
.593C-C5
.5923-35
.5928-CE
.5932-25
.5932-C5
.5931-D5
.5334-C5
.ECOC+C1
.29S6-C5
.2966-CE
.2955-CE
.29FE-CE
.2964-35
.22C4-CE
.2956-CE
.29B6-CE
.29G5-C5
.2892-C5
.1CCO*C1
.5931-06
.5931-06
.5930-06
.5928-06
.5928-06
.5933-06
.5931-06
.5931-06
.5909-06
.1122-06
300% Excess Air
Species Name
TEMP. K
.3000*03
.4000+C3
.50004-03
.6000*03
.7000*03
.8QGO*C3
.9000*03
.1000*04
.1100*04
.12DO+DU
PbCl,
.15CO+C2
.4511-05
.4511-05
.4511-05
.4512-05
.4513-05
.4510-05
.4510-05
.4511-L5
.4511-05
.4489-05
.3UU7-U5
,3UUb-Ub
.JU1.3-U5
.3UU7-U5
.JUUb-GS
,3UOo-L5
.3UL7-U5
.3UU7-L5
.30U7-05
.2a7b-05
.5uOL*lil
.15U4-05
.15U3-05
.1504-05
.1503-05
.1504-05
.15U3-U5
.150.1-05
.15U4-U5
.1504-05
.1411-05
.10UO*01
.3008-06
.3QC8-U&
.3008-06
.3006-06
.3006-06
.3006-06
.3007-06
.30U7-06
.2986-06
.5894-08
System: C-H-N-0-S-Cl-K-Na-Pb
75
-------
TABLE A13. PbCl.,
90% S Removal
10% Excess Air
Species Name
TEMF. K
.30PC*D3
.4000*03
.50DO+03
.6000*03
.7000*03
.8000*03
.9000*03
.1000*04
,1100*U4
.1200*04
PbCl,
,1500*02 ATM
.DODO
.0000
.8987-33
.1130-25
.2173-2L
.2204-16
.2854-13
.8971-11
.9779-09
.5235-07
PRESSURES
.1000+02 ATM
. LUOU
.0000
.S68U-33
.1324-25
.2632-20
.2691-16
.3539-13
.1099-10
.1203-08
.6767-07
5UOO*01 ATM
.0000
.0000
.1117-32
•1762-2b
.3676-20
.3787-16
.5000-13
.1553-10
.1726-U8
.1125-06
,1000*OlATM
.0000
.0000
.1692-32
.3594-25
.8U45-2U
.8425-16
.1115-12
.3492-10
.4464-08
.2669-06
100% Excess Air
Species Name
TEMP. K
.JOCC+CJ
.»OOD*C3
.5CCO*C3
.6000*C3
,70CC*C3
.8003*03
.1000*04
.11CP+C4
.1230*C4
PbCl,
,15CO+~2
.cccc
PRESSURES
.72IE-33
.5757-25
.1115-2C
.1C87-15
.14C9-13
.4355-11
.47EE-C9
.2522-C7
.CDCC
.OCDD
.7E34-33
.7740-26
.1360-2C
.1343-16
.1726-13
.5341-11
,5869-CS
.3439-C7
OCCC
.8469-33
.9833-25
.1878-2C
.1354-16
.2473-13
.7549-11
.8459-C9
.5932-07
.1000*01
.OCOC
.OCCC
.1157-32
.1886-25
.3963-2C
•VD13-16
.5%15-13
.1700-10
.227B-C8
.9984-07
Species Name
TEMP. K
.3000*03
.4000*03
.5000*03
.6000*03
,70PO*03
.8000*03
.9000*03
.1000*04
.1100*04
.1200*04
300% Excess Air
PbCl2 G
,1500*02
. OOCC
.OOCC
.6897-33
.5989-26
.9411-21
.9567-17
.1,163-13
.3588-11
.5950-09
.2373-07
PRESSURES
10UO+C2
.LULL
.0000
.7243-33
.6752-26
.1126-211
.141S-J.3
.3257-U7
5UOO*01
.UUUU
• UOOU
.7964-33
.8573-26
.1537-20
• 154o-le
.1958-13
.6208-11
.7162-09
.ol5U-D7
.1000*01
.0000
.QQOU
.1061-32
.1603-25
.3275-20
.3451-16
.4446-13
.1408-10
.2190-08
.1790-07
System: C-H-N-0-S-Cl-K-Na-Pb
76
-------
90% S Removal
TABLE A14. PbO
10% Excess Air
Species Name PbO
TZ».r ,
.3UUU-K 3
.1UOU+C3
. 7Ul'l'+C3
.aucc+L-3
.12GO*U1
, 15QL+C2 ATM
luouo
Icutiu
.1076-3U
.1263-24
.7733-15
.182$;-11
.1376-08
. lUULi + L^ ATM
. uUL'U
. LULU
. UL'L'l'
.7757-2-t
, 5UUU*01 ATM
. uObU
.UOUU
. bt;Ub
.LiUULi
.533ci-3U
.2185-23
.31162-18
,1000+Ui ATM
.ODOb
.0000
.UUUL
.9033-38
.5712-29
.2117-22
-3H31-17
.1572-13
100% Excess Air
Species Name PbO
TEMP. K
.3ccc-»cr
.103C+C2
.5DCC+C3
.602D*C3
•7CCD+C?
•9CCC+C3
,1000*21
.11CC+C1
,1200+CI
.CCCC
.C23C
.CCCC
.cccr
.1C17-3C
.331G-21
.5191-15
.57S2-1E
.1591-11
.1255-C8
.CCCC
.CC2C
r f r r
• «j L •- L
««p,— r-
* u L w w
.1S91-3C
.7123-71
.2TZC-1S
.1Z1^-11
.226C-11
.CCCC
.OCCD
.cere
.OCC2
.5111-2C
.1322-23
.2E77-18
.35C3-11
.8697-11
.1117-C7
.icoa*ci
.CCCC
.accc
.CCCC
.3129-33
.5C9C-Z3
.2C11-22
.2965-17
.3971-13
.1113-C3
.3716-OB
.300D+P3
.1000*03
.50PO+U3
.6000+03
.70rO+t)3
.80004-03
1000*01
11DLI+D1
1200*01
300% Excess Air
Species Name PbO
15UL-HJ2
.UOuG
.Ut'L.t
. CDUl;
.1779-31.
.8153-19
.1033-11
.2E32-11
System: C-H-N-0-S-Cl-K-Na-Pb
LUul.
LiUUU
l.'Ul.U
3l2u-
1S.JB-.L1
57S1-US
SUULi+Ul
. LDUU
.uUUG
.ul'LU
.UUUO
.3212-2J
.1311-13
.J07a-07
.lOUD-HJl
.LOUU
.OQOU
.OUL'L
.1535-37
.8351-29
.3576-22
.1808-17
.6519-13
.3155-U9
.2717-06
77
-------
TABLE A15. PbCl
90% S Removal
Species Name
TEMP. K
.3UOO*U3
.40LO+C3
.50UO*G3
.7UGC*&3
.90GC*G3
.10t'U+04
.1100*04
10% Excess Air
PbCl G
• 150L+L2 ATM
.0000
.UCLD
.0000
.tlUl'ti
.1359-22
.1441-23
.7109-13
.4U1F-15
.4721-12
.1911-09
iObb+L2 ATM
.OODu
. JjUUO
.QuCU
.UUUb
.2218-^d
.2361-^:3
.1173-18
.66b*»-l5
.7887-12
.344fc-US
.5bLU+Ul ATM
.UOUU
.UOUU
.bOOU
.5224-37
.517 J— 2 y
.5623-23
.2796-la
.1585-14
Il053-0fi
.10UU+U1 ATM
.OUCU
.0000
.OOOC
.34U5-36
.3748-23
.4171-22
.2083-17
.1194-13
.1788-1U
.1521-U7
100% Excess Air
Species Name
TEKP. K
.303C*D3
PbCl
PRESSURE.
70SO*C3
.8CCC+C3
.90DC*C3
*1CCOC<»
.iion*c«»
.12CC+C4
.2CCC
.cccc
.CDCZ
.rccc
.B59C-3D
.EEFS-24
.3221-19
.181£-I5
.2141-12
.SD2E-1C
.CCCC
r* r -^ r>
» W h_ k* W
.cccc
.ir-aa-29
.1119-23
.5344-13
.3C11-15
.3534-12
.1C63-T9
5CCC+C1
.CCD2
.CCCC
.cccc
.252C-29
.2E66-23
.12GS-18
.7155-15
.377^-12
.E379-C9
.1CCC+C1
.DCCC
.cccr
• ccor
.172E-3C
.1723-23
.1827-22
.9392-13
.54CE-14
.3672-11
•59E7-CE
300% Excess Air
Species Name PbCl
TEMP. K
.3000*03
.40TD+D3
.5000*03
.6000+U3
.7000*03
.8000-»03
.9000*03
.10LD+04
.1100*04
.1200+04
15LL*t2
.OOUC
.cr.tr
.uoun
.urn
.191 1-15
System: C-H-N-0-S-Cl-K-Na-Pb
PRESSURES
.UOUU
.UuOU
. LiUUO
.118L-23
.5596-19
.3152-15
.3827-12
.2157-05
.UOUO
.L/UtU
.UUOU
.3324-37
.1322-18
.74Ss«»-15
.bl26-Q9
.10UO+U1
.OOOL
.OUPL
.QUOU
,1898-ifc
.1822-28
.2U47-22
.9814-13
.5722-14
.1151-10
78
-------
APPENDIX B
PARTIAL PRESSURES OF GASEOUS TRACE COMPOUNDS
PRODUCED AT 1200 K FOR HIGH COAL-HIGH
DOLOMITE AND MEAN COAL-LOW DOLOMITE
SYSTEMS OPERATING AT 100 PERCENT EXCESS
AIR WITH 90 PERCENT SULFUR REMOVAL
79
-------
TABLE Bl. FLUORINE COMPOUNDS
100 Percent Excess Air - 90 Percent Sulfur Removal - 1200 K
Trace
Compounds
HF
KF
NaF
HF
KF
NaF
Higji Coal - Higi Dolomite
15 atm
0.9829-04
0.6007-08
0.1784-08
10 atm
0.6553-04
0.6417-08
0.1906-08
5 atm
0.3275-04
0.7153-08
0.2124-08
1 atm
0.6538-05
0.9019-08
0.2679-08
Mean Coal - Low Dolomite
15 atm
0.7394-04
0.3724-08
0.1106-08
10 atm
0.4929-04
0.4013-08
0.1192-08
5 atm
0.2464-04
0.4580-08
0.1360-08
1 atm
0.4919-05
0.6253-08
0.1857-08
System: C-H-N-0-S-Cl-K-Na-F
80
-------
TABLE B2. BERYLLIUM COMPOUNDS
100 Percent Excess Air - 90 Percent Sulfur Removal - 1200 K
High Coal - High Dolomite
Trace
Compounds
BeS04(s)
Be (OH) 2
BeSO^s)
Be(OH)2
15 atm
0.8651-05
10 atm
0.5768-05
5 atm
0.2883-05
1 atm
0.5766-06
Mean Coal - Low Dolomite
15 atm
0.6647-05
10 atm
0.4428-05
5 atm
0.2214-05
1 atm
0.4430-06
Sys tem: C-H-N-0-S-Cl-K-Na-Be
81
-------
TABLE B3. MERCURY COMPOUNDS
100 Percent Excess Air - 90 Percent Sulfur Removal - 1200 K
High Coal - High Dolomite
Trace
Compound
Hg
HgO
HgCl2
Hg
HgO
HgCl2
15 atm
0.7559-07
0.3461-08
0.2311-09
10 atm
0.5085-07
0.1915-08
0.7934-10
5 atm
0.2576-07
0.5322-09
0.8872-11
1 atm
0.5412-08
0.5683-10
0.4881-13
Mean Coal - Low Dolomite
15 atm
0.2652-07
0.2115-08
0.2711-10
10 atm
0.1338-07
0.8714-09
0.7006-11
5 atm
0.6811-08
0.3138-09
0.1043-11
1 atm
0.1827-08
0.3763-10
0.6750-14
System: C-H-N-0-S-Cl-K-Na-Hg
82
-------
TABLE B4. LEAD COMPOUNDS
100 Percent Excess Air - 90 Percent Sulfur Removal - 1200 K
Trace
Compound
PbCl4
PbCl2
PbCl
PbO
PbCl4
PbCL2
PbCl
PbO
High Coal - High Dolomite
15 atm
0.8867-05
0.2622-07
0.9026-10
0.1265-08
10 atm
0.5894-05
0.3439-07
0.1663-09
0.2675-08
5 atm
0.2892-05
0.5932-07
0.5379-09
0.1147-07
1 atm
0.1122-06
0.9984-07
0.5963-08
0.3746-06
Mean Coal - Low Dolomite
15 atm
0.4183-05
0.6445-07
0.5064-09
0.1621-07
10 atm
0.2715-05
0.8165-07
0.8965-09
0.3273-07
5 atm
0.1177-05
0.2766-06
0.2456-08
0.1172-06
1 atm
0.3432-08
0.1463-07
0.1912-08
0.2629-06
System: C-H-N-0-S-Cl-K-Na-Pb
83
-------
APPENDIX C I
THERMOCHEMICAL PROPERTIES OF FLUID-BED
COMBUSTION GASES CONTAINING TRACE
COMPOUNDS
85
-------
TABLE Cl. THERMOCHEMICAL PROPERTIES OF FLUID-BED COMBUSTION
GASES CONTAINING TRACE COMPOUNDS
HIGH COAL-HIGH DOLOMITE 108 EXCESS
AIK / 908 S REMOVAL
H/RT
300.0 DEGK
500.0 DEGK
700.0 OEGK
900.0 OEGK
1000.0 DEGK
1100.0 OEGK
1200.0 DEGK
15.0 ATM
-.316073+02
-.174394*02
-.112993*02
-.784564*01
•.6623634-01
-.b61709*Ul
•.177252*01
10.0 ATM
-.316073*02
-. 174393*02
-.112989*02
-,784bS4*01
-.662371*01
-.561703*01
-.•477266*01
b.O ATM
•.316073*02 •
-.174391*02 •
-.112984*02 •
-.784534*01
••6623bO*01
-.561696*01
-.477317*01
1.0 ATM
.316073*02
.174386*02
.1 12979*02
.784482*01
.662312*01
.561731*01
.477595*01
G - KCAL/MOL»OEG K
300.0 DtCiK
500.0 DEGK
700.0 OEGK
900.0 OEGK
1000.0 OEGK
1100.0 DiGK
1200.0 DEGK
15. U ATM
.132668*09
.170278*09
.210544*09
.252807*09
.274561*09
.296683*09
.319151*09
10.0 ATM
-.133679*09
-. 171964*09
-.212901*09
-.255841*09
-.2/7932*09
-.300391*09
-.323199*09
5.0 ATM
-. 135408*09
-. 174845*09
-.216932*09
-.261027*09
-.283693*09
-.306730-*09
-.330124*09
1*0 ATM
•. 139*J23*09
•,18153H*09
-.226295*09
•.273067*09
•.297072*09
•,321tS7*09
>.3<46230*09
SPECIFIC ENTROPY-JOULES/KG
300.0 OEGK
500.0 OEGK
700.0 DEGK
900.0 DEGK
1000.0 DtGK
1100.0 OtGK
1200.0 DEGK
lb.0 ATM
.596808+OH
.65U505*0
-------
TABLE Cl. (Cont'd)
HIGH COAL-HIGH DOLOMITE 10« EXCESS
AIK / 90S S REMOVAL
COMPRESSIBILITY FACTOR
30U.O DLGK
SOO.O DLGK
700.0 DEGK
900.0 DEGK
1000.0 DEGK
1100.0 DE&K
1200.0 DLGK
15.U ATM
.382719*02
.382731*02
.382783*02
.382809*02
.382818*02
.382826*02
.382838*02
10.0 ATM
.382719*02
.302732*02
.3827b8*U2
.382810*02
.3d2819*02
.382827*02
.382839*02
5.0 ATM
.382719*02
.382734*02
.382796*02
.382812*02
.382822*02
.382830*02
.382849*02
1.0 ATM
.382720*02
.382738*02
.382802*02
.382818*U2
.382828*02
.382841*02
.382898*02
DENSITY-KG/MS
300.0 DE6K
500.0 DLGK
700.U DLGK
900.0 OEGK
1QOO.O DE&K
1100.0 DLGK
1200.0 DEGK
1S.O ATM
.183177*02
.109903*02
.784918*01
.610451*01
.549393*01
.499439*01
.457822*01
10.0 ATM
.122118*02
.732685*01
.523272*01
.406966*01
.366260*01
.332959*01
,3Ub2l7*01
5.0 ATM
.610591*01
.366341*01
.261631*01
.203402*01
.183129*01
.166479*01
.Ib26l3*01
1*0 ATM
.122118*01
.732673*UU
.523253*00
.406957*00
.366253*00
.332965*00
.305273*00
CP-JOUL£/K
-------
TABLE Cl. (Cont'd)
HIGH COAL-HIGH DOLOMITE 10* EXCESS
A1K / 90* S tVtMOVAL
MOL•*T.-KG/MOLE
300.0 DEGK
500.0 OEGK
700.0 DtGK
9UO.O Dt6K
1UOO.O DEGK
1100.0 DEfaK
1200.0 DtGK
1S.O ATM
. 3006184-02
.300609+U2
.300569+02
.300519+02
.300512+02
.300537+02
.300538*02
10.0 ATM
.300618+02
.3006084-02
.300565+02
.300518+02
.3U0511+02
.300536+02
.300511+02
5.0 ATM
.300618+02
.300607+02
.300560+02
.300516+02
.300539+02
.300535+02
.300550+02
1.0 ATM
.300618+02
.3006034-02
.300551+02
. 300512 + 02
.300535+02
.300511+02
.3005964-02
TOTAL MOLtS
300.0 DEGK
500.0 OEGK
700.0 DLGK
900.0 DtGK
1000.0 DEGK
1100.0 OEGK
1200.0 DEGK
Ib.O ATM
.362719+02
.382731+02
.382783+02
.382809+02
.382818+02
.382826+02
.382835+02
10.0 ATM
.382719+02
.362732+02
.382788+02
.3(42810 + 02
.382819+02
•3d2827+02
.382839+02
5.0 ATM
.382719+02
.382731+02
.382795+02
.382812+02
.382822+02
.382830+02
.382819+02
1.0 ATM
.382720+02
.3827384-02
.382802+02
.382818+02
.382828+02
.382811+02
.382898+02
MASS-KG
300*0 DEGK
500.0 DtGK
700.0 DtGK
900.0 DEGK
1000.0 DEGK
1100.0 DtGK
1200.0 DtGK
5.0 ATM
150524-01
15052+01
15053+01
15053+01
15053+Ul
15053+Ul
15057+01
10.0 ATM
15052+01
15052+01
15053+01
15053+01
15053+01
15053+01
15059+01
5.0 ATM
1 15052 + 01
1 15052+01
1 15053+01
1 15053+01
115053+01
1 15051+01
115065+01
1.0 ATM
15052+01
15052*01
15053+01
I50b3+0l
15053+01
15060+Ul
15098+01
fLOX-AATTS/CM2.ATM
300.0 UEGK
500.0 DtGK
700.0 DEGK
900.0 DEGK
1000.0 DtGK
1100.0 OtGK
1200.0 DtGK
15.0 ATM
>.10U101+06
•.761 158 + 05
-.578157+05
-.152168 + 05
•.101518+05
-.356278 + 05
•.315160+05
10.0 ATM
-.108105+06
-.761119+05
-.576162+05
-.152158+05
-.101515+05
-.356266+05
-.315169+05
5.0 ATM
••108105 + 06
••761135+05
-.578185+05
••152110+05
••101511+05 •
••356267+05
•.315197+05
1.0 ATM
.108101+06
.761081+05
.578510+05
.152105+05
.101536+05
.356291+05
.315635+05
88
-------
TABLE Cl. (Cont'd)
HIGH COAL-HIGH OOLOMITE 108 EXCESS
A1K / 90S S KEMOVAL
GAMMA
300.0 DEGK
bOO.O DEGK
700.0 DEGK
900.0 DEGK
1000.0 DtGK
1100.0 DtGK
1200.0 DEGK
15.0 ATM
137259*01
134107*01
131771+01
130055+01
129329*01
128705*01
128130*01
1U.O ATM
1372b9*01
134105*01
131781*01
130052*01
129332*01
128699*01
128130*01
5.0 ATM
137261*01
134103*01
131801*01
130018*01
129337*01
128702*01
128129*01
l.U ATM
137257*U1
13<«091*01
131823*U1
1300H3*U1
1293*47*U1
12B706+U1
128111*U1
ACOUSTIC VtLOClTY-M/SEC
300.0 DEGK
SOO.O DEGK
700.0 DEGK
900.0 DEGK
1000.0 DEbK
1100.0 DEGK
1200.0 DEGK
15.0 ATM
.337472*03
.430651*U3
.505129*03
.569039*03
.598151*03
.625836*03
.652199*03
10.0 ATM
.337473*03
.430648*03
.505151*03
.569034*03
.598158*03
.625823*03
•6b2197*Q3
5.0 ATM
.337475*03
.430645*03
.505193*03
.569026*03
.598171*03
.625831*03
.652185*03
1.0 ATM
.337471*03
.430629*03
.505240*03
.569020*03
.598198*03
.625833*03
.652091*03
89
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-78-050
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE Evaluation Qj ^^ Element
from Fluidized-bed Combustion Systems
5. REPORT DATE
March 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
M.A.Alvin, E. P. O'Neill, L.N.Yannopoulos , and
D. L. Keairns
8. 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.
EHE623A
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. TYPE OF REPORT AND PERIOD COVERED
Final; 12/75-1/77
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES jjERL-RTP project officer is D
919/541-2825. EPA-650/2-75-027c is the previous
.Bruce Henschel, Mail Drop^l,
report relating to this work.
16. ABSTRACT
The report gives results of an investigation of four trace elements: lead,
beryllium, mercury, and fluorine. The chemical fate of minor and trace elements
is important in assessing the environmental impact of the fluidized-bed combustion
(FBC) process and, for certain elements, in determining the potential for deposits
or corrosion in process equipment. Equilibrium product distributions for these
elements, at operating conditions corresponding to atmospheric and pressurized
FBC systems, are projected on the basis of thermodynamic calculations. Results
show which elements are likely to be volatilized in the high-temperature zone of the
combustor and which are likely to condense on cooling the gases. The projections
are compared with available experimental plant data. Alternatives for continuously
monitoring the release of the four toxic trace elements in the laboratory were also
investigated. The thermodynamic analysis shows that essentially all the lead, mer-
cury, fluorine, and beryllium can be volatilized in the FB combustor. Partial
beryllium and fluorine condensation in the form of clay and alkali compounds will
occur. Lead condensation is affected by the chlorine available. These thermodynamic
projections provide a basis for experimental and monitoring studies. Initial plant
data generally confirm the projections.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Chemical Analysis
Coal
Combustion
Fluidizing
Lead
Beryllium
Mercury
Fluorine
Thermodynamics
Pollution Control
Stationary Sources
Trace Elements
Fluidized-bed Combus-
tion
13B
07D
21D
21B
07A,13H
07B
20M
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report]
Unclassified
21. NO. OF PAGES
105
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
90
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