EPA-600/2-76-273b
October 1976
Environmental Protection Technology Series

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                  RESEARCH REPORTING  SERIES


Research reports of the Office of Research and  Development,
U.S. Environmental Protection Agency, have been grouped into
five series.  These five broad categories were  established to
facilitate further development and application  of environmental
technology.  Elimination of traditional  grouping was  consciously
planned to foster technology transfer and a  maximum interface in
related fields.  The five series are:

          1.  Environmental Health Effects Research
          2.  Environmental Protection Technology
          3.  Ecological Research
          4.  Environmental Monitoring
          5.  Socioeconomic Environmental Studies

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.

                      EPA REVIEW NOTICE

This report has been reviewed by the U. S. Environmental Protection
Agency, and approved for publication.  Approval does not signify that
the contents necessarily reflect the views and policies of the Agency, nor
does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
This document  is available  to  the  public through the National
Technical  Information  Service,  Springfield,  Virginia  22161.

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                                         EPA-600/2-76-273b

                                         October 1976
EXPERIMENTAL AND THEORETICAL STUDIES

       OF  SOLID SOLUTION FORMATION

  IN  LIME  AND  LIMESTONE  SO2  SCRUBBERS

               VOLUME H. APPENDICES
                           by

Benjamin F.  Jones, Philip S. Lowell, and Frank B.  Meserole

                   Radian Corporation
               8500 Shoal Creek Boulevard
                  Austin, Texas  78766
                   Contract 68-02-1883
              Program Element No. EHE624
        EPA Project Officer:  Robert H. Borgwardt

       Industrial Environmental Research Laboratory
         Office of Energy, Minerals, and Industry
            Research Triangle Park, NC  27711


                      Prepared for

      U.S.  ENVIRONMENTAL PROTECTION AGENCY
            Office of Research and Development
                 Washington, DC 20460

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                           VOLUME I
                        TABLE OF CONTENTS
          ABSTRACT	   i


          ACKNOWLEDGEMENTS	  ii
1.0       SUMMARY AND CONCLUSIONS	   1

          1.1  Verification of the Existence of
               the Calcium Sulfite-Sulfate Solid
               Solution	   2
          1.2  Quantitative Measurement of the
               Sulfate Content of the Calcium
               Sulfite-Sulfate Solid Solution	   3

          1.3  Development of Sampling Methods
               for Slurries Containing High-Liquid
               Phase Magnesium Concentrations	   4

          1.4  Effect of Relative Saturation of
               Calcium Sulfate Hemihydrate.	   4

          1.5  Effect of the Calcium Sulfite
               Precipitation Rate	   5
          1.6  Effect of Magnesium and Carbonate
               Liquid-Phase Concentration on the
               Precipitation Rate of Calcium
               Sulfite Hemihydrate	   6

          1.7  Coprecipitation of Calcium Carbonate
               with the Calcium Sulfite-Sulfate
               Solid Solution	   6
2 . 0       BACKGROUND AND APPROACH		   7
3.0       THEORETICAL FRAMEWORK OF THE CALCIUM
          SULFITE-SULFATE SOLID SOLUTION	   9
4.0       EXPERIMENTAL APPROACH	  14
          4.1  Description of Equipment	  15

          4.2  Sampling Techniques Utilized
               in Kinetic Experiments	  23
                              111

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                    TABLE OF CONTENTS (Cont'd)

                                                          Page

          4. 3  Analytical Techniques	  25
          4. 4  Experimental Calculations	  27

5.0       RESULTS	  29
          5.1  Physical Characterization  of the
               Calcium Sulfite-Sulfate Solid Solution	  41

6 .0       DISCUSSION OF RESULTS	  51
          6.1  Effect of Relative Saturation of
               CaS04-%H20	  58
          6.2  Effect of Calcium Sulfite  Precipitation
               Rate	....'.	  62
          6.3  Comparison of Lime and Limestone Tests
               With Clear Liquor Results.	  64
          6.4  Effects of High Levels of  Chloride
               and Magnesium	  64
          6 . 5  Effect of Temperature	  65

7.0       REVIEW OF PLANT AND PILOT PLANT DATA	  68

8. 0       RECOMMENDATIONS	  73
                              IV

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                          VOLUME II
                          APPENDICES

                      TABLE OF CONTENTS
                                                          Page
APPENDIX A  "Thermodynamics of the Solid Solution
            Series (CaSOs/CaSO,) ^HaO" 	   1

APPENDIX B  "A Review of Plant and Pilot Plant Data
            Relating to the Formation of Solid Solution
            Series (CaSO 3/CaSOO -%H20"	11

APPENDIX C  Experimental Equipment and Sampling Techniques
            Utilized in the Experimental Studies of
            Solid Solution Formation	  52

APPENDIX D  "Analytical Techniques Utilized in the
            Experimental Studies of Solid Solution
            Formation"  	  ....... 84

APPENDIX E  Analytical Results, Reactor Material
            Balances, Solid Material Balances, and
            Computer Equilibrium Data of Laboratory
            Experimental Runs	 119

APPENDIX F  Infrared Spectra of Precipitated Solids
            from Laboratory and Pilot Plant Studies .  .  .   .274

APPENDIX G  Differential Scanning Calorimetry
            Patterns of Precipitated Solids 	   .367
                               v

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              APPENDIX A

"THERMODYNAMICS OF THE SOLID SOLUTION
      "SERIES (CaSOs/CaSOO -%H20"
             Prepared by:
           Philip S.  Lowell
                  -1-

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                      TABLE OF CONTENTS
                                                      Page
1.0       INTRODUCTION 	    3

2.0       THEORY	    4

3.0       COMPUTATIONAL PROCEDURES 	    7

          REFERENCES	   10
                              -2-

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1.0       INTRODUCTION

          The Environmental Protection Agency has done a
considerable amount of work that indicates that sulfate can
be removed from aqueous solution as a "coprecipitate" of
calcium sulfite.  Borgwardt and co-workers (BO-143, B0-144)
OP-012, OP-014) have  established that this phenomenon depends on
solution composition, precipitation rate, and other variables.

          Radian is under contract to EPA to help explain
and quantify this phenomenon.   A first step is to determine
if the coprecipitation is predominantly an equilibrium or
a kinetics effect.   Because the driving force for many rate
processes is a difference between actual and equilibrium
conditions,  a description of the equilibrium phenomenon will
be of value no matter what the predominant effect (kinetics
or equilibrium) is.

          In Section 2.0 a relationship between aqueous and
solid phase calcium sulfite and sulfate will be developed.
Then in Section 3.0 a means of quantifying the relationship
from experimental data will be given.
                           -3-

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2.0       THEORY

          Components in two different  phases  are  in equilibrium
when the chemical potentials in both phases are equal.  The
problem then,  is to relate  the  chemical potentials in the aque-
ous and solid phases .

          The chemical potential of a component "i" in a phase
"j" may be defined in terms of an activity, a-jj , and a stan-
dard state potential, \i°. . .

                    ytj  =  V?j + RT £n atj               (2-1)

          For convenience we define:
                                       £
               i  =  1  =>  CaS03'%H20
               i  =  2  =>  CaSCK"%H20

               j  =  s  =>  Solid
               j  =  £  =>  Liquid

For the solid we will define the standard state as the pure
component.  For a solid solution mixture we will consider
deviations from ideal solutions based on mole fraction.  Solid
phase activity coefficients are defined by Equation 2-2.

                        ais  =  Cixi                      (2-2a)

                        a2s  ~  a2x2                      (2-2b)
          The activities of CaS03 and CaSCK in the liquid  phase
are defined in Equation 2-3.
                            -4-

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                                                           (2-3b)
          The liquid phase is in equilibrium with the solid
phase when the chemical potentials are equal.  Equating chemi-
cal potentials gives Equation 2-4.

                          y-   =   U-o                      (2-4)
                           is      i£

          Substituting in the definitions  in Equations  2-1,  2-2,
and 2-3 into 2-4 gives Equation 2-5.

             y?s + RT £n a±x±  =   y?£ +  RT JLn  a±^          (2-5)

          Equation 2-5 may be solved for the activities.
                       £-£7  "  e

                             =  K±                         (2-6b)

          The equilibrium constant, Kj_,  turns  out  to be  the
solubility product constant.  This may be  seen by  taking the
limit of pure components, i.e., cj^Xj_ -> 1.  The relationship
between solid and liquid at equilibrium  for  the  species  is
written out in explicit form.

                aCa-hfaSOfaw  =  KiaCaS03XCaS03             (2-?a)

                      SOTaw  =  K2CTCaSO,XCaSCK             (2'7b)
                               -5-

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          The coprecipitation of sulfate is thermodynamically
stable so long as there is no other mechanism that will cause
an even greater decrease in system free energy.  One such point
is the transition from solid solution in sulfite to pure hemi-
hydrate sulfate.  This occurs at the point given in Equation
2-8.

                         a2s  =  1 < a2x2                 (2-8)

          A second limit would be the formation of gypsum.  The
solubility product of gypsum is given in Equation 2-9.
              CaSO^-2H20^^  •*  Ca   4- SO., + 2H20          (2-9a)

                                      a2
                                      J2	               -(2-9b)
          The  sulfate  transition  from  solid  solution  hemihydrate
 to  gypsum is given  in  Equation  2-10.
            CaSCK-%H20(s) + 3/2H20  -»•  CaS04 • 2H20(g)        (2-10)

The criterion  for  this  transition  to  take  place  is  Equation 2-11

                           I1- a2x2a                        (2-11)
                           K.3      W
                              -6-

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3.0       COMPUTATIONAL PROCEDURES

          The only unknowns at present are solid phase activity
coefficients.  What is required is a plot of solid phase
activity coefficients as a function of solid phase composition.
This is shown schematically in Figure 3-1.   Liquid and solid
phase composition data are required for the aqueous and solid
phases in equilibrium.

          Our task is to relate chemical potential  in  the liquid
phase to chemical potential in the solid phase.  Activities may
be used to relate chemical potentials  through Equations 2-1  or
2-6.

          Liquid phase activities may  be calculated from known
phase compositions in a routine fashion using the  Radian Aqueous
Ionic Equilibrium (AIE) program.  The  thermodynamic constants
relating liquid phase activities  to  solid  phase  activities
(solubility product constants) are also known.

          The solid phase activity coefficients,  the  a-j_'s of
Equation 2-6b or 2-7 are not known at  this  time.   These must be
calculated from liquid phase compositions  in equilibrium with
solid phase compositions at a known  temperature.
          Since the activity coefficient data will be obtained
at constant temperature and pressure,  they may be checked for
thermodynamic consistency using a modified form of the Gibbs-
Duhem equation as shown in Equation 3-2.
                             -7-

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•H
CJ
•1-1
IM
4-1

cd
 O
 cfl
             Unstable Region
 Solid
Solution
 Region
                                  !  @ T2
                    , mole  fraction CaS03
   FIGURE 3-1 - SCHEMATIC SOLID  STATE ACTIVITY COEFFICIENT
                         -8-

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               y
               Xl
          The procedure for calculating and correlating solid
phase activity coefficients will be as follows.

               The liquid phase composition will be input to
               the Radian AIE program.  The activities of
               Ca"^", S07,  SO^,  and H20 will be calculated.

               Liquid phase activities for CaS03 and CaSO^
               will be calculated from Equation 2-3.

               From the above and the solid phase composition
               the solid phase  activity coefficient will be
               calculated for one composition with Equation
               3-1.

               A series of different solid-liquid equilibria
               points will be calculated,  plotted as in
               Figure 3-1, and  the thermodynamic consistency
               checked with Equation 3-2.
                            -9-

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                          REFERENCES

BO-143    Borgwardt, R. H. ,  Limestone Scrubbing of SOz a_t
          EPA/RTP Pilot Plant, Progress Report 21, Research
          Triangle Park, N.C., EPA, June 1975.

BO-144    Borgwardt, R. H.,  Sulfate Scale Control in Lime/
          Limestone Scrubbers by_ Unsaturated Operation, Draft
          Report, Research Triangle Park, N.C., EPA, May 1974.

OP-012    Opferkuch, R. E. ,  Limestone Scrubbing of_ SO; a_t
          EPA Pilot Plant, Progress Report 10, Research Tri-
          angle Park,  N.C.,  EPA, p. 6, May 1973.

OP-014    Opferkuch, R. E.,  Limestone Scrubbing of S02 at
          EPA Pilot Plant, Progress Report 11, pp. 6-9,
          Research Triangle Park, N.C., EPA, June 1973.
                           -10-

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          APPENDIX B

"A REVIEW OF PLANT AND PILOT PLANT DATA
    RELATING TO THE FORMATION OF THE
SOLID SOLUTION SERIES (CaS03/CaSOO-%H20"
         Prepared by:
        Jay R.  Hoover

         Reviewed by:
        W.  E.  Corbett
           -11-

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                       TABLE OF CONTENTS



                                                 Page



1.0       INTRODUCTION	  13






2.0       METHODS OF DATA ANALYSIS	15





3.0       RESULTS	  23





4.0       DISCUSSION	  31






5.0       REFERENCES 	 ........  50
                              -12-

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1.0       INTRODUCTION

          Radian is under contract to EPA to perform a
theoretical and experimental study of the factors which control
the coprecipitation of calcium sulfate with calcium sulfite
in lime/limestone S02 scrubbing systems.  As part of an early
phase of this program, pilot plant and full scale system per-
formance data relating to the coprecipitation phenomenon which
were available to EPA were reviewed by Radian.  The purpose
of this data review was twofold:

               to define ranges of operating conditions
               under which coprecipitation is observed to
               occur.  This information is important because
               it defines the variables to be considered
               in the experimental phases of the program
               which follow.

               to provide a basis for comparing the results
               obtained in Radian laboratory experiments
               with "real" system performance.

          In this technical note, results of Radian's data
review subtask are reported.  Soluble component activities which
were calculated using Radian's aqueous ionic equilibrium program
are reported for those cases where sufficient data were given.
Calculated precipitation rates based upon EPA pilot unit data
are also presented.

          All of the data which were reviewed by Radian as
part of this effort were supplied by EPA.  These data came
from four major sources.
                              -13-

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          The Environmental Protection Agency has obtained
a considerable amount of data on calcium sulfite/sulfate
coprecipitation in lime and limestone wet scrubbing systems
in pilot plant studies conducted at Research Triangle Park,
North Carolina.  In addition, data supplied to EPA by Imperial
Chemical Industries (ICI) on their Bankside power plant, by
Arthur D. Little, Inc. (ADL) in the report "Scale Control in
Limestone Wet Scrubbing Systems", and by Louisville Gas and
Electric (LG&E) on their Paddys Run scrubber were made avail-
able to Radian.  Also, considerable data from the TVA-Shawnee
facility were supplied to Radian by Bechtel Corporation.
                             -14-

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2.0       METHODS OF DATA ANALYSIS

          The types of information which are considered to be
potentially important for purposes of characterizing calcium
sulfate/sulfite coprecipitation in lime/limestone S02 scrubbing
systems are listed below:

               liquid phase compositions and pH,

               liquid phase activities,

               driving forces for precipitation (relative
               saturations),

               precipitation rates of calcium sulfite
               and sulfate,

               solid phase'compositions.

Liquid phase activities and relative saturations were calculated
using the Radian aqueous ionic equilibrium program for all
data points for which the composition and pH of the hold tank
liquor were known.  Precipitation rates were also calculated
whenever possible.

          The ICI and ADL data transmitted to us were incomplete
as far as this program was concerned since no liquor composi-
tions or hold tank data were reported.   Complete liquid and
solid phase analyses for a significant fraction of the LG&E test
runs were also not available.  For this reason, almost all of
the meaningful test data considered here are based upon EPA/RTP
pilot plant studies.  Only the three complete LG&E data points
are reported.   Sources of these data are  listed in the Reference
Section.   An example of a typical EPA data reporting sheet is
shown in Figure 1.
                            -15-

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300 cfir,
G>125°F
    9
          81Z
          removal
           SO
            S03
            so,
            CO
            Ca
                    ocoocooco
                    ooc ccoo:oi
                              pH 4.9
Liquid  Phase

  3300  mg/1
  1110
    42
   883
                                             Oxidation      = 0.25
                                             Utilization    - 0.98    ;
                                             Stoichlcrretry  = 1.0
)

V

11
ft/
GCO^C-
|
.5
;ec

19.5 gpm (L/G = 50)

Liatnd Phase Solid Phase
SO, 2980 ng/1 125 ir,g/g
SO, 216 378
CO, 29 7
Ca^ 585 305
Mg 546


                              5.01?/hr Linis
                                    96% CaO
                                     0.4%  MgO
                                                                       pH 6.1
             FIGURE  1 - TYPICAL EPA PILOT UNIT DATA REPORT SHEET
                                    -16-

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          An indication of some of the problems involved in
analyzing the EPA and LG&E results can be gained by considering
the simplified schematic representation of an S02 scrubbing
process shown in Figure 2.  In this figure, the significant
vessels, i.e., scrubber and hold tank, and the phenomena which
take place in each are identified.

          S02 sorption is the primary function of the scrubber.
Sulfite oxidation can occur in both the scrubber and the hold
tank.  Sulfite precipitation (and sulfate coprecipitation)
takes place in the hold tank.

          As S02 is sorbed, the pH of the scrubber liquor and
the relative saturation of CaS03 tend to drop.  Under these
conditions, some dissolution of CaSOs solids would be expected.

          Obviously the relative rates at which these various
reactions proceed are extremely complex functions of the
operating variables and process configurations involved in each
case.  Finding a meaningful basis for the separation of these
various effects was the key problem which was faced in the
analysis of the data.

          Some of the equations which can be written to
describe the steady state performance  of the system shown in
Figure 2  are discussed below.

For the Overall System

    S02 Sorption Rate x (1 -  OX)
        =  Sulfite Solids Removal (or Accumulation)  Rate
                                                        (2-1)
                              -17-

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 Flue Gas.
    In
 Lime or .
Limestone
                          Flue  Gas
                             Out
    SCRUBBER



  S02 Sorption

Sulfite Oxidation

 Sulfite/Sulfate
   Dissolution
                          HOLD TANK
                      Sulfite Oxidation

                       Sulfite/Sulfate
                        Precipitation
                       Net Solids Out
    FIGURE 2 - SIMPLIFIED SCHEMATIC VIEW OF TYPICAL S02
               SCRUBBING PROCESS
                            -18-

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   S02 Sorption Rate x OX  =  Sulfate Solids Removal (or
                                Accumulation)  Rate       (2-2)

where OX is the fraction of the incoming sulfur in the +4
oxidation state (S02 or SOJ) which is ultimately  oxidized and
removed from the system as sulfur in the +6 oxidation state
(SOT)•  Physically, OX is defined by Equation 2-3.

              Sulfite Oxidation Rate in Scrubber
       nv  -   + Sulfite Oxidation Rate in Hold Tank     (f) -,<,
       UA               S02 Sorption Rate                ^    ;

however, OX can also be accurately approximated as
                 Sulfate in Net Solids Out               n  ,-.
                                                         ^    ;
          _
          Total Sulfur (SOT + SO^) in Net Solids Out
For the Circulating Sorbent Liquor

   S02 Sorption Rate
       =  Sulfite Oxidation Rate (Scrubber + Hold Tank)
          + Sulfite Precipitation Rate (Scrubber + Hold Tank)
                                                        (2-5)

      Sulfite Precipitation Rate (Scrubber + Hold Tank)
           Sulfite Solids Removal (or Accumulation) Rate
                                                        (2-6)
                             -19-

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    Sulfite  Oxidation Rate  (Scrubber  4- Hold Tank)

       =   Sulfate  Precipitation Rate  (Scrubber 4- Hold Tank)

          Sulfate  Solids  Removal (or  Accumulation)  Rate
                                                         (2-7)
 As  these  equations  are  written,  sulfite/sulfate dissolution
in the scrubber is treated as a negative precipitation term.

           An  additional equation which can be written to
 describe  the  performance of  the  hold tank is

    Hold Tank  Sulfite  In (Liquid  Phase)
    -  Hold Tank Sulfite  Out  (Liquid Phase)

          = Sulfite Precipitation Rate (Hold  Tank)
            4- Sulfite Oxidation  Rate (Hold Tank)         (2-8)

           It  follows  from Equation 2-8 that when  the sulfite
 oxidation rate is zero  (sealed hold tank  runs),  the sulfite
 precipitation rate  in the hold tank can be calculated as

    Sulfite Precipitation Rate  (gmoles/min)

     =  [Liquid Phase  Sulfite In  (gmoles/2,)
        - Liquid  Phase  Sulfite Out (gmoles/£)]

        x Liquid  Flow Rate  (2,/min)                       (2-9)

An equivalent expression can be used to calculate sulfate
precipitation rates for sealed hold tank runs.

          If the sulfite oxidation rate in the hold tank is
significant and unknown, the direct computation of sulfite
precipitation rates from hold tank data is impossible.   Sulfite

                             -20-

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and sulfate precipitation rates cannot be calculated from
solid phase analyses because the quantity of solids precipi-
tated in the hold tank is small compared to the quantity of
seed crystals present.

          As a result of these considerations, hold tank
precipitation rates were not calculated for unsealed hold tank
runs or for runs in which inlet and outlet hold tank liquor
compositions were not given. In some such cases, net sulfite
precipitation rates were calculated from Equations 2-1 and 2-6.
This term was determined only because it was not possible to
calculate gross precipitation rates (hold tank only).   Obviously,
gross precipitation rates would be more appropriate for pur-
poses of determining whether a correlation exists between S07
precipitation rates and solid phase sulfite/sulfate ratios.
Depending on the relative significance of the scrubber solids
dissolution rate term, the net precipitation rates calculated
using .this approach may or may not be a good approximation of •
true gross hold tank precipitation rates.
          The LG&E data were given for runs in which an unsealed
hold tank was used.  However, the surface area to volume ratio
was so small (due to the 220,000 gallon capacity) that the hold
tank oxidation rate was assumed negligible and these data were
treated in the same fashion as the EPA sealed hold tank results.

          In addressing the influence of kinetics on solids
composition it is necessary to normalize the data to a meaning-
ful consistent basis.  This was done by calculating precipitation
rates on the basis of moles precipitated/min/gram seed.  The
procedures used to normalize the precipitation rates calculated
by the procedures described above will now be discussed.
                            -21-

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           In the case of the EPA test results, the amounts of
 calcium sulfite  and sulfate seed were calculated from reported
 CaC03  slurry densities and CaC03-to-CaS03 molar ratios using
 Equations  2-10 and 2-11.

 Sulfite Seed («  CaS03-%H20>)  =
              \       x/     /
  /129  g CaS03 -%H20\  /Mole Ratio of \ /gmole CaC03\ (g CaC03/£\
  \gmole CaS03-%H20/  \CaS03 to CaC03/ \100 g CaC03 / \in Slurry/
                                                       (2-10)

 Sulfate Seed (*  CaSO;.%H20\  ,
              \      •<-     /

   *  I*-*,  c  A   /OX \/145 g/mole
   Sulfite  Seed
                         .29 g/mole CaS03 -%H2

These quantities were  then used to  normalize the calculated
precipitation rates  to units  of (gmole/min)/g total seed
(CaS03 + CaSOO .

          LGaE  seed  concentrations  were calculated directly
from solid phase analyses  as  shown  in  Equations  2-12 and 2-13.

Sulfite  Seed k CaS03-%H20\   =
              \      Jl      /
/gmole  S07(S02)\ /129  g  CaS03-%H20\ /0.1 g Solids^  /1100 g Slurry
\  g  Solids    j ^   gmole so=    ^  g Slurry  /  (      £
                                                               (2-12'
                                      „,         Slurry Specific
                                    10/. Solids   Gravity =  1.1
                                     Assumed       /A      ,N
                                                   (Assumed)
 Sulfate  Seed fs CaSO,-%H2o
              V      2,     /
/gmole  SOu(S03)] /145  g CaSO,-%H20\ /O.I g Solids) /1100 g Slurry\
^   g Solids   / ^    gmole so=   y ^  g Slurry  j ^    ^       /
                                                              (2-13
                             -22-

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3.0       RESULTS

          The EPA and LG&E field data which were considered in
this subtask are reported in Tables 3-1 and 3-2.  Table.3-1
summarizes unsealed hold tank data and includes pH, liquid com-
position data, and solid composition data.  Table 3-2 presents
sealed hold tank data which include not only pH, liquid and
solid concentrations, but also precipitation rates.  Precipi-
tation rates were determined by the methods discussed in
Section 2.0.

          Sealed hold tank data were further analyzed at Radian
by inputting pH and liquid phase composition into Radian's
aqueous ionic equilibrium program.  Ionic strength, solution
activities, and relative saturations of major species were
computed.  Activities for calcium, magnesium,- chloride,  carbonate,
sulfite and sulfate are presented in Table 3-3.  Relative
saturation of calcium sulfite hemihydrate, calcium sulfate hemi-
hydrate, and calcium sulfate dihydrate are also reported.  The
mole fraction of sulfite and sulfate in the solid phase have
also been calculated based on the solid concentration of sulfite
and sulfate.

          Considerable experimental data from EPA's alkali
scrubbing test facility located at TVA's Shawnee Power Station
in Paducah, Kentucky, have also been examined.  These data
covered testing between June 1975 and January 1976 with their
venturi/spray tower lime scrubber and their total contact absorber-
limestone scrubber.  These data, as supplied by Bechtel, include
liquid and solid composition data, ionic strength, and relative
saturation of calcium sulfate dihydrate.  The raw data are
not presented but will be graphically presented in Section 4.0.
EPA/RTP data will also be analyzed and discussed in Section 4.0.
                             -23-

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TAHI.K 3-1
REI'OKTLD USKKA1.ED HO'..D TANK
DVTA RUN
Hold Tank lii.uid Corr.posiu 0.1
Run Date
19^3
Oct 29-Nov 1
Oct 8-11
Nov 13-15
Nov 19-21
Nov 27-30
Dec 3-7
Sept 6-11
Sepc 11-14
Sepc 17-21
Sept 24-28
Occ 1-5
1974:
Mar 4-8
Har 13-22
Mar 25-29
Apr 22-26
Apr 1-5
Kay 6-10
May 13-17
Hay 20-24
May 28-31
June 3-7
June 10-14
1972:
Aug 22-23
Sepc 12-22
Occ 2-6
Nov 27-29
Nov 30- Dec 5
Apr 19-27
Apr 30-May 4
Nov 6-10
Nov 14-16
Nov 17-22
1973;
Apr 19-27
May 2-4
May 8-10
May 14-Jun 6
Jun 7-22
Jul 23-Aug 1
Jun 21-22
Jun 25-29
July 2-6
July 17-20
Apr 29-iiay 3
May 6-10
May 13-17
May 20-24
May 23-31
Feed

LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS

LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
LS

LS
LS
LS
LS
LS
LS
LS
LS
LS
LS

LS
LS
LS
LS
LS
LS
LS
LS
LS
LS
L
L
L
L
L
Eii_

5 8
5.7
5.7
5.6
5.9
5.9
6.1
7.1
8.2
9.3
10 2

6.0
5.8
5 9
5.5
5.6
6.0
5.7
5.8
5.3
5.1
5.3

6.4
6.3
6.4
6.2
6.3
6.1
6.4
6.6
6 6
6 4

6 3
6 4
6.5
5.2
5.8
6 3
5.9
5 8
6.3
6.2
7.3
7.0
7.3
7.5
7.1
Cn

0.0335
.034
.034
.034
.036
.037
.0146
.0143
.0167
.0211
.0224

.057
.033
.019
.006
.014
.0125
.0093
.0108
.0055
.0195
02

.0153
.016
.018
.016
.0155
.0118
0084
.0155
.0158
.015

0 012
.0084
.0028
.0082
.015
.0194
Oil
0023
005
.0024
.133
.085
.155
.22
.165
i'.'

0.036
.021
.031
.035
.030
.029
.023
.042
.018
.002
.0005

.0625
.0917
.10
.325
.238
.392
.696
.563
.308
.304
.246

NR
035
019
.033
.036
022
NR
.0197
.0278
.030

NR
NR
NR
NR
NR
NR
0.040
041
.028
.022
.0021
.0125
.0125
0083
.0083
Cl

0 033
.056
071
.074
.08
.072
NR
NR
NR
NR
NR

.188
.194
.191
.177
.226
.171
.397
.240
.120
.22
.237

NR
NR
NR
NR
NR
NR
NR
NR
NR
NR

NR
NR
NR
NR
NR
NR
NR
NR
NR
MR
0.237
.16
.291
.42
.311
CO;

0.002S
0041
. 0047
002C
.0036
.0028
.0007
.0006
.0002
.0005
.0002

NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR

.0064
.0082
.0036
.0061
.0066
.0059
.0059
.0043
0036
.0036

0.0059
.0059
.0036
.0059
.0056
.0022
.0051
0058
.0068
0076
NR
NR
NR
NR
HR
•1 l-PA/RfP PILOT I'SIT STUDIES
(<•,;.,-, u./
SO.

0.0032
0043
.0057
0078
.0053
.0081
.0034
.0029
0014
.0010
0005

.0034
.0078
.0078
.0375
.0188
.0313
.144
103
.042
.013
0155

0026
0033
0025
005
0041
.0066
0052
.0025
.0029
.0036

0.0066
0062
0075
0073
.0121
.0027
.0121
0133
.0082
.0123
0003
.0005
.0011
.0008
.0008
O
SO,

0 0226
.0194
0248
.00271
00263
.0216
.0373
.0545
.0314
.0204
.0186

0245
.0463
.0438
.200
1188
.250
.374
350
.139
-183
.131

033
.043
036
042
.045
.025
.019
039
.041
.041

0.024
.019
013
.024
.035
021
.030
027
.026
0155
0083
.0063
.0034
.0085
.0121
Solids
C.i

0 C074
.0061
.0077
0074
.0077
0051
.0076
0076
0076
0076
0076

0079
0077
.0076
.C074
0077
0076
0072
.0071
0076
0078
.0078

NR
NR
NR
NR
NR
NR
NR
NR
NR
NR

0 0078
.0079
.0080
.0080
.0079
0049
NR
NR
NR
NR
.0053
0052
0074
.0075
.0074
Co-pO'.J
CO,

0.0022
.0022
.0029
.0017
.0021
.0014
.0002
.0003
.0008
.0008
.0008

.0029
.0022
.0026
0030
0034
.0038
0022
.0017
.0029
.0024
.0028

NR
NR
NR
NR
NR
NR
NR
NR
NR
NR

0 0015
.0021
0017
.0022
.0028
.0015
NR
NR
NR
. NR
0004
. 0006
. 0004
0004
.0003
lior. (r-..
so.

0.0031
0028
.0034
0023
.0035
.0024
.0059
.0059
0056
.0054
.0053

0037
.0025
.0039
.0039
.0026
0038
.0033
0034
0041
.0039
.0041

NR
NR
NR
NR
NR
NR
NR
NR
SR
NR

0.0053
.0053
.0056
.0052
0044
0021
NR
NR
NR
NR
.0033
0044
.0053
.0058
0055
.
-------


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-30-

-------
4.0       DISCUSSION

          As stated earlier, the purpose of this data review
was twofold:

          1)  to define ranges of operating conditions under
              which coprecipitation is observed to occur,

          2)  to provide a basis for comparing the results
              obtained in Radian laboratory experiments with
              actual scrubber performance.

          Key operating parameters which were identified as
possibly having an effect on the coprecipitation were the
sulfite precipitation rate, relative saturation of calcium
sulfate dihydrate, relative saturation of calcium sulfate hemi-
hydrate, chloride concentration, magnesium concentration, and
activity of the sulfate ion.

          The ranges of these operating conditions under which
coprecipitation of sulfate with sulfite was observed in the
EPA/RTP field data are as follows:

          Sulfite precipitation rate:  .001 - .100 millilPole
                  r    r                            gm-mm
      Relative saturation CaSOlt-2EzO:  .07  -1.10

      Relative saturation CaSC\*%H20:  .03  - .52

              Chloride concentration: . .005 - .42  mole/liter

              Magnesium concentration: .0005- .70  mole/liter

                     Sulfate activity: .0005- .0082
                             -31-

-------
Radian's laboratory program was designed to encompass these
ranges of operating parameters.

          The EPA/RTP,  LG&E and Shawnee data were analyzed
according to the theoretical framework developed by Philip S.
Lowell in Appendix A.   This theoretical framework and Radian
experimental data suggest that the sulfate mole fraction is best
correlated with the relative saturation of calcium sulfate hemi-
hydrate.  The results  of a graphical analysis of this correlation
for the EPA/RTP and LG&E data is shown in Figure B-l.

          There is a significant degree of scatter in the data;
part of this scatter is very likely due to analytical inaccuracies
in the determination of the sulfate content of the solids.  Also,
correlation of these pilot unit data with liquid phase properties
is difficult since a change in one parameter is usually accompanied
by other changes.   However, the high sulfate content of the
solids precipitated in the field limestone runs made at high
liquid phase magnesium concentrations cannot be solely explained
by analytical inaccuracies.  Experimental difficulties associated
with the sampling and sample handling of slurries containing high
liquid phase magnesium sulfate concentrations can account for some
scatter.  Additional chemical analyses and characterization of
field solids would be required to determine if the high liquid
phase magnesium concentrations are having a significant effect
on the level of sulfate coprecipitated.

          The EPA/RTP pilot plant data do show, as do Radian
experimental data,that gypsum unsaturated operation is possible
and that the relative saturation of calcium sulfate does affect
the sulfate content in the solids even in unsaturated operation.
                              -32-

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                              -33-

-------
          Experimental data from EPA's alkali scrubbing test
facility located at TVA's Shawnee Power Station were also
examined.  The sulfate content of the solids has been compared
with the liquid phase relative saturation of calcium sulfate as
a function of time for both lime and limestone runs.  This allows
solids residence time to be included in the analysis as the
residence time of the solids is in the order of days.  Graphical
results of these comparisons in the TCA-limestone runs for the
time period June through December 1975 are presented in Figures
B-2 to B-9.  Comparisons of the sulfate mole fraction with the
relative saturation of calcium sulfate dihydrate for the
venturi/spray tower-lime runs are presented in Figures B-10
to B-15 and encompass the same time period as the TCA-limestone
runs .

          The solids residence time in the system is the slurry
volume of the system divided by the rate of slurry withdrawal
from the system.  This usually varies from many hours to several
days.   A sample of slurry is, therefore, a composite of what has
happened over the last several days.  For a chemical analysis of
the solids to be representative of the liquid surrounding them at
the sampling time, the liquid must have been constant for at least
one residence time and preferably longer.

          One other factor is significant.  Gypsum will probably
be formed when its relative saturation is greater than 1.0.  Just
as it takes time (1-2 days) to grow a large gypsum crystal, so
it takes time to dissolve one.  Those periods of time during which
the relative saturation of gypsum was greater than one, and for
a day or so after, the sulfate in the solids will consist of both
solid solution sulfate and gypsum sulfate.  A total solid sulfate
analysis will not be an accurate description of what is presently
being precipitated from solution.
                               -34-

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          An examination of the data in Figures B-2 through B-15
shows that there were never periods of reasonably constant rela-
tive saturation.  Furthermore, there were several periods during
which gypsum could be formed.  The suitability of the Shawnee data
for this particular correlation is somewhat doubtful.

          In view of these considerations, analysis of the
Shawnee data was limited to observation of general trends.  Anal-
ysis of Figures B-10 to B-15 reveals that an increase in the
relative saturation of calcium sulfate dihydrate was accompanied
by an increase in the sulfate content of the solids  (higher sul-
fate mole fraction).  Also, a decrease in the relative saturation
of calcium sulfate dihydrate was accompanied by a general decrease
in the sulfate content of the solids.
                             -49-

-------
                         REFERENCES

BO-097    Borgwardt, R. H.,  Limestone Scrubbing of_ S02 at EPA
          Pilot Plant, Progress Report #13, EPA, North Carolina.

BO-098    Borgwardt, R. H. ,  Limestone Scrubbing o_f_ S02 at EPA
          Pilot Plant, Progress Report #14, EPA, North Carolina,
          January 1974.

BO-106    Borgwardt, R. H. ,  Limestone Scrubbing o_f SO2 at
          EPA/RTP Pilot Plant, Progress Report #16, EPA/RTP,
          North Carolina, June, 1974.

BO-143    Borgwardt, R. H. ,  Limestone Scrubbing of_ S02 at
          EPA/RTP Pilot Plant, Progress Report #21, EPA/RTP,
          North Carolina, June, 1975.

BO-148    Borgwardt, R. H. ,  Limestone Scrubbing of_ S02 at
          EPA/RTP Pilot Plant, Progress Report #17, EPA/RTP,
          North Carolina, July 1974.

BO-149    Borgwardt, R. H. ,  Limestone Scrubbing of S02 at
          EPA/RTP Pilot Plant, Progress Report #19, EPA/RTP,
          North Carolina, April 1975.

OP-Oil    Opferkuch, R. E.,  Limestone Scrubbing of S02 at EPA
          Pilot Plant, Progress Report #9, EPA, North Carolina,
          April 1973.

OP-012    Opferkuch, R. E. ,  Limestone Scrubbing o_f S02 at EPA
          Pilot Plant, Progress Report #10, EPA, North Carolina,
          May 1973.
                            -50-

-------
OP-013    Opferkuch, R. E. ,  Limestone Scrubbing of_ S02 at. EPA
          Pilot Plant, Progress Report #12, EPA, North Carolina,
          July 1973.

OP-014    Opferkuch, R. E. ,  Limestone Scrubbing o_f S02 a_t EPA
          Pilot Plant, Progress Report #11, EPA, North Carolina,
          June 1973.

OT-025    Ottmers, Jr. , D. M. ,  Review and Analysis p_f Louis-
          ville Gas and Electric Scrubbing System Data, Draft
          Final Report.

WE-172    Wen, C.  Y.,  et al., Scale Control in Limestone Wet
          Scrubbing Systems,  EPA 650/2-75-031, Contract No.
          68-02-1013,  Research Triangle Park,  North Carolina,
          Control Systems Lab., NERC,  April 1975.
                           -51-

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                APPENDIX C
"EXPERIMENTAL EQUIPMENT AND SAMPLING TECHNIQUES'
             Prepared by:



           Larry A.  Rohlack
                  -52-

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                     TABLE OF CONTENTS

                                                      Page
1.0       INTRODUCTION	54

2.0       EARLY PHASE EQUILIBRIUM APPARATUS 	 55
          2.1  Constant Temperature Precipitation
               Vessel	55
          2.2  Condenser	'	57
          2.3  Constant Vacuum System 	 57
          2.4  Constant Head Device	57
          2.5  Sulfite Saturator	58
          2.6  Sampling Train	58
3.0       EQUILIBRIUM EXTRACTION APPARATUS	60
          3.1  Plexiglas Box	60
          3.2  Temperature Control System 	 62
          3.3  Mechanical Tumbler 	 62
          3.4  570 ml Plexiglas Vessel	63
          3.5  Sampling Train	63
4.0       EXPERIMENTAL APPARATUS UTILIZED IN THE KINETIC
          STUDIES	67
          4.1  Description of Equipment	67
          4.2  Continuous Liquid/Slurry Feed System   68
          4.3  Reactor	70
          4.4  Ball Mill	73
          4.5  Continuous Mixed Product Removal System 74
          4.6  pH Monitor	75
5.0       SAMPLING TECHNIQUES	.76
6.0       OPERATIONAL PROCEDURE	 .79
                              -53-

-------
1.0       INTRODUCTION

          The laboratory equipment used to fulfill the
experimental segment of this program is described in this
appendix.  Experimental measurements were made to characterize
those factors which influence the formation of the solid
solution.

          Three different types of experimental equipment were
utilized during this program.  They were:

          •  an early phase equilibrium apparatus,

         .•  an equilibrium extraction apparatus,
             and

          •  a kinetics apparatus.

          The early phase equilibrium apparatus was designed to
establish whether a solid solution would precipitate from various
solutions near equilibrium conditions.   The equilibrium extraction
apparatus was used to obtain equilibrium data from solids grown
using the kinetics apparatus.  A kinetics apparatus was set up
to obtain quantitative measurements relating variables which
influence the formation of the double salt.   Along with the
three types of experimental apparati, the sampling trains,  samp-
ling techniques,  and operational procedures  will be discussed
in the remainder of this Appendix.
                             -54-

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2.0       EARLY PHASE EQUILIBRIUM APPARATUS

          The primary purpose of the early phase equilibrium
apparatus was to grow calcium sulfite hemihydrate (CaS03'%H20)
at conditions approaching equilibrium in order to establish
whether a true solid solution would precipitate.   Also a quan-
titative relationship between equilibrium liquid and solid phase
composition was to be established using this equilibrium device.
          A schematic diagram of this apparatus is shown in
Figure 2-1.  The primary components are:

          •  a constant temperature precipitation
             vessel,

          •  condenser and vacuum control system,

          •  constant head device,

          •  sulfite saturator,  and

          •  sampling train.

2.1       Constant Temperature Precipitation Vessel

          The primary purpose of the constant temperature vessel
was to allow precipitation to occur at precisely controlled
conditions.  A 22-liter West-ef flask served as the precipitation
vessel while a 22-liter heating mantle supplied heat to the liquor
within the precipitation vessel.  A thermistor was used to both
monitor and maintain a constant temperature within the vessel.
Liquor agitation within the precipitation vessel was accomplished
by using a laboratory stirrer and a West-ef vacuum-tight stirring
apparatus.  Oxygen-free nitrogen gas was slowly bubbled just below

                              -55-

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the surface of the liquor in the precipitation vessel to minimize
oxidation and to break up the surface tension and therefore
equalize the evaporation rate.

2.2       Condenser

          Water vapor leaving the precipitation vessel passed
through a specially designed condenser.   This condenser was
designed and built at Radian because of the inability of commer-
cially available condensers  to work efficiently in this situation.
Condensed water leaving the  condenser passed through a West-ef
right-angle glass joint.   To the top of this joint,  a vacuum line
was attached and to the bottom a constant head device was
attached!.

2.3       Constant Vacuum System

          The vacuum within  the system was maintained at a
constant value by using a vacuum pump, a mercury manometer, and
a vacuum regulator/controller unit.  By maintaining a constant
vacuum in the system, a constant evaporation rate could be
maintained.

2.4       Constant Head Device

          Condensed liquor leaving the right-angle joint entered
the constant head device.  This device consisted of a thick-walled
glass cylinder and a rubber  stopper with two movable glass tubes
in it.  The center glass tube allowed liquor to flow to the
sulfite  saturator while the outside glass tube allowed liquor
to flow directly to the precipitation vessel.  By raising or
lowering the outside tube,  different pressure heads could be
placed on the center glass tube thus varying the liquor flow to
the sulfite saturator.  Any  liquor not passing through the center
                               -57-

-------
glass tube was channeled back to the precipitation vessel by
means of the outside glass tube.

2.5       Sulfite Saturator

          Water leaving the constant head device by means of
the center glass tube entered at the bottom of the Plexiglas
sulfite saturator.   In the saturator, the liquor was thoroughly
mixed with calcium sulfite hemihydrate crystals allowing the
liquor to become saturated with calcium sulfite .  The liquor
then passed through a nuclepore polycarbonate filter in the top
of the saturator in order to separate undissolved solids from
the liquor.  Gravity flow then  forced the liquor back to the
precipitation vessel.

2.6       Sampling Train

          Two types of sampling trains were used during this
segment of the program: a vacuum sampling train which was used
during the run,and a pressure sampling train used after the
completion of a run.  Each sampling  train was designed so that
minimal changes in sample composition occurred  during sampling
and that sampling effects on the equilibrium of the system were
kept to a minimum.

 2.6.1     Vacuum  Sampling

          Two vacuum  sampling  trains were designed  to sample  the
 liquor  in  the  precipitation  vessel and the  liquor leaving
 the  saturator without  having to bring  the system  to atmospheric
 or positive  pressure.

          A  rather  uncomplicated but effective  sampling  train
was  used  in  sampling  the  liquor leaving  the  saturator.   A 500-ml
Erlenmeyer flask  fitted with a  one-hole  stopper served as  the
                              -58-

-------
collection device,  A vacuum greater than that in the precip-
itation vessel was pulled on the 500-ml Erlenmeyer flask.  This
flask was then attached to the line leading from the saturator
to the precipitation device.  The vacuum in the flask was allowed
to equilibrate with the vacuum in the precipitation device causing
saturator liquor to flow into the flask.  After detaching the
flask, nitrogen was used to equalize the pressure in the flask
with that of the atmosphere.  The liquid could then be analyzed
or stored in the proper medium.

          The second vacuum sampling train was used to sample
the precipitation vessel liquor during a run.   This sampling train
consisted of a vacuum pump,  a collection device,  a filter and a
teflon line.   The vacuum pump was used to slowly  pull liquor out
of the precipitation vessel through a teflon tube suspended below
the liquor level.  Liquor leaving the precipitation vessel passed
through a filter and was then collected in the collection device.
After sufficient sample was collected,  the collection device
vacuum was equalized with nitrogen gas.   The liquor could then
be analyzed or stored in the proper medium.

2.6.2     Pressure Sampling

          After the completion of a run, the solids in the
precipitation vessel along with the final liquor  samples  were
collected.  This was accomplished by forcing oxygen-free  nitrogen
gas into the precipitation vessel which in turn forced the slurry
out of the vessel by means of the teflon sampling line.   The
slurry then passed through a filter where the solids were separated
from the liquor.  A portion of the filtrate was collected for
analysis of liquid phase cations and anions.  After filtration
of the precipitation vessel liquor was completed,  nitrogen gas
was used to purge the filter cake of excess water and to  partially
dry the solids.  This final step minimized oxidation problems.

                              -59-

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3.0       EQUILIBRIUM EXTRACTION APPARATUS

          In-order to differentiate between the equilibrium and
kinetic effects on the sulfate content of solids grown under
various kinetic conditions, an equilibrium extraction apparatus
was designed and constructed.   This apparatus was so designed
that solids would be allowed to dissolve and reprecipitate very
slowly in a liquor similar to the liquor in which the solids
were grown.  This slow dissolution/precipitation process should
allow the kinetic effect(s) to be extracted from the equilibrium
effect.

          Primary components of the equilibrium extraction device
(Figure 3-1) include:

             a Plexiglas box,

             the temperature control system,

             a mechanical tumbler,

             570 ml plexiglas cylinder, and

             a sampling train.


3.1       Plexiglas Box

          The primary purpose of the plexiglas box was to
provide an enclosure in which the equilibrium apparatus could
be maintained at a controlled temperature  in an oxygen-free
atmosphere.
                             -60-

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3.2       Temperature Control System

          In order to simulate the conditions at which the solids
were grown, the liquor temperature had to be maintained as close
to the actual run temperature as possible during the equilibrium
experiment.  This was accomplished by using a temperature con-
trol system which is described in the following paragraph.

          Two heat lamps suspended from the top of the plexiglas
box provided an excess of radiant heat needed to maintain a
temperature of 50°C inside the enclosure.  Two small circulating
fans were used to circulate the nitrogen atmosphere within the
enclosure ensuring that there were no temperature gradients within
the plexiglas box.  To ensure that there were no drastic tempera-
ture gradients within the enclosure,  temperature measurements
taken simultaneously at different points inside the box showed
a temperature deviation of less than 1 C at any two points in
the box.  A thermistor attached to a temperature controller main-
tained a constant temperature within the enclosure by cycling
the heat lamps on and off'.  The temperature controller was able
to maintain 50°C at the thermistor within 4- 0.4 C.
3.3       Mechanical Tumbler

          The primary purpose of the mechanical tumbler was
to provide a means of simultaneously rotating six sample
vessels horizontally in order to mix the vessels' contents.
The vessels were situated on two rotating shafts that were
rotated by a variable speed motor which enabled the vessels to
be rotated at rates as low as one revolution per minute.
(Average vessel rotation speed was 4-5 revolutions per minute.)
The entire tumbler arrangement was mounted on a stationary
base and set inside the temperature controlled box.
                              -62-

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3.4       570 ml Plexiglas Vessel

          The plexiglas container served as a reaction vessel
for the equilibration of the kinetic run solids with an appro-
priate liquor characteristic of their mother liquor.  The
containers were made of half-inch plexiglas and held 570 ml
+ 5 ml.   A threaded hole in the side of the plexiglas container
was used for charging the containers with the appropriate
slurry and also enabled samples to be taken from the vessel.
Quarter-inch burundum cylinders were placed in the vessels to. helo
mix the contents and enhance dissolution of reactor solids by
grinding up the solids and thus exposing new surfaces to the
liquor.
3.5     - Sampling Train

          The sampling train described in Figure 3-2 was
designed so a representative sample of the filtered vessel
liquor could be obtained without any undesirable changes in
the actual sulfite and sulfate liquor or solid composition.

          A pH meter utilizing a combination electrode was
used to measure the pH of the liquor in situ,  (as illustrated in
Figure 3-2).   A nitrogen blanket was kept directly above the
vessel's sample port to minimize the chances of sulfite oxidation
during pH measurement and aqueous sampling.

          A peristaltic pump was used to transfer the liquor
from the plexiglas vessel to the proper collection device  for
analysis or storage.  Upon leaving the plexiglas vessel, the
liquor passed through a 47 mm filter holder where the solids
were separated from the liquor so any suspended solids would not
interfere with the analysis of the liquor phase.
                              -63-

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                          <
                          5
                          C/l

                          rj
-64-

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          Nalgon or silicon tubing was used in the sampling
train because of their chemical inertness to the species in
question.  Also, all sampling lines were kept as short as
possible in order to minimize transit time.

          A description of the samples and the sampling
techniques used in obtaining solid and aqueous samples during
this segment of the project are given in Table 3-1.   All
sampling and sample handling techniques used during this seg-
ment of the project were found to be consistent with the
accurate measurement of both sulfite and sulfate in the solid
and liquid samples.
                              -65-

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                                 TABLE 3-1
                        SAMPLE COLLECTION TECHNIQUES
  Sample
Aqueous
Species in Question

SOI (Sulfite)
        Sampling Technique Used
A known volume of aqueous sample is
collected in a glass bottle containing
a known volume of  buffered  standard
iodine solution.
Diluted
Filtrate
Total Sulfur,
Calcium, Sodium,
Magnesium, and
Chloride
A known volume of aqueous sample is
collected in a linear polyethylene
bottle containing a known amount of
water and hydrogen peroxide.  The per-
oxide converts any sulfite to sulfate
so no sulfur is lost to the atmosphere.
Solids in
Vessel
Sulfite, Sulfate,
and Calcium
The slurry remaining in the vessel
after collection of aqueous samples
is filtered under a nitrogen blanket
using a nuclepore filter and a 47 mm
millipore filter apparatus.  Filtered
solids are then rinsed with acetone
to remove excess liquor.   They are
                o,
                                    then dried at 40
                                    phere.
                                       C in an  inert  atmos-
                                    -66-

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4.0       EXPERIMENTAL APPARATUS UTILIZED IN THE KINETIC
          STUDIES

          This kinetic apparatus served as a precipitation
device from which quantitative measurements could be obtained
for correlating variables which influence the formation of the
double salt.  With this apparatus, experimental conditions such
as temperature, calcium sulfite precipitation rate, relative
saturation of calcium sulfate, magnesium concentration, and
ionic strength could all be varied independently to simulate
the reactor compositions required by the scope of work in this
program.

          Topics discussed in the remainder of this Appendix
are:

          (1)  description of equipment,

          (2)  sampling train,

          (3)  sampling techniques,  and

          (4)  operational procedure.
4.1       Description of Equipment

          This segment of Appendix C describes the various
components which comprised the kinetics apparatus.  This
equipment was adequate in studying the precipitation of cal-
cium sulfite hemihydrate at various conditions which favor
the formation of the double salt.
                              -67-

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          A schematic diagram of this apparatus is shown in
Figure 4-1.  The essential components are:

           (1)  continuous liquor/slurry feed system,
           (2)  reactor,
           (3)  ball mill,
           (4)  continuous mixed product removal system, and
           (5)  pH monitor.
4. 2       Continuous Liquid/Slurry Feed System

          The continuous liquid/slurry feed system supplies
the reactor with two well-defined feed streams.  Parameters
such as liquor composition, flow rate, and temperature can
be varied and accurately controlled to study the effect these
variables have on the mole fraction sulfate in the solids.

                                                          o     '
          Two 60-liter linear polyethylene containers were
used to mix and store the feed stream solutions.   Whenever
a slurry feed stream was used, a stirrer maintained a homo-
geneous mixture in the feed tank.  Peristaltic pumps and con-
trollers were used in transferring the feed streams from the
feed tanks to the reactor at accurately controlled flow rates.
Because the feed stream liquor density usually changed from
run to run, a rotameter was used to monitor the flow rate of
the feed streams.  Before entering the reactor, the feed streams
passed through a constant temperature water bath so the reactor
temperature could be varied as desired from 30°C to 60°C.  Upon
leaving the constant temperature bath the feed streams passed
through a three-way stopcock.   At this point the feed streams could
be diverted from the reactor to the feed stream sampling points.
                              -68-

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-69-

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4.3       Reactor

          A specially designed 2750 ml plexiglas reactor, as
described in Figure 4-2, served as a reaction vessel for the
mixing of the feed streams and the precipitation of the calcium
sulfite-sulfate double  salt.

          The feed streams were input to the reactor at angles
of 180 degrees to each  other and directed toward a propeller
to insure minimum mixing time of the feed streams.  A second
propeller near the bottom of the reactor suspended the solids
while baffles broke up  the circular motion of the liquor and
enhanced mixing.  Oxygen-free nitrogen gas could be forced into
the top of the reactor  to either purge the system of oxygen or
force liquor from the reactor.  The reactor liquor tempera-
ture was monitored by a thermometer mounted in a hole in the
top of the reactor.   A  142 mm diameter nuclepore filter in
the bottom of the reactor was used to separate the solids from
the liquor to obtain a  clear effluent for pH monitoring and
chemical analysis.

          Two of the factors affecting the calcium sulfite
precipitation rate are  the number and particle size of the
calcium sulfite seed crystals.  It was desirable in the
kinetic studies to maintain a constant precipitation rate dur-
ing an experimental run and during a series of experimental runs.
A ball mill (Figure 4-3) was designed and built especially for
use with the kinetics apparatus to maintain a constant particle
size at a fixed slurry removal rate during a run.  This facilitated
the accurate assessment of kinetic influences of the calcium
sulfite precipitation rate.
                             -70-

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              STIRRER
              SUPPORT
TO GRINDER
                  ^—BAFFLE
                                   FROM
                                  GRINDER
                                              y—THERMOMETER
                                *-STIRRER
                                  SHAFT
                                   •PROPELLOR
                                       BAFFLE-
                                    PROPELLOR
                                                       PLEXI-GLAS
                                                        REACTOR
FIGURE 4.2.  PLEXI-GLAS REACTOR USED IN THE KINETIC STUDIES
                              -71-

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                                    I-J
                                    J
                                    H
                                    PQ
                                    on
                                     i
                                    vf

                                    0)
-72-

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4.4       Ball Mill

          The primary components of the ball mill are a 500 ml
plexiglas cylinder, a tumbling device,  a peristaltic pump, and
transfer lines as illustrated in Figure 4-3.  Materials used to
build the ball mill were chosen because of chemical inertness
and ability to be fabricated.

          The primary purpose of the plexiglas vessel was to
provide an enclosure in which the reactor slurry could be
placed and rotated.  Burundum cylinders (1/4-inch outside
diameter) were placed inside the plexiglas vessel with the sole
purpose of grinding up particles passing through the ball mill.
Baffles were installed in the plexiglas vessel to keep the
contents homogeneous and to provide a mechanism by which the
burundum cylinders could ride partially up the wall of the
plexiglas vessel and then fall to the bottom to grind particles.
Threaded holes on either side of the vessel allowed Cajon fit-
tings to be attached to the vessel.

          The Cajon fittings in either end of the plexiglas
vessel enabled the vessel to rotate without rotating the glass
inlet and outlet tubes.  The remainder of the tumbling device
was comprised of two shafts, a motor, and a means of support.
The plexiglas vessel sat on the two rotating shafts.  A small
variable speed motor and pulley arrangement enabled the two
shafts and thus the vessel to be rotated at a controlled rate
from 10 to 100 revolutions per minute.   Most runs were made
with a  rotational speed of 25 to 50 revolutions  per minute
depending on run time and precipitation rates.

          A peristaltic pump was used to draw reactor slurry
from the bottom of the reactor (refer to Figure 4-1) to the
plexiglas vessel.  This continuous transfer of slurry from the
                              -73-

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reactor  caused slurry  to flow through the ball mill allowing
grinding  to occur.  Slurry leaving the ball mill passed first
through  a one-fourth inch glass tube, then a teflon tee, and
then re-entered the reactor at the top (again refer to Figure
4-1).  All transfer lines were of glass or silicone tubing due
to their  chemical inertness to the species in question.
 4. 5      Continuous Mixed Product Removal System

          Because the number of particles present in a system
at  any one time affects the precipitation rate, a means of
maintaining a constant number of particles in the reactor had
to  be developed.  A continuous mixed product removal system
was incorporated into the kientics apparatus so the number of
particles in the reactor would remain constant during a run.
The primary components of this system are a teflon tee, a peri-
stalti,c pump, and a time sequence unit.

          Slurry leaving the ball mill passed through a teflon
tee where a slipstream was removed from the system by means of
a peristaltic pump.  At a constant particle size, temperature,
and driving force the precipitation rate would be held at a
desirable level by maintaining a constant slurry density.
Slurry density could be controlled by the flow rate of the slip
stream.

          The slurry removal pump had a capacity range of 10-
150 ml slurry/min.   If the calculated flow rate needed to main-
tain a certain solids content was less than 50 ml per minute,
a time sequence unit was used to cycle the peristaltic pump off
and on.  The peristaltic pump's flow rate would be set at 50 ml
per minute and then the time sequence unit would be adjusted
to be on for a specified time and then off for a specified
time resulting in the desired removal rate.  Periodic removal
at a higher flow rate was  used to ensure that representative
slurry was removed.
                               -74-

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4.6       pH Monitor

          Effluent leaving the bottom of the reactor passed
through a 100 ml three-necked flask where the pH of the solution
was monitored.  Inlet and outlet lines and thermometer were
situated in the center port of the flask, while the two pH
electrodes were situated in the other ports.  Because of the
small volume the residence time was kept short, thus minimizing
the possibility of change in solution composition.   Effluent
leaving the pH monitor was collected periodically during a run
for analysis.
                             -75-

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 5.0       SAMPLING TECHNIQUES

          Sampling and sample handling techniques developed
 for use during this segment of the program were made to be
 consistent with accurate measurements of sulfite and sulfate
 in both liquid and solid phases.  Sampling techniques used
 during this segment of the program can be found in Table 5-1.

          Collection of Solids in the Presence of MgSCU

          One of the difficult problems in characterizing the
 solids precipitated from these solutions is the contamination
 of the solids by high liquid phase magnesium sulfate.  This
 contamination results from the adhesion of the liquid phase
 to the filtered solids with subsequent crystallization of the
 magnesium sulfate during drying.  Therefore, every possible
 precaution must be taken to ensure minimal reactor  liquid
 contact with the solids after filtration.

          The procedure which was developed to remove reactor liquor
 from filtered solids consisted primarily of washing the solids
 several times under a nitrogen blanket with saturated calcium
 sulfite liquor.  A saturated solution of calcium sulfite was
 prepared by dissolving calcium sulfite solids in oxygen free
 deionized water.   After the solids from a run containing high
 MgS04 were filtered,  about 50 to 100 ml of the saturated cal-
 cium sulfite liquor was added to the solids to form a slurry.
 This slurry was then filtered and the washing step repeated.
 After three or four calcium sulfite washings,  several acetone
washings were performed.   All of these washings and filterings
were performed under a nitrogen blanket to minimize any oxida-
 tion of sulfite to sulfate.   The final washed solids were
 placed in a nitrogen-purged oven set at 40 to 45°C for final
 drying.

                            -76-

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                                            TABLE 5-1

                                  SAMPLE COLLECTION TECHNIQUES
     Samole
                             Location
                                              Technique Used
Aqueous SO2
                     Sulfite Feed and Effluent
                                Sample collected in a glass bottle contain-
                                ing a buffered iodine solution.
Diluted Filtrate
                     Limestone Feed
                                Sample collected in a linear polyethylene
                                bottle containing a known amount of hydro-
                                chloric acid.
Diluted  Filcraca    Calcium Feed  (clear liquor)
                                Sample collected in a linear polyethylene
                                bottle containing a known amount of water.
Diluted Filtrate
                     Sulfite Feed and Effluent
                                Sample collected in a linear polyethylene
                                bottle containing a known amount of water
                                and hydrogen peroxide.
Aqueous C02
                     Effluent
                                Effluent collected in a linear polyethylene
                                bottle containing 5 ml of C02  buffer.
Weight % Solids
Exit Side of Solids Removal
Pump
100 milliliters of reactor sLurry was col-
lected in a volumetric flask,  slurry was then
filtered using a 47 millimeter aillipore
apparatus.
 Reactor  Solids
Exit Side of Solids Removal
Pump
Reactor slurry is forced through 3 nuclepore poly-
carbonate filter held in a \\~! millimeter millipore
filter apparatus.  Excess liquor is separated
from solids by forcing nitrogen through Che poly-
carbonate filter.
 Reactor  Solids
 in Presence  of
 High Magnesium
 Concentrations
Exit Side of Solids Removal
Pump
Same as reactor solids above except these
solids are thoroughly washed with a saturated
sulfite solution to remove any liquid phase
magnesium sulface.
                                               -77-

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          Upon analyzing the washed and dried solids there
were negligible amounts of magnesium found in the solids, thus
verifying the effectiveness of this procedure.  The amount of
magnesium found in the solids represented a positive error in
the sulfate analysis of less than 170.
                              -78-

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6.0       OPERATIONAL PROCEDURE

          In this section of Appendix C the operational
procedure used in performing kinetics runs shall be discussed.
All of the operational procedures used during this segment of
the program were developed to minimize undesirable changes in
either the solid or liquid phases within the feed tanks, trans-
fer lines, or reactor.  Steps were also taken to ensure maximum
ease of operation during the kinetics run, thus enabling the
operator to concentrate on the progress of the experimental run
and ensuring the collection of more viable data.  For a given
set of operating conditions, the following operational procedures
were developed to fulfill the objectives of the run.

          Initially, the temperature bath was turned on and
the proper temperature setting selected.   Then the two feed
tanks were thoroughly cleaned and filled with the appropriate
quantity of deionized water.   In order to minimize oxidation
during a run,  oxygen-free nitrogen gas was bubbled through the
feed tanks,  thus purging any dissolved oxygen from the deionized
water and forming a blanket of inert nitrogen gas above the
water.  This protective blanket of nitrogen gas was maintained as
the liquid level decreased during the run.

          During the purging by nitrogen gas, there was
sufficient time to thoroughly clean the reactor and grinder.
All foreign material was removed by first rinsing the reactor
and grinder with a dilute HC1 solution which helped loosen
and dissolve any scale which may have formed during the previous
run.  After sufficient HC1 solution had been rinsed through
both grinder and reactor, a sufficient amount of deionized water was
used to finish cleaning the reactor and grinder.  After rinsing,
                             -79-

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the reactor and grinder were examined for physical abnormalities
which were corrected before final assembly of the two units.
Oxygert-free nitrogen gas was used to purge any oxygen in the
reactor and grinder prior to the run.  After final inspection
of the reactor and grinder the proper quantities of chemicals
were added to the already purged feed tanks.  Then, depending
on the amount of agitation required to completely dissolve
the chemicals in the feed tanks,either manual stirring or a
laboratory stirrer was used to agitate the liquor.  Whenever a
slurry feed stream was used,a laboratory stirrer was used to
maintain a homogeneous solution throughout the course of the
run.  A flotation lid was used whenever possible to minimize
liquid-air contact and a plexiglas lid was kept on top of the
feed tanks at all times in order to keep out foreign particles
and also minimize any air turbulence above the flotation lid.

          After the feed tanks were properly prepared and the
reactor and grinder were ready for use, feed stream flow rates
were then ready to be set and feed stream samples were ready to
be taken.   The peristaltic pumps used to control the flow rates
of the two feed streams were turned on and flow was diverted
to the sample ports.   Rotameters gave a visual indication as
to the amount of flow occurring and were used to maintain a
constant flow throughout the course of a run.  By adjusting
the peristaltic pump controller, the flow rate as indicated by
rotameter could be set to a desired level.  This flow rate was
then verified by measurement with volumetric flask and stopwatch.
After verification, feed stream samples were collected in the proper
collection medium  for analysis or storage.
                             -80-

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          Next,  the feed-stream flows were diverted back into
the reactor at which time the reactor was allowed to fill with
the two feed streams.   The reactor stirrer was  turned on and a
stirring rate set by adjusting the voltage with a Variac. For
the majority of the runs the stirring rate was  maximum allowing for
optimum agitation of reactor contents.   While the reactor was filling
the seed crystals to be used for that particular run were added
through the thermometer port and immediately mixed by the stirrer.
Seed crystals were generally added at the start of reactor
fill up in order to prevent homogeneous nucleation from occur-
ring, thus increasing the amount of seed crystals and possibly
changing the seed crystal composition.  After the seed crystals
were added, the thermometer was positioned and any nitrogen
escaping the reactor during fill up passed through the loosened
stirrer fitting.  While the reactor was filling the peristaltic
pump that controlled flow through  the grinder was turned on and
the grinder was filled with reactor slurry.  After the grinder
had been filled with slurry, the Variac controlling the grinder
rotation speed was adjusted in order to obtain the desired
revolutions per minute.  The grinder speed used for most of the
runs ranged from 25 to 50 rovolutions per minute with the
grinder speed being dependent on the type of run and the run
time.  As soon as the reactor and grinder were filled with the
liquor, the stirrer fitting was tightened down and liquid was
forced through the filter membrane in the bottom of the reactor.
At this time the timer was started and the run officially
began.  Liquor leaving the reactor was forced through a  100
milliliter pH monitor where two buffered pH electrodes were
used to monitor the pH of the effluent.  Liquor leaving the
pH monitor could either be collected for analysis or discarded
to waste.
                             -81-

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          As soon as an approximate precipitation rate could
be calculated (usually within 30 to 40 minutes into the run),
a solids removal rate could be set in order to maintain a con-
stant number of crystals in the reactor.  Therefore, about 15
minutes into the run an effluent sulfite sample was taken and
an outlet sulfite concentration obtained from which a precipi-
tation rate was calculated.  At approximately the same time a
solids content sample was taken and a solids density value
obtained.  From these two values a slurry removal rate was
calculated and the peristaltic pump attached to the outlet of
the grinder was turned on and set at a rate equivalent to the
slurry removal rate.  The slurry removal rate used during the
majority of the runs ranged from 10 to 100 milliliters per
minute.  Whenever the solids removal rate was less than 50
milliliters per minute, the peristaltic pump controller was
plugged into a sequential timer.  This enabled the peristaltic
pump to be pumping slurry at a faster rate than required, but
because of the cycle time of the sequential timer the required
solids removal rate could be achieved.

          In order to characterize the precipitated solids
with any degree of accuracy, it is necessary to minimize the
fraction of the seed crystals found in the solids collected
at the end of the run.   This was accomplished by removing
solids at a rate equal to the precipitation rate for a period
of time equal to three residence times of the solids.   This
reduces the original seed contribution to less than 5%.

          Sulfite feed stream samples were taken at the start
and end of a run if the run time was two to three hours,.   But,
if more time was required to make the run,  sulfite feed stream
samples were also taken during the middle of the run to monitor
any oxidation which might have occurred.  The feed stream
supplying calcium to the reactor was usually only sampled at the
end of the run because of the stability of the feed stream.
                             -82-

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          Effluent sulfite samples were collected to monitor
approach to steady state and to monitor precipitation rate.
Feed stream and effluent diluted filtrate samples were usually
only taken at the end of the run with duplicate samples being
taken of the effluent to ensure representative data.

          Throughout the course of a run several parameters
were monitored in order to ensure that the run conditions re-
mained constant during the run.  Feed stream flow rates were
closely monitored by visual observation of the rotameter setting
and by monitoring the total effluent flow rate.   By controlling
the feed stream flow rates, accurate precipitation rates could
be determined and reactor conditions could be controlled through-
out the course of a run.   Feed stream flow rates were very
stable with any fluctuations being easily and quickly readjusted
with the peristaltic pump.  The temperature of the water bath
was monitored quite frequently during a run to ensure proper
heating of the feed streams.  Temperature fluctuations in the
water bath were not noticeable as long as the feed stream flow
rates remained constant.   Slurry removal flow rates were very stable
throughout the course of a run, yet slurry removal samples were
taken every half hour to an hour to confirm the flow rate sta-
bility and to determine the concentration of the solids.  The
grinder revolving rate was stable within the limitations of the
apparatus as long as the inlet and outlet glass tubes did
not become misaligned.
                             -83-

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              APPENDIX D
"ANALYTICAL TECHNIQUES UTILIZED IN EXPERIMENTAL
     STUDIES OF SOLID SOLUTION FORMATION"
             Prepared by:
          Benjamin F. Jones
         Donnie L.  Heinrich
                 -84-

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                     TABLE OF CONTENTS

                                                        Page
1. 0     INTRODUCTION	   86

2. 0     LIQUOR ANALYSIS	   87
2.1     Calcium,  Magnesium,  and Sodium	   87
2.2     Sulfite	   92
2.3     Sulfate	   97
2 . 4     Chloride	  104
2 . 5     Aqueous C02	  107

3.0     ANALYTICAL PROCEDURES FOR CHARACTERIZATION OF
        SOLIDS	  109
3 .1     Solid Phase Sulfite	:	  109
3 . 2     Specific Sulfate	  Ill
3 . 3     Solid Carbonate	  114
3.4     Solid Dissolution	116
3 . 5     X-Ray Diffraction Analysis	  118
3.6     Infrared Analysis of the Solid Phase	118
                           -85-

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1.0        INTRODUCTION

           The analytical techniques documented in this technical
note were utilized in determining the solid and liquid phase
composition for the equilibrium and kinetic experimental studies
of EPA Contract 68-02-1883.   Significant analytical developments
within this contract include modifications of the solid and liquid
sulfite analyses and the development of a technique for the
specific determination of the sulfate concentration in solids in
the presence of large excesses of calcium sulfite.  These pro-
cedures allow the accurate measurement of sulfite and sulfate
in both the liquid and solid phases.

           Characterization of the liquid phase consisted of pH,
temperature, calcium, magnesium,  sodium,  chloride, carbonate,
sulfite and sulfate measurements.  Quantitative analysis of the
solids included the determination of calcium, magnesium, sodium,
carbonate,  total sulfur,  sulfite and sulfate concentrations.
Qualitative identification and characterization of the coprecipi-
tation product was made with X-ray diffraction and infrared
techniques.
                              -86-

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2.0        LIQUOR ANALYSIS

           Chemical analysis of the liquid phase of the
equilibrium and kinetic experimental studies consisted of
quantitative measurement of the calcium, magnesium, sodium,
chloride, carbonate, sulfite and total sulfur ions.  These
procedures are documented in the following sections.

           Analytical results of these determinations are
utilized along with pH and temperature measurements as inputs
into Radian's aqueous chemical equilibrium program.  The program
calculates the activities of the ions and ion pairs and the
relative saturation of key species such as calcium sulfate
dihydrate and calcium sulfite hemihydrate.  These calculations
will be used with solid phase analyses to interpret the influence
of liquid phase composition on the solid solution formation.

2.1       Calcium, Magnesium, and Sodium

          Total calcium, magnesium, and sodium present in the
liquid phase of the equilibrium and kinetic studies were
determined by chemical analysis of the diluted filtrate sample
utilizing atomic absorption spectroscopy.

          Instrument

          All absorbance measurements were made with the Perkin-
Elmer Model 503 atomic absorption spectrophotometer.  Operational
instructions, provided with the instrument, were followed for
the work.

           The absorbance measurements,  accrued internally,  were
illuminated on a four-digit readout  and recorded manually.   The
output was also  recorded directly  using a  strip-chart recorder.
                              -87-

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          Hollow cathode tubes provided the radiation source for
the absorption process.  Single element lamps were used for each
of the ions tested.

          Laboratory Equipment

           (1)  Atomic Absorption Spectrophotometer

           (2)  Hollow Cathode Tubes:  Sodium,
               Calcium, and Magnesium

           (3)  Air:   A clean dry air supply capable of
               maintaining 50 psi at a 55 liters/min.
               flow rate.


           (4)  Fuel:  Acetylene

           (5)  Glassware:
               a.   1 ml pipette
               b,   2 ml pipette
               c.   3 ml pipette
               d.   4 ml pipette
               e.   5 ml pipette
               f.   10 ml pipette
               g.   25 ml pipette
               h.   50 ml pipette
               i.   100 ml pipette
               j.   50 ml volumetric flasks
               k.   100 ml volumetric flasks
                              -88-

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           Reagents

           (1)   Calcium -  1000  mg/2,  Fisher  certified
                atomic  absorption  reference solution.

           (2)   Magnesium  -  1000 mg/£  Fisher certified
                atomic  absorption  reference solution.

           (3)   Sodium  - 1000 mg/2, Fisher certified
                atomic  absorption  reference solution.

           (4)   Hydrochloric acid

           (5)   Lanthanum  chloride hexahydrate

           Interferences

           The analysis of the liquor samples for calcium,
magnesium and sodium from the equilibrium  and kinetic studies
are carried out in the presence of a number of other ions which
occur concurrently in the  system.   Sample aliquots are diluted
in a 17o lanthanum solution to suppress known interferences.
The effectiveness of this  solution has been documented in
Radian Technical Note 200-006-20.

           Procedure

           Preparation of  Lanthanum Chloride Solution
           (1% Lanthanum,  5% HC1)

           Transfer 50.8 g LaCl3-6H20 or 35.3 g LaCl3 (anhydrous)
to a 2-liter volumetric flask,  add 200-300 ml deionized water and
then add 100 ml concentrated HC1.   After the LaCl3 has dissolved,
bring to volume with deionized water and store in a polyethylene
bottle.

                             -89-

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          Calculation

          The calculations were performed using a linear least
squares regression on the standards to obtain a calibration curve
from which the concentrations of the samples could be determined
utilizing the following equation:

          ..g/liter - 
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           Preparation of Standards

           The standards are prepared by diluting the certified
1000 ppm atomic adsorption reference solution to obtain concen-
trations in the optimum working range of the atomic absorption
spectrometer.   The standards are prepared with each new solution
of 170 lanthanum.

           (1)  Calcium - 4 mg/£ and 2 mg/£ standard
                solutions are prepared from the
                reference standard (1000 mg/£)

           (2)  Magnesium - .4 mg/& and .2 mg/£
                standard solutions are prepared from
                the reference standard (1000 mg/£)
                                     *

           (3)  Sodium - 1 mg/5, and .5 mg/£
                standard solutions are prepared
                from the reference standard (1000
                rng/i)


           Preparation of Samples

           The samples should be diluted within the following
ranges for optimum sensitivity.

           (1)  Calcium - 1-4 mg/2,
           (2)  Magnesium -  .1-.4 mg/£
           (3)  Sodium -  .2-1 mg/I

If necessary, two step dilution may be made,  the first in deionized
water and the second in the lanthanum chloride solution.  The
accuracy for  each of these analyses within  the range indicated
is ±17o.

                             -91-

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 2.2       Sulfite

           Sulfite in the liquid phase of the equilibrium and
 kinetic studies was determined by an iodometric titration with
 sodium arsenite as the titrant.  The iodometric method
 employed in this project is a modification of the  standard
 iodine oxidation of sulfite ions designed to avoid interferences
 from nitrite which may be present in solutions from lime/limes tone
 scrubbing processes.   The accuracy of the procedure at the 95%
 confidence level is ±2% over the range of .001-.100 moles/ I
 S03~2.  Utilizing a microburette, the method can be extended to
 .0001 moles S03~2/£ with an accuracy of ±470 at the 95% confidence
 level.

           The sample is added to an excess of buffered iodine
solution.  The iodine remaining after the stoichiometric oxidation
of sulfite is titrated with standard sodium arsenite solution.
An amperometric dead-stop method is used for the end-point
detection.

           The iodine solution is buffered to a pH of 6.0-6.2 to
inhibit sulfite-nitrite and nitrite-iodine reactions.  This also
inhibits the hydrolysis of the iodine and enhances  the complete
reaction of sodium arsenite and iodine.  Arsenite solutions give
more accurate results than thiosulfate solutions in the presence
of nitrite and are also more stable under ordinary  conditions.
The dead-stop end-point detection method gives more reliable
and accurate results than starch indicators.  In practice, the
dead-stop method is also convenient and simple.
                             -92-

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          Equipment

          (1)   50 ml buret,  10 ml microburette

          (2)   magnetic stirrer

          (3)   pipets (including 2 ml and 10 ml sizes);  bulb
               pipet fillers;  and 100 ml graduated cylinder

          (4)   150 ml beakers  (preferably graduated)

          (5)   four-ounce small mouth glass bottles

          (6")   microammeter  apparatus:
                                                      ^
               (a)  two 1-cm square platinum-sheet
                    electrodes mounted about 1 cm
                    apart

               (b)  1.5 volt dry cell battery (a
                    #735 "hobby" battery works well)

               (c)  electrometer or microammeter,
                    0-25 u amp

               (d)  voltage  divider


          Reagents and Solutions

          D.I.  water and reagent grade chemicals should be used
for all solutions.
                             -93-

-------
          1.   Sodium Arsenite Stock Solution (^ 0.010 mole/'l )

               Dissolve 1.3 grams of NaAsOz into one liter of
D.I. water.   Standardize this solution using reagent grade 0.1
N standard iodine.
                                 (ml I2) (normality of la)
          (molarity of NaAs02) = 	2  (ml NaAs02)	

          2.   Preparation of ^ 0.1 Normal Iodine Solution

               Dissolve 25 grams of potassium iodide (KI) in as
little D.I.  water as possible.  Weigh accurately 12.69 grams of
resublimed iodine and dissolve it completely in the saturated
potassium iodide  solution.  When the dissolution of the  iodine is
completed, dilute with D.I. water accurately to cfne liter.  A
larger solution can be made up at one  time, if desired.  Iodine
should be kept in a well stoppered, dark colored bottle, in a
cool place.   It need not be standardized if only used for the
sulfite analysis  since a blank is also run.

          3.   pH 6 Buffer

               This solution contains 1 mole/2, NaAc and 0.05
mole/£ HAc.   Pipet 2.9 ml of glacial acetic acid into 500 ml of
D.I. water.   Stir in 82 grams of NaAc and when completely dissolved
make up to one liter.   It is convenient to prepare several liters
of this solution at a time since 50 ml is used for each analysis.

          Procedure for Aqueous  S02_ Determination

          The  sample  should be  taken into  a tared  250 ml bottle
 containing  the  iodine  and  buffer solution.
                             -94-

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(1)   Pour the  buffered excess  iodine  sample
     bottle  contents  into  a well  washed 150
     ml beaker containing  a magnetic  stirring
     bar.  Rinse  the  sample bottle  well with
     buffer  and add the rinse  to  the  beaker.

(2)   Place the platinum electrodes  in the
     solution, stir and connect the micro-
     ammeter.   The  current should be  15-24
     microamps.

(3)   Begin the titration with  the .01 mole/2,
     sodium  arsenite  solution  using the 50
     ml buret.  The .color  of the  solution
     serves  as a  rough indicator  of the
     state of  the titration.   The iodine
     color (red)  changes to yellow  5  ml
     before  the endpoint is reached.   When
     the solution turns light  yellow,  the
     titration should be carried  out  drop-
     wise.   The solution will  become
     colorless one  to two  drops before the
     endpoint.  The titration  is  completed
     when the  current reaches  3-4 micro amp.

(4)   After the titration is completed,
     record  the ml  of sodium arsenite used
     and rinse the  electrodes with  D.I.  water
     after removing them from  the solution.

(5)   Blanks  are to  be run each day  using
     the above procedure without  the
     addition  of the sample.
                   -95-

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          Calculations

          The concentration of total S02 in the sample can be
calculated using the following equation.

            = (B-S)M
where ,

          C = concentration of total SO 2 (mole/liter)

          B = volume of arsenite solution needed to
               titrate the blank (ml)

          S =  volume of arsenite solution needed to
               titrate the sample (ml)

          M =  molarity of the arsenite solution,
               mole/liter (usually 0.0100)

         \J i =  weight of bottle plus fixing solution
               (grams)

         W2 = weight of bottle plus  fixing solution
               plus sample (grams)
                              -96-

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2.3        Sulfate

           Total sulfate present in the liquid phase of the
equilibrium and kinetic studies was determined by indirectly
measuring the total sulfur concentraton and subtracting the
aqueous sulfite concentration.  This section will discuss the
method used in the analysis for total sulfur.

           The aqueous sulfite is converted to the sulfate ion
by oxidation of the liquor with a two-fold excess of H202
during sampling.   The liquor is diluted to prevent the precipi-
tation of CaS03-%H20 and/or CaSOi+-2H20 due to any sxipersaturation
of these species.   An aliquot of the oxidized diluted filtrate
is passed through the hydrogen-form cation exchange column to
convert all sulfates to sulfuric acid.  The sample is then taken
to dryness at 75°C to remove all volatile acids.   An acid-base
titration is then used to determine the concentration of sulfate.
This concentration of sulfate represents the total sulfur species
which include sulfate and sulfite.

           All acids not volatile at 75°C interfere.   In the
equilibrium and kinetic studies, the only acids present in the
sample after passage through the ion exchange column, will be
HC1 and H2SCK.   HC1 is volatile at 75°C and should not interfere.
The only other interference in the procedure would be any free
ammonia present in the laboratory.
                              -97-

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Laboratory Equipment

(1)  Ion-exchange columns with internal
     diameter of 1.2 cm and 20 cm high are
     used.  These should be equipped with
     sintered glass filter and stopcock
     control.  A 25 ml reservoir bulb at
     the top of column is convenient.

(2)  Microburet, 10 ml with 0.02 ml
     graduations.

(3)  pH meter

(4)  Graduated 100 ml beakers

(5)  Hot plate and steam bath (75°C);
     surface thermometer (0-110°C)

(6)  Pipets

Reagents

(1)  Strong acid resin, 100-200 mesh size,
     hydrogen form (Styrene-divinylbenzene
     copolymer, 87o cross linkage,  with
     sulfonic functional group).   Possible
     choices are Dowex SOW, Amberlite CG-120,
     or Rexyn 101 (Fisher brand).

(2)  5 M hydrochloric acid for regenerating
     the resin

(3)  Hydrogen peroxide (3070)

                   -98-

-------
          (4) Standard sodium hydroxide (0.05-0.1 N).
              Commercially available standard solution
              concentrate may be used.

          (5) pH 4 Buffer to standardize pH meter

          Preparation of Ion Exchange Column

          Place a strong acid-type resin,  100-200 mesh size,
into a beaker and mix with water.  If a cloudy suspension occurs,
decant the liquid several times to remove fine resin particles
which may otherwise pass through the columns during the sulfate
determinations.
          Transfer 20-25 ml of resin as a slurry through a
funnel into the column, and drain sufficient water to settle
the resin bed.  The resin bed should be at least 17 cm high.
Add more resin as required.  Stopper the top of the column and
shake it horizontally with 10 ml of water.  This step releases
the air bubbles and renders the resin bed homogeneous.  For
optimum packing, allow the resin to settle for at least 5 min-
utes before draining.  Air voids below the sintered disk may
be eliminated by backwashing the column (with or without resin).
If the resin needs to be regenerated, pass 50 ml of 5 M hydro-
chloric acid through the column and rinse with 50 ml of water.

          The ion exchange column is ready to process at least
seven 10 ml samples of a cation concentration normally encoun-
tered in limestone based SOa  scrubbers.  However, if the resin
is mixed after a sample has been processed,  it is necessary to
regenerate the resin.  The bottom 6 cm height of the resin column
must be completely in the hydrogen form.  Any other cations pre-
sent on the resin within this region would be eluted during the
processing of samples, resulting in low sulfur values.
                              -99-

-------
          If a large number of columns are to be used, it is
recommended that the resin be regenerated in one batch using
a larger column.  Less time and hydrochloric acid would be
required.  The regenerated resin may be stored as a slurry in
bottles and be transferred, when needed, to smaller columns.
Spent resin can be stored similarly until a sufficient amount
is accumulated to make its regeneration in a big column worth-
while .

          After the resin is stored for several days, the
supernatant liquid may acquire a yellow tinge.  This "color
throw" from the resin is easily removed by rinsing in a
column.  When eluting with 5 M hydrochloric acid, the extent
of regeneration may be verified by evaporating about 5 ml of
effluent in a beaker on a hot plate.  If no residue is obtained,
the resin is completely regenerated.

          Procedure for the Determination of Sulfate

          (1) Allow the liquid in the column to drain
              to the top of the resin bed.  Introduce
              a sample aliquot containing 0.02-0.25
              mmole total sulfur to the column.  A
              10 ml aliquot is preferable.  The total
              cation concentration (including H ) shot
              be less than 0.7 equiv./liter.
           (2) Collect the effluent in a graduated 100 ml
              beaker.  Allow the column to drain on top
              of resin bed.  When 100-200 mesh resin is
              used surface tension is sufficient to keep
              liquid on resin and thus prevent the forma-
              tion of air pockets in column.  Rinse the
                              -100-

-------
    column reservoir with 5-10 ml of water,
    using a wash bottle,  and drain again.
    Rinse the resin column with an additional
    40 ml of water.   If a 10-ml aliquot  was
    used in step (a),  collect a total of 60
    ml of effluent in the beaker.   The col-
    umn is ready for another sample.

(3)  Place the beaker on a hot plate and
    evaporate the solution down to 5  ml.
    Do not boil   or allow the sample  to  go
    dry on the hot plate.   If the effluent
    contains a noticeable amount of resin,
    it should be filtered prior to the
    evaporation  step.   A suction funnel  may
    be used.

(4)  Place the sample in a water bath  at
    75 C for 2 hours,  or until all the
    volatile acids have evaporated (odor
    test).   The  residue should appear oily
    with no trace of solids.   Evaporation
    should be made in an area free from
    ammonia and  other vapors that may react
    with the acid mixture.   It is acceptable
    to leave samples overnight in the water
    bath at 75°C.

(5)  Dissolve the residue with a few ml of water,
   and  titrate with 0.0500 N  sodium hydroxide
   until  the  pH  is  4.6.  Both hydrogens in
   sulfuric  acid  are  titrated  at  this pH.  The
   effect  of  a  snail  amount  of  carbonate in  the
   standard base  and  also that  of  atmospheric
                   -101-

-------
                carbon dioxide is  minimized by stopping
                the  titration at pH = 4.6.

          Calculation  for Total Sulfur for Liquid-Phase Samples
          Analyzed by  Ion-Exchange Method

          No significant amount of phosphate has been  found in
scrubbing liquors so  the calculations outlined below assume that
phosphate is absent.
                    C  =       D
                    Cs    2V   DF
where,
          C  = concentration of  total sulfur as
           s
               sulfate  (S03) in  sample  (moles/liter)

          MR = molarity of sodium hydroxide
               (moles/liter)

          V-n = volume of sodium  hydroxide required
               for titration (ml)

          D-r. = dilution factor  (if any)
           r

          If the concentration of sulfate sulfur is desired then
the values for sulfite  (S02) must be known.

                    C 2 = C 3 - C i

where ,

          C2 = concentration of  sulfate sulfur (moles
               S03/liter)

                              -102-

-------
           C3 = concentration of total sulfur as sulfate,
                (SO 3) in sample (moles/liter)

           G i = concentration sulfite sulfur (moles
                SO 2/liter)

           Accuracy

           The accuracy of the described method is within 170 for
 samples containing at least 0.1 mmole of sulfate. The presence
 of salt residues after the evaporation of samples usually results
 in low values for sulfate.  When this occurs,  it is suggested
 that the resin be regenerated or a larger column be used.  High
 sulfate values are obtained if resin particles pass through the
 column into the effluent.  However, the resin is easily recognized
 after evaporation, and the solution turns yellow when titrated
 with base.

           For an independent quality control check, a sulfate
standard (Na2SOO or a reference solution containing a known
concentration of CaSCU in the same range as the actual samples,
should be passed through the ion-exchange column and titrated
with the sodium hydroxide solution until the pH is 4.6.
                               -103-

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2.4        Chloride

           Chloride present in the liquid phase of the equilibrium
and kinetics studies was determined by a manual potentiometric
titration with a standard silver nitrate solution.  The detection
limit for the analysis is .02 mmoles/2..  The accuracy of the
procedure at the 9570 confidence level is ±270 over the range of
1-200 mmoles of chloride/£,.

          Apparatus

          Silver Electrode  -  a cup  type, Fisher  No.
          13-639-122  is  suitable  -  a solid  silver
               cylinder may  also be  used.

          Adaptor  for Silver  Electrode - designed to
          fit  into pH meter connection designed  for
          glass electrode and to  accept pin from
          silver electrode.

          Reference Electrode - a silver-silver  chlo-
          ride with a sodium  sulfate bridge is recom-
          mended.  Fisher No.  9-313-216 is  an  example
          which is commercially available.

          pH Meter -  any standard pH meter  with  a milli-
          volt scale  is  suitable.

          Microburet  - 10 ml  capacity

          Magnetic Stirrer
                              -104-

-------
Reagents

0.0200 M Silver Nitrate - Dilute 400 ml com-
mercially prepared 0.1000 M silver nitrate
standard solution to 2000 ml.

.1000 M Hydrochloric Acid - Prepare from
standard solution concentrate or purchase
this concentration of solution.


0.01 M Hydrochloric Acid - Dilute 100 ml
0.100 M hydrochloric acid to 1000 ml.

Acetate Buffer Solution  (.4 M sodium
acetate and 0.4 M acetic acid)  - Dissolve
54.4 g Na(C2H302)- 3 H20 in about 400 ml
water.  Add 24 ml glacial acetic acid and
dilute to one liter.

Non-Ionic Detergent - Tergitol non-ionic
NPX or equivalent

Concentrated Nitric Acid - Reagent grade

Sodium Nitrite - Reagent grade

Procedure  for  the Determination of  Chloride

 (1)   Standardize  pH meter  to 0  millivolts
      while on  standby  and  in the ±  millivolts
      mode.
                    -105-

-------
           (2)  Pipette a suitable aliquot  (.01-.20
               millimoles of chloride) into a 150 ml
               beaker containing a stirring bar.

           (3)  Dilute to approximately 50 ml with
               deionized water.

           (4)  Add approximately 50 ml of the acetate
               buffer solution.

           (5)  Add 3 drops of nonionic detergent.

           (6)  Stir and titrate with  .0200 M silver
               nitrate to a potentiometric end-point
               of -260 millivolts.

          Electrode Cleaning

          Clean the metallic silver electrode before each series
of titrations and after about 15 titrations if more are run at
one time.  Prepare the cleaning solution by adding 50 ml
concentrated nitric acid, 50 ml water and 20 milligrams of
sodium nitrate just before use.  Dip the electrode in the
cleaning solution for only a few seconds and wash thoroughly
with D.I. water.

          Calculations

          Concentrations of chloride in solution can be calculated
using the following formula.
                    (Vs- VB)M
               Ca	c—
                             -106-

-------
where,

          C  = concentration of chloride (moles/Z),
           Si

          Vs = volume of silver nitrate for sample
               titration (ml),

          V,j = volume of silver nitrate for blank
           D
               titration (ml),

           M = molarity of the  silver nitrate solution,
               and
          V.  = aliquot size of sample.
2.5       Aqueous CO 2

          Carbonate in the liquid phase of the equilibrium and
kinetic studies was determined by chemical analysis of the
aqueous COz sample utilizing a nondispersive infrared analyzer.
The operational procedure of the instrument is described in
detail in Radian Technical Note 200-403-50.  The detection limit
is .1 ppm COz with the optimum range as 25-100 ppm C02 ± 3%
accuracy.

          In general, the aqueous C02 sample is injected with
a microsyringe into an acid pool which liberates C02.   The C02
liberated is then measured by the nondispersive infrared analyzer
The output of the analyzer is coupled with a recorder equipped
with disc-chart integrator for determining the peak area (pro-
portional to the amount of C02  injected).   The peak area for the
samples and standards along with calibration data is input into
a linear least squares program.  The program is used to determine
the C02 concentrations of the injected samples in moles/liter.
                            -107-

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Apparatus

(1)  QIC total carbon system equipped with
     disc-chart integrator

(2)  Hamilton injection syringe

(3)  Injector ampules with seal and septum

(4)  Glass drying tubes filled with fresh
     magnesium perchlorate
Reagents
 (1)   10% KH2?(\  stock  solution

 (2)   6% HaPO^  stock  solution

 (3)   Na2C03 reagent  grade

 (4)   Methyl red  indicator

 (5)   Magnesium perchlorate, anhydrous  flake
                    -108-

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3.0        ANALYTICAL PROCEDURES FOR CHARACTERIZATION OF SOLIDS

           Characterization of the precipitated solids was
performed in three phases.  The first phase consisted of chemical
analysis to determine the chemical composition of the solids.
The solids were then analyzed with X-ray diffraction techniques
to identify any pure crystalline phases.  Finally the solids
were analyzed by infrared analysis to confirm X-ray analysis
and to identify possible crystalline structures of coprecipitation
product.

           Chemical analyses of the solids consists of a solid
sulfite analysis, specific sulfate analysis,  solid carbonate
analysis, and a solid dissolution from which calcium, magnesium,
sodium and total sulfur were determined with the appropriate
analytical procedures.

3.1        Solid Phase Sulfite

           Solids obtained from the equilibrium and kinetic
studies were analyzed for their sulfite concentration by an
iodometric titration with sodium arsenite.  The theory and sensi-
tivity of the analysis is similar to the aqueous sulfur dioxide
determination.   However, the procedure has been modified to
accommodate complete dissolution of sulfite without degradation
of the iodine.

           Procedure for Solid Sulfite Determination

           (1)   Weigh 0.06 g of solid sample to the
                nearest 0.1 mg.

           (2)   Pour 60 ml of pH 6 buffer solution
                into a 4 oz glass bottle with cap and
                add stirring bar.

                               -109-

-------
           (3)  Pipet 10 nil of 0.1 N standard iodine
                solution into the bottle, cap and
                begin stirring.

           (4)  Add the weighed solid sample and recap.

           (5)  Stir for 30 minutes .

           (6)  Empty bottle quantitatively into a
                150 nil beaker and titrate as described
                in the procedure for aqueous S02
                (Section 2.2) .

           Calculations

           The concentration (mmole/gram) of sulfite present in
the solid sample can be determined by use of the following
equation:
                      W

where ,

           C = concentration of sulfite (in rnmoles/g)

           B = volume of arsenite used to titrate the
                blank in ml

           S = volume of arsenite used to titrate the
                sample in ml

           M = concentration of the sodium arsenite
               (moles/2,)

           W = weight of sample used in grams

                               -110-

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3.2        Specific Sulfate

           This method allows a specific determination of the
concentration of sulfate in the solids.   This differs from
techniques discussed earlier which determine sulfate by the
difference between the total sulfur and the solid sulfite.

           In the procedure, a representative sample of the solids'
is dissolved in 0.1 N HC1 oxygen-free solution to quantitatively
decompose the sulfite to SOz gas which is eluted by constant
bubbling of C02 gas through the  solution.  When all S02 has been
evolved, the acidic sulfate solution is quantitatively transferred
to an ion-exchange column and the total sulfur procedure  described
in Section 2.3 is followed.  The  detection  limit  is  0.075 mmoles/g
(0.01 mole fraction sulfate).  The accuracy at any level  is
±0.004 mmoles SCU~2(0.100 gram of solids).

           Apparatus

           (1)  CO2 tank - oxygen free

           (2)  C02 regulator

           (3)  gas manifold

           (4)  midget impingers

           (5)  hydrogen-form cation exchange columns

           (6)  hot plate

           (7)  75°C water bath

           (8)  100 ml beakers
                               -111-

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 (9)   pH meter

(10)   microburet

(11)   magnetic stirrer and bar

(12)   analytical balance

 Reagents

 (1)   0.1 N HC1

 (2)   0.05 N NaOH (±0.0001 N)

 Procedure

 (1)   Weigh 100 mg solid sample to the
      nearest 0.1 mg.

 (2)   Fill midget impinger with 20 ml of
      an acidic solution (0.1  N HC1)  and
      purge with oxygen-free C02 gas  for
      10 minutes at a flow rate of 100 ml
      C02/min to remove dissolved oxygen
      from acidic solution.

 (3)   Quantitatively transfer  100 mg  sample
      to midget impinger containing 20 ml
      of the oxygen-free 0.1 N HC1 with a
      few ml (<5 ml) of oxygen-free DI HaO.

 (4)   Purge with oxygen-free COz for  30
      minutes to strip the sulfur
      dioxide from the acidic  solution.

                    -112-

-------
           (5)  Quantitatively transfer acidic solution
               to hydrogen-form cation exchange columns
               and follow total sulfur procedure
               described in Section 2.3.
           Calculations

           The concentration of the solution (mmoles/g) may be
calculated by use of the following formula.
where ,

           C = concentration of sulfate in the solids
               (mmole/g)

          NB = normality of the NaOH solution

          VD = volume of the NaOH solution used to
           a
               titrate sample

           W = weight of sample used

and 2 is the number of equivalents per mole (or meq/mmole) of the
HzSOit formed by the ion-exchange column.
                             -113-

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3. 3        Solid Carbonate

           Carbonate present in the solid phase of the equilibrium
and kinetic studies was determined by nondispersive infrared
analysis.   The apparatus, reagents and solution, preparation of
standards, and calculations are described in Radian Technical
Note 200-403-50.   The following section will document the
procedure used for the adaptation of the method for solid
carbonate analysis.

           Procedure

           (1)  Dry the filtered solids at least 48
                hours at a maximum temperature of
                60°C.

           (2)  Weigh out 200 mg (±0.01 mg) solids
                for analysis (30 mg CaC03 for
                standards) and transfer to 100 ml
                volumetric flask.

           (3)  Rinse neck of flask with C02 free
                DI H20 (freshly boiled DI H20).

           (4)  Pipet 10 nil of freshly prepared
                C02 buffer into volumetric flask.

           (5)  Fill each volumetric flask to mark
                with C02 free DI H20.

           (6)  Add teflon magnetic stirring bar
                to each flask and stir for 30 minutes
                with flasks tightly stoppered.
                              -114-

-------
           (7)  Remove stirring bar and rinse the
                clean 60 ml polypropylene bottle
                with small aliquot of sample.

           (8)  Fill sample bottles to neck,  tighten
                cap and seal with tape until  analysis.

           (9)  Run the samples and standards on the
                nondispersive infrared analyzer in
                the same method as employed in
                aqueous C02 determination with the
                exception of a modified acid  pool
                (a mixture of 95 mis of 10% KH2PCU,
                5 mis of 5% H3P04, and 1 ml 30% H202).

           Calculations

           A computer program is utilized to  calculate the
concentration of carbonate in moles/liter of  the solution '
injected into the analyzer.  Utilization of the computer program
is described in detail in Section 8 of Radian Technical Note
200-403-50.  The following equation was used  for calculation of
the solid carbonate concentration in moles/gram.

                    C2V
where,
           G! = concentration of carbonate in solid
                sample (moles/gram)

           C2 = concentration (moles/liter) of carbonate
                of solution injected into analyzer
                (dissolution concentration)

                               -115-

-------
           V = volume of volumetric flask used in
               dissolution step (100 ml)

           W = weight of solid sample dissolved in
               volumetric O200 mg)

3 . 4        Solid Dissolution

           The following technique was used for dissolving solids
recovered from the equilibrium and kinetic studies.   It entails
dissolving a known weight of dried solid in an acidic medium
containing a sufficient amount of H202 to oxidize the sulfite to
sulfate.   Following filtration, the-liquid may be analyzed for
calcium,  sodium, magnesium,  and total sulfur according to technique
described in Sections  2.1 and  2.3.

           Apparatus

           (1)   2 100 ml volumetric flasks

           (2)   100 ml graduated cylinder

           (3)   10 nil graduated cylinder

           (4)   1 ml graduated pipet

           (5)   magnetic stirrer

           Reagents

           (1)   HC1 concentrated (12 Molar reagent
                grade)

           (2)   1 M HC1 (approximate ) -  84 ml concentrated
                HC1  diluted with D.I. H20 to 1 liter

                               -116-

-------
 (3)   hydrogen peroxide -  30%

 Procedure

 (1)   Accurately weigh 0.200 g (±0.1 ing)
      of solids.

 (2)   Quantitatively transfer solids to a
      clean 100 ml volumetric flask.

 (3)   Add approximately 50 ml of DI water.

 (4)   Pipet 0.3 ml of 30%  H202 into flask.

 (5)   Insert stirring bar  and stir, tightly
      stoppered,  for 10 minutes.

 (6)   Pipet 0.4 ml of 1 M  HC1 into the flask
      and stir for 30 minutes with stopper
      secure.

 (7)   Add by graduated cylinder an additional
      5  ml of 1 M HC1 and  stir for an addi-
      tional 30 minutes with stopper secure.

 (8)   Additional HC1 may be added to the
      solution, remembering that the (H+)
      adds to the total cation concentration.

 (9)   Remove the stirring  bar and dilute
      to volume.

(10)   Filter.
                    -117-

-------
           (11) Transfer to a clean 120 ml polypropylene
                bottle, cap and seal with tube until
                ready for use.  All liquor analyses
                except for chloride may then be performed
                on the solid dissolution following
                procedures described in Section 2 of
                this report.

3.5        X-Ray Diffraction Analysis

           Selected solids from the experimental runs were
analyzed utilizing an automatic X-ray diffractometer to identify
crystalline phases present in the precipitated solids with
particular emphasis on the crystalline form of the solid phase
sulfate.  The intensity of the diffracted beam is recorded
continuously on a strip chart and compared with published
patterns and with reference standards prepared by Radian for
identification.

           Reference standards of calcium sulfite hemihydrate,
calcium sulfate dihydrate and calcium sulfate hemihydrate were
prepared under controlled laboratory conditions and analyzed
chemically for purity.  Reference standards and solid samples
were ground with mortar and pestle, and classified.  Solids
smaller than 44 micrometers were stored in vials in an inert
atmosphere until analysis.   X-ray diffraction patterns of the
samples were compared to the standards for identification.

3.6        Infrared Analysis of the Solid Phase

           Infrared analyses were performed on all experimental
solids to distinguish between pure sulfate compounds and sulfate
contained within the sulfite crystalline lattice.  Spectra of
standards prepared in the laboratory and published spectra were
used for reference in interpretation of the spectra of experimental
solids.
                              -118-

-------

-------
                    APPENDIX E

  ANALYTICAL RESULTS, REACTOR MATERIAL BALANCES,
SOLID MATERIAL BALANCES,  AND COMPUTER EQUILIBRIUM
      DATA OF LABORATORY EXPERIMENTAL RUNS
                   Prepared by:
                Benj amin F.  Jones
                 Larry A. Rohlack
                        -119-

-------
                       TABLE OF CONTENTS

                                                     Page
1.0       INTRODUCTION	121

2.0       ANALYTICAL RESULTS, OPERATING DATA,
          AND COMPUTER SUMMARY	 123
2.1       Analytical Results	123
2.2       Operating Data	125
2.3       Computer Summary	125
2.4       Mole Fraction of Sulfite and Sulfate
          in the Precipitated Solids .  .-	125

3.0       REACTOR MATERIAL BALANCES  	 ...  .128

4.0       SOLID MATERIAL BALANCES 	 131

5.0       COMPUTER RESULTS	-.  .   . .133
                              -120-

-------
1.0       INTRODUCTION

          This appendix presents the experimental data, calcu-
lations, and material balances for experimental kinetic runs 44-71,
and equilibrium extraction runs 1-12.  Extensive analysis of
experimental data has been performed on each of these experimental
runs.  Four data sheets have been required to fully characterize
each run.  The first sheet contains a summary of analytical
results, operating conditions and computer results.  The second
sheet presents the material balance calculations around the
reactor.  The third sheet presents the material balances for the
solids only.  The results of computations by Radian's ionic equi-
librium program are printed and presented as the fourth data
sheet.

          The following four sections are provided as explanations
for the content of each of the four data sheets.  Equationsoare .
provided as needed for the calculations presented in the data
sheets.  The precipitation apparatus utilized in the kinetic
studies is depicted in Figure 1.  This diagram will facilitate
the understanding of the experimental data and of the mass
balances which follow.
                              -121-

-------


y
~^y <*

=} l
z
0
0
a
z
c_
[ill
(— [ — i — ! — *! — r^^J

UJ
3
0
o
                 •i i
-122-

-------
2.0       ANALYTICAL RESULTS, OPERATING DATA, AND COMPUTER
          SUMMARY

          An example of the first data sheet for each set is
shown on the following page.

2.1       Analytical Results

          Analytical concentrations are presented for the two
feed streams into the reactor and the effluent and solids leaving
the reactor.  These concentrations in millimole per liter represent
the average values of duplicate or triplicate determinations.
Major ions, including calcium, magnesium, sodium, chloride,
carbonate,  total sulfur, sulfite, and sulfate,  have been deter-
mined by the analytical techniques documented in Appendix C.

          A set of quality control analytical standards were
prepared.  These standards were analyzed each time a set of exper-
imental samples was  characterized.  The concentration of the
ions in the standards were as follows:

             Calcium - 50 mmole/liter
             Magnesium - 8 mmole/liter
             Sodium - 10.6 mmole/liter
             Chloride - 99.5 mmole/liter
             Total sulfur and sulfate - 18.8 mmole/liter

          The concentration of the standard as measured with each
set of experimental samples is then compared to the actual con-
centration as presented above.  The resulting standard deviation
is calculated.   This standard deviation in 7= is then presented
in the column labeled "Standards" under the analytical results
section of the first data sheet.
                              -123-

-------
       HUM :,'Q.  44

       OATH    i/27/76
                                                                       -T/T
                                     /0,'Ai YTICAL RrSUI.TS
             Standards       C<1'  Feed
 Species'  (''- Deviation)    (mnolo/1)
  "2
Ca
Nat1

Cl"1
C03":
S03"
              1-0
                            64.3
  6.39
131.
                                          S03~2 Feed
                                          (ranole/1)
                                           1380.
                                            390.
                                                          Effluent
                                                          (rmr.olc/1)
                                                            766
                                               Solids
                                                                           .02
 Time
 (mir.)

. 30

 60
 90
 150
 130
pH
6.43
6.31
6.29
6.25
6.22
Temp
(°0
47.3
43.0
43.6
50
50
                                        OPERATING DATA

                               -             Solids
                                 SOj"2        Removal
                               (nraiola/1)      (ml/min)
                                 17.5
                                 17.10
                                                32
                                                           Solids
                                                           (wc%)

                                                             .25
                                             Solids
                                              (g)

                                              3.2
                                       COMPUTER RESULTS
 Ionic
Strength

   1.35
                  Residual
              ElectroneuCralicy

                  -.063
                                        Relative  Saturation
            7.4
                          ' 2';!20   CuSO., • ^

                        1.01         0.46
                                                                             Mole  FractJO"
                                                                               SO,"

                                                                               .33
SO,,
                                           -124-

-------
2.2       Operating Data

          Operating conditions are monitored throughout each
experimental run to determine approach to steady state and to
determine how close the actual operating conditions are to the
design of the experiment.  Key parameters which are monitored are
pH, temperature, sulfite concentration, solids removal rate, and
concentration of solids in the reactor.  The concentration of the
solids is presented as the total mass of seed crystals and as a 70
of the total weight of the slurry.

2.3       Computer Summary

          Key computations of the Radian aqueous ionic equilibrium
program are summarized in this section of data sheet #1.   The
ionic strength, residual electroneutrality,  relative saturation
of calcium sulfite hemihydrat;e, calcium sulfate dihydrate, and
calcium sulfate hemihydrate are presented.  The residual electro-
neutrality is a rough indication of the accuracy of the input
concentrations of the major species.   The 70 error is obtained by
dividing the residual electroneutrality by the ionic strength and
multiplying the quotient by one hundred.
2.4       Mole Fraction of Sulfite and Sulfate in the
          Precipitated Solids

          The mole fractions of the precipitated sulfite and
sulfate were calculated by the following equations:
                              -125-

-------
                                Cp(S03"2)
                X   - 2  =  	:	         and
                 bUa     cpcsor2) +  cpcsor2)
-2 =
                                                      where
                         Cp(SO,~2) +  Cp(S03~2)
                Xcn -2  =  sulfite mole  fraction;  i.e., the
                 bU 3
                         ratio  of sulfite  in  the precipitated
                         solids to  that  of the  total  sulfur in
                         the  precipitated  solids.

             Cp(S03~2)  =  concentration of  precipitated  sulfite
                         in millimoles of  sulfite per gram of
                         precipitated  solid.
                                        £
             Cp(SCU~2)  =  concentration of  precipitated  sulfate  in
                         millimoles of sulfate  per  gram of pre-
                         cipitated  solid.

             y
              SOit"2  =    sulfate mole  fraction  or the ratio of
                         precipitated  sulfate to that of the
                         total  sulfur  precipitated.

The concentration (Cp)  of the solid ion  of interest,  either
calcium,  sulfite or sulfate,  is calculated using the  following
equation.

                    <*  =
                    Ce = concentration  (mmole/gram)  of  species
                         (calcium,  sulfite,  or  sulfate) present
                         in the solids  at  the end of the  experi-
                         mental run.

                             -126-

-------
          Me = total mass (grams) of solids present in the
               reactor at the end of the run

               Me = We x Vr                           where

               We = concentration of solids (g/&) at end of run
               Vr = volume of reactor in liters = 3.25 liters

          Cs = concentration (mmole/gram) of species present in
               the seed charge at the beginning of the run

          Ms = mass of initial seed charge present in the reactor
               at the end of the run.

The mass of the initial seed charge present in the reactor at the
end of the run can be calculated by the following equations:

                         -T/ T
               Ms = Mi x e                              where

               Ms = mass  of initial seed charge present at
                    end of run

               Mi = mass  of initial seed charge in reactor at
                    the beginning of run

                -T/ T
               e  '   = fraction of initial seed charge
                       remaining in reactor at end of run

               T = elapsed time of run (minutes)

               T = «—• = residence time of solids in reactor
                                                    where
                   Vr = reactor volume = 3.25  liters
                   Fs = solids removal rate (liters/min)
                             -127-

-------
3.0       REACTOR MATERIAL BALANCES

          Material balances for the reactor are presented on
the second data sheet for each run.  An example of the sheet
is shown on the following page.  In addition, precipitation rate
for each species calcium, sulfite,  and sulfate have been normalized
to the precipitation rate of the total solids.

          Material balances have been calculated for each of the
major ions of interest and include calcium, sodium, magnesium
chloride, sulfite, sulfate, and carbonate.   This is accomplished
by calculating the millimolar flow rate of each species into the
reactor and comparing it to the corresponding rate leaving the
reactor.
                                                          a

          For the inlet, these rates are calculated for each feed
stream by multiplying the volume flow rate (ml/min) by the con-
centration of species (mmole/ml).   The resulting millimolar rates
of each ion for two feed streams are then summed.

          For the outlet, similar calculations are made for the
millimolar rate in the liquid phase.  These effluent liquid phase
millimolar rates are then added to the corresponding effluent
solid phase millimolar flow rate.   Solid phase millimolar flow
rate is determined by multiplying the solid phase concentration
(millimoles/gram) by the product of the slurry, removal rate
(liters/minutes), and the solids concentration (grams/liter).

          After calculating the precipitation rate (mmole/min)
of each ion of interest  (calcium,  sulfite and sulfate) the rate
is normalized to the total solids precipitation rate (grams/minute)
This is accomplished by dividing the individual rate (mmole/min)
                              -128-

-------
                        REACTOR MATERIAL  BALANCE CALCULATION'S
                        Run  '/  44
                                                 Data  1/27/76
INLET

Flow Race (mi
crl
C03~
S03"
SOu"
        (moola/niin)
        (nnnola/iiin)
        (minola/ain)
        (aniole/'ain)
        (mmole/tnin)
        (mnole/^in)
        (nmole/niin)
                                         50
                                                      50
                                                       2.28
                                                                           100
                                                                             3.22
                                                                            59.5
                                                                             3.38
                                                                            75.6

                                                                             2.23
                                                                            19.5
OUTLET

Flow Race (ml/mia)

Ca z    (mmcla/min)
Mg A    (mmole/aiin)
Na2     (nmole/tnir.)
Cl"1    (mmola/min)
CDs     (mnole/min)
S03     (mmola/min)
SOu     (amole/min)
                                          3.04
                                        76.6

                                         1.71
                                        20.0
                                                    Solid
                                                     Q."'!
                                                      .003
                                                      .002
                                                      .63
                                                      .105
                                                            (g/min)
                                                                            •3.28
                                                                             3.04
                                                                            76.6

                                                                             2.34
                                                                            20.1
PREC. RATE


     Solid


     S0>,~2
                                        mmola/aln  nmole/9
                                                                          0.098
                                                                           .090
                                                                           .089
                                                                         -0.449
                                       -129-

-------
by its concentration in the solid (mmole/gram).   This normalizes
each of the rates and allows another independent check
of the accuracy of the analytical measurements and flow rate
measurements .'
                              -130-

-------
4.0       SOLID MATERIAL BALANCES

          Material balances were also calculated for the solid
phase alone.  An example data sheet is presented on the following
page.  Balances were calculated by multiplying the solid concen-
tration of each ion (mmole/gram) by its molecular weight (g/mmole)
to obtain its fractional equivalent of the total solid.  The
water content of the solids was determined by assuming % mole of
water for each mole of sulfite and % mole of water for each mole
of sulfate present.  These fractions were then summed and compared
to an optimum balance of one gram.
                              -131-

-------
                        SOLIDS MATERIAL BALANCE
                        Run //   44      Date 1/27/76
                g/mmole           mmqle/gram               g/gram
  -•'2              ---               7.24                    0.290
Ca'              .040
Mg+2             .024                .035                    .001




Na2+2            .046                .02                     .001




Cl"1             .035               	                     	
C03~2            .060
S03~2            .080               6.43                     -514




   '2            .096               ^O7                     -103
%H20             .009               7'5Q                     -068
                                   -132-

-------
5.0       COMPUTER RESULTS

          As stated earlier, the pH, temperature, and molar
concentrations of the major cations and anions are input into
Radian's aqueous ionic equilibrium program.   This program takes
the inputs for each case, together with the relevant dissociation
and solubility product constants, and calculates pertinent equi-
librium data.  Activities of the major ions  and ion pairs and
the relative saturation of relevant solid species are calculated,
In addition, the ionic strength and residual electroneutrality
are calculated and printed.
                              -133-

-------
EXPERIMENTAL DATA
       -134-

-------
      . RUN NO.   44
       DATE
                1/27/76
                                     ANAJ YTTCAL RESULTS
                                                                       -T/T
                                                                             .^15	
Species
Ca
Mg
  + 2
  +2
Nat1
Cl
CO;
Ts"
S0:
SO 4
  -i
    2
    2
   '2
           Standards
          (%  Deviation)
               -.1
                .3
              1.0
                            Ca+ Feed
                           (mmole/1)

                             64.3

                              6.89
                            131.
                                          S03~2 Feed
                                          (raiiole/1)
                                           1190.
                                             60.6
                                           1380.
                                            436.
                                             45.6
                                            390.
Effluent
(mrr.ole/l)
  25.7
 560
  30.4
 766
                                                             217.
                                                              17.1
                                                             200.
  Solids
 (mmole/o)

  7.24
    .035
    .02
                6.43
                1.07
 Time
(min)
 30
 60
 90
150
180

pH
6.43
6.31
6.29
6.25
Temp
(uc)
47.3
48.0
48.6
50
                                    ~2
                                 S03"
                               (mmole/1)
                                 17.5
           6.22
                   50
                                        OPERATING DATA
                                             Solids
                                             Removal
                                             (ml/min)
                                                32
                                 17.7
                                                33.
                                                29.
                                                31.
                                                50.
 Solids
 (wt%)
  .25
  .26
  .29
  .32
  .29
Solids
 (g)
 8.2

 9.3
10.4
 9.31
                                       COMPUTER RESULTS
 Ionic
Strength

   1.35
                 Residual
             Electroneut ra! ity

                  -.063
                                        Relative  Saturation
                                       7.4
                                                     1.01
   CaSO., • ^
      0.46
                                                                             Hole  Fracti
                                                                             S0
                                                                                ~2
      .33
                                                                                        SOu
                                            -135-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
  +2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
OUTLET

Flow Rate (ml/min)
Ca
Na2+2
ci-1
C03~2
so3~2
Ca£

Na2+:
Cl L
CO 3
S03
SO 4
-2
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC._RATE

     Solid

     S03~2
Run // 44 Date 1/27/76
A
50
B
50
3.22 	
	 59.6
.35
6.54
3.03
69.1
— __ — —
	 2.28
	 19.5
Liquid
inn
2.57
56.
3.04
Solid
0.098 (g/min)
0.71
.003
.002
76.6 	
	 	
1.71
20.0
mmole/min
0.65
.57
-0.48
.63
.105
mmole/g
7.24
6.43
1.07
                                                                          100
                                                                         3.22
                                                                        59.6
                                                                         3.38
                                                                        75.6

                                                                         2.28
                                                                        19.5
                                                                            3.28
                                                                           56.
                                                                            3.04
                                                                           76.6

                                                                            2.34
                                                                           20.1
                                                                         grams/min
                                                                         0.098
                                                                          .090
                                                                          .089
                                                                        -0.449
                                         -136-

-------
                        SOLIDS MATERIAL BALANCE
                        Run //   44      Date 1/27/76
                g/mmole           mmole/gram               g/gram






Ca~!2              .040               7.24                   0.290
Cl               .035
C03"2            .060
                                   -137-
Mg+2             .024                .035                    .001
Na2+2            .046                .02                     .001
S03~2            .080               6-^3                     .514
                 .096               1-07                     .103
%H20             .009               7'50                     -068
                                                         z.o-977

-------
                       KINETIC  RUN 44
76    14S15I37.27H
PH S
                      INPUT snecus
                                        CC2
                                        302
                                        S03
                                                                 9e,0«a  DEC.  c.
                                    1 .1 ja-"7
                                                       t .367«.:»^
                                                       <», 764-^1
VI4SH4-
CU-
                 3.7«b-Ct
                             1., -107-1-4
                             I ,55'J-.'J
                                    0.327-CS
                                                       I .2t>7*"C>
503--
CASi.n(«)         i'.f??

M-j533C5)         8,<4?i!

  "i? * 2.17441-07  ATH.
                                    ( .1195.«4
                                    5.127-C3
                                            ACTIVITY

                                                3.77«-17


                                                9[724-16
              IONIC STRENGTH > 1 ,3S
                                                                  t.
                                                           SA7UHATTO"
                                                «£S. fc.N. «  -P.
                                -138-

-------
       iUIM NO.   45
       DATE      2/2/76
                                                                       -T/T
                                                                              .06
                                     ANALYTICAL  RESULTS
 Species
   + 2

   + 2
Ca
Mg
Nat1
Cl

CO 3

Ts"

SO 3
   -i
    -2
   -2
 Standards
(%  Deviation)

    -.1
              -.8
               .3
              1.0
              1.0
 Ca   Feed
(mmole/1)

  61.9


   6.70

 125.
                                          S03~2  Feed
                                          (mmole/l)
                                             1030.

                                              40.7

                                             1400.
                                    418.

                                    33.3
                                    385.
          Effluent
          (mn;olc/l)

            27.7
           529. _
            23.6

           819-
                                  222.

                                  14.9
                                  207.
                                                                          Solids
                                                                          5.58
                                                                            .18
                                                                            .01
                                                                          5.6
                                                                          1.52
                                                                          4.40
                                        OPERATING DATA
 Time
(min)
                   Temp.
PH
6.30
6.19
6.19
6.18
6.18
47.3
48.8
51-0
49.9
50.0
so3~2
(mmole/1)
16.3
16.2
15.8
15.9
15.5
Solids
Removal
(ml/min)

18.5
16.9
21.4

Solids
(wt%)

.14
.16
.19
.20
Solids
(g)

4.5
5.1
6.0
6.4
                                       COMPUTER  RESULTS
  Ionic
 Strength

    1.40
                 Residual
             Electroneutrality

                    .115
                                        Relative  Saturation
                                      6.7
CnS(V2U20

   1.15
                                                      0.52
                                                                             Mole   Fract5<
                                                                             SO
                                                                                -2
0.20
                                                            0.80
                                             -139-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
                        Run # 45
                                             Date  2/02/76
INLET

Flow Rate (ml/min)
                                     50
                                             50
                    100
Ca+2
Mg+2
Na2+2
ci-1
Ts
SO 3
S0«,
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                     3. 1 Q
                                      .34
                                       ?ft
51.5
 2.04
70.3
20.9
 1 . fi7
19.7
 3...1Q
 51. 5
  2.3.8
7fi.fi
20-9	
 1.67*
19.2
OUTLET

Flow Rate (ml/min)
^z
Mg+2
Na2 2
Cl"1
Ts
S03 2
scu"2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                    Liquid

                                     100
                                         2.77
                                         S2.9
                                         2.36
                                         81.9
                                        22.2
                                         1.49
                                        20.7
                                           Solid

                                            0.042   (g/min)

                                            0.235
                                                   .008
                                                   .0004
                                                 0.25
                                                   .064
                                                   .188
                     3.01
                    52.9
                     2.35
                    81.9
                    22.5
                     1.55
                    20.9
PREC. RATE
                                    mmole/min  mmole/j
     Solid
     C.+1,
     S03
     SO 4
     -2
                                0.33
                                 .18
                               -2.3
5.58
1.52
4.40
 O.Q42
   .059
   .118
-  .523
                                         -140-

-------
                        SOLIDS MATERIAL BALANCE







                        Run //   45      Date   2/2/76






                g/mmole
Ca+2             .040




Mg+2             .024
                 .046
C03~2            .060




S03~2            .080
mmole/gram
5.58
.18
.01
g/gram
0.223
.004 .
.001
	 	
	 	
1.52 .122
4.40
.423
5.92 .053
4.40
.119
                 .096




%H20             .009



1%H20            .027



                                                       E     .94
                                   -141-

-------
                          KINETIC  RUN 45
f. »
                      INPUT SPECTES

             • 5.:>v«;>*>ii
                  .4 Q.I- •/
                                         HCl
                                         C02
                                         J02
                                         S03
                                    ^.KV 7. "7

                                    1 .1 w?«C7
                                    I ,4l?-;'J
                                    7 . .1 1 •« - -i 7

                                    4 t97*-i'3
                                    l.li;2-»>t
                                    1 ,55"-3i3
                                    7.54-1-33
                                                8.
                                                2.
                                                 SCTIV1TY
•i.ft.-7-M
a.«i«-Ji

2.437-dl
?,«l«-Bt
t .
                                                                        oes. c.
v \ s n i.
                 a.645-1?
                 ^.^''n- "5
                 1.251-/.3
                                     1.327— '2
                                     I ,S4v).?i
                                     1.
S.-J3--
                 7 ,
                                ACTIVITY
                                    4,
                                                   RELATIVE  SATUH4TTQ«

                                                       9.»lf-12
              IQ»'IC STSEMGTn i 1.4P221+/"        RES.  e.M.  «  -1.153-01
                              -142-

-------
       RUM NO.   46
       DATE     2/3/76
                                                                       -T/T
                                                                           .012
                                     ANA!YTTCAL RESULTS
Secies
Nat1
Cl
co,
Ts~
S03
  -i
-^
-2
        Standards
       (%  Deviation)
            -.1
             .3
            1.0
 Ca+ Feed
(mrnole/1)
   61.9

    6.7
  126.
S03 2 Feed
(rnmole/1)
   -2
               1.0
                                          506.
                                          36.4
                                          647 •
                  273 .
                   34.5
                  240.
                                             Effluent
                                             (mmole/1)
                                               24.6
                                              248
                                               19.9
                                              384
                 128.
                  10.3
 Solids
(mmolc/o)

  7.12
   .015
   .01
                                                             6.70
                                                             6.22
                                                              1.08
                                        OPERATING DATA
Time
(min)
30
60
110
pH
6.4
6.3
6.28
Temp
48
48.5
49.1
190

S03 *
(mmole/1)
12. 7
11.9
11. 7
10.3

Solids
Removal
(ml/min)
75.5
75.5
75.5


Solids
(wt%)
.22

.'12 	
Solids
(s)
7.1

L n

                                       COMPUTER RESULTS
 Ionic
Strength
   n.715
    Residual
Electroneutrality

     -.053
                                        Relative  Saturation
              6.7
                                             CaSO,,'2!!20   CaSO., -^11
                                                0.95          0-42
                                                                          Hole  Fracti
                                                   S03
                                                   .85
                                                                             -2
                                            .15
                                             -143-

-------
                        REACTOR MATERIAL  BALANCE  CALCULATIONS
INLET
Flow Rate  (ml/min)
Ca
  + 2
Mg
Naz
Cl
Ts
S03
  .+2
  -1
   -2
   -2
OUTLET
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
Flow Rate  (ml/min)
y
Mg 2
Na2+2
Cl *
Ts
so3"2
soC2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE
     =====


     Solid

     S03~2
        -2
Run // 46 Date 2/03/76
A
50
B
50
3.10 	
25.3
.34
6. 3?
1 .8?
37. 4
__— _ _____
	 1.73
___ —
Liquid
100
2.46
24.8
1.99
Solid
0.664
.0014
.0009
38.4 	
12.8 	
1.03
11.8
mmole/min
0.64
.70
.16
. 580
.10
mmole/g
7.12
6.22
.70
                                                                          100
                                                                          3.10
                                                                          25.3
                                                                          13.7
1 .73
                                                                          3.12
                                                                         24.8
                                                                          1.99
                                                                           1.61
                                                                          11.9"
                                                                         grams/min
                                                                         0.093
                                                                           .090
                                                                           .113
                                                                           .229
                                         -144-

-------
                        SOLIDS MATERIAL BALANCE






                        Run // _46	    Date    2/03/76






                g/mmole           mmole/gram               g/gram






Ca+2             .040               7-12                    0-285




Mg+2             .024               .015                     -001




Na2+2            .046               .01                      .001




Cl"1             .035               	                     	
C03~2            .060
S03"2            .080                6.22                     .498




SO
-------
                                               KINETIC  RUN  46
93
       76
             14115139,9«SJ
                  ct><
                                          INPUT  SPECIES
        CAD
        >«GO
                                • 5.35/62+vM
                                i 2, **>."**-*?
                    5r>j-
                                   »G'I£OUS
                                    7.S37-/17
HCL
co?
M203
                                                            SO?
                                                            SU3
                                                        ?, 247-^7

                                                        a. "31 --19
                                                  TEMPERATURE    49,law  OES.  C.
                                                                             CTtFFICTEvT
                   CAS04


                   -G**
                   •ur.<
llrt-
Cl-
                 1 .4M-/IS


                 5^344-ii3


                 I.hi5-/1



                 s|9<4-^3



                 o!j2'3-l 1


                 1 . 19.)-i' 3
                                                        ".757-H3
                                                        <,76fl-H2

                                                        ?,72'-»2
                                                        7.17^-li'
                                                        9.791-^8
                                                        2.344-PIJ
              1.

              7,-67-Cl
              1.13.1»on

              7.4ua-^i
                   W&S03CS)
                                    5.142-1-2            5,36

                                    -P1.4I-TTV        ACTIVITY

                                    ».e*C               3.872-17
                                      ATM,
                                                            SATH^ATIO«

                                                       1,143-11

                                                       9ls39-fll

                                                       9.323-t»2
                                                                                 -5.324-^3
                                                  -146-

-------
        RUN NO.	47_	
        DATE      2/3/76
                                     ANA! YTTCAL RESULTS
                                                                       -T/T
                                                                              .066
           Standards
Species   (% Deviation)
Ca+2        -.1
Nat1
 Cl
 CO
   1
    2
            1.0
                          Ca   Feed
                          (nmolo/1)
                              6.7
                            125.
                                          S03~2  Feed
                                          (ranole/1)
 SO-,
   "2
            i.n
                                            694.
                                             40.5
                                            106.
                                             230.
                                              33.4
                                             197.
                                             Effluent
                                             (mmolc/1)
                                               22.7
                                              354
                                               22.7
                                              634
                                                            116.
                                                             12.9
                                                            103.
 Solids
(mmolc/o)

   7.32
   .03
   .03
                                                             6.63
                                                             6.38
                                                             1.07
                                        OPERATING DATA
 Time
(min)
 20
 30
 90
180
           pH
          6.20
          6.22
          6.22
          6.18
                   Temp.
                   48.5
                   48.5
                   49.0
                   49.5
S03 2
(ramole/1)
12.9
13.4
12.9
Solids
Removal
(ml /rain)
47.5
47.5
5J3.9
Solids
(wt%)
.17
17
'. 19
Solids
(g)
5.5
6.2

                                       COMPUTER RESULTS
 Ionic
Strength

 1.03
                  Residual
                                         Relative   Saturation
Electroneutrality    CaSOs'%H20

     -0.0642            6.21
                                                   0.61
                                                              CaSO., -

                                                                0.26
                                                                             Mole  Fracti
                                                                             S03
                                                                             .85
                                                                                 -2
             SOu
             .15
                                            -147-

-------
                        REACTOR MATERIAL  BALANCE  CALCULATIONS
                        Run #  47
                                         Date 2/3/76
INLET

Flow Rate (ml/min)
                                          50
                                              50
                                                                            100
  ,+2
   +2
M
Na2
ci-1
Ts
S03
S0i»
   -2
   -2
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/rain)
     (mmole/min)
     (mmole/min)
                                          3.10
                                           .3
                                          6.26
                                              34.7
                                               2.03
                                              53.1
                                              11.5
                                               1.67
                                               9.9
                                                                    3.10
                                                                          _34._7__
                                                                           2.37
                                                                           59.4
                                                                           11..5
                                                                            1.67
                                                                            9.9
OUTLET

Flow Rate (ml/min)
Na2
Cl
Ts
SO 3
SO 4
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                       Liquid
                                         100
                                           2.27
                                          3S.4
                                           2.27
                                          63.4
                                          11.63
                                           1.29
                                          10.34
                                            Solid

                                              .096  (g/min)

                                              .70
                                              .003
                                              .003
                                              .67
                                              .61
                                              .10
                                                                           2.97
                                                                          35.4
                                                                           2.27
                                                                          63.4
                                                                          12.3
                                                                           1.90
                                                                          10.4
PREC. RATE
                                mmole/min  mmole/g
     Solid
     SO.
     SO 4
 -2
I
 -2
                                       .83
                                       .38
                                     -.78
                                                     7.11
                                                     6.38
                                                      .59
                                                                           .096
                                                                           .117
                                                                           .060
                                                                         -1.32
                                        -148-

-------
                         SOLIDS MATERIAL BALANCE
                        Run //  47       Date 2/03/76
                g/mmole           mmole/gram               g/gram






Ca                .040                7.32                     .293
                 .035
C03~2            .060
                                  -149-
Mg+2             .024                 .03                     .001
Na2+2            .046                .03                     .001
S03"2            .080               6.38                     .511




SO*"2    -        .096               1-07                     .103
%H20             .009               6-97                     -063
                                                         E-  "972

-------
                                              KINETIC RUN 47
03
I4:i!
                                            INPUT
                             CAO
                      2.2;
                      3.24/.!»P-k. 1
                      2.27*VK-i.?
                                                               C 0 2   x '.i, ? f-i it* n
                                                                     « d . 0 fl « a fl
                                                                     » vi . #??•**
                                                               S02   » 1.29.1H-J-
                                                               SC.3   » 1.
                    OH  s   *.?; '-'1
                                              sol
;n.-iPf>.£ . r
HT
•«2fl
-;?.+
C 4 S f j »
T * s r, 
«H-
n
5
g
2
u
1
I
1
3
2
4
*
5
4
s
e
1
ouALir*
.73.5-^7
.5*7- >°
.4«iy-; ^
. 4 f f - .- 7
. a 1 2 - f '
.21 J-i a
. 18-l-C .<,
. ^ 7 ^ - -- 1
.f-7-,-1
.575-- «
.J*'1-'I3
. 7 1 7 . ,- ?
,4P4-k'?
.-32-1 •
i 7 t *•
, l/i - - "••
. fiA-..M
.',-5a- -7
iCTIVpY 4CTIVITY C°cFr
«. 3^18-^7 t . 100+avt
O H O -< "1 <
^.B^n-^l
t.!9«-C'7 I.ty7*"f
1 ,4t*7-'-. 3 «,PMQ.'^ i
4.31*-"7 7,hni?--It
''.t-il
*.45^-"4 7.<>Sfl-i-M
a.9'jt-'-n ;.HPP-SI
                                                                                         49.5CH OEG. r.
                    Cl-
      5 0 A - -

     ;r -tpi.s f.1 1

      C4fOHJ?(S)
      r«5 f 3 c")
      CASP4C?)
      •'G fOHj ? (. S)
                                                           ) . P 1 P - " 4
                                                      4CTIVITY
                                                           4. 1 7Q-n7
                     10WIC STRfe^GTh  s  1 ,
                                                                      T   <=£LATlvh
                                                                               , P / d . fl 1
                                                                           ,  E.N.
                                                  -150-

-------
       RUM NO.

       DATE
                    8
                 2/4/76
                                     ANA I YTTCAL  RESULTS
                                                                       -T/T
 Species
   + 2
   +2
Ca
Mg
Nat1
Cl

CO 3

Ts"

SO 3

80s,
   -i
    -2
    -2
           Standards
           » Deviation)

             -.1
               .3
             1.0
       Ca  Feed
      (mmole/1)

         65
                              2.7

                            130
                                          S03  2  Feed
                                          (ramole/1)
                                            1060
                                             360
                                            1600
                                             214
             1.0
                                             27.8

                                            186
                                                Effluent
                                                (mmolc/1)

                                                   30.8

                                                  520 ,
                                                   19.8
                                                  880
                                                             95.7
                                                             10.3

                                                             85.4
                                                                          Solids
                                                                         (mmolc/cO

                                                                           7.06

                                                                            .07
                                                                            .03
                                                                 6.98
                                                                 5.97

                                                                 1.16
                                        OPERATING DATA
 Time
(min)
 pH

6.36
6.27

6.24
6.27
6.24
Temp.
C°0

49
50.2

51.0
50.6
51.0
                                    ~2
                                 S03
                               (mmole/1)

                                 11 .3
                                  11.0
                                 10. J_
                                 10.4
                                 10.3
                                             Solids
                                             Removal
                                             (ral/min)
                                               24

                                               25.4
                                               46.8
                                               46.9
                                                 Solids
                                                            .23
                                                            .22
                                                            .16
                                                                       Solids
                                                                         (g)
                                                                        7.4.
                                                                         fi.l
                                                                        S.I
                                       COMPUTER  RESULTS
 Ionic           Residual
Strength     Electroneutrality
                                        Relative   Saturation
                                   CaS03-^H20    CnSOM-2i!20
                                                                             Mole  Fracti
                                                                             SO
                                                                                -2
    1.48
                   0.070
                                                   .54
                                                       .7.5
                                                                               .84
                                             -151-

-------
                        REACTOR MATERIAL  BALANCE CALCULATIONS
                        Run  //  K-48
                                        Date  2/4/76
INLET

Flow Rate  (ml/min)
Ca+2
Mg+2
Na2+2
ci-1
TS-
S03
SO
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET

Flow Rate  (ml/min)
  + 2
Cl"1
Ts
SO 3
   ~2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE
     -- . —^__"—

     Solid

     S03~"
     SO.
         2
A
48.9
B
49.7
3.18
52.7
.13
6.36
1.79
79.5
10.6
1.38
9.2
Liquid
98.6
3.04
Solid
.074 (g/min)
.52
51.3
1.95
86.8
9.4
1.02
8.42
mmole/min
.14
.36
.78
.52
.44
.09
mmole_/g
7.06
5.97
1.16
                                                                   98.6
                                                                            3.18
                                                                           52.7
                                                                            1.92
                                                                           85.9
                                                                           10.6
                                                                            1.38
                                                                            9.2
                                                                    3.56
                                                                   51.3
                                                                    1.95
                                                                   86.8
                                                                    9.92
                                                                    1.46
                                                                    8.53
                                                                   .074
                                                                   .020
                                                                   .060
                                                                   .672
                                         -152-

-------
                        SOLIDS MATERIAL BALANCE
                        Run //  48        Date  2/4/76
                g/mmole           mmole/grain               g/gram



  -f-2
Ca               .040                 7.06                   .282


Mg+2             .024                  .07                   .002


Na2+             .046                  .03                   .001


Cl"1             .035                 	                   	
C03~2            .060
S03              .080                 5.97                   .478


S04~2            .096                 1.16                   -111


%H20             .009                 7.13         '         -064
                                                             .938
                                    -153-

-------
                            KINETIC  RUN  48
                         INPUT  SPECUS

                 3.35fc«a»v1l
                                           MCL
                                           CC.2
                                           S03
                                                                            0£G. C.
 ->2S" '
 iSOo-
 < 31-14-
                  AQUEOUS SOLCTIT

                   ""I.4LITV
j T U I " " I »

 ACTIVITY     JCTIVITY

 S.75S.P/           i,;
 7.S/6--P4
 5.3/1-f7
 5.C7?-"1
 C 4 •"...!
                  6 , 7 * 3 - •• B
                  J.nSS-t 5
                  5.15.1-1 '
 t.475.
 7,1'jf.
 
-------
                       -T/T
RUN
DATE
Species (%
Nat1
cr1
C03~2
Ts~2
S03"2
Time
(min)
50 6
130 5
200 6
320 6
410 6
495- 6
583 6
Ionic
Strength
1.43
NO. 49 c .24
2/10/76
ANALYTICAL RESULTS
Standards Ca+ Feed S03~2 Feed Effluent Solids
Deviation) (mmole/1) (ranole/1) (mmole/1) (mmole/jO
-.1 62 — 2J9..4 7.45
0 — 940 500 .05
s 2.4 41.6 22.2 .03
^ 126 1670. 853
	
1.0 — • 230 101 6.95
18.2 7.69 6.30
	 719 at. QC
i.o /iz yj •y-5
OPERATING DATA
Solids
Temp. SOs"2 Removal Solids Solids
pH (°C) (mmole/1) (ml/min) (wt%) (g)
.18 AQ.l • 8. S
45
.00 50.0 9.5 8.0 .125 4.1
.21 51.2 8.3 8.0 .153 5.0
.19 51.1 8.30 7.9 .165 5.4
.10 51.0 8.7 7.8 .202 6.6
.20 50.9 8.0 7.8 .179 5.8
.21 50. Q 7.7 7.8 .201 6.5
COMPUTER RESULTS
. , Relative Saturation Mole Fract
Residual • 	 - 	 ••
Electroneutra] i ty CaS03'i;H20 CaSOi, ' 2V.20 CaSOi, '^r^O S03 SO
-049 3.92 .57 .26 .85
-155-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca+2
Mg+2
Na2+2
ci-1
is
S03
SO 4
   -2
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate (ml/min)
y
Mg 2
Na2 2
Cl~l
Ts
S03 2
so,"2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE


     Solid

     S03~2
        -2
Run // K-49 Date 2/10/76
A
50.2
B
50.2
3.11
47.2
.12
6.33
2.09
81.8
11.5
.91
10.6
Liquid
100.4
2.95
Solid
.0157 (g/min)
.117
50.0
2.23
- 88.4
10.1
.77
9.25
mmole/min
.16
.14
1.25
.109
.099
.015
mmo 1 e / g
7.45
6.30
.95
                                                                          100.4
  3.11
 47.2

~90.1~
 11.5
   .91
 10.6
                                                                            3.07
                                                                           50. D
                                                                            2.23
                                                                           88.4
                                                                           10.2  _
                                                                             .87
                                                                            9.37
                                                                           .0157
                                                                           .0215
                                                                           .0222
                                                                          1.32
                                         -156-

-------
                        SOLIDS MATERIAL BALANCE
                        Run // 49        Date    2/10/76
                g/rcmole           mmole/grara               g/grarc
Ca+2             .040                7.45                   .298


Mg+2             .024                  .05                   .001


Na2+2            .046                  .03                   .001


Cl"1             .035
C03              .060
S03"2            .080                 6.30                   -504


SO,"2            .096                  .95                   -091


%H20             .009                 7.25                   -Q65


                                                            .961
                                                         E	
                                   -157-

-------
                                      KINETIC  RUN  49
IS
       7o
                          C»0  « 2.
                          -U"  > s.

                          K'A2li a 2.
                                              secies  c ini.es)

                                                         *ci
                                                         CD 2
                                                         Su3
                                                                                        uFG.
                                  ALir-cl:
                                                      ACTIVITY
                                                                            •"•FTC r?« r
                   f S u A '
                  CL-

3 ,ff 1 -•'*
1 ,-'M -• ?
3.137-1-7
2.952-..?
1 . /d"-». s
7.. ,53- 'i
5l.047-.-3
i.332-"1
7 . 2^4-y'f5
5 , .«-(• 4 5
S.7?i-/7 <(
6.55?-F3 S
\ ^S \ d.^j H
J. ••*"*- •< 1
3.75-«-v:j 1
!.Jc?-*l 3
*.?•'! -PI '
7,'1«7-i''v} '
7.J/«-->a 1
3.'74«"a 7
7 . i 1 >* - I -! t
?.7l<3-f-S '
t.lll.,-' a P
f.a«J-?S 1
4.7«3-ai "<
.757- •[
,7ri4» i '
. S i 7 - -•' 1
,«7?—'l
.4S"-.-l
.I/*- U
,?^4-f^-.
.?•>•»*'..
.1^1-^1
.'~72--l
, 9 h
-------
        RUN N0._

        DATE
                   50
                   2/17 7-76
                                                                       -I/
                                                                             < .01
 Species
Ca

Mg

Nat1
   + 2
Cl

CO 3

Ts~

S03
   -i
    -2
-2
           Standards
           (mnioles/1)
                       Ca+ Feed
                      (mmolo/1)
                             36.9
                            74.8
                                     ANALYTICAL  RESULTS
                                          S03  2  Feed
                                          (rnmole/l)
                                             43.1
                                             42.4
                                             20.8
                                             21.6
Effluent
(mmolc/1)

   9.53
                                                         20.2

                                                         43.3
                                                             9.7
                                                             1.90
                                                             7.8
  Solids
 (mmolG/cO

    7.36

                                        OPERATING DATA
 Time
(min)

 58
           pH

          7.95
                   Temp.
                 40
                                          Solids
                             S03~2        Removal
                            (mmole/1)      (ral/min)

                                               400
 Solids
 (wt%)

 Q.1Q2
Solids
 (g)

 2.79
                                       COMPUTER  RESULTS
  Ionic
 Strength

  0.0677
    Residual
Electroneutra]ity

      -0.0032
                                         Relative   Saturation
                                      6.6
                                               0.25
                                                                0.09
                                                                             Hole  Fracti
                                                                             SO
                                                                                 2
                    0.91
                                                                                   SO
               0.0
                                            -159-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca+2
Mg+2
Na2+2
ci-1
Ts
SO 3
SO 4
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate (ml/min)
Ca
Mg 2
Na2 2
Cl'1
Ts
S03 2
sor2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE
     Solid
  S03
  so ^
        -2
Run // 50 Date 2/17/76
A
200
B
200
7.38 	
	 	
	 8.62
15.0 	
	 8.48
	 4.16
	 4.32
Liquid
400
3.81
Solid
.408 (g/min)
3.00
	 	
8.08 	
17.3 	
3.88 	
0.76
3.12
mmole/min
3.57
3.40
1.20
2.86
0.30
mmole/g
7.36
7.00
0.73
                                                                           400
                                                                           7.38
                                                                           8.62
                                                                          15.0
                                                                           8.48
                                                                           4.16
                                                                           4.32
                                                                           6.81
                                                                           8.08
                                                                          17.3

                                                                           3.62
                                                                           3.42
                                                                        grams/min
                                                                           0.408
                                                                           0.485
                                                                           0.486
                                                                           1.64
                                         -160-

-------
                        SOLIDS MATERIAL BALANCE







                        Run #   50      Date  2/17/76







                g/mmole           mmole/gram               g/gram






Ca+2             .040                 7.36                  0.295




Mg+2             .024               	                 	




Na2+             .046               	                 	




Cl'1             .035               	                 	




C03~2            .060	                 	




S03~2            .080                 7.00                    .560




SOr2            .096               	-J2_                   -070




%H20             .009                 7.73                    .070






                                                           0.995
                                   -161-

-------
                                                 KINETIC  RUN  50
15
        7*>
17:11: 4-J.s
                               CAH   a
                                               INPUT  SPECIcS
                                                    C02   s  <, ,,'* /' "* '•
                                                    * 2 0 5 s  •*£  0 E 6 . C .
                     SU3!i45A I I'^ATI
                                                                 r:vm
                                                              ACTIVITY  C">i<=> TCIc''T
M +
" 2 '"'
~ ? S . : 3
H s -1 /i -
-•,-.«-
C' »<•
CA 'ri*
r 4 s i ,1
C i "> !. 4
•-A +
-.'»!>.
v A S ; ' ? -
JAS--.4-
ru.-
CL-
SO?--
504 —
o«o."v.£sr
X . A 3 0 - L H

.;. 572-11
». . yap-.1, fi
4.57<:-/9
C. "«!••-•• 3
5 . 3 9 2 - •"• 7
j . 4 1 f< - 1 3
1.44S-'M
s.ya-1-. ?
2.243- *?
n.53C)-"-«
«.ST5!--i
3.27o--'*
a .3?s--'?
4.253-'^
5.a5.".-f 3
H .1 1 A L T T V
t . t 22-Hrt

4 ,fi?7- \ 1
3 . T 1 1 - ' 5
3.5S3-"'.J
?.775-~J
t .9--1 -'V
l.5
3.32*'--*2
2 ,?7'i.p «
S.5.}4-,^
3 . Q M 3 - '•* ^
2 , H 1 4 - '/ r>
3 . .1 <* 4 - 1 2
1 .7 i 'S-^u
2 , 1 4 'v - 0 J
ACTIVITY o 3 ; j ,i -j r; )•
a
'>
1
7
7
4
7
1
!
q
1
7
7
7
7
4
?
^dliT
. 1 y t- - '
e o i) A - '
, ' 1 2 +•»'
, OhO. i
.<»><)- •
.IpP-'
. o 7 o - -
.'"!?*'
•"1?*r'
.^•^w
!"12 + -'
. y 7 1 -
.07Q-"
,079.-
, '-• 11 - '
."33- •••
.«/3-i
i °v c 3 A
1
i

t
1
I
i


1

s
1
1
I
1
1
1
                     CASM3C?)
                           (*)           fc.tvi'^                 5.945-J6            2.537--J

                         2 s  * . JP772-1 ;   ATM,



                                      IONIC 3TU-fGTn  *  5.77294-,'}?        P£S.  E.N.  *   -•
                                                        -162-

-------
        RUN KO.
        DATE
                 51
                2/17/76
                                     ANA! YTICAL  RESULTS
                                                                               0.01
 Snccics
 Ca
 MS
+ 2
+ 2
 Nat1
Cl
CO 3
Ts~
SO 3
so-.,
   -1
    -2
    -2
         Standards
         (mnioles/l)
                          Ca  Feed
                          (mmolo/1)
                            36.9

S03~2 Feed
(raiole/1)

                                          42.4
                                          20.8
                                          21.6
                                                          Effluent
                                                          (mmole/1)
                                                             9.02

                                                            JU.JL
                                                            10.5
                                                             1.84
                                                             8.7
 Solids
(mmolo/cO
   7.34
                                  6.70
                                   .69
                                        OPERATING DATA
 Time
(min)
  68
         pH
        8.70
                 Temp.
                    41

so3~2
(mmole/1)
1.84
Solids
Removal
(ml/min)
200

Solids
(wt%)
0.101

Solids
(g)
2.77

                                       COMPUTER RESULTS
 Ionic
Strength

 0.0673
                  Residual
                   -Q.QQ31
                                        Relative   Saturation
              Electroneutrality    CaSOr^hO


                                                              0.10
                                                                          Mole.   Fractii
                                                                           SO
                                                                                -2
                                             -163-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET

Flow Rate (ml/min)
Ca'1
Na2
ci-1
Is
   +2
SO 3
SO 4
   -2
   -2
        (mmole/min)
        (inmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
OUTLET
Flow Rate (ml/min)
  +2
Na2
Cl"1
Ts
SO 3
SOn
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE


     Solid

     S03~"
     so
        '2
Run /' si
A
100
Date 2/17/76
B
100
3.69 	
	 	
	 4.31
7.50 	
	 4.24
	 2.08
	 2.16
Liquid
200
1.80
Solid
0.202 (g/min)
1.48
	 	
4.10
8.20
2.10 	
0.368
1.74°
mmole/min
—
1.89
1.71
.42
1.77
0.14
mmole/g
7.34
6.70
.69
                                                                           200
                                                                           3.69
                                                                  4.31
                                                                  7.50
                                                                  4.24
                                                                  2.08
                                                                  2.16
                                                                           3.28
                                                                           4.10
                                                                           8.20

                                                                           2.14
                                                                           1.88
                                                                         grams/min
                                                                          0.202
                                                                           .257
                                                                           .255
                                                                           .61
                                        -164-

-------
                        SOLIDS MATERIAL BALANCE







                        Run *   SI       Date   2/177 76






                g/mmole           mmole/gram               g/gram






Ca+2             .040                 7.34                  0.294




Mg+2             .024
Na2+             .046
Cl"1             .035
C03              .060               	                	




S03~2            .080                 6.70                    .536




SOT2            .096                  .69                    .066




%HzO             .009                 7.39                    -067






                                                         7    .963
                                   -165-

-------
I? -AS?  7-     I7:n:*s.s*a
                    P M  a   9 . 7 , " t-
                                                KINETIC  RUN  51
                                                   SPFCItS
H20   a  5.
      s  9. ^2t"/"-: 3
                                                                HCL   a «.
                                                                CU2   a v> . <
                                                                      a  ,-.,. •:•
                                                                502   »  i ,s* ::
                                                                SC:3   s  u.7 "-•>'•
                                                                                                      . c,
                                                              r«''U
                   cc
                                       >.37:>-',-s
                                                                         4 C f t V
                                                                                         <• L T £ .. I
                                                                                     ,-f>l
«*[.
u 2 s n
Mj>n3-
•-.b'"4-
Ca +»
i" crr*
r r. <"• :*
C .» " -j &
~ u *
'• i\,"h
v ASu.S-
' .,S< 4-
On-
CL-
$ j3 —
sn/--

l
a
q
3
1
1
1
4
i
7
5
1
4
4
P

.5*0-12
.<*> j-v*
,4K 3-1"
.llT- '3
.32?-.'?
,J7h- T
,5??-/3
..14 !-2
.3^.4-.. 7
.34J-. ^
.74^-' -1
.567-:?
.llC»-- 2
. d"7-' 4
,«>Cl-t 3

J.
7.
7.
?.
1 .
\.
I.
?.
1 .
=>.
4.
I .
3.
' .
2.

f»h4.J2
•< t- 2 - •' i
•)S*-tv
Sijw-i' j
J-iS. -K
^--1- 'I
^ii'' - fj
?.'•*•-' '£
-1*>:-:'7
* ^ 4. 'fi
K^?-^4
5dQ-o-b
?4.1-".2
7 >.i /I . if 4
42";-''3
o.Qb4--
1 . >' 1 ? + '
7,t,o'3--.
7.079--^
4. t p-.p.r
7 . p 7 <; - •
1 . f" 1 2 1 '
t . v l 2 + 1
c.?vir.- •
!.'!?*'
7 ,U7Q.
7.^/0-
7.9/0..-
7.91?- '
" ,yij>*--
3.P/4-.
1

I
1
1
1

•
1

1
1
]
i
i
1
      IQMTC Sretv-GTM  s 5.732P3-..?
                                                                            ,  £ . r. .  =  -1 ..'53-'i,5
                                                   -166-

-------
        RUN NO.
        DATE
                   52
         2/17/76
                                                                       -T/T
                                                                   <0.01
                                     ANAIYTICAL  RESULTS
 Species
   + 2
Ca
Mg+2
Nat1
Cl"1
C0,~:
Ts
SOL
SOt,
    -2
    -2
 Standards
(mmoles/1)
                           Ca   Feed
                          (mpiolo/1)
                            .36.9
                             74.8
S03~2 Feed
(mnole/1)
                                             43.1
                                  42.4
                                  20.8
                                  21.6
                                                          Effluent
                                                          (mmolc/1)
                                                             9.01
                                                  21.4
                                                  40.6
                                                             9.5
                                                             1.59
                                                             7.9
 Solids
(inmole/cO
   7.51.
                                  6.22
                                   .37
                                        OPEMTING  DATA
 Time
(min)
   83
Solids
Temp. S03~2 Removal
pH (°C) (mmole/1) (ml/min)
8.11 49.1 • -. 1.59 200

Solids Solids
(wt%) (g)
0.097 2.67




                                       COMPUTER  RESULTS
  Ionic
 Strength
   0.0666
       Residual
   Electroneutrality
         0.0013
                                      5.37
                                                   Saturat ion
      CnS(V2H20
         0.25
                                                               0.11
                                                                      >0
                                                                  Mole   Fracti
    S03
   0.89
                                                                                -2
0.1]
                                             -167-

-------
                        REACTOR MATERIAL  BALANCE  CALCULATIONS
INLET

Flow Rate (ml/rain)
         (mmole/min)
         (mmole/min)
         (mmole/min)
         (mmole/min)
         (mmole/min)
         (mmole/min)
         (mmole/min)
Naif"'
ci-1
Ts
SO 3
so 4
-2
-2
OUTLET

Flow Rate (ml/min)
Na2
Cl'1
Ts _
SO 3
   + 2
    2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
PREC. RATE
     .—	, .—

     Solid

     S03~2
     en ~2
Run # 52
A
100
Date 2/12/76
B
100
3.69 	
	 	
	 4.31
7.48 	
	 4.24
	 2.08
	 2.16
Liquid
?on
1 .80
Solid
0.194 (g/min)
1.46
— — — — _____
4.28 	
8.12 	
1.90 	
.32
1.58
mmole/min
1.89
1.76
.58
1.28
.02
mmole/g
7.51
6.62
.37
                                                                           200
                                                                           3.69
                                                                           4.31
                                                                           7.48
                                                                           4.24
                                                                           2.08
                                                                           2.16
                                                                           3.26
                                                                           4.28
                                                                           8.12
                                                                           1.60
                                                                           1.60
                                                                         grams/min
                                                                           0.194
                                                                            .252
                                                                            .266
                                                                           1.57
                                         -168-

-------
                        SOLIDS MATERIAL BALANCE



                        Run //  52       Date  2/17/76



                g/mmole           mmole/gram               g/gram



Ca+2             .040                 7.51                  0.301
  +2
Mg               .024


Na2+             .046
Cl""1             .035
C03~2            .060
S03~2            .080                 6.62                   .530
SO.T2            .096                  .80                   .077
%H20             .009                 6.99                   .063
                                   -169-

-------
15 -4°  7t-     i7:11:«7 ,4is
                                                 KINETIC RUN 52
                                               INPUT species
                               CA",   = ti.i-!»?'.;--•>
                               ."G"   a f-.^.pv.'n
                               »-A?f!  3 2. 14i»fH'-{-
HCL   s 4 , j P .1 :u-
CD2   a KI.K.-'.V..
      e ^ .-• -«  tcv
                                                                            7.
                         a   f-.il-'.
                        -C "f-'M
                      « i r. t .
                      C * f •- *
                     CL-
                     303 —
                                         f ,
                                         b.b3?-. 3

                                               IT y
ACTIvjTir
7.7^--,
9 '.5 !<•-.••!>
l.S.i-5-','.}
3.4-- fl-rv
4]771--'f>
1.4. •.•"-» 4
4 C T i ',' i T f C ? >• P H
8.-?77-fi
7.5^7- • i
4.12s;- 1
'!*!?» •
7 '^7"'", '
/:«"i.'!
                                                                     fiPOPuCT
                                                                                             f'li, 4TTI'
                     CAS"3(S)
                     r A s p 4 (n j
     <:.?5-t-.                 i.ior'-t3

     »i. c «i-'                 5 .4 7 5 -'/' c

"'I-11   ATI-.



 IONIC  STKE^GTM s  6,66437-k'?.
                 ..17 4 t"/
                                                                             ff.S.  t.r .  s    t
                                                      -170-

-------
      1UJM  NO.
                   53
                  2/17/76
                                      /uNMYTICAL RESULTS
 Species
 Ca

 Mg
 Nat1
+ 2
 Cl
 Ts
 S03
   -i
 -2
    -2
         Standards
         CmmolfS/1)
Ca Feed
(mmolo/1)
36.9
S03 * Feed
(rmno] e/1)
Effluent Solids
(niniolc/1) (mmolc/cO
fi.92 . 7. AO
	
__«.
74.8
43
—
.1
—
21.3
39.6
	 	 	
	
	
	
42
20
21
.4
.8
.6
11.1
1.44 6.69
9.66 .84
 Time
(min)

  • 65
         pH

        8.30
                 Temp.
                                    -2
  S03"
(mmole/1)

   1.44
OPERATING DATA

     Solids
     Removal       Solids       Solids
     (ml/min)      (wt%)         (g)

       200          Q.125         3.44
                                       COMPUTER RESULTS
  Ionic
Strength

   0.0658
    Residual
ElectroneuLra]ity

      -0.0044
                                        Relative  Saturation
                                                                          Hole  Fracti
                                    4.33
                   0.23
                              CaSO.t-%!I20
                       0.13
                                                                          SOj
                                                                             -2
                                              -171-

-------
                        REACTOR MATERIAL  BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca+/i
Mg+2
Na2+2
ci-1
Ts
S03
   -2
   -2
     (mmole/min)
     (mmole/rain)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
OUTLET

Flow Rate (ml/min)
Ca+l
Na2+:
Cl"1
Ts
SO 3
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE
     •.'.. : rr—rvsr :,•:

     Solid

     S03~2
Run // 53
Date 2/17/76

TOO
100
3.69 	
	 	
	 4.31
7.48 	
	 4 . 24
2.08
2.16
Liquid_
?00
1 .38
" Solid
D.7SO (g/min)
1 .88
_— — — — — —
-4.28 	
7.92 	
2.22
0.29
1.93
mmole/min
: =
2.31
1.79
.23
1.88
1.67
0.21
mmole/g
7.40
6.69
.84
                                                                            200
                                                                            3.69
                                                                   4.31
                                                                   7.48
                                                                   4.24
                                                                   2.08
                                                                   2.16
                                                                            3.26
                                                                            4.28
                                                                            7.92
                                                                            4.10
                                                                            1.96
                                                                            2.14
                                                                         grams/min
                                                                            0.250
                                                                             .312
                                                                             .268
                                                                             .274
                                          -172-

-------
                        SOLIDS MATERIAL BALANCE




                        Run it   53       Date  2/17/76



                g/mmole           mmole/gram               g/gram


  +2
Ca               .040                 7.40                  0.297


Mg+2             .024
   +2
Na2              .046
Cl'1             .035
C03~2            .060
S03~2            .080                 6.69                    .535


S04~2            .096                  .84                    .081


%H2d             .009                 7.53                    .068



                                                         £ -.981
                                    -173-

-------
                                          KINETIC RUN 53
7"     17111 :4d.l,'i                                                TErP£PATuS£     f \.4Vf  I,PG. C
                                     INPUT sp?crts  (-OLESI
                            s  5.5?tc«?*v. I                 HCL   «  ,J.*hv.fltf~>?
                      CAO   i  i.&2?-,<.--K3                 CD2   «  *../.3 —
••v'LM
t.c'i--:

1.5?r
i.e-iv
«.o

:-ll
• - ;•• "5
,-, 3
)-'. ^
M (^
--•3
-' 3
-:;?
- '7
. • A
- • 4
-':5
-.1?
.1-4
--13
*CT1"IT' iCTlViTy Cr£P(-TCT'; r
5." 1 l-i" i >f.34!5- '1
Q. OH 4-^1
'..^•*«-ll I. "12*%
?.?!.5-/f) 7eQl,.,-.,
3,9" «-' y 7,Oi»-.> i
',7n.?-"J /I ,i»40.-' i
1 ."oS-MS 7.^1"- ' 1
r.-'SP-.'j i. -!?+••
t.5--)-'3 1. "!?+••
.'. 442-^2 «.!»,}"GTH  s  6.5a4«e-«;2        P£S.
                                                -174-

-------
         RUN NO.    56
         DATF,     2/24/76
                                                                               0,018
 Species
Ca

Mg
 Nat1
   + 2
 Cl
 CO-
 TS"
 so 3
 so!_
   -1
   -2
   -2
           Standards
           (mmoles/l)
                           Ca  Feed
                          (mmolo/1)
                             43.2
                            80.
                                      ANA!YTICAL RESULTS
S03~2 Feed
(mmole/1)
                                             42.3
                                             40.3
                                             22.3
                                             18.0
Effluent
(mmolc/1)
                                                              21.0
                                                              44.2
                                                              10.8
                                                               2.08
 Solids
 (mmolc/cO

 _____ 7 ..3.9
                                  6.72
                                                                            0.62
 Time
(min)
  55
           pH
          828
                    4.10
                                         OPERATING DATA

Temp.
C°0 .

S03~2
(ramole/1)
Solids
Removal
(ml/min)
                                   2.08
                                                200
                                                200
     200
                                        COMPUTER RESULTS
                                                            Solids
                                                            (wt%)
  0.115
                              Solids
                               (g)
3.16
 Ionic
Strength

   0.0774
                  Residual
                                         Relative  Saturation
              ElcctroneuLrality    CaS03-%H20    CnSOil'2H20   CaSO,t • %!

                   0.0054             7.94         _ 0-39          0.14
                                                                             Mole  Fracti
                                                                             0.91
                                              -175-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET

Flow Rate (ml/min)
Na2+2
ci-1
Ts
SO 3
SO 4
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate (ml/min)
Na2
Cl'1
Ts
SO 3
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE


     Solid

     S03~2
        -2
Run // 56 Date 2/24/76
A
inn
B
100
4.32 	
__ — — — —
	 4.28
8.00 	
4.03
	 2.23
	 1.80
Liquid
Solid
?nn 0.230 (g/min)
7.94
1.70
	
4.20 	
8.84
2.16
.416
1.76
mmole/min
1.36
1.81
0.04
1.69
1.55
0.14
mmole/g
7.39
6.72
.62
                                                                           200
                                                                           4.32
                                                                           4.28
                                                                           8.00
                                                                           4.03
                                                                           2.23
                                                                           1.80
                                                                            4.64
                                                                           -4 ..20
                                                                            8.84
                                                                            3.85
                                                                            1.97
                                                                            1.90
                                                                         grams/min
                                                                           0.230
                                                                            .184
                                                                            .270
                                                                            .065
                                         -176-

-------
                        SOLIDS MATERIAL BALANCE




                        Run #  56        Date  2/24/76




                g/mmole           mmole/gram               g/gram




Ca+2             .040                  7.39                  0.296


M+2             .024
   +2
Na2              .046
Cl"1             .035
                 .060               _                 __


S03~2    .        .080             "     6.72                    .538


SOr2            .096               _ -62                    .060


%H20             .009                  7.34                    -066




                                                             0.960
                                    -177-

-------
                                        KINETIC RUN 56
7-.     l 7: u :43.7«4                                                Tf hP£P»T.jB£     4i. v?/  ,;FG.  r,
                                      INPUT SPF.CILS  f-")LP5)
                            s  i, «7 ;•?/-'?
                      "GO   s  '., *c3.»
                      k t?(j  s  2. 1 -'• c^r-i"?                 ':2n;j  a .'./••"/••'i
                                                         SO 2   = 2. ".•.', ->
                                                         S03   s 1,-vv.v/-
             S U P E » 5 A T i > ? i T T f: N  a u L 0 J
4'.."fc"lUj SOL'jl
c...»vt-.r -cuairv
• * t .?.'-•- j 9
"Sr
r-2c,"'» /. 572-12
-ar,i- i ,81 7-; =>
»5^u- a.l^-kO
CA + + l.i:7--,P
C ''"•-+ >. ,5^-''7
CAS-J.^ I./)?-*''
C A«.'.4 i.??4-, *
• A -t- c , 1 .1 r> - ', 2
- i^n ? ,S^<--^
4.3. ?-"j
*.7o-3-.'7
I . 7j'3-.-o
3.??-S. M
3.3??- -2
5.3 JJ- 'i
4 . 3 w J - ' o
4.PJl-.'4
".On*-:-,
3 , "i o ^ - ''V
t , ,T^ ^ . " u
2.' 5--J
ACTIvTTr fiSi.ijjCT

crr,ITY
« ^
c, ,
' .
7.
7.
3.
7\
i .
' .
n .
t .
7.
7.
7.
7.
?.
'* •
9feu,ri

CCcPr
is#:. ,
i# e L< - ' 1
.-1 -i* •,
P/ a. • ]
H;,-- ']
0»n. -i
S,«.-.. {
'Ud*
-!
-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
CI-
TS
so 3
   1
   -2
   -2
OUTLET

Flow Rate (ml/min)
<;
Na2+:
Cl"1
Ts _.
SO 3
SOi
    2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
PREC. RATE


     Solid

     S03~2
Run // 59 Date 3/10/76
A
200
B
100
4.12 	

1.60
5.27

9.72
4.07
5.65
Liquid
300
2.38
Solid
0.0311 (g/min)
0.28
	 	
6.84
	
7.11
2.78
4.32
mmole/min
2.74
1.29
1.33
0.051
0.047
0.004
mmole/g
8.97
1.50
0.14
                                                                           300
                                                                           4.12
                                                                           6.87
                                                                           9.72
                                                                           4.07
                                                                           5.65
                                                                           2.66
                                                                           6.84
                                                                           7.16
                                                                           2.83'
                                                                           4.32'
                                                                        grams/min


                                                                          0.0311	
                                                                           .305	
                                                                           .86  	
                                                                          9.5
                                         -179-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    59

Date     3/10/76


                      g/mmole       mmole/gram       g/gram

          Ca++         °-040           8.97           0.359

                        .024          	         	

          Na"          -046          	         	

          Cl"           .035          	         	

          C07           -060           (7.33)*         (.440)*

          S07           .080           1.50             .120

          S07           .096             .14             .013

          %H20          .009           1.64             .015


                                                   Z    .947
*  Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                             -180-

-------
                   59
         JUJM NO.	

         DATE      3/10/76
                                      ANAIYTICAL  RESULTS
                                                                               .57
 Secies
             Standards
                           Ca   Feed
                           (mmolo/1)
                             SO3  2  Feed
                             (mmole/1)
                                                         Effluent
                                                         (mn'.olo/l)
                                                                           Solids
                             20.
                                                              7.92
                                                               8.Q7
t'
-1
 Na1
 Cl
 co-
 Ts"2
 SO.

 SO.,
    -2
    -2
                             8.0
                                97.2
                                40.7
                                56.5
                                                22.8
                                                               5.2
                                                              23.7
                                                               9.25
                                                              14.4
                                                                          1.45
                                                                          1.50
                                                                           .14
 Time
(rnin)
152
150
            pH
6.15
6.25
                    Temp.
50
52
54
                    S03  2
                  (mmole/1)

                    13.4
                                 13.8
                                  9.25
                             OPERATING DATA

                                   Solids
                                   Removal
                                   (ral/min)

                                     10
                                                10
                                                         Solids
                                              0.311
                                                                        Solids
                                                                         (g)
                                                                       10.11
 Ionic
Strength

  0.0584
    Residual
Elcctroneulrality

      0.0170
                                       COMPUTER  RESULTS
Relative Saturation
CaSO
7.
3-%H20 CnSOi/2H20 CaSO.,-%lI20
87 0.11 n.is
                                                                             Mole   Fraci
                                                                              SO
                                                                                 "2
                                           -181-

-------
                                    KINETIC RUN  59
43 WAY 7S
             16:
H20  •
CAH  •

M420 «
                       INPUT SPECIES  ClOLES)

                        11                WCL
                        13                C02
                                         1203
                        12                N205
                                         502
                                         S33
                                                                    TEMPERATURE
                                                                                   54.<)00  OEG.  C.
                                                                  i.20*00-03
                  H2C03
                  HC03-
                  H2S03
                  M503-
                  HS04-

                  CA» +
                  CAOH*
                  CAHC03*
                  CAC03
                  CAS03
                  CAHS03+
                  CASCM
                  MAOH
                  NAC03-
                  NAS03-
                  NAS04-
         5,690-97

         2,341-03
         2.69i)-e3
         3.58J-37
         5,8,198-H5
         a.9«2-a7
         1,795-03
         4,874-84
         1,949-03

         4,344-02
         I,156-09
         7,436-35
         1,159-06
         3,257-04
         1.1S7-33
EOUILI8RIA

   ACTIVITY

   5,623-07

   2,365-03
   2,157-03
   3,620-07
   4,662-03
   5,641-07

   1,530-33
   5,367-09
   7,377.35
   8,994-37
   1,814-33
   3,909-04
   1,969-03

   3,530-02
   1,168-09
   7.SH2-05
   9.297-07
   a.612-04
   9,359-04
                                                 ACTIVITY COEFFICIENT

                                                      8,4U5-01
                                                      9,988-01
                                                      1.010*00
                                                      8,017-01
                                                      1,010*08
                                                      8,017-01
                                                      8,019-01

                                                      4,254-81
                                                      8.019-01
                                                      8,019-01
                                                      1,010+00
                                                      i,aia*a(j
                                                      8,019-31
                                                      i,aia«aa

                                                      8,128-01
                                                      1.310+03
                                                      1,010*00
                                                      8,019-81
                                                      8,919-01
                                                      8,019-01
                  OH-
                  C03 —
                  S03--
                  SG4-.
        1,533-07
        6,474-07
        8.124-34
        1,126-32

        MOLALITY
CAfQH)2CS)        0.H00
CACn3(S)          0,000
CAS03CS)          8.000
CAS04(5)          41.30P

PC02 • 1.3SS72-01  ATM,
PS02 • 7.81601-M7  ATM,
                                    1,229-07
                                    2,875-07
                                    3,357-04
                                    4,276-33
                    8,019-01
                    4,132-81
                    4.132-01
                    3,789-01
                                                  ACTIVITY  PRODUCT   RELATIVE SATURATION
                                                      2,311-17
                                                      4,392-18
                                                      5,132-07
                                                      6,526*06
                                             7,627-12
                                             2,618-01
                                             7,865*00
                                             3.863-01
                                  MOLECULAR  KATER  •  9,99875-31  KGS,

                                IONIC  STRENGTH  « 5.S4B93-.I2        RES.  E.N.  «
                                                     1.999-02
                                             -182-

-------
        RUM  NO.

        DATE
                    60
                    3/11/76
                                     ANAJYTICAL RESULTS
                                                                        -i/ i
                                                                 0.07
            Standards
 Species   Cmmolps/l)
 Ca
  +2
              Ca  Feed
             (mmolo/1)
               22.8
                                          S03~2 Feed
                                          (mmole/1)
                                                           Effluent
                                                           (mir.olc/1)

                                                              4.^4
                                                                 Solids
                                                                (mmolc/o)

                                                                  7.S4
Nat1
 Cl
 co.
 Ts~
 SO 3
  '1
    "2
   ~2
                                             72.9
                                             82.8
                                             49.3
                                             33.6
                                               38.7
                                                             10.8
                                               33.3
                                               18.9
                                               14.4
                                                                           6.00
                                                                           5.58
                                                                           0.52
                                        OPERATING DATA
 Time
(min)

30
 PH

 5.62

J±~1J>


 5.66
 5.70
Temp.
C°0
 53
                     54.2
                     55
                                 S03~2
                               (iranole/1)
"Solids
 Removal
 (ml/min)

   36

   A8

   32

   31

   32
                                              Solids
                                              1L_LHS2-

                                                .1877
                                                                        Solids
                                                                         (g)
                                                                         6.12
                                                                         6.10
                                                           fi.in
                                       COMPUTER RESULTS
 Ionic
Strength
    Residuol
                                        Relative  Saturation
ElectroneuLrality    CaS03-%H20    CnS(V2H20   CaSO.,-^
                                                                Hole  Fracti
                                                                             SO
                                                                   -2
   . 0771 .

                                                                 0.07
                                            -183-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET

Flow Rate (ml/min)
Ca
  +2
Naa
ci-1
Ts
   + 2
S03
   -2
     (mmole/min)
     (mmole/rain)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
OUTLET
Flow Rate (ml/min)
N32
cr1
Ts
SO 3
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE
     Solid
     SO
     SO
        -2
       '-2
Run // 60 Date 3/11/76
A
0.100
B
0.100
2.28

0.50
7.29

8.28
4.93
3.36
Liquid
0.200
0.85
Solid
0.195 (g/min)
1.47

7.74

6.66
3.78
2.88
mmole/min
1.43
1.15
0.48
1.19
1.09
0.10
mmole/g
7.54
5.58
0.52
                                                                           0.200
                                                                           2.28
                                                                           7.79
                                                                           8.28
                                                                           4.93
                                                                           3.36
                                                                           2.32
                                                                           7.74
                                                                           7.85
                                                                           4.87
                                                                           2.98
                                                                        grams/min
                                                                        0.195
                                                                        0.190
                                                                         .206
                                                                         .92
                                         -184-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    60

Date    3/11/76
                      g/mmole       tnmole/gram       g/gram

                       0.040            7.54            0.302

          Mg'1          .024          	         	

          Nat*          -046          	         	

          Cl"           .035          	         	

          COT           -060           (1.44)*          (.086)'

          SOl           .080            5.58    -        .446

          SO;           .096             -52             .050

          %H20          .009            6.10             -055


                                                    Z    .939
   Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                              -185-

-------
                                    KINETIC  RUN  60
03
       76
             16:12102,312
                           M20
                           CAQ
                           *GQ
                           NA20
      INPUT SPECIES (MOL£S)

     >««ii                HCL
       (3                C02
                        N203
       12                N205
                        S02
                        S03
                                                                    TEHPEP. ATUP.E
                              1 ,M830 0-32
                                                                  1 .89003-02
                                                                  1.44033-02
                                                                                          OEG.  c.
                   M20
                   M2CU3
                   HC03-
                   H2SQ3
                   MSOJI-
                   HS04-

                   CA + +
                   C*SQ3
                   C»«SO
                   C»S04

                   NA*
                   NAOH
                   VAC03-
                   NAS03-
                   NAS04-
AUUEDUS SOLUTION

 MOL»LITY


 7,986-03
1,641-^2
2,421-36

1.931-H3
l,en-t)9
4,4*9-03
1 ,208-37
S,S?,&-34
6,899-84
8,947-<)4
 ,-f
5,812-13
1.235-34
5,514-37
4,351-^4
1,366-^3
                                                       ACTIVITY

                                                       1.9Y5-06
                    2,375-03
                    3,590-CS
                    1.285-^2
                    1, 9(13-86

                    7,345-34
                    7,935-lB
                    3.52J-35
                    1,224-37
                    8,901-04
                    5.437-W4
                    9,369-94

                    5,976-«12
                    5,991-13
                    1.222-34
                    4,327-37
                    3,414>34
                    1 ,464.03
                                                                   ACTIVITY
                                     8,318-^1
                                     9.980-31
                                     1 ,014*00
                                     7,830-01
7,833-01
7, 847-31

3.98S-31
7,847-01
7,847-01
 ,
1,014*00
7,347-31
1,014+00

7,967-31
1,014+08
1,314+03
7,847-31
7,847-01
7,847-01
                   OH-
                   C03--
                   S03—
                   S04 —

                  COMPONENT

                   CAtOH)2(S)
                   CACQ3CS)
                   C»S03CS)
4,663-08
1,944-37
6.816-04
1,If 4-32
0,303
                        »  4.8534S-31   ATM,
                   PS02  •  7.7S421-38   *TM.
                    3.663-03
                    7,386-08
                    2,502-04
                    3,932-03
7,847-01
3,759-01
3,759-31
3,377-31
               ACTIVITY PRODUCT  RELATIVE SATURATION
                    1,012-18
                    5,512-11
                    l,931-»7
                    2,955-06
3,419-13
3,655-02
2,979+00
1,399-31
                                   HQLECUL**  *ATER  «  9,99877.01  KGS,

                                 IONIC  STRENGTH  • 7,70614-02        R£S,  E,N,
                                             3,358-02
                                           -186-

-------
         KUN  NO.     61

         DATF-     3/19/76
                                                                         • JL. / I
                                                                     13:
                                      ANAIYTICAL RESULTS
 Species
Ca  i

Mg+2
Nat1
Ci

CO 3

Ts~

S03

SO;,
   -i
    -2
    -2
 Standards
(mmoles/1)
                           Ca+ Feed
                          (mmolo./l)
                             10.8
                             1Q.8
                                          SO3  2  Feed
                                          (mmole/1)
                                              150
                                              27.4
                                               9.4
                                             180.
Effluent
(mtr.olc/1)
                                                  35.2
                                                  Q.4
                                                 44.2

                                                 20.5
                                                 23.7
 Solids
(mmole/cO

  8.61
                                                                            5.1
                                                                            0.40
                                        OPERATING DATA

Time
(min)
50
120
165
280


pH
5.86
6.00
6.10
6.23

Temp.
(°C) .
55.9
58.2
55.8
56.2

S03~2
(mmole/1)
22.6
21.9
22.1
20.5
Solids
Removal
(ml/min)
35
20
20
20

Solids
(vt%)
0.48
.34
.33
.27

Solids
(g)
15.5
11.1
10.8
8.9

                                       COMPUTER RESULTS
 Ionic
Strength
                 Residual
             Electroneutra]ity
                                        Relative  Saturation
                                     CaSOi/2H20   CaSOi,-%Ii20
                                                                  Mole  Fracti
                                                                             SO
                                                                     -2
   0.09
        0.005
                                     2.19
                                                  0.152
     Q.076
                                                                                      .n.n
                                             -187-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET

Flow Rate  (ml/min)
Ca+2
Mg«;
Na2+
ci-1
C03~2
S03~2
OUTLET
      (mmole/min)
      (mmole/min)
      (mmole/min)
      (mmole/min)
      (mmole/min)
      (mmole/min)
      (mmole/min)
Flow Rate (ml/min)
Na_2
Cl
C03
S03
so
 -2
 -2
'-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC ._RATE

     Solid

     S03~2
Run # 61 Date 3/19/76
A
150
B
50
1.62

7.50
*
1.62
4.445
9.26
Liquid
?nn
n.sa
Solid
D.DS4 (g/min)
0.47

7.05

1.88
4.1
4.74
mmole/min
0.94
0.345
4.52
0.17
0.28
0.02
mmole/g
8.61
4.91
0.44
                                                                           200
                                                                          1.62
                                                                           7.5
                                                                          1.62
                                                                          4.445
                                                                          9.26
                                                                          1.15
                                                                           7.05
                                                                           2.05
                                                                           4.38
                                                                           4.76
                                                                           0.054
                                                                           0.109
                                                                            .070
                                                                         10.3
                                          -188-

-------
                    SOLIDS MATERIAL BALANCE

Run No.      61

Date    3/19/76
                      g/mmole       mmole/gram       g/gram

                       0.040           8.61           0.344

                        .024          	         	

                        .046          	         	

          Cl"           .035          	         	

          COT           .060          (2.59)*        (0.155)*

          SOl           .080           5.50            .440

          SO;           .096             -52            -050

          %H20          .009           6.02            -054


                                                   Z  1.043
   Excess calcium ([Ca]  - [Ts]) is assumed to be calcium
   carbonate.
                              -189-

-------
                                      KINETIC RUN  61
33 HAY 78
             16:12:0-1.422
                                         INPUT  SPECIES
                           H20   •  5.53PS2+U1
                           CAO   »  3,4C"«)C<,)-H3
                           MGO   «
                   PH  •
                        HCL
                        C02
                        N203
                        N205
                        308
                        303
                                                                    TEMPERATURE
                                                                                   55.8»a  DEC.  c.
            ,
           9,4000(5-03
           B,000041
           0,30008
           2,05008-02
           2.3730B-<)2
                   SUPE'SATUHATIQN
                   H*
                   H20
                   M2C03
                   HC03-
                   H2S03
                   HS03-
                   HS04-

                   CA + +
                   CAQM*
                   CAHC03+
                   CAC03
                   CAS03
                   CAMSQ3+ .
                   CAS04

                   NA +
                   NAOH
                  NAC03-
                  MAS03-
                  NA3Q4-
                                   AWUEOUS  SOLUTION  EQUILIBRIA

                                    MOLALITY            ACTIVITY
6.94S-03
2.338-03
3,934-06
1,827-02
4,235-06

1,389-33
7,237-10
2.S80-B5
7,167-09
3,216-04
5,253-04
9,784-04

6.720-92
5,372-10
9,264-05
4,348-07
4.275-04
2,897-33
1,993-flS

7,056-33
1 ,3i)5-«3
3,997-id6
1,410-02
3,127.06

5,389-34
5,624-10
2,077-115
7,280-08
5,096.04
4.071.H4
9,940-04

3,293«02
5,458-10
9,411-03
3,3751-07
3,313-04
                               ACTIVITY COEFFICIENT

                                     8,276-01
                                     9,980-01
                                     1,016+00
                                     7,720-01
                                     i,?i6»ae
                                     7,720-01
                                     7,750-01

                                     3,717-01
                                     7,750-01
                                     7,750-01
                                     1,»16*99
                                     1,016+00
                                     7,750-01
                                     1,016+00
                                     7,878-01
                                     1,016+00
                                     1.21S+00
                                     7,750-01
                                     7,730-31
                                     7,750-01
                  OH-
                  C03—
                  303--
                  S04 —

                 COMPONENT
                  CAC03CSJ
                  CASD3C3]
                  CASC4CS)
                  PC02
                  PS02
1.799-07
7,826-04
2.003.02

MOLALITY
0,000
                       • 3,86985-36
  ATH.
  ATM,
                   3,831.08
                   6,391-38
                   2,781-04
                   6,310-03
                  7.750.31
                  3,553-01
                  3,553-01
                  3,150-01
                                                  ACTIVITY PRODUCT  RELATIVE SATURATION
                   7,468-19
                   3.252-11
                   1.414-M7
                   3,198-06
                  2,569-13
                  2,218-02
                  2,193+00
                  1.52S-01
                                  MOLECULAR HATER • 9,99fi83-0l KG3,

                                IONIC STRENGTH • 9,(»1060-02       RE3, E.N. «   S,139-93
                                               -190-

-------
         UUM NO.

         DATE
                     62
         3/25/76
                                       ANAJ YTICAL RESULTS
                                                                         -T/T
                                                                        0.19
  Species
Ca ^
Mg+2
Nat1
Cl

CO 3

Ts~

SO.

SOt,
    -i
     -2
    -2
  Standards
 (mmoles/1)
                           Ca  Feed
                          (mmolo./l)
                             25
                                          S03~2 Feed
                                          (mmole/1)
                                               286
                                              470
                                              182
                                              288
           Effluent
           (mmole/1)

              10.78
                                                   64.
                                                   36.4
                                                   52.8
             Solids
            (mmolc/tO

               8.94
                                                                            5.74

                                                                             .89
 Time
(min)

 60
120
         Temp,
 pH

5.69
5.69
                    54.8
                                         OPERATING DATA

S03~2
(itrmole/1)
Solids
Removal
(ml/min)

Solids
(wt%)

Solids
(g)
                                32.8
                                                25
55
0.44
 .40
JL4.2

 13.1
                                        COMPUTER RESULTS
  Ionic
 Strength
       Residual
                                         Relative  Saturation
   ElectroneuLral ity    CaS03-%H20    CnS04'2ll20   CaSOt,
                                                                             Mole  Fracti
                                                                             SO-T2    SOt.
   0.160
         0.020
                                     7.46
                                                  0.49
               0.24
                                              -191-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET
Flow Rate (ml/min)
Ca+2
Mg+2
Na2+2
ci-1
C03~2
S03~2
SO.T2
OUTLET
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
Flow Rate (ml/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
Cl
Ts
S03
-2
-2
PREC. RATE
     ——	   —

     Solid

     S03~~
     so
        '2
Run // 62
A
200
Date 3/25/76
B
50.8
4.94



4.94
9.24
14.63
Liquid
250.8
2.704
Solid
0.222 (g/min)
1.985




8.7?
13,24
mmole/min
- =
0.25
-0.12
1.16
1 .14
0.231
mmole/g
8.94
5.12
1.04
                                                                           250.8
                                                                           4.94
                                                                           4.94
                                                                           9.24
                                                                          14.63
                                                                           4.69
                                                                           Q.36
                                                                          13.47
                                                                           0.222
                                                                           0.028
                                                                           0.023
                                                                           1.11
                                         -192-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    62

Date    3/25/76
                      g/mmole       mmole/gram       g/gram

                       0.040           8.94           0.358

                        .024          	         	

          Na            .046          	         	

          Cl"           .035          	         	

          COl           -060          (2.81)*         (.169)*

          SOT           .080           5.24            .419
          SOI           .096            .89            .085
          %H20          .009           6.13            .055
                                                   S  1.086
*  Excess calcium ([Ca]  - [Ts]) is assumed to be calcium
   carbonate.
                              -193-

-------
14
       76
             15:47139.92i>
                           H20  «
                           CAO  •
                           "GO  «
                   PH »  S.SiCl*
                                     KINETIC RUN  62
                                         INPUT SPECIfcS
                          C02
                          N203
                          N215
                          302
                          303
                                                                    TEMPERATURE
                                                   34.6(13  OEG.  C.
                                           SOLUTION
                   M20
                   H2CC3
                   HC03-
                   H2S03
                   HS03-
                   HSH4-
                   CAC03
                   CAS03
                   CAS04

                   SA*
                   N»OH
                   HAMC03
                   NAC03-
                   XAS03-
                   NAS04-
   1.445-H2
   5,392-33
   5,429-«)«

   4,047-83
   1,696-09
   1.417-«4
   3.4S2-37
   1.678-«3
   l,844-«3
   8,326-l!1
   3,25l-?4
   1.548-a«
   1,349-^3
   S, 298-03
ACTIVITY

2.M42-!1!)

1,44«-P2
3,727-^3
5,5b9-S")
I.9ft9-i!2
4.3JS-HS

l,259-«3
1,26^-19
1,?33-C4
3.561-W7
t ,72^-f3
1.37t-"3
3.163-C3

9.1HS-SI2
S.5S3-IC1
3,344-04'
i,i3t-ca
7,7S4-a4
4,S32-i?3
                                                                   ACTIVITY COEFFICIENT

                                                                         », 213-^1
                                                                         3,112-"!
                                                                         7,434-ai
                                                                         1 ,««»&*
                                                                         7,434-5(1
                                        7. 353-31
7,434-31
7,434-tU
7,434-31
                   OM-
                   CQ3—
                   SQ3--
                   304 —
                   CA(nH)2t3)
                   CAC03CS)
                   CAS03CS)
                   CAS04C3)
    ,-
   4,453--)7
   1.343-M3
   3,443-02

   MOLALITY
   H ,M»IH
   8,51055
                   PC12  •  8,94793-111   ATI,
                        >  1,19933-35   ATM,
3,494-83
1,279-37
3,8SS-ei4
7.434-ai
2.S72-H1
2,872-511
2,433-?!
                                                   ACTIVITY PSUOUCT  9ELATIVE SATURATION
1,537-18
1,6151-1(9
4,847-C7
3.145-13
I ,S<52-t)l
7,459+3H
  10LECULAR WATEP « 9,99431-"! 
-------
        RUM  NO.     63
        DATE    3/29/76
                                                                       -T/T
                                                                                 0.37
Species
  + 2
Ca
Nat1
Cl
CO-
TS"
so 3
SO*
  -1
   -2
   -2
            Standards
           (mmolps/1)
 Ca+ Feed
(mmolo/1)
                            25
                           _25_
                                     ANAIYTICAL  RESULTS
  SO3  2  Feed
  (mmole/1)
                                             410
                                             394
                                             110
                                             300
Effluent
(mr.olo/1)
 14.9
                                 55.
                                   19.4
                                   61.2
  Solids
 (mmole/o)
                                   2.04
                                    .53
 Time
(min)
 33
 60
130
           pH
          5.71
          5.70
          5.68
                    Temp.
                    (°0
                    55
                    54.2
                    55.
                                    -2
       S03
     (tnmole/1)
       17.99
       18.46
       19.35
OPERATING DATA
     Solids
     Removal
     (ml/tnin)
       25	
       25
       25
 Solids
 (wt%)
   0.0409
    .050
    .050
Solids
 (g)
1 .33
1.62
1.62
                                       COMPUTER RESULTS
 Ionic
                 Residual
                                        Relative  Saturation
Strength     Elcctroneutrality     CaS03'%H20

 0.175              -0.0104           6.10
                                                   0.93
                                   CaSO.,-^n20

                                      0.47
                                                                             Mole   Fracti
                                                                             SO
                                                                                -2
                                             -195-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
                        Run  #   63
                                                 Date  3/29/76
INLET

Flow Rate  (ml/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
Na2
ci-1
CO
SO.*
   -2
  !
   -2

   -2
                                         200
                                         6.10
                                         6.10
                                            50
                                                     10.3
                                                      4.79
                                                     14.96
                       250
                                                                            6.10
                      10.3
                       6.1
                       4.79
                      14.96
OUTLET

Flow Rate (ml/min)
Na2
Cl"
C03
so3
   ~2
   ~2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(nnnole/min)
(mmole/min)
                                        Liquid
                                         250
                                         3.73
                                        13.75
                                         4.85
                                        15.3
                                           Solid

                                            0.0125  (g/min)
0.025
0.007
                                                                            3.73
                      13.8
 4.88
15.31
PREC. RATE
                                        mmole/min  rnmole/s
                                                                 grams/min
     Solid
      S03
      SO.,
        "2
                                          -196-

-------
                    SOLIDS MATERIAL BALANCE



Run No.    63



Date    3/29/76

Ca^
I/' ++
Mg
Nat4"
Cl"
coT
sol
« —
%H20
g/mmole
0.040
.024
.046
.035
.060
.080
.096
.009
                                    mmole/gram       g/gram
                                      2. 04            0.163



                                      0.53              .051



                                      2.57              .023
                              -197-

-------
14  AP
-------
                                      KINETIC RUN  63-B
93
       76
             is:12:14.394
M20
CAO
                                         INPUT  SPECIES  (HOLES)
                                  5.55W62«B1
                                  1 .
       HCL
       C02
       N203
       N205
       302
       S03
                                                                   TEMPERATURE
                                       a.00000
                                                        5s.0ea OES.  c.
                   PH  «
                  COMPONENT
                   H20
                   H2SQ3
                   HS03-
                   HS04-
                   CAOM*
                   CAS03
                   CAS04
                   MQOH*
                   MGS03
                   MGHS03*
                   HGS04

                   NA +
                   NAOH
                   NAS03-
ALLOWED

AQUEOUS SOLUTION

 MOLALITY

 1.231-06

 3.062-06
 2,o6t)-02
 1.374-05

 4,013-03
 1.142-09

 9,491-04
 6,786-03

 2.804-01
* 2,061-06
 3,007-02
 3.326-02
 4,387-01

 4,816-01
 2,498-09
 2.490-03
 6,423-02
                            ACTIVITY

                            1.995-06

                            4,252-06
                            1,522-02
                            1,353-05

                            l.iai-03
                            1,124-08
                            1,192-03
                            9,342-04
                            9.424-C3

                            1.029-01
                            2.029-06
                            4,176-02
                            3,274-02
                            8,393-31

                            3,823-01
                            3,469-09
                            2,452-03
                            6,323-02
                                                                  ACTIVITY COEFFICIENT
                     9,892-SU
                     1,389*00
                     5,723-01
                     9,844-Ctl

                     2,743-81
                     9,844-fU
                     l,389*t)0
                     9,844-01
                     1 ,389*110

                     3,669-fll
                     9,844-1*1
                     1,389*140
                     9,844-nt
                     1.389*190
                      7,524-01
                      1,389*^0
                      9,844-91
                      9,844-^1
                   OH-
                   3Q3--
                   SQ4--

                  C01PQNENT
                   CAS031SD
                   CAS04(S)
                   NG(OM)2CS)
                   HGSU3CS)
         3,614-28
         2.829-03
         4.988-01

         "OLALITY

         0.000
         a.e»«»i
         a.pag
         0,000
    3,557-08
    3,034-94
    2,800-02
                                      9,844-dl
                                      1,073-Ul
                                      5.614-512
ACTIVITY  PPOOUCT   RELATIVE  SATURATION
    1.393-18
    3,2d8-C7
    2,896-05
    1.302-16
    2,842-05
                                      4,704-13
                                      5.073+0B
                                      1,372*00
                                      1.456-05
                                      6,490-01
                   PS02 • 9,49244-06  ATM,

                                   MOLECULAR HATER • 9.99452-01  KGS,

                                 IONIC STRENGTH i 1,87660*00       RES,  E,N,  «  -1,205-08
                                              -199-

-------
         HUN  NO.
         DATE
                   64
                  4/02/76
                                                                               0.131
                                      ANAIYTICAL  RHSUI/TS
             Standards
 Species
Ca
 Mg+2
 Nat1
 Cl
 CO;
 Ts"
 SO
 SO.,
   -1
   -2
   -2
                           Ca   Feed
                          (mmolc/1)
                             32.4
                           414
                           828
                            32.4
                             SO3  2  Feed
                             (mmole/1)
                                1400
                                 700
                                 567
                                 108
                                 459
                   Effluent
                   (nimolc/1)
                     13.8
                    710
                    784
                      5.2
                    329
                     38.7
                    290.
                                                                           Solids
                                                                             8.86
                                                              (6.97)
             1.79
             0.10
 Time
(min)
           pH
           5.84
          _5_.90
           5.93
Temp.


 53.2
 53.
                                     ~2
                    S03
                  (romole/1)
                    37.1
                                  38.0
                                  38.7
OPERATING DATA
     Solids
    o Removal.
     (ml/min)
        .2.5
                                    30
                                                           Solids
                      .296
         Solids
          (g)
           11 .Q
            9.62
                                        COMPUTER RESULTS
 Ionic
Strength
    Residual
ElectroneuLrality
                                         Relative  Saturation
                                                                            Mole  Fraction
                                                                             SOj
                                                                                -2
 1.523
                   0.025
                        10.1
           D.84R
0.41
                                              -200-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca
  +2
  -1
Naa
CI
C03~2
so3~2
so.r2
OUTLET
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(ramole/min)
(mmole/min)
(mmole/min)
Flow Rate (ml/min)
Naa '
Cl"1
S03
SO 4
   -2
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE


     Solid

     S03"2
        -2
Run # 64 Date 4/02/76

192.3
101
6.23

79-6
159.
142
70.7
6.23
10.91
46.36
Liquid
293.3
4.05
Solid
0.089 (g/min)
0.788

208.2
230.
1.53
11.35
84.76
mmole/min
1.39
0.54
-38.4
0.677
0.10
0.01
nrmole/g
8.86
1.13
.116
                                                                          293.3
                                                                            6.23
                                                                           222.
                                                                           230.
                                                                             6.23
                                                                            10.91
                                                                            46.36
                                                                           4.84
                                                                         208.
                                                                         230.
                                                                           2.21
                                                                          11.45
                                                                          85.77
                                                                           0.089
                                                                           0.157
                                                                           0.478
                                                                         -331.0
                                         -201-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    64

Date    4/02/76
                      g/mmole       mmole/gram       g/gram

                       0.040            8.86           0.354

                        .024          	         	

                        .046          	         	

          Cl"           .035          	         	

          GOT           .060           (6.97)*          (.418.)*

          SOl           .080            1.79             .143

          S(5r           .096             .10             .010

          %H20          .009            1.89             .017


                                                    E    -942
*  Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                              -202-

-------
                                     KINETIC  RUN  64
33 HAY 76
             16112100,
-------
        RUN N0._

        DATE
               65
              4/05/75
                                                                        -T/T
                                                     JL03.
                                      ANA1.YTICAL RCSULTS
 Species
   -t-2
 Ca
 Nat1
 Cl

 CO;

 Ts"

 SO 3

 SO:,
   - 1
-2
-2
        Standards
       (mmoles/l)
 Ca  Feed
(mmolo./l)

   30
                        J1CL
                               S03~2 Feed
                               (mmole/1)
                                          1130

                                          .500
                     160
                     500
                    1750
                                       Effluent
                                       (mmole/1)

                                         7.75
                                       574.

                                       155.
                                                  4.7
                                                855.
                                                155.
                                                700.
              Solids
              (mmolc/cO

                9.88
                                                        1.17
                                                        0.05
• Time
(min)

   46
  160
 pH

 5.8
_5._8
 5.8
Temp.



 55
 55
                                     "2
                              S03
                            (mmole/1)
              OPERATING DATA

                   Solids
                   Removal
                   (ml/rain)

                       50
                              155
                                                 80
                       80
Solids
(wt%)
Solids
 (g)

 18.2
 16.5
                                        COMPUTER RESULTS
  Ionic
 Strength

   1.40
              Residual
          Electroneulrality

                -0.144
                                         Relative  Saturation
                CaS03-%H20

                  6.03
                                         0.64
                                    CaSO,, -

                                      0.32
                                                                          Hole  Fraction
                  SO

                  0.95
                                                       -2
               SOu  "

               0.05
                                               -204-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca
  +2
Mg
Na2
Cl
C03
S03
SO 4
  +2
   +2
  -'
   -2

   -2
   -2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
OUTLET
Flow Rate (ml/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
CO 3
S03
S0i»
   _2

   -2
    2
PREC.  RATE

     Solid

     S03~2
Run f? 65 ' Date 4/05/76
A
200
B
100
5.98
167
35.8

5.98
50.0
174.0
Liquid
300
2.32
Solid
0.406 (g/min)
4.01
172
46.5

1.41
46.5
210.
mmole/min
6.64
3.5
-36.
3.52
0.48
0.02
mmole/g^
9.88
1.17
0.05
                                                                           300
                                                                           5.98
                                                                         167.
                                                                          35.8

                                                                           5.98
                                                                          50.0
                                                                         174.
                                                                           6.33
                                                                         172.
                                                                          46.5

                                                                           4.93
                                                                          47.0
                                                                         210.
                                                                           0.406
                                                                            .672
                                                                           3.0
                                                                         - 0.720
                                          -205-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    65

Date    4/05/76
                      g/mmole       mmole/gram       g/gram

                       0.040            9.88           0.395

                        .024          	         	

                        .046          	         	

          Cl~           .035          	         	

          GOT           -060           (8.66)*         (.520)"

          SOT           .080            1.17             .094

          SOT           .096             .050            .005

          %H20       .   .009            1.22             .011


                                                   z  1.025
*  Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                              -206-

-------
                                   KINETIC  RUN  65
33 *AY 7»
             16!12:fl7.!52S
                           H20  •  5.:
                           CAO  »  7,7535*3-^3

                           NA20  •  l,55Z33-
-------
        RUN NO.   66

        DATE      A / n ^ / 7 e,
                                                                       -T/T
                                                                                ,08
 Species
Ca

Mg
Nat1
   +2
Cl

CO 3

Ts~

SO 3

SO.,
   -i
           Standards
           (mmolPS/1)
             Ca  Feed
            (mmolo./l)

               30
                                     ANALYTICAL RESULTS
                                          S03 2 Feed
                                          (raraole/1)
                             30
                                              113Q_
                                              . 500
                                               160

                                               500
                                              1310
           Effluent
           (mmolc/1)

              7.00
            516.
            156.
                                                             3.5
                                                           795-
                                                           647
                                                                          Solids
                                                                          (mmole/
-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
                        Run  #   66
                                                Date   4/05/76
INLET

Flow Rate  (ml/min)
Ca"*
Mg
Naz
CI
CO 3
S03
  .+2
   +2
  -1
   -2
   -z
   -2
(nunole/min)
(mmole/min)
(mmole/min)
(tmnole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate  (ml/min)
Ca
Mg'
  +2
  '+2
N32
Cl"

CO 3
   + 2
   -2
SO 3
SO I,
   -2
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
PREC. RATE

     Solid

     S03"2
200
B
100
5.98
128
32.3

5.98
40.0
120.0
Liquid
300
2.10
Solid
0.397 (g/min)
3.55
155.
46.8

1.05
44.4
194.
mmole/min
3.88
4.4
74.
3.15
0.38
0.02
mmole/g
8.94
0.95
0.05
                                                                            300
    5.98
  128.
   32.3

    5.98
   40. Q
  120.0
  5.65
155.
 46.8

  4.20
445.
194.
                                                                          grams/min
                                                                           0.397
                                                                           0.434
                                                                          -4.63
                                                                       -1480.
                                          -209-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    66

Date    4/05/76
                      g/mmole       mmole/gram       g/gram

                       0.040            8.94          Q.358

                        .024          	         	

                        .046          	         	

          Cl"           .035          	         	

          COT           .060           (7.94)*        (0.476)*

          S07           .080            0.95             .076

          SOT           .096            0.05             .005

          %H20          .009            1.00             .009


                                                   Z  0.924
*  Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                             -210-

-------
                                      KINETIC  RUN  66
33 WAY 76
             181121919.198
                           N20
                           CAO
                           NA20
               INPUT  SPECIES  (HOLES)

                n                HCL
                13                C02
                                                           N20S
                                                           5G2
                                                           SOJ
                                                                    TSMPESATUP.E
                                        J ,
                                                                                   58,,ia0  OEG,  C.
                   SUPEH3A1IHATION
                   H2C03
                   HCQi-
                   H2S03
                   HSOJ-
                   HS04-

                   CA + *
                   CAOH*
                   CAHCOJ
                   CACQ3
                   C»S03
                   CAHS03
                   CAS04

                   MG»»
                   HGQM*
                   MGC03
                   MGS03
                   MGHS03*
                   MG504
                                   AQUEOUS  SOLUTION  EOUtLIHT*

                                                       ACTIVITY
1,288-36

1,929-33
7,581-24
5.128-S6
2,595-((2
3,626-66

4,699-194
9,339-10
8,17H-a6
4,537-08
1.3B4-03
7,526-«l4
3.734-a3

5,634-32
2,125-86
4,552-34
8,762-36
8,356-5)2
3,293-32
3,345-31
                                                                   ACTIVITY
          1.531-133
          1,285-83
          4,»tri-ns
          4.548-02
          1,884-05

          1,998-33
          1.073-89
          9,7aa-«iS
          3. 602-08
          1,099-83
          2.52J-V16
          5.524-34
          6.957-3S
          5,047-aa
          3, 913-32
          2,417-ai
9,887-31
1.259*3e
5.899-31
1,259+38
5,899-31
8.423-31

2,351-31
8.423-31
8,423-31
1. 259+08
1.269+M8
8,423-31
1,259*33

3,853-91
8,423-»l
8.423-31
1 ,259 + a«)
1.259+30
8,423-81
1,259+30
                   NA +
                   MAOH
                   NAHC03
                   MAC03-
                   NAS03-
                   NAS04-

                   OH-
                   C03--
                   SOJ--
                   S04--
                   CA(OH)2(3)
                   CAC03CS)
                   CASQ3CS)
                   CASC4f5)
                   MGSQ3(S)
          2,713-Bl
          2,749-»)9
          1.159-04
          9,886-^7
          4.283-B3
          3. 633-32

          7.817-«8
                                    3.659-01

                                    MOUALITY
                   PCQ2
                   PSH2
1,25517-01
1.2.14J3-&15
                                      ATM,
1. 954-31
3,462-39
1 ,459-34
8.327-37
s.eBS-fs
3.U7-82

6.584-CJ3
4,218-38
7.99C-34
2.513-B2
1,2S9+ae
1.259+30
8.423-31
8,423-31
8.423-31

8,423-ai
1.211-31
1,211-31
8,868-32
                                                   ACTIVITY  PRODUCT   RELATIVE  SATURATION
                             2,5137.18
                             1,982-1 1
                             3,718-37
                             1.136-HS
                             2,442-16
                             2,?4?.«9
                             4,246-35
                  7,375-13
                  1,463-32
                  5.855+3H
                  5,539-31
                  2.817-35
                  2.174-34
                  1.353+33
                                   MOLECULA*  WATER  •  9.99183-ai

                                 IONIC  STRENGTH  •  1.31793 + BPI
                                        RES, E.N,  •   -1.485.H1
                                             -211-

-------
       RUN NO.      67
       DATE     4/06/76
                                                                        -T/T
Species
  + 2
Ca
Nat'
Cl
CO;
Ts"
SO 3
so*,
  -1
    -2
    -2
    -2
            Standards
           Cmnioles/1)
 Ca  Feed
(rr.molo/1)
   30
                                     ANAJYTICAL  RESULTS
                                          S03  2  Feed
                             30
                                          (raniole/1)
                                               ,1300
                                               • 500
                    1580
                     500
                    1540
                                                 Effluent
                                                 (mmolc/1)
                                                      fi.08
                                                    43 6_ ._
                                                    166
                                                                5.4
                                                              686.
                                                              159.
                                                              527
                                                       Solids
                                                      (nunole/o')
                                                         9.43
                                                                  Q.474
                                                                  0.035
 Time
(min)
  30
 60
100
 PH
 5.81
-LuSD
 5.80
 5.79
Temp.

4 2.4
il . 7
41.2
43.
                                    ~2
       S03
     (mmole/1)
                                        OPERATING DATA
                                             Solids
                                             Removal
                                             (inl/min)
                                                  Si
                                 159
                                                 115
                                                 115.
                                                  122
                                                            Solids
                                                            0.404
                                                              .326
                                                             "." 267
Solids
 (g)
 13.2
                                                                         10.6
                                                R f,
                                       COMPUTER RESULTS
 Ionic
Strength
  1.16
                  Residual
                                         Relative  Saturation
              Electroneulra] ity    CaS03-%H20   CaSOM'21!20   CaSO.,-^1120
                    -0.057             7.46         0.50	       0.19
                                                                               Mole  Fraction
                                                    SO
                                                                                  -2
                                                                                       SOu
                                                             0.03
                                              -212-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca
  +2
Mg
Na2
CI
CO 3
  "
   +2
  -1
   -2
SO.
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET

Flow Rate (ml/min)
Ca
   2
  +2
Cl l
C03~2
so3~2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/min)
PREC. RATE

     Solid

     S03"2
Run # 67 Date 4/06/76
A
182.9
B
105.3
6.05
124.
39.9

6.05
52.7
162.2
L_i_qui_d_
288.2
2.01
Solid
0.324 (g/min)
3.06
126.
47.7

1.55
45.8
151.9
mmole/min
4.04
6.8
10.3
0.15
0.003
irrmole/g
9.43
0.474
0.35
                                                                        288.2
                                                                          6.05
                                                                        124.
                                                                         39.9

                                                                          6.05
                                                                         52.7
                                                                        162.2
                                                                           5.07
                                                                         126.
                                                                          47.7
                                                                          46.0
                                                                         151.9
                                                                           0.324
                                                                           0.428
                                                                          14.4
                                                                          294.
                                          -213-

-------
                    SOLIDS MATERIAL BALANCE

Run No.    67

Date    4/06/76


                      g/mmole       mmole/gram       g/gram

          Ca++         0.040            9.43           0.397

          M"^          .024          	         	

                        .046          	         	

          Cl"           .035          	         	

          COl           -060           (8.92)          (.597)*

          S07           .080            0.474            .038

          SCC           .096             .035            .003

          %H20          .009             .509            .005


                                                    Z  1.040
*  Excess calcium ([Ca] - [Ts]) is assumed to be calcium
   carbonate.
                              -214-

-------
                                          KINETIC RUN  67
19 APR
                  :Jd.293
M20
CAP
MGO
•1*20
                                         INPUT SPECIES

                                  5.55«S2*^l
                                         HCL
                                         C02
                                         «203
                                        . N205
                                         S02
                                         S03
                                                                    TElPtRATURt
                                                                   l , << f .<
                                                                  «i .
                                                                                           OEii.  C.
                   H20
                   H2C')3
                   HCOJ-
                   H2S03
                   HSOJ-
                   Hjru-

                   CA»*
                   CAOH +
                   CAHC03*
                   CAC03
                   CASC,3
                   CAH503+
                   C4S04
                   MGOH*
                   PGHC03 +
                   MGCQ3
                   MQS03
                   MGH503*
                   HGS04
A(,UEOUS SOLUTION

 MOLALITY

 l,39b-0b

 2,777-1*3
 1.774-31
 5.348-H5
 S.976-H2
 7.912-vS

 2,141-*3
 3,589-1?
         1.351-33
         9,593-k)*
         2,521-*3

         1,631-ai
         6.3a5-«7
         6,535-4)4
         5,177-fS
         4,4a9-«<2
         3,913-82
                                                       ACTIVITY

                                                       1.S22-KO
                            1 ,373-«3
                            «, 557-^6
                            1.615-H2
                            «. 43^-516
                                     2,917-lvJ
                                     1.127-05
                                     4,ay5-eb
                                     1 ,857-«3
                                     7,797-«4
                                     4, 912-6)2
                                     5,125-917
                                     5,312-f4
                                     S, 347-4)6
                                     5,504-92
                                     3.iaa-aa
                                     2,312-ai
                                                                   ACTIVITY
                                                        9,823-'n
                                                        I ,?^^+^<^j
                                                        6,H49-»n
                                                        1 ,226'ft1
                                                        6.5140-ai
                                                        », 128-^1
8,128-01
8.128-"!
1,226 + f,^
1 ,226»'*n
8,128-^1
8.128-811
8.128-H1
1.22S+HM
1,226*«B
8,128-91
1.22S + SI0
 NAHH             9.935-10
 NAHC03           1,8?6«H4
 NACQ3-           9,755-87
 NAS03-           S,211-03
 NASQ4-           3.59b-4«2

 OM-              2.6S8-k>*
 C03--            J.Z93--07
 SQ3--            7,»4?-?3
 S04--            3,!i'M4-fll

COMPONENT         MOLALITY

 CA(OH32tS)       Z.aca
 CAC03CS)         fi.aa?
 CASosts)         a,ae«
 CAS!14(S)         B.ffM
 HG(u«)2CS)       a.a^w
 «i,CQ3(S)         a,a«a
 MGS03CS)         iS,H0{l

 PC02 •  1,5^275-^11  ATM,
 Pb02 •  1,*H272-«I5  ATM,
                                                       2.895-81
                                                       1,218-09
                                                       2.214-B4
                                                       7,928-tf7
                                                       4.235-P3
                                                       4, 1
                        ACTIVITY PRODUCT

                            2.350-19
                            2.094-11
                            5,2b«-?i7
                            1.165-B5
                            2.2V2-17
                            1,927-09
                            4,886-85
                                              8, 128-H1
                                              8, i29-*l
                                              6,12B-«1
                                                                         7.94S-H2

                                                                     RELATIVE 5ATUHATIQN

                                                                         8,0991-14
                                                                         8.921-^3
                                                                         2.256-^6
                                                                         1.364-B4
                                   HOLECULAR WATER • 9,99d28-Bl NGS,

                                  QwIC STRENGTH • 1.16431»J«       "ES,
                                                  -215-

-------
UUN NO.
          68
                                                            c   T  •-0.063
DATE A /nfi /7ft
Species
Ca*2
»g+2
Nat1
cr1
C03~2
Ts~2
S03~2
SO,,"2
Time
(min)
• 60
^120
180
240
300
Ionic
Strength
1.03
ANALYTICAL RESULTS -...
Standards Ca Feed S03~2 Feed Effluent Solids
(ramolps/l) (rr.mole/1) (nmole/1) (mmolc/1) (mroole/jO
18 7.79 8.52
1200 404.
315 148.

18 4.7 0T8S2
1490 540.
315 92. .852
1350 448 .035
OPERATING DATA
Solids
Temp. SOs"2 Removal Solids Solids
pH (°C) (ramole/1) (ml/min) (wt%) (g)
5.72 53.0 30" 0.?R 9.1.
5.72 52.4 30 .28 9.1
5.70 51.2 30 .21 6.6
5.69 50.2 30 .142 4.5
5.67 51.3 92.1 30 .146 4.6
COMPUTER RESULTS
e •! T Relative Saturation Hole Fraction
ElectroneuLral ity CaS03-%H20 CaS0^2i:20 CaSOi.-^IhO S03~2 S0u~2
0.101 4.12 0.58 . 0.?7 n.Qfi n 04
                                       -216-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
                        Run i?   68
                                           Date  4/08/76
INLET

Flow Rate (ml/min)
                                        201.3
                                                99.2
                                                                          300.5
Ca
  +2
Mg
N32
CI
  +2
   +2
   1
CO 3
S03
   -2
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                     3.60
                                          3.60
                                                    113.
                                                     31.3
                                                    134.
                                                                            3.60
                                                                    113.
                                                                      3.6
                                                                     31.3
                                                                    134.
OUTLET

Flow Rate (ml/min)
                                       Liquid
                                              Solid
                                                            (g/min)
Cl J
C03~2
S03~2
so.* 2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                            2.34
                                          121.
                                           44.5
                                            1.41
                                           27.6
                                            1.35
                                               0.36
                                               0.04
                                               0.01
                                                                           2.70
                                                                         121.
                                                                          44.5
                                                                          27.7
                                                                         135.
PREC. RATE
                                  mmole/min  mmole/§
     Solid
S0
so,,
        _
         2
                                          1.26
                                          3.61
                                         -0.7
                                                    8.52
                                                    0.852
                                                    0.064
                                                                   0.042
                                                                   0.148
                                                                   4.24
                                                                 -10.9
                                         -217-

-------
                    SOLIDS MATERIAL  BALANCE

Run No.   68

Date    4/08/76


                      g/tnmole        mmole/gram       g/gram

          Ca4"1"         0.040            8.52            0.341

          Kg4"4           .024           	         	

          Nat4"           .046           	         	

          Cl"            .035           	         	

          C07            .060           (7.60)*          (.456)-

          SOl            .080            0.852           .068

          SO;            .096             .064           .006

          %H20           .009          '   .916           .008


                                                    E  0.879
*  Excess calcium ([Ca] -  [Ts]) is assumed  to  be  calcium
   carbonate.
                             -218-

-------
                                      KINETIC RUN  68
19 »P»  7ft
                   PH
                           H20  » 5,5.-
                           CAO  • 7,7^
                           HliO  » 4.
                           NA20  « 1,
                                         INPUT SPECIES
                        HCl
                        CC2
                                                           M215
                                                           302
                                                           503
                               i , 7 0 vi fl / -
                               & , tf ** H v v)
                                                                  4.
                                                                                          OE(,. C,
                                   »Bt'£rjuS  SOLUTION
                   H*
                   H2G
                   H2COJ
                   hCQJ-
                   "2SOJ
                   HS03-
                   H304-

                   C4 + +
 2.756-.J3
 1.1S2-SI5
                                    8, <
                    2. 108-HS
2.133-^2
9.139-06
                                                       1,142-05
ACTIVITY COtF* TCItNT


      9.*847-'H

      «.C79-"I1


      7.863-M1

      ?.?76-0t
      7,fto3-^l
      7.863-i«l
CAS03
CAHSPJ*
C4S04
MGOH*
MGHC03+
MGS03
MGH5D3*
«GS04
2.962-H3
7,911-34
9.2?2-94
3.1S5-83
1.773-ai
5.3I'7-»)4
21233-32
2.773-82
1,759-01
9.45Q-34
7.252-44
3,739-03
5. 122-82
4,244-34
2|673-<>2
2,1«5-»1
iilE?
2,881-^1
7,a«3-f>i
7,8o3-l»l
l.l»7+M«l
7,863-vtl
                  MAC03-
                  UAS03-
                  NAS04-

                  OH-
                  CQ1--
                  SU3--
                  304--
                  CA(UHJ8(S)
                  CAS03CS)
                  CASO-l(S)
                  "IGC03CS)
                  HG3Q3CS)

                  PCH2  «  1,
                  PS02  •  1,
 2,t>40-<)l
 J, 157-29
 1,222-04
 5,827-87
 2,138-813
 2.912-02

 3,4*9-08
                                    2.411-Ml
 H , /) 0 H

1   ATM,
5   ATM,
1,887-01
1 ,385-09
1 ,463-04
4.582-C7
l,681-!'3
2,290-«2

2,727-5«8
2.513-Pa
4.174-B4
1 ,9a5-v)2
4,918-19
l.'iS'J-ll
2.737-07
1.272-05
3,810-17

2,342-35
                                                                         7,127-^1
      7, 863-^1
      7,863-5)1
      7,863-Bl

      7,863-01
      1 ,36fi-fll
      I ,3ofi-t»l
      8,265-^2
                                                            P9QOOCT   =!£LATIVt
                                      1.526-13
                                      9,629-^3

                                      S.832-01
                                      4, lk)2-t)6
                                      1 ,«38-5)4
                                 IONIC  STȣ*GTH
                                                                   RES,  £,N.  <
                                                                                 t.a 14
                                              -219-

-------
        RUN  NO.     69

        DATE     A/27/76
                                                                       -T/T
                                                                            > 0.01
Species
Nat1

Cl"1
C03~:
TS
so 3
so,,
-2
-2
            Standards
                       Ca   Feed
                       (mmole/1)

                         40.0



                         77.7
                                     ANALYTICAL  RESULTS
           S03~2 Feed
           (mrnole/l)
                                              .26.6
                                               0.
                                              27.2
                                           21.2
                                            6.0
                                                          Effluent
                                                          (mmolc/1)

                                                             9.3
                              13.0
                              38.4
                                                          2.76
                                .70
                               2.06
                                    Solids
                                   (mmolc/cO

                                      7.68
                                                                            7.47
                                                                            7.02
                                                                            0.478
Time
[mirj

 •90
        PH

       7.91
                Temp.
         OPERATING DATA

              Solids
  SO3~"       Removal
(mmole/1)     (ml/min)
                                    -2
   0.7Q
                                               12S
                                                           Solids
                                                           (wt%)

                                                           0.194
                                  Solids
                                   (g)

                                   6.29
                                       COMPUTER TIESULTS
 Ionic
Strength

    0.051
              Residual
          Electroneutralicy

                 0.0007
                                        Relative  Saturation
2.45
                                                     -21120

                                                    0.092
                                 0.042
                                                                                Fraction
S03~2     S0u~

0.936    0.064
                                             -220-

-------
                        REACTOR MATERIAL BALANCE CALCULATIONS
INLET

Flow Rate (ml/min)
Ca+2

Na2+2
ci-1
Ts
S03
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate (ml/min)
Na2
Cl"1
Ts _
S03_
SO i,
   + 2
        (mmole/min)
        (mmole/min)
        (mmole/min)
        (mmole/rain)
        (mmole/min)
        (mmole/min)
        (mmole/min)
PREC. RATE

     Solid

     S03~"
     so,,
        "2
Run # 69 Date 4/27/76
A
100
B
100
4.0

2.66
7.77

2.12
.60
Liquid
200
1.86
Solid
0.24.1 (g/min)
1.86

2.60
7.68

0.14
0.412
mmole/min
2.14
1.98
0.188
1.70
0.116
mmole/g
7.68
7.02
0.478
                                                                           200
                                                                             4.0
                                                                             2.66'
                                                                             7.77'

                                                                             2.12'
                                                                             0.60"
                                                                           3.72
                                                                           2.60
                                                                           7.68

                                                                           1.84
                                                                           0.53
                                                                         grams/min
                                                                           0.243,
                                                                           0.229
                                                                           0.282
                                                                           0.39
                                          •221-

-------
                    SOLIDS MATERIAL BALANCE



Run No.   69



Date   4/27/76
Ca++
Mg4^
Nat4"
Cl"
col
sol
so;
%H20
g/mmole
0.040
.024
.046
.035
.060
.080
.096
.009
mmole/gram
7 6ft




7.02
.48
7.50
g/gram
0.^07




.562
.046
.067
                                                      0.982
                            -222-

-------
33 *AY 76
             lot 12114,6Si
                           CAO
                           M50
                           NA20
                   PH  s   7,913*
                                       KINETIC  RUN  69
     INPUT SPECIES CiriLES)

       it                HCL
       i3                C02
                                                           N205
                                                           502
                                                           303
                                                                                   5B.2W0  OEG,  C,
                                                                  3.34333-32
                                   iOUEOUS  SOLUTION
                   H»
                   H20
                   H2S03
                   MSQ3-
                   4504-

                   C*» +
                   CAOH +
                   CAS03
                   CAHS03+
                   C*S04

                   MA*
                   MAOH
                   NAS03-
                   M4SU4-

                   Ort-
                   CL-
                   S03 —
                   304 —

                  COMPONENT
1.455-38

2.25SI-11
1 .618-85
1.7S6-39

8,172-83
5.621-37
5.539-^4
2.944-05
5,707-4)4

2.588-512
2,552-38
2,499-35
8,937-85

5,559-38
3,539-32
1,343-34
1,403-33

MOLAIITY
                                    ACTIVITY

                                    1.23B-88

                                    2.369-11
                                    1.312-5<5
                                    1.432-39

                                    3.623-33
                                    4,556-?7
                                    5.55S-H4
                                    2.386-36
                                    5,759-34

                                    2.124-32
                                    2,578-38
                                    2.326-35
                                    7.223-35

                                    4.536-3S
                                    3,393-32
                                    4,529-35
                                    5,594-34
ACTIVITY  COEFFICIENT

      8.456-VM
      9,988-31
      1 ,flH9»Hti
      3,138-31
      8,136-31

      4,434-dl
      8,126-01
      I,«a9 + 5>*i
      8, i«!6-e
-------
        RUM NO.   70	

        DATE      4/27/76
                                                                       -T/T
                                                                                 > 0.01
                                     ANALYTICAL UHSULTS
Species

Ca+2
            Standards
           fmmolfS/1)
                       Ca+  Feed
                       (mmole/1)

                         39.2
                       S03  2  Feed
                       (raraole/1)
                                             Effluent
                                             (mmole/1)

                                                8.59
                                                                          Solids
                                                                           7.61
 Nat1
 Cl

 CO;

 Ts"

 SO 3

 SO-.,

~2
-2
-2
                             76.9
                                        43,5
                                         0.
                                        44.0
                                        20.1
                                        23.9
                                         22.3
                                         38.2
                                         10.4
                                         '0.73
                                          9.67
                                                       7.41
                                                             6.62
                                                             0.826
 Time
(tain)
        PH
Temp.
C°c)
                    _S1 .8
                          OPERATING DATA

                                Solids
                   SOj"''        Removal
                  (nmole/1)      (ral/min)
                                    rir A

                                                200,
                                                        Solids
                                                         0.094
                                                                        Solids
                                                                         (g)

                                                                        2.61
                                        COMPUTER RESULTS
  Ionic
 Strength

  0.068
    Residual
Elect roneu I mlity

       0.0028
                                         Relative   Saturation

                                             CnSCK • 2U20


                                                                          Mole  Fraction
                                                          SO
                                                                             -2

                                                                                       0.11
                                               -224-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
                        Run #   70
                                                Date  4/27/76
INLET

Flow Rate (ml/min)
Ca
  ,+2
  .+2
Mg
Naa
ci-1
Ts
   + 2
S03
SO.,
   -2
   -2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                        100
                                         3.92
                                         7.69
                                           100
                                                   4.35
                                                    2.01
                                                   2.39
                                                                   200
                                                                    3.92
                                                                   4.35
                                                                   7.69

                                                                   2.01
                                                                   2.39
OUTLET

Flow Rate (ml/min)
Ca
Mg'
  + 2

  '+2
Cl'1
Ts
S03
SO 4
   -2
   -2
(mraole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
                                       Liquid
                                         200
                                 1,.72
4.46
7.64

0.146
1.93
           Solid

           n.188   (g/min)

           1.43
                                            1.24
                                                   0.155
                                   3.1
                                   4.46
                                   7.64

                                   1.39
                                   2.08
PREC. RATE
     Solid
     SO
 -2
I
 -2
                                        mmole/min  mmole/g
2.20
1.86
0.46
                                                    6.62
                                                    0.826
                                                                   0.188

                                                                   0.289
                                                                   0.281
                                                                   0.557
                                           -225-

-------
                    SOLIDS MATERIAL  BALANCE



Run No.     7Q




Date   4/'27/76
Ca^
vr' ++
Mg
Nat*
Cl"
col
soT
so;
%H20
g/mmole
0.040
.024
.046
.035
.060
.080
.096
.009
mmole/gram g/gram
7.61 0.304




6.62 .530
.826 .079
7.44 .067
                                                        .980
                              -226-

-------
                                     KINETIC  RUN  70
»3 HAY 7d
             16112: t 1.412
                           H20
                           CAO
                   Pii  »
           SPECIES  C10LES5

                       HCL
                       CO?
                       MJ03
                       N2Q5
                       S02
                       S03
                                                                   TEMPERATURE
                                                                  , 8 J C! Jl d
                                                                                         DEC, c,
                   H20
                   H2S03
                   MSOJ-
                   HS04-
                   CAOH*
                   CAS03
                   CAHS03+
                   CASQ4
                   NAUH
                   NAS03-
                   OH-
                   CL-
                   303 —
                   804 —
ALLOWED

AiUEOUS  SOLUTION

 1QLALITV

 9.871-B9

 1.365-11
 l,357-<)5
 5.324-P9

 6.221-33
 7,226-*)7
 5,085-34
 1,787-36
 1 ,855-413

 4.383-32
 7,527-88
 5.62i-3S
 6,934-34

 1,312-35
 3,819-32
 1 ,496-34
 7,119-33
                   ACTIVITY

                   7.585-39

                   1,377-11
                   1.375-85
                   4,223-6)9

                   2,535-33
                   5,731-37
                   5,148-04
                   l,418-*6
                   1,877-33

                   3,527-32
                   7.S17-38
                   4,463-35
                   5,499-34

                   8,324-36
                   3,31)2-32
                   5,893-35
                   2,544-33
            ACTIVITY  COEFFICIENT

                  8,362-MJ
                  9.984-31
                  1 .312+3B
                  7.922-31.
                  7.932-31.

                  4,874-31
                  7.932-31
                  1 ,s>i2*aa
                  7,932-31
                  8,346-31
                  1 ,312»Hf
                  7,932-eil
                  7,932-01

                  7,932-ai
                  7.862-31
                  3,938-31
                  3,574-31
                                                  ACTIVITY PRODUCT  RELATIVE SATURATION
                   CA(OH)2(S)
                   CASO.H5)
                   CA5U4(S)
3,3513
1,532-13
1.492-37
5.428-36
                                      5,123-38
                                      2,252*ctu
                                      2.963-31
                   Pi02 •  2.124M3-H   ATM,

                                   HOLECULA9  WATER  «  t,3«3J4»33  
-------
        RUN NO.   71

        DATE   	A/27/7A_
                                                                        -T/T
                                                                     <0,01
                                      ANALYTICAL RESULTS
Species

Ca 2
            Standards
           (mmoles/1)
                Ca  Feed
               (mroole/1)

                  39.7
                       S03~2 Feed
                       (nsnole/1)
                                                           Effluent
                                                           (rnmole/1)

                                                             10.1
                                                                          Solids
                                                                         (mmole/o')

                                                                           7.46
 Nat1
Cl
CO-
TS"
S03
so
    -2
    -2
    -2
                             82.0
                                   42.6
                                    0.
                                    0.63
                                   44.1

                                   21.0
                                   23.1
                                          21.8
                                          42.0
                                           0.251
                                          11.3

                                         '2.24
                                           9.06
                                                                            0.12
                                                                            7.22

                                                                            6.56
                                                                            0.865
 Tiroe
(min)

 12.5
 PH

6.87
Temp.
C°0

52.0
                                        OPERATING DATA

                                             Solids
                                 S03~2       Removal
                               (nrnole/11     (ml/min)

                                  2.74         200
Solids
(wt%)
0.085
Solids
(g)
                                       COMPUTER RESULTS
 Ionic           Residual
Strength     Electroneutra]ity

  0.071             -0.0004
                                        Relative   Saturation
                  5.30
                                     CaS04-2U20

                                        0.30    '
                                                                 0.14
                                                                  Mole  FractJo:
                                                                              SO
                                                                                 -2
                                                                   SO,
                                             -228-

-------
                        REACTOR MATERIAL BALANCE  CALCULATIONS
INLET

Flow Rate (ml/min)
  +2
Ca
N321
Cl
  -1
C03

SO 3
-2
-2
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
(mmole/min)
OUTLET
Flow Rate (ml/min)
Na2
Cl"1
C03~2
S03 2
soi,"2
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (mmole/min)
     (minole/min)
PREC. RATE
     Solid
     SO;
     SO 4
        -2
Run // 71 Date 4/27/76
A
100
B
100
3.97

4.26
8.2
0.063
2.1
2.31
Li _qui_d_ •
Solid
?nn 0.178 (g/min)
2.02
1.33

4.36
8.4
0.050
0.448
1.82
mmole/min
1.95
1.65
0.49
0.021
1.17
0.15
mmole/g
7.46
6.56
0.865
                                                                            200
                                                                            3.97
                                                                           4.26
                                                                           8.2
                                                                           0.063
                                                                           2.1
                                                                           2.31
                                                                            3.35
                                                                           4.36
                                                                           8.4
                                                                           0.071
                                                                           1.162
                                                                           1.97
                                                                         grams/rni-n
                                                                         0.178
                                                                         0.261
                                                                         0.252
                                                                         0.566
                                          -229-

-------
                    SOLIDS MATERIAL BALANCE




Run No.     71



Date    4/27/76
C.+*
. ' -H-
Mg
Nat4"
Cl"
col
sol
so;
%H20
g/mraole
0.040
.024
.046
.035
.060
.080
.096
.009
mmole/gram
7.46



.12
6.56
.865
7.42
g/gram
0.298



.007
.525
.083
.067
                              -230-

-------
                                      KINETIC RUN  71
83
       76
               :i?I 12,>172
                           HZO  « ;
                           CAO  « 1.9H000-H2
                           NA2Q
                                         INPUT SPECIES (HOLES)
                       HCL
                       C02
                       N203
                       N205
                       302
                       303
                                                                    TEMPERATURE
           4,20909-92
           2.:
                                               32.800 OES. c.
                                                                  2.24/1JM-03
                                   *aueous SOLUTION
                  COMPONENT
                   H2U
                   H2CC13
                   H2S03
                   HS03-
                   HSH4-
                   CAOH +
                   C4HCC1-3 +
                   CAC03
                   CAS03
                   CAHSH3+
                   MA*
                   NAOH
                   NAMC03
                   NACQ3-
                   NASOJ-
t.sis-a?

3.95S-35
1.933-^4
7,J78-H9
5.2H-04
8,S«8-B3

6,928-a3
4,779-88
1,194-05
4.673-97
1.2i»l-a3
7,7ia-a5
l,878-«3

4,284-83
4,369-89
5,134-99
3,319-97
l.iai-84
6,179-94
ACTIVITY

1 ,349-07
1.52S-94
7,473-09
4.] 18-04
2.788-0J
3. 779-518
9.439-ae
4.731-f 7
1.216-»3
6,102-35
1. 901-03

3,437-32
4,423-!»9
5.168-BS
2.624-07
9.343-015
4,885-04
                               ACTIVITY  COEFFICIENT

                                     8,349-ai
                                     9,9tt3-31
                                     1 ,312 + 3!"
                                     7.895-i»l
                                     1.312 + ai!
                                     7,895-31
                                     7,94)7-01

                                     4,325-Hl
                                     7,94J7-dl
                                     7.9a7-ai
                                     1 ,312»d0
                                     i.ai2*0?
                                     7,907-ai
                                     1,212+00
                                     7,907-«ll
                                     7.9d7-0t
                                     7,987-31
                   OH-
                   cu-
                   CQ3--
                   303--
                   SQ-l —
                   CACOH)2tS)
                   CACU.M5)
                   CAS03CS)
                   CASQ4C3)
6,847-97
4,193-02

3.219-04


MOL*LITY
0,000
3,300
                   PC02  > 2,28blb-?3  ATM,
                   PSQ2  • 1.51731-88  ATI,
                   4.781-37
                   3,289-02
                   7,314-08
                   1,251-04
                   2.307-03
                  7,907-01
                  7,834-01
                  3.885-.01
                  3,833-01
                  3,516-01
                                                   ACTIVITY PRODUCT  RELATIVE SATURATION
S,374-16
2.179-10
3.4U4-07
8.411-06
                                     2,047-18
                                     1,335-01
                                     5,296+00
                                     2,977-01
                                   MOLECULAR WATER • l,B3037+«0 KGS,

                                  IONIC STRENGTH « 7.08080-02       RES, E.N,  i
                                             .4.160-04
                                               -231-

-------
       RUN NO.
DATE 1/71/76
ANALYTICAL RESULTS
Standards Initial
Percent Liquor Solids
Jpecies Deviation (mmole/1) (mmole/g)
:a+2 +.2 . 10.55 7.60
~^"2 _ l±
la+l +-2 10.Q 	
:i-1 +.8 21.1 	
:s"2 +.2 10.0 7.42
;o3~2 ' o. 6.65
;04~2 +-2 ' 10.0 0.77
OPERATING DATA
:ime Temp. S03~2
lin) pH (°C) (mmole/1)
0 	 50 0.
'020 7.29 50 0.336


Final
Liquor
(romole/l)
13.0
10.0
21.1
13.3
0.336
13.0

Solids
(wt%)
0.357
.304



Solids
(mmole/1 )
7.10
0.05
	
7.10
6.85
0.24

Solids
(g)
2.001
1.700
                                      COMPUTER RESULTS
Ionic           Residual
Strength     Electroneutrality
 .0563
                                       Relative  Saturation
                  CnS03-%H20    CaS0lt-2H20
-0.001704
1.153
0.60
0.27
                                                           Mole  Frnction
                                      SO
                                                              -2
0.97
                                  srV
0.03
                                          COMMENTS

-9 solids with grinding.
nitial liquor concentrations normalized to final sodium and  chloride  concentrations,
                                             -232-

-------
RUN NO.  E*-l
DATE  1/21/76
           REACTOR MATERIAL BALANCE CALCULATIONS
           Run # E*-l
                              Date 1/21/76
         INLET
                     Liquid
                     560 ml
                                       Solid
                                       2.001 g
     Na2+2
     or1
      s
     so3
     S0
   ~2
   ~2
(mrnole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
                          5.91
 5.60
11.82
 5.60
 0.
 5.60
                                 15.2
14.85
13.3
 1.54
                                               21.11
                                                        5.60
                                                       11.'ST
                                                7.14
     OUTLET
       + 2
Na2
Cl"
Ts
S03"
S04"
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
                     Liquid

                      560 ml
                            7.28
              5.60
             11.82
              7.46
              0.188
              7.27
                        Solid

                         1.700 g

                         12.07
             12.07
             11.65
              0.40
                                                       19.35
                                                             5.60
                                                            11.82
                                                            TOT
                                                            11.84
                                                             7.67
                                        -233-

-------
                         SOLIDS MATERIAL BALANCE
                         Run //  E*-l      Date 1/21/76
                 g/mmole           mmole/gram               g/grara




 Ca+2             .040               7.10                   0.284
   +2
 Mg               .024
 Na2+2            .046               0.05                   0.002
 Cl               .035


 C03~2             .060
 S03"2             .080                6.85                   0.548
  > 3                                 	                 	


SO,"2            .096                0-24                   0.023


                 >009                7.09*                  0.064
                                                          z °-921
*  Water concentration  is  based  on the hypothesis that solid sulfate and

   sulfite each have  one-half waters of hydration.
                                     -234-

-------
        RUH NO.
                 E*-2
DATE 1/21/76
ANALYTICAL RESULTS
Species
Ca+2
Mg+2
Na+1
cr1
C03~2
Ts~2
S03"2
SO;,"2
Standards
Percent
Deviation
+ .2
-.4
+.2
+.8"

+ .2
+.2
Initial
Liquor
(mmole/1)
10.7
	
10.3
21.3
	
10.3
0.
10.3

Solids
(mmole/g)
7.60
	
	
	
	
7.42
6.65
0.77

Liquor
(mmole/1)
13.1
	
10.3
21.3
	
13.44
0.32
13.12
Final
Solids
(mmo 1 e / 1 )
7.38
	
0.03
	
	
7.19
6.89
0.25
                                        OPERATING DATA
Time
(min)
0
7020

pH
	
7.30
Temp.
(°C)
	
50
S03~2
(mmole/1 )
0.
0.324
Solids
(wt%)
0.345
.296
Solids
(g)
2.001
1.717
                                       COMPUTER RESULTS
 Ionic           Residual
Strength	ElertroncMitr.il i ty
 0.0570
-0.00146
                                        Relative  Saturation
CaSO r V:i ?0   Ca SO;.' 21! 20    CaSO u • foI ? 0

   1.115         0.61         0.28
                                                           Mole
                                                 'rar t io
0.96
0.04
                                            COMMENTS

 K-9  solids without  grinding.
 Initial liquor concentrations normalized  to final  sodium and  chloride  concentrations.

                                             -235-

-------
RUN NO.  E*-2

DATE    1/21
        776
      REACTOR MATERIAL BALANCE CALCULATIONS
      Run #  E*-2
                                   Date 1/21/76
   INLET
                          Liquid

                          0.580 ml
                          Solid
                          2.001 g
                                                       mmole
Ca+2
Mg+2
Na2+2
ci-1
Ts
so3
SO.
        ~2
         2
(mmole )
(nmole )
(mmole )
(mmole )
(mmole )
(mmole)
(mmole )
                            fi,18
                           12.16
                            5.95
                            5.95
15.71
13.51
13.31
 1.54
                     21.39
                      5.95
                     12.36
                     19.46
                     13.31
                      7.49
OUTLET
                                 Solid
Cl'1
so3~2
(mmole)
( mmo 1 e )
(mmole)
(mmole)
(mmole)
(mmole)
    2
             0.S80 ml

             7.60
                     5.95
        (mmole)
            12.36
             7.80
             0.188
             7.61
                                    1.717
                                  12.67
12.34
11.83
 0.43
                                                           "out
                                                             mmole
                                                            20.27
                                                             5.95
                                                            12.36
                                                            20.14
                                                            12.02
                                                             8.04
                                   -236-

-------
                         SOLIDS MATERIAL BALANCE
                         Run // E*-2      Date 1/21/76
                 g/mmole           mmole/gram               g/gram


 Ca+2              .040               7.38                   0.295
 Mg+2              .024
 Na2+2             .046                0.03                   0.001
 Cl                .035

 C03~2             .060
 S03~2             .080                6.89                   0.551

 SO.'2             .096                °-25                   C
%H20              .009                7.14*                  0.064
                                                            0.935
*  Water concentration  is based on the hypothesis that the solid sulfate
   and sulfite  each  have one-half waters of hydration.
                                     -237-

-------
       RUN NO.  E*~3
DATE 1/21/76
ANALYTICAL RESULTS
Standards
Percent
Species Deviation
i 2 i o
.a "t~. •£
g 2 -.4
a+1 +-2
II"1 +.8
's~2 +.2
0^
n.-2 +.2

• Liquor
(mrnole/1)
10.8
	
10.3
21.6
10.3
0.
10.3
Initial
Solids
(mmole/g)
7.15
0.03
0.04
	
6.75
5.65
1.11

Liquor
(mmole/l)
12.4
0.01
10.25
21.6
12.7
0.37
12.3
Final
Solids
(mrno ] c / 1 )
7.28
	
0.03
	
7.35
6.55
0.78
                                       OPERATING  DATA
ime
in)
0
020

pH
—
7.38
Temp.
(°0
—
50
S03*-2
(mmole/] )
0.
0.369
Solids
(wt%)
0.207
0.170
Solids
(g)
1.199
0.987
Ionic
.0553
                Residual
            Electro n c u _c_r qjl_i_t y^
                 -0.00161
                                      COMPUTER RESULTS
                                       Relative  Snturncion
                                               CnSO,. -2H20
1.279
0.56
0.25
                                                                            Mol e  Frnrtion
            SO,
                                                                               -2
0.89
                                  SO,.'
0.11
                                           COMMENTS

-38 solids used with grinder.

nitial liquor concentrations normalized to final sodium and chloride concentrations,

                                             -238-

-------
RUN NO.  E*-3

DATE
1/21/76
           REACTOR MATERIAL BALANCE CALCULATIONS
Run // E*~3
INLET
Ca+2
Mg+2
Na2+2
ci-1
Ts
so3~2
S0n~2
OUTLET
<2
2"+'
Na2
Cl'1
Ts
so3~2
sn,,~2
(mmole )
(mmole )
(mmole )
(mmole )
(mmole )
(mmole)
(mmole)
(mmole )
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
( mmn IP)
Date I-/21/76
Liquid
ssn mi
6.26
	
5.95
12.S2
5.95
_.__._ —
5.95
Liquid
580 ml
7.19
0.003
5.95
12.53


0.214
7.35
Solid
1 .19941 ?
8.58
o.rn
0.05
	 	 	
8.09
6.78
1.33
Solid
0.987 R
7.19

0.03
	


6.46
0.774
                                                           mmnl
                                                           14.84
                                                            n.m
                                                            6. 00
                                                           12.52
                                                           14 . 04
                                                            6.78
                                                            7.28
                                                             mmole
                                                           14.38
                                                            0.003
                                                            5.98
                                                           12.53

                                                            6.6T~
                                                            8.12
                                       -239-

-------
                         SOLIDS RATERIAL BALANCE
                         Run // E*-3       Date  1/21/76
                 g/minole           mmole/gram                g/gram


   +2             .040                7.28                    0.291
                 • -024                	                   	

    +2             nAfi                0.03                    0.001
 Na2

 Cl"1              .035
 C03~2            .060
 S03~2            .080                6.55                   0.524
 S04  2            .096                0.78      [             0.75
                  .009                7.33*                  0.066
                                                            .0.957
*  Water concentration is  based  on the  hypothesis  that  solid  sulfate and sulfite
   each have one-half waters of  hydration.
                                       -240-

-------
RUN NO. E*-4
DATE 1/21/76
ANALYTICAL RESULTS
Standards Initial
Percent Liquor Solids
Species Deviation (mmole/1) (mmole/g)
Ca+2 +.2 16.4 7.29
Mg+2 -.4 	 0.04
Na+1 +.2 16.2 0.05
Cl"1 +.8 32.8 	
C03~2 	 	
Ts~2 +.2 16.2 6.99
SOT2 0. 6.06
qn, ~2 +2 16-2 l-08
DU -4 i * £•
OPERATING DATA
Time Temp. S03~2
(min) pH ( C) (mmole/])
0 	 - 0.
JS
7020 7!31 50 0.392
COMPUTER RESULTS
,. . n . , , Relative Saturn
Strength Eleotronou trnl i ty CnSOs'V-^O C.iSO., ' 2H
0.0799 -0.00137 1.380 0.82
CO>C»IENTS
Final
Liquor Solids
(mmole/1) (mmole/1)
17.3 7.34
0.182 	
16.2 0.03
32.8 	
17.9 7.24
0.39 6.22
17.5 1.05
Solids Solids
(wt%) (g)
0.351 2.000
0.321 1.827
t ion Mo1 e Frart io
20 CaSOt,-%H?0 S03~2 SOU~
0.37 0.86 0.14
K-41 solids with grinder.
Initial liquor concentrations  normalized  to  final sodium and chloride concentrations.
                                             -241-

-------
RUN NO.  E*-4

DATE
1 721776
           REACTOR MATERIAL BALANCE CALCULATIONS
Run # E*-4
INLET
Ca+2
Mg+2
Na2+2
ci-1
Ts
so3~2
S04~2
OUTLET
<
&>
Cl"1
Ts
S03 2
SOu 2
(mmole )
(r.imole )
(mraole )
(mmole )
(mrnole )
(mmole)
(mmole )
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
("mmo 1 o)
Liquid
570 ml
9.35

9.21
18.70
9.21


9.21
Liquid
570 ml
9.86
0.10
9.21
18.70
10.22
0.22
10.00
Date 1/21/76
Solid
2.00014 g
14.58
0.104
0.08


13.98
12.12
2.16
Solid
1.827 g
13.41
	
0.055
	
13.23
11.36
1.92
                                                            mmole
                                                            23.93
                                                             0.10
                                                             9.29
                                                            18.70
                                                            23.19
                                                            12.12
                                                            11.37
                                                            mmole
                                                            23.27
                                                             0.10
                                                             9.27
                                                            18.70
                                                            23.45
                                                            11.58
                                                            11.92
                                      -242-

-------
                         SOLIDS MATERIAL BALANCE
                         Run // E*-4      Date  1/21/76
                 g/mmole           mmole/gram               g/gram
 Ca+2             .040               7.34                   0.294
 Mg+2             .024
 Na2+2            .046               0.03                   0.001

 Cl"1             .035               	                  	
 C03~2            .060
 S03~2            .080                6.22                   0-498

 SO."2            .096                1-05                   0.101
 %H20             .009                7.27*                 0.065
*  Water concentration  is based on the hypothesis that the solid sulfate
   and sulfite each  have one-half waters of hvdration.
                                      -243-

-------
RUN NO. E*-5
DATE 1/21/76
ANALYTICAL RESULTS
Standards Initial
Percent Liquor Solids
Jpccics Deviation (mmole/1) (mmole/g)
;a+2 +.2 16.2 7.29
g+2 ...4 	 0.05
a+i +.2 16.3 0.04
;1-i +.8 32.3 	
,s-2 +>2 16.3 6.99
,0 -2 0. 6.06
n -2 +2 16-3 1-08
L/LI
OPERATING DATA
ime Temp. S03~2
in) pH (°C) (mmole/1)
0 	 -- 0.
020 7.33 50 0.406
COMPUTER RESULTS
Ionic Rc-ijuil Relative Saturn
irenfith Electronou t rnl i tv C.riS03-^H?0 CnSOi, ' 2H
.0781 -0.00164 1.425 0.78
COMMENTS
Final
Liquor Solids
(mmole/1) (mniolc/1)
16.6 7.30
0.18 	
16.3 0.03
32.3 	
17.5 7.39
0.41 6.25
17.1 1.12
Solids Solids
(wt%) (g)
0.351 2.000
0.319 1.820
tion Mole. Fraction
20 CaSOu-'.?H?0 S03~2 SO!,"2
0.35 0.85 0.15
-41 solids with grinding.
litial liquor concentrations normalized to final sodium and chloride concentrations

                                            -244-

-------
RUN NO. T7*_s

DATE    1/21/76
           REACTOR MATERIAL BALANCE CALCULATIONS
           Run //  E*-5
         Date  1/21/76
         INLET
Liquid

570 ml
                                       Solid
                                      2.00014 g
                    	L
                    	 -LI
                    mmole
     Ca
       +2
Naa
ci-1
Ts
   + 2
     S03
        -2
        (mmole)
        (mmole)
        (mmole)
        (mmole)
        (mmole)
        (mmole)
        (mmole)
                           9.21
                           9.12
                          18.42
                           9.12
                           9.12
             14.58
              0.10
              0.08
             13.98
             12.12
              2.16
                     23.79
                      0.10
                      9.20
                     18.42
                     23.10
                     12.12
                     11.28
     OUTLET
                          Liquid
            Solid
                                                              mmole
Naa
Cl
Ts
S03'
S04
         2
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmo 11?)
 9.46
 0.10
 9.26
 18.41
 9.96
 0.23
 9.72
                                       13.29
                                        0.055
13.45
11.38
 2.04
                                                       22.75
                                                        0.10
                                                        9.32
                                                       18.41
                                                       23.41
                                                       11.61
                                                       11.76
                                       -245-

-------
                          SOLIDS  MATERIAL BALANCE
                          Run  #  E*-5      Date 1/21/76
                  g/minole            mmole/gram               g/gram



 Ca+2              .040                7.30                   0.292
                   .024
    +2
 Na2               .046                0.03                   0.001
 Cl'1              .035
 C03 2            .060
 S03 2            .080                6.25                   0.500
 SCH i            .096                1.12                   0.108
 %H20             .009                7.37*                  0.066
                                                             0.967
*  Water concentration  is  based  on  the  hypothesis that the solid sulfate
   and sulfite each have one-half waters  of hydration.
                                     -246-

-------
        RUN  NO.   E*-6
DATE i/?i /7ft
ANALYTICAL RESULTS
Standards Initial
Percent Liquor Solids
Species Deviation (mmole/1) (mmole/g)
Ca+2 +.2 16.4 6.96
•^2 IL
£\CT • H- — — — — ___.—
Na+1 +.2 16.3
cr1 +.8 32.8 	
C03~2 	 	 '
Ts~2 +.2 16.3 7.06
S03~2 0. 5.89
SO."2 +.2 16.3 - 0.74
OPERATING DATA
Time Temp. S03~2
(min) pH (°C) (mmole/1)
0 	 — 0.
7020 7.38 50 0.317

Liquor
(mmole/1)
17.1
	
16.3
32.8
	
18.0
0.32
17.7
Solids
(vt%)
0.213
0.179
Final
Solids
(mrnole/ 1 )
6.63
	
0.03
	
	
6.85
6.09
0.73
Solids
(g)
1.216
1.022
 Ionic


Strength
0.0799
Residual
                                       COMPUTER RESULTS
                                        Relative  Saturation
Elertronrutr.-i1_i ty  	C nSO 3;VH?0   CnSO.. '2H20_




    -0.00208           1.127          0.82
                                                  •'.;!! ?_0




                                               C.37
Mol e   Fract io


cn  -2     cn -
oU 3       bUu





0.89     0.11
                                            COMMENTS


K-19  (0.947 g)  and K-20  (0.270  g) were mixed and used  in  these  equilibrium studies

with  grinding.


Initial  liquor  concentrations normalized  to final  sodium  and  chloride  concentrations.




                                             -247-

-------
RUN NO.  E*-6

DATE    1/21/76
           REACTOR MATERIAL BALANCE CALCULATION'S
           Run  I?   E*-6
         Date 1/21/76
        INLET
Ca+^
Mg+2
Naa+2
ci-1
TS
so3~2
SOiT2
(mmole )
(mmole )
(mmole )
(mmole )
(mmole )
(mmo 1 e )
(mmole)
Liquid

570 ml
                           9.35
 9.26
18.70
 9.26
                           9.26
             Solid
            1.21568 g
              8.46
              8.58
              7.16
              0.90
                                                             mmole
                                  17.81
                                                             9.26
                                                            18.70
                                                            17.84
                                                             7.16
                                  10.16
     OUTLET
<:
Na2+:
Cl'1
so3~:
SOiT:
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmo1e)
(mmole)
                         Liquid
            Solid
                           9.75
 9.26
18.70
10.26
 0.18
10.08
                                      1 n22 a.
              6.78
                                        0.03
              7.00
              6.22
              0.74
                                    mmole

                                  16.53
                                   9.29
                                                            18.70
                                                            17.26
                                                             6.40
                                                            10.82
                                      -248-

-------
                         SOLIDS MATERIAL BALANCE
                         Run //  E*-6      Date  1/21/76
                 g/mmole           mmole/grain               g/gram


 Ca+2             .040                6.63                   0.265
                  .024
 Na2+2            .046  '              0.03                   0.001
 Cl               .035

 C03~2            .060
 S03~2            .080                6.09                   0.487
 SO* 2            .096                0.73                   0.070
  H20             .009                6.82"                 0.061
                                                            0.884
*  Water concentration  is based on the hypothesis that the solid sulfate
   and sulfite  each  have one-half waters of hydration.
                                      -249-

-------
N NO.  E*-7

.TE    2/11/75
     Secies
       +2
     Ca
     Nat1
    Cl

    CO;

    Ts"

    SO;

    SO.
        1
        -2
        -2
        "2
               St amlards
              % Deviation)

                 -.1	

                 0
                   .3
                  1.0
                  1.0
                                  ANALYTICAL RESULTS
INITIAL
Liquid Solid
(mmole/1) (nmole/g)
0 7.58
0
0
0
FINAL
Liquor
(mmole/1)
1.16
0
.30
0

Solids
(mmole/cO
L>
7.55
—
.05
—
o
0 -
0 7.50
0 .08
1.00
.53
.47
7.20
7.41
.07
           Time
           (hr)

           0

          288
                     PH
                   7.51
                             Temp.
                              49.3
                                     OPERATING DATA
  S03~2
(ramole/1)
Solids
(wt%)
Solids
 (g)

.2.OOP
 1.586
 .onic
 irength

  .0032
                 Residual
                                      COMPUTER RESULTS
                                       Relative  Saturation
            Electroneutrality    CaS03'%H20   CaSO,'2lI20

                  . OQIQ             1.20 ...         nnQ


                                        COMMENTS

:aS03'%H20  seed  crystals added to boiled DI H20.
                                                                            Mole  Fraction
                                            .01
                                             -250-

-------
         E*-7
RUN NO.	
DATE      2/11/76
           REACTOR MATERIAL BALANCE CALCULATIONS
           Run  # E*-7
                           Date 2/11/76
        INLET
     Flow Rate
     Ca'
     Mg+2
     Na2+2
     ci-1
     Ts
     SO 3
     SO 4
-2
-2
(mmole )
(mmole)
(mmole)
(ramole)
(mmole)
(mmole)
(mmole)
                  Liquid

                   560 ml
                          Solid_
                         2.000 g

                        15.2
15.2
15.0
	.2
                                                            15.2
15.2
15.0
  .2
     OUTLET
Flow
+ 2

Mg 2
Na2+
Cl"1
TS
S03~
SOt*
Rate

(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
                  Liquid_

                   560 ml
                          0.65
                            .17
                            .56
                            .30
                            .26
                                      Solid
                                      1.59 g
                             12.0
                                .08
                             11.5
                             11.8
                                7TT
                                               12.7

                                                 T25"

                                               12.1
                                              T2TT~
                                       -251-

-------
                        SOLIDS MATERIAL BALANCH
                        Run # E//-7      Date  2/11/76
                g/mnole           mmole/gran               g/gram



Ca+2             .040                 7.55                   .302


Mg+2             .024                 —                     —
C03~2            .060
   +2
Na2              .046                  .05                   .002


Cl"1             .035                —                     —
S03~2            .080                 7.41                   .593
                 .096                  .067                  .006


%H20             .009                 7.47                   .067



                                                         Z  -970
                                    -252-

-------
                                 EQUILIBRIUM  RUN  7
74    J4IIM12.842                                             TEMPERATURE    48.3*8 OEG.  C.
                                   INPUT JHFCIE3
                    W2n   *  b.5;u«2»ot                HCL  « u.
                    C»n   t  nv»rvi-:i.t                C(j2  . ?ti,
                    •* G1   »  ;•, ? " »H' „
                                                     SU?  s 5.

                                                     103  « 4.

-ipFi-F£Mr
•4 <*
(C
««+
r.i^1^*
'Zss.j-*
'•asm
-* & *
"i'n.i-
» i .S Q A -
^-»»
S.T3 —
5 ' 1 - -
;~ P.V t-n T
C*fM'-)2(S)
ACijfcfliiS SOIJTION £f!iitL IH"I A
.<"1L4LIT'' »CTIVITy
3gA~tBjiA ^iiQa^aa
^•cUH" O»^:»»' — ("0
J^oj-13 3.5/t5-l!»
9.S9E-^5 H. 995-1*5
2.1^'J-itq !.977-ng
?..l?'?-«!4 *. 453-1*4
J.2V-r» i.^4^-^9
2,/;iH-.-M J.7.1Q-H4
b.71<*-n-i s. 723-^3
5.973-t4 S.SdS-^4
2<.£Q_in 'J^Tnlj
• J:f— I'7 ^,3/^-1^
l,4Ca-C>« t. VI 1 -t^C
3SC-«1
37S-ni
753-(»l
375-fl
H«l »<"/!
(»^ t *""
380. m
375-H1
37-i-^l
371-^1
745>-e>i
fidfl-tf 1
Vt SAT
^ 4 7 - 1 «;
            ri''-;1i';j          c-.-'PB               ».«!7«-?a           i.i9flto>ki
                              *•.»"«•               2.?4I-^7           9.213-33


                   6. J1S77-1!"  «Tl.


                                   .A»  itfcTfcU  r P.Oijgvj').?! K^b.


                                 ST^'eMFJT^  :  3.i5S77-.'1       9E3. E.N.  i    1,
                                            -253-

-------
'* NO.   E*-S
IE     2/11/76
    Species
    Ca
  + 2


  + 2
    Mg

    Nat1
Cl

CO;

Ts"

SO-
      '1
       ~2
       -2
       -2
                                 ANALYTICAL RESULTS
Standards
Deviation)
-.1
INITIAL
Liquid Solid
(mmole/1) (mnole/g)
9.5 7.58
FINAL
Liquor
(mmole/1)
11.4

Solids
(mmole/cO
LJ
7.44
0
-.8
.3
9.5
19
11.1
20.6
.06
—
—
1.0
—
1.0
9.5
7.50
9.5 .08
11.3
.322
11.0
7.02
7.30
.10
Time
(hr)


 0

288
                   7.08
                             Temp.
                          50
                                   OPERATING DATA
                              SO 3  2
                             (mmole/1)
                                 .322
Solids
(wt%)
                                                                Solids
                                                         2.000

                                                         1.592
Dnic
rcngth


 .0529
           Residual
                                    COMPUTER RESULTS
                                     Relative  Saturation
Electroneutrality    CaS03'%H20


     .0018             1.00
                                        .49
                                                          .22
                                                                      Mole  Fraction
                                                                      SO
                                                                         -2
                                                                                  -2
.99
                           .01
                                       COMMENTS
                                           -254-

-------
          E*-8
RUN NO.	

DATE     2/11/76
           REACTOR MATERIAL BALANCE CALCULATIONS
           Run 1t  E*-8
                            Date 2/11/76
         INLET
     Flow Rate
     Ca
     M
+2

 + 2
     Naa
     ci-1
     SO 3
 -2
 -2
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
                   Liquid

                    580 ml
                           5.51
 5.51
11.0
 5.51
                           5.51
                        _So.lid_

                        2.000 g

                        15.2
15.2
15.0
  .2
                                                             20.7
  5.5T
 11.0 ~
"20TT~
 15.0
  5.7
     OUTLET

     Flow Rate
                                      Solid
     Ca
     Mg
+ 2
'+2
     Na2
     Cl"
        + 2
     SO
 -2
 i
 -2
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
(mir.o 1 e)
(mmole)
                    S80 ml
                           6.61
 6.44
11.95
 6.55
  .19
 6.38
                         1.59  g

                                         .1
11.2
11.61
  .16
                                                18.4
  6.54
 11.95
 17.7
 11.8
  6.5
                                       -255-

-------
                        SOLTDS MATERIAL BALANCE







                        Run $  E//-8      Date   2/11/76







                g/mniole           mmole/gram                g/gram







Ca+2             .040                 7.44                    .298




Mg+2             .024

Na2+2            .046                  .06                    .003




Cl~!             .035                 —                      —




C03~2            .060
S03 2            .080                 7.30                    .584




SOT2            .096                  -10                    -010




%H20             .009                 7.40                    .067






                                                         E   -961
                                    -256-

-------
                                 EQUILIBRIUM  RUN  8
7 ft    1 41 I 9:I 4.3<
                                         SF*fCTES
CAT  « 1 , 1 <1 niV> •
^G^  • i*,?ay^'.i
                                                     C02
                                                     "203
                                                     S02
                                                     503
                                                              TEMPEPATUI'E     SB.ada  UEC.  C.
                                    SOLUTION fc(.UtLIh«JA
                                                                           Itlf'T
                             a.i! J-t?
                             6.377-^3
                            ^.»c 1-1 »•
                            J.SS^-c-5
                            5. !St -CS
            r A « ,-j •«
                             2. 178--»2
                             3.137-/9
            50 •« —
                             7.571--3
                                                I .97 1-P
                                            iCTJ«ITt P=)C')JCr
                                                1.S59-15
        "Ol.ECLiLA"  '-IATE9 « l.

      TC*-IC  STPfc^(;Tr « 5.29«
                                                                   4.P81-SM
                                                         KGS.

                                                            R£S. E..H.
                                       -257-

-------
N NO. E*-9
TE   2/11/76
                                  ANALYTICAL  RESULTS
                                      INITIAL
               Standards
    Species  (% Deviation)
                                                                     FINAL
      + 2
Ca
Ms
    Nat1
    cr1
    C03~:
    Ts~2
    S03~:
1.0
                  1.0
              Liquid
            (mmole/1)
               14
               419
               607
   130
                                130
                  Solid
                (mmole/g)
                  7.58
                              7.50
                               .08
       Liquor
      (mmoJe/l)
        16.6
       419
                                  607
                                  146
                                    3.23
                                  143
         Solids
        (mrnole/fO
           7.43
            .02
            .05
                       7.03
                       7.30
                        .06
                                    OPERATING DATA
          Time
          (hr)
         288
   PH
  7.20
           Temp.
49
            S03~2
           (mmole/1)
                                          3.23
Solids
(wt%)
Solids
 (g)
2.000
1.318
                                     COMPUTER RESULTS
onic
rength
1.09
           Residual         —
       Electroneutrality    CaS03-%H20
               -.03              1.27
                                      Relative   Saturation
                    .57
                                             .25
                                                        Mole  Fraction
                  S03
                  .99
                                                           -2
               SOu
                .01
                                                                    -2
                                       COMMENTS
                                           -258-

-------
RUN NO.   E*~9

DATE     -7 /i i
           REACTOR MATERIAL BALANCE CALCULATIONS
           Run //  E*-9
                     Date    2/11/76
         INLET
     Flow Rate
Ca+2
Mg+2
Na2+2
cr1
S03
S04
        ~2
        ~
(mmole)
(mmole)
(mraole)
(mmole)
(mmole)
(ramole)
(mmole)
            Liquid

             580 ml
  8.12
243.
                         352.
                          75.4
                          75.4
 Solid,

2.000 g

15.2



15.2
15.0
  .2
                                                           243.
                                   352
                                    90.4
                                    15.
                                    75.6
OUTLET

Flow Rate
+ 2
+ 2
Naa 2
Cl'1
Ts
S03 2
— 2
(mmole)
( mmo 1 e )
(mmole)
(mmole)
(mmole)
(mmole)
(mmole)
                          Liquid
                           85.
                            1.87
                           83. •
                        Solid
                                      q.si
                                       .07
             9.28
             9.64
              .08
                                               19.4
                                              243.	
                                              	.07
                                              352.	
                                               94.3
                                               11.5
                                               83.1
                                        -259-

-------
                        SOLIDS MATERIAL BALANCE
                        Run //  E#-9     Date   2/11/76
                g/mmole           mmole/gram               g/gram







Ca+2             .040                 7.43                    .297




Mg+2             .024                  .02                    .001




Na2+2            .046                  .05                    .002




Cl'1             .035
C03              .060
S03 2            .080                 7.30                   .584




S04~2            .096                  .06                   .006




%H20             .009                 7.36          °        -066
                                                             -'956
                                     -260-

-------
70    MI15M9.4A1
                    CA(]
            Pri
                         « a. -
                                  EQUILIBRIUM RUN 9
                                  INPUT  SPFCIES  c
                                                    HCL   •  6.07flOM-flt
                                                    C02   •  i
                                                                  -v3
                                                    302   •  3.
                                                    S03   •  1.
                                                                            49.4H» 0£G.  C.
                                    SOLUTION
                                                            ACTIVITY
H +
Hi3 2
«.«'i7-fB o7
2,t 5
2.^4^-?5 1
4<3^q.n3 s
. 1 31*01"
,«24-(M
.?! 1+^v
,^brt-Pl
.983-01
.3*16-01
.9»3-t»l
.21 l+'H
.211 •^^t'
,932-ni
,9»3-«l
.21 t+Oa)
.211 +^t"
,9S3-fl
,HJS-i?l
.345-!"t
,^4P-«I2
            ~tS')^ f S I          5> . ' 1.!
            :*so4isj          /j.p-»'i
1 .977-15
^.«4-a.^jj
1 .P/'-fS
•i.934-1 4
1.274*«ii«
?.71«-iM
5,540-03
                                                         
-------
N MO. E*-10
TE
2/11/76
                                  ANALYTICAL RESULTS
     Snccies
    Nat1
     Cl
     CO.
     Ts~
     S03
      -i
  -2
  -2
  -2
 Standards
i Deviation)
   -.1
                   .3
            1.0
                  1.0
                          Liquid
                        (mmolc/1)
                            18
                          487
                                636
187
                                187
     _I NITIAL	
                Solid
              (nimole/g)
                                                                      FINAL
                                                7.29
                                                 .05
                                           .04
6.99
6.06
1.08
                Liquor
              (mmole/1)
                 23.7
                479
                                                          654
                                                 197
                                                   3.61
                                                 193
                                                                              Solid
                                               6.86
                                                .08
                                                .07
6.53
5.80
1.05
                                    OPERATING DATA
Time Temp. SO 3
(hr) PH (°C) , (mmole/1)
0
Solids
(wt%)

288 7.11 48.9 3.61



                                                                     Solids
                                                                      .9383
                                                                      .4162
                                      COMPUTER RESULTS
 onic
 rength

   1.22
                Residual
                                       Relative  Saturation
       Electroneutrality     CaS03'%H20   CaSO,'2H20   CaSO., •J
                                             .98          .43
             -.042
                               1.78
                                                                           Mole  Fraction
                                           S03
                                           .85
                                                                         -2
                                    SOu
                                    .15
                                                                                        -2
                                        COMMENTS
                                            -262-

-------
RUN NO.   E*-10
DATE     2/11/76
           REACTOR MATERIAL BALANCE  CALCULATIONS
Run # E*-10
INLET

Flow Rate
Ca (mmole)
Mg+2 (mmole)
Na2+ (mmole)
Cl"1 (mmole)
TS (minole)
S0a~2 (mmole)
SO^'2 (mmole)
OUTLET
Flow Rate
Ca (mmole)
Mg 2 (mmole)
Na2 (mmole)
Cl"1 • (mmole)
TS (mmole)
S03~2 (mmole)
SCli, 2 Cmmnlp)
Date 2/11/76
Liquid
570 ml
10.3
278.
	
369.
107.
	
107.
Liquid
S70 ml
•n.si
273.
_— —
373.
11"*
7,06
iin.
Solid
0.938 g
6.84
.05
.04
	
6.56
5.68
1.01
Solid
0.416 g
2.85
	
.03
	
2.72
2.41
.44
                                                            17.1
                                                           278.
                                                              .04
                                                           369.
                                                           114.
                                                             5.68
                                                           108.
                                                            16.4
                                                           273.
                                                               .03
                                                           373.
                                                           116.
                                                             4.47
                                                            110.
                                      -263-

-------
                       SOLIDS  M-\TLRTAL BALANCE
                      Run  II  E//-10
      Date    2/11/76
              g/mmole_
mmole/graip.
g/gram
+2
Ca
Mg+2
+ 2
Na2
cr1
C03~2
so3~2
soT2
%H20
.040
.024

.046
.035
.060
.080
.096
.009
                                    6.86
                                     .08
                                     .07
                                    5.80
                                    1.05
                                    6.85
                           .274
                           .002
                           .003
                           .464
                           .101
                           .062
                                                           .906
                                   -264-

-------
                                       EQUILIBRIUM  RUN  10
93 HA» 76    1411311 a.74S
                                          INPUT SPECIES
                           »GO   •  4,
                           MA20  *  3,
                   Ph I  7.1
                                                            CQ2
                                                            302
                                                            sci3
                                                                                     48.9*3 OEG. C,
                   Si, <--
                                            SOLUTION  E.Ti.'
                                     6. ;
                                     1.312-B2
                                     O.J13-""
                                     ,).a7'i->>4
                                     5 . 1 1 « - f 7i
ACTIVITY    ACTIVITY  COEFFICIENT

7,7b1-to           1.194 + <7iv*
5.1 J9>-?5
8.2S5-f8

4.263-C3
7,«58-H«
-I. •< 5 "5 - 'i 4
6.3?«-TJ

1.07?-Ml
3.S2C-C5
3.C57.;'J
1 .OS-t-i

5.487-!'7
3.7bl-?l
                                                                          5.593-fI
                                        2. 353-31
                                        8.223-cit
                                        t ,?-37»»Ji
                                        I .237 + 33
                                                                          1 .237*!!^
                                                                          l.?J7»nn

                                                                          1.223-^1
                                                                          S.76t-H
                                                                          t .29^-^1
                                                             ?»ur)uCT
                                                                               SA|Hh»TTON
                   C 4 C • -1 ) 9 ( S )
                                                        1 .7J4.IS
                                                                          5.274-!f
                      .'M CS)
1 *  ATM.

 "OLECuUao

li'iIC ST9I-MGTH •
         *r,S.

            9ES. E.N.
                                                                                 -4.1S3-n2
                                                   -265-

-------
N NO. E*-ll

JE    2/11/76
     Species
   Ca

   Mg
      + 2
     Nat1
     c
     C0

     Ts

     S0
        1
       ~2
       -2
        -2
                                  ANALYTICAL  RESULTS
Standards
Deviation)
_ i
0
.8
.3

1.0
__
1.0
INITIAL
Liquid
(mrnolc/1)
18
487
—
636
—
187 .
—
187

Solid
(rnmole/g )
7.24
.04
.02
—
—
7.02
6.43
1.07
FINAL
Liquor
(mmole/l)
23.2
479
—
660
—
192
3.44
188

Solids
(mmole/g')
7.21
.05
.05
—
—
6.96
6.26
.92
Time
(hr)

  0

288
                      PH
                    7.13
                             Temp
                             48.7
                        OPERATING DATA


                              so3~2
                            (mmole/1)
                             3.55
Solids
(wt%)
                                                                    Solids
            2.010

            1.522
onic
rength

1.3-2
                Residual
                                      COMPUTER  RESULTS
                                       Relative   Saturation
Electroneutrality    CaS03-%H20   CaSOu'2H20   CaSO,,'

      -.038             1.72            .94         .41
                                        COMMENTS
                                                                           Mole  Fraction
                                                                           SO 3

                                                                           .87
                                                                              -2
                                                                          .13
                                            -266-

-------
RUN NO.
         E-ll
DATE    9/11/7A.
           REACTOR MATERIAL BALANCE CALCULATIONS
Run // E*-ll
INLET

Flow Rate
Ca+2 (mmole)
Mg+2 (mmole)
Naa (mmole)
Cl"1 (mmole)
TS (mmole)
SOs"2 (mmole)
S0i4~ (mmole)
OUTLET
Flow Rate
Ca (mmole)
Mg _? (mmole)
Naa (mmole)
Cl~: (mmole)
TS (mmole)
SOa"2 (mmole)
Sfh, fmmni rO
Liquid
570 ml
10.3
278.
	
362.
107.
	
107.
Liquid
570 ml
IV 77
273.

376.
109.
2.02
107.
Date 2/11/76
Solid
2.011 g
14.6
.08
.04
	
14.1
12.9
2.2
Solid
1.52 g
11.0
__« —
0.08
	
10.6
9.52
1.4
                                                             24.9
                                                           T78~:
                                                               .04
                                                            362.	
                                                            121.	
                                                             12.9
                                                            109.
                                                             24.2
                                                            273.	
                                                           	0.08
                                                            376.	
                                                            120.	
                                                             11.5
                                                            108.
                                      -267-

-------
                         SOLTDS  MATERIAL RALANC"




                         Run  /•  E//-11     Date  2/11/76




                 g/inrr.ole            mmole/gram               g/gram




Ca+2              .040                 7.21                   .288
Cl                .035
C03               .060
'2'
                                      -268-
Mg+2              .024                  .05                   .001
Na2+2             .046                  .05                   .002
S03 2  '           .080                 6.26                   .501
  4 2             .096                   .92                   .088
%H20              .009                 7.18                   .065
                                                             .945
                                                          Z 	

-------
                       EQUILIBRIUM  RUN  11
                      INPUT SHFCTtS


             » J.JS1S2*.'!
                                        MCL
                                        en?
                                        N203
                                        M2nj
                                        502
                                        S()3
J.bS.t<»i»-u3
1. a f t n -f - ft i
                                                                48.7»9 OEG. C,
           r T jv, n_| J .
                    iL r i v
                                 1-nulL T''-» J 4
                                                4 C T I « I T Y  CnEfFtt:t£^T
•*?* H
^4*1
r«4.»
C.-- +
C 4 ': • > -1
CiS'J-l
•(;++
"'J''K-»
v t ^ J
"Is^tM
"'n-
TL-
S'l,^--
« . 4--
n-Pn^evr
J. 537-1^ 4.4.. 4-l,i
7.9'il-i'S 4,7^^-f5
1./87-.'? 4 .?-.,, l.nj
y,/)^^.,'^ 7.?!'-11-!
3. l^>i-« A 3JQ1 l-C"4
4.377— .'3 S.?JO.,-!i
3.50^-^1 l.«"«-ri
4.5a?-'3 3, 7St!-''b
2,^l/-v'! 3,*l'-"3
1.134-v-l 1.4/.4->-l
b. 134-^7 5.711-07
S .5s I- ' 1 3, 7S4-P I
2.154-.-4 2.7rjq.?b
^,.i
-------
N NO. E*-12
TE    2/11/76
    Snocies
    r
    Ca
    f!C
    Naa 1
c
C0
Ts
S0
        1
        ~2
Standards
 Deviation)

 -.1
                  .3
                 1.0
                 1.0
                                  ANALYTICAL RESULTS
                                      INITIAL
                            Liquid
                         (mmole/1)
                             18
                            487
                                636
                                187
                            187
                   Solid
                 (rnrnole/g)
                   7.24
                    .04
                    .02
                   7.02
                   6.43
                   1.07
                                                                 FINAL
                                 Liquor
                                (mir.ole/1)
                                  23.1
                                 482
                                                           655
                                 198
                                   3.59
                                 194
                     Solids
                    (minole/g)
                       7.11
                        .04
                        .05
                      698
                       6.32
                        .94
                                    OPERATING  DATA
          Time
          (hr)

            0
          288
                 PH
                6.95
Temp.
(°0
50
48
                                              ~2
            S03
           (mmole/1)
             3.59
Solids
(wt%)
                                                                 Solids
                                                                 2.000
                                                                 1.510
                                      COMPUTER  RESULTS
 onic           Residual
 rcngth     Electroneutrality

 1.22              --040
                                       Relative  Saturation
    CaSOr%H20   CaSO<,-2H20
        1.70          .96
                                                           .41
                                                                       Mole  Fraction
                                                                       SO
                                                                          -2
                                                      SOu
                                                                                   -2
                                             .87
                                        COMMENTS
                                             -270-

-------
RUN N0._

DATE
E*-12
2/11/76
           REACTOR MATERIAL BALANCE CALCULATIONS
Run # E*-12
INLET

Flow Rate
Ca+2 (mmole)
Mg+2 (mmole)
Naa (mmole)
Cl"1 (mmole)
TS (mmole)
S03~2 (mmole)
S0i4~ (mmole)
OUTLET
Flow Rate
Ca (mmole)
Mg (mmole)
Naa (mmole)
Cl"1 (mmole)
TS (mmole)
S03~2 (mmole)
SO i, ("rnrnn IP)
Liquid
570 ml
10.3
278.
	
362.
107.
	
107.
Liquid
57D ml
•n.?
275.
— ,___
173.
113.
205.
111.
Date 2/11/76
Solid
2.000 g
14.5
.08
.04
	
14.0
12.9
2.1
Solid
1 . 51 g
10.7
__— _ —
.08
— — _-
10.53
9.54
1.42
                                                            24.8
                                                           278.	
                                                           	.04
                                                           362.	
                                                           121.	
                                                            12.9
                                                           109.
                                                            23.9
                                                           275.	
                                                           	.08
                                                           373.	
                                                           124.
                                                            11.6
                                                           112.
                                      -271-

-------
                        SOLIDS KATCRTAL  BALANCE
                        Run //  E//-12     Date   2/11/76
                g/rumple           mmole/gram                g/gram






Ca+2             .040                 7.11                   .284
Cl"1             .035
C03              .060
                                     -272-
Mg+2             .024                  .04                   .001
Na2              .046                  .05                   .002
S03 2            .080                 6.32                   .506
SOT2            .096                  .94                   .090
%H20             .009                 7.26                   .065

-------
                                          EQUILIBRIUM RUN 12
H3
       75
                                                                     T€HPE<»ATUDfc
                                                SPECIES c-nt.es)
                                                            HCL
                                                                                            DEC, C.
                   PM s  8.35"!
                                                            SCi?
                                                            S03
                                    *UUfef".iS  SOLUTION E"UILToRI4

                                     •""LiLtTY            ACTIVITY
«•*•
-^:
CA + *
CAS" <
^**
XG1' r (
" G 5 w •'.
n^-
CL-
S 0 J - -
snt —
^.3?5-v.A
1.413-^7
U/7?-M
3iltn-' 4
a:'?i^i
?. 932-3 3
1.172-.U
b.Pi4-«;7
O.S12-J1
2 . 1 S 4 - ,) 4
7.374-.1?
1 .122-1-7
1 . 1 63-.T7
4.17^-13
iiiis^i
?'36^'/5
3 ."5 1 *-'*3
1 .431-"!
4.?3!-.^7
3,'7bS-:n
2 .79^-?5
5, 14^.13
                                                                   U.dflvtOtl
                                                                    ACTIVITY COEFFICIENT

                                                                           1 . 1 95+^n
                                                                           O.p^c.at
                                                                           » .JjS*1!'
                                                                           5.0J<5-<* I
                                                                           8.231-1" I

                                                                           9..350-"!
                                                                           8.7Jl-'l
                                                                           1 . JJB».1,1
                                                                           1 .?,}«»<' I"
                                                                          7,540-'';)
                                                    4CTIVITT
                   " 5 ' L' L") 2 15 J
                                  IO"IC
                                                        7.544-16
                                                        1 .136-117
2.1 74-in
t ,fi99»:»n
9.^75-C!
2.?41-"3
4.735-v1?
                                                 -273-

-------
                 APPENDIX F

INFRARED SPECTRA OF PRECIPITATED SOLIDS FROM
     LABORATORY AND PILOT PLANT STUDIES
              Prepared by:

            Benjamin F.  Jones
            Frank B. Meserole
                    -274-

-------
                       TABLE OF CONTENTS
                                                          Page
1.0       INTRODUCTION	    276

2.0       QUALITATIVE APPLICATION OF INFRARED
          SPECTRAL ANALYSIS	    277

3.0       QUANTITATIVE APPLICATION OF INFRARED
          SPECTRAL ANALYSIS  	    281

          INFRARED SPECTRA
                               -275-

-------
1.0       INTRODUCTION

          Infrared spectroscopy has been applied to both the
qualitative identification and quantitative determination of the
calcium sulfite-sulfate solid solution.   Infrared spectral analysis
has been performed on selected solids precipitated in the equi-
librium runs and the kinetic runs.  Pure phase calcium sulfite hemi-
hydrate, calcium sulfate dihydrate, calcium carbonate, and dolo-
mite have been analyzed by infrared spectroscopy for reference
purposes.  In addition, actual pilot plant scrubber samples from
the EPA scrubber at Research Triangle Park, North Carolina, and
the Radian/Joy/PP&L scrubber at Sunbury, Pennsylvania have been
analyzed by IR spectroscopy.
                               -276-

-------
2.0       QUALITATIVE APPLICATION OF INFRARED SPECTRAL ANALYSIS

          Infrared spectroscopy was successfully used to confirm
the presence of sulfate in the calcium sulfite solids.   The
infrared absorption due to the sulfate ion showed that the
incorporation occurred by the substitution of a sulfate ion for
a sulfite ion in the crystal lattice.   The vibrational spectral
structure of any pure phase sulfate compound such as 03504*21120
in the 1100 cm"1 region is characteristically broad with little
or no resolution of the three component bands.   In case of the
matrix isolation as occurs in a solid solution, the peak positions
shift and a greater degree of resolution can be observed.  Solids
identified as containing sulfate by chemical analysis and spectro-
scopically appeared to be solid solutions were analyzed by X-ray
diffraction and differential scanning calorimetry.  Both techniques
failed to show the presence of a pure phase sulfate compound,
specifically indicating that no gypsum was present.

          For comparative purposes, the IR spectra of pure calcium
sulfite hemihydrate and calcium sulfate dihydrate are shown in
Figure 2-1.  The absorption structures of interest are the major
sulfite band at approximately 980 cm"1 and the sulfate band near
1130 cm'1.  The structure in the 3200-3600 cm"1 and 1600-1700  cm"1
ranges are a result of the waters of hydration of the two solids.
The absorption bands in the 600-700 cm J region are due to the
sulfite and sulfate ions but are not as distinctive as the major
bands.

          The infrared spectra of two solid samples from the
experimental precipitaiton studies are shown in Figure 2-2.  The
upper spectrum is that of the solids precipitated from a solution
supersaturated in calcium sulfite hemihydrate and subsaturated
                               -277-

-------
                                                \r\
•4C C C
        20 « n
        w >J vj
                                                     .000
       FIGURE  2-1.
INFRARED S?ECTH--i.  OF  PURE CALCIUM SULFI^E
KEMIHYDRATE AND CALCIUM SULFATE DIHYDRAT1
                                  -278-

-------
•z.
a

CO
to
                         SOLID SOLUTlOSi
C

1-
LJ

O

C

LJ

C_
                            Solid  Solucior. -r


                                    2
                o
                r-.
                                                    Gypsun

                                                    Masked Macrix

                                                   Isolated Sulface

                                                   1120 ar.d 1140
   o
   •x
     -4000
                                     2000
1000
                                    FREQUENCY  (C.V.*1)
                   FIGURE 2-2.   INFILLED SPECTRA OF  REACTOR PRODUCTS



                                           -279-

-------
with respect to calcium sulfate dihydrate.   The band structure
encircled is indicative of the IR absorption due to matrix
isolated sulfate ion.

          The lower spectrum is that of the solids precipitated
from a solution supersaturated in both calcium sulfite hemihydrate
and calcium sulfate dihydrate.  In this case, the structure in
the sulfate sorption region shows the presence of sulfate as both
pure phase gypsum and in solid solution with calcium sulfite
hemihydrate.  The presence of gypsum was verified using X-ray
diffractions and DSC analyses.

          The following is a simplified explanation of the spectral
differences of the sulfate ion in a pure phase crystal or in solid
solution with another compound.  In the^first place, the absorp-
tion of electromagnetic radiation in this spectral region results
from a coupling of the incident radiation with the vibrational
modes of the sulfate ion.  Quantum theory predicts three different
frequencies.  In the case of a pure phase sulfate compound, the
frequency range of these vibrations is broadened due to the
interaction or coupling of the vibrational modes of neighboring
sulfate ions.  The matrix isolation of sulfate ions in the solid
solution effectively dilutes the sulfate ions as compared to a
pure phase system and thus reduces the coupling effect.  The
frequency shifts and narrowing of the bands are a direct result
of the decoupling of the intermolecular interaction of the
sulfate ion vibrational modes.

          Thus, the combination of these instrumental techniques
has been used to verify the existence of the coprecipitation of
sulfate with calcium sulfite as a solid solution.  In addition,
it was demonstrated that the IR spectroscopy can be used to
distinguish between the sulfate in a solid solution or as gypsum.
                               -280-

-------
3.0       QUANTITATIVE APPLICATION OF INFRARED SPECTRAL ANALYSIS

          Infrared analysis was also used to quantitatively
measure the sulfate concentration in the solid solution.  The
technique was initially calibrated by comparison of the ratio
of the sulfate absorbance at 1220 cm"1 to that of the water band
at 1620 cm  1 with sulfate concentrations determined by the
specific chemical method.  In the absence of gypsum, the following
equation is used to calculate mole fraction of sulfate, xqn -2
                                                         o U i^
in a solid from the infrared sorption measurements:
                 -,
                  2
                                              T.
                                                  so
•u
*- N no  2
                     2 a
                       •-j _ i i     i_i _ 11
                                          (log =ii) H20
                                               m
where,
          CgQ -2 = the concentration of sulfate in the solids
                   (mole SCU~2/g sample),

             Cm  = the concentration of sulfate plus sulfite in
               3   the solids (mole SCU~2 + S03"2/g sample),

            CTT Q = concentration of the hydration water in  the
                   solids (mole H20/g sample),

               k = a constant,

             -2  - the IR absorbance at 1220 cm 1,

             LT Q = the IR absorbance at 1620 cm 1, and
                               -281-

-------
       Tv/T  = the ratio of the percent transmission values at
        b'  m                    *
               the base line and transmission minimum for the
               appropriate band.

          The correlation of the spectral and chemical results
are shown graphically in Figure 2-3.  The accuracy limits at the
95% confidence level is ±.02 in the sulfate mole fraction based
on a linear least square fit to the data.
                               -282-

-------
                                                    j- <
                                                    < -.
                                                    < '-J
                                                    — 2
                                                    t: <
                                                    C-t

                                                    P  C

                                                    <  o
                                                    < Zl


                                                    5 P
                                                       2
                                                    VI C
                                                    -  ;—
                                                    :a u
                                                    IT. <
                                                    CO
                                                     I
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            APPENDIX G

DIFFERENTIAL SCANNING CALORIMETRY
 PATTERNS OF PRECIPITATED SOLIDS
                 -367-

-------
1.0       DESCRIPTION OF DIFFERENTIAL SCANNING
          CALORIMETRY PATTERNS

          Two instrumental techniques based on the thermal proper-
ties of solids were utilized in characterizing the calcium sulfite-
sulfate solid solution.  Thermogravimetric analysis (TGA) was
utilized to determine the weight change upon loss of water as the
temperature is raised past the dehydration temperature.  Both the
weight loss and the temperature of dehydration are useful to
characterize the solids.

          Differential scanning calorimetry was also used to
characterize the precipitated solids by monitoring the enthalpy
change as a function of temperature.  Phase changes, marked by
rapid changes in the heat capacity, were observed in the temper-
ature ranges of 120-140°C for gypsum and 350-430°C for calcium
sulfite hemihydrate and the solid solutions.  These changes
represented by dips in the scans are associated with the loss of
waters of hydration.  If gypsum is not present in the solids, no
enthalpy change will be observed at 120-140°C.

          Three distinct patterns have been observed in the
350-430°C range which result from the dehydration of CaS03'%H20
and solid solution.  These include an endothermic reaction at
410°C, and a complex endothermic reaction in the range of 350-
400°C.  Possible explanations for the three different patterns
include a different crystal structure of the calcium sulfite
hemihydrate resulting from impurities, such as sulfate, in the
crystal and/or particle size.  X-ray powder diffraction patterns
have identified only one crystalline structure of calcium sulfite
hemihydrate.  This pattern is consistent with literature values
(TE-055) and standards prepared in the laboratory.  The complex
                              -368-

-------
endothermic reactions between 350-400°C were observed only in
runs utilizing the grinder in line.  This is a strong indication
that particle size may have an effect on the temperature
of dehydration of the calcium sulfite hemihydrate during analysis
of DSC.

          Actual scans of precipitated solids and standards by
differential scanning calorimetry are presented in the remainder
of this appendix.  Two levels of sensitivity have been employed.
Unless stated otherwise,  the less sensitive scanning level is at
0.5 meal/second, and the more sensitive scanning level" is at 0.2
meal/sec.  In each run the less sensitive scan is the upper and
the more sensitive scan is the lower one.
                             -369-

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DIFFERENTIAL SCANNING CALORIMETRY
 PATTERNS OF PRECIPITATED SOLIDS
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TECHNICAL REPORT DATA
(Please read hinnicnons on the reverse before completing)
\. REPORT NO. 2.
EPA-600/2-76-273b
4. TITLE AND SUBTITLE
Experimental and Theoretical Studies of Solid Solution
Formation in Lime and Limestone SO2 Scrubbers --
Volume II. Appendices
7-AUTHOR(S) Benjamin F. Jones, Philip S. Lowell, and
Frank B. Meserole
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Boulevard
Axistin, Texas 78766
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESS ION- NO.
5. REPORT DATE
October 1976
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
EHE624
11. CONTRACT/GRANT NO.
68-02-1883
13. TYPE OF REPORT AND PERIOD COVERED
Final; Through May 1976
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES iERL_RTp project Officer for this report is R.H. Borgwardt,
919/549-8411 Ext 2234, Mail Drop 65.
is. ABSTRACT
                     gives results of a theoretical and experimental study to charac-
 terize the coprecipitation of calcium sulfate with calcium sulfite hemihydrate.  A
 coprecipitation product had been suggested to explain the mechanism by which  sulfate
 could be precipitated from a scrubber solution subsaturated with respect to calcium
 sulfate.  Lime and limestone SO2 scrubbing systems with oxidation rates below 20%
 had been operated long-term  at steady state with liquors subsaturated with respect to
 all known calcium sulfate solid forms and yet sulfate was measured in the solids.
 The existence of a calcium sulfate /calcium sulfite solid solution has been confirmed
 experimentally and a theoretical formulation has been established. Calcium sulfite
 hemihydrate was  precipitated under  controlled laboratory conditions from solutions
 subsaturated in calcium sulfate. Specific chemical analysis and infrared spectroscopir
 techniques were used to identify sulfate in the solids. The precipitate's sulfate conten
 was studied as a function of the relative saturation of calcium sulfate and the precip-
 itation rate of calcium sulfite hemihydrate. Also, the effects of high magnesium con-
centrations and limestone dissolution on the sulfate content of the solids were
measured.
17. KEY WORDS AND DOCUMENT AN ALYSIS
a. DESCRIPTORS
Air Pollution
Calcium Oxides
Limestone
Flue Gases
Scrubbers
Sulfur Dioxide
13. DISTRIBUTION STATEMENT
Unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Stationary Sources
19. SECURITY CLASS 1 This Report)
Unclassified
20 SECURITY CLASS (Tins page)
Unclassified
c. COSATi Field/Group
13B
07B
08G
21B
07A
21. NO. OF PAGES
419
22. PRICE
EPA Form 2220-1 (9-73)
                                      -414-

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