RESEARCH REPORT
INVESTIGATION OF THE REACTIVITY OF
LIMESTONE AND DOLOMITE FOR
CAPTURING SO2 FROM FLUE GAS
to
NATIONAL AIR POLLUTION
CONTROL ADMINISTRATION
June 27, 1969
BATTELLE MEMORIAL INSTITUTE
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SUMMARY REPORT
on
INVESTIGATION OF THE REACTIVITY OF
LIMESTONE AND DOLOMITE FOR
CAPTURING SO2 FROM FLUE GAS
to
NATIONAL AIR POLLUTION
CONTROL ADMINISTRATION
June 27, 1969
by
R. W. Coutant, B. Campbell, R. E. Barrett,
and E. H. Lougher
Contract No. PH 86-67-115
BATTELLE MEMORIAL INSTITUTE
Columbus Laboratories
505 King Avenue
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TABLE OF CONTENTS
Page
INTRODUCTION 1
SUMMARY 1
Experimental Results 1
Conclusions and Recommendations 2
EXPERIMENTAL DETAILS 3
Materials Preparation and Analysis 3
Particle Sizing 3
Calcination and Hydration 4
Chemical Analyses 4
Results and Discussion 6
General Characteristics of SO2 Reaction 6
Effect of SOz Concentration 9
Effect of Particle Size 11
Effect of Chemical State of Stone 15
Effect of Temperature 15
Recommended Future Work 20
APPENDIX A
DISPERSED-PHASE REACTOR A-l
APPENDIX B
SPECTROCHEMICAL ANALYSIS OF STONES B-l
APPENDIX C
REACTOR DATA C-l
APPENDDC D
TREATMENT OF DATA D-l
APPENDIX E
TEMPERATURE DEPENDENCE OF RATE DATA E-l
APPENDIX F
INVESTIGATION OF TVA STONES F-l
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INVESTIGATION OF THE REACTIVITY OF LIMESTONE AND
DOLOMITE FOR CAPTURING SO2 FROM FLUE GAS
to
NATIONAL AIR POLLUTION CONTROL ADMINISTRATION
by
R. W. Coutant, B. Campbell, R. E. Barrett,
and E. H. Lougher
INTRODUCTION
This investigation, conducted under Contract No. PH 86-67-115, is concerned with
some of the fundamental aspects of the reactivity of limestones and dolomites with SO2-
Work done under the first segment of this program has been reported in the Summary
Report* dated August 30, 1968. The purpose of the current work was to extend the mea-
surements of the rate of reaction of several lime stone-based materials with SO2 under
varied conditions of SO2 concentration, temperature, particle size, and solid composi-
tion so as to develop further understanding of the nature of physicochemical processes
that are important to utilization of limestone as an agent for SO2 removal from flue gas.
This Summary Report covers work done on the program during the period July 1, 1968,
through February 28, 1969.
SUMMARY
Experimental Results
The reaction of SO2 with limestones, dolomites, and limes was studied under sim-
ulated boiler conditions with the dispersed-phase reactor.** This reactor provides for
injection of limes or stones into a flue-gas stream. As in the case of injection into a
power boiler, the particles are dispersed in the gas; also, as in a boiler, the samples
are near room temperature when injected, and must heat up (and calcine in the case of
raw stones) before reacting with the SO2 present. Conditions differ from those in a
boiler in that the walls are kept hot to maintain relatively constant gas temperature, and
the samples are small compared with the amount of gas so that the SO2 level remains
essentially constant.
For the experiments conducted, gas temperatures were between 1300 and 2100°F
and residence times were from 0. 1 to 0. 5 seconds at 2100°F and from 0. 4 to 2. 1 seconds
at the lowest temperature. The highest calcium utilization observed under the conditions
employed was about 27 percent. In general, the reaction with raw stones is
"Summary Report on "Investigation of the Reactivity of Limestone and Dolomite for Capturing SC>2 From Flue Gas", to National
Air Pollution Control Administration, August 30, 1968.
""See Appendix A for description.
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characterized by incomplete calcination within all but the longest residence times at the
highest temperatures when -140 + 200 U. S. Standard mesh stone is used. Concurrent
with the calcination process is the formation of calcium sulfite and calcium sulfate. It
was found that sulfite is the predominant form of sulfur at short residence times and that
the fraction of sulfur present as sulfite can be correlated with the degree of calcination.
A study of the effect of particle size on the apparent rate of reaction at 1900°F and
0. 5 second for two limestones, Nos. 1683 and 1373*, and two dolomites, No. 1337 and
Basic Chemicals, Inc. , dolomite, suggested an inverse relationship between size and
reactivity as average particle size was varied from 130 to about 50 microns. With
smaller particles (down to 5 to 10 microns), the results were somewhat erratic, but no
significant further increase in reactivity was apparent. This trend can be explained at
least partly on the basis of the rate of heatup of the particles and the nature of the initial
chemical reactions.
Investigation of the effect of SC>2 concentration on the apparent reaction rate of
No. 1359 and the Basic Chemicals dolomite at 2000°F and 0. 12 second showed reactivity
increasing with concentration up to about 0. 1-0. 2 volume percent SC>2 but no significant
increase in reactivity at higher concentrations. It is believed that this observation can
also be explained in terms of transport processes.
The current results suggest that the hydrated limes may have a peak reactivity in
the neighborhood of 2000°F. For No. 1337, a dolomite, the dihydrate is the most reac-
tive form in the temperature range studied, with the order of reactivity being dihy-
drate > raw stone > monohydrate > burnt lime. For No. 1359, a high-purity limestone,
the order of reactivity is raw stone > hydrate > burnt lime.
Apparent activation energies for SC>2 reaction, obtained from Arrhenius plots of
the data, ranged from about 11 to about 28 kcal/mole for the various stones and burnt
limes studied. ** Because of the complexity of the reaction process, and because gas
temperatures rather than the unknown reaction temperatures are used in the Arrhenius
plots, the activation-energy values obtained should not be considered as indicative of
any specific chemical or physical processes, but rather as overall trends in the data.
Conclusions and Recommendations
The overall reaction between raw stones and SC>2 in the reactor follows a complex
path, the nature of which is due in part to the slow heatup of stone particles as a result
of the thermal requirements for calcining the stone. Sulfite formation is the primary
mode of sulfur pickup during the early stages of the process, during which time the stone
is still relatively cool. In later stages of the process, as the stone heats up to temper-
atures above the thermodynamic limit for sulfite existence (about 1400°F), the sulfite
can calcine and sulfur is lost from the particles. Concurrent with these steps, the sul-
fite can be oxidized and/or disproportionate to form sulfate and sulfide. The net result,
however, is a maximum in sulfur pickup during the first second of exposure in the
reactor. The time required for attainment of this maximum and the magnitude
of the maximum pickup are likely to depend upon factors which influence the
"Stone numbers used in this report are those used by NAPCA and other NAPCA contractors.
""Values were not obtained for the hydrates, since the data did not fit an exponential relationship.
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heatup time and the rate of oxidation or disproportionation, e.g. , particle size, injec-
tion temperature, oxygen pressure, the duration of exposure at a given temperature,
and the details of the physical state of the lime formed during the calcination step. If,
for example, injection in a boiler is made at very high temperatures (» 2300°F) and in a
region of the boiler where temperature does not change rapidly with time, then heatup,
calcination, and sulfite formation and decomposition might take place within such a short
time scale that the maximum in the sulfur pickup curve might be undetectable and rela-
tively unimportant in the overall process. On the other hand, if injection in the boiler
is made near the superheater section where the gas temperature begins to drop off very
rapidly, calcination may not be complete within the time available, and sulfite may be
the principal product of sulfur pickup. However, this effect would be reduced with the
use of very small particles because of their rapid heatup.
The results of the current work provide at least a qualitative understanding of the
overall reaction trajectory of the limestone-SO2 reaction and a possible connection
between the results of the relatively long-term experiments carried out by NAPCA and
others and the short-term exposure in the dispersed-phase reactor or in a boiler. A
detailed set of recommendations directed toward further clarification of the limestone -
SO2 reaction has been submitted to NAPCA. In essence, on the basis of the results
obtained in this program, it is recommended that consideration be given to a detailed
fundamental study of the calcination and SC>2 reaction for short residence times such as
would be encountered in a boiler, with the goal of elucidating the importance of heat
transport, mass transport, and chemical reaction rate to the overall sequence of events
occurring when limestone is injected into flue gas.
EXPERIMENTAL DETAILS
In the current series of experiments, study of the reaction between limestone-
based materials and SC>2 was continued using the dispersed-phase reactor. Results of
the previous work, along with details of construction and operation of the reactor are
given in the Summary Report dated August 30, 1968. A brief description of the reactor
also is presented in Appendix A. In this reactor, sized particles of stone, burnt lime,
or hydrated lime are injected into a nearly isothermal stream of flue gas and are trans-
ported by the gas stream to a collection probe, whence they are withdrawn from the flue
gas for chemical analysis. Residence time in the reactor is determined by probe spacing
and gas-stream velocity. The samples are small compared with the volume of gas to
which they are exposed, so the particles encounter essentially constant SC>2 concentra-
tion throughout the run. The nominal gas temperature reported for the reaction is that
on the centerline at a point midway between the injection and collection probes.
Materials Preparation and Analysis
Particle Sizing
For the most part, the samples of stones and limes used in this study were
-140 + 200 U. S. Standard mesh, obtained by grinding and sieving bulk samples provided
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by NAPCA. For the particle-size study, the three larger sizes, -100 + 120, -140 + 200,
and -270 + 325 U. S. Standard mesh, were sieved with wire-mesh screens. For the
three smaller sizes, 20-40, 10-20, and 5-10 microns, electroformed screens were
used.
Calcination and Hydration
Specimens were calcined in a laboratory rotary kiln under conditions specified by
the Sponsor: 2 hours at 1800°F in flowing nitrogen. A stainless steel kiln, lined with
pyrophillite (a refractory ceramic) to prevent reaction of the limes with the metal-oxide
surface of the kiln, was used for the calcination. The same kiln was used with a Pyrex
liner for preparing the hydrated limes. A schematic drawing of the hydration apparatus
is shown in Figure 1.
Conventional laboratory procedures for hydration of limes involve addition of
liquid water to the lime. Because of the strongly exothermic nature of the reaction,
this type of hydration is normally quite violent and causes disruption of the burnt-lime
particles. In the current work it was desired to retain original particle size so that
comparison of the reactivity of hydrated limes with that of burnt limes could be made
without change in relative particle size. The following procedure for hydration was
adopted. The lime is first heated to about 660°F and steam is admitted to the kiln at a
pressure of 1 atmosphere. The temperature of the kiln is then allowed to decrease
gradually over a period of several hours to 230 to 250°F while steam is admitted contin-
uously. With this procedure, the rate of hydration is kept low and disruption of the lime
particles is minimized. After completion of the temperature program, dry nitrogen is
passed over the lime to remove any excess water from the kiln. The resultant limes
are dry powders having approximately the same particle-size range as the original
stone, as indicated by sieving, and containing stoichiometric quantities of water, as
judged by thermogravimetric analyses of the products. Because of the resistance of
MgO to hydration, only the calcium oxide portion of a lime is hydrated by this method.
However, substantial fractions of the MgO in a dolomitic lime can be hydrated by
increasing the steam pressure. By maintaining steam pressure at 80 to 90 psi and lime
temperature at 300 to 320°F for 12 hours, a sample of dihydrated No. 1337 was prepared
in which 80 percent of the MgO was hydrated. This material was used in experiments
with dihydrated lime.
Chemical Analyses
Reacted specimens obtained from the dispersed-phase reactor were analyzed for
total sulfur, calcium, and magnesium content, and selected specimens also were ana-
lyzed for sulfite content. Both calcium and magnesium were determined by atomic-
absorption photometry. Total sulfur was determined as CaSO^.- 2H2O by the wet-
chemical method outlined in the Summary Report dated August 30, 1968. An essential
step in this procedure is the oxidation of non-sulfate sulfur to sulfate using hydrogen
peroxide. Sulfite analysis was made by the same procedure, but the oxidation step was
not performed. Instead, the solution of the reacted specimen was swept with nitrogen
to remove SO2- The remaining sulfate was then determined in the usual manner and the
sulfite content was obtained by difference. The accuracy of the method has not been
tested. No analyses for sulfide were made.
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Adjustable
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Lime
Steam source
A-55878
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Analytical data for most of the limes were supplied by Bituminous Coal Research,
Inc. , and are given in Appendix B. Two new stones used in the current work, the Basic
Chemicals dolomite and the TVA (Colbert County) limestone, were analyzed for calcium
content by atomic-absorption photometry. The burnt limes obtained from these stones
were found to contain 61 and 95 weight percent CaO, respectively.
Results and Discussion
A complete listing of experimental conditions, analytical results, calculated val-
ues of reactivity, and percentage calcination for all runs made on this segment of the
program is given in Table C-l in Appendix C. Data displayed in tables and figures
discussed below are abstracted from this table. Mathematical procedures for calcula-
tion of reactivity and percent calcination are given in Appendix D.
General Characteristics of SC>2 Reaction
All of the stones and limes were reacted for three residence times at each of
several temperatures. At temperatures between 1500 and 2100°F the qualitative features
of the observed reaction trajectory were the same for all materials. The total sulfur
content of samples exposed for the longest residence time at a given temperature was
lower than that found in the same material exposed for the intermediate residence
time.* In some cases, there was even less sulfur in the long-residence time samples
than in those exposed for the shortest period. That is, for all materials, a definite
maximum in sulfur pickup was observed within the range of residence times used in the
reactor.
It was also found, for -140 + 200 mesh stone, that calcination is generally incom-
plete during the exposure in the reactor, except for experiments at the longest residence
times at the highest temperatures.
Selected samples of several reacted stones were analyzed for sulfite as well as for
sulfate content. The results of these measurements are shown in Table 1. It can be
seen that sulfite is the predominant form of sulfur for runs made at the shortest resi-
dence times and lowest temperatures, whereas sulfate is predominant only for longer
residence times at higher temperatures. The presence of sulfite at gas temperatures
above the thermodynamic stability point of the sulfite, about 1400°F, suggests that an
appreciable part of the residence time in the reactor is consumed before particle tem-
perature approaches gas temperature. Figure 2, plotted from data in Table 1, shows
that the fraction of the sulfur as sulfite is also related to the degree of calcination, sug-
gesting either that one process controls the other or that the rates of calcination and
sulfite formation are related through a common mechanism.
*For example, see Figures 8 and 9.
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TABLE 1. SULFITE ANALYSES
Sample
No.
10-24-L
11-1-E
1-28-R
10-30-L
11-7-E
11-19-A
1-13-D
1-13-L
1-13-Y
10-18-C
10-18-E
10-18-L
10-28-C
10-28-D
11-6-A
11-6-B
1-6-J
1-6-K
11-4-E
11-4-F
11-24-N
11-7-M
11-19-1
1-28-V
1-28-W
Stone
No.
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1337
1337
1337
1337
1337
1337
TVA
TVA
TVA
TVA
TVA
TVA
TVA
Particle
Size^a'
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
20-40 ju
10-20 M
5-10 IJL
-100+120
-140+200
-270+325
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
-140+200
Temp,
°F
1800
1800
1800
2000
2000
2000
1900
1900
1900
1900
1900
1900
2000
2000
2000
2000
2000
2000
1800
1800
1800
2100
2100
1800
1800
Residence
Time,
sec
0.58
0. 18
0.95
0.34
0. 10
0.50
0.51
0.51
0.51
0.47
0.47
0.47
0.40
0.40
0. 12
0. 12
0.61
0.61
0. 18
0. 18
0.58
0. 10
0.50
0.95
0.95
Total S
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90
80
CO 70
10
D
C
CD
O
10
0
:;
0 10 20 30 40 50 60 70 80 90 100
Percent Calcination
FIGURE 2. MOLAR PERCENTAGE OF SULFUR OCCURRING AS SULFITE
AS A FUNCTION OF PERCENTAGE CALCINATION
The following mechanism is hypothesized as being consistent with these general
experimental observations:
(1) The initial temperature of a particle of stone injected into the reactor
is low relative to the temperature of the gas.
(2) The time required to heat a particle essentially to gas temperature
is not negligible compared with its total residence time in the reactor.
The length of this heating period depends partly upon the kinetics and
heat of reaction of the calcination process. Thus, for example, raw
stone heats up more slowly than burnt lime because of the endothermic
calcination reaction.
(3) In calcination, while the particle is still at relatively low temperature,
SO2 begins to react with the lime forming calcium sulfite, which may
gradually oxidize and/or disproportionate to CaSO4 and CaS. # That is,
•The work of K. H. vanHeekandH. Juntgen (discussed at the Third Limestone Symposium, St. Petersburg, Florida,
December 4-8, 1967) and of S. Sprung in Schriftenreihe der Zimentindustrie 31, 1-67 (1964), indicates direct reaction of
SC>2 with uncalcined limestone. However, the conditions employed in their work were quite different from those in the work
reported here, and the results cannot be directly related.
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CaO + SO2 - CaSO3;
then CaSC>3 + 1/2O2 - CaSCXj
and 4CaSO3 - CaS + 3CaSO4 .
(4) As the temperature of the particle continues to increase approaching
gas temperature, some of the sulfite decomposes to yield SC>2 and
free lime. At the same time, disproportionation and/or oxidation
of the remaining sulfite may continue at an increased rate.
(5) Once the particle achieves gas temperature (above the decomposition
point of the sulfite), the reaction continues at a new rate with 803 and
O2 to yield sulfate:
CaO + SO2 + 1/2O2 -* CaSO4 .
According to this hypothesis, the initial reaction rate should be essentially charac-
teristic of formation of sulfite at reduced temperatures. The total sulfur content may
then go through a maximum before the characteristic high-temperature formation of
sulfate commences. Work at NAPCA* and TVA**, as well as earlier work at
Battelle***, has indicated lower rates of SO2 sorption than those reported here. This
may be a result of the longer term experiments employed in these studies; the maximum
pickup point may have been passed in the course of the experiments, giving a lower
average rate.
Effect of SO2 Concentration
The effect of the concentration of SO2 in the flue gas on the apparent reaction rate
was studied using a limestone, No. 1359, and the Basic Chemicals dolomite (-140 + 200
U. S. Standard mesh). Exposure in the dispersed-phase reactor was at a mean gas
temperature of 2000°F for a residence time of 0. 12 second. Concentrations of SO2 em-
ployed ranged from 100 ppm to about 6000 ppm; the amount of reaction at ,100 ppm was
too slight to be measurable.
The effect of changing concentration on the reactivities of the two stones is shown
in Figures 3 and 4. Data used in constructing these plots are taken from the Summary
Report of August 30, 1968, as well as from the current data. The behavior noted in
Figures 3 and 4 is at variance with the linear dependence indicated by the preliminary
data given in the above-mentioned Summary Report. Although there is considerable
scatter in the data, it is clear that there is little dependence on concentration except at
very low SO2 levels. This fact is consistent with the notion that the rate of reaction is
not controlled by the chemical reaction rate or the rate of admittance of SO2 to the par-
ticle during the early reaction stages, but rather depends upon the availability of lime
for reaction, i. e. , on the calcination rate, which in turn may depend upon the rate of
heat transfer to the particle.
*R. H. Borgwardt, "Kinetics of the Reaction of SC>2 With Calcined Limestone", presented at Symposium on Limestone-Sulfur
Dioxide Reaction Kinetics and Mechanisms, Cincinnati, Ohio, February 5-6, 1969.
**R. C. MullinsandJ. D. Hatfield, "Effects of Calcination Conditions on the Properties of Lime", presented at the Symposium
on Lime, Annual Meeting of ASTM, Atlantic City, New Jersey, June 23-27, 1969.
"""Summary Report, August 30, 1968.
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10
Q>
C
jy
o
o
0>
10
o
CO
0>
E
i\j\j
90
80
70
60
50
40
30
20
T = 2000°F
t = 0.12 sec
—
- j
4 >
- ( 1 •
rJ-
T
f *
'f
of 1 1 1 1 1 1
O.I 0.2 0.3 0.4 0.5
Volume Percent S02
0.6
0.7
FIGURE 3. EFFECT OF SO2 CONCENTRATION ON REACTIVITY
OF NO. 1359 LIMESTONE
Q)
T = 200CTF
t = O.I 2 sec
0.2 0.3 0.4
Volume Percent
0.5
0.6
0.7
FIGURE 4. EFFECT OF SO2 CONCENTRATION ON REACTIVITY
OF BASIC CHEMICALS DOLOMITE
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11
It is emphasized that the dependence shown in Figures 3 and 4 may not hold for
reaction at the longer residence times of interest in boiler operation but is indicative
only of the behavior during the initial portion of the reaction process. In fact, studies
of SO2 sorption at longer residence times have indicated a first-order dependence on
SO2 concentration. *
Effect of Particle Size
A study of the effect of particle size on the apparent rate of reaction of two lime-
stones, Nos. 1373 and 1683, and two dolomites, No. 1337 and the Basic Chemicals
dolomite, was carried out in the reactor at a gas temperature of 1900 F with a residence
time of 0. 5 second. Particle sizes used were 125-149, 88-105, and 44-53 microns
(-100 + 120, -140 + 200, and -270 + 325 U. S. Standard mesh) and 20-40, 10-20, and
5-10 microns. For the four larger sizes noted, the sample injector used was the same
as was used with all other runs made in the reactor.** However, this injector could not
be used with the two smaller sizes because of agglomeration of the particles. A special
injector, shown in Figure 5, was constructed for use with these small particles. With
this injector, an appropriate amount of stone is placed in an airtight aluminum box
which communicates with the reactor inlet through a short aluminum tube. The box is
vibrated in line with the tube and reactor inlet, causing the particles to drift along the
tube into a small mixing chamber wherein they are picked up by a stream of nitrogen
and blown into the reactor. Rates of injection can be varied reliably through alteration
of the amount of stone in the box and variation of the amplitude of vibration.
The effect of particle size on SC>2 pickup for the two limestones and two dolomites
examined is shown in Figures 6 and 7. Contrary to preliminary estimates of the
particle-size dependence***, the rate of reaction is not simply inversely proportional
to particle size. This type of dependence may be a limiting case for the larger particle
sizes, as indicated by the points for the three larger particle sizes on Figures 6 and 7,
but with the smaller sizes there seems to be little or no dependence on size. It is also
noted that there is considerable scatter in the data, particularly for the dolomitic
stones. With these materials, especially No. 1337, extensive fragmentation was
observed to accompany calcination of particles in the size range of -140 + 200 mesh. It
may be that fragmentation is less pronounced with smaller particle sizes and that the
size of particles actually taking part in the reaction with SC>2 was essentially independent
of initial size. However, the limestones also show a leveling off of reactivity at the
smaller particle sizes. Aggregation of the smaller particles into clusters may also be
a factor.
These data for the effect of particle size on apparent rate of reaction are consis-
tent with the sulfite-formation model discussed earlier. For smaller particles the rate
of heatup should be greater than that of the larger particles, so that, for a given resi-
dence time, the smaller particles should be further along their respective reaction tra-
jectories. Thus, the failure of the smallest particles to have high reactivity may indi-
cate that they are further down the desorption side of the reaction curve. Possibly, their
"Summary Report, August 30, 1968, Figure 7, and R. H. Borgwardt, op. cit.
"Summary Report, August 30, 1968, Figure 1.
""Summary Report, August 30, 1968, Figure 14. Increasing reactivity with decreasing particle size also is indicated by the
investigation of K. M. Zentgraf, K. Tanaka, and Y. Ishihara (discussed at the Third Limestone Symposium, St. Petersburg,
Florida, December 4-8, 1967) and by the work of R. C. Attig (Progress Report, December 10, 1968, Contract No.
PH 86-67-127).
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1Z
Sealed box with sample
Vibration
Rubber
seal
Mixing chamber
To reactor
FIGURE 5. SMALL-PARTICLE INJECTOR
A-57836
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13
200
100
80
60
o
O 40
en
•••M
No. 1373
T=I900°F
t = 0.5 sec
\
10
20
40 60 80 100
200
ro
O
C/5
D>200
E
100
80
60
An
_
T
"I ^^-^
t """" -^^^
•^ .^
: i
i i i
No. 1683
T=I900°F
t = 0.5 sec
^X.
X
1 1 1
10 20 40 60 80 100 200
Average Particle Size,microns
FIGURE 6. EFFECT OF PARTICLE SIZE ON REACTIVITY
OF TWO LIMESTONES
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14
£UU
100
c 80
•~
"5 60
O
^J)
A O
1 T^f.
•
—
1 1 1
BASIC
T= I900°F
t = 0.5 sec
v.
\
1
^ HU 10 20 40 60 80 100 200
lO
o
<°200
O>
E
100
80
60
4O
T
I
X
• I
X
_-
—
1 1 III
•^-^
No. 1337
J= 1900 °F
t = 0.5 sec
1
10 20 40 60 80 100 200
Average Particle Size, microns
FIGURE 7. EFFECT OF PARTICLE SIZE ON REACTIVITY
OF TWO DOLOMITES
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15
reactivity would be greater than that of the larger particles for the longer residence
times which would be used in a boiler, i. e. , after SO£ desorption has been completed
and sulfate formation has become the dominant mode of sulfur pickup.
Effect of Chemical State of Stone
The question exists as to whether or not more efficient scrubbing of the SO2 from
flue gas can be achieved by injecting burnt or hydrated lime instead of raw stone. To
explore this question, two stones were exposed in the reactor in different chemical
forms at temperatures of 1500 to 2100°F. For limestone No. 1359, the reactivity of the
burnt lime and hydrate was compared with that of the raw stone. For dolomite No. 1337,
both the monohydrate and the dihydrate were studied, along with the burnt lime and raw
stone. Special procedures outlined in the section on materials preparation were used to
insure that the initial particle size was not a variable in these studies.
Figures 8 and 9 illustrate the results obtained at 2000°F. Qualitatively similar
results were obtained at other temperatures. Regardless of residence time, the follow-
ing order of reactivities was observed:*
Dolomite reactivity: dihydrate > raw stone > monohydrate > burnt lime
Limestone reactivity: raw stone > hydrate > burnt lime.
Scatter in the data does not permit quantitative conclusions on the relative efficacy
of the various forms. However, over the temperature range used, the best materials
were clearly the raw limestone and the dihydrate and raw stone in the case of the dolo-
mite. Burnt lime was definitely inferior in both cases. A factor which may be partially
responsible for the low ranking of the burnt lime is that this material was prepared by
calcination for a. long period of time - two hours at 1800°F - conceivably causing some
sintering of the lime. The reason for the improved reactivity of the hydrates is not
known; it may be related to the fact that the carbonate and hydrate have different crystal
structures so that the CaO formed by calcination may, at least temporarily, have differ-
ent structure or porosity in the two cases. With the dihydrate, there may be some addi-
tional fragmentation which occurs upon calcination, thus resulting in higher reactivity
than for the raw dolomite, but no information concerning this point is available.
The data for the hydrates suggest a possible maximum in reactivity at about
2000°F. However, because of scatter in the data, the existence of a maximum cannot be
established with certainty.
Effect of Temperature
The apparent reaction rate, i.e. , the amount of SO2 pickup per unit time, was
determined at temperatures between 1300 and 2100°F for the various stones and limes
examined in this program. Because of the complexity of the overall reaction process
during exposure in the reactor, a true specific rate constant cannot be determined within
"Zentgraf, op. cit., found the order to be calcium hydrate > dolomite monohydrate > raw limestone > burnt lime (high calcium)
for injection into a boiler at about 2100 F, but the ranking appeared to change with injection temperature. Also, his particle
size was not the same for all specimens.
-------
H
m
r
r
m
2
m
2
o
H
C
H
m
i
o
o
r
c
s
CD
C
m
o
H
O
5
m
o>
Di hydrate
Raw stone
"•—M on oh yd rate
Burnt lime
0 O.I 0.2 0.3 0.4 0.5 0.6 0.7
t, sec
FIGURE 8. COMPARISON OF VARIOUS FORMS
OF DOLOMITE NO. 1337 AT 2000°F
200
180
160
0)
O 120
o>
\ 100
10
O
o»
E
80
60
40
20
x-Raw stone
Hydrate
0 O.I 0.2 0.3 0.4 0.5 0.6 0.7
t, sec
FIGURE 9. COMPARISON OF VARIOUS FORMS OF
-------
17
the limits of current understanding of the reaction process. Also, particle tempera-
tures and, hence, true reaction temperatures probably are not well approximated by the
mean gas temperature in the reactor. To the contrary, the actual reaction temperature
undoubtedly varies considerably within the span of an exposure. If, as suggested above,
the controlling mechanism in the overall process is heat transfer to and within the par-
ticles, the use of an Arrhenius-type equation, which applies strictly only to activated
processes, is not entirely correct. However, Arrhenius plots are a convenient means
for organizing the reaction-rate data and may provide useful comparisons of the reac-
tivities of various materials.
Figures 10 and 11 show examples of Arrhenius plots, with lines fitted by least-
square analysis, which were made for the various materials studied on this program,
with the exception of the hydrates. (Plots for the remaining materials are presented in
Appendix E. ) As indicated above, the latter materials tend to display a maximum in
reactivity as a function of temperature and, hence, cannot be approximated by an expo-
nential relationship. Because of the complexity of the residence time-sulfur pickup
relationship, three apparent rate curves, one for each residence time, were plotted for
each temperature. These are identified in the figures by the subscripts S, M, and L,
referring to short, medium, and long residence times. Apparent activation energies,
in kilocalories per mole, also are indicated in the figures for short, medium, and long
residence-time data. It is not intended that these energies should be taken as an indi-
cation of any specific physical or chemical processes but rather that they show approxi-
mate overall trends in the data. In fact, it may be noted that, almost without exception,
the experimental data are fitted better by curves concave downward than by straight
lines. In most cases, the apparent activation energies for the short and medium resi-
dence times are within the probable error limits of each other, and the long-residence-
time energies are slightly lower, suggesting that the sulfur pickup might be governed by
one process up to the neighborhood of the maximum in the pickup curve, and that other
processes such as calcination and oxidation of the sulfite may be more influential in
determining the temperature dependence during the later stages of the reaction.
The apparent activation energies range from 11 to 15 kcal/mole for No. 1683 and
the burnt limes to 24-28 kcal/mole for the other limestones and dolomites. The latter
values are in agreement with the 28 kcal/mole previously reported for the reaction of
No. 1359. The low values for the burnt limes are consistent with the fact that calcina-
tion is not required with these materials, so that the overall thermal requirements for
the burnt limes should be lower. However, the low apparent activation energies for
No. 1683 are not consistent with the values obtained for other raw stones. This may be
related to the fact that No. 1683 is an aragonite rather than a calcite as are the other
limestones.
It should be noted that the activation energies of raw stones indicated above are
appreciably higher than those previously reported (12 to 17 kcal/mole) under Contract
No. PH 86-68-84, Task 11, for a special series of high-purity limestones being
screened for the full-scale TVA dry-limestone injection tests (see Appendix F). In the
latter case, the size of particles examined was 20-40 microns, considerably smaller
than the -140 + 200 mesh material used in the current tests. If, indeed, heat transport
is an important factor in determining the overall reaction rate, it might be expected that
the apparent thermal requirements would decrease as particle size is decreased since
the rate of convective heat transfer per unit area increases with decreasing particle size
for these small particles.
-------
18
o
D
cr
c
o
"o
D
d>
cr
O>
O
Q.
Q.
100
10
o Short residence time Es = 13 ± 3
x Medium residence time EM = 16 ± I
• Long residence time EL = II ±2
M
L
0.6
0.7
0.8
0.9
I03/T°K
1.0
1.2
FIGURE 10. ARRHENIUS PLOT FOR NO. 1359C
-------
19
1000
o Short residence time ES = 17 ± 2
_x Medium residence time EM = 16.2 ± 0.7
_• Long residence time E, = I3±2
0.6
IOVT°K
FIGURE 11. ARRHENIUS PLOT FOR NO. 1337C
-------
20
Recommended Future Work
Results obtained during the current contract period have indicated that, when
limestone particles are injected into a hot flue gas stream under nearly isothermal con-
ditions, certain time factors become important. Heat-up and calcination of the particles,
for example, require exposure to the hot gases for several tenths of a second. During
part of this time, the temperature of the lime shell which is formed is low enough, that
SC>2 can be absorbed to form calcium sulfite. The sulfite can, in turn, either dispropor-
tionate or be oxidized to yield calcium sulfate. As the calcination process continues,
the temperature of the lime shell rises to a point at which the calcium sulfite begins to
calcine. As a result, the particles undergo a net loss in sulfur content during the later
stages of calcination and heat-up. After this initial series of processes, the fully cal-
cined particles may be expected to continue to pick up sulfur at a rate characteristic of
the formation of calcium sulfate.
In a boiler, where gas temperatures drop off very rapidly between, say, 2300 and
1500°F, the heat-up and calcination problem is likely to be accentuated over that ob-
served in nearly isothermal experiments. It is, therefore, highly important that the
nature of the physical and chemical processes occurring during heat-up and calcination
be thoroughly understood so that valid extrapolations from the pilot experimental work
to boiler performance can be made. It is implicit that this understanding should be based
upon the following factors;
(1) The rate of heat transport to and within a limestone particle
(2) The rate of mass transport to, from, and within the particle
(3) The rates of the chemical processes occurring within the particle:
(a) Calcination
(b) Formation and decomposition of sulfite
(c) Formation of sulfate.
The program outlined below is suggested as a logical route for gaining insight into
the above factors. It is recommended that the work be performed with a single well-
defined limestone, with the purpose of developing understanding of the mechanics of the
overall process.
The program would be conducted in a dispersed-phase reactor of the type used to
date. However, because of the need for obtaining longer residence times and higher tem-
peratures than are currently possible, a new dispersed-phase reactor would be required.
This reactor would be approximately twice as long as the existing one, so that residence
times of about 2 seconds could be achieved at 1800°F, and would be constructed of mate-
rials to permit operation up to about 2500°F. It would also be necessary to construct an
appropriate calciner and preheater.
The recommended program is as follows:
(1) Conduct preliminary experiments to establish qualitatively the effect
of oxygen and nitrogen oxide content of the flue gas on the reactivity
of limestone with
-------
21 and 22
(2) Study the course of the reaction of raw limestone with respect to cal-
cination, sulfite formation, and sulfate formation as a function of
temperature.
(3) Study the course of the reaction of precalcined stone with SC>2 with
respect to sulfite and sulfate formation. The stone would be calcined
under conditions simulating those in the dispersed-phase reactor.
(4) Study, the calcination rate in the reactor, using flue gas containing no
s ulf ur.
(5) Attempt to construct a mathematical model of the reaction system in
terms of gas temperature, particle composition, and time.
-------
APPENDIX A
DISPERSED-PHASE REACTOR
-------
A-l
APPENDIX A
DISPERSED-PHASE REACTOR
Figure A-l is a sketch of the dispersed-phase reactor as shown in the previous
Summary Report dated August 30, 1969- In the current work, the reaction section was
lengthened from 60 to 72 inches to allow for more versatility in operation, and a new
shell of 316 stainless steel was installed to reduce corrosion problems. Not shown in
Figure A-l are radiation screens which were placed at the top and bottom of the reaction
section to reduce radiation losses and to smooth out gas flow.
Injection and collection of particles is made through the series of ports spaced
every 6 inches along the reaction section. Probes for these operations are described in
the body of this report and in the previous Summary Report. In operation, the mean
gas temperature is determined with a multiple-shielded 10%Rh, Pt-Pt thermocouple
which is inserted midway between the injection and collection probes.
Input gas-flow rates to the combustor are mete red by differential flow manometers;
the residence times of particles in the reactor can be determined from probe spacings
and gas velocities. Reynolds numbers for the flue gas are determined from the mean
temperatures and the viscosity data of Geiringer. *
The uppermost ports of the reactor are also used for withdrawal of gas samples
for analysis. Probes inserted in these ports lead directly to Orsat (for CO2 and 03) or
titration apparatus (for sulfur oxides). Techniques used in these analyses are discussed
further in the text of this report.
"P. L. Geiringer, Handbook of Heat Transfer Media, Rheinhold Publishing Corp. , New York, 1962.
-------
60 in.
24 in.
A-Z
-pss?
!2in. diam -*•
i
I
T-
I
I
^a
Air, gas, H2S
>4--in. insulation
Ports for particle
injection and sampling
Combustion chamber
-Burner
Inlet manifold
FIGURE A-1. DISPERSED-PHASE REACTOR
-------
APPENDIX B
SPECTROCHEMICAL ANALYSIS OF STONES
-------
TABLE B-l. SPECTROCHEMICAL ANALYSIS OF STONES(a)
Results Reported as Percentage by Weight of Ignited Sample (900 C)
Stone
Number (b)
> 1337
H 1337
r 1337
m !337
2 1337
m
0 1359
f 1359
r 1359
z 1359
M
q 1360
c 1360
m 1360
' 1360
0 1360
r
2 1373
0)
c 1373
CO
r
m 1384
g 1384
5 1384
g 1384
w 1683
1683
1683
1683
1683
AR
B
C
F
M
AR
B
F
10/28M
AR
B
C
F
10/28M
B
1 Qt.FR
B
C
F
M
B
C
F
M
1 Qt. FR
Loss on
Ignition
(900°C)
47.5
47.5
47.3
47.3
47.3
43.6
43.6
43.6
43.6
43.7
43.7
43. 1
44.2
44.5
41.8
41.9
43.6
44. 0
43. 8
43. 8
44.2
44.3
44.3
43.7
44.5
Component
Si02
0.78
0.77
0.92
0.86
0.78
0.85
1.13
0.90
1.07
4.08
3.85
5.20
2.74
3.65
4.20
3.75
<1. 0
<1. 0
1.2
1.2
1. 10
1.40
1.76
4.09
1.00
A1203
0. 15
0. 13
0. 15
0. 15
0. 14
0.30
0.27
0.30
0.29
0.29
0.32
0.40
0.35
0.27
0.95
1. 02
<0.3
<0.3
<0.3
<0.3
<0.3
<0. 20
<0. 20
<0.20
<0.3
Fe203
0.25
0.24
0.33
0.25
0.36
0. 17
0.23
0.20
0.22
2. 04
1. 83
1.67
1. 84
1.25
1.06
1.23
<0. 2
<0. 2
0. 36
<0. 3
<0.2
0.42
0. 11
0.23
<0.2
MgO
45. 0
43.5
44. 0
42.5
43. 0
1. 07
1. 11
1. 10
1. 16
14.6
13.4
13.3
18.5
13. 0
5.30
6.0
0.93
0.99
1. 24
1.24
0.80
2.36
0. 83
2.23
0.82
CaO
53
54
54
56
55
97
97
97
97
78
80
79
76
81
85
87
97
97
96
96
Bal.
94
96
92
Bal.
Ti02
0. 02
<0. 02
<0. 03
<0. 03
<0. 03
<0. 05
<0. 05
<0. 05
<0. 05
0. 05
<0. 05
<0. 05
<0. 05
<0. 05
0. 07
0.07
<0. 03
0. 04
0. 04
0. 04
<0. 05
<0. 03
<0. 03
<0. 03
<0.05
SrO
<0. 03
<0. 03
<0. 03
<0. 03
<0. 03
0. 07
0. 08
0. 07
0.07
0. 05
<0. 05
0. 05
0. 05
0. 05
Na2O
<0. 02
<0. 02
<0. 02
<0. 02
<0. 02
<0.02
<0. 02
<0. 02
<0. 02
0. 06
0.05
0. 07
0. 06
0. 05
0.07
0. 12
0. 06
0. 03
0. 03
0. 03
0.44
0.48
0.28
0.53
0.40
K20
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
<0.1
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
0.20
0.22
<0. 1
<0. 1
<0. 1
<0. 1
<0. 1
<0. 10
<0. 10
<0. 10
<0. 1
MnO2
<0. 03
<0. 03
<0. 03
<0. 03
<0. 03
<0. 05
<0. 05
<0. 05
<0. 05
0.25
0.21
0. 17
0.21
0. 16
0.33
0.37
<0. 03
<0. 03
<0. 03
<0. 03
<0. 05
0. 06
<0. 03
<0. 03
<0. 05
a
,L
PJ
s
a
to
ro
(a) Supplied by Bituminous Coal Research, Inc.
-------
APPENDIX C
REACTOR DATA
-------
TABLE C-l. REACTOR DATA
Injection Data
to
-\
H
m
r
r
m
2
m
o
5
>
r
z
-------
TABLE C-l. (Continued)
Injection Data
m
H
H
m
r
r
m
2
m
2
O
5
>
r
_
z
u>
H
H
C
m
i
0
o
r
c
2
0)
c
r
0)
o
H
0
5
in
Run
Number
2-6-P
2-6-Q
2-5-R
2-5-S
2-4-R
2-4-S
2-6-E
2-6-F
11-4-P
11-4-Q
10-23-J
10-23-K
1-28-J
1-28-K
11-6-J
11-6-K
10-28-A
10-28-B
1-6-G
1-6-H
10-30-C
10-30-D
1-23-N
1-23-O
12-20-G
12-20-H
12-3-E
12-3-F
1-23-C
1-23-D
Stone
Number(a)
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359C
1359
1359
1359
1359
1359
1359
1359
1359
Time,
min
1
1
3.5
4
2.5
2.5
5
5
2
2
3
3
3
3
2
2
3
3
3
3
3
3
1
1
1
2
2
1.5
1
1.3
Rate,
g/min
1.5
1.5
1.2
1.1
2.1
2.1
1.0
1.0
9
1.6
1.20
0.50
2.2
1.1
1.1
0.8
0.80
0.65
2.5
N.S.
0.6
0.8
2.8
2.4
1.0
1.2
1.3
1.3
3.0
1.9
Gas
Temp,
°F
1500
1500
1504
1504
1506
1506
1500
1500
1800
1800
1800
1800
1803
1803
2006
2006
1996
1996
2000
2000
2100
2100
2006
2006
2001
2001
2000
2000
2006
2006
Reynolds
Number
1700
1700
1700
1700
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
3500
3500
3400
3400
3300
3300
3800
3800
3600
3600
3400
3400
3300
3300
3700
3700
Residence
Time,
sec
0.36
0.36
1.14
1.14
1.7
1.7
1.72
1.72
0.18
0.18
0.58
0.58
0.95
0.95
0.12
0.12
0.40
0.40
0.61
0.61
0.34
0.34
0.11
0.11
0.12
0.12
0.13
0.13
0.12
0.12
Product Analysis^3)
Ca
69.6
68.5
61.6
62.2
66.8
66.5
64.6
62.5
66.6
64.7
59.5
56.7
70.5
69.3
60.9
62
57.1
55.0
60.0
..
65.2
65.8
43.5
43.0
42.4
42.6
40.4
37.8
45.9
45.0
Mg
0.4
0.4
0.6
0.6
0.7
0.7
0.6
0.6
0.6
0.7
0.8
0.7
0.7
1.1
0.7
0.7
0.6
0.5
0.8
..
0.5
0.6
0.6
0.6
0.4
0.4
0.5
0.3
0.4
0.4
SOJ
1.4
2.3
8.0
6.7
6.7
6.6
6.9
6.3
6.8
5.4
6.5
6.4
4.7
4.8
5.3
4.9
10.9
11.5
10.0
..
13.4
12.8
5.9
6.1
5.4
5.7
6.2
5.8
2.8
2.0
Percent CaO
Utilization
0.5
0.8
3.0
2.5
2.3
2.3
2.5
2.3
2.4
1.9
2.5
2.6
1.6
1.6
2.0
1.8
4.4
4.9
3.9
__
4.8
4.5
3.2
3.3
3.0
3.1
3.6
3.6
1.4
10.0
SO3, mg
per gram
calcine
6
11
42
35
32
32
34
32
33
27
35
36
21
22
28
25
62
67
54
__
66
63
44
46
41
43
49
49
20
14
Calculated
Percent
Calcination
101
100
92
92
101
101
97
92
101
96
85
78
106
104
87
89
84
79
90
- _
104
105
31
28
25
26
16
0
37
32
Gas Analysis, volume percent^0'
S02
0.300
0.300
0.300
0.300
0.303
0.303
0.300
0.300
0.304
0.304
0.300
0.300
0.303
0.303
0.300
0.300
0.295
0.295
0.302
0.302
0.299
0.299
0.652
0.652
0.033
0.033
0.583
0.583
0.026
0.026
S03
0.0049
0. 0049
0. 0049
0.0049
0. 0053
0. 0053
0. 0049
0. 0049
0.0028
0.0028
0.0029
0. 0029
0.0038
0.0038
0. 0028
0. 0028
0. 0029
0. 0029
0. 0033
0. 0033
0.0029
0. 0029
0.004
0.004
0.007
0.007
0. 0033
0. 0033
0.0009
0. 0009
C02
10.0
10.0
10.0
10.0
10.2
10.2
10.0
10.0
10.2
10.2
10.4
10.4
10.6
10.6
10.0
10.0
10.8
10.8
10.9
10.9
10.0
10.0
10.6
10.6
10.3
10.3
10.4
10.4
10.6
10.6
02
3.0
3.0
3.0
3.0
2.6
2.6
3.0
3.0
2.8
2.8
2.9
2.9
2.4
2.4 O
IV
2.5
2.5
2.6
2.6
2.7
2.7
3.0
3.0
2.8
2.8
2.9
2.9
2.7
2.7
2.8
-------
TABLE C-l. (Continued)
Injection Data
m
H
H
m
r
r
m
S
m
2
O
£
r
z
(A
H
C
H
m
i
o
o
r
c
2
CO
c
w
r
CD
O
jj
H
O
jj
ni
en
Run
Number
1-23-E
1-23-F
1-9-R
1-9-S
1-9-T
1-9-U
2-6-GG
2-6-HH
2-5-G
2-5-H
2-4-A
2-4-B
2-6-A
2-6-B
11-4-C
11-4-D
10-24- C
10-24-D
1-28-C
1-28-D
10-4-C
10-4-D
10-4-E
1-13-A
1-13-B
1-13-J
1-13-K
10-18-G
10-18-H
10-10-A
10-10-B
Stone
Number^3)
1359
1359
1359
1359
1359
1359
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic(h)
Basic(h)
Basic(i)
Basic(i)
Basic(g)
Basic(g)
Basic(f)
Basic(f)
Time,
min
1
1
1.5
1.5
1.5
2
1
1
2.5
3
3
3
2.5
2.5
1.5
1.5
3
3
2
3
3
3
3
2
2
4
4
3
4
4
4
Rate,
g/min
2.3
2.7
2.9
2.7
2.1
2.0
1.2
1.2
2.2
2.2
9
2.0
3.2
3.2
1.3
1.6
0.50
1.40
2.8
2.0
1.16
1.05
1.10
1.3
1.0
0.22
0.45
0.60
0.60
1.10
1.40
Gas
Temp,
°F
2006
2006
2000
2000
2000
2000
1500
1500
1504
1504
1506
1506
1500
1500
1800
1800
1802
1802
1803
1803
1902
1902
1902
1903
1903
1903
1903
1900
1900
1903
1903
Reynolds
Number
3600
3600
3300
3300
3300
3300
1720
1720
1700
1700
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
3200
3200
3200
2900
2900
2900
2900
3100
3100
3100
3100
Residence
Time,
sec
0.12
0.12
0.13
0.13
0.13
0.13
0.36
0.36
1.14
1.14
1.7
1.7
1.72
1.72
0.18
0.18
0.58
0.58
0.95
0.95
0.46
0.46
0.46
0.51
0.51
0.51
0.51
0.47
0.47
0.47
0.47
Product Analysis^5)
Ca
45.8
45.8
42.1
41.3
42.1
40.3
20.6
20.5
21.6
21.5
24.3
25.4
26.1
26.0
24.6
24.9
27.0
29.1
32.9
32.1
31.0
NS
NS
33.8
33.4
31.9
32.8
31.3
31.7
31.0
33.3
Mg
0.4
0.4
0.5
0.4
0.4
0.4
12.4
12.4
13.1
13.2
14.9
15.3
14.8
15.1
14.7
14.8
24.3
19.4
19.8
19.6
18.3
NS
NS
20.4
20.0
20.4
19.8
19.3
19.4
17.1
19.2
SC>4
~0
~0
6.5
5.1
5.8
5.5
~0
~0
6.1
5.5
10.7
12.3
6.8
6.2
12.3
9.0
24.3
21.9
20.6
25.9
20.9
17.4
20.5
18.6
19.8
26.1
24.1
27.9
26.2
15.5
16.3
Percent CaO
Utilization
--
—
3.6
2.9
3.2
3.2
—
._
4.2 ± sW
3.7 ±0. ?(d)
7.5 ±1.3(d>
8.7 ± 1.5(d)
4.3 ± 0.8(d)
4.2 ± 0.8(d>
11.6
8.4
20.9
17.5
14.6
18.8
15.7
12.7 ±2.l(d)
15 2 ± 2 5^d)
12.8
13.8
19.0
17.1
20.7
19.2
11.6
11.4
S03, mg
per gram
calcine
--
--
50
40
44
44
--
—
37 ± 7
33 ± 6
65 ± 11
76 ±13
37 ± 7
37 ± 7
101
73
182
153
127
164
137
110 ± 18
132 ± 22
112
120
166
149
181
167
101
99
Calculated
Percent
Calcination
--
--
25
19
24
14
--
__
--
--
__
--
-_
--
-30
-34
27
42
71
75
57
--
__
73
73
74
76
73
73
46
66
Gas Analysis, volume percent(c)
S02
0.0073
0.0073
0.077
0.077
0.18
0.18
0.300
0.300
0.300
0.300
0.303
0.303
0.300
0.300
0.304
0.304
0.303
0.303
0.303
0.303
0.300
0.300
0.300
0.296
0.296
0.296
0.296
0.297
0.297
0.303
0.303
S03
Not
meas.
0.0015
0. 0015
0.0028
0.0028
0.0049
0.0049
0.0049
0.0049
0. 0053
0. 0053
0.0049
0.0049
0.0028
0.0028
0. 0035
0. 0035
0.0038
0. 0038
0. 0032
0. 0032
0.0032
0. 0036
0. 0036
0.0036
0. 0036
0.0027
0. 0027
0. 0028
0.0028
C02
10.6
10.6
9.9
9.9
9.9
9.9
10.0
10.0
10.0
10.0
10.2
10.2
10.0
10.0
10.2
10.2
10.2
10.2
10.6
10.6
10.0
10.0
10.0
10.6
10.6
10.6
10.6
10.2
10.2
10.2
10.2
02
2.8
2.8
2.8
2.8
2.8
2.8
3.0
3.0
3.0
3.0
2.6
2.6
3.0
3.0
2.8
2.8
2.8
2.8
2.4
2.4
2.8
2.8
2.8
2.7
2.7
2.7
2.7
2.8
2O
. O
2.8
-------
TABLE C-l. (Continued)
Injection Data
0)
H
H
m
r
r
m
2
m
2
0
3)
>
r
z
(A
H
H
C
H
m
i
o
o
r
c
0)
c
r
m
0
H
O
5
m
(A
Run
Number
1-13-R
1-13-S
12-20-E
12-20-F
12-20-C
12-20-D
12-20-A
12-20-B
12-3-G
12-3-H
12-3-A
12-3-B
12-3-C
12-3-D
1-23-G
1-23-H
1-23-J
1-23-K
1-23-L
1-23-M
1-23-A
1-23-B
1-9-V
1-9-W
1-9-P
1-9-Q
11-7-C
11-7-D
10-30-P
10-30-Q
Stone
Number^3)
Basic(J)
Basic(J)
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Basic
Time,
min
2
2
1
1
1
1
1.5
1
1.25
1
2
2
1
1
1
1
1
1
1
1
2
1
1.5
1.5
1
2
2
2
3
3
Rate,
g/min
2
2
2.5
1.9
2.9
2.5
2.6
2.6
1.3
1.5
1.5
1.25
1.5
1.2
2.8
2.9
3.0
2.7
4.6
3.0
2.5
2.7
2.2
1.6
4
1.5
1.2
1.5
1.1
0.95
Gas
Temp,
°F
1903
1903
2001
2001
2001
2001
2001
2001
2000
2000
2000
2000
2000
2000
2006
2006
2006
2006
2006
2006
2006
2006
2000
2000
2000
2000
2100
2100
2100
2100
Reynolds
Number
2900
2900
3400
3400
3400
3400
3400
3400
3300
3300
3300
3300
3300
3300
3600
3600
3600
3600
3600
3600
3700
3700
3300
3300
3300
3300
3900
3900
3800
3800
Residence
Time,
sec
0.51
0.51
0.12
0.12
0.12
0.12
0.12
0.12
0.13
0.13
0.13
0.13
0.13
0.13
0.12
0.12
0.12
0.12
0.11
0.11
0.12
0.12
0.13
0.13
0.13
0.13
0.10
0.10
0.34
0.34
Product Analysis(b) Percent CaO
Ca
30.3
31.5
29.4
29.9
28.0
27.2
27.6
27.3
26.1
24.4
25.6
25.8
25.1
25.5
31.3
31.6
30.5
28.2
26.1
26.9
27.9
27.9
25.7
25.5
28.6
27.8
23.0
25.1
32.3
32.5
Mg
17.7
18.3
16.9
17.2
15.9
15.8
16.4
15.8
15.5
14.7
14.6
15.9
14.8
15.2
18.0
18.2
17.5
15.9
15.3
15.3
16.4
16.2
16.3
16.1
17.6
17.5
17.0
12.2
18.0
18.4
SC>4
27.0
20.7
8.4
9.4
8.6
8.5
12.0
9.3
10.6
6.8
11.2
9.8
9.1
11.4
--
--
10.8
6.8
8.0
9.4
5.0
5.4
10.1
10.3
12.4
12.3
19.9
16.1
24.0
29.1
Utilization
20.7
15.3
6.6
7.3
7.1
7.3
10.1
7.9
9.4
6.5
10.2
8.8
8.4
10.4
--
--
7.6
5.6
7.1
8.1
4.2
4.5
9.1
9.4
10.1
10.3
15.8(£)
12.7(e>
17.3
20.8
S03, mg
per gram
calcine
180
133
58
64
62
63
88
69
82
56
89
77
73
91
--
--
66
49
62
71
36
39
80
82
88
90
138
111
151
181
Calculated
Percent
Calcination
63
60
17
24
3
-6
6
-3
-15
-47
-20
-20
-30
-20
--
--
31
1
-21
-8
-6
-5
-21
-23
17
9
39
34
73
84
Gas Analysis, volume percent(c)
S02
0.293
0.293
0.033
0.033
0.083
0.083
0.128
0.128
0.198
0.198
0.289
0.289
0.583
0.583
0.0073
0.0073
0.1375
0.1375
0.652
0.652
0.026
0.026
0.18
0.18
0.077
0.077
0.298
0.298
0.299
0.299
S03
0.0032
0. 0032
0.007
0.007
0. 0016
0. 0016
0.0020
0.0020
0. 0020
0.0020
0.0025
0. 0025
0. 0033
0. 0033
Not
meas.
0. 0023
0. 0023
0.004
0.004
0.0009
,0. 0009
0.0028
0. 0028
0.0015
0.0015
0. 0023
0.0023
0. 0029
0.0029
C02
10.2
10.2
10.3
10.3
10.3
10.3
10.3
10.3
10.4
10.4
10.4
10.4
10.4
10.4
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
9.9
9.9
9.9
9.9
11.0
11.0
10.0
10.0
02
3.0
3.0
2.9
2.9
2.9
2.9
2.9
2.9
2.7
2.7
2.7
2.7
2.7
2.7
2.8
2.8
2.8
2.8
2.8
20
. o
2O
. o
20
. 0
2.8
2.8
2.8
2.8
2.6
2.6
3.0
3.0
-------
TABLE C-l. (Continued)
Injection Data
0>
H
H
m
r
r
m
m
2
O
TO
>
r
_
z
(n
H
H
C
H
m
i
o
o
r
c
2
m
c.
en
r
0)
0
H
O
5
m
Run
Number
11-19-E
11-19-F
10-18-C
10-18-D
10-18-L
10-18-M
1-13-X
1-13-Y
1-13-C
1-13-D
1-13-L
1-13-M
2-6-X
2-6-Y
2-5-C
2-5-D
2-4-E
2-4-F
11-1-E
11-1-F
10-24-L
10-24-M
1-28-R
1-28-S
10-18-E
10-18-F
11-7-E
11-7-F
10-30-L
10-30-M
Stone
Number(a)
Basic
Basic
1683(f)
1683(f)
1683(g)
1683(g)
16830)
16830)
1683(h)
1683(h)
1683^)
1683^)
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
1683
Time,
min
3
3
3
3
4
4
2
2
1.5
1.5
4
1
1
1
2.5
2
3
2.5
1
1
3
3
1.5
1.5
3
3
2
2
3
3
Rate,
g/min
1.7
1.9
1.60
0.60
1.05
0.87
1.5
2.3
2.8
0.9
0.35
2
2
1.5
2.9
2.5
2.6
2.5
2.5
1.4
1.00
0.40
4.0
2.1
1.80
1.60
1.7
1.95
1.0
0.8
Gas
Temp,
°F
2100
2100
1900
1900
1900
1900
1903
1903
1903
1903
1903
1903
1500
1500
1504
1504
1506
1506
1800
1800
1802
1802
1803
1803
1900
1900
2100
2100
2100
2100
Reynolds
Number
3800
3800
3100
3100
3100
3100
2900
2900
2900
2900
2900
2900
1700
1700
1700
1700
1700
1700
2600
2600
2700
2700
2500
2500
3100
3100
3900
3900
3800
3800
Residence
Time,
sec
0.50
0.50
0.47
0.47
0.47
0.47
0.51
0.51
0.51
0.51
0.51
0.51
0.36
0.36
1.14
1.14
1.7
1.7
0.19
0.19
0.58
0.58
0.95
0.95
0.47
0.47
0.10
0.10
0.34
0.34
Product Analysis^1)
Ca
30.7
42.8
54.3
52.9
54.1
NS
51.0
53.2
59.2
58.5
52.6
51.7
38.5
37.7
40.4
40.4
45.2
45.4
42.9
40.7
43.2
44.4
58.6
57.3
57.1
57.0
53.5
42.0
53.5
44.5
Mg
19.6
18.8
0.4
0.3
0.5
NS
2.1
1.1
0.5
0.5
0.6
0.6
0.3
0.3
0.4
0.4
0.4
0.4
0.5
0.4
0.5
0.5
0.5
0.5
0.4
0.3
0.3
0.3
0.5
0.4
504
22.3
21.6
11.2
8.9
16.9
23.6
25.5
23.7
12.3
15.7
21.1
15.9
3.6
3.7
6.3
7.4
9.8
9.9
5.9
7.4
18.6
20.4
11.4
13.7
14.1
14.4
4.1
5.0
15.3
15.4
Percent CaO
Utilization
16.9
16.1 ±2. 6(d>
4.8
3.9
7.3
12.7 ±3(d)
11.6
10.4
4.8
6.2
9.3
7.2
2.2
2.3
3.6
4.3
5.0
5.1
3.2
4.2
10.0
10.7
4.5
5.6
5.7
5.9
2.0 ± 0.5(d)
2.8
6.7
8.0
S03, mg
per gram
calcine
147
140 ± 23
64
53
98
171 ± 41
156
139
64
83
125
96
29
31
49
57
68
68
43
57
134
143
61
75
77
79
27 ±7
37
89
108
Calculated
Percent
Calcination
57
--
81
74
87
88
92
94
96
87
78
5
0
20
21
48
48
32
23
51
59
92
91
91
91
__
26
83
52
Gas Analysis, volume percent(c)
SO2
0.302
0.302
0.297
0.297
0.297
0.297
0.293
0.293
0.296
0.296
0.296
0.296
0.300
0.300
0.300
0.300
0.303
0.303
0.301
0.301
0.303
0.303
0.303
0.303
0.297
0.297
0.298
0.298
0.299
0.299
S03
0.0026
0.0026
0.0027
0.0027
0.0027
0.0027
0. 0032
0. 0032
0. 0036
0.0036
0. 0036
0.0036
0.0049
0.0049
0.0049
0.0049
0. 0053
0. 0053
0.0026
0.0026
0. 0035
0. 0035
0.0038
0. 0038
0.0027
0.0027
0.0023
0. 0023
0.0029
0.0029
C02
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.6
10.6
10.6
10.6
10.0
10.0
10.0
10.0
10.2
10.2
11.0
11.0
10.2
10.2
10.6
10.6
10.2
10.2
11.0
11.0
10.0
10.0
02
2.6
2.6
2.8
2.8
2.8
2.8
3.0
3.0
2.7
2.7
2.7
2.7
3 0
3'.o 9
Ul
3.0
3.0
2.6
2.6
2.5
2.5
2.8
2.8
2.4
2.4
2.8
2.8
2.6
2.6
3.0
-------
TABLE C-l. (Continued)
Injection Data
CD
H
H
m
r
r
m
2
m
2
O
5
r
z
M
H
H
C
H
m
i
o
o
r
c
2
CD
C
M
r
CD
O
X
-)
0
5
in
M
Run
Number
11-19-A
11-19-B
2-6-AA
2-6-BB
2-5-A
2-5-B
2-4-G
2-4-H
11-4-G
11-4-H
10-24-G
10-24-H
1-28-N
1-28-0
11-7-G
11-7-H
10-30-J
10-30-K
11-19-G
11-19-H
2-6-EE
2-6-FF
2-5-L
2-5-M
2-4-L
2-4-M
11-4-E
11-4-F
10-24-N
10-24-O
Stone
Number^
1683
1683
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
1384
TVA
TVA
TVA
TVA
TVA
TVA
TVA
TVA
TVA
TVA
Time,
min
3
3
1
1
3
2.5
2.5
3
1.5
1.5
3
3
2
2
2
2
3
3
4
4
1
1
2.5
2.5
3
2.5
1.5
1.5
3
3
Rate,
g/min
1.7
1.2
1.5
1
2.0
2.4
2.0
1.9
9
0.8
0.50
1.00
3.5
3.3
1.4
1.15
1.2
1.1
1.4
1.4
2.8
1
2.5
2.0
3.1
2.5
1.1
1.5
1.43
0.43
Gas
Temp,
°F
2100
2100
1500
1500
1504
1504
1506
1506
1800
1800
1802
1802
1803
1803
2100
2100
2100
2100
2100
2100
1500
1500
1504
1504
1506
1506
1800
1800
1802
1802
Reynolds
Number
3800
3800
1720
1720
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
3900
3900
3800
3800
3800
3800
1720
1720
1700
1700
1700
1700
2700
2700
2700
2700
Residence
Time,
sec
0.50
0.50
0.36
0.36
1.14
1.14
1.7
1.7
0.18
0.18
0.58
0.58
0.95
0.95
0.10
0.10
0.34
0.34
0.50
0.50
0.36
0.36
1.14
1.14
1.7
1.7
0.18
0.18
0.58
0.58
Product AnalysisC5)
Ca
53.0
79.4
38.6
38.8
39.8
39.4
44.1
44.1
40.1
40.0
42.6
43.6
54.9
54.3
33.8
36.9
55.7
53.7
50.5
78.4
36.8
36.1
36.4
35.7
42.0
41.5
41.0
41.9
45.2
42.1
Mg
0.4
0.5
0.3
0.3
0.5
0.5
0.5
0.5
0.6
0.6
0.7
0.6
0.5
0.5
0.4
0.3
0.5
0.5
0.7
0.5
0.7
0.7
0.6
0.6
0.6
0.6
0.4
0.4
0.8
0.7
S0|
13.4
13.8
~0
~0
5.6
5.0
8.8
8.0
7.1
8.1
21.8
22.6
16.2
14.1
7.8
7.0
21.4
21.4
16.2
14.5
~0
~0
5.0
4.5
7.3
6.8
7.2
5.6
21.5
22.0
Percent CaO
Utilization
5.9
7.0 ± 1.8(d)
--
--
3.3
3.0
4.6
4.2
4.1
4.7
11.9
12.1
6.9
6.0
3.7 ± l.oW
3.4 ± 0. 9(d)
8.9
9.3
7.5
7.3 ±1.8
--
--
2.4 ± 0. 6(d)
2.2 ± 0.6(d>
4.0
3.8
4.1
3.1
11.1
12.1
S03, mg
per gram
calcine
79
95 ±24
--
--
45
41
64
58
57
65
165
167
95
84
52 ± 14
47 ± 12
124
128
103
100 ±25
--
--
33 ±9
29 ±8
55
52
56
42
150
165
Calculated
Percent
Calcination
79
--
--
--
11
8
37
36
15
16
49
79
84
80
__
--
92
86
71
._
--
--
--
__
28
25
23
25
62
50
Gas Analysis, volume percent^0)
S02
0.302
0.302
0.300
0.300
0.300
0.300
0.303
0.303
0.304
0.304
0.303
0.303
0.303
0.303
0.298
0.298
0.299
0.299
0.302
0.302
0.300
0.300
0.300
0.300
0.303
0.303
0.304
0.304
0.303
0.303
S03
0. 0026
0. 0026
0.0049
0. 0049
0. 0049
0. 0049
0.0053
0.0053
0. 0028
0.0028
0. 0035
0.0035
0.0038
0. 0038
0. 0023
0.0023
0. 0029
0. 0029
0. 0026
0. 0026
0. 0049
0. 0049
0. 0049
0. 0049
0. 0053
0. 0053
0. 0028
0. 0028
0. 0035
0. 0035
C02
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
10.2
10.2
10.2
10.2
10.6
10.6
11.0
11.0
10.0
10.0
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
10.2
10.2
10.2
10.2
°2
2.6
2.6
3.0
3.0
3.0
3.0
2.6
2.6
2.8
2.8
2.8
2.8
2.4
2.4
2.6
2.6
3.0
3.0
2.6
2.6
3.0
3.0
3.0
3.0
2.6
2.6
2.8
2.8
2.8
2.8
-------
TABLE C-l. (Continued)
Injection Data
0)
H
m
r
r
m
2
m
2
O
5
r
z
(A
H
H
C
m
i
o
o
r
c
2
CD
c
CO
r
GD
0
3)
H
O
5
m
w
Run
Number
1-28-V
1-28-W
11-7-L
11-7-M
10-30-R
10-30-S
11-19-J
11-19-K
2-6-CC
2-6-DD
2-5-J
2-5-K
2-4-J
2-4-K
2-6-C
2-6-D
11-4-A
11-4-B
10-24-J
10-24-K
1-28-T
1-28-U
11-7-J
11-7-K
10-30-N
10-30-O
11-19-L
11-19-M
2-12-A
2-12-B
Stone / Time,
Number(a) min
TVA
TVA
TVA
TVA
TVA
TVA
TVA
TVA
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1360
1337
1337
1.5
1.5
2
2
3
3
4
4
1
1
2
3
3
2.5
2.5
2.5
1.5
1.5
3
3
1.5
1.5
2
2
3
3
4
4
2
2
Rate,
g/min
4.0
3.5
1.4
1.0
?
1.5
1.8
1.7
1.8
1.3
3.0
2.2
3.4
2.7
2.9
2.9
1.6
1.6
0.90
1.40
4.6
5.2
1.8
1.6
1.5
1.3
1.8
1.9
1.0
0.8
Gas
Temp,
T
1803
1803
2100
2100
2100
2100
2100
2100
1500
1500
1504
1504
1506
1506
1500
1500
1800
1800
1802
1802
1803
1803
2100
2100
2100
2100
2100
2100
1305
1305
Reynolds
Number
2500
2500
3900
3900
3800
3800
3800
3800
1720
1720
1700
1700
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
3900
3900
3800
3800
3800
3800
1600
1600
Residence
Time,
sec
0.95
0.95
0.10
0.10
0.34
0.34
0.50
0.50
0.36
0.36
1.14
1.14
1.7
1.7
1.72
1.72
0.18
0.18
0.58
0.58
0.95
0.95
0.10
0.10
0.34
0.34
0.50
0.50
0.44
0.44
Product Analysis^3)
Ca
51.8
50.7
42.5
40.4
48.6
55.0
49.9
66.8
25.6
23.5
25.4
24.6
29.4
29.2
27.5
27.5
22.5
32.1
28.3
30.6
40.3
40.0
24.2
36.5
22.2
26.8
39.5
49.4
20.0
20.1
Mg
0.7
0.7
0.6
0.4
0.9
11.0
0.7
0.7
8.0
7.9
8.1
7.8
8.4
8.8
8.9
9.0
9.3
9.5
10.9
11.3
9.9
10.2
8.0
6.3
12.9
12.3
8.1
10.1
12.4
12.4
504
15.0
15.3
10.0
7.1
18.0
18.9
13.0
16.0
3.0
3.2
5.4
6.6
8.3
7.8
7.4
6.7
11.7
10.6
19.1
21.0
17.6
16.3
10.2
9.1
22.2
24.5
17.6
21.0
2.1
1.8
Percent CaO
Utilization
6.7
7.0
5.5
4.1
8.6
8.0
6.1
8.2 ±2. O(d)
1.6 ± 0.4(d)
1.7 ± 0.4(d)
3 ± 0.7(d)
3.7 ± 0.8(d)
/ J \
4.7 ± l(d)
4.4 ± 1^)
4.2 ± 0.9(d)
3.7 ± 0.8(d)
6.7 ± 1.4(d)
6.1 ± 1.4(d)
15.7
16.0
10.2
9.5
5.8±1.3
5.8
13.5 ±2.7(d)
15.1 ± 3.0(d)
10.4
12.7 ± 2.6^)
1.5±0.32
92
95
74
56
117
109
82
111 ± 28
19 ±4
20 ± 5
34 ± 8
42 ± 10
53 ± 12
50 ± 11
47 ± 11
42 ± 10
76 ± 17
68 ±12
177
180
115
107
66 ± 15
65
150 ± 30
170 ± 35
117
144 ±30
12 ±2
10 ± 1
76
73
34
19
69
89
87
__
--
--
--
--
_-
--
0 (-18)
6
62
59
--
27
__
--
58
--
--
0.303
0.303
0.298
0.298
0.299
0.299
0.302
0.302
0.300
0.300
0.300
0.300
0.303
0.303
0.300
0.300
0.304
0.304
0.303
0.303
0.303
0.303
0.298
0.298
0.299
0.299
0.302
0.302
0.300
0.300
S03
0. 0038
0.0038
0.0023
0.0023
0.0029
0.0029
0.0026
0.0026
0.0049
0.0049
0.0049
0.0049
0. 0053
0. 0053
0.0049
0.0049
0.0028
0.0028
0. 0035
0. 0035
0. 0038
0. 0038
0.0023
0.0023
0.0029
0.0029
0. 0026
0.0026
0. 0005
0. 0005
C02
10.6
10.6
11.0
11.0
10.0
10.0
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
10.0
10.0
10.2
10.2
10.2
10.2
10.6
10.6
11.0
11.0
10.0
10.0
10.2
10.2
10.0
10.0
°2
2.4
2.4
2.6
2.6
3.0
3.0
2.6
2.6
3.0
3.0
3.0
3.0
2.6
2.6 0
3.0 -1
3.0
2.8
2.8
2.8
2.8
2.4
2.4
2.6
2.6
3.0
3.0
2.6
2.6
3.0
-------
TABLE C-l. (Continued)
Injection Data
Run Stone
Number • Number^3)
CD
>
H
m
r
r
m
2
m
2
O
5
r
z
H
C
H
m
i
o
o
r
c
CD
C
w
r
co
o
'
H
0
5
m
(A
2-12-L
2-12-M
2-12-N
2-12-O
2-6-T
2-6-U
2-5-N
2-5-0
2-4-N
2-4-O
11-1-C
11-1-D
10-23-G
10-23-H
1-28-A
1-28-B
10-4-A
10-4-B
11-6-A
11-6-B
10-28-C
10-28-D
1-6-J
1-6-K
10-30-A
10-30-B
2-12-C
2-12-D
2-12-J
2-12-K
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337
1337C
1337C
1337C
1337C
Time,
min
3.5
3.5
4
4
1
1
3.5
3
1.5
2.5
1.5
1
3
3
2
3
3
3
1.5
1.5
3
3
2
2
3
3
3
1.5
5
4
Rate,
g/min
2.05
2.0
3.0
2.5
2.7
1.5
1.9
2
2.8
2.6
1.8
1.3
3.30
1.20
2.7
2.3
0.95
1.00
0.9
1.7
1.03
1.90
5.5
2.8
1.0
0.76
1.7
0.55
0.9
1.5
Gas
Temp,
°F
1339
1339
1372
1372
1500
1500
1504
1504
1506
1506
1800
1800
1800
1800
1803
1803
1902
1902
2006
2006
1996
1996
2000
2000
2100
2100
1305
1305
1339
1339
Reynolds
Number
1600
1600
1600
1600
1700
1700
1700
1700
1700
1700
2600
2600
2700
2700
2500
2500
3200
3200
3500
3500
3400
3400
3300
3300
3800
3800
1600
1600
1600
1600
Residence
Time,
sec
1.39
1.39
2.1
2.1
0.36
0.36
1.14
1.14
1.7
1.7
0.19
0.19
0.58
0.58
0.95
0.95
0.46
0.46
0.12
0.12
0.40
0.40
0.61
0.61
0.34
0.34
0.44
0.44
1.39
1.39
Product Analysis^5)
Ca
22.2
22.1
21.7
21.9
21.6
21.4
21.1
21.3
25.2
26.2
26.0
23.8
26.8
27.0
33.1
33.0
28.0
NS(C)
15.5
24.5
29.2
30.0
34.4
34.3
19.8
27.7
39.7
38.8
40.4
39.8
Mg
12.6
12.4
12.4
12.5
13.0
13.0
13.1
13.4
14.4
14.8
14.8
14.6
19.8
20.3
20.0
19.9
17.8
NS
17.1
17.2
19.4
19.5
20.6
20.6
19.2
17.9
23.3
23.0
23.7
22.7
S04
2.6
2.6
3.1
3.2
~0
~0
5.9
5.6
9.8
11.0
11.7
10.4
19.5
25.2
20.6
22.7
19.0
17.8
12.5
11.8
25.3
27.0
22.1
22.8
24.1
24.0
4.0
4.3
6.5
6.4
Percent CaO
Utilization
7.9 ± O.s(d)
7. 9 ± O.s(d)
2.3 ± 0.4(d)
2.3 ± 0.4(d>
--
--
4.8 ± 0.7W
4.2 ± 0. ?(d)
9.0
9.8
10.4
10.2
16.9
21.7
14.5
16.0
15.8
14.1 ±2.2(d>
9. 6 ± 1.6(d)
9.1 ± 1.5(d)
20.1
20.9
14.9
15.4
19.2(e)
20.1
2.3
2.6
3.7
3.7
S03, mg
per gram
calcine
15 ±3
15 ±3
18 ±3
18 ±3
--
--
34 ± 6
33 ±6
71
77
82
80
133
171
114
126
124
111 ± 17
75 ± 12
71 ± 11
158
164
117
121
151
158
18
20
29
29
Calculated
Percent Gas Analysis, volume percent^
Calcination SO2
_.
__
__
__
--
--
--
-6
10
9
24
37
52
95
98
48
-_
--
--
73
84
106
107
71
56
108
104
116
113
0.300
0.300
0.300
0.300
0.300
0.300
0.300
0.300
0.303
0.303
0.301
0.301
0.300
0.300
0.303
0.303
0.300
0.300
0.300
0.300
0.295
0.295
0.302
0.302
0.299
0.299
0.300
0.300
0.300
0.300
S03
0. 0005
0. 0005
0.0005
0. 0005
0. 0049
0.0049
0.0049
0. 0049
0. 0053
0. 0053
0.0026
0. 0026
0. 0029
0. 0029
0. 0038
0. 0038
0. 0032
0. 0032
0.0028
0. 0028
0.0029
0. 0029
0. 0033
0.0033
0. 0029
0. 0029
0.0005
0.0005
0.0005
0. 0005
co2
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.2
10.2
11.0
11.0
10.4
10.4
10.6
10.6
10.0
10.0
10.0
10.0
10.8
10.8
10.9
10.9
10.0
10.0
10.0
10.0
10.0
10.0
°2
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
2.6
2.6
2.5
2.5
2.9
2.9
2.4
2.4
2.8
2.8
2.5
2.5
2.6
2.6
2.7
2.7
3.0
3.0
3.0
3.0
3.0
3.0
-------
TABLE C-l. (Continued)
Injection Data
CD
H
H
m
r
r
m
2
m
2
O
3
>
r
_
z
H
C
H
m
I
o
0
r
c
2
m
c
r
m
o
H
O
5
m
tn
Run
Number
2-12-P
2-12 -Q
2-6-R
2-6-S
2-5-P
2-5-Q
2-4-P
2-4-Q
11-4-R
11-4-S
10-23-C
10-23-D
1-28-L
1-28-M
11-6-L
11-6-M
10-28-E
10-28-F
1-6-L
1-6-M
10-30-E
10-30-F
2-6-J
2-6-K
2-5-X
2-5-Y
2-4-V
2-4-W
2-6-G
2-6-H
Stone
Number^*)
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337C
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
Time,
min
6
6
1
1
2.5
4
2.5
2.5
2
2
3
3
3
3
2
2
3
3
3
3.5
3
3
4
3
4
4
2.5
3
5
5
Rate,
g/min
0.95
0.95
0.75
1.0
1.3
1.5
1.9
1.5
1.0
1.3
0.55
0.70
1.5
1.0
1.3
0.75
0.60
1.00
0.8
1.05
0.9
1.1
0.75
0.33
1.2
1.3
1.5
1.5
0.9
0.8
Gas
Temp,
°F
1372
1372
1500
1500
1504
1504
1506
1506
1800
1800
1800
1800
1803
1803
2006
2006
1996
1996
2000
2000
2100
2100
1500
1500
1504
1504
1506
1508
1500
1500
Reynolds
Number
1600
1600
1700
1700
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
3500
3500
3400
3400
3300
3300
3800
3800
1700
1700
1700
1700
1700
1700
1700
1700
Residence
Time,
sec
2.1
2.1
0.36
0.36
1.14
1.14
1.7
1.7
0.18
0.18
0.58
0.58
0.95
0.95
0.12
0.12
0.40
0.40
0.61
0.61
0.34
0.34
0.36
0.36
1.14
1.14
1.7
1.7
1.72
1.72
Product Analysis(b) Percent CaO
Ca
39.4
39.7
40.0
40.5
35.9
36.4
38.8
37.9
33.9
35.6
34.6
33.3
38.7
38.4
30.3
37.3
32.2
46.2
36.0
36.9
37.4
35.8
34.5
33.7
34.2
34.0
35.5
32.6
33.7
33.2
Mg
23.1
23.3
24.2
23.9
21.3
22.4
22.4
22.3
21.1
21.7
13.5
21.6
22.4
22.4
21.6
20.4
19.3
21.4
21.8
21.6
19.7
22.8
22.0
20.9
22.1
21.9
21.6
20.4
21.4
20.5
S05
7.9
7.7
3.5
3.2
9.6
10.1
11.2
9.3
6.6
8.7
13.5
17.4
5.8
7.7
8.1
12.0
18.7
17.8
16.8
13.3
13.5
15.2
9.0
9.2
12.7
14.3
11.9
17.2
19.2
20.7
Utilization
4.7
4.5
2.0
1.8
6.2
6.5
6.7
5.7
4.5
5.7
9.1
12.1
3.5
4.7
5.7
7.5
13.5
9.0
10.8
8.4
8.4
9.9
6.1
6.3
8.6
9.8
7.8
12.3
13.2
14.5
SO3, mg
per gram
calcine
37
35
16
14
49
51
53
45
36
47
71
95
27
37
45
52
106
70
85
65
66
76
48
50
68
77
61
96
104
113
Calculated
Percent
Gas Analysis, volume percent(c)
Calcination SC>2
113
114
109
112
95
99
114
106
75
91
93
90
106
107
70
102
85
158
107
107
110
104
84
79
88
90
96
85
97
96
0.300
0.300
0.300
0.300
0.300
0.300
0.303
0.303
0.304
0.304
0.300
0.300
0.303
0.303
0.300
0.300
0.295
0.295
0.302
0.302
0.299
0.299
0.300
0.300
0.300
0.300
0.303
0.303
0.300
0.300
so3
0. 0005
0.0005
0.0049
0.0049
0.0049
0.0049
0. 0053
0.0053
0.0028
0.0028
0.0029
0.0029
0. 0038
0.0038
0.0028
0.0028
0.0029
0.0029
0. 0033
0. 0033
0.0029
0.0029
0.0049
0.0049
0.0049
0.0049
0. 0053
0. 0053
0.0049
0.0049
C02
10.0
10.0
10.0
10.0
10.0
10.0
10.2
10.2
10.2
10.2
10.4
10.4
10.6
10.6
10.0
10.0
10.8
10.8
10.9
10.9
10.0
10.0
10.0
10.0
10.0
10.0
10.2
10.2
10.0
10.0
02
3.0
3.0
3.0
3.0
3.0
3.0
2.6
2.6
2.8
2.8
2.9
2.9
2.4
2.4 0
i
2.5 "-0
2.5
2.6
2.6
2.7
2.7
3.0
3.0
3.0
3.0
3.0
3.0
2.6
2.6
3.0
-------
TABLE C-l. (Continued)
Injection Data
0)
H
H
HI
r
r
rn
2
m
2
O
5
r
z
(A
-|
C
H
m
i
o
o
r
c
2
OJ
c
01
r
0)
o
H
0
5
m
Run
Number
11-4-L
11-4-M
10-23-A
10-23-B
1-28-E
1-28-F
11-6-E
11-6-F
10-28-J
10-28-K
1-6-C
1-6-D
11-7-P
11-7-Q
11-13-C
11-13-D
11-19-P
11-19-Q
2-6-N
2-6-0
2-5-T
2-5-U
2-4-T
2-4-U
11-4-N
11-4-0
10-23-E
10-23-F
1-28-G
1-28-H
Stone
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337MH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
Time,
min
2
2
3
3
5
4
1.5
1.5
2
2
3
3
2
3
3
3
4
5
2
1.5
5
5
2.5
3
2
2
3
3
4
3
Rate,
g/min
1.0
1.0
0.30
0.70
1.0
0.9
1.8
?
1.70
1.10
0.9
1.2
1.1
1.1
1.3
1.3
1.0
0.8
0.5
0.9
1.0
0.8
1.9
2.9
1.0
0.8
0.80
1.10
1.6
1.0
Gas
Temp,
°F
1800
1800
1800
1800
1803
1803
2006
2006
1996
1996
2000
2000
2100
2100
2102
2102
2100
2100
1500
1500
1504
1504
1506
1506
1800
1800
1800
1800
1803
1803
Reynolds
Number
2700
2700
2700
2700
2500
2500
3500
3500
3400
3400
3300
3300
3900
3900
3600
3600
3800
3800
1700
1700
1700
1700
1700
1700
2700
2700
2700
2700
2500
2500
Residence
Time,
sec
0.18
0.18
0.58
0.58
0.95
0.95
0.12
0.12
0.40
0.40
0.61
0.61
0.10
0.10
0.36
0.36
0.50
0.50
0.36
0.36
1.14
1.14
1.7
1.7
0.18
0.18
0.58
0.58
0.95
0.95
Product Analysis^3)
Ca
32.3
39.9
26.9
33.4
37.1
35.2
27.7
19.9
33.5
32.8
35.5
36.2
46.8
46.2
39.7
43.3
40.6
31.0
32.1
32.3
32.8
32.6
34.5
33.3
25.4
21.8
26.3
28.7
35.8
35.8
Mg
19.5
21.8
20.9
22.0
22.3
21.0
19.3
18.0
21.0
20.7
21.5
21.4
21.4
20.5
19.8
20.0
21.3
20.7
19.3
19.6
20.9
20.3
20.9
20.0
17.8
17.2
20.8
19.7
21.5
21.5
504
13.9
13.3
18.3
14.0
13.0
18.1
8.7
6.3
19.1
23.2
18.4
19.4
8.0
10.1
18.8
20.7
14.2
16.5
12.3
12.3
18.2
20.7
17.0
21.5
22.3
23.4
26.9
24.5
15.4
15.4
Percent CaO
Utilization
10.0
9.3
14. 5(e)
15.8(£)
10.2(£)
12.4
8.9
8.9
12.9
14.8
11.5
15.0
19. l(£)
20.8(e>
23.8
19.9
10.0
10.0
S03, mg
per gram
calcine
79
73
124
77
64
94
54
36 ±6
104
129
95
98
45
59
114
124
80
97
70
70
101
116
90
118
150
163
187
156
79
79
Calculated
Percent
Calcination
76
82
35
85
108
105
40
__
95
98
107
113
68
60
68
75
78
71
72
73
88
91
98
98
46
39
48
67
104
104
Gas Analysis, volume percent(c)
SO2
0.304
0.304
0.300
0.300
0.303
0.303
0.300
0.300
0.295
0.295
0.302
0.302
0.298
0.298
0.300
0.300
0.302
0.302
0.300
0.300
0.300
0.300
0.303
0.303
0.304
0.304
0.300
0.300
0.303
0.303
S03
0.0028
0.0028
0. 0029
0. 0029
0.0038
0. 0038
0. 0028
0. 0028
0. 0029
0. 0029
0. 0033
0. 0033
0. 0023
0.0023
0. 0028
0. 0028
0.0026
0.0026
0.0049
0.0049
0. 0049
0. 0049
0. 0053
0.0053
0. 0028
0. 0028
0. 0029
0.0029
0. 0038
0.0038
C02
10.2
10.2
10.4
10.4
10.6
10.6
10.0
10.0
10.8
10.8
10.9
10.9
11.0
11.0
10.2
10.2
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
10.2
10.2
10.4
10.4
10.6
10.6
°2
2.8
2.8
2.9
2.9
2.4
2.4
2.5
2.5
2.6
2.6
2.7
2.7
2.6
2.6 <~>
i
2.8 S
2.8
2.6
2.6
3.0
3.0
3.0
3.0
2.6
2.6
2.8
2.8
2.9
2.9
2.4
-------
TABLE C-l. (Continued)
Injection Data
CD
H
H
m
r
r
m
2
m
2
0
£
r
z
M
•H
3
c
H
m
I
o
0
r
c
2
C
w
r
CD
o
H
O
5
m
Run
Number
11-6-G
11-6-H
10-28-L
10-28-M
1-6-A
1-6-B
11-7-R
11-7-S
11-13-E
11-13-F
11-19-R
11-19-S
10-10-C
10-10-D
1-13-P
1-13-Q
10-18-J
10-18-K
1-13-V
1-13-W
1-13-G
1-13-H
10-10-G
10-10-H
1-13-N
1-13-0
1-13-T
1-13-U
1-13-E
1-13-F
Stone
Number(a)
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337DH
1337(1)
1337(f)
1337^
1337(i)
1337(8)
1337(g)
1337(J)
1337(J)
1337(h)
1337(h)
1373(g)
1373(g)
1373(0
1373(1)
13730')
13730)
1373(h)
1373(h)
Time,
min
2
2
2
2
3
3
2
2
3
3
4
4
4
4
1.5
1
4
4
2
2
1.5
1.5
4
4
2
2
2
2
1.0
1.0
Rate,
g/min
0.8
0.9
2.00
1.40
0.5
0.7
1.1
0.9
1.4
1.3
1.0
0.7
0.80
0.65
1.35
2
0.70
0.55
1.8
1.8
1.3
1.3
0.60
0.45
1
1
2.5
2.5
1.4
1.0
Gas
Temp,
T
2006
2006
1996
1996
2000
2000
2100
2100
2102
2102
2100
2100
1903
1903
1903
1903
1900
1900
1903
1903
1903
1903
1903
1903
1903
1903
1903
1903
1903
1903
Reynolds
Number
3500
3500
3400
3400
3300
3300
3900
3900
3600
3600
3800
3800
3100
3100
2900
2900
3100
3100
2900
2900
2900
2900
3100
3100
2900
2900
2900
2900
2900
2900
Residence
Time,
sec
0.12
0.12
0.40
0.40
0.61
0.61
0.10
0.10
0.36
0.36
0.50
0.50
0.47
0.47
0.51
0.51
0.47
0.47
0.51
0.51
0.51
0.51
0.47
0.47
0.51
0.51
0.51
0.51
0.51
0.51
Product Analysis^*5)
Ca
20.4
21.4
33.9
29.2
34.0
34.4
33.2
34.7
35.3
39.8
40.8
31.8
31.3
31.2
33.9
33.7
31.7
NS
32.3
31.9
34
33.4
51.9
52.0
48.1
48.2
46.0
47.3
49.4
48.9
Mg
17.2
16.2
20.0
18.9
20.1
20.5
18.5
20.3
17.3
18.9
20.6
20.9
18.5
17.4
20.8
20.2
19.4
NS
17.6
17.8
20.5
20.1
2.0
1.9
2.8
3.1
2.9
2.0
3.3
3.6
504
17.9
14.8
26.8
27.0
23.1
22.6
11.8
15.9
25.6
25.2
21.4
19.2
18.7
18.9
18.9
19.5
29.3
30.9
23.9
24.1
17.8
19.6
17.8
18.8
27.7
25.9
25.2
23.0
20.8
22.0
Percent CaO
Utilization
15.9(e)
13. 6
-------
TABLE C-l. (Continued)
Injection Data
Run Stone Time, Rate,
Number Number^ min g/min
10-10-£ 1373(0 4 1.50
10-10-F 1373(0 4 1.25
m 2-6-V 1373 1 3.5
> 2-6-W 1373 1 1
H
m 2-5-E 1373 2.5 2.2
r 2-5-F 1373 2.5 2.7
m 2-4-C 1373 3 2.3
^ 2-4-D 1373 4 1.9
O 11-1-A 1373 1.5 1.25
2 11-1-B 1373 1.5 1.85
r 10-24-E 1373 3 0.80
Z 10-24-F 1373 3 0.70
w
3 1-28-P 1373 2 4.5
C 1-28-Q 1373 1 3.7
H
HI 10-18-A 1373 3 0.75
1 10-18-B 1373 3 0.80
0
° 11-7-A 1373 2 1.6
C 11-7-B 1373 2 1.8
2
° 10-30-G 1373 3 1.6
<° 10-30-H 1373 3 1.1
r
> 11-19-C 1373 3 1.3
O 11-19-D 1373 3 1.3
Gas Residence
Temp, Reynolds
°F Number
1903 3100
1903 3100
1500 1700
1500 1700
1504 1700
1504 1700
1506 1700
1506 1700
1800 2600
1800 2600
1802 2700
1802 2700
1803 2500
1803 2500
1900 3100
1900 3100
2100 3900
2100. 3900
2100 3800
2100 3800
2100 3800
2100 3800
H (a) Stone numbers alone indicate raw stone. Suffixes on numbers
Time,
sec
0.47
0.47
0.36
0.36
1.14
1.14
1.7
1.7
0.19
0.19
0.58
0.58
0.95
0.95
0.47
0.47
0.10
0.10
0.34
0.34
0.50
0.50
indicate
Product
Ca
46.6
46.5
35.4
34.7
33.1
31.5
38.2
38.2
29.6
37.8
36.4
33.3
46.6
46.1
41.4
43.1
40.8
38.4
43.5
48.1
45
66.8
Analysis(b)
Mg SOf
2.6 11.1
2.5 11.1
2.4 1.9
2.3 2.9
2.1 5.8
2.0 5.0
2.5 10.2
2.5 13.1
3.4 10.6
3.3 11.0
3.4 20.2
4.1 23.1
2.7 19.5
2.4 18.2
2.8 18.8
2.1 23.6
2.1 8.1
1.7 6.1
3.4 20.8
3.4 21.0
2.4 16.9
1.8 16.4
other chemical states
Percent CaO
Utilization
5.5
5.6
1.2
1.9
3 ± O.?(d)
2.6 ±0.6
5.9 ±1.4(d)
12.9
16.1
9.7
9.2
10.6
12.7
4.6
3.7
11.1
10.1
8.7
9 1 ± 2^d)
SOg, mg Calculated
per gram Percent
calcine
68
68
15
24
37 ±9
32 ±8
76
98
70 ± 17
72 ± 17
159
198
120
113
130
156
57
45
137
125
107
Gas Analysis, volume percent(c)
Calcination SC>2
68
67
-5
-9
__
--
26
31
..
--
32
18
79
75
56
71
37
21
68
86
69
111 ± 25
as follows: C-calcined;
0.303
0.303
0.300
0.300
0.300
0.300
0.303
0.303
0.301
0.301
0.303
0.303
0.303
0.303
0.297
0.297
0.298
0.298
0.299
0.299
0.302
0.302
S03
0. 0028
0. 0028
0. 0049
0.0049
0.0049
0. 0049
0. 0053
0.0053
0. 0026
0.0026
0. 0035
0. 0035
0. 0038
0. 0038
0.0027
0.0027
0.0023
0. 0023
0.0029
0.0029
0.0026
0.0026
C02
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
11.0
11.0
10.2
10.2
10.6
10.6
10.2
10.2
11.0
11.0
10.0
10.0
10.2
10.2
02
2.8
2.8
3.0
3.0
3.0
3.0
2.6
2.6
2.5
2.5
2.8
2.8
2.4
2.4 O
i
2.8 £
2.8
2.6
2.6
3.0
3.0
2.6
2.6
H -hydrate; MH-monohydrate; DH-dihydrate.
3 (all -140 + 200 mesh unless otherwise noted).
jij (b) Weight percent. SO^ is expressed as
CaSO4-2H20.
w (c) CC>2 and O2 by Orsat, SO2 and 803 by titration.
(d) Calculated as indicated in Summary
(e) Calculated from Mg analysis.
(f) -100 + 200 mesh.
(g) -270 + 325 mesh.
(h) 20-40 micron.
(i) 10-20 micron.
(j) 5-10 micron.
Report dated August 30,
1968. Error range
indicated is
only that resulting from computational
procedure.
-------
APPENDIX D
TREATMENT OF DATA
-------
D-l
APPENDIX D
TREATMENT OF DATA
Analytical data obtained on reacted samples are in the form of weight percentage
of CaSC>4' ZHzO, calcium and magnesium. These data are transposed to more useful
forms as follows:
Let
y = weight fraction CaSC>4' 2H2O
x = weight fraction calcium
R = weight of CaO which has reacted with SC>2 per gram of sample
U = weight of calcium compounds which have not reacted, expressed
as CaO, per gram of sample
z = fractional utilization of total calcium in sample
g = weight of nonreactive material per gram of sample
M = average molecular weight of unreacted CaO species
, CaO, etc.)
S = grams of 803 sorbed per gram of completely calcined stone
C = fraction of CaCO3 which has been calcined.
For computational purposes, it is assumed that
(1) Only CaO reacts with the SO2.
(2) Unreacted CaO is present as either CaO or CaCO3.
(3) The analyses of calcined stones obtained by Bituminous Coal
Research, Inc., apply to currently used specimens (see Summary
Report dated August 30, 1968).
(4) Any MgCO3 is completed calcined.
Then
g = K(R + U), where K can be calculated from the BCR data, ( 1)
y = R(17Z/56), (2)
and
x = (R+U)(40/56) ; (3)
therefore,
z = (40/172)(y/x) (4)
-------
D-2
and
(80/56) R _ 80z
R+U+g 56(1+K) ' ( '
Now
g = 1 - R(172/56) - U(M/56) ; (6)
using Equation (1) for g, and solving Equations (2), (3), and (4) for R and U in terms of
y and z, Equation (6) can be rearranged to yield
^ 172(l-y) - 56K(y/z)
Y/z - Y ' (?)
Then, to evaluate the percent calcination,
let p = the weight of CaO per gram of sample which has not reacted
and
q = the weight of CaCC>3 remaining in 1 gram of sample.
Thence,
C= (R + p)/(R + U) (8)
and M may be defined as
M= (p + q)/(p/56 + q/100) . (9)
Since
q = (U - p)(100/56) , (10)
p may be evaluated in terms of U and M :
p = (100-M)U/44 . (11)
Substituting the value of p from Equation (11) in Equation (8) yields
R + U
But R/(R+U) = z and U/(R+U) = 1-z .
Therefore,
' 100-M
, , ,v
(12)
-------
D-3
The calculated values of the fractional utilization of calcium, z, in the sample and
the 803 pickup, S, thus depend upon the measured quantities x and y in a way such that
minor inaccuracies in x, the calcium analysis, affect the values of z and S more strongly
than do comparable inaccuracies in y, the sulfate analysis. This sensitivity to the
accuracy of the calcium analysis is accentuated in the calculation of percentage calcina-
tion because of the ratio of differences involved in the calculation of M. With dolomites,
in which there is less calcium to begin with, the sensitivity to errors in analysis is
increased further. As an example, Figure D-l shows the calculated values of percentage
calcination as a function of weight percent calcium for a relatively pure dolomite and a
relatively pure limestone at two levels of sulfate content. It can be seen that the calcu-
lated value of percentage calcination for a dolomitic sample is strongly dependent upon
calcium analysis, especially for low true calcination percentages.
-------
wmoo - axnxixsNi -iviaowaw amgxxv
culated Percent Calcination
OCH^OlOI^IOOtoC
3OOOOOOOC
3 0 0™
sj —
DO
BUS LABORATORIES
—
—
—
/
-1
/
/
1 1
/
A-y
/
\
B = 20 /
'
/
B = 5
/
/
/
/
\
^
s
\
/
^
A = Percen
3 = Percer
1
^
^
\ CaO in
it Ca S04 •
1
^
calcine
2 H20 in s
^
sample
1
^
\
2 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 7(
Weight Percent Calcium
-------
APPENDIX E
TEMPERATURE DEPENDENCE OF RATE DATA
-------
E-l
APPENDIX E
TEMPERATURE DEPENDENCE OF RATE DATA
Examples of Arrhenius plots for the apparent rates of reaction of stones No. 10
and No. 11 are given in the main body of this report. Arrhenius plots for the remaining
stones and limes studied during this contract period are shown in Figures E-l through
E-7 of this Appendix. As stated in the text, apparent activation energies associated
with these plots cannot at this time be related to individual chemical or physical pro-
but, rather, the plots serve as a convenient means of organization of the data.
-------
E-2
1000
o
O)
CO
0>
E
o
or
o
o
O)
o:
-»—
c
cu
k.
o
CL
o.
oShort residence term ES = 23 ± I
xMedium residence term EM = 26 ±
Long residence term E, = 25±l
10V T°K
FIGURE E-l. ARRHENIUS PLOT FOR NO. 1337
-------
E-3
1000
Ifl
I
•S1
cf
CO
o>
o
cc
o
o
S
o:
0>
o
Q.
O.
100
Short residence time Es=25±2
10
x Medium residence time
• Long residence time EL = I9±I
EM=25±3
I
0.6
0.7
0.8
0.9
I03/T°K
1.0
1.2
FIGURE E-2. ARRHENIUS PLOT FOR NO. 1360
-------
E-4
1000
o
0)
cf
(f)
o>
E
K 100
o
o>
CC
o
Q.
Q.
M
o Short residence time ES=2I ±3
x Medium residence time E=25±3
M
10
0.6
Long residence time EL=II±I
I
0.7
0.8
0.9
I03/T°K
1.0
I.I
1.2
FIGURE E-3. ARRHENIUS PLOT FOR NO. 1373
-------
E-5
1000
o
o>
10
C?
o
cc.
c
o
t3
o
0)
o:
•4—
C
2
o
Q.
CL
100
o Short residence time Es = 8±l
x Medium residence time EM=22±3
• Long residence time EL=I3±0.6
10
0.6
0.7
0.8
0.9
I03/T°K
1.0
1.2
FIGURE E-4. ARRHENIUS PLOT FOR NO. 1384
-------
E-6
1000
o
o 100
cn
c.
o
«l—
o
o
ce
"c
o>
o
a.
QL
o Short residence time Es= I3±2
x Medium residence time EM=I7±2
• Long residence time Eu = II i 0.7
10
0.6
0.7
0.8
0.9
1.0
1.2
IOVT°K
FIGURE E-5. ARRHENIUS PLOT FOR NO. 1683
-------
E-7
1000
o
o>
v>
I
10
I
o
o
I
c
0)
D
a.
a.
100
o Short residence time Es = 28 ± 3
x Medium residence time EM = 26 ± 2
• Long residence time EL = 19 ± 2
10
0.6
0.7
0.8
0.9
IOVT°K
1.0
1.2
FIGURE E-6. ARRHENIUS PLOT FOR BASIC DOLOMITE
-------
E-8
1000
o
o>
O
cn
en
E
f
a>
o
cr
c
g
+-
o
o
Q)
cr
"c
d)
o
Q.
Q.
• 100
o Short residence time Es= I9±3
x Medium residence time EM=24±3
• Long residence time EL= I4±l
10
0.6
I
I
0.7
0.8
0.9
I03/T°K
1.0
1.2
FIGURE E-7. ARRHENIUS PLOT FOR TVA LIMESTONE
-------
APPENDIX F
INVESTIGATION OF TVA STONES
-------
F-l
APPENDIX F
INVESTIGATION OF TVA STONES
The dispersed-phase reactor was used to study the SO2 sorption characteristics of
15 stones under consideration for use in full-scale boiler trials by TVA. Analytical data
for the stones are given in Table F-l.
Screening Program
The initial phase of this program was concerned with the screening of fifteen stones
supplied by NAPCA for the purpose of selecting the five most promising materials for
use in a full-scale demonstration of the dry-limestone injection process. This initial
screening program was carried out using a single set of reaction conditions - 0. 61 second
at 2000°F in simulated flue gas containing 0. 3 volume percent SO2- The results of these
screening tests are shown in Table E-2.
For most of the stones listed in Table 1, the calcium utilization was about 10 per-
cent and the 803 pickup was in the range of 110 to 150 mg/g of calcine. Nos. 2060,
2064, and 2069 had 803 pickups above this range, and seem to be the best sorbents under
the conditions employed. Nos. 2060 and 2069 also performed well in the fixed-bed tests
conducted by NAPCA, but No. 2064 was one of the poorest sorbents in the fixed-bed tests.
However, these tests were conducted under different conditions from those used by
Battelle, and relative performance may be a function of conditions used.
Calculated values of percent calcination of the reacted stones are also shown in
Table E-2. These calculated values are quite sensitive to minor variations in the accu-
racy of the analytical data, and values of 90 to 110 percent probably should be considered
as indicating essentially complete calcination.
Because of the possible changes in ordering of stone reactivities at temperatures
different from that used in the initial screening tests, five stones were selected for fur-
ther examination at other temperatures to determine activation energies for the reac-
tivity of these materials. This set of five stones was composed of the three outstanding
materials listed above plus two stones, Nos. 2061 and 2062, selected by NAPCA.
Further Testing
The essence of the hypothesized model for the reaction mechanism discussed
earlier in this report is that heat transfer and/or mass transport controls the rates of
the two endothermic reactions (calcination of carbonate and sulfite). One consequence of
this mechanism is that total sulfur pickup can go through a maximum during the initial
portion of the reaction trajectory, as has been observed with samples run at different
residence times under Contract No. PH 86-67-115.
-------
CD
H
m
r
r
m
2
m
o
z
H
C
H
m
i
o
o
m
(A
o
o
H
O
5
m
M
TABLE F-l. SPECTROCHEMICAL ANALYSIS OF STONES(a)
Results Reported as Percent by Weight
of Ignited Sample (900 C)
Stone
No.
2057
2058
2059
2060
2061
2062
2063
2064
2065
2066
2067
2069
2070
2071
2072
Loss on
Ignition
(900°C)
43.4
43.2
44.1
41.5
43.4
43.4
43.2
43.3
43.3
43.1
42.9
46.1
39.4
41.2
40.6
SiO2
1.50
2.95
5.10
8.30
1.40
2.25
1.40
<1.0
1.00
2.20
2.60
2.63
8.20
1.83
2.70
A1203
<0.2
0.74
0.63
1.50
<0.2
<0.2
0.53
0.26
0.31
0.39
0.22
0.72
1.58
0.59
0.59
Fe203
0.19
0.62
0.64
0.72
0.27
0.31
0.25
<0.2
<0.2
<0.2
<0.2
0.70
1.37
<0.2
0.31
MgO
1.50
6.20
21.3
6.60
1.77
2.42
1.92
0.95
1.55
1.13
0.08
36.0
2.00
3.20
2.40
CaO
95
89
69
81
95
94
95
96
95
93
94
58.0
85
92
92
Ti02
0.03
0.05
0.03
0.07
0.03
0.03
0.05
0.03
0.04
0.04
0.04
0.05
0.08
0.04
0.05
SrO Na2O
0.02
0.04
0.05
0.09
<0. 02
<0. 02
0.05
<0. 02
<0.02
0.03
0.02
0.06
0.16
0.05
0.04
K20
<0.1
0.10
0.24
0.31
<0.1
<0.1
0.13
<0. 1
<0. 1
<0. 1
<0. 1
0.47
0.22
0.23
<0.1
MnC>2
<0. 03
<0.03
<0.03
<0. 03
<0.03
<0. 03
<0. 03
<0. 03
<0.03
<0.03
<0.03
<0.03
0.09
<0. 03
-------
F-3
This fact had an important bearing on the manner in which the five candidate stones
were tested for dependence of reactivity on temperature. As test temperatures are
lowered, the maximum pickup is shifted to longer residence times. To accommodate
this feature of the reaction trajectory, residence times were not held constant for runs
at the various temperatures, but were lengthened as the temperature was lowered. Con-
sequently, it is believed that the results represent similar portions of the pickup curve
and it is valid to compare results obtained at various temperatures.
Test conditions, chemical analyses, and calculated values of reactivity are given
in Table F-2. Apparent rates of reaction of the five stones at five temperatures are
summarized in Table F-3. Arrhenius plots constructed from these data and apparent
activation energies obtained by a least-squares treatment of these rates are shown in
Figures F-l to F-5. Errors indicated for the activation energies are most-probable
errors obtained from the least-squares treatment. In making these calculations, all
measured points were included in the computations except for the one pair of points
which are obviously in error for No. 2060. It must be recognized that the values
obtained are not true activation energies, since the temperatures plotted on the figures
are gas temperatures; actual reaction temperatures are not known.
300
200
v>
i
o»
E 100
I 80
o:
c 60
o
Q.
Q.
40
30
E = 12.0 ±0.8 kcal/mole
I
0.7
0.8
IOOO/T,°K
0.9
FIGURE F-l. REACTIVITY OF NO. 2060
Two of the five stones, Nos. 2064 and 2069, have high apparent activation energies
and would be logical choices for trial in a boiler, providing that long-enough residence
times could be achieved at higher temperatures. However, this may not be possible in
the boiler if injection is made at temperatures near 2300°F, since gas temperature in a
boiler drops off very rapidly below this point. If injection is made at about 2300°F,
No. 2060 might be a better choice since this material has relatively high reactivity over
a broad temperature range.
-------
TABLE F-2. REACTOR DATA
CD
H
H
m
r
r
m
2
m
0
7S
>
r
z
H
H
C
H
m
i
o
o
r
c
2
CD
c
r
m
o
>
H
0
3
m
w
Run
Number
2 -3 -A
2-3-B
2-3-C
2 -3-D
2-3-E
2-3-F
2-3-G
2-3-H
2-3-K
2-3-L
1-30-L
1-30-M
1-30-N
1-30-O
1-30-R
1-30-S
1-30-P
1-30-Q
1-30-T
1-30-U
1-29 -A
1 -29 -B
1-29-C
1-29-D
1-29-E
1-29-F
1-29-G
1-29-H
1-29-J
1-29-K
Stone
Number
2060
2060
2061
2061
2062
2062
2064
2064
2069
2069
2060
2060
2061
2061
2062
2062
2064
2064
2069
2069
2060
2060
2061
2061
2062
2062
2064
2064
2069
2069
Gas
Temp,
°F
1603
1603
1603
1603
1603
1603
1603
1603
1603
1603
1681
1681
1681
1681
1681
1681
1681
1681
1681
1681
1807
1807
1807
1807
1807
1807
1807
1807
1807
1807
Reynolds
Number
1920
1920
1920
1920
1920
1920
1920
1920
1920
1920
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2600
2600
2600
2600
2600
2600
2600
2600
2600
2600
Residence
Time, sec
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.43
1.29
1.29
1.29
1.29
1.29
1.29
1.29
1.29
1.29
1.29
0.93
0.93
0.93
0.93
0.93
0.93
0.93
0.93
0.93
0.93
Product Analysis,
weight percent
Ca
38.8
38.2
44.9
45.0
42.9
42.9
46.0
45.8
27.5
27.2
40.6
40.6
47.8
48.3
45.3
46.3
48.1
40.4
30.5
30.2
44.5
44.5
53.3
54.3
50.5
50.6
49.5
51.5
31.7
31.3
Mg
3.7
3.7
0.4
0.4
1.7
1.8
0.4
0.4
17.5
17.0
4.5
4.9
0.4
0.4
1.8
1.7
0.4
0.4
18.7
18.7
5.0
5.1
0.5
0.5
2.0
2.0
0.5
0.5
19.4
19.4
S0=(a)
23.7
26.4
16.9
17.4
16.4
18.6
16.0
15.1
19.5
16.9
25.4
25.1
20.0
21.2
23.1
24.4
26.3
23.5
20.9
21.7
25.1
26.2
24.2
21.8
23.4
24.2
28.1
27.8
22.3
24.8
Percent CaO
Utilization
14.2
16.1
8.8
9.0
8.9
10.1
8.1
7.7
16.5
14.4
14.5
14.4
9.7
10.2
11.9
12.2
12.7
13.5
15.9
16.7
13.1
13.7
10.6
9.3
10.8
11.1
13.2
12.6
16.3
18.4
S03, mg
per gram
calcine
164
186
119
122
119
135
111
105
137
120
168
166
132
139
159
166
174
185
132
138
152
158
143
127
145
149
181
172
136
153
Calculated
Percent
Calcination
60
62
55
56
47
50
56
54
32
23
72
71
69
73
66
71
77
43
63
62
87
89
91
91
84
85
84
89
76
78
Gas Analysis,
volume percent
so2
0.302
0.302
0.302
0.302
0.302
0.302
0.302
0.302
0.302
0.302
0.303
0.303
0.303
0.303
0.303
0.303
0.303
0.303
0.303
0.303
0.295
0.295
0.295
0.295
0.295
0.295
0.295
0.295
0.295
0.295
so3
0. 0053
0. 0053
0. 0053
0. 0053
0. 0053
0. 0053
0. 0053
0. 0053
0.0053
0.0053
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0043
0. 0039
0. 0039
0. 0039
0.0039
0. 0039
0. 0039
0.0039
0.0039
0.0039
0.0039
co2
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
°2
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
-------
TABLE F-2. (Continued)
CD
H
H
m
r
r
m
2
m
0
5
r
z
H
H
C
H
m
i
o
o
r
c
2
CD
C
w
r
CD
O
JO
H
0
5
m
Run
Number
1-30-J
1-30-K
1-30-G
1-30-H
1-30-E
1-30-F
1-30-C
1-30-D
1-30 -A
1-30-B
1-9-C
1-9-D
1-3-L
1-3-M
1-9-E
1-9-F
1-9-L
1-9-M
1-3-N
1-3-O
1-9-G
1-9-H
1-9-J
1-9-K
1-9-N
1-9-O
1-3-G
1-3-H
1-3-E
1-3-F
Stone
Number
2060
2060
2061
2061
2062
2062
2064
2064
2069
2069
2057
2057
2058
2058
2059
2059
2060
2060
2061
2061
2062
2062
2063
2063
2064
2064
2065
2065
2066
2066
Gas
Temp,
°F
1910
1910
1910
1910
1910
1910
1910
1910
1910
1910
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
Reynolds
Number
2900
2900
2900
2900
2900
2900
2900
2900
2900
2900
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
3300
Residence
Time, sec
0.77
0.77
0.77
0.77
0.77
0.77
0.77
0.77
0.77
0.77
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
0.61
Product Analysis,
weight percent
Ca
45.0
45.4
55.5
55.1
53.2
52.3
53.4
52.3
32.1
32.1
54.7
53.2
53.0
50.4
37.9
38.4
47.3
47.6
56.6
55.4
56.4
54.7
57.6
58.2
53.1
53.3
57.8
57.2
56.1
56.3
Mg
4.3
4.7
0.5
0.5
1.9
1.6
0.5
0.5
19.2
19.2
0.6
0.9
3.0
3.9
13.2
13.3
3.5
3.1
0.5
0.6
1.5
1.7
0.7
0.7
0.4
0.4
0.7
0.6
0.8
0.7
so|(a)
28.2
27.3
21.9
21.8
21.5
23.2
26.0
22.7
23.2
25.7
23.3
21.8
24.8
28.3
22.0
21.1
29.2
31.4
24.7
25.9
25.1
24.1
21.1
24.7
31.3
31.9
21.6
24.0
25.4
24.5
Percent CaO
Utilization
3.5
4.7
9.2
9.2
9.4
10.3
11.3
10.1
16.8
18.6
9.9
9.5
10.9
13.1
13.5
12.8
14.4
15.3
10.1
10.9
10.3
10.2
8.5
9.9
13.7
13.9
8.7
8.8
10.5
10.1
SO3, mg
per gram
calcine
27
37
125
125
126
139
155
138
139
154
134
129
138
166
133
126
166
178
138
148
139
138
116
134
188
191
118
119
140
134
Calculated
Percent
Calcination
106
107
94
93
89
89
92
85
81
85
94
88
100
97
80
81
103
107
100
99
101
96
99
104
98
99
100
98
103
102
Gas Analysis,
volume percent
so2
0.296
0.296
0.296
0.296
0.296
0.296
0.296
0.296
0.296
0.296
0.295
0.295
0.300
0.300
0.295
0.295
0.295
0.295
0.300
0.300
0.295
0.295
0.295
0.295
0.295
0.295
0.300
0.300
0.300
0.300
so3
0. 0035
0. 0035
0. 0035
0. 0035
0. 0035
0. 0035
0.0035
0. 0035
0. 0035
0. 0035
0. 0039
0. 0039
0. 0034
0. 0034
0. 0039
0. 0039
0.0039
0.0039
0. 0034
0.0034
0. 0039
0. 0039
0. 0039
0.0039
0.0039
0. 0039
0. 0034
0. 0034
0. 0034
0. 0034
co2
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.6
10.0
10.0
10.2
10.2
10.0
10.0
10.0
10.0
10.2
10.2
10.0
10.0
10.0
10.0
10.0
10.0
10.2
10.2
10.2
10.2
°2
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
2.7
2.7
2.6
2.6
2.7
2.7
2.7
2.7
2.6
2.6
2.7
2.7
2.7
2.7
2.7
2.7
2.6
2.6
2.6
-------
TABLE F-2. (Continued)
ID
H
H
rn
r
r
m
2
m
2
O
3)
^
r
z
(0
H
C
H
m
i
o
o
r
c
2
CD
C
W
r
CD
O
H
0
5
m
Run
Number
1-9 -A
1-9-B
1-3 -A
1-3-B
1-3-C
1-3-D
1-3-P
1-3-Q
1-3-J
1-3-K
Stone
Number
2067
2067
2069
2069
2070
2070
2071
2071
2072
2072
Gas
Temp,
°F
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
Product
Reynolds Residence weight
Analysis,
percent
Number Time, sec Ca Mg SO|(a)
3300 0.61 54.0 0,
3300 0.61 53.4 0,
3300 0.61 30.2 18,
3300 0.61 31.8 20.
3300 0.61 53.0 1.
3300 0.61 53.3 1.
3300 0.61 52.9 2,
3300 0.61 52.5 2,
3300 0.61 56.1 1.
3300 0.61 54.4 1.
.7 23.8
.5 24. 0
.4 27.9
. 0 27.4
. 0 26.1
. 0 27.9
.9 22.2
.9 24. 0
.2 23.5
. 1 26.2
SO3, mg
Percent CaO per gram
Utilization calcine
10.2 138
10. 5 140
21.5 178
20.0 166
11.5 139
12. 1 148
9.8 128
10.6 140
9.7 128
11.2 147
Calculated
Percent
Calcination
94
93
75
86
108
111
92
93
102
100
Gas Analysis,
volume
so2 so3
0.295 0.0039
0.295 0.0039
0.300 0.0034
0.300 0.0034
0. 300 0. 0034
0.300 0.0034
0.300 0.0034
0. 300 0. 0034
0. 300 0. 0034
0.300 0.0034
percent
C02
10.0
10.0
10.2
10.2
10.2
10.2
10.2
10.2
10.2
10.2
°2
2.7
2.7
2.6
2.6
2.6
2.6
2.6
2.6
2.6
2.6
(a) Expressed as CaSC>4-2H2O.
-------
F-7
300
in
CT 20°
in
a
a:
"c
0)
a
a.
ex
100
90
80
70
E = 13.5 ±0.6 kcal/mole
I
0.7 0.8
IOOO/T,°K
FIGURE F-2. REACTIVITY OF No. 2061
0.9
300
o
"c
0>
o
Q.
Q.
200 -
E = 11.9 ± 0.7 kcal/mole
IOOO/T,°K
A-57S79
FIGURE F-3. REACTIVITY OF No. 2062
-------
F-8
o
0>
E
oT
"o
o:
"c
S
o
Q.
Q.
400
300 -
200 -
E = 17 ± I Kcal/mole
0.8
1000/T, °K
FIGURE F-4. REACTIVITY OF No. 2064
0.9
o
0)
in
i
d°
in
Cf>
£
c
O)
o
ex
Q.
400
300
200
100
90
80
70
6°0.7
E =15.7 ± 0.7 kcal/mole
0.8
IOOO/T,°K
A-57880
0.9
FIGURE F-5. REACTIVITY OF No. 2069
-------
F-9 and F-10
The current work emphasizes the need for further development of means for re-
lating the results obtained in the dispersed-phase reactor to the performance of a stone
in a boiler. In particular, a model of the reaction system which takes into account the
differences in the thermal history of a stone particle in boiler and reactor environments
is needed.
TABLE F-3. SUMMARY OF APPARENT REACTION RATES (a)
Temperature and Residence Time
1603°F
Stone No.
2060
2061
2062
2064
2069
1.48
122
84
89
76
90
sec
±
±
±
±
±
8
1
6
2
6
168
1.29
129
105
126
139
105
1°F
sec
± 1
± 3
± 3
± 4
± 2
1807°F
0. 93 sec
167 ± 3
145 ± 9
158 ± 2
190 ± 5
155 ± 9
1910°F
0. 77 sec
42 ±
162 ±
172 ±
190 ±
190 ±
6
0
8
11
10
2000°F
0.61
282
234
227
311
282
sec
±
±
±
±
±
10
8
1
2
10
(a) mgSO3/g-sec.
------- |