Lime/Limestone Scrubbing for SO2 and Particulate Removal in a Marble Bed Scrubber


EPA-650/2-75-052

June 1975       Environmental Protection Technology Series
            LIME/LIMESTONE SCRUBBING
       S02  AND  PARTICUIATE  REMOVAL
           IN A  MARBLE  BED SCRUBBER
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                                    EPA-650/2-75-052
      LIME/LIMESTONE  SCRUBBING

FOR S02  AND PARTICULATE  REMOVAL

      IN  A MARBLE  BED  SCRUBBER

                        by
          M. R. Gogineni, K. Maiki,  and D. C. Borio
               Combustion Engineering, Inc.
                 1000 Prospect Hill Road
               Windsor, Connecticut  06095
                 Contract No. 68-02-0221
                  ROAP No. 21ACY-020
               Program Element No. LAB013
            EPA Project Officer:  Julian W. Jones

                Control Systems Laboratory
            National Environmental Research Center
            Research Triangle Park, N. C.  27711
                    Prepared for

          U.S. ENVIRONMENTAL PROTECTION AGENCY
           OFFICE OF RESEARCH AND DEVELOPMENT
                WASHINGTON,  D.C. 20460

                      June 1975
-------
                       EPA REVIEW NOTICE

This report has been reviewed by the National Environmental Research
Onti:r - Research Triangle Park, Office of Research and Development.
EPA, and approved for publication.  Approval does  not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
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mental Protection Agency, have been grouped into series.  These broad
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in related fields.  These series are:

          1.  ENVIRONMENTAL HEALTH EFFECTS RESEARCH

          2.  ENVIRONMENTAL PROTECTION TECHNOLOGY

          3.  ECOLOGICAL RESEARCH

          4.  ENVIRONMENTAL MONITORING

          5.  SOCIOECONOMIC ENVIRONMENTAL STUDIES

          6.  SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
          9.  MISCELLANEOUS

This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution.   This work provides the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
 This document is available to the public for sale through the National
 Technical Information Service, Springfield, Virginia 22161.

                Publication No. EPA-650/2-75-052
                                11
-------
                                   ABSTRACT

                 The Environmental  Protection Agency (EPA)  awarded a contract
to Combustion Engineering, Inc. (C-E) to conduct research  and development work
on S02 scrubber systems using the C-E test equipment and facilities.
                 Sixteen once-through soluble system tests  using sodium
carbonate scrubbing solution were conducted.   The results  showed that the
marble bed scrubber is a very good liquid-gas contacting device for SOg
removal from flue gases with an overall  efficiency of 90 to 95 percent.
Liquid to gas ratio and scrubber liquid  composition significantly affected
the S02 removal while other variables had little or no effect on S02 removal.
                 Six limestone furnace injection systems tests were conducted
using boiler calcined limestone and flyash mixture.  The results also showed
that solids concentration in the spray slurry and liquid to gas ratio
significantly affected the S02 removal.
                 Six limestone tail-end  system tests were  conducted using
commercial limestone in a dual marble bed scrubber.  It was determined that
the S(L removal efficiencies of the low  and upper beds are  the same, based
on the SOo concentrations entering the respective beds.
                 It was demonstrated that scale-free operation of both the
furnace injection and tail-end systems can be achieved in  a closed loop system
without employing the liquid blowdown by maintaining 8 to  10% solids in the
spray slurry.
                                     iii
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                                  CONTENTS

ABSTRACT	    1H
1.  PROGRAM OVERVIEW 	    1-1
    1.1  Introduction	    1-1
    1.2  Summary of Results and Conclusions	    1-3
    1.3  Test Equipment	    1-6
2.  ONCE-THROUGH SOLUBLE SYSTEM TESTS  	    2-1
    2.1  Test Description	    2-1
    2.2  Data Evaluation	    2-3
    2.3  Calculation of Stage Efficiency 	    2-8
3.  LIMESTONE FURNACE INJECTION SYSTEM TESTS 	    3-1
    3.1  System Chemistry  	    3-1
    3.2  Test Description	    3-1
    3.3  Data Evaluation	    3-7
    3.4  Conclusions	    3-23
4.  LIMESTONE TAIL-END SYSTEM TESTS  	    4-1
    4.1  System Chemistry  	    4-1
    4.2  Test Description	    4-1
    4.3  Data Evaluation	    4-6
    4.4  Conclusions	    4-21
                                    iv
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                                APPENDICES


A.   GAS  FLOW  CHECK	    A-l


B.   SOLUBLE SYSTEM  TEST DATA AND  RESULTS  	    B-l


C.   SOLUBLE SYSTEM  ANALYTICAL RESULTS   	    C-l


D.   ANALYTICAL  PROCEDURES  FOR ARCS SAMPLES  	    D-l
E.  SOLUBLE SYSTEM STAGE EFFICIENCY
    CALCULATION DIAGRAMS 	    E-l
F.  LIMESTONE FURNACE INJECTION SYSTEM OPERATING
    DATA AND ANALYTICAL RESULTS   	    F-l
G.  LIMESTONE FURNACE INJECTION SYSTEM
    PROBLEMS AND MODIFICATIONS 	    G-l
H.  LIMESTONE FURNACE INJECTION SYSTEM MATERIAL
    BALANCES AND RATE CALCULATIONS	    H-l
I.  LIMESTONE FURNACE INJECTION SYSTEM ADDITIVE
    DISSOLUTION RATE DETERMINATION DIAGRAMS   	    1-1
J.  LIMESTONE TAIL-END SYSTEM OPERATING DATA
    AND ANALYTICAL RESULTS 	   J-l
K.  LIMESTONE TAIL-END SYSTEM MATERIAL
    BALANCES AND RATE CALCULATIONS	    K-l
L.  LIMESTONE TAIL-END SYSTEM DISSOLUTION
    RATE DETERMINATION DIAGRAMS  	   L-l
-------
                                     FIGURES



1-1.   C-E ARCS Prototype 	   1-7


2-1.   Once-Through Soluble System  	   2-2


2-2.   Overflow Pot and Downcomer Arrangement 	   2-7


2-3,   Sodium Carbonate System - Stage Efficiency
      Determination  	   2-11


3-1.   Limestone Furnace Injection System - No Recycle  	   3-3


3-2.   Limestone Furnace Injection System - With Recycle  	   3-4


3-3.   Plot of Operating Line for Experiment 17R  	   3-18


3-4.   Plot of Calcium vs. Partial Pressure of S0?
      for Scrubber Effluent - Experiment 17R .	3-20


4-1.   Limestone Tail-End System  	   4-3


4-2.   Plot of Operating Line for Experiment 25R	4-16


4-3.   Plot of Calcium vs. Partial Pressure of S02
      for Scrubber Effluent - Experiment 25R . .*	4-17


4-4.   Plot of Operating Line for Experiment 28R	4-19


4-5.   Plot of Calcium vs. Partial Pressure of S0?
      for Scrubber Effluent - Experiment 28R .	4-20
                                   vi
-------
                                  TABLES
2-1.  Test Parameters for the Soluble System 	   2-4
2-2.  Total Sulfur Material Balance	   2-9
                                                                         j
2-3.  Summary of Stage Efficiency Calculations 	   2-13
3-1.  Test Parameters for the Limestone
      Furnace Injection System 	   3- 5
3-2.  Summary of Limestone Furnace Injection
      Tests Performance Results	   3-8
3-3.  Summary of Rate Results from Limestone
      Furnace Injection Tests  	   3-13
3-4.  Criteria for Determination of Limestone
      Furnace Injection Test Reliability 	   3-15
3-5.  Summary of Calcium Hydroxide Dissolution
      Calculations for Marble Bed  	   3-21
3-6.  Comparison of Calcium Sulfate Supersaturation
      and Scrubber Performance 	   3-22
4-1.  Test Parameters for the Limestone
      Tail-End System	   4-5
4-2.  Summary of Limestone Tail-End Tests
      Performance Results  	   4-7
4-3.  Summary of Rate Results from Limestone
      Tail-End Tests 	   4-10
4-4.  Criteria for Determination of Limestone
      Tail-End Test Reliability  	   4-13
4-5.  Summary of Calcium Carbonate Dissolution
      Calculations 	   4-13
4-6.  Assumed S(L Removal for Lower Bed In Two-Bed
      Calcium Carbonate Tests  	   4.18
4-7.  Calcium Sulfate Supersaturation   	   4-22
                                  vii
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                                  SECTION  1
                               PROGRAM OVERVIEW

1.1              INTRODUCTION
                 Combustion Engineering  (C-E)  has  developed an Air Pollution
Control System (APCS) employing lime/limestone wet scrubbing.  At the time of
contract negotiations between C-E and EPA  in  1970,  the C-E APC systems at
Union Electric (St. Louis) and Kansas Power and  Light (Lawrence) were
experiencing calcium sulfite and sulfate scaling problems.
                 The purpose of the contract was to analyze the previous C-E
APCS data and to conduct research and development  on small pilot scale (KDL
pilot plant), large pilot scale (KDL  prototype), and full plant scale versions
of C-E lime/limestone wet scrubbing process  (limestone furnace injection system
with single marble bed scrubbers) in  order to  accelerate its commercial
development by solving the calcium sulfite and sulfate scaling problems.
The original purpose of the contract  was later revised to include the following:
                 (1)  Confirm the adequacy of the  methods developed fay C-E to
control calcium sulfate and sulfite scaling  in the system.
                 (2)  Obtain the vapor-liquid and  solid-liquid mass transfer
rate data that could be used in the design of the  APCS.
                 (3)  Predict two marble bed  scrubber system performance from
the performance of a single marble bed scrubber  system.
                                     1-1
-------
                 Experimental  work under the contract was  carried out on the
prototype scrubber system at the Kreisinger Development  Laboratory  (KDL) of
Combustion Engineering in Windsor.  Three kinds  of  systems were studied:
(1) once through Soluble System using sodium carbonate scrubbing solution,
(2) Limestone Furnace Injection System using boiler calcined  limestone  and
flyash mixture as the additive, and (3) Limestone Tail-End System.
                 The Soluble System tests were  run  to obtain  data pertaining to
the absorption characteristics of the-marble bed scrubber.  Since no solids
were present in the system, material balances could be made more accurately
for the marble bed and overall system.  This information was  then used  to calculate
the stage efficiency of the marble bed for various  test  conditions.
                 In order to develop a better understanding of the  Limestone
Furnace Injection System and Limestone Tail-End System,  detailed material
balances were carried out for all of the tests  run. These material balances
permitted the calculation of dissolution and precipitation rates for important
chemical species in the marble bed and associated equipment.   Supersaturation
of sulfur compounds was also investigated using these test data and the
equilibrium computer program.
                                      1-2
-------
 1.2             SUMMARY OF RESULTS AND CONCLUSIONS
 1.2.1           Previous C-E APCS Data
                EPA was supplied with the technical  information  generated  by
 C-E  in previous and current APCS development work.   This  information  consisted  of
 reports covering the work on the KDL Prototype  and  the.field units  at Detroit Edison
 Company, Union Electric Company, and Kansas  Power and Light Company.   An oral
 presentation was made on October 13, 1971 in Windsor by C-E personnel  to EPA and
 Radian Corporation personnel covering C-E's  experience with Air  Pollution  Control
 Systems both in the field and in the laboratory.
                The objective was to analyze previous C-E APCS data and use this
 data in the development of a test program to be carried out on the  KDL Prototype.
 The purpose of this program was to determine a  set  of optimum operating conditions
 for improving the operation of C-E APCS field units.  Radian and EPA  concluded
 that the previous C-E APCS data were incomplete and could not be used in the
 development of the KDL Prototype test program.
 1.2.2           Collection and Storage of Boiler Calcined Material
                A mixture of boiler calcined limestone and flyash was used in
 six tests conducted on the KDL prototype.  Considerable effort and  funds were
 expended in the collection and storage of the boiler calcined material. The
 boiler calcined material and flyash were collected  from unit No. 2  of the
Meramec plant of Union Electric Company, St. Louis.   About 30 tons  of boiler
 calcined limestone and flyash mixture, 65 tons  of boiler  calcined dolomite and
 flyash mixture, and 50 tons of flyash was stored in 50 Ib bags in the warehouse
of Pozament Corporation in Mil ford, Connecticut.  About 135 tons of boiler
calcined limestone and flyash mixture was initially stored in North Haven,
Connecticut for six months in a silo rented  from Guyott Co. (owned  by
                                     1-3
-------
Connecticut Highway Equipment Co.) and was later transferred to  Pozament
Corporation.  Only a small fraction of this boiler calcined material was  used
and the leftover material was disposed of as instructed by EPA personnel.
1.2.3           Soluble System Tests
                Soluble System experiments were performed to determine  the
vapor-liquid mass transfer characteristics (overall  tray efficiency) of the
marble bed scrubber using once-through sodium carbonate scrubbing  solution.
These tests showed that:
                (1)  The marble bed scrubber is a good liquid-gas  contacting
device with an overall tray efficiency of 90 to 95 percent.
                (2)  The SOp removal in the marble bed scrubber  is limited by
the vapor-liquid equilibrium.
                Liquid to gas ratio (L/G) and the scrubber liquor  composition
strongly influence the S02 removal.  For example, increasing L/G from 15  to 20  GPM
per 1000 CFM raised S02 removal from 60% to 77%.   Increasing the sodium carbonate
concentration in the scrubber from 25 to 120 millimoles per liter  raised  the S0«
removal from 64% to 95%.  Variables such as gas and liquid temperatures,  scrubber
feed location (above or below the bed) and gas flow do not seem  to affect the
S09 removal.  No NO  removal  can be obtained with sodium carbonate scrubbing
  £                A
solution.
1.2.4           Limestone Furnace Injection System Tests
                Limestone Furnace Injection System experiments were performed
to determine the system performance and the solid-liquid mass transfer
characteristics  in the marble bed scrubber and the hold tank (reaction  tank)
using boiler calcined limestone and flyash mixture as  the additive.
                                    1-4
-------
                These tests showed that the major parameters influencing the
S(L removal of the system are liquid to gas ratio and the solids content of the
spray slurry.  An increase in L/G from 20 to 35 GPM/1000 CFM improved S02
removal from 60 percent to 70 percent with other factors held constant.   S02
removal was improved from 36 percent to 68 percent by increasing the solids
content of the spray slurry from 0.7 percent to 3.5 percent.  Further increases
in slurry concentration up to 8 percent did not result in additional improvement
in SOp removal.
                Calcium sulfate scaling 1n the Furnace Injection System  can be
prevented by maintaining the relative supersaturation of this material below 1.3.
This was achieved in a closed loop system with no liquid blowdown by maintaining
8 percent total solids (including flyash) in the spray slurry.  Calcium  sulfite
scaling, on the other hand, occurs in the scrubber when the spray slurry pH
reaches 11 with CaO or Ca(OH)2 solids entering the scrubber.
1.2.5           Limestone Tail-End System Tests
                The Limestone Tail-End System tests were performed in order to
determine whether two marble bed scrubber performance (S02 removal and scaling)
can be predicted by extrapolating the single marble bed scrubber performance of
the C-E scrubber at Shawnee (EPA test facility).  Information concerning the
solid-liquid mass transfer characteristics in the marble bed scrubber and the
hold tank was also desired.
                The tests revealed that the S02 removal  efficiency and scaling
tendencies of a scrubber with two marble beds can be predicted by extrapolating
single bed test results at Shawnee.  The S02 removal efficiencies of the lower
and upper beds appear to be the same based on the S02 concentrations entering
the respective beds.   S02 removal  can be improved significantly (from 76 percent
                                    1-5
-------
removal to 87 percent removal)  by increasing  L/G  from 15 to 25 GPM/1000 CFM
with other factors held constant.  Limestone  feed rates above 10035 stoichiometry
have little or no effect on S0« removal  efficiency in high solids systems.  In
these tests more than half the  additive  dissolution occurs in the marble bed
in spite of the short residence time  there.
                Calcium sulfate scaling  can be controlled in the system by
maintaining the relative supersaturation level  below 1.7.  This can be achieved
in a closed loop system without employing liquid  blowdown by maintaining 8 to
10 percent solids (excluding flyash)  in  the spray slurry.
1.3             TEST EQUIPMENT
1.3.1           General Description
                The Prototype is located at Kreisinger Development Laboratory
of Combustion Engineering, Inc. in Windsor, Connecticut.  A schematic of the
system is shown in Figure 1-1.   The system consists of all components of the
C-E field units.
                The flue gas from an  oil fired boiler (30,000 to 40,000 pounds
of steam per hour) passes through a heat extractor in which the gas can be
cooled down to any desired temperature between 150 and 300°F before entering
the scrubber.  The flue gas from the heat extractor passes through the scrubber
inlet section, marble beds, demister, and reheater before entering the stack.
The scrubber inlet section is about 8 ft. long and converges towards the scrubber.
Provisions are made for introducing either flyash or additive or both into the
inlet either to simulate coal firing  or  furnace injection.  The inlet is kept
from plugging with deposits by the periodic operation of  a soot blower.
                                     1-6
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                              TO
                             STACK
                                                   LIMESTONE
                                                    FEEDER
 FLUE GAS
 FROM V.P. -
 BOILER
  HEAT
EXTRACTOR
                                    REHEATER
                                       DEMISTER


                                      .MARBLE BED


                                         SPRAY WATER(SWU)
                                         SCRUBBER LIQUID (SLU)
                                      MARBLE BED


                                         SPRAY WATER (SWL)
                                         SCRUBBER LIQUID(SLL)
                                    SOLIDS TO
                                     DISPOSAL
O
C
3)
m
                                      VACUUM
                                      FILTER
                               CE  AQCS  PROTOTYPE
-------
                The marble bed consists of a 5 ft.  by  5  ft.  perforated,
stainless steel plate supporting 3/4 inch diameter  glass spheres  (marbles)
3 Inches deep; five overflow pots of 10 inch diameter; and five downcomers
of 3 inch pipe.  The overflow and pot height controls  the turbulent  layer
height and is usually set at 9 inches from the perforated plate,  but can be
varied by making some minor changes.  A stainless steel  perforated plate with
3/8 inch holes and 35 percent open area supports the marbles.  There are 36
commercial spray nozzles under the bed and 8 nozzles consisting of 1  inch pipes
with splash plates above the bed.  The spray slurry or spray liquid  can be
introduced either under or above the bed or both.   There are two  marble beds in
the scrubber.  The upper bed can be removed from the scrubber when it is not
needed.
                The chevron type demister made of stainless  steel separates
the entrained liquid from the gas and prevents the  reheater  from  plugging.  The
gas leaving the scrubber is heated 25 to 50°F in the reheater to  protect the
1.0. fan.
                Clarified liquid from the clarifier or the reaction  tank (hold
tank) effluent can be used as spray water or spray  slurry.  Make-up  water
and additive for the soluble and tail-end systems are  added  to the hold
tank.
1.4.2           Flow Measurement
                Liquid flow in the system is measured  by magnetic flow meters
which are calibrated both electrically and by manually measuring  the flow.  For
the manual calibration, the hold tank is filled with water and the flow through
the flow meter is set at a particular value.  Water levels in the hold tank at
the beginning and end of the calibration procedure  are noted and  the flow
                                    1-8
-------
meter reading is checked against the flow rate obtained from the difference
in water level in the hold tank.
                Additive feed rate is controlled by using Wallace & Tiernan
feeders.  These feeders are calibrated both by using the calibration weights
and by weighing a collected sample from the feeder.  The manual  sample is
checked against the feeder reading.
                Gas flow is measured with a pi tot tube located at the center
of the duct in the stack after the I.D. fan.  The single point pitot tube
gas flow measuring technique was checked against the multiple point pitot
tube traverse and the S(L tracer gas method.  The gas flow check is given  in
detail in Appendix A.
                S02 concentrations were measured using both the manual  method
and the Dupont 400 Photometric Analyzer.   The manual  method consists of
absorbing S02 gas into 3 weight percent Hfa solution and titrating with 0.1N
(for the inlet sample) and 0.01N (for the outlet sample)  NaOH solution.  The
Dupont Analyzer was calibrated with SOo gas from standard gas cylinders.   The
gas cylinder concentrations were also verified by the manual  method described.
                                    1-9
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                                 SECTION 2
                     ONCE-THROUGH SOLUBLE SYSTEM TESTS

 2.1              TEST DESCRIPTION
                 The objective of the once-through soluble system tests was to
 determine the  vapor-liquid mass transfer characteristics (overall tray
 efficiency)  of the marble bed scrubber using sodium carbonate scrubbing
 solution.
                 The operation of the KDL Prototype for the once-through
 soluble  system tests is schematically represented in Figure 2-1.  Flue gas
 from  the package boiler (burning oil) entered the scrubber after it passed
 through  a  heat extractor.  The flue gas was cooled to any desired temperature
 between  150  and 300°F in the heat extractor.  Sulfur dioxide (S02) gas was
 added to the flue gas in order to increase the scrubber inlet SOp concentration
 to approximately 2,000 PPM (0.2 mole %).  The flue gas passed through the
 marble bed and the turbulent layer where it was in contact with the scrubbing
 liquor.  The flue gas left the system after passing through a deraister and a
 reheater.
                 Scrubbing liquor was prepared by mixing solid sodium carbonate
 (Na2C03) and well water in the hold tank.  The hold tank of approximately
 6,000 gallon capacity represented an average residence time of 30 to 40 minutes
 for most of the soluble system tests.  Thus, fluctuations in the scrubber
 liquor composition due to minor fluctuations in the solid Na9CO_ feed to the
                                                            £  >J
 hold tank could be assumed negligible.   Scrubber liquor (Na2C03 solution) was
 introduced into the scrubber through 36 spray nozzles  under the bed and/or
 through eight pipes with splash  plates  at the end above the bed.  The bed
 reject was drained through the scrubber bottom while the liquid from the
turbulent layer was drained through  the overflow pot-downcomer arrangement.
                                     2-1
-------
                             TO
                            STACK
PO
I
ro
  FLUE 6AS
  FROM V.P.

  BOILER
  HEAT
EXTRACTOR

                                   REHEATER
                                  \
                            I	1
 LADDER
      VANES
                                     DEMISTER
                                        SCRUBBER Fl
              MARBLE BED


              _ _ SPRAY WATER (SW)
              ^ SCRUBBER LIQUID (SL)
                                                    r
                                                                               NaCOi
                                                                    HOLD TANK
                                               SCRUBBER BOTTOMS (SB)
                                                                                u
                                                                     CLARIFIER
 c
 JO
 ro
ONCE  THROUGH  SOLUBLE  SYSTEM
-------
 Liquid  from  the downcomers and the scrubber bottoms was pumped out of the
 system  through the clanfier which was used as a liquid disposal tank during
 the  once-through soluble system tests.  Scrubber bed height or turbulent
 layer height was varied by varying the overflow pot height.
                The test program for the soluble system tests was designed
 to study the effect of operating parameters such as gas flow rate, liquid
 flow rate, liquid to gas ratio, scrubbing liquor composition and temperature,
 scrubber inlet gas temperature and scrubber bed height on the vapor-liquid
 mass transfer characteristics of the marble bed scrubber.  The proposed test
 program is shown in Table 2-1.  Actual test conditions and test data are
 given in detail in Appendix B and are very nearly the same as the proposed
 test conditions given in Table 2-1.
 2.2             DATA EVALUATION
 2.2.1           System Performance
                The test data and results are given in detail in Appendix B.
 Several runs were repeated because the total  sulfur material balance did not
 close within +_ 10%.  The data and results of the runs for which the material
 balance did not close within +_ 10% are-not given in this report.  Gas flow
 checks, as described in Appendix A, and liquid flow calibration checks were
made periodically.
                In  all  the runs except run 10R the overflow pot height was
set  at 9 inches from the perforated plate.  At this setting the bed drained
normally with most  of the water draining through the overflow pots and
downcomers, and with very little water draining through the bed itself.  But,
1n run 10R, the overflow pot height was set at 15 inches from the perforated
plate.  Seepage through the bed was excessive; about 95% of the water drained
through the bed while only 5% drained through  the overflow pots.  This was
                                   2-3
-------
                                              TABLE 2-1.  TEST PARAMETERS
                                                          FOR THE SOLUBLE SYSTEM

Experiment
Number
1R
2R
3R
4R
5R
6R
7R
8R
9R
10R
11R
12R
13R
14R
15R
16R

Comments
Low Gas Temp.
SF Only
SW Only Amb. Liq. Temp.
SW Only
High Gas Flow
Low Gas Flow
High L/G
Low L/G
Base Cond.
High Bed Ht.
SW Only Amb. Liq. Temp.
Base Cond.
Base Cond.
Low L/G
High Gas Flow
Low Gas Flow

FG Rate
(ACFM)
11,000
11,000
1 1 ,000
11,000
13,000
9,000
11,000
1 1 ,000
11,000
11,000
11,000
11,000
11,000
11,000
13,000
11.000

SF Rate
CGPM)
55
165
0
0
55
55
70
35
55
55
0
55
55
35
55
55
SF
Composition
M Moles/Lit.
25
25
25
25
25
25
25
25
25
25
120
120
35
35
35
35

SW Rate
(GPM)
no
0
165
165
no
no
150
75
no
no
165
no
no
75
no
170
SW
Composition
M Holes/Lit.
25
25
25
25
25
25
25
25
25
25
120
120
35
35
35
35
Inlet Gas
Temperature
(°F)
225
300
300
300
300
300
300
300
300
300
300
300
300
300
300
225
Scrubber Bed
Height
(inches)
9
9
9
9
9
9
9
9
9
15
9
9
9
9
9
9


Hold Tank
Temp. (°F)
110
110
70
110
110
110
110
no
110
no
70
no
110
no
no
no
















Note:
Inlet S02  is 2000 PPM
-------
 because the gas could not support a high enough turbulent layer to facilitate
 bed  drainage through the overflow pots.  Also, it was observed that the
 seepage through the bed increased when the scrubbing liquor was introduced
 into the scrubber above the marble bed rather than under the marble bed.
                The results show that liquid to gas ratio (L/G) and scrubber
 liquor composition significantly affect the S(L removal in the scrubber.   For
 example in experiments 4R and 7R while keeping other conditions the same, an
 increase in L/G from 15 to 20 GPM/1000 CFM resulted in SCL removal increase
 from 60 to 77%.  Furthermore, an increase in liquor composition from 25 to
 120  m moles/lit result in an increase in S02 removal from 64 to 95%.  The
 other variables such as gas and scrubbing liquor temperatures, gas flow and
 feed location do not seem to have significant effect on S02 removal  in the
 marble bed scrubber.  The inlet and outlet NOx concentrations given in
 Appendix B are approximately the same within the accuracy of the experimental
 measurements.  Therefore, it can be concluded that no NOx removal can be
 obtained with sodium carbonate scrubbing solution.
 2.2.2           Sampling and Analytical Methods
                The pH measurements were made with a SS-3 Zeromatic Beckman
 pH meter, which was carefully standardized and temperature compensated.   The
 pH meter was always located 1 to 2 feet away from the sample points  for better
 pH representation of the sample.  The sample temperatures were measured with
 a mercury thermometer during sampling.
                Samples were pumped through a Millipore filter holder (142 mm
 in diameter) and filtered through a ly Millipore membrane.  The filtering
equipment was set up 4 to 5 feet away from the sampling point to minimize the
transport time between the sample point and filtration.  The greater the
                                      2-5
-------
transport time the greater the chance for oxidation of sulflte to sulfate.   A
screw type pump was used to transport the sample isokinetically.
                The analytical methods are given in detail  in Appendix D.
The analytical procedures used by Combustion Engineering (C-E) and Radian
Corporation are different.  At the instructions of the EPA  project officer,
the sulfite analysis was made using Radian's procedure although it is more
laborious and time consuming than C-E's method.  Sodium and total  sulfur
analyses were made using C-E's method.  In a few runs, sulfite analysis was
made using both the C-E and the Radian methods to compare the accuracy of the
two methods.  The liquid phase analytical results given in  Appendix C show
that the C-E and Radian methods are comparable in results.
2.2.3           Analytical Results
                The liquid phase analytical  results and pH's are  given in
Appendix C.  The preliminary tests showed that the marble bed liquor
composition was not uniform over the entire cross-section of the  marble bed.
This probably resulted from non-uniform gas distribution to the marble bed.
                The scrubber liquor discharges through three downcomers as
shown in Figure 2-2.  In order to determine which downcomers should be
sampled to get a reasonable value for the concentration of  sulfite (S0~ + HSO")
in the bed, all the three downcomers were sampled for a few runs.   Based on  the
results of these runs, it was decided to sample the downcomers from both
sides of the bed for sulfite and average the results to obtain the values for the
concentration of sulfite in the bed.  All other analyses for the  bed liquor
 composition were made on pump discharge from the surge tank.   The pump discharge
is a good average of the three downcomers, since all three  downcomers discharge
into the surge tank, from which liquor is pumped to the clarifier tank for
disposal.
                                      2-6
-------
ro


                         GAS
 o
 c
 a
 ni
OVERFLOW POT AND DOWNCOMER  ARRANGEMENT
 ro
-------
 2.2.4           Material Balance
                The results of the total sulfur material balance for the
 scrubber  are shown in Table 2-2.  The sulfur removed from the gas AS-, and the
 sulfur  absorbed by the liquid, A$L> are calculated, for all the liquid streams
 entering  and leaving the scrubber, from the following relationships:
                A$G = (Gas Flow Rate X S(L concentration) in
                      - (Gas Flow Rate X S02 concentration) out
                AS.  = I (Flow X Total Sulfur Concentration) out
                      -z (Flow X Total Sulfur Concentration) in
                The inlet gas flow rates were calculated from the measured
 outlet  gas flow rates by correcting for liquid evaporated or condensed in the
 scrubber  and for the 6.7% air leakage  into the system between the inlet and
 outlet  sampling points.
                The results are within the accuracy of the experimental  errors
 indicating adequacy of the flow measurements, sampling and analytical
 techniques.
 2.3             CALCULATION OF STAGE EFFICIENCIES
                Of the sixteen experiments run with sodium carbonate  as  the
 additive  on the KDL ARCS Prototype, five were chosen from which to calculate
stage efficiencies based on maximum theoretical  absorption of S(L.
Experiments 1R, 5R,  8R,  12R,  and 14R were evaluated since they represented
variations in L/G, stoichiometry,  inlet SOp, and other operating parameters.
                The theoretical  maximum amount of S(L which could have been
absorbed in each experiment was  determined by the following method.   Soluble
analyses from the marble bed effluent were the input to an equilibrium
1.  Determined by Orsat measurement of oxygen in  flue  gas  entering and
    leaving scrubber.
                                2-8
-------
                                            TABLE 2-2.   TOTAL SULFUR MATERIAL BALANCE
ro
i
10
Experiment
Number
1R Set 1
Set 2
2R Set 1
Set 2
3R Set 1
Set 2
4R Set 1
Set 2
5R Set 1
Set 2
6R Set 1
Set 2
7R Set 1
Set 2
8R Set 1
Set 2
9R Set 1
Set 2
10R Set 1
Set 2
11R Set 1
Set 2
12R Set 1
Set 2
13R Set 1
Set 2
14R Set 1
Set 2
15R Set 1
Set 2
16R Set 1
Set 2
Gas Flow
(CFM)
Date (0 130°F)
10/29/71
10/29/71
10/27/71
10/27/71
10/14/71
10/14/71
10/28/71
10/28/71
ll/ 2/71
ll/ 2/71
ll/ 2/71
ll/ 2/71
11 / 3/71
11 / 3/71
ll/ 3/71
11 / 3/71
10/29/71
10/29/71
11 / 9/71
ll/ 9/71
10/14/71
10/14/71
ll/ 9/71
ll/ 9/71
ll/ 4/71
ll/ 4/71
ll/ 5/71
ll/ 5/71
ll/ 5/71
ll/ 5/71
ll/ 5/71
11 / 5/71
10,960
10,960
10,750
10,800
11,200
11,200
10,800
10,800
12,980
12,980
9,180
9,180
11,240
11,240
11,200
11,190
1 1 ,000
10,910
10,680
10,690
11,500
11,400
11,210
11,200
11,330
11,400
11,300
11,360
12,980
12,980
11,500
11,500
Liquor Flow
(GPM)
Below/Above
107/54
107/54
165/0
165/0
170/0
170/0
170/0
170/0
106/55
107/55
110/55
110/55
152/69
152/69
73/36
73/36
116/54
116/54
112/53
112/53
165/0
169/0
110/53
110/53
110/54
110/54
75/36
75/36
110/55
110/55
110/55.5
110/55.5
SOo Concentration
(PPM)
In
2,018
2,018
2,050
2,050
2,095
2,095
2,030
2,030
2,275*
2,290*
-
2,050
2,000
2,000
-
1,782*
2,050
2,010
1,980
1,960
1,980
1,980
2,020
1,980
2,000
1,980
2,070
2,040
2,040
2,040
2,010
2,020
Out 1
880
860
750
750
860
860
800
790
1 ,020*
1 ,048*
-
480
450
460
-
829*
700
732
540
520
120
120
80
100
420
320
780
780
500
500
350
350
Sulfur
Removed
From Gas
% S02 ASQ
temoval (g Moles/Ml n)
61.4
62.3
63.5
63.5
59.0
59.0
60.7
61.2
55.2
54.3
-
76.5
77.5
77.0
-
53.5
65.9
63.7
72.6
73.5
94.0
94.0
94.4
94.3
81.5
86.3
62.4
61.7
75.6
75.6
82.5
83.2
11.92
11.92
12.78
12.57
14.18
14.18
12.10
12.21
14.72
-
-
14.06
16.28
16.16
-
9.39
13.76
12.96
14.22
14.32
22.25
22.06
20.61
20.15
17.78
19.11
13.20
12.91
18.97
18.97
18.03
18.14
Sulfur
Absorbed
By the Liquid
AS,
(g Moles/Mi n)
12.63
12.38
13.23
13.18
14.73
14.45
12.21
12.10
14.35
-
-
13.84
16.58
16.61
-
9.65
14.38
14.27
14.08
14.36
22.40
24.75
20.10
19.35
18.06
18.23
12.93
12.80
18.85
18.79
17.86
17.90
ASg - AS[_ x 100
S5Q
- 6.0
- 3.9
- 3.5
- 3.1
- 3.9
- 1.9
- 0.9
+ 0.9
2.5
-
-
- 1.6
- 1.8
- 2.8
-
- 2.8
- 4.5
-10.1
1.3
- 0.3
- 0.7
- 7.7
2.5
4.0
- 7.6
- 3.0
2.0
0.9
0.6
1.0
1.1
1.3
     *Manual  S02  Readings
-------
computer program (obtained from EPA and modified by C-E) which calculated the
partial pressure of S02 in equilibrium with the downcomer liquid at the
scrubber operating conditions.  To obtain an equilibrium line, the computer
calculation was repeated for incremental amounts of total S(L (SOl and HSCL)
added to the liquid over what was actually present in the analysis.  For
Experiment 1R - Set 1 (Figure 2-3) two variations in this approach were
tried:  in the first case, the amount of total S(L which had oxidized in the
liquid to sulfate was held constant as additional amounts of total S(L (liquid)
were input to the computer program, while in the second case the ratio of
sulfate to total S(L in the actual analysis was held constant as additional
sulfur was added to the liquid.  As can be seen in Figure 2-3, keeping the
ratio constant caused only a small change in the equilibrium line and
subsequently only a very small change in the stage efficiency calculation.
For this reason, the equilibrium line for the other experiments was obtained
by the first method described above.
                Following construction of the equilibrium line on axes of
mole fraction S02 in the gas versus mole fraction total sulfur in the liquid,
an operating line was derived for each experiment and plotted on the same
diagram.  This operating line was obtained from the material  balance equation
                L '"out - Xtn> ' G   Xout + t  Xin
                                    2-10
-------
10
c

CD
ro
   22


   20


   18


S  16
X
    o
    a
       1A
       14
       12
       10
    <   8
    u_

    3   6
    S

        4


        2


        0
                                           T	T
                                                        T	T
                                                                      T	T
                              ACTUAL OUTLfT S02 = 913 PPM
                            S04/S02 RATIO IN LIQUID

                            CONSTANT =0.184
               OPERATING POINT
               OF SYSTEM
S04MOL£ FRACTION IN

LIQUID = CONSTANT -

0.54xlO"4
             0.1
0.2 V3.4      3.5       3.6      3.7      3.8

    MOL£ FRACTION - TOTAL SULFUR IN LIQUID x 10"4
        3.9
4.0
               SODIUM  CARBONATE  SYSTEM  -  STAGE  EFFICIENCY  DETERMINATION
-------
                Corrections in S02 concentrations  and gas  flow rates  were  made
for air leakage and changes in humidity across the marble  bed.  The point  of
maximum theoretical S02 absorption was obtained from the intersection of the
operating and equilibrium lines.
                The diagrams for the other experiments done are presented  in
Appendix E.  Efficiencies were obtained from
                Inlet S02 - Outlet S02 (Actual)
                Inlet S02 - Outlet S02 (Theoretical)
and the results tabulated along with operating parameters  in Table 2-3.
                The actual operating point of the  marble bed for experiment
1R Set 1 was plotted in Figure 2-3 by averaging the analysis of the downcomer
and bottoms streams and using the corrected S02 outlet concentration.  If  the
material balance for this experiment had closed completely, the point would
have fallen on the operating line.  As can be seen, some deviation exists  and
causes a small error in the efficiency calculation.  In the other experiments,
the point fell either slightly above or below the  operating line causing a
maximum +_ 5% error to be introduced into the efficiency calculation.
                The values for the stage efficiencies in Table 2-3 are very
close for all of the experiments except 8R.  This  low value is caused by
errors in material balance and analysis and is not due to  any operating
condition.  In fact, no conclusions can be made regarding  which film, gas  or
liquid, controls mass transfer based on these test data since too many
conditions are varied from test to test.
                In general, the data indicates that the marble bed is an
efficient S02 contractor and that S02 removal was  limited  by vapor-liquid
equilibria in the test run.  Assuming that the bed is well-mixed, the rate
of mass transfer is controlled by the composition  of the bulk liquid  which
determines the rate of product and reactant diffusion through the liquid film.
                                    2-12
-------
             TABLE 2-3.  SUMMARY OF STAGE EFFICIENCY  CALCULATIONS
Experiment
Number/
Set Number
IR/Set 1
IR/Set 2
5R/Set 1
8R/Set 2
12R/Set 1
14R/Set 1
L/6
15.2
15.2
12.8
10.0
15.2
10.1
Moles Na2C03
Moles S02
0.284
0.291
0.255
0.295
1.89
0.307
Inlet*
so2
1980
1980
2175
1680
1920
1940
Outlet*
so2
913
902
1055
857
83
805
Equilibrium
Outlet Stage
S02 Efficiency
850
840
1010
690
0
720
94.5
94.5
96
83
95.5
93
*Inlet and outlet S02 values represent concentrations  immediately  before  and
 after the marble bed, not at the points  where they were  actually  measured.
 Corrections for humidity were made for both  inlet and outlet  values while
 corrections for leakage were made for inlet  but  not outlet  values.
                                     2-13
-------
                Calculation of gas-phase  mass  transfer coefficients  (K a) for
the experiments run was not attempted because  of the  difficulty in determining
the gas phase driving force.  By examining  the plot of Experiment 1R in
Figure 2-3 it can be seen that small  errors  in the scrubber effluent analysis
can cause large errors in the calculated  S02 partial  pressure of the sample.
For example, if the actual  mole fraction  of total sulfur  in the liquid is
3.65 X 10"4 corresponding to partial  pressure  of 500  ppm  S02> an error of
+ 3% in the analysis would cause the  calculated S02 partial pressure to
fluctuate from 100 to 1000 ppm S02.
                If we use the relationship
                f a X N   T.U. = constant
to calculate K a;
                where G        = gas  flow rate
                      K a      = gas  phase  mass transfer  coefficient
                      N   T.U. = number of  gas phase  transfer units
                       og
N   T.U. is determined from
                           Y S02 in  - Y S02 out
                Nog TiU> =     (Y -  Y*) 1m
which reduces to
                N.. T.U. = In
Y SO, in - Y*
V           Y*
1 S02 out - T
for a well-mixed reactor where Y* is the S02 partial  pressure over the
liquid.  From these equations it can be seen that determination of S02
partial pressure over the liquid is an important step in obtaining K a's  and
any error in partial pressure calculations would be reflected in the K a.
values.
                                    2-14
-------
                                 SECTION 3
                  LIMESTONE FURNACE INJECTION SYSTEM TESTS

 3.1             SYSTEM CHEMISTRY
                The process of removing S0« from the flue gas using boiler
 calcined  limestone (CaO) as the additive in the limestone furnace injection
 system consists of the following reactions:
                CaO + H20  -*  Ca(OH)2                                      (1)
                Ca(OH)2 + 2S02 + H20  -»•  Ca{HS03)2 + HgO                   (2)
                CaS03 + S02 + H20  -*  Ca(HS03)2                            (3)
                Ca(HS03)2 + Ca(OH)2  -»  2CaS03 + 2H20                      (4)
                CaS03 + 1/2 02  -»•  CaS04                                   (5)
                The CaO coming from the furnace is first hydrated as shown in
 reaction  1.  Removal  of SOp in the limestone furnace injection system depends
 upon the  formation of calcium bisulfite by reaction of suspended calcium
 sulfite (reaction 3)  and calcium hydroxide (reaction 2) with sulfur dioxide and
water.
                The reactions in which soluble bisulfite is  converted to
 insoluble calcium sulfite (reaction 4) and sulfite is oxidized to sulfate
 (reaction 5) account  for the water products as well as the regeneration  of
the solid calcium sulfite reactant that is recirculated to the scrubber.
3.2             TEST  DESCRIPTION
                The purpose of the furnace injection test series was to
determine the solid-liquid mass transfer characteristics in  the scrubber and
the hold tank, and to define a range of satisfactory operating conditions for
application to the field units.  In addition the following information was
determined because of its importance in designing furnace injection S0«
scrubbing systems:
                                    3-1
-------
                (1)  Rate of hydration and dissolution  of  calcined limestone.
This determines the alkalinity in the scrubber bed  and  the size of the reaction
tank.  This rate can be determined either using a material balance or using
equilibrium methods.
                (2)  Rate of precipitation of calcium sulfate, calcium
sulfite and calcium carbonate.  These rates assist  in designing the reaction
tank so that the exiting stream will  be close enough to saturation to prevent
calcium sulfate scaling in the scrubber.
                (3)  Rate of oxidation to sulfate.  This determines the
incremental increase in supersaturation of calcium  sulfate in the marble bed
and determines the liquid to gas ratio (L/G)  and the limit on supersaturation
entering the scrubber needed to prevent calcium sulfate scaling in the scrubber
system.
                (4)  A correlation between the reactivity  of the calcined
limestone and its rate of hydration and dissolution.  The  design of the S(L
scrubbing system will  not only depend on  the above  measurements but will very
strongly depend on the reactivity of the additive entering the system.  The
reactivity in turn usually depends on the following variables:  type of
limestone, temperature of calcination and place of  injection in the furnace.
                Figure 3-1 is the flow arrangement  for  experiment 17R and
Figure 3-2 is for experiments 18R, 19R, 20R,  21R and 22R.  The test conditions
are shown in Table 3-1.  In these tests,  the furnace injection ARC System was
simulated by blowing a mixture of boiler calcined limestone and flyash mixture
into the scrubber inlet gas stream.  Liquid SCL was vaporized using steam and
then injected into the flue gas, FG (generated from an  oil fired boiler) to
increase the S02 concentration to 0.15 to 0.2 mole  percent, depending on the
test requirement.   In  Experiment 17R, the slurry from the  marble bed turbulent
                                  3-2
-------
                              TO
                             STACK
1
GO
   FLUE GAS
   FROM V.P.
   BOILER

                               1
                                                                          MAKE-UP
                                    REHEATER
  HEAT
EXTRACTOR
                                    \
                                      DEMISTER
             FLY ASH

             ADDITIVE
                                      MARBLE BED

                                         SPRAY WATER (SW)
                            SCRUBBER LIQUID (SL)
SCRUBBER BOTTOMS (SB)
                                                   LIQUID
                                   SOLIDS TO
                                   DISPOSAL
  O
  c
                                  VACUUM
                                  FILTER
  Of
           LIMESTONE  FURNACE  INJECTION  SYSTEM-NO RECYCLE
-------
                            TO
                           STACK
                                                       MAKE-UP

                                                       WATER
GJ
FLUE GAS

FROM V.P.
BOILER


MAKE-UP

SOz
          1
                       /
             HEAT
           EXTRACTOR
' ^
«?i «• r*'
i j i j i
s s

DEMISTER
MARBLF BFD
^ SPRAY WATER (SW)
SCRUBBER LIQUID (SL)
SCRUBBER BOTTOMS (SB) _

 2)
 m

 OJ
 i
 ro
                                                LIQUID
                                SOLIDS TO

                                DISPOSAL
                                          VACUUM

                                          FILTER
        LIMESTONE FURNACE  INJECTION  SYSTEM-WITH  RECYCLE
-------
                   TABLE 3-1.   TEST PARAMETERS FOR THE LIMESTONE
                               FURNACE  INJECTION SYSTEM
Test No.                          17R      18R      19R      20R      21R       22R
Gas Flow Rate, ACFM @ 120°F      11,000   11,000   10,000   10,000   10,000    10,000
Inlet S02, PPM                    1,500    1,500    2,000    2,000    2,000     2,000
Additive (Flyash &
  calcined limestone)
  feed rate (% of
  stoichiometry)                    75       75       75       75   75-100    75-100
Underbed Slurry (GPM)               110      198      205      205      200       350
Liquid to Gas Ratio, L/G
  (GPM/1000 CFM)                    10       18       20       20       20        35
Overbed Spray, GPM                   000000
Excess 02 %                          5        5        -        -        8         5
Inlet Gas Temp (°F)                 300      300      300      300      300       300
Liquid Slowdown (GPM)               55        0        -        -        0         0
Clarifier Liquid (GPM)                0       25        -        -       15        15
Hold Tank, Tank Capacity (GAL)     6,000    6,000    6,000    6,000    3,000     5,200
Hold Tank Stirring                Max.     Max.     Max.     Max.     Max.      Max.
Make up Water (GPM)                 55        5                           55
Solid Concentration in
  Spray Slurry (%)                   032188
                                        3-5
-------
layer (SL) left the scrubber through  the overflow pots into the downcomers and
then discharged into the hold tank.   The turbulent  layer provided gas liquid
contacting for S0« absorption.  The  scrubber  bottom slurry (SB), which is
rejected spray water, flyash and additive, was  also discharged into the
hold tank.  The hold tank provides good  solid liquid contacting and thus allows
for hydrolysis and subsequent dissolution of  calcined limestone.  The slurry
entering the hold tank had a pH of 4-6;  the slurry  leaving had a pH of 10-11.
The hold tank effluent was discharged into the  clarifier where the solids were
settled, and the clarifier underflow  was sent to the vacuum filter where the
solids were further concentrated and  then sent  to disposal.  Most of the
clear liquid (165 gallons per minute) was carried to the scrubber as spray
water (pH - 10.5 -11) and the remaining  clarifier liquid of about 50 gallons
per minute was blowdown.
                In experiments 18R, 21R  and 22R, part of the hold tank effluent
was used as spray water, while the rest  was sent to the clarifier, and the
liquid returned to the hold tank.  In these tests the solid concentration in
the slurry was maintained between 3 and  8 percent (30% to 60% flyash, see
Table F-7).
                In experiments 19R and 20R, the solid concentration in the
slurry was about 1 and 2 percent, and therefore a larger portion of the hold
tank effluent was sent to the clarifier.  Part  of the clarifier liquid
separated in the clarifier was removed from the system as "blowdown" and the
rest was returned to the hold tank.
                The flow rates for all the streams  in experiments 17R to 22R are
shown in Table F-l in Appendix F.
                                    3-6
-------
                To determine when the system reached steady state,  samples
were taken from the spray water (SW), and the clarifier liquid (CL) and analyzed
for calcium, sulfite and sulfate.  Steady state in these tests was  defined  as
the point when the calcium and total sulfur concentration in the filtrate of
the clarifier liquid (CL) and the spray water (SW) were reasonably  close.
Depending upon the test conditions, steady state was usually reached after
6-20 hours of operation.  These analyses of the samples to determine steady
state are shown in Tables F-2 to F-4 in Appendix F.
                Spot checks of the liquid and gas flowmeters were made on a
regular basis before every test.  These checks showed that the original
calibration curves prepared during the soluble tests were still valid.   A
listing of these procedures is available in the soluble system section and
in Appendix A.  Major mechanical modifications which were made between
experiments are listed in Appendix G.
3.3             DATA EVALUATION
3.3.1           System Performance
                Table 3-2 summarizes the limestone furnace injection results.
In experiments 21R and 22R, while holding other conditions the same, the S02
removal efficiency increased from 59 percent to 72 percent with an  increase of
L/G from 20 to 36 GPM/1000 CFM.  Therefore, the SOp removal efficiency tends
to increase with liquid to gas ratio.  In experiments 20R, 19R and  18R,  as
the solids concentration in the slurry increased from 0.7 to 3.5 the SO-
removal efficiency increased from 36 to 68 percent, while in experiments 18R
and 21R no further increase in the S02 removal efficiency was observed as the
solid concentration in the slurry was increased from 3.5 to 7.4 percent.
Therefore, it can be concluded that no improvement in S02 removal efficiency
can be obtained by increasing the solid concentration in the spray  water
                                    3-7
-------
              TABLE 3-2.   SUMMARY OF LIMESTONE FURNACE INJECTION TESTS
                          PERFORMANCE  RESULTS
Experiment No.*                  17R      20R      19R      18R      21R       22R
Gas Flow ACFM 0 130°F            11,000   10,020   10,000   11,000   9,800     9,900
L/G, GPM/100 CFM                 10.0     20.3     20.2     18.6     20.4      36
Inlet S02 Cone. (PPM)            1,456    1,950    1,882    1,471    1,992     2,020
Solid in Underbed Slurry (%)      0        0.7      1.3      3.5      7.4       8.9
Solid Recycle (X)                0        72       85       89       95        95
Spray Water pH                   11.2     5.8      5.5      10.6     8.6       6.0
Stoichiometry (*)                71.0     85.5     89.1     72.8     90.1      88.1
S02 Removal Efficiency (%}        43.0     35.7     43.6     67.6     59.2      72.5
Liquid Slowdown to
  Control Calcium
  Sulfate Scale                  Yes      Yes      Yes      No       No        No
Calcium Sulfate Scaling          No       Yes      Yes      Yes      No        No
Calcium Sulfite Scaling          Yes      No       No       No       No        No
* The listing of experiments  is  based on the order in which they were conducted.
                                       3-8
-------
 beyond 3.5  percent  for this system.  Table 3-2 also shows that the solid
 recycle increase  is  accompanied by an increase in spray water pH and SO.
 removal  efficiency.  This is believed to be the result of increased retention
 time  of the solids  in the system, which allows the hydration and dissolution
 of CaO to near  completion and thus provide greater alkalinity and consequently
 results  in  greater  pH and S(L removal efficiency.
                In experiment 17R the spray water pH was about 11 and minor
 calcium sulfite scaling resulted.  Calcium sulfate scaling did not occur
 anywhere above  a  solids concentration in the slurry of about 8 percent,  but
 did occur at solids  concentrations below 3.5 percent.  This leads to the
 conclusion  that liquid blowdown is not needed to control calcium sulfate
 scaling  when high solid concentration in the slurry is utilized.
                The  problems associated with the furnace injection system test
 are listed  in Appendix G.
 3.3.2           Analytical Results and Sampling Methods
                A solid-liquid separation device consisting of a Millipore
 filter and  filter holder was used to obtain solid and liquid samples. The
 samples  were drawn such that the residence time in the sampling system was
 much smaller than in the vessel  from which the sample was drawn.  Since  the
 marble bed  slurry discharge had to flow a long distance before entering  the
            •f
 hold tank,  samples from both the marble bed and the scrubber liquid at the
 hold tank were taken to determine if any change had taken place while flowing
 in the pipe.  The same technique was  used with the scrubber bottom, where
 samples were taken at both the scrubber and the hold tank.
                Since Radian Corp. was  performing most of the solid and  liquid
 chemical analyses, C-E decided to analyze the liquid samples for soluble
calcium, sulfite and sulfate mainly for control  purposes.  In experiments
17R and 18R, C-E used the same method used by Radian for the sulfite
                                    3-9
-------
analysis, namely the Arsenlte method.   In experiments  21R and 22R,  C-E  used
the sodium thiosulfate back titration  method,  while in experiments  19R  and 22R, no
analyses were made by C-E.
                A summary of each analytical procedure is given  in  Appendix D.
The C-E and Radian Analytical results  in experiments 17R, 18R, 21R, and 22R are
within 10 percent of each other, except for the marble bed samples  from
experiments 21R and 22R which differed by about 40 percent.   The difference
between the C-E and Radian results in  the marble bed is attributed  to
difficulties in sampling.
                Results of the individual liquid and solid analysis made by
C-E and Radian are listed in tables F-5 through F-16 in Appendix F.  The
chemical analysis of the additive is listed in Tables  F-17 and F-18 in
Appendix F.
3.3.3           Total Sulfur Material  Balance
                Detailed calculations  of the total  sulfur material  balances of
the limestone furnace injection experiments are listed in Table  H-l through
H-4 in Appendix H.  The results showed unexpectedly good material balance
closure.  The purpose of performing sulfur material  balances  was to check
the reliability of the flow measurements and the analytical results and as
a criterion for determining the reliability of the tests.  Of the experiments
with high solid concentration in the slurries, only experiment 18R  was  used
to perform a total sulfur material balance. The closure errors  between the total
sulfur in entering and leaving streams were relatively low within 9 percent in
the hold tank and within 13 percent in the marble bed.
3.3.4           Rate Calculations with Slurries of Low Solid  Concentrations
                It was found that in order to  successfully and completely
characterize the streams in the system, only slurries  with low solids
                                    3-10
-------
 concentration could be used.  This Is because in the case of high  solid
 slurries, a difference in the calculated rates resulting from a  slight change
 in solid concentration was masked by that resulting from the error in solid
 concentration measurement.  For example, when the error involved in the  solid
 concentration measurement is +5%, then a change in solid concentration of +2%
 due to  precipitation or dissolution will be completely masked by  that error.
 With zero or low solid concentration in the slurry, the rates of formation,
 dissolution and oxidation were successfully calculated without making any
 significant assumptions.  These calculations which are listed in Table H-5 to
 H-7 in Appendix H were made for experiments 17R, 19R and 20R.  While experiment
 17R gave consistent results, experiments 19R and 20R gave very inconsistent
 results.
 3.3.5           Rate Calculations With Slurries of High Solid Concentrations
                As mentioned in the previous section, a detailed species
  \
material balance cannot be performed successfully in experiments with high
solids concentrations due to high experimental errors.  Therefore  a slightly
different approach had to be taken in calculating the rate of precipitation,
dissolution and oxidation.  Based on the results obtained in the experiment
with low solids concentration (17R), the following assumptions were made:
                (1)  All of the oxidation in the system occurred in the
marble bed.
                (2)  Total oxidation in the system is the ratio  of the total
sulfate to total  sulfur in both the solid and liquid streams leaving the
system.
                            (SO/) Liquid + (SO.") Solid
                Ox1dat1on =        Total Sulfur	
                                    3-11
-------
                (3)   Formation of CaC03 in the scrubber is negligible.
                (4)   The  amount of COp transferred to the hold tank from the
atmosphere is  negligible.
                These assumptions were applied to data from experiments 17R,
19R and 20R,  as  well  as to  experiments 18R, 21R and 22R.  The rate calculations
using a liquid material balance and the above assumptions are shown in
Table H-8 to  H-13 in  Appendix H.
                Tables 3-3a and 3-3b summarize all the rate results obtained
for all the experiments.  The following criteria were used to determine the
reliability of the results:
                (1)   Total  calcium hydroxide dissolution rate in the system
should not exceed the total calcium feed  rate to the system with the additive.
                (2)   The  rate of S(L removal from the gas should
always be greather than the calcium sulfite and calcium sulfate precipitation
rates in the  whole system.
                (3)   The  rate of S02 oxidation anywhere in the system cannot
be negative.
                (4)   The  rate of Ca(OH)2  dissolution anywhere in the system
cannot be negative.
                (5)   The  error  in the  total sulfur material balance around
both the hold tank and the  marble bed  should not exceed 10 percent.
                Table 3-4 lists these  criteria for all  the furnace injection
experiments,  and indicates  whether or  not each of these crtieria is satisfied.
Calculated rate  data  for  the following tests are considered reliable:
                17R,  (17R), 18R,  (19R),  (20R)
                                    3-12
-------
          TABLE  3-3a.  SUMMARY OF RATE RESULTS
                      FROM LIMESTONE FURNACE INJECTION TEST
Experiment 17R
Experiment 19R
                                                                              Experiment 20R
Location
Outlet Flue Gas How
(CFM 0 130°F)
Liquid to Gas Ratio -
(GPM/1000 CFM)
CaO Feed Rate (M Moles /Win)
Stoichiometry based on inlet
S02 Removal Eff. (%)
Solid Cone, in Spray Slurry
(wt. X)
ASg (Amount of SO, absorbed
(M Moles/Min) i
Ca(OH)2 Dissolution
(M Moles/Min)
Sulfite Oxidation
(M Moles/Min)
CaSO. -1/2 H?0 formation
(M3Moles/Min)
CaSOj -2 H,0 formation
(MMoles/Min)
CaCOj formation
(M Moles/Min)
Error in Total Sulfur
Material balance
/In - Out» v ,nn ,,\
Marble
Set #1
11,000
10
11,306
71.0
43.0
NONE
7.077
2,196
( 5,007)
3,130
( 3,107)
1,307
{ 1,355)
- 955
( 1,592)
- 216
_ in 7
Bed
Set 92
11,000
10
11,306
71.0
43.0
NONE
7,077
2,698
( 5.358)
4,305
( 2,951)
791
( 2,144)
- 539
( 784)
16
- 17 d
Hold
Set 01







1,900
( 1,151)
224
1,848
( 2,083)
331
( 6)
790
( 226)
i c
Tank
Set 92







1,488
( 717)
281
1,960
{ 2,193)
- 57
(- 549)
577
( 158)
- 7 T
Marble
Set #1
10,000
20
15,750
88.0
43.7
1.14
5,766
3,006
( 268)
- 600
( 3,775)
-1,021
(-4,550)
- 899
(- 105)
- 985
en
Bed
Set 82
9,940
20
75,750
89.5
43.6
1.46
5,368
7,844
( 1,965)
-2,994
( 3,275)
1,358
(-4,200)
- 550
(- 273)
565
q n
Hold
Set tl







3,687
( 2,579)
530
5,329
( 5,858}
2,198
( 383)
142
( 320}
5_n
Tank
Set #2







3,006
( 2,577)
508
4,804
( 5,312)
1,223
( 186)
- 32
( 68)
2.3
Marble
Set #1
10,020
20
15,750
85.0
36.1
0.69
6,616
6,138
( 3,865)
557
( 3.652)
1,209
(-1,887)
- 725
(- 480)
- 612
5.2
Bed
Set n
10,020
20
15,750
86.0
35.3
0.7
6.400
2.600
( 3,726)
1,339
( 3.488)
395
(-1.741)
-2.024
( 544)
- 660
- 0.7
Hold
Set 01







3,136
( 867)
- 133
3,707
( 2,811)
1,133
(- 433)
- 34
( 159)
3.6
Tank
Set #2







3,127
( 494)
260
2,681
( 2,941)
1,392
(-1,360)
210
( 170)
5.2
-------
                                                   TABLE 3-3b.  SUMMARY OF RATE RESULTS
                                                                FROM LIMESTONE FURNACE INJECTION TESTS


                                         Experiment 18R	  	Experiment 21R	  	Experiment 22R
Location
Outlet Flue Gas Flow
(CFM » 130°F)
Liquid to Gas Ratio -
(GPM/1000 CFM)
CaO Feed Rate (M Moles/Min)
Stoichiometry based on inlet
S02 (Z)
S02 Removal Eff. (*)
Solid Cone, in Spray Slurry
(wt. Z)
aSg (Amount of SO, absorbed)
(M Moles/Min) c
Ca(OH)? Dissolution
(M Mole/Mi n)
Sulfite Oxidation
(M Moles/Min)
CaS03 -1/2 H,0 formation
(M Holes/Min5n)
CaSOfl -2 HyO formation
(M Moles/Mi n)
Marble
Set #1
11,000
18.6
11,503
72.8
67.6
3.67
10,717
6,137
2,990
5,943
- 1 ,339
Bed Hold Tank
Set #2 Set #1 Set #2
1 1 ,000
18.6
11,503
72.8
67.6
3.35
10,717
6,868 3,387 3.286
3.097
5,027 1 ,435 1 ,849
- 560 1,711 1,069
Marble
Set #1
9,670
20.6
16,599
91.5
57.7
8.02
13,917
5,179
4,968
2,563
1,150
Bed Hold Tank
Set #2 Set #1 Set #2
10.000
20
16,599
88.8
60.7
6.67
14.703
9,422 -10.894 - 6,564
3.910
4,380 - 280 556
459 - 1,391 - 3,985
Marble Bed ' "Hold Tank
- Set #1 Set #2 Set #1 Set #2
9.940 9,900
36 35.5
16.599
87.8 88.4
70.8 74.2
8.58
16.760
14.745 15.167
5.799
4,664 17.265
4,664 9.442
CaCOo formation
  UJ? formation
  (M Moles/Min)                                                                          -    72       594                           398
Error in Total  Sulfur
  Material  balance
            x 100 {«)           13.5       12.2       0.3   -   9.2
-------
U)

en
                                           TABLE 3.4.  CRTIERIA FOR DETERMINATION OF LIMESTONE FURNACE
                                                       INJECTION TEST RELIABILITY
                                                                                    Ca(OH)2 Dissolution in      Error  in  Total  Sulfur
NO. >

17R
(17R)
18R
19R
(19R)
20R
(20R)
21 R
22R
Ca++ in
Set #1
X
X
X
X
X
X
X
X
*
Additive
Set #2
X
X
X
X
X
X
X
X
_
+CaS04
Set #1
X
X
X
X
X
X
X
X
X
•ZHgO > 0 Hold Tank and
Set $2
X
X
X
X
X
X
X
X
_
Set #1
X
X
X
*
X
X
X
X
X
Set #2
X
X
X
*
X
X
X
X
_
Set #1
X
X
X
X
X
X
X
*
X
Marble Bed > 0 Material Balance > 10%
Set #2
X
X
X
X
X
X
X
*
_
Set #1
X
X
X
X
X
X
X
-
_
Set #2
*
*
X
X
X
X
X
-
.
          KEY:  ( ) Calculated by assuming all the oxidation occurs in marble bed
                 X  Good
                 *  Bad
                 -  No Data
-------
                The  parentheses indicate that the rate calculations for the
 high  solid slurry experiments were determined assuming all the oxidation
 occurred in the marble bed.
                Table 3-3a and 3-3b summarize the rates of CaS(yi/2H20 and
 CaSO.'2H-0 precipitation, sulfite oxidation and Ca(OH)2 dissolution.   In
 the low slurry solid concentration experiments, most of the CaS(L*1/2H20
 precipitation occurred in the hold tank, while in the high solid concentration
 experiments, most of the calcium sulfite precipitated in the marble bed.
 Calcium sulfate precipitation rate data were inconsistent, and therefore it
 was almost impossible to detect the trend and location of its precipitation.
 The dissolution rate of Ca(OH)2 in the marble bed was always greater than
 50  percent of the total dissolution except in experiment T9R, where it was
 30  percent.
                This leads to the conclusion that most of the additive
 dissolves  in the marble bed.  It is important however, to point out that
 the percent of total dissolution in the marble bed should be controlled
 so  that  calcium sulfite scaling will  not occur.
                It should also be noted that in most experiments the rate of
 CaC03 formation was negligible in both the marble bed and the hold tank.
 In  addition, out of the total S02 absorbed in the system, the fraction that
 underwent  oxidation was higher (40-55 percent) in the low solid slurry
 experiments than in the high solid slurry experiments (25-35 percent).
 3.3.7           Calculation of Additive Dissolution Rate From Equilibrium Data
                Based on the results  of the stage efficiency calculations for
 the soluble system tests,  additive dissolution rates were determined  for the
 furnace  injection tests by using vapor-liquid equilibria.  Two major  assumptions
were made  in these calculations:
                                    3-16
-------
                 (1)  Stage efficiency remained constant at 90% (from the
 soluble system tests).
                 (2)  The marble bed operated as a well mixed reactor and
 additive dissolved at  a fixed rate to maintain a constant partial pressure
 of S02  exerted by the  liquid in the bed.
                 Figure 3-3 is an operating and equilibrium line diagram of
 experiment  17R.  The equilibrium line on the diagram represents the soluble
 portion of  the scrubber feed.  The abscissa is constructed so that the total
 sulfur  concentration in the liquid entering the scrubber is represented by
 the vertical  line at the far left of the graph.  The point on the abscissa
 corresponding  to the actual S(L removal is the total sulfur concentration in
 the liquid  leaving the scrubber.  This concentration does not exist in the
 actual  data taken but  is equal to the weighted average of the downcomers and
 scrubber bottoms concentrations assuming no precipitation of sulfur compounds
 in  the  scrubber.
                If no  additive dissolution had occurred, the S(L outlet
 concentration  could have been no lower than 1260 ppm as represented by the
 intersection of the operating and equilibrium lines.  Since the actual S(L
 outlet  concentration obtained during the test was 770 ppm, some additive
 dissolution had to occur.   Assuming the stage to be 90% efficient for
 770 ppm  outlet S02, the outlet S02 equivalent to 100 percent stage efficiency
would be 680 ppm  (according to the previously stated assumption,.the rate of
 additive dissolution should be sufficient to maintain 680 ppm S0? partial
pressure over the liquid).   Even if the stage efficiency-is less than
100 percent, the rate of additive dissolution would be the same.  In order to
calculate the dissolution,  the simplest method would be to determine what
quantity was necessary to maintain 680 ppm S02 over the liquid if S02 removal
equal to 100 percent stage  efficiency was obtained.
                                    3-17
-------
VjJ
 I

oo
         22


         20


         18
     d-
     S  16


     i  14
 ~ 12
o
o
i—i
o
         10


         8
                                           T
                                    EQUILIBRIUM LINE
                                    FOR SPRAY SLURRY
                                    FILTRATE

                                                                   ACTUAL SO,

                                                                   REMOVAL
                                                                          100% STAGE '
                                                                          EFFICIENCY
                 SPRAY COMPOSITION
                                I
              2.0
  (D
                          3.0               4.0               5.0
                      MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10'4
                                                                             6.0
                       PLOT  OF OPERATING LINE  FOR  EXPERIMENT  17R
-------
                To quantitatively determine the additive  dissolution, varying
amounts of calcium were input to the computer equilibrium program along with
most of the spray water composition.  Only soluble carbon dioxide values were
taken from the downcomer analysis, and sulfite and sulfate were those derived
from Figure 3-3 for 100% stage efficiency.  Total  system  oxidation was used
to determine the ratio of sulfate and sulfite at this  point.   Partial
pressure of S02 over the liquid for varying amounts of soluble calcium is
plotted for experiment 17R in Figure 3-4.   The concentration  of calcium
producing a partial pressure of 680 ppm SOp was found  to  be 24.45 ""i^gp5  •
By subtracting the amount of soluble calcium entering  the scrubber from this
value and multiplying the difference by the flow rate, a  dissolution rate  of
4950 m rc?rc    was obtained.  This procedure was carried out for experiments
18R to 22R; the graphs are presented in Appendix I. Table 3-5 contains a
summary of these results along with the results obtained  by material balance
methods.
                Agreement of the dissolution rates obtained by equilibrium
data with those done by liquid species material balance is reasonable in
most cases.  Experiments 18R and 22R exhibit the most  deviation.  Comparing
the dissolution rates to the S02 absorption rates indicates that additive
dissolution is responsible for an average  of two-thirds of the S0« removal.
3.3.8           Super-saturation of Calcium Sulfate and Sulfite
                Using the soluble chemical analyses from  marble bed samples
and the equilibrium computer program, supersaturation  values  of calcium
sulfate (ratio of the activity product to  solubility product) were calculated
for experiments 17R through 22R.  Table 3-6 contains these results along
with an indication of any calcium sulfate  scaling which occurred during the
tests.  A supersaturation value of approximately 1.3 appears  to be the
threshold for calcium sulfate scaling in these tests.
                                    3-19
-------
ro
CD
10
 VjJ
   22




   20




   18





r  16
o

 x 14

CO

§ 12





CO
     o
        0
                                     I
        23
24                   25

 CALCIUM-m MOLE/LITER
                                                                26
          PLOT OF CALCIUM vs PARTIAL  PRESSURE  OF S02 FOR  SCRUBBER

                           EFFLUENT - EXPERIMENT 17R
-------
                   TABLE 3-5.  SUMMARY OF CALCIUM HYDROXIDE DISSOLUTION
                               CALCULATIONS FOR MARBLE BED
                               All values are In
    M Moles
    "MTrT
                   Liquid Species Material
Experiment              Balance Using
                 Results From
Solids Species   Equilibrium
Amount of
No.
17R
18R
19R
20R
21 R
22R
Set No.
1
2
1
2
1
2
1
2
1
2
1
Assumed Oxidation*
5000
5400
6100
6900
3000
7800
6100
2600
5200
9400
14700
Material Balance
2200
2700

300
2000
3900
3700


Diagrams
5000
2800
5200
4200
8200
8800
SOp absorbed
7100
7100
10700
10700
5800
5400
6600
6400
13900
14700
16800
* Oxidation value obtained for entire system was assumed to occur only in marble bed.
                                          3-21
-------
                 TABLE 3-6.  COMPARISON OF CALCIUM SULFATE
                             SUPERSATURATION AND SCRUBBER PERFORMANCE
                    Relative Supersaturation             Did  Calcium Sulfate
Test No.              Of Calcium Sulfate*                  Scaling  Occur?
  17R                          0.97                              No
  18R                          1.33                              Yes
  19R                          1.84                              Yes
  20R                          2.03                              Yes
  21R                          1.18                              No
  22R                          1.32                              No
               [Ca activity in marble bed]  [SO.  activity  in marble  bed]
*Definedb*:  	ksp of CaSQ4  at  T*	at T°
                                  3-22
-------
                Values of supersaturation for calcium sulfite in the marble
 bed were not calculated because of the large fluctuations with pH.   Although
 a supersaturation value can be obtained for the marble bed samples,  this
 probably does not represent the actual value in the bed itself.  Any dissolution
 of additive while the sample was being taken would raise the pH and  increase
 the calcium sulfite supersaturation.
 3.4             CONCLUSIONS
                In summary, the following conclusions can be drawn from
 the limestone furnace injection system tests.
                (1)  S02 removal can be improved significantly (8 to 10
 percentage points) by increasing the liquid to gas ratio from approximately
 20 to 35 GPM/1000 CFM.
                (2)  S02 removal can be improved significantly by increasing
 the solids concentration in the spray slurry from 0 to 3.5%.
                (3)  No improvement in S02 removal could be obtained by
 increasing the solids in the spray slurry beyond 3.55L
                (4)  Calcium sulfate scaling was controlled in a closed loop
 system without employing liquid blowdown by maintaining 8% total solids
 (30^-608 flyash) in the spray slurry.  (Based on a maximum continuous run  time
of 10 hours).
                (5)  Calcium sulfate scaling can be controlled by maintaining
the supersaturation level  below 1.3.
                (6)  Calcium sulfite scaling in the scrubber can be  controlled
by maintaining the spray slurry pH below 11  to insure that no CaO or Ca(OH)2
solids enter the scrubber.
                (7)  More  than half the additive dissolves in the scrubber bed
in spite of the short residence time in the bed.
                                    3-23
-------
                                  SECTION 4
                        LIMESTONE TAIL-END SYSTEM TESTS

 4.1              SYSTEM  CHEMISTRY
                 The  process of removing S02 from the flue gas using lime-
 stone in  the  limestone  tail-end system consists of the following reactions:
                 CaC03 + C02 + H20  -*•  Ca(HC03)2                            (1)
                 2S02 +  Ca(HC03)2  -^  Ca(HS03)2 + 2C02                      (2)
                 CaS03 + S02 + H20  -»  Ca(HS03)2                            (3)
                 Ca(HS03)2 + CaC03 —*  CaS03 + Ca(HC03)2                    (4)
                 CaS03 + 1/2 02  -»  CaS04                                   (5)
 Reactions  1,  2 and 3 are the principal absorption reactions.  Sulfur dioxide
 reacts with relatively  soluble bicarbonate to form calcium bisulfite.  In
 addition,  solid  calcium sulfite recycled from the reaction tank or hold tank
 reacts with S02  to form calcium bisulfite.
                 The  reactions in which sulfite is oxidized to sulfate
 (reaction  5)  and soluble bisulfite is converted to insoluble calcium
 sulfite (reaction 4) account for the waste products as well  as the regenera-
 tion  of the solid calcium sulfite reactant that is recirculated to the
 scrubber.  The ratio of calcium sulfite to calcium sulfate found in the
 ARCS  solid waste depends upon the extent to which these reactions go to
 completion.
 4.2             TEST DESCRIPTION
                The  C-E scrubber at  EPA's alkali  Scrubbing Test Facility
 (at TVA's Shawnee steam plant) has only one marble bed, while current
commercially offered C-E scrubbers have two marble beds.  On the other
hand, the other two  scrubbers at the facility are similar to current
commercially offered designs.   Therefore, it was  felt that comparing the
                                   4-1
-------
performance of the C-E scrubber with the other two test scrubbers at
Shawnee might be difficult.  Therefore, the one and two marble bed tail-
end  limestone tests using the KDL prototype were designed to assist EPA
in extrapolating the single marble bed results from Shawnee to predict the
performance of the C-E scrubber with two marble beds.  The tests also
provided data for determining the solid-liquid mass transfer rates in the
scrubber and the hold tanks.  In addition, the following information was
sought which would greatly assist in designing a limestone tail-end system
for  scrubbing SO^:
                (1)  Rate of dissolution of limestone (CaCO,).  This would
determine the alkalinity in the scrubber bed and the proper size of the
reaction tank.  The rate can be determined either using a material balance
or using equilibrium methods.
                (2)  Rate of precipitation of calcium sulfate and calcium
sulfite.  The rates would assist in designing the reaction tank such that
the exiting stream will be close enough to saturation to prevent calcium
sulfate scaling in the scrubber.
                (3)  Rate of oxidation to sulfate.  This would determine
the incremental  increase in supersaturation of calcium sulfate in the
marble bed and therefore would determine both the liquid to gas ratio
(L/G) and the limit on supersaturation entering the scrubber needed to
prevent calcium sulfate scaling in the scrubber system.
                Contrary to the furnace injection tests where the additive
was introduced into the scrubber along with the flue gas, the additive in
the tail-end system was introduced into the hold tank as shown in Figure
4-1.   Liquid S02 was vaporized using steam and then injected into the flue
gas (FG) in order to increase its StL concentration to about 0.25 mole
percent.  The slurry (SL) from the marble beds' turbulent layers (pH of
                                  4-2
-------
                             TO
                           STACK
                                   REHEATER
                                     DEMISTER


                                     MARBLE BED


                                       SPRAY WATER (SWU)
                                       SCRUBBER LIQUID (SLLM
                                     MARBLE BED


                                       SPRAY WATER (SWU
                                       SCRUBBER LIQUID (SLL)
                                   SOLIDS TO
                                   DISPOSAL
O
C
3D
m
VACUUM
FILTER
             LIMESTONE
              FEEDER

                N*/
                        LIMESTONE  TAIL-END  SYSTEM
-------
5-5.5} left the scrubber through the overflow pots into the downcomers and
was  then discharged into the hold tank (10 feet diameter by 10 feet high).
The  scrubber bottom slurry (SB) which was rejected spray water was also
discharged into the hold tank.  The hold tank provided good solid liquid
contacting and allowed for the limestone dissolution.  The test conditions
for  the six tests are listed in Table 4-1 and the operating data is given
in Table J-l in Appendix J.
                In experiments 25R, 26R and 27R, only one marble bed was
used, while in experiments 28R, 29R and 30R, two marble beds were used.
Most of the slurry leaving the hold tank was introduced under the marble
bed through the spray nozzles.  The spray water pH varied between 6.0 and
6.5.  The marble bed together with the turbulent layer the volume of which
is about 20 cubic feet, provided good mixing where the absorption of S(L
took place.  A portion of the hold tank effluent was pumped to the
clarifier to maintain about 8 percent solid concentration in the slurry.
The solids were settled in the clarifier and the clarified liquid (CL)
was returned to the hold tank.  The hold tank was maintained at full
capacity of about 6000 gallons at all times.  The reaction tank residence
time at a 500 gpm pumping rate is about 12 minutes.
                To determine when the system reached steady state, samples
taken from the spray water (SW) and the clarifier liquid (CL) were
analyzed for calcium,  sulfite and sulfate.  Steady state in these tests
is defined as the point when the calcium and total sulfur concentration
in the filtrate of the clarified liquid (CL) and the spray water (SW) were
reasonably close.   The analyses of the samples used to determine steady
state are shown in Table J-2 in Appendix J.
                                   4-4
-------
              TABLE 4-1.  TEST PARAMETERS FOR THE LIMESTONE TAIL-END SYSTEM
Experiment No.
Number of beds
Gas Flow Rate
  ACFM @ 120°F
  ft/Min
Inlet S02, PPM
Limestone Feed Rate
  (% Stoleniometry)
Fly Ash Feed Rate (Gr/SCFM)
Underbed Slurry
  GPM/bed
  L/G, GPM/1000 CFM
Overbed Spray, GPM/bed

Solid Cone. In Slurry, wt. %    8         8         8
25R
1
10,000
450
2,400
100
0
250
25
0
26R
1
10,000
450
2,400
150
0
250
25
0
27R
1
10,000
450
2,400
150
0
150
15
0
28R
2
10,000
450
2,400
150
0
150
15
0
29R
2
10,000
450
2,400
150
0
250
25
0
30R
2
10,000
450
2,400
100
0
250
25
0
                                          4-5
-------
 4.3             DATA EVALUATION
 4.3.1           System Performance
                The results of the tail-end tests are summarized in Table
 4-2.  While holding all other conditions the same in single bed experiments
 26R and  27R, the S02 removal efficiency increased by 8 percentage points
 when the liquid to gas ratio (L/G) was increased from 15 to 25 GPM/1000 CFM.
 In double bed experiments 28R and 29R, the overall S02 removal increased
 by 11 percentage points when the L/G was increased from 15 to 25 GPM/1000
 CFM per  bed.  It can be concluded therefore, that the liquid to gas ratio
 has a significant effect on the SOp removal efficiency.
                The overall S02 removal efficiency remained unchanged in
 both single and double marble bed tests while the additive feed rate was
 increased from about 100 to 150 percent stoichiometry with all the other
 conditions kept the same.  This leads to the conclusion that in high
 solids systems when the additive feed rate is increased beyond 100 percent,
 the S02  removal efficiency remains unchanged and as a result, the additive
 utilization tends to decrease.
                While the solid concentration in the slurry in all tail-
 end experiments was maintained between 6.5 and 8.5 percent, no calcium
 sulfite  or calcium sulfate scaling was observed.  Liquid blowdown was not
 used during these tests to control calcium sulfate scaling.  Therefore,
 it can be concluded that calcium sulfate scaling in a limestone tail-end
 system can be controlled by maintaining a solid concentration in the slurry
 of about 8 percent (excluding fly ash).
                The S02 removal efficiency in the upper and the lower
marble beds based on the S02 concentrations in the gas entering the
respective marble beds, was the same.  For example, in experiment 27R, the
 lower marble bed removed about 50 percent of about 2400 ppm S02 entering
                                    4-6
-------
                    TABLE 4-2.  SUMMARY OF LIMESTONE TAIL-END TESTS
                                PERFORMANCE RESULTS

Experiment No.                     25R      26R      27R      28R      29R      30R
No. of Marble Beds Used            111222
L/G (GPM/1000 CFM) - Lower Bed     24.5     24.0     15.0     16.0     24.5     25.0
L/G (GPM/1000 CFM) - Upper Bed              -        -        15.0     22.5     23.5
Solids in Spray water (%)          7.4      6.5      7.5      6.7      8.6
Inlet S02 (PPM)                    2345     2505     2315     2420     2435     2380
Solid Recycle - (%)                96       94       92       95       97       96
Stoichiometry (%)                  98       145      156      152      148      94
S02 removal efficiency (%)*        55.5     57       49       76       87       86
Additive Utilization - %           57       39       31       50       59       91
Calcium Sulfite Scale              None     None     None     None     None     None
Calcium Sulfate Scale              None     None     None     None     None     None
Liquid Slowdown                    None     None     None     None     None     None
*Corrected for Air leakage

The gas flow was maintained at about 10,000 CFM @ 130°F,  1  atm in all  tests,
                                         4-7
-------
 it,  and in  experiment  28R,  both marble beds removed about 75 percent of the
 S(L  (2400 ppm)  entering  the lower bed.  This means that the lower bed
 removed 50% of  the  2400  ppm S02 entering it while the upper bed removed
 another 50% of  the  remaining 1200 ppm SOp entering the upper bed.  This
 resulted in an  overall removal of 75%.  Therefore, it can be concluded that
 single  marble bed S02  removal efficiency for the range of inlet S02
 concentration studied  can be extrapolated to predict two marble bed SO*
 removal  efficiency.
 4.3.2           Analytical  Results and Sampling Methods
                The furnace injection sampling method was also used in the
 tail-end tests, and the  corresponding samples from the upper marble bed
 were added  to the list of samples used in the furnace injection tests.  C-E,
 however,  did not perform chemical analysis on any of the tail-end test
 series  in order not to duplicate Radian Corporation's effort.   The results
 of the  solid analyses are listed in Tables J-3 through J-8, and those of
 the liquid  analysis are listed in Tables J-9 through J-14, in Appendix J.
 In their July, 1972 Progress  Report to EPA, Radian indicated a significant error
 in the  liquid sulfite analysis in experiment 25R.  This caused an error in
 the sulfate results, since  sulfate is obtained by the difference between
 total sulfur and sulfite.  The remainder of the analyses were fairly
 accurate except for the marble bed sulfite and sulfate results which are
 slightly in error due to a relatively large residence time in the sampling
 lines thus allowing further time for reaction and oxidation.   The samples
 for obtaining solid concentration in the slurry in experiment 30R were
accidentally discarded, thus preventing total  sulfur material  balance
calculation  for that test.
                                   4-8
-------
4.3.3           Total Sulfur Material Balance
                Detailed calculations of the total sulfur material balance
of the limestone tail-end experiments are summarized in Tables K-l through
K-5  in Appendix K, and the results are summarized in Tables 4-3a and 4-3b.
The  results show low errors considering the analytical and sampling problems,
and  the  inaccurancy in sampling for high solid concentration in the slurry.
In arriving at the amount of total sulfur in the slurry streams, the specific
gravity  of the slurry used was assumed to be 1.0 in order to convert the
slurry flow rate from GPM to pounds per minute.
4.3.4           Rate Calculations
                Since the solid concentration in all of the limestone tail-
end  tests was high, a material balance calculation to determine the rates
was  not  feasible without making certain assumptions.  In the case of high
solid slurries, a difference in a rate resulting from a slight change in
solid concentration was masked by that resulting from the error in the
solid concentration measurement.  Therefore, in order to obtain the rates
of precipitation and dissolution, the following assumptions and observations
were used:
                (1)  All  of the oxidation in the system occurred in the
marble bed.  (From experiment 17R, furnace injection.)
                (2)  Total  oxidation in the system is the ratio of the
total sulfate to total  sulfur in both the solid and liquid streams leaving
the systems.
                Oxidation =
       (SO/) Liquid +  (SO/) Solid
• i nn —    ^	.1	
                                     Total  Sulfur
                (3)  The amount of CO- transferred to the hold tank from
the atmosphere is negligible.
                                   4-9
-------
                                                     TABLE 4-3a.  SUMMARY OF  RATE  RESULTS
                                                                  FROM LIMESTONE TAIL  END  TESTS
                                           .§5B?r'!!?!3t_2§?

Location
Inlet Blue Gas Flow (CFM @130°F)
Liquid to Gas Ratio - Upper
per Bed
(GPM/1000 CFM) - Lower
Additive Feed Rate (M Moles/Min)
Stoichiometry based on inlet SCL(%)
S02 Removal Eff. (%)
Solid Cone, in Spray Slurry
(wt. %)
£ ASc (Amount of SO- absorbed)
o (M Moles/Min) i
Sulfite Oxid. (%)
Sulfite Oxidation (M Moles/Min)
CaSOs -1/2 H20 formation
(M Moles/Min)
CaS04 -2 H20 formation
(M Moles/Min)
CaCOs dissolution (M Moles/Min)
Marble Bed
Set #1 Set 92
9,950 9,900
24.1 25.2

98.5 97.6
56.2 54.7
7.55
12,770 13,501
25.0 23.4
3,192 3,159
745
4,997
4,832
Syst. Remainder Marble
Set #1 Set #2 Set #1
10,060
24.3
24,062 24,062
144.5
56.5
-
14,081
26.1
3,675
10,497 10,127 -3,122
1,233 -2,201 2,898
5,586 4,281 6,769
Bed
Set n
10,100
23.3

.46.1
57.0
6.57
11,911
23.8
2,834
-1,146
-274
5,413
Sy_st. Remainder
Set #1 Set #2
10,250
14.6
38,590 38,590
156.7
48.2
7.18
11,237
26.4
2,966
13,769 13,098
1,568 3,000
6,801 7,647
Marble Bed
Set sill Set #2
10,180
14.7

156.6
49.4
7.69
11,438
24.9
2,848
-2,907 247
3,160 885
5,092 6,954
Syst. Remainder
Set #1 Set #2

-
39,044 39,044






11,279 8,255
-742 1 ,854
5,937 7,565
Error in Total  Sulfur material
  balance
  (In "n°ut) x  100                    -3.1               -0.2     -0.5              -20.7                3.7     -9.2    -13.1      -3.3      -1.9

*System remainder includes hold tank,  surqe  tanks  and  clarifier.
-------
                                                     TABLE 4-3b.  SUMMARY OF RATE RESULTS
                                                                  FROM LIMESTONE TAIL END T£STS
                                   ___	Experiment_28R___	_	§x[>eriment_29R
Location
Inlet Flue Gas Flow (CFM @ 130°F)
Liquid to Gas Ratio - Upper
per Bed
(GPM/1000 CFM) - Lower
Additive Feed Rate (M Moles/Mi n}
Stoichiometry based on inlet S02(%)
S02 Removal Eff. (%)
Solid Cone, in Spray Slurry (wt.JS)
&SR (Amount of SO- absorbed)
(M Moles/Min) e~
Sulfite Oxid. (%)
Sulfite Oxidation (M Moles/Min)
CaSOg -1/2 H20 formation
(M Moles/Min)
CaS04 -2 HgO formation
(M Moles/Min)
CaC03 dissolution (M Moles/Min)
Error in Total Sulfur material
balance
rln - Outx .. 100
Set 01
10,160
14.8
15.5

152.4
75.5
6.40
17,002
24.4
4,150
1,319
1,430
9,503
-14.8
Set n
10,400
14.4
15.3

151.7
76.0
6.71
18,057
25.9
4,680
10
1,721
10,102
-3.9
Set #1 Set #2 Set #1
10,200
22.0
24.0
39,044 39,044
147.8
87.1
8.41
21 ,489
27.9
5,995
13,009 12,991 2,825
3,695 3,346 -676
7,893 7,744 12,601
-5.6 2.2 -16.0
Set #2
10.400
21.6
23.5

147.5
87.6
8.72
21,050
28.4
5,978
3,076
-262
12,152
-20.9
Set #1 Set n
10,280
22.8
24.3
39,044 39,044
97.1
84.4
-
19,643
30.0
5,893
11,687 11,562
6,839 6,373
7,782 9,124
-31.2 -4.5
Set #1 Set n Set #1
10,280
22.8
24.3
24,213
90.0
87.3
-
20,463
30.5
6,241
-3,306 -5,086 23,284
161 1,120 6,154
9,861 9,394 15,975

Set n


24,213






19,592
2,205
8.199

*System remainder includes hold tank, surge tanks and clarifier
-------
                A  summary of the rate calculations are shown in Tables K-6
 through  K-ll  in Appendix K.  Tables 4-3a and 4-3b summarize the rate results
 obtained from the  limestone tail-end tests.  In order to determine the
 reliability of rate data from these experiments, the following criteria were
 used:
                (1)  The rate of SCL removal from the gas should always be
 greater  than  the sum of calcium sulfite and calcium sulfate precipitation
 rates  in the  system (marble bed and system remainder).
                (2)  The rate of SOp removal from the gas should be equal
 to  the rate of limestone dissolution in the system (marble bed and system
 remainder).
                (3)  The sulfite analysis should be reliable (discussed in
 section  4.3.2).
                Table 4-4 lists these criteria for the limestone tail-end
 experiments and indicates whether or not each criterion is satisfied.  The
 following tests were considered reliable:
                26R(1), 27R(1, 2), 28R(2), 29R(1, 2), 30R(2).
                The parentheses indicate the set number.   The negative
 calcium  sulfite and calcium sulfate precipitation rates in the marble bed
 and the  hold tank could be attributed to one or both of the following:
                (1)  Errors resulting from the liquid sulfite analysis
and/or liquid sampling techniques.
                (2)  The assumption that all of the oxidation in the
system occurred in the marble bed may not be true.   The calculation of
the rate of limestone dissolution,  however, should  not be affected by the
calcium sulfite and calcium sulfate precipitation rates,  since the rate
of limestone dissolution depends on the total  sulfur analysis which in
this case is relatively accurate.
                                  4-12
-------
                    TABLE 4-4.  CRITERIA FOR DETERMINATION RELIABILITY
                                OF LIMESTONE TAIL-END TEST
Test No.     CaS03.l/2H20 + CaS04.2H20     AS6 = CaC03 Dissolution    Sulfite Analysis

25R
26R
27R
28R
29R
30R
Set 1
*
X
X
*
X
*
Set 2
-
*
X
X
X
X
Set 1
*
X
X
X
X
*
Set 2
-
X
X
X
X
X
Set 1
*
X
X
X
X
X
Set 2
X
X
X
X
X
X
X - Good

* - Bad

- - No Data
                                         4-13
-------
                 In  all  the  limestone tail-end experiments, most of the
 calcium sulfite precipitation occurred  in the hold tank.  The fraction of
 total  precipitation occurring in  the marble bed could not be determined
 due to the  error involved in the  determination of sulfite concentration
 in the liquid.
                 Most of the calcium sulfate precipitation occurred in the
 hold tank when  two  marble beds were used.  However, when one marble bed
 was used, the calculated precipitation  rates fluctuated appreciably.  This
 inconsistency prevented drawing any conclusions regarding where most of
 the calcium sulfate precipitation took  place.  The calcium sulfate precipi-
 tation rates, like  the  calcium sulfite  precipitation rates, were in error
 for the  reasons  discussed above.
                 During  the experiments with one marble bed, the rates of
 limestone dissolution in the marble bed and the hold tank were approximately
 equal.   The  dissolution rates in the marble bed basically did not change
 with the liquid  to  gas  ratio.  When two marble beds were employed, the
 fractional  rate  of  dissolution of limestone in the marble bed increased
 from 50  percent  to  about 60 percent.  This was expected since it was
 accompanied  by an increase in SOp removal  efficiency.
 4.3.5            Calculation of Additive Dissolution Rate From Equilibrium Data
                 The dissolution rate of calcium carbonate in the marble bed
was calculated from an equilibrium approach in the same manner as described
 in  the furnace injection tests.   For the first single bed calcium carbonate
test, 25R, the operating line is plotted in Figure 4-2.  As was determined
 in the soluble system tests, a stage efficiency of 90% was used in making
dissolution  rate calculations.   The amount of calcium needed in solution in
the marble bed to maintain the partial  pressure corresponding to 100% stage
                                   4-14
-------
efficiency was determined for experiment 25R from Figure 4-3.*  To
calculate the dissolution rate, the concentration of soluble calcium in
the scrubber feed was subtracted from the calcium concentration determined
above and the difference was multiplied by the inlet liquor flow rate.
These results are summarized in Table 4-5.
                Calculation of dissolution rates for the tests with two
marble beds presented one major problem:  no measured sulfur dioxide
concentration between the first and second beds.  If liquid analyses were used,
corrections would have been necessary to account for amounts of calcium sulfite
and sulfate precipitated in the scrubber or in the lines before the sample was
taken.  'Since gas-side analysis is needed to determine the amounts of calcium
sulfate and sulfite precipitated, a value for the amount of sulfur dioxide
removed in the first bed could not be obtained from liquid analyses either.
For these reasons, assumptions for the amount of sulfur dioxide removed in
the first bed were made based on results from the single bed tests.  These
values were correlated to the single bed tests according to the L/G in each
test; included in the L/G for the bottom bed in the two bed tests was the
amount of slurry rejected from the top bed.  These calculated sulfur dioxide
values are presented in Table 4-6.
                Figure 4-4 is the operating line diagram for the upper bed
in experiment 28R; the diagram for the determination of calcium concentra-
tion is shown in Figure 4-5.  Appendix L contains the diagrams for tests
29R and 30R.  The rates for dissolution of calcium carbonate for the upper
bed are listed in Table 4-5 along with a total dissolution rate for both
beds using average dissolution values from the single-bed tests.  Calcium
carbonate dissolution values by material balance are also listed in Table 4-5.
*A11 diagrams .for experiments 26R and 27R are given in Appendix L.
                                   4-15
-------
   22


   20


   18



T  16
 o
 x 14
 CO
 g 12
  O  o
  p  8
  o
                       T	
           	1	1	T
                                                         T	1	1	T
                                                                S02 REMOVAL
                                                                    STAGE EFFICIENCY
            SPRAY COMPOSITION
ro
          5.Q
      6.0                   7.0
MOLE FRACTION - TOTAL SULFUR IN LIQUID x
                                                            10
                                                              -4
                                                                        8.0
                    PLOT  OF OPERATING  LINE FOR EXPERIMENT 25R
-------
        22



        20
r
i—i
*«J
        18
     S  16
                                                      30
31
                             CALCIUM -m MOLE/ LITER
          PLOT OF CALCIUM vs PARTIAL PRESSURE OF S02 FOR SCRUBBER

                           EFFLUENT - EXPERIMENT 25R
-------
            TABLE 4-5.  SUMMARY OF CALCIUM CARBONATE DISSOLUTION CALCULATIONS
                                All values are In
M Moles
 Min.
Experiment
25R
26R
27R
28R
29R
30R
Bottom Bed
3030
6880
5700
5700
6880
6880
Top Bed



2380
2520
3080
Total for
Both Beds Bottom Bed
4832
6769
5092
8080
9400
9960
Total for
Both Beds



9503
12601
9861
Amount of
S02 absorbed
12770
14081
11237
17002
21489
19643
TABLE 4-6.  ASSUMED S02 REMOVAL FOR LOWER BED IN  TWO-BED CALCIUM  CARBONATE  TESTS
   Experiment                 28R     29R      30R
   S02 entering lower bed     2223    2248     2240
   S02 leaving lower bed      1091      943      940
   S02 leaving top bed        563     299      377
   S02 values are corrected  for  humidity  and  air  leakage.
                                         4-18
-------
in
   22


   20


   18



   16

   14


   12
 CM -irt
o  10
to
y  o

o

£  6



i  4


   2


   0
                                                     ACTUAL S02 REMOVAL

                ~Z~~~~:L^^~~Z~Z~™:L^^±^^^ 100% STAGE EFFICIENCY
                    SPRAY COMPOSITION
                         1
                                              1

                         5                     6             /.
                        MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10"4
                PLOT OF OPERATING LINE  FOR EXPERIMENT 28R
-------
-fa.
ro
  CD
  vii
         0
                              CALCIUM-m MOLE/LITER
PLOT OF CALCIUM  vs PARTIAL  PRESSURE OF  S02  FOR SCRUBBER
                 EFFLUENT - EXPERIMENT  28R
-------
                 Overall, the agreement between the two methods of
 calculation  is  very  good.  Due to the inaccurate sulfite analyses in experiment
 25R,  the  dissolution rates obtained are probably not reliable.  In general,
 one half  of  the total  system dissolution took place in the marble bed,
 indicating that half of the SCL removal was because of additive dissolution
 and half  by  the soluble alkali in the scrubber feed.
 4.3.6           Supersaturation of Calcium Sulfate and Sulfite
                 Values for the degree of supersaturation of calcium sulfate
 in  the marble bed were calculated for Tests 25R-30R.  The soluble analyses
 from  the  marble bed  samples were input to a computer equilibrium program
 to  determine.the activities of calcium and sulfates.  Table 4-7 presents
 the results  of  these calculations.
                 No calcium sulfate scaling was observed for any of the
 six tests, although  supersaturation values are higher than the threshold
 values of 1.3 obtained in the furnace injection tests.  No definite
 explanation  can  be given at this time for the fact that supersaturation
 values as high  as 1.7 did not cause calcium sulfate scaling in the calcium
 carbonate tests.
                Values of supersaturation for calcium sulfite were not
 calculated for  the same reasons as given in Section 3.3.8 (Furnace Injection
 Tests).   No  calcium sulfite scaling was observed during the tests.
 4.4             CONCLUSIONS
                The following conclusions can be drawn from the tail-end
 limestone system tests:
                (1)  The performance (S02 removal  efficiency and scaling)
of the scrubber with two marble beds can be predicted by extrapolating
the single marble bed test results of the C-E scrubber at Shawnee (EPA
                                   4-21
-------
             TABLE 4-7.  CALCIUM SULFATE SUPERSATURATION
Experiment
No.

25R
26R
27R
28R

29R

30R

Bed

Bottom
Bottom
Bottom
Bottom
Top
Bottom
Top
Bottom
Top
Temp(°C)

49
48
47
44
47
46
46
43
47
Relative

0.92
1.62
1.40
1.73
1.70
1.53
1.61
1.54
1.57
Supersaturation
RADIAN*
0.87
1.51
1.32
1.34
1.44
1.40
1.40
1.37
1.37
*Determined by Radian Corporation under EPA Contract 68-02-0023
                               4-22
-------
test facility).  The S02 removal  efficiencies of the lower and upper beds
appear to be the same based on the S02 concentrations entering the
respective beds.
                (2)  Above 100% stoichiometry, limestone feed rate has
little or no effect on S02 removal efficiency in high solids  systems.
                (3)  Calcium sulfate scale can be controlled  in a  closed
loop system without employing liquid blowdown by maintaining  8 to  10%
solids (excluding flyash) in the spray slurry.  (Based on a maximum
continuous run time of 10 hours).
                (4)  S02 removal  can be improved significantly (8  to 10
percentage points) by increasing the liquid to gas ratio from approximately
15 to 25 GPM/1000 CFM.
                (5)  Calcium sulfate scaling can be controlled by  maintaining
the supersaturation below 1.7.
                (6)  More than half the additive dissolution  occurs in  the
marble bed in spite of the short residence time in the bed.
                                    4-23
-------
  APPENDIX A



GAS FLOW CHECK
-------
                                 APPENDIX A
                               GAS FLOW CHECK

                The gas flow check was divided Into two parts.
                a.  Determination of the duct coefficient which is defined as
 the  ratio of the average velocity to the center line velocity.
                b.  Comparison of gas flows obtained by using the pitot tube
 located at the center of the duct and the S02 tracer gas method.
                The flow arrangement used for gas flow check is shown in
 Figure A-l.  The gas flow was set at approximately 12,500 CFM at 130°F and
 1 atmosphere.  Six sets of pitot tube traverses were taken in two perpendicular
 directions using a standard pitot tube and the equal area method.  These
 results are shown in Table A-l.  The duct coefficient is defined as the ratio
 of the average velocity obtained by multiple point pitot tube traverse to the
 center line velocity.  Once the duct coefficient is determined, the need for
 a multiple point velocity traverse is eliminated.  The center line velocity
 obtained by using the pitot tube fixed at the center of the duct could be
 converted to the average velocity that could have been obtained with the
multiple point pitot tube traverse by multiplying the center line velocity by
 the average duct coefficient.  The average duct coefficient was found to be
0.932.
                A measured quantity of gaseous S02 was introduced into the
duct right after the boiler and long before it gets to the scrubber.  The S02
concentrations at the inlet, outlet and stack sampling stations measured
simultaneously with the center line velocity taken at the stack sampling
station were used to calculate the gas flow rate and the leakage into the
system.  The center line velocity was converted to the average velocity of
                                    A-l
-------
ro
                            BOILER STACK
                               DAMPER
                                     SCRUBBER
                                      DAMPER
                        SO e .
                      INJECTION
                       POINT
                                                         STACK
                                                       )SAMPLI NO-
                                                        STATION
                     d
                                                                          OUTLET
                                                                          SAMPLING
                                                                          STATION
               J_
                                                                I. D. FAN
  S02

VAPORISER
SO* FLOW METER
  (ROTA METER)
                                              LIQUID  S02
                                                CYLINDER
                                                                           HEAT
                                                                         EXTRACTOR
INLET
                                              MM
                                                                                         taata
                                       REHEATER

                                       DEMISTER
                                                    MARBLE
                                             SCRUBBER
  O
  c
  JO
  m
                        CE   AQCS  PROTOTYPE—GAS  FLOW  CHECK
-------
               TABLE A-l.  C-E ARCS - GAS FLOW CHECK
                           DUCT COEFFICIENT* - VELOCITY TRAVERSE
                    Set No. 1
                Velocity, Ft/Sec.
                             Set No. 2
                         Velocity, Ft/Sec.
                                         Set No.  3
                                     Velocity, Ft/Sec.
HtOt
Tube
Location
1
2
3
4
5
6
7
Average
Duct*
Coefficient
N-W
Direction
63.8
70.7
74.7
77.5
76.8
74.9
67.7
71.7
0.925
S-W
Direction
69.6
73.7
75.8
77.7
74.9
70.8
64.9
71.8
0.925
N-W
Direction
62.9
71.9
74.8
76.9
77.4
74.9
67.5
71.9
0.935
S-W
Direction
67.4
74.8
76.8
77.3
74.9
69.6
64.0
71.6
0.925
N-W
Direction
62.5
71.1
74.6
77.3
77.6
74.9
70.3
71.8
0.93
S-W
Direction
69.0
74.7
75.6
77.3
76.6
69.7
63.5
71.7
0.927
                    Set No. 4
                             Set No. 5
                                         Set No. 6
1
2
3
4
5
6
7
61.7
69.1
70.6
71.0
69.1
66.4
61.3
60.9
67.3
70.2
70.2
68.7
65.3
60.5
63.3
68.0
70.6
71.0
69.1
66.9
61.3
59.6
66.4
68.7
71.0
69.1
65.7
59.6
63.3
68.7
71.0
70.6
68.7
66.1
59.6
59.6
66.4
68.7
69.5.
68.4
65.7
61.3
Average
66.3
65.6
66.4
66.5
66.2
65.1
Duct*
Coefficient
 0.934
 0.935
 0.936
 0.936
 0.936
 0.936
Average Duct Coefficient = 0.932

*Duct Coefficient = Average velocity/center line velocity

                                     A-3
-------
the multiple point velocity traverse by multiplying it with the average duct
coefficient.  No liquid was introduced into the scrubber.  A mixture of air
and flue gas from the boiler, to which gaseous S02 was added, passed through
the scrubber.  The boiler was operated on natural gas so that the S02 added
to the duct at the S02 injection point shown in Figure A-l was the only source
of S02.  The boiler operation was necessary to provide the steam needed to
vaporize S02 in the S02 vaporizer.  Liquid S02 taken from the S02 cylinder
was measured using a rotameter before it reached the S02 vaporizer.  Manual
SCL method was used to measure the S(L concentrations at the inlet, outlet
and stack sampling stations, because the DuPont S02 analyzer cannot measure
S02 concentration at more than one location at any given time.  The results
shown in Table A-2 show that there is very good agreement in gas flow obtained
using pi tot tube and S02 tracer gas methods.  Since the gas flow measured
with the pi tot tube checked very well with that obtained using S02 as tracer
gas, an independent method, it could be concluded that pi tot tube is a
reasonably good instrument to measure gas flow on the KDL prototype scrubber.
                S02 concentrations at the stack sampling station should be
less than or equal to those at the outlet sampling station depending upon
whether or not there is leakage into the system between the stack and the
outlet sampling stations.  Slightly higher S02 concentrations at the stack
compared to the outlet shown in Table A-2 are within the accuracy limits
(+^4.25%) of the manual S02 method.  Since the leakage into the system
given in Table A-2 is calculated from the S02 concentrations at the inlet,
outlet and stack, the leakage between the inlet and outlet sampling stations
appears to be slightly higher than the leakage between the inlet and stack
sampling stations.  The air leakage into the system was found to be 5 to
8 percent of the gas flow measured at the stack sampling station.
                                    A-4
-------
           TABLE A-2.  COMPARISON OF PITOT TUBE AND SOg TRACER GAS METHODS



Date of Run                                10/8/71  10/8/71   10/11/71  11/1/71  11/11/71

Gas Flow, CFM @ 1 atm. and 130°F

  Center Line Velocity Converted to
  Multiple Point Pi tot Tube Traverse
  using Duct Coefficient Measured at
  the Stack Sampling Station                11,950   11,900   11,510    11,900   12,285

  S02 as Tracer Gas - Measured at the
  Stack Sampling Station                    12,150   12,010   11,540

  SOo as Tracer Gas - Measured at the
  Outlet Sampling Station                        ...    12,590   12,315

S02 Concentration in the Gas, PPM

  Inlet Sampling Station                     1,659    2,241     2,930     2,182    1,704

  Outlet Sampling Station                    1,548    2,122    2,710     2,013    1,561

  Stack Sampling Station                     1,581    2,121     2,770

Leakage into the System, % of Gas Flow
Measured at the Stack Sampling Station

  Between Inlet and Stack Sampling
  Stations                                     5.0      5.3      5.5

  Between Inlet and Outlet Sampling
  Stations                                     7.2      5.3      7.5       7.8      8.4
                                        A-5
-------
       APPENDIX B







SOLUBLE SYSTEM TEST DATA



      AND RESULTS
-------
                                      APPENDIX B

                         SOLUBLE SYSTEM TEST DATA AND RESULTS
           °F
           °F
Experiment No.
Date of Run

Set No.

F6 Rate (CFM @ 130°F)
Feed Composition
SW Rate (GPM)
SF Rate (6PM)
SL Rate (GPM)
SB Rate (GPM)
SW, SF Temp. (°F)
SL Temp.
SB Temp.
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
H. Extractor Outlet Gas Temp. (°F)
Reheater Inlet Gas Temp. (°F)
Overflow Pot Height (Inches)
Inlet S02» ppm - Manual
Inlet S02, ppm - Analyzer
Outlet S02, ppm - Manual
Outlet S02, ppm - Analyzer
% S02 Removal
% Stolchlometry
Sulfur removed from Flue Gas
  ASQ, gmole/min.
Sulfur absorbed by Na-CO,
  A$L, gmole/min.
    - AS,
                                                 1R
                                              10/29/71
                  2R
               10/27/71
10,960
Dilute
107
54
149
20
111
121
120
117
112
231
124
9
2,138
2,018
960
880
61.4
30.8
11.92
12.63
10,960
Dilute
107
54
149
20
111
121
120
117
112
231
124
9
2,090
2,018
936
860
62.3
30.8
11.92
12.38
10,750
Dilute
0
165
88
77
112
129
129
118
123
294
130
9
2,025
2,050
796
750
63.5
40.4
12.78
13.23
10,800
Dilute
0
165
85
80
111
129
129
118
123
292
130
9
2,045
2,050
830
750
63.5
40.6
12.57
13.18
   ASr
          X 100
                                           -6.0
-3.9
-3.5
-3.1
0? in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

CO? in the Flue Gas, %
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  Inlet
  Outlet
                                                 3.7
                                                 5.4
                                                12.1
                                                11.5
                  3.9
                  3.1
                  5.0
                 12.7
                 12.4
                                        B-l
-------
Experiment No.
Date of Run

Set No.

F6 Rate (CFM @ 130°F)
Feed Composition
SW Rate (GPM)
SF Rate (GPM)
SL Rate (GPM)
SB Rate (GPM)
SW, SF Temp. (°F)
SL Temp. (°F)
SB Temp. (°F)
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
H. Extractor Outlet Gas Temp. (°F)
Reheater Inlet Gas Temp. (°F)
Overflow Pot Height (inches)
Inlet S02, ppm - Manual
Inlet S02, ppm - Analyzer
Outlet 563, ppm - Manual
Outlet S02» ppm - Analyzer
% S02 Removal
% Stoichiometry
Sulfur removed from Flue Gas
  ASg, gmole/min.
Sulfur absorbed by Na2C03
  ASL, gmole/min.
   3R
10/14/71
      4R
   10/28/71
11,200
Dilute
170
0
160
15.0
52
105
102
112
91
318
108
9
2,215
2,095
880
860
59.0
35.6
14.18
14.73
11,200
Dilute
170
0
160
15.0
52
105
102
112
91
318
108
9
2,215
2,095
880
860
59.0
33.4
14.18
14.45
10,800
Dilute
170
0
152.5
15.5
114
128
126
118
121
306
130
9
2,080
2,030
875
800
60.7
36.9
12.10
12.21
10,800
Dilute
170
0
150
15.5
117
129
126
118
121
309
130
9
2,080
2,030
875
790
61.2
36.9
12.21
12.10
X 100
                                           -3.9
         -1.9
-0.9
+0.9
02 in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas, %
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  inlet
  Outlet
                           3.8
                           3.6
                           5.1
                          13.1
                          12.7
                                        B-2
-------
Experiment No.
Date of Run

Set No.

FG Rate (CFM 0 130°F)
Feed Composition
SW Rate  GPM
SF Rate  GPM
SL Rate  GPM
SB Rate (GPM)
SW, SF Temp. (°F)
SL Temp. (°F)
SB Temp. (°F)
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
H. Extractor Outlet Gas Temp. ('
Reheater Inlet Gas Temp. (°F)
Overflow Pot Height (inches)
Inlet S02> ppm - Manual
Inlet S02, ppm - Analyzer
Outlet S02, ppm - Manual
Outlet S02, ppm - Analyzer
% S02 Removal
% Stoichiometry
Sulfur removed from Flue Gas
  ASg, gmole/min.
Sulfur absorbed by Na-CO-
  AS|_, gmole/min.
F)
    - AS
                 5R
               11/2/71
                                                               6R
                                                             11/2/71
12,980
Dilute
106
55
150
14
102
120
125
117
120
298
122
9
2,275
*
1,020
*
55.2
26.0
14.72
14.35
12,980
Dilute
107
55
145
14
102
120
125
117
120
299
122
9
2,290
*
1,048
*
54.3
26.0
-
_
9,180
Dilute
no
55
135
29
115
125
125
122
121
303
127
9
-
*
-
*
-
-
-
_
9,180
Dilute
110
55
135
24
115
125
125
122
121
304
127
9
2,110
2,050
450
480
76.5
52.3
14.06
13.84
X 100
                                            2.5
                                               -1.6
02 in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas, %
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  Inlet
  Outlet
                 3.6
                 143
                 159
                                                               3.8
                                                               3.1
                                                               4.5
                                         6.4
                                         6.8
                                                                162
                                                                170
                                       B-3
-------
 Experiment  No.
 Date  of  Run

 Set No.

 FG Rate  (CFM  @ 130°F)
 Feed  Composition
 SW Rate  (GPM)
 SF Rate  (GPM)
 SL Rate  (GPM)
 SB Rate  (GPM)
 SW, SF Temp.  (°F)
 SL Temp.  (°F)
 SB Temp.  (°F)
 Inlet Gas Dew Point  (°F)
 Outlet Gas Dew Point (°F)
 H. Extractor Outlet Gas Temp.
 Reheater  Inlet Gas Temp. (°F)
 Overflow  Pot Height  (inches)
 Inlet S02, ppm - Manual
 Inlet S02, ppm - Analyzer
 Outlet S02, ppm - Manual
 Outlet S02, ppm - Analyzer
 % S02 Removal
 % Stoichiometry
 Sulfur removed from Flue Gas
  ASg, gmole/min.
 Sulfur absorbed by Na2CO,
  AS,  , gmole/min.
AS/. - AS,
   AS
          X 100
  7R
11/3/71
  8R
11/3/71
11,240
Dilute
152
69
185
34.5
112
120
122
116
123
291
122
9
1,815
2,000
310
450
77.5
51.3
16.28
16.58
11,240
Dilute
152
69
185
34.5
112
121
123
116
123
298
122
9
1,770
2,000
670
460
77.0
52.4
16.16
16.61
11,200
Dilute
73
36
93
15
109
121
124
116
123
312
125
9
*
-
*
_
_
-
-
_
11,190
Dilute
73
36
90
15.5
110
125
125
116
123
300
125
9
1,782

829
_
53.5
34.9
9.39
9.65
                                           -1.8
       -2.8
       -2.8
Op in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas, %
  Scrubber Inlet
  Scrubber Outlet

NOX, Ppm
  Inlet
  Outlet
 3.9
 6.3
 7.3
10.4
10.3
 178
 194
 4.1
 5.2
 7.0
11.2
10.0
                                      B-4
-------
 Experiment No.
 Date of  Run

 Set No.

 FG Rate  (CFM (P 130°F)
 Feed Composition
 SW Rate  (GPM)
 SF Rate  (GPM)
 SL Rate  (GPM)
 SB Rate  (GPM)
 SW, SF Temp. (°F)
 SL Temp.  (°F)
 SB Temp.  (°F)
 Inlet Gas Dew Point (°F)
 Outlet Gas Dew Point (°F)
 H. Extractor Outlet Gas Temp. (°F)
 Reheater  Inlet Gas Temp. (°F)
 Overflow  Pot Height (inches)
 Inlet S02, ppm - Manual
 Inlet S02, ppm - Analyzer
 Outlet S02, ppm - Manual
 Outlet S02. ppm -. Analyzer
 % SC>2 Removal
 % Stoichiometry
 Sulfur removed from Flue Gas
  A$G> gmole/min.
 Sulfur absorbed by Na2C03
  AS|_, gmole/min.
    - AS
   9R
10/29/71
    10R
  11/9/71
11,000
Dilute
116
54
155
14.5
110
121
120
115
119
292
124
9
-
2,050
-
700
65.9
35.7
13.76
14.38
10,910
Dilute
116
54
155
14.5
110
121
120
115
119
295
124
9
-
2,010
-
732
63.7
36.5
12.96
14.27
10,680
Dilute
112
53
154
9.9
110
120
120
114
120
302
120
15
2,040
1,980
620
540
72.6
41.2
14.22
14.08
10,690
Dilute
112
53
153
10.7
111
120
121
114
120
304
121
15
2,070
1,960
615
520
73.5
41.4
14.32
14.36
   55
X 100
                                           -4.5
        -10.1
1.3
-0.3
0? in the Flue Gas, /
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas,
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  Inlet
  Outlet
   4.1
   3.9
   5.0
  13.5
  12.1
     3.9
     3.7
     5.0
    12.1
    11.6
                           159
                           153
                                       B-5
-------
 Experiment No.
 Date of Run

 Set No.

 F6 Rate (CFM @ 130°F)
 Feed Composition
 SW Rate (GPM)
 SF Rate (GPM)
 SL Rate (GPM)
 SB Rate (GPM)
 SW, SF Temp. (°F)
 SL Temp. (°F)
 SB Temp. (°F)
 Inlet Gas Dew Point (°F)
 Outlet Gas Dew Point (°F)
 H. Extractor Outlet Gas Temp. (°F)
 Reheater Inlet Gas Temp. (°F)
 Overflow Pot Height (inches)
 Inlet S02> ppm - Manual
 Inlet S02, ppm - Analyzer
 Outlet S02, ppm - Manual
 Outlet S02, ppm - Analyzer
 % S02 Removal
 % Stoichiometry
 Sulfur removed from Flue Gas
  ASg, gmole/min.
 Sulfur absorbed by Na^CO,
  ASL, gmole/min.
    - AS
   AS,
X 100
       11R
     10/14/71
   1
11,500      11,400
   CONCENTRATED
                                           -0.7
              -7.7
       12R
     11/9/71
   1
11,210      11,200
   CONCENTRATED
165
0
155
14
52
105
100
113
90
288
108
9
2,084
1,980
118
120
94.0
146
22.25
22.40
169
0
160
13
52
105
105
113
90
289
108
9
2,084
1,980
118
120
94.0
155
22.06
24.75
110
53
150
17
110
121
122
114
118
295
122
9
2,090
2,020
113
80
94.4
184
20.61
20.10
110
53
150
17
110
121
123
114
118
296
122
9
2,080
1,980
113
100
94.3
192
20.15
19.35
   2.5
4.0
Oo in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas, %
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  Inlet
  Outlet
                                3.9
                                4.1
                                5.3/
                               11.0
                               10.6
                                        B-6
-------
Experiment No.
Date of Run

Set No.

F6 Rate (CFM @ 130°F)
Feed Composition
SW Rate (GPM
SF Rate (GPM
SL Rate (GPM
SB Rate (GPM)
SW, SF Temp. (°F)
SL Temp. (°F)
SB Temp. (°F)
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
H. Extractor Outlet Gas Temp.
Reheater Inlet Gas Temp. (°F)
Overflow Pot Height (inches)
Inlet S0£, ppm - Manual
Inlet S02, ppm - Analyzer
Outlet S02> ppm - Manual
Outlet S02» ppm - Analyzer
% S02 Removal
% Stoichiometry
Sulfur removed from Flue Gas
  ASr, gmole/min.
Sulfur absorbed by Na-OL
  ASL, gmole/min.

ASr - AS,
       13R
     11/4/71
       14R
     11/5/71
   1
11,330      11,400
   INTERMEDIATE
110
54
153
54
110
120
120
116
123
298
122
9
2,050
2,000
380
420
81.5
46.5
17.78
18.06
110
54
153
54
no
119
120
116
123
298
122
9
2,040
1,980
280
320
86.3
46.5
19.11
18.23
   1
11,300      11,360
   INTERMEDIATE
                                           -7.6
              -3.0
                            75
                            36
                            95
                            15
                           115
                           122
                           122
                           113
                           122
                           300
                           129
                             9
                         2,100
                         2,070

                           780
                          62.4
                          31.5

                         13.20

                         12.93
   2.0
                75
                36
                95
                14
               115
               122
               122
               113
               122
               299
               129
                 9
             2,070
             2,040
               775
               780
              61.7
              32.8

             12.91

             12.80
0.9
02 in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

CO? in the Flue Gas, I
  Scrubber Inlet
  Scrubber Outlet

NOX, ppm
  Inlet
  Outlet
        4.2
        3.7
        4.3
       14.2
       12.8
        152
        148
         4.2
         4.4
         5.3
        12.8
        12.8
                                        B-7
-------
          rop

          rop
Experiment No.
Date of Run

Set No.

FG Rate (CFM g 130°F)
Feed Composition
SW Rate (GPM)
SF Rate (GPM)
SL Rate (GPM)
SB Rate (GPM)
SW, SF Temp. (°F)
SL Temp. (<
SB Temp. ('
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
H. Extractor Outlet Gas Temp. (°F)
Reheater Inlet Gas Temp. (°F)
Overflow Pot Height (inches)
Inlet S02» ppm - Manual
Inlet S02, ppm - Analyzer
Outlet S02, ppm - Manual
Outlet S02, ppm - Analyzer
% S02 Removal
% Stoichiometry
Sulfur removed from Flue Gas
  ASg, gmole/min.
Sulfur absorbed by Na2C03
  AS. , gmole/min.
    - AS,
                                                15R
                                              11/5/71

                                            1           2

                                         12,980      12,980
                                            INTERMEDIATE
110
55
145
16.5
110
120
120
115
118
302
120
9
2,100
2,040
528
500
75.6
43.7
18.97
18.85
110
55
145
16.5
110
120
120
115
118
299
121
9
2,090
2,040
540
500
75.6
43.5
18.97
18.79
                16R
              11/5/71
            1
         11,500      11,500
            INTERMEDIATE
110
55.5
145
20
no
115
116
111
118
223
116
9
2,042
2,010
-
350
82.5
48.6
110
55.5
145
20
no
114
115
111
118
222
115
9
2,052
2,020
389
350
83.2
48.6
   AS,
          X 100
                                            0.6
1.0
                                                                  18,03

                                                                  17.86
1.1
                      18.14

                      17.90
1.3
02 in the Flue Gas, %
  Boiler Outlet
  Scrubber Inlet
  Scrubber Outlet

C02 in the Flue Gas, 1
  Scrubber Inlet
  Scrubber Outlet

NOX» ppm
  Inlet
  Outlet
                                                  3.8
                                                  4.1
                                                  5.1
                                                 12.8
                                                 12.8
                  4.0
                  4.4
                  5.5
                 12.8
                 12.8
                                       B-8
-------
            APPENDIX C
SOLUBLE TESTS - ANALYTICAL RESULTS
-------
10/29/71
Experiment No. 1R

Set 1
Time
Total Sulfur as SO/
1 )
        +  HSO
 2)   so: + HSO:
 Na+   J       J
 pH,  initial
 pH,  final

 Set  2
 Time
 Total Sulfur  as SO^

 1)   SOg + HSOj

 2)   50= H
 Na+    J
 pH,  initial
 pH,  final
10/27/71
Experiment No. 2R

Set 1
Time"
Total Sulfur as S

1 )  SOg + HSOg

2)  so" + HSO:
pH, initial
pH, final

Set 2
TTme"
Total Sulfur as
1 )
     SO  + HSO"
2)   so! + HSO:
Na+    3      d
pH, initial
pH, final

*1 ) C-E Method
 2) Radian Method
                                    APPENDIX  C

                       SOLUBLE TESTS  - ANALYTICAL RESULTS
                                               M Mole/Liter
                       Downcomer   Downcomer  Downcomer    Pump     Scrubber   Scrubber
                           1           2          3       Discharge     Feed      Bottom
                           SL          SL         SL        SL      (SW, SF)      SB
1052
15.5
16.7
5.2
4.5
1115
15.1
16.0
5.28
5.19
1400
21.8
17.7
15.4
28.6
5.95
5.9
1420
21.8
17.0
15.5
27.8
6.0
5.95
1055
14.4
16.3
5.5
5.4
1117
14.0
16.2
5.42
5.35
1409
22.7
13.3
13.2
28.6
6.30
6.20
1422
22.3
13.5
12.6
27.8
6.3
6.25
1058
14.8
16.4
5.5
5.35
1120
14.8
15.2
5.1
5.02
1411
22.9
16.9
15.7
27.8
6.05
5.95
1424
22.9
16.3
13.1
27.8
6.05
6.00
1100
20.3
15.0
16.2
21.1
5.38
5.1
1125
19.7
14.8
16.7
21.1
5.1
5.02
1416
20.6
15.2
15.3
27.8
6.05
5.95
1429
20.9
14.4
27.6
6.05
6.00
1110
0.3
0.12
21.0
10.3
1117
0.3
-
21.0
10.30
1418
0.3
0.12
27.6
10.45
1430
0.3
0.12
27.3
10.45
1106
18.0
13.0
15.8
21.0
5.65
1130
18.4
13.4
15.8
21.1
5.92
6.0
1414
22.3
15.8
14.6
27.8
6.05
5.95
1428
21.8
15.5
27.6
5.95
5.90
                                       C-l
-------
10/14/71
Experiment No. 3R

Set 1

Time
Total Sulfur as S

so! + HSO!
                         M Mole/Liter
Oowncomer  Downcomer  Downcomer    Pump     Scrubber  Scrubber
    1          2          3      Discharge    Feed     Bottom
    SL         SL         SL        SL      (SW, SF)     SB
pH, Initial
pH, final

Set 2

Time
Total Sulfur as SO^

SO" + HSO"
Na*      J
pH, initial
pH, final
10/28/71
Experiment   No. 4R

Set 1
   1200
   22.91

   22.70
   26.96
   4.65
   4.40
   1200
   22.59

   21.80
   25.21
   4.0
   3.68
1200
0.34
26.96
10.93
1200
0.34
25.21
10.9
1200
18.75

18.70
26.08
6.00
5.75
1200
19.27

18.90
25.65
5.9
5.62
Time
Total Sulfur as SO^
so! + HSO:
Na* *
pH, initial
pH, final
Set 2
Time
Total Sulfur as SO^
so! + HSO!
Na* J
pH, initial
pH, final
1215
20.6
17.6
18.6
24.5
3.75

1221
20.8
17.5
18.0
25.2
3.93
1216
19.7
15.5
16.9
24.7
5.20

1222
20.3
15.4
16.6
25.0
5.35
1218
20.5
16.0
17.7
24.5
5.29

1223
19.7
16.2
17.8
25.0
5.36
1219
19.7
16.8
17.3
24.5
4.38

1224
20.3
16.5
18.2
25.0
4.50
-
0.3
0.12
-
24.3
-

1227
0.3
0.12
-
24.1
-
1220
17.1
13.70
15.1
24.5
5.90

1225
16.6
13.7
14.8
25.0
6.02
                                      C-2
-------
 11/2/71
 Experiment  No.  5R

 Set  1

 Time
 Total Sulfur  as SOj

 so:!  + HSO:
 Na*       J
 pH,  initial
 pH,  final

 Set  2
Time
Total Sulfur as SO

so! + HSO:
'4

pH, initial
pH, final

11/2/71
Experiment No. 6R
Set 1

Time
Total Sulfur as SO,

so:; + HSO:
Na*      d
pH, initial
pH, final

Set 2

Time
Total Sulfur as SO^

so" + HSO:
Na*      3
pH, initial
pH, final
Downcomer
1
SL
1548
2Q.72
5.48
5.32
1601
21.01
5.30
5.35
1320
21.02
5.95
5.92
1348
20.41
5.95
5.88
Downcomer
3
SL
1551
19.28
5.55
5.54
1603
19.37
5.55
5.52
1322
20.40
6.05
1351
20.51
6.08
5.99
M Mole/Liter
Pump
Discharge
SL
1553
23.75
25.00
5.57
5.48
1604
23.95
24.34
5.58
5.43
1324
24.01
26.95
6.12
6.08
1356
24.06
26.72
6.12
6.02
Scrubber
Feed
(SW, SF)
0.28
0
24.56
10.37
0.28
0
24.34
10.38
1332
0.28
0
26.95
10.35
1353
0.28
0
26.86
10.35
Scrubber
Bottom
SB
1554
19.79
21.38
24.56
5.82
5.85
19.79
21.36
24.34
5.85
5.85
1330
18.75
14.92
26.95
6.44
6.32
1359
18.95
16.67
26.60
6.43
6.38
                                        C-3
-------
11/3/71
Experiment  No. 7R

Set  1

Time
Total  Sulfur  as  SOj

so"  +  HSO:
Na*      J
pH,  initial
pH,  final

Set  2

Time
Total  Sulfur  as  S0
pH, initial
pH, final
11/3/71
Experiment No. 8R
Set 1

Time
Total Sulfur as SO

     H HSO:
                  '4
pH, initial
pH, final

Set 2

Time
Total Sulfur as

SOj + HSOj

pH, initial
pH, final
Downcomer
1
SL
1200
20.13
6.15
6.05
1210
18.43
6.20
6.06
1527
20.75
6.00
5.87
1645
21.63
5.64
5.56
Downcomer
3
SL
1201
19.55
6.31
6.25
1212
16.91
6.35
6.326
1529
25.05
5.87
5.78
1647
22.04
5.65
5.55
M Mole/Liter
Pump
Discharge
SL
1204
20.20
27.17
6.40
6.21
1220
20.31
26.73
6.22
6.20
1532
27.60
33.04
5.92
5.84
1650
25.52
29*13
5.62
5.62
Scrubber
Feed
(SW, SF)
1207
0.28
0
27.17
10.70
1227
0.28
0
26.52
10.68
1536
0.27
0
32.39
10.46
1654
0.27
0
29.13
10.38
Scrubber
Bottom
SB
1205
20.31
18.55
26.95
6.20
6.15
1225
20.20
18.60
26.52
6.18
6.06
1533
20.05
17.62
31.52
6.48
6.52
1652
19.27
18.49
29.34
6.38
6.37
                                       C-4
-------
10/29/71
Experiment No. 9R
                         M Mole/Liter
.Downcomer   Downcomer  Downcomer    Pump     Scrubber  Scrubber
     1           2          3      Discharge    Feed      Bottom
     SL          SL         SL        SL      (SW,  SF)     SB
Set 1
Time
Total Sulfur as SO^
1 }* SO^ + HSOg
2) so* + HSO:
Na+ 3 J
pH, initial
pH, final
Set 2"
Time
Total Sulfur as S0]j
I) SOg + HSO"
2) so! + HSO:
Na+ J J
pH, initial
pH, final
1602
18.4
18.4
5.65
5.69

1621
18.0
19.4
5.45
5.52
1607
16.0
16.9
5.95
5.97

1625
15.6
16.3
5.87
5.92
1610
17.0
18.2
5.90
5.85

1627
16.4
16.9
5.84
5.79
1613
23.1
16.8
17.7
24.3
5.82
5.75

1628
22.8
16.7
17.8
23.9
5.71
5.72
1610
0.3
0.12
24.3

1625
0.3
0.12
24.1
10.38
1615
20.1
15.4
18.2
24.3
6.02
6.00

1633
20.1
15.1
18.7
23.9
5.97
5.98
*1) C-E Method
 2) Radian Method
                                       C-5
-------
11/9/71
Experiment No. 10R

Set 1

Time
Total Sulfur as SOj

S0= * HSO;

pH, initial
pH, final

Set 2

Time
Total Sulfur as SOj

so" + HSO:
Na*      J
pH, initial
pH, final

10/14/71
Experiment No. 11R

Set 1

Time
Total Sulfur as SO^

so! + HSO;
Na*      J
pH, initial
pH, final

Set 2

Time
Total Sulfur as SO^

SO! + HSOl
Na*      J
pH, initial
pH, final
Downcomer
1
SL
1305
20.78
5.62
5.62
1316
20.53
5.75
5.65
1430
34.37
34.25
109.56
7.4
7.2
1430
38.02
33.25
114.78
7.5
7.28
M Mole/Liter
Downcomer Pump
3 Discharge
SL SL
1308 1312
22.91
19.41
26.52
5.62 5.80
5.55 5.73
1318 1321
23.43
18.73
26.73
5.85 5.85
5.62 5.77




Scrubber
Feed
(SW, SF)
1314
0.27
0
26.73
10.38
10.35
1322
0.27
0
26.73
10.37
10.32
1430
0.44
0.13
110.86
11.5
1430
0.51
0.38
115.65
11.44
Scrubber
Bottom
SB
1311
24.06
20.44
26.73
6.04
5.88
1320
23.95
19.88
26.73
6.08
5.95
1430
41.66
34.75
110.43
7.8
7.55
1430
42.18
34.85
114.78
7.5
7.25
                                       C-6
-------
11/9/71
Experiment No. 12R-

Set 1

Time
Total Sulfur as S04

SO* + HSO:
Na*      J
pH, initial
pH, final

Set 2

Time
Total Sulfur as S0]j

so! + HSO:
Na*   "   *
pH, in.itial
pH, final
11/4/71
Experiment No. 13R

Set 1

Time
Total Sulfur as S04
so!
      HSO:
Na*       J
pH, initial
pH, final

Set 2

Time
Total Sulfur  as

so!; + HSO:
Na*       J
pH, initial
pH,- final
Downcomer
1
'SL
1510
30.10
7.85
7.78
1520
29.15
8.00
7.97
1218
24.88
6.05
5.95
1228
25.65
6.18
6.08
Downcomer
3
SL
1512
27.23
8.00
7.95
1522
26.97
8.15
8.12
1220
23.51
6.18
6.13
1230
24.30
6.35
6.22
M Mole/Ltter
Pump
Discharge
SL
1513
31.66
130.43
8.02
7.95
1523
30.46
133.91
8.12
8.05
1223
28.64
33.91
6.22
6.12
1237
28.90
36.30
6.35
6.10
Scrubber
Peed
(SW, SF)
1517
0.39
0
130.43
10.80
10.75
1526
0.39
0
133.47
10.80
10.70
1225
0.27
0
34.13
10.48
1234
0.27
0
36.73
10.52
Scrubber
Bottom
SB
1515
37.29
34.15
130.43
7.75
7.62
1525
35.62
32.86
133.91
7.95
7.82
1224
26.56
22.05
34.34
6.42
6.38
1233
26.82
23.10
36.30
6.45
6.42
                                      C-7
-------
Experiment No.

Set 1

Time
Total Sulfur as SO],

SO! + HSOZ
Na*      J
pH, initial
pH, final

Set 2

Time
Total Sulfur as SO*

SO- + HSOg

pH, initial
pH, final
11/5/71
Experiment No. 15R

Set 1

Time
Total Sulfur as SOI

SO" + HSOI
Na?      3
pH, initial
pH, final

Set 2

Time
Total Sulfur as SOjj

SOJ

pH, initial
pH, final
Downcomer
1
SL
1511
26.79
5.87
5.75
1521
25.73
5.78
5.78
1324
26.38
5.97
5.42
1335
26.58
6.08
5.96
Downcomer
3
SL
1513
26.50
5.75
5.63
1523
25.45
5.75
5.72
1326
25.91
6.18
6.04
1337
25.10
6.05
6.08
M Mole/ Liter
Pump
Discharge
SL
1514
32.70
33.47
5.87
5.77
1524
32.50
••
33.04
5.81
5.72
1327
31.25
36.08
6.18
6.08
1338
31.14
36.08
6.25
6.08
Scrubber
Feed
(SW, SF)
1518
0.27
0
33.69
10.37
1527
0.27
0
32.60
10.45
10.37
1330
0.27
0
36.08
10.38
1341
0.27
0
35.86
10.38
Scrubber
Bottom
SB
1516
22.91
21.23
33.47
6.55
6.48
1526
23.17
20.18
32.60
6.53
6.47
1329
30.00
25.72
36.30
6.35
6.32
1340
29.89
25.40
35.86
6.25
6.22
                                      C-8
-------
11/5/71
Experiment No. 16R

Set 1

Time
Total Sulfur as SOj

gj * ™>'3

pH, initial
pH, final

Set 2

Time
Total Sulfur as SOJ

so! + HSO:
pH, initial
pH, final
Downcomer
    1
    SL
  1137
  25.30

  6.05
  6.03
  1148
  27.14

  6.05
  6.02
Downcomer
    3
    SL
  1139
  24.57

  6.35
  6.22
  1149
  22.99

  6.32
  6.18
M Mole/Ltter
  Pump       Scrubber
Discharge      Feed
   SL        (SW, SF)
  1141
  29.58
  35.24
  6.42
  6.28
  1151
  29.39
  35.21
  6.35
  6.25
1144
0.27

0
35.43
10.38
1153
0.27

0
35.52
10.38
           Scrubber
            Bottom
              SB
1143
26.30

18.81
34.95
6.45
6.37
1154
26.22

22.49
35.21
6.55
6.44
                                       C-9
-------
      APPENDIX D






ANALYTICAL PROCEDURES



   FOR ARCS SAMPLES
-------
                                 APPENDIX D
                   ANALYTICAL PROCEDURES FOR ARCS SAMPLES

                The procedures for quantitatively analyzing solutions
containing sulfite, sulfate, calcium, magnesium and sodium used in the
APCS testing follow.  These methods are time-tested and generally follow
currently accepted analytical practices.  It should be stressed that the
instability of scrubber samples produces obvious variations and that sampling
techniques are extremely important.  The methods referred to are for control
testing and in the hands of a good analyst produce results within 5% of the
actual  concentration.
                                  D-l
-------
                                ARCS SULFITE*
                              Analysis (Liquid)

                1.  Transfer 20 ml of standard potassium iodide-iodate
(0.0125 N = 0.5 mg S03/ml) to a 150 ml beaker.
                Note:  If sample contains solids it must be pressure
filtered at the point of sampling prior to Step 2.   The sample bottle (250
ml or less) should be filled to the top and capped  immediately.  A nitrogen
purge can be maintained on samples during titration where sulfite values  are
below 200 ppm and precision is necessary.  Samples  must be analyzed within
10 minutes from time of sampling.
                2.  Pipet a sample volume (freshly  taken-middle of sample
bottle) containing less than 10 mg SOg beneath the  surface of the KI-KIOj
(if a 5 ml sample volume is used, procedure is good to 2000 ppm).
                3.  To the 150 ml beaker containing the sample and KI-KI03
add 1 ml of 1 + 1 HCL, and 1 ml of starch solution.  Stir gently and
immediately back titrate to a colorless end point with 0.100 N sodium
thiosulfate.
                Calculations:
                (ml of KI-KI03)  (Normality) - (ml  of Na2S203)  (Normality)
                                             = meq  SO,/sample
                "* S03 x Samp1e°Vol  x 40   = PPm  S03
                                               S03x 0.800 = S02

*The EPA Arsenite method was used for comparison.  This method fixes the
sulfite at the point of sampling.  It may be slightly more precise but
requires considerably more time in preparation.
                                   D-2
-------
                                ARCS SULFATE
                           Analyses (Soluble S0|)

                 INTRODUCTION
                 This procedure is for total sulfur as S04<  All sulfite is
oxidized to sulfate in this method.
                 1.  Pi pet a filtered sample volume (see note) into a 1
liter  volumetric flask containing 2 ml of 1 + 1.HC1,  1 ml of 30% H202 and
approximately 300 ml of D. I. water.  Stir on magnetic stirrer and dilute
to  1 liter mark.
                 NOTE:  For best sulfate results when using turbidmetric
method, the diluted volume should contain between 20 and 80 ppm.  Run at
least  two standards near level expected and check curve routinely.
                 2.  ASTM 516-68 modified sulfate method:
                A.  Pipet 25 ml of sample into four separate beakers.
                 B.  Place beakers on magnetic stirrers and insert plastic
magnets.  Adjust to reasonable mixing speed.
                 C.  Add simultaneously to all beakers 10 ml glycerol and
5 ml of sodium chloride solution.
                D.  Add 0.3g of barium chloride dihydrate crystals to
only three samples.  (Triplicate analyses)  Leave one sample as, reagent
blank.
                E.  Begin timing.  Stir all solutions for 1 minute and
then remove beakers.
                F.  Fill  a 2 cm cell with reagent (blank) not containing
barium chloride and prepare spectrophotometer as shown below.
                                   D-3
-------
                                  Model DU
                Wavelength - 400 nm     Sensitivity - 2
                Slit       - 0.1        Phototube   - Blue

                G.  Let solutions containing barium chloride stand for
4 minutes +_ 30 seconds and return to stirrer for 15 seconds.
                H.  Set spectrophotometer at zero absorbance on the
reagent blank not containing the barium chloride.  Then read.
                CALCULATIONS
                I.  Record optical density of triplicate samples.  If 0.  D.
varies on any one sample more than 0.007 units, repeat analyses.
                J.  Run at least two standards in area of expected concen-
tration to determine slope of curve.  Whenever new reagents are made or if
the room temperature varies more than 2°F, check curve with standards before
running samples.
                REAGENTS: Barium Chloride - Crystals of barium chloride
(BaCl2  2H20 screened to 20 to 30-mesh).
                Glvcerol Solution - (1 +1) - Mix 1 volume of glycerol
with 1 volume of water.
                Sodium Chloride Solution (240 g per liter) - Dissolve 240g
of sodium chloride (NaCl) in water containing 20 ml of concentrated
hydrochloric acid (HC1, sp gr 1.19), and dilute to 1-liter with water.
Filter the solution if turbid.
                Sulfate. Standard Solution (ml = 0.100 mg SO --).  Dissolve
                                                            4
0.1479 g of anhydrous sodium sulfate (Na^SO.) in water, and dilute with
water to 1 liter in a volumetric flask.  Standardize by the procedure
prescribed in Section 2.
                              D-4
-------
                            ARCS SODIUM ANALYSIS

                 1.  Take the diluted sample used In the sulfate determina-
 tion  and  determine the sodium concentration by flame emission.
                 2.  Prepare the necessary calibration curves using the
 following settings:
           MODEL  B                0 - 10 ppm      10 - 25 ppm      20 - 50 ppm
 A  = 589 nm        Photomultiplier   D                D                C
 H2 =  3.5  psi       Sensitivity       2                1                1
 02 =  10.5 psi
                 3.  In the concentration range expected adjust the slit to
 approximately 50% transmittance with the maximum curve standard.  Peak out
 wavelength for optimum sensitivity and then readjust slit opening to 100% t.
                 4.  Continually flush distilled water through aspirator
 when  not  running sample.
                 5.  When reading sample or standard allow 30 seconds for
 meter reading to stabilize.  Record transmittance of sample and read from
 graph.
                6.  Routinely check the transmittance of at least two
 standards  during sample analyses.
                REFERENCE:   ASTM D 1428
                REAGENTS:   Sodium Chloride (0.2542 g per liter).  Dry sodium
chloride  (NaCl) to constant weight at 105 C.   Dissolve 0.2542 g of NaCl in
water and dilute to 1  liter with water.  Dilute 10 ml  of this solution to 1
liter and store in polyethylene or equally alkali-metal-free containers.
The latter solution contains 1000 ppb sodium.   This solution can be
further diluted to provide  a known standard of any sodium concentration
less  than 1000 ppb Na+.
                                   D-5
-------
                                APCS  CALCIUM
                              Analysis  (Liquid)

                1.   Take a portion of the  diluted  sample  prepared under
the sulfate determination and read on atomic absorption.   Dilute sample
so that % absorption falls between 15 and  75% (absorbance 0.070 to  0.600).
                2.   With A/A warmed up and set properly according to
P. E. book run at least three standards of a similar matrix  salt to
prepare a calibration curve.  (5,  10  and 15 ppm with 3 slot  burner  should
be adequate).   Use  422.7 nm wave length.
                Calculations:
                Read off curve or set up ratio of  absorbance to nearest
standard.  Then multiply by dilution  factor to obtain ppm of Ca.
                Ca  X 1.40 = CaO
                                   D-6
-------
                          X-RAY  METHOD  FOR CALCIUM
                         SULFATE SOLUTIONS ANALYSIS

                The x-ray fluorescence  method is  advantageous when  rapidity
of analysis is an important factor.   Analytical results  in  most cases  are
comparable and in some cases superior to those attainable by "wet chemical"
methods.
                Presently the technique has  been  applied to the analysis
of sulfur (40 ppm and greater) and calcium (2 ppm and greater)  in solutions.
                1.  Procedure
                a)  Dilute 10 ml of unknown  1:1 with 10% HN03 (by volume)
spiked with H202 prepared from cone.  HN03 (sp. gr.  = 1.42).
                b)  Transfer 5 ml of sample  to specimen  cup and obtain
count at S K a  (1) and Ca Ka (1) peaks.  Correct count  for background.
                                   D-7
-------
                               APCS MAGNESIUM
                              Analysis (Liquid)

                1.   Take a portion of the diluted  sample  prepared  under
the sulfate detennination and read on atomic absorption.   Dilute sample
so that % absorption falls between 15 and 75% (absorbance 0.070 to 0.600).
                2.   With A/A wanned up and set properly according  to
P. E. book run at least three standards of a similar  matrix  salt to prepare
a calibration curve.  (0.5, 1.0,  2.0 ppm with 3  slot  burner  should be
adequate).  Use 285.2 nm wave length.
                Calculations:
                Read off curve or set up ratio of  absorbance to nearest
standard.  Then multiply by dilution factor to obtain ppm of Mg.
                Mg  X 1.646 = MgO
                                   D-8
-------
                     PROCEDURE FOR THE DETERMINATION OF
                       TOTAL S02 IN AQUEOUS SOLUTIONS
                Introduction
                This method Is Intended to give an accurate determination
of total S02 In aqueous solutions taken from limestone injection  -  wet
scrubbing processes and containing interfering substances  such  as nitrite
ion.  The sample is added to an excess of buffered iodine  solution.  The
iodine remaining after the stoichiometric S02 oxidation is titrated with
standard sodium arsenite solution using an amperometric dead-stop method
for endpoint detection.

                The iodine solution is generated as needed for  each
determination using standard iodate solution and excess iodide  ion  at low
pH (^1-2).  This method is more convenient and reliable than using  standard
iodine solutions.  The iodine solution is buffered to pH 6.0-6.2  to inhibit
sulfite-ni trite and nitrite-iodine (iodide) reactions.  This also inhibits
the air oxidation of iodide.  Arsenite solutions give more accurate
results than thiosulfate solutions in the presence of nitrite and are
also more stable under ordinary conditions.  The deadstop  end-point
detection method gives more reliable and accurate results  than  starch
indicators, etc.  In practice, the deadstop method is also convenient and
simple.
                In this method the order of addition of reagents  and other
procedures are critical and the procedure given should be  followed  closely.
                Apparatus
                1)  50 ml burette (preferably an automatic burette)
                2)  magnetic stirrer

                                     D-9
-------
                3)  pipets (including 2 ml  and 20 ml  sizes)  and bulb
pi pet fillers
                4)  400 ml beakers (preferably graduated)
                5)  deadstop apparatus:
                a)  two platinum electrodes
                b)  1.5 volt dry cell battery (a #735 "hobby battery
works fine)
                c)  electrometer or 0-15 or 20 yA microammeter
                d)  voltage divider: 1.5 v  to 0.1 v
                Connect one electrode to one terminal of the voltage
divider output (0.1 volt).  Place the meter in series with the second
electrode and the other voltage divider terminal.
                Reagents and Solutions
                Use distilled water and reagent grade chemicals for all
solutions.
                CAUTION:  Arsenic is toxic  and care should be taken when
preparing and handling these solutions.
                1)  Sodium arsenite stock solution (0.100 mole/liter) -
Weigh out accurately 9.893g arsenic trioxide (As203, primary standard,
99.99%) and dissolve in about 100 ml 2M NaOH (8g NaOH/100 ml) with stirring.
Adjust the pH to about 7 to 8 with first concentrated, then IN HC1.  Add
about Ig NaHC03, transfer the solution quantitatively to a 1 liter volume-
tric flask and dilute to the mark with distilled water.  This solution
will be used to make up the standard solution for iodine titration.
                                     D-10
-------
                2)   Sodium arsenite  standard  solution  (0.0100 mole/liter) -
Pipet 100.0 ml  of the 0.100 mole/1 sodium arsenite  solution prepared in 1)
into a 1 liter volumetric flask and  dilute  to the mark with distilled water.
This solution is most conveniently and  safely handled  in an automatic
burette assembly.
                3)   Potassium iodide (50 f/liter) - Dissolve 50g of iodate
free KI and 0.5g of NaHCOg in freshly boiled  and cooled distilled water
and dilute to one liter.   Alternatively, 45g  of iodate-free Nal may be
used in place of the KI.   The water  is  boiled or otherwise deaerated to
remove dissolved oxygen which might  oxidize iodide  to  iodine causing
errors in the determination.
                4)   Potassium iodate standard solution (0.0833) mole/liter)-
Dissolve 8.917g of potassium iodate  (KIOJ, dried at 120°C, and 0.5g of
                                       0
sodium bicarbonate (NaHC03) in distilled water and  dilute to 500 ml in a
volumetric flask.
                5)   IN HC1 - Dilute  86  ml of  concentrated reagent grade
hydrochloric acid (36%) to 1 liter with distilled water.
                6)   pH 6.0 buffer (1 mole/liter sodium acetate, 0.05 mole/
liter acetic acid)  - This solution should contain 82 g/liter anhydrous
sodium acetate (or 136 g/liter of the trihydrate) and  2.9 ml/liter glacial
acetic acid.  It is convenient to prepare several liters of this solution
at a time since about 175 ml is used for each determination.  The water
used to prepare this solution should be deaerated by boiling or bubbling
nitrogen through it.
                                  D-ll
-------
                Procedure
                The iodine-buffer solution should be prepared just prior
to addition of the sample.  The order of the following steps is important
and should be maintained.
                a)  Place 20 ml of KI solution (3) in a 400 ml beaker
containing a magnetic stirring bar.
                b)  Accurately pipet 2.00 ml of the KI03 solution (4) into
the beaker.
                c)  Add 2.0 ml IN HC1 and swirl the beaker for about 10-15
seconds to ensure complete mixing and reaction.
                d)  Immediately add about 175 ml  pH 6.0 buffer (6) being
careful not to lose any solution due to splashing.  Stir the solution with
the magnetic stirrer at low speed.
                e)  Place the platinum electrodes in the solution and
hook up the deadstop equipment (see apparatus).  The current should be
about 10-15 microamps.
                f)  Accurately pipet a volume of sample containing between
      -5           -4
5 x 10   and 5 x 10   mole total S02 into the iodine-buffer solution.  For
the in-house test about 10 ml of sample should probably be used (also see j),
                g)  Increase the stirrer speed and begin the titration with
the 0.01 mole/liter sodium arsenite solution (2)  using a 50 ml burette.
The color of the solution may be used as a rough  guide to the approach of
the end point.  The iodine-red color changes to yellow about 10 ml before
the end point.  When the solution becomes light yellow the titration should
be continued dropwise.  The solution usually becomes colorless a few drops
before the end point.   The current will decrease  about 0.2 to 1 microamp
immediately before the end point and then decrease about 8-9 microamp at
the end point.

                                     D-12
-------
                h)  When the large current drop described above occurs
stop the titration and record the ml of sodium arsenlte used.   Rinse the
electrodes with distilled water after removing them from the solution.
                i)  Run blanks each day using the above procedure without
the addition of a sample.  Two blanks should agree within 0.1  ml.  Record
the volume of titrant used in the blanks (it should be about 50 ml).
                j)  If the iodine color is completely discharged (the
solution becomes colorless) when the sample is added, prepare  a fresh
iodine-buffer solution and use a smaller sample volume (5 ml).  If the
volume of titrant taken for the blank and sample are within 5  ml of each
other, repeat the determination, using a correspondingly larger sample.
If very low S02 concentrations are encountered modify the reagent concen-
trations for the determination.
                Calculation and Accuracy
                The concentration of total S0« in the sample can be
calculated using the following equation.
                r - (B-S)M
                L "    V
                where:
                C = concentration of total S02 (mole/liter)
                B = volume in milliliters of arsenite solution needed to
titrate the blank
                S = volume in milliliters of arsenite solution needed to
titrate the sample
                M = molarity of the arsenite solution, mole/liter (normally
0.0100)
                V = volume of sample used, milliliters.
                Using a NO^SC^ mole ratio of 50:1 the SOg determination
has been made with a 1-3% error using this procedure.  Five determinations
of K2S03 without nitrite added gave a relative deviation of 0.255L
                                  D-13
-------
              APPENDIX E

            SOLUBLE SYSTEM
STAGE EFFICIENCY CALCULATION DIAGRAMS
-------
   22


   20


   18


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I    I
            ACTUAL OUTLET S02 - 902 PPM
             0.1
0.2/3.4       3.5      3.6       3.7      3.8
  MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10'4
                                               3.9
4.0
               SODIUM  CARBONATE SYSTEM - EXPERIMENT  1  R-SET  2
-------
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                 0.1
                              ACTUAL OUTLET S02 = 1055 PPM
                     0.2//4.2     4.3      4.4      4.5      4.6

                     MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10~4
4.7
4.8
                  SODIUM CARBONATE  SYSTEM  -  EXPERIMENT 5 R-SET 1
-------
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                                      ACTUAL OUTLET S02 = 857 PPM
            0.1
0.2/4.5      4.6       4.7      4.8      4.9
  MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10'4
5.0
5.1
                   SODIUM CARBONATE SYSTEM  -  EXPERIMENT  8  R-SET  2
-------
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    0
            0.1
            ACTUAL OUTLET S02 - 805 PPM
0.2 1/5.4      5.5      5.6      5.7      5.8
  MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10"4
5.9
6.0
                   SODIUM  CARBONATE SYSTEM - EXPERIMENT  14  R-SET  1
-------
            APPENDIX F

LIMESTONE FURNACE INJECTION SYSTEM
          OPERATING DATA
               AND
        ANALYTICAL RESULTS
-------
                                     TABLE F-l.   C-E  ARCS PROTOTYPE
                                                 FURNACE INJECTION TESTS
Experiment No.
Date of Run
Set No.
Time
Flue Gas (F6) Rate (CFM G> 130°F)
Fly Ash + Additive Feed Rate (Ib/hr.)
Spray Water SW (gpm)
Scrubber Liquid SL (gpm)
Scrubber Bottom SB (gpm)
Clarifier Liquid CL (gpm)
Liquid Slowdown LB (gpm)
Clarifier Feed CF (gpm)
Clarifier Bottom CB (gpm)
Filter Liquid FL (gpm)
Spray Water SW (°F)
Scrubber Liquid SL (°F)
Scrubber Bottom SB (°F)
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
Reheater Inlet Gas Temp. (°F)
Heat Extractor Outlet Gas Temp. (°F)
Inlet S02 (ppm)
Outlet SO? (ppm)*
Inlet 02 (%)
Outlet 02 (%)
Inlet C02 (%)
Outlet C02 (%)
S02 Removal Efficiency ($)
Stoichiometry (%)
Solid Concentration in Spray Water (%.)
Average Air Leakage (%)**
Dust Loading on the Outlet (gr./SCFM)
17R
12/28/71
1
1320-1405
1 1 ,000
270
110
89
25
165
55
165
4
4
100
123
121
127
122
128
304
1,456
764
5.6
6.1
9.3
7.8
43.0
71.0
-
6.7
0.033
2
1550-1650
1 1 ,000
270
110
87
28
165
55
165
4
4
100
121
119
126
121
124
305
1,456
764
5.6
6.1
9.3
7.8
43.0
71.0
-
6.7
0.033
1
RR
3/8/72
1
1800-1900
11,000
270
205
178
30
20
0
25
3
3
120
122
122
122
121
125 -
285
1,471
447
4.5
5.8
6.2
6.2
67.6
72.8
3.67
6.7

2
1900-2030
11,000
270
205
182
30
20
0
25
3
3
120
123
123
122
121
125
285
1,471
447
4.5
5.8
6.2
6.2
67.6
72.8
3.35
6.7

19R
4/21/72
1
1130-1200
10,000
370
201
175
20
0
35
35
3
2
106
115
116
112
106
112
293
1,883
925
10.7
12.0
7.0
6.0
43.7
88.8
1.14
15.0
0.002
2
1250
9,940
370
201
175
20
0
35
35
3
2
108
115
118
_
_
112
289
1,881
925
-
-
-
-
43.6
89.5
1.46
15.0
0.003
 +High soot concnetration due to low 02 cone,  in the boiler
 *Uncorrected for air leakage.
**Average air leakage.
-------
                                             TABLE F-l.   C-E ARCS PROTOTYPE
                                                         FURNACE INJECTION TESTS (Continued)
I
IX)
Experiment No.
Date of Run
Set No.
Time
Flue Gas (FG) Rate (CFM 
-------
                 TABLE F-2.   ANALYSIS OF FILTRATE  SAMPLES  FOR  STEADY  STATE  DETERMINATION
                             EXPERIMENT 17R

                                               12-27-71
Time
0920
1145
1315
1430
1540

0820
0930
1030
1250
1400
1750
1835
1915
2015
f
1
2
3
4
5

6
7
8
9
10
11
12
13
14
EB
Ca Na Mg
909 <1
650 16
603 3
568 6
567

628 <1
513 18 <1
504 18 <1
549
528
485
424
408 14
420
ci so4
1699
1516
1434
1208
1033

1628
90 1160
90 1100
1051
1007
1012
919
70 969
1066
Ca
1140
761
768
747
831


752
828
824
734
759
608
623
598
SL
Na Mg CI
17
17
10
12

12-28-71

19 13 110
18 21 100




14 70

so4
2982
2230
2322
2175
2200


2193
2041
2154
1872
2071
1745
1693
1718
Ca Na Mg
1078 <1
540 3
525 <1
569 <1
632

490 <1
588 18 <1
579 18 <1
610
560
517
513
479 14
473
ci so4
1986
1566
1132
1192
1161

1700
100 1172
90 1128
1020
1036
974
915
60 1019
990
EB - Hold Tank Effluent
SR - Scrubber Liquid
SW - Spray Water Feed
-------
    TABLE  F-3.   ANALYSIS OF  FILTRATE  SAMPLES  FOR
                STEADY STATE DETERMINATION
                EXPERIMENT 18R
Cl  (ppm)
2-1-72

     SL (ppm)
SW (ppm)
Time #
1305 1
Ca++
524
=
-
SQ-
1170
PH
7.20
Ca++
1469
S03
1232
so;
1461
pH
5.45
Ca++
908
S03
0
4
1820
PH
5.75
2-2-72
0848 2
1030 3
1130 4
1200 5
1230 6
1300 7
1330 8
520
566
598
599
613
636
664
140
20
44
32
40
52
40
1172
1346
1477
1271
1342
1407
1472
7.28
8.62
7.38
8.43
9.31
9.25
9.38
741
1209
1221
922
1151
1136
917
_
1352
1232
800
796
712
320
_
2217
3021
2260
2564
2425
2066
_
5.51
5.45
5.65
5.82
6.21
8.29
_
756
830
807
914
929
909
_
100
160
56
56
40
48
_
1960
2348
2232
2422
2312
2142
_
8.32
6.78
8.52
9.49
9.73
10.01
2-3-72
1130 9
1300 10
1500 11
1530 12
1600 13
1630 14
1700 15
700
736
790
632
740
794
792
60
60
40
32
40
32
34
1538
1508
1682
1475
1510
1553
1557
10.87
11.16
10.91
11.22
11.18
11.22
11.18
_
800
826
660
794
816
828
60
60
192
232
256
12
252
_
1658
1999
1677
1862
1755
1753
11.48
8.11
6.52
6.49
9.75
6.39
6.24
1052
1000
926
748
912
850
918
56
60
56
56
32
32
32
1312
1528
1922
1598
1679
1741
1679
12.01
11.65
10.95
10.92
10.88
11.19
10.98
-------
TABLE F-4.  FILTRATE ANALYSIS AND SOLID CONCENTRATION VALUES
            FOR STEADY STATE DETERMINATION
CL
                                                        SW
Experiment
No. Time

20R
20R

20R
20R
20R
20R
20R

20R
20R
20R
20R
20R
20R

19R
19R
19R
19R
19R
19R
19R
19R

moo
1600

1200
1300
1400
1500
1600

0700
0730
0830
0900
0930
1000


0800
0830
0900
0930
1000
1030
1100
Ca++
(PPM)

594
659

792
663
811
800
823

745
894
893
857
877


904
892
890
906
900
876
880
855
SOo
(PPM)
4-18-72
352
412
4-19-72
380
552
320
316
304
4-20-72
252
240
312
336
380
432
4-21-72
460
444
452
472
444
452
452
448
Total
Sulfur As
SOJ PPM

1860
1920

2290
1950
2340
2230
2260

2040
2280
2550
2440
2650


2850
2760
3000
2890
2940
2710
2690
2660
$04
(PPM)

1437
1420

1834
1287
1956
1850
1859

1737
1992
2175
2036
2194


2298
2227
2457
2323
2407
2167
2147
2122
PH

6.2
6.0



6.0
6.1


6.25
6.2
6.3
6.3




5.7

4.8
4.9


5.0
Ca-H-
(PPM)

660
784

882
790
878
879
855

902
952
886
829
813


1034
983
978
965
875
841
830
836
so|
(PP8)

644
552

592
132
376
324
268

180
440
356
352
300
320

72
472
632
700
572
624
632
612
Total
Sulfur As
SO? PPM
4-18-72
2130
2150
4-19-72
2540
2230
2470
2390
2200
4-20-72
2140
2630
2370
2440
2340

4-21-72
2100
3050
3340
3420
2890
2730
2790
2820
SO*
(PPM)

1357
1487

1829
2071
2018
2001
1878

1924
2102
1942
2017
1980


2013
2483
2581
2580
2203
1981
2031
2085
Percent
pH Solids

5.8
5.7

6.7

6.3
6.3


9.00
6.4
5.8
5.8
5.8



5.7

5.4
5.7


5.5

0.4
0.3

0.5
0.5
0.6
0.8
1.1

1.1
1.1
1.1
0.9
0.7


0.8
1.6
2.4
1.5
1.7
1.4
1.7
2.2
-------
                        TABLE F-4.   FILTRATE  ANALYSIS AND SOLID CONCENTRATION VALUES
                                    FOR STEADY  STATE DETERMINATION (Continued)

                            CL                                                 SW
Experiment
No. Time
Ca++
(PPM)
SOo
(PP»)
Total
Sulfur As
S0= PPM
4
(PPfl) pH
Ca++
(PPM)
S03
(PPM)
Total
Sulfur As
SOJ PPM
SOi"
(PPM)
PH
Percent
Solids
                        4-25-72                                         4-25-72
21R        1300
21R        1400
21R        1500
21R        1530
21R        1600
778
679
733
744
712
900
240
120
_
120
3450
2580
2590
2720
2870
2370
2292
2446
-
2726

6.1
7.0
7.3

4.4
6.1
7.9

8.5
                        4-26-72                                          4-26-72
21R        0630     789      20      1960       1936        1297     140      1470       1302           13.5
21R        0700     808      60      1940       1868        1297      40      1550       1502           10.3
21R        0730     818      60      2190       2118         686     120      2280       2136            9.1
21R        0830     849      80      2030       1934         791     112      2260       2125            9.7
21R        0900     853      80      2110       3014         721      80      2640       2544            6.8
21R        1000     844      92      2150       2039         825     128      2550       2396      6.7   6.8
21R        1100     833      64      2140       2063         853     140      2820       2652      6.2   7.8
2iR        1200                                             866     108      2700       2570      6.2   6.3
21R        1300     846      120      2190       2046         776      88      2780       2674     9.15   5.4

                         4-28-72                                          4-28-72

           Q750
           Q83Q
           0900
           0930
22R        1000
2?R        1110
OOR        J210
22R        1315     860      56      1990       1992
791
857
913
848
817
756
729
719
44
60
40
52
64
336
124
40
2060
2290
2320
2250
2440
3340
3960
3020
2067
2218
2272
2187
2363
2936
2811
2972
9.4
7.4


6.7


9.5
6.5
7.1
10.2
10.5
9.0
8.4
9.5
8.6
-------
                                  TABLE  F-5.  RESULTS OF SOLID PHASES ANALYSES
                                             EXPERIMENT 17R
    Sample Location
Set 1

Marble Bed Front
Marble Bed Back
Scrubber Bottom "S"
Spray
Hold Tank Effluent
Set 2

Scrubber Liquid "T"
Scrubber Liquid "T"
Scrubber Liquid "T"
Scrubber Bottom "T"
Scrubber Bottom "T"
Hold Tank Effluent
Marble Bed Front
Marble Bed Back
Scrubber Bottom "S"
Spray
Clarifier Bottom
Filter Liquid
Filter Solid
  Date
12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
                                                        Composition in Millimole/Gram Solid
1
2
3
1
2








12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
12/28/71
1 2/28/71
12/28/71
12/28/71
12/28/71
0.274
0.251
0.269
0.850
0.904
0.327
0.163
0.293
1.11
0.0103
1.11
0.0139
79.6
Wt % Solids
 in Slurry    Total  S    Ca
   0.211
   0.316
    1.02
   .0078
   0.327
                          0.939
                          1.002
                          0.914
                          1.012
                          1.012
                           1.74
                          0.765

                          0.692

                           2.10

                          0.538
Mg
SO,
SO.
CO,
3.22
5.68
4.57
3.40
3.68
3.57
5.52
5.59
4.56
3.28
5.80
3.87
4.15
.522
.402
0.479
.448
.488
.506
.430
.435
.479
.498
.416
.516
.868
0.80
0.59
1.51
0.52
0.55
0.49
0.88
0.78
1.51
0.30
0.50
1.76
0.45
0.07
0.09
0.23
0.42
0.45
0.42
0.13
0.23
0.23
0.46
0.14
0.34
0.09
0.220
0.362
0.650
0.227
0.236
0.224
0.566
0.554
0.650
0.296
0.511
0.755
0.595
  Weight
% Undissolved
                                   51.3

                                   35.5

                                   41.4
                                                                    49.6
                                                                    53.7
                                                                    51.7
                                                                    41.9
                                                                    41.5
                                                                    41.4
                                                                    55.7

                                                                    41.2

                                                                    40.5

                                                                    40.5
-------
 I
CD
         Sample Location
     Set 1

     Scrubber Liquid:
     Scrubber Bottoms:
Clarifier Liquid
Hold Tank Effluent
Marble Bed:  Front
             Back
Scrubber Bottoms S
Scrubber Spray
Additive

Set 2

Scrubber Liquid:
     Scrubber Bottoms:
     Hold Tank Effluent
     Marble Bed:   Front
                  Back
     Scrubber Bottoms S
     Scrubber Spray
     Clarifier Bottoms
                  Tl
                   2
                   3
                  Tl
                   2
                   3
                                       TABLE F-6.   RESULTS  OF SOLID PHASES ANALYSES
                                                   EXPERIMENT 18R
                             Date
2/ 3/72


2/ 3/72
2/ 3/72
21 3/72
21 3/72
21 3/72
21 3/72
21 3/72
21 3/72
Tl
2
3
Tl
2
3
21 3/72
21 3/72
                           21 3/72
                           21 3/72
                           21 3/72
                           21 3/72
4.45
4
5
5
6
6
46
28
83
00
15
                                              .017
                                              4.
                                              4.
                                              4.
                                              5,
  50
  17
  10
  39
3.67
              4.07
              4.12
               .93
               .26
               .61
               .79
               .66
               .10
               .91
              4.99
              3.35
3.
5.
5.
5.
3.
4.
3.
                                                              Composition in Millimole/Gram Solid
           Wt % Solids
            in Slurry    Total  S
3.
3.
3.
2,
2,
15
10
04
50
62
                                                          2.60
          3,
          3.
          3.
          2,
          3.
  08
  33
  34
  51
  01
                                                          0.51
            28
            16
            20
            36
          2.42
          2.66
            98
            18
            19
            43
            08
                      Ca
                            Mg
                          SO,
                                SO,
CO,
                          2.98
4.50
4.57
4.60
4.81
4.62
4.69
4.47
4.56
4.52
4.85
4.59
5.97
4.59
4.54
4.49
4.80
4.85
4.64
4.57
4.50
4.54
4.93
4.47
4.33
0.34
0.34
0.34
0.41
0.41
0.40
0.40
0.31
0.32
0.41
0.41
0.50
0.33
0.33
0.33
0.41
0.41
0.41
0.41
0.32
0.32
0.40
0.40
0.43
2.26
2.27
2.18
1.57
1.63
1.73
2.22
2.31
2.34
1.73
2.17
0.06
2.26
2.32
2.36
1.63
1.67
1.89
2.12
2.32
2.36
1.69
2.20
2.13
0.87
0.83
0.86
0.93
0.99
0.87
0.86
1.02
1.00
0.785
0.84
0.45
1.02
0.84
0.84
0.73
0175
0.77
0.865
0.86
0.83
0.745
0.88
0.85
0.58
0.55
0.50
0.52
0.61
0.73
0.63
0.59
0.60
0.49
0.58
0.39
0.51
0.54
0.58
0.62
0.63
0.63
0.64
0.49
0.52
0.59
0.54
0.54
  Weight
% Undissolved
           34.6
           32.1
           34.8
           35.1
           35.9
           36.0

           34.1
                                                      .3
                                                      .2
           33.
           34.
           36.0
           34.9
           46.3
                                                      34.0
                                                      34.5
                                                      34.6
                                                      36.
                                                      36.
                                                      36.
                                                                                                             .3
                                                                                                             .5
                                                                                                             .3
                                                      34.0
                                                      33.2
                                                      34.6
                                                      35.1
                                                      34.6
                                                      35.3
-------
vo
        Sample Location
71  Set 2
    Scrubber Liquid Tk 1
    Scrubber Liquid Tk 2
    Scrubber Liquid Tk 3
    Scrubber Bottoms Tk 1
    Scrubber Bottoms Tk 2
    Scrubber Bottoms Tk 3
    Hold Tank Effluent
    Marble Bed: Front
    Marble Bed: Back
    Scrubber Bottoms S
    Scrubber Spray
    Fly Ash and Lime
    Fly Ash and Lime
                                      TABLE  F-7.  RESULTS OF SOLID PHASES ANALYSES
                                                 EXPERIMENT 19R
    Set 1

    Scrubber Liquid Tk 1
    Scrubber Liquid Tk 2
    Scrubber Liquid Tk 3
    Scrubber Bottoms Tk 1
    Scrubber Bottoms Tk 2
    Scrubber Bottoms Tk 3
    Hold Tank Effluent
    Marble Bed:  Front
    Marble Bed:  Back
    Scrubber Bottoms S
    Scrubber Spray
  Date
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
4/21/72
                                                            Composition in Millimole/Gram Solid
Wt % Solids
 in Slurry    Total  S   Ca
   1.22
   1.22
   1.23
   2.61
   2.73
   3.28
   1.39
   1.50
   1.38
   3.21
   1.14
   1.21
   1.35
   1.34
   3.27
     .54
     .10
3.
3.
1.49
1.67
1.52
4.19
1.46
                             Mg
SO,
SO,
CO,
1.96
1.90
1.95
2.06
1.64
1.88
2.26
1.83
1.90
1.53
2.21
3.30
3.31
3.45
4.10
4.93
4.53
3.85
3.68
3.47
4.88
3.73
0.224
0.222
0.228
0.329
0.321
0.330
0.200
0.244
0.221
0.341
0.197
1.32
1.29
1.34
1.57
1.28
1.52
1.60
1.24
1.28
1.47
1.62
0.64
0.61
0.61
0.49
0.36
0.36
0.66
0.59
0.62
0.06
0.59
0.175
0.166
0.177
0.271
0.240
0.237
0.172
0.171
0.171
0.280
0.215
1.85
1.84
1.77
2.13
1.85
1.90
2.05
1.66
1.79
1.42
2.01
0.45
0.54
3.39
3.52
3.50
4.19
4.72
4.16
3.84
3.98
3.89
5.01
4.01
5.81
5.78
0.240
0.243
0.235
0.336
0.334
0.334
0.215
0.265
0.255
0.350
0.224
0.500
0.498
1.22
1.23
1.15
1.58
1.37
1.45
1.45
1.18
1.15
1.33
1.41


0.63
0.61
0.62
0.55
0.48
0.45
0.60
0.48
0.64
0.09
0.60


0.161
0.209
0.201
0.333
0.349
0.335
0.189
0.198
0.243
0.402
0.180
0.455

Weight
Undissolved
                                                                 53.0
                                                                 50.
                                                                 50.
                                                                 44.
                                                                 42,
                                                                 45.1
                                                                 47
                                                                 51
                                                                 51
                              ,7
                              .1
                              .7
                                                                 45.1
                                                                 45.6
                                                                   .1
                                                                   .9
                                                                   ,5
                           51
                           51
                           50.
                           44.0
                           42.0
                           43.4
                           45.
                           48.
                           48.
                           42.4
                           45.4
                           45.8
                           47.6
                                                                      .5
                                                                      .6
                                                                      .9
-------
                                 TABLE F-8.  RESULTS OF SOLID PHASES ANALYSES
                                             EXPERIMENT 20R
                                                        Composition In Mil 11mole/Gram Solid
    Sample Location
  Date
Set 1

Scrubber Liquid Tk 1
Scrubber Liquid Tk 2
Scrubber Liquid Tk 3
Scrubber Bottoms Tk 1
Scrubber Bottoms Tk 2
Scrubber Bottoms Tk 3
Clarifier Liquid
Hold Tank Effluent
Marble Bed:  Front
Marble Bed:  Back
Scrubber Bottoms S
Scrubber Spray
Scrubber Liquid Tk 1
Scrubber Liquid Tk 2
Scrubber Liquid Tk 3
Scrubber Bottoms Tk 1
Scrubber Bottoms Tk 2
Scrubber Bottoms Tk 3
Hold Tank Effluent
Marble Bed:  Front
 Marble Bed:  Back
Scrubber Bottoms S
Scrubber Spray
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4.20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
4/20/72
Wt % Solids
 in Slurry    Total  S    Ca      Mg
   0.735
   0.743
   0.691
    2.67
    1.87
   2.27
   0.013
   0.738
   0.983
   0.868
    2.53
   0.694
    0.72
   0.703
   0.697
    2.03
    2.06
    2.06
   0.665
   0.843
   0.756
    2.26
   0.699
1.67
1.57
1.58
1.72
1.98
1.83

2.05
1.53
1.47
1.36
2.00
1.46
1.42
1.41
1.79
1.73
1.59
1.93
1.26
1.21
1.21
1.79
                          SO,
SO.
CO,
3.18
3.34
3.79
4.61
4.73
4.41

3.73
3.67
3.40
4.87
3.77
2.72
3.08
4.46
3.05
4.53
4.28
3.61
3.70
3.21
4.86
3.70
0.300
0.307
0.370
0.483
0.578
0.482

0.241
0.315
0.290
0.364
0.251
0.251
0.290
0.366
0.287
0.367
0.362
0.249
0.318
0.320
3.84
0.250
0.98
0.98
1.03
1.37
1.53
1.51
0.93
1.44
1.05
0.97
1.20
1.42
0.93
0.95
0.94
1.26
1.44
1.24
1.30
1.03
0.88
1.16
1.28
0.69
0.59
0.55
0.35
0.45
0.32

0.61
0.48
0.50
0.16
0.58
0.53
0.47
0.47
0.53
0.29
0.35
0.63
0.23
0.33
0.05
0.51
0.205
0.209
0.172
0.384
0.199
0.327

0.201
0.210
0.150
0.249
0.181
0.163
0.204
0.158
0.278
0.310
0.346
0.217
0.223
0.192
0.299
0.192
  Weight
% Undissolved
                   50,
                   51,
                   52,
                   40.8
                   42.2
                   44.1

                   41.9
                   51.4
                   54.1
                   44.3
                   48.8
                    55.4
                    58.3
                    58.8
                    45.2
                    45.2
                    44.0
                    47.9
                    54.2
                    55.7
                    49.1
                    49.1
-------
                                  TABLE  F-9.  RESULTS OF SOLID PHASES ANALYSES
                                             EXPERIMENT 21R
    Sample Location
Set 1

Hold Tank Effluent
Marble Bed:  Front
Marble Bed:  Back
Clarlfler Bottoms

Set 2

Hold Tank Effluent
Marble Bed:  Front
Marble Bed:  Back
                              Composition in Millimole/Gram Solid

           Wt % Solids
  Date      in Slurry    Total  S    Ca      Mg      S0?     SO.
4/26/72       8.02
4/26/72       8.09
4/26/72       9.10
4/26/72
4/26/72       6.67        3.20      4.11     .186    2.35
4/26/72       7.65        3.38      4.11     .184    2.28
4/26/72       7.83        3.35      4.51     .194    2.22
        CO,
3.53
3.46
3.65
2.65
4.37
4.46
4.50
4.21
.245
.216
.200
.295
2.27
2.26
2.40
1.66
1.26
1.20
1.25
0.99
0.250
0.235
0.227
0.394
0.85   0.200
1.10   0.241
1.13   0.211
                                                                                                       Wei ght
                                                                                                     % Undissolved
                   36.2
                   36.7
                   34.7
                   32.9
35.9
36.5
36.0
-------
                                     TABLE F-10.   RESULTS OF SOLID  PHASES ANALYSES
                                                  EXPERIMENT 22R
        Sample  Location
                Date
    Set 1

    Hold Tank  Effluent
    Marble Bed:   Front
    Marble Bed:   Back
    Set 2

    Marble Bed:
    Marble Bed:
    Additive
Front
Back
              4/28/72
              4/28/72
              4/28/72
4/28/72
4/28/72
                                                           Composition in Mi Hi mole/Gram Solid
           Wt % Solids
            in Slurry    Total S    Ca
              8.58
              7.84
              8.51
9.18
9.82
            3.55
            3.61
            3.83
3.75
3.85
0.50
          4.37
          4.44
          4.52
4.44
4.53
6.09
                              Mg
        .190
        .200
        .188
.172
.155
.483
                          S0n
        2.32
        2.35
        2.52
2.40
2.51
0.08
                        SO.
                        CO,
        1.23   0.205
        1.26   0.196
        1.31   0.243
1.35   0.146
1.34   0.133
0.42   0.469
                         Weight
                       % Undissolved
                   35.3
                   35.7
                   35.1
34.9
34.6
47.4
ro
-------
TABLE F-ll.  LIQUID CHEMICAL ANALYSIS AT STEADY STATE
             EXPERIMENT 17R

           Concentration in m moles/liter
Set
No.
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2

Time
1331
1322
1347
1400
1445
1457
1537

1701
1650
1712
1725
1505
1517
1537
1605


Sampling Point
Marble Bed Back
Marble Bed Front
Scrubber Bottoms (Scrubber)
Spraywater
Scrubber -Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Make Up Water
Marble Bed Back
Marble Bed Front
Scrubber Bottom (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottoms at Tank
Hold Tank Effluent
Clarifier Bottoms
Make Up Water
Ca++

RAD.
18.6
22.0
16.8
12.6


12.6
1.08
21.45
19.0
16.0
13.5
19.8
17.5
12.6
16.2
1.08

C-E
19.3
18.8
16.8
13.7
19.9
17.4
11.7

20.0
18.2
16.3
12.8
19.6
17.6
11.7
17.2


Mg++

0.20

0.01


0.07


0.27

0.02
0.35
0.01
0.07



Na+

0.76

0.74


0.68
0.45
0.75
0.68
0.74
0.68
0.77
0.77
0.68
0.66
0.45

co=3

1.10
0.27
0.13


0.26


0.87
0.20
0.10
0.96
0.06
0.26
0.12

Total S S0~

RAD.
25.5
22.2
12.9
10.3


10.0

25.2
21.6
12.6
9.6
22.3
10.7
10.0
8.5


C-E
25.84
21.98
12.61
11.27
23.75
11.30
10.90

24.06
21.08
13.00
10.68
21.95
12.74
10.90
10.00


RAD.
8.57
8.95
1.26
0.84


1.30

9.23
7.57
1.30
0.89
8.06
1.00
1.30
0.58


C-E
8.9
9.0
1.0
1.0
8.9
1.0
1.5

8.6
5.8
1.7
1.3
9.2
1.1
1.5
0


Cl-

2.65
2.81
2.13


2.06


2.29
2.39
11.02
2.63
2.81
2.06
0.73

PH

N Low / High

0.73 4.5S/ 5.5
0.73 10. 6/ 10.8
11.18
5.78/ 5.86
11.15/11.22
10.75

4.45/ 4.75
4.52/ 5.08
9.9/ 10.5

5.78/ 5.86
11.15/11.22
10.75
11.85

Temp
°C

49.5
47.0
37.5


37.5

47.5
46.5
46.5
37.0
50.5
48.0
36.5
25.0

-------
Set
No.  Time
     1905
     1854
     1913
     1923
     1757
     1805
     1838
     1833

     2022
     2030
     2040
     2050
     1933
     1939
     2011
     2067
                                        TABLE F-12.  LIQUID CHEMICAL ANALYSIS AT STEADY STATE
                                                     EXPERIMENT 18R
                                                   Concentration in m moles/liter
                                                Ca++
       Sampling Point
                                            3.60
                                            3.70
                                            3.41
                              RAD.    C-E

Marble Bed Back                24.4  24.80
Marble Bed Front               22.8  24.10
Scrubber Bottoms (Scrubber)     25.7  24.42
Spray Water                    23.5  22.52
Scrubber Liquid at Tank         20.6  21.25
Scrubber Bottom at Tank         33.2  32.72
Hold Tank Effluent             23.3  22.97
Clarifier Liquid               20.9  20.60
Marble Bed Back               24.7  26.12   3.40
Marble Bed Front              26.0  26.87   3.42
Scrubber Bottoms (Scrubber)    25.5  24.95
Spray Water                   23.2  23.25
Scrubber Liquid at  Tank        21.8  22.17   3.40
Scrubber Bottom at  Tank       34.30  34.30
Hold Tank Effluent             23.9  24.20
Clarifier Liquid              22.0  22.35
Na+   CO"

1.10
1.05
1.14
1.10
1.10
1.11
1.06
0.93

1.11
1.13
1.17
1.09
1.12
1.14
1.11
0.94
SO'
RAD.
19.47
21.25
17.41
17.56
18.56
17.20
17.5
16.38
22.26
22.73
18.60
18.6
19.78
17.69
19.0
17.1

C
24
24
19
18
19
17
17
16
22
27
19
19
20
18
18
16

-E
.64
.04
.09
.15
.98
.20
.35
.49
.33
.97
.02
.67
.46
.51
.68
.96

RA
7
2
0
0
3
1
0
0
5
7
0
0
4
0
1
0
S03
D.
.43
.55
.74
.64
.64
.10
.80
.57
.14
.47
.92
.68
.92
.91
.31
.73

C
3
2
0
0
2
0
0
0
5
2
0
0
3
0
0
0

-E
.85
.06
.45
.35
.57
.89
.53
.56
.75
.60
.42
.38
.25
.72
.55
.40

C

6
6
6
6
6
6
3

6


6
7
6
4
T/\4-
lOt.
1- N

.44
.89
.11
.33
.91
.17
.91

.49


.45
.15
.28
.40
pH
Low /
5.
6.
10
10.
6.
11
10.
11.
6
6.
10.
10
5.
11.
10
11

High
75
23
.6
75
45
.4
75
05
.0
05
45
.4
90
46
.6
.2
T-a.ii.in.
Temp
°C
45.0
43.0
47.0
46.0
47.9
47.9
46.0
37.5
45.0
45.0
47.0
47.0
47.8
47.5
46.0
37.9
-------
TABLE F-13.   LIQUID CHEMICAL ANALYSIS AT STEADY STATE
             EXPERIMENT 19R

           Concentration In m moles/Hter
Set
«JC U
No.
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2

Time
1215
1208
1225
1230
1125-1145
11 30-1 T 52
1200
1157

1340
1330
1345
1325
1243-1305
1248-1310
1320
1315

Sampling Point
Marble Bed Rock
Marble Bed Front
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Make Up Water
Marble Bed Back
Marble Bed Front
Scrubber Bottom (Scrubber)
Spray Hater
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
RAD. C-
34.4
34.4
27.7
25.7
35.3
23.8
24.5
22.5
1.08
34.8
34.5
276
25.2
35.3
22.2
25.5
22.6

E Mg-
4
4
4
4
4
4
4
3

4
4
4
4
4
4
4
3

H- Na+
.52
.49
.20
.67
.50
.38
.30
.41
.45
.37
.40
.24
.23
.41
.07
.23
.45

2
1.83
1.86
0.83
1.12

0.75
1.10
0.24

1.97
1.83
0.83
1.00
1.36
0.17
0.97
0.22
so4
RAD. C-
26.8
26.1
24.45
20.35
25.1
22. 5
20.6
23.1

27.45
25.55
23.65
21.45
25.2
21.9
20.85
22.85
S03
E RAD. C-l
26.6
27.1
14.75
15.55
28.6
7.9
15.7
6.0

25.45
26.35
13.65
15.15
27.31
4.5
15.05
5.95

E C1- N

2.32
3.24
2.13
1.33
3.36
2.10
2.00


2.30
3.25
2.08
2.26
3.17
2.03
2.03
pH
Low / High
4.5
4.7
5.6
5.5
4.98
5.88
5.43
5.30

4.65
4.90
5.6
5.5
5.02
6.15
5.50
5.60
i T it inn
' 1 Clfl^/
i °C
41.5
41.0
44
39
43.4
43.8
39.0
23.5

42.0
41.50
44.0
37.0
44
44
39
23.5
-------
I
at
                                             TABLE F-14.  LIQUID CHEMICAL ANALYSIS AT STEADY STATE
                                                          EXPERIMENT 20R

                                                        Concentration In m moles/liter
Cpf
OC L
No.
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2

Time
1105
1140
1200
1208
1036-1105
1048-1110
1125

1340
1350
1357
1330
1232-1300
1240-1307
1323
1320

Sampling Point
Marble Bed Back
Marble Bed Front
Scrubber Bottom at Scrubber
Scrubber Spray
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Make Up Water
Marble Bed Back
Marble Bed Front
Scrubber Bottom at Scrubber
Scrubber Spray
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarlfler Liquid
Ca++
RAD. C-E
32.5
32.0
26.1
23.4
31.6
21.6
23.6
1.08
33.8
33.1
30.0
26.6
33.9
24.7
25.9
22.9

Mg++
3.59
3.44
3.32
3.18
3.20
3.30
3.24

3.73
3.80
3.62

3.65
3.58
3.57
3.28

Na+ CO!
1
0.40 1
1
0
0.38
0
0.38 0
.45
1
1
0
0
1
0
0
0

3
.69
.49
.38
.93

.06
.95

.27
.74
.70
.98
.42
.48
.87
.57
S04
RAD. C-E
31.25
30.15
25.3
24.7
30.1
18.9
24.45

29.15
30.25
26.6
25.5
29.1
23.3
24.65
20.9
S03
RAD. C-E
15.25
14.75
8.1
7.9
15.6
1.01
7.45

17.05
16.65
12.0
10.2
18.3
2.85
10.25
7.4
Tnt
1 U I •
Cl- N

2.23
3.01
1.89

3.11
2.03


2.38
3.13
2.03
2.04
3.12
2.13
1.95
PH
Low / High
4.53
4.7
5.93
5.72
5.21
10.9
5.75

4.55
4.70
5.70
5.87
5.10
6.30
5.70
5.80
Tomn
• cmp
°c
42
42.5
44
39.0
44
45.3
40

42.5
40
42.5
44.5
43.5
44.5
40.0
39.0
-------
TABLE F-15.  LIQUID CHEMICAL ANALYSIS  AT STEADY STATE
             EXPERIMENT 21R

           Concentration in m moles/liter

CM*
bet
No.
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2


Time
1430
1422
1440
1500
1320-1350
1327-1355
1405
1400
1642
1633
1652
1700
1528-1605
1535-1610
1623
1618


Sampling Point
Marble Bed Back
Marble Bed Front
Scrubber Bottom at Scrubber
Scrubber Spray
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Back
Marble Bed Front
Scrubber Bottom at Scrubber
Scrubber Spray
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca+-

RAD.
22.6
23.6
20.0
16.8
24.7
24.3
18.1
19.4
23.6
20.5
19.4
16.9
19.8
21.1
16.9
17.6
i-

C-E
24.91
23.05
21.75
21.79
30.20
28.75

20.8
25.45
24.72
20.90
18.59
21.17
25.80

20.7


Mg++ Na+
16.0
16.8
10.5
13.9
16.0 1.11
1.29
11.7 1.06
4.30
16.6
16.8
12.0
13.9
17.3
9.8
15.1 1.09
4.72


C0=
1.94
1.98

0.23
0.18
0.23
0.28
0.3
2.04
1.89
0.52
0.15
1.42
0.19
0.50
0.29
S0=
H
RAD.
33.6
27.8
25.9
28.1
27.4
21.6
26.7
21.3
34.4
26.8
27.9
27.8
34.4
27.8
28.8
20.8


C-E
31.15
29.30

24.82
25.50
21.30

22.40
32.50
29.40
25.60
25.82
24.70
16.33

22.35
so:
w
RAD.
7.60
6.70

1.28
5.05
0.9
1.10
0.85
1.20
1.29
1.12
1.32
7.6
1.2
1.73
0.98


C-E
10.9
9.50
1.60
0.90
0.70
1.00

1.10
11.65
9.14
1.25
1.00
2.60
1.35

1.50

Tot
1 U V* •
Cl- N

9.22

8.70
9.19
10.7
8.85
3.94

9.13
10.0
8.56
9.00
10.3
8.73 0.3
4.60
PH

Low / High
5.48
5.69
8.18
8.30
6.01
9.77
8.52
9.85
5.38
5.50
6.42
8.90
5.37
9.48
7.03
9.90

Temp
°C
46.0
44.0
47.5
45.5
46.8
45.0
45.0
29.0
46.5
44.0
47.8
46.0
47.2
46.0
45.0
29.9
-------
    Set
    No.  Time
i
00
1605
1555
1610
1620
1335
1330

1340
                                            TABLE F-16.   LIQUID CHEMICAL ANALYSIS AT STEADY STATE
                                                         EXPERIMENT 22R
                                                       Concentration in m moles/liter
       Sampling Point

Marble Bed Back
Marble Bed Front
Scrubber Bottom at Scrubber
Scrubber Spray
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
RAD. C-E
22.10
21.75
22.05
17.98
27.20
19.58
16.4
21.10

Mg++
19.9
19.9
19.0
19.8
18.5
15.5
17.9
5.20
S°4
Na+ COl RAD.
0.90
1.44
2.09
0.62
0.79
1.38
1.15 0.65
0.23 22.55
so:
C-E RAD.
35.05
32.10
27.6
31.10
39.50
30.43
29.77
21.50
}
C-E
8.05
9.64
7.19
3.75
18.55
4.75
1.93
0.75

Cl- N

9.81
10.4
9.75
9.30
9.92
9.56 0.3
5.58
PH
Low / High
5.44
5.35
5.67
6.05
5.27
6.50
6.81
8.88

Temp
°C
42.5
44.0
45.5
45.0
46.0
46.5
45.5
28.0
-------
   TABLE F-17.   CHEMICAL ANALYSIS OF CANNED SAMPLES OF ADDITIVE FROM ST. LOUIS
                                     (Htf)

                       Boiler Calcined Limestone and Flyash
Sample #
LF1
LF2
LF3
LF4
LF5
LF6
LF7

DPI
DF2
DF3
DF4
Si02
29.1
31.6
33.9
31.4
27.4
15.8
20.8

52.0
39.1
50.2
28.4
A12°3
10.3
11.8
11.3
10.5
10.1
7.4
10.4
Boiler
24.8
17.8
25.8
16.0
Fe2°3
9.0
10.0
9.3
8.3
8.0
7.5
7.4
Calcined
6.4
10.5
6.4
6.6
CaO
39.2
29.6
34.6
36.1
36.6
44.9
37.2
Dolomite
1.5
3.8
1.9
25.7
MgO
0.6
2.8
3.0
3.0
3.1
2.8
3.6
and
1.5
1.0
1.4
7.4
Na20
0.3
0.7
0.5
0.5
0.7
0.4
0.8
Flyash*
0.3
0.3
0.5
0.6
K20
1.1
1.6
1.4
1.1
1.1
0.9
1.2

3.0
1.9
2.7
2.0
T102
0.5
1.1
0.5
1.3
0.9
0.7
0.7

1.3
1.1
1.8
0.8
!?!
4.6
5.0
3.6
4.0
4.4
4.4
4.6

0.3
1.2
0.4
2.3

Fl
F2

50.9
48.1

23.3
24.4

7.0
6.1
Flyash
4.9
3.5

1.5
1.6

0.4
0.4

2.5
2.7

11.3
1.2

1.1
0.8
*  Although these samples  were  marked  as  Boiler Calcined Dolomite and Flyash,
   there appears to be very little  dolomite  in DF1, DF2, and DF3.

   These samples were taken randomly and  the sample numbers are for C-E's use
   only.
                                      F-19
-------
TABLE F-17 (Continued).  CHEMICAL ANALYSIS OF BAGGED BOILER
                         CALCINED ADDITIVE AND FLYASH
oawyie ff
04012
04009
05011
05012
05013
05014
05015
05016
05017
oou
33.6
31.9
31.2
30.9
29.7
30.9
30.9
31.8
32.4
nyu oiUn ninw> ? 1
2.6 26.1 14.3 6.9
3.3 20.0 13.0 7.7
2.4
2.5
2.3
2.5
2.4
2.4
2.4
llwnw WWM 1 IUj
0.3 trace 0.4
0.7 3.6 0.6







                               F-20
-------
  TABLE F-18.  CHEMICAL ANALYSIS OF ADDITIVE  SAMPLES
               FROM UNION ELECTRIC
       Canned Boiler Calcined Limestone and Flyash
                        (m mole/g)
Sample Number                  CaO                    S03


LF1                            7.00                   0.58
LF2                            5.29                 0.625
LF3                            6.18                   0.45
LF4                            6.45                   0.50
LF5                            6.54                   0.55
LF6                            8.02                   0.55
LF7                            6.64                   0.54
       Bagged Boiler Calcined Limestone and Flyash
                        (m mole/g}
04012                          6.00
04009                          5.70                  0.45
05011                          5.57
05012                          5.52
05013                          5.30
05014                          5.52
05015                          5.52
05016                          5.68
05017                          5.79
                       F-21
-------
               APPENDIX G

LIMESTONE FURNACE INJECTION SYSTEM TESTS
       PROBLEMS AND MODIFICATIONS
-------
                                 APPENDIX G
   LIMESTONE FURNACE INJECTION SYSTEM TESTS ~ PROBLEMS AND MODIFICATIONS

                Mechanical Perfonuance:  During the furnace injection tests
several problems were encountered, resulting in lost down and correction time.
The following summarizes these problems:
                Additive Injection System:  The additive feed into the system
could not be maintained initially due to constant tripping of the fan motor
used to blow the additive into the inlet gas stream.  Since there was a
vacuum being pulled on the discharge side of the blower, a high gas flow
resulted which overloaded the motor.  The problem was solved by installing an
orifice on the suction side of the blower.
                Scrubber Bottom Tank:  The outlet line was frequently plugged
as a result of solids settling due to low flow rate and lack of mixing.  The
problem was solved by installing a mixer and a recycle line to increase the
flow rate.
                S02 Analyzer:  Dust from the gas inlet leaked into the S02
analyzing system despite the availability of a filter.  This problem was
corrected first by introducing the sampling probes ahead of the point of
additive injection, and then by shielding it with a piece of pipe with the
pipe cross-sectional area perpendicular to the gas flow.
                Nozzle Erosion and Plugging:  Nozzle erosion was an operating
problem since the nozzle material (brass) was not a good erosion resistant
material.  Nozzle erosion resulted in a change in the spray pattern, and
therefore a disruption of liquid distribution.  This problem was corrected
by replacing the eroded nozzles.
                                    G-l
-------
                Spray nozzle plugging was a persistent problem during the last
test (18R) with boiler calcined limestone.  This nozzle plugging was suspected
to be the result of either or both of the following:
                a.  Presence of particles larger than the nozzle orifice
diameter.
                b.  Maldistribution of fine particles in the three spray
headers.
                The first type of plugging was caused by particles with sizes
larger than the spray nozzle orifice diameter (1/8").  When the nozzles were
blocked with large particles, subsequent buildup of fine particles resulted.
The source of large particles was suspected to be the additive itself, and
chips peeling off both the Hold Tank and pipe walls and then carried to the
nozzles in the slurry.  A screen was installed on the outlet of the additive
feeder to prevent the large particles in the additive from getting into the
system.  The second source was eliminated by installing a strainer in the
slurry feedline to the scrubber as shown in Figure 6-1.  The strainer
prevented large particles from the peeling of previous scale in both the
Tank and pipes from reaching the spray nozzles.
                The second type of nozzle plugging was a result of
maldistribution of fine additive particles in the three headers.  As the feed
slurry, a, in the main external header turned 90° to enter spray header No. 1
(shown in Figure G-2), a centrifugal force would pull some of the solids
toward spray headers No. II and III and hence increase the solid concentration
in Stream b.
                                    6-2
-------
Spray Nozzle
Spray Header
                                                               Strainer
                                    External  Header
             Large Particle Eliminator  in  the Spray  Water
                            6-3
                                                          FIGURE 6-1
-------
                By the same token Stream c was higher in solid concentration
than b and c.  Thus the solid concentration in spray header III was greater
than II, which in turn was greater than I.  This was evident in the nozzle
plugging pattern.  To eliminate this maldistribution in the headers, the
external spray header was modified to receive the slurry feed in two locations
rather than one as shown in Figure 62.  This improved the solids distribution
in the three spray headers, and eliminated plugging.  Also the dead space
labeled (d) in Figure G-2 at the end of each spray header was removed to avoid
buildup which eventually would plug the nozzles.
                Heat Extractor Plugging;  After the last EPA test series,
deposit formation was noticed on the gas and liquid sides of the heat
extractor tubes.  The deposit on the gas side was mechanical Coil ash) In
nature, and was cleaned by means of high pressure water.  The deposit on the
water side was chemical in nature and was cleaned using dilute acid.  The
heat Extractor and the duct cleanup was made as part of a maintenance repair
to keep the equipment in good enough, condition to carry out test work.
                Air Leakage Due the Additive Injection System;  The 02
concentration at the scrubber inlet is considerably higher than at the
boiler because of the air leakage into the system between the scrubber and
the boiler.  Thus, with a minimum excess 02 of 5% in the boiler, the 02
concentration in the scrubber inlet was about 10%,  Therefore, under these
conditions, Test 21R had to be eliminated since it called for 5 percent 02
in the flue gas at the scrubber inlet.
                                    G-4
-------
Before Modification
                                          External  Header
1
i 	 •
c
c
c
c
c
c

_ (c) . (b) ,, — uj — ^vi_::.U111
r


in



d
^^^^H


3 C
3 C
3 C
3 C
D C
b c

I


II



d
•^v

3 C
3 C
3 C
3 C
3 C
3 C

I


I



d

3
3
3
3
D
3

                             Dead Zone Accumulating
                                  Fine Particles
                        Solids Concentration 1n I
-------
            APPENDIX H

LIMESTONE FURNACE INJECTION SYSTEM
         MATERIAL BALANCE
               AND
        RATE CALCULATIONS
-------
                                    TABLE H-l.  TOTAL SULFUR MATERIAL BALANCE

                                                  Experiment 17R
Marble Bed  (Set #1)
  Entering  Streams   Spray Water
                     Additive
                     Gas In
  Leaving Streams
Gas Out
Scrubber Liquid
Scrubber Bottom
                                            Flow Rate
   406 1/min
 2,010 g/m1n
10,950 g mole/mln

11,605 g mole/mln
   329 1/min
   102 1/min
                                        Solid
                                       Content
                                                             2.635
                                                              10.2
                               Total  S
                               In Solid
                              (m mole/g)
                                                    0.55
0.869
0.677
            Total S
           In Liquid
           (m mole/1)
                                                                11.27
23.41
12.61
           Total S   Total S
            In Gas   (m mole/
            (jpm)      mln)
                         1.456

                           764
 4,576
 1,106
15,943

 8,866
 8,455
 1,991
                                  Total Sulfur In = 21,625 - Total Sulfur Out = 19,312
Marble Bed (Set #2)
  Entering Streams   Spray Uater
                     Additive
                     Gas In
  Leaving Streams
                      431  1/min
                    2,010 g/mln
                   10,950 g mole/mln
0
2.28
11.1
0.55
0.765
0.692
10.68
22.57
13.0
1,456
764
4,603
1,106
15,943
8,866
7,999
2,109
Gas Out
Scrubber
Scrubber

Liquid
Bottom
Total
Scrubber Liquid
Scrubber Bottom
Make Up Uater
11,605
329
102
Sulfur
329
102
208
g mole/mi n
1/min
1/min
In = 21 ,652
1/min
l/m1n
1/min
2.28
11.1
- Total
2,635
10.20
0
0
Sulfur
0
0
.765
.692
Out =
.869
.677
22.
13
18,974
23.
11
57
.0

75
.3
Hold Tank (Set #1)
  Entering Streams
  Leaving Streams    Hold Tank Eff.        639 1/min          3.27       1.73         10.9

                                  Total Sulfur In = 10,424 - Total Sulfur Out = 10,580
                                                                                       8,567
                                                                                       1,857
                                                                                      10,580
Hold Tank (Set #2)
  Entering Streams   Scrubber Liquid       329 l/m1n
                     Scrubber Bottom       102 1/min
                     Make Up Water         208 1/min
  Leaving Streams    Hold Tank
                                         2.65
                                         8.77
                                 0.95
                                1.012
             21.95
             12.74
                      631  1/min          3.27        1.74         10.9

             Total  Sulfur  In  =  10,255  -  Total  Sulfur Out =  10,468
                       8,050
                       2,205
                                                                   10,468
                                                      H-l
-------
                                    TABLE H-2.   TOTAL SULFUR MATERIAL BALANCE

                                                  Experiment 18R
Flow Rate
Hold Tank
(Set #1)
Entering Streams

Scrubber
Scrubber

Liquid
Bottom
Clarlfier Liquid
Leaving

Hold Tank
Streams

(Set #2)
Entering Streams


Hold Tank Eff.


Scrubber
Scrubber
Total

Liquid
Bottom
Clarlfier Liquid
Leaving

Marble Bed
Entering


Leaving



Marble Bed
Entering


Leaving


Streams

(Set #1}
Streams


Streams



(Set #2)
Streams


Streams


Hold Tank Eff.


Inlet Gas
Scrubber
Additive
Total


Spray

Outlet Gas
Scrubber
Scrubber


Inlet Gas
Scrubber
Additive
Liquid*
Bottom
Total


Spray

Outlet Gas
Scrubber
Scrubber
Liquid
Bottom

682
114
76
872
Sulfur

682
114
76
872
Sulfur

10,820
796
2,045
11,630
682
114
Sulfur

10.820
796
2,045
11,630
682
114

1/min
l/m1n
l/m1n
1/min
In = 135,994

1/min
1/min
1/min
l/m1n
In = 123,879

g mole/ml n
1/min
g/mln
g mole/mi n
l/m1n
1/min
In = 119,621

g mole/mi n
1/min
g/mln
g mole/mi n
1/min
1/min
Solid
Content

47
60
0.
45

.3
.0
17
.0
- Total

40
55

36

.4
.5

.6
- Total


36


41
53


.7


.4
.9
- Total


33


40
49


.5


.5
.9
Total S
in Solid
(m mole/g)

3
2

3
Sulfur

3
2

2
Sulfur


3
0

3
2
Sulfur


3
0

3

.09
.57
-
.08
Out =

.21
.49

.98
Out =


.01
.51

.34
.51
Out =


.08
.51

.18
2.435
Total S
in Liquid
Cm mole/1 )

22.
18.
17.
17.
136,450

23.
19.
17.
19.

55
09
05
88


71
23
36
99
112,538


18.


27.
19.


50


30
54
135,773


20.


29.
19.


05


30
44
                                  Total  Sulfur In  =  115,049  -  Total Sulfur Out = 129,082
                                                                                               Total S   Total S
                                                                                                in Gas   (m mole/
                                                                                                (ppm)      mlnj
                                                                                                         115,058
                                                                                                          19,641
                                                                                                           1,295

                                                                                                         136,450
                                                                                                         104,614
                                                                                                          17,946
                                                                                                           1,319

                                                                                                         112,538
                                                                                                1,471
                                                                                                  447
                                                                                                1,471
                                                                                                  447
 15,920
102,658
  1,043

  5,200
112,923
 17,650
 15,916
 98,091
  1,042

  5,198
107,817
 16,067
^Average of Back and Front Marble Bed
                                                       H-2
-------
                                    TABLE H-3.  TOTAL SULFUR MATERIAL BALANCE
                                                  Experiment 19R



Solid
Total S
Content In Solid

Marble Bed (Set #1)
Entering Streams


Leaving Streams



Marble Bed (Set #2)
Entering Streams


Leaving Streams



Hold Tank (Set #1)
Entering Streams




Gas In
Scrubber Spray
Additive
Gas Out
Scrubber Liquid
Scrubber Bottom
Total

Gas In
Scrubber Spray
Additive
Gas Out
Scrubber Liquid
Scrubber Bottom
Total

Scrubber Liquid
Scrubber Bottom
Make Up Mater
Flow Rate

9,200 g mole/mi n
738 1/mln
2,800 g/mln
10,555 g mole/m1n
662 1/mln
76 1/mln
Sulfur In = 68.029

9,120 g mole/mln
738 1/mln
2,800 g/mln
10,487 g mole/mi n
662 l/m1n
76 l/m1n
Sulfur In = 67,255

662 1/min
76 l/m1n
133 1/mln
g/1


13.9


14.4
32.10
- Total


14.60


15.90
41.90
- Total

12.20
28.70

(m mole/g)


2.21
0.55

1.87
1.83
Sulfur Out = 72


2.0
0.55

1.73
1.82
Sulfur Out = 73

1.68
2.17

Total S
in Liquid
(m mole/1 )


35.90


53.30
39.20
,113


36.60


52.40
37.30
,315

53.7
30.4

  Leaving Streams
Hold Tank (Set #2)
  Entering Streams
  Leaving Streams
Hold Tank Eff.        871 1/min         13.90       2.26         36.3

             Total Sulfur In = 56,162 - Total Sulfur Out = 58,979
Scrubber Liquid
Scrubber Bottom
Make Up Water
662 1/min
 76 l/m1n
133 1/min
13.0
33.0
1.69
2.09
52.51
 26.4
Hold Tank Eff.         871  1/min         14.90       2.05        35.90

             Total  Sulfur  In = 56,554 - Total Sulfur Out => 57,873
                                                                                                Total S   Total S
                                                                                                 In Gas   (m mole/
                                                                                                 (ppm)      min)
                                                                                                 1,883
                                                                                                 1,095
                                                                                                 1,881
                                                                                                 1,124
                                                                                      17,324
                                                                                      40,165
                                                                                       1,540

                                                                                      11,558
                                                                                      53,111
                                                                                       7,444
                                                                                      17,155
                                                                                      48,560
                                                                                       1,540

                                                                                      11,787
                                                                                      52,898
                                                                                       8,630
                                                                                                           49,118
                                                                                                            7,044
                                                                58,979
49,306
 7,248
                                                                57,873
                                                      H-3
-------
TABLE H-4.  TOTAL SULFUR MATERIAL BALANCE
              Experiment 20R

Marble Bed (Set #1)
Entering Streams


Leaving Streams



Marble Bed (Set #2}
Entering Streams


Leaving Streams



Hold Tank (Set #1)
Entering Streams



Leaving Streams

Hold Tank (Set #2)
Entering Streams



Leaving Streams


Gas In
Scrubber Spray
Additive
Scrubber Liquid
Scrubber Bottom
Gas Out
Total

Gas In
Scrubber Spray
Additive
Gas Out
Scrubber Liquid
Scrubber Bottom
Total

Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
Make Up Water
Hold Tank Eff.
Total

Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
Make Up Water
Hold Tank Eff.
Flow Rate

9,400 g mcle/min
757 Vmin
2,800 g/min
681 1/min
76 1/min
10,850 g mole/mi n
Sulfur In = 55,028

9,400 g mole/mi n
757 1/min
2,800 g/irin
10,850 g mole/min
681 1/min
76 1/min
Sulfur In = 56,071

681 1/min
76 1/min
151 1/min
151 1/min
1,059 I/min
Sulfur In = 48,064

681 1/min
76 1/min
151 1/min
151 1/nin
1,059 I/rain
Solid Total S Total S
Content in Solid In Liquid
g/1 (m mole/g) (m mole/1)


6.94 2.0
0.50
9.25 1.50
25.3 1.53

- Total Sulfur Out =


6.99 1.78
.50

8. 00 1.23
22.6 1.48
- Total Sulfur Out -

7.33 1.61
22.7 1.80
0.13

7.38 2.05
- Total Sulfur Out =

7.07 1.43
20.5 1.69


6.65 1.93


32.6

45.7
33.4

57,878


35.7


46.55
38.60
55,705

45.7
19.9

28.40
31.90
49,804

47.4
26.1

28.3
34.90
Total S Total S
in Gas (m mole/
(ppm) min)

1,962 18,443
35,185
1,400
40,571
5,480
1,090 11,827


1,939 18,227
36,444
1,400
1,090 11,827
38,402
5,476


39,158
4,618

4,288
49,804


39,164
4,617

4,273
50,551
                                           50,551
                  H-4
-------
                            TABLE H-5.  RATE CALCULATION USING SOLID MATERIAL BALANCE
                                                  Experiment 17R

                                                                                                         Total
                                                            Slurry     Concert,     Concert.    Concen.   Species
                                                            Solid      In Solid   In Liquid   In Gas   Flow Rate
	  Stream Flow Rate   Conti (g/11  (m rnole/g)  (m mole/1)   tPPHJ   m mole/min
Marble Bed (Set 41)
1.  CaS03  1/2 H20 Formation
    Entering Streams                       -                    .....
    Leaving Streams  Scrubber Liquid*    329 l/m1n          2.635         0.80                              693
                     Scrubber Bottom     102 l/m1n         10.200         0.59                              614
                     Rate of CaS03  1/2 H?0 Formation = CaSOj 1/2 H20 (Out) - CaS03 1/2 HgO (In)
                                                      = 693 + 614 = 1307 m mole/min.
2.  S02 Oxidation
    Entering Streams Inlet Flue Gas   10,950 g mole/min                                        1|456     15,943
                     Scrubber Spray      406 1/min                                     1.0                  406
    Leaving Streams  Outlet Flue Gas  11,605 g mole/min                                          764      8,866
                     Scrubber Liquid*    329 1/min                                    8.95                2,944
                     Scrubber Bottom     102 1/min                                     1.0                  102
                     Rate of S02 Oxidation = S02 (In) - S02 (Out) - CaSOj 1/2 H20 Formation Rate
                                           = 16,349 - 11,912 - 1,307 = 3,130 m mole/min.
3.  Ca S04 2 HjO Formation
    Entering Streams (Additive)        2,010 g/min                        0.55                            1,105
    Leaving Streams  Scrubber Liquid*    329 1/min          2.635        0.069                             59.8
                     Scrubber Bottom     102 1/min           10.2        0.087                             90.5
                     Rate of Ca S04 2 H20 Formation = CaS04 2 H20 (Out) - CaSO, 2H20 (In)
                                                    =  90.5 + 59.8 - 1,105 - 150 - 1,105
                                                    = -955 m mole/min
4.  CaCQ- Formation
    Entering Streams (Additive)        2,010 g/min                        0.39**                          784.0
    Leaving Streams  Scrubber Liquid     329 1/min          2.635        0.220                              191
                     Scrubber Bottom     102 1/min           10.2        0.362                              377
                     Rate of CaC03 Formation = CaC03 (Out) - CaC03 (In)
                                             = 191 + 377 - 784 = -216 m mole/min
5.  Ca(OH)2 Dissolution
    Entering Stream  Scrubber Spray      431 1/min*                                   13.7                5,905
    Leaving Streams  Scrubber Liquid     329 1/min                                    19.0                6,251
                     Scrubber Bottom     102 l/m1n                                    16.8                1,714
                     Rate of Ca(OH)2 Dissolution = Ca(liq.) Out - Ca(11q.) In + CaCOj + CaS04 2 HgO + CaSOjl/2 H20 Form
                                                 = 6.251 + 1.714 - 5,905 + (1.307 - 955 - 216)
                                                 - 2,196 m moles/mln.
 *Average of marble bed front and back
**From Radian Corp.
 •(•Subtotal of Scrubber Bottom + Scrubber Liquid

                                                      H-5
-------
                            TABLE H-5.  RATE CALCULATION USING SOLID MATERIAL BALANCE (Continued}
Total
Slurry Concen. Concen. Concen. Species
Solid In Solid In Liquid In Gas Flow Rate
Stream Flow Rate Cont. (g/1) (m mole/g) (m mole/1) (PPM) m mole/rain
Hold Tank (Set #1)
1.




2.

CaS03 1/2 H20 Formation
Entering Stream
Leaving Streams



S02 Oxidation
Entering Stream
Leaving Streams
Scrubber Liquid
Scrubber Bottom
Make Up water
Hold Tank Eff.°
Rate of Ca S03 1/2


Scrubber Liquid
Scrubber Bottom
Make Up Water
Hold Tank Eff.°
329 1/mln 2.635 0.80
102 1/min 10.20 0.59
208 1/min
639 1/min* 3.27 1.51
H20 Formation = CaS03 1/2 H20 (Out) - CaS03 1/2 H20 (In)
= 3,155 - 693 - 614
= 1 ,848 m moles/mi n.
329 1/min 8.9
102 1/min 1.0
208 1/min
639 l/min+ 1.5
Rate of S02 Oxidation = S02 (liq.) In - S02 (liq.) Out - CASOj 1/2 H20 Formation


3.



4.





= 2,928 + 102 - 958 - 1,848
= 224 m mole/mi n.
693
614
3,155



2,928
102
958
Rate


CaS04 2H20 Formation
Entering Stream
Leaving Stream


CaC03 Formation
Entering Stream
Leaving Stream
Scrubber Liquid
Scrubber Bottom
Make Up Water
Hold Tank Eff.
Rate of CaS04 2H20

Scrubber Liquid
Scrubber Bottom
Make Up Mater
Hold Tank Eff.
329 1/min 2.635 0.069
102 1/min 10.2 0.087
208 1/min
639 1/min 3.27 0.23
Formation = CaS04 2H20 (Out) - CaSO^ 2H20 In
= 481 - 90 - 60 = 331 m mole/min.
329 1/min 2.635 0.220
102 1/min 10.2 0.362
208 1/min
639 1/min 3.27 0.650
60
90
481


191
377
1,358
Rate of CaCOj Formation = CaC03 (Out) - CaCO, (In)



= 1,358 - 377 - 191 = 790 m mole/min.

5. Ca(OH)2 Dissolution

Entering Stream
Scrubber Liquid
Scrubber Bottom
Make Up Water
329 l/m1n 19.9
102 1/min 17.4
208 1/min 1.08
6,547
1,774
224
   Leaving Stream    Hold Tank Eff.
639 1/min
11.7
7,476
                     Rate of Ca(OH)2 Dissolution = Ca(liq.) Out - Ca(liq.) In + CaC03 + CaSO^ 2H20 + CaS03 1/2 HgO
                                                 = 7,476 - 6,547 - 1,774 - 224 + 1,848 + 331 + 790
                                                 = 1,900 m moles/min
+Subtotal of Scrubber Bottom + Scrubber Liquid
"Stream characterization is assumed to be the same as in Set 2 since the sample was taken in between the two sets.
                                                       H-6
-------
Marble Bed (Set #2)

1. CaS03 1/2 H20 Formation

   Entering Stream

   Leaving Streams   Scrubber Liquid
                     Scrubber Bottom
                            TABLE H-5.  RATE CALCULATION USING SOLID MATERIAL  BALANCE  (Continued)
                                                                                                         Total
                                                            Slurry     Concen.      Concen.     Concen.    Species
                                                            Solid      In  Solid    In  Liquid   In Gas   Flow Rate
                                      Stream Flow Rate   Copt,  (g/1)   (m mole/g)   (m  role/1)    (Pf H)   m mole/mln
                    329 1/min
                    102 1/rnin
 2.28
11.10
 0.30
 0.50
  225
  566
                     Rate of CaS03 1/2 H20 Formation = CaS03 1/2 HgO (Out)  -  CaS03 1/2 H20 (In)

                                                     " 791  m mole/mi n
2. SO- Oxidation

   Entering Stream
Inlet Flue Gas   10.950 g moles/mln
Scrubber Spray      431 1/min
Outlet Flue Gas  11,605 moles/mi n
Scrubber Liquid     329 l/m1n
Scrubber Bottom     102 1/min
                                                                                       1.3

                                                                                       7.2
                                                                                       1.7
                                   1,456

                                     764
                                15,943
                                   560
                                 8,866
                                 2,368
                                   173
                     Rate of S02 Oxidation = S02 (In) - S02 (Out)  - CaS03 1/2 H20 Formation Rate
                                             15,943 + 560 - 8,866 - 2,368 - 173 - 791  = 4,305 m mole/min
3. CaS04 2H20 Formation

   Entering Stream   Additive

   Leaving Streams   Scrubber Liquid
                     Scrubber Bottoms
                  2,010 g/m1n

                    329 1/min
                    102 1/min
 2.28
 11.1
 0.55

0.465
0.192
1,105

  349
  217
                     Rate of CaS04 2H20 Formation = CaS04 2H20 (Out)  - CaS04 2H20 (In)

                                                  = 217 + 349 - 1,105 = - 539 m mole/min
4. CaC03 Formation
Entering Stream
Leaving Stream
Additive
Scrubber Liquid
Scrubber Bottom
2,010 g/min
329 1/min
102 1/min

2.28
11.1
0.39
0.296
0.511
                                                                                                            784

                                                                                                            222
                                                                                                            578
                     Rate of CaC03 Formation = CaCOj (Out)  CaC03 (In)

                                             = 222 + 578 - 784 = 16 m mole/min

5. Ca(OH)2 Dissolution
Entering Stream
Leaving Stream
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
431 1/min
329 1/min
102 1/min
                                                                                      12.8

                                                                                      19.1
                                                                                      16.3
                                                                                     5,516

                                                                                       628
                                                                                     1,662
                     Rate of Ca(OH)2 Dissolution = Ca(11q.) Out - Ca(l1q.) In = CaC03 + CaS04 2H20 + CaSOj 1/2

                                                 = 6,284 + 1,662 - 5,516 + 791 - 539 + 16

                                                 = 2,698 m mole/min
                                                      H-7
-------
Hold Tank (Set #2)

1. CaS03 1/2 H20 Formation

   Entering Stream   Scrubber Liquid
                     Scrubber Bottom
                     Make Up Water
                                   o
   Leaving Streams   Hold Tank Eff.
                           TABLE H-5.   RATE CALCULATION  USING  SOLID MATERIAL  BALANCE  (Continued)


                                                                                                         Total
                                                            Slurry      Concen.      Concen.     Concen.    Species
                                                            Solid       In  Solid    In  Liquid    In  Gas    Flow Rate
                           	  Stream Flow Rate   Cont.  (g/1)   On mole/g)   (m  mole/1)    (PPM)    m mole/mln
329 1/mln
102 1/min
208 1/min
2.65 0.52
8.77 0.83
-
639 1/min
3.27
1.51
                     Rate of CaS03 1/2 H20 Formation = CaS03  1/2  HgO  (Out)  -  CaSOj  1/2  HgO  (In)

                                                     = 3,155  -  453  -  742  =  1,960 m  mole/min
2. S02 Oxidation
Entering Stream
Scrubber Liquid
Scrubber Bottom
Make Up Water
329 1/min
102 1/min
208 1/min
   Leaving Stream    Hold Tank Eff.
639 1/min
                                                                                       9.2
                                                                                       1.7
                                                                                       1.5
                     Rate of S02 Oxidation = S02 (llq)  In -  S02 (liq)  Out  -  CaS03  1/2 HgO Formation Rate

                                           = 3,026 + 173 - 958 - 1,960 = 281.00 m  mole/min
3. CaS04 2H20 Formation

   Entering Streams  Scrubber Liquid     329 1/min
                     Scrubber Bottom     102 1/min
                     Make Up Water       208 1/min

   Leaving Stream    Hold Tank Eff.       639 1/min
                    2.65
                    8.77
                    3.27
             0.43
            0.182
             0.23
                     Rate of CaS04 2H20 Formation = CaS04 2H20 (In)

                                                  = 481  - 375 - 163  = 57 m mole/min
4. CaCO, Formation
   Entering Streams  Scrubber Liquid     329 1/min          2.635        0.229
                     Scrubber Bottom     102 l/m1n           10.2        0.560
                     Make Up Water       208 1/min

   Leaving Streams   Hold Tank Eff       639 1/min           3.27        0.650

                     Rate of CaC03 Formation = CaC03 (Out) - CaC03 (In)

                                             = 1,358 - 198 - 583 = 577 m mole/min

5. Ca(OH)2 Dissolution

   Entering Streams  Scrubber Liquid     329 1/min
                     Scrubber Bottom     102 1/min
                     Make Up Water       208 1/min

   Leaving Streams   Hold Tank Eff.      639 l/m1n
                                             19.6
                                             17.6
                                             1.08

                                             11.7
                                                                   453
                                                                   742
3,155
                                                                 3,026
                                                                   173
                                                                   958
                                  375
                                  163
                                                                   481
                                                                   198
                                                                   583
                                                                 1,358
                                             6,448
                                             1,795
                                                225

                                             7,476
                     Rate of Ca(OH) Dissolution = Ca (liq.) Out - Ca (liq.) In + CaCOg + CaS04 2H20 + CaS03 1/2 HgO

                                                = 7,476 - 6,448 - 1,795 - 225 + 1,960 - 57 + 577 = 1,488 m mole/min
                                                      H-8
-------
                                                      Experiment 19R
                                                                Slurry     Concen.     Concen.    Concen.
                                                                Solid      In Solid    In Liquid   In Gas
                                           Stream  Flow  Rate   Cont.  (g/1)   (m mole/g)   (m mole/1)    (PPH)
                                                                                       Total
                                                                                      Species
                                                                                     Flow Rate
                                                                                     m mole/mln
 Marble Bed (Set
 1. CaS03 1/2 H20 Formation
Entering Streams
Leaving Streams
Scrubber Spray
Scrubber Liquid*
Scrubber Bottom
738 l/m1n
662 1/min
76 l/m1n
13.94
14.4
32.10
1.62
1.26
1.47
16,618
12,011
3,586
                       Rate of Ca S03 1/2  HgO Formation = CaS03 1/2 H20 (Out) - CaS03 1/2 HgO (In)
                                                         =  (12,011 + 3,586) - 16,618
                                                         =  15,597 - 16,618
                                                         =  -1,021 m mole/ml n
 2. S02 Oxidation
    Entering Streams    Inlet Flue  Gas
                       Scrubber Spray
                    9,200 g mole/mln
                      738 1/mln
    Leaving Streams    Outlet Flue Gas     10,555 g mole/mln
                       Scrubber Liquid*      662 1/min
                                             76 1/min
                                                                  15.55
                                                                   26.8
                                                                  14.75
         1,883

         1,095
Scrubber Bottom
Rate of S02 Oxidation = S02 (In)  - S02 (Out)  -  CaS03  1/2  H20 Formation  Rate
                        = 28,800  - 30,421  + 1,021  = -600  m mole/mln
 3.  CaS04 2 H20 Formation
                       Rate of  CaS04 2H20  Formation = CaS04 2H20  (Out) - CaS04 2H20 (In)
                                                   = 6,693 - 7,592
                                                   = -899 m mole/mi n
4.  CaCO,  Formation
                      Rate of CaC03 Formation = CaC03  (Out) - CaCOj (In)
                                                = 2,313 - 3,298
                                                = -985 m mole/min
5. Ca(OH)2 Dissolution
   Entering Stream
   Leaving Streams
Spray Mater
Scrubber Liquid*
Scrubber Bottom
                      738  l/m1n
                      662  1/min
                       76  l/m1n
25.7
34.4
27.7
17,324
11,476
11,558
17,742
 1,121
Entering Streams
Leaving Streams
(Additive)
Spray Water
Scrubber Liquid*
Scrubber Bottom
2,800 g/min
738 1/min
662 1/min
76 1/min
13.9
14.4
32.1
.55
.59
.61
.36
1,540
6,052
5,815
878
Entering Streams
Leaving Streams
(Additive)
Spray Water
Scrubber Liquid*
Scrubber Bottom
2,800 g/min
738 1/min
662 1/min
76 1/min
13.9
14.4
32.1
.39
.215
.171
.280
1,092
2,206
1,630
683
18,967
22,773
 2,105
                      Rate of Ca(OH)2 Dissolution = Ca(liq) Out - Ca(liq) In + CaC03 + CaS04 2H20 + CaS03  1/2 H20  Form
                                                    = 24,878 - 18,967 + -985 - 899 - 1,021
                                                    = 3,006 m mole/mln
*Average of Marble bed front and back
ASame as the hold tank effluent
^Subtotal of scrubber bottom and scrubber liquid
                                                          H-9
-------
                               TABLE H-6.   RATE CALCULATION USING SOLID MATERIAL  BALANCE  (Continued)

                                                                                                             Total
                                                                Slurry     Concen.      Concen.     Concen.    Species
                                                                Solid      In Solid   In  Liquid   In  Gas   Flow Rate
                                          Stream Flow Rate   Cont. (g/1)  (m mole/g)   (m  mole/1)    CPfH)   m mole/min
Hold Tank (Set #1)

1. CaS03 1/2 H20 Formation

   Entering Liquid



   Leaving Streams
Scrubber Liquid
Make Up Water
Scrubber Bottom
Hold Tank Eff.
662 l/m1n
133 1/min
76 1/min
871 1/min
12.20
-
28.70
13.9
1.32
-
1.55
1.60
                                                                                      10,661

                                                                                       3,381

                                                                                      19,371
                      Rate of CaS03 1/2 HgO Formation = CaS03 1/2 H20 (Out)  - CaS03 1/2 H20 (In)

                                                      = 19,371  - 14,042

                                                      = 5,329 m moles/mln
2. S02 Oxidation

   Entering Streams
Scrubber Liquid
Scrubber Bottom
Make Up Water
   Leaving Streams    Hold Tank Eff.
662 1/min
 76 1/min
133 1/roin

871 1/min
                          28.6
                           7.9
                                                                                         15.7
                               18,933
                                  600
                                                                                      13,674
                      Rate of S02 Oxidation = S02 (liq.) In - S02 (liq.) Out - CaS03 1/2 HgO Formation Rate

                                            = 19,533 - 13,674 - 5,329

                                            = 530 m moles/min
3. CaS04 2H20 Formation
   Entering Streams
Scrubber Bottom T
Scrubber Liquid T
Make-Up Mater
   Leaving Streams    Hold Tank Eff.
 76 1/min
662 1/min
133 1/min

871 1/min
28.70
12.20
                                                               13.90
 .36
 .62
                                                        .66
  785
5,008


7,991
                      Rate of CaS04 2H20 Formation = CaS04 2H20 (Out) CaS04 2H20 (In)

                                                   = 7,991 - 5,793

                                                   = 2,198 m mole/min
4. CaC03 Formation

   Entering Streams
Scrubber Bottom T
Scrubber Liquid T
Make Up Water
 76 1/min
662 1/min
133 1/min
28.70
12.20
   Leaving Streams    Hold Tank Eff.        871 1/min          13.90

                      Rate of CaCCL Formation = CaCO, (Out) CaCO, (In)

                                              = 2,082 - 1,940

                                              = 142 m mole/min

5. Ca(OH)2 Dissolution

   Entering Streams   Scrubber Bottom T      76 1/min
                      Scrubber Liquid T     662 1/min
                      Make Up Water         133 1/min

   Leaving Streams    Hold Tank Eff.        871 1/min
.249
.173
                                                       .172
  543
1,397


2,082
                                                                   23,8
                                                                   35.3
                                                                   1.08

                                                                   24.5
                                                                  1.809
                                                                23,369
                                                                    144

                                                                21,340
                      Rate of Ca(OH)2 Dissolution = Ca(liq.) Out - Ca(liq.) In + (CaC03 + CaS04 2H20 + CaSOj 1/2

                                                  = 21,340 - 25,322 + (142 + 2,198 + 5,329)

                                                  = 21,340 - 25,322 + (7,669)

                                                  = 3,687 m moles/min
                                                          H-10
-------
                               TABLE H-6.   RATE CALCULATION USING SOLID MATERIAL BALANCE (Continued)

                                                                                                            Total
                                                               Slurry     Concen.     Concen.    Concen.   Species
                                                               Solid      In Solid   In Liquid   In Gas   Flow Rate
                                          Stream  Flow Rate   Cont. fg/1)  (m mole/g)  On mole/1)   (PPH)   m mole/mln
                                                                                                           15,192

                                                                                                           12,315
                                                                                                            4.235
Marble Bed (Set #2)


1 . CaS03 1/2 H20 Formation
Entering Streams
Leaving Streams



2. S02 Oxidation
Entering Streams
Leaving Streams



Scrubber Spray 738 1/mln 14.60 1.41
Scrubber Liquid* 662 1/mln 15.9 1.17
Scrubber Bottom 76 1/min 41.90 1.33
Rate of CaS03 1/2 Formation = CaS03 1/2 H20 (Out) - CaS03 1/2
= 16,550 - 15,192
= 1,358 m mole/ml n
Inlet Flue Gas 9,120 g mole/ml n
Scrubber Spray 738 1/mln
Outlet Flue Gas 10,487 g mole/mi n
Scrubber Liquid* 662 1/min
Scrubber Bottom 76 1/mln
Rate of S02 Oxidation = S02 (In) - S02 (Out) - CaS03 1/2 H20
= 28,334 - 29,970 - 1,358
= -2,994 m mole/ml n


H20 (In)


15.15
25.90
13.65
Formation Rate


3. CaS04 2H20 Formation
Entering Streams
Leaving Streams



4. CaCO. Formation
Entering Streams
Leaving Streams



Additive 2.800
Spray Water 738 1/mln 14.60
Scrubber Liquid* 662 1/mln 15.90
Scrubber Bottom 76 1/mln 41.90
Rate of CaS04 2H20 Formation = CaS04 2H20 (Out) - CaS04 2H20
= 7,454 - 8,004
= - 550 m mole/mi n
Additive 2,800 g/mln .39
Spray Water 738 1/min 14.60 .18
Scrubber Liquid* 662 1/mln 15.90 .22
Scrubber Bottom 76 1/mln 41.90 .402
Rate of CaC03 Formation = CaC03 (Out) - CaC03 (In)
= 3,596 - 3,031
= 565 m mole/ml n
0.55
.60
.56
.49°
(In)







5. Ca(OH)2 Dissolution
Entering Stream
Leaving Stream
Spray Water 738 1/min
Scrubber Liquid* 662 1/m
Scrubber Bottom 76 1/mln
25.2
34.7
27.6
                                                                                                 1,881


                                                                                                 1.124
17,154
11,180

11,787
17,146
 1,037
                                                                                                              1,540
                                                                                                              6,464

                                                                                                              5,894
                                                                                                              1,560
                                                                                                             1,092
                                                                                                             1,939

                                                                                                             2,316
                                                                                                             1.280
"Same as scrubber bottom at tank
                                                                                                            18,598

                                                                                                            22,971
                                                                                                             2.098

                      Rate of Ca(OH)2 Dissolution = Ca(11q.)  Out - Ca(11q.)  In + CaCOj + CaS04 2HgO + CaSOj 1/2 HgO Form

                                                  = 25,069 -  18,598 + (565 - 550 + 1,358)

                                                  = 25,069 -  18,598 + (1,373)

                                                  • 7,844 m mole/ml n

                                                         H-ll
-------
                               TABLE H-6.  RATE CALCULATION USING SOLID MATERIAL BALANCE (Continued)
                                                                Slurry     Concen.     Concen.    Concen.
                                                                Solid      In Solid   In Liquid   In Gas
                                          Stream Flow Rate   Cont. (g/1)  (m mole/g)  (m mole/1)   (PPH)
Hold Tank (Set #2)
1. CaS03 1/2 H20 Formation
Entering Streams
Scrubber Liq. T
Scrubber Bottom
Hake Up Water
662 1/min
76 1/min
133 l/m1n
13.0
33.0
1,20
1.47
    Leaving Streams    Hold Tank Eff.
                      871 I/rain
14.90
1,45
                      Rate of CaS03 1/2 H£0 Formation = CaS03 1/2 HgO (Out) - CaS03 1/2 H20 (In)
                                                      = 18.818 - 14,014
                                                      = 4,804 m mole/min
 2.  S02 Oxidation
    Entering Streams   Scrubber Liquid T     662 1/min
                      Scrubber Bottom T      76 1/min
                      Make Up H^O           133 1/min
    Leaving Streams    Hold Tank Eff.        871 1/min
                                                                  27.31
                                                                    4.5
                                                                  15.Q5
                      Rate of S02 Oxidation = S02 (liq) In - S02 (liq) Out - CaS03 1/2 H20 Form Rate
                                            = 18,421 - 13,109 - 4,804
                                            = 508 m mole/min
3. CaS04 2H20 Formation
   Entering Streams   Scrubber Bottom T      76 1/min           33.0          .49
                      Scrubber L1q. T       662 1/min           13.0          .62
                      Nake Up Water         133 l/m1n
   Leaving Streams    Hold Tank Eff     '    871 1/min          14.90          .60
                      Rate of CaS04 2H£0 Formation - CaS04 2H20 (Out] - CaS04 2H20 (In)
                                                   = 7,787 - 6,564
                                                   = 1,223 m mole/min
4. CaCO, Formation
   Entering Streams   Scrubber Bottom        76 1/raln
                      Scrubber Liquid       662 l/m1n
                      Make Up Uater         133 1/min
   Leaving Streams    Hold Tank Eff.
                                          33.0
                                          13.0
                      871 1/min           14.9
Rate of CaC03 Formation = CaC03 (Out) - CaC03 (In)
                        = 2,453 - 2,485
                        = - 32 m mole/rain
              .339
               .19
              .189
5. Ca(OH)2 Dissolution
   Entering Streams   Scrubber Liq T        662 1/min
                      Scrubber Bottom T      76 l/m1n
                      Make Up Uater         133 1/min
   Leaving Streams    Hold Tank Eff.        871 1/min
                                                                   35.3
                                                                   22.2
                                                                   1.08
                                                                   25.5
                                                                                       Total
                                                                                      Species
                                                                                     Flow Rate
                                                                                     m mole/min
                                                                                                            10,327
                                                                                                             3,687
18,818
                                             18,079
                                                342
                                             13,109
                                                                                       1,228
                                                                                       5,336
                                                                                       7,787
                                  850
                                1,635
                                2,453
                      Rate of Ca(OH)2 Dissolution = Ca(liq) Out - Ca(liq) In + (CaC03 + CaS04 2H20 + CaS03
                                                  = 22,211 - 25,200 + (-32 * 1,223 +
                                                  = 3,006 m mole/min
                                                          H-12
                                             23,369
                                              1,687
                                                144
                                             22,211
                                            1/2 H20)
-------
                                TABLE H-7.   RATE CALCULATION USING SOLID MATERIAL BALANCE

                                                      Experiment  20R

                                                                                                             Total
                                                                 Slurry     Concert.     Concen.     Concen.   Species
                                                                 Solid      In Solid    In Liquid    In Gas    Flow  Rate
                               	  Stream flow Rate  Cont. (a/11   On mole/al   (m mole/1}    CPPHj    m mole/ml n
 Marble Bed (Set #1)

 1. CaS03 1/2 H20 Formation


    Entering Stream    Scrubber Spray

    Leaving Stream     Scrubber Spray
                       Scrubber Bottom
                       757  1/mln

                       681  1/nln
                        76  1/mln
                       6.94

                       9.25
                       25.3
1.42

1.01
1.20
                       Rate of CaS03   1/2  H20 Formation = CaS03  1/2 H20 (Out) - CaS03  1/2 H20 (In)

                                                       = 8669 - 7460

                                                       = 1209 m mole/mln
 2. S02 Oxidation

    Entering Stream


    Leaving  Stream
 Inlet Flue  Gas
 Scrubber Spray

 Outlet Flue Gas
 Scrubber Liquid
 Scrubber Bottom
 9,400 g mole/rain
   757 l/m1n

10.850 g mole/mln
   631 1/mln
    76 1/mln
                       Rate of Oxidation of S02 = S02 (In) - S02 (Out) - CaS03  1/2 H20 Formation Rate

                                               = 24,423 - 22,657 - 1,209

                                               • 557 m mole/mln
3. CaS04  2 H20  Formation
                      Rate of CaS04  2 HgO Formation = CaS04  2 H20 COut) - CaS04  2 H20 (In)

                                                     = 3,721 - 4,447

                                                     • - 725 m mole/mln
4. CaCOj Formation
                      Rate of CaC03 Formation = CaCOj COut) - CaC03 (In)

                                              = 1,613 - 2,225

                                              • - 612 m mole/mln

5. Ca(OH) Oissolutlon

   Entering Stream    Scrubber Spray        757 1/mln
   Leaving Stream
Scrubber Liquid
Scrubber Bottom
  681  1/mln
   76  1/mln
           •23.4

            32.3
            26.1
 7,460

 6,362
 2,307
7.9
15.00
8.1
1,962
1,090
18,443
5,980
11,826
10,215
616
Entering Stream
Leaving Stream
Additive
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
2,600 g/raln
757 l/rn1n
681 1/rnin
76 1/ntin
6.94
9.25
25.3
0.5
0.58
0.49
0.33
1,400
3,047
3,087
635
Entering Stream
Leaving Stream
Additive
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
2,800 g/mln
757 l/m1n
681 l/m1n
76 l/m1n
6.94
9.25
25.3
0.455
0.181
0.180
0.249
1,274
951
1,134
479
17,714

21.996
 1,984
                      Rate of Ca(OH)2 Dissolution = Ca(Hq) Out -'Ca(llq) In + (CaCOj -f CaS04  2 HjO + CaSOj  1/2

                                                  = 23,980 - 17,714 + - 612 + - 725 + 1209

                                                  = 6,138 m moles/min

                                                          H-13
-------
                             TABLE H-7.  RATE CALCULATION USIN6 SOLID MATERIAL  BALANCE (.Continued)



Stream Flow Rate
Total
Slurry Concen. Concen. Concen. Species
Solid In Solid In Liquid In Gas Flow Rate
Cent, (g/1) (m mole/g) (m mole/1) (PPM) m mole/mi n
Hold Tank (Set #1)
1.




2.

CaSOj 1/2H20
Entering Stream
Leaving Stream



S02 Oxidation
Entering Stream
Leaving Stream
Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
Makeup Water
Hold Tank Eff.
Rate of CaS03 1/2


Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
Makeup Water
Hold Tank Effluent
681 1/min
76 1/min
151 l/m1n
151 l/m1n
1,059 1/min
Formation = CaS03
= 11,254
= 3,707 m
681 1/min
76 1/min
151 1/rnln
151 1/min
1,059 1/min
Rate of S02 Oxidation = S02 (In) - S02



= 11,464 - 7,890
7.33 1.00
22.7 1.47
0.13 0.93
7.38 1.44
1/2 H20 (Out) - CaS03 1/2 H20 (In)
- 7,547
mole/ml n
15.6
1.01
5.05
7.45
(Out) - CaS03 1/2 H20 Form Rate
- 3,707
4,992
2,536
19
11,254



10,624
77
763
7,890


= - 133 m mole/ml n
3.




4.

CaS04 2 H20 Formation
Entering Stream
Leaving Stream



CaC03 Formation
Entering Streams
Leaving Stream
Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
Makeup Water
Hold Tank Effluent
Rate of CaS04 2 H-


Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
Makeup Mater
Hold Tank Effluent
681 1/min
76 1/min
157 I/rain
151 1/min
1,059 1/nvin
,0 Formation = CaS04
= 4,767
= 1,133
681 1/min
76 I/rain
151 l/m1n
151 1/min
1,059 1/min
Rate of CaCOj Formation = CaC03 (Out)
7.33 0.61
22.7 .33
0.13
7.38 0.61
2 H20 (Out) - CaSO, 2 HgO (In)
- 3,634
m mole/mi n
7.33 0.195
22.7 0.355
0.13
7.38 0.201
- CaC03 (In)
3,045
569
20
4,767



973
612
20
1.571

= 1,571 - 1,605
= -34 m mole/mi n

Ca(OH)2 Dissolution
Entering Stream
Scrubber Liquid
Scrubber Bottom
Clarlfier Liquid
Makeup Mater
681 1/min
76 l/m1n
151 1/min
151 1/min
31.6
21.6
22.1
1.08
21,520
1,642
3,337
163
Leaving Stream     Hold Tank Effluent  1,059 1/min
23.6
24,992
                   Rate of Ca(OH)2 Dissolution = Ca(liq) Out - Ca(liq) In + (CaS04  2 HgO + CaC03 + CaS03  1/2 H20)
                                               = 24,992 - 26,662 + 1,133 - 34 + 3,707
                                               = 3,136 m nwle/min
                                                        H-14
-------
Marble  Bed  (Set #2)
1.  CaS03  1/2 H20 Formation
    Entering Stream    Scrubber Spray
    Leaving Stream     Scrubber Liquid
                      Scrubber Bottom
                               TABLE H-7,  RATE CALCULATION USING SOLID MATERIAL BALANCE (Continued)
                                                                                                             Total
                                                                Slurry     Concen.      Concen.     Concen.    Species
                                                                Solid      In Solid   In Liquid   In Gas   Flow Rate
                              	  Stream Flow Rate   Cont. (g/1)  fm role/g)   (m mole/1)    (PPH)   m mole/mln
                      757 l/m1n
                      681 1/min
                       76 l/m1n
                      6.99
                      8.00
                      22.6
             1.28
             0.95
             1.16
                      Rate of CaS03  1/2 H20 Formation » CaS03  1/2 HgO (Out)- CaSOj  1/2 HgO (In)
                                                       = 7,168 - 6,773
                                                       • 395 m mole/mtn
2.
S02 Oxidation
Entering Stream
Leaving Stream
Inlet Flue Gas
Scrubber Spray
Outlet Flue Gas
Scrubber Liquid
Scrubber Bottom
9,400 g mole/mln
757 1/mln
10,850 g mole/mln
681 1/mln
76 1/mln
                                                                                         10.2
                                                                                        16.85
                                                                                        12.00
                                                                            1,939

                                                                            1,090
                      Rate of S02 Oxidation = S02 Hq (In) - S02 llq (Out) - CaS03  1/2 H20 Formation
                                            = 25,948 - 24,214 - 395
                                            * 1,339 m mole/mtn
3. CaS04  2 H20 Formation
   Entering Stream
   Leaving Stream
Additive
Scrubbing
Scrubber Liquid
Scrubber Bottom
2,800 g/m1n
  757 l/m1n
  681 1/mln
   76 l/m1n
6.99
8.00
22.6
0.50
0.51
0.28
0.32°
                      Rate of CaS04  2 H20 Formation = CaS04  2 H20 (Out) - CaS04  2 H20 (In)
                                                     = 2,075 - 4,099
                                                     » - 2,024 m mole/mtn
4. CaC03 Formation
Entering Stream
Leaving Stream
Additive
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
2,800 g/mtn
757 1/mtn
681 1/mln
76 1/mtn
6.99
8.00
22.6
0.455
0.192
0.205
0.299
                      Rate of CaC03 Formation = CaC03 (Out) - CaC03 (In)
                                              = 1,630 - 2,290
                                              = - 660 m moles/mtn
5. Ca(OH)2 Dissolution
   Entering Stream
   Leaving Stream
Scrubber Spray        757
Scrubber Liquid       681
Scrubber Bottom        76
                                   26.6
                                   33.4
                                   30.0
                                6,773
                                5,176
                                1,992
                                                                  18,227
                                                                   7,721
                                                                  11.827
                                                                  11,475
                                                                     912
1,400
2,699
1,525
  550
                                                                                                             1,274
                                                                                                             1,016
                                                                                                             1,116
                                                                                                               514
                                            20,136
                                            22,745
                                             2,280
                      Rate of Ca(OH)2 Dissolution = Ca(ltq) Out - Ca(ltq) In + (CaC03 + CaS03 /1/2 HgO + C«S04  2 H20)
                                                  = 25,025 - 20,136 + - 660 + 395 + - 2,024
                                                  • 2,600 m moles/mtn
"Scrubber bottom of tank was used
                                                         H-15
-------
                            TABLE H-7.  RATE CALCULATION USING SOLID MATERIAL BALANCE  (Continued)
Slurry Concert. Concert. Concen
Solid In Solid In Liquid In Gas
Stream Flow Rate Cont. (g/1) (m mole/g) (m mole/1) (PPM)
Total
Species
Flow Rate
m mole/ml n
Hold Tank (Set #2}
1.

CaS03 1/2 H20 Formation
Entering Streams
Leaving System
Scrubber Liquid
Scrubber Bottom
Clarlfier Liquid
Makeup Water
Hold Tank Effluent 1
681 l/m1n
76 1/min
151 l/m1n
151 1/nrin
,059 l/m1n
Rate of CaS03 1/2 H20 Formation = CaS03


2.




3.




4.



S02 Oxidation
Entering Streams
Leaving Stream





Scrubber Liquid
Scrubber Bottom
Clarlfier Liquid
Makeup Mater
Hold Tank Effluent 1
Rate of S0~ Oxidation


= 9,155
= 2,681
681 1/min
76 1/min
151 1/min
151 1/min
,059 1/min
= S02 (liq) In - SO
= 13,796 - 10,855 -
= 260 m mole/mi n
7.07 0.94
20.5 1.25
6.65 1.30
(Out) - CaS03 In
- 6,474
m mole/mi n
18.3
2.85
7.4
10.25
2 (I1q) Out - CaS03 1/2 H20 Formation
2,681

4,526
1,948
9,155



12.462
217
1,117
10,855



CaS04 2 H20 Formation
Entering Streams
Leaving Stream



CaCOj Fonnation
Entering Stream
Leaving Stream
Scrubber Liquid
Scrubber Bottom
Hold Tank Effluent 1
Rate of CaS04 .2 H20


Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
Makeup Water
Hold Tank Effluent 1
681 1/min
76 1/min
,059 1/min
Formation = CaS04 .2
= 4,436 -
= 1,392 m
681 1/min
76 1/min
151 1/min
151 1/min
,059 1/min
7.07 .49
20.5 .44
6.65 .63
H20 (Out) - CaS04 .2 HjO (In)
3,044
mole/mi n
7.07 .173
20.5 .311
6.65 0.217
2,359
685
4,436



833
485
1,528
Rate of CaCO, Formation = CaCO, (Out) - CaCO, (In)


5.




= 1,528 - 1,318
= 210 m moles/min




Ca(OH)2 Dissolution
Entering Stream
Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
Makeup Water
681 1/min
76 1/min
151 1/min
151 1/min
33.9
24.7
22.9
1.08
23,086
1,877
3,458
163
Leaving Stream     Hold Tank Effluent  1,059 1/min
25.9
27,428
                   Rate of Ca(OH)2 Dissolution = Ca(Hq)  Out - Ca(liq)  In + CaC03  +  CaS04  .2  H20  +  CaS03  .1/2
                                               = 27,428 - 28,584 + 210  +  1,392  + 2,681
                                               = 3,127 m  mole/rrrln
                                                       H-16
-------
                           TABLE H-8.  RATE CALCULATIONS USING LIQUID MATERIAL BALANCE
                                                 Experiment 17R
Marble Bed (Set SI)

1. CaS03 . 1/2 H20

   Entering Streams   Inlet Flue Gas
                      Scrubber Spray
                                        Stream Flow Rate
                                                              Species  Cone.       Species  Cone.
                                                            in Liq-.  (nrmolt/1)    In  Gas  (ppm)
                                                                           Species  Flow Rate
                                                                             (m mole/nrin)
                                        10.950 g mole/min
                                           431 1/min
    Leaving Streams
Outlet Flue Gas   11,605 g mole/mln
Scrubber Liquid*     329 1/mln
Scrubber Bottoms     102 1/mln
                                               1.0
                                                                    8.95
                                                                     1.0
1,456
764
15,943
431
8,866
2,944
102
                      Rate of CaS03   1/2 HgO = S02 IN - S02 OUT » Oxidation Rate

                                              = 15,943 + 431 - 8,866 - 2,944 - .439 (15,943 - 8.866) - 102

                                              = 4,462 - 3,107

                                              = 1,355 m mole/rain
2. CaS04  2
   Entering Streams   Scrubber Spray
   Leaving Streams
Scrubber Liquid*
Scrubber Bottom
                                           431  l/ra1n

                                           329  l/m1n
                                           102  1/min
10.27

14.46
11.61
4,426

4.757
1,164
                      Rate of CaS04   2 H20 = S04 (Liq.) IN - S0fl (L1q.) OUT + Oxidation Rate

                                            = 4,426 - 5,941 + 3,107

                                            = 1,592 m mole/ml n
3.  Ca(OH)2 Dissolution


    Entering Streams  Scrubber Spray       431  l/m1n

    Leaving Streams   Scrubber Liquid*     329  1/mln
                      Scrubber Bottom      102  1/mln
                                                                    13.7

                                                                    19.0
                                                                    16.8
                                                                                 5,905

                                                                                 6,251
                                                                                 1,714
                      Rate of Ca{OH)2 Dissolution = Ca OUT - Ca IN 4 Ca Free.  Rate

                                                  = 7,965 - 5.905 + 2,947

                                                  = 5,097 in mole/mln
*Ave. of Marble Bed Front and Back
                                                       H-17
-------
                           TABLE H-8.   RATE CALCULATIONS USING LIQUID MATERIAL BALANCE (Continued)
                                        Stream Flow Rate
                                                  Species  Cone.
                                                 in  Liq.  (m mole/1)
                                                                              Species  Cone.
                                                                              in  Gas  (ppm)
                              Species Flow Rate
                                (m mole/mln)
Hold Tank

1. CaSO,
1/2 H20
   Entering Streams
           Scrubber Liquid
           Scrubber Bottom
           Make Up H0
Leaving Streams    Hold Tank Eff.

                   Rate of CaSO,
2. CaS04   2H20


   Entering Streams
   Leaving Streams
           Scrubber Liquid
           Scrubber Bottom
           Make Up H20

           Hold Tank Eff.
     329 1/min
     102 1/min
     208 I/rain

     631 1/min

1/2 H20 = S02 IN - S02 OUT

        = 3,030 - 947

        = 2,083 m mole/min
                                        329 1/min
                                        102 1/min
                                        208 1/min
                                        631  1/min

                   Rate of CaS04   2H20 = S04 (IN)  - S04  (OUT)

                                        = 5,937 - 5,931

                                        = 6  m mole/min
3. CaC03

   Entering Streams   Scrubber Liquid.
                      Scrubber Bottom
                      Make Up H20

   Leaving Streams    Hold Tank Eff.

                      Rate of CaC03 = C03 IN - C03 OUT

                                    = 390 - 164

                                    = 226 m mole/min
                                329 1/min
                                102 1/min
                                208 1/min

                                631 1/min
4. Ca(OH)2 Dissolution


   Entering Streams
   Leaving Streams
           Scrubber Liquid
           Scrubber Bottom
           Make Up H20

           Hold Tank Eff.
                                        329 1/min
                                        102 1/min
                                        208 1/min
                                                                 8.9
                                                                 1.0
                                                                     1.5
14.85
 10.3
                                                                     9.4
                                                                  1.1
                                                                  .27
                                                                  .26
 19.9
 17.4
 1.08

 11.7
                                        631  1/min

                   Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec.  Rate

                                               = 7,383 - 8,547 + (226 + 6 + 2,083)

                                               = 1,151 m mole/min
 +Values from Marble Bed Front and Back
++Values from Scrubber Bottom at Scrubber
                                    2.928
                                      102
                                                                                              947
                                                                 4,886
                                                                 1,051
                                    5,931
                                      362
                                       28
                                                                                                      164
                                                                 6,547
                                                                 1,775
                                                                   225

                                                                 7,383
                                                        H-18
-------
                           TABLE H-8.  RATE CALCULATIONS USING LIQUID MATERIAL BALANCE (Continued)
Species Cone.
Stream Flow Rate 1n L1g. (m mole/1)
Marble Bed (Set 42)
1. CaS03 1/2 H20
Entering Streams
Leaving Streams
Inlet Flue Gas
Scrubber Spray
Outlet Flue Gas
Scrubber Liquid
Scrubber Bottom
10,950 g mole/rain
431 1/mln
11,605 g mole/mln
329 l/m1n
102 l/m1n
1.3
7.2
1.7
Species Cone. Species Flow Rate
1n Gas (ppm) (m mole/mln)
1.456 15,943
560
764 8,866
2,369
173
                      Rate of CaS03   1/2 H20 = S02 IN - S02 OUT - OXID.  Rate
                                              = 16,503 - 11,408 - .417 (7,077)
                                              = 16,503 - 11,408 - 2,951
                                              = 2,144 m mole/mln
2. CaS04   2H20
   Entering Streams
   Leaving Streams
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
Rate of CaSO.
431 1/mln
329 l/m1n
102 l/m1n
 9.38
15.37
 11.3
                                      2H20 = S04  IN - S04 OUT + OXID. Rate
                                           = 4,043  - 6,210 +  2,951
                                           = 784  m  mole/mln
3. Ca(OH)2 Dissolution
   Entering Streams   Scrubber Spray
   Leaving Streams
Scrubber Liquid
Scrubber Bottom
431 l/m1n
329 l/m1n
102 l/m1n
 12.8
 19.1
 16.3
                      Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec. Rate
                                                 = 7,947 - 5,517 + (784 + 2,144)
                                                 = 5,358 m mole/mln
4,043
5.057
1,153
5,517
6.284
1.663
                                                      H-19
-------
                            TABLE  H-8.   RATE CALCULATIONS USING LIQUID MATERIAL BALANCE  (Continued)
                                         Stream  Flow  Rate
                                                           Species Cone.
                                                         in Lid, (m mole/1)
Hold Tank
1.




2.


CaS03 1/2 H20
Entering Streams
Leaving Streams



CaS04 2 H20
Entering Streams
Leaving Streams

Scrubber Liquid
Scrubber Bottom
Make Up H20
Hold Tank Eff.
Rate of CaS03


Scrubber Liquid
Scrubber Bottom
Make Up HgO
Hold Tank Eff.
Rate of CaSO.
329 1/min
102 1/min
208 1/min
631 1/min
1/2 H20 = S02 IN - S02 OUT
= 3,139 - 946
= 2,193 m mole/mi n
329 1/min
102 1/min
208 1/min
631 1/min
2 H20 = S04 IN - S04 OUT
9.2
1.1
1.5



12.75
11.64
9.4

                                      Species Cone.
                                      in Gas (ppiti)
                            Species Flow Rate
                              (m mole/mln)
3. CaCO,
   Entering Streams
                   Scrubber Liquid
                   Scrubber Bottom
                   Make Up HO
Leaving Streams    Hold Tank Eff.
                                            = 5,382 - 5,931

                                            = - 549 m mole/min
329 1/min
102 1/min
208 1/min

631 1/min
.96
.06
                                                                     .26
                      Rate of CaC03 = C02 IN - C02 OUT

                                    = 322 - 164

                                    = 158 m mole/rain

4. Ca(OH)2 Dissolution


   Entering Streams   Scrubber Liquid      329 1/min
                      Scrubber Bottom      102 1/min
                      Make Up H20          208 1/min

   Leaving Streams    Hold Tank Eff.        631 1/min
                                                                 19.6
                                                                 17.6
                                                                 1.08

                                                                 11.7
                      Rate of Ca(OH)2 Dissolution = Ca OUT Ca IN + Ca Free. Rates

                                                  = 7,383 - 8,468 + (158 - 549 + 2,193)

                                                  = 717 n mole/min
                                                                                                       3,027
                                                                                                         112
                                                                                                         946
                                                                                                       4,195
                                                                                                       1,187
                                                                                                       5,931
316
  6
                                                                                                         164
                                                            6,448
                                                            1,795
                                                              225

                                                            7,383
                                                       H-20
-------
                               TABLE H-9.  RATE CALCULATIONS USING LIQUID BALANCE

                                                   Experiment  18R
                                        Stream Flew Rate
                                        Spectes Cone.
                                      tn Ltt. fa mole/1)
                                         Species Cone.
                                         tn Gai (p0m)
 Marble  Bed  (Set  #1)

 1.  CaS03    1/2 H20

    Entering Streams


    Leaving  Streams
2. CaSOj,
   Entering Streams

   Leaving Streams
Inlet Flue Gas
Scrubber Spray

Scrubber Liquid*
Scrubber Bottom
Outlet Flue Gas
10,820 g mole/mln
   796 1/mln

   682 l/m1n
   114 l/m1n
11,630 g mole/mln
  .35

 2.95
  .45
                  1,471
                                                                                       447
                      Rate of CaS03   1/2 H20 = 502 IN - S02 OUT - Oxidation Rate

                                              = 16,195 - 7,262 - .279 (15,916 - 5,199)

                                              = 8,933 - 2,990 -

                                              = 5,943 m mole/mln
Scrubber Spray

Scrubber Liquid*
Scrubber Bottom
   796 1/mln

   682 I/rain
   114 1/mln
18.15

24.34
19.09
                      Rate of CaSO,
                2H20
     S04 IN - S04 OUT + Oxidation Rate

   = 14,447 - 18,776  + 2,990

   = -1,339 m mole/min
3. Ca(OH)2 Dissolution

   Entering Streams

   Leaving Streams
Scrubber Spray

Scrubber Liquid*
   796 1/mln

   682 1/m1n
   114 1/mln
22.52

24.45
24.42
                      Scrubber Bottom

                      Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN t Ca Prec. Rates

                                                  = 19,459 - 17,926 + (-1,339 + 5,943)

                                                  = 6,137 m mole/mln
                              Species Flow Rate
                                Cm mole/mln)
15,916
   279

 2,012
    51
 5,199
14,447

16,600
 2,176
17,926

16,675
 2,784
*Ave. of Marble Bed Front and Back
                                                       H-21
-------
                               TABLE H-9.  RATE CALCULATIONS USING LIQUID BALANCE (Continued)
                                        Stream Flow Rate
                                                              Species Cone.
                                                            In L1q.  (m mole/I)
                                                                              Species Cone.
                                                                              ^n 6as
Hold Tank

1.  CaSO,
    Entering Streams
    Leaving Streams
Scrubber Liquid
Scrubber Bottom
Clarified Liquid

Hold Tank Eff.

Rate of CaSO,
                                           682 1/mtn
                                           114 l/m1n
                                            76 I/rain

                                           872 I/rain
                                                                 2.57
                                                                  .89
                                                                  .56
                                                                  .53
                                      1/2
2. CaSO,
           2H20
Leaving Streams    Hold Tank Eff.

                   Rate of CaSO.
3. CaC03 (No C02 Data are Available)
                                              Form = S02 IN - S02 OUT

                                                   = 1,897 - 462

                                                   = 1 ,435 m mcle/min
Entering Streams
Scrubber Liquid
Scrubber Bottom
Clarified Liquid
682 1/min
114 1/min
76 1/min
872 1/min

= S04 IN - S04 OUT

= 16,840 - 15,129

= 1,711  m mole/min
                                                                   19.98
                                                                   17.20
                                                                   16.49

                                                                   17.35
                                                      Species Flow Rate
                                                        fan
                                                            1,753
                                                              101
                                                               43

                                                              462
                                                                                                      13,626
                                                                                                       1,961
                                                                                                       1,253

                                                                                                      15,129
1. Ca(OH)2 Dissolution
   Entering Streams   Scrubber Liquid      682 1/min
                      Scrubber Bottom      114 1/min
                      Clarified Liquid      76 1/min
                                                                   21. Z5
                                                                   32.72
                                                                    20.6
   Leaving Streams    Hold Tank Eff.        872 1/min               22.97

                      Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec.  Rates

                                                  = 20,030 - 19,789 + (3,146)

                                                  = 3,387 IT mole/min
                                                                                                   14,493
                                                                                                    3,730
                                                                                                    1,566

                                                                                                   20,030
                                                      H-22
-------
                                TABLE H-9.   RATE CALCULATIONS  USING LIQUID BALANCE  (Continued)
 Marble Bed (Set 2)

 1. CaS03   1/2 H20

    Entering Streams   Inlet Flue  Gas
                       Scrubber Spray
                                         Stream Flow Rate
                                                   Species Cone.
                                                 1n Ltg. (
                                         Species Cone.
                                         tn Gas (ppm)
                                Species  Flow Rate
                                  to nole/roln)
    Leaving Streams
           Outlet Flue Gas
           Scrubber Liquid
           Scrubber Bottom
10,820 g mole/mln
   796 l/m1n

11,630 g mole/mln
   682 1/min
   114 l/m1n
                                                          .38
                                                                   4.175
                                                                     .42
                   1,471


                     447
                       Rate of  CaS03    1/2 H20 = S02  IN - S02 OUT - Oxidation Rate

                                              = 16,218 - 8,094 - .289 (10,717)

                                              = 16,218 - 8,094 - 3,097

                                              = 5,027 m mole/mln
 2.  CaSO,
2H20
    Entering Streams

    Leaving Streams
           Scrubber Spray

           Scrubber Liquid*
           Scrubber Bottom
   796 1/min

   682 1/nrin
   114 l/m1n
 19.67

 25.15
 19.02
                      Rate of CaS04   2H20 - S04 IN - S04 OUT + Oxidation Rate

                                           = 15,657 - 19,320 + 3,097

                                           = -566 m mole/mln
3. Ca(OH)2 Dissolution

   Entering Streams

   Leaving Streams
           Scrubber Spray

           Scrubber Liquid*
           Scrubber Bottom
  796 1/mln

  682 1/mln
  114 1/mln
 23.25

26.495
 24.95
                      Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Free.  Rate

                                                  = 20,914 - 18,507 + (4461)

                                                  = 6,868 m mole/mln
15,916
   302

 5,199
 2,847
    48
15,657

17,152
 2,168
18,507

18,070
 2,844
*Ave. of Marble Bed Front and Back
                                                     H-23
-------
                               TABLE H-9.  RATE CALCULATIONS USING LIQUID BALANCE (Continued)
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    1n L1q. (m mole/1)   In Gas fppm)      (m mole/mini
 Hold  Tank

 1.  CaS03    1/2 H20

    Entering Streams
        Scrubber Liquid
        Scrubber Bottom
        Clarified Liquid
   Leaving Streams    Hold Tank Iff.
682 1/mln
114 1/mln
 76 1/mln

872 l/m1n
 3.25
  .72
  .40
                                                       .55
                      Rate of CaS03   1/2 H20 Form = S02 IN - S02 OUT

                                                   = 2,329 - 480

                                                   = 1,849 m mole/mln
2. CaSO.   2 H
2°
.Entering Streams


Scrubber Liquid
Scrubber Bottom
Clarified Liquid
682 l/m1n
114 l/m1n
76 1/min
20.46
18.51
16.96
   Leaving Streams    Hold Tank Eff.       872 l/m1n               18.68

                      Rate of CaS04   2H20 Form = S04 IN - S04 OUT
                                                = 17,353 - 16,289

                                                = 1,064 m mole/min
3. CaC03 (No C02 Data Was Available)

4. Ca(OH)2 Dissolution
   Entering Streams
        Scrubber Liquid
        Scrubber Bottom
        Clarified Liquid
682 1/mln
114 1/mln
 76 1/mln
22.17
34.30
22.35
   Leaving Streams    Hold Tank Eff.
                             872 1/mln                24.20

        Rate  of Ca(OH)2 Dissolution = Ca  OUT -  Ca  IN + Ca Free.  Rates

                                    = 21,102 -  20,729 t 2,913

                                    = 3,286  m mole/min
 2,217
    82
    30

   480
                                                                                        13,954
                                                                                         2,110
                                                                                         1,289

                                                                                        16,289
15,120
 3,910
 1,699

21,102
                                                      H-24
-------
                               TABLE H-10.  RATE CALCULATIONS USING LIQUID BALANCE

                                                  Experiment 19R
 Marble Bed (Set #1)

 1. CaS03   1/2 H20

    Entering Streams  Inlet Flue Gas
                      Scrubber Spray
                                         Stream Flow Rate
                                                   Species Cone.
                                                 in Llq.  fin mole/1)
                                         Species Cone.
                                         In Gas (pom)
    Leaving Streams
          Outlet Flue Gas
          Scrubber Liquid*
          Scrubber Bottom
 9,200 g mole/mln
   738 l/m1n

10,555 g mole/m1n
   662 l/m1n
    76 1/mln
                                                        15.55
                                                                    26.85
                                                                    14.75
                  1,884


                  1,060
                      Rate of CaS03-   1/2  HgO = S02  IN -  S02 OUT - OXIO. Rate

                                             = 28,809 -  30,084 - .533  (17,333  - 11,188)

                                             = - 4,550 m mole/min
 2.  CaSO.
2 H20
    Entering  Streams   Scrubber Spray
    Leaving  Streams
          Scrubber Liquid*
          Scrubber Bottom
   738 1/min

   662 l/m1n
    76 1/min
20.35

26.45
24.45
                     Rate of CaS04 = S04  IN - S04 OUT + OX ID. Rate

                                   = 15,018 - 19,368 + 3,275

                                   = - 1,075 m mole/mln
3. Ca(OH)2 Dissolution


   Entering Streams  Scrubber Spray
   Leaving Streams
          Scrubber Liquid*
          Scrubber Bottom
  738  1/min

  662  l/m1n
   76  1/min
 25.7

 34.4
 27.7
                     Rate of Ca(OH)2 Dissolution = CA OUT - Ca IN + Ca Prec. Rates

                                                 = 24,878 - 18,967 + - 4,550 - 1,075

                                                 = 286 m mole/mln
                              Species  Flow  Rate
                                 On mole/min)
17,333
11,476

11,188
17,775
 1,121
15,018

17,510
 1,858
18,967

22,773
 2,105
*Ave. of Marble Bed Front and Back
                                                       H-25
-------
                              TABLE H-10.  RATE CALCULATIONS USING LIQUID BALANCE  (Continued)
  Hold  Tank

 1.  CaS03    1/2 H20

    Entering  Streams  Scrubber Liquid
                     Scrubber Bottom
                     Make Up H20

    Leaving Streams   Hold Tank Eff.
                                        Stream Flow Rate
                                                   Species Cone.
                                                 1n Llg.  (m mole/1)
                                662 l/m1n
                                 76 1/mln
                                133 1/mln
                                871  1/mln

          Rate of CaS03   1/2 H20 =  S02 IN - S02 OUT

                                  =  19,533 - 13,675

                                  =  5,858 m mole/rain
2. CaSO,
2 H20
   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Make Up H20

   Leaving Streams   Hold Tank Eff.
                                662 1/mln
                                 76 1/mln
                                133 1/mln

                                871 1/mln
                                               28.6
                                                7.9
                                               15.7
                                               25.1
                                               22.5
                                               20.6
                                                            Species Cone.
                                                            in Gas (ppm)
Species Flow Rate
  (m mole/mln)
     18,933
        600

     13,675
     16,616
      1,710
     17,943
3. CaCO,
                                           Ua ill - Ju*
                                            4        4

                                          18,326 - 17,943

                                          383 m mole/mln
   Entering Streams  Scrubber Liquid       662 1/mln
                     Scrubber Bottom        76 1/mln
                     Make Up H20           133 1/mln

   Leaving Streams   Hold Tank Eff.        871 1/mln

                     Rate of CaC03 = C02 IN - C02 OUT

                                   = 1278 - 958

                                   = 320 m mole/mln

4. Ca(OH)2 Dissolution

   Entering Streams  Scrubber Liquid       662 l/m1n
                     Scrubber Bottom        76 1/mln
                     Make Up H20           133 l/m1n

   Leaving Streams   Hold Tank Eff.
                                                        1.845
                                                          .75
                                                         1.10
                                                         35.3
                                                         23.8
                                                         1.08

                                                         24.5
                      871 l/m1n

Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec, Rate

                            = 21,340 - 25,322 + (320 + 383 + 5,858)

                            - 2,579 m mole/m1n
                                                                                  1,221
                                                                                     57
                                                                                    958
     23,369
      1,809
        144

     21,340
                                                      H-26
-------
Marble Bed (Set 2)
1. CaS03   1/2 H20
   Entering Streams  Inlet Flue Gas
                     Scrubber Spray
                              TABLE H-10.  RATE CALCULATIONS USING LIQUID BALANCE (Continued)
                                                              Species Cone.      Species Cone.
                                        Stream Flow Rate    tn L1q. On mole/1)   tn Gas (ppm)
                              9.120 g mole/mln
                                738 l/m1n
                        15.15
   Leaving Streams
          Outlet Flue Gas    10,487 g mole/mln
          Scrubber Liquid*      662 1/mln                25.9
          Scrubber Bottom        76 1/mln               13.65
          Rate of CaS03 = S02 IN - S02 OUT - OXID.  Rate
                        = 28.336 - 29,299 - .536 (17,155 - 11.116)
                        = 28.336 - 29,299 - .536 (6,039)"
                        = 28.336 - 29,299 - 3,237
                        = -4,200 m mole/mln
2. CaSO.
2 H20
   Entering Streams  Scrubber Spray
   Leaving Streams
          Scrubber Liquid*
          Scrubber Bottom
738 1/mln
662 l/m1n
 76 1/mln
21.45
 26.5
23.65
                     Rate of CaS04   2 H20 = S04 IN - S04 OUT + OXID.  Rate
                                           = 15,830 - 19,340 + 3,237
                                           » -273 m mole/min
3. Ca(OH)2 Dissolution
   Entering Streams  Scrubber Spray
   Leaving Streams
          Scrubber Liquid*
          Scrubber Bottom
738 1/mln
662 1/mln
 76 1/mln
 25.2
34.65
 27.6
                  1,881

                  1,060
                     Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec.  Rate
                                                 = 25,036 - 18,598 + (- 273 - 4,200)
                                                 = 25,036 - 18,598 + -4,473
                                                 = 1,965 m mole/m1n
                                                                                      Species Flow Rate
                                                                                        On mole/mtn)
17,155
11,181
11,116
17.146
 1,037
15,830
17,543
 1,797
18,598
22,938
 2,098
                                                      H-27
-------
                              TABLE H-10.  RATE CALCULATIONS USING LIQUID BALANCE  (Continued)
                                                              Species Cone.      Species Cone.   Species Flow  Rate
                              	  Stream Flow Rate    In Llq. (m mole/1)   1n Gas (ppm)       (m mole/mln)
 Hold  Tank
 1.  CaS03    1/2 H20
    Entering Streams  Scrubber Liquid       662 1/min               27.31                              18,079
                     Scrubber Bottom        76-1/mln                 4.5                                 342
                     Make Up H20           133 1/mln
    Leaving  Streams   Hold Tank Eff.        871 1/mln               15.05                              13,109
                     Rate of CaS03   1/2 H20 = S02 (IN) - S02 (OUT)
                                             = 18,421 - 13,109
                                             = 5,312 m mole/mln
 2.  CaS04    2 H20
    Entering Streams  Scrubber Liquid       662 1/mln                25.2                              16,682
                     Scrubber Bottom        76 1/mln                21.9                               1,664
                     Make Up HgO           133 1/mln
    Leaving  Streams   Hold Tank Eff.        871 1/mln               20.85                              18,160
                     Rate of CaS04   2 H20 = S04 (IN) - S04 (OUT)
                                           = 18,346 - 18,160
                                           • 186 m mole/mln
 3.  CaC03
    Entering Streams  Scrubber Liquid       662 l/m1n                1.36                                 900
                     Scrubber Bottom       133 1/mln                0.17                                   13
                     Make Up H^O
    Leaving Streams   Hold Tank Eff.        871 l/m1n                0.97                                 845
                     Rate of CaC03 = C02 (IN) - C02 (OUT)
                                   = 913 - 845
                                   = 68 m mole/mln
4. Ca(OH)2 Dissolution
   Entering Streams  Scrubber Liquid       662 l/m1n                35.3                              23,369
                     Scrubber Bottom        76 1/mln                22.2                               1,687
                     Make Up H20           133 1/mln                1.08                                 144
   Leaving Streams   Hold Tank Eff.        871 l/m1n                25.5                              22,211
                     Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec. Rates
                                                 = 22,211 - 25,200 + (5,566)
                                                 = 2,577 m mole/mln
                                                      H-28
-------
                               TABLE H-Tl.   felE CALCULATIONS  USING LIQUID BALANCE
                                                     Expertment 20R
                                                               Species  Cone.       Species  Cone.    Species  Flow Rate
                                         Stream Flow Bate     In Llq.  On mole/1)    In  Gas  (ppm)       fo mole/rain)
 Marble Bed (Set #1)
 1.  CaS03   1/2 H20
    Entering Streams   Inlet  Flue  Gas       9,400 g mole/mln                            1,962             18,443
                      Scrubber Spray        757"l/m1n                 7.9                                5,980
    Leaving Streams   Outlet Flue Gas     10,850 g mole/mln                            1,090             11,827
                      Scrubber Liquid*      681 1/mln                15.0                               10,215
                      Scrubber Bottom        76 1/mln                 8.1                                  616
                      Rate of CaS03   1/2  H20 « S02 (IN) - S02 (OUT) - Oxidation Rate
                                             = 24,423 - 22,658 - .552 (18,443 - 11,827)
                                             a 24,423 - 22,658 - .552 (6,616)
                                             = 24,423 - 22,658 - 3,652
                                             = -1,887 m mole/mln
2.  CaS04    2H20
    Entering Streams   Scrubber Spray        757 1/m1n                24.7                              18,698
    Leaving Streams    Scrubber Liquid*      681 l/m1n                30.7                              2.0,907
                      Scrubber Bottom        76 l/m1n                25.3                                1,923
                      Rate of CaS04 - S04  (IN)  - S04 (OUT) + Oxidation Rate
                                   = 18,698 -  22,830 + 3,652
                                   = - 480 m mole/m1n
3. Ca(OH)2 Dissolution
   Entering Streams  Scrubber Spray        757 l/m1n                23.4                              17,714
   Leaving Streams   Scrubber Liquid*      681  1/mln               32.25                              21,962
                     Scrubber Bottom        76 1/m1n                26.1                               1,984
                     Rate of Ca(OH)2 Dissolution  - Ca (OUT)  - Ca  (IN)  t  Ca Prec.  Rate
                                                 = 23,946 -  17,714  + (-542 - 1,769)
                                                 =  23,946 -  17.714  + (-2,367)
                                                 -   3,865 m  mole/mln
                                                     H-29
-------
                              TABLE H-ll.  RATE CALCULATIONS USING LIQUID BALANCE (Continued)
Species Cone. Species Cone. Species Flow Rate
Stream Plow Rate In Llq. fm mole/1) 1n Gas (ppm) (m mole/min)
Hold Tank
1.




2.




3.





4.
CaS03 1/2 H20
Entering Liquid
Leaving Streams



CaS04 2 H20
Entering Liquid
Leaving Streams



CaCO,
Entering Liquid
Leaving Streams



Scrubber Liquid
Scrubber Bottom
Make Up H-0
Clarified ''Liquid
Hold Tank Eff.
Rate of CaS03


Scrubber Liquid
Scrubber Bottom
Make-Up H,0
Clarlfled^Llq.
Hold Tank Eff.
Rate of CaSO.



Scrubber Liquid
Scrubber Bottom
Make-Up H-0
ClarlfledUlquld
Hold Tank Eff.
Rate of CaCO. =
&
s
681 l/m1n
76 l/m1n
151 l/m1n
151 l/m1n
1,059 l/m1n
1/2 H20 = S02 IN - S02 (OUT)
= 10,701 - 7,890
= 2,811 m mole/m1n
681 l/m1n
76 1/mln
151 1/mln
151 l/m1n
1,059 1/mln
2H£0 = S04 IN - S04 OUT
= 25,460 - 25,893
= -433 m mole/ml n

681 l/m1n
76 l/m1n
151 l/m1n
151 l/m1n
1,059 l/m1n
C02 IN - C02 OUT
1,165 - 1,006
159 m mole/m1n
15.6
1.01
5.05
7.45



30.1
18.9
23.35
24.45




1.59 A
.06
.5?
.95



10,624
77
763
7,890



20,498
1,436
3,526
25,893




1,083
5
77
1,006



Ca(OH)2 Dissolution
Entering Streams
Scrubber Liquid
Scrubber Bottom
Make-Up H,0
Clarlfled'Llquld
681 1/mln
76 l/m1n
151 l/m1n
151 1/mln
31.6
21.6
1.08
22.1
21 ,520
1,642
163
3,337
   Leaving Streams   Hold Tank Eff.
1.059 l/m1n
23.6
                     Rate of Ca(OH)2 Dissolution - Ca OUT - Ca IN + Ca Free. Rate
                                                 = 24,992 - 26,662 + (2,811 - 433 + 159)
                                                 = 24,992 - 26,662 + 2,537
                                                 = 867 m mole/ml n
24,992
iFrom marble bed front and back
                                                      H-30
-------
                               TABLE  H-ll.   RATE  CALCULATIONS USING LIQUID BALANCE  (Continued}
                                                              Species Cone.      Species Cone.    Species  Flow Rate
                                        Stream Flow Rate    in L1q. (m mole/1)   1n Gas (ppm)       fa mole/mln)
 Marble  Bed  (Set  2)
 1.  CaS03    1/2 H20
    Entering Streams   Inlet Flue Gas      9,400 g mole/mln                            1,939            18,227
                      Scrubber Spray        751 l/m1n                10.2                               7,721
    Leaving  Streams    Outlet Flue Gas    10,850 g mole/mln                            1,090            11,827
                      Scrubber Liquid*      681 l/m1n               16.85                              11,475
                      Scrubber Bottom        76 l/m1n                12.0                                 912
                      Rate CaS03   1/2 HjO Form - S02 IN - S02 OUT - OXID. Rate
                                               = 25,948 - 24,214 - .543 (18,227 - 11,827)
                                               = 1,734 - 3,475
                                               • -1,711 m mole/mln
2.  CaS04    2H20
    Entering Stream    Scrubber Spray        757 l/m1n                25.5                              19,304
    Leaving Streams    Scrubber Liquid*      681 1/mln                29.7                              20,226
                      Scrubber Bottom        76 1/min                26.6                               2,022
                      Rate of CaS04   2H20 = S04 IN - SO^ OUT + OXIO.  Rate
                                          = 19,304 - 22,248 + 3,488
                                          = 544 m mole/rain
3. Ca(OH)2 Dissolution
                                                                                                      20,136
                                                                                                      22,779
                                                                                                       2,280
                     Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN t Ca Pre.  Rate
                                                 = 25,059 - 20,136 t  (544 -  1,741)
                                                 = 25,059 - 20,136 +  (-1,197)
                                                 = 3,726 m mole/mln
Entering Streams
Leaving Streams
Scrubber Spray
Scrubber Liquid*
Scrubber Bottom
757 1/mln
681 1/min
76 I/rain
26.6
33.45
30.0
                                                      H-31
-------
                               TABLE H-ll.  RATE CALCULATIONS USING LIQUID BALANCE Continued)
                                         Stream Flow Rate
                                                           Species Cone.
                                                         In L1q.  (m mole/1)
                                         Species  Cone.
                                         In Gas  (ppm)
 Hold Tank

 1.  CaS0    1/2
    Entering Streams  Scrubber Liquid
                      Scrubber Bottom
                      Make Up H.O
                      Clarified*L1qu1d
                                        681  l/ra1n
                                         76  l/m1n
                                        151  1/mln
                                        151  1/mln
    Leaving Streams   Hold Tank Eff.      1,059 1/mln

                      Rate of CaS03   1/2 H20 = S02 IN - S02 OUT

                                              = 13,796 - 10,855

                                              = 2,941 m mole/mln
 2. CaSO.
          H20
Entering Streams  Scrubber Liquid
                  Scrubber Bottom
                  Make Up H,0
                  Clarlfled'Llquld
                                            681  l/m1n
                                             76  1/mln
                                            151  l/m1n
                                            151  l/m1n
    Leaving Streams   Hold Tank Eff.       1,059 1/mln

                      Rate of CaS04   2H20 =  S04 IN - S04 OUT

                                           =  24,744 - 26,104
 3.  CaCO,
    Entering Streams   Scrubber  Liquid
                      Scrubber  Bottom
                      Make  Up H,0
                      Clarlfled'M.lquld
                                             -  1,360 m mole/mln
                                       681 1/mln
                                        76 1/mln
                                       155 1/mln
                                       155 1/mln
    Leaving Streams   Hold Tank  Eff.       1,059  1/mln

                     Rate of CaC03 = C02  IN - C02 OUT

                                   = 1,091 - 921

                                   = 170 m mole/m1n

4.  Ca(OH)2 Dissolution
   Entering Liquid
                 Scrubber Liquid
                 Scrubber Bottom
                 Make Up H70
                 Clarlfled^Llquld
   Leaving Streams   Hold Tank Eff.
  681 1/mln
   76 1/mln
  155 1/mln
  155 1/mln

1,059 1/mln
                            18.3
                            2.85

                            7,4

                          10.25
                           29.1
                           23.3

                           20.9

                          24.65
                           1.42
                            .48

                            .57

                            .87
33.9
24.7
1.08
22.9

25.9
                     Rate of Ca(OH)2 Dissolution » Ca OUT - Ca IN + Ca Free. Rates

                                                 = 27,428 - 28,680 + 1,751

                                                 - 499 m mole/m1n
                              Species  Flow Rate
                                (m mole/mini
                                   12,462
                                     217

                                   1,117

                                   10,855
                                  19,817
                                   1,771

                                   3,156

                                  26,104
                                     967
                                      36
                                                                                                     921
23,086
 1,877
   167
 3,550

27,428
*Ave. of Marble Bed Front and Back
                                                      H-32
-------
                              TABLE H-12.   RATE  CALCULATIONS  USING  LIQUID BALANCE

                                                Experiment 21R
                                        Stream Flow Rate
                         Species  Cone.
                       in Llg.  On mole/1)
                                                                                 Species Cone.
                                                                                 In Gas  (ppm)
Marble Bed (Set #1)

1. CaS03   1/2 H20

   Entering Streams  Inlet Flue Gas
                     Scrubber Spray

   Leaving Streams   Outlet Flue Gas
                     Scrubber Liquid*
                     Scrubber Bottom
   10,200 g mole/mln
      758 l/m1n

    8,820 g mole/mln
      681 1/min
       76 1/min
                     .9
                   10.2
                    1.6
2.000


  735
                     Rate of CaS03   1/2 H20 Form = S02 IN - S02 OUT - Oxld.  Rate

                                                  = 21,082 - 13,551  - .357 (20,400 - 6,483)

                                                  = 21,082 - 13,551  - 4,968

                                                  = 2,563 m mole/min
2. CaS04   2H20
   Entering Streams  Scrubber Spray

   Leaving Streams   Scrubber Liquid*
                     Scrubber Bottom

                     Rate of CaSO.
      758 1/min

      681 l/m1n
       76 l/m1n
                  24.82

                  30.27
                  26.55
2H20 Form
S04 IN - S04 OUT - Oxld. Rate

18,814 - 22,632 + 4,968

1,150 m mole/ml n
3. Ca(OH)2 Dissolution


   Entering Streams  Scrubber Spray

   Leaving Streams   Scrubber Liquid*
                     Scrubber Bottom
      758 1/min

      681 1/min
       76 1/min
                  21.79

                  23.98
                  21.75
                     Rate of Ca(OH)2 Dissolution = Ca (OUT) - Ca (IN) + Ca Prec. Rate

                                                 = 17,983 - 16,517 + (2,563 + 1,150)

                                                 = + 5,179 m mole/mi n
                                                Species Flow Rate
                                                  Cm mole/ml n)
20,400
   682

 6,483
 6.946
   122
                 18,814

                 20,614
                  2,018
                 16,517

                 16,330
                  1,653
*Average of marble bed front and back
                                                       H-33
-------
                               TABLE  H-12.   RATE  CALCULATIONS USING LIQUID BALANCE  (Continued)
                                         Stream  Flow  Rate
                                                           Species Cone.
                                                         In Llg. (m mole/1)
 Hold Tank
 1.  CaS03   1/2 H20
Entering Steams
Scrubber Liquid
Scrubber Bottom
Clarified Liquid
681 l/m1n
76 l/m1n
38 1/mln
   Leaving Streams   Hold Tank Eff.        795 1/mln
                                                                   .7
                                                                  1.0
                                                                 1.10

                                                                 1.10
                      Rate  of  CaS03    1/2 H20
                                               S02 IN - S02 OUT

                                               595 - 875

                                               -280 m mole/ml n
2. CaSO.
            2H20
Entering Streams  Scrubber Liquid
                  Scrubber Bottom
                  Clarified Liquid

Leaving Streams   Hold Tank Eff.

                  Rate of CaSO.
                                        681 1/min
                                         76 l/m1n
                                         38 1/mln

                                        795 1/m1n

                                  2H20 Form = S04 IN - S04 OUT

                                            = 19,836 - 21,227

                                            = - 1,391 m mole/m1n
                                                                    25.5
                                                                    21.3
                                                                    22.4

                                                                    26.7
3.
CaCO,


Entering Streams  Scrubber Liquid
                  Scrubber Bottom
                  Clarified Liquid

Leaving Streams   Hold Tank Eff.

                  Rate of CaC03 Form
4. Ca(OH2) Dissolution


   Set #1 Marble Bed

   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarified Liquid

   Leaving Stream    Hold Tank Eff.
                                           681 1/m1n
                                            76 1/mln
                                            38 1/m1n

                                           795 l/m1n

                                          C02 IN - C02 OUT

                                        = 151 - 223

                                        = 72 m mole/m1n
                                           681  1/mln
                                            76  1/mln
                                            38  l/m1n

                                           795  l/m1n
                                                                     .18
                                                                     .23
                                                                      .3

                                                                     .28
                                                                 30.2
                                                                28.75
                                                                 20.8

                                                                 18.1
                                                                                 Species Cone.
                                                                                 In Gas (ppm)
                                                                                              Species Flow Rate
                                                                                                Cm mole/ml n)
                     Rate of Ca(OH2) Dissolution = Ca OUT + Ca  IN + Ca Free. Rate

                                                 = 14,390 - 23,541 +  (-72 -1391  -280)

                                                 = - 10,894 m mole/mln
                                                                                                          477
                                                                                                           76
                                                                                                           42

                                                                                                          875
                                                                                                      17,366
                                                                                                       1.619
                                                                                                         851

                                                                                                      21,227
                                                                                                      123
                                                                                                       17
                                                                                                       11

                                                                                                      223
                                                                                                   20,566
                                                                                                    2,185
                                                                                                      790

                                                                                                   14.390
                                                      H-34
-------
                               TABLE H-12.   RATE CALCULATIONS  USING  LIQUID  BALANCE  (Continued)
Set K Marble Bed

1. CaS03   1/2 H20


   Entering Streams  Inlet Flue Gas
                     Scrubber Spray
                   Stream Flow Rate
                                                              Species Cone.
                                                            In Ltq. Cm mole/1)
                                                                                  Species  Cone.    Species  Flow Rate
                                                                                  1n  Gas  (ppm)       to mole/mln)
   Leaving Streams
Outlet Flue Gas
Scrubber Liquid*
Scrubber Bottom

Rate of CaS0    1/2
                                     10,550 g raole/mln
                                        758 1/mln

                                      9,200 g mole/mln
                                        681 1/mln
                                         76 1/mln
                                               1.00
                                                                   10.39
                                                                    1.25
                                                                                     1,985


                                                                                       678
                                             Form = S02  IN - S02  (OUT) - Oxid. Rate

                                                  = 21,699 - 13,409 - 0.266  (14,703)

                                                  = 4,380 m mole/mi n
2. CaS0
            2H20
Entering Streams  Scrubber Spray
   Leaving  Streams
                  Scrubber Liquid*
                  Scrubber Bottom
                      758 1/mln

                      681 1/mln
                       76 1/mln
                                                                   25.82

                                                                   30.95
                                                                    25.6
                     Rate of CaS04   2H20 = S04 IN - S04 OUT + Oxd. Rate

                                          = 19,572 - 23,023 + 3,910

                                          = 459 m mole/mi n
3. Ca(OH)2 Dissolution
Entering Streams
Leaving Streams
Scrubber Spray
Scrubber Liquid*
Scrubber Bottom
758 1/min
681 l/m1n
76 1/mln
18.59
25.09
20.9
                     Rate of Ca (OH)2 Dissolution = Ca OUT - Ca IN + Ca Free. Rate

                                                  = 18,674 - 14,091 + (459 + 4,380)

                                                  = 9,422 m mole/mln
'Average of marble bed front and back
                                                                                                       20,941
                                                                                                          758

                                                                                                       6,238
                                                                                                       7,076
                                                                                                          95
                                                                                                      19,572

                                                                                                      21,077
                                                                                                       1,946
                                                                                                      14,091

                                                                                                      17,086
                                                                                                       1,588
                                                       H-35
-------
                              TABLE H-12.  RATE CALCULATIONS USING LIQUID BALANCE  (Continued)
                                                              Species Cone.      Species Cone.
                                        Stream Flow Rate    1n L1g. (m mole/1)   1n Gas (ppm)
                                                                                      Species Flow Rate
                                                                                        On mole/mln)
Hold Tank

1.  CaSO,   1/2
   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarified Liquid

   Leaving Streams   Hold Tank Eff.
                                681 l/m1n
                                 76 1/mln
                                 38 l/m1n

                                795 l/m1n
 2.6
1.35
1.50

1.73
                     Rate of CaS03   1/2 H.,0 Form = S02 IN - S02 OUT

                                                  = 1,931 - 1,375

                                                  = 556 m mole/mln
2. CaSO.
2H20
   Entering Streams  Scrubber Liquid       681 l/m1n
                     Scrubber Bottom        76 1/min
                     Clarified Liquid       3B l/m1n

   Leaving Streams   Hold Tank Eff.        795 l/m1n

                     Rate of CaS04   2H20 = S04 IN - S04 OUT

                                          » 18,911 - 22,896
                                                         24.7
                                                        16.33
                                                        22.35

                                                         28.8
3. CaCO
       3
   Entering Stream   Scrubber Liquid
                     Scrubber Bottom
                     Clarified Liquid

   Leaving Streams   Hold Tank Eff.
                                            -3,985 m mole/mln
                                681  l/m1n
                                 76  1/min
                                 38  l/m1n

                                795  1/nrin
1.42
 .19
 .29

 .50
                     Rate of CaC03 = C02 IN - C02 OUT

                                   = 992 - 398

                                   = 594 m mole/mln

4. Ca(OH)2 Dissolution

   Entering Stream   Scrubber Liquid       681 1/mln
                     Scrubber Bottom        76 1/min
                     Clarified Liquid       38 1/mln

   Leaving Streams   Hold Tank Eff.        795 1/min
                                                        21.17
                                                        25.80
                                                         20.7

                                                         16.9
                     Rate of Ca(OH2) Dissolution = Ca OUT - Ca IN + Ca Free. Rate

                                                 = 13,436 - 17,165 - 2,835

                                                 = -6,564 m mole/min
1,771
  103
   57

1,375
                                  16,821
                                   1,241
                                     849

                                  22,896
  967
   14
   11

  398
                                  14,417
                                   1,961
                                     787

                                  13,436
                                                      H-36
-------
                              TABLE H-13.   RATE CALCULATIONS USING LIQUID BALANCE

                                              Experiment 22R
                                        Stream Flow Rate
                         Species Cone.      Species Cone.
                       tn Llg. (m mole/1)   In Gas (ppm)
 Marble Bed

 1.  CaS03   1/2  H20

    Entering Streams   Inlet  Flue Gas
                      Scrubber Spray'

    Leaving  Streams    Outlet Flue Gas
                      Scrubber Bottom
                      Scrubber Liquid*
   10,466 g mole/m1n
    1,355 1/mln

    9,075 g mole/mln
      380 1/mln
      977 1/mln
  3.75
  7.19
  8.85
2,021


  484
                      Rate of CaS03   1/2 H20 = SOg  IN - S02 OUT - OXID. Rate

                                             = 26,233 - 15,770 - .346  (21,152 - 4,392)

                                             = 26,233 - 15,770 - .346  06,760)

                                             = 26,233 - 15,770 - 5,799

                                             = 4,664 m mole/mln
2. CaS04   2 H20
   Entering Streams  Scrubber Spray      1,355 1/mln

   Leaving Streams   Scrubber Liquid*      977 l/m1n
                     Scrubber Bottom       380 1/mln
                              31.10

                              33.58
                               27.6
                     Rate of CaSCL





3. Ca(OH)2 Dissolution

   Entering Streams  Scrubber Spray

   Leaving Streams   Scrubber Liquid*
                     Scrubber Bottom
2 H20 = S04 IN - S04 OUT + OXID. Rate

      = 42,140 - 43,295 + 5,799

      = 4,644 m mole/min
    1,355 l/m1n

      977 1/mln
      380 1/min
 17.98

21.925
 22.495
                     Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Free. Rates

                                                 = 29,799 - 24,362 + (4,664 + 4,644)

                                                 = 14,745 m mole/min
                               Species Flow Rate
                                 (m mple/mln)
21,152
 5,081

 4,392
 2,732
 8,646
                                    42,140

                                    32,807
                                    10,488
                 24,362

                 21,420
                  8,379
*Ave. of Marble Bed Front and Back
                                                      H-37
-------
                              TABLE H-13.  RATE CALCULATIONS USING LIQUID BALANCE  (Continued)
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    in Llq. (m mole/1)   In Gas (ppm)       (m mole/mln)
 Hold  Tank
 1.  CaS03    1/2 H20
    Entering Streams  Clarified Liquid       38 l/m1n                 .75                                  29
                     Scrubber Liquid       977 l/m1n               18.55                              18,123
                     Scrubber Bottom       380 l/ra1n                4.75                               1,805
    Leaving  Streams   Hold Tank Eff.      1,395 1/mln                1.93                               2,692
                     Rate of CaS03   1/2 H20 = S02 IN - S02 OUT
                                             = 19,957 - 2,692
                                             = 17,265 m mole/ml n
 2.  CaS04    2 H20
   Entering Streams  Scrubber Liquid       977 1/mln                39.5                              38,591
                     Scrubber Bottom       380 l/m1n               30.43                              11,563
                     Clarified Liquid       38 1/mln                21.5                                 817
   Leaving Streams   Hold Tank Eff.      1,395 1/mln               29.77                              41.529
                     Rate of CaS04   2 H20 = S04 IN - S04 OUT
                                           = 50,971 - 41 ,529
                                             9,442 m mole/m1n
3. CaC03
   Entering Streams  Scrubber Liquid       977 1/mln                 .79                                 772
                     Scrubber Bottom       380 1/mln                1.38                                 524
                     Clarified Liquid       38 1/mln                 .23                                   9
   Leaving Streams   Hold Tank Eff.      1,395 l/m1n                 .65                                 907
                     Rate of CaC03 = C02 IN - C02 OUT
                                   = 1,305 - 907
                                   = 398 m mole/m1n
4. Ca(OH)2 Dissolution
   Entering Streams  Scrubber Liquid       977 l/m1n                27.2                              26.574
                     Scrubber Bottom       380 1/mln               19.58                               7,440
                     Clarified Liquid       38 1/mln                21.1                                 802
   Leaving Streams   Hold Tank Eff.      1.395 1/mln                16.4                              22,878
                     Rate of Ca(OH)2 Dissolution = Ca OUT - Ca IN + Ca Prec. Rate
                                                 = 22,878 - 34,816 + (17,265 + 9,442 + 398)
                                                 = 15,167 m mole/rain
                                                       H-38
-------
                   APPENDIX I

       LIMESTONE FURNACE INJECTION SYSTEM
ADDITIVE DISSOLUTION RATE DETERMINATION DIAGRAMS
-------
      22


      20


      18


      16
    x 14
   CO
   c?
      10
      A
      8
                SPRAY COMPOSITION
                        I
                                                                  ACTUAL SO,
                                                                   REMOVAL

                                                                   100% STAGE
                                                                   EFFICIENCY
                                                                   I  .
CD
3.2  3.4  3.6 3.8  4.0
                 5.0                 .
MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10'4
6.0
                    PLOT  OF OPERATING  LIME FOR EXPERIMENT 18R
-------
CD
   tn
22



20




18




16



14




12
   sT 10
   2   8
   6   8
       4
       0
                                                                 29
 26                  27                 28

                   CALCIUM -mMOLE/ LITER


   PLOT OF CALCIUM vs PARTIAL PRESSURE OF S02 FOR  SCRUBBER


                    EFFLUENT - EXPERIMENT  18R
-------
22
20
18
16
o
t—I



oo






I—I

 CM
12
10
 o

 8
   4



   2
 o
                           T	T
                      ACTUAL S02 REMOVAL


	1—-f^iuu% STAGE EFFICIENCY


                         I
              SPRAY COMPOSITION
                 I
                     I	I
 6.4  6.6  6.8  7.0
                                      8.0                   9.0

                        MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10~4
                                                      10.0
                 PLOT  OF OPERATING  LINE FOR  EXPERIMENT 19R
-------
I
       22


       20


       18


       16
    x  14
    to
    o
    to
       12
       10
    S  8
    s  8

    I  6

    §  4
                            I
                           i!
31
32                  33
 CALCIUM-m MOLE/LITER
34
        PLOT OF CALCIUM vs PARTIAL PRESSURE OF S02 FOR  SCRUBBER

                         EFFLUENT -  EXPERIMENT  19R
-------
  T
   CD
   CO

   g
I

01
   CO
   22




   20



   18




   16




   14



   12



   10
o
1-^

5
   0   8
   i—i   o
 3     0
                                       ACTUAL S02 REMOVAL
STAGE EFFICIENCY
                SPRAY COMPOSITION
        6.4 6.6  6.8  7.0
 CD


 l—l

 I
                                       8.0                   9.0

                          MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10'4



                     PLOT  OF OPERATING LIN  FOR EXPERIMENT 20R
                                      10.0
-------

I
   22

   20

   18

   16
x  14
to
5  12
to

1  8
o
O£  a
   0
T	T
T	T
                        I
                               I
T	1	1	T
    31
           32                  33
           CALCIUM-m MOLE/LITER
                           34
    PLOT OF CALCIUM vs PARTIAL  PRESSURE OF  S02 FOR SCRUBBER
                     EFFLUENT - EXPERIMENT  20R
-------
CO

3
   to
22

20

18

16

14

12

10
   D—  f
   y
   i  4
 0
                                                                 ACTUAL S02 REMOVAL
                                                                         100% STAGE
                   SPRAY COMPOSITION
       5.0
                      6.0                  7.0
                      MOLE FRACTION - TOTAL SULFUR IN LIQUID x 10"4
8.0
                    PLOT OF  OPERATING LINE  FOR EXPERIMENT 21R
-------
OB
 00
T
 o
           22

           20

           18

           16

           14
        CO
        S 12
        CO
        O  Q
        i—i  O

        2f  6
        iiJ
        i  4
            0
                         I
            26
27                   28
CALCIUM-m MOLE/LITER
                                                                29
     PLOT OF  CALCIUM vs PARTIAL, PRESSURE OF S02  FOR SCRUBBER
                       EFFLUENT  -  EXPERIMENT  21R
-------
to
to
22



20



18



16



14



12




10
§•
<
O£L  f
U-  0

o
?   0
^   6.0
                                           ACTUAL S02 REMOVAL
                                          •
    	—AvlOO% STAGE EFFICIENCY
            SPRAY COMPOSITION
                       7.0                  8.0             -

                        MOLE FRACnON - TOTAL SULFUR IN LIQUID x 10"4
                                                             9.0
               PLOT  OF OPERATING LINE FOR  EXPERIMENT 22R
-------
•3'
c
22


20



18


16
       x 14
       tn


       *»
6


4


2


0
                   T	T
                                                         OUTLET S02 FOR

                                                             100% STAGE
                                                            „ EFFICIENCY

                                                           I
                                                           I
                      I
I
          21
                     22                   23

                      CALCIUM-m MOLE/LITER
                    24
           PLOT OF  CALCIUM  vs  PARTIAL PRESSURE OF S02  FOR SCRUBBER

                             EFFLUENT - EXPERIMENT 22R
-------
        APPENDIX J

LIMESTONE TAIL-END SYSTEM
      OPERATING DATA
           AND
    ANALYTICAL RESULTS
-------
                                  TABLE J-l.  C-E ARCS PROTOTYPE
                                              TAIL-END LIMESTONE TESTS


Experiment No.                                     25R                   26R                   27R
Date of Run                                       7/7/72               7/10/72               7/11/72
Set Number                                     12121          2
T1me     ,  %       ,                        1045-1200  1230-1315  1400-1500  1515-1600  0920-1030  1030-1130
Flue Gas (F6)  Rate (cfm @  130°F)              9,950      9,900     10,060     10,100     10,250     10,180
Additive Feed Rate (Ib/hr)                      318        318        510        510        516        516
Spray Water Lower (SWL) Rate  (gpm)              240        250        245        235        150        150
Spray Water Upper (SWU) Rate  (gpm)
Scrubber Liquid Lower (SLL) Rate  (gpm)          180        195        180        178        135        135
Scrubber Liquid Upper (SLU) Rate  (gpm)            _____
Scrubber Bottom (SB)  Rate  (gpm)                  60         55         65         58         15         15
Clarifier Liquid (CL) Rate  (gpm)                 10         10         15         15         12         12
Liquid Slowdown (LB)  Rate  (gpm)                   000000
Clarifier Feed (CF)  Rate (gpm)                   10         10         15         15         12         12
Clarifier Bottom (CB) Rate  (gpm)                                       3          3
Filter Liquid (FL) Rate (gpm)                     ______
Spray Water (SW) Temp.  (°F)                     122        121        120        120        120        120
Scrubber Liquid (SL)  Temp.  (°F)                 122        121        122        122        121        121
Scrubber Bottom (SB)  Temp.  (°F)                 134        135        131     ,135        131        131
Inlet Gas Dew Point  (°F)                       114        114        113        113      104.5      104.5
Outlet Gas Dew Point  (°F)                     121.5      121.5        119        119      117.5      117.5
Reheater Inlet Gas Temp. (°F)                   125        124        121        122        122        122
Heat Extractor Outlet Gas Temp. (°F)            295        298        315        315        298        305
Inlet S02 (ppm)                              2,329      2,362       2,519      2,490      2,306      2,323
Outlet S02 (ppm)                               956        997       1,023        999      1,114      1,099
Inlet 02 (%)*                                 10.6       10.6        9.8        9.8       10.0       10.0
Outlet 62 (*)                                     -          -        10.3       10.3       10.6       10.6
Inlet C02 (%)*                                 8.0        8.0        8.2        8.2        8.4        8.4
Outlet COo (%)                                   -          -        7.8        7.8        7.5        7.5
Outlet SOJ> corrected  for air  leakage (ppm)    1,022      1,070       1,097      1,072      1,195      1,177
S02 Removal  Efficiency (%)                     56.2       54.7        56.5       57.0       48.2       49.4
Stoichiometry (%)                             98.5       97.6       114.5      146.1      156.7      156.6
Solid Concentration  in Spray  Water             7.56       7.14          -       6.57       7.18       7.69

* Average Air Leakage 7.2%
-------
                                      TABLE J-l.  (Continued)
Experiment No.
                              r.
                       .*    F)
         Feed Rate (Ib/hr)
Spray Water Lower (SWL) Rate (gpm)
Spray Water Upper (SWU) Rate (gpm)
Scrubber Liquid Lower (SLL) Rate (gpm)
Scrubber Liquid Upper (SLU) Rate (gpm)
Scrubber Bottom (SB) Rate (gpm)
Clarifier Liquid (CL) Rate (gpm)
Liquid Slowdown (LB) Rate (gpm)
Clarifier Feed (CF) Rate (gpm)
Clarifier Bottom (CB) Rate (gpm)
Filter Liquid (FL) Rate (gpm)
Spray Water (SW) Temp. (°F)
Scrubber Liquid (SL) Temp. (°F)
Scrubber Bottom (SB) Temp. (°F)
Inlet Gas Dew Point (°F)
Outlet Gas Dew Point (°F)
Reheater Inlet Gas Temp. (°F)
Heat Extractor Outlet Gas Temp. (°F)
Inlet SO? (ppm)
Outlet SO? (ppm)
Inlet 02 («)*
Outlet 02 (%)
Inlet C02 (%)*
Outlet C02 (%)
Outlet S02 corrected for air leakage (ppm)
SO- Removal  Efficiency („)
StBichiometry (%)
Solid Concentration in Spray Water
28R 29R 30R
7/12/72 7/13/72 7/14/
1
1445-1545
10,160
516
158
150
168
112
28
15
0
15
125
125
125
119.3
125
125
308
2,392
546
9.3
9.8
8.4
8.1
585
75.5
152.4
6.39
2
1605-1705
10,400
516
160
150
170
no
30
15
15
15
126
121
132
119.3
125
126
312
2,432
543
9.3
9.8
8.4
8.1
582
76.0
151.7
6.97
1
1100-1200
10,200
516
245
225
210
170
90
15
0
15
126
137
127
114
125.5
125
315
2,456
297
10.6
11.6
7.4
6.7
318
87.0
147.8
8.40
2
1245-1315
10,400
516
245
225
200
180
90
15
0
15
125
134
126
114
125.5
125
305
2,415
280
10.6
11.6
7.4
6.7
300
87.6
147.5
8.75
1
0950-1050
10,280
320
250
235
215
180
90
10
0
10
124
130
125
115
122
125
340
2,300
334
_
_
_
_
358
84.4
97.1
-
2
1125-1225
10,280
320
250
235
215
180
90
10
0
10
123
136
125
115
122
125
340
2,457
405
_
_
_,
_
434
87.3
90.94
_
* Average Air Leakage 7.2%
-------
         TABLE J-2.   SPRAY  WATER  FILTRATE ANALYSIS AND SOLIDS CONCENTRATION
                     DATA FOR  STEADY STATE DETERMINATION
7/7/72    26R
7/10/72
                               Sampling for Test 25R
18
19
20
21
22
23
24
25
26
27
28



1330
1400
1500
1600
1700
0800
1000
1030
1100
1200
1300
1630
1645
1700
777
741
525
787
750
796
756
780
700
761
780



396
376
328
408
112
272
92
220
192
188
192



2790
2410
1780
2740
2560
2780
2510
2780
2690
2640
2680
2314
1958
1386
2250
2425
2453
2399
2516
2459
2414
2449
                                                                       6.10

                                                                       6.10
                                                                       6.10
                                                                        6.0
                                                                       6.02

                                                                       6.10
                                                                              Solid
Data
7/5/72

'i
7/6/72

»
»
n
»
"
"
"
11
11
7/7/72

n
11
Test
No.
25R
n
"
25R
»
"
n
n
n
n
n
n
n
11
11
n
11

Sample
No.
1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17

Time
1200
1300
1340
0900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
0730
0800
0900
1000
Ca++
(ppm)
1272
1287
962
755
524
793
760
799
754
737
701
753
758
776
786
761
758

S05
(ppm)
952
852
524
376
376
412
404
412
392
404
352
360
412
404
104
352
372

Total Sulfur
as SOJ (ppm)
4460
4700
3080
2450
1740
2540
2400
2550
2650
2680
2350
2390
2490
2430
2620
2580
2620

S04
(ppm)
3317
3677
2451
1998
1317
2045
1915
2055
2179
2195
1927
1958
1995
1945
2495
2157
2173

PH






6.15
6.05
6.05
6.13
6.19
6.18


6.20
6.20

6.10
Cone.
1.3
1.8
2.6
3.3
4.3
4.7
5.2
5.8
7.4
7.9
7.5
7.4
7.2
7.3
7.0
6.4
6.8
6.9
7.2
7.5
7.0
6.4
6.4
6.2
6.5
6.0
6.6
7.3
6.9
5.5
6.1
6.8
                               Sampling for Test 26R
                                         J-3
-------
TABLE J-2.   (Continued)
Test
Data No.
7/11/72 27R
n ii
n n


7/12/72 28R
n n
n n
n n
n n
n n
n n
n n
n M
M n

7/13/72 29R
n n
n n
n n
M n
"

7/14/72 30R
n n
n n
n n
„

Sample
No.
29
30
31


32

33

34

35
36

37

38

39




40

41

42

Time
0800
0830
0900

and
0900
0930
1000
1030
1100
1130
1200
1300
1330
1400

0800
0840
0900
0930
1000
1030

0645
0715
0745
0815
0845

Ca++
(ppm)
823
812
802
Sampling
503 Total .Sulfur SOj
(ppm) as SO^ (ppm) (ppm)
272
192
184
for Test 27R
3010
2770
2870

2683
2539
2649

Solid
Cone.
PH (%)
6.1 5
6
6.1 6

.9
.5
.0

Installing Upper Marble Bed
784

882

845

824
772

756
Sampling
781

806



Sampling
716

655

718
Sampling
232

212

192

216
172

156
for Test 28R
252

268



for Test 29R
292

196

196
for Test 30R
2700

3070

2860

3010
2880

2840

2970

3070




3200

2850

3030

2421

2815

2629

2750
2673

2652

2667

2748




2849

2614

2794

6.61 6
6
6.50 6
6
6.40 6
6
6.50 6
6.50 12
6
6.40 5

6.1 6
6
6
6
9
6

7
7
7
7
6

.0
.1
.1
.1
.8
.6
.9
.8
.6
.5

.3
.1
.2
.0
.6
.8

.4
.7
.4
.5
.9

         J-4
-------
c_

01
           Sample Location
                                TABLE J-3.  RESULTS OF SOLID PHASE ANALYSES
                                            EXPERIMENT 25R
       Set 1

       Scrubber Liquid Tk
       Scrubber Bottoms Tk
       Hold Tank Effluent
       Marble Bed:   Front
       Marble Bed:   Back
       Scrubber Bottoms S
       Scrubber Spray
Set 2

Scrubber Liquid Tk
Scrubber Bottoms Tk
Hold Tank Effluent
Lime Stone
Lime Stone
                                  1235
                                  1240
                                  1300
                                                   7/7/72
                                 Wt % Solids
                          Time     in Slurry
1055
1100
1120
1130
1142
1155
1203
7.13
7.74
7.79
7.32
6.32
7.90
7.55
7.04
7.29
7.14
                                                            Composition in Millimoles/Gram
           Total  S    Ca
                                                  .74
                                                  .42
                                                4.28
                                                4,
                                                5,
                                                4,
              64
              39
              61
                                                4.36
 4.85
 4.67
 4.31
0.002
0.015
                 Mg
SO,
SO,
CO,
7
7
7
7
7

7
7
7
7
9
9
.29
.38
.46
.22
.32
.40
.39
.31
.48
.31
.50
.45
0
0
0
0
0
0
0
0
0
0


.030
.031
.032
.029
.023
.030
.032
.027
.028
.029
0.13
0.13
3
3
3
3
4
3
3
3
3
3


.57 1
.27
.21
.50
.02
.42
.32
.70
.51
.30
- 0
- 0
.17
.15
.07
.14
.37
.19
.04
1.16
1.16
1.01
.002
.002
2
3
3
2
2
2
3
2
2
2
9
9
.70
.09
.24
.73
.08
.94
.05
.69
.81
.94
.24
.40
   Weight
% Undissolved
                                                  1.64
                                                  2.18
                                                  2.18
                                                  1.90
                                                  2.05
                                                  2.07
                                                  2.50
                         1.73
                         2.09
                         2.04
                         2.60
                         2.26
-------
                               TABLE J-4.   RESULTS OF SOLID PHASE ANALYSES
                                           EXPERIMENT 26R
c..
CM
          Sample Location
                                                  7/10/72
      Set 1

      Scrubber Liquid Tk
      Scrubber Bottoms Tk
      Hold Tank Effluent
      Marble  Bed:  Front
      Marble  Bed:  Back
      Scrubber Bottom S
      Scrubber Spray
Set 2

Scrubber Liquid Tk
Scrubber Bottoms Tk
Hold Tank Effluent
Marble Bed:   Front
Marble Bed:   Back
Scrubber Bottoms S
Scrubber Spray
                           Time
                           1400
                           1405
                           1420
                           1435
                           1445
                           1450
                           1455
                                1515
                                1525
                                1547
                                1555
                                1602
                                1615
                                1610
Wt % Solids
 in Slurry
   6.24
   6.34
   6.43
   7.94
   6.65

   6.57
                                                           Composition  in  Millimoles/Gram
Total S
               4.94
               4.92
               4.59
               5.02
               5.26
               4.54
               3.94
 4.54
 4.38
 4.12
 4.31
 4.45
 4.43
 3.82
Ca
Mg
SO,
SO,
CO,
7.73
7.69
7.83
7.72
7.67
7.92
8.05
7.67
7.84
7.71
7.69
7.60
7.68
7.90
0.04
0.04
0.04
0.04
0.03
0.04
0.05
0.06
0.05
0.06
0.06
0.05
0.06
0.06
3.69
3.76
3.39
3.76
4.02
3.40
2.90
3.39
3.30
3.14
3.29
3.38
3.37
2.94
1.25
1.16
1.20
1.26
1.24
1.03
1.04
1.15
1.08
0.98
1.02
1.07
1.06
0.88
2.87
2.86
3.23
2.75
2.57
3.40
4.37
3.30
3.40
3.61
3.40
3.38
3.40
4.03
   Weight
% Undissolved
                                                  1.59
                                                  1.43
                                                  1.80
                                                  1.53
                                                  1.43
                                                  2.08
                                                  2.89
                                       1.84
                                       1.97
                                       1.93
                                       1.97
                                       1.95
                                       1.73
                                       2.44
-------
    Sample Location
                          TABLE J-5.   RESULTS OF SOLID PHASE ANALYSES
                                      EXPERIMENT 27R
Time
Set 1

Scrubber Liquid Tk
Scrubber Bottoms Tk
Hold Tank Effluent
Marble Bed:  Front
Marble Bed:  Back
Scrubber Bottoms S
Scrubber Spray
                                             7/11/72
Wt % Solids
 in Slurry
0935
0940
0953
1000
1007
1015
1020
6.70
5.94
7.43
6.46
7.52
6.92
7.18
                                                      Composition  in Mi 111moles/Gram
Total S
Ca
Mg
SO,,
SO.
CO,
4.02
4.53
3.60
4.22
3.98
4.07
3.57
8.04
7.95
8.13
7.84
7.95
7.93,
8.08
0.5
0.5
0.06
0.06
0.06
0.06
0.07
3.05
3.53
2.65
3.26
3.04
3.17
2.70
0.97
1.00
0.95
0.96
0.94
0.90
0.87
3.82
3.22
4.36
3.81
4.02
3.79
4.54
 Weight
Undissolved
                                                                       2,
                                                                       1,
                                                                       2
                                                                       2,
                                                                       2,
                                                                       1,
                                                                  37
                                                                  79
                                                                  70
                                                                  24
                                                                  91
                                                                  64
                                                                       3.16
Set 2

Scrubber Liquid Tk
Scrubber Bottoms Tk
Hold Tank Effluent
Marble Bed:  Front
Marble Bed:  Back
Scrubber Bottoms S
Scrubber Spray
1040
1045
1100
1110
1115
1122
1128
6.80
7.47
7.38
7.08
7.97
7.49
7.69
3.91
3.72
3.49
4.24
4.44
3.69
3.53
8.00
8.06
8.07
8.01
7.96
8.12
8.08
0.06
0.07
0.06
0.06
0.06
0.06
0.06
2.94
2.78
2.62
3.23
3.45
2.76
2.74
0.98
0.93
0.87
1.01
0.99
0.93
0.79
4.00
4.28
4.65
3.79
3.55
4.50
4.45
                                                                       2.03
                                                                       2.12
                                                                       2.28
                                                                       1.96
                                                                       1.83
                                                                       2.72
                                                                       2.58
-------
c_

00
                                TABLE J-6.   RESULTS OF SOLID  PHASE ANALYSES
                                            EXPERIMENT 28R
    Sample Location

Set 1

Scrubber Liquid Tk Lower
Scrubber Liquid Tk Upper
Scrubber Bottoms Tk
Hold Tank Effluent
Marble Bed:   Front-Upper
Marble Bed:   Front-Lower
Marble Bed:   Back-Lower
Scrubber Bottoms S
Scrubber Spray
      Set 2

      Scrubber Liquid Tk Lower
      Scrubber Liquid Tk Upper
      Scrubber Bottoms Tk
      Hold Tank Effluent
      Marble Bed:  Front-Upper
      Marble Bed:  Front-Lower
      Marble Bed:  Back-Lower
      Scrubber Bottoms S
      Scrubber Spray
                                 Time
                                                   7/11/72
Wt % Solids
 in Slurry
0250
0255
0300
0312
0325
0345
0355
0330
0337
6.04
6.07
6.60
6.17
6.61
8.45
4.72
6.93
6.40
0405
0410
0420
0440
0512
0447
0455
0505
0520
6.05
6.17
6.60
6.47
6.13
6.61
4.46
7.67
6.71
                                                           Composition  in Mi 111moles/Gram
Total S
               4.74
               4.31
               4.09
               4.02
               4.30
               4.07
               5.49
               4.16
               3.84
                                                4.
                                                4,
                                                4.
                                                5,
                                                4,
                                                5,
                                                4,
                 46
                 52
                 22
                                                4.06
                 07
                 18
                 90
                 50
Ca
Mg
SO,
SO,
CO,
                                                4.21
7.82
7.87
7.94
7.88
7.86
7.95
7.52
7.90
8.01
7.82
7.83
7.85
7.77
7.67
7.76
7.45
7.84
7.92
0.06
0.06
0.07
0.07
0.06
0.07
0.04
0.07
0.07
0.04
0.05
0.06
0.06
0.04
0.06
0.03
0.05
0.06
3.19
3.26
3.07
3.04
3.21
3.00
4.26
3.14
2.86
3.34
3.36
3.15
3.01
3.90
3.11
4.71
3.39
3.13
1.05
1.05
1.02
0.98
1.09
1.07
1.23
1.02
0.98
1.12
1.16
1.07
1.05
1.17
1.07
1.19
1.11
1.08
3.65
3.70
3.70
3.74
3.40
3.79
2.16
3.67
3.91
3.30
3.20
3.49
3.90
2.88
3.53
1.87
3.00
3.48
   Weight
% Undissolved
                                                   2.11
                                                   1.92
                                                   1.93
                                                   2.12
                                                   1.81
                                                   2.12
                                                   1.20
                                                   2.02
                                                   1.99
                                                   1.99
                                                   1.80
                                                   1.98
                                                   1.97
                                                   1.02
                                                   1.96
                                                   0.83
                                                   2.04
                                                   1.64
-------
I
10
                                TABLE J-7.  RESULTS OF SOLID PHASE ANALYSES
                                           EXPERIMENT 29R
    Sample Location

Set 1

Scrubber Liquid Tk Lower
Scrubber Liquid Tk Upper
Scrubber Bottoms Tk
Hold Tank Effluent
Marble Bed:  Front-Upper
Marble Bed:  Front-Lower
Marble Bed:  Back-Lower
Scrubber Bottoms S
Scrubber Spray
      Set 2

      Scrubber Liquid Tk Lower
      Scrubber Liquid Tk Upper
      Scrubber Bottoms Tk
      Hold Tank Effluent
      Marble Bed:  Front-Upper
      Marble Bed:  Front-Lower
      Marble Bed:  Back-Lower
      Scrubber Bottoms S
      Scrubber Spray
                                Time
                           1225
                           1230
                           1235
                           1256
                           0135
                           0110
                           0118
                           0130
                           0140
                                                  7/13/72
Wt % Solids
 in Slurry
1100
1105
1115
1130
1203
1141
1155
1145
1210
7.21
7.32
7.59
10.05
11.31
7.86
6.18
7.09
8.41
   7.21
   8.19
  10.27
   8.85
  12.34
   8.99
   6.87
   9.17
   8.72
                                                           Composition in Hi Hi moles/Gram
Total S
                                                      4.75
                                                      4,
                                                      4,
                                                      4,
                                                      5,
                                                      4,
                                                      6,
                                                      4
                 69
                 56
                 51
                 32
                 55
                 09
                 80
               4.53
 5.04
 4.75
   65
   61
   60
   68
   05
   07
Ca
Mg
SO,
SO.
CO,
 5.00
7.72
7.85
7.80
7.62
7.36
7.57
7.19
7.54
7.55
7.45
77
7.54
7.47
7.30
7.46
7.22
7.43
7.46
0.05
0.05
0.06
0.08
0.06
0.08
0.05
0.06
0.07
0.07
0.07
0.07
0.07
0.04
0.06
0.03
0.05
0.05
3.42
3.40
3.28
3.25
3.88
3.37
4.54
3.45
3.27
3.59
3.36
3.33
3.30
4.10
3.32
4.50
3.58
3.63
1.32
1.28
1.28
1.26
1.44
1.18
1.55
1.35
1.26
1.45
1.39
1.32
1.31
1.50
1.36
1.55
1.49
1.37
3.00
2.95
3.04
2.93
2.13
2.92
1.32
2.73
2.90
2.59
2.75
2.85
2.93
2.06
2.97
1.34
2.40
2.67
 Weight
Undissolved
                                                  1.60
                                                  1.44
                                                  1.75
                                                  1.76
                                                  1.14
                                                  1.77
                                                  0.66
                                                  1.49
                                                  1.83
                                       1.47
                                       1.66
                                       1.75
                                       1.68
                                       0.98
                                       1.79
                                       0.76
                                       1.42
                                       1.62
-------
                               TABLE J-8.   RESULTS OF SOLID PHASE ANALYSES
                                           EXPERIMENT 30R
                                                  7/14/72
I
o
         Sample Location
                          Time
Wt % Solids
 in Slurry
Set 1

Scrubber Liquid Tk-Lower   1000
Scrubber Liquid Tk-Upper   1005
Scrubber Bottoms Tk        1015
Hold Tank Effluent        1031
Marble Bed:   Front-Upper   1052
Marble Bed:   Front-Lower   1038
Marble Bed:   Back-Lower   1045
Scrubber Bottoms S        1058
Scrubber Spray            1105
      Set  2

      Scrubber Liquid Tk-Lower   1125
      Scrubber Liquid Tk-Upper   1130
      Scrubber Bottoms Tk 1      1135
      Hold Tank  Effluent         1150
      Marble  Bed:   Front-Upper   1210
      Marble  Bed:   Front-Lower   1200
      Marble  Bed:   Back-Lower    1205
      Scrubber Bottoms S         1218
      Scrubber Spray             1227
                                                          Composition  in Millimoles/Gram
Total S    Ca
                                                     5.79
                                                     5.67
                                                       .52
                                                       .63
                                                     6.10
                                                     5.81
                                                     6.46
                                                     5.66
                                                     5.70
               5,
               5.
                                                5.81
                                                5.82
                                                 .64
                                                 .67
                                                 .12
                                                 .88
                                                 .39
                                                 .95
Mg
SO,
SO,
CO,
                                                5.63
7.10
7.09
7.13
7.16
7.10
7.01
7.04
7.17
7.15
7.09
7.15
7.15
7.14
7.03
7.10
7.00
7.09
7.13
0.05
0.06
0.05
0.05
0.04
0.05
0.03
0.05
0.05
0.04
0.04
0.05
0.05
0.05
0.05
0.04
0.04
0.06
4.08
4.00
3.87
3.94
4.30
4.04
4.62
3.89
3.87
4.02
4.02
3.89
3.94
4.25
4.06
4.56
4.17
3.91
1.71
1.68
1.65
1.69
1.80
1.77
1.84
1.77
1.83
1.79
1.80
1.75
1.73
1.87
1.82
1.83
1.78
1.72
1.45
1.59
1.82
1.82
1.19
1.49
0.87
1.82
1.67
1.46
1.47
1.59
1.64
1.33
1.27
0.86
1.27
1.68
   Weight
% Undissolved
                                                   1.10
                                                   1.35
                                                   1.55
                                                   1.46
                                                   1.00
                                                   1.21
                                                   0.64
                                                   1.34
                                                   1.40
                                                                1.34
                                                                1.35
                                                                1.59
                                                                1.51
                                                                0.99
                                                                1.26
                                                                0.71
                                                                1.22
                                                                1.85
-------
TABLE J-9.   LIQUID CHEMICAL ANALYSIS  AT  STEADY  STATE
             EXPERIMENT 25R
                       7/7/72
           Concentration in m moles/liter
Set
No.
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2

Time
1142
1130
1155
1203
1055
1100
1120
1115




1235
1240
1300
1255

Sampling Point
Marble Bed Back
Marble Bed Front
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Back
Marble Bed Front
Scrubber Bottom (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid

Ca++
24.67
25.85
24.35
24.03
22.55
20.58
17.94
15.83




22.0
21.32
17.80
15.98

Mg++
3.32
3.29
3.26
3.14
3.23
3.20
3.11
0.90




3.24
3.21
3.18
0.96

Na+
0.72
0.70
0.71
0.83
0.69
0.68
0.69
0.90




0.71
0.70
0.69
0.91

C03
2.14
1.48
3.15
5.35
6.52
6.08
6.56
2.01




5.15
5.29
6.36
2.12

S04
13.82
-
24.67
18.52
8.54
8.94
15.1
12.8




9.99
8.95
12.05
10.02

s°;
21.0
45.6
9.95
8.51
21.55
18.56
6.57
4.02




20.96
19.90
9.62
6.98

Cl-
1.38
1.43
1.32
1.31
1.44
1.44
1.39
1.36




1.31
1.30
1.32
1.15
Tot.
N
0.3
0.3
0,3
0.3
0.3
0.3
0.3
0.3




0.3
0.30
0.3
0.3

PH
5.29
5.31
5.23
6.02
5.50
5.59
6.05
6.99




5.45
5.56
6.02
6.96
Temp.
°C
-
-
49.0
-
50.5
49.8
49.0
27.5




49.3
49.0
48.5
28.0
-------
                                TABLE J-10.   LIQUID CHEMICAL  ANALYSIS AT STEADY STATE
                                             EXPERIMENT 26R
                                                       7/10/72
                                          Concentration in m moles/11ter
C-i
I
ro
Set
No.
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
Time
1445
1435
1450
1455
1400
1405
1420
1425
1602
1555
1615
1610
1515
1520
1547
1542
Sampling Point
Marble Bed Back
Marble Bed Front
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Back
Marble Bed Front
Scrubber Bottom (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
28.5
30.7
27.5
21.5
24.8
24.2
19.7
17.5
29.4
32.1
27.9
22.5
25.3
27.36
20.5
17.7
Mg++
3.52
3.56
3.54
3.45
3.57
3.73
3.35
1.84
3.52
3.60
3.54
3.56
3.54
3.57
3.38
1.95
Na+
0.88
0.89
0.88
0.87
0.87
0.88
0.87
0.98
0.88
0.87
0.87
0.87
0.86
0.88
0.85
0.97
C03
3.09
3.80
3.41
5.67
6.43
5.69
6.52
3.39
3.93
3.59
3.68
6.16
6.48
5.26
5.65
4.26
S04
24.1
22.5
19.3
21.4
24.50
21.3
20.4
18.0
23.8
24.3
23.8
-
21.86
24.36
20.60
18.2
S0=3
15.8
21.8
17.0
3.73
12.30
9.62
3.31
0.74
18.6
19.5
15.5
-
12.60
11.03
3.36
0.76
Cl-
1.30
1.35
1.33
1.37
1.34
1.37
1.35
1.14
1.18
1.28
1.22
1.21
1.30
1.22
1.19
1.12
Tot.
N
0.5
-
-
-
0.5
0.5
0.5
0.5
-
-
0.5
-
0.5
0.5
0.5
0.5
PH
5.13
4.97
5.32
5.97
5.30
5.32
6.00
7.19
5.24
5.19
6.05
5.29
5.39
5.41
6.07
7.15
Temp.
°C
48.0
48.0
48.5
47.0
49.0
48.7
48.0
31.0
47.0
46.0
47.0
47.0
49.0
48.5
47.0
31.5
-------
                                 TABLE J-ll.   LIQUID CHEMICAL  ANALYSIS AT  STEADY  STATE
                                              EXPERIMENT 27R
                                                        7/11/72
                                            Concentration in m moles/liter
CO
Set
No.
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
Time
1007
1015
1020
0935
0940
0953
0950
2022
2030
2040
2050
1040
1045
1100
1056
Sampling Point
Marble Bed Back
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Back
Marble Bed Front
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
27.70
26.90
19.10
24.33
22.06
19.40
17.90
29.80
30.20
28.50
19.60
24.46
21.66
24.88
17.60
Mg++
4.04
3.92
3.80
's.94
3.92
3.86
2.43
3.86
3.97
3.92
3.89
4.10
3.97
3.84
2.45
Na+
0.88
0.89
0.88
0.86
0.88
0.86
0.92
0.90
0.91
0.92
0.89
0.86
0.92
0.88
0.95
C03
3.01
3.49
7.77
7.45
6.60
6.63
4.33
2.79
3.98
3.20
7.51
7.65
7.21
6.85
5.34
so=
20.00
16.60
20.00
22.65
21.62
20.80
18.70
23.10
25.40
24.30
-
22.96
20.83
14.9
18.4
S
22
23
3
10
7
2
1
16
18
16

10
7
1
1
°3 l
.60 1
.80 1
.04 1
.02 1
.17 1
.65 1
.08 1
.90
.90
.20
-
.44
.99
2.5
.12

.30
.34
.29
.35
.43
.33
.22
.25
.22
.26
.41
.40
.30
1.38
1.24
Tot.
N
.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
pH
5.28
5.27
6.10
5.42
5.68
6.05
6.68
5.59
5.31
5.49
6.22 .
5.52
5.67
6.12
6.81
Temp.
°C
47.4
48.2
47.7
49.2
48.3
48.0
32.5
47.2
48.5
47.7
48.1
49.8
49.1
, 47.4
33.9
-------
TABLE J-12.   LIQUID CHEMICAL  ANALYSIS AT STEADY STATE
             EXPERIMENT 28R
                       7/11/72
           Concentration In m moles/liter
Set
No.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
Time
0325
0355
0345
0330
0377
0250
0255
0300
0312
0309
0512
0455
0477
0505
0520
0410
0415
0420
0440
0436
Sampling Point
Marble Bed Front-Upper
Marble Bed Back -Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower
Scrubber Liquid at Tank-Uper
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Front-Upper
Marble Bed Back-Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower
Scrubber Liquid at Tank-Upper
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
27.22
26.41
28.86
26.95
21.80
24.65
22.55
23.10
20.06
19.68
26.90
26.35
28.23
25.73
20.03
23.52
24.25
23.93
19.80
18.85
Mg++
4.53
4.48
4.72
4.55
4.51
4.50
4.34
4.50
4.33
3.19
4.84
4.83
4.82
4.90
4.75
4.65
4.72
4.75
4.63
3.37
Na+
0.65
0.65
0.64
0.64
0.62
0.70
0.70-
0.68
0.68
0.90
0.70
0.68
0.70
0.64
0.65
0.66
0.67
0.66
0.72
0.88
C°3
2.85
2.75
3.86
4.16
7.66
6.71
6.90
5.83
6.63
4.59
3.79
3.32
2.91
3.68
6.87
5.33
5.38
5.58
6.07
4.57
»;
25.15
21.38
25.49
22.22
21.18
22.30
21.62
21.44
20.92
19.61
26.07
24.90
21.41
22.53
21.65
22.34
22.87
23.32
21.27
20.04
so=3
11.40
16.12
16.14
16.14
3.98
12.60
8.19
8.83
3.48
2.12
11.25
12.68
18.88
15.68
3.06
10.05
10.41
9.05
3.27
1.21
Cl-
1.24
1.17
1.22
1.26
1.20
1.15
1.11
1.16
1.21
1.19
1.22
1.25
1.28
.29
.27
.19
.20
.27
.25
.22
Tot.
N
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
-
05
0.5
0.5
0.5
0.5
0.5
0.5
PH
5.76
5.61
5.66
5.67
6.42
5.69
5.96
5.91
6.31
7.02
5.95
5.80
5.81
5.79
6.49
5.98
5.96
6.00
5.45
7.10
Temp.
°C
46.6
50.0
44.2
50.5
50.0
51.4
51.1
50.3
50.3
37.0
47.5
49.0
46.0
50.8
50.8
51.5
51.4
50.9
50.8
38.0
-------
                                TABLE J-13.   LIQUID CHEMICAL ANALYSIS  AT STEADY STATE
                                             EXPERIMENT 29R
                                                       7/13/72
                                           Concentration in m moles/liter
c*
I
CJI
Set
No.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
Time
1203
1155
1141
1145
1210
1100
1105
1115
1130
1125
0135
0118
0110
0130
0140
1225
1230
1235
1256
1252
Sampling Point
Marble Bed Front-Upper
Marble Bed Back-Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower
Scrubber Liquid at Tank-Upper
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Marble Bed Front-Upper
Marble Bed Back -Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower
Scrubber Liquid at Tank-Upper
Scrubber Bottom at Tank
Hold Tank Effluent
Clarifier Liquid
Ca++
23.97
25.80
26.66
26.63
19.60
23.87
21.99
23.26
19.40
18.28
23.85
24.57
25.85
24.13
19.22
23.01
22.10
22.10
18.91
18.45
Mg++
5.84
5.94
5.84
5.83
5.89
5.65
5.51
5.80
5.67
3.67
6.13
6.07
6.25
6.28
6.23
6.10
6.06
6.25
6.13
3.79
Na+
0.68
0.66
0.66
0.66
0.66
0.65
0.66
0.65
0.66
0.82
0.70
0.68
0.70
0.70
0.66
0.67
0.68
0.66
0.70
0.82
C0=
4.34
4.05
3.65
3.09
3.09
6.54
3.74
4.87
4.91
3.69
3.34
3.28
3.75
3.59
5.40
6.22
4.20
6.97
5.38
3.81
soj
26.62
27.43
23.74
22.13
21.53
23.36
24.02
23.72
21.41
20.64
26.48
26.79
24.48
23.14
21.96
23.10
22.76
24.49
21.85
20.85
S03
5.81
9.91
15.32
15.51
3.58
10.57
6.04
9.54
4.03
0.88
6.50
9.96
12.87
14.29
3.34
10.42
8.43
7.50
3.50
0.90
Cl-
1.34
1.35
1.36
1.37
1.36
1.36
1.33
1.35
1.36
1.20
1.35
1.36
1.33
1.37
1.37
1.46
1.26
1.39
1.36
1.21
Tot.
N
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.4
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
PH
5.81
5.40
5.36
5.29
6.02
5.50
5.79
5.49
6.04
6.80
5.68
5.45
5.59
5.31
6.10
5.50
5.70
5.54
6.03
7.00
Temp.
°C
45.5
48.5
46.0
50.5
50.5
51.5
51.5
51.3
51.2
35.5
46.0
45.8
43.0
50.7
50.00
50.9
50.9
50.5
50.4
35.5
-------
TABLE J-14.   LIQUID CHEMICAL  ANALYSIS AT  STEADY  STATE
             EXPERIMENT 30R
                       7/14/72
           Concentration in m moles/liter
Set
No.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
Time
1052
1045
1038
1158
1105
1000
1005
1020
1031
1023
1210
1205
1200
1218
1227
1125
1130
1135
1150
1145
Sampling Point
Marble Bed Front-Upper
Marble Bed Back-Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower*
Scrubber Liquid at Tank-Upper*
Scrubber Bottom at Tank*
Hold Tank Effluent
Clarifier Liquid
Marble Bed Front-Upper
Marble Bed Back-Lower
Marble Bed Front-Lower
Scrubber Bottoms (Scrubber)
Spray Water
Scrubber Liquid at Tank-Lower*
Scrubber Liquid at Tank-Upper*
Scrubber Bottom at Tank*
Hold Tank Effluent
Clarifier Liquid
Ca++
24.09
26.59
27.18
26.92
18.78
23.57
22.39
25.21
18.53
18.57
24.43
27.63
25.53
26.98
18.59
24.75
22.68
25.12
18.91
18.26
Mg++
6.62
6.92
6.53
6.89
6.86
6.67
6.46
6.71
6.45
4.60
6.78
7.03
6.95
7.09
6.97
6.89
6.77
6.84
6.92
4.70
Na+
0.55
0.60
0.60
0.52
0.55
0.58
0.57
0.58
0.56
0.85
0.50
0.48
0.48
0.45
0.42
0.47
0.45
0.45
0.47
0.90
C0=3
2.52
2.81
2.89
2.92
5.91
5.45
3.85
3.58
4.77
4.09
3.08
3.10
2.36
2.90
6.34
4.85
4.70
4.33
5.28
4.75
so;
26.44
26.27
24.24
23.95
22.34
23.61
23.90
25.24
22.06
20.47
25.36
26.61
21.14
23.55
21.59
24.27
23.66
24.39
21.91
20.38
S0=3
8.04
14.66
17.28
18.26
4.18
12.50
9.02
11.74
4.40
1.73
9.70
17.09
20.48
20.03
5.13
14.02
10.50
15.13
4.89
2.16
Cl-
1.31
1.37
1.36
1.34
1.37
1.34
1.31
1.37
1.33
1.27
1.34
1.34
1.34
1.35
1.35
1.35
1.34
1.36
1.36
1.25
Tot.
N
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
PH
5.60
5.09
5.50
5.11
5.90
5.36
5.58
5.30
5.91
6.68
5.94
5.02
5.08
5.09
5.84
5.30
5.49
5.25
5.80
6.60
Temp.
°C
47.0
49.3
43.0
49.6
50.0
50.7
50.5
50.0
50.0
36.0
47.0
49.9
47.80
50.00
50.00
50.9
50.5
50.3
50.00
37.0
-------
        APPENDIX K







LIMESTONE TAIL-END SYSTEM



    MATERIAL BALANCES



           AND



    RATE CALCULATIONS
-------
                                    TABLE K-l.  TOTAL SULFUR MATERIAL BALANCE

                                                  Experiment 25R

Marble Bed (Set #1 )
Entering Streams
Leaving Streams

Spray Water
Gas In
Gas Out*
Scrubber Liquid
Scrubber Bottom
Flow Rate
908 1/min
9,792 g mole/mln
10,497 g mole/m1n
681 l/m1n
227 l/m1n
Solid
Content
75.5 g/1
68.2 g/1
79.0 g/1
Total S
In Solid
(m mole/g)
4.36
5.01
4.61
Total S
In Liquid
(m mole/1 )
27.03
34.82
34.62
Total S
In Gas
(ppm)
2,329
956
Total S
(m mole/
m1n)
323,438
22,805
10.035
256,397
90,529
                     Total Sulfur In = 346,243 m mole/nln - Total Sulfur Out • 356,961 m mole/mln
Hold Tank (Set #1}
  Entering Streams   Scrubber Liquid
                     Scrubber Bottom
                     ClaHfler Liquid
  Leaving Streams
Hold Tank Eff.

Total Sulfur In
                      681  1/nrin
                      227  l/m1n
                       38 l/m1n
                     71.3 g/1
                     77.4 g/1
              4.74
              4.42
            30.09
            27.50
            16.82
    946 1/min        77.9 g/1      4.28        21.67

335,237 m mole/mln - Total Sulfur Out = 335,907 m mole/mln
                    250,643
                     83,901
                        693

                    335,907
Hold Tank (Set #2)
  Entering Streams
Scrubber Liquid
Scrubber Bottom
Clarlfler Liquid
    738 1/min
    208 1/min
     38 1/min
  Leaving Streams    Hold Tank             984 l/m1n

                     Total Sulfur In = 342,401
70.4 g/1
72.9 g/1
4.85
4.67
30.96
28.85
17.00
                                       71.4 g/1       4.73        21.67

                                     - Total  Sulfur Out = 344,298
•260,680
 81,245
     676

344,298
'Average of marble bed front and back
"From hold tank eff.
                                                       K-l
-------
                                    TABLE K-2.  TOTAL SULFUR MATERIAL BALANCE

                                                  Experiment 26R
Marble Bed (Set #1)
  Entering Streams   Spray Water
                     Gas In
  Leaving Streams
Gas Out
Scrubber Liquid
Scrubber Bottom
                                            Flow Rate
                                        Solid
                                       Content
                               Total S
                               In Solid
                              (m mole/g)
                      Total S
                     1n Liquid
                     (m mole/1)
                      Total S   Total S
                       In Gas   (m mole/
                       (ppm)      mln)
Marble Bed (Set #2)
  Entering Streams   Spray Water
  Leaving Streams
Gas In

Gas Out
Scrubber Liquid
Scrubber Bottom
   889 1/min          65.7        3.82        23.96
 9,940 g mole/mln

10,655 g mole/mln
   674 l/m1n          72.9        4.38        43.10
   219 l/m1n          63.4A       4.43        39.20
                                                                                                  2,490

                                                                                                    999
                                             244,416
                                             24,751

                                             10,644
                                             244,258
                                             70,094
                     Total Sulfur In = 269,167 m mole/mln - Total Sulfur Out - 324,995 m moles/min
Hold Tank (Set #2)
  Entering Streams
Scrubber Liquid
Scrubber Bottom
Clarifler Liquid
   674 1/mln
   219 l/m1n
    57 1/min
62.4
63.4
  Leaving Streams    Hold Tank             946 1/min

                     Total Sulfur In = 283,844
4.54
4.38
34.5
35.4
19.0
                                         64.3        4.12         24.0

                                     - Total Sulfur Out = 273,314
214,194
 68,567
  1,083

273,314
AScrubber bottom at tank
                                                      K-2
-------
                                     TABLE  K-3.  TOTAL  SULFUR MATERIAL BALANCE

                                                   Experiment 27R
 Marble  Bed  (Set  #1)
   Entering  Streams    Spray Water
                      Gas  In
                                            Flow Rate
   Leaving  Streams
Gas  Out
Scrubber Liquid
Scrubber Bottom
   568 1/min
10,100 g mole/rain

10,820 g mole/rain
   511 1/min
    57 1/min
                                        Solid
                                       Content
                                         71.8
                                                              69.9
                                                              69.2
                               Total S
                               1n Solid
                              (m mole/g)
            3.57
             4.1
            4.07
                      Total S
                     1n Liquid
                     (m mole/1}
            23.04
                              Total Sulfur In = 181,947 - Total Sulfur Out = 198,626
 Marble  Bed  (Set  #2)
   Entering  Streams   Spray Water
                     Gas  In
  Leaving Streams
Gas Out
Scrubber Liquid-
Scrubber ^Bottom
   568 1/min          76.9        3.53
10,000 g mole/nin

10,730 g mole/mln
   511 1/min         75.25        4.34
    57 1/min          74.9        3.69
             42.6
             40.4
                                                                  27.4*
                                                                                      42.15
                                                                                       40.5
                      Total S    Total  S
                        in Gas    (m mole/
                        (pom)      mln)
                                   2,306

                                   1,114
                                                                            2,323
                                   1,099
                   158,657
                    23,290

                    12,053
                   168,216
                    18,357
                                169,750
                                 23,230

                                 11,792
                                188,424
                                 18.062
                              Total Sulfur In = 192,980 - Total Sulfur Out = 218,278
Hold Tank (Set #1}
  Entering Streams
  Leaving Streams
Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
   511  l/m1n
    57  1/min
    45  1/min
67.0
59.4
4.02
4.53
Hold Tank Eff.        613 1/min          74.3        3.60

         Total Sulfur In = 172,678 - Total Sulfur Out = 178,371
33.6
28.4
19.8

23.5
154.802
 16,985
    891

178,371
Hold Tank (Set 92)
  Entering Streams
  Leaving Streams
Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
   511  1/min
    57  1/min
    45  1/min
68.0
74.8
3.91
3.72
33.4
28.8
19.5
Hold Tank             613 I/rain          73.8        3.49         27.1

         Total  Sulfur In = 171,312 - Total  Sulfur Out = 174,498
152,932
 17,502
    878

174,498
*Hold Tank Eff.
                                                      K-3
-------
                                   TABLE K-4.  TOTAL SULFUR MATERIAL BALANCE
                                                 Experiment 28R
Total S
Solid In Solid

Marble Bed (Set #1)
Entering Streams




Leaving Streams






Marble Bed (Set #2)
Entering Streams




Leaving Streams






Hold Tank (Set #1)
Entering Streams





Leaving Streams

Hold Tank (Set #2)
Entering Streams







Spray Mater-
Lower Bed
Spray Water-
Upper Bed
Gas In
Gas Out
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Total Sulfur In =

Spray Water-
Lower Bed
Spray Water-
Upper Bed
Gas In
Gas Out
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Total Sulfur In =

Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Clarifier Liquid
Hold Tank Eff.
Total Sulfur In =

Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
ClaHfler Liquid
Flow Rate


613 1/min

583 1/mln
9,950 g mole/mi n
10,700 g mole/mi n

653 1/min

435 1/min
109 l/m1n
347,820 m moles/mi n


622 1/min

583 1/min
9,870 g mole/mi n
10,950 g mole/mi n

660 1/min

427 1/min
117 1/min
394,181 m moles/ml n


653 1/min

435 1/min
109 1/min
58 l/m1n
1,254 1/min
371,374 m moles/ml n


660 l/m1n

427 1/min
117 1/min
58 1/min
Content (m


64.00

64.00



65.85

66.10
69.30
- Total Sulfur


67.1

67.1



55.4

61.30
76.70
- Total Sulfur


60.4

60.7
66.0

61.7
- Total Sulfur


60.5

61.7
66.0

mole/g)


3.84

3.84



4.48

4.30
4.16
Out = 399


4.21

4.21



5.04

5.07
4.50
Out = 409


4.74

4.31
4.09

4.02
Out = 341


4.46

4.52
4.22

Total S Total S
In Liquid In Gas
(m mole/1) (ppm)


25.16

25.16
2,392
546

39.51

36.55
38.36
,425 m moles/ml n


24.71

24.71
2,432
543

38.94

37.32
38.21
,424 m moles/ml n


34.90

29.81
38.36
21.73
24.40
,632 m moles/min


32.41

33.28
38.21
21.25
Total S
(m mole/
mln)


166,074

157,946
23,800
5,842

218,440

139.539
35,604



191,079

179,098
24,004
5,946

209,983

148.643
44,853



209,740

126,770
33,604
1,260
341 ,632



199,478

133,294
37,057
1,232
Leaving Streams    Hold Tank Eff.
1,263 1/min
64.7
4.06
24.54
362,761
                   Total Sulfur In = 371,061 m moles/min - Total Sulfur Out = 362,761 m moles/min
                                                    K-4
-------
TABLE K-5.  TOTAL SULFUR MATERIAL BALANCE
              Experiment 29R










Flow Rate

Solid
Total S
In Solid
Content (m mole/g)
Total
S Total S
in Liquid 1n Gas
(m mole/1 ) (ppm)
Marble Bed (Set #1)
Entering Streams

Leaving







Streams






Spray Water-Lower
Spray Water-Upper
Gas In
Gas Out
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Total Sulfur In •
927
852
10,050
10,750

794

643
341
747,346
1/min
1/mln
g moles/mi n
g moles/mi n

1/min

1/min
1/min
m moles/mi n
84.1
84.1



70.2

113.1
70.9
- Total
4.53
4.53



5.32

5.32
4.80
Sulfur Out =
25.
25.



38.

32.
37.
11
11
2,456
297

20

43
64
Total S
(m mole/
mln)

376
345
24
3

326

407
128

9
9
t
9

•

9
>

439
983
924
193

861

740
884
866,678 m moles/ml n
Marble Bed (Set #2)
Entering Streams


Leaving






Hold Tank
Entering





Leaving

Hold Tank
Entering







Streams






(Set #1 )
Streams





Streams

(Set #2)
Streams





Leaving Streams


Spray Water-Lower
Spray Water-Upper
Gas In
Gas Out
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Total Sulfur In =

Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Clarifier Liquid
Hold Tank Eff.
Total Sulfur In =

Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Clarifier Liquid
Hold Tank Eff.
Total Sulfur In =
927
852
10.250
10,980

757

680
341
845.583


794

643
341
57
1,836
669.529


757

680
341
57
1,836
761,187
l/m1n
1/min
g moles/ml n
g moles/ml n

l/m1n

1/min
1/min
m moles/mi n


1/min

1/min
1/min
1/min
1/min
m n»les/m1n


1/min

1/min
1/min
1/min
l/m1n
m moles/ml n
87.2
87.2



79.8

123.4
91.7
- Total


72.1

73.2
75.9

100.5
- Total


72.1

81.9
102.7

88.5
- Total
5.00
5.00



5.36

5.60
5.07
Sulfur Out =


4.75

4.69
4.56

4.51
Sulfur Out =


5.04

4.75
4.65

6.61
Sulfur Out =
25.
25.



37.

32.
37.
1.018.544


33.

30.
33.
21.
25.
40
40
2,415
280

05

98
43
m moles/m1n


93

06
26
52
44
427
393
24
3

351

492
171



298

240
129
1
878
•
»
9
9

9

•
9



9

9
9
9
9
717
112
754
074

836

333
301



865

075
363
226
884
878,884 m moles/ml n


33.

31.
31.
21.
25.


52

19
99
75
35


300

285
173
1
795


9

9
9
9
t


456

746
745
240
603
795,603 m moles/ml n
                   K-5
-------
                                          TABLE K-6.  RATE CALCULATIONS
                                                  Experiment  25R
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    In Llq. (in mole/1)   1n Gas (ppm)       Cm irole/nrin)
Marble Bed (Set #1)
1. CaS03   1/2 H20
   Entering Streams  Flue Gas In         9,792 g nole/nrin                            2,329            22,805
                     Scrubber Spray        908 1/min                8.51                               7,727
   Leaving Streams   Flue Gas Out       10,497 g mole/min                              956            10,035
                     Scrubber Liquid       681 1/min                21.0*                             14,301
                     Scrubber Bottom       227 1/nin                9.95                               2,259
                     Rate of CaS03   1/2 HgO - S02 In - S02 Out - Oxld. Rate
                                             • 30,532 - 26,595 - .25 (22,805 - 10,035)
                                             = 30,532 - 26,595 - 3,192
                                             = 745 m mole/mln
2. CaS04
Entering Streams
Leaving Streams

Scrubber Spray
Scrubber Liquid
Scrubber Bottom
908 1/min
681 1/min
227 1/min
18.5
13.82*
24.67
                                                                                                       16,816
                                                                                                       9,411
                                                                                                       5,600
                     Rate of CaS04   2 H20 = ES04 In - ES04 Out + Oxid. Rate
                                           = 16,816 - 15,011 + 3,192
                                           = 4,997 m mole/rain
3. CaCO, Dissolution
   Entering Streams  Scrubber Spray        908 1/min               24.03                               21,819
   Leaving Streams   Scrubber Liquid       681 1/min               25.26                               17,202
                     Scrubber Bottom       227 1/min               24.35                                5,527
                     Rate of CaC03 Dissolution = zCa Out - zCa In + zCa Free. Rates
                                               = 21,819 - 22,729 + 4,997 + 745  .
                                               = 4,832 m mole/m1n

*Value from marble bed back only
                                                       K-6
-------
                                          TABLE K-6.  RATE CALCULATIONS (Continued)
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    1n L1q. (m mole/1)   In Gas (ppm)      (m mole/mln)
System Remainder
(Hold Tank, Surge Tanks and Thickener)
1. CaS03   1/2 H20
   Entering Streams  Scrubber Liquid       681 1/mln               21.00                              14,301
                     Scrubber Bottom       227 1/mln                9.95                               2.258
                     Clarlfler Liquid       38 l/m1n                4.02                                 153
   Leaving Streams   Hold Tank Eff.        946 l/m1n                6.57                               6,215
                     Rate of CaS03   1/2 H20 = S02 In - S02 Out
                                             = 16,712 - 6,215
                                             = 10,497 m mole/mln
2. CaS04   2 H20
   Entering Streams  Scrubber Liquid       681 1/min               13.82                               9,411
                     Scrubber Bottom       227 l/m1n               24.67                               5,620
                     Clarifler Liquid       38 1/min                12.8                                 486
   Leaving Streams   Hold Tank Eff.        946 1/min                15.1                              14,284
                     Rate of CaS04   2 H20 = ES04 In - sS04 Out
                                           = 15,517 - 14,284
                                           = 1,233 m mole/mln
3. CaC03 Dissolution
   Entering Streams  Scrubber Liquid       681 1/mln               25.26                              17,202
                     Scrubber Bottom       227 1/mln               24.35                               5,527
                     Clarlfler Liquid       38 1/min               15.83                                 601
   Leaving Streams   Hold Tank Eff.        958 1/min               17.94                              17,186
                     Rate of CaCO, = ECa Out - ECa In + ECa Formation Rates
                                   = 17,186 > 23,330 + 10,497 + 1,233
                                   = 5,586 m mole/mln
                                                       K-7
-------
                                           TABLE  K-6.   RATE  CALCULATIONS  (Continued)
 System  Remainder
 (Hold Tank, Surge Tanks and Thickener)

 1.  CaS03   1/2 H20
                                       Stream Flow Rate
                    Species Cone.
                  In Llg. (m mole/1)
                                                                                 Species  Cone.    Species  Flow Rate
                                                                                 In  Gas  (ppm)       (in mole/rain)
  Entering Streams  Scrubber Liquid
                    Scrubber Bottom
                    Clarifier Liquid

  Leaving Streams   Hold Tank Eff.

                    Rate of CaS0    1/2
2. CaS0
  Entering Streams  Scrubber Liquid
                    Scrubber Bottom
                    Clarifier Liquid

  Leaving Streams   Hold Tank Eff.

                    Rate of CaS0    2
3. CaCO,
  Entering Streams   Scrubber Liquid
                    Scrubber Bottom
                    Clarifier Liquid

i; Leaving  Streams    Hold  Tank Eff.
 738 1/min                21.0
 208 1/min                19.9
  38 1/min                6.98

 984 1/min                9.62

gO = S02 In - S02 Out

   = 19.343 - 9,216

   = 10,127 m mole/mi n
 738 1/min                9.99
 208 1/min                8.95
  38 1/min               10.02

 984 1/min               12.05

 = ES04 In - ZS04 Out

 = 9,343 - 11,544

 = -2,201  m mole/m1n
 738 1/min                22.0
 208 1/min               21.32
  38 1/min               15.98

 984 1/min               17.80
                     Rate of CaC03 = ECa In - zCa Out + zCa Formation Rate

                                   = 17,052 - 20,697 + 10,127 - 2,201

                                   = 4,281  m moles/ml n
                                                                                                       14,700
                                                                                                       4,378
                                                                                                          265

                                                                                                       9,216
                                                                                                       6,993
                                                                                                       1,969
                                                                                                         381

                                                                                                      11,544
                                                                                                      15,400
                                                                                                       4,690
                                                                                                         607

                                                                                                      17,052
                                                       K-8
-------
                                           TABLE  K-7.   RATE  CALCULATIONS
                                                   Experiment 26R
                                                              Species Cone.      Species  Cone.    Species  Flow Rate
                                         Stream Flow Rate    In L1q.(m mole/1)   In Gas  (ppffl)       fm  mole/rain)
 Marble Bed (Set #1)
 1. CaS03   1/2 H20
    Entering Streams  Inlet Flue Gas       9,900 g mole/mln                            2,519             24,938
                      Scrubber Spray         927 1/mln                3.73                                3,457
    Leaving Streams   Outlet Flue Gas     10,613 g mole/mln                            1,023             10,857
                      Scrubber Liquid*       681 1/mln                18.8                               12,803
                      Scrubber Bottom        246 1/mln                17.0                                4,182
                      Rate  of CaS03   1/2 H20 = S02  In - S02 Out - Ox1d. Rate
                                             « 28,395 - 27.842 - .261 (14,081)
                                             = 28,395 - 27,842 - 3,675
                                             = 3,122 m mole/ml n
 2. CaS04   2 H20
    Entering  Streams   Scrubber Spray        927 l/m1n                21.4                               19.837
    Leaving Streams    Scrubber Liquid*      681 1/mln                23.3                               15,867
                      Scrubber Bottom       246 1/mln                19.3                                4,747
                      Rate of CaS04   2 H20 = IS04  In - ES04 Out + Oxidation Rate
                                           = 19,837 - 20,614 + 3,675
                                           = 2,898 m mole/ml n
3.  CaCO, Dissolution
    Entering  Streams   Scrubber Spray        927 l/m1n                21.5                               19,930
    Leaving Streams    Scrubber Liquid*      681 1/mln                29.6                               20,158
                      Scrubber Bottom       246 l/m1n                27.5                                6,765
                      Rate of CaC03 Dissolution = iCa Out - iCa In t ECa Free. Rates
                                               = 26,923 - 19,930 + (-3.122 + 2.898)
                                               • 6,769 m mole/mln
*Ave. of marble bed front and back
                                                       K-9
-------
System Remainder
(Hold Tank, Surge Tanks and Thickener)
1 . CaS03   1/2 H20
                                          TABLE K-7.  RATE CALCULATIONS  (Continued)
                                                              Species Cone.      Species Cone.    Species  Flow  Rate
                                        Stream Flow Rate    In Liq. (m mole/1)   In Gas (ppm)       (m mole/mln)
   Entering Streams  Scrubber Liquid       681 1/min                18.8                               12,802
                     Scrubber Bottom       246 1/min                17.0                               4,182
                     Clarifier Liquid       57 1/min                 .74                                  42
   Leaving Streams   Hold Tank Eff.        984 1/min                3.31                               3,257
                     Rate of CaS03   1/2 H20 = S02 (In) - S02 (Out)
                                             = 17,026 - 3,257
                                             - 13,769 m mole/mi n
2. CaS04   2 H20
   Entering Streams  Scrubber Liquid       681 1/min                23.3                              15,867
                     Scrubber Bottom       246 1/min                19.3                               4,748
                     Clarifier Liquid       57 1/min                18.0                               1,026
   Leaving Streams   Hold Tank Eff.        984 1/min                20.4                              20,073
                     Rate of CaS04   2 H20 = iS04 In - zS04 Out
                                           = 21 ,641  - 20,073
                                           = 1,568 n mole/mi n
3. CaCO, Dissolution
   Entering Streams  Scrubber Liquid       681 1/min                29.6                              20,157
                     Scrubber Bottom       246 1/min                27.5                               6,765
                     Clarifier Liquid       57 1/min                17.5                                 998
   Leaving Streams   Hold Tank Eff.        984 1/min                19.7                              19,384
                     Rate of CaCO, Dissolution = ECa Out - zCa In + ECa Pres. Rates
                                               = 19,384 - 27,920 + (13,769 + 1,568)
                                               = 6,801 m mole/mln
                                                      K-10
-------
                                          TABLE K-7.  RATE CALCULATIONS (Continued)
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    1n Llq. (m mole/1)   In Gas (ppm)      (m mole/m1n)
Marble Bed (Set #2)
1. CaS03   1/2 H,0
Entering Streams

Leaving Streams


Inlet Flue Gas
Scrubber Spray
Scrubber Liquid*
Scrubber Bottom
Outlet Flue Gas
9,940 1/min
889 1/mln
674 1/mln
219 1/mln
10,655

3.36+
19.05
15.5

                                                                                     2,490            24,750
                                                                                                       2,987
                                                                                                      12,839
                                                                                                       3,394
                                                                                       999            10,644
                     Rate of CaS03   1/2 HgO = S02 In - S02 Out - Ox1d. Rate
                                             = 27,737 - 26,877 - .238 (24,750 - 12,839)
                                             = 29,584 - 27,896 - 2,834
                                             = - 1,146 in mole/mln
2. CaS04
   Entering Streams  Scrubber Spray        889 1/min                20.6+                             18,313
   Leaving Streams   Scrubber Liquid       674 1/min               24.05                              16,209
                     Scrubber Bottom       219 1/mln                23.8                               5,212
                     Rate of CaS04   2 H20 = £S04 In - zS04 Out + 0x1 d. Rate
                                           = 18,313 - 21,421 + 2,834
                                           = -274 m mole/mi n
3. CaC03 Dissolution
   Entering Streams  Scrubber Spray        889 1/min                22.5                              20,002
   Leaving Streams   Scrubber Liquid       674 1/mln               30.75                              20,725
                     Scrubber Bottom       219 1/min                27.9                               6,110
                     Rate of CaCO, Dissolution = zCa Out - zCa In + ECa Free. Rates
                                               = 26,835 - 20,002 + (-274 + - 1,146)
                                               = 5,413 m mole/min

•(•Value taken from hold tank off
                                                       K-ll
-------
                                          TABLE K-7.  RATE CALCULATIONS (Continued)
                                        Stream Flow Rate
                                                              Species Cone.
                                                            In L1g. (m mole/1)
System Remainder
(Hold Tank, Surge Tank and Thickener)

1. CaS0    1/2 H0
Entering Streams  Scrubber Liquid
                  Scrubber Bottom
                  Clarifier Liquid

Leaving Streams   Hold Tank Eff.

                  Rate of CaSO,   1/2
2. CaSO,
   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaS04   2
3. CaC03 Dissolution


   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.
 674 1/min
 219 1/min
  57 1/min

 946 1/min

20 = S02 In - S02 Out

   = 16,276 - 3,178

   = 13,098 m mole/min
                                           674 1/min
                                           219 1/min
                                            57 1/min

                                           946 1/min

                                           = £S04 In - zS04 Out

                                           = 22,458 - 19,487

                                           = 3,000 m mole/mi n
                                           674 1/min
                                           219 1/min
                                            57 1/min
                                           946 1/min
                                                                   19.05
                                                                    15.5
                                                                     .76

                                                                    3.36
                                                                24.05
                                                                 23.8
                                                                 18.2

                                                                 20.6
                                                                30.75
                                                                 27.9
                                                                 17.7

                                                                 20.5
                                                                              Species Cone.
                                                                              1n Gas (ppm)
                     Rate of CaCO, Dissolution
                                               = cCa Out - zCa In + zCa Prec. Rates

                                               = 19,393 - 27,844 + (13,098 + 3,000)

                                               = 7,647 m mole/min
                                                       Species Flow Rate
                                                         (m mole/ml n)
                                                                                                      12,839
                                                                                                       3,394
                                                                                                          43

                                                                                                       3,178
                                                            16,209
                                                             5,212
                                                             1,037

                                                            19,487
                                                            20,725
                                                             6,110
                                                             1,009

                                                            19,393
                                                       K-12
-------
                                          TABLE K-8.  RATE CALCULATIONS
                                                  Experiment 27R
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    In L1q. (m mole/1)   in Gas (ppm)      (m mole/mln)
Marble Bed (Set #1)
1. CaS03   1/2 H20
   Entering Streams  Flue Gas In        10,100 g mole/m1n                            2,306            23,290
                     Scrubber Spray        568 1/mln                3.04                               1,727
   Leaving Streams   Flue Gas Out       10,820 g mole/m1n                            1,114            12,053
                     Scrubber Liquid*      511 1/mln               22.60                              11,548
                     Scrubber Bottom        57 1/mln                23.8                               1,357
                     Rate of CaS03   1/2 H20 = S02 In - S02 Out - Oxid. Rate
                                             = 25,017 - 24,958 - 0.269 (23,290 - 12,053)
                                             = 25.017 - 24,958 - 2,966
                                             = -2,907 m mole/mln
2. CaS04   2 H20
Entering Streams
Leaving Streams
Scrubber Spray
Scrubber Liquid
Scrubber Bottom
568 1/min
511 1/min
57 1/min
                                                                    20.0                              11,360
                                                                    20.0                              10,220
                                                                    16.6                                 946
                     Rate of CaS04   2 H20 = £S04 In - IS04 Out + 0x1d. Rate
                                           = 11,360 - 11,166 + 2,966
                                           = 3,160 m mole/mi n
3. CaC03 Dissolution
   Entering Streams  Scrubber Spray        568 1/mln                19.1                              10,849
   Leaving Streams   Scrubber Liquid*      511 1/mln                27.7                              14,155
                     Scrubber Bottom        57 1/mln                26.9                               1,533
                     Rate of CaCO, Dissolution = zCa Out - zCa In + zCa Free. Rates
                                               = 15,688 - 10.849 + (3,160 - 2,907)
                                               = 5,092 m mole/mln

*Taken from marble bed back
                                                      K-13
-------
                                          TABLE K-8.  RATE CALCULATIONS (Continued)
                                        Stream Flow Rate
                                         Species Cone.
                                       In Llg. fm mole/1)
                                                            Species Cone.
                                                            In Gas (ppm)
                              Species Flow Rate
                                (m mole/mln)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

1. CaS03   1/2 H20


   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid
   Leaving Streams
                      511 1/mln
                       57 1/mln
                       45 1/min

                      613 1/min
Hold Tank Eff.

Rate of CaS03   1/2 H20 = S02 In - S02 Out

                        = 12,904 - 1,625

                        = 11,279 m mole/min
2. CaSO.
   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaSO.
                2 H20
3.  CaCO,
   Entering Stream
Scrubber Liquid
Scrubber Bottom
Clarifier Liquid
   Leaving Streams   Hold Tank Eff.
                      511  1/min
                       57  1/min
                       45  1/min

                      613  1/min

                        ESQ.  In - HSO.  Out
                           4          4

                      = 12,008 - 12,750

                      = -742  m mole/min
                      511  1/min
                       57  1/min
                       45  1/min

                      613  1/min
22.60
 23.8
 1.08

 2.65
                                               20.0
                                               16.6
                                               18.7

                                               20.8
 27.7
 26.9
17.90

19.40
                     Rate of CaC03 = ECa In - ECa Out + iCa Formation Rates

                                   = 11,892 - 16,492 + 11,279 - 742

                                   = 5,937  m mole/min
11,548
 1,356
    48

 1,625
                                   10,220
                                      946
                                      842

                                   12,750
14,154
 1,533
   805

11,892
                                                      K-14
-------
                                          TABLE K-8.   RATE CALCULATIONS (Continued)
                                        Stream Flow Rate
                                                   Species  Cone.
                                                 In Llg.  (m mole/1)
              Species Cone.
              In Gas (ppm)
Marble Bed (Set 2)
1. CaSO,
1/2 H20
   Entering Streams  Inlet Flue Gas
                     Scrubber Spray

   Leaving Streams   Outlet Flue Gas
                     Scrubber Liquid
                     Scrubber Bottom
                             10,000 g mole/mln
                                568 1/mln

                             10,730 g mole/mln
                                511 l/m1n
                                 57 1/min
 3.04°
 17.9
 16.2
2.323


1,099
                     Rate of CaS03   1/2 H20 = S02 In - S02 Out - 0x1d.  Rate

                                             = 24,957 - 22,723 - (23,230 - 11,792) .249

                                             = 24,957 - 22,723 - 2,848

                                             - 247 m mole/mln
2. CaSO,
   Entering Streams  Scrubber Spray

   Leaving Streams   Scrubber Liquid
                     Scrubber Bottom
                                568 1/min

                                511 1/min
                                 57 l/m1n
 20.0

24.25
 24.3
                     Rate of CaS04   2 H20 = sS04 In - IS04 Out + Ox1d. Rate

                                           = 11,814 - 13,777 + 2,848

                                           = 885 m mole/mi n
3. CaC03 Dissolution


   Entering Streams  Scrubber Spray        568 1/min

   Leaving Streams   Scrubber Liquid^      511 l/m1n
                     Scrubber Bottom        57 l/m1n
                                                         19.6

                                                         30.0
                                                         28.5
                     Rate of CaC03 Dissolution = ECa Out - JCa In + zCa Prec. Rate

                                               = 16,955 - 11,133 + C247 +885)

                                               = 6,954 m mole/mln
"Values taken from SS Set 1
^Average of marble bed front and back
                                                                                                 Species Flow Rate
                                                                                                   (m mole/mi n)
23,230
 1,727

11,792
 9,147
   923
                 11,814

                 12,392
                  1,385
                                   11.133

                                   15,330
                                    1,625
                                                      K-15
-------
                                          TABLE K-8.  RATE CALCULATIONS (Continued)
                                        Stream Flow Rate
                    Species Cone.
                  In L1q. (m mole/1)
                                                            Species Cone.
                                                            In Gas (ppm)
                                                                                                 Species Flow Rate
                                                                                                   (m mole/ml n)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

1. CaS03   1/2 H20

   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaS0    1/2
2. CaS0
   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaS0    2
3. CaCO, Dissolution


   Entering Streams  Scrubber Liquid
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.
 511 1/nin
  57 l/m1n
  45 1/min

 613 1/min

gO = S0.2 In - SOg Out

   = 10,119 - 1,864

   = 8,255 in mole/mi n



 511 1/min
  57 1/min
  45 1/min

 613 1/min

 = ZS04 In - zS04 Out

 = 14,604 - 12,750

 = 1,854 m mole/mi n
 511  1/min
  57  1/min
  45  1/min

 613  1/min
                                               17.9
                                               16.2
                                               1.12

                                               3.04°
                                              24.25
                                               24.3
                                               18.4

                                               20.8"
                                              30.00
                                               28.5
                                               17.6

                                               24.8
Rate of CaC03 Dissolution
                                               = zCa Out - zCa In + Ca Free. Rates

                                               = 15,202 - 17,746 + (8,255 + 1,854)

                                               = 7,565 m mole/min
                                                                                                       9,146
                                                                                                         923
                                                                                                          50

                                                                                                       1,864
                                                                                                      12,391
                                                                                                       1,385
                                                                                                         828

                                                                                                      12,750
                                                                                                      15,330
                                                                                                       1,624
                                                                                                         792

                                                                                                      15,202
                                                      K-16
-------
                                         TABLE  K-9.  RATE CALCULATIONS

                                                  Experiment 28R


                                                             Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    1h L1q.  (m mole/1)   In Gas (ppm)      (m mole/mln)
Marble Bed (Set #1)
CaS03 1/2 H20
Entering Streams
Leaving Streams
Gas Inlet
Spray Water-Lower
Spray Water-Upper
Gas Outlet
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
9,950 g mole/mi n
613 1/min
583 1/min
10,700 g mole/mi n
653 1/min
435 1/min
109 1/min
3.98
3.98
16.13
11.40
16.14
                                                                                    2.392            23,800
                                                                                                      2,439
                                                                                                      2,320

                                                                                      546             5,840

                                                                                                     10,532

                                                                                                      4,959
                                                                                                      1,759

                     Rate of CaS03   1/2 H20 Formation  =  zS03(liq.)  In -  ES03(l1q.) Out - Oxid. Rate

                                                       =  28,559  -  23,090  -  0.24  (17,002)

                                                       =  1,319 m mole/mi n

2. CaS04   2 H20

   Entering Streams  Spray Water-Lower     613 1/min                21.8                              13,363
                     Spray Water-Upper     583 1/min                21.8                              12,709

   Leaving Streams   Scrubber Liquid-
                      Lower                653 1/min               23.63                              15,430
                     Scrubber Liquid-
                      Upper                435 1/min               25.15                              '10,940
                     Scrubber Bottom       109 1/min               22.22                               2,422

                     Rate of CaS04   2 HgO Formation =  ES04(l1q.)  In - zS04(Hq.)  Out  + Oxid.  Rate

                                                     =  26,072 -  28,792 +  4,150

                                                     =  1,430 m mole/mi n

3. CaC03 Dissolution

   Entering Streams  Spray Water-Lower     613 1/min               21.80                               13,363
                     Spray Water-Upper     583 l/m1n               21.80                               12,709

   Leaving Streams   Scrubber Liquid-
                      Lower                653 1/min               27.64                               18,048
                     Scrubber Liquid-
                      Upper                435 1/min               27.22                               11,841
                     Scrubber Bottom       109 1/min               26.95                                2,937

                     Rate of CaC03 Dissolution = ECa(liq.) Out  - ECa(1fq.)  In + ECa Formation Rates

                                               = 32,826 - 26,072 + 1,134  + 1,615

                                               = 9,503  m mole/min
                                                      K-17
-------
                                          TABLE K-9.  RATE CALCULATIONS (Continued)
                                                              Species Cone.      Species Cone.    Species Flow Rate
                                        Stream Flow Rate    In Liq.  (m mole/1]    In Gas (ppm)      (m mole/min)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

I. CaS03   1/2 H20


   Entering Streams  Scrubber Liquid-
                      Lower                653 1/nrin               16.13                              10,532
                     Scrubber Liquid-
                      Upper                435 I/rain               11.40                               4,959
                     Scrubber Bottom       109 1 /rain               16.14                               1,759
                     Clarifier Liquid       58 1/min                2.12                                 123

   Leaving Stream    Hold Tank Eff.      1,254 1/min                3.48                               4,364

                     Rate of CaS03   1/2 HgO Formation = zS03(11q.) In - ES03(Hq.) Out

                                                       = 17,373 - 4,364

                                                       = 13,009 m mole/min

2. CaS04   2 H20
   Entering Streams  Scrubber Liquid-
                      Lower                653 1/min               23.63                              15,430
                     Scrubber Liquid-
                      Upper                435 1/min               25.15                              10,940
                     Scrubber Bottom       109 1/min               22.22                               2,421
                     Clarifier Liquid       58 1/min               19.61                               1,137

   Leaving Stream    Hold Tank Eff.      1,254 l/ra1n               20.92                              26,233

                     Rate of CaS04   2 H20 Formation = iS04(liq.) In - lS04(liq.) Out

                                                     = 29,928 - 26,233

                                                     = 3,695 m mole/min

3. CaC03


   Entering Streams  Scrubber Liquid-
                      Lower                653 1/min               27.64                              18,048
                     Scrubber Liquid-
                      Upper                435 1/nrin               27.22                              11,840
                     Scrubber Bottom       109 I/rain               26.95                               2,937
                     Clarifier Liquid       58 l/ro1n               19.68                               1,141

   Leaving Streams   Hold Tank Eff.      1,254 1/min               20.06                              25,155

                     Rate of CaCO, Dissolution = zCa(liq.) Out - zCa(liq.) In + z:Ca Formation

                                               = 25,155 - 33,966 + 13,009 + 3,695

                                               = 7,893 m mole/m1n
                                                      K-18
-------
                                          TABLE K-9,.  RATE CALCULATIONS (Continued)


                                                              Species Cone.       Species  Cone.    Species  Flow Rate
                                        Stream Flow Rate    In Llq.  (m mole/1)    In  Gas  (ppm)       (m mole/mln)
Marble Bed (Set 2)

1. CaS03   1/2 H20
Entering Streams


Leaving Streams





Gas Inlet
Spray Water-Lower
Spray Mater-Upper
Gas Outlet
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
9,870 g mole/ml n
622 1/min
583 1/min
10,950 g mole/ml n

660 l/m1n

427 1/min
117 1/min

3.06
3.06


15.78

11.25
15.68
                                                                                     2,432             24,003
                                                                                                       1,903
                                                                                                       1.784

                                                                                       543              5,946

                                                                                                      10,415
                     Rate of CaS03   1/2 HgO Formation = zS03(liq.)  In  -  cS03(Hq.)  Out  -  Oxid,  Rate

                                                       = 27.690 -  23.000  -  0.259  (24,003-5,946)

                                                       = 10 m mole/rain
2. CaS04
Entering Streams

Leaving Streams




Spray Water-Lower
Spray Water-Upper
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
622 l/m1n
583 1/min

660 1/min

427 l/m1n
117 1/min
21.65
21.65

23.15

26.07
22.53
                                                                                                       4,804
                                                                                                       1,835
                                                                                                      13,466
                                                                                                      12,622
                                                                                                      15,279

                                                                                                      11,132
                                                                                                       2,636-
                     Rate of CaS04   2 H20 Formation =  zS03(liq.)  In  -  zS03(liq.) Out + 0x1d.  Rate

                                                     =  26.088  -  29,047  +  4.680

                                                     =  1,721 m mole/ml n

3. CaCO, Dissolution


   Entering Streams  Spray Water-Lower     622  1/min               20.03                               12,459
                     Spray Water-Upper     583  1/min               20.03                               11,677

   Leaving Streams   Scrubber Liquid-
                      Lower                660  1/min               27.29                               18,011
                     Scrubber Liquid-
                      Upper                427  1/min               26.90                               11,486
                     Scrubber Bottom        117  1/min               25.73                               3,010

                     Rate of CaC03 Dissolution  =  sCa(11q.) Out - zCa(liq.)  In + zCa Formation  Rates

                                               =  32.507 - 24.136 +  50 + 1,681

                                               =  10,102 m mole/mi n
                                                     K-19
-------
                                          TABLE K-9.   RATE CALCULATIONS (Continued)
                                        Stream Flow Rate
                                                   Species  Cone.
                                                 1n Llq.  (m mole/11
                                                                              Species Cone.
                                                                              1n Gas (ppm)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

1. CaS03   ,1/2 H20

   Entering Streams  Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.
                                660 1/min

                                427 1/min
                                117 1/min
                                 58 1/min

                              1,263 1/min
                                                                15.78

                                                                11.25
                                                                15.68
                                                                 1.21

                                                                 3.27
                     Rate of CaS03   1/2 H20 Formation = zS03(liq.)  In - £S03(liq.}  Out

                                                       = 17,121  - 4,130

                                                       = 12,991  m mole/min
2. CaSO,
2 H20
Entering Streams  Scrubber Liquid-
                   Lower
                  Scrubber Liquid-
                   Upper
                  Scrubber Bottom
                  Clarifier Liquid

Leaving Streams   Hold Tank Eff.

                  Rate of CaSO.   2
                                           660 1/min

                                           427 1/min
                                           117 1/min
                                            58 1/min

                                         1,263 1/min
                                                        23.15

                                                        26.07
                                                        22.53
                                                        20.04

                                                        21.27
                                           Formation = SSO^liq.)  In - zS04 (llq.)  Out

                                                     = 30,208 - 26,864

                                                     = 3,346 m mole/min
                                                                                              Species Flow Rate
                                                                                                (m mole/min)
                                                                                                   10,414

                                                                                                    4,803
                                                                                                    1,834
                                                                                                       70

                                                                                                    4,130
                                                                                                   15,279

                                                                                                   11,131
                                                                                                    2,636
                                                                                                    1,162

                                                                                                   26,864
3.  CaCO,
Entering Streams  Scrubber Liquid-
                   Lower                660 1/min
                  Scrubber Liquid-
                   Upper                427 1/min
                  Scrubber Bottom       117 1/min
                  Clarifier Liquid       58 l/m1n

Leaving Streams   Hold Tank Eff.
                                                                   27.29

                                                                   26.90
                                                                   25.73
                                                                   18.85
                                         1,263 1/min               19.80

                     Rate of CaCOj Dissolution = zCa(liq.) Out - zCa(liq.) In + zCa Formation

                                               = 25,007 - 33,600 + 12,991 + 3,346

                                               = 7,744 m mole/min
                                                                                           18,011

                                                                                           11,486
                                                                                            3,010
                                                                                            1,093

                                                                                           25,007
                                                      K-20
-------
                                         TABLE K-10.  RATE CALCULATIONS

                                                  Experiment 29R


                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    In L1q. (m mole/1)   in Gas (ppm)      (m mole/mtn)
 Marble  Bed  (Set  #1)

 1.  CaS03    1/2 H20

    Entering Streams  Gas  Inlet          10,050 g mole/min                            2,456            24,682
                     Spray Mater-Lower     927 1/min                3.58                               3,318
                     Spray Water-Upper     852 I/min                3.58                               3,050

    Leaving  Streams   Gas  Outlet         10,750 g mole/mln                              297             3,193
                     Scrubber Liquid-
                      Lower                794 1/min               12.61                              10,012
                     Scrubber Liquid-
                      Upper                643 1/min                5.81                               3,736
                     Scrubber Bottom       341 1/min               15.51                               5,289

                     Rate of CaS03   1/2 H20 Formation = lS03(liq.) In - zS03(11q.) Out - Oxid. Rate

                                                       = 31,050 - 22,230 - 0.279 (24,682 - 3,193)

                                                       - 2,825 m mole/mln

2.  CaS04    2 H20
   Entering Streams  Spray Water-Lower     927 1/min               21.53                              19,958
                     Spray Hater-Upper     852 1/min               21.53                              18,344

   Leaving Streams   Scrubber Liquid-
                      Lower                794 1/min               25.58                              20.310
                     Scrubber liquid-
                      Upper                643 1/min               26.62                              17,117
                     Scrubber Bottom       341 1/min               22.13                               7,546
                     Rate of Ca S04   2 HjO Formation = £S04(liq.) In - ES04(l1q.)  Out t Oxid.  Rate

                                                      = 38,302 - 44,973 + 5,995

                                                      = -676 m mole/mln

3. CaC03 Dissolution


   Entering Streams  Spray Mater-Lower     927 1/min               19.60                              18,169
                     Spray Mater-Upper     852 1/min               19.60                              16,699

   Leaving Streams   Scrubber Liquid-
                      Lower                794 1/min               26.23                              20,827
                     Scrubber Liquid-
                      Upper                643 1/min               23.97                              15,412
                     Scrubber Bottom       341  1/min               26.63                               9,081

                     Rate of CaC03 Dissolution = ECa(liq.)  Out - lCa(liq.) In + ECa Formation Rates

                                               = 45,320 - 34,868 + 2,825 - 676
                                                       K-21
-------
                                         TABLE K-10,   RATE CALCULATIONS  (Continued)
                                        Stream Flow Rate
                     Species Cone.
                   in Llg. (m mole/1)
              Species Cone.
              1n Gas (ppm)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

1. CaS03   1/2 H20

   Entering Streams  Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.
  794 1/min

  643 1/min
  341 I/rain
   57 1/min

1,836 1/min
12.61

 5.81
15.51
 0.88

 4.03
                     Rate of CaS03   1/2 HgO Formation  =  £S03(Hq.)  In -  ESOjfUq.) Out

                                                       =  19,086  -  7,399

                                                       =  11,687  m  mole/min
2. CaSO,
   Entering Streams  Scrubber Liquid-
                      Lower                794 1/min
                     Scrubber Liquid-
                      Upper                643 1/min
                     Scrubber Bottom       341  l/m1n
                     Clarifier Liquid       57 1/min

   Leaving Streams   Hold Tank Eff.       1,836 1/min
                          25.58

                          26.62
                          22.13
                          20.64

                          21.41
                     Rate of CaS04   2 H20 Formation =  iS04(liq.)  In  -  lS04(liq.) Out

                                                     -  46,148  -  39,309

                                                     =  6,839 m mole/m1n
3. CaCO

   Entering Streams  Scrubber Liquid-
                      Lower                794  1/min
                     Scrubber Liquid-
                      Upper                643  1/min
                     Scrubber Bottom       341  l/m1n
                     Clarifier Liquid        57  1/min
                          26.23

                          23.97
                          26.63
                          18.28
   Leaving Streams   Hold Tank Eff.
Species Flow Rate
  (m mole/mln)
                     Rate of CaC03 Dissolution
1,836 1/min               19.40

      = zCa{liq.) Out - £Ca(l1q.) In + Eta Formation Rates

      = 35,618 - 46,362 + 11,687 + 6,839

      = 7,782 m mole/mln
     10,012

      3,735
      5,289
         50

      7,399
                                   20,310

                                   17,116
                                    7,546
                                    1,176

                                   39,309
                                   20,826

                                   15,413
                                    9,081
                                    1,042

                                   35,618
                                                      K-22
-------
                                         TABLE K-10.  RATE CALCULATIONS (Continued)
                                                              Species Cone.      Species Cone.   Species Flow Rate
                                        Stream Flow Rate    in Llq. fro mole/I)   1n Gas (ppm)      (m mole/rain)
 Marble  Bed  (Set  2)

 1.  CaS03    1/2 H20


    Entering Streams  Gas  Inlet          .10,250 g mole/mln                            2,415            24,754
                     Spray Uater-Lower     927 1/min                3.34                               3,096
                     Spray Water-Upper     852 1/min                3.34                               2,846

    Leaving  Streams   Gas Outlet         10,980 g mole/min                              280             3,704
                     Scrubber Liquid-
                      Lower                757 1/min               11.42                               8,645
                     Scrubber Liquid-
                      Upper                680 1/min                6.50                               4,420
                     Scrubber Bottom       341 l/m1n               14.29                               4,873

                     Rate of CaS03   1/2 HgO Formation = lS03(liq.] In - £S03(Hq.) Out - Oxld.  Rate

                                                       = 30,696 - 21,642 - 0.284 (24,754-3,704)

                                                       = 30,696 - 21.642 - 5,976

                                                       = 3,076 m mole/mln

2.  CaS04    2 H20


                                                                                                      20,356
                                                                                                      18,710


                                                                                                      19,409

                                                                                                      18,006
                                                                                                       7,891

                     Rate of CaS04   2 H20 Formation = ES04(11q.) In - £S04(11q.)  Out + Qx1d.  Rate

                                                     = 39,066 - 45,306 + 5,978

                                                     = -262 m mole/mln

3. CaCO, Dissolution

   Entering Streams  Spray Uater-Lower     927 1/min               19.22                              17,817
                     Spray Mater-Upper     852 1/min               19.22                              16,375

   Leaving Streams   Scrubber Liquid-
                      Lower                757 1/min               25.21                               19,084
                     Scrubber Liquid-
                      Upper                680 l/m1n               23.85                              16,218
                     Scrubber Bottom       341 1/min               24.13                               8,228

                     Rate of CaC03 Dissolution =  ECa(Hq.)  Out - iCa(11q.]  In  + ECa Formation  Rate

                                               =  43,530 - 34,192 + 3,076 -  262

                                               =  12,152 m mole/mln
Entering Streams

Leaving Streams




Spray Mater-Lower
Spray Water-Upper
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
927 1/min
852 1/min

757 1/nrin

680 1/min
341 1/min
21.96
21.96

25.64

26.48
23.14
                                                      R-23
-------
                                         TABLE K-10.  RATE CALCULATIONS (Continued)
                                                              Species Cone.       Species Cone.    Species Flow Rate
                                        Stream Flow Rate    in Llg.  (m mole/1)   In Gas (ppm)       On mole/min)
System Remainder
(Hold Tank, Surge Tanks,  and Thickener)

1. CaS03   1/2 H20

   Entering Streams  Scrubber Liquid-
                      Lower                757 1/min
                     Scrubber Liquid-
                      Upper                680 l/m1n
                     Scrubber Bottom       341 1/min
                     Clarifier Liquid       57 l/m1n

   Leaving Streams   Hold Tank Eff.       1,836 1/min
                           11.42

                            6.50
                           14.29
                            0.90

                            3.50
                     Rate of CaS03   1/2 H20 Formation = ES03(liq.)  In -  sS03(liq.)  Out

                                                       = 17,988 -  6,426

                                                       = 11,562 m  mole/mi n
2. CaS0
   Entering Streams   Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams    Hold  Tank Eff.

                     Rate  of CaS0   2
3. CaCO, Dissolution


   Entering Streams  Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.
   757 1/min               25.64

   680 1/min               26.48
   341 1/min               23.14
    57 1/min               20.85

 1,836 1/min               21.85

gO = ES04(liq.) In - ES04(liq.) Out

   = 46,489 - 40,116

   = 6,373 m mole/m1n
                                           757  1/min

                                           680  l/m1n
                                           341  1/min
                                            57  1/min

                                         1,836  1/min
                           25.21

                           23.85
                           24.13
                           18.45

                           18.91
                     Rate of CaCO, Dissolution = zCa(liq.)  Out -  £Ca(l1q.)  In + ECa Formation Rate

                                               = 34,718 - 43,529  + 11,562 + 6,373

                                               = 9,124 m moles/min
                                                                                                       8,644

                                                                                                       4,420
                                                                                                       4,873
                                                                                                          51

                                                                                                       6,426
                                                                                                      19,409

                                                                                                      18,006
                                                                                                       7,890
                                                                                                       1,188

                                                                                                      40,116
                                                                                                      19,083

                                                                                                      16,218
                                                                                                       8,228
                                                                                                       1,051

                                                                                                      34,718
                                                      K-24
-------
                                         TABLE  K-ll.   RATE CALCULATIONS

                                                 Experiment  30R

                                                             Species Cone.      Species Cone.   Species  Flow Rate
                                        Stream  Flow Rate    In L1q.  (m mole/1)   1n Gas  (ppm)       (m mole/mln)
Marble Bed (Set #1)

1. CaS03   1/2 H20


   Entering Streams  Inlet Flue Gas     10,116 g  mole/mln                             2,300             23,267
                     Scrubber Spray-
                      Lower                946 1/mln                 4.18                                3,954
                     Scrubber Spray-
                      Upper                889 l/m1n                 4.18                                3,716

   Leaving Streams   Outlet Flue Gas    10,845 g  mole/m1n                               334              3,624
                     Scrubber Liquid*-                                                                „ „„
                      Lower                814 1/mln                15.97                               13,000
                     Scrubber Liquid*-
                      Upper                681 1/mln                 8.04                                5,499
                     Scrubber Bottom       341 1/mln                18.26                                6,227

                     Rate of CaS03   1/2 H20 = ES03 (llq.)  IN - iSOg (llq.)  OUT - Oxidation Rate

                     Precipitation           = 30,937 - 28,350 - 0.3 (19,643)

                                             = -3,306 m mole/mln


2. CaS04   2 H20


   Entering Streams  Scrubber Spray-
                      Lower                946 1/mln                22.34                               21,134
                     Scrubber Spray-
                      Upper                889 1/min                22.34                               19,860

   Leaving Streams   Scrubber Liquld*-
                      Lower                814 1/mln                25.25                               20,553
                     Scrubber Liquld*-
                      Upper                681 1/mln                26.44                               18,006
                     Scrubber Bottom       341 l/m1n                23.95                                8,167

                     Rate of CaS04   2 HgO = ES04 (llq.) IN - ZS03 (llq.) OUT + Oxidation Rate

                     Precipitation         = 40,994 - 46,726 + 5,893

                                           = 161  m mole/mln

3. CaCO, Dissolution


   Entering Streams  Scrubber Spray-
                      Lower                946 l/m1n               18.78                              17,766
                     Scrubber Spray-
                      Upper                889 1/mln               18.78                              16,695

   Leaving Streams   Scrubber Liquid*-                                                                   nan
                      Lower                814 l/m1n               26.88                              21,880
                     Scrubber Liquld*-
                      Upper                681 1/min               24.09                              16,405
                     Scrubber Bottom       341 l/m1n               26.92                               9,180

                     Rate of CaC03 Dissolution - sCa (I1q.) OUT - ECa (llq.) IN + ZCa Formation Rates

                                               = 47,465 - 34,461 - 3,145

                                               = 9,861 m moles/mln



"Average of Marble Bed Front and Back
                                                      K-25
-------
                                         TABLE K-ll.   RATE CALCULATIONS (Continued)


                                                              Species Cone.       Species Cone.    Species Flow Rate
                                        Stream Flow Rate    1n Llq.  (m mole/1)    in  Gas (ppm)       Cm mole/min)
System Remainder
(Hold Tank, Surge Tanks, and Thickener)

1. CaS03   1/2 H20
Entering Streams





Leaving Streams


Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Clarifier Liquid
Hold Tank Eff.
Rate of CaS03 1/2
Precipitation

814 1/mln

681 1/min
341 1/min
57 1/min
1,892 1/mln
H20 = ZS03 (liq.) IN - i:
= 24,804 - 8,325

15.97

8.04
18.26
1.73
4.40
S03 (llq.) OUT

                                                                                                      12,999

                                                                                                       5,480
                                                                                                       6,226
                                                                                                          99

                                                                                                       8,325
                                             = 16,479 m mole/mi n
2. CaS04   2 H20
Entering Streams





Leaving Streams


Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Clarifier Liquid
Hold Tank Eff.
Rate of CaS04 2
Precipitation

814 1/min

681 1/min
341 1/min
57 1/min
1,892 1/min
H20 = IS04 (liq.) IN -
= 47,891 - 41,737

25.25

26.44
23.95
20.47
22.06
ES04 (liq.) OUT

                                                                                                      20,553

                                                                                                      18,005
                                                                                                       8,166
                                                                                                       1,167

                                                                                                      41,737
                                             6,154 m mole/mi n
3. CaCO, Dissolution
   Entering Streams  Scrubber Liquid-
                      Lower                814 1/min               26.88                              21,880
                     Scrubber Liquid-
                      Upper                681 1/min               24.09                              16,405
                     Scrubber Bottom       341 1/mln               26.92                               9,179
                     Clarifier Liquid       57 1/min               18.57                               1,058

   Leaving Streams   Hold Tank Eff.       1,892 1/min               18.53                              35,059

                     Rate of CaCO, Dissolution = iCa (liq.) OUT - zCa (liq.)  IN + ECa Formation Rates

                                               = 35,059 - 48,522 + 16,479 + 6,154

                                               = 9,170 m mole/min
                                                      K-26
-------
                    TABLE K-ll.  RATE CALCULATIONS (Continued)
                                         Species Cone.      Species Cone.
                                       1n Llq. On mole/1)   In Gas (ppm)
Species Flow Rate
  (m mole/mini
Marble Bed (Set #2)
1. CaS03 1/2 H20
Entering Streams Inlet Flue Gas
Scrubber Spray-
Lower
Scrubber Spray-
Upper
Leaving Streams Outlet Flue Gas
Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Rate of CaS03 1/2
Precipitation

2. CaS04 2 H20
Entering Streams Scrubber Spray-
Lower
Scrubber Spray-
Upper
Leaving Streams Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom
Rate of CaS04 2 H
Precipitation

3. CaC03 Dissolution
Entering Streams Scrubber Spray-
Lower
Scrubber Spray-
Upper
Leaving Streams Scrubber Liquid-
Lower
Scrubber Liquid-
Upper
Scrubber Bottom

10,116 g mole/min
946 1/min
889 1/mln
10,845 g mole/min
814 1/mln
681 1/min
341 1/mln
H20= IS03 (liq.) IN -
= 34,269 - 33,114 -
= -5,086 m mole/mi n
946 1/mln
889 1/mln
814 1/min
681 1/min
341 1/min
20= sS04(11q.) IN-ZS
= 39,617 - 44,738 t 6
= 1,120 m mole/min
946 1/mln
889 1/mln
814 1/min
681 1/mln
341 1/min

2,457
5.13
5.13
405
18.78
9.70
20.03
zS03 (llq.) OUT - Oxidation Rate
0.305 (24,855 - 4,392)

21.59
21.59
23.88
25.36
23'. 55
04 (llq.) OUT t Oxidation Rate
,241

18.59
18.59
26.58
24.43
26.98

24,855
4,853
4,561
4,392
15,286
6,606
6,830



20,424
19,193
19,438
17,270
8,030



17,586
16,526
21 ,636
16,636
9,200
Rate of CaCOj Dissolution = zCa (I1q.) OUT - sCa (liq.) IN + ECa Formation Rate

                          = 47,472 - 34,112 - 3,966

                          = 9,394 m mole/min
                                 K-27
-------
                                         TABLE  K-ll.   RATE  CALCULATIONS  (Continued)
                                         Species  Cone.       Species Cone.
                   Stream Flow Rate    In Llq.  (m mole/1)   tn Gas (ppm)
System Remainder
(Hold Tank, Surge Tanks and Thickener)

1. CaS03   1/2 H20

   Entering Streams  Scrubber Liquid-
                      Lower                814 l/m1n
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     ClaHfier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaS03   1/2 H20 =
                                              18.78
681 1/min
341 1/min
57 1/min
,892 1/min
,0 = ZSO, (liq.) IN - z
9.70
20.03
2.16
4.89
SO, (liq.)


OUT
Precipitation
2.  CaS04   2
   Entering Streams  Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifier Liquid

   Leaving Streams   Hold Tank Eff.

                     Rate of CaS04   2

                     Precipitation
3. CaC03 Dissolution

   Entering Streams  Scrubber Liquid-
                      Lower
                     Scrubber Liquid-
                      Upper
                     Scrubber Bottom
                     Clarifler Liquid

   Leaving Streams   Hold Tank Eff.
                                             =  28,844  -  9,252

                                             =  19,592  m  mole/mi n
                      814 1/min

                      681 1/min
                      341 1/min
                       57 1/min
                                                                   23.88

                                                                   25.36
                                                                   23.55
                                                                   20.38

                                                                   21.91
                    1,8921/min

                   20 = IS04 (liq.) IN - ES04 (liq.) OUT

                      = 45,905 - 43,700

                      = 2,205 m mole/min
                                           814 1/min

                                           681 1/min
                                           341 1/min
                                            57 1/min

                                         1,8921/min
                                              26.58

                                              24.43
                                              26.98
                                              18.26

                                              18.19
                                                                                                 Species  Flow  Rate
                                                                                                   (m mole/ml n)
                                                                                                      15,286

                                                                                                       6,605
                                                                                                       6,830
                                                                                                         123

                                                                                                       9,252
Rate of CaCOj Dissolution = zCa (I1q.) OUT - zCa (I1q.) IN + ECa Formation

                          = 34,415 - 48,013 + 19,592 + 2,205

                          = 8,199 m moles/mi n
                                                                                                Rate
                                                                                                      14,438

                                                                                                      17,270
                                                                                                       8,030
                                                                                                       1,167

                                                                                                      43,700
                                                                                                      21,636

                                                                                                      16,636
                                                                                                       9,200
                                                                                                       1,041

                                                                                                      34,415
                                                       K-28
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          APPENDIX L







  LIMESTONE TAIL-END SYSTEM



DISSOLUTION RATE DETERMINATION



           DIAGRAMS
-------
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-------
                                 TECHNICAL REPORT DATA
                           (Please read Inunctions on the reverse before completing}
  1. REPORT NO.
  EPA-650/2-75-052
                            2.
                                                       3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE
 Optimization of a Lime/Limestone Wet Scrubbing
     Process for SO2 and Particulate Removal in a
     Marble Bed Scrubber      	
                                                     6 REPORT DATE
                                                     June 1975
                                                     6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S) ,
          Project Director M. Rao Gogineni,
  K. Malki, and B.C.  Borio
                                                       8. PERFORMING ORGANIZATION REPORT NO,
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  C-E Power Systems
  Combustion Engineering Inc.
  1000 Prospect Hill Road
  Windsor, Connecticut  06095	
                                                     10. PROGRAM ELEMENT NO.
                                                     1AB013; ROAP 21ACY-020
                                                     11. CONTRACT/GRANT NO.
                                                     68-02-0221
 12. SPONSORING AGENCY NAME AND ADDRESS
  EPA, Office of Research and Development
  NERC-RTP, Control Systems Laboratory
  Research Triangle Park, NC  27711
                                                     13. TYPE OF REPORT AND PERIOD COVERED
                                                     Final:7/l/71 - 12/21/72
                                                     14. SPONSORING AGENCY CODE
 16. SUPPLEMENTARY NOTES
. ABSTRACT
               report gives results of extensive testing of a prototype marble bed
 scrubber system.  Results of 16 once-through soluble system tests, using sodium
 carbonate scrubbing solution, showed that  the scrubber is a very good liquid/gas
 contacting device for SO2 removal from flue gases with an overall efficiency of 90 to
 95 percent.  Liquid/gas ratio and scrubber liquid composition significantly affected
  SO2 removal; other variables had little or no effect.  Results of six limestone fur-
 nace injection system tests, using boiler calcined limestone and fly ash mixture,
 showed that solids concentration in the spray slurry and liquid/gas ratio signficantly
 affected SO2 removal.  Results of six limestone tail-end system tests, using com-
 mercial limestone in a dual marble bed scrubber, showed that the SO2 removal
 efficiencies of the lower and upper beds are the same, based on the SO2 concentra-
 tions entering the respective beds.  It  was demonstrated  that scale-free operation
 of both the furnace injection and the tail-end systems can be achieved  in a closed loop
 system, without employing liquid blowdown, by maintaining 8 to 10 percent solids in
 the spray slurry.
                             KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                           b.lOENTIFIERS/OPEN ENDED TERMS
                                                                 c. COSATI Field/Croup
 Air Pollution
 Scrubbers
 Calcium Oxides
 Limestone
 Flue Gases
 Fly Ash
                     Sulfur Dioxide
Air Pollution Control
Stationary Sources
Particulates
Marble-Bed Scrubber
13B
07A
07B

21B
 !. DISTRIBUTION STATEMENT
                                           19. SECURITY CLASS (ThisReport)
                                           Unclassified
                                                                 21. NO. OF PAGES
                                                                 243
 Unlimited
                                        20. SECURITY CLASS {nilpage)
                                         Unclassified
                                                                 22. PRICE
EPA Form 2220-1 (9-73)
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