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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uiapnragm
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FIGURE 15. CHLORINE AND CAUSTIC SODA VIA ELECTROLYSIS
29
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. 7,8
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Cooling
Cooling HzO
Heat
Evaporation/
crystallization
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H20-
Heat -
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at — i
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9
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1
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FIGURE 16. BORAX, BORIC ACID AND COLEMANITE FROM EVAPORITES
Calcined
•^•fcolemanltel
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Hydrochloric
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58
Filtration
16
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FIGURE 21. SODIUM METAL VIA DOWNS CELL
35
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FIGURE 23. SODIUM CHLORATE VIA ELECTROLYSIS
37
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Open pit mining
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FIGURE 24. LITHIUM VALUES FROM
SPODUMENE
38
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9
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
White, N. C., and C. A. Arend, Jr. Potash Production at
Carlsbad. Chem. Eng. Progr. 46: 523-531, October 1950.
47
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
Detectable amounts of MgCl2 particles and HC1 vapor-
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.
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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
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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
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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-
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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
-------
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
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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
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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
-------
[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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
•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
-------
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
-------
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
-------
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
-------
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
-------
Yaron, F. Chapter 1. In: Bromine and Its Compounds,
Jolles3 Z. E. (ed.). London, Ernest Benn, Ltd.,
1966. p. 3-^2.
153
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
(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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
APPENDIX A
RAW MATERIALS LIST
251
-------
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
-------
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
-------
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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