EPA-600/2-77-0230
 February 1977                             Environmental Protection Technology  Series

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                RESEARCH REPORTING SERIES

Research reports of the Off ice 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.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                            EPA-600/2-77-023o
                                            February 1977
         INDUSTRIAL PROCESS PROFILES

            FOR ENVIRONMENTAL USE

                  CHAPTER 15

    BRINE AND EVAPORITE CHEMICALS INDUSTRY
                      by

P. E. Muehlberg, B. P. Shepherd, J. T. Redding,
              and H. C. Behrens
                 Dow Chemical
            Freeport, Texas  77541

                Terry Parsons
              Radian Corporation
             Austin, Texas  78766
           Contract No. 68-02-1319
               Project Officer
               Alfred B. Craig
   Metals and Inorganic Chemicals Branch
Industrial Environmental Research Laboratory
             Cincinnati, Ohio  45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI, OHIO  45268

             •7 «r*.; .  j~^ ~

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                                 DISCLAIMER
       This report has been reviewed by the Industrial Environmental Research
Laboratory - Cincinnati, U.S. Environmental Protection Agency, and approved
for publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorsement
or reconmendation for use.

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                         TABLE OF CONTENTS
                            CHAPTER 15
                                                                Page
INDUSTRY DESCRIPTION	     1
     Raw Materials	     2
     Products	     3
     Companies	     4
     Environmental Impact	     5
     Bibliography	     6

INDUSTRY ANALYSIS	     7
     Brine and Evaporite Chemicals Industry Processes	     8
     Borax and Boric Acid Segment Processes	    11
     Chlorine-Caustic Segment Processes	    12
     Lithium Chemicals Segment Processes	    13
     Magnesium Metal Segment Processes	    14
     Potash Segment Processes	    15
     Sodium Metal Segment Processes	    16

Process Descriptions
     Process No. 1. Screening/Chlorination	    39
     Process No. 2 . Bicarbonate Removal	    41
     Process No . 3 . Solution Mining	    43
     Process No. 4. Shaft Mining	    45
     Process No. 5 . Open-Pit Mining	    48
     Process No . 6 . Coarse Crushing	    50
     Process No. 7. Settling/Filtration	    52
     Process No. 8. Carbonation/Filtration	    54
     Process No. 9. Solidification	    61
     Process No. 10. Evaporation/Solidification	    66
     Process No. 11. Drying	    92
     Process No. 12. Drying/Calcination	   108
     Process No. 13 . Solar Evaporation	   113
     Process No. 14. Washing/Draining	   123
     Process No. 15 . Froth Flotation	   125

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              TABLE OF CONTENTS (Continued)
                       CHAPTER 15
Process No.  16.  Filtration	 130
Process No.  17.  Liquid-Liquid Extraction	 135
Process No.  18 .  Stripping	 137
Process No.  19.  Dissolution  (Salt Cavern)	 139
Process No.  20.  Crystallization/Filtration	 140
Process No.  21.  Brine Desulfurization	 143
Process No.  22.  Acidification	 144
Process No.  23.  -Chlorination/Stripping	 146
Process No.  24.  Gravity Separation	 149
Process No.  25.  Spent Brine Neutralization	 151
Process No.  26.  Distillation	 154
Process No.  27.  Iodine Stripping	 156
Process No.  28 .  Iodine Absorption	 158
Process No.  29.  Iodine Reduction	 160
Process No.  30.  Iodine Oxidation	 162
Process No.  31.  Iodine Finishing	 164
Process No.  32.  Digestion	 166
Process No.  33.  Lithium Carbonate Separation	 168
Process No.  34.  Clarifying	 171
Process No.  35.  Dissolution/Clarifying	 173
Process No .  36.  Carbonation	 178
Process No.  37.  Absorption	 180
Process No.  38.  Calcination/Slaking	 183
Process No. 39. Ammonia Regeneration	186
Process No. 40. Dechlorination	189
Process No. 41.  Mercury Cell Electrolysis	191
Process No. 42. Diaphragm  Cell  Electrolysis	193
Process No. 43. Sodium Amalgam  Decomposition	195
Process No. 44. Cooling/Compression	197
Process No . 45 . Liquefaction	199
Process No. 46 . Crushing/Grinding	201
                          IV

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     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
     Process  No.
  TABLE OF CONTENTS (Continued)
           CHAPTER 15
                                               Page
47 .  Leaching/Clarifying	 205
48 .  Calcination	 209
49 .  Fusion/Grinding	 211
50.  Tabling	 214
51.  Wet Grinding	 216
52 .  Debrining	 218
53 .  Sulfur Combustion	 219
54.  Leaching	 221
55 .  Hargreaves Process	 223
56 .  Neutralization	 225
57 .  Evaporation/Filtration	 227
58.  Electrolysis	 229
59.  Hydrochloric Acid Formation	 232
60.  Fusion	 233
61 .  Filtration/Crystallization	 234
62 .  Calcination/Grinding	 235
63.  Digestion	 239
64.  Leaching/Filtration/Evaporation	 241
65 .  Dissolution	 244
66.  Electrolytic Chlorate Production	 246
67. Sodium Chlorate Drying
248
Appendix A - Raw Material List	 251

Appendix B - Product List	 257
Appendix C - Company/Product List	 261

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                       LIST OF FIGURES
                          CHAPTER 15

Figure                                                      Page
  1       Sample Process Description Format,  j  	      9

  2       Chemical Tree - Brine and Evaporite Chemicals
            Industry	     10

  3       Principal Raw Material Sources 	     17

  4       Magnesium Chemicals from Brines	     18

  5       Sodium Chloride and Bitterns from Seawater ...     19

  6       Chemicals from Great Salt Lake	     20

  7       Chemicals from Searles Lake, Upper Level ....     21

  8       Chemicals from Searles Lake, Lower Level ....     22

  9       Chemicals from Bristol Lake, Salduro Marsh and
            Texas Brines	      23

 10       Bromine Recovery from Various Brines 	      24

 11       Chemicals from Michigan Brines 	      25

 12       Iodine Recovery  from Michigan Brines 	      26

 13       Lithium Carbonate  from Two  Different Brine
            Sources	     27

 14       Solvay Soda  Ash  and Sodium  Bicarbonate	     28

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                  LIST OF FIGURES (Continued)
                          CHAPTER 15

Figure                                                     Page

 15      Chlorine and Caustic Soda Via Electrolysis. .  .      29

 16      Borax, Boric Acid, and Colemanite from
           Evaporites	      30

 17      Potassium Chloride from Sylvinite 	      31

 18      Potassium Sulfate from Langbeinite and Sylvite.      32

 19      Soda Ash from Trona	      33

 20      Magnesium and Chlorine Via MgCl2 Electrolysis .      34

 21      Sodium Metal Via Downs Cell	      35

 22      Lithium Chloride, Sodium Iodide and Sodium
           Bromide	      36

 23      Sodium Chlorate Via  Electrolysis	      37

 24      Lithium Values  from  Spodumene  	      38
                              vn

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                        LIST OF TABLES
                          CHAPTER 15

Table                                                      Page
 1       Utilities Consumed by Various Applications of
           Process 9	   64

 2       Function of Various Applications of Process 10  .   68

 3       Input Materials to Various Applications of
           Process 10	   72

 4       Utilities Consumed in Various Applications
           of Process  10	   79

 5       Waste Streams  Resulting  from Various Applications
           of Process  10	   83

 6       Function and  Input Materials for Applications
           of Process  11	   94

 7       Operating Parameters  and Utilities  for
           Applications of  Process 11	    98

 C-l      Company/Product List	   262
                               vm

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                       ACKNOWLEDGEMENTS
This catalog entry was prepared for EPA by Dow Chemical U.S.A.,
Texas Division,  under Contract No.  68-02-1329, Task 7.   The
contributions of P. E. Muehlberg,  B.  P. Shepherd,  J.  T. Reding,
and H. C. Behrens in preparing this report are gratefully
acknowledged.

Helpful review comemnts from C. Fred Gurnham and Alan D.  Randolph
were received and incorporated into this chapter.

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            BRINE AND EVAPORITE CHEMICALS INDUSTRY
INDUSTRY DESCRIPTION

The Brine and Evaporite Chemicals Industry encompasses all
first-level Inorganic compounds derived from subterranean
brines, from existing or historic salt lakes, and from sea-
water.  Additionally, certain second-level inorganic com-
pounds derived from these sources are included in the
industry when produced in the same facility as the parent
compound.

Within the industry thus defined, six industry segments are
recognized.  These have been assigned the following titles:

    •Borax and Boric Acid
    •Chlorine-Caustic
    •Lithium Chemicals
    •Magnesium Metal
    •Potash
    •Sodium Metal

A wide diversity of both raw materials and products, in types
of operations, and in individual process parameters  is
characteristic of the industry.  This fact and the existence
of many recycle streams result in an apparent complexity of
flow diagrams.  The latter are shown on 22 individual flow-
sheets, many of them interrelated through flows of inter-
mediate products.

The 78 identified end products of the industry were produced
in a total of 280 separate facilities (1972) from 21 raw
materials.

The size  of a single facility varies from an estimated half-
dozen employees recovering salt or calcium chloride brine at
Bristol Lake, California, to between 1,500 and 2,000
employees engaged in processing bedded salt and subterranean
brine to  chlorine, caustic, bromine, and compounds of
magnesium and calcium.  In the former example, the equipment
involved  might be valued at a few hundred thousand dollars,
while the total fixed investment in the latter instance
might reach one-quarter billion dollars.

Total employment in the industry is estimated here to lie
somewhere between 70,000 and 120,000 persons during the
present biennium.  A more precise estimate is prevented by
the undifferentiated employment statistics for single
facilities conducting operations in two or more industries.

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The combined dry-basis weight of all products leaving the
industry during 1972 approximated 55 million metric tons.
This amount of net industry product was produced from an
estimated 90 million metric tons of mined, dry raw materials
(evaporites) plus 300 million cubic meters of seawater,
subterranean brines, and salt lake brines.

The industry is distinctly raw material oriented.  With few
exceptions, production facilities are located close to raw
material sources.  Exceptions are the facilities for up-
grading certain crude intermediate materials into end-
products and the cases of prior existence of a center of
population near a recent raw materials find.

The average growth rate for the entire industry during the
past five years has been about two percent per year.  The
chlorine-caustic segment individually experienced a growth
rate of nearly 10 percent during the same period.

The need for process steam and the energy-intensive character
of the chlorine-caustic, magnesium metal, and sodium metal
segments account for the relatively high proportion of on-
site power generation within the industry.  About thirty
(estimated here) industry plants generate a major portion of
their electrical energy requirements.  These plants are
usually either multi-product facilities or are located in
relatively sparsely populated regions.  Searles Lake, and
Boron, California, and Green River, Wyoming, are examples of
the latter.

Raw Materials

Industry raw materials are typically unmined ores in place,
unproduced brines in subterranean reservoirs or in  lakes,
and seawater.  Generally, industry companies control their
raw materials, either by fee ownership, lease, or royalty
payment.  Limestone, sulfuric acid, and sulfur are  the only
raw materials  supplied from  sources outside  the industry.
In most situations,  notably  in  the  case of  rock  salt,  a
considerable portion of the  mined material  is sold  directly
by the producing  company for consumption  both inside and
outside the industry.

A  total of  21  distinct industry  raw materials are included
in the general categories mentioned above.   A complete  list
of these,  along  with  their compositions,  is  given in
Appendix A.

With  three  exceptions  all  the raw materials  are  considered
nontoxic.   Sulfuric  acid  is both  toxic and corrosive.
Kernite and native  borax are moderately toxic.

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Pour general types of adverse environmental impact  occur in
producing the raw materials:

    •Fugitive atmospheric emissions of particulates (dusting)
     in open-pit mining.
    •Creation of tailings piles, mounds of stripped over-
     burden, and "cratered" landscapes in both shaft mining
     and open-pit mining operations.
    •Disposal of spent brines, bitterns, and other  waste
     liquors.
    •Inadvertent leaks and spills of liquid raw materials,
     as in cases of pipeline ruptures.

Products

Approximately 45 percent of the combined gross tonnage of
all industry end products is consumed by the industry itself
in producing other industry end products.  ("The chemical
industry feeds on itself.")  About the same fraction of the
total combined tonnage of end products leaving the  industry
is consumed by other chemical industries.  The most notable
specific example of this situation is the 24 million metric
tons of salt (NaCl) used by the Industry for producing
chlorine, caustic soda^ and soda ash, out of the total gross
salt production (1972) of 40 million metric tons.

Annual net production varies widely among the 78 industry
products.  The five products listed below accounted for about
90 percent (estimated) of the combined tonnage of all pro-
ducts leaving the industry during 1972.  Tonnages leaving the
industry are expressed in (estimated) millions of metric
tons per year on a dry-weight basis.

    •Salt, all forms                16
    •Caustic soda, all forms        10
    •Chlorine, gas and liquefied     9
    •Soda ash, Solvay and natural    7
    •Potash, total weight            4

The combined annual net production of the five products
listed below accounted for less than 0.1 percent of the com-
bined tonnage of all products leaving the industry during
1972.

    •Lithium nitrate
    •Lithium oxide
    •Lithium peroxide
    •Lithium iodide
    •Iodine

Except for potash and some of the  individual small-production
lithium  compounds, all of the industry  end products have a

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wide spectrum of uses outside the industry.   The largest
single tonnage use (or use category)  outside the industry
for ten industry end products is given below.   Numbers  are
estimates in millions of metric tons  per year for the period
1972 through 197^.

    •Salt                   8       Highway use
    •Chlorine               6       Chlorinated organics
    •Potash chemicals       4       Fertilizers
    •Soda ash               3       Glass
    •Caustic soda           1       Pulp and paper
    •Sodium sulfate         0.8     Kraft paper
    •Magnesium hydroxide    0.6     Refractories
    •Bromine                0.3     Motor fuel antiknock
    •Calcium chloride       0.3     Highway use
    •Borax                  0.2     Glass and ceramics

The myriad of other uses for industry end products range from
medlcinals through detergents to cattle feed and vary from a
few hundred kilograms to several million metric tons per year.

A complete list of industry end products is shown in
Appendix B.

Companies

The industry included a total of 140 companies during 1972.
The companies differ widely from aspects of total size,  total
number of industry products manufactured, degree of partici-
pation in nonindustry production, and total tonnage produced.
There are also  considerable differences In the number of
companies producing  any one Industry product.

Extremes in total size are represented by a company recover-
ing calcium chloride  from Bristol Lake in California with an
estimated total of a  dozen employees to multiindustry, multi-
facility organizations exemplified by Allied Chemical
Corporation or  Dow Chemical U.S.A., each with more than  twen-
ty thousand employees and each  with greater than five thousand
persons  working Inside the industry.

Considerably more than one-half of the industry companies
make  at  least two Industry end  products.  Dow Chemical U.S.A.,
Poote Mineral Company, and Lithium Corporation  of America
each  produce more than 15 Industry end products.  Several
dozen  companies,  notably  the producers of salt., produce  but
a  single  industry product.   Several dozen other companies also
produce  end products  belonging  to other  industries.

Total combined  annual net tonnage of  industry  end products
produced by  any one  company  varies  from  a  few  hundred

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kilograms (estimated) of lithium chemicals  produced  by
a chemical specialty company to greater than seven million
metric tons of various end products  produced by  Dow  Chemical
U.S.A.

Salt is produced by  53 companies.  Elemental iodine is
produced by only one.

A complete list of companies competing within the industry is
shown in Appendix C.

Environmental Impact

Disposal of spent brines is the chief environment-related
problem continually  facing the industry.  At least two
companies were forced to cease their Solvay-type operations
producing soda ash during the past three years because an
acceptable means of  disposal of weak calcium chloride brine
was lacking.  Generally, reinjection of waste liquors into
subterranean strata  is the disposal method employed at
inland facilities.   Waste bitterns are usually sluiced into
tidewater at seaboard locations with little or no adverse
environment effects.

Dusting, tailings piles, and "cratered" landscapes, mentioned
above, under "Raw Materials," occur almost entirely in
sparsely populated,  near-desert locations.  Adverse environ-
mental impact is therefore minimal.

Elimination of atmospheric emissions of "sniff" chlorine
from  chlorine-caustic facilities has been almost entirely
Implemented throughout the industry, usually through  use  of
caustic exhaust scrubbers.

Several cases of liquid chlorine release from railroad cars
or barges, resulting from collisions or derailments,  are
reported each year.

U. S. Borax and Chemical Corporation successfully concluded
a three-year, ten-million-dollar dust  abatement program in
1972  at Boron, California.

Little mention is made, in  this chapter, of  indirect  wastes,
as from leaks, spills and clean up operations.  It  is not the
intent, in this study, to overlook such wastes.  They are less
significant here than in most  other industries, but they  are
real, nonetheless, and should be considered  in any  comprehensive
study of wastes from individual processes.

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Bibliography


(1)   Chlorine Institute Pamphlet 10:   North American Chlor-
      Alkali Industry Plants and Production Data Book,  New
      York, Chlorine Institute,  Inc.,  January 1975.

(2)   Eilertson,  D.  E. Potash,  In:   Minerals Yearbook,  1972,
      Schreck, A. E. (ed.), Washington, U.  S. Department of
      the Interior,  1974, 1:1055-1967.

(3)   Keyes, W. F.,  Potash in 1974, In:  Mineral Industry Surveys,
      Washington, U. S. Dept. of the Interior, March 1974, 9 p.

(4)   Keyes, W. F.,  personal communication, May 1975.

(5)   Klingman, C. L., personal communication, May 1975.

(6)   MacMillan,  R.  T., Salt, In:  Minerals Yearbook, 1972,
      Schreck, A. E. (ed.), Washington, U.  S. Dept.  of the
      Interior, 1974,  1-235-236.

(7)   McCaleb, K. E. (ed.), Chemical Economics Handbook, Menlo
      Park, Stanford Research Institute.

(8)   Reed, A. H., Calcium and Calcium Compounds, In:  Minerals
      Yearbook, 1972,  Schreck, A. E.  (ed.), Washington, U. S.
      Dept. of the Interior, 1974, I_:235-236.

(9)   Wang, K. P., Boron, In:  Minerals Yearbook, 1972, Schreck,
      A. E. (ed.). Washington, U. S.  Dept.  of the Interior, 1974.
      1:217-221.

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INDUSTRY ANALYSIS


Published data pertaining to some of the processes shown here
are either mutually conflicting, incomplete, or simply do not
exist.  This situation is particularly true for information
pertaining to emissions.   In these cases a general range is
given here for the probable types of equipment used and for
operating parameters.  The nature and quantity of emissions
is then inferred from known characteristics of similar
equipment operating on closely related materials.

Published technological data for the entire industry are
organized for display in a sequence of 22 flowsheets, Figures
3 through 24.  The entire sequence diagrammatically describes
the operations of the industry as a whole without regard to
the existence of industry segments; i.e., no single flow-
sheet completely describes any one of the six industry
segments.

The interior of each of the rectangular "process blocks"
appearing on the flowsheets represents at least one, and
usually several, of the sequential, real processes of the
prototype operations depicted by the flowsheets.  In the
ensuing context, the word "process" refers to what occurs
inside the process block.

A number has been assigned to each of the process blocks,
uniquely identifying the process it represents with an
appropriate  title and with a process description.  Where
substantially the same process is used more than once
throughout the industry, its process number and title remain
unchanged; i.e., more than one process block may bear
identical numbers and titles.

Flag  symbols at the  upper right-hand corner of the process
block are used to indicate the nature of the waste streams,
if any, discharged  from the process—a circle for atmos-
pheric emissions, a  triangle for liquid wastes, and a rhom-
bus for solid wastes.  The flags do not differentiate
between inadvertent  (fugitive) and designed wastes.

A verbal process description has been written to characterize
each  process further, to relate  it to other processes,  and to
quantify its operating parameters.  Where  the same process finds
application  in a number of industry operations,  the various
elements of  the process description are divided  into  sub-elements,
each  identified with a lower case  letter.  Each  sub-element  re-
lates to a specific  industry operation.  The  same letter designa-
tion  is retained in  each element  to identify  information specific
to particular industry operations.  In  cases where the  same  pro-
cess  is used in a large number of  industry operations,  its nrocess
description  may contain  the data  in tabular form.

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A sample process description format is illustrated on
Figure 1, showing the type of information given.

The set of completed process descriptions immediately follows
the sequence of flowsheets.

As an overview of the material flow of the entire industry, a
chemical tree, Figure 2, has been included under the subject
heading immediately following.

Brine and Evaporite Chemicals Industry Processes

Twenty-six Industry products are produced outside any recog-
nizable industry segment.  Each of these is listed below,
along with the figure numbers of the flowsheets which
collectively describe all stages of its production.  The
product is emergent on figures whose numbers are underlined.

    Bromine
        Figures 3, 7, 10.
    Calcium chloride, 35% liquor
        Figures 3, 9_, 11
    Calcium chloride, T8% flake
        Figures 3, 9, 11
    Calcium chloride, anh. flake
        Figures 3, 11.
    Magnesium carbonate trihydrate
        Figures 3, ^
    Magnesium carbonate, basic
        Figures 3, ^_
    Magnesium chloride,  32%  liquor
        Figures 3, 1, 9_
    Magnesium chloride,  ^6%  liquor
        Figures 3, 6.
    Magnesium chloride,  50$  flake
        Figures 3, ^
    Magnesium hydroxide,  slurry
        Figures 3, ^_
    Magnesium hydroxide
        Figures 3, £
    Magnesium oxide,  caustic-calcined
        Figures  3, ±
    Magnesium oxide,  dead-burned
         Figures  3,  4_
    Magnesium  sulfate  (epsom salt)
         Figures  3> ^
    Hydrochloric  acid (note  paragraph following)
         Figures  3,  17,  18.
dried

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BRINE AND EVAPORITE CHEMICALS                  PROCESS NO. l8_


                           STRIPPING

1.  Function

    A brief description of Process 18, entitled "Stripping",
    is given here.

2.  Input Materials

    All materials entering the process are Identified here
    and quantified in metric units per metric ton of the
    principal end product produced in the operation.

3.  Operating Parameters

    Listed here is available information on pertinent operat-
    ing variables and general operating conditions, such as
    temperature, pressure, flow rates, catalysts, if any, and
    equipment size.

4.  Utilities

    Identified and quantified in metric units per metric ton
    of principal end product.

5-  Waste Streams

    Liquid wastes, solid wastes, and emissions to the atmos-
    phere are identified here and quantified in metric units
    per metric ton of principal end product.

6.  EPA Source Classification Code

    Given here if one exists.

7.  References

    Information  sources are  listed here using the format pre-
    scribed by the EPA style manual,  "Interim Specifications
    for OR & M Grant, Contract and In-House Reports."
         FIGURE 1.   SAMPLE PROCESS  DESCRIPTION FORMAT

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    Iodine
        Figures 35  1J2.
    Sodium bicarbonate
        Figures 3,  Iji
    Sodium bromide
        Figures 33  10, 22_
    Sodium carbonate
        Figures 3,  7., %, ±±, 19
    Sodium chloride 3 brine
        Figure 3.
    Sodium chloride 3 crude, dried
        Figures 3,  5.
    Sodium chloride, crude, washed
        Figures 33  ^_3 6_
    Sodium chloride, refined
        Figures 3,  ^_5 1_1
    Sodium chloride, rock salt
        Figure _3
    Sodium iodide
        Figures 3,  12, 22_
    Sodium sulfate  (note paragraph following)
        Figures 3,  6_, 1, 8, 9., 2j4

The Hargreaves-type process, shown on Figure 18, specifically
for producing hydrochloric acid and potassium sulfate,
additionally is intended to be exemplary for the production
of hydrochloric acid plus sodium sulfate by the Hargreaves
process and by the  Mannheim process, using as raw materials,
respectively, sodium chloride plus sulfur, and sodium chloride
plus sulfurlc acid.  The latter two processes are not shown
on any of the following flowsheets.

Borax and Boric Acid Segment Processes

The products of this segment are defined here as first-level
inorganic borates and forms of boric acid.  The end products
are thus the various hydrates of sodium tetraborate (borax),
anhydrous borax, various forms of boric acid, fused boron
oxide, and calcium berate.  Sodium sulfate is a by-product  of
the segment.

Facilities of the segment are located entirely in Kern, Inyo,
San Bernardino, San Mateo,  and Los Angeles counties,
California.  They account for all the domestic production and
the major portion of the world supply of boron products.

Sources of the boron values are mainly near-surface deposits
of borax, kernlte, and  colemanite, and, secondarily, the
brine of Searles Lake.

-------
Five companies operate ten facilities inside the segment.
One of these, U.  S.  Borax and Chemical Corporation, has more
than 70 percent of the estimated 650 thousand metric tons
annual B£03 capacity.

About one-half of the  total tonnage of end products is ex-
ported.  Production of glass (principally fibers), enamel
frits, and detergents  accounts for an estimated 75 percent of
domestic consumption.

Processes of the segment operations are diagrammed on the
flowsheets shown on the figures listed below.  Flowsheets
showing the emergent products are indicated by underlined
numbers.

    Figures 3, ]_, 8_, 16.

Chlorine-Caustic Segment Processes

This  large-tonnage segment consists of companies electrolyz-
ing mainly sodium chloride brine and, to a much lesser extent,
potassium chloride brine to obtain five products.  Chlorine,
sodium hydroxide  (caustic soda), sodium chlorate,  and potas-
sium  hydroxide are four products of the segment and are also
industry end products.  The hydrogen, always co-produced with
any of the other  four, is an industry by-product.

Competing within  the  segment are 33 producers  conducting
electrolysis operations in 68 installations.   Six  of the
companies producing chlorine and caustic soda  also make
caustic potash.   Eight recover hydrogen beneficially in a
total of 18  facilities.  Sodium chlorate is produced by a
total of 9 companies,  5 of whom produce chlorine and caustic
soda.

Five  companies collectively produce  about  70 percent of the
segment output:

    Dow Chemical  U.S.A.
    PPG Industries, Incorporated
    Diamond  Shamrock  Corporation
    Hooker Chemical Corporation
    Allied Chemical Corporation

The segment  produced  approximately  9  million metric tons  of
chlorine during  1972  and about  an  equal tonnage of caustic
soda.   Caustic potash production traditionally equals  about
3  percent  of  that of  caustic  soda.   Sodium chlorate produc-
tion  tonnage is  slightly less than  that of caustic potash.
Co-produced hydrogen  is usually flared, but  the number of
installations beneficially recovering it is  increasing.

-------
Most of the chlorine and roost of recovered hydrogen are used
captively to make other chemicals belonging to other indus-
tries.  During 1974 more than 65 percent of the chlorine was
consumed in the manufacture of plastics monomers, chlorinated
solvents, and other organic chemicals.   The largest single
use for caustic soda occurs in the manufacture of pulp and
paper, where between 12 and 15 percent  of its total consump-
tion is used.  Caustic potash is used mainly in producing
soap and in manufacturing other potassium compounds.  The
chief use for sodium chlorate is in the pulp arid paper
industry.

Processes conducted by the industry segment are diagrammed
on the flowsheets shown on the figures listed below.  Figure
numbers are underlined for flowsheets showing the emergent
products.

    Chlorine, caustic soda, and hydrogen: Figs. 3,5,11,15
    (Figure 15 is also exemplary for caustic potash.)

    Sodium  chlorate and hydrogen:  Figs. 3 ,5 ,11,2_3

Fifty percent caustic soda, as a by-product of the  lithium
segment, is also shown on Figure 24.

Lithium  Chemicals Segment Processes

The two  principal end products of the segment are  lithium
carbonate  arid lithium hydroxide.  From these two first-level
compounds  are derived 29  second-level lithium chemicals, also
included in the  segment.  Crude phosphoric acid and 50 percent
sodium hydroxide solution are by-products  of the segment.

Raw materials are spodumene ore*, mined exclusively  in  North
Carolina,  the subterranean brine of Silver Peak, Nevada, and
the brine  of Searles Lake., California.

Ten companies compete within  the segment with operations con-
ducted in  a total of 12  facilities.  Of these ten  companies,
three are  major  tonnage  producers, producing either the
carbonate  or the hydroxide.   Foote Mineral Company  is  be-
lieved to  be the major producer, with an estimated 40  to 50
percent  of the total  segment  output tonnage.   It processes
both  spodumene ore  and brines.   The minority large-tonnage
producer,  Kerr-McGee  Chemical Corporation, division of Kerr-
McGee Corporation,  produces  from Cearles Lake brine an esti-
mated 15 to 20 percent  of  the total, segment  output.
 "Because  of  the  increasing  importance  of  their  brine  source,
  lithium  compounds  are  included  in  the Brine  and  Evaporite
  Chemicals Industry.  Spodumene  ore, a nonevaporite,  is
  believed to be  the current major source.
                               13

-------
Production and capacity information is officially withheld.
Total annual segment capacity in 1972, estimated here,  was
between 10 and 20 thousand metric tons of Li20 equivalent.
Annual production of some of the second-level lithium
chemicals Is believed to approximate less than several
hundred kilograms.

Principal consumption areas for lithium chemicals are
aluminum cell bath, ceramics, greases, and large air-
conditioning installations.

Processes included in the segment are diagrammed on the flow-
sheets shown on the figures listed below.  Principal end
products are shown emergent on flowsheets indicated by under-
lined figure numbers.

    Lithium carbonate:      Figs. 3,  7, 13, 24_
    Lithium chloride:       Figs. 3.  7, 13, 2_2, 24
    Lithium hydroxide:      Fig.  2_4
    Crude phosphoric acid:  Figs. 3,  7, 13
    50% sodium hydroxide:   Fig.  2j£

Figure 22, in addition to showing the production of lithium
chloride, is also exemplary for the production  of many of the
second-level lithium compounds.

Magnesium Metal  Segment  Processes

In all three  operations  of  this  segment,  primary magnesium
metal  is  produced as  end product by  the  electrolysis of
magnesium chloride.   Two of the  operations  are  also net
producers of  co-generated chlorine,  a by-product  of the
segment.  Of  the latter  two operations,  one derives magnesium
chloride  from the brine  of  Great Salt Lake; the other, from
subterranean  brine  of  western Texas.   The third operation,
at Freeport,  Texas,  depends partly  on seawater  and partly on
dolomitlc lime  for  its supply of magnesium ion.   It is a  net
consumer  of  chlorine.

Three  companies  currently (1975) compete within the segment.
Dow Chemical  U.S.A.  produced between 85  and 95  percent of the
 197^  total  domestic  production of  primary magnesium in its
 facilities  at  Freeport,  Texas.   The  other two companies—
N L Industries,  operating at Rowley,  Utah, and American
Magnesium Company,  at  Snyder, Texas—have entered the  segment
during the  past  five years.  Their facilities,  not yet under
 capacity  operation,  will collectively represent an estimated
 30 to  35  percent of total domestic  capacity.

A potential fourth producer, Aluminum Company of America, has
 a plant  under construction at Addy,  Washington, to employ an
 electrothermal process.
                               14

-------
Total domestic production of primary magnesium during 1973
Is estimated to be 120 thousand metric tons, representing a
i| to 5 percent annual growth rate for the segment during the
previous five-year period.  An equal or greater growth rate
is anticipated for the next five years.

About one-fourth of the domestic production is exported.  The
principal areas of domestic consumption are in aluminum
alloys, structural products, and in organic chemical
production.

Operations of the industry are diagrammed on the flowsheets
shown on Figures 35 6, and 20.  Metallic magnesium emerges
as end product on Figure 20.

Potash Segment Processes

Companies populating the Potash Segment mine bedded potash
ores, recover potassium values from salt lakes, and produce
large-tonnage quantities of several potassium salts which
they market almost entirely to the Phosphate Rock and Basic
Fertilizer Materials Industry.

Total production of the segment during 197^ was reported to
be 2.36 million metric tons of K20 equivalent (estimated here
to be !-\ million metric tons total weight).  This total was
produced in 12 separate facilities located in New Mexico,
Utah, California, and Texas.

Bedded potash ores of the Carlsbad, New Mexico, area account
for approximately 70 percent of total raw material supply.
The remainder comes from wet-mined ore at Moab, Utah, and
from the brines of Searles Lake, California, Great Salt Lake,
and Salduro Marsh, Utah.

Specific end products of the segment are potassium chloride,
potassium  sulfate, and magnesium potassium sulfate (lang-
beinlte).  The latter is Intended here to Include the so-
called "manure salts."  Potassium hydroxide, an industry end
product, is produced in the Chlorine-Caustic Segment.

Ten companies operate in the industry segment.  All of  these
produce other products.

Imports of potash, currently (1975) exceeding domestic  produc-
tion, do not play a role in the industry.  Imported potash is
either acquired directly by companies outside the industry
(usual) or, if received by industry companies, does not
undergo further processing prior to resale.
                              15

-------
Annual production has remained almost constant over the past
seven years, experiencing a slight decline recently.  Despite
the current increased demand for fertilizers, a zero segment
growth is forecast in view of available Canadian imports.

Approximately 55 percent of the total segment capacity re-
sides in the facilities of the four largest producers, named
in order of decreasing capacity:

    International Minerals & Chemical Corporation
    Duval Corporation
    Potash Company of America
    AMAX Chemical Corporation

Figure numbers of flowsheets collectively describing all
stages of production of each of the end products of the
segment are listed below.  The end product is emergent on
figures whose numbers are underlined.

    Potassium chloride:  Figs. 3, 7, 9_, 17
    Potassium sulfate:   Figs. 3, b", 7, %7 l8
    Magnesium potassium
              sulfate:   Figs. 3, 18.

Sodium Metal Segment Processes

The  companies competing within  this  segment  electrolyze
molten sodium chloride to  produce metallic sodium  as  end
product.   The co-produced  chlorine  is  a segment  by-product.

Three companies  conduct  operations  in  a total of five
facilities.  Two of  the  three—E. I. duPont  de  Nemours and
Ethyl Corporation—each  operate  two  facilities,  collectively
representing about 80  percent  of the total domestic capacity.

Between  80 and  90 percent  of the total sodium metal consump-
tion is  in production  of  lead alkyls used in motor fuel anti-
knock fluids.

Segment  operations are shown on Figures  15 and 21, with the
metallic sodium emerging as  product  shown on the latter-
named figure.
                              16

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                             29

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       HaO.

     Steam
                                                       to flares
                                 I	Bad,

                                     Urea
                                    	A
                       Evaporation/
                      crystallization
                                 in
                      Sodium chlorate
                        drying  67
FIGURE 23.    SODIUM  CHLORATE  VIA  ELECTROLYSIS

                                37

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                         Open  pit mining
                                      5
                                                                    no—j


Froth
Flotation
15
^0
^ '
                                                            I Fsiurried solids
       Fine  CaCO,
Water
Heat
)»-*•

~L
l_to pona gr \i\ it; j ^
t 9 Heat -1 t
Calcination/
grinding ,

Calcination/
grinding
?
                         Ground
                        alkaline
                        clInker
Heat
IL
!
r
A
Leaching/
Clarifying
47
-4
     Grour
       6-
   spodumene
  V  clInker  /
                                                     Heat
         Cooling
               Heat
                         Moist
                        L10H-H,0
                        crystals
                                           [Cone. H2SO,
                                        Waste solids
                                       [to pond or pile
1 ^
r
Digestion
63
                                                Ca(OH)a
 Leaching/
filtration/
evaporation
sat— i ,
r
Drying/
Calcination "\2
                                           Cooling H20;
                                               Rpfrig.-
                                                Na,CO,-
fsiurried solid
|to pond or
                                                      Heat
  Evaporation/
crystall ization
             10
                                                      Hea
                  /Na2SO.
                  j  mother
                  V  liquor
                   Heat
Dry1 ng
11
FIGURE  24.    LITHIUM VALUES  FROM

              SPODUMENE
                                                38
1 '
t
Dryi ng
11
9

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BRINE AND EVAPORITE CHEMICALS                 PROCESS  NO.  1


                  SCREENING/CHLORINATION

1.  Function

    This process (see Figure 3) accomplishes two objectives:
    (1) removes floating debris from seawater prior to the
    latter 's entry into intake pump suctions and seawater
    pipelines; and (2) kills marine organisms present  in
    raw seawater, thereby preventing fouling of seawater
    pumps and pipelines.

    Trash screens are usually about 3-cm2  mesh of corro-
    sion resisting alloy wire.  Screens are either removable
    or of self-cleaning "roller towel" type.  Screens  are
    usually protected by a steel-bar grizzly.  Chlorinating
    equipment may be of standardized off-the-shelf design.

    This process also includes seawater pumping.  The
    screened/chlorinated seawater is forwarded to Process 2.

2.  Input Materials

    Raw seawater - Quantities required in cubic meters per
    metric ton of product assuming 3-3$ salinity and 100$
    extractive efficiencies:
        Mg(OH)2
        Mg metal       800

    Chlorine - Kilograms of C12 (average) per metric ton of:

        Seawater       0.002
        Mg(OH)2        0.6
        Mg metal       1. 5

    Operating Parameters

    Prevailing near-shore salinity and temperature - Pepends
    on exact location of intake.

    Chlorination - Either by diffuse bubbling of chlorine gas
    below the surface of seawater in flumes or by injection
    into pipelines.  Chlorination may be either continuous
    or intermittent at 12-hour intervals and is usually
    controlled to approximately 1 ppm residual Cla.
                             39

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i».   Utilities

    Electric energy consumption (for pumping seawater)
    expressed in kWh per metric ton of product, assuming
    same seawater conditions named in 2 above, and assuming
    10-foot total head and 75$ overall efficiency of
    pump-motor unit:

        Mg(OH) 2      3 to 4
        Mg metal     8 to 9

5.  Waste Streams

    Amount of C12 entering atmosphere is sufficient to
    detect by smell in immediate vicinity.

    Trash recovered from screens is incinerated or
    buried.

6.  EPA Source Classification  Code

    None established.

7.  References

    Mangum, D. C.,  B.  P. Shepherd, and W.  P.  Mcllhenny.
    Methods for  Controlling Marine Fouling in Intake
    Systems.  U. S. Department of the  Interior, Washington,
    D.  C.  Office  of  Saline Water R  &  D  Progress  Report
    No. 858.   (PB  221 909).  June 1973.   124  p.

    Shepherd, B. P.,  P.  G.  LeGros, J.  C.  Williams,  and
    D.  C. Mangum.   Intake  Systems for  Desalting Plants.
    U.  S. Department  of  the Interior,  Washington, D.  C.
    Office of  Saline  Water R  & D  Progress  Report  No.  678.
    April 1971.  222  p.

    White, G.  C.  Handbook  of  Chlorination.  New York,
    Van Nostrand Reinhold.  1972.   7^4 p.
                             40

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BRINES AND EVAPORITE CHEMICALS                  PROCESS  NO.  2


                    BICARBONATE REMOVAL

1.  Function

    This process (see Figure 3) eliminates or substantially
    reduces the concentration of bicarbonate ions  plus  sus-
    pended solids contained in seawater from Process 1.   It
    also increases the level of purity of the Mg(OH)2 pre-
    cipitated in Process 7, Figure 4.

    Major equipment includes agitated flocculator, plus
    settling ponds or thickening tanks.

    This process may be bypassed if the Mg(OH)2 subsequent-
    ly produced is used for production of magnesium metal.

2.  Input Materials

    Quantities of materials per metric ton of product
    (typical):

                            For Mg(OH)g     For Mg metal

        "Sterile" seawater    3^0 m3          800 m3
        Ca(OH)2, or            90 kg          220 kg
        NaOH                   97 kg          240 kg

3.  Operating Parameters

    The process is conducted at ambient temperatures.  A
    clarifying tank is typically about 160 meters (500 feet)
    in diameter by 4 meters  (12 feet) side wall depth for
    a seawater flow of 80 cubic meters per minute (20,000
    gpm) .

    Additions of Ca(OH)2 or NaOH are typically controlled
    to precipitate approximately 5% of the total magnesium
    content,  corresponding to pH values in the neighborhood
    of 9-5.

4.  Utilities

    Approximately 5 kW  for  clarifier tank plus, typically,
    50  kW  for flocculator tank.  Total electric power
    expressed in kWh per metric ton of product:

        Mg(OH)2        2 to  4
        Mg  metal       5 to  10
                             41

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5.   Waste Streams

    The sole waste stream is  a slurry  of CaC03  and  clay
    particles suspended in seawater, typically  carrying
    150 grams total suspended solids per liter.   The  waste
    stream is innocuous.   Depending upon conditions,  it
    may be:

    •Diluted with seawater and discharged into  the  tidal
     system.
    •Neutralized with dilute  HC1,  the  resulting neutral
     solution then being discharged into tidewater.
    •Discharged into diked ponds,  where further thickening
     occurs, qualifying the disposal  as landfill operation.

6.   EPA Source Classification Code

    None established.

7.   References

    Schambra, W. P.  The Dow Magnesium Process  at Preeport,
    Texas.  Trans. Am. Inst.  Chem. Eng. 4^:35-513 January
    1945.
                              42

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BRINE AND EVAPORITE  CHEMICALS                PROCESS NO. 3


                      SOLUTION MINING


1.   Function

    This process (see Figure 3) obtains the desired mineral
    in solution form at the surface,  by dissolving the under-
    ground mineral deposit with injected water.   This process
    applies to the recovery of sodium chloride from salt domes
    and layered deposits at several locations and to the re-
    covery of sylvinite at Moab, Utah.

    Equipment consists essentially of high-pressure pumps and
    piping.  The latter, both for injection water and solu-
    tion, is typically contained inside casing cemented into
    both overburden and producing formation.  Solution tub-
    ing may be concentric with injection water tubing, or
    be contained in separate well casing.

    This process includes storage for both water and solution
    and equipment for water treating.  The NaCl brine is for-
    warded to Process 3^, Figure 14,  or Process 35, Figure 15.

2.   Input Materials

    In the case of solution mining salt domes for NaCl re-
    covery, the total weight of solids dissolved from the
    deposit Is only slightly greater than the weight of NaCl
    produced.

    Approximately 2.5 metric tons of sylvinite ore are dis-
    solved per metric ton of KC1 produced.

3.  Operating Parameters

    Injection water temperatures vary seasonally between 0°
    and 25°C.  Recovered brine temperatures are as high as
    35°C.

    A typical salt "well" may produce between 250 and 1,000
    metric tons per day of NaCl.

    In sylvinite mining, between ^ and 12 cubic meters per
    minute  (1,000 to  3,000 gpm) is the typical flow  from an
    extraction well.
                             43

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4.   Utilities

    Water requirement in cubic  meters  per  metric  ton  of
    product:

        NaCl                      2.8  to 3.0
        KC1                      7.0  to 8.0

5.   Waste Streams

    Fragments of anhydrite,  gypsum and sand  are carried
    in the brine from the solution cavity  of a salt dome.
    This is settled out in a pond or  tank.  Their ultimate
    disposal  is by landfill  (abandonment in  pond).  This
    waste is  estimated at <0.5$ by weight  of the NaCl in
    the recovered brine.

    Solid wastes of sand and clay particles  are believed
    to result from solution mining potash, but no quantit-
    ative information is available.

6.  EPA Source Classification Code

        None established

7.  References

    Jackson,  D.  Solution Mining Pumps New Life into  Cane
    Creek Potash Mine.  Eng./Min. J.  174:59-69.  July 1973.

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO. 4


                       SHAFT MINING


1.   Function

    This  process  (see  Figure 3)  brings  ore  to  the  surface
    from  a relatively  deep ore body  using dry,  mechanical
    methods and without the necessity  of removing  the  over-
    burden.  (Similar  to classical concept  of  coal mining.)

    This  process  usually involves  sinking a central shaft.
    Mining proceeds by "room-and-pillar", or similar methods,
    employing various  devices of attacking  the  ore in  place:
    drilling and  blasting, use  of  "continuous  mining"  equip-
    ment , etc .

    Equipment is  identical or similar  to  that  used in  under-
    ground coal mining:  rock drills,  undercutters, front-
    end loaders,  roof-bolting equipment, belt  conveyors, central
    elevator, etc.

2.   Input Materials

    Subsurface  ore  deposits are  the  starting materials  for  this
    process.   The weight of ore  removed per metric ton  of end
    product varies  widely from mine  to mine for any one material
    Estimates of  this  ratio are:

        Halite  to crushed rock salt:     <1.02:1
        Sylvinite to granular KC1:         2.5:1 to 4:1
        Langbeinite to K2SCU:              1.1 to  1.5:1
        Trona to  soda  ash:                 l.if  to  1.6


3.   Operating Parameters

    A typical scale of mining operations  for a single  mine  in
    terms of product output in thousands  of metric tons per
    year  capacity:

        Crushed rock salt:                 800 to  1,500
        KC1 plus  K2S04:                    500 to  1,000
        Soda ash:                          500 to  1,500

4.   Utilities

    Electric power  is  the chief  form of energy used in  under-
    ground mining operations.  Requirements are 1  to 20 kWh
    per metric  ton  of  any of the products mentioned in this
    process description.
                               45

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5.   Waste Streams

    Mining operations are inherently dusty.   Dust-laden
    air in the underground galleries, frequently contain-
    ing gaseous products of blasting, is carried by the
    ventilating system and exhausted to the  atmosphere
    in undisclosed quantities and concentrations.

    From a practical standpoint, there are no liquid emis-
    sions from underground mining operations of evaporites.

    Solid wastes associated with shaft mining processes
    result directly from crushing, screening and sizing
    processes and in this study are listed in the descrip-
    tions of the latter.

 6.  EPA Source Classification Code

         3-05-022-01  Mine-Grind/Dry

 7.  Preferences

    First Symposium  on  Salt.  Bersticker, A. C.  (ed.).
    Cleveland, Northern Ohio  Geological  Society, 1963.
    661  p.

    Harley,  G. T., and  G.  E.  Atwood.   Langbeinite—Mining
    and  Processing.  ind.  Eng.  Chem.   39: 43-47, January 1947.

    Jacobs,  J. J.  Potassium  Compounds.   In:  Kirk-Othmer
    Encyclopedia of  Chemical  Technology,  2nd Edition.
    Standen,  A.  (ed.).   New  York,  John Wiley and Sons,  Inc.,
    1968.   16.: 369-^00.

    Kellogg,  H.  H.   Energy Efficiency  in the Age of  Scarcity.
    Journal of Metals.   26:  25-29,  June  1974.

    Magraw,  R. M.  New  Mexico Sylvinite.  Ind.  Eng.  Chem.
    _3_0:  861-871, August 1938.

    Second  Symposium on Salt.   Raw,  J.  L.  (ed.).   Cleveland,
    Northern Ohio  Geological  Society,  1966.  443 p.

    Third Symposium  on  Salt.  Raw,  J.  L.  and L.  Dellwig (ed.).
    Cleveland, Northern Ohio  Geological Society, 1970.   486 p.

    Turrentine,  J. W.   Potash in North America.  ACS Mono-
    graph Series,  No.  91.  New  York,  Reinhold,  1943.  186  p.

    von  Perbandt,  L. K.  Salt Mining.   In:   Sodium Chloride.
    ACS  Monograph Series,  No. 145.   Kaufmann,  D. W.  (ed.).
    New  York, Reinhold, I960.  p.  109-126.


                              46

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White, N. C., and C. A. Arend, Jr.  Potash Production at
Carlsbad.  Chem. Eng. Progr.  46: 523-531, October 1950.
                         47

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BRIIIE AND EVAPORITE CHEMICALS                   PROCESS NO. 5


                      OPEN-PIT MINING

1 .   Function:

    The process (see Figure 3) recovers ore from an orebody,
    by removing the overburden, either prior to or during the
    removal of the ore itself.  This process is applicable to
    the mining of kernite and colemanite.

    Equipment employed includes power shovels, draglines,
    front-end loaders, scrapers, bull dozers, dump trucks,
    conveyor belts, blasting equipment and other excavating
    and earth-moving machinery.

    The process may include the steps of crushing, grinding,
    and drying.  The mined ore is forwarded to Process 6.

2.  Input Materials

    The unmined ore is the input material.  Ratios of weight of
    ore mined to weight of product recovered are estimated as
    follows for the products involved in this process :
    Kernite to BaOa contained in products:  4 to 5
    Colemanite to calcined colemanite:  1.3 to 2.0

3.  Operating Parameters

    As an indication of the scale of specific open-pit
    mining processes applied to kernite and colemanite,
    typical mining capacities of a single operation are
    given below in thousands of metric tons per year of
    the stated material.  These values have been inferred
    from published information.

        Kernite       1,000
        Colemanite      150

lJ.  Utilities

    Most equipment is usually powered by  self-contained
    internal  combustion prime-movers, consuming gasoline
    or diesel fuel.  Other units use compressed air.   In
    some cases electrical energy is used, supplied either
    by trolleys or trailing cables.  Total energy consump-
    tion obviously varies over a wide range, depending on
    type and  depth of overburden and identity of the ore.
                            48

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5
Total consumption of energy in all forms is estimated
to vary from 2 to 20 kWh per metric ton of end products
involved.

It is conjectured that fresh water may be consumed for
dust abatement.  Quantitative information is
unavailable.

Waste Stresms

Open pit mining is inherently a dusty process, producing
considerable quantities of particulate emissions from
the blasting, crushing and loading steps.  Inadequate
quantitative information is available.

Particle size range of atmospheric emissions in kernite
mining is 0.5 to 20 microns.  These dusts amount to an
estimated 4 to 5 kilograms per metric ton of B203
contained in the various forms of borate end-products.

EPA Source Classification Code
        3-05-023-01
        3-05-040-01
        3-05-040-02
        3-05-040-03

    References

    Chem.  Wk. 109:
                 Mining/Processing
                 Open Pit-Blasting
                 Open Pit-Drilling
                 Open Pit-Cobbing
                39-40, August 11, 1971.
    Kellogg, H. H.  Energy Efficiency of the Age of
    Scarcity.  Journal of Metals.  26: 25-29   June 1974.

    Wang, K. P.  Boron.  In:  Minerals Yearbook, 1971.
    Schreck, A. E. (ed.). Washington, U. S. Bur. Mines,
    U. S. Dept. of the Interior, 1973-  1:228.

    Woodmansee, W. C.  The Mineral Industry of California,
    In:  Minerals Yearbook, 1971. Schreck, A. E. (ed.).
    Washington, U. S. Bur. Mines, U. S. Dept. of the
    Interior, 1973.  2:139.
                            49

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 6


                      COARSE CRUSHING


1.  Function

    This process (see Figure 3) reduces the maximum size of
    large lumps of ore to sizes permitting accommodation by
    subsequent handling equipment such as stockpile conveyors,
    storage hoppers or railcar and truck loading equipment.
    This process may be required on only a portion of the
    ore mined and in some operation is omitted entirely.

    Equipment used includes any of several types of primary
    crushers such as jaw crushers, cone crushers and roll
    crushers.  Screens and other size-separation equipment
    may be included.

2.  Input Materials

    Coarser fractions of the mined ore: ^1 metric ton per
    metric ton of product.

3.  Operating Parameters

    Capacities of crushing equipment employed vary as much
    as several hundred metric tons per hour.  Crushed
    material output varies from 5-cm lumps to A- or 8- mesh.
    Crushing equipment may be located both inside the mine
    and at the surface.

4.  Utilities

    Input electrical energy  varies with hardness of ore and
    size-reduction ratio, between 0.5 and  5 kWh per metric
    ton crushedproduct,  corresponding to  estimated electrical
    energy inputs per metric  ton of  finished product as
    follows:

        NaCl  (from rock  salt)    1 to  2
        KC1  (from  sylvinite)     3 to  6
        Calcined colemanite      2 to  3
        Borax  decahydrate
         (from  kernite)           1 to  2
        Soda  ash  (from  trona)     4 to  5

5.  Waste Streams

     Particulate atmospheric  emissions  almost  invariably
     accompany  crushing  and  dry screening processes.  No
                             50

-------
    quantitative  information  is  available  on the materials
    considered  here.

    Solid waste streams  consisting of  the  gangue material
    may be separated  from the ore  in amounts estimated
    between 1%  and 10%  of the feed weight.   The  identity of
    the gangue  is listed below for some  of the ores  under
    consideration.

           Ore                      Usual  gangue

        Rock salt            Anhydrite,  sand, gypsum
        Sylvinite            Clay, anhydrite, sand
        Colemanite           Clay
        Trona                Shale

6.   EPA Source  Clas s if i c a t i o n Code

        3-05-040-30  Primary  Crusher
        3-05-022-01  Mine-Grind/Dry
        3-05-040-34  Screening

7.   References

    Lincoln, T. W., and A. L. Stern.   Size Reduction and
    Size Enlargement.  In:  Chemical  Engineers'  Handbook,
    4th Edition.   Perry, R. H., C. H.  Chilton,  and  S. D.
    Kirkpatrick (ed.).   New York,  McGraw-Hill,  1963.
    p. 8.: 1-64.

    Turrentine, J. W.  Potash in North America.   ACS
    Monograph Series No. 91>  New York, Reinhold,  1943.
    186 p.

    White, N. C., and C. A. Arend, Jr.  Potash  Production
    at Carlsbad.   Chem.  Eng.  Progr.  4_6:523-531,
    October 1950.
                            51

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BRINE AND EVAPORITE CHEMICALS                 PROCESS NO. 7


                   SETTLING/FILTRATION

1.  Function

    This process (See Figure 4)  obtains magnesium hydroxide
    in the form of washed filter cake from various brines
    and semi-processed liquors from Processes 1  and 2,
    Figure 3.

    Magnesium hydroxide is precipitated from the brine in
    an agitated flocculator tank by the addition of lime,
    dolime or caustic soda and then allowed to settle out
    and thicken in settling tanks.  The thickened sludge
    is filtered and water-washed to yield a filter cake
    containing approximately 35 weight percent magnesium
    hydroxide.  The filter cake is forwarded to Process 56,
    Figure 20, or Processes 8, 10, or 12, Figure 4 .

2.  Input Materials

    These may be seawater or any other surface brine,
    bitterns resulting from the solar evaporation of sea-
    water, or natural underground brines (notably well
    brines from various formations underlying the state
    of Michigan).  The magnesium content of these materials
    varies from approximately 0.12% Mg in the case of sea-
    water, through 0.8% Mg in some Michigan brines, to as
    high as 1% in the case of seawater bitterns.

    Typical quantities of input materials per metric ton
    of magnesium hydroxide recovered:

        Seawater              300 to 350 cubic meters
        Seawater bitterns     5 to 7 cubic meters
        *Ca(OH)2 or           1.3 metric tons
        *NaOH                 1.4 metric tons
        *An excess of approximately 20% is required if the
         Mg(OH)a is used to produce magnesium metal.

 3.  Operating Parameters

    In the case of seawater, sizes of settling or thickening
    tanks are typically 50 to 80 meters in diameter by 3
    meters side wall depth, or may be square ponds approxi-
    mately 150 meters on edge, equipped with several raker
                            52

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    arms.   One 60-meter  diameter  settling  tank  is required
    to produce approximately  35 metric  tons  per day  of
    magnesium hydroxide.

4.   Utilities

    The major consumer of electrical  energy  in  this  process
    is the agitator (circulating  pump)  in  the flocculator
    tank.   This uses about 80%  of the 13 kWh total per metric
    ton of magnesium hydroxide  in the case of seawater.

5.   Waste  Streams

    The supernatant spent brine from  the settling tanks  and
    the filtrate (identical in  composition to the former)
    are the two waste streams.  Together,  they  amount to
    between 300 to 350 cubic  meters per metric  ton of mag-
    nesium hydroxide.  These  streams  are usually neutralized
    with waste HC1 prior to discharge.  In the  case  of
    seawater, the waste  stream  is discharged into tide
    water.  In the case  of Michigan brines,  the stream
    of spent brine is used to beneficially recover sodium
    and calcium chlorides or  may  be  sent to  injection wells.

6.   EPA Source Classification Code

        None established

7•   References

    Schambra, W. P.  The Dow Magnesium Process  at Freeport,
    Texas.  Trans. Am. Inst.  Chem. Eng. 41:35-51, January
                            53

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 8

                   CARBONATION/FILTRATION


1.  Function

   *a.  For magnesium chloride production (Figure 4) - To
        form magnesium chloride solution from magnesium hydrox-
        ide, calcium chloride and carbon dioxide.  The process
        includes the sequential steps of carbonation, thicken-
        ing, filtration, displacement washing, and evaporation.
        Equipment consists essentially of a carbonation tank,
        thickeners, and filters (which may be of either the
        continuous rotary or the Moore type),  and evaporators.
        The latter may be either steam-tube or vertical
        falling-film evaporators.

    b.  For magnesium carbonate production  (Figure 4) - To
        f"orm either magnesium carbonate crystals  [MgCo3-3H20]
        or basic magnesium carbonate [5MgO*4C02'6H20] from a
        magnesium hydroxide slurry and carbon dioxide.  Essen-
        tial equipment includes a carbonating tank, and thick-
        ening and filtration equipment.  The latter may be either
        Moore filters or continuous rotary vacuum filters.

    c.  For Searles Lake brine  (lower level)  (Figure  8) - To
        form and to recover sodium bicarbonate from lower level
        brine of Searles Lake.  Addition of carbon dioxide con-
        verts the sodium carbonate in solution to sodium bi-
        carbonate.  The sodium bicarbonate precipitates from
        solution and is removed by filtration.

        The mechanism of carbonation (acidification in general)
        shifts the borax equilibrium from the soluble metaborate
        form to the crystallizable tetraborate form,  resulting
        in  an increased yield of borax.  Sodium bicarbonate
        can be separated from the borax due to the metastability
        of  borax at the lower supersaturations occurring  in car-
        bonation towers.

        The process consists of sequential  steps  of carbonation,
        settling, filtration, and displacement washing.

        Essential equipment consists of a series  of carbonating
        towers, settling tanks, and continuous rotary filters.

    d.  For production  of soda  ash by the Solvay  Process  (Figure
        14)- to form and to remove sodium  bicarbonate  from a
* Separate  industry operations  employing  the process  are
  identified with  a specific  lower  case letter which  is
  retained  as  an identifier in  each element of this process
  description.
                             54

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        sodium chloride brine saturated  with  ammonia.
        Addition of carbon dioxide causes  sodium bicarbon-
        ate to precipitate from solution,  with the  formation
        of ammonium chloride in solution.

        The process includes the steps  of  carbon dioxide
        compression, carbonation, filtration, and displace-
        ment washing.

        Major equipment employed consists  of:

            •Centrifugal compressors for compressing stack
             gas and recycled carbon dioxide.
            •Several carbonating towers  in series ("Solvay
             Towers").
            •Coolers for removing heat  of  reaction released
             in the carbonating towers.   These are either
             tube-and-shell exchangers,  submerged pipe
             coils, or water-sprayed pipe  banks.
            •Filtration equipment, either  rotary vacuum
             filters or centrifuges.

2.   Input Materials

    a.  Washed magnesium hydroxide, calcium chloride solution,
        and carbon dioxide (flue gas or lime-kiln stack gas)
        are fed to the process in the quantities listed, as
        metric tons per metric ton of MgCl2 product, assuming
        100% recovery efficiencies.'

            Mg(OH)2	0.61
            OcLOJ-2""""""""™™• — — — — — — _]_ t J_ Q
            C02	0 . 46
                             (equivalent to 250 cubic meters
                             of free, 100$ C02)

    b.  Washed magnesium hydroxide and carbon dioxide (flue
        gas or lime kiln stack gas) are fed to the process in
        the quantities listed, as metric tons per metric ton
        of MgC03»anh. product, assuming 100$ recovery efficien-
        cies :

            Mg(OH)2	0.7
            C02	0 . 5
                             (equivalent to 280 cubic meters
                             of free, 100$ C02)

    c.  Raw brine from the lower structure and carbon dioxide
         (flue gas, plus recycled calciner gas) are fed to the
        process in the estimated quantities shown per ton of
        soda ash produced:
                            55

-------
            Raw brine	20 cubic meters
            Make-up  C02	0.1 metric ton
                             (50 cubic meters of free, 100%
                            C02)

    d.   Ammonia-saturated  sodium chloride brine and  carbon
        dioxide  (flue  gas  plus lime kiln stack gas)  are  fed
        to the process.  The quantities of materials actually
        consumed  in  the  process  (weight entering minus weight
        leaving)  per metric ton  of soda ash  produced are es-
        timated as  follows:

            NaCl	1.1 metric tons
            C02	0.5 metric ton

        Total quantities of materials  entering the process,
        in metric tons per metric ton  of soda ash produced
        are estimated  as follows  :

            NaCl	1.5 metric tons
            NH3	0.5 metric ton
            C02	1.2 metric tons

        The numbers  given  above  indicate the considerable
        quantities  of  materials  that  are required to be
        recycled.

3.   Operating Parameters

    a.   The process  is conducted at  atmospheric  temperatures
        and pressures.  Flue  gas is  required at  a  typical
        gage pressure  of about one  kg/cm2.

    b.   Process  is conducted  at  atmospheric  temperatures and
        pressures.   Flue gas  or  lime  kiln  stack  gas  is  re-
        quired at gage pressure  of  about  1  kg/cm2.

    c.   Process  operates at  atmospheric  temperature  and atmo-
        pheric pressure, except  for  the  flue gas  (12?0  C02)
        and recycled carbon  dioxide  from calciners  (about
        7570 C02)  which is  required  at approximately  3  kg/cm2
        gage pressure.

        Carbonating towers are approximately 7  meters  in
        diameter x 21  meters  high.   Six  towers  are  required
        to produce approximately 180 metric  tons  per day of
        soda ash.  Three primary towers  intake  12%  C02  and
        three secondary towers intake 75%  C02.   Towers  are
        operated as fully-flooded bubble towers.   Dorr  thick-
        ening tanks and rotary vacuum drum filters  are  used.
                            56

-------
d.  Maximum temperature of carbonation Is controlled
    to 28°C, and pressures at the top of carbonating
    towers are slightly greater than atmospheric.

    Towers are 28 meters high and are operated as
    liquid-filled bubble towers}  in series-connected
    pairs.  Strong C02 (73 to 77%), recycled from  cal-
    ciners, enters the bottom of  secondary towers.
    Lime kiln stack gas (37 to 42% C02) enters the  middle
    of the secondary towers and also the base of the
    primary towers.  Nitrogen, containing 3 to 7%  C02,
    is collected from the top of  both towers and recycled
    to the ammonia absorption system.  Carbon dioxide
    gas pressures of 3.2 kg/cm2 are required.

    Conversion of sodium chloride approximates T5%  per
    pass.  The presence of about  80% more ammonia  than
    is stoichlometric is required In the feed.

Utilities

a.  Total electric power requirement is estimated  to be
    90 to 100 kWh per metric ton of MgCl2, most of which
    is used for carbon dioxide (flue gas) compression.

    Fresh water for displacement  washing of calcium
    carbonate filter cake Is estimated at 1.1 cubic
    meter per metric ton of magnesium chloride.

b.  Total electric power requirement is estimated  to be
    100 to 120 kWh per metric ton of magnesium carbonate,
    most of which is consumed in flue gas compression.

    Fresh water for displacement  washing of magnesium
    carbonate filter cake is estimated at 0.8 cubic
    meter per metric ton of magnesium carbonate.

    A heat source, usually low pressure steam, is  needed
    to heat to boiling the slurry of MgC03»3H20 prior to
    its filtration in the case of basic magnesium carbon-
    ate production.  This is estimated to be between
    500,000 and 600,000 kcal per metric ton of basic
    magnesium carbonate.

c.  Total electric power requirement is estimated to be
    100 to 120 kWh per metric ton of soda ash produced,
    most  of which  is consumed in compression of C02-bear-
    ing gases.
                        57

-------
        Fresh water  required  for  displacement  washing  of
        bicarbonate  filter  cake  is estimated  at 0.1  cubic
        meter per metric ton  of soda  ash.  Cooling  water
        is  required  to  remove 350,000 to  450,000  kcal  per
        metric ton of soda ash  produced.

    d.   Total electric  energy requirement  is estimated to
        be  150 kWh per  metric ton of  soda  ash, most of which
        is  consumed  in compressing C02-bearing  gases.

        Fresh water  required  for  displacement  washing  of
        bicarbonate  filter  cake  is inferred from published
        information  to  be  between 0.05 and 0.15 cubic  meter
        per metric ton  of  soda  ash.

5-   Waste Streams

    a.   Carbon dioxide  is  vented  to  the atmosphere  from the
        carbonating tanks  (Figure 4).

        An undisclosed  fraction of the spent wash water from
        the filters  is  wasted to  the  main spent brine  system
        for eventual Injection to the brine  source  formation.
        Principal dissolved constituent is magnesium chloride.

        Sole solid waste is calcium carbonate  filter cake.
        Depending on economics, this  is used to produce lime
        and carbon dioxide, or is slurried in  water and ponded,
        eventually becoming landfill.  This  amounts to approx-
        imately 0.05 metric tons  of solids per metric  ton of
        magnesium chloride.

    b.   Carbon dioxide  is  vented  to the atmosphere  from the
        carbonating tanks  (Figure 4).

        Filtrate from the  magnesium carbonate  filters  is the
        sole liquid waste stream.  This quantity is estimated
        to be 6 to 10 cubic meters per metric  ton of magnesium
        carbonate.

    c.   Carbon dioxide from the top of secondary absorber-
        towers constitutes the sole atmospheric emission
         (Figure 8).

        There are no solid wastes emitted.

        There are no liquid waste streams.  Clears from
        thickening tanks  and filtrate  from  bicarbonate filters
        are  forwarded to  Process  10  for borax recovery; spent
        wash water is recycled to carbonating towers.
                             58

-------
    d.  Approximately 0.05 kg of gaseous ammonia per metric
        ton of soda ash enters the atmosphere during transfer
        of sodium bicarbonate filter cake to Process 12 (Figure
        14).

        There are no liquid or solid waste streams.

6.  EPA Source Classification Code

    a.  None established

    b.  None  established

    c.  3-01-021-02  Handling

    d.  3-01-021-02  Handling

7.  References

    a.  Boeglin, A. F., and T. P. Whaley.  Magnesium
        Compounds.  In:  Kirk-Othmer Encyclopedia of
        Chemical Technology, 2nd Edition.  New York, John
        Wiley & Sons, Inc., 1967.  l_2:708-736.

    b.  Havighorst, C. R., and S. L. Swift.  Magnesia
        Extraction from Seawater.  Chem. Eng.  New York.
        7_2:84-86, September 2, 1965.

        Schambra, W. P.  The Dow Magnesium Process at
        Freeport, Texas.  Frans. Amer. Inst. Chem. Eng.
        £1:35-51, January 19^5.

        Schreve, R. N.  Chemical Process Industries, 3rd
        Edition.  New York, McGraw Hill, 1967.  183-185.

    c.  Bixler, G. H., and D. L. Sawyer.  Boron Chemicals
        from Searles Lake Brines.  Ind. Eng. Chem.
        £2:322-333, March 1965.

        Hightower, J. V.  New Carbonation Technique - More
        Natural Soda Ash.  Chem. Eng.  5_8_:l62-l63, May  1951.

        Mies,.!!. P.   Boron Compounds  (Oxides, Borates).
        In:  Kirk-Othmer Encyclopedia,  of Chemical Technology,
        2nd Edition.  Standen, A. (ed.).  New York, John
        Wiley 8- Sons, Inc., 1964.  3_:6o8-652.

        Plant Expansion at Trona Boosts Soda Ash and Borax
        Capacity.  Chem. Eng.   56_:102-103, April 19^9.
                            59

-------
Deutsch, Z. G., C.  C.  Brumbaugh, and F. H.  Rockwell.
Alkali and Chlorine Industry.   In:  Kirk-Othmer
Encyclopedia of Chemical Technology, 2nd Edition.
Standen, A. (ed.).   New York,  John Wiley & Sons, Inc.,
1963.  l.:668-758.
Shreve, R. N.  Chemical Process Industries,
Edition.  New York, McGraw-Hi-1, 1967.  227-231.
                     60

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BRINE AND EVAPORITE CHEMICALS                   PROCESS  NO.  9


                      SOLIDIFICATION

1.   Function

    The process yields some solid form of the desired
    material from solution:

   *a.  Magnesium chloride in the form of 50% flake and
        anhydrous poMer from nominally 'JU% magnesium
        chloride liquor.(See Figure h).

    b.  78% calcium chloride_flake from 78% calcium chloride
        liquor. (See Figure gT).

    c.  Calcium chloride in the forms of 78% flake, 78%
        pellets and anhydrous flake from Michigan brines
        (See Figure 11).

    d.  Sodium hydroxide in the forms of flake, beads and
        _drurnrned~solldrfrom 73% sodium hydroxide solution?
        (See Figure 15 )i

    e.  Magnesium chloride in the form of electrolysis
        cell feed   (See~~Flgure 20).

    The following sequential steps are included in  the
    process:

    a.  Evaporation  (30% to 50$ MgCl2)
        Flaking
        Drying  (if  anhydrous form is desired)
        Packaging  (in  bags)

    b.  Flaking
        Packaging  (In  bags)

    c.  Flaking
        Drying  (if  anhydrous form Is desired)
        Packaging  (in  bags)

    d.  Evaporation (to molten  99.5% solid),  or
        Flaking  (to 99% flakes), or
        Pelletizing
        Packaging  (In  drums)
 * Separate industry operations employing the process are
   identified with a specific lower case letter which is
   retained as an identifier in each element of this
   process description.
                              61

-------
    e.   Flaking
        Drying

    Major equipment generally  consists  of  the  following:

           a,b,c:       Steam-heated  "boil-down"  kettles
       a,b,c,d,e:       Water-cooled  flaking rolls
           a,c,e:       Shelf dryer or fluidized-bed  dryer
               d:       Flash-type, tube evaporators;
                       gas-fired furnaces; "shot-towers"
           a,b,c:       Standardized  drumming equipment for
                       single-trip drums

2.   Input Materials

    a.   Concentration of feed liquor may vary  between 20%
        and 30% magnesium chloride.   Quantity  required,  in
        cubic meters per metric ton of product:

        For 50% flake:       2 to 2.5
        For anhydrous flake: 4 to 5

    b.   Quantity of 7%% CaCl2 feed liquor per metric
        ton of 78% flake is approximately 0.6  cubic  meter.

    c.   Quantity of 78% CaCl2 feed liquor in cubic
        meters per metric ton of product:

        For 78% CaCl2 flake: approximately 0.6
        For anhydrous flake: approximately 0.7

    d.   Quantity of 73% sodium hydroxide  solution required
        per metric ton of any one of the  three solid forms
         (drummed solid, flake or beads) is approximately
        0.8 cubic meter.

    e.   Quantity of 50% magnesium chloride liquor required
        per metric ton of magnesium metal produced is
         6  cubic meters.

3.  Operating  Parameters

    a.  Process operates at atmospheric pressure.  Temperature
        of boiling 50% MgCl2 liquor  in boil-down kettles  is
        in the range  of 155°C to  175°C  (46% to  50% MgCl2).
        A  typical  size  for  a flaking roll is  1 meter diameter
        x  1.25 meters long, water-cooled  internally.

    b,c. Process operates at atmospheric  pressure.  Tem-
        perature range  of the boiling  nominally 78% CaCl2
         liquor in  open  boil-down  kettles  is l87°C to  195°C.


                            6,2

-------
    d.   Process  operates  at  various  temperatures  and
        pressures.   Typical  are:

        •120°C and  slightly  greater  than atmospheric
         pressure for 73% NaOH entering gas-fired tube
         furnaces.
        •480°C and  approximately  370 mm.  Hg absolute
         pressure for NaOH stream inside tube furnaces.
        •500°C and  150 mm.  Hg absolute  pressure  for molten
         anhydrous  NaOH inside vacuum flash tank.
        •400°C arid  atmospheric pressure for molten anhydrous
         NaOH entering "shot tower", or flowing  to flaker
         roll.

    e.   Process  operates  at  atmospheric pressure.  Typical
        temperatures are:

        •155°C to 175°C in boil-down kettles and  1?5°C for
         flaking-roll feed.
        •l80°C to 250°C temperature  range of air  to shelf
         driers  or  spray  dryers.

4.   Utilities

    Utilities consumed by each of the applications of
    Process 9 are shown in Table  1.

5.   Waste Streams

    a.   MaCl crystals precipitated during the concentration
        step amount to approximately 20 kg MaCl  per metric
        ton of 50$  MgCl2  flake produced.  The NaCl crystals
        are removed in filter presses,  slurried  in water,
        and are eventually injected  into the producing
        formation.

        If anhydrous MgCl2 flake  is  produced, entailing
        further drying of the 50% flake in an atmosphere
        of HC1,  atmospheric emissions of gaseous  HC1 usually
        result.   No quantitative  information is  available.

        Detectable quantities of  MgCl2  particles  and HC1
        vapor constitute an atmospheric emission from boil-
        down kettles and flaking  rolls.

    b,c. Atmospheric emissions of HC1 vapor are  possible
        at flaking-roll temperature  resulting from catalyzed
        decomposition of CaClz.  No  quantitative  information
        is available.
                            63

-------















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    d.   No waste streams or emissions

    e.   Detectable amounts  of undivulged quantities of
        HC1,  MgCl2  particles  and MgO particles  are  present
        in the exhaust air  stream from MgCl2  dryers of  any
        type,  whether spray dryers,  shelf  dryers, or  fluidized-
        bed dryers.

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        constitute an atmospheric emission from boil-down
        kettles and MgCl2 flakers.

        A bleed stream from the recycled  liquor from the
        scrubber towers of  MgCl2 dryers of any  type con-
        stitutes a liquid waste.  The  main flow of  scrubber
        tower effluent is recycled to  Process 58, but the
        bleed-stream is neutralized  with  NaOH and is either
        discharged into tidewater,  or  sent to injection
        wells.  Composition of the bleed-stream is  typically
        2% HC1 and 3% MgCl2 in aqueous solution. Its quantity
        is in the range of 10 to 20  liters per  metric ton of
        Mg metal produced.

6.   EPA Source Classification Code

    a,b,c,d,e:  None established


7.   References

    a.   Boeglin, A. F. and T. P. Whaley.   Magnesium
        Compounds.  In:  Kirk-Othmer Encyclopedia of
        Chemical Technology, 2nd Edition.  New York, John
        Wiley & Sons, Inc., 196?. 12_:?08-736.

    b,c,d. Deutsch, Z. G.,  C.  C. Brumbaug, and  F. H.
        Rockwell.  Alkali and Chlorine Industry.  In:
        Kirk-Othmer Encyclopedia of Chemical Technology,
        2nd Edition, Standen, A. (ed.). New York,  John
        Wiley & Sons, Inc., 1963. .1:668-758.

    e.   Schambra, W. P.  The Dow Magne'sium Process  at
        Freeport, Texas.  Trans. Am. Inst. Ch.  Eng.
         41:35-51, January  1945.
                            65

-------
BRINE AND EVAPORITE CHEMICALS                  PROCESS NO. 10


                EVAPORATION/CRYSTALLIZATION


1.  Function

    Essentially, the process creates at least two physically
    separable phases from a single Input material, for example,
    the formation of sodium chloride crystals plus mother
    liquor from sodium chloride brine.  The separation and
    recovery of the phases may occur in another process, or
    be effected in subsequent steps of this process.  If
    separation is accomplished in this process, then any or
    all of the following steps may be included;

        Evaporation
        Crystallization
        Dissolution
        Filtration
        Centrifuging
        Displacement washing
        Decantation washing
        Thickening
        Exchange cooling and heating
        Evaporative cooling
        Drying  (of filter cakes on filter drum)
        Chemical reaction

    The process steps named may be arranged in any  sequence
    and may occur several times.  Many internal recycle  flows
    may be required.

    Generally the fundamental process  steps are evaporation
    and crystallization, occurring almost always  in the  order
    named.

    In the present context, the process may involve many
    separate flows of both  input materials and intermediate
    products.   Also, two of the input  materials may chemically
    react; for  example, magnesium hydroxide with  sulfuric
    acid  in the production  of Epsom salt.

    The process may include any of the following  equipment:

        Horizontal  steam-tube evaporators
        Vertical-tube evaporators
        Falling-film evaporators
        Boll-down  kettles
        Direct-fired evaporators
                            66

-------
        Submerged combustion evaporators
        Vacuum crystallizers
        Crystallizing pans
        Moore filters
        Vacuum drum filters
        Belt filters
        Pressure filters
        Centrifuges
        Thickener tanks
        Dissolving tanks
        Vacuum coolers
        Heat exchangers

    Table 2 lists the specific functions  of the various
    applications of Process  10.

2.   Input Materials

    Table 3  lists the compositions of the input materials,
    and the quantity of each consumed per metric ton of
    principal end-product,  for each of the applications of
    Process 10.

3.   Operating Parameters

   *a.  'Neutralization of Mg(OH)2 conducted at atmospheric
         temperature and pressure.
        •Evaporation of MgSCu liquor commences at 105°C in
         multi-effect evaporators and crystallization of
         MgSO««7H20 at 50°-60°C (estimated) in vacuum
         crystallizers.
        •Equipment sized for 100-200 metric tons per day.

    b.  'Evaporation of NaCl brine in multi-effect basket-type
         evaporators commences at about 110°-120°C and crystal-
         lization is at 600 to 700 mm. Hg vacuum.
        •Equipment sized for about 200-250 metric tons NaCl per
         day;  evaporators are about 3 to 4 meters diameter by
         about 12 to 13 meters high.

    c.  'Process generally conducted at atmospheric pressure.
        •Low temperature (estimated 10°C) required if process
         involves separation of Na2SOu«10H20 crystals.
        •Actual crystallization paths employed are not dis-
         closed.

    d.  »0pen boil-down kettles operate at atmospheric pressure
         and inside a temperature range of 155°C to 175°C for
         46 to 50% MgCl2 liquor.
  Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.


                            67

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e. 'Pressure - Generally, all process steps are conducted
    close to atmospheric pressure.

   •Temperatures -

    1)  KC1 brine, containing KBr, is made by dissolving
        KC1 crystals; it leaves the process at 95° to
        105°C (estimated) and is recycled to the process
        at 105° to 110°C (estimated).

    2)  Burkeite liquor, containing Li values, is made
        from burkeite crystals; it exits from and re-
        cycles to the process within an estimated
        temperature range of 75° to 90°C.

    3)  KC1 is crystallized from KCl-Na2Bi+07 liquor
        (burkeite mother liquor) at 38°C.

    4)  Borax pentahydrate is crystallized at 24°C;
        seeding required.

    5)  Mixtures of burkeite, Na2C03, NaCl, and NaLi2P(\
        are crystallized from a mixture of raw brine plus
        mother liquor within an estimated range of 115°
        to 125°C.  Na2SOi+»10H20 crystals are removed at
        22°C, mixed with NaCl brine, and recrystallized
        as Na2SOi+-anh. at 17°C.

    6)  Na2C03-10H20 crystallized at 5°C.
        Na2C03-H20 crystallized at 90° to 95°C  (estimated).

f.  Process conducted at atmospheric pressure and at a
    temperature of 20°C  to crystallize and filter off
    borax  decahydrate.

g.  Atmospheric pressure; estimated  temperature range is
    50° to 60°C.

h.  Atmospheric pressure; estimated  temperature is l85°C
    for  78% CaCl2.

i.  Atmospheric pressure; estimated  temperature of 110°C.

J.  'Process conducted in multiple-effect  evaporators  and
    in boil-down  kettles.

    •Temperature range is 60°  to l85°C.
                           76

-------
k. "Operating conditions:

    For evaporating to 50% NaOH—
      60° to 170°C temperature range and pressure range
      of 660 mm. Hg vacuum to 2 kg/cm2 absolute pressure;
      liquor cooled to 20°C for final NaCl crystalliza-
      tion.
    For salt extraction by liquid ammonia—
      60°C and 28 kg/cm2.
    For evaporating to 73% NaOH—
      132°C and 700 mm. Hg vacuum.
    For producing anhydrous NaOH in tube furnace—
      Most severe conditions are 330°C; atmospheric
      pressure,

   •Ammonia makeup required for final NaCl removal by
    liquid ammonia extraction process is estimated at
    2 kg NH3 per metric ton of 100$ NaOH.

1.  ^Vacuum-cooled; approximately 65°C for crystal-
    lizing borax pentahydrate; 35° to 50°C (estimated)
    for crystallizing borax decahydrate.

m.  Atmospheric pressure; estimated temperature range for
    crystallizing H3B03 is 25° to 35°C.

n.  Atmospheric pressure; 25°C is optimum temperature for
    crystallizing K2SOk.

o. 'Range of pressures from initially atmospheric down to
    700 mm. Hg vacuum; temperatures from 90°C  (estimated)
    initial down to 60°C final.
   •Na2S added for corrosion control.  Surfactants used
    to prevent foaming.

p.  Essentially atmospheric pressure; temperature of
    evaporation is maintained constant at approximately
    100°C.

q.  Usual pressure range from 2 kg/cm2 gage down to 680
    mm. Hg vacuum, corresponding to temperature range of
    about 135°C down to  55°C.

r. 'Atmospheric pressure; estimated temperature range of
    evaporation is 110°  to 120°C if boildown kettles are
    used.
   •Crystallization temperature must  bo maintained above
    95°C to prevent formation of LiCl«H20 crystals.

s.  Atmospheric pressure; estimated evaporating tempera-
    ture -  110° to 115°C; crystallization probably at
    room temperature.


                          77

-------
   t.  Atmospheric pressure; estimated evaporating tempera-
       ture 110° to 115°C; crystallization probably at room
       temperature .

   u.  Atmospheric pressure; evaporating temperature is
       probably less than 100°C to prevent decomposition
       of Fe3Br8«l6H20.

   v.  -Temperature range in double-effect evaporators is
       probably 60° to 120°C, corresponding to approximately
       0.2 to  1.5  kg/cm2 absolute pressure.
       •Temperature of NaClOs crystallization is estimated
       at 40°  to 60°C.

   w.  'Pressure range of triple effect-evaporation probably
       commences at 1 to 2 kg/cm2 gage and finishes at 650
       to 700  mm.  Hg vacuum, corresponding to estimated
       boiling temperatures initially near 160°C  and finally
       near 60°C.
       •Final temperature of crystallization of LiOH«H20 is
       probably in the range of 30°  to 40°C.
       •Recrystallization of LiOH»H20 is necessary.
       •NaOH mother liquor is recycled within the  process  for
       lithium recovery.

   x.  -Atmospheric pressure; precipitation, filtration,
       and washing of Li2C03 is conducted  close to 100°C.
       •Mother  liquor is chilled close to  0°C for  separation
       of Na2S04 •10H20 crystals.  Latter  are subsequently
       redissolved for crystallization of Na2SOi+  in tempera-
       ture range  of 110° to 115°C,  probably in  submerged
       combustion  evaporators.

   Utilities
    Utilities  consumed by  various  applications  of Process  10
    are shown  in Table 4.

    Waste Streams
    Table 5 lists the identity and estimated quantity of the
    principal waste streams associated with the various
    applications of Process 10.

6.   EPA Source Classification Code

    a.  through z:  None established
                             78

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-------
7 •   References

    Process
    Applic.

    a   Boer-:lJn, A. P.,  arid  T.  I-1.  VJhaley.   flo^nes i urn
        Compounds .  In:   K Irk-Otbrnor Krio.ye | oped i 'j of
        ChemJ caJ Technology ,  2nd  Kd i t i on ,  'Jl^nden ,  A .
        (ed.).  Hew York,  J nlx'psc i once  Pub I I shops ,  IhoY.
        l£:Tr^.

    b   VerPlank,  W.  F,. ,  and P.  F.  Heizor.  ,,'aH in
        California.   Calif.  Dept.  of Hat' 1.  Her;., bl d. ) .   Mew  York Jnter-
        science  Publishers,  1964.  3:621-650.
                             87

-------
Plant Expansion at Trona Boosts Soda Ash and
Borax Capacity.  Chem. Eng.  5_6>: 102-103 , April 1949.

Robertson, G. R.  Expansion of the Trona Enterprise.
Ind. Eng. Chem.  3^:133-137, February 1942.

Shreve, R. N.  Chemical Process Industries, 3rd
Edition.  Now York, McGraw-Hill, 196?.  905 p.

Teeple, J. E.  The Industrial Development of
3earl.es Lake Brine.  ACC Monograph "cries, No. 19,
New York, Reirihold, 1929.  182 p.

Turrentine, J. W.  Potash in North America.  ACC
Monograph Series, Mo. 91-  New York, Reinhold, 1943.
186 p.

Woodmansee, W. C.  The Mineral Industry of California.
In:  Minerals Yearbook 1971, Schreck, A. E. (ed.).
Washington, U . S. Dept . of Interior, Bur. of Mines,
1973-  ^
Bixler, G. H., and D. L. Sawyer.  Boron Chemicals
from Searles Lake Brines.  Ind. Eng. Chem.
49.:322-333, March 1957-

Hightower, J. V.  Mew Carbonation Technique - More
Natural Coda Ash.  Chem. Erig .   5^:162-163, Ma.y 1951.

Mum ford, R. W.  Potassium Chloride  from the brine
of Cearles Lake.  Ind. Eng. Chem.   3^:872-877,
August 1938.

Nies, N. P.  Boron Compounds  (Oxides, Borates).
In:  KIrk-Othmer Encyclopedia  of Chemical Tech-
nology, 2nd Edition, Standen,  A. ( ed . ) .  New York,
Interscience Publishers, 1964.  3_:621-650.

Plant Expansion at Trona Boosts Soda Ash and Borax
Capacity.  Chem. Eng.   5^:102-103,  April 1949.

Shreve, R. N.  Chemical Process Industries, 3rd
Edition.   New York,  McGraw-Hill, 196?.  905 P-

Turrentirio, J. W.  Potash in  North  America.  ACC
Monograph)  Ceries, No. 91.  New York, Heinhold, 1943.
186  p.

Woodmansee, W.  C.  The  Mineral Industry of  California.
In:  Minerals Yearbook  1971,  Cchreck,  A. E.  ( ed . ) .
Washington,  (J .  S. Dept. of Interior, Bur. of Mines,
1973.  "2:119-168.

-------
g    Havighorst, C. R.  New Process Separates Borates
     from Ore by Extraction.  Chem. Eng.  (New York).
     7_0:228-232, November 11, 1963.

     Woodmansee, W. C.  The Mineral Industry of
     California.  In:  Minerals Yearbook  1971, Schreck,
     A. E. (ed.).  Washington, U. S. Dept. of Interior,
     Bur. of Mines, 1973-  2:119-168.

h    Hadzeriga, P.  Some Aspects of the Physical
     Chemistry of Potash Recovery by Solar Evapora-
     tion of Brines.  Trans. Soc. Min. Eng.  229 :l69-
     17^, June 1964.

I    Faith, W. L., D. B. Keyes, and R. L. Clark.
     Industrial Chemicals, 3rd Edition.   New York,
     John Wiley and Sons, 1965-  ^52 p.

j    VerPlarik, W. E., and R. F. Heizer.   Salt in
     California.  Calif. Dept. of Nat' 1 .  Re:;., biv.
     of Mines, Bulletin  175, San Francisco, 195^.
     168 p.

k    Deutsch, Z. G.,  C.  C. Brumbaugh,  and F. H.  Rockwell
     Alkali and Chlorine Industry.  In:   KIrk-Othmer
     Encyclopedia of  Chemical Technology, Standen, A.
     (ed.).  New York, Interscience Publishers,  1963.
     1:671-702, 7^0-756.

1    Bixler, G. H., and  D. L. Sawyer.  Boron Chemicals
     from Searles Lake Brines.  Ind. Eng. Chem.   4_9_:
     322-333, March 1957.               '

     Mies, M. P.  Boron  Compound;;  (0/Jdo;;, liorato;;).
     In:  Klr-k-Othmer Encyclopedia  of  Chemical Tech-
     nology, 2nd Edition, Standen,  A.  (ed . ) .  Mow  York,
     Intor;;oi erico Puh'J l:;ber-:;, \()(>]\ .   3:621-6^0.

rn    R;Jxler, f j . If., and  D.  L. Sawyer.   Boron Chemical;;
     from Searles Lake Brines.   I rid.  Enp. Chem.
     49_:322-333, March 3957-

     Nies, N. P.  Boron  Compounds  (Oxides, Borates).
     In:  Kirk-Othmer Encyclopedia  of Chemical  Tech-
     nology, 2nd Edition, Standen,  A.  (ed.).  New  York,
     Interscience Publishers, 1964.   3_:621-650.

n    Harley, G. T., and  G. E. Atwood.   Langbeinite,
     Mining and Processing.   Ind.  Eng.  Chem.  39:43-48 ,
     January 1947.
                       89

-------
n    Jacobs, J. J.  Potassium  Compounds.  In:   Kirk-
     Othmer Encyclopedia of Chemical Technology,
     2nd Edition, Standen, A.  (ed.).  New York,
     Ihterscience Publishers,  1968.  l6_:371-397-

     Potassium Chloride and Potassium Sulfate.   Chem.
     Eng.  57*168-171, January 1950.

     Shreve, R. N.  Chemical Process Industries,
     3rd Edition.  New York, McGraw-Hill, 1967.
     905 P-

     Turrent Lne, J. W.  Potash in  North  America.   ACS
     Monograph Series, No. 91-  New York, RoLnhold,  19]I3.
     186 p.

     White, N. C., and C.  A. Arond, Jr.   i'ot;K;h
     Product'3 on at Card :;bad .   Cbern. Kng.  Progr.
     16:5^3-530, October  1950.

o,p  Rau, E.   Sodium  Compounds (Carbonates).   In:
     Kirk-Othmer Encyclopedia  of  Chemical Technology,
     2nd Edition, Standen, A.  (ed. ) .  New York,  Inter-
     science Publishers,  1969.  1_8_: 458-468 .

q    Lemke, C. H.  Sodium.   In:   Kirk-Othmer  Encyclo-
     pedia of  Chemical Technology, 2nd  Edition,
     Standen,  A.  (ed.).   New York, Interscience  Pub-
     lishers,  1969.   lS_:432-457.

     Sittig, M.  Sodium Its  Manufacture, Proper-tier;,
     and User;.  ACS Monograph  Series, No.  133-
     Mew York, Roinho'ld,  1956.  p. 33-

r    Bach, R.  0., C.  W. Karri ionr;ki, and  h.  I',.  K1 I o;;t;j
-------
u    Jacobs, J. J.   Potassium Compounds.  In:  Kirk-
     Othmer Encyclopedia of Chemical Technology,
     2nd Edition, Standen, A. (ed.).  New York, Inter-
     science Publishers, 1968.  l6_:371-397.

v    Clapper, T. W.,and  W. A. Gale.  Chloric Acid
     and Chlorates.  In:  Kirk-Othmer Encylopedia
     of Chemical Technology, Standen, A. (ed.).
     Now York, Interscience Publishers, 1%^I.
     5:50-59.

     Chreve, R. N.   Chemical Process Industrie;;, 'jf'd
     Edition.  New York, McGraw-Hill, 196?.  900 p.

w,x  Bach, R. D., C. W. Karnienski, and R. B. Ellestad.
     Lithium and Lithium Compounds.  In:  Kirk-Othmer
     Encyclopedia of Chemical  Technology, 2nd Edition,
     Standen, A. (ed.).  New York, Interscience Pub-
     lishers, 1967.  1^:530-5^6.

     Luckenback, W. F.  Lithium (Annual Review, 1967).
     Eng./Min. J.  168:152, February 1967-
                       91

-------
BRINE AND EVAPORITE CHEMICALS                  PROCESS NO. 11


                          DRYING

1.  Function

    The process removes, almost always  by evaporation,
    at least a portion of the water contained in the input
    material, thereby yielding a product of lower total
    water content.  "Drying" generally involves only the
    removal of "free" water, as opposed to the intended
    function of "Drying/Calcination" (Process 12), which
    generally alters the input composition in additional
    ways, including the removal of combined water.

    Input materials may be liquids or solids, but the
    product is always a solid.  The product of the drying
    process is usually the end product of the operation,
    but in some cases may be an intermediate product,
    transferred to a subsequent process.

    The process may occasionally include the following
    additional steps:

        Grinding
        Cooling
        Screening

    The specific  type of equipment used  in drying processes
    depends both  on economics and on the chemical and
    physical nature of the substances involved.  The equip-
    ment types in general use in the various applications
    of Process 11, described below, include:

        Rotary -  direct fired
               -  externally heated
               -  steam-coil heated
               -  cocurrent
               -  countercurrent
               -  double-cone  (batch)
        Shelf
        Tray
        Pan
        Tunnel
        Spray
        Pluidized bed
        Belt
        Hot-air drying  cycle  on continuous  filters
                            92

-------
    Most of the types  of  dryers mentioned  above  may  be
    operated in continuous,  intermittent-continuous, or
    batch modes, and are  represented in a  wide range of
    production capacities.   Double-cone and tray dryers
    are usually for small outputs and are  usually
    operated batchwise.

    The specific funtion  and type of dryer used in each of
    the applications of  Process  11 are listed in Table  6.

    Rotary coolers are usually used for cooling the  dried
    product, although water-jacketted trough-and-screw
    coolers are sometimes employed.

2.   Input Materials

    The identity and estimated quantity of the respective
    input materials fed  to the various applications  of
    Process 11 are listed in Table 6.

3.   Operating Parameters

    Operating temperatures are listed in Table 7.

4.   Utilities

    Quantities of heat and electrical energy consumed are
    listed in Table 7.

5.   Waste Streams

    All types of solids-drying equipment,  when producing
    dry bulk solids, invariably release particulate matter
    to the atmosphere as  a fugitive emission.  Most
    frequently, fine particles of the substance being dried
    are carried suspended in the exhaust air issuing from
    the dryer.  Even when little or no air is used as the
    direct heating agent, as is the case with a steam-coil
    dryer or a double-cone dryer, dusts arise in the
    discharging and the  immediately subsequent handling of
    the dried product.

    Generally, direct-fired rotary dryers  generate the
    highest absolute quantity of particulate matter per
    unit of product.  Conversely, indirectly heated dryers,
    represented by steam-tube or double-cone rotating types,
    usually produce the  smallest amount of dust per unit of
    product.
                             93

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    In  light  of the a.bove  generalization,  each of the appli-
    cations of Process  11  produces  atmospheric emissions
    of  fine particles of the respective material being
    dried.  Almost no factual information is available
    on  either the quantity or the distribution of the
    particulates from any  of the specific applications.
    Published information  on the airborne dust from rotary
    lime kilns is the basis for estimating the range of  the
    amount  of particulate  emissions from direct-fired
    rotary  dryers:

        0.05  to 0.15 metric tons per metric ton of product,
        when  operating without control equipment.

        0.0005 Lo 0.0? rnotrJc tori3  per metric tori of
        product, when operating with emission control
        equipment.   The latter may  include spray chamber:;,
        bag-filters, cyclones, arid  electrostatic
        precipitators.

    Estimated quantity of  airborne  particulates from spray
    dryers  is in the range given above.

    Estimated quantity of  airborne  particulates from non-
    airswept  dryers is less than 0.005 metric tons per
    metric  ton of product.

6.   EPA Source Classification Code

    a to e.   None established
         f,   3-01-036-Q2  Kilns
    g to n.   None established
    o to q.   None established
         r,   3_o5-040-33  Ore Dryer
    n to y.   None established

7.   References

    k,l,x,y.
        Bach, R. 0., C. W. Kamienski, and R. B. Ellestad.
        Lithium and Lithium Compounds.  In:  Kirk-Othmer
        Encyclopedia of Chemical Technology, 2nd Edition,
        Standen, A.(ed.).  New York, Interscience Publishers,
        1967.  12:529-556.
                             101

-------
m.  Barrett, W. T., and B. J. O'Neal, Jr.  Recovery of
    Lithium from Saline Brines using Solar Evaporation.
    In:  3rd Symposium on Salt. Rau, J. L. , and L. F.
    Dellwig (ed.). Cleveland, Northern Ohio Geological
    Society, 1970.  1:47-50.

k,o,p.
    Bixler, G. H., and D. L. Sawyer.  Boron Chemicals
    from Searles Lake Brines.  Ind. Eng. Chem. 49:322-
    334, March 1957-

a.  Boeglin, A. P., and T. P. Whaley.  Magnesium
    Compounds.  In:  Kirk-Othmer Encyclopedia of
    Chemical Technology,  2nd Edition.  Standen, A. (ed.).
    New York, Interscience Publishers, 1967. 12:708-736.

w.  Clough, R. W.  Miscellaneous Heavy Chemicals.  In:
    Reigels Handbook of Industrial Chemistry, 7th
    Edition.  Kent, J. A. (ed.).  New York, Reinhold,
    1974. p. 137.

i,y. Faith, W. L. , D. B. Keyes, and R. L.  Clark.
    Industrial Chemicals, 3rd Edition.   New York,
    John Wiley and Sons,  Inc. 1965-  852  p.

e.  Hadzeriga, P.  Some Aspects of the Physical
    Chemistry of Potash Recovery by  Solar Evaporation
    of Brines.  Trans. Soc.  Win. Eng.  229:169-174,
    June 1964.

r,s. Hartley, G. T., and G. E. Atwood.  Langbenite—
    Mining  and processing.   Ind. Eng.  Chem. 39:43-47,
    January 1947-

b.  Havighorst, C. R. and S. L. Swift.   Magnesia
    Extraction from Seawater.   Chem. Eng.  (New  York).
    71:84-86,  September  2,  1965.

c,d. Hester, A. S., and H. W. Diamond.  Salt Manufacture.
    In:  Modern Chemical  Processes.  Murphy, W. J.  (ed.)
    New  York,  Reinhold,  1956.   4:152-163.

n.  Hou, T. P.  Alkali and  Chlorine  Production.   In:
    Roger's Industrial Chemistry,  6th  Edition.  Furnas,
    C.  C.  (ed.).   New York,  Van Nostrand,  1942.
    1:402-450.

q.  Jackson,  D.,  Jr.   Solution  Mining  Pumps New Life
    Into Cane  Creek Potash  Mine.  Eng./Min.  J.   174:59-
    69,  July  1973.
                        102

-------
g,e,q,r,s,v,w.
    Jacobs, J. J.  Potassium Compounds.  In:  KIrk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition.
    Standen, A.(ed.).  New York, Interscience Publishers,
    1968.  16:371-397.

t.  Lemke, C. H.  Sodium.  In:  Kirk-Othmer Encyclopedia
    of Chemical Technology, 2nd Edition.  Standen, A.
    (ed.).  New York, Interscience Publishers, 1969.
    18_: 432-457.

General:
    Lewis, C. J., and B. B. Crocker.  The Lime Industry's
    Problem of Airborne Dust.  J. Air Pollution Contr.
    Assoc.  1_9.: 31-39, January 1969.

q.  Mapjraw, R. M.  New Mexico Sylvlnite.  I rid. Knr,.
    Chem.  3_0: 861-871, August 1938.

General:
    McCormick, P. Y., R. L. Lucas, and D. F. Wells.
    Section 20.  In:  Chemical Engineer's Handbook,
    4th Edition. Perry, R. H. (ed.). St. Louis,
    McGraw-Hill, 1963. p. 20-1 to 20-96.

g.  Mumford, R. W. Potassium Chloride from the Brine
    of Searles Lake.  Ind. Eng. Chem. 3_0_: 872-877,
    August, 1938.

m.  Nevada Brine Supports a Big New Lithium Plant.
    Chem. Eng.  (New York).  7_3_:86-88, September 15,1966.

o,p. Nies, N. P.  Boron Compounds  (Oxides, Borates).
    In:  Kirk-Othmer Encyclopedia of Chemical
    Technology, 2nd Edition.  Standen, A.(ed.). New
    York, Interscience Publishers, 1964.  3_:621-650.

e , q, r, s .
    Potassium Chloride and Potassium Sulfate.  Chem.
    Eng.  (New York).  57:168-171, January 1950.

n,u Rau, E.  Sodium Compounds (Carbonates).  In:
    Kirk-Othmer Encyclopedia of Chemical Technology,
    2nd Edition.  Standen, A.(ed.).  New York,
    Interscience Publishers, 1969.  l8_:458-468.

g.  Robertson, G. R.  Expansion of the Trona Enterprise.
    Ind. Eng. Chem.  34:133-137,  February 1942.
                       103

-------
b.  Schambra, W. P.  The Dow Magnesium Process at
    Preeport, Texas.  Trans. Amer , Inst. Chem. Eng.
    11=35-51, January
b,g,k,l,q,s.
    Shreve j R. N. Chemical Process Industries,
    Edition, New York, McGraw-Hill, 1967. 905 p.

t.  Sittig, M.  Sodium, Its Manufacture, Properties, and
    Uses.  ACS Monograph Series, No. 133. New York,
    Reinhold, 1956. p. 33.

f.  Smith, E. E., and H. J. Andrews.  Mining Great
    Salt Lake — A $75 Billion Reserve of Lithium and
    Sodium Salts.  Unpublished paper presented at
    February 21, 1967 meeting of Am. Inst. Min. Eng.,
    Los Angeles.

g.  Tuple, J. E.  The Industrial Development of Searles
    Lake Brine.  ACS Monograph Series, No. 19, New
    York, Reinhold, 1929-  182 p.
    Turrentine, J. W,  Potash in North America.
    ACS Monograph Series, No. 91. New York, Reinhold,
    19*13 .  186 p.

v.  Two Men and a Tub.  Chem. Wk.  73.: 7 7- 83,
    December 5, 1953.
    VerPlank, W. E., and R. P. Heizer.  Salt in
    California.  Bulletin  1975,  California Dept .  of
    Nat'l. Res. San Francisco. March  1958.  168 p.

q,r,s.
    White, N. C., and  C. A. Arend, Jr.  Potash
    Production at Carlsbad.   Chem. Eng. Progr.  46 : 5?3
    531,  October 1950.

g,h. Woodrnansee, W. C.  The Mineral Industry of
    California.  In:   Minerals Yearbook 1971.
    Schreck,  A.E.(ed.).  Washington,  U. 3. Dept.  of
    the  Interior, Bur. of  Mines,  1973.  2:119-168.
                        104

-------
BRINE AND EVAPORITE CHEMICALS                PROCESS NO. 12


                    DRYING/CALCINATION

1.  Function

    Generally, the process alters the chemical composition
    of the input material by heating and simultaneously
    removes all or most of the "free" water.  Most frequently,
    the chemical changes involved are the removal of combined
    water and carbon dioxide.

    The various applications of the process may include any
    of the following steps:

    •Grinding (of input material or intermediate product)
    •Product cooling
    •Product briquetting
    •CO2 recovery

    Essential equipment may be identical or similar to that
    used for drying, and is usually represented by one of
    the following types:

    •Rotary
        Direct-fired
        Externally heated
        Steam-coil heated
        Cocurrent
        Countercurrent
    •Shelf
    •Tray
    • Pan
    •Spray
    •Pluidized bed

    Any of the types of dryer-calciners mentioned above may
    be operated in continuous, intermittent-continuous, or
    batch modes, and are represented in a wide range of
    production capacities.  Rotary dryer-ca]cinero and rotary
    coolers are the type most frequently encountered in the
    various applications of Process 12.

    Table  8 identifies the specific applications of Process
    12 and lists the types of equipment used.

2.  Input Materials

    The identity and quantity of the input materials
    corresponding to each of the applications of Process 12
    are given in Table 8.
                              105

-------
























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-------
 Operating Parameters

*a.   1)   Dried Mg(OH)2
         Kiln temperature is 200°  to 250°C.   Pressure is
         atmospheric.

     2)   Caustic-calcined MgO
         Kiln temperature is 400°  to 600°C.   Pressure is
         atmospheric.

     3)   Dead-burned MgO
         Kiln temperature is l800°C at the sintering
         section.   Residence time  in the kiln is 2.5 to
         4 hours.

 b.   Na2C03 from Na2C03»H20 (Searles Lake, upper level)

     •Calcination temperature is 125°C (estimated)
     •Pressure is atmospheric.

 c.   Na2COs from NaHC03 (Searles Lake, lower level)

     •The calciner temperature reaches 400°C.
     •Pressure is atmospheric.

 d.   Na2CC>3 from the Solvay Process

     •Final Na2C03 temperature is 175° to 225°C.
     •Pressure is atmospheric.
     •Steam-heated calciners with a capacity of 360
      metric tons per day are 2.5 meters in diameter
      by 30 meters long containing finned tubed.

 e.   Na2C03 from Na2C03»NaHC03•2H20 (Wyoming)

     •Calcination temperature is 200°C.
     •Temperature for gas-fired calciners is 250°C.
     •Pressure is atmospheric.

 f.   Crude Na2COs from trona ore (Wyoming)

     •Temperature is 150° to 200°C.
     •Pressure is atmospheric.

 g.   Na2C03 from Na2C03»H20  (Wyoming)

     •Calcination temperature is 125°C  (estimated).
     •Pressure is atmospheric.
Separate industry operations employing  the process are
identified with a specific lower case letter which is
retained as an identifier in each element of this
process description.


                          108

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h.  Dried LiOH

    •Temperature is 200°C
    •Pressure is slightly below atmospheric.

Utilities

a.  1)  Dried Mg(OH)2 product

        •Natural gas
          100 cubic meters per metric ton dried Mg(OH)2
        •Electrical energy
          10 to 20 kWh per metric ton dried Mg(OH)2

    2)  Caustic-calcined MgO

        •Natural gas
          150 cubic meters per metric ton MgO
        •Electrical energy
          10 to 20 k¥h per metric ton MgO

    3)  Dead-burned MgO

        •Natural gas
          200 cubic meters per metric ton MgO
        •Electrical energy
          10 to 20 kWh per metric ton MgO

b.  Na2C03 from Na2C03-H20 (Searles Lake)

    •Steam
      0.5 metric tons per metric ton Na2C03
    •Electrical energy
      10 to 20 kWh per metric ton Na2C03

c.  Na2C03 from NaHC03 (Searles Lake)

    •Natural gas
      120 cubic meters per metric ton Na2C03
    •Electrical energy
      10 to 20 kWh per metric ton Na2C03

d.  Solvay Na2C03 from NaHC03

    •Steam (30 kg/cm2)
      2 metric tons per metric ton Na2C03
    •Electrical energy
      10 to 20 kWh per metric ton Na2C03
                         109

-------
    e.   Na2C03  from Na2C03«NaHC03»2H20  (Wyoming)

        •Steam
          1 metric ton per metric ton Na2C03
        •Electrical energy
          10  to 20 kWh per metric ton Na2C03

    f.   Crude Na2C03  from trona  ore  (Wyoming)

        •Steam
          1 metric ton per metric ton crude Na2C03
        •Electrical energy
          10  to 20 kWh per metric ton Na2C03

    g.   Na2C03  from Na2C03»H20  (Wyoming)

        •Steam
          0.5 metric  tons per metric ton  Na2G03
        •Electrical energy
          10  to 20 kWh per metric ton Na2C03

    h.   Dried LiOH

        •Steam  (30 kg/cm2)
          1 metric ton per metric ton LiOH
        •Electrical energy
          10  to 20 kWh per metric ton LiOH

5.   Waste Streams

    a.   Particulate emissions  in the kiln exhaust  gases  to
        the  atmosphere vary  with the recovery  equipment
        used.  Good practice should  limit emissions  to less
        than  0.001 metric  ton  per metric  ton Mg(OH)2 or
        MgO.

        Some  under-burned  and  over-burned MgO  is  collected
        during  start-ups and periods of erratic  operation.
        This  material Is used  as landfill. No quantitative
        information  Is  available.

    b,c,d,  Particulate  emissions In the  kiln  exhaust gases
    e,f,g.  to  the  atmosphere  vary  with the recovery
            equipment used.   Good practice should limit
            these emissions  to less  than  0.001 metric ton
            per metric  ton Na2C03.

    h.   Particulate  emissions  in the dryer exhaust gases to
        the atmosphere  are estimated to be less than 0.001
        metric  ton per metric  ton of LiOH.
                             no

-------
6.   EPA Source Classification Code

    a.through h:  None established


7.   References

    a.   Boeglin, A. P., and T. P. Whaley.  Magnesium
        Compounds.  In:  Kirk-Othmer Encyclopedia of
        Chemical Technology, 2nd Edition. Standen, A.  (ed.)
        New York, Interscience Publishers, 196?. 12:
        724-728.

        Havighorst, C. R.  Magnesia Extraction from
        Seawater.  Chem. Eng. (New York). 7_2:84-86,
        August 2, 1965.

    b.   Hightower, J. V.  The Trona Process. .  . and its
        Unique Features.  Chem. Eng. (New York). 58:104-
        106, August 1951.

    b,d,g.  Deutnch, Z. G., C. C. Brumbaugh, and E. F.
        Rockwell.  Alkali and Chlorine (Sodium Carbonate).
        In:  Kirk-Othmer Encyclopedia of Chemical
        Technology, 2nd Edition. Standen, A. (ed.).  New
        York, Interscience Publishers, 1963. I:712-7lj8.

    b,e,g.  Sommers, H. A. Soda Ash from Trona. Chem.  Eng.
        Progr. ^6:76-79,  February I960.

    c.   Nies, N. P.  Boron Compounds (Oxides, Berates).
        In:  Kirk-Othmer Encyclopedia of Chemical
        Technology, 2nd Edition. Standen, A. (ed.). New
        York, Interscience Publishers, 1964. 3_:636.

        Plant Expansion at Trona Boosts Soda Ash and Borax
        Capacity. Chem. Eng.  (London). 5^.: 102-103,  April
        1949.

    d.   McCormick, P. Y., R. L. Lucas, arid D. P. Wells.
        Section  20.  In:  Chemical Engi necr-r;' Handbook,
        4th EdiaUon.   Perry, K. II. (od.). ,'ji,.  Loujr,,
        McGraw-UllL, Ifj63 . p. 20-]^ to 20-V) .

        ohreve,  R. N.   Chemical Process Industries, 3rd
        Edition. New York, McGraw-Hill, 1967, p. 230.
                             in

-------
e,f,g.  Rau, E.  Sodium Compounds (Carbonates).   In:
    Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
    Edition. Standen, A. (ed.). New York, Interscience
    Publishers, I960, 1^:461-465.

h.  Bach, R. D.} C. W. Kamienski, and R. B. Ellestad.
    Lithium and Lithium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A. (ed.). New York, Interscience
    Publishers, 1967, 12:545.
                        112

-------
BRINE AND EVAPORITE CHEMICALS                PROCESS NO. 13


                     SOLAR EVAPORATION

1.  Function

   *a.  As applied to "solar salt" production at tidewater
        locations (Figure 5) - The process evaporates
        seawater in open, diked ponds, producing moist
        crystals of crude sodium chloride (NaCl) bulk-
        loaded in tramcars or dump trucks.  The crude salt
        is forwarded to Process ]_1|5 Figure 5.  Seawater
        "bitterns", the mother liquor from the NaCl
        crystallization, also result as a by-product.

        The process includes the sequential steps of:

        •Seawater intaking (gravity flow or pumping)
        •Transporting partially evaporated seawater
         ("pickle")through pond system (gravity flow or
         pumping)
        •Discharging bitterns
        •Salt (NaCl) harvesting

        Ponds may be hundreds of hectares in area,, and
        generally about one meter in depth, with compacted
        clay floor.  Harvesting equipment includes
        elaborate, specially constructed motorized equip-
        ment, front-end loaders, bulldozers, dump trucks,
        locomotive-drawn tramcars, and belt conveyors.

    b.  As applied to processing Great Salt Lake brine
        (Figure 6) - The process evaporates brine from Great
        Salt Lake to obtain a moist mass of mixed crystals
        of sodium chloride (NaCl) and several double salts,
        including astrakanite  (MgSO^-NaaSO^•4H20), leonite
        (MgSCU'KzSOit-lJHzO), kainite (KCl-MgSOi, • 3H20) , and
        possibly carnallite (KCl-MgCl2-6H20).  The NaCl is
        generally unwanted.  A magnesium chloride bittern
        is also obtained as a potentially marketable by-
        product.  The mixed crystals are forwarded to
        Process 10, Figure 6.

        Sequential process steps and equipment used  are
        almost identical to those in a, above.
 *  Separate  industry  operations  employing  the  process  are
   identified with  a  specific  lower  case letter which  is
   retained  as  an identifier  in  each element of this
   process description.
                             113

-------
c.   As applied to processing Searles Lake brine (Figure
    7) - This process is a recently(1973)commenced
    alternative to some of the steps of Process 10,
    Figure 7.

    The process crystallizes sodium chloride (NaCl)
    from Searles Lake brine by solar evaporation.
    (It is surmised that the brine is pumped from  the
    upper crystal body of the lake.)  The process  is
    restricted to amounts such that only NaCl pre-
    cipitates.  The MaCl solids are wasted or periodically
    harvested by outside contractors as a crude NaCl
    product.  The process is conducted solely as a
    brine preconcentrator.

    The process includes the following sequential  steps:

    1)  Brine pumping and gathering
    2)  Solar evaporation
    3)  Crystal harvesting
    4)  Bittern removal for further processing

d.  As applied to processing brine from Bristol Lake,
    California  (Figure 9 ) - The processevaporates brine
    pumped from Bristol Lake, obtaining a nominal  35%
    calcium  chloride  (CaCl2) liquor, whose actual  CaCl2
    content  approaches  40%.  Sodium chloride  (NaCl)
    crystallizes from the brine but is abandoned  in the
    solar ponds.

    The process includes the sequential steps  of  pumping
    brine into the  solar ponds arid pumping 35%  CaCl2
    liquor from the  ponds into tank cars, either  as a
    marketable product  or for transfer to Process  10,
    Figure 9-

e.  As applied to processing brine  from Salduro Marsh,
    Bonneville, California  (Figure  9) - Process obtains
    crystalline mixtures of sodium  chloride  (NaCl),
    potassium chloride  (KC1), and double  salts  of potas-
    sium  and magnesium, such as kainite  (KCl-MgSCU »3H20)
    and carnallite  (KCl«MgCl2»6H20),  by evaporating
    brine pumped from Salduro Marsh in  solar  evaporating
    ponds.   The mixed crystals arc  forwarded  to
    Procfjrin  "I 5, Figure  9.   A  final  bittern  (;ont;i i n 1 n,«;
    appro/ Lrrirj to Jy  3?% MgCJ.2 i;; also obtained.   This i :;
    sometimes sold  as a by-product.

f .  As  applied  to process ing brlno__?jt _HI_l_vo^.J.'(^>!<_,
    N e v a d a  (F i g u r e  13 )  -  The process  remover;  sodium
    chloride CNaCl) and potassium chloride  (KO'l)  plus
    smaller  quantities  of magnesium hydroxide
                         114

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        [Mg(OH)2],  and calcium sulfate (CaSCU)  from
        lithium-bearing well  brine  by solar evaporation.
        The concentrated brine is forwarded to  Process  33,
        Figure 13  for lithium recovery.

        Process includes the  following sequential steps:

        •Brine production and gathering
        •Solar evaporation
        •Bittern pumping

    g.   As applied  to recovery of sylvlnite (mixed KCl-NaCl)
        from brine  resulting  from solution-mining potash
        deposits at Moab, Utah (Figure 17)  - Process
        recovers mixed crystals of  potassium chloride (KC1)-
        sodium chloride (NaCl) by evaporating the KCl-NaCl
        brine forwarded from  Process  3,  Figure  3.  The
        mixed crystal slush or slurry Is pumped to Process
        51, Figure  17.

        Equipment consists of diked,  earthen-bottom,  PVC-
        lined solar evaporating ponds, crystal-harvesting
        equipment consisting  of specialized scraper-loaders,
        slurry pumps, and pipeline  system.

2.   Input Materials

    a.   Seawater.  Depending  upon prevailing coastal  salin-
        ities, between 38 and 45 cubic meters are required
        per metric  ton of crude NaCl  produced.   Seawater
        from the "open sea" has the following composition
        with respect to the major dissolved ions:

               Ion             ppm

            Chlorine         19,360
            Sodium           10,767
            Magnesium         1,297
            Sulfate           2,652
            Calcium             408
            Potassium           388
            Bromine              66
            Bicarbonate         140

        The concentration of the ions shown above in
        coastal waters may vary widely; from 50 to 120% of
        the concentrations shown is a typical range.

    b.  Brine  from  the  northern arm  of  the  Great  Salt Lake
        has  the  following  typical  composition  (1963-1965),
        with  seasonal variations:


                           115

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           Ion             ppm

        Magnesium        12,200
        Potassium         7,200
        Sulfate          23,800
        Chloride        149,200
        Sodium           80,000

    In practice, the specific brine consumption may
    differ widely from the values given above, depend] rip;
    on ability to market arid upon the specific method
    of operation.

c.   Brine from the upper crystal body of Searles Lake
    has the following approximate composition:
                  'f-'
           Ion             ppm

        Sodium          111,400
        Potassium        25,700
        Lithium              80
        Chloride        120,900
        Bicarbonate       1,100
        Carbonate        26,900
        Sulfate          45,600
        Tetraborate      12,200

    Per metric ton of each of the products of interest
    currently produced, the quantities of raw br i ne
    theoretically required are:

                       Brine Required
         Product       (cubic meters)

        Na2S04              12.4
        Na2C03              16.8
        Na2Bit07»5H20        36.2
        KC1                 17.0

d.  Brine from Bristol Lake typically contains the
    following quantities of calcium chloride  (CaCl2)
    and sodium chloride (NaCl):
        CaCl2
        NaCl           14$

    On a theoretical basis, the quantity of brine
    required per metric ton of Ca.Cl2  (100$ basis)  is
    6.3 cubic meters.
                         116

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Brine collected from Salduro Marsh has the following
typical composition:
     Dissolved
    Constituent

       NaCl
       KC1
       MgCl2
       LiCl
   Percent

  18 to 24
  0.8 to 1.2
  0.9 to 1.2
  0.2 to 0.3
  0.3 to 0.4
  0.03 to 0.04
On a theoretical basis, the brine required per
metric ton of each of the desired products, con-
currently produced is:
    Product
Brine Required
(cubic meters)
     KC1             69 to 104
     MgCl2           69 to  93
     (100$ basis in 32$ solution)

The actual brine requirement is probably at least
150% of the values listed above.

Well-brines at Silver Peak, Nevada, typically have
the following composition:
       Ion

    Sodium
    Potassium
    Magnesium
    Lithium
    Calcium
    Sulfate
    Chloride
  Percent

   6.2
   0.8
   0.04
   0.04
   0.05
   0.71
  10.1
On a theoretical basis, 430 cubic meters of brine
are required per metric ton of Li2C03 produced.

An undisclosed quantity of calcium hydroxide,
estimated to be 0.7 metric tons per metric ton of
Li2C03, is added to the brine entering the first
pond, to precipitate magnesium as Mg(OH)2.

The brine fed to the solar ponds is a saturated
aqueous solution of KC1 and NaCl, containing about
                     117

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        12% KC1  and 20%  NaCl  at  34°C.   Theoretically,  7
        cubic  meters of  this  brine  are  required  to  produce
        1 metric ton of  KC1 product.

        Approximately 2.5 metric tons  of mixed crystals
        from the solar ponds  are required per ton of KC1
        produced.

3.   Operating  Parameters

    Items a through g.  All solar evaporation processes  are
    necessarily  operated at prevailing  year-round atmospheric
    temperatures.   Annual net evaporation rate,  rainfall
    pattern, and temperature  pattern are critical factors.

    a.   The following parameters partially describe the
        solar evaporation of  seawater on the California
        coast:

        •Annual  net evaporation rate is 85 to 110 cm.
       - »Water of San Francisco Bay typically contains 26.5
         gms.  NaCl per liter.
        •Ratio of evaporating pond area to crystallizing
         pond area is about 15:1.
        •Salt is harvested once per year.  Specific produc-
         tion rate is approximately 85 metric tons NaCl  per
         year per hectare of  total pond area.
        •Total solar pond area in salt production on the
         California coast is  between 13,000 and 17,000
         hectares.

    b.   Annual net evaporation rate ranges from 80 to 106 cm.
        Approximately 5,600 hectares of solar ponds adjoin-
        ing Great Salt Lake are devoted to KaSCH-NaaSOit
        recovery.

    c.   Only an estimated 20% of the total brine taken from
        Searles Lake  is processed in solar pondy.

    d.   Scale of CaCl2 recovery operations  at Bristol Lake.
        is undisclosed.

    e.   Production of KC1 from Salduro Marsh brine
        approximates  55,000 metric tons per year (1971).

    f.   Annual net evaporation rate averages 145 cm.  Total
        solar pond area is approximately 1,590 hectares
        and has capacity to produce between 4,500 and 6,000
        metric tons per year of Li2C03.
                            118

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g.  Temperature of brine from Process 3 is invariant at
    34°C, governed by prevailing temperature in mine at
    approximately 1,000 meters subsurface.

    Approximately 180 hectares of pond area are
    required to sustain an annual production rate of
    275,000 metric tons of KC1 product.

    Crystal slurry harvested from solar ponds and pumped
    to Process 51 averages 35% solids.

Utilities

Electrical energy - Estimates of consumption for driving
pumps is shown below.  Where applicable, this includes
well-pumps.

a.  Between 0.5 arid 1.5 kWh per metric ton of NaCl.

b.  Between 0.75 and 1.5 kWh per metric ton of K2SCu.

c.  Between 1 and 2 kWh per metric ton of Na2SOit.

d.  Between 0.2 and 0.3 kWh per metric ton of CaCl2
    (100% basis).

e.  Between 2 and 3 kWh per metric ton of KC1.

f.  Between 250 and 400 kWh per metric ton of Li2C03.

g.  Estimated electrical energy required to fill solar
    ponds with brine is 20 kWh per metric ton of KC1
    produced.

    Estimates of fuel required to power crystal-
    harvesting equipment, where applicable, would be
    based on data too remote to produce meaningful
    numbers.

Water -  Fresh or brackish water is required to flush or
dissolve unwanted NaCl crystals from  the solar ponds
at Great Salt Lake.  The requirement  is estimated to
be 15 to 30 cubic meters per metric ton of K2SCU
produced.

Waste Streams.

a.  Unless marketed, the final bitterns (mother  liquor)
    from crystallizing ponds constitute a waste  stream
    and  are drained into tidewater.   The quantity is
                        119

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    approximately  1  cubic  meter  per  metric  ton  of
    crude  NaCl  produced, and  the composition  at a
    specific  gravity of 30°Be is typically:

        NaCl             12.5%
        MgCl2             8.7
        MgSCU             6.1
        KC1               1.9
        MgBr2             0.18

    Between 6 and  10 metric tons of  NaCl per  metric
    ton of K2S(H produced  is  returned to Great  Salt
    Lake in the form of a  solution or slurry  of
    crystals, amounting to 15 to 30  cubic meters per
    ton of
    A MgClz-rich bittern,  sometimes wasted by being
    returned to Great Salt Lake, is estimated to contain
    1 metric ton of MgCl2  per metric ton of KaSOi,
    produced.  Stream size is estimated to be 4 cubic
    meters per metric ton  of K2SOit.  This stream in
    sometimes combined with another stream from Fjfnj.ro
    4 and the total forwarded to Process 10, Figure 4.

c.  This process is relatively new (1972).  No informa-
    tion on waste streams  is available.

d.  Approximately one metric ton of NaCl crystals are
    abandoned in solar ponds per ton of CaCl2 produced.

e.  NaCl crystals (16 to 20 metric tons per metric ton
    of KC1) are abandoned  in solar ponds.  There are no
    liquid waste streams.

f .  A total of 64 metric tons of solids per metric ton
    of Li2CC>3 produced are abandoned in solar ponds.

    Composition of solids  varies from pond to pond,
    from impure NaCl to a mixture of NaCl, KC1, and
    glaserite  (3Na2S04 «K2SOi» ) .

g.  A slurry consisting of solid NaCl crystals plus clay
    particles in NaCl brine is discharged to tailing:;
    ponds.  The total amount of solids discharged is
    estimated at 1.5 to 1.8 metric tons per metric ton
    of KC1 produced.

EPA Source Classification Code

a through g:  None established
                         120

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7-   References

    a.   VerPlank, W.  E. ,  arid H.  F. lleixer.   Salt in
        California.   Bulletin 175,  San Francisco.  California
        Dept. of Nat'l.  Res., March 1958, 168 p.

    b.   Glassett, J.  M.,  and B.  J. Anderson.  The Recovery
        of Salts from the Waters of Great Salt Lake.
        Bulletin No.  21,  University of Utah, Salt Lake
        City, May 1964,  80 p.

        Handy,  A. H., and D. C.  Hahl.   Great Salt Lake:
        Chemistry of  the  Water.   In:  Guidebook to the
        Geology of Utah,  No. 20:  The  Great Salt Lake.
        Stokes, W. L. (ed.). Salt Lake City, Utah Geology
        Soc., 1966,  p. 135-151.

        Smith,  E. E., and H. J.  Andrews.  Mining Great Salt
        Lake - A $75  Billion Reserve of Lithium, Magnesium,
        Potash and Sodium Salts.  Unpublished paper-
        presented at  the  Meeting of the Amor. Inst. of
        Mining Eng.,  Los  Angelos, February 21, 1967-

    c.   Shreve, R. N.  Chemical Process Industries.  3rd
        Edition. New York, McGraw-Hill, 1967, p.  287-

    c,d. Woodmansee,  W.  C.  The Mineral Industry of
        California.   In:   Minerals Yearbook - 1971, Shreck,
        A. E. (ed.).  Washington, U. S. Dept. of the
        Interior, 1973.  2:119-168.

    d.   VerPlank, W.  E.,  and R. F. Heizer.  Salt in
        California.   Bulletin 1975, San Francisco,  California
        Dept. of Nat'l.  Res., March 1958, 168 p.

    e.   Hadzeriga, Pablo.  Some Aspects of the Physical
        Chemistry of Potash Recovery by Solar Evaporation
        of Brines.  Trans. Am. Inst. Min. Met. Petr. Eng.,
        Soc. Mln. Eng. of AIME.   2_2j9:169-174 , June 1^64.


        Mitko,  F. C.   The Mineral Industry of Utah.  In:
        Minerals Yearbook - 1971, Shreck, A. E.  (ed.).
        Washington,  U. S. Dept.  of the Interior, 1973.
        2_:723-738.

    f.   Barrett, W.  T.,  and B. J. O'Neill,  Jr.  Recovery of
        Lithium from Saline Brines using Solar Evaporation.
        In:  Third Symposium on Salt.   Rau, J. L.,  and
        L. F. Dellwig (ed.). Cleveland, Northern Ohio
        Geological Society, 1970. 2:47-50.
                             121

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    Nevada Brine Supports a Big Lithium Plant.  Chem.
    Eng. 73:86-88,  Aug.  15, 1966.

g.  Jackson, Daniel, Jr.   Solution Mining Pumps New
    Life into Cane Creek Potash Mine. Eng./Min. J.
    17^:59-69,  July 1973.
                        122

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BRINE AND EVAPORITE CHEMICALS                  PROCESS NO.  14


                     WASHING /DRAINING

I.  Function

    This process (See Figure 5) further removes impurities,
    namely clay and adhering bitterns, from harvested
    salt .

    Harvested salt is discharged from dump cars into a con-
    centrated brine pit.  Centrifugal pumps move the slurry
    to a spiral classifier.  There a countercurrent concen-
    trated brine wash separates dirt from the harvested
    salt.  The salt is then screened to remove large clay
    balls before entering a log washer, where the remaining
    clay balls are broken up.  The salt proceeds to an in-
    clined dewatering drag containing a fresh water rinse
    that further removes magnesium-containing salts.  The
    salt is then conveyed to storage, Process 10 or
    Process 11.

2.  Input Materials

    Harvested salt contains about 97-8% NaCl.  Its
    impurities include clay, gypsum, and adhering bitterns.

3 .  Operating Parameters

    A double 0.6 by 6 meter spiral classifier has a
    capacity of 136 metric tons of salt per hour.  The
    screens are 2 1/2-cm mesh, followed by double steel
    0.6 by 6 meter log washers.  The inclined dewatering
    drag is 3 by 30 meters.

4.  Utilities
    Fresh water - Rinse for dewatering drag - approximately
    0.05 cubic meter per metric ton of NaCl.

5 .  Waste Streams

    All drain streams are pumped to a wash brine circulating
    pond where dirt and gypsum settle, constituting a land-
    fill disposal method.  The estimated sediments are
    0.001 to 0.01 metric ton per metric ton of NaCl.

    Fresh brine make-up replaces a small pond bleed-off to
    prevent accumulation of magnesium salts.  This bleed
                             123

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    stream is  estimated to  be  0.05 cubic  meter per metric
    ton of Had.   The bleed stream is  discharged into
    tidewater.

6.   EPA Source Classification  Code

    None established.

7•   References

    VerPlank,  W.  E.} and R. P. Heizer.  Salt in California.
    Bulletin 175, San Francisco, California. Dept. of Nat'1
    Res., March 1958. 168 p.
                             124

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BRINE AND EVAPORITE CHEMICALS                  PROCESS  NO.  15


                       FROTH FLOTATION

1.  Function

   *a.  As applied to the separation of dilithium sodium
        phosphate from burkeite liquor at Searles Lake,
        California (Figure 7) - The process recoversa~
        froth of dilithium sodium phosphate (LiaNaPOit)
        crystals from burkeite (Na2C03 • 2Na2SOit) liquor
        forwarded from Process 10, (see Figure 5).  The
        Li2NaPOit froth is forwarded to Process 16, Figure
        7 and the Li-stripped burkeite liquor  is returned
        to Process 10 for further processing.

        Major equipment consists of specialty  designed,
        vertical, cylindrical flotation tanks.

    b.  As applied to pot_assium chloride recovery from
        mixed crystals of potassium chloride and sodium
        chloride (Figure 9) - The process separates crystals
        of potassium chloride (KC1) from a mixture of KC1
        crystals and sodium chloride (NaCl) crystals
        received from Process 13.  The KC1 crystals are
        forwarded to Process 11, while the NaCl crystals
        are wasted.

        Essential equipment consists of banks  of flotation
        cells of conventional design.

        The step of wet-grinding the feed crystals may be
        included.

    c.  As applied to the recovery of KC1 from natural
        sylvinite (mixed KCl-NaClj in the Moab, UbaTTand
        the Carlsbad, N.M7 areas (Figure 17) -The process
        separates KC1 crystals from a slurry of mixed
        KCl-NaCl crystals received from Process 51.  The
        KC1 crystals are then forwarded either to Process 11,
        or to the potassium sulfate (K2S02,) operations shown
        on Figure 18.  The NaCl crystals are wasted.

        The process application is almost identical to that
        of b, above, and uses similar equipment.

* Separate  industry  operations  employing  the  process  are
   identified with  a  specific  lower  case  letter which  is
   retained  as  an identifier  in  each element  of this
   process description.


                            125

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        In most  cases,  KC1  crystals  are  froth-floated  away
        from  NaCl  crystals,  but  the  reverse  situation  Is
        also  commercial.

    d.   As applied to  lithium-value  recovery from spodumene
        ores  (Figure  24)  -  The process recovers  a lithium-
        rich  concentrate  from ground spodumene  ore (a
        lithium  silicate, LiAlSiaOe).  The ground ore  is
        received from  Process 5-   The  concentrated spodumene
        from  the froth is forwarded  to Process  62 of either
        of two alternative  operations  for lithium recovery.
        The gangue material is wasted  to a tailings pond  or
        pile.

        Major equipment is  similar to  that of b, above.

        The process includes the initial step of slurrying
        the  input  ore  in water.

2.   Input Materials

    a.   Burkeite liquor,  prepared in Process 10 by dissolving
        burkeite crystals in hot water,  is  fed to the  process.
        The  liquor is  actually  a slurry  of fine Li2NaPOit
        crystals.   An approximation of the  feed slurry com-
        position entering the process  is:
                              22%
            Na2C03             8%
            Li2NaP04 (in
             suspension)       0.4%
            H20               69.6%

        Approximately 350 cubic meters of this slurry is
        required per metric ton of Li2C03 produced.

        Various flotation agents, usually soaps and kerosene,
        are added to the entering slurry in amounts
        believed to be 10 to 20 kilograms per metric ton
        of Li2C03 .

        The principal input stream is a KCl-NaCl crystal
        slush, received from Process 13, containing about
        30% of KC1 on a dry basis.  The crystals are
        believed to be slurried in a saturated KCl-NaCl
        brine from an internal recycle flow, and then wet-
        ground prior to flotation.

        Estimated consumption of the KCl-NaCl mixture is 3
        to 4 metric tons per metric ton of KC1 produced.
                             126

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        Estimated  requirement  of  make-up  water  Is  1  to  2
        cubic  meters  per  metric ton  of  KC1  produced.

        Various  flotation agents,  usually aliphatic  amines,
        are  added  to  the  flotation cell feed  slurry  in
        amounts  estimated between 1  and 5 kilograms  per ton
        of KC1 produced.

    c.   Principal  input  stream consists of  a  pumpablo  slurry
        of a mixture  of  KCl-NaCl  crystals in  saturated
        NaCl-KCl brine.   Overall  slurry compositions vary
        widely with exact identity of sylvinite ore  mined.
        A typical  composition  is:

            Suspended KC1      6%
            Suspended NaCl    12%
            Saturated brine    82%

        Approximately 15  cubic meters of  the  slurry  are re-
        quired per metric ton  of  KC1 produced.

        Various  conditioners,  depressants and flotation agents
        are  added  to  the  entering stream  in amounts  estimated
        between  1  and 5  kilograms per metric  ton of  KC1
        produced.

    d.   The  principal input  stream is finely  ground
        spodumene  ore containing  0.5 to 1.0 percent  Li.
        Estimated  requirement  of  the ore  Is 20  to  40 metric
        tons per metric  ton  of LI2C03 produced.

        An estimated  80  to 150 cubic meters of  water per
        metric ton of Li2C03 Is required  to slurry the  ore.
        Most of  the water may  be  recycled.

        Various  conditioners,  depressants and flotation
        agents are required  in amounts estimated between
        50 and 100 kilograms per  metric ton of  Li2COs
        produced.

3.   Operating  Parameters

    a.   Process  is conducted at 40°C (estimated) and at
        atmospheric pressure.

        Only one operation exists producing LI2C03 via
        Ll2NaPOit.   This  produces  an  estimated 2,000  metric
        tons per year Li2C03,  corresponding to  a volume
        flow entering the process estimated to  be  1.5  to
        2.0  cubic  meters  per minute.
                             127

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    b.  The  process  is  conducted  at  atmospheric pressure and
        ambient  temperature.

    c.   Process  is  conducted  at  ambient  temperatures  and
        at  atmospheric pressure.

        A typical operation produces  approximately  500,000
        metric  tons per year  of  KC1 corresponding to  a  flow
        of  slurry entering the process estimated to be  14
        to  20  cubic meters per minute.

    d.   Process  is  believed to be  conducted  at ambient
        temperature and at atmospheric pressure.

        Two companies  conduct operations which process
        spodumene ore.  Total annual production  of  Li2G03
        at  one  of these is estimated to  be  5,000 metric
        tons.

4.   Utilities

    Consumption of  electrical energy is  estimated to  be:

    a.   50  to  100 kWh  per metric ton of  Li2C03

    b,c. 60 to 80 kWh  per metric ton of  KC1

    d.   400 to 800  kWh per metric  ton of Li2C03

5.   Waste Streams

    a.   The process produces  no  waste streams.

    b,c. Almost all applications of Process  15  to  the
        recovery of KC1 from  KCl-NaCl mixtures  discard the
        NaCl crystals, pumping them in slurry form  to a
        tailings pond, where  they eventually constitute a
        solid  waste pile, or  landfill.   Clear brine may be
        recycled to the process.

        The quantity of NaCl  wasted varies widely  with ore
        quality.  Estimates  place the quantity  between 2
        and 3  metric tons per metric ton of KC1  produced.

    d.   Approximately 10 to  30 metric tons of ore  tailings
        result per  metric ton of LizCOs  produced.   Tailings
        are wasted  to a tailings pile.   At times tailings
        may be further beneficiated with respect to Al and
        Si content  and supplied to the ceramic  industry.
                             128

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6.   EPA Source Classification Code

    a.   None established.

    b,c. 3-05-040-32  Ore concentrator

    d.  3-05-040-32  Ore concentrator

?•  References

    a,d. Bach, R. 0., C. W.  Kamienski, and R. B. Ellestad.
        Lithium and Lithium  Compounds.  In:   Kirk-Othmer
        Encyclopedia of  Chemical  Technology,  2nd Edition.
        Standen, A.  (ed.). New York, Interscience
        Publishers, 196?. 12:530-533.

    a.  Blxler, G. H., and D. L.  Sawyer.  Boron and  Boron
        Compounds from Searles Lake Brines.  Ind. Eng.  Chem.
        ^9:322-33^,  March 1957.

    b.  Hadzeriga, P., Some  Aspects of the Physical  Chemistry
        of  Potash Recovery by Solar Evaporation of Brines.
        Trans. Soc. Min. Eng. 2_29.: 169-174,   June 1964.

    a.  Hightower, J. V.  The Trona Process	and its
        Unique Features.  Chem. Eng.  (New York) 5^_: 104-106,
        August, 1951.

    c.  Magraw, R. M.  New Mexico Sylvinite.  Ind. Eng.  Chem.
        30:861-871,  August  1938.

    c.  Shreve, R. N.  Chemical Process Induotrion,  3rd
        Edition. New York, McGraw-Hill, Inc., 1967.  p.  ?M-
        299.

    b,c,d.  Taggart, A. F.  Flotation.  In:   Handbook of
        Mineral Dressing.  New York, John Wiley & Sons,
        Inc.,  19^5- p. 12-01 to 12-130.

    b,c. Turrentine, J.  W.   Potash in North  America.
        ACS Monograph Series, No.  91. New York, Reinhold,
        1943.  p. 105-175-

    c.  White, N. C., and C. A. Arend, Jr.   Potash Production
        at  Carlsbad. Chem. Eng. Progr. _4_6:523-531,   October
        1950.
                             129

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BRINE AND EVAPORITE CHEMICALS                 PROCESS NO. 16


                        FILTRATION

1.  Function

   *a.  As applied to the recovery of lithium values from
        burkeite liquor at Searles Lake/ California (Figure 7) •
        The process recovers a filter cake of dllithium sodium
        phosphate  (Li2NaPCU) crystals, washed free of sodium
        sulfate (Na2SOu) and sodium carbonate (Na2C03), from
        a slurry of Li2NaPCu froth In residual burkelte (NaC03»
        2Na2SOu) brine.

        The Li2NaPOu froth forwarded from Process 15, con-
        taining considerable quantities of Na2C03, Na2SCu
        and water, is filtered, washed free of burkeite brine
        and transferred to Process 11 (see Figure 13).   The
        filtrate and wash water is recycled to Process 10 for
        recovery of Na2C03 and Na2SOu.

        The specific type of filtration equipment has not
        been disclosed.  Either centrifuges or continuous
        rotary vacuum filters are practical.  If the latter
        are used,  then the process step of partially drying
        Li2NaPOi» cake on the filter may be included.

     b.  As applied to production of sodium bicarbonate from
        soda ash (Figure 14) - The process recovers a moist
        washed filter cake of fine sodium bicarbonate  (NaHC03)
        crystals from a slurry of NaHC03 in sodium  carbonate
         (Na2C03) brine received from  Process 36.  The NaHC03
        cake is transferred  to Process 11, and the  filtrate
        and wash water are recycled to Process 36.

        The process step of  displacement-washing the NaHC03
        cake is Included

        Major  equipment consists of continuous vacuum  rotary
        drum filters and batch-type centrifuges.

     c.  As applied to  soda-ash recovery from mined  trona  ore
         (Figure 19! -  The process removes  a relatively small
         amount  of  organics  plus any suspended  solids from
 * Separate industry operations  employing  the  process  are
   identified with a specific  lower case letter  which  is
   retained as an identifier in  each element of  this
   process  description.
                             130

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        the  crude  trona  (Na2C03-NaHC03»2H20) liquor forwarded
        from Process  35-  The clear, purified trona liquor
        produced is forwarded to  Process 10.

        The  steps  of  removal of organic materials with porous
        carbon  added  to  the crude  feed liquor and displace-
        ment washing  the filter cake are included.

        Equipment  consists of agitated holding tanks  (infer-
        red) for carbon  addition,  and  Sweetland® pressure
        filters.

    d.   As applied to metallic  calcium removal in sodium
        metal production (Figure  21) - The  process mechanical-
        ly removes suspended impurities contained in  the crude
        molten  sodium metal produced in the electrolytic cell
        of Process 58.   Suspended impurities consist  of calcium
        metal,  calcium chloride and sodium  oxide.  The product
        of the  process is molten  sodium metal of approximately
        99.95$  purity.

        The  subsequent step of  packaging in tank cars and
        drums is also included  in the  process.  This  step  is
        conducted  under  a padding of gaseous nitrogen.

        Equipment  consists  of a specially designed  filtration
        device  using  alloy  wire mesh filter elements  and
        operating  under  a padding of nitrogen.

2.   Input Materials

    a.   Quantitative  composition  of the Li2NaPCU  froth  (or
        slurry) is undisclosed.   A gross  estimate  is:

            Li2NaPCU  (suspended )    20%
            Na2S04 (dissolved)        6%
            Na2C03 (dissolved)       18J6
            Water                    56%

        Between 7  and 8  cubic meters  of  slurry  are  required
        per metric ton of Li2C03  produced.

    b.   Estimated  composition of  the  feed  slurry  entering  the
        process is«

            NaHC03 (suspended)       32 to  36$
            NaHC03 (dissolved)        4 to   5%
            Na2C03 (dissolved)        5 to   6%
            Water                   50 to 60%

        Approximately 4 cubic meters  of the feed slurry are
        required per metric ton of sodium bicarbonate produced.
                             131

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c.  Estimated quantity of the crude trona liquor  entering
    the process is between 4  and 5  cubic  meters per  metric
    ton of soda ash produced.  It is estimated to contain
    between 26 and 30 percent trona.

d.  Estimated quantity of crude molten sodium metal  enter-
    ing the process is 1.1 metric tons per metric ton of
    sodium produced.

    The crude molten sodium contains an estimated 3  percent
    total impurities.  About  6 percent of crude sodium
    entering the process leaves with the  sludge removed.

Operating Parameters

a.  The process operates at atmospheric pressure  and within
    a temperature range estimated to be 75° to 100°C.
    Wash-water temperature is believed to be nearly  100°C.

b.  The process operates at atmospheric pressure and at
    approximately 40°C.

c.  Operating pressure of the SweetlandQy pressure filters
    is pump discharge pressure, probably  5 to 7 kg/cm2.

    Porous carbon,  in undisclosed amounts, is added to the
    crude Na2C03  liquor to remove organic impurities and
    to de-colorize  the liquor.

    Diatomaceous  earth is used as a filter-aid.  Temperature
    is estimated  to be 90° to 100°C.

d.  The process operates principally at  0.1 to 0.3 kg/cm2
    below atmospheric pressure, with intermittent surges,
    to slightly above atmospheric pressure for " back-
    washing"  the filter elements.  Normal operating tem-
    perature  is 100°C.  Nitrogen padding  is used.

Utilities

a.  Electrical  energy consumption  is estimated to be
    between  5 and 10 kWh per metric ton  of Li2C03
    produced.

    Wash-water  consumption is estimated  to be between  0.5
    and  1.0  cubic meters per metric ton  of Li2C03 produced.

b.  Electrical  energy  consumption  is estimated to be
    between  15  to 20  kWh per metric ton  of NaHC03 produced.
                         132

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    Wash-water consumption is  estimated  to  be  between
    0.5 and 1.0 cubic meters per metric  ton of NaHC03
    produced.

c.  Electrical energy consumption is  estimated to  be
    between 2  and 4 kWh per metric ton of Na2C03 produced.

    Wash-water required is estimated  to  be  between 0.05
    and 0.1 cubic meter per metric ton of Na2C03 procuced.

d.  Estimated  consumption of electrical  energy is  between
    5 and 10 kWh per metric ton of Na produced.

    Estimated  consumption of nitrogen for purging  and
    padding is probably close  to 1.0  cubic  meter  (STP)
    per metric ton of Na produced.

Waste Streams
a.  No waste streams are produced.   All filtrate and wash-
    water is reprocessed.

b.  A bleed stream of a solution of about 5 percent NaHC03
    is discharged if the operation is not integrated with
    a Solvay operation.  The bleed is presumeably discharged
    into natural streams.  Its estimated quantity is less
    than 10 liters per metric ton of NaHC03.

c.  Solid waste, consisting of a mixture of spent carbon,
    diatomaceous earth and slimes is discharged from the
    process.  It is probably conveyed as a slurry to a
    tailings pond.  Its quantity is estimated at less than
    0.05 metric ton per metric ton of Na2C03  produced.

d.  Approximately 0.1 metric ton of sludge results per
    metric ton of Na produced.  Sludge composition approx-
    imates :

        Na metal
        Ca metal, CaCl2,
        NaCl, Na20

    Sludge disposition is undisclosed.

EPA Source Classification Code

a through d:  None established
                         133

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7 •   References

    a.  Bach, R. 0., C. W.  Kamienski, and R. B. Ellestad.
        Lithium and Lithium Compounds.  In:  Kirk-Othmer
        Encyclopedia of Chemical Technology.  2nd Edition,
        Staden, A. (ed.).  New York, Interscience Publishers,
        1967.  12_:529-556.

        Bixler, G. H., and D. L. Sawyer.  Boron Chemicals
        from Searles Lake Brines.  Ind. Eng. Chem. 49.: 322-33^ ,
        March 1957.

        Shreve, R. N.  Chemical Process Industries,  3rd
        Edition.  New York, McGraw-Hill, 196?. 905 p.


    b.  Hou, T. P.  Alkali and Chlorine Production.  In:
        Rogers Industrial Chemistry, 6th Edition   Pumas,
        C. C.  (ed.).  New York, Van Nostrand,  1942.  1_
        Rau, E.  Sodium Compounds  (Carbonates).  In:  Kirk-
        Othmer Encyclopedia of Chemical Technology,  2nd
        Edition,  Standen, A. (ed.).  New York, Interscience
        Publishers, 1969.  l8_:458-468.

    c.  Rau, E.  Sodium Compounds  (Carbonates).  In:  Kirk-
        Othmer Encyclopedia of Chemical Technology,  2nd
        Edition,  Standen, A. (ed.).  New York, Interscience
        Publishers, 1969.  l8_:458-468.

    d.  Gilbert, H. N.  Purifying  Light Metals.  U.S. Patent
        1,943,307.  Jan.  16, 1934.
                            134

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BRINE AND EVAPORITE CHEMICALS                  PROCESS NO.  17


                 LIQUID-LIQUID EXTRACTION

1.  Function

    This process (see Figure 8) recovers sodium and potassium
    borates from Searles Lake brine (presumably from the lower-
    level salt body), producing them in solution in an organic
    extractant.  The borates are then stripped from the extract-
    ant in Process 18.

    Brine and the immiscible extractant are agitated together
    in a closed contacting tank after which the two liquid
    phases are allowed to separate by gravity in a separator
    tank.  The two tanks plus the required pumps and agitat-
    ors comprise the essential equipment.

2.  Input Materials

    Searles Lake brine  (lower-level), containing approximately
    4,000 ppm boron in the form of poly- and metaborate ions,
    18,000 ppm potassium ion, and much higher concentrations
    of sodium ion, is required in the ratio of 35 to 40 cubic
    meters per metric ton of boric acid  (H2B03) produced.

    Boron,  potassium,  and sodium values are also extracted
    from weaker plant brines and end liquors by this process.

    The extractant is apparently a kerosene solution of poly-
    ols.  Make-up quantities of fresh extractant, required
    to replenish loss from its slight solubility in the spent-
    brine raffinate, are not divulged.  The kerosene make-up
    alone is estimated  at 8 to 10 liters per metric ton of
    boric acid  (H3B03).

3.  Operating Parameters

    The process is operated at atmospheric temperature and
    pressure.  Total brine flow capacity is estimated be-
    tween 4 and 12 cubic meters per minute.

4.  Utilities

    Electric power consumption, principally for agitation and
    pumping, is estimated between 30 and 80 kWh per metric
    ton of boric acid (H3B03).

5.  Waste Streams

    Kerosene vapor is the only atmospheric emission (inferred).
    Quantitative information  is not available.


                              135

-------
    Spent brine,  35 to 40 cubic meters per metric ton of
    H3B03, is the only liquid waste stream.  It is returned
    to Searles Lake. Estimated kerosene content:  ^200 ppm.

    There are no solid wastes.

6.   EPA Source Classification Code

         None  established

7•   References

    Havighorst, C. R.  AP&CC's New Process Separates Borates
    from Ore by Extraction.  Chem. Eng. 7_C_: 228-232, November
    11,  1963.
                             136

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO.  18


                         STRIPPING

I.  Function

    The process (see Figure 8) recovers an aqueous solution
    of boric acid, potassium sulfate, and sodium sulfate from
    the loaded extractant from Process 17.  Also, this process
    includes the step of adsorption of organic materials on
    porous carbon.

    The loaded extractant is stripped of the recoverable
    values by washing with sulfuric acid.  The solution
    formed is forwarded to Process 10 for separation of
    boric acid.

    Essential equipment consists of an agitated contactor
    tank, a separator tank, a carbon-packed adsorption column,
    all plastic or rubber-lined, and heat exchangers.

2.  Input Materials

    An undivulged amount of loaded extractant plus 25 percent
     (estimated) aqueous sulfuric acid is fed to the process.
    The requirement of the latter is approximately 2.5 metric
    tons H-jSOn (100$ basis) per metric ton of boric acid
     (H3B03).

3.  Operating Parameters

    The process operates at atmospheric pressure and at a
    temperature estimated to be 50°C.

H.  Utilities

    Electric power requirement is estimated to be 20 to ^40 kWh
    per metric ton of boric acid  (H3B03).

5.  Waste Streams

    Kerosene vapors are the only atmospheric emission  (in-
    ferred).  Quantitative information is not available.

6.  EPA Source Classification Code

        None established
                             137

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7•   References

    Havighorst, C. R.  AP&CC's New Process Separates  Berates
    from Ore by Extraction.  Chem. Eng, £JD-.228-232, November
    11, 1963.
                             138

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO.  19


                DISSOLUTION (SALT CAVERN)

1.   Function

    The process (see Figure 9) saturates natural sodium
    sulfate brine with sodium chloride in order to supress
    the solubility of sodium sulfate during its separation
    in Process 20.  This process also includes the immediately
    prior step of brine production.   Process 19 is similar to
    solution mining.  The sodium sulfate brine is injected
    into a cavity in a salt stratum and subsequently is  forced
    to the surface, saturated with NaCl.

2.   Input Materials

    Natural sodium sulfate wells of Gains County, Texas,
    contain 7 to 11 percent sodium sulfate (Na2SOu) and
    smaller percentages of sodium chloride and magnesium
    chloride.  Ten to 1*1 cubic meters of brine are required
    per metric ton of sodium sulfate (Na2SOu)  produced.

    A gross estimate of the quantity of sodium chloride
    dissolved from the salt cavern is 1 metric ton per
    metric ton of sodium sulfate produced.

3.   Operating Parameters

    Estimated salt cavern temperature is 30° to 35°C

4.   Utilities

    Estimated power consumption is 50 to 70 k¥h per metric
    ton of sodium sulfate.

5.   Waste Streams

    There are no waste streams.

6.  EPA Source Classification Code

         None established

7.  References

    Faith, L. P., D. B. Keyes, and R. L. Clark.   Industrial
    Chemicals,  2nd Edition.  New York, John Wiley & Cons,
    Inc. , 1957.  H5"2 p.
                              139

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BRINE AND EVAPORITE CHEMCIALS               PROCESS  NO.  20


                CRYSTALLIZATION/FILTRATION

1.  Function

   *a.  Production of sodium sulfate from Gaines County, Texas
        brine (Figure 9) - The process crystallizes  Glauber's
        salt (Na2SOu •10H20) from the sodium chloride-sodium
        sulfate brine obtained from Process 19 and then filters
        the Glauber's salt crystals from the mother liquor.
        Essential equipment includes a brine chiller, crystal-
        lizing tank, and a rotary drum filter or centrifuge.

    b .  Production of potassium chloride from Sylvinite
        (Figure 17)"- The process crystallizes potassium
        chloride  TKC1) from a sodium chloride-potassium
        chloride liquor forwarded from Process ^7, then
        filters the potassium chloride crystals from the
        mother liquor.  The crystals are air-dried on the
        filter.

        The process includes the sequential steps of*

            evaporative cooling
            crystallization
            settling  (thickening)
            filtration
            crushing  and screening
            packaging (railroad cars)

        Essential major equipment consistc  of evaporative
        coolers,  crystalllzer tanks, settling tanks, con-
        tinuous rotary drum  filters with provisions  for
        drying, crushing rolls, and vibrating screens.

 2.   Input  Materials

     a.  Sodium sulfate brine, saturated with sodium  chloride
        from Process  19, has the following  approximate  com-
        position:
             Na2S04         7  to
             NaCl          23  to  25%
             MgCl2         not divulged
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.
                             140

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        The quantity  of  brine  entering  Process  20  is
        estimated  to  be  13  to  20  cubic  meters per  metric
        ton of sodium sulfate  produced.   This quantity
        includes recycled mother  liquor.

    b.   Sodium chloride-potassium chloride  leach liquor
        from Process  47  is  estimated  to have the following
        composition:

            KC1        22 to 24%
            NaCl        14 to 16%

        The quantity  of liquor entering the process,  includ-
        ing recycled  KC1, is estimated  to be between  7 and
        8 cubic meters per  metric ton of  potassium chloride
        produced.

3.   Operating Parameters

    a.   Crystallizers operate  at  -7°  to -9°C, and  at
        atmospheric pressure.

        Tube-and-shell exchangers chill incoming brine with
        cool mother liquor  leaving the  process.  Final brine
        cooling is by ammonia  refrigeration coils.

    b.   The temperature of  the incoming NaCl-KCl brine from
        Process 47 is between 105° and  110°C, and  is  cooled
        in direct-contact  condensers  to 25° to  27°C prior
        to entry  into crystallizer-settling tanks.  Filtration
        is conducted  at 27°C.   Filtration occurs at atmospheric
        pressure.   Cooling  occurs at  0.1  kg/cm2 absolute
        pressure.

4.   Utilities

    a.   Estimated  electrical energy consumption,  including
        refrigeration requirement, is 60  to 80  kWh per metric
        ton of sodium sulfate produced.

        Cooling water requirement is  estimated  at  10 to  15
        cubic meters   (once-through basis) per metric ton of
        sodium sulfate produced.

    b.   Estimated  electrical energy consumption is 15 to 20
        kWh per metric ton of potassium chloride  produced.

        Approximately 50 cubic meters of  cooling water
        (once-through basis) are required for barometric
        condensers.

        Steam is consumed by ejectors (estimated  less than
        0.01 metric tons per metric ton of Na2SCU).


                             141

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Waste Streams

a.  There are no atmospheric emissions or solid wastes.

    A portion of the mother liquor recycled from Process
    20 to Process 19 is bled off to intermediate waste
    storage ponds and thence to injection wells.  The
    quantity of bleed is estimated to be between 2 and 4
    liters per metric ton of sodium sulfate produced.

b.  There are no atmospheric emissions or waste flows.

EPA Source Classification Code

a.   None established

b.   None established

References

a.  Faith, L. P., D. B. Keyes, and R. L. Clark.  In-
    dustrial Chemicals ,  2nd Edition.  New York, John
    Wiley & Sons, Inc., 1957.  852 p.

b.  Jacobs, J. J.  Potassium Compounds.  In:   Kirk-Othmer
    Encyclopedia of Chemical Technology ,  2nd  Edition ,
    Standen, A.  (ed.).  New York, Interscience Publishers,
    1966.  16_
    Magraw, R. M.  New Mexico  Sylvinite.   Ind. Eng.  Chem.
    3_0:86l-871, Aug.  1938.

    Shreve, R. N.  Chemical  Process  Industries ,   3rd
    Edition.   New  York, McGraw-Hill,  1967.   905 p.

    Turrentine, J. W.  Potash  in  North  America.   New York,
    Reinhold,  1943.  186 p.

    White,  N.  C.,  and Carl A.  Arend .   Potash Production
    at  Carlsbad.   Chem. Eng.  Progr.  4_6:523-530, October
    1950.
                        142

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BRINE AND EVAPORITE CHEMICALS                 PROCESS  NO.  21


                    BRINE DESULFURIZATION


1.  Function

    This process (See Figure 10) permits the evolution of
    traces of hydrogen sulfide gas (H2S) from brine produced
    from the Smackover formation in Arkansas.  The hot brine
    from wells is held in a surge pond to allow H2S gas to
    be evolved and to be oxidized to elemental sulfur in the
    atmosphere.  The elemental sulfur formed floats on the
    brine as scum.

    This process includes the step of brine production from
    the formation.

2.  Input Materials

    Arkansas brine, containing between 3,500 and 5,000 ppm
    bromine, yields 170 to 250 cubic meters per metric ton
    of bromine.

3.  Operating Parameters

    Ambient temperature and atmospheric pressure.

4.  Utilities

    Electrical energy (includes brine production) - 400 to
    1,200 kWh per metric ton of bromine.

5-  Waste Streams

    Gaseous H2S - Detectable quantities evolved into cur-
    sounding atmosphere.  No quantitative information is
    available.

    Elemental Sulfur - Collected as elemental sulfur and
    buried(landfill).  No quantitative information is
    available.

6.  EPA Source Classification Code

    None Established.

7 •  References

    None.   (Information presented above is based on first-
    hand knowledge.)


                             143

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO.  22


                        ACIDIFICATION

1.  Function

    This process (See Figure 10) lowers the pH of bromide-
    containing brine by addition of hydrochloric acid (HC1).
    Enough chlorine (012) may also be added to the brine at
    this point to oxidize a portion of the bromide to
    elemental bromine (Bra).

    The following brines are treated with HC1 before
    entering Process 23:

    a.  Process 21 Arkansas  (Smackover formation)
    b.  Raw Michigan brine  (various formations)
    c.  Process 27, Figure  12 Iodine-stripped Michigan brine
    d.  Process 10, Figure  7 Potassium chloride brine
        (intermediate product in Searles Lake operations)

    Enough HC1  (or HaSCu) is added to decrease the pH of
    the brines to approximately 3-5.  An undivulged portion
    of the Cl2 necessary to  oxidize bromide to Br2 may also
    be added to the brines.

2.  Input Materials

    Bromide-containing brines -  m3 per metric ton of Br2:

    a.  170 to  250
    b.  600
    c.  350
    d.  200

    HC1  (on a 100 percent HC1 basis)  -

    a,c. Sufficient to adjust the  pH  to  3-5  (quantity used
        is not  divulged)
    b,d. 0.008  to 0.009 metric tons per  metric ton of Br2

    C12 -

    a,b,c. A portion of  the 0.45 metric  tons  per metric  tori
        of Bra  is required  to oxidize bromide to bromine.
        The remainder  is added in  Procer;r;  23.
                             144

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d.   None.  Chlorine is added in Process 23.

Operating Parameters

a,b,c,d.

    Temperature - 70 to 80°C

    Pressure - slightly above atmospheric

    pH of brine - approximately 3.5

Utilities

Electrical energy consumption per metric ton of Br2:

a.   10 kWh
b.   30 kWh
c.   20 kWh
d.   10 kWh

Waste Streams

None

EPA Source Classification Code

None established

References

b.   Faith, W. L., D. B. Keyes, and R. L. Clark.
    Industrial Chemicals, 3rd Edition. New York, John
    Wiley & Sons, Inc., 1965.  852 p.

d.   Robertson, G  R.  Expansion of the Trona Enterprise,
    Industrial and Engineering Chemistry.  34:133-137
    February 19*12.

a,b,c,d.
    Stenger, V. A. Bromine.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition.
    Standen, A. (ed.).  New York, John Wiley and Sons,
    Inc., 196M. 3=750-766.
                         145

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO.  23


                  CHLORINATION/STRIPPING


1.  Function

    This process (See Figure 10) completes the oxidation by
    chlorine (C12)  of the bromide ion in acidified brine
    coming from Process 22.  It also strips elemental bromine
    (Br2) from the brine by the use of a counter-current flow
    of steam upward through a packed tower.

    The major liquid stream, entering the tower near the top
    is the acidified, and partially chlorinated brine from
    Process 22.  An additional liquid stream, water saturated
    with C12 and Br2, is recycled to the tower from Process 2*)
    and  Process 26.  Gaseous C12, injected into the tower at
    several points, and the low-pressure steam admitted at the
    bottom are the major geseous streams.  A stream of non-
    condensible gases from Process 2^, containing C12 and Br2
    is fed to the tower near the top.

    Br2  vapor, plus unreacted C12 are carried by the steam
    from the top of the tower to a condenser.  The two con-
    densed liquid phases then flow to Process 24.  The stripped
    brine flows from the tower bottom to Process 25-

2.  Input Materials

    Acidified brine from Process 22, originating from any one
    of the respective sources listed below*.

       *a.  Process 21, Arkanses (Smackover  formation) -
            170 to 250 cubic meters per metric ton of Br2, or
         b.  Raw Michigan brine  (various formations) -
            6>00 cubic meters per metric ton  of Br2, or
         c.  Process 27, Figure  12,  iodine-stripped Michigan brine
            350 cubic meters per metric ton  of Br2.
         d.  Process 10, Figure  7, potassium  chloride brine formed
            in  the Searles  Lake operations - 200 cubic meters
            per metric ton  of Br2.
 * Separate industry operations employing the process are
   identified with a specific lower case letter which is
   retained as an identifier in each element of this
   process description.
                             146

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   •Cla :

    a,b,c.   The remaining portion  of  the  0.45  metric  ton  C12
       per metric  ton of Br2  that is required to  oxidize
       bromide to  Br2.  (Some  C12  was added  in Process  22).
    d.   0.^5 metric ton per metric ton of Br2

   •Steam:

    a,b,c,d.  2 to  15 metric tons  per metric ton of Br2

   •Non-condensible gases containing  C12  and Br2 from
    Process 24 :

    a,b,c,d.  Undivulged quantity.

3.   Operating Parameters

    a,b,c,d.
       •Temperature is 85 to 95°C
       •Pressure is slightly above atmospheric
       •The pH of the brine is approximately 3-5
       •The oxidation-reduction potential of the brine  is
        0.88 to 0.97 volts (platinum  versus  saturated calomel)

4.   Utilities

    a ,b,c,d.
       •Cooling Water
        30  to 100 cubic meters per metric ton  of Br2

5.   Waste Streams

    a,b,c,d.
       •A gas stream containing primarily non-condensible
        gases is vented to the atmosphere.  This stream
        contains some C12 and Br2.  The C12  plus Br2  portion
        of the stream is estimated to be less  than 0.001
        metric ton per metric ton of Br2 product.

6.   EPA Source Classification Code

        None established

7.   References

    a,b,c,d.
        Stenger, V. A.  Bromine.  In:  Kirk-Othrner Encyclo-
        pedia of Chemical Technology, 2nd Edition.  Standen,
        A.   (ed.).  New York, John Wiley and Sons,  Inc., 1964.
        3:   750-766.
                             147

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    Yaron, F.  Chapter 1.   In:   Bromine and Its
    Compounds.  Jolles, Z.  E.  (ed.).   London, Ernest
    Benn, Limited, 1966.  p.  3-42.

d.  Robertson, G. R.  Expansion of the Trona Enterprise
    Industrial and Engineering Chemistry.  3^:  133-137,
    February 1942.
                         148

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO. 24


                    GRAVITY SEPARATION


1.  Function

    This process (See Figure 10) separates crude liquified
    bromine (Br2) from water and noncondensible gases.

    The condensed halogen and water-laden vapors from
    Process 23 flow to a corrosion-resistant gravity separator.
    The high-density crude bromine exits the bottom through a
    trap and goes to Process 26.  Lower density water saturated
    with Br2 and chlorine (C12) is returned to the stripping
    tower of Process 23.  Noncondensible gases containjng some
    Br2 and C12 are returned to the upper part of the stripping
    tower of Process 23.

    The contexts referred to below are:

       *a.  Arkanses brine
        b.  Michigan brine
        c.  Iodine-stripped Michigan brine
        d.  Searles Lake process potassium chloride brine

2.  Input Materials

    a,b,c,d.

        Condensed vapors from Process 23  (primarily Br2i ClgJ
        and water) - 2 cubic meters per metric ton of Br2

3.  Operating Parameters

    a 3b,c,d.
        Temperature is approximately 0 to 10°C above ambient,
        pressure is approximately atmospheric.

4.  Utilities

    a,b,c,d.  None
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.
                             149

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5.   Waste Streams

    a,b,c,d.   None

6.   EPA Source Classification Code

        None  established

7 •   References

    a,b,c,d.

        Stenger, V. A.  Bromine.  In:  Kirk-Othmer
        Encyclopedia of Chemical Technology, 2nd Edition,
        Standen, A. (ed.).  New York, John Wiley and Sons,
        Inc., 196^4.  3750-766.

        Yaron, F.  Chapter 1.  In:  Bromine and Its Compounds,
        Jolles, Z. E. (ed.).  London, Ernest Benn, Ltd., 1966.
        p. 3-42.
                             15Q

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 25


                SPENT BRINE NEUTRALIZATION


1.   Function

    This process (See Figure 10) neutralizes the acidity of
    the bromine-stripped brine effluent from Process 23 pre-
    paratory to disposal of further processing.

    Lime (CaO) or caustic soda (NaOH) is added to the bromine-
    stripped brine leaving Process 23.  Usually the neutralized
    brine is cooled by exchanging heat with brine entering
    Process 22.  The neutralized bromine-stripped brine is
    then either:

   *a.  Arkansas brine - Returned to original source strata.

    b.  Michigan brine - Forwarded to Process 7, Figure 4.

    c.  Iodine-stripped Michigan brine - Forwarded to Process
        7, Figure 4.

    d.  Searles Lake process potassium chloride brine -
        Forwarded to Process 10, Figure 7.

2.   Input Materials

    Bromine-stripped brines - m3 per metric ton of Brg:

    a.  170 to 250
    b.  600
    c.  350
    d.  200

    Lime  (CaO) - metric tons per metric ton Brg:

    a.  0.007
    b.  0.02
    c.  0.01
    d.  0.008
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.
                            151

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    Operating  Parameters

    Temperature  -

    a,b,c,d.
        90°C entering  the  neutralizer
           40 to  90°C after exchanging heat with brine
           entering Process 22

    Pressure -

    a,b,c,d.   Near atmospheric

    EH  -

    a,b,c,d.   Entering  at approximately 3.5.  Exiting at
        approximately  7«

    Utilities

    Electrical energy  -

    a.   Primarily  for  pumping bromine-stripped  brine into
        source strata.
            50 kWh per metric ton  of Br2
    b,c,d.
        Primarily  for  pumping bromine-stripped  brine to  the
        next process.
        Less than  20 kWh per metric  ton  of Br2

    Waste Streams
    Bromine-stripped neutralized brine -

    a.   170 to 250 cubic meters per metric ton of Br2
        returned to source strata

    b,c,d.   None

6.   EPA Source Classification Code
        None established

    References

    a,b,c,d.
        Stenger, V. A.  Bromine.  In:  Kirk-Othmer Encyclo-
        pedia of Chemical Technology, 2nd Edition,  Standen,
        A. (ed.).  New York, John Wiley and Sons, Inc.,
        1964.  3: 750-766.
                             152

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Yaron, F. Chapter 1.  In:  Bromine and Its Compounds,
Jolles3 Z. E. (ed.).  London, Ernest Benn, Ltd.,
1966.  p. 3-^2.
                     153

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 26


                       DISTILLATION


1.  Function

    This process (See Figure 10) separates halogenated hydro-
    carbons and water saturated with chlorine (C12) from
    crude bromine (Br2) coming from Process 2^1.

    Crude Br2 from Process 2k is fed to a distillation column.
    Higher-boiling halogenated hydrocarbons are  removed from
    the bottom of the column.  Bromine and C12 boil off the
    top and are cooled in a reflux condenser.  Most of the
    cooled chlorine returns to Process 23, whereas the cooled
    liquid bromine goes to a final distillation column.
    Bromine with a purity of 99-8$ is the bottom product from
    the column, while a rich chlorine overhead stream is re-
    turned to Process 23.

    The contexts referred to below are:

   *a.  Arkansas brine
    b.  Michigan brine
    c.  Iodine-stripped Michigan brine
    d.  Searles Lake process potassium chloride brine

2•  Input Materials

    Crude Br2 -

    a,b,c,d.  1.1 metric ton per metric ton of Br2 product.

3•  Operating Parameters

    Temperature -

    a,b,c,d.  Temperature ranges  from  ambient to 100°C.

    Pressure -

    a,b,c,d.  Near atmospheric.
*  Separate  industry operations employing the process are
   identified with  a specific  lower  case letter which is
   retained  as an identifier in each element of this
   process description.
                            154

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4.   Utilities

   •Steam:

    a,b,c,d.   0.4 metric ton per metric ton of Br2

   •Cooling water:

    a,b,c,d.   10 metric tons per metric ton of Br2

   •Electrical energy:

    a,b,c,d.   Less than 1 kWh per metric ton of Br2

5.   Waste Streams

   •Halogenated hydrocarbons (liquid);  burned in sludge-pit:

    a,b,c,d.
        Undivulged quantities estimated to be less than
        0.01 metric ton per metric ton of Br2.

6.   EPA Classification Code

        None established

7.   References

    a,b,c,d.
        Stenger, V. A.  Bromine.  In:  Kirk-Othmer Encyclo-
        pedia of Chemical Technology, 2nd Edition.  Standen,
        A. (ed.)«  New York, John Wiley and Sons, Inc.,
        1964.  3: 750-766.
                           155

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 27


                     IODINE STRIPPING


1.  Function

    This process (see Figure 12) recovers elemental iodine
    (I2) as a dilute vapor in air from Michigan brines.
    Steps involved include acidification, oxidation and air
    stripping.

    A brine stream containing approximately 40 ppm I2 is
    sprayed into a steel tower lined with acid-proof briick
    and packed with ceramic rings.  Hydrochloric acid and
    chlorine are injected into the brine feed line ahead
    of the tower.  A large counter-current flow of air stripe
    the released elemental I2 from the brine spray and con-
    veys it to Process 28.

2.  Input Materials

   •Michigan brine, containing approximately 40 ppm iodine -
        23,000 cubic meters per metric ton of iodine

   •Hydrochloric acid -
        0.3 metric ton (100% basis) per metric ton of  iodine

   •Chlorine -
        0.28 to  0.30 metric tons per metric ton of iodine

   «Air -
        90,000 to  120,000 cubic meters per metric ton  of iodine

3.  Operating Parameters

    Ambient temperature and atmospheric pressure.

4.  Utilities

   •Electrical energy -
        approximately 4000  kWh  per metric  ton  of  iodine

5.  Waste  Streams

    None
                             156

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6.   EPA Source Classification Code

        None established

7.   References

    Sawyer, P. G., M. F. Ohman, and F. E. Lusk.  Iodine
    from Oil Well Brines.  Industrial and Engineering
    Chemistry.  4l: 15^7-1552, August 19^9-
                            157

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 28


                     IODINE ABSORPTION


1.  Function

    This process (see Figure 12) removes iodine (I2) from
    the iodine-laden'air coming from Process 27 and absorbs
    it into an acid solution.

    Cooled iodine-laden air flows up through an acid-proof
    packed tower.  A counter-flow of HI-H2S04 solution
    from Process 29 absorbs the iodine vapor from
    the air.  The air is returned to the iodine stripping
    tower of Process 27.

2.  Input Materials

    •Iodine-laden air -
        90,000 to 120,000  cubic meters per metric ton of iodine

    •HI-HaSQu solution -
        80 to 100 cubic meters per metric ton of iodine

3.  Operating Parameters

    Up to 10°C above ambient temperature
    Atmospheric  pressure

4.  Utilities

    • Cooling  w_ater -
        250  cubic meters per metric  ton  of  iodine

5.  Waste Streams

    •Air-bleed to the atmosphere -
        Iodine'  content  is  undisclosed  but  estimated to  be
        very minute.  The  total bleed  is  less  than  1 per-
        cent of  the  air input  into  Process  27.

 6.   EPA  Source  Classification  Code

        None established
                             158

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References

Development Document for Proposed Effluent Limitations
for the Significant Inorganic Products  Segment of the
Inorganic Chemicals Manufacturing Point Source Category
(Draft).  General Technologies Corporation.  December
1973.

Sawyer, P. G., M. F. Ohman, and F. E. Lusk.  Iodine from
Oil Well Brines.  Industrial and Engineering Chemistry.
JQ:  1547-1552.  August 1949.
                         159

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BRINE AND EVAPORITE CHEMICALS             PROCESS  NO.  29


                     IODINE REDUCTION


1.  Function

    This process (see Figure 12 ) reduces elemental iodine
    to iodide.  The iodine enters this process from Process
    28, where it was absorbed into a HI-H2SOU solution.

    Sulfur dioxide is dissolved into the HI-H2SCu solution
    in an acid-proof vessel to reduce absorbed iodine to
    hydroiodlc acid.  A portion of the acid solution is
    recycled to Process 28 to absorb additional iodine.
    The remainder of the solution is forwarded to Process 30

2.  Input Materials

   •HI-HgSOit, solution containing absorbed iodine -
        80-100 cubic meters per metric ton of iodine

   •Sulfur dioxide -
        0.25 metric ton  per metric ton of iodine

   •Water -
        ?3 cubic meters per metric ton of Iodine

3.  Operating Parameters

    Ambient temperature and atmospheric pressure

4.  Utilities

   •Electrical energy -
        4 to  5 kWh per metric ton of iodine

5.  Waste Streams

    None

6.  EPA Source Classification Code

        None  established
                             160

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References

Development Document for Proposed Effluent Limitations
for the Significant Inorganic Products  Segment of the
Inorganic Chemicals Manufacturing Point Source Category
(Draft).  General Technologies Corporation.  December
1973.

Sawyer, P. G., M. F. Ohman, and P. E. Lusk.  Iodine from
Oil Well Brines.  Industrial and Engineering Chemistry.
41:  1547-1552.  August 1949.
                         161

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 30


                     IODIDE OXIDATION


1.  Function

    This process (see Figure 12) oxidizes iodide in the
    HI-H2S04 solution from Process 29.  The resulting
    Iodine precipitates, and is ultimately forwarded to
    Process 31.

    The HI-H2SOU solution from Process 29 is forwarded
    to a brick-lined conical precipitating tank.  Chlorine
    gas is bubbled into the solution from Pyrex® tubes.
    The chlorine oxidizes the iodide to iodine.  The iodine
    precipitates and passes through a porcelain valve into
    a wooden box filter.  The wet iodine cake collects on
    a Saran® filter cloth and then is transferred to Process
    31.  The HC1-H2SO*  filtrate is used elsewhere in the
    plant.

2.  Input Materials

    •HI-HgSOu solution -
        f3  cubic meters per metric ton of iodine

    •Chlorine -
        0.28 metric ton per metric ton of iodine

3.  Operating  Parameters

    Ambient temperature and atmospheric pressure

4.  Utilities

    None

5.  Waste  Streams

    Detectable but  unquantified amount of chlorine  may
    escape  to  the  atmosphere.

6.  EPA Source Classification  Code

        None established.
                             162

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References

Development Document for Proposed Effluent Limitations
for the Significant Inorganic Products  Segment of the
Inorganic Chemicals Manufacturing Point Source Category
(Draft).  General Technologies Corporation.  December
1973-

Sawyer, P. G.3 M. F. Ohman, and P. E. Lusk.  Iodine from
Oil Well Brines.  Industrial and Engineering Chemistry.
41:  15M7-1552.  August 1949.
                         163

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO.  31


                     IODINE FINISHING

1.  Function

    This process (See Figure 12) melts the wet  iodine from
    Process 30, pours the molten iodine into ingots, pul-
    verizes the ingbts, and packages the crushed iodine.

    Wet iodine from Process 30, along with strong sulfuric
    acid (over 60$), is heated in a steam-jacketed kettle.
    The acid chars residual organic impurities  and removec
    water from the iodine.  After prolonged heating, the
    sulfuric acid is poured off the top of the  kettle,
    after which the molten iodine is poured into enamel-
    lined slop sinks.  After cooling, the iodine ingots are
    crushed and packaged in wooden kegs.  The wet sulfuric
    acid is used elsewhere in the plant.

2.  Input Materials

    •Wet iodine -

        1.1 metric ton per metric ton of iodine

    •Sulfuric acid  (over 60% H2S04) -

        0.2 to 0.3 cubic meter of acid  solution per metric
        ton of iodine.

3.  Operating Parameters

    Temperature is  120° to l60°C.
    Pressure is atmospheric.

4.  Utilities

     •Steam -

         100,000 to  200,000 kcal per metric  ton  of iodine.

     •Cooling water  -

         1 to 2  cubic meters  per metric  ton  of iodine.

     •Electrical  energy -

         1  to 2  kWh  per metric  ton of  iodine.
                            164

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5.   Waste Streams

   •Water vapor containing a detectible but unquantified
    amount of iodine escapes to the atmosphere.

6.   EPA Source Classification Code

        None established

7.   References

    Development Document for Proposed Effluent Limitations
    Guidelines and New Source Performance Standards for
    the Signigicant Inorganic Products Segment of the In-
    organic Chemicals Manufacturing Point Source Category
    (Draft).  General Technologies Corporation.  December
    1973-

    Sawyer, F. G., M. F. Ob-man, and F. E. Lusk.  Iodine
    from Oil Well Brines.  Industrial and Engineering
    Chemistry.  4l: 1547-1552.  August 1949.
                             165

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BRINE AND EVAPORITE CHEMICALS                 PROCESS NO. 32


                         DIGESTION

1.  Function

    The process (see Figure 13) generates mixed crystals of
    lithium sulfate (Li2SCu) and sodium sulfate (Na2SOtt)
    from a filter cake of dilithium sodium phosphate
    (Li2NaPOu) by treatment of the latter with sulfuric acid
    (H2SCU).  A mother liquor containing a high concentra-
    tion of phosphoric acid (H3P04) is also produced.  The
    process also includes the subsequent step of centrifug-
    ing the mixed sulfates from the phosphoric acid mother
    liquor and the step of concentrating the mother liquor
    by evaporation to a marketable, crude phosphoric acid.

    The mixed sulfate crystals are forwarded to Process 33.

2.  Input Materials

    Between 1.8 and 1.9 metric tons of Li2NaPOi, from Process
    11 are required per metric ton of Li2C03 produced.
    Approximately two metric tons of concentrated H2SOi, are
    consumed per metric ton of Li2C03 produced.

3.  Operating Parameters

    The process is conducted at atmospheric pressure at a
    temperature of 115°C.

    It is estimated here that the average production rate of
    L12C03 at one of the plants operating on Searles Lake
    brine is between 5 and  8 metric tons per day.  This
    relatively small rate would indicate either batchwise or
    intermittent-continuous modes of operation.

i\.  Utilities

    Electric energy consumption is estimated here to be in
    the range of 15 to 20 kWh per metric ton of Li2C03
    produced.

    Steam consumption, probably at a gage pressure of  10
    kg per  cm2, is estimated to be between  1 and 2 metric
    tons per metric ton  of  Li2C03 produced.

5.  Waste Streams

    There are no known atmospheric, liquid,  or solid wastes.

                            166

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EPA Source Classification Code

None established.

References

Bach, R. 0., C. W. Kamienski, and R. B. Ellestad.
Lithium and Lithium Compounds.  In: Kirk-Othmer
Encyclopedia of Chemical Technology, 2nd Edition,
Standen, A. (ed.).  New York, Interscience Publishers,
1966.  12_:529-556.

Bixler, G. H., and D. L. Sawyer.  Boron Chemicals from
Searles Lake.  Ind. Eng. Chem.  4£:322-332, March 1957.

Shreve, R. N.  Chemical Process Industries, 3rd Edition.
New York, McGraw-Hill, 1967.  905 p.
                        167

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 33


               LITHIUM CARBONATE SEPARATION

1.  Function

   *a.  In lithium carbonate production from Searles Lake
        brine (see Figure 13) - The process obtains moist
        lithium carbonate(Li2C03)  crystals from a mixed
        crystal mass of lithium sulfate (Li2SOn) and sodium
        sulfate (NaaS04), obtained as a centrifuge cake
        from Process 32.  The process comprises the sequen-
        tial steps of dissolution of the mixed sulfate
        crystals in water, precipitation of Li2C03 by addition
        of sodium carbonate  (Na2C03) solution and centrifuging
        the resulting slurry to obtain a moist, washed cake of
        Li2C03 crystals.

        Sodium sulfate  (Na2SOn) liquor is obtained as a by-
        product and is  forwarded to Process 10, Figure 7> for
        Na2SOi» recovery.

    b.  In lithium carbonate production from Silver Peak,
        Nevada brine  (see Figure 13) - Moist lithium carbonate
        (Li2C03)crystals are obtained from the "bitterns"
        resulting from  Process 13.  The moist crystals are
        forwarded to Process 11 for drying.

        The process comprises the sequential steps of precip-
        itation of Li2C03 from the bitterns by addition of
        sodium carbonate  (Na2C03) solution and filtration of
        the resulting slurry on a belt-filter.

 2 .   Input Materials

     a.  The mixed Li2S04-Na2S04 crystals entering  the process
        contain between 7 and 8 percent lithium on a dry
        weight basis.   Between  2.5  and 2.6 metric  tons of
        the crystals  are  consumed per metric ton  of Li2C03
        produced.

        Between 1.45  and 1.50 metric tons  (100% basis) of
        sodium carbonate (Na2C03) are required  per metric ton
        of  Li2C03 produced.
 * Separate industry operations employing the process  are
   identified with a specific lower case letter which  is
   retained as an identifier in each element of this
   process description.
                            168

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    b.  The bitterns fed to the process contain between 3
        and 6 percent lithium chloride (LiCl),  11 percent
        potassium chloride (KC1), and approximately 22 per-
        cent sodium chloride (NaCl).   Between 15 and 30
        cubic meters of bitterns are  consumed per metric tori
        of Li2C03 produced.

        Between 1.^5 and 1.50 metric  tons (100$ basis) of
        sodium carbonate are required per metric ton of
        Li2C03 produced.

3.  Operating Parameters


    a,b.   The process is conducted at atmospheric pressure.
        It is conjectured that the precipitation and filtra-
        tion steps at both the Searles Lake  and Silver Peak
        locations are conducted at temperatures near 100°C.

        The relatively small estimated average  production
        rates (between 5 and 8 metric tons per  day for the
        Searles Lake operation and between 15 and 25 metric
        tons per day for Silver Peak, Nevada) indicate either
        batchwise or intermittent-continuous  modes of operation

4.  Utilities

    a.  Total consumption of electrical energy  is estimated  to
        be between 15 and 30 kWh per  metric  ton of Li2C03 pro-
        duced.

        Steam,  probably at a gage pressure near 10 kg/cm2,
        is needed to heat process water.  Assuming no heat
        recovery, the steam requirement is estimated to be
        between 1.5 and 2.0 metric tons per  metric ton of
        Li2CO3.

        Total process water requirement,  including process
        steam make-up, is estimated to be bewteen 10 and 12
        cubic meters per metric ton of Li2C03.

    b.  Total consumption of electrical energy  is estimated
        to be between 20 and 40 kWh per metric  ton of Li2C03
        produced.

        Steam,  probably at a gage pressure near 10 kg/cm2,
        is required to heat the entering bitterns and the
        wash water.  Assuming 75 percent heat recovery, the
        steam consumption is estimated to be between 1.0 and
        3.0 metric tons per metric ton of Li2C03 produced.
                             169

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        Estimated water consumption,  including process  steam
        makeup,  is between 1.5  and 4.0  cubic  meters  per metric
        ton of Li2C03  produced.

5.   Waste Streams

    a,b.  There are no atmospheric emissions  from the process
        as operated at either Searles Lake or Silver Peak.

    b.  At Silver Peak, the process discharges the mother
        liquor from the Li2C03  precipitation.  This is a
        brine containing about  10 percent KC1 and 24 percent
        NaCl.  It is estimated  to amount to between 18 and
        36 cubic meters per metric ton of Li2C03 produced.
        It is impounded and allowed to evaporate, leaving
        behind 6  to 12 metric  tons of solids per metric tori
        of Li2C03 produced.

6«   EPA Source Classification Code

    None established.

7.   References

    a.  Bach, R. 0., C. W. Kamienski, and R.  B. Ellestad.
        Lithium and Lithium Compounds.  Encyclopedia of
        Chemical Technology, 2nd Edition, Standen, A.  (ed.).
        New York, Interscience Publishers, 1967.  12:529-556.

        Shreve, R. N.   Chemical Process Industries,  3rd Edition.
        New York, McGraw-Hill, 1967.  905 p.

    b.  Barrett, W. T., and B. J.  O'Neal, Jr.  Recovery of
        Lithium from Saline Brines using  Solar Evaporation.
        In:  Third  Symposium on Salt, Rau, J. L., and  L. P.
        Dellwig  (ed.).  Cleveland, Ohio,  Northern Ohio Geo-
        logical Society,  1970.  2_:47-50.

        Luckenpach, W. F.  Year's  End Report  on  LJthium.
        Eng./Min. J.   168:152, February 1967.
                             170

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BRINE AND EVAPORITE CHEMICALS             PROCESS NO.  34


                         CLARIFYING

1 .   Function

    The process (see Figure 14 )  removes calcium, magnesium,
    and heavy rnetal ions from saturated sodium chloride brine.
    Controlled additions of soda ash and lime cause the ions
    to form insoluble compounds  which form a mud precipitate.
    The process occurs in settling tanks.  Clarified brine is
    fed to Process 37.

2 .   Input Materials

    Saturated sodium chloride brine - 5.7 cubic meters per
    metric ton of soda ash.

    Soda ash  (Na_g_C03) - Quantity varies depending primarily
    on total calcium in brine.  In one case, 0.031 metric
    ton per metric ton of soda ash was used.

    Lime (CaO) - Quantity varies depending primarily on total
    magnesium In brine.  In one case, 0.0036 metric ton per
    metric ton of soda ash was used.

3.   Operating Parameters

    The process is conducted at atmospheric pressure and
    ambient temperature.

4.   Utilities
    Electrical energy is used primarily for pumping.  The re-
    quirement is less than 10 kWh per metric ton.

 5.  Waste Streams

    The underflow mud from settling tanks which consists
    primarily of calcium carbonate and magnesium hydroxide
    Is transferred to pondage.  Solids become landfill, while
    water evaporates or flows Into natural streams.  The size
    of this  stream depends on the quantity of calcium and
    magnesium in the brine.  In one case, this stream was 0.1
    cubic meter per metric ton soda ash.  It contained 0.06
    metric  ton solids per metric ton soda ash.

 6.  EPA Source Classification Code

        None established
                             171

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References

Deutsch, Z. G., C. C. Brumbaugh, and F. H. Rockwell.
Alkali and Chlorine Industry.  In:  Kirk-Othmer Encyc-
lopedia of Chemical Technology, 2nd Edition ,  Standen,
A.  (ed.).  New York, John Wiley & Sons, Inc., 1963-
1:668-758.
                        172

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 35


                  DISSOLUTION/CLARIFYING

1.  Function

    In general, the process forms a relatively impure solution
    by dissolving a crude material in water.   It then removes
    dissolved or suspended contaminants from the solution by
    some combination of the steps of precipitation, settling
    and filtration.  The specific functions of the several
    applications of the process are listed below.

   *a.  As applied to the production of soda ash by the
        Solyay operation  (see Figure ik) - The process
        dissolves rock salt(NaCl; in water,  forming a
        saturated NaCl brine containing undesired minor
        concentrations of calcium (Ca) and magnesium (Mg)
        ions plus suspended Insolubles.  The Ca and Mg are
        precipitated by addition of NaOH and Na2C03, and
        removed either by settling and filtration or settling
        alone.  The purified brine is forwarded to Process 37.

        Essential equipment consists of agitated dissolving
        tanks, settling tanks, and in some cases, continuous
        filters.

    b.  As applied to the preparation of saturated NaCl brine
        for the electrolytic production of chlorine and caustic
        (see Figure 15) - The process application Isalmost
        identical to^a" , above, except that in most opera-
        tions the NaCl recovered from the evaporation of
        caustic (Process 10) is also added to the agitated
        dissolving tanks.  Additionally, alternative NaCl
        sources may be either granular salt, or solution-
        mined NaCl brine.  In the latter case, the dissolution
        step is omitted.  The clarified brine from this process
        Is forwarded to Process Ml or ^2.

    c •  As applied to the "Sesquicarbonate"  operations for
        production of natural soda ash (see Figure 1 J -
        The process forms a saturated aqueous solution of
        trona  (Na2C03»NaHC03"2H20) by dissolving crushed trona
 * Separate  industry  operations  employing  the process  are
   identified with  a  specific  lower  case letter which  is
   retained  as  an  identifier in  each element of this
   process description.
                             173

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2.
    d.
    e.
    in  hot mother  liquor recycled from  Process 10, and
    subsequently clarifying  the  solution by settling out
    the insoluble  gangue material.  The clarified trona
    liquor is  forwarded to Process  16 for  further pur-
    ification.

    Essential  equipment consists of agitated dissolving
    tanks and  Dorr-type settling tanks  or  clarifiers.

    As  applied to  the  " Monohydrate" operation for pro-
    duction  of natural soda  ash  (see Figure 19)  -
    Crude soda ash recieved  from Process 12 is dissolved
    in  water to form a saturated aqueous sodium  carbonate
    (Na2C03) solution, which is  then forwarded to Process
    10  for recovery of Na2C03«H20 crystals.

    Essential  equipment consists of agitated dissolving
    tanks, settling tanks, and continuous  filters.

    As  applied to  the preparation of re-purified NaCl
    for the  electrolytic production of  sodium metal  in
    th~e_ Downs  cell' (see Figure '?!)  -  The  process ap-
    plication  is similar to  that described in 11a" and
           T!
               above except  that  already-purified  NaCl  is
    the raw material,  and the degree of purity of the
    brine produced is  higher.  The sulfate content of
    the entering NaCl  is  removed in the process by pre-
    cipitation with BaCl2.  The purified brine is for-
    warded to Process  10.

Input Materials

a.  Quantity consumed  per metric ton of Na2C03 produced _
        Rock salt
        Water
        Sodium hydroxide
        Sodium carbonate
                         1.5 to 1.6 metric tons
                         4   to 6   cubic meters
                         5 kilograms (estimated)
                        20 kilograms (estimated)
    Quantity consumed per metric ton of Clg produced -


                         1.8 to 2.0 metric  tons
        Rock salt,
        (or granular)
        Salt brine,
        (alternative input)    6  to 7  cubic  meters
        Water (for dry-
        salt input)            5  to 6  cubic  meters
        Sodium hydroxide     5 kilograms (estimated)
        Sodium carbonate    20 kilograms (estimated)
                           174

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c>   Quantity consumed per metric ton Na2C03 produced -

    Crushed trona        l.ty  to 1.5 metric tons
    Make-up water        1   to 2   cubic meters (gross est.)
    Recycled mother      2   to 3   cubic meters (gross est.)
    liquor

d.   Quantity consumed per metric ton Na2C03 produced1 -

    Crude Na2C03         1.1 to 1.2 metric tons
    Wat.er                3-5 to 4   cubic meters
    Porous carbon        undisclosed quantity, estimated
                         20 kilograms

e.   Quantity consumed per metric ton Na metal produced -

    NaCl                 3.5 to 4.0 metric tons
    NaOH                 2   to 5   kilograms (estimated)
    BaCl2                0.5 to 1.0 kilogram
    FeCl3                2   to 3   kilograms
    Water                9   to 11  cubic meters

Operating Parameters

a,b,e.  Atmospheric pressure and temperature slightly above
        ambient.

c.   Atmospheric pressure and near the atmospheric boiling
    point of saturated trona liquor, estimated to be
    95° to 100°C.

d.   Atmospheric pressure and temperatures  slightly below
    the atmospheric boiling point, 95° to  100°C.

Utilities

a»d.   Per metric ton _Na2Cp3 produced -

    Electrical  energy consumed    10 to 15 kWh (gross  est.)

b.  Per metric  ton Gig produced -

    Electrical  energy consumed     5 to 15 kWh (gross  est.)

c.  Per metric  ton NaaC03 produced -

    Electrical  energy consumed    15 to 20 kWh
    Low pressure (2 kg/cma)       0.5 to 1.0 metric ton
    steam                         (gross est. )
                        175

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    e.   Per metric  ton Na  metal  produced  -

        Electrical  energy  consumed      25 to  40  kWh  (gross  est.)

5.   Waste Streams

    a.   Underflow  slurry from settling  tanks,  or slurried
        filter cake,  consisting  of  Mg(OH)2, CaC03, and  clay
        particles,  is presumed to be  wasted to tailings ponds.
        Solids become landfill;  water evaporates,  or is sluiced
        to natural  streams.   Estimated  quantity.'  10 to 20  kg
        total solids, plus 0.1 to 0.3 cubic meters water per
        metric ton Na2C03  produced.

    b.   Slurries similar in composition to those of  "a" ,
        above are  also presumed  to  be wasted  to  tailings
        ponds.  Estimated quantity:   10 to 20 kg solids plus
        0.1 to 0.2  cubic meters  H20 per metric ton C12  pro-
        duced.

    c,d.  Solids,  consisting principally  of gangue materials
        (clay, shale  and sand),  plus  some finely divided CaC03
        and Mg(OH)2,  is wasted to tailings ponds or  piles.
        It is presumed the solids are conveyed in slurry form.
        Estimated quantity:   0.09 to  0.12 metric tons solids,
        plus 0.5 to 0.7 cubic meters  water (presumed) per
        metric ton of Na2C03 produced.

    e.  Slurries similar in composition to those of  " a" ,  above
        but containing additionally approximately 1  kg BaS04
        per metric ton Na metal, are wasted  presumably by  sim-
        ilar means.

        Estimated quantity:  10  to  15 kg solids  plus 0.1 to
        0.15 cubic meters water per metric ton of Na metal
        produced.

6.  EPA Source Classification Code

    a through e:  None established
                            176

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7.   References

    a.  Deutsch, Z. G., C. C. Brumbaugh, and F. H. Rockwell.
        Alkali and Chlorine.  In:  Kirk-Othmer Encyclopedia
        of Chemical Technology, 2nd_ Edition, Standen, A. (ed.).
        New York, Interscience Publishers, 1963.~  l_:668-758.

        Faith, W. L., D. B. Keyes, and R. L. Clark.  Industrial
        Chemicals, 3rd_ Edition.  New York, John Wiley & Sons,
        Inc., 1965.  p. 664-667.

        Shreve, R. N.  Chemical Process Industries, 3rd
        Edition.  New York, McGraw-Hill, Inc., 1967. p. 225-230.


    b.  Deutsch, Z. G., C. C. Brumbaugh, and F. H. Rockwell.
        Alkali and Chlorine.  In:  Kirk-Othmer Encyclopedia
        of Chemical Technology, 2nd_ Edition, Standen, A. (ed.).
        New York, Interscience Publishers, 1963." 1:668-758.


    c,d.  Rau, E.  Sodium Compounds (Carbonates).  In:  Kirk-
        Othmer Encyclopedia of Chemical Technology,  2nd Edition,
        Standen, A. (ed.).  New York, Interscience Publishers,
        1969.  l8_:46l-464.


    e.  Lemke, C. H.  Sodium.  In:  Kirk-Othmer Encyclopedia
        of Chemical Technology, 2nd Edition, Standen, A. (ed.).
        New York, Interscinece Publishers, 1969.   1_8_: 442-445.

        Sittig, M.  Sodium, Its Manufacture, Properties and
        Uses.  New York, Reinhold Publishing Corporation,
        1956.  529 p.
                             177

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BRINE AND EVAPORITE CHEMICALS                  PROCESS NO.  36


                        CARBONATION

1.  Function

    The process (see Figure 14) converts soda ash (Na2C03)  to
    sodium bicarbonate (Na2C03) by carbonation with stack gas.

    Soda ash is dissolved in a weak solution of soda ash and
    sodium bicarbonate recycled from Process 16 and contacted
    in an absorption tower with a countercurrent flow of C02
    (stack gas).  The most common tower used is the classical
    Solvay tower, equipped with stacked, single bubble-cap
    sections positioned above cooling sections.  The carbonated
    slurry is forwarded to Process 16.

2.  Input Materials

    Soda ash - 0.63 to 0.7 metric ton per metric ton of
    sodium bicarbonate.

    Stack gas containing 16 to 20 percent C02 - 800 to 900
    cubic meters per metric ton of sodium bicarbonate.

    Recycled brine from Process 16 containing; some soda ash
    and sgdium bicarbonate - 3 to 5 cubic meters per metric
    ton of sodium bicarbonate.

3.  Operating Paramet ers

    The process is conducted at atmospheric pressure and at
    a temperature of 4o°C.

4.  Utilities
    Electrical  energy - 100 to 200 kWh per metric ton of
    sodium bicarbonate  (gross estimate).

 5.  Waste Streams

    Tail gas  from  carbonating towers is discharged to the
    atmosphere.  This is mainly nitrogen and carbon dioxide.
    Estimated quantities are 650 to 750 cubic meters N2 plus
    10  to 50  cubic meters  C02 per metric ton of NaHC03.

 6.  EPA Source  Classification Code

        None  established
                            178

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7.   References

    Deutsch, Z.  G., C.  C.  Brumbaugh, and F.  H.  Rockwell.
    Alkali and Chlorine.  In:   Kirk-Othmer Encyclopedia of
    Chemical Technology, 2nd Edition, Standen,  A.  (ed.).
    New York, Interscience Publishers, 1963.  1.: 668-758.

    Faith, W. L.,  B. D. Keyes, and R. L. Clark.  Industrial
    Chemicals, 3rd Edition.  New York, John Wiley  & Cons,
    Inc., 1965.   852 p.

    Shreve, R. N.   Chemical Process Industries.  New York,
    McGraw-Hill, 1966.   905 p.
                            179

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BRINE AND EVAPORITE CHEMICALS                PROCESS  NO.  37


                         ABSORPTION

1.  Function

   *a.  In its application to the Solvay process (See
        Figure 14) for soda ash, this process produces
        ammoniated NaCl brine by absorbing NHs gas in
        purified, saturated NaCl brine.

        Nearly saturated sodium chloride brine, previously
        purified, is fed into a cylindrical absorption
        tower, countercurrent to a gas flow containing a high
        concentration of ammonia.  The ammoniated brine is
        carbonated during and/or following the absorption
        process.

    b.  In the Hargreaves-type process, this process (See
        Figure l8) absorbs the HC1 gas produced in Process
        55 in water to form a 30% hydrochloric acid solution.
        A mixture of HC1 and N2 gas from a Hargreaves-type
        process reactor is fed into a vessel countercurrent
        to a water stream.  The absorption of HC1 in water
        is highly exothermic, requiring significant cooling.
        The corrosiveness of hydrochloric acid necessitates
        use of Karbate for construction of the heat exchanger
        and absorption tower.  The exit Nz gas is scrubbed
        with water or NaOH solution in a packed tower.

2.  Input Materials

    a.  Sodium chloride brine - 5-7 cubic meters per metric
        ton of soda ash

        Ammonia  (makeup only) - 1 kg per metric ton of ;jodo
        ash

    b.  HCl/Nz gas mixture - 1230 cubic meters per metric
        ton of HC1 (100% basis)

        Water -  2.33 cubic meters per metric ton of HC1
         (100% basis)
 *  Separate  industry operations employing the process are
   identified  with  a specific  lower case letter which is
   retained  as an identifier in each element of this process
   description.
                            180

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Operating Parameters

a.   Exit liquid temperature - 25°C

    Exit liquid concentration - 83 g. NH3 per liter of
    brine

b.   Exit liquid temperature - 25°C

    Exit liquid concentration - 30% HC1 solution

Utilities

a.   Non-contact cooling water - 3 to 3-5 cubic meters
    per metric ton of soda ash

b.   Non-contact cooling water (once-through basis) -
    35 cubic meters per metric ton of HC1 (100 basis)

Waste Streams

a.   Atmospheric discharge - approximately 0.05 kg NH3
    per metric ton of soda ash produced.

b.   Nitrogen gas is vented to the atmosphere in a stream
    estimated to be 615 cubic meters per metric ton of
    HC1 (100? basis).

    A NaCl - NaOH solution is wasted to ponds from the
    tail-gas scrubber.  This is estimated to contain
    5% NaCl and 5% NaOH.  Its amount is estimated to be
    30 kg of solution per metric ton of HC1 (100 % basis)
    produced.

EPA Source Classification Code

a.   None established

b.   None established

References

a.   Deutsch, Z. G., C. C. Brumbaugh, and P. H. Rockwell.
    Alkali and Chlorine.  In:  Kirk-Othmer Encyclopedia
    of Chemical Technology, 2nd Edition. Standen, A.(ed.)
    New York, Interscience Publishers, 1963. 1:668-758.

    Shreve, R. N.  Chemical Process Industries, 3rd
    Edition, pp. 227-229, New York, McGraw-Hill, 1966.
                         181

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b.  Jacobs, J. J.  Potassium Compounds.  In:  Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd
    Edition. Standen, A. (ed.). New York, Interscience
    Publishers, 1968. ]J5_: 3 69-^00.

    Kleckner, W. R., and R. C. Sutter.  Hydrochloric
    Acid.  In:  Kirk-Othmer Encyclopedia of Chemical
    Technology, 2nd Edition.  Standen, A.(ed.). New
    York, Interscience Publishers, 1968. 11:307-337.

    Shreve, R. N.  Chemical Process Industries, 3rd
    Edition, New York, pp. 343-346, McGraw Hill, 1966.
                          100
                          0£

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BRINE AND EVAPORITE CHEMICALS             PROCESS NO.  38


                     CALCINING/SLAKING

1.  Function

    The process (see Figure I1))  forms calcium hydroxide
    slurry (Ca(OH)2), or "milk-of-lime", by  calcining
    limestone (CaC03), then slaking the resulting calcium
    oxide (CaO) in an excess of water.  Carbon dioxide
    (C02) gas is also formed in the process, resulting from
    both the calcination of the limestone, and as a product
    of combustion of the fuel, usually coke.

    The Ca(OH)2 slurry is transferred to Process 39 for re-
    generating ammonia.  Part of the C02, as stack gas, is
    compressed and conducted to Process 8 for brine carbona-
    tion.

    The steps of cooling and cleaning a portion of the C02-
    containing kiln stack gas is included in the process.
    Essential equipment consists of vertical "stack" kilns,
    rotary slakers, and cyclone separators.

2.  Input Materials

    The process consumes the following typical quantities of
    input materials per metric ton of soda ash (Na2C03)
    produced:

        Crushed limestone            1.2 metric tons
        Fuel (almost always coke)    0.08 to 0.11 metric torn
        Slaking water                2 to 2.5 cubic meters

3.  Operating Parameters

    Pressure - Essentially atmospheric.

    Maximum  kiln temperature - 1000° to 1300°C

    Maximum  slaker temperature - approximately 100°C

    A typical stack kiln is 20 to 30 meters total height by
    3.5 to 6 meters cylinder diameter, and can produce 250
    to 400 metric tons CaO per day.

4.  Utilities

    Heat  (supplied by the coke mentloned_above) required per
    metric ton of  soda ash produced  -  0.7 to 0". 8 x  106 kcal.
                            183

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    Electrical energy consumption -  Grossly  estimated  to  lie
    between 10 and 20 kWh per metric ton of  soda  ash produced.

5.   Waste Streams

    Uncollected kiln exhaust gases,  vented to the atmosphere,
    are estimated to amount to 1,000 to 1,200 standard cubic
    meters per metric ton of soda ash produced.   The exhaust
    gases contain about 35 to 40 percent C02 (lower if kiln
    is fueled with natural gas), oxides of sulfur if high-
    sulfur coal is burned, water vapor, and  nitrogen.   Par-
    ticulates are almost always present and  consist of fly
    ash, lime, and limestone dust.  A stack  kiln, operating
    without solids-collecting equipment on exhaust, produces
    exhaust gases containing typically 0.7 to 2.3 grams or
    partlculates per cubic meter.  These values  correspond
    to 0.7 to 2.7 kilograms .per metric ton of soda ash pro-
    duced.  Operating with glass bag filters on  the exhaust
    stream, the same kiln might produce exhaust  gases contain-
    ing 5 to 10 percent of the values mentioned  above.

    Chemical composition  (by weight percent) of  the particulates
    in the exhaust gases  is typically:

        CaO                  66
        CaC03                23
        Ca(OH)2               6.4
        MgO                   1.4
        CaS04                 1.2
        Heavy metal oxides    1.0
        Acid insolubles       1.0

    The size range of the particulates emitted during opera-
    tion without the use  of collection equipment is 30 percent
    below 5 microns and 10 percent below 2 microns.

    Solid wastes  (handled as a  slurry) discharged  from rotary
    lime  slakers consist  of Ca(OH)2  (inadvertent), CaC03,  GaO
    (overburned  lime), heavy metal oxides, and acid insolubles.
    Their particle-size distribution  is typically  0.07 mm  to
    2 mm  diameter.  The quantity  varies with the purity of the
    limestone used.  This is typically as high as  20 kg per
    metric ton of  soda ash produced.  The ultimate disposal
    is  used  as landfill.

 6,  EPA Source Classification  Code

         None  established
                             184

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7.   References

    Deutsch, Z.  G., C.  C.  Brumbaugh,  and P. H.  Rockwell.
    Alkali and Chlorine (Sodium Carbonate).   In:   Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A.  (ed.).   New York, Interscinece  Publishers,
    1963.  1:707-740.

    Faith, W. L.,  D. B. Keyes, and R. L. Clark.  Industrial
    Chemicals, 3rd Edition.  New York, John  Wiley & Sons,
    Inc., 1965.   p. 664-66?.

    Shreve, R. N.   Chemical Process Industries, 3rd Edition.
    New York, McGraw-Hill, Inc., 1967.  p. 225-230.
                            185

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 39


                   AMMONIA REGENERATION

1.  Function

    The process (see Figure l4) recovers both the "free"
    ammonia and the "fixed" ammonia (NHi»Cl) from the mother
    liquor received from Process 8.  All the recovered am-
    monia, as NH3, together with some recovered C02 , is then
    recycled to Process 37-

    Essential equipment consists of two stripping columns
    and an agitated lime reaction tank.  The two columns
    are sometimes combined, one above the other, each form-
    ing a section of a structurally single tower.

2.  Input Materials

    A typical composition, by weight percent, of the mother
    liquor received from Process 8 is estimated to be:

        NaCl                 5.4
        NH»C1               13.0
        ITFree" NH3
        (as NHuOH, carbonates
        & carbamate)         2.3
        Total C02
        (as carbonate &
        carbamate)           2.7
        Water               76.7

    The estimated consumption  of mother liquor  is between  f>
    and 7 cubic meters per metric  ton of soda ash produced.

    Consumption of milk-of-lime, or calcium  hydroxide  slurry
     (Ca(OH)2), is estimated to be  between  2.0 and 2.6  cubic
    meters per metric ton  of soda  ash produced.  This  cor-
    responds to 0.8 to 0.85 metric tons of  Ca(OH)2 per metric
    ton of soda ash produced.

    The composition of the milk-of-lime usually varies between
     300 and  390 gms Ca(OH)2  per  liter  of slurry.

 3.   Operating  Parameters

     The process is  operated  at pressures slightly greater
     than  atmospheric, typically  up to  0.5  kg/cm2 gage  pressure
                            186

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Operating temperatures vary inside the stripping
columns ;•    approximately 100°C throughout  most  of
the height, and 50° to 60°C at the top of the "free"
column.

The two stripping columns (the "free" still,  and the
"fixed" still) are approximately 35 and 15  meters high,
respectively, for a wide range of production capacities.
If the two columns are combined, the total  height can
reach 55 meters.

For daily capacities of about 700 metric tons Na2C03,
column diameters are 3-5 to 4.0 meters.

Still-columns may contain bubble-cap plates,  or  may be
coke-packed.

The lime reaction tank requires violent agitation.

Utilities

Consumption of low-pressure steam (1.0 to 1.5 kg/cm2
gage), is estimated to be 1 to 2 metric tons per metric
ton of soda ash produced.

Cooling water consumption is grossly estimated to be
between 10 and 15 cubic meters per metric ton of soda
ash produced.

Estimated electrical energy consumption is  5 to  8 kWh
per metric ton of soda ash produced.

Waste Streams
Between 10 and 11 cubic meters  (9 to 10 metric tons)
of waste liquid is discharged per metric ton of soda ash
produced.  The composition of this liquid in weight per-
cent is estimated to be:

    CaCl2                9
    NaCl                 3 to 4
    Ca(OH)2
     suspended           0.5 to 1.0
    Water                balance

The stream also contains fractional percentages of R203,
Si02 and CaSOu.

The stream may be processed for economic recovery of
CaCl2, but usually is discharged to natural streams.
                        187

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    Solid waste,  chiefly  CaSCU ,  is  discharged  at  annual
    tower cleanout  periods.   This is  estimated to amount
    to less  than  0.1  kg per  metric  ton  of  soda ash produced.
    Probable disposal method is  as  landfill.

    It is suspected that  detectable quantities of NH3  gas
    are inadvertently discharged to the atmosphere.  These
    are estimated to be less than 0.1 kg NH3  per  metric  ton
    of soda ash produced.

6.   EPA Source Classification Code

    3.-01-021-01  Ammonia  Recovery

7.   Preferences

    Deutsch, Z. G. , C. C. Brumbaugh,  and F.  H. Rockwell.
    Alkali and Chlorine (Sodium Carbonate).   In:   Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A. (ed.).  New York, Interscience Publishers,
    1963-  ^:707
    Faith, W. L., D. B. Keyes, and R. L.  Clark.  Industrial
    Chemicals, 3rd Edition.  New York, John Wiley & Sons,
    Inc., 1965.  p. 664-667.

    Shreve, R. N.  Chemical Process Industries, 3rd Edition.
    New York, McGraw-Hill, Inc., 1967.  p. 225-230.
                              188

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 40


                      DECHLORINATION

1.  Function

    This process removes dissolved chlorine from the spent
    sodium chloride brine used in a mercury electrolysis
    cell for chlorine production " (See Figure 15).

    The brine stream exiting a mercury electrolysis cell
    contains dissolved chlorine in the form of hypochlorite.
    The stream is treated with hydrochloric acid to reduce
    chlorine solubility.  It then is fed to a flash vessel
    where practically all of the chlorine is evolved along
    with water vapor.  Chlorine and water are separated in
    another vacuum column.  Chlorine is fed to the chlorine
    product line leaving the electrolysis cell.  The water
    flows out as waste.  The dechlorinated brine is recycled
    to Process 35 for resaturation with salt.

2.  Input Materials

    Spent Brine Containing Dissolved C12 - approximately
    40 cubic meters brine per" metric ton of C12 produced.

    HC1 - 0.03 cubic meters of 32$ HC1 per metric ton of C12
    produced.

3.  Operating Parameters

    The chlorine collection manifold operates at a slight
    vacuum.  The flash tank pressure is typically 0.28 kg
    per square centimeter (6" Hg) absolute.  The temperature
    ranges from approximately 80°C (175*F) in the acidification
    tank to 75°C (165°F) in the flash vessel to 60°C (135°F)
    in the water-chlorine separation column.

4.  Utilities

    Electrical energy requirements are less than 5 kWh per
    metric ton of chlorine.

5.  Waste Streams

    0.6 cubic meter water per metric ton chlorine produced.
                            189

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6.   EPA Source Classification Code

    3-01-008-05  Air-Blow Mercury Cell Brine

7.   References

    Deutsch, Z. G. ,  C.  C. Brumbaugh, and P.  H.  Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:   Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Stand n, A. (ed.).   New York, Interscience Publishers,
    1963.   :6?l
    Yen, Y. C.  Chlorine, Supplement A.  Stanford Research
    Institute, Menlo Park, California.  Process Economics
    Program, Report No. 6lA.  May 197^.  256 p.
                            190

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BRINE AND EVAPORITE CHEMICALS
         PROCESS NO. 41
                 MERCURY CELL ELECTROLYSIS
1.  Function

    This process (see Figure 15) separates sodium chloride
    brine from Process 35 into chlorine gas and a sodium-
    amalgam in an electrolytic cell that uses mercury as the
    cathode.
    Most cells are constructed with a flat-bottomed steel
    trough.  Mercury flows across the bottom and serves as
    the cathode.  Sodium chloride brine flows between the
    mercury and coated titanium anodes.  The anodes are
    shaped as flat plates parallel to the mercury surface and
    are supported from a cell cover.  The cell cover material
    is inert to chlorine gas corrosion.  Chlorine gas evolves
    from the anode and collects beneath the cell cover prior
    to forwarding to Process 44.

    Sodium combines  with the mercury to form an amalgam.
    The sodium-mercury amalgam flows to Process 43.  The
    spent brine, containing some chlorine, goes to Process 40.

2.  Input Materials

    Brine saturated with dry, sod I urn chloride -
        1.7 metric tons of purified NaCl per metric ton of
        chlorine.

3.  Operating Parameters
    Volts per cell
    Current density
         (amps/cm2) cathode
    Salt conversion
    Brine flow

    Mercury flow

    Pressure
    Temperature

 4.  Utilities
0.59-1.35
     cubic meters per
 metric ton of chlorine
20-25 cubic meters per
 metric ton of chlorine
approximately atmospheric
75-85°C (167-185°F)
    Electrical energy requirements for electrolysis -
         3500 kWh per metric ton of chlorine.
                            19.1

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5.   Waste Streams

    Some leakage of chlorine gas around cell-cover seams  may
    occur.  The estimated quantity is  less than 0.0001
    metric ton per metric ton of chlorine.

6.   EPA Source Classification Code

    3-01-0008-02 Liquefaction/Mercury  Cell

7.   References

    Deutsch, Z. G., C. C. Brumbaugh, and P. H. Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:   Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A.  (ed.).  New York, Interscience Publishers,
    1963.  1:671-702.

    Yen, Y. C.  Chlorine, Supplement A.  Stanford Research
    Institute, Menlo Park, California.  Process Economics
    Program, Report No. 6lA.  May 197^.   256 p.
                             192

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BRINE AND EVAPORITE CHEMICALS                 PROCESS  NO.  42


                 DIAPHRAGM CELL ELECTROLYSIS

1.  Function

    This process (See Figure 15) separates sodium chloride
    brine into chlorine and hydrogen gas and sodium hydroxide
    solution in an electrolytic cell containing a diaphragm
    to separate the gaseous products.

    Brine is fed continuously from Process 35-  It flows from
    the anode compartment through an asbestos diaphragm into
    the cathode compartment.  The brine then leaves the cell.
    Chlorine gas forms at the graphite anode and is collected
    in an overhead manifold for transporting to Process 44.
    Hydrogen gas and sodium ions collect at the iron cathode.
    The hydrogen is collected in a separate manifold for
    transporting to another application of Process 44.  The
    sodium hydrolyzes Into sodium hydroxide in the brine.
    The brine is collected for transporting to Process 10.

2.  Input Materials

    Purified brine saturated with sodium chloride - 1.8 metric
    tons of sodium chloride per metric ton of chlorine.

3.  Operating Parameters

    Volts per cell           3.8
    Current density
      (amps/cm2) cathode     0.11
    Salt conversion         ^50%
    Brine flow
      (m.3/m. ton of C12)   ^13
    Pressure                ^ atmospheric
    Temperature (°C)        ^90

4.  Utilities

    Electrical power for electrolysis - 3,000 kWh per metric
    ton of chlorine

5.  Waste Streams

    Some leakage of chlorine gas around cell-cover seams
    may occur.  It is estimated to be less than 0.000]
    metric tons per metric ton of chlorine produced.
                             193

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6.   EPA Source Classification Code

    3-01-008-01  Liquefaction-Diaphragm

7•   References

    Deutsch, Z. G., C. C. Brumbaugh, and P. H. Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:  Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition.
    Standen, A. (ed.). New York, Interscience Publishers,
    1963. 1:671-702.

    Yen, Y. C.  Chlorine, Supplement A.  Stanford Research
    Institute, Menlo Park, California, Process Economics
    Program, Report No. 6lA. May 197*1. 256.
                            194

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BRINE AND EVAPORITE CHEMICALS                   PROCESS NO.  43


               SODIUM AMALGAM DECOMPOSITION
1.   Function

    This process decomposes the sodium amalgam transported
    from Process 41 by adding purified water to the mercury
    stream (See Figure 15).

    Purified water is fed to the mercury stream, usually
    countercurrent to the amalgam flow.  Through the use
    of a short-circuited electrode system, the sodium leaves
    the amalgam and combines with water to form aodium
    hydroxide in the electrolyte.  Hydrogen ga:; is generated
    at the iron or graphite cathode.  Thin gas in collected
    and forwarded to Process 44.

    V/ater is added at a rate to produce a 50$ sodium hydroxide
    solution essentially free of sodium chloride.  This solu-
    tion is forwarded for use as an end product or for further
    concentration in Process 10.  The  sodium-stripped merc-ury
    is returned to Process 41 for reuse.

2.   Input Materials

   •Mercury-sodium amalgam -
        ^20 cubic meters per metric ton of chlorine.
   •Purified water -
        ^1.6 cubic meters water per metric ton of chlorine.

3.   Operating Parameters

    Water flow  is adjusted to obtain the desired sodium
    hydroxide concentration  (^50$).  The operating procure
    is approximately atmospheric arid the temperature is
    approximately 80°C  (l80°F).

4.  Utilities

    Electrical  energy for water and mercury pumps is approx-
    imately 15  kWh per metric ton of chlorine.

5.  Waste Streams

    None.
                            195

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6.   EPA Source Classification Code

        None established

7.   References

    Deutsch, Z. G., C.  C.  Brumbangh, and P.  H.  Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:  Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A. (ed.).   New York, Interscience Publishers,
    1963.  1:671-702.
                            196

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BRINE AND EVAPORITE CHEMICALS                 PROCESS  NO.  44


                    COOLING/COMPRESSION

1.  Function

    This process (See Figure 15) cools and compresses the
    chlorine and hydrogen gases produced in electrolysis
    cell processes.

   *a.  Chlorine gas from electrolysis cells is collected
        in manifolds at a slight vacuum., cooled in suitably
        corrosion resistant heat exchangers and transported
        through sulfuric acid drying towers.  Water is the
        non-contact cooling medium.  The sulfuric acid is
        recirculated in towers countercurrent to the
        chlorine flow to remove moisture from the gas.
        Either rotary or reciprocating compressors with
        special seals are used to compress the chlorine for
        ultimate packaging or liquefication.  The sulfuric
        acid enters the drying towers at a concentration
        above 90% and leaves at about 60% for other plant
        use.

    b.  Hydrogen gas is cooled by direct contact with cool-
        ing water prior to being compressed by conventional
        types of positive displacement compressors.

2.  Input Materials

    a.  Chlorine leaving electrolysis cells - 1.2 to 1.5
        metric tons of chlorine-laden vapor per metric ton
        of chlorine product.

        Sulfuric acid (>99% purity) - ^0.05 cubic meters
        per metric ton of chlorine.

    b.  Hydrogen leaving electrolysis cells - 0.04 to 0.4
        metric tons of hydrogen-laden vapor per metric ton
        of chlorine produced.

3.  Operating Parameters

    a.  The temperature of the cooled chlorine is approxi-
        mately 40°C.  The absolute pressure before entering
        Process 45 is 2 to 3 kg per square centimeter.
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.

                            197

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    b.   The temperature of the  cooled hydrogen is  approxi-
        mately 30°C.   The final pressure is usually  1.2 to
        2 kg per square centimeter.

4.   Utilities

    Electrical energy -

    a.   10 kWh per metric ton of chlorine for chlorine
        compression.

    b.   2 kWh per metric ton of chlorine for hydrogen
        compression.

    Cooling Water -

    a.   2 to 8 cubic  meters per metric ton of chlorine.

    b.   Less than 1 cubic meter per metric ton of  chlorine.

5.   Waste Streams

    a.   None

    b.   None

6.   EPA Source Classification Code

        None established

7.   References

    Deutsch, Z. G., C. C. Brumbaugh, and F. H. Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:   Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A. (ed.). New York, Interscience Publishers,
    1963. 1=671-702.

    Yen, Y. C. Chlorine, Supplement A.  Stanford Research
    Institute, Menlo Park, California, Process Economics
    Program, Report No. 6lA. May 1974. 256.
                            198

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO.  45


                       LIQUEFACTION

1.  Function

    This process liquefies chlorine gas by successive stages
    of compression with interstage cooling, plus a final
    cooling with a refrigerant.

    Chlorine gas at absolute pressures from 2 to 3 kilograms
    per square centimeter is compressed further and then
    cooled for condensation.  Noncondensible diluent gases
    are vented to a scrubber system to recover their chlorine
    content.  Gome plants include a packed tower in which a
    countercurrent liquid chlorine stream is used to remove
    low-boiling organics from the chlorine gas.

2.  Input Materials

    Chlorine gas containing 1 to 10  percent noncondensible
    diluent gases.

3.  Operating Parameters

    The final chlorine absolute pressure varies from 5 to
    10 kilograms per square centimeter.  The final temper-
    ature is -10° to 30°C (10° to ?2°F).

4.  Utilities

    Electrical energy requirement is approximately ^10 to 80
    kWh per metric ton of chlorine.  This includes chlorine
    compression and refrigerant compression requirements.
    Cooling water requirement for the compressor intercooler
    is approximately 1 cubic meter per metric ton of chlorine
    Refrigeration requirements are approximately 90,000 kcal
    at -20°C per metric ton of chlorine (30 tons at 0°F per
    metric ton of chlorine).

5.  Waste Streams

    Noncondensables amounting to 0.02 metric ton per metric
    ton of chlorine produced are vented to the atmosphere.
    This stream has gone through a C12 scrubber and contains
     less  than  0.2  ppm  C12.

6.  EPA Source Classification Code

         None  established
                             199

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7.   References

    Deutsch, Z.  G., C.  C.  Brumbaugh, and F.  H.  Rockwell.
    Alkali and Chlorine Industry (Chlorine).  In:  Kirk-
    Othmer Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A.  (ed.).   New York, Interscience Publishers,
    1963.  1:671-702.

    Faith, W. L., D. B. Keyes, and R.  L. Clark.  Industrial
    Chemicals.  New York, John Wiley & Sons, Inc., 1950.
    p. 216-217.

    Yen, Y. C.  Chlorine.  Process Economics Program Report
    No. 61A.  Menlo Park, California,  Stanford Research Inst-
    itute, May 1974.  256 p.
                             200

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BRINE AND EVAPORITE CHEMICALS                PROCESS NO. 46


                     CRUSHING/GRINDING

1.  Function

    In general, the essential function of the process is
    size reduction of the input material necessitated by a
    requirement of a subsequent process or process step.  The
    specific functions of the various applications of the
    process are given below.

   *a.  As applied to processing of colemanite ore (see Figure
        16) - The process further reduces the size of coarse-
        crushed colemanite ore from Process 6, Figure 3, to
        permit handling by conveyors and trucks and to satisfy
        requirements of calcination equipment of Process 48.
        Ore beneficiation by screening (surmised) may be a
        process step.

        The operation became operative relatively recently
        (197D.  Information identifying the types of equip-
        ment used is unavailable.  Jaw crushers, hammermills,
        or roll-crushers are possibilities.

    b.  As applied tothe processing of sylvinite (KCl-NaCl)
        ore (see Figure 17; - The process further reduces the
        size range of coarse-crushed sylvinite ore, received
        from Process 6, Figure 3, to the fineness necessary
        for the "unlocking" of the unit crystals of sylvite
        (KC1) and halite (NaCl).  The ground material is then
        forwarded to either Process 47, Process 50, or Process 51.


        Screening steps (size separation) are usually included.

        Essential equipment may be one or several of the
        following types:

        hammermill
        raymond pulverizer
        cone crusher
        vibrating or shaking screens
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.


                             2Q1

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c.   As applied to the processing of langbeinite (K2SCU*
    2MgSO») ore (See Figure Ib) - The process further
    reduces the size range of coarse-crushed langbeinite
    ore, received from Process 6, Figure 3,  to the degree
    of fineness required for the rate-of-solution sep-
    aration of halite (NaCl) from the langbeinite (K2SC>4»
    2MgSO») in Process 54.

    The process includes the step of screening.

    Essential equipment may be identical to  that listed
    in  "b", above.

Input Materials

a.   Colemanite ore  (Ca2B6Oii *5H20 plus clay  gangue) -
    Gross estimate of amount consumed is 1.5 to 2.0
    metric tons per metric ton of calcined colemanite
    produced.

b.  Coarse-crushed sylvlnite ore (12 cm maximum lump
    dimension) - Estimated quantity consumed is 2 to 4
    metric tons per metric ton of KC1 produced.

c.  Coarse-crushed langbeinite ore - Estimated quantity
    consumed is 1.1 to 1.5 metric tons per metric ton
    of  K2SCU produced.

Operating Parameters

a.  No  quantitative information  is available.  Gross
    estimate of size required of process output ir:
    less than  1-cm  size lumps.

    Operation  is designed to process approximately
    130,000 metric  tons per year of raw ore.

b.  Sylvinite  is ground to  the following size  ranges'.

    4-mesh to  14-mesh  for input  to Process  47
    6-mesh to  100-mesh for  input to Process  50
    20-mesh to 40-mesh  (estimated) for  input to Process  51

    Annual capacities  of  a  single operation are in  the
    range  of  300 to  800 thousand metric tons of KC1.

 c.  Particle  size range of  ground langbeinite  ore is
    typically  80 percent  between 8-mesh and 80-mesh.
                        202

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4.   Utilities

    Estimated electrical energy consumption -

    a.  2 to 5 kWh per metric ton of calcined colemanite.

    b.  4 to 8 kWh per metric ton of KC1.

    c.  3 to 6 kWh per metric ton of K2SCU.

5.   Waste Streams

    a,b,d.  It is surmised that particulate fugitive emissions
    to the atmosphere result from all three applications of
    the process.  It is inferred that this dusting would be
    particularly troublesome in crushing colemanite (applica-
    tion a).

    No quantitative information is available pertaining to
    either absolute quantities or particle size distribution.

6.   EPA Source Classification Code

    a,b,c.   None established

7.   References

    Chem. Wk.  1£9.:39-^0, August 11, 1971.

    Cramer, T. M.  Production of Potassium Chloride in New
    Mexico.  Ind. Eng. Chem.  3_0:865-867, August 1938.

    Harley, G. T. , and G. E. Atwood.  Langbeinite - Mining
    and Processing.  Ind. Eng. Chem.  39_: ^3-47, January 1947.

    Jacobs, J. J.  Potassium Compounds.  In:  KIrk-Othmer
    Encyclopedia of Chemical Technology, 2nd_ Edition, Standen,
    A. (ed.).  New York, Interscience Publishers, 1968.
    16:371-383.

    McGraw, R. M.  New Mexico Sylvinite.  Ind. Eng. Chem.
    3_0_:86l-864, August 1938.

    Potassium Chloride and  Sulfate.  Chem. Eng.  New York,
    51:168-171, January 1950.

    Shreve, R. N.  Chemical Process Industries, 3rd Edition.
    New York, McGraw-Hill,  Inc., 1967.  p. 294-29B7
                            203

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Turrentine, J. W.   Potash in North America.  New York,
Reinhold Publishing Corp., 19*13.  p. 135-171.

White, N. C., and C. A. Arend, Jr.  Potash Production at
Carlsbad.  Chem. Eng. Progr.  46_:523-530, October 1950.

Woodmansee, W. C.   The Mineral Industry of California.
In:  Minerals Yearbook 1971, Schreck, A. E.  (ed.).
Washington, U.S. Dept. Interior, Bur. Mines, 1973.
2:139.
                       204

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BRINE AND EVAPORITE CHEMICALS                  PROCESS  NO.  47


                     LEACHING/CLARIFYING

1.   Function

   *a.  As applied to processing borax and kernite from the
        Kramer District at Boron, California (Figure ~l£T -
        The process produces clear borax (^261*07) li'quor
        from crushed kernite (Na2Bit07« 4H20) and borax
        (Na2Bit07»10H20) ores, forwarded from Process 6,
        Figure 3.  The borax liquor is forwarded to
        Process 10.

        The following sequential process steps are included:

            Leaching
            Wet screening
            Countercurrent thickening and washing

        Major equipment consist of steam-heated leach tanks,
        vibrating screens, and clarifiers (thickening tanks).

    b.  As applied to potassium chloride production at
        Carlsbad, New Mexico (Figure 17) - The process uses
        a sodium chloride(NaCl)-potassium chloride  (KC1)
        brine, recycled from Process 10, to extract KC1
        from ground sylvinite (mixed NaCl-KCl crystals),
        forwarded from Process 46, producing a. hot liquor
        saturated with both KC1 and NaCl.  The liquor is
        forwarded to Process 20.

        The process includes the sequential steps of:

            Leaching, including brine-heating
            Countercurrent thickening
            Centrifuging and washing

        Major equipment consists of agitated leach tanks,
        thickener-clarifier tanks and continuous centrifuges.

    c.  As applied to processing calcined lithium ore
        Tspodumene) concentrates at Kings Mountain, N'.C.
        fFigure 2*1 ) - The process extracts lithium hydroxide
* Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.
                            205

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        (LiOH)  from the  3-spodumene  clinker  resulting  from
        Process 62, producing  an  impure  LiOH liquor  which
        is subsequently  purified  in  Process  10.

        The following sequential  steps  are  included:

            Leaching
            Thickening and clarifying
            Filtration and washing

        Major equipment  consists  of  thickening tanks and a
        continuous drum filter (the  latter  in inferred).

2.   Input Materials

    a.   Estimated amount of crushed  ore entering the process
        is about 1.7 metric tons  per metric  ton of NaaB^Oy*
        lOHzO produced.   (Based on assumed  weight ratio of
        gangue to ore of 1:1 and  assumed mole ratio  of borax
        to kernite of 1:1).

    b.   The composition of the brine recycled to this
        process from Process 10 is:

            11% KC1
            20$ NaCl
            69% H20

        Approximately 6 cubic meters of recycled brine are
        required per metric ton of KC1 produced.

        The composition of the ground sylvinite entering the
        process varies with ore quality.  A typical
        composition might be:

            30% KC1
            70% NaCl

        Approximately 3.5 metric tons of ground sylvinite
        of this composition would be required per metric
        ton of KC1 produced.

    c.  Alkaline clinker entering the process contains
        typically about 1% to 1.3$ Li.  About 25 to 30
        metric tons of ground clinker are required per metric
        ton of LiOH produced.

        Leach water amounts to 10 to 15 metric  tons per
        metric ton of LiOH.
                            206

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    Operating  Parameters

    a.   Leaching  Is  conducted  at  approximately  100°C,  and  at
        atmospheric  pressure.   Gangue  (clay  plus  rock)  in
        thickener underflow  ranges  from  2  cm. diameter to
        60-mesh.   Leach-tanks  are 8 cubic  meter capacity.
        Each of four thickener tanks is  70 meters In diameter
        by  2.5 meters side wall depth.

    b.   Process operates  at  atmospheric  pressure  and about
        150°C.  Brine recycled from Process  10, enters  this
        process at 25° to 27°C.   Recycled  brine flow is
        typically 2  to 3  cubic meters per  minute,

    c.   Leaching  is  conducted  at  elevated  temperatures, probably
        in  excess of 75°C and  at  atmospheric pressure.

    Utilities

    Estimated  requirements are:

                      Steam,        Electrical       Per
         Water,      low  pressure       energy       m.  ton
           m.3        (m.  tons)        (kWh)         of
    a.     4.2            2.0          5  to  10     B203  equiv.

    b.    <0.1       0.3  to 0.5*        5  to  10        KC1

    c.   10 to 15    1.0  to 1.5       35  to  50        LIOH
        *  Assuming 75% heat recovery.

5 .   W a s t e S t r e am s

    a.  Slimes and sand are discharged  from thickeners as
        slurries and larger size material is rejected by
        shaking screens.  Collectively,  all wastes evolve
        into solids wasted to tailings  piles, and amount
        to an estimated 0.7 metric ton  per metric ton of
                    O produced.
    b.   NaCl,  wasted to tailings pond,  Is estimated at 2.3
        metric tons per metric ton KC1  produced.

        Slimes and insolubles are estimated at 0.2 metric
        ton per metric ton of KC1 and are also discharged to
        tailings pond.
                            207

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    c.   Total solid wastes  are  estimated at 25 to 30 metric
        tons  per metric  ton LiOH produced.   Conjectured
        method disposal  is  to transport  a slurry of the
        solids to tailings  pond or pile.

    a,b,c.  A  part of the aqueous portion of the slurries
        carrying the above  solid wastes  to pondage might
        reach natural streams.   No quantitative estimate
        of the liquids is available.

6.   EPA Source Classification Code

    a,b,c.  None established

7.   References

    a.   Nies, N. P.  Boron Compounds (Oxides, Borates).
        In:  Kirk-Othmer Encyclopedia of Chemical
        Technology, 2nd Edition.  Standen, A.(ed.). New
        York, Interscience Publishers, 1964. 3.: 609-652.

    b.   Cramer, T.M.   Production of Potassium Chloride in
        New Mexico. Ind. Eng. Chem., 3J3:865-867, August
        1938.

        Shreve, R. N.  Chemical Process Industries, 3rd
        Edition. New York, McGraw-Hill,  Inc., 1967.
        p. 294-495.

        Turrentine, J. W.  Potash in North America.  ACS
        Monograph f3eries, No. 91. New York, Reinhold
        Publishing Corp., 1943. p. 135-167.

        White, N. C., and Carl A. Arend, Jr.  Potash
        Production at Carlsbad. Chem. Eng. Progr.,
        46:523-530, October  1950.

    c.  Bach, R. 0., C. W. Kamienski, and R. B.  Ellestad.
        Lithium  and Lithium  Compounds.  In:  Kirk-Othmer
        Encyclopedia of Chemical Technology, 2nd Edition,
        Standen, A.(ed.). New York, Interscience Publishers,
        1967.  12:530-533.

        Faith, W. L., 0. B.  Keyes, and  R. L. Clark.
        Industrial Chemicals, 3rd Edition. New York,
        John  Wiley & Sons, Inc.,  1965.  p.  492-494.
                           208

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO.  48


                       CALCINATION

1.  Function

    The process (see Figure 16) removes the water of hydra-
    tion from crushed colemanite (Ca2B6Ou • 5H20) ore re-
    ceived from Process 46 prior to rail shipment of the
    calcined material as end product.   The chief objective
    of water removal is weight reduction.   The product weighs
    78 percent of the input material per unit of contained
    boron.

    The sole existing operation began  in 1971.   Little quanti-
    tative  information is  available.

    The steps of cooling and product screening are presumably
    included in the process.

    Essential equipment presumably consists of an oil-fired
    rotary kiln, rotary cooler, and vibrating, or shaking
    screens.

2.  Input Materials

    Crushed colemanite ore.  Some gangue material (clay)
    may be present.

    Estimated consumption is 1.3 to 1.5 metric tons per  metric
    ton of calcined colemanite.

3. ' Operating Parameters

    Pressure - Atmospheric

    Estimated temperature pange of calcination - 250° to 350°C


    No  information  Is  available on size requirement for
    kiln feed.

4.  Utilities

     (Per metric ton of calcined colemanite):

    Heat, presumably  supplied by combustion_of fuel oil -
    Estimated 0.7  x 10° to  1.0 x 10° kcal.
                           209

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    Electrical energy - Estimated 20  to  30  kWh.

5.   Waste Streams

    (Per metric ton of calcined colemanite):

    If beneficiation of the calcined  product  is  required,
    a solid waste of gangue material  could  result.   This
    may amount to as much as 0.1 metric  ton.

    Atmospheric emissions of fine particulates of calcium
    borate and gangue are surmized.  Inferred  from known
    characteristics of limestone calcination in rotary kilns,
    the quantity may be in the range  of 30  to 90 kilograms.

    No factual information is available

6.  EPA_ Source Classification Code

         None  established

7.  References

    Chem. Week.  10£:39-^0S August 11, 1971.

    Woodmansee, W. C.  The  Mineral Industry of California.
    In:  Minerals Yearbook 1971, Schreck, A. E. (ed.).
    Washington, U.S. Dept. of Interior, Bur. of Mines, 1973-
    2:139.
                             210

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BRINE AND EVAPORITE CHEMICALS                  PROCESS  NO.  49


                       FUSION/GRINDING

1.  Function

   *a.  As applied to production of anhydrous borax
        (Figure i£) - The process converts borax decahydrate
        (NazBitO? • 10H20) from Process 10 into ground, fused,
        anhydrous borax (^281,07).  The following sequential
        process steps are included:

            Calcination
            Fusion
            Cooling
            Crushing and grinding
            Size separation
            Packaging

        Equipment consists of:

            Rotary calciner
            Specially-designed fusion furnace
            Pan coolers or chilling rolls
            Roll crushers and rod mill
            Shaking screens
            Bagging or drumming equipment

    b.  As applied to production of anhydrous boric acid
        (boric oxide) (Figure 16) - The process converts
        boric acid(H3B03) from Process 10 into ground,
        fused, anhydrous boric acid or boric oxide  (B20s).
        The process steps and equipment are identical with
        those described in "a", above.

    c.  As applied to production of boron oxide (Figure 16)
        The process converts borax pentahydrate (NazBijC^
        from Process 10 and concentrated sulfuric acid
        (HaSOij) into ground, fused, boron oxide (B203 ) .

        The process steps are similar to those of "a",
        above, except that a product of fused, impure
        Na2SOi» is obtained, which is eventually dissolved
        and forwarded to Process 10 (see Figure 7).
  Separate industry operations employing the process are
  identified with a specific lower case letter which is
  retained as an identifier in each element of this
  process description.
                            211

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        The "anhydrous boric acid" produced in "b"  above
        has a higher purity level than the "boron oxide"
        produced here.  Theoretically, the two substances
        are chemically identical.

2.   Input Materials

    a.   Theoretically, 1.9 metric tons of borax (Na2Bit07«
        10H20) are required per metric ton of NaaBuO? produced
        Either dry or moist borax may be fed.  It is impract-
        icable to use NazBi+O? • 5H20 as feed, because of
        excessive dusting.

    b.   Theoretically, 1.9 metric tons of H3B03 are required
        per metric ton of BjOa  produced.
    c.  Theoretically, 1.71 metric tons of borax penta-
        hydrate (NazBi+Oy* 5H20) and 0.6 metric ton of con-
        centrated sulfuric acid are required per metric ton
        of 6203 produced.

3.  Operating Parameters

    a.  Fusion furnace is of special design, is gas-fired
        from above, and continuously fed.  Molten charge
        is supported by a bed of solid feed.  Rotary cal-
        ciners are 2.5 meters diameter x 22.5 meters long,
        are fed concurrent  to  760°C gases exhausting
        from fusion furnace.  Maximum temperature of about
        980°C.  All equipment operates at atmospheric pressure,

    b.  Very similar to those of "a", above, except that
        temperatures are lower.  Molten charge temperature
        is probably about 800°C to 850°C.

    c.  Little quantitative information is available.
        Fusion furnace operates at 800°C to 900°C, yield-
        ing a two-phase melt:  upper layer of B203 and
        lower layer of Na2S04.  Operation is at atmospheric
        pressure.

4.  Utilities

    a,b,c.  Estimated total heat input is in neighborhood
        of 0.5 to  1.5 x  106 kcal per metric ton of product.

5.  Waste Streams
    a,b,c.  There are no designed waste  streams.   It  is
         inferred that particulate emissions  (dusting)  to
         the atmosphere  from  calciners, fusion  furnace


                             212

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        and crushing equipment is a problem.  Fumes of S03
        are probably emitted by the boron oxide fusion
        furnace.

6.   EPA Source ClassificationCode

    None established

7.   References

    Bixler, G. H., and D.  L. Sawyer.  Boron Chemicals from
    Searles Lake Brines.  Ind. Eng. Chem.  4_9:322-333, March
    1957.

    Nies, N. P.  Boron Compounds  (Oxides, Borates).  In:
    Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
    Edition.  Standen, A.(ed.). New York, John Wiley, &
    Sons, Inc., 1966. 3:608-652.
                             213

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 50


                          TABLING


1.  Function

    The process (See Figure 17) separates potassium chloride
    (KC1) crystals and sodium chloride (NaCl) crystals from
    the crystal mixture (fine sylvinite)  forwarded from
    Process 46.  The principal product is actually a slurry
    of KC1 crystals in saturated KCl-NaCl brine, forwarded
    to Process 52.  The NaCl crystals are usually wasted to
    a tailings pond, although sometimes are dried and sold.

    This process does not effect as clean a separation of
    KC1 from NaCl as either the hot-leach method or the
    froth-flotation method.  Consequently, it is being re-
    placed by the latter two processes.

    This process also includes the steps of:

        •Slurrying of ground sylvinite crystals in makeup
         water and recycled brine.

        •De-sliming the crystal slurry.

        •De-brining the NaCl crystal fraction.

        •De-brining and recycling a "middlings"  crystal
         fraction.

        •Wet screening the "middlings" fraction.

2.  Input Materials

    Principal  entering material is a mixture of fine  crystal:;
    of KC1 and NaCl containing particles of  gangue.   Its
    weight composition varies widely with quality  of  sylvinite
    ore used,  ranging between  25 and  50 weight percent of  KC1.

    A  stream of brine, saturated with  KC1 and NaCl, enters  the
    process as a  recycle  flow  from Process  52.  Its quantity is
    estimated  to  be between  5  and  10  cubic  meters  per metric ton
    of KC1 produced.

    Addition of minor amounts  of  "collecting agents1'  and
    oil may be necessary  to  enhance  the difference  in crystal
    densities  of  KC1 and  NaCl.   Quantitative information  is
    unavailable.
                            214

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3.   Operating Paramet er s

    Process is conducted at  atmospheric  pressure  and  normal
    room temperatures.

    A typical operation produces approximately 200,000 metric
    tons per year of KC1, corresponding  to a flow of  slurry
    entering the process of  3 to 6 cubic meters per minute.

4.   Utilities

    Estimated requirements per metric ton of KC1  produced:

        Makeup water             0.5 to  1 cubic meter
        Electrical energy        5 to 10 kWh

5.   Waste Streams

    Depending upon the  quality of sylvinite ore,  between 2  and 3
    metric tons of NaCl are  wasted to tailings ponds  per metric
    ton of KC1 produced.  A  part of the  aqueous portion of  this
    stream may reach natural streams.  No quantitative estimate
    of the liquid waste is available.

6.   EPA Source Classification Code

        None  established

7.   References

    Jacobs, J. J.  Potassium Compounds.   In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition, Standen,
    A.  (ed.).  New York, Interscience Publishers, 1966.  16:
    376.

    Shreve, R. N.  Chemical Process Industries, 3rd Edition.
    New York, McGraw-Hill, 1967.  p. 295.

    Turrentine, J. N.   Potash in North America. ACS Monograph
    Series, No. 91.  New York, Reinhold Publishing Company,
    1943.  p. 135-167.
                            215

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BRINE AND EVAPORITE CHEMICALS             PROCESS NO. 51


                       WET GRINDING


1.  Function

    The process (See Figure 17) reduces the particle size of
    sylvinite crystals forwarded from either Process 13, as
    conducted at Moab, Utah, or Process 46, as conducted at
    Carlsbad, New Mexico, in order to "unlock"  intermeshed
    crystals of potassium chloride (KC1) and sodium chloride
    (NaCl).  The product is a slurry of MaCl and KC1 crystals
    of approximately 100-mesh size suspended in saturated
    KCl-NaCl brine forwarded to Process 15.

    The process includes the steps of brine addition and wet
    size classification.

    Rod mills or ball mills are the principal equipment, with
    wet screens, spiral classifiers, drag classifiers, and
    hydroclones included as auxiliaries.

2.  Input Materials

    Approximately  2 to 3 metric tons of coarse-ground
    sylvinite (NaCl-KCl crystal mixture) enter the process
    per metric ton of KC1 produced.  This ratio varies with
    ore composition.

    Between  10 and 15 cubic meters  (estimated) of saturated
    KCl-NaCl brine per ton of  KC1 produced also enter the
    process  as a recycle flow  from Process ]5«

3.  Operating Parameters

    The process is conducted at atmospheric pressure and
    normal room temperatures.

    A  typical operation produces approximately 200,000 metric
    tons per year  of  KC1.  This production rate corresponds
    to average, continuous-flow rates of approximately  one
    metric ton per minute  of entering coarse-ground  sylvinite
    ore and  3 to 5 cubic meters per minute of recycled brine.

4.  Utilities

    Estimated  electrical  energy consumption per metric  ton of
    KC1 produced is  10  to  20 kWh.
                          216

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5.   Waste Streams

    Estimated amount of clay particles  discharged to tailings
    ponds as slimes from hydroclones and thickeners  is 0.1
    metric ton per metric ton KC1 produced.   A part  of the
    aqueous portion of this stream may  reach natural streams.
    No quantitative estimate of the liquid waste is  available.

6.   EPA Source Classification Code

        3-05-022-01  Mine-Grind/Dry

7.   References

    Jacobs, J. J.  Potassium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition, Standen,
    A. (ed.).  New York, Interscience Publishers, 1966.
    16:37^-376.

    Magraw, R. M.  New Mexico Sylvinite.  Ind. Eng.  Chem.
    3£:86l-864, August  1938.

    White, N. C., and C. A. Arend, Jr.   Potash Production at
    Carlsbad.  Chem. Eng. Progr.  _^6_:523-533, October 1950.
                            217

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BRINE AND EVAPORITE CHEMICALS                   PROCESS NO.  52


                         DEBRINING


1.   Function

    The process recovers potassium chloride (KC1) crystals
    from the slurry of KC1 crystals in saturated brine
    forwarded from Process 50.  Principal equipment consists
    of drag classifiers, but may include centrifuges if the
    KC1 crystals are to be washed  (See Figure 17).

2 .   Input Materials

    The estimated composition of the slurry entering the
    process is:

        Suspended KC1        10 to 15$
        Saturated brine      85 to 90%

    Approximately 10 cubic meters  of entering slurry is re-
    quired per metric ton of KC1 produced.

3.  Operating Parameters

    The process is conducted at atmospheric pressure and
    normal room temperature.

4.  Utilities

    Electrical energy consumption  is estimated  to be less
    than  3 kWh per ton  of KC1 produced.

5.  Waste Streams

    No wastes are generated.

6.  EPA Source Classification Code

        None established

7 •  References

    White, N.  C.,  and  C.  A.  Arend, Jr.    Potash Production  at
         Carlsbad.    Chem. Eng.  Progr.   46:523-531,  October  1950.
                            218

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO. 53


                     SULFUR COMBUSTION


1.  Function

    The process (See Figure 18) converts elemental sulfur,
    either solid or liquid, into sulfur dioxide (15 to 19%
    S02) by combustion in air.  The sulfur dioxide is con-
    ducted to Process 55.

    Commonly used essential equipment consists of a sulfur
    melting chamber, a rotating cylindrical sulfur vaporizer,
    where partial combustion takes place, and a combustion
    chamber in which the sulfur vapor is completely burned
    and which also heats the melting chamber.  If solid
    sulfur is used, a feeding device is included, usually
    a small screw conveyor.  If liquid sulfur is fed, the
    melting chamber is unnecessary.

2.  Irrput_ Materials

    Either solid (lump or powder) or liquid sulfur is fed.
    The choice is based on economics.  In either case approx-
    imately 0.2 metric ton of sulfur is consumed in producing
    1 metric ton of KaSO^.

3.  Operating Parameters

    Equipment operates generally at atmospheric pressure.
    A slight negative gage pressure is maintained inside the
    vaporizer and combustion chamber to minimize atmospheric
    emission of sulfur dioxide.

    Temperature ranges are between 250° and 350°C in the
    melting chamber, 500° to 700°C in the vaporizer, and 700°
    to 850°C in the combustion chamber.

    A typical capacity for sulfur-burning equipment is between
    10 and 15 metric tons of sulfur per day.   Larger units are
    available.

4.  Utilities

    Between 1 and 2 kWh of electrical energy are required per
    metric ton of K2SO^ produced.
                            219

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5.   Waste Streams

    Minor periodic emissions of sulfur dioxide (S02)  into the
    atmosphere are unavoidable during normal operation of the
    equipment.  No quantitative information is available.

6.   EPA Source Classification Code

        None established

7 .   References

    Jacobs, J. J.  Potassium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition,
    Standen, A,  (ed.).  New York, Interscience Publishers,
    1968.  16_
    Kleckner, W. R., and R. C. Sutter.  Hydrochloric Acid.
    In:  Kirk-Othmer Encyclopedia of Chemical Technology,
    2nd Edition, Standen, A. (edl).  New York, Interscience
    Publishers, 1966.  11:310-311.

    Shreve, R. N.  Chemical Process Industries, 3rd Edition
    New York, McGraw-Hill, 1966.  p. 3^3-3^6.
                            220

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BRINE AND EVAPORITE CHEMICALS             PROCESS  NO.  54

                         LEACHING


1.  Function

    The process (See Figure 18) removes sodium chloride
    (NaCl) from ground langbeinite (K2S04«2MgSOu)  ore for-
    warded from Process 46.  The removal is accomplished by
    selectively dissolving the NaCl from the langbeinite.

    The process includes the consecutive steps of pulping
    (slurry formation), wet classification, settling, and
    centrifuging.   Major equipment includes rotary washing
    tumblers, Dorr classifiers, wet cyclones, and either
    centrifuges or rotary drum filters.

    The wet product is forwarded to Process 11.

2•  Input Materials

    Between 2.5 and 2.8 metric tons of crushed langbeinite
    ore from Process 46 are consumed per metric ton of dried
    langbeinite .(98% K2SOu«2MgSOu) produced.  A typical screen
    analysis of the crushed ore feed is:

        Mesh                 Cumulative % Retained

          4                             0
          6                             2
          8                            12
         10                            25
         14                            40
         20                            55
         28                            6?
        200                            97

3.  Operating Parameters

    The process operates at atmospheric temperature and
    pressure.  Control of washing time (contact time) and
    ore-water ratio are critical parameters.

    Typical equipment  sizes for a plant producing 500 metric
    tons per day of product are:

        Dorr classifier  (2 in  series)   7.7 m dia x 2.5 m deep
        Settling cone  (1)               5.5 rn dia
        Byrd solid-bowl centrifuge  (1)  1.0m dia x 1.25 m face
                            221

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4.   Utilities

    Total water requirement  approximates  6 cubic  meters  per
    metric ton of dried langbeinite.

    Estimated electrical energy consumption is between 6 and
    12 kWh per metric ton of dried langbeinite.

5.   Waste Streams

    There are no atmospheric emissions.

    Total quantity of liquid wastes is approximately 6.5
    cubic meters per metric  ton of dried langbeinite, com-
    prising a 20 to 22$ sodium chloride brine.  This is  ponded,

    Solid wastes consist of  a variable quantity of fine  mud
    and slimes suspended in  the waste brine, estimated less
    than 0.3 metric tons per metric ton of dried langbeinite.

6,   EPA Source Classification Code

        None  established

7.   References

    Hartley,  G. T., and G. E. Atwood.  Langbeinite - Mining
    and Processing.  Ind. Eng. Chem.  39.: 43-47, January 1947.

    Jacobs, J. J.  Potassium Compounds.   In:   Kirk-Othmer
    Encyclopedia of Chemical Technology,  2nd Edition, Standen,
    A.  (ed.).  New York, Interscience Publishers, 1968.
    1(5:381-384.

    Turrentine, J. W.   Potash in North America.  New York,
    Reinhold,  1943.  p. 181.

    White, N.  C., and  C. A.  Arend, Jr.  Potanh Production  at
    Carlsbad.  Chem. Eng. Progr.   46:523-530,  October 1950.
                            222

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BRINE AND EVAPORITE CHEMICALS               PROCESS NO. 55


                    HARGREAVES PROCESS


1.  Function

    The process (See Figure 18) forms potassium sulfate
    (K2S04) and gaseous HC1 by reacting potassium chloride
    (KC1), sulfur dioxide (S02), steam, and ain

        2KC1 + S02 + |02 + H20 ->- K2S04 + 2HC1

    The sulfur dioxide is forwarded from Process 53, and
    the potassium chloride from either Process 15 (Figure 17),
    or Process 20 (Figure 17).

    The process is a modification of the classical Hargreaves
    process for production of salt cake.  It includes the
    steps of briquetting, reaction, cooling, grinding, and
    packaging (RR cars) of the K2SCu produced.

    Major equipment consists of briquetting rolls, reaction
    furnace (multiple chambers in cyclic countercurrent
    operation), and a rotary cooler.

2.  Input_ Materials

    Approximately 0.38 metric tons of S02  (100$ basis) are
    consumed per metric ton of K2SOU produced.  This is
    equivalent to 782 standard cubic meters of  17% S02 gas.

    Between 0.85 and 0.90 metric ton of potassium chloride
    is consumed  per metric ton of K2SOU produced.

3.  Operating Parameters

    All steps of the process are conducted at essentially
    atmospheric pressure.  The reaction furnaces are operated
    under a slightly negative pressure to minimize atmospheric
    emissions.  Temperatures inside the reaction mass are
    maintained between  400° and 650°C  (690°C is the melting
    point of the KCl-K2SOn eutectic).  Temperature is controlled
    by admission of additional air,  since the reaction is exo-
    thermic.  Heat is added initially only to bring a reaction
    mass up to temperature.

    Reaction chambers are stationary and are manifolded to
    effect flow of S02  coumtercurrent to the passage of KC1.
                            223

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   Quantities  in excess of  stoichiometric  amounts  of both
   steam  and air are used.

U.   Utilities

    Estimated requirement  of low pressure steam is  0.5  metric
    ton per metric  ton of  K2SOU produced.

    Estimated electrical energy consumption is less than 5  kWh
    per metric ton of K2SOU  produced.

    The consumption of fuel  gas is negligible, less than 10
    cubic meters per metric  ton of K2SOu.

5•   Waste Streams

    Fugitive emissions of gases containing both S02 and HC1
    are conjectured in the  vicinity of the reaction furnaces
    during the periodic operation of the gas flow valving.
    Specific information is  not available.

6.   EPA Source Classification Code

        None  established

7.   References

    Hartley, G. T., and G. E. Atwood.  Langbeinite	Mining
    and Processing.  Ind.  Eng.  Chem.  39_:^3-4?, January

    Jacobs, J. J.  Potassium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition, Stand en,
    A.  (ed.).  New York, Interscience Publishers, 1968.  16 :
    381-397.

    Kleckner, ¥. R., and R.  C.  Sutter.   Hydrochloric Acid.
    In:   Kirk-Othmer Encyclopedia of Chemical Technology,
    2nd Edition, Standen, A. (ed.).  New York, Interscience
    Publishers, 1966.  11:312.

    Turrentine, J. W.  Potash  in North America.  New York,
    Reinhold,  19^3.  p. 181.

    White, N.  C.,  and  C. A. Arend, Jr.   Potash Production
    at  Carlsbad.   Chem. Eng. Progr.  46:523-530, October 1950.
                            224

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BRINE AND EVAPORITE CHEMICALS            PROCESS NO. 56


                      NEUTRALIZATION


1.  Function

    This process (See Figure 20) neutralizes magnesium
    hydroxide [Mg(OH)2] filter cake received from Process 7,
    Figure 2, with make-up hydrochloric acid (HC1)  and HC1
    recycled from Process 59 to produce magnesium chloride
    (MgCl2) liquor.

    Filter cake is introduced into an agitated neutralizer
    tank, along with a controlled stream of hydrochloric
    acid.  A stream of H2SC\ is also introduced in an amount
    equivalent to soluble calcium present.   The resulting,
    impure MgCl2 brine or liquor is forwarded to Process 57.

2.  Input Materials

    Washed, filtered 35% MK(OH)2 filter cake -

        8 metric tons per metric ton of magnesium metal.

    H2S04 -

        0.2 metric tons (100% basis) per metric ton of
        magnesium metal.

    HC1 -
        3-5 metric tons (100$ basis) per metric ton of
        magnesium metal.

3-  Operating Parameters

    The process is conducted at atmospheric pressure and
    at temperatures between ^0° and 50°C.

14 •  Utilities

    Electrical energy -

        10 kWh per metric ton of magnesium metal.

5.  Waste Streams

    Mists of MgCl2 are caused by breaking of C02 bubbles.
    The MgCl2 in these mists is less than 0.001 metric ton
    per metric ton of magnesium.
                            225

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EPA Source Classification Code

    None established

References

Comstock, H. B.  Magnesium and Magnesium Compounds.
U.S. Government Printing Office, 1973.

Mcllhenny, W. F.  Dissolved Deposits.  Society of Mining
Engineers Handbook, 1973.  2_: Article  20.^.1.

Schambra, W. P.  The Dow Magnesium Process at Freeport,
Texas.  Trans. Amer. Inst. Chem. Eng.  4l:35-51j
January 19^5.
                        226

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BRINE AND EVAPORITE CHEMICALS              PROCESS  NO.57


                  EVAPORATION/FILTRATION


1.  Function

    This process (See Figure 20) concentrates a 30 to 3*J%
    magnesium chloride (MgCl2) solution to 50 to 55$ MgCl2
    and also removes impurities.

    Direct-fired or submerged combustion evaporators are
    used to concentrate the MgCl2 solution from Process 56.
    The more concentrated MgCl2 solution is cooled by
    vacuum evaporation, sent to settling tanks, and then
    through filters where  calcium sulfate, sodium chloride,
    and magnesium hydroxide are deposited.  The filtered
    MgCl2 solution is then further concentrated to 50 to 55$
    in steam-heated, boil-down kettles.  The 50 to 55$ MgCl2
    stream then goes to Process 9.

2.  Input Materials

    MgCl2 solution (30 to 34$ MgCl2) -

        10 cubic meters per metric ton of magnesium metal.

3.  Operating Parameters

    Temperatures are approximately 115°C  (240°F) in the first
    evaporation step, 40°C (100°F) in the settling step,
    ambient in the filtration step, and 1?5°C  (3^5°F) in the
    final evaporation step.

    Pressures are atmospheric for all these steps except for
    the vacuum evaporation, which is at an absolute pressure
    of 0.2 kg per square centimeter.

4.  Utilities

    Electrical energy -
        Less than 10 kWh per metric ton of magnesium metal.

    Natural gas -
        100 to 200 cubic meters  per metric ton of magnesium
        metal.

    Steam  (28 kg/cm2) -

        3 to 5 metric tons per metric ton of magnesium metal.
                            227

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    Quench water -

        25 cubic meters1 .per  metric  ton of  magnesium metal.

    Filter wash water -

        0.5 cubic meters  per metric ton of magnesium metal.

5.   Waste Streams

    Combustion gases from submerged combustion evaporator -

        Contain detectable amounts  of MgCl2,  HC1,  and MgO.
        Quantitative information is unavailable.

    Filtercake slurry (primarily calcium  sulfate  and sodium
    chloride) -

        0.1 metric ton solid per metric ton of magnesium is
        slurried with 0.5 cubic meter water per metric ton
        of magnesium.  The  slurry  is discharged to tidewater

6.   EPA Source Classification Code

        None established

7.   References

    Comstock, H. B.  Magnesium and Magnesium Compounds.
    U.S. Government Printing Office, 1963.

    Gross, W. H.  Magnesium and Magnesium Alloys.   In:
    Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
    Edition, Standen, A.   (ed.).  New York, John Wiley and
    Sons,  Inc.,  1967.  l_2:66l-708.

    Mcllhenny, W. P.  Dissolved Deposits.   Society of
    Mining Engineers Handbook, 1973-   2_:Article 20.4.1.
                            228

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BRINE AND EVAPORITE CHEMICALS            PROCESS  NO.  58


                       ELECTROLYSIS


1.   Function

   *a.   As applied to the production of magnesium metal
        (See Figure 20) -  The process forms magnesium'
        metalCMg) and gaseous chlorine (C12) by electro-
        lysis of the solid magnesium chloride (MgCl2)
        received from Process 9.

        Granular MgCl2 is added to a bathtub-shaped steel
        cell containing a bath of fused salts.  High-amperage
        electrical current is passed through the bath to
        generate molten elemental Mg and C12 gas.  The Mg is
        dipped from the top of the bath and cast into ingots.
        The C12 is collected and conveyed to Process 59, or
        alternatively, to Process 44 (See Figure 15).

    b.   As applied to the production of sodium metal (See
        Figure 21) -The processformssodium metal(Na)
        and gaseous chlorine (Cla) from the sodium chloride
        (NaCl) received from Process 11.

        Dry purified NaCl is fed to the Downs cell.  The
        latter is a closed, refractory-lined steel box with
        separate anode and cathode compartments.  High-
        amperage electrical current is passed through the
        bath to generate a molten mixture of Na and calcium
        (Ca).  The molten alloy flows upward into a compart-
        ment sealed to protect the Na from oxidation.  The
        molten alloy flows to Process 16, and the gaseous
        Cla is transferred to Process 44 (See Figure 15).

2.   Input Materials

    a.   MgCl2 feed  (Solid granules, containing 72 to 78%
        MgCl2f 0.5% CaClg,, !%_ Nad, 1 to 2% MgO, remainder
        water) ~

            5 metric tons per metric ton of Mg.
* Separate  industry operations employing  the process  are
  identified with a specific  lower case letter which  is
  retained  as an identifier in each element of this
  process description.
                            229

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        Graphite  anodes  -

            0.1 metric ton per  metric  ton  of  Mg.

    b.   NaCl (Dry purified)  -

            3 metric  tons  per metric  ton of Na.

        Graphite  anodes-

            0.01  to 0,02 metric tons  per metric  ton  of  Na.

3.  Operating Parameters

    a.   Mg cell temperature is  700°C.

        Cell pressure is approximately atmospheric.

        The cell  bath contains  20% MgCl2,  2Q% CaCl2, 57%  NaCl,
        2% KC1, \% CaP2.

    b.   Downs (Na) cell  temperature is 580°C.

        The cell  bath contains  58 to 59$ CaCl2,  41 to ^2%  NaCl,
        (There may be some use  of NaCl-CaCl2-BaCl2 baths).

4.  Utilities

    Electrical energy -

    a.   19,000 kWh per metric  ton of Mg.

    b.   13,000 kWh per metric  ton of Na.

    Natural gas -

    a.   10 to 100 cubic  meters  per metric  ton of Mg.

5.  Waste Streams

    a.   Chlorine gas collection system leakage - Absolute
        amount is not divulged.  Ventilation systems are
        designed to maintain less than 1 ppm C12.

        Sludge consisting primarily of CaCl2t MgCl2, NaCl,
        and MgO - 0.1 metric ton per metric ton of Mg.

    b.  Chlorine gas collection system leakage - Absolute
        amount is not divulged.

        Sludge consisting primarily of NaCl and CaCl2 -
        0.002 to  0.005  metric  tons per metric ton of Na.
                            230

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6.   EPA Source Classification Code

    a.   None established

    b.   None established

7 •   References

    a.   Gilroy, D.  The Electrowinning of Metals.   In:
        Industrial Electrochemical Processes, Kuhn, A. T.
        (ed.).  New York, Elsevier Publishing Company,
        1971.  p. 175-217.

        Schambra, W. F.  The Dow Magnesium Process at Freeport,
        Texas.  Trans. Amer. Inst . Chem. Eng.  41:35-31,
        January
        Faith, W. L., D. B. Keyes, and R. L. Clark.  Industrial
        Chemicals, 3rd Edition.  New York, John Wiley and Sons,
        Inc. , 1965.  852 p.

        Kuhn, A. T.  The Chlor-Alkali Industry.  In:  Industrial
        Electrochemical Processes, Kuhn, A. T. (ed.).  New York,
        Reinhold Publishing Corporation, 1956.  529 p.

        Sittig, M.  Sodium (Its Manufacture, Properties, and
        Uses).  Mew York, Reinhold Publishing Corporation,
        1956.  529 p.
                            231

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO.  59


                HYDROCHLORIC ACID FORMATION


1.  Function

    This process (See Figure 20) forms hydrochloric acid (HC1)
    from the chlorine (C12) gas recycled from Process  58 by
    reacting the latter with steam.

    Chlorine gas, formed by electrolysis in Process 58, is
    collected by suction fans and conveyed to a refractory
    checker-work, regenerative-type furnace.  The C12  ir;
    converted to HC1 gas, which is absorbed in water to form
    hydrochloric acid.  The latter supplies the major  fraction
    of the HC1 consumed in Process 56.

    The absorption of HC1 gas constitutes a step in the process

2.  Input Materials

    C12 - 2 to 2.5 metric tons per metric ton of magnesium  (Mg)

3.  Operating Parameters

    Temperature  is 1200°C, and pressure is atmospheric.

4.  Utilities

    Methane - 300 cubic meters per metric ton of Mg.

    Process water for absorption tower - 5 to 7 cubic  meter:;
    per metric ton of Mg.

    Steam - 0.9  to 1 metric  ton per metric ton of Mg.

5.  Waste, Streams

    Combustion products  leaving the absorption tower  - 1200
    cubic meters per metric  ton of Mg.

6.  EPA  Source  Classification  Code

         3-01-011-02  Byproduct w/Scrubber

7•  References

    Schambra, W. P.  The Dow Magnesium  Process at Freeport,
    Texas.  Trans. Amer.  Inst.  Chem.  Eng.   4l_: 35-51,  January

                            232

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BRINE AND EVAPORITE CHEMICALS              PROCESS NO.60


                          FUSION


1.  Function

    This process (See Figure 22) reduces the iodatec contained
    in a mixture of sodium iodide and sodium iodate crystals
    from Process 10 to iodides, by complete fusion in a smelt-
    ing pot at 600°C.  Addition of charcoal assures complete
    conversion of the iodates.  This process is typically an
    overnight batch operation.  The sodium iodide (Nal) is
    forwarded to Process 10.

2.  Input Materials

    Sodium iodide - sodium Iodate crystal mixture - 1.06
    to 1.08 metric tons per metric ton of Nal(estimated).

3.  Operating^ Parameters

    Temperature of fusion charge - 600°C.

    Pressure - atmospheric.

4.  Utilities

    Heat (fuel gas or fuel oil) - 500,000 kcal per metric ton
    of Nal.

5.  Waste Streams

    None

6.  EPA Source Classification Code

        None established

7.  References

    Jacobs, J. L.  Potassium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical Technology, 2nd Edition,  Standen,
    A.  (ed.).  New York, Interscience Publishers, 1968.   16:392

    Two Men and a Tub.  Chem. Wk.  7_3.:77-33, December  5,  1953.
                             233

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BRINE AND EVAPORITE CHEMICALS              PROCESS  NO.61
                FILTRATION/CRYSTALLIZATION


1.  Function

    This process (See Figure 22) forms sodium bromide (NaBr)
    from ferrosoferric bromide hexadecahydrate (Fe3Br8»16H20)
    crystals from Process 10 by the addition of aqueous sodium
    carbonate.

2.  Input Materials

    Fe3Bre*l6H20 crystals - 1.33 metric tons per metric ton
    of NaBr crystals(stoichiometric).

    Soda ash  (added as 20 to 3Q% solution) - 0.52 metric tons
    (100$ basis) p~er metric ton of NaBr crystals (stoichio-
    metric) .

3.  Operating Parameters

    Reaction  is conducted at ambient  temperatures and atmos-
    pheric  pressure as a small-scale  batch operation.

    Crystallization and filtration are both conducted at
    atmospheric pressure and at temperatures between 55°
    and 100°C.

4.  Utilities

    Heat -  2  to 2.5 metric tons of steam per metric ton of  IlaBr.

5.  Waste Streams

    Ferric  oxide sludge to landfill - 0.28 metric ton per
    metric  ton of NaBr (stoichiometric).

6-  EPA Source  Classification  Code

        None  established

7.  References

    Clough, R.  W.   Miscellaneous Heavy Chemicals.   In:  Riegel's
    Handbook  of Industrial Chemistry, 7th  Edition,  Kent, J. A.
     (ed.).  New York, Reinhold Publishing  Corporation,  1974.
    p.  137.
                             234

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BRINE AND EVAPORITE CHEMICALS             PROCESS  NO.  62


                   CALCINATION/GRINDING


1.  Function

    This process (See Figure 24) has two applications.  The
    basic function of the process in the two operations is
    the same, but operating conditions and procedure differ
    sufficiently to describe the two applications  separately.

   *a.  In the Foote Mineral Company operation, the process
        converts spodumene ore concentrates received from
        Process 15, containing lithium values in chemically
        unreactive form, to finely ground material, contain-
        ing soluble lithium hydroxide (LiOH).  The ground
        product is then forwarded to Process 47.

        The following sequential steps are included:

            •Mixing ground limestone, ore concentrates, and
             water.
            •Calcination of the resulting slurry.
            •Cooling
            •Grinding

        Essential equipment consists of:

            •Agitated mixing tanks  (surmised)
            •Rotary, coal-fired kiln
            •Rotary cooler
            •Hammermill (surmised grinding equipment type)

    b.  In the Lithium Corporation of America operation, the
        process converts the cc-spodumene content of spodumene
        ore concentrates, received from Process 15, to the
        more reactive 3-spodumene.  The calcined concentrates
        are then ground and forwarded to Process 63 .

        The following sequential process steps are included:

            •Calcination
            •Cooling
            •Grinding
 * Separate industry operations employing the process are
   identified with a specific lower case letter which is
   retained as an identifier in each element of this
   process description.

                             235

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        Major  equipment  comprises:

            •Rotary kiln
            •Rotary cooler (surmised  type)
            •Ball mills

2.   Input Materials

    a.   Per metric ton of LiOH produced:

        Spodumene ore concentrates  (containing 5 to 6%  Li20)  -
        11 to  13 metric  tons.

        Finely ground limestone - 38  to 45  metric tons.

        Water  - 50 to 60 cubic meters (gross estimate).

    b.   Per metric ton of Li2C03 produced:

        Spodumene ore concentrates  (containing 5 to 6%  Li20)  -
        6 to b metric tons.

3.   Operating Parameters

    a.   Pressures for all steps of the process - atmospheric.

        Kiln discharge temperature - 1030°  to 1050°C.

        Clinkers discharged by kiln - about 2 to 3 centimeters
        diameter.

        Rotary kiln - 3.1 meters diameter x 105 meters  long.
         (for estimated annual capacity, about 5,000 metric
        tons LiOH).

        Ground product - 50 to 100 mesh (estimated).

    b.   Pressures  for all steps of the process - atmospheric.

        Maximum temperature of kiln  load - 1075° to  1100°C.

        Kiln size  - 75 meters long (for estimated annual
        capacity  <5,000 metric tons  Li2C03).

        Ball-milled product - approximately 100 mesh.

4.  Utilities

    a.   Per metric  ton  of LiOH produced:

        Heat  (in  form of  coal) - 40  x  10s  to  80  x  10s kcal
         (gross  estimate).
                              236

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        Electrical energy - 150 to 300 kWh (gross  estimate).

    b.   Per metric ton of Li2C03 produced:

        Heat (in form of fuel gas) - 5 x 106  to 8  x 106  kcal
        (gross estimate).

        Electrical energy - 150 to 300 kWh (gross  estimate).

5.  Waste Streams

    a.   Quantities are per metric ton of LiOH produced:

        Surmised fugitive emissions to atmosphere  of particulate
        material (ore and limestone) escaping the  kiln-exhaust'
        quencher - Quantitative information on amount and
        particle-size distribution unavailable.  Estimated
        to be between 0.1 and 1 metric ton, depending on type
        of dust collectors on kiln exhaust.

        Surmised fugitive emissions to atmosphere  of particulate
        material (calcined clinker) from clinker cooler and from
        grinding equipment - Quantitative information on
        quantity and particle-size distribution unavailable.
        Estimated to be between 5 and 50 kilograms, depending
        on type of dust collection system used.

        Kiln discharge into atmosphere - Between 20 x 103 and
        35 x 10"3 standard cubic meters of C02.

    b.   Quantities are per metric ton of Li2C03 produced:

        Surmis_ed fugitive emission to atmosphere of particulate
        material' (ore dus't) escaping the kiln - Quantitative
        information on amount and particle-size distribution
        is unavailable.  Estimated to be between 10 and 200
        kilograms total solids, depending on type of dust
        collectors used on kiln and grinding equipment.

        Surmised fugitive emissions to atmosphere of particulate
        material Iclinker_ dust) from clinker cooler and grinding
        equipment - Quantitative information is unavailable.
        Estimated to be between 0.1 and 1 kilogram, depending
        on type of dust collection system used.

        Kiln discharge  into atmosphere - Between 4 x 10s and
        7 x""l"03 standard cubic meters of C02  (gross estimate).
                             237

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6.   EPA Source Classification Code

    a.  None established

    b.  None established

7.   References

    Bach, R. 0., C. W. Kamienski, and R. B. Ellestad.  Lithium
    and Lithium Compounds.  In:  Kirk-Othmer Encyclopedia of
    Chemical Technology, 2nd Edition, Standen, A. (ed.).
    New York, Interscience Publishers, 1967.  12:530-533.

    Ellestad, R. B., and C. W. Kamienski.  Lithium.   In:
    Chemical and Process Technology Encyclopedia, Considine,
    D. M. (ed.).  New York, McGraw-Hill, Ind., 197^. p. 700.
                              238

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BRINE AND EVAPORITE CHEMICALS            PROCESS HO.  63


                         DIGESTION


1.  Function

    The process (See Figure 24) converts the lithium (Li)
    values of calcined spodumene ore received from Process
    62, to water-soluble lithium sulfate (Li2S04) by reaction
    with concentrated sulfuric acid.  The digested ore is
    forwarded to Process 64.

    Essential equipment comprises one or more heated reaction
    chambers.  It Is surmised that these are operated batch-
    wise and may be rotating cylinders.  The method of heating
    is unknown but may be by external firing with o31 or coal.

2.  Input Materials

    Per metric ton of Li2C03 produced:

    Calcined spodumene ore, containing approximately 5 to
    6% Li20 equivalent~ 6 to 8 metric tons.

    93% H2S04  (66% Be acid) - 0.8 to 0.85 cubic meter of
    acid  (1.4 to 1.6 metric tons H2SOU).

3.  Operating Parameters

    The process is conducted at atmospheric pressure (surmised)
    and at temperatures ranging between 200° and 250°C.

    Time required for digestion Is not published, but is
    estimated here to be less than one hour.

4.  Utilities
    Per metric ton of Li2C03 produced:

    Heat  (_supplied by combustion of either coal or fuel oil -
    300 x~10^ to 600 x 103 kcal (gross estimate).

    Electrical energy consumption - 30 to 60 kWh (estimated).

5.  Waste Streams

    Surmised fugitive emissions of S03 mist may occur during
    charging or discharging periods of digestion vessel, if
                             239

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    operation is batchwise.   Factual information is  unavail-
    able.   Estimated quantity is less than 2  kg S03 per metric
    ton of Li2C03  produced.

6.   EPA Source Classification Code

        None established

7 •   References

    Bach,  R. 0., C.  W.  Kamienski, and R.  B. Ellestad.  Lithium
    and Lithium Compounds.   In:   Kirk-Othmer  Encyclopedia of
    Chemical Technology, 2nd Edition, Standen, A. (ed.).
    New York, Interscience Publishers, 1967.   12:530-533 .

    Faith, W. L.,  D. B. Keyes, and R. L.  Clark.  Industrial
    Chemicals, 3rd Edition.  New York, John Wiley and Sons,
    Ind.,  1965.  p.  492-494.
                             240

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BRINE AND EVAPCRITE CHEMICALS                PROCESS NO. 64


              LEACHING/FILTRATION/EVAPORATION


1.   Function

    The process recovers the soluble lithium (Li) values from
    acid-digested spodumene ore received from Process 63,
    producing impure 20% lithium sulfate (Li2SCU) liquor,
    which is forwarded to Process 10 (See Figure 24).

    The following major sequential steps are included:

        •Leaching digested ore (gangue plus solubles) with
         water and with recycled mother liquor.

        •Neutralization of the leachate with ground limestone.

        •Clarifying (implied) and filtration of the leachate.

        •Evaporation of the leachate to a concentration of
         20% LiaSOu.
        •Clarifying (surmised) and filtration Of the impure
         20% Li2S04 solution for removal of previously
         precipitated CaC03 and Mg(OH)2.

    Major essential equipment includes:

        •Open-top leach tanks (presumed)

        •Agitated neutralization tanks

        •Settling tanks

        •Rotary vacuum filters (presumed type).

        •Five-effect vacuum evaporators.

2.   Input Materials

    Quantities expressed are per metric ton of Li2C03 produced

    Major input is acid-digested spodumene ore  (containing 5
    to 6% LijaO.) - 6' to 8 metric tons.

    Recycledjnother liquor from Process 10 containing soluble
    Li values^ at'estimated concentrations between 0.2 and oTT$
    Ljl - 9 to 12 cubic meters of solution, containing 0.025
    to 0.035 metric tons Li.

    Total water added - 7 to 8 cubic meters  (gross estimate).
                             241

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   Ground limestone - 0.2 to 0.5 metric tons consumed (gross
   estimate) .

   Hydrated  lime -  0.02 to 0.05 metric tons consumed (gross
   estimate) .
   Soda ash, added as 3®% solution for Ca removal - 0.5 to
   2.0 metric tons Na2C03.

   Operating Parameters

   Leaching^ clarifying, and filtration steps - conducted
   at atmospheric pressure and in temperature range estim-
   ated to be 40° to 70°C.

   Range  of physical conditions during evaporation, con-
   ducted in a  five-effect evaporator  (gross estimate) -
   3 kilograms  per square centimeter absolute pressure and
   135°C  to 630 millimeters Hg vacuum and 50°(J.

   Second clarifying and filtration - conducted at approx-
   imately 50°C and at atmospheric pressure  (inferred).

   Utilities
    Quantities  expressed  are  per metric  ton  of  Li2C03  produced.

    Steam (presumed  at  3.5  kilograms per square centimeter
    absolute  pressure)  -  2  to 4 metric tons(estimated).

    Cooling watejr (at  least a part  of this may  be  identical
    with the  make-up water  mentioned under 2, above)  -
    Up to50  cubic meters(once-through  basis).


    Electrical  energy  - Between  100 and  200  kVJh (gross estimate
    of total  amount  consumed).

5.   Waste Streams

    Quantities  expressed are  per  metric  ton  of  Li2C03 produced.

    Solid wastes - 5 to 7 metric  tons  of fine  inert gangue,
    0.02 to 0.05 metric tons   (gross estimate)  of Mg(OH)2, and
    up to 1.5 metric tons (gross  estimate)  of  finely divided
    CaC03.  All the  solids mentioned  are discharged from the
    process as slurries  (presumed).  It  is  surmised that the
    solids are settled out and abandoned in  tailings ponds  or
    piles.
                             242

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    ¥ater - At  least  part  used  to  transport  the  waste
    solids to tailings  ponds  is not  recycled.   Presumably
    it evaporates  from  the tailings  ponds  or is  wasted  to
    natural streams.  A gross estimate of  the  quantity  is
    3 to 5 cubic meters.

6.   EPA Source Classification Code

        None established

7.   References

    Bach, R. D., C.  W.  Kamienski,  and R.  B.  Ellestad.
    Lithium and Lithium Compounds.  In:  Kirk-Othmer
    Encyclopedia of Chemical  Technology,  2nd Edition,
    Standen, A. (ed.).   New York,  Interscience Publishers,
    1967.  11:530-533.

    Faith, W. L.,  D.  B. Keyes,  and R. L.  Clark.   Industrial
    Chemicals, 3rd Edition.  New York, John  Wiley and  Sons,
    Inc., 1965.  852 p.
                              243

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BRINE AND EVAPORITE CHEMICALS             PROCESS NO. 65


                        DISSOLUTION


1.  Function

    The process (See Figure 23) forms saturated sodium chloride
    (NaCl) brine from:

        •Make-up granular NaCl

        •NaCl crystals plus mother liquor, both recycled from
         Process 10.
        •Make-up softened water.

    The saturated brine thus produced constitutes the feed to
    the electrolytic cell of Process 66.

    Included in the process are the steps of clarifying and
    filtration of the NaCl brine.

    Major equipment consists of agitated dissolving tanks, a
    retention or settling tank, and filtration equipment,
    presumed to be a sand filter.

2.  Input Materials

    Per metric ton of sodium chlorate (NaC103) produced:

    Make-up NaCl - Between 0.55 and 0.60 metric tons.

    Recycled NaCl - Estimated  between 0.1 and  0.3 metric tons.
    The quantity varies with operating conditions of the sub-
    sequent electrolysis.  Estimated quantity  of NaC103 in
    recycled mother liquor is  0.3 metric tons.

    Make-up water - Estimated  between 1.5 and  1.7 cubic meters.

    Sodium carbonate  (NaaCOa)  and Ca(OH)2 for  Mg and Ca removal -
    Less  than  5 kilograms each.

3•  Operating  Parameters

    All  equipment  is  operated  at atmospheric pressure.  Possible
    exception  is the  filtration  equipment.  Pressure filters,
    if used, may require pressures up to  3 to  4 kilograms per
    square centimeter.
                             244

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    Temperatures  are estimated  in the  range  of  35°  to  4o°C.

4.   Utilities

    Electrical energy consumption is  estimated  to be between
    10 and 20 kWh per metric ton of NaC103 produced.

5.   Waste Streams
    Depending on the amount of impurities present  in both the
    make-up salt and make-up water,  up to 20 kilograms  of
    solids per metric ton of NaC103  is "discharged  in the
    back-washings from the sand filter.   The solids  are
    chiefly magnesium hydroxide and  calcium carbonate.   The
    filter back-washings are presumably ponded.  The settled
    solids constitute a landfill.

6.  EPA Source Classification Code

        None established

7 •  References

    Clapper, T. W., and W, A. Gale.   Chloric Acid  and Chlorates
    In:  Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
    Edition, Standen, A. (ed.).  New York, Interscience
    Publishers, 1964.  5/50-59.

    Shreve, R. N.  Chemical Process  Industries,  3rd  Edition.
    New York, McGraw-Hill, 1966.  p. 255-256.
                             245

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BRINE AND EVAPORITE CHEMICALS            PROCESS NO. 66
             ELECTROLYTIC  CHLORATE PRODUCTION
1.  Punct ion

    Sodium chlorate (NaC103) and hydrogen gas (H2) are
    produced in a diaphragmless electrolytic cell by the
    electrolysis of saturated sodium chloride (NaCl) brine
    received from Process 65 (See Figure 23).  The cell
    effluent is forwarded to Process 10, Figure 23.  The
    hydrogen gas is assumed to be flared.

    Essential equipment consists of a series of rectangular
    steel cells, operated without diaphragms between the
    cathode and anode surfaces.  Graphite anodes are usually
    employed, spaced close to the steel cathodic surf'acon.
    Cells are estimated to be approximately 0.5 meter by
    2.5 meter by 1.2 meter high, and are water-cooled in-
    ternally by pipe coils.

2.  Input Materials

    Per metric ton of sodium chlorate (NaC103) produced:

    Saturated NaCl brine from Process 65 - Estimated 2.3
    cubic meters (2.7 metric tons), containing about 0.9 metric
    tons NaCl and some recycled NaC103.

    Sodium chromate (for corrosion protection and hypochlorite
    suppression) -Estimated 1 to 2 kilogram.

    Hydrochloric acid  (for pH control)  - Estimated  6 to 12
    kilogram of HC1.

    Graphite consumed by anode degradation - 10 to  20 kilograms

3.  Operating Parameters

    Cells operate at atmospheric pressure and inside a  tem-
    perature range of  ^0°  to  45°C.

    Optimum pH  of cell brine  is  6.8 to  7.0.

    Anodic  current density  is  In the range of 1,000 to  1,300
    amperes per square meter.
                             246

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Concentration of NaC103 in cell effluent varies within
a broad range, depending on exact method of operation,
estimated from 200 to 600 grams per liter.

Utilities

Per metric ton of sodium chlorate (NaC103)  produced:

Electrical energy (D.C. current for electrolysis) -
5,000 to 5,200 kWh.

Cooling water - Estimated 150 to 170 cubic  meters.

Gaseous_ nit;rogen; bled into the cell to provide a slight
positive internal pressure -  Estimated 5 to 10 standard
cubic meters.

Waste Streams
Fugitive emissions of gaseous chlorine from cell and
cell-fittings (surmised) - Estimated lessthan 0.1 ppm
C12 in air in the vicinity of the cell.

Emission to the atmosphere of water vapor from the flared
hydrogen gas - Estimated approximately 0.5 metric tons
of H20 per metric ton NaC103, representing an estimated
700 standard cubic meters of hydrogen.

EPA Source Classification Code

    None established

References

Clapper, T. W., and W. A. Gale.  Chloric Acid and Chlorate:
In:  Kirk-Othmer Encyclopedia of Chemical Technology,
2nd Edition, Standen, A. (ed.).  New York, Interference
Publishers, 1964.  5_:50-59-

Creighton, H. J., and W. A. Kohler.  Principles and
Applications of Electrochemistry, 2nd  Edition.  New York,
John Wiley and Sons, Ind. , 1944.  2_: 283-287.

Shreve, R. N.  Chemical  Process Industries, 3rd Edition.
New York, McGraw-Hill, 1966. p. 255-256.
                          247

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BRINE AND EVAPORITE CHEMICALS             PROCESS  NO.  67


                 SODIUM CHLORATE DRYING


1.  Function

    The process (See Figure 23) reduces the water  content of
    the moist sodium chlorate (NaC103) crystals received from
    Process 10, from an estimated 5% to approximately 0.2%.
    The dried NaC103 is the end product of the operations.

    Rotary dryers and batch tray dryers are alternatively
    employed.  Both types are steam-coil heated externally.

2.  Input Materials

    Moist NaC103 crystals containing an estimated  5% free
    moisture - 1.05 metric tons per metric ton of  NaC103
    produced.

3.  Operating Parameters

    Drying NaClOs is a critical and potentially hazardous
    process.  The material must not be subjected to even
    moderately high temperatures.  Information on precise
    drying temperatures is not available.  It is surmised
    here that air-swept dryers (rotary or tray type) are
    used, preventing the NaC103 from contacting any surface
    hotter than an estimated 40° to 45°C.

    The NaC103 must be prevented from  contacting any organic
    materials, or any reducing agent.

    Use of cyclone collectors and glass-cloth bag-filters
    on dryer exhausts is imperative.

    Accumulations of NaC103  dust from  seal leakages must  be
    prevented.

4.  Utilities

    Per metric ton of dry  NaC103 produced:

    Low-pressure  (1 to 2 kilogram per  square  centimeter)
     steam  -  Estimated  0.2  metric tons.

    Electrical  energy  - Estimated 15  to  25 kWh.
                             248

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5.   Waste Streams

    Fugitive emissions of NaC103  dust  particles  to  the
    atmosphere are presumed to be of very  small  magnitude.
    Information about precise values are unavailable.   Estim-
    ated amount is less than 0.01 kilogram per metric  ton of
    NaC103 produced,  assuming control  devices are operative.

6.   EPA Source Classification Code

        None established

7.   References

    Clapper, T. W., and W. A. Gale.   Chloric Acid and  Chlorates
    In:  Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
    Edition, Standen, A. (ed.).  New York, Interscience Pub-
    lishers, 1964.  5.:50-59.

    Shreve, R. N.   Chemical Process  Industries,  3rd Edition.
    New York, McGraw-Hill, 1966.   p. 255-256.
                             249

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    APPENDIX A





RAW MATERIALS LIST
          251

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                         APPENDIX A

                      RAW MATERIAL LIST

           Composition and Occurrence Information


1.   Seawater

    •  Concentration in ppm of the ten most prevalent dissolved
       elements in "normal" seawater:

          Cl - 18,360
          Na - 10,768
Mg -
S -
Ca -
K -
Br -
C —
Sr -
B -
1,298
900
408
388
66
28
14
5
    •  Relative proportion of elements listed is invariant.

    •  Absolute concentrations at shore locations vary typically
       between 1Q% and 110$ of values listed.

2 •  Michigan subterranean  brines commercially exploited

    Typical composition in ppm of brines obtained from three
    members of the Sylvania formation:

     Dissolved
    Constituent     Marshall      Dundee       Monroe
Na
K
Ca
Mg
Cl
Br
I
50,100
998
35,900
8,890
168,212
1,500
nil
55,044
nil
32,432
7,650
164,877
1,500
nil
20,444
8,794
68,468
9,307
188,283
2,600
38
3.  Nevada subterranean brine

    •  Typical concentration in percent, of dissolved ions in
       Silver Peak Playa brine, Clayton Valley, Esmeralda
       County, Nevada.

           Na -   6.2
           K  -   0.8
           Mg -   0.04
           Li -   0.04
           Ca -   0.05
           S(H -  0.71
           Cl - 10.1
                              252

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Appendix A (Continued)

    •  Producing formation lies 100 to 250 m below surface.

4.  Arkansas brine

    •  Typical concentration in percent, of dissolved ions in
       brine from the Smackover formation near Magnolia,
       Arkansas:

           Na - 6.35
           Cl - 9.65
           Br - 0.45 to 0.52

    •  Producing formation lies approximtely 1,800 m below
       surface.

5.  Western Texas brines

    •  Typical composition in percent, of brine from reservoir
       underlying Howard, Glasscock and Scurry counties:

           NaCl  - 12.0
           MgC]2 - 11.0
           CaCl2 -  0.78
           KC1   -  0.23
           Br    -  0.13

    •  Typical concentration of Na230<» in brine from reservoir
       underlying V/ard and Terry counties:

           9% - Na2SO,t

6.  Great Salt Lake brine

    Typical concentrations in ppm:

               Northern Arm.
               (G.S.L. Min. &       Southern Arm.
              	Chem. Corp.)       (NL industries)

    Na             82,800                71,900
    Mg             12,420                 7,960
    K               7,120                 4,870
     Ca                100                   136
     Li                60                    35
     Cl            146,280               132,000
    SCU            25,200                15,600
    HC03              350                   397

7.   Searles Lake  brine

    Typical concentrations in ppm:
                            253

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Na
K
Li
Cl
scu
C03
HC03
BiiO?
B2CK
Br
As
Bristol Lake
111,400
25,700
80
120,900
45,600
26,900
1,100
12,200
nil
850
160
brine
   Appendix A  (Continued)

                  Upper  stratum       Lower  stratum

                                       117,100
                                        18,400
                                            40
                                       111,600
                                        40,600
                                        36,800
                                         nil
                                        12,000
                                         4,900
                                           710
                                           160

 8.

     Typical  composition in percent:

         CaC]2 - 14
         NaCl   - 14

 9.   Salduro  Marsh brine

     Average  composition in percent:

         NaCl   - 18 to 24
         KC1    - 0.8 to 1.2
         MgCl2 - 0.9 to 1.2
         MgSCU - 0.2 to 0.3
         CaSCU - 0.3 to 0.4
         LiCl  - 0.03 to 0.04

10.   Sodium chloride

     Composition range of bedded deposits and salt  domes, in
     weight percent:

         NaCl, deposit average:     80 to 99
         NaCl, individual layers:  up to 100
         Anhydrite, overall:       0 to 2
         Br,  intracrystalline:      0 to 0.01
         Mg,  overall:              0 to 0.5

11.  Sylvinite

     •  Composition range of bedded deposits of New Mexico and
        Utah, weight percent:

         KC1 - 15 to 40
         NaCl - 60 to 85

     •  Interspersed with clay, sand, and anhydrite.
                               254

-------
Appendix A (Continued)

12.   Langbeinite (2 MgSCU »K2SOi, )

     Inferred composition range of bedded deposits of the
     Carlsbad, New Mexico area:

         50 to 90% langbeinite

13.   Trona (NaHC03 • Na2CQ3-2H20)

     Reported average composition of bedded trona of the Green
     River formation in Wyoming:
         95 to 96%  NaHC03'2Na2C03'2H20

14.  Kernite
        Inferred composition of kernite deposits of Kern County,
        California :
             B203

     •  Deposit is associated with borax.

15.  Borax (Na2Blt07«10H20)

     •  Inferred composition of borax deposits of Kern County,
        California:

          30% B203

     •  Deposit is associated with kernite

16.  Colemanlte (2CaO'3B203 • 5H20)

     •  Major deposit is near Death Valley Junction, Inyo
        County, California.

     •  Assay of ore body is not available.

17.  Spodumene (LiAlSi206)

     Typical lithium content of the spodumene ore deposits near
     Kings Mountain and Bessemer City, North Carolina:

         1 to 2%  Li20

18.  Sulfur  (S); purchased raw material

     Usually contains between 99-5 and 99.95% sulfur.
                               255

-------
Appendix A ( Concluded)

19-   Su If uric acid (H2SOi,); purchased raw material

     Commercial acid usually contains either 95 to 98}! H2SOtt
     or about 80% HaSC^.

20.   Lime (CaO or Ca(OH)2); purchased raw material

     Typical composition range:

        CaO      95 to 97$
        CaC03  - 1 to 2%
        Si02   - 0.5 to 3%
        R203   - 0.5 to 3%

21.   Dollme (CaOMgO); usually a purchased raw material

     Typical composition range:

        MgO  - 37 to 41%
        CaO  - 55 to 58%
        Si02 - 0.5 to 3%
        R203 - 0.5 to 3%

22.   Limestone (CaCOs); usually a purchased raw material

     Typical composition range:

        CaC03 - 95 to 99%
        Si02  - 0.5 to 1.5%
        R203  - 0.5 to 1.558
                              256

-------
 APPENDIX B





PRODUCT LIST
     257

-------
                        APPENDIX B

                       PRODUCT LIST

 Industry by-products are indicated by an *.


                   Products

 Boric acid - H3B03
 Boric acid anhydride - B203
 Boron oxide - fused B203
 Bromine, elemental - Br2
 Calcium borate (calcined colemanite) - 2 CaO»3B203
 Calcium chloride, 35% liquor - CaCl2
 Calcium chloride, 78% flake - CaCl2
 Calcium chloride, anh. flake - CaCl2
 Chlorine, gas - C12
 Chlorine, liquefied - C12
 Hydrochloric acid, 30% solution - HC1
*Hydrogen, gas - H2
 Iodine, elemental - I2
 Lithium acetate - LiC2Hs02
 Lithium aluminate - LiA102
 Lithium amide - LiNH2
 Lithium bromate - LiBr03
 Lithium bromide - LiBr
 Lithium carbonate - Li2C03
 Lithium chloride - LiCl
 Lithium cobaltate - Li2Co02
 Lithium fluoride - LIP
 Lithium fluoroborate - LiBFi*
 Lithium hydride - LiH
 Lithium hydroxide - LiOH
 Lithium hypochlorite - LiCIO
 Lithium iodide - Lil
 Lithium iodide trihydrate - LiI«3H20
 Lithium manganite - Li2Mn03
 Lithium metaborate - LiB02
 Lithium metaphosphate - LiP03
 Lithium metasilicate - Li2Si03
 Lithium molybdate - Li2Mo04
 Lithium nitrate - LiN03
 Lithium nitride - Li3N
 Lithium orthophosphate -  LisPOi*
 Lithium orthosilicate - ]
 Lithium oxide - Li20
 Lithium peroxide - Li202
 Lithium sulfate - Li2SOit
 Lithium sulfide - Li2S
 Lithium tetraborate -
 Lithium titanate - Li2Ti03
 Lithium zirconate - Li2Zr03
 Magnesium, metal - Mg
                               258

-------
 Appendix B (Concluded)

 Magnesium carbonate trihydrate - MgC03«3H20
 Magnesium carbonate, basic - 5 MgO»4C02«6H20
 Magnesium chloride, 32% liquor - MgCl2
 Magnesium chloride, 46% liquor - MgCl2
 Magnesium chloride, 50% flake - MgCl2
 Magnesium hydroxide, slurry - 35-50% Mg(OH)2
 Magnesium hydroxide, dried - Mg(OH)2
 Magnesium oxide,  caustic-calcined -  MgO
 Magnesium oxide,  dead-burned - MgO
 Magnesium potassium sulfate (commercial  langbeinite ) - 2MgSOt, «K2SOit
 Magnesium sulfate (Epsom Salt) - MgSCU
*Phosphoric acid,  crude, 50% - H3PCU
 Potassium chloride - KC1
 Potassium hydroxide - KOH
 Potassium sulfate - KaSO^
 Sodium, metal - Na
 Sodium bicarbonate - NaHC03
 Sodium bromide -  NaBr
 Sodium carbonate  (soda ash) - Na2C03
 Sodium chlorate - NaC103
 Sodium chloride,  dried crude - NaCl
 Sodium chloride,  dry refined - NaCl
 Sodium chloride,  rock rock salt - NaCl
 Sodium chloride,  saturated brine - NaCl
 Sodium chloride,  washed, crude - NaCl
 Sodium hydroxide, 50% liquor - NaOH
 Sodium hydroxide, 75% liquor - NaOH
 Sodium hydroxide, solid - NaOH
 Sodium iodide - Nal
 Sodium sulfate, anh. (salt cake) - Na2SOit
 Sodium tetraborate, anhydrous (anhydrous borax) - NaaBitO?
 Sodium tetraborate decahydrate (borax)  - Na2BitOy »10H20
 Sodium tetraborate pentahydrate - Na2Bi»07» 5H20
                                259

-------
     APPENDIX C





COMPANY/PRODUCT LIST
           261

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                                  TECHNICAL REPORT DATA
                           (Please read lii^inictions on the rcvcnv before completing)
  REPORT NO.
  EPA-600/2-77-023o
                                                          3. RECIPIENT'S ACCESSIOr»NO.
4. TITLE AND SUBTITLE
                                                          5. REPORT DATE
  Industrial Process Profiles  for Environmental Use:
  Chapter 15-  Brine and  Evaporite Chemicals Industry
                                  6. PERFORMING ORGANIZATION CODE
                                                            February 1977
7. AUTHOR(S)
  P.E. Muehlberg, B.P.Shepherd,  J.T.  Redding, and
  H.C.Behrens  (Dow Chemical)  Terry Parsons, Editor
                                                          8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Radian Corporation
 8500 Shoal Creek  Boulevard
 P.O. Box  99H8
 Austin, Texas   78766
                                  10. PROGRAM ELEMENT NO.

                                   1AB015
                                  11. CONTRACT/GRANT NO

                                   68-02-1319, Task
12. SPONSORING AGL-'NCY NAME AND ADDRESS
 Industrial  Environmental Research Laboratory
 Office of Research and Development
 U.S. ENVIRONMENTAL PROTECTION*AGENCY
 Cincinnati, Ohio   U5268
                                   13. TYPE OF REPORT AND PERIOD COVERED
                                   Initial:  8/75-11/76
                                   14. SPONSORING AGENCY CODE
                                     EPA/600/12
16. SUPPLEMENTARY NOTES
16. ABSTRACT
  The catalog  of  Industrial Process Profiles for Environmental Use vas developed  as  an
  aid in  defining the  environmental impacts of industrial  activity in the United  States
  Entries  for  each industry are in consistent format  and form separate chapters of the
  study.   The Brine and Evaporite Chemicals Industry encompasses all first-level in-
  organic  compounds derived from subterranean briner,,  from existing or historic salt
  lakes,  and from sea  water.   Certain second-level  inorganic compounds derived from
  these sources are included when produced in the same facility as the parent compound.
  The industry is discussed in six segments:  (l) Borax and Boric Acid, (2) Chlorine-
  Caustic,  (3)  Lithium Chemicals, (U) Magnesium Metal, (5) Potash and (6) Sodium  Metal,
  One chemical tree, twenty-two process flow sheets,  and sixty-seven process descrip-
  tions have been prepared to characterize the industry.   Within each process descrip-
  tion  available  data  have been presented on input  materials, operating parameters,
  utility requirements and waste streams.  Data relating to the subject matter, in-
  cluding company, product and raw material data, are included as appendices.
 17.
 a.
                               KCY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
  Pollution
  Brine
  Evaporites
  Inorganic Compounds
  Salt
  Sea Water
  Borax
  ..Boric  Acirl
Chlori ne-Cauntic
Lithium Chemicals
Magnesium Metal
Potash
Sodium Metal
Process Description
                      h.lDENTIFIEFiS/OPEN ENDED TERMS
Air Pollution Control
Water Pollution  Control
Solid Waste Control
Stationary Sources
Inorganic Chemicals
c. COSATI 1 icId/Group
  """ "07B
     13B
 13. DISTRIBUTION STATEMENT
     Release to Public
                                              19. SECURITY CLASS (This Report)
                                               Unclassified
                                                21. NOiOF PAGES
                                                      324
                      VO. JLCJRiTY CLASS film page)

                        I In P1 n ^ ci i "T i P»ri
                                                                        22. PRICE
 EPA Form 2220-1 (9-73)
                     314

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