EPA-650/2-74-122
NOVEMBER 1974
Environmental Protection Technology Ser
les
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environ'
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields* These series are:
1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH
2 . ENVIRONMENTAL PROTECTION TECHNOLOGY
3. ECOLOGICAL RESEARCH
4. ENVIRONMENTAL MONITORING
5 . SOCIOECONOMIC ENVIRONMENTAL STUDIES
6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
9. MISCELLANEOUS
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution. This work provides the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
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EPA-650/2-74-122
TRACE POLLUTANT EMISSIONS
FROM THE PROCESSING
OF NON-METALLIC ORES
by
V. Katari, G. Isaacs, and T. W. Devitt
PEDCo-Environmental Specialists, Inc.
Suite 13
Atkinson Square
Cincinnati, Ohio 45246
Contract No. 68-02-1321, Task 4
ROAP No. 2lAUZ-02a
Program Element No. 1AB015
EPA Project Officer: D. K. Oestreich
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for:
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
November 1974
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EPA REVIEW NOTICE
This report has been reviewed b'y the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.
11
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TABLE OF CONTENTS
Page
List of Figures vii
List of Tables x
Acknowledgement xiv
1.0 INTRODUCTION 1-1
2.0 CEMENT INDUSTRY 2-1
2.1 Industry Background 2-1
2.2 Raw Materials 2-2
2.3 Products 2-4
2.4 Process Description 2-4
2.4.1 Mining 2-7
2.4.2 Size Reduction and Blending 2-7
2.4.3 Calcination 2-11
2.4.4 Finishing Operations 2-15
2.5 Major Pollutant Sources 2-19
3.0 CLAY PRODUCTS 3-1
3.1 Industry Background 3-1
3.2 Raw Materials 3-2
3.3 Products 3-4
3.4 Process Description 3-4
3.4.1 Mining 3-4
3.4.2 Beneficiation 3-9
3.4.3 Porcelain Manufacturing 3-12
3.4.4 Refractory Manufacturing 3-14
3.4.5 Brick Manufacturing 3-16
3.5 Major Pollutant Sources 3-18
ill
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TABLE OF CONTENTS
Page
4.0 GYPSUM INDUSTRY 4-1
4.1 Industry Background 4-1
4.2 Raw Materials 4-2
4.3 Products 4-4
4.4 Process Description 4-5
4.4.1 Mining 4-5
4.4.2 Upgrading 4-5
4.5 Major Pollutant Sources 4-9
5.0 LIME INDUSTRY 5-1
5.1 Industry Background 5-1
5.2 Raw Materials 5-2
5.3 Products 5-2
5.4 Process Description 5-2
5.4.1 Mining 5-5
5.4.2 Beneficiation 5-7
5.4.3 Calcination 5-8
5.4.4 Finishing Operations 5-11
5.5 Major Pollutant Sources 5-13
6.0 PHOSPHATE ROCK INDUSTRY 6-1
6.1 Industry Background 6-1
6.2 Raw Materials 6-3
6.3 Products 6-5
6.4 Process Description 6-8
6.4.1 Mining 6-8
6.4.2 Beneficiation 6-10
6.4.3 Thermal Reduction Method (Elemental 6-12
Phosphorus Production)
6.4.4 Phosphoric Acid Production 6-16
6.4.5 Superphosphoric Acid (SPA) 6-20
Production
IV
-------
TABLE OF CONTENTS
Paqe
6.4.6 Normal Superphosphate 6-21
6.4.7 Triple Superphosphate Production 6-23
6.4.8 Diammonium Phosphate Production 6-25
6.4.9 Nitrogen Fertilizers 6-25
6.5 Major Pollutant Sources 6-26
7.0 POTASH 7-1
7.1 Industry Background 7-1
7.2 Raw Materials 7-2
7.2.1 Description of the Typical Potash 7-3
Ores
7.3 Products 7-6
7.4 Process Description 7-7
7.4.1 Mining 7-7
7.4.2 Potassium Chloride Production 7-8
7.4.3 Potassium Sulphate Production 7-13
7.4.4 Potassium Nitrate Production 7-16
7,5 Major Pollutant Sources
8.0 BORON COMPOUNDS 8-1
8.1 Industry Background 8-1
8.2 Raw Materials 8-2
8.3 Products 8-3
8.4 Process Description 8-4
8.4.1 Mining 8-5
8.4.2 Beneficiation 8-5
8.4.3 Borax Production 8-6
8.4.4 Anhydrous Borax Production 8-7
8.4.5 Boric Acid Production 8-8
8.4.6 Boric Oxide Production 8-9
8.5 Major Pollutant Sources 8-9
9.0 MICA INDUSTRY 9-1
9.1 Industry Background 9-1
v
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TABLE OF CONTENTS
Page
9.2 Raw Materials 9-3
9.3 Products 9-3
9.4 Process Description 9-3
9.4.1 Mining 9-3
9.4.2 Beneficiation 9-6
9.4.3 Grinding 9-8
9.5 Major Pollutant Sources 9-10
10.0 FLUORSPAR 10-1
10.1 Industry Background 10-1
10.2 Raw Materials 10-2
10.3 Products 10-4
10.4 Process Description 10-7
10.4.1 Mining 10-7
10.4.2 Beneficiation 10-7
10.5 Major Pollutant Sources 10-13
11.0 RECOMMENDATIONS 11-1
APPENDIX A PRODUCTION AND CONSUMPTION STATISTICS A-l
APPENDIX B CEMENT PRODUCTION STATISTICS B-l
APPENDIX C CLAY PRODUCTION STATISTICS C-l
APPENDIX D GYPSUM PRODUCTION STATISTICS D-l
APPENDIX E LIME PRODUCTION STATISTICS E-l
APPENDIX F PHOSPHATE INDUSTRY STATISTICS F-l
APPENDIX G POTASH PRODUCTION STATISTICS G-l
APPENDIX H BORON PRODUCTION STATISTICS H-l
APPENDIX I MICA INDUSTRY STATISTICS 1-1
APPENDIX J FLUORSPAR INDUSTRY STATISTICS J-l
VI
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LIST OF FIGURES
Figure Page
2.1 Cement Industry 2-8
3.1 Clay Industry 3-7
4.1 Gypsum Industry 4-6
5.1 Lime Industry 5-6
6.1 Phosphate Rock Industry 6-9
7.1 Potash Industry 7-9
8.1 Boron Industry 8-5
9.1 Mica Industry 9-4
10.1 Fluorspar Industry 10-8
A-l Abrasive Materials Production and Consumption A-2
Statistics (1971).
A-2 Asbestos Production and Consumption Statis- A-3
tics (1971).
A-3 Boron Production and Consumption Statistics A-4
(1971).
A-4 Cement Production and Consumption Statis- A-5
tics (1971).
A-5 Clay Production and Consumption Statistics A-6
(1971).
A-6 Diatomite Production and Consumption Statis- A-7
tics (1971).
A-7 Feldspar Production and Consumption Statis- A-8
tics (1971).
A-8 Fluorspar Production and Consumption Statis- A-9
tics (1971).
vii
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LIST OF FIGURES
Figure Page
A-9 Natural Graphite Production and Consumption A-10
Statistics (1971).
A-10 Gypsum Production and Consumption Statistics A-ll
(1971).
A-ll Kyanite and Related Minerals Production and A-12
Consumption Statistics (1971) .
A-12 Lime Production and Consumption Statistics A-13
(1971).
A-13 Mica Production and Consumption Statistics A-14
(1971).
A-14 Peat Production and Consumption Statistics A-15
(1971).
A-15 Perlite Production and Consumption Statistics A-16
(1971).
A-16 Phosphate Rock Production and Consumption A-17
Statistics (1971).
A-17 Potash Production and Consumption Statistics A-18
(1971).
A-18 Pumice Production and Consumption Statistics A-19
(1971).
A-19 Salt Production and Consumption Statistics A-20
(1971).
A-20 Sand and Gravel Production and Consumption A-21
Statistics (1971).
A-21 Sodium Sulfate Production and Consumption A-22
Statistics (1971).
A-22 Sodium Carbonate Production and Consumption A-23
Statistics (1971).
A-23 Sulfur and Pyrites Production and Consumption A-24
Statistics (1971).
A-24 Stone Production and Consumption Statistics A-25
(1971).
Vlll
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LIST OF FIGURES
Figure Page
A-25 Talc, Soapstone, etc., (pyrophyllite)
Production and Consumption Statistics (1971). A-26
A-26 Vermiculite Production and Consumption A-27
Statistics (1971).
IX
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LIST OF TABLES
Table Page
1.1 Quantities of Ore Mined and Processed in the 1-2
United States
1.2 Number of Domestic Nonmetal Mines in 1971, by 1-3
Commodity and Magnitude of Crude Ore Production
2.1 Daily Clinker Production Capacities of Cement 2-1
Plants in the United States - 1971
2.2 Typical Sources of Raw Materials Used in Manu- 2-2
facture of Portland Cement
2.3 Percent Oxide Composition of Typical Cement 2-5
Raw Materials
2.4 Typical Composition of Various Cements 2-6
2.5 Size Distribution of Dust Emitted from Kiln 2-13
Operations in Cement Manufacturing Without
Controls
2.6 Typical Emission Data from Five Cement Kilns and 2-16
Coolers in the United States
2.7 Range of Trace Materials from Cement Plants 2-18
3.1 Analyses of Clay Minerals 3-5
3.2 Spectrographic Analysis of Bentonite from Clay 3-6
Spur, Wyoming
4.1 Crude Gypsum Mined in the United States, by 4-2
State
4.2 Calcined Gypsum Produced in the United States, 4-2
by State
4.3 Analysis of Gypsum 4-4
5.1 Lime Produced in the United States, by Size of 5-1
Plant
x.
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LIST OF TABLES
Table Paqe
5.2 Representative Chemical Analyses of Different 5-3
Types of U.S. Limestone
5.3 Spark Source Mass Spectrographic Analyses of 5-4
Limestones
5.4 Typical Analyses of Commercial Quicklimes 5-5
5.5 A Typical Overall Kiln Exhaust Gas Composition 5-9
5.6 Typical Exhaust Gas Production for Various 5-9
Kiln Sizes
5.7 Typical Chemical Analysis of Lime Kiln Emissions 5-10
(Producing Quicklime)
5.8 Typical Chemical Analysis of Lime Kiln Emissions 5-11
(Producing Dolomite Lime)
5.9 Range of Typical Chemical Analyses of Commercial 5-12
Hydrates
5.10 Reported Dust Emission Values from Lime Plant 5-14
Operations
6.1 Production of Phosphate Rock in the United 6-3
States, by State
6.2 Analysis of Phosphate Rock: Florida 6-4
6.3 Representative Analysis of Commercial Phosphate 6-6
Rocks
6.4 Quantitative Spectrographic Analysis from the 6-7
Four Areas of Eocene Rocks Studied in Wyoming
and from the Uinta Basin, Utah
6.5 Size Distribution of Florida Pebble Phosphate 6-11
Slimes
6.6 Chemical and Mineralogical Analysis of Typical 6-11
Phosphatic Slime
6.7 Particulate Emission Factors for Phosphate Rock 6-12
Processing Without Controls
6.8 Operating Data for a Phosphorus Furnace 6-14
6.9 Average Analysis of Typical Phosphorus Furnace 6-14
Slag
xi
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LIST OF TABLES
Table Page
6.10 Components of Typical Wet-Process Acid 6-16
6.11 Typical Analysis of a Commercial Food-Grade 6-19
Phosphoric Acid
6.12 Analysis of Typical Streams 6-22
6.13 Fluorine Emissions for Various Processes 6-28
7.1 Potash Minerals 7-4
7.2 Composition of Potash 7-5
7.3 Typical Mineralogical Analysis of Potash Ore of 7-6
Carlsbad-New Mexico
7.4 Typical Analysis of Flotation Grade of Potassium 7-11
Chloride
7.5 A Typical Analysis of Mother Liquor and Waste 7-15
Liquor from Hydrator
8.1 Principal Boron-Containing Minerals 8-2
8.2 Analysis of Borate Ore from Kramer District 8-5
(California)
10.1 Analysis of Fluorspar 10-5
10.2 Spectrographic Analysis of Fluorite from 10-6
Illinois and Kentucky
10.3 Representative Screen Analysis of Classifier 10-10
Overflow
10.4 Analysis of Acid Fluorspar Concentrate 10-12
A-l Factors for Conversion of English to Metric A-2
Units
B-l Principal Producers of Cement in the United B-2
States
B-2 Production of Cement in United States, by B-6
State, 1971
C-l Principal Producers of Clay in the United States C-2
C-2 Production of Clays in the United States, by C-4
State, 1971
D-l Principal Producers of Gypsum in the United D-2
States
xii
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LIST OF TABLES
Table Page
D-2 Principal Gypsum Producing States in the D-6
United States, 1971
E-l Principal Producers of Lime in the United States E-2
E-2 Production of Lime in the United States, by E-4
State, 1971
E-3 Lime Produced in the United States, by Size E-5
of Plant
F-l Principal Phosphate Rock Producing Companies F-2
in the United States
F-2 Normal Superphosphate PlantsMajor Producers, F-3
1968
F-3 Triple Superphosphate PlantsJune 1968 F-12
F-4 Ammonium Phosphate Fertilizer Plants (Solid) F-14
1968
F-5 Fertilizer Granulation PlantsDecember 1967 F-18
F-6 Phosphoric Acid Plants (Wet Process)June 1968 F-34
F-7 Phosphoric Acid and Superphosphoric Acid Plants F-37
(Thermal Process)June 1968
G-l Principal Producers of Potash in the United G-2
States
H-l Principal Producers of Boron in the United H-2
States
1-1 Mica Grinders in 1960 1-2
j-1 Principal Producers of Fluorspar J-2
xiii
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ACKNOWLEDGMENT
This report was prepared for the U.S. Environmental
Protection Agency by PEDCo-Environmental Specialists, Inc.,
Cincinnati, Ohio. Mr. Timothy W. Devitt was the PEDCo
Project Manager. Principal authors of the report were Mr.
Vishnu Katari, Mr. Gerald Isaacs and Mr. Devitt.
Mrs. Anne Cassel was the project editor. Mr. Chuck
Fleming was responsible for report graphics and final report
preparation.
Mr. D. Oestreich was the Project Officer for the U.S.
Environmental Protection Agency. PEDCo appreciates the
assistance and cooperation extended by the Project Officer,
various members of the Control Systems Laboratory, and Mr.
Paul W. Spaite, EPA consultant.
xiv
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1.0 INTRODUCTION
The objective of this study was to identify significant
sources of emissions of potentially hazardous trace pollutants
from mining and processing of nonmetallic minerals. For selecting
some industries for study, the data on production, imports,
exports, and consumption of each ore were assembled. Table 1.1
presents 1971 production and processing data on the quantities
of 26 ores mined and processed in the United States. Figures
A-l through A-26 in Appendix A give production, import, and export
data (including uses) for each ore. Table 1.2 gives the number
of domestic nonmetallic mines in 1971, by commodity and magnitude
of crude ore production.
After review of data on domestic ore processing, and
consideration of the toxicity of potential pollutants and the
significance of fugitive dust emissions, the following
industries were selected for further study.
0 Cement Industry
0 Clay Industry
0 Gypsum Industry
0 Lime Industry
0 Phosphate Rock Industry
0 Potash Industry
0 Boron Industry
0 Mica Industry
0 Fluorspar Industry
1-1
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Table 1.1 QUANTITIES OF ORE MINED AND PROCESSED
IN THE UNITED STATES
Type of Ore
Abrasive Materials
Asbestos
Boron
Cement
Clays
Diatomite
Feldspar
Fluorspar
Graphite
Gypsum
Kyanite & Related Mater:
Lime
Mica
Peat
Perlite
Phosphate Rock
Potash
Pumice
Salt
Sand & Gravel
Sodium Sulfate
Sodium Carbonate
Sulfur & Pyrites
Stone
Talc, Soapstone, etc.
Vermiculite
Amount of ore
mined in U.S.,
(metric tons)
517,100
118,800
949,800
70,870,000
51,710,000
485,400
601,500
739,400
W
Lais W
17,770,000
216,800,000
549,800
449,000
116,100,000
4,153fOOOC
3,008,000
39,990,000
834,300,000
668,600
6,386,000
7,138,000
272,200
934,400
272,200
Amount of ore
processed in U.S.,
(metric tons)
517,100a
736,600
956,200
73,760,000
41,710,000
186,200
601,500
1,713,000
52,620b
14,970,000
l,089b
17,900,000
216,800,000
816,500
319,900
116,100,000
8,342,000
3,371,000
43,540,000
834,300,000
912,600
6,486,000
8,618,000
272,000a
952,600
272,200
a) Not including imports (data not available).
b) Includes domestic processing of only imported ore.
c) The quantity includes the potash from brine.
W) Withheld.
1-2
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Ul
Table 1.2 NUMBER OF DOMESTIC NONMETAL MINES IN 1971, BY COMMODITY
AND MAGNITUDE OF CRUDE ORE PRODUCTION PER ANNUMa
(short tons)
Total
Less
number than
of
Commodity mines
Abrasives 14
Asbestos 9
Barite 35
Boron minerals 2
Diatomite 11
Feldspar 40
Fluorspar 21
Gypsum 65
Mica 20
Perlite 14
Phosphate rock 55
Potassium salts 8
Pumice 107
Salt 20
Sodium carbonate
(natural) 3
Talc, soapstone,
pyrophyllite 55
Vermiculite 3
OtherC 25
Total nonmetals 507
Grand total 1,299
1000
tons
3
3
1
-
2
2
4
2
8
2
1
-
18
-
-
7
-
10
63
327
1000
to
10,000
tons
7
-
4
-
1
22
10
6
5
5
9
-
36
3
-
22
1
3
134
341
10,000 100,000
to
100,
to
000 1,000,000
tons tons
3
1
18
1
7
12
5
18
5
5
8
-
45
2
-
25
5
160
295
1
5
12
-
1
4
2
39
2
2
17
1
8
9
1
1
2
7
114
220
1,000,000 More
to than
10,000,000 10,000,000
tons tons
_ _
_.
-
1
_ _
-
- -
-
- -
-,
16 4
7
_ _
6 ~"
2
_ _
_
- -
32 4
99 17
a) Excludes wells, ponds, or pumping operations.
b) Emery, garnet, and
c) Aplite, graphite,
tripoli.
greensand
marl , iron
oxide
pigments (crude) ,
kyanite, lithium mineral
magnesite, millstones, olivine, wollastonite, and zerolite.
d) In addition, there were 1398 clay mines, 7110 sand and gravel operations, 4715 crushed
and broken stone operations, and 478 dimension stone operations, but specific data on
these operations are not available.
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Process flow diagrams identifying major processes and material
flow were prepared for these selected industries. Sources of
emissions of various pollutants are identified. Descriptions
of processes are presented in Chapters 2 through 10.
These chapters are further divided into five sections. The
first section presents background information, including overview
of industry as well as industrial and processing trends. The
second section describes raw material according to type of ore
and area of availability. The third section lists the products
and by-products of the industry. ,The fourth section describes
the process, process operating conditions, process emissions,
and material handling procedures. Emphasis was given to obtaining
information on emission composition. The fifth section identifies
the most significant emission sources within the industry.
In Chapter 3, the refractory and brick manufacturing proce-
dures, and in Chapter 6, the fertilizer manufacturing procedures
were investigated along with the main industrial processes because
of their integrated relationship. In the study of potash and
boron (Chapters 7 and 8, respectively), brine processing methods
are not included.
In conducting this study a common set of nomenclature devel-
oped by EPA's Control System Laboratory was used so that the
output of this study would parallel that of other CSL contractors
studying other industries. The terms used and their definitions
are listed below.
1. RAW MATERIALS are feed materials for processes. They
are of two types: primary raw materials that are used
1-4
-------
in the chemical form that they were taken from the
land, water or air and secondary raw materials that
are industrial intermediate products.
2. INDUSTRIES are made up of groups of companies that are
considered competitors in production of the same pro-
ducts. Industries have an identifiable population of
companies and have a high degree of commonality with
respect to raw materials consumed, processes employed,
products produced, environmental control problems
experienced, pollutants produced, and control equipment
used.
3. OPERATIONS are general industrial procedures by which
materials are processed or products produced. Oper-
ations can consist of a series of processes, or can be
accomplished by two or more alternative processes.
4. PROCESSES are the basic units that collectively de-
scribe industries. Processes comprise specific arrange-
ments of equipment that accomplish, in a distinct way,
chemical or physical transformation of input materials
into end products, intermediate products, secondary
raw materials or waste materials. Other process out-
puts include waste streams to the air, water, or land.
Input materials can include primary or secondary raw
materials, waste materials, or intermediate products.
Where two or more different combinations of process
steps accomplish the same chemical or physical trans-
formation but have different environmental impacts
(e.g., different emission characteristics), each com-
bination is a distinct process.
5. PROCESS STEPS are the basic components of a process
that utilizes process equipment or materials handling
equipment (process equipment does not include control
equipment). In cases where a piece of process equip-
ment has two or more cycles or phases of operation
with distinctly different emissions to the atmosphere,
such cycles or phases can be considered sequential
process steps.
6. SOURCES are process steps from which significant
amounts of air, water, or land pollution can be dis-
charged .
7. CONTROL EQUIPMENT is equipment whose primary function
is to reduce emissions to the atmosphere. Its presence
is not essential to the economic viability of the
process.
8. COMPANIES include corporate subdivisions that have a
product state similar to other companies in an industry
1-5
-------
9. PLANTS are comprised of collections of processes to
produce the products associated with their industry.
Individual plants within an industry may employ dif-
ferent combinations of processes but all plants will
have some of the processes that are common to the
industry.
10. END PRODUCTS incluse only those process outputs that
are marketed for use or consumption in the form that
they exit from the process. After use, an end product
becomes a waste material.
11. INTERMEDIATE PRODUCTS are process output streams that
go either to other processes in the same industry in
which they are produced, or to other industries where
they become secondary raw materials.
12. WASTE MATERIALS are either process outputs that go to
a scavenging industry, or are used end products that
are disposed or processed to recover reusable constitu-
ents .
The relative toxicity of various pollutants is presented
in Table 1.2.
Chapter 11 identifies the most significant sources of emis-
sions discussed in the preceding chapters. Appendices A through
J present relevant industry statistics.
1-6
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2.0 CEMENT INDUSTRY
2.1 INDUSTRY BACKGROUND
In 1971, the United States produced an estimated 71
billion kilograms (417 million barrels) of cement, which is
12 percent of world production, and consumed approximately
74 billion kilograms (434 million barrels), which is 13
percent of the world total. About 63.1 percent was used
to produce ready-mix concrete, 13.4 percent for concrete
blocks, concrete pipes, and other concrete products, 9.4
percent for highway construction, 8.5 percent for building
materials, and the remaining 5.6 percent for miscellaneous
uses.
In the United States cement is produced in 26 states,
principally in California, Pennsylvania, Texas, and Ohio.
In 1971 there were 170 clinker-producing plants, ex-
cluding five plants operating only on imported or purchased
clinker or that obtained in interplant transfers. Table 2.1
shows the capacities of plants.
Table 2.1
CEMENT PLANTS IN THE UNITED STATES - 1971
DAILY CLINKER PRODUCTION CAPACITIES OF
1
Barrels 170.6 kg
(376-pound) per
24-hour period
Loss than 3,000
3,000 to 6,000
6,000 to 9,000
9,000 to 12,000
12,000 to 15,000
16,000 and over
Total
Number
o£ a
plants
6
49
65
23
11
11
170
Kilnsb
10
98
170
95
37
56
466
Total
capacity
14,206
215,183
473,017
2a3,8l7
152,841
222,193
1,366,287
Porcent of
to";-U
capacity
1.0
15.8
34.6
21.1
11.2
16.3
100.0
a) Includes white-cement-producing facilities.
b) Total number in operation at plants.
2-1
-------
The raw materials used in manufacturing cement are
abundant and widely distributed throughout the country. The
plants generally locate close to major markets.
Table B-l in Appendix B lists the companies processing
cement, and Table B-2 in Appendix B gives cement production
by state.
Currently the industry shows a trend toward larger
grinding mills with greater horsepower consumption, probably
because of the lower capital costs, lower building space
requirements, and better grinding efficiency of larger
mills.
In 1971 there were 17 process-control computers de-
signed to control kiln and clinker cooler functions, 15
computers designed to control the raw mix operations, and 8
to control mill loads.
2.2 RAW MATERIALS3
Portland cement is made by sintering a mixture of raw
materials, one of which is composed mainly of calcium car-
bonate. Table 2.2 presents the typical sources of raw
materials used in the manufacture of portland cement.
Table 2.2 TYPICAL SOURCES OF RAW MATERIALS USED IN
MANUFACTURE OF PORTLAND CEMENT3
Lima
Cement rock
Limestone
Marl
Alkali waste
Oyster shell
Coquiua shell
Chalk
Marble
Silica
Sand
TraprocJc
Calcium-silicate
Quartzite
Fuller's earth
Alumina
Clay
Shale
Slag
Fly ash
Copper slnfj
Aluminum-ore
refuse
Staurolite
Diaspora clay
Granodiorite
Kaolin
Iron
Iron ore
Iron calcino
Iron dust
Iron pyrita
Iron sinters
Iron oxide
Blast-furnace
flue dusk
2-2
-------
The following paragraphs characterize briefly the major
raw materials of cement manufacture.
Cement rock - A low-magnesium limestone containing
clay. This rock approaches the ideal in relative propor-
tions of lime, alumina, and .silica.
Limestones - Composed essentially of calcium carbonate,
magnesium carbonate, and some impurities of clay and sand.
Many accessory minerals may be present, including iron and
manganese oxides; sulfides of the common metals; feldspar,
mica, gypsum, quartz, and clay minerals; and bituminous
matter.
Mar_ls_ - Earthy, friable accumulations of calcareous
material secreted by plants and animals in lakes and marshes.
Marls are important in Michigan and Ohio as raw materials
for cement manufacture. Shell marls are found in Virginia,
North Carolina, and Florida.
Alkali waste - A waste byproduct of limestone pro-
cessing accumulated from years of activity plus current
output.
Alumina waste - Obtained from alumina plants; may be
very high in alumina and iron or in dicalcium silicate.
Sand and Sandstone - Used to correct silica deficien-
cies. These materials are chiefly quartz but may contain
varying amounts of clay and other minerals.
Clay and Shale - Required as additives when limestone
contains insufficient alumina and silica. Minerological and
chemical contents of both clay and shale vary widely. Some
2-3
-------
clays and shales consist essentially of aluminum silicates,
whereas others may contain more than 50 percent free silica.
Fly ash - Generated from power stations with direct-
fired coal burners. Fly ash composition is fairly close to
that of the argillaceous raw materials used in portland
cement manufacturing.
Iron materials - Development of cements with low heats
of hydration has created a demand for raw materials having
high iron content. Those commonly used are pyrite cinders
(the calcination product of pyrite) and mill scale (from
hot-rolling of ingots, billets, and other forms of steel).
Table 2.3 lists the composition and ignition loss of
some typical raw materials.
2.3 PRODUCTS
Cement industries in the United States produce five
types of portland cements (in major proportions) and some
other cements including masonry, pozzalan, and slag cements
(in lesser amounts). The portland cements account for 96
percent of United States cement production. Table 2.4 gives
a typical composition of various cements.
2.4 PROCESS DESCRIPTION
Figure 2.1 illustrates the processes in the cement
industry. As shown in this figure the following operations
are used: mining, size reduction and blending, calcination
and finishing operations. The processes within these
2-4
-------
Table 2.3 PERCENT OXIDE COMPOSITION OF TYPICAL CEMENT RAW MATERIALS
to
en
Type
Limestone
Limestone
Limestone
Limestone
Limestone
Cement Rock
Cement Rock
Sand
Clay
Clay
Shale
Shale
Shale
Pyrite Cinders
Pyrite Cinders
Slag
Marl
Sea Shells (Unwashed)
Sea Shells (Washed)
Fly Asha
Ply Asha
Fly Asha
Si02
1.2
3.2
5.6
21.1
23.6
8.1
14.2
89.7
67.8
57.4
64.3
63.0
53.8
6.3
13.0
37.8
6.0
15.8
1.5
51.2
44.0
45.8
A1203
0.5
1.1
1.0
1.7
3.4
2.3
4.8
2.4
14.3
15.3
15.8
20.0
18.9
2.1
3.8
11.4
0.6
4.2
0.4
25.6
25.0
13.5
Fe2°3
0.4
0.7
0.5
1.0
1.6
1.0
1.6
0.7
4.5
6.8
4.0
5 5
7.7
86.7
67.5
1.0
2.3
2.7
1.2
8.5
15.0
6.6
CaO
54
52.4
50.7
41.3
37.4
46.2
40.2
0.6
0.9
1.1
3.5
0.7
3.2
0.02
1.4
46.1
49.1
39.23
52.28
1.6
6.0
12.0
MgO
0.6
0.5
0. 8
0.6
-
2.5
2.8
0.7
1.2
0.9
2.9
2.7
2.2
0.1
4.5
2.0
0.4
1.2
0.7
0.9
1.0
2.7
Ignition
Loss
43.2
42.2
41.2
34.1
32.7
38.6
34.2
5.9
8.0
13.3
6.1
6.0
8.2
2.6
8.1
-
40.4
33.8
41.8
8.6
9.0
16.9
a)Carbon content may vary between 0.2-15.6,
-------
Table 2.4 TYPICAL COMPOSITION OF VARIOUS CEMENTS
to
I
SiO- Al_0_
£ £* -J
Portland, type I, %
Portland, type II, %
Portland, type III, %
Portland, type IV, %
Portland, type V, %
Portland white, %
Natural %
High alumina, %
21
22
20
24
25
25
23
5
.3
.3
.4
.3
.0
.5
.7
.3
6.0
4.7
5.9
4.3
3.4
5.9
4.1
39.8
Fe
2
4
3
4
2
0
0
14
2°3
.7
.3
.1
.1
.8
.6
.8
.6
CaO
63.
63.
64.
62.
61.
65.
64.
33.
2
1
3
3
1
0
5
5
MgO
2.9
2.5
2.0
1.8
1.9
1.1
1.6
1.3
so3
1.8
1.7
2.3
1.9
1.6
0.1
2.2
0.1
Loss
1.3
0.8
1.2
0.9
0.9
a
3.0
0
Insol
0.2
0.1
0.2
0.2
0.2
a
a
4.8
a) Not determined.
-------
operations and their emissions are described in the fol-
lowing sections.
2.4.1 Mining
(1*) Deposits of cement rock, limestone, and clay are mined and
brought together. These materials are often found close
together or overlying one another. The limestone is mined
from open quarries and also by underground methods. Other
raw materials are extracted in the same manner except that
clay may be extracted with power shovels.
A significant amount of fugitive dust is emitted and
easily spreads throughout the quarry area. Many plants
control dust with emulsifying agents.
Trucks are used for haulage.
2.4.2 Size Reduction and Blending
Size reduction is accomplished by crushing, grinding,
and blending the ore to obtain the fineness and surface
characteristics that will permit efficient chemical re-
actions among the components. Grinding and blending are
done by wet and dry processes.
(2) Crusher - The raw materials are fragmented by crushers and
screened. The material is then transferred to a storage
area and deposited in separate compartments for cement rock,
limestone, shale, and others.
Particulate is emitted from crushers, storage areas,
receiving bins, and elevators.
* Numbers refer to corresponding processes in Figure 2.1.
2-7
-------
MINING
I
CEMENT HOCK
LIMESTONE
SHALE, etc.
CRUSHER
^
u
8
K1LH
1_
9
COOUR
1
u
10
MILL
AIR
Figure 2.1 Cement industry
2-8
-------
Storage bins are filled by bucket elevators or by
pneumatic conveyors. The bucket elevators used for cement
service are totally enclosed and fed by screw conveyors.
Leakproof conveyors minimize dust problems.
2.4.2.1 Dry Process - In the dry process, the free moisture
content of crushed material is reduced to less than 1 per-
cent moisture before and during grinding. Process steps are
drying, grinding and separation, and blending.
(3) Dryer - The limestone, cement rock, and shale are dried to
remove free water. In the heating process no flames impinge
directly on the material. Fuels are oil or natural gas.
Emission gases contain dust of limestone, shale, or
other materials being dried. The concentration of dust in
the exit gases is related to the velocity of the gases and the
quantity and size of the fine particles. Dust concentra-
tions of 11.5 to 23 gm/m (5 to 10 grains per cubic foot) of
2
rotary dryer discharge gas can be expected.
(4) Grinding and Separation - A proportioned amount of dry
product is ground to powder in one or several stages by one
of a variety of mills. Fines are separated from the ground
material by flowing air cross current to the direction of
flow of the fines. The oversize fraction is recycled for
additional grinding. Conveyors are used for material
transfer.
About 33.5 grams of particulate is emitted per kilogram
(67 Ib/ton) of cement from dryers and grinders.
2-9
-------
(5) Blending - The finely ground material is blended to a pre-
scribed composition and stored for calcination in kilns.
2.4.2.2 Wet process - Slurry is prepared by adding water to
the initial grinding. The process sequences are propor-
tionating and grinding followed by slurry blending.
(6) Proportionating and Grinding - The raw materials are care-
fully proportioned and passed to a grinding mill. Water is
added to the raw materials prior to grinding for slurry
formation.
For effective handling, the water requirement of the
slurry is reduced by addition of a very small amount (0.05
to 0.10 percent) of an agent such as waste sulfite liquor,
sodium carbonate, sodium silicate, sodium tri-polyphosphate
or tetra sodium pyrophosphate.
Particulate is generated from proportionating equip-
ment. Since grinding is a wet operation, emissions from the
process are negligible. Emissions from the overall oper-
ation are about 12.5 grams of particulate per kilogram (25
Ib/ton) of product.
(7) Slurry Blending - Excess water of the ground material may be
reduced by filtration or by a series of hydroseparators,
classifiers, and thickeners. Sometimes the separated size
fractions are treated by flotation in a series of cells with
fatty acids and a frothing agent to remove undesirable
constituents such as mica, quartz, pyrite, or feldspar and
increase the CaO concentration.
The final slurry product is thoroughly mixed and
blended for calcination.
2-10
-------
The process involves no known air pollution problems.
The water waste from the filtration or flotation is re-
jected.
2.4.3 Calcination
The blended material from either the dry or wet process
is calcined in a kiln at high temperature. A variety of
kilns are used.
(8) Kiln - The material is fed to the kiln. Heat is provided by
burning oil, gas, or pulverized coal. Combustion air is
mixed with preheated air from cooling the clinker. A max-
imum temperature of 1595°C is maintained inside the kiln.
As the charge is heated, organic matter is burned out and
sulfates are decomposed, with liberation of CO,, and for-
mation of CaO and MgO. In the burning process, about one-
third of original dry weight of the feed is lost. In the
hot zone, about 20 to 30 percent of the charge is converted
to liquid and it is through this medium that the chemical
reactions principally proceed. The product of the calci-
nation, "cement clinker," comes out from the lower end of
the kiln and its temperature is quickly reduced in a cooler.
Fuel requirements are about 890 kcal/kg (1600 BTU/lb) of
clinker for vertical kiln and about 1480 kcal/kg (2660 BTU/lb)
4
of clinker for rotary kiln. Wet-process kilns are generally
longer than dry-process kilns, since one-fourth of the length
must be used for evaporation.
The calcining kiln is the major source of particulate
emissions in cement plants. About 83.5 grams of particulate
2-11
-------
per kilogram (167 Ib/ton) of cement are emitted. The kiln
dusts have been reported variously as harmful, harmless, or
indirectly beneficial. Research in Poland shows that the
dust emissions from kilns contain potassium in the form of
chlorides, fluorides, and silicates of various composition.
This is because the K_0 content of raw material combines
with free anions of decomposition products of raw materials
(aluminum silicates in the crude clay) at high temperature.
Analysis has established that the cement dust can be used as
7
a fertilizer. Table 2.5 gives a size distribution of dust
emitted from the kilns.
In addition to the dust, the average kiln also produces
approximately 5.32 grams of hot gases per gram of cement.
o
They exit the kiln at 760°C. Compounds in the dust and gas
phases include Si02, AI^O^, Ti02' P2°5' Fe2°3' Mn2°3' Ca0'
MgO, SO.,, K2O, Na-O, CO2/ C, and H2O. They also contain
nitrogen, oxygen, and a negligible amount (except during
start-up) of carbon monoxide. The sulfur dioxide content of
Q
gases is very low. It has been concluded that the occur-
rence and magnitude of an S02 emission depends on the
presence of the alkali in the gas phase. If the waste gases
contain SO- then the amount emitted may be reduced only when
conditions are created for a reaction between S02 and CaCO.,.
This reaction may take place in the presence of oxygen at
400 to 500°C, to form CaSO,. Observations of kilns show
that the amount of SO2 emitted may be reduced by drying the
raw material before treating it in the kiln.
2-12
-------
Table 2.5 SIZE DISTRIBUTION OF DUST EMITTED FROM KILN
OPERATIONS IN CEMENT MANUFACTURING WITHOUT CONTROLS
Particle size,ym
60
50
40
30
20
10
5
1
Kiln dust finer than corresponding
particle size, %
93
90
84
74
58
38
23
3
2-13
-------
At equilibrium, the entire charge of the fluoride would
be evolved as gaseous HF (at 1480°C) and would subsequently
react with the dispersed limestone and high free lime in the
kiln to form CaF^. Fluorine is partially driven out of raw
materials and fuel in the kiln. The kiln emissions do not
contain fluorine gas but contain fluoride solids, which can
be removed by electrostatic precipitators. If raw materials
contain excess CaO, the fluorine is converted to CaF_.
The gas stream in a cement kiln also contains alkali sul-
fates, alkali chlorides, and calcium fluoride formed by a
reaction in the kiln gas after vaporization. These com-
pounds may react with or precipitate on the material in the
12
colder parts of the kiln.
The alkali materials present in the raw materials are
volatilized and subsequently condensed to form fine par-
ticulate matter. One advantage in using an electrostatic
precipitator is that the smaller particle sizes are more
difficult to collect, and a higher percentage of these
particles are collected primarily in the final stages of the
precipitator. This is desirable since only a limited amount
of alkali can be recycled to the kiln (to maintain the
clinker within acceptable alkali limits). Since this dust
is difficult to collect, a disproportionately higher amount
of alkali is emitted. The alkali-rich dust which is col-
lected is often disposed of in abandoned quarries.
2-14
-------
The oil combustion products in the emissions are 2.1
grams S, and coal combustion products are 3.45 grams per
kilogram (6.8 Ib/ton) of cement produced, where S denotes
sulfur content of fuel.
Cement plants can also release appreciable quantities
of mercury to the atmosphere.
Table 2.6 gives typical emission data from five cement
kilns and coolers in the United States.
(9) Cooler - The temperature of hot clinker is reduced imme-
diately and the clinker sent to storage for subsequent
grinding. Often integral coolers are attached to the kiln
below the burning zone. In other designs the clinker is
carried on a perforated grate through which air is forced.
In either case air is the cooling agent, and particulate is
emitted. Only 10 to 15 percent of dust particles from a
2
cement clinker-cooler are below 10 microns diameter.
Cooled clinker is conveyed to storage by bucket con-
veyors .
Detailed data on emissions from a typical cement
clinker-cooler are presented in Table 2.6.
2.4.4 Finishing Operations
(10) Grinding Mill - Gypsum is added to the clinker in prescribed
proportions for making portland cement. In production of
cements other than portland, different materials are added.
For example, limestone is added to make masonry cement and
slag is added to make slag cement. The proportionated
2-15
-------
Table 2. 6 SUMMARIES OF TYPICAL EMISSION DATA FROM FIVE U. S. CEMENT KILNS AND COOLERS
Run No.
Date
Stack Flow Rate, Nm /sec
dry (21 °C, 76 cm Hg)
% Water Vapor, % vol
% CO2 , vol % dry
%O2, vol % dry
SO2 Emissions , ppm dry
NO Emissions, ppm dry
"*X
Particulates
Front Half Catch
gram/Nm dry
gram/m at stack
conditions
grams/sec
Total Catch
gram/Nm
gram/m3 at stack
conditions
grams/sec
gram /kg kiln feed
Plant 1 Kiln
1
4/29
24.1
2.0
7.5
15.5
295
147
0.0218
0.0161
31.5
0.0464
0.0342
67.2
0.101
2
4/29
23.8
2.1
16.8
16.8
396
292
0.0269
0.0197
38.4
0.0423
0.0310
0.2
0.0870
3
4/30
23.6
2.4
16.8
16.8
196
150
0.0248
0.0180
35.2
0. 0402
0.0291
56.8
0.0875
Plant 2 Clinker Cooler
1
5/18
48.8
1.60
0.03
20.95
__
--
0. 00412
0.00336
11.7
0. 00917
0.00748
26.6
0.0284
2
5/18
47.1
1.73
0.03
20.95
__
--
0.00766
0.00606
21.2
0.00142
0. 01120
40.1
0.0422
3
5/18
48.0
1.65
0.03
20.95
--
--
0.00522
0. 00412
14.6
0.00856
0.00668
24.6
0.0255
Plant 3 Kiln
1
8/26
25.4
41.2
14.9
8.6
--
--
0.148
0.0507
22.6
0.2279
0. 0842
34.8
0.386
2
8/27
25.3
41.2
21.0
4.5
--
--
0.190
0.0721
28.9
0.3642
0.1384
55.3
0.650
3
8/27
24.6
39.8
21.0
4.5
--
--
0.171
0.0648
25.2
0.2773
0.1052
41.0
0.505
I
I*
o>
-------
Table 2. 6 (cont) Summaries of Typical Emission Data from Five U.S. Cement Kilns and Coolers
Run No.
Date
Stack Flow Rate ,
Nm3/sec dry
(21°C, 76 cm Hg)
% Water Vapor ,
% vol
%C02, vol % dry
% O2 , vol % dry
Particulates
Front Half Catch
gram/Nm
gram/m at
stack conditions
grams/sec
Total Catch
a
gram/Nm dry
2
gram/m at
stack conditions
gram/sec
grani/kg kiln feed
NOX Emissions ,
ppm dry
Plant 4 Clinker Cooler
1
3/18
45.27
0.5
0.03
20.95
0.1174
0.1036
31.8
0.2686
0.110
34.0
0.218
2
3/19
44.99
0.4
0.03
20.95
0. 1306
0. 1178
35.2
0.1354
0.1231
36.6
0.236
--
3
3/19
44.58
0.3
0.03
20.95
0.1597
0.1347
42.7
0.1629
0.1476
43.6 :
0.275
--
Plant 4 Kiln
1
3/24
50.23
29.3
17.0
8.0
0.2137
0.0801
64.7
0.2325
0.0869
70.3
0.446
--
2
3/24
48.92
31.5
17.0
8.0
0.2434
0.8809
71.4
0.2707
0.0982
79.4
0.506
--
Plant 5 Clinker Cooler
1
2/25
9.165
2.03
0.03
21.0
0.059
0.048
32.8
0.064
0.053
35.2
0.056
2
2/25
8.164
1.91
0.03
21.0
0.064
0.053
31.4
0.071
0.057
34.8
0.056
3
2/25
8.930
1.86
0.03
21.0
0.046
0.037
24.5
0.050
0.041
27.0
0.044
--
Plant 5 Kiln
1
2/26
26.04
30.4
10.5
13.0
0.124
0.055
19.3
0.137
0.059
21.5
0.352
179
2
2/26
25.55
28.9
10.5
13.0
0.204
0.089
31.7
0.238
0.105
36.4
0.60
179
3
2/26
24.49
29.0
10.5
13.0
0.373
0.165
54.8
0.396
0.174
58.0
0.955
179
-------
material is ground in the same kind of mill in which raw
materials are ground. Power requirements of typical cement
plant grinding mills are about 105 to 117 KWH/ton of cement.
Particulate emissions result from this operation. Dust
collected from mill systems, raw or finish transfer points,
and conveyors present only minor air pollution problems as
these are essentially closed systems and dust is returned
2
into the unit from which it was collected.
Gypsum is brought in by trucks and conveyed from
storage and grinding mill by bucket and belt conveyors.
(11) Storage and Bagging - Fine materials are separated from the
coarse materials in the mill discharge. Cement of the
proper fineness is sent to storage, and the oversize mate-
rials are returned to the mill for regrinding. Particulate
emissions occur in significant amounts. The fine materials
are transferred either in bags or in bulk by rail or truck.
Cement handling entails a potential for considerable par-
ticulate emissions; high value of cement products, however,
generally ensures efficient control.
Table 2.7 summarizes the metal content of particulate
emissions from cement plants.
Table 2.7 RANGE OF TRACE MATERIALS IN
PARTICULATE FROM CEMENT PLANTS
15
o.oi
0.1
Concentration, ppm
10 100 1,000 10,000
100,000
Be
Cd
Cr
Cu
Fe
Hn
Ni
Pb
Sb
Sr
V
2-18
-------
2.5 MAJOR POLLUTANT SOURCES
The main source of pollution in the cement industry is
the kiln. Other sources are dryers, grinders, and material
handling.
0 Kiln - About 83.5 grams of particulate are released
(uncontrolled) from processing one kilogram of cement (167
Ib/ton). Almost all plants control particulate emissions to
a relatively high extent. In 1970, 95 percent of plants
applied control equipment operating at an overall efficiency
of 95 percent. The resulting emissions were 675,900 metric
tons of particulate from a production of nearly 75 million
tons of cement. As shown in Table 2.5, the particulate
contains the following elements in trace quantities: Be, Cd,
Cr, Cu, Fe, Mn, Ni, Pb, Sb, Sr, and V. According to some
reports, mercury may be present in emissions. Most of the
emitted particulate matter is smaller than 10 microns in
size.
Plants were originally built away from highly populated
areas, but this has been negated by increasing urban sprawl.
2-19
-------
REFERENCES FOR CHAPTER 2
1. Brown, B.C. Cement, In: Minerals Year Book, Vol. 1,
U.S. Bureau of Mines, 1971.
2. Kreichelt. T.E., D.A. Kemmitz, and S.T. Cuffe. Atmo-
spheric Emissions from the Manufacturing of Portland
Cement.
3. Industrial Minerals and Rocks. Seeley W. Mudd Series.
American Institute of Mining, Metallurgical and Petro-
leum Engineers. New York, 1960.
4. Kirk-Othmer. Encyclopedia of Chemical Technology. New
York, John Wiley and Sons, Inc., Second Edition. 1969.
5. Dannielson, J.A. Air Pollution Engineering Manual, Air
Pollution Control District County of Los Angeles,
Second Edition, 1973.
6. Vandegrift, A.E. and others. Particulate Air Pollution
in the United States. Journal of Air Pollution Control
Association, Vol. 21, No. 6, June 1971.
7. Oleksynowa, K. Chemical Characteristics of Waste
Cement Dusts and their value for agriculture, Cement,
WAPNO, GIPS 11/20, (3) 62-4, 1965. Text in Polish.
8. Doyle, C.D. and S.A. Reigel. Cooling hot gases from
dry process cement kilns. Pit and Quarry. July 1971.
9. Compilation of Air Pollution Emission Factors. U.S.
Environmental Protection Agency, Raleigh, North Carolina.
Publication Number AP-42. April 1973.
10. Koehler, W. Present Position in Combating Air Pol-
lution and Nuisance in the Cement Industry. Text in
German. November 1969.
11. Sprung, S., and H.M.V. Seebach. Fluorine balance and
Fluorine Emissions from Cement Kilns. Text in German.
Zement-Kalk-Gips (Wiesbaden), 21 (1): 18, January 1968.
2-20
-------
REFERENCES FOR CHAPTER 2 (continued).
12. Locher, F.W. and others. Reactions Associated with the
Kiln Gases. Cyclic Processes of Volatile Substances,
Coatings, Removal of Rings, 1-12, January 1972.
13. Weiss, Herbert V., Minoru Koide, and Edward D. Goldberg.
Mercury in a Greenland Icesheet. Evidence of recent
input by man. Science, 174 (4010): 692-694, November
1971.
14. Standards of Performance for New Stationary Sources.
15. Bergstom, J.H. Cement Plants of the 60's. Rock
Products Mining and Processing. May 1964.
16. Lee, R.E., Jr. and D.J. Von Lehmden. Trace Metal
Pollution in the Environment. Journal Air Pollution
Control Association. Vol. 23, No. 10. October 1973.
2-21
-------
3.0 CLAY PRODUCTS
3.1 INDUSTRY BACKGROUND
Clay is a hydrated aluminum silicate rock composed of very
fine particles. When suitably crushed and pulverized, it becomes
plastic when wet, rigid when dry, and when fired becomes vitrified,
A total of approximately 52 million metric tons of clay
was produced in the United States in 1971. Every state except
three (Alaska, Rhode Island, and Vermont) produced some clay.
The leading producers were Georgia, Texas, Ohio, North Carolina,
Alabama, and California. Table C-l of Appendix C lists principal
producers of cement and Table C-2 gives clay production by
state.
The basic categories of clay products are kaolin, ball
clay, fire clay, bentonite, fuller's earth, and miscellaneous
or common clay. In 1968, approximately 50 percent of the
kaolin production was by four major firms; a total of 42 firms
operating 57 mines accounted for all of the kaolin production.
Ball clay was produced by 11 firms operating 14 mines. Bentonite
was produced by 25 firms operating 47 mines. The majority of
fuller's earth production was by 8 firms operating 10 mines.
Numerous mines throughout the country supply common clay. Table
C-2 of Appendix C lists the principal producers of clay in the
United States.
3-1
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The projected demand for clay in the year 2000 is between
2
123.8 and 184.6 million metric tons. Reserves appear ample
to meet the projected needs.
Although very few major advances have been made in clay
mining and processing technology, the technological advances
in earth-moving methods, equipment, and automation of processing
methods have been very beneficial to the clay processing industry.
3.2 RAW MATERIALS
The U. S. Bureau of Mines classifies clay deposits according
to the six product categories, that is, kaolin, ball clay, fire
clay, bentonite, fuller's earth, and miscellaneous or common
clay.
Each clay deposit has as the major component one of the
following clay minerals: kaolinite, halloysite, montmorillonite,
palygorskite (or attapulgite), or illite. Some deposits may
have one or more of these minerals as a minor component. All
clays also contain various amounts of impurities such as quartz,
mica, feldspar, and iron minerals.
Kaolin, ball clay, and fire clay are chiefly composed of
kaolinite. Bentonite is composed mainly of montmorillonite.
Fuller's earth is composed of montmorillonite or palygorskite
or both. Miscellaneous clay is composed mainly of illite, although
some deposits have kaolinite and montmorillonite as the major
components.
Kaolinite is a mineral composed of approximately 39.50
percent Al203, 46.54 percent Si02, and 13.96 percent H20. The
3-2
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structural formula is (OH)gSi.Al.0,Q. Kaolin is approximately
the mineral kaolinite. Ball clay consists mainly of kaolinite
and sericite micas. Fire clay is composed of kaolinite and
usually other materials such as diaspore, ball clay, bauxite
clay, and shale. Kaolin is mined primarily in Georgia, with
South Carolina, Ohio, Arkansas, and Alabama being other major
contributors. Ball clay is mined largely in Tennessee, followed
by Kentucky, Mississippi, Texas, Maryland, California, New
York, and New Jersey. Fire clay is produced in 22 states, the
outputs coming from Missouri, Ohio, Pennsylvania, and Alabama.
Montmorillonite has the structural formula of (OH),Sig
(Al_ T4Mgn c.c.^2n' Bentonite (composed primarily of montmoril-
lonite) is mined mainly in Wyoming, with small amounts also mined
in Montana and South Dakota. The type found in those deposits is
the high-swelling or sodium bentonite. Low-swelling or calcium
bentonite is found in Mississippi, Alabama, and Texas, among
others. A small portion of the fuller's earth mined is made up
of predominately montmorillonite. This type of fuller's earth
is mined primarily in Mississippi, Texas, and Utah.
Palygorskite (or attapulgite) has the structural formula
of (OHO.Mg-Si 02Q:4H2O. It is the major component of the
fuller's earth in Georgia and Florida, which constitutes most
of the fuller's earth nationwide.
Illite has the approximate structural formula of (OH).K2
(Si,-A12)A1402Q. It is the predominant mineral in miscellaneous
3-3
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clay and is mined in every state except Alaska, Rhode Island,
and Vermont. The leading states in the mining of illite are
Texas, North Carolina/ Ohio, California, Alabama-, and Michigan.
Table 3.1 presents an analysis of clay minerals from
different areas in the United States and Table 3.2 gives a de-
tailed spectrographic analysis of bentonite clay.
3.3 PRODUCTS
The six basic products of clay processing have been mentioned.
The main finished products of the clay industry are porcelain,
refractory, brick, tile, and pottery.
One kaolin firm produces bauxite as a by-product and another,
flake mica. Two produce silica as a coproduct. Clay is also
produced occasionally along with sand, gravel, and stone.
3.4 PROCESS DESCRIPTION
Figure 3.1 illustrates the clay industry segment. The
processes are mining, beneficiation , and production of the finished
product. These processes are discussed in the following section.
3.4.1 Mining
(1) Most clay deposits are mined by open-pit methods. As of
1968, only about 2-1/2 percent of the clay production was from
underground mines. A portion of kaolin is produced by hydraulic
mining. Open-pit mining involves the use of such equipment
as drag-lines, power shovels, scraper-loaders, and trucks for
transport.
Water pollution is a major problem in mining of clay.
*Numbers refer to corresponding processes in Figure 3.1.
3-4
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Table 3.1 ANALYSES OF CLAY MINERALS
4,5
Composi-
tion (Pet)
Si02
Pe203
FeO
CaO
MgO
K20
Na20
Ti02
H20
Moisture
co2
1
44.90
38.35
0.43
Tr
0.28
0.14
1.80
14.20
2
59.92
27.56
1.03
Tr
Tr
0.64
0.64
9.7
1.12
3
82.45
10.92
1.08
0.22
0.96
1.00
2.40
4
47.92
14.40
3.60
12.30
1.08
1.20
1.50
1.22
4.85
9.50
1.44b
5
90.00
4.60
1.44
0.10
0.10
Tr
Tr
0.70
3.04
3.04
6
45.78
36.46
0.28
1.08
0.50
0.04
0.25
0.25
0.25
13.4
2.05
7
49.56
15.08
3.44
1.08
7.84
0.40
22.96
8
53.12
18.72
1.12
^.40
6.92
5.72
Tr
12.04
9
68.62
14.98
4.16
1.48
1.09
3.36
3.36
3.55
2.78
10
54.64
14.62
5.69
5.16
2.90
5.89
5.89
3.74
0.85
4.80
0.35
11
57.62
24.00
1.90
1.20
0.70
0.30
0.50
0.20
10.5
2.7
0.35
12
42.68
38.49
1.55
0.08
0.49
0.28
2.90
14.07
13
53.96
29.34
0.98
0.37
0.30
0.28
0.12
1.64
12.82
0.03
14
45.44
38.52
0.80
C.08
3.08
0.14
0.66
0.16
13.6
15
38.07
9.46
2.70
15.84
8.50
2.76
2.76
2.49
20.46
16*
61.47
22.17
4.32
0.14
2.73
0.03
3.18
0.09
6.02
U)
I
en
a) Also 1.34 organic matter. 9)
1) Typical sedinentary kaolin, S.c., Ga., Ala. 10)
2) Flint fire clay, Salineville, Ohio. 11)
3) Siliceous clay, Rusk, Texas. 12)
4) Shale clay, Ferris, Texas. 13)
5) Sandy brick clay, Comesneil, Texas. 14)
6) Washed kaolin, Webster, N. C. 15)
7) Bentonite, Otay, Calif. 16)
8) Potash-bearing bentonite, High Bridge, Ky.
Loess, Guthrie Center, La.
Brick shale. Mason City, La.
Plastic fire clay, St. Louis, Mo.
Flint fire clay, near Owensville, Mo.(81).
Qall clay, Tennessee.
Kaolinite, Roseland, Va.(72).
Brick clay, Milwaukee, wis.
Bentonite, Clay Spur, Wyoming.
* For spectrographic analysis of bluish-gray and olive green
bentonite of Clay Sour, (from same pit) Wyoming. See Table
3.2, where the oxides of minor elements are listed.
-------
Table 3.2 SPECTROGRAPHIC ANALYSIS OF BENTONITE
FROM CLAY SPUR, WYOMING6
Oxide
K.O
Li2°
Zr02
Ti02
MnO
BaO
B2°3
Y2°3
Yb2°3
Mo03
PbO
BeO
Bentonite
Bluish-gray
0.3
0.01
0.03
0.05
0.001
0.003
0.002
0.006
0.0008
0.001
0.003
0.0004
Green
0.2
0.008
0.03
0.05
0.001
0.003
0.002
0.006
0.0008
0.0008
0.003
0.0004
Note: Minor elements looked for but not found were
Zn, Cd, Cu, Bi, As, Sb, Sn, Ag, Au, Pt, Bd, Re,
Tl, In, Ge, V, Cr, Cb, Ta, W, Ni, and Co.
Samples of bentonite from deposits of the marine cre-
taceous formation of this district and from the
surrounding region are, weakly radioactive. This
bentonite was found to contain 0.001% of uranium.
3-6
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rORCElAIH MANUFACTUIIIM
b
lEKFICIATIOii
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rl»ATEt f1""i-
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1 """* ~O«I - * sc«EE»l« TIO« Vjlll Vy^
"r i i i «on»
O <> CO O IKTOIITE
y/ »^, ^- 1((ll ^^
FIRE CLAT
NISC. CLAT
L _ J
i 1
TFLIIT
JFflOSMI
(1«it. .. Tut Jin
UotfLOCcuu.: JJLAsticiItM rfruEi riruct
»ou« t»u cut ^ . ^ rlirri ^ ,.., __ ,, _ tll, f ^.
["" "" I ' " ' " FO«C1UI'. 01
A Cb «"lf£«»IE
L J
REFRACTORY NAMUMCTMM8
r J*" J*11 i
rJlATtl rl!"Cl fl!"'1 O '
nil CLAY ^ MUIM " "" " " | ^~N
roi«i«« i \ J
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IRICI MA*UFACTUIIIII
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rbATEi MFUEL MFUIL
o [L U o L a
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MlCt 01
MCAT1 ClAf
MOOUCTS
L J
Figure 3.1 Clay industry
-------
Ground water percolates up through the earth, picks up clay
as suspended solids, and runs off to a stream. This source
of pollution may be controlled by providing a sump in the mine.
The excess water is then pumped to a holding basin and the waste
is settled out.
Kaolin has the highest ratio of waste to clay, about 7
to 1. Kaolin mining spoils are a mixture of sands and clays,
including nonmarketable kaolin. The kaolin industry generates
about 27 million metric tons per year of solid waste. Bentonite
mining in Wyoming generates about 4.5 million metric tons,
fuller's earth mining in the Florida-Georgia area produces
over 1.8 million metric tons, and ball clay mining accounts
for less than 0.9 million metric tons of waste per year.
By comparison, the production of miscellaneous clay creates
the least waste (waste-to-clay ratio of about 0.25 to 1); however,
because much of the miscellaneous clay mining is done near urban
or populated areas, the waste and pollution generated by these
operations may cause significant problems.
Clay is most commonly transported from the mine by trucks.
Other methods involve conveyor belts, or rail cars, or pipelines
in the case of hydraulic mining.
Fugitive dust from the mined clay is normally not a problem,
since the clay may contain 25 to 30 percent moisture and is
not readily windblown. Fugitive dust from stockpiled clay may
be a problem, as with bentonite, which is sometimes stockpiled
to let it weather. The emission factor for a clay stockpile
3-8
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is 17 grains per kilogram (34 Ib/ton) of product.
3.4.2 Beneficiation
Because the physical properties and impurities of clays
vary greatly, it is often necessary to upgrade the clay by
beneficiation.
(2) Crushing and Screening - Initial crushing and screening are
done to break up lumps and agglomerates of the raw clay. This
process involves no chemical changes. Crushing is done by
conventional methods, with jaw or gyratory crushers, cone crushers,
impact mills, attrition mills, or roller mills. The clay usually
is first passed through a large screen to remove material too
large for the primary crusher.
Since crushing is carried out at ambient temperatures and
pressures, there are no emissions of hazardous materials. A
sodium salt may sometimes be added to bentonite clay before
drying.
If the moisture content of the raw material clay is high,
it may be partially dried before crushing. If the material
is uniform in size, crushing may not be needed and the clay
is sent directly to the next process.
After crushing, miscellaneous clay is in usable form and
needs no further beneficiation. It may be used in manufacture
of light-weight aggregate or cement or be formed into heavy clay
products such as brick.
An uncontrolled grinding process in ceramic clay manufactur-
ing generates about 38 grains particulate per kilogram (76 Ib/ton)
3-9
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input to the process. If the process is controlled by a cyclone,
emissions are reduced to 9.5 grams per kilogram (19 Ib/ton); with
a cyclone and scrubber the emissions are negligible.7 If scrubbers
are used, the scrubbing liquid must be treated to prevent water
pollution.
Material is transferred to the next operation by belt or
screw conveyor. Particulates may be emitted at the transfer
points.
(3) Concentration - Concentration involves the removing of impurities
and further upgrading of the clay by physical processes.
In the case of kaolin, water and clay are mixed in a blunger
to form a "slurry". Coarse materials are removed by settling
and other impurities by flotation. Iron compounds and mica
are removed from the slurry by magnetic separation. Particle
size classification may also be done at this time by centrifuging
or gravity settling. The slurry is then dewatered by centrifuges,
filter presses, or vacuum filters. Air pollution is not a problem
in these operations, but the water removed in the dewatering
steps must be treated for dissolved and suspended solids. Solid
wastes are also evolved. In processing of kaolin, about 40
percent of the material is discarded. About 30 percent of all
fuller's earth material that is beneficiated is discarded.
These are the only two clays that generate significant solid
2
waste in the beneficiation process.
In wet grinding processes the clay is mixed with water
as it is ground. Sands may settle out, and the remaining slurry
is classified as to particle size and then dewatered. If dry
grinding is done, the process may generate air pollution.
3-10
-------
Concentration is not required for all clays, but is done
only when a very pure product, such as kaolin, is required.
(4) Dryer - Drying removes the remaining moisture and any volatile
matter present in the clay. Rotary drums, apron dryers, or
spray dryers are used. The dryer is fired by natural gas, oil,
coal, or wood.
Clay direct from the mine, crushed or uncrushed, may be
dried to remove moisture. Clay that has been made into a slurry,
after it has been dewatered, is sent to the dryer. The drying
process involves driving off free water and dehydrating the
hydrated clay molecules. Dehydration occurs from 150 to 650°C.
When dry kaolin and fire clay are calcined at high tempera-
tures carbon dioxide is often driven off. Calcination tempera-
tures range from 600 to 9QO°C. Oxidation of ferrous iron and
organic matter in the clay take place from 350 to 900°C.
In addition to the normal products of combustion, clay
particles are entrained by the gas and carried from the dryer.
The emission factor for the drying of ceramic clay is 35 grams
of particulate per kilogram (70 Ib/ton) of input to the dryer.
The exhaust gas also contains some organics and ferrous oxide.
Hydrogen fluoride is emitted from the dryer and from the firing
kilns. Acid gases formed by combining small amounts of fluoride
and silicate into fluosilicic acid may also be emitted from the
dryers.
The material is often conveyed to the next process by belt
conveyors, with possible particulate air pollution discharge
3-11
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at the transfer points.
(5) Finishing - Finishing operations involve physical changes of
the clay to prepare it to final specifications.
The first step involves grinding the clay to the desired
size. Fine grinding is done in a hammer, roller, ball, or impact
mill. As the clay is ground, it is continuously screened and
sized to meet product specifications. Screens and air flotation
are also used for particle size classification. Some special
additives are mixed with the clay at this point.
The clay is then prepared for shipping by bagging or it
is shipped as dry bulk in rail cars. Some kaolin is shipped
in slurry form in tank cars. Since high temperatures are not
involved in these processes no hazardous materials are emitted.
Particluate is emitted from grinding and screening operations
and during bagging or bulk loading.
The beneficiated ores of kaolin, ball clay, fire clay,
bentonite, fuller's earth, and miscellaneous clay are then used
in manufacture of final products, described in the following
sections.
3.4.3 Porcelain Manufacturing
(6) Mixer - The raw materials, kaolin, ball clay, flint, and feldspar
are mixed and agitated with water to form a slurry, which is
then filtered and run through a magnetic separator. The only
pollution evolved in this process is the solid waste removed
by the magnetic separators and screens. Since this process
is operated at ambient temperatures and the clay moves to the
3-12
-------
next process in a slurry, there is no fugitive dust potential.
(7) Filter - A filter press is often used to remove the water from
the slurry. The slurry is forced onto a filter medium and solids
are collected as a cake on the filter surface. Another dewa-
tering method is vacuum filtration. The water removed in this
process is a potential source of water pollution. Transport
of the filter cake to the forming operation is not likely to
cause fugitive dust since the clay contains sufficient moisture
to prevent dust emissions.
(8) Forming - The clay from the filter is form-pressed either by
extrusion or slip casting. Plasticizers in the form of gums,
starches, polyvinyl alcohol, or waxes may be added at this point.
Water may be added to achieve the desired plasticity. A vacuum
of approximately 74 centimeters (29 inches) of mercury is main-
tained in the extruder to remove any pockets of air and to make
the clay denser. The clay is then forced out the extruder by an
auger, cut to the specified length, and formed into the desired
shape by jiggering. These processes are normally done at ambient
temperatures.
In slip casting, the slurry (or slip) is poured into a
porous plaster of paris mold. Water is absorbed into the mold,
and the solid particles are deposited on the mold interior.
The forming process, either by extrusion or slip casting,
is a negligible source of pollution. The formed ware is sent
to the dryer.
(9) Dryer - The clay ware in the dryer is heated slowly so as to
prevent cracking when it enters the kiln. Temperatures in the
3-13
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4 5
dryer range from 50 to 200°C. ' The dryers are heated by the
exhaust gases from the kilns, or fueled by natural gas, oil,
or coal. Emissions from dryers are mainly particulates, with
possibly some ferrous oxides, fluorides, organics, or organic
acids.
The ware is sprayed with a glaze before or after the dryer,
depending on the operation. Spraying may generate small amount's
of particulate emissions. The ware goes directly to the kiln
after drying.
(10) Kiln - In the kiln the ware is fired and vitrified. Tunnel
kilns are the most common; periodic kilns are also used. Porpe-
lain or whiteware products are fired at temperatures between
1200 and 1500°C. Firing time is generally from 40 to 270 hours.10
The kiln is fired with oil/ natural gas, or coal.
Emissions from firing include products of combustion and
fluorine emissions in the form of hydrogen fluoride, a hazardous
material. If the clay contains sulfur, additional SO- is given
off in excess of that formed by combustion. Any appreciable
amount of organic matter is volatilized and combusted, forming
a small amount of black smoke. Acids could be formed by the
combining of fluorine and silicate into fluosilicic acid.
The porcelain or whiteware product removed from the kiln
requires no further processing.
3.4.4 Refractory Manufacturing
Refractories are materials that maintain their physical
shapes and chemical identities when subjected to high temperatures.
3-14
-------
A wide variety of refractories is manufactured from different
clays. Although all clays are used for refractory materials,
fire clay predominates; bentonite, kaolin, and ball clay are
used in lesser amounts. Following are descriptions of the
processes for manufacturing refractories.
(11) Mixing and Forming - Mixing and tempering are often done in
a dry-pan muller-mixer, which thoroughly mixes all raw materials
and distributes any added water. This operation promotes plasti-
city while reducing the amount of entrapped air. Most refractory
brick is formed by dry or hydraulic pressing of damp mix in
a mold. Sometimes the brick is deaired by application of a
vacuum to the surface of the brick through small openings in
the press plates.
Although this process is carried out at ambient temperatures
and emissions are minimal, some particulate emissions may be
given off during the dry mixing.
(12) Dryer - Very large refractories are dried on a temperature-
controlled hot floor, heated by steam or air ducts. Smaller
shapes are generally processed in a tunnel dryer, which is heated
by waste heat from the kiln, or by burning of natural gas, oil,
or coal. The dryer may be humidity controlled. Dryer tempera-
9
tures range from 50 to 200°C.
Emissions from the dryer are mainly particulate, with the
possibility of some ferrous oxides, fluorides, or organics;
the latter are not likely because of the relatively low operating
temperatures. From the dryer, the refractory goes to the firing
3-15
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kiln.
(13) Kiln - Refractories are normally fired in a tunnel kiln. Periodic
kilns are used to a lesser extent. In the kiln the fire clay
is vitrified at temperatures ranging from 1200 to 1900°C.
Firing times range from 40 to 270 hours.
Emissions are the same as those from firing of porcelains:
products of combustion, hydrogen fluoride, and SO-, the latter
two depending on the amounts of fluorine or sulfur in the clay.
Volatilization and combustion of organic matter forms some black
smoke. A small amount of fluosilicic acid may be emitted.
When the fired refractory is taken from the kiln, it may
need some grinding to achieve the desired size and surface finish.
Grinding is a potential source of additional particulate emissions.
3.4.5 Brick Manufacturing
Miscellaneous clay is most commonly used in manufacturing
structural or heavy clay products; the brick manufacturing opera-
tion shown here is typical.
(14) Grinding - Dry-pan -crushers are often used to reduce the size
of the clay particles in preparation for extrusion. The grinding
is usually dry and at ambient temperatures and thus is a possible
source of particulate emissions. The emission factor for all
raw material handling, dryers, and grinders in brick manufacturing
is 48 grams (96 pounds/ton) of brick produced. When ground clays
are held in storage before extrusion, the emissions from storage
are about 17 grams per kilogram (34 Ib/ton) of brick produced.
Since the clay is finely ground, and relatively dry as
it is conveyed to the extruder, particulate emissions may occur
3-16
-------
at the transfer point.
(15) Extruding - In this process, the clay is mixed with water and
forced through an opening by an auger. A vacuum is drawn in
the extruder to remove air from the clay. As the clay is
extruded, it is cut off in block form then sent for drying.
Extrusion causes no known pollutant emissions.
(16) Dryer - To remove moisture before firing, brick is dried in
various ways: outdoors, in sheds, or in tunnel kilns. Tunnel
kilns are the most common. Temperatures in kilns for drying
q
brick range from 50 to 200°C. The dryers may be heated by
waste heat from the kilns, or fired by natural gas, oil, or
coal.
The major pollutants from dryers are particulate emissions.
Some emission of ferrous oxides, fluorides, or organics may
occur, but these are not likely because of the relatively low
operating temperatures. No emissions are evolved in the transfer
of brick from dryer to kiln.
(17) Kiln - Brick is normally fired in a tunnel kiln, with some use
of periodic kilns. The miscellaneous clay is vitrified at tem-
peratures ranging from 800 to 1100°C over periods of 40 to 270
hours. As with the other clay products, firing requires approxi-
mately 0.83 to 1.4 x 10 calories per kilogram (3 to 5 x 10
BTU per ton) of brick.10
Emissions from firing also are similar to those of other
clay products: products of combustion, fluorine as hydrogen
fluoride, possible additional S02, black smoke from any organic
matter, and possibly a small amount of fluosilicic acid.
When the brick is removed from the kiln it is ready for
3-17
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market.
3.5 MAJOR POLLUTANT SOURCES
Most of the environmental problems related to clay mining
and processing are concerned with miscellaneous clays. Clay
mining and kiln operations of the industry are important pollutant
sources.
° Clay Mining
A large number of mines are located in heavily populated
areas and cause some environmental problems. A considerable
amount of dust is generated, which does not create any known
hazardous effects, but does produce nuisance problems. Annual
emissions are approximately 30 million tons of waste material
from mining kaolin in Georgia, 2 million tons from mining fuller's
earth along the Georgia-Florida border, and 5 million tons
from mining bentonite in Wyoming.
Surface water pollution is also a problem in mining clay.
0 Kilns (for Porcelain, Refractory, and Brick Manufacturing)
Usually these kilns operate at high temperatures (800 to
1900°C) . Emissions include products of combustion. If the
clay contains sulfur, sulfur dioxide is emitted in excess of
that formed by fuel combustion. An appreciable amount of organic
matter is volatilized and combusted, forming a small amount of
black smoke. Fluorine is evolved as hydrogen fluoride.
3-18
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REFERENCES FOR CHAPTER 3
1. Ampian, S.G. Clays. In: Minerals Yearbook, 1971. U.S.
Bureau of Mines.
2. Cooper, J.D. Clays. In: Mineral Facts and Problems.
U.S. Department of the Interior, Washington, D.C., Bureau
of Mines Bulletin 650, 1970.
3. Brobst, D.A., and W. P. Pratt. United States Mineral
Resources. U.S. Department of the Interior, Washington D.C.,
1973.
4. Industrial Minerals and Rocks. Seeley W. Mudd Series. Ameri-
can Institute of Mining, Metallurgical, and Petroleum Engineers,
New York, 1960.
5. Kirk-Othmer Encyclopedia of Chemical Technology. New York,
McGraw-Hill Book Company. 1967.
6. Bentonite Deposits of Northern Black Hills Districts: Wyoming,
Montana, South Dakota. U.S. Geological Survey Bulletin No.
1082-M. U.S. Bureau of Mines. 1962.
7. Compilation of Air Pollution Emission Factors. U.S. Environ-
mental Protection Agency, Raleigh, N.C. Publication No.
AP-42. April 1973.
8. Shreve, R. N. Chemical Process Industries. New York, McGraw-
Hill Book Company. 1967.
9. Norton, F. H. Refractories, 3rd Edition. New York, McGraw-
Hill Book Company. 1949.
10. A Screening Study to Develop Background Information to Deter-
mine the Significance of Brick and Tile Manufacturing. Contract
No. 68-02-0607 Task 4. Research Triangle Institute, 1972.
11. Air Pollution Control Technology and Costs in Nine Selected
Areas. Industrial Gas Cleaning Institute, Inc., Stanford,
Connecticut. Prepared for Environmental Protection Agency
under Contract No. 68-02-0301. September 1972.
3-19
-------
4.0 GYPSUM INDUSTRY
4.1 INDUSTRY BACKGROUND
Gypsum is a natural mineral form of calcium sulfate
dihydrate (CaSG>4:2H20) occuring as a hard solid rock.
In 1971, the United States produced an estimated 9.45
million metric tons and consumed approximately 15 million
metric tons of gypsum. Main consumption of gypsum is as
prefabricated products (67.7 percent), portland cement
retarder (21 percent), and agricultural products (7 per-
cent) .
The projected demand for gypsum in the year 2000 is
between 29 and 43.5 million metric tons. Domestic reserves
of gypsum are estimated to contain 18.14 billion metric tons
and are distributed in 23 states.
In the United States about 80 percent of gypsum is
produced from open-pit mines and the remaining 20 percent
from underground mines.
Table 4.1 lists the states producing gypsum ore and the
number of active mines in each state. Table 4.2 lists the
states producing calcined gypsum and the number of active
plants.
Research in this industry is aimed at recovering sulfur
from crude or by-product gypsum.
4-1
-------
Table D-l in Appendix D lists the companies mining
gypsum.
Table 4.1 CRUDE GYPSUM MINED IN THE
UNITED STATES, BY STATE2
(thousand short tons and thousand dollars)
Btata
Ariiona »...,
California
Iowa
Michigan ....
ttovada
Naw YocX
Oklahoma ,.
South Dakota _ _
T«xaa
Wyoming .
Othar Statoa"
Total
fcctlv*
Inaa
4
7
12
(9
1910
Quantity
II
1.132
1.13C
1.312
491
42S
674
IS
1,220
211
2,557
9,436
Vilua
SJbl
J.271
4.293
5.061
1.457
2,737
2.616
61
4,252
XI
10,221
35,1)2
Actlra
dna
4
20
67
1*71
Ovuntlty
1.352
1.1S4
1,433
«9S
415
1.022
21
1,)0)
232
2,7»1
10, «H
Valoa
»J.»»«
4,4(0
5.515
2.372
2,37*
3,071
13
4,§0(
Sl«
11,900
39,057
H Withheld to avoid diaelojln? individual company confidantItl datai include with 'Other
State*.*
1 Includaa the following Statea to avoid diicloalng individual company oonlco (1171), Ohio, and Utah, 2 !» aaohi Kaiiaaa, 1 Binat I117t)>
Colorado, and Mm twxico (1170) 4 mlrwa.
Table 4.2 CALCINED GYPSUM PRODUCED IN THE
UNITED STATES, BY STATE2
(thousand short tons and thousand dollars)
Stat*
California
Florida
Gaorqia
lova
Michigan
Navadj
K*w J«ra«y
Maw Vork ~
Ohio
T«x»a ,_
Oth«r 3tAtaa_
Total
1970
Actlv*
Dlanta
7
3
3
S
4
3
4
7
3
7
30
76
Ouan-
_ lltv
122
431
531
713
32S
240
334
(74
321
870
2,974
1,449
Valua
110,403
5.194
1,432
12,301
(,130
3,435
4,715
11,551
4,9(4
14,273
47,5<»
132,047
Caleinln?
aquipaent
Kottlti
*
IS
22
»
12
t
21
9
2«
7>
229
Other-1
2'
II
Tl
1971
Actlva
Dlantj
1
1
5
4
3
4
7
3
7
29
74
Ouan-
Utv
111
ill
616
798
373
330
452
922
356
1,035
3,245
I.S26
Valua
"{16.131
S.7S9
ll.OSI
13.704
7.2C3
4.851
7.3(9
IS, (81
5,790
17,074
52.517
151,991
Calcining
^ulpiMnt
KattlB.
9
IS
22
9
12
9
21
9
30
77
231
Other1
1
4
1
(
4
8
1
1
37
49
1 Includaa rotary and b««hivo kilna, irlmllng-calolnlng onlti, Molo-rlltai, and Hydrocal cylind«ra.
2 Co«tprliea stataa and nuvbar of planta ai followat Ariiona, Arkanaaa, Colorado, Conneetlout, Dalawan,
lllinola, Haaaachuaatta, Montana. N«w na*f>ahlr«r Naw Haxlcx} (1971), r^nnaylvania and Washington, 1 plant
aachi Xanaaa, Loulalana, Maryland, Maw Kaxlco (1970), OUahona, Utah, Virginia and Hyo«lnj, 2 plant*
aachf and Indiana, 3 plant*.
4.2 RAW MATERIALS
Gypsum is classified according to the nature of its
occurrence. The several types of gypsum deposits are de-
scribed in the following paragraphs.
4-2
-------
1. Bedded Deposits - The most important commercial
source is gypsum beds, in which massive gypsum occurs in one
or more layers, associated with such materials as limestone,
shale, and sandstone in stratified series. In many dis-
tricts like those of New York, Michigan, Ohio, Iowa, and
Kansas, the gypsum and enclosing strata are nearly hori-
zontal.
2. Surface Deposits - Accumulations of loose or earthy
gypsum are common in dry or semiarid climates, where the
ground waters come in contact with buried gypsum beds.
After dissolving the sulphate, the water reprecipitates it
in the form of gypsum or anhydrite when it reaches the
surface and evaporates. Gypsite is a very fine, almost
impalpable aggregate in which microscopic crystals of gypsum
(also anhydrite) are mixed with clay, carbonates, sand, and
organic matter.
3. Veins - Small fissures and cavities in the vicinity
of gypsum beds are likely to be filled by selenite and satin
spar that have been deposited by underground waters. The
shales and limestone associated with the gypsum beds of New
York are quite commonly intersected by innumerable small
veins.
4. Disseminated Gypsum - Clay and soft shale commonly
contain flakes and crystals of gypsum sparsely distributed
through their mass. Deposits of disseminated gypsum are of
no commercial value.
5. California Gypsum - Three types of gypsum occurring
as gypsite deposits have been recognized in California;
4-3
-------
those that form caps on upturned gypsiferous beds, those
that occur along the margins of periodic lakes, and those
that have formed in the beds of dry washes.
Gypsum in the form of selenite crystals dispersed in
mud occur in Bristol Lake, San Bernardino County, and in the
neighboring Cadiz and Danby Lakes.
At San Bernardino County, gypsum, salt, and celesite
occur in zones. They consist of a gypsum-bearing unit, a
salt-bearing unit, and saline-free sedimentary rocks that
enclose the gypsum and salt beds. The gypsum-bearing unit
consists of 183 to 244 meters (600 to 800 ft.) of predomi-
nantly light tan sedimentary rocks in which gypsum occurs as
relatively thin beds alternating with greenish, gypsiferous
clay.
4.3 PRODUCTS
Plaster of paris and gypsum board are the main commer-
cial forms of gypsum. An analysis of gypsum from Michigan
and California is given in Table 4.3.
Table 4.3 ANALYSIS OF GYPSUM
(percent)
Composition
Si02
R2°3
CaO
Mgo
Ignition loss
S03
Combined H_O
Free water
Iron & aluminum oxide
co2
Not determined
Michigan3
0.36
0.74
32.68
0.99
22.61
42.45
-
-
-
-
4
California
18.52 (includes
solubles)
24.36
0.46
33.70
15.53
2.88
1.86
1.07
1.62
4-4
-------
4.4 PROCESS DESCRIPTION
In processing of gypsum, the mined ore is upgraded by
crushing, screening, and calcining before treatment to pro-
duce different forms of gypsum. The flow chart in Figure
4.1 illustrates gypsum processing.
4.4.1 Mining
About three-fourths of the gypsum is mined by open-pit
methods and the remainder by underground methods.
(1)* Open-pit mining - requires careful selection of deposits
that contain minimum overburden.
Air pollutant emissions are significant and a consid-
erable amount of solid waste is generated. About 1.1 tons of
overburden waste is produced for each ton of gypsum mined.
The overburden may contain glacial silt, sand, gravel, clay,
limestone, shale or other material. The gypsum dust gen-
erated from mining is harmless and is considered as a cure
for tuberculosis.
Overburden is removed by a variety of scrapers, power
shovels, and drag lines. After drilling, the broken ore is
loaded by power shovels into trucks.
(2) Underground mining - is usually done with open stop, room
and pillar methods. Environmental problems are negligible.
4.4.2 Upgrading
The gypsum ore is upgraded by crushing and grinding.
(3) Crushers and Mill - Primary crushing of the ore is accom-
plished at the mines. A secondary crushing is the initial
* Numbers refer to corresponding processes in Figure 4.1.
4-5
-------
BEHTONITE
CELLULOSE FIBER
OETERGEHT AND
LIGMXN
PERLITE
KLUtllMUH SULFATE
RETARDER
CVPSUM
BOARD
Figure 4.1 Gypsum industry
-------
operation at the plant. The material is milled and then may
be dried with air heated by an oil or natural gas unit.
About 0.5 gram of particulate is emitted per kilogram (1
Ib/ton) of gypsum milled. If a dryer is used, about 20
grams of particulate per kilogram (40 Ib/ton) of gypsum is
emitted to the atmosphere. Emissions from the dryer can be
reduced to about 0.1 gram of particulate per kilogram (0.2
Ib/ton) of gypsum by use of fabric filters.
(4) Calcination - The dried material is calcined in heated,
agitated kettles for about 2 to 3 hours at a constant
temperature of 160°C. During calcination, water of hydra-
tion is released from the gypsum rock resulting in a gas
stream containing moisture. Calcium chloride is added
during calcination to reduce the moisture content of the
calcined product.
Both vertical and rotary kilns fired by oil or natural
gas are in use. When the ground ore is heated at 121 to
149°C, the product is first-settle plaster (CaSO4-l/2 H20),
which is used to make gypsum board. Further heating to
190°C yields an anhydrous product called second-settle
plaster.
The most significant source of emissions in gypsum
processing is the calcining operation. The turbulent gases
created by the release of the water of crystallization
carry calcined and partially calcined gypsum into the
atmosphere.
4-7
-------
About 45 grains of particulate per kilogram (90 Ib/ton)
of gypsum is emitted from calcining operations; these emis-
sions can be controlled by using fabric filters.
The dust particles are relatively large compared with
those from processes in which the material is vaporized and
condensed. Since the moisture content of the dust is
significant, resistivity is not a problem.
The gas flow ranges from a minimum around 0.14 x 10 to
6 3
37.8 x 10 cm /sec for rotary calciners. Gas velocities
range from 45.7 to 244 cm/sec (1.5 to 8 ft/sec). Dust
loadings are around 9.1 to 137 x 10~ gm/scm d. Gas tem-
peratures are around 93 to 177°C.
(5) Mill and Mixer - The calcined product is ground in a mill to
a finished size of 100 mesh (99%) and marketed as stucco, or
further processed for making gypsum plaster by addition of
wetting agents (detergents, cellulose fibers, etc.) and
several fillers. The calcined gypsum is also used to pro-
duce gypsum board.
Considerable amounts of dust are evolved from the
mills.
(6) Mixer (for gypsum board production) - The calcined gypsum
entering this section of the plant is slurried with paper
pulp. Fillers such as raw gypsum and foam are added to
lighten the slurry. The paper pulp is prepared by adding
paper, water, potash, lignin, and starch.
Emissions are negligible.
4-8
-------
(7) Chipboard and Cutter - The slurry is sandwiched between two
thin sheets of special chipboard, the thickness is adjusted,
and the board is cut into sections.
Solid particles are emitted.
(8) Dryer - The board enters the dryer and is exposed to re-
circulating air fanned through steam coils. The entering
board contains 32 percent moisture, most of which is re-
moved .
Particulates are emitted, but emission rate data are
not available.
4.5 MAJOR POLLUTANT SOURCES
Gypsum dust is generated by mining and processing, but
is supposedly one of the least harmful dusts.
Overburden of open-pit mining is indicated to be
removed in a ratio of about 1.1 tons of waste for each ton
of gypsum mined. Calciners and dryers are main pollution
sources of the industry. Emissions from the calciner
include about 45 grams of calcined and partially calcined
gypsum per kilogram of gypsum produced.
4-9
-------
REFERENCES FOR CHAPTER 4
1. Schroder, J.H. Gypsum. In: Mineral Facts and Prob-
lems. U.S. Department of Interior. Washington, D.C.
Bureau of Mines Bulletin Number 650. 1970.
2. Reed, A.J. Gypsum. In: Minerals Yearbook. U.S.
Bureau of Mines, 1971.
3. Private communication with Michigan Gypsum Co., Saginaw,
Michigan.
4. Ver Tlanck, W.E. Gypsum in California. California
Division of Mines Bulletin, 1952.
5. Compilation of Air Pollution Emission Factors. Con-
tract No. CPA-22-69-119.
6. Southern Research Institute. A Manual of Electrostatic
Precipitator Technology. Part II - Application Areas.
Contract No. CPA-22-69-73.
7. Taeler, David H. Gypsum Plant by the Numbers. Minerals
Processing, January 1967.
8. Seeley W. Mudd Series. Industrial Minerals and Rocks.
The American Institute of Mining, Metallurgical, and
Petroleum Engineers. New York, 1960.
4-10
-------
5.0 LIME INDUSTRY
5.1 INDUSTRY BACKGROUND1
In 1971, the United States produced and consumed an
estimated 17.8 million metric tons of lime. Though there
was an increase in production, the number of producing
plants decreased from 209 in 1967 to 187 in 1971. Four
principal usages of lime were chemical, 79 percent; con-
struction, 12 percent; refractory, 8 percent; and agricul-
tural, 1 percent. In 1969, about 5 percent of the limestone
2
mined in the United States was used for lime production.
Lime is produced in 42 states and consumed by all
states. Six states, Ohio, Pennsylvania, Missouri, Texas,
Michigan, and New York, produce about 59 percent of total
domestic output. Five states, Ohio, Pennsylvania, Texas,
Michigan, and Indiana, accounted for 50 percent of total
lime consumption. Table 5.1 gives the number and production
of domestic plants.
Table 5.1 LIME PRODUCED IN THE UNITED STATES,
BY SIZE OF PLANT1
(thousand short tons)
III* of Plant
L*** than 10.000 ton*
10,000 to 35,000 ton*
25.000 to 50,000 ton*
30,000 to 100,000 ton*
100,000 to 200,000 ton.
200,000 to 400,000 ton>
Mora than 400,000 tone.
Total
1171
riant*
10
17
17
21
25
26
7
111
Quantity
131
S»0
1,401
1,175
3.105
7,215
4.701
11. US
P*rc*nt
of Total
1
1
' 7
»
19
17
24
100
1) exclude! r*q*n*r*,t*
-------
Most lime producers own their source of supply and have
ample reserves of ore.
Table E-l of Appendix E lists companies processing
lime, Table E-2 gives lime production in the United States
by state, and Table E-3 gives lime production in the United
States by size of plant.
5.2 RAW MATERIALS
The main raw material "limestone" is composed of at
least 50 percent calcium carbonate and various impurities,
such as magnesium carbonate, alumina, silica and iron com-
pounds. The limestone is referred to as high calcium when
it contains less than 5 percent magnesium carbonate and as
dolomite when it contains 30 to 45 percent magnesium car-
bonate. Table 5.2 gives a typical analysis of limestones
from different sources in the United States, and Table 5.3
gives the mass spectrographic analyses of limestones.
A small percentage of lime is manufactured from oyster
shells. Although limestone deposits are found in every
state in the U.S., only a small portion is pure enough for
industrial use.
5.3 PRODUCTS
The usual products are limestone, quicklime, and
hydrated lime. Table 5.4 lists the typical analyses of
commercial quicklimes.
5.4 PROCESS DESCRIPTION
Lime (CaO) is produced by calcining limestone and
dolomite at high temperatures. The lime is further reacted
5-2
-------
Table 5.2 REPRESENTATIVE CHEMICAL ANALYSES OF DIFFERENT TYPES OF U. S. LIMESTONES
Component
CaO
MgO
C02
Si°2
A12°3
Fe203b
S03°
P2°5
Na2°
K2°
H2°
Other
Limestone, %a
1
54.54
0.59
42.90
0.70
0.68
0.08
0.31
0.16
2
38.90
2.72
33.10
19.82
5.40
1.60
3
41.84
1.94
32.94
13.44
4.55
0.56
0.33
0.22
0.31
0.72
1.55
0.29
4
31.20
20.45
47.87
0.11
0.30
0.19
0.06
5
29.45
21.12
46.15
0.14
0.04
0.10
0.05
0.01
0.01
0.16
0.01
6
45.65
7.07
43.60
2.55
0.23
0.20
0.33
0.04
0.01
0.03
0.23
0.06
7
55.28
0.46
43.73
0.42
0.13
0.05
0.01
0.08
8
52.48
0.59
41.85
2.38
1.57
0.56
n.d.
0.20
in
I
CJ
a) 1 = Indiana high-calcium stone. 5
2 = Lehigh Valley, Pa., "cement reck". 6
3 = Pennsylvania "cement rock". 7
4 = Illinois Niagaran dolomitic stone. 8
Northwestern Ohio Niagaran dolomitic stone.
New York magnesian stone.
Virginia high-calcium stone.
Kansas Cretaceous high-calcium stone (chalk)
b) Includes some Fe as FeO.
c) Includes some elemental S.
-------
Table 5.3 SPARK SOURCE MASS SPECTROGRAPHIC ANALYSES OP
LIMESTONES (WEIGHT PERCENT)
Element
Mn
Fe
Cu
Zn
As
Rb
Sr
Y
Cs
Ba
Pb
Br
Li
B
C
N
F
Na
Mg
Al
P
S
Cl
K
Ti
V
Cr
Si
Ca
Ga
Ms
Sn
Ni
Co
Mo
Limestone
(1)
0.0140
0.25
N.D.
0.0059
N.D.
0.00017
0.15
N.D.
N.D.
0.001
N.D.
N.D.
0.00018
0.00015
0.49
0.00045
0.0012
0.036
(>1%)
0.42
0.0085
0.022
0.0038
0.058
0.044
0.0015
0.0076
Limestone
(2)
0.015
0.09
N.D.
0.0006
0.0011
0.00007
0.022
N.D.
N.D.
0.000031
0.00008
0.00022
0.00043
0.17
0.4
0.33
0.005
0.003
0.00043
0.033
0.016
0.00053
0.0019
Limestone
(3)
0.025
0.07
0.00
N.D. <0.06
0.039
N.D. <0.20
N.D. <0.01
N.D. <0.005
TR <0.06
0.3
0.009
N.D. <0.5
-
N.D. <0.004
-
0.001
0.24
39
N.D. <0.006
-
N.D. <0.008
N.D. <0.002
N.D. <0.002
Limestone
(4)
0.011
0.10
0.00011
0.078
N.D. <0.01
N.D. <0.005
0.036
2.9
0.012
N.D. <0.20
N.D. <0.003
0.00084
0.65
35
N.D. <0.002
N.D. <0.001
N.D. <0.001
Nil
5-4
-------
with water to form calcium hydroxide Ca(OH)_, which is
called hydrated lime when it is in a dry state, or slaked
lime when it is marketed wet. The flow diagram in Figure
5.1 shows the steps involved in lime processing.
Table 5.4 TYPICAL ANALYSES OF COMMERCIAL QUICKLIMES2
Component
CaO
MgO
Si°2
Fe2°3
A12°3
H2°
CO 2
High-Calcium
Quicklimes, Range
Percent
93.25-98.00
0.30- 2.50
0.20- 1.50
0.10- 0.40
0.10- 0.50
0.10- 0.90
0.40- 1.50
Dolomitic Quicklimes,
Range Percent
55.50-57.50
37.60-40.80
0.10- 1.50
0. 05- 0.40
0.05- 0.50
0. J.O- 0.90
0.40- 1.50
5.4.1 Mining
Limestone is obtained by open-pit and underground
mining methods.
(1*) Open-pit mining - Dust is released to the atmosphere from
open-pit quarrying, loading, and unloading of quarry ore.
The composition of dust is the same as that of limestone
quarried (see Table 5.1). Dust suppression is achieved by
spraying water and by treating roads with CaCl. and road
oil.
* Numbers refer to corresponding processes in Figure 5.1.
5-5
-------
ASPHALT BASED OIL
I
O5
FERROSILICON
MAGNETITE ORE
DIFFERENT SIUO
REFRACTORY GRAINS OF
-BURN LIME
uATEIt
AIR
la.
HfORATOSI
u
-"1
DRYER
QUICK LIME
STREAH
Figure 5.1 Lime industry
-------
Broken stones from quarries are loaded into cars and
transferred to the crushing plants.
(2) Underground mining - This is costlier than open-pit mining
and does not involve stripping operations.
The process releases less dust to the atmosphere than
does open-pit mining.
The rock is mined and loaded into cars and hauled to
crushing plants in car trains by locomotives.
5.4.2 Beneficiation
Involves a series of crushing, screening, and con-
centration operations.
(3) Crushing and Screening - The rock is reduced to lumps by
crushing in primary and secondary crushers and screened.
Usually the primary crushers are located at the mine site.
Crushing and screening cause considerable emission of
dust, which is usually collected and either discarded or
blended with the finest size stone product. Without con-
trols, about 15.5 grams (31 Ib/ton) of dust from the primary
crusher and 1 gram (2 Ib/ton) of dust from the secondary
crusher are emitted per kilogram of product crushed.
The ore is brought to the crushing units in car trains.
The crushed product is dropped onto a feed hopper located
just above a belt conveyor, which takes the crushed product
to storage.
Concentration - For further upgrading, some plants use
heavy-media separators to remove granite and silica from the
crushed ore. The heavy-media separator contains a mixture
5-7
-------
of ferrosilicon and magnetite ore (Fe_0.). Recycled water
is introduced into the separator from the side and air under
pressure from the bottom. The ore is segregated by air
flotation. The dolomite sinks to the bottom by specific
gravity and is forced out through a pipe, whereas the
lighter reject rock floats on the surface and is skimmed off
separately. Undesirable silica and granite ores are dis-
posed of as solid waste. Both dolomite and reject rock are
washed to recover the media. Some plants use thickeners and
a magnetic separator. Some companies occasionally dry the
limestone in a rotary drier for better grinding.
5.4.3 Calcination
Calcination is the major source of particulate emis-
sions in lime manufacturing. The different sized ores are
calcined at different temperatures to produce refractory
(dead-burned dolomite), lime, and quicklime.
Calcining is accomplished in several types of kilns,
differing in configuration, capacity, fuel economy, size
stone required, and product. Vertical kilns are the most
efficient in fuel usage. Rotary kilns give much higher
production rates but also produce more particulate emis-
sions. Slightly more than 80 percent of the total lime
produced in the U.S. is calcined in rotary kilns.
Kilns are fired with natural gas or pulverized coal.
Calcination of the materials for quicklime and re-
fractory lime produces similar emissions. Rotary kilns emit
about 90 grains (180 Ib/ton) of particulate and vertical
5-8
-------
kilns emit only 3.5 grains (7 Ib/ton) of particulate per
kilogram of lime produced. The particulate emissions
include raw limestone, lime dust, and fly ash in the range of
4.6 to 45.8 x 10 grams/scm .
The gaseous effluents consist of carbon dioxide, water
vapor, and nitrogen. Sulfur dioxide and sulfur trioxide are
also emitted if sulfur-containing oil or coal is used as
fuel. Temperature of the gaseous effluent is usually
between 420 and 980°C. Table 5.5 gives a typical exhaust
gas composition, and Table 5.6 gives the amount of exhaust
gas produced from various sizes of rotary kilns.
Table 5.5 A TYPICAL OVERALL KILN EXHAUST
GAS COMPOSITION7
N2
C02
H2°
°2
-
59.7%
24.3%
15.3%
0.7%
(by vol.)
Table 5.6 TYPICAL EXHAUST GAS PRODUCTION FOR
VARIOUS KILN SIZES7
Exhaust Gas, sm /sec
Process wt.
tons lime
produced per day
113
227
454
Gas-
fired
kiln
5.19
12.6
22.1
Fuel/lime ratio
coal-fired kiln
1:3
8,800
17,600
35,200
1:4
6,900
13,800
27,600
1:5
5,700
11,400
22,800
5-9
-------
The lime industry also causes odor pollution, mainly
g
due to kiln operations.
(5) Kiln - In calcination for quicklime concentrated limestone
of proper size is calcined at temperatures ranging from 1100
to 1370°C. The product is sold directly or further pro-
cessed for hydrated lime.
The limestone dust released in the kiln becomes more
friable as it approaches the decomposition temperature.
Dust emissions from rotary kilns range from 5 to 15 percent
of the weight of the lime produced. Temperatures of exhaust
gases from the kiln vary from 310 to 980°C. Particulate
composition may be raw limestone or dolomite dust, or cal-
cined product dust. Calcining a metric ton of high-calcium
quicklime requires approximately 780 million calories of
heat. After the calcined material is cooled and screened,
the fines are used as by-products and the coarse material
stored for sale.
Table 5.7 gives a typical chemical analysis of emis-
sions from a kiln producing quicklime.
Table 5.7 TYPICAL CHEMICAL ANALYSIS OF LIME
KILN EMISSIONS4
Component
CaO
CaCO3
Ca(OH)
MgO
CaSO
r j
Heavy metal oxides
Acid insoluble
High-calcium
operation, %
66.32
23.06
6.37
1.4
1.22
0.97
0.66
5-10
-------
If pulverized coal is used as a fuel, the particulates
would also include fly ash (consisting mostly of the oxides
of silicon, aluminum and iron) and soot and tars resulting
from incomplete combustion.
(6) Kiln - The concentrated limestone of 0.635 cm screen over-
flow is combined with iron oxide (about 5% by weight) and
calcined in the kiln at 1820°C. The calcined product is
called burned dolomite. Heat requirements are about 720
million calories per metric ton of dolomite quicklime
produced. Particulate emissions are similar to those from
calcination for quicklime. Table 5.8 gives an analysis of
emissions from a kiln producing dolomite lime.
Table 5.8 TYPICAL CHEMICAL ANALYSIS OP LIME
KILN EMISSIONS4
Component
CaO
CaCO,
Ca (OH) 2
MgO
CaSO.
Heavy metal oxides
Acid insoluble
Dolomitic
operation, %
7.23
64.3
28.2
0.27
0.35
0.45
If pulverized coal is used as a fuel, the particulates
would also include fly ash (consisting mostly of the oxides
of silicon, aluminum and iron) and soot and tars resulting
from incomplete combustion.
5-11
-------
5.4.4 Finishing Operations
(7) Crushing and Screening - The dead-burned dolomite is crushed;
part is sent for coating, and the remainder is screened to
yield various sizes of refractory grains.
Without controls, a small amount of dust is emitted to
the atmosphere. Lime dust is friable and can cause irri-
tation of the nose and throat.
(8) Coating - In the coating section, the crushed dead-burned
dolomite is coated with asphalt-based oil and heated to 82°C
to prevent hydration. Hydrocarbons may be emitted.
(9) Hydrator - Although most of the quicklime is marketed, a
small portion is reacted with water to produce hydrated
lime. In the hydrator, water is added to the quicklime and
agitated to produce intimate contact. The lime (CaO)
reacts with water to produce hydrated lime Ca(OH)2. Large
amounts of steam and air are discharged to maintain constant
pressure in the hydrator. Table 5.9 gives a range of
typical chemical analyses of commercial hydrates.
Table 5.9 RANGE OF TYPICAL CHEMICAL ANALYSES OF
COMMERCIAL HYDRATES7
Con.ponent
CaO
MgO
H,O
CO,
Si02
High-calcium, %
71-74
0.5-2
24-25
0.3-0.7
0.2-0.5
0.1-0.3
Highly hydrated
dolomitie, »
45-41
25-30
27-28
0.3-0.7
0.2-0.5
0.1-0.3
The exothermal reaction of lime and water produces
hydrated lime powder (which is semidry). Fine dust, driven
5-12
-------
out by steam and moist air, has the same composition as the
hydrated lime being produced. On settling, this dust may
react with carbon dioxide in the air to form calcium and
magnesium carbonates.
Particulates are emitted in concentrations from 0.02 to
fi O
2.15 x 10 gram/cm .
(10) Dryer - The hydrated lime is dried in a dryer fired with
natural gas or oil. If excess water has been added in the
hydrator, additional heat must be supplied during drying.
Particulate emissions may be substantial.
(11) Milling and Bagging - The product is milled, then bagged for
subsequent shipping.
Table 5.10 summarizes overall particulate emissions
from lime processing. Material handling in the lime plant
emits about 2.5 grams of particulate per kilogram (5 Ib/ton)
of lime produced.
5.5 MAJOR POLLUTANT SOURCES
Many operations of the lime industry emit air pollu-
tants, but the kiln exhaust gases represent the single
largest source of airborne particulate matter.
0 Kiln Operations - As discussed in preceding sections,
both rotary and vertical kilns are used in calcining for
lime product. Rotary kiln emissions are large in comparison
to those from vertical kilns.
The nature and composition of air pollutants emitted
from the rotary lime kilns are functions of the type of
5-13
-------
Table 5.10 REPORTED DUST EMISSON VALUES FROM LIME PLANT OPERATIONS
Operation
Limestone primary crushing
Limestone secondary crushing
Crushed stone stockpile
Pulverized limestone dryer
Limestone screening
Bulk loading
Stone unloading
Vertical lime kiln
Rotary kiln
Rotary kiln
Rotary kiln
Rotary kiln
Rotary kiln
Rotary kiln
Rotary kiln
Calcimatic kiln
Lime convey ing- transfer
points
Lime distribution system-
airveyor
Hydrating
Hydrating
Hydrating
Particulate
Emission
gm/m
0.037
0.124
0.004
4.67
0.378
0.020
Q. 69-2. 29
0.002
0.16-0.18
0.04
9.8
0.50
0.27-0.57
0.7-0.9
0.04
0.4-1.8
0.02
0.02-2.2
0.165
0.02
Collection
Efficiency
Poor
Good
60-70%
99.99
97.5
99.7
70.0
95.0
96-97
97.5
99.2
99+
Control Method
Water sprays
Cyclone & bag filters
Water sprays
Cyclone collector
None
None
Water sprays
None
Glass bag filter
4-stage cyclonic scrubber
4-stage cyclonic scrubber
High-efficiency cyclones
Single-stage precipitator
Venturi scrubber
Impingement scrubber
Glass bag filter
Cyclone collector
Cloth bag filter
Water sprays in stack
Wet scrubber
Wet scrubber
en
I
-------
Table 5.10 (continued). REPORTED DUST EMISSION VALUES FROM LIME PLANT OPERATIONS
l
i-1
Ul
Operation
Hydrating
Hydrating
Hydrate milling
Hydrate loader and packer
Particulate
Emission
igm'/ni
0.04
0.082
No visible dust
O.Q2
Collection
Efficiency
99+
99+
Control Method
Wet scrubber
Wet scrubber
Bag filter
Bag filter
-------
limestone charged and of fuel burned. The particulate
emissions include raw limestone and completely calcined lime
dust, fly ash, tar, and unburned carbon. The quantity of
dust emitted from a rotary lime kiln can be as high as 15
percent of the product lime weight. About 90 grams of
particulate are released in treating one kilogram (180
Ib/ton) of lime. The size of the dust being discharged from
the kiln may be as much as 30 percent below 5 microns and 10
percent below 2 microns. The dust emissions are considered
mainly a nuisance rather than a health hazard although lime
is irritating to eyes., respiratory membrane, and moist skin.
The gaseous effluent is usually between 420 and 980°C
and is composed of carbon dioxide, water vapor, and nitrogen.
Sulfur dioxide and sulfur trioxide are also emitted if
sulfur-containing oil or coal are used as fuels. An over-
all kiln exhaust gas composition is presented in Table
5.5.
These emissions can be controlled by use of proper
control equipment. Table 5.10 presents control methods and
collection efficiency of equipment.
0 Crushing Operations - Crushing and material handling
operations are another significant source of particulate
emissions in the lime industry. The crushers emit about 12
grams of particulate per kilogram (24 Ib/ton) of rock
crushed.
5-16
-------
REFERENCES FOR CHAPTER 5
1. Reed, A.H. Lime. In: Minerals Year Book, U.S. Bureau
of Mines. 1971.
2. Kirk-Othraer, Encyclopedia of Chemical Technology. New
York, John Wiley and Sons, Inc., Second Edition. 1967.
3. Radian Corporation's Report, Radian Corporation,
Austin, Texas. Contract No. 68-02-0046.
4. Resource Research, Inc., A Study of the Lime Industry
in the State of Missouri for the Conservation Commission
of the State of Missouri. January 1968.
5. Compilation of Air Pollutant Emission Factors. U.S.
Environmental Protection Agency. Raleigh, North
Carolina. Publication Number AP-42. April 1973.
6. Mitchell, R.J., Going Underground for Limestone. Rock
Products, Mining Processing. April 1964.
7. Hardison, L.C., et al. Study of Technical and Cost
Information for Gas Cleaning Equipment in the Lime and
Secondary Non-Ferrous Metallurgical Industries. Indus-
trial Gas Cleaning Institute, Inc., Rye, New York.
8. Laamanen, Arvo. Views on Clean Air Protection Per-
taining to Construction Material Production, Construc-
tion, and Buildings. Text in Finnish. Rapenuustek-
nikka, Vol. 5:256, 1969.
9. Lewis, C.J. and B.B. Crocker, The Lime Industry's
Problem of Airborne Dust. Journal of Air Pollution
Control, Vol. 19, No. 1, January 1969.
5-17
-------
6.0 PHOSPHATE ROCK INDUSTRY
6.1 INDUSTRY BACKGROUND1'2
The United States is the largest producer and consumer
of phosphate rock in the world, producing an estimated 40
percent and consuming approximately 35 percent of the
world's supply. In 1973, the U.S. produced approximately
38.6 million metric tons of rock and consumed 28.6 million
metric tons, exporting the remainder. About 70 percent of
domestic consumption of phosphate rock is as fertilizer.
The other major uses are in animal feeds, detergents,
electroplating and polishing of metals, insecticides, and
medicines.
Demand for phosphorus in the year 2000 is projected to
be 8 to 14.2 million metric tons for the United States and
29 to 56.2 million metric tons for the rest of the world.
In the United States phosphate rock deposits are found
in 23 states. Florida, the leading producer for many years,
furnished 83 percent of domestic production. Tennessee
produced 6 percent and western states (Idaho, Montana, Utah,
and Wyoming) produced 11 percent of domestic phosphate in
1971. North Carolina accounts for a small percentage.
Commercial deposits from Florida are expected to contain an
6-1
-------
ample supply of ore to the year 2000. High-grade Tennessee
deposits may last for only 10 to 20 years; large deposits of
low-grade ore are available in that area, however. Deposits
in the western states are located far from seaports and fer-
tilizer-consuming areas. Most of these deposits are very
deep and require underground mining.
In 1968, there were 28 companies (10 in Florida) and
the Tennessee Valley Authority operating phosphate rock
mines. Most manufacture phosphate fertilizers or elemental
phosphorus, usually in plants near mining operations. Six
companies and the TVA manufacture elemental phosphorus in 11
plants in six states. There are more than 1600 fertilizer
mixing plants in the United States. In 1968, about ten
Florida firms mined and processed phosphate rock and manu-
factured phosphoric acid and fertilizers.
Table F-l of Appendix F lists companies processing
phosphate rock, Table F-2 major producers of normal super-
phosphate, Table F-3 major producers of triple superphos-
phate, Table F-4 major producers of fertilizer granules,
Table F-5 producers of wet-process phosphoric acid, and
Table F-6 lists producers of thermal process phosphoric acid
and superphosphoric acid.
Research is required to solve problems concerning the
recovery of by-products, and disposal of wastes from mining
and processing. The phosphate industry faces environmental
problems, particularly in the southeastern states, where
6-2
-------
phosphate mining and processing industries are located very
close to urban areas.
6.2 RAW MATERIALS
. Most of the phosphorus occurs in minerals of the apa-
tite group, Ca1Q(P04, CO3)g(F, OH, Cl)2. Usually small
amounts of VO4,
substitute for PO. and Na, Sr, U, Th
and the rare earths substitute for Ca of phosphate rock.
Silica, clay, aluminum, and fluorine are present as im-
purities. Phosphatized limestones, sandstones, shales, and
igneous rocks are referred to as phosphate rock.
The tricalcium phosphate content of ore is also known
as B.P.L. (bone phosphate of lime). One percent of tri-
calcium phosphate is equivalent to 0.458 percent (P9O_) ;
« J
quantities vary from one deposit to another. The rock is
graded according to its B.P.L. content.
Table 6 . 1 shows the main phosphate rocrk producers in
the United States .
Table 6.1 PRODUCTION OF PHOSPHATE ROCK IN THE
UNITED STATES, BY STATE1
State
Florida
Tennessee
Western States
Mine production
Amount in metric tons
of total ore mined
97,220,000
4,309,000
4,420,000
?20^ content
of the rock
14.1
21.1
26.0
The phosphate ores found in different states are
described below.
6-3
-------
Florida - Production of rock in Florida, now the
world's leading producer, started in 1888. Of the two
available rocks, pebble and hard rock, pebble phosphate is
the more important, with B.P.L. content ranging from 66 to
70 percent. In the original sediment, the soft rock is
associated with the land pebble, which is a mixture of
phosphatic clays and sand. Exploiting the land pebble
deposits is a major problem of the phosphorus industry. The
uranium content of pebble fraction is higher than that of
the concentrate. Table 6.2 gives analysis for ?20 , CaO,
F, and U of Florida phosphate rock.
Table 6.2 ANALYSIS OF PHOSPHATE ROCK: FLORIDA
(in percent)
Compo-
sition
P2°5
CaO
F
U
Bone Valley Formation
Pebble
30.8
43.7
3.4
0.015
Concentrate
32.5
43.2
3.6
0.010
Hawthorn Formation
Pebble
23.8
40.0
2.7
0.009
Concentrate
29.9
44.8
3.3
0.007
Tennessee - Of the brown, blue, and white phosphate
rocks available, the brown variety is the only one of in-
dustrial importance. It contains about 60 percent B.P.L.
and the remainder is iron, aluminum, silicon, and calcium.
Production of phosphate rock in Tennessee began in 1894.
6-4
-------
Western States - The leading western producers, in
order of quantity produced, are Idaho, California, Montana,
Utah, and Wyoming. The B.P.L. content of western rocks
ranges from 60 to 70 percent. Uranium is found in the
phosphatic beds in amounts ranging from 0.01 to 1.2 percent
U2°5* Takle 6.3 presents typical analyses of commercial
phosphate rock. Table 6.4 presents a spectrographic anal-
ysis of eocene rocks from four areas in Wyoming and Utah.
6.3 PRODUCTS
The major product of the phosphate rock industry is
fertilizer. The major phosphatic fertilizer of the several
kinds produced is triple or concentrated superphosphate.
Other fertilizers are ammonium phosphates, ammonium phos-
phate sulfate, calcium metaphosphate, and magnesium ammonium
phosphate. Elemental phosphorus and phosphoric acid are
also produced. Ferrophosphorus is produced, primarily in
Tennessee, and sold as a ferroalloy to the steel industry.
Minor elements that can be recovered as by-products
include fluorine, vanadium, uranium, scandium, and rare
earths. Because of the vast tonnages available, marine
phosphorites constitute significant resources of these
elements. All these elements except scandium have been or
are being recovered from the wet phosphoric acid manufac-
turing process; vanadium is recovered in the thermal phos-
phoric acid manufacturing process.
The wet process of producing phosphoric acid also
produces impure calcium sulfate (gypsum) as a by-product.
6-5
-------
Table 6.3 REPRESENTATIVE ANALYSIS OF COMMERCIAL PHOSPHATE ROCKS"
Component
P,0_
2 3
CaO
MgO
A1203
Fe2°3
SiO-
S03
F
Cl
C°2
Org. Carbon
Na,0
K2°
H20
Zr.O
Location sr.d Type
Florida
High Grade
Land Pebble
35.5
48.8
0.04
0.9
0.7
6.4
2.4
4.0
0.01
1.7
0.3
0.07
0.09
0.09
1.8
Furnace Grade
Land Pebble
30.5
46.0
0.4
1.5
l.S
8.7
2.6
3.7
0.01
4.0
0.5
0.1
0.1
0.1
2.0
Hard Rock
High Grade
35.3
50.2
0.03
1.2
0.9
4.3
0.1
3.8
0.005
2.8
0.3
0.4
0.3
0.3
2.0
Tennessee
Hard Rock
Waste Pond
23.0
28.5
0.4
14.8
2.9
19.8
0.01
2.1
0.005
1.4
0.3
0.1
0.4
0.4
7.0
Brown Rock
High Grads
34.4
49.2
0.02
1.2
2.5
5.9
0.7
3.8
0.01
2.0
0.2
0.2
0.3
0.3
1.4
Brown Rock
Furnace Grade
21.2
29.1
0.6
10.0
6.2
25.6
0.4
2.2
1.2
0.3
0.3
0.4
2.4
2.5
Western States
High Grade
Phosohate Rock
32.2
46.0
0.2
1.0
0.3
7.5
1.7
3.4
0.02
2.1
1.8
0.5
0.4
0.4
2.5
Low Grade
Phosphate Rock
X9.0
23.3
1.4
5.9
4.0
27.4
1.9
1.8
4.0
5.0
1.5
1.0
2.5
3.5
-------
Table 6.4 QUANTITATIVE SPECTROGRAPHIC ANALYSIS FROM THE
FOUR AREAS OF EOCENE ROCKS STUDIED IN WYOMING AND FROM
THE UI.NTAH BASIN, UTAH (in percent)4
Elementa
Si
Al
Fe
Mg
K
Na
Ca
Ti
Ba
V
Mn
Sr
Zr
B
Cr
Cu
Ni
La
Y
Sc
CO
Pb
Ga
Kb
Yb
Be
Mo
Li
Ce
Nd
Th
Sn
Sm
Dy
Er
Gd
Wyoming
Area 1 (Green River) Area 2 Area 3 Area 4
Zone 1
>10
7.0
1.5
3.0
5.0
7.0
>10
0.3
0.07
0.015
0.07
0.15
0.03
0.015
0.007
0.007
0.003
0.015
0.05
0.005
0.007
0.007
0.0015
0.0015
0.007
0.0003
0.0003
0.0
0.05
0.03
0.03
0.010
0.015
0.0
0.0
0.0
Zone 2
>10
7.0
3.0
7.0
3.0
3.0
>10
0.15
0.07
0.015
0.03
0.3
0.005
0.007
0.007
0.003
0.003
0 .007
0.015
0.0015
0.0007
0.003
0.0007
0.0
0.0015
0.0
0.0
0.015
0.0
0.007
0.03
0.0
0.0
0.0
0.0
0.0
Zone 3
7
3
0.7
7.0
3.0
1.5
>10
0.07
0.15
0.007
0.03
0.3
0.003
0.007
0.003
0.0015
0.0015
0.0
0.007
Trace
0.0003
0.0
0.00015
0.0
0.0007
0.0003
0.0007
0.0150
0.000
0.0
0.0
0.0
0.0
0.0
0.0
0.0
(Pino Moun-
tain)
>10
5.0
2
0.7
1.5
3.0
>10.0
0.1
0.1
0.01
0.07
0.2
0.03
0.0
0.007
0.003
0.003
0.003
0.007
0.0015
0.0015
0.005
0.0005
0.0
0.0007
0.0003
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.007
0.007
0.007
Bo.iver-
dcnicis
>10
7.0
1.5
1.5
7.0
3.0
7.0
0.15
0.15
0.015
0.07
0. 15
0.015
0.003
0.007
0.007
0.003
0.07
0.03
0.0015
0.0007
0.003
0.0015
0.0
0.0015
0.0
0. 0007
0.0
0.07
0.03
0. 03
0.0
0.0
0.0
0.0
0.0
Lysito
Mountain
>10
7.0
1.5
0.7
5.0
1.5
>10.0
0.15
0.07
0.007
0.07
0.15
0. 007
0.0
0.003
0.0015
0.0015
0.007
0.007
0,003
0.0005
0. 0015
0.0007
0.0
0.0007
0.00015
0.0007
0.0
0.03
0.015
0
0.0
0.0
0.0
0.0
0.0
Utah
Ointah Basin
>10
7.0
3.0
3.0
3.0
3.0
>10.0
0.15
0.07
0.015
0.07
0.07
0.015
0.007
0.007
0.007
0.003
0.003
0.007
0.0015
0.0007
0..015
0.0007
0.0
0.0015
0.0
0.0
0.007
0.0
0.0
0
0.0
0.0
0.0
0.0
0.0
a) Elements looked for but not found: Aq, As, Au, Di , Cd, Eu, Ge, tlf, lig,
Ho, Ln, Ir, Lu, Os, Pd, Pr, Pt, Re, Ru, Sb, Ta, Tc, Ti, Tm, W, 7,n.
Elements not looked for: Cs, F, Rh.
The values of U and P arc omitted.
6-7
-------
The slag from phosphorus furnaces is normally wasted.
At some plants it is crushed and used as aggregate and
ballast for railroads.
6.4 PROCESS DESCRIPTION
The following sections describe the processes involved
in the production of phosphate products.
(1*) 6.4.1 Mining
Most of the phosphate rock is mined by open-pit meth-
ods. Some producers in western states also practice under-
ground mining.
In Tennessee, Florida, and western states vast deposits
of phosphatic limestone are found above, below, and inter-
bedded with phosphate strata. These limestones vary greatly
in phosphate content.
A considerable amount of dust is evolved from mining.
In preparation of Florida pebble phosphate, approximately
one-third of the P2°5 ^n ^e ^eP°sits is discharged as
waste. This material consists of clay and finely divided
phosphate minerals. Ores are usually covered by 1.2 to 9.1
meters overburden.
In Florida, large electric, dragline excavators equipped
with buckets are used for stripping of overburden and mining
the ore, which is slurried and pumped to the washing plant.
In Tennessee and western states the ore is mined with
small dragline excavators and shovels, then transported to
beneficiating plants by trucks.
* Numbers refer to corresponding processes in Figure 6.1.
6-8
-------
O5
I
CO
MHFICATIM
2
MUIIC
-
)
wtfi ADO
ncvwn iS2.
novwuc Kit,
ncsmMi HU_
'".r'
?
IfAClOl
?
II
AND QilEI
MUI
tOOlti
?
(IA»UL>TOI
AID OltEl
1
1
|
1 \ /
| SU'EI
1
1 /^~*\
1
'.O
1 \J
I 01AMMOIIUK
Figure 6.1 Phosphate industry
-------
Top slicing and sublevel stopping methods are used in
western underground mines.
6.4.2 Beneficiation
All North Carolina, Florida, and Tennessee ores must be
beneficiated before further processing. Much of the western
phosphate rock does not need beneficiation. The ore is
washed, dried, and ground.
(2) Washing - The sand and clay impurities of ore are removed by
washing and screening, by use of a log washer and various
other types of classifiers. Mills are used to disintegrate
the large clay balls. When required, the ore is further
concentrated with flotation agents. In 1968, there were two
flotation units and several washing units in operation.
Slime from the washer is discharged to slime ponds.
After initial settling, the clear water is returned to the
raining and washing operations. The discarded slime contains
about 30 percent of mined ore matrix and occupies approxi-
mately 50 percent more volume than original phosphate matrix
mined. Years of settling is required before the land is
reclaimed. Approximately 1.14 tons of slimes are rejected
for each ton of high-grade pebble phosphate produced. When
the slime is discharged as slurry after flotation, it con-
tains only 2 percent solids. Actually, the material dis-
charged from the washer (solids and water) amounted to
larger quantities than the slime. Since the slime solids
are colloidal, they contain a higher percentage of water
even after they have been settled.
6-10
-------
Table 6. 5 gives size distributions of slimes from Florida pebble
phosphate. Table 6, 6 gives chemical and mineralogical analysis of
typical phosphate slime.
Table 6. 6 Chemical and
Mineralogical Analysis of
Typical Phosphatic Slime7
Table 6. 5 Size Distribution of
Florida Pebble Phosphate
Slimes7
Particle Size,
Microns
Over -14
44/28
28/9
9/3
3/0.3
Under 0.3
\ of Total. Weight
(Range o£ Typical
Analyses)
1 to 3
1 to 4
12 to 18
11 to 14
.14 to 27
44 to 52
Ingredient
P2os
SiO,
CaO
Fe
F
Loss on ignition
Miscellaneous
Total
Apatite, Ca5(PO<.).JF
Kaolinite. A120,. 2SiO2. 2h'20a
Wavellite, JAlPOj. 2A1 (OHO.jt9H2C
Limonite, 2Fe,0,. 3H-O
Quartz, SiO2
Feldspar, KAlSi^O
Dolomite, CaMg (CO.) 2
Organic (not determined)
Miscellaneous
Total
*
20.0
21.0
18.0
20.0
4.5
1.7
12.0
2.8
100.0
38.0
30.0
)15.0
7.0
5-.0
1.5
1.0
1.5
1.0
100.0
aA more reasonable assurptic-. is that
the cl^y cc.'-tor.t is sror.tror : 1 lor.: to
and/or attJ;-Jlcite rather than kaolin.
(3)
Phosphatic slimes not only retain significant phosphate
values, but also constitute a potential reserve of water.
In I960, treatment of Florida land pebble phosphate rock
produced slimes containing at least 30.3 billion liters of
P
water. The Florida phosphate slimes can be used as binder.
Dryer and Grinding - The washed rock is dried to remove
moisture and ground to increase total surface area and
reactivity.
6-11
-------
Emissions from the dryer include particulates and
combustion products. Table 6.7 gives emission factors for
phosphate rock processing.
The beneficiated material is sent to open storage
piles.
Table 6.7 PARTICULATE EMISSION FACTORS FOR
PHOSPHATE ROCK PROCESSING WITHOUT CONTROLS9
Type of Source
Drying
Grinding
Transfer and storage
Open storage piles
Emissions,
Ib/ton
15
20
2
40
a) per ton of phosphate rock input.
Barges and railcars are used for transporting bene-
ficiated rock to fertilizer manufacturing centers. The
trend is to manufacture the fertilizers at the mine site and
ship them directly to consumers.
The beneficiated material is used as fertilizer or
further processed to yield higher fertilizers, elemental
phosphorus, and phosphoric acid.
6.4.3 Thermal Reduction Method (Elemental Phosphorus Production)
The thermal reduction method involves smelting of
phosphate rock with carbon and silica in an electric fur-
6-12
-------
nace. Since finely divided phosphate rock in the charge
would block the release of phosphorus vapors, the feed is
agglomerated by various methods.
(4) Agglomeration - The rock is agglomerated by pelletizing,
nodulizing, sintering, briquetting , or flaking. Moisture
content of the rock , which is objectionable in the electric
furnace charge, is driven off by agglomeration. Most
plants in the United States apply the nodulizing method,
heating the kiln with oil or natural gas to a maximum
temperature of 1200 to 1480°C. Gases released from the
nodulizing kiln contain 4 to 12 percent water vapor. Twenty
to 45 percent of input fluorine is emitted from nodulizing
and 30 to 40 percent of input fluorine is emitted from
sintering.
(5) Electric Furnace - The furnace charge contains phosphate
rock lumps, coke, and silica. Temperatures in the furnace
are maintained at 1260 to 1482°C. Heat is supplied by
passage of high-voltage current through carbon electrodes in
the furnace. About 12,500 to 13,500 KWH power is consumed
in producing a metric ton of elemental phosphorus.
In the furnace, the silica is reacted with phosphorus
to produce phosphorus pentoxide (P2°5^ ' whi-ch ^n turn
produces elemental phosphorus by reacting with carbon.
Furnace products include liquids and gases. Table 6.8 gives
typical operating data for a phosphorus furnace.
Liquid products of the furnace contain a calcium
silicate slag and ferrophosphorus, which are run off sep-
6-13
-------
arately. The slag may be sold as ballast, aggregate, or
fill. Table 6.9 gives an analysis of typical phosphorus
furnace slag.
Table 6.8 OPERATING DATA FOR A PHOSPHORUS FURNACE
Raw materials consumed per kilogram of elemental
phosphorus produced
power, KWH
phosphatic material, kg
silica material, kg
coke material, kg
Baked carbon electrodes, kg
Products formed per kb of elemental
phosphorus produced
slag, kg
ferrophosphorus, kg
carbon monoxide, kg
Recovery, as the element, of the
phosphorus charged, %
Temperature of offgases, °C
Temperature of slag at tapping, °C
14.3
10.0
1.5
1.5
0.015
8.9
0.30
2.8
87
370
1480
Table 6.9 AVERAGE ANALYSIS OF TYPICAL PHOSPHORUS
FURNACE SLAG5
( 'iiiislitiimt.
OiO
SiO,
AUO,
F
K,O
SO,
Permit.
IS. -17
40 :W
4 Sfi
a.w.
1 (IS
0.5!)
( 'itiisl.il urnl
MkO
P
N:i?O
I'V.O,
MnO
tViri-nl.
1) 1S
(1 17
(1 .(_'
1 )._'">
0. IS
6-14
-------
The gaseous products containing phosphorus, silicon
tetrafluoride, carbon dioxide, and large volumes of carbon
monoxide are treated for dust removal, then sent to the
condenser.
Large amounts of hazardous fumes, evolved during
tapping, are presented in the immediate furnace area of the
building and escape to the atmosphere. Much of the vanadium
present in the ore charge is taken up by the ferrophosphorus.
Pretreatment of the phosphate feed at temperatures in
the range of 954 to 1316°C results in liberation of lesser
quantities of the rock constituents such as water of hy-
12
dration, organics, CO2 , and fluorine. The gas velocity
ranges from 30 to 183 cm/sec. Average gas temperatures
range from 260 to 316°C. Dust loadings range from 9.15 to
,, , , -6 , 3 11
34.3 x 10 gm/scm .
(6) Condenser - The phosphorus is condensed from the furnace
gases by spraying water in a tower. Recovery efficiency is
a function of exit temperature, cooling rates, and total
residence time of gases in the condenser. The liquid phos-
phorus is run into a sump, where small amounts of impurities
are precipitated. Then it is pumped into storage tanks,
where the last traces of mud settle to the bottom.
During condensation, the dusts from furnace gases form
into sludge, having a typical analysis of 65 percent phos-
phorus, 25 percent water, and 5 to 10 percent dust. Mostly,
the dust is recycled to the furnace. The condenser water,
6-15
-------
(7)
which is called phossy water, contains significant amounts
of phosphorus, much of which is emulsified phosphorus. The
phossy water is centrifuged to reduce the phosphorus content
to the lowest possible level (7 ppm) and sent to a large
settling pond prior to disposal.
6.4.4 Phosphoric Acid Production
Phosphoric acid is produced by two methods: (1) the wet
process, which is the most economical but needs purifica-
tion, and (2) thermal treatment of elemental phosphorus,
which yields a product of high purity called furnace acid.
6.4.4.1 Phosphoric Acid Production by the Wet Process -
Phosphate rock is treated with sulfuric acid to form dilute
phosphoric acid and calcium sulfate. Most of the wet-
process phosphoric acid is used for fertilizers.
Reactor - After treatment of the rock with sulfuric acid,
the phosphoric acid (30 to 35 percent acid) is separated
from the calcium sulfate and other solids by filtration.
The slurry is sent to a pond for settling of the gypsum in
water.
The product acid is sent to market or further con-
centrated to 55 percent P2°5 content. Table 6.10 gives a
typical composition of wet-process acid.
Table 6.10 COMPONENTS OF TYPICAL WET-PROCESS ACID
13
CJultipiilitMll
,,.,,.
Ca
Kf
Al
Ct
V
lt.,() .mil ulhl.T
wiMiiin. -;.
r.a.4
0-1
1.2
0.6
0 3
0 01
o.oa
37.56
Cuuipoiii'HI
Nil
K
K
S03
SiO.>
C
solid
WriBlil. "C
02
0.01
o.u
1.5
0-1
0.1!
a.«
6-16
-------
During the reaction, fluorine gases are released as
hydrogen fluoride. The hydrogen fluoride reacts with
silicon dioxide in the phosphate rock, producing silicon
tetrafluoride gas. Fluoride gases are also released from
gypsum filteration. Offgases typically contain 5.66 to 14.2
mg/m of SiF4, and filter effluent contains 0.28 to 0.85
3 14
mg/m of SiF.. They also contain SO,, and odorous pol-
lutants. Reactor emissions include some particulates. In
addition, the fluorides are emitted from the gypsum settling
pond at a minimum rate of 0.018 gram per square meter (0.16
Ib/acre) of surface area per day. The water from the pond
after the gypsum settles out contains a considerable amount
of phosphoric acid and is circulated through a cooling pond
into the plant.
(8) Flask Chamber - The dilute acid is concentrated by evap-
oration in two or three vacuum evaporators. The product
acid (54 percent P2°5^ ^s condensed and stored.
Fluoride-containing gases SiF. and HF (2 to 5 percent
F) are released and sent to the scrubber.
(9) Scrubber for Fluosilic Acid Recovery - All fluorine-con-
taining gases from the reactor and flash chamber are passed
through the scrubber, where they are contacted with recycled
fluosilic acid. Part of the scrubber product acid is re-
moved as product and the remainder is recirculated. Most of
the product fluosilic acid is sent to storage ponds to
prevent pollution of local water supplies. A small amount
6-17
-------
is used for water fluoridation or for manufacturing cryo-
lite. In 1970, two companies in Florida developed a method
of converting fluosilic acid to hydrofluoric acid. The U.S.
Bureau of Mines developed a method yielding a synthetic
fluorspar as the product of fluorine-containing gases from
the reactor.
6.4.4.2 Phosphoric Acid from Elemental Phosphorus (Thermal
Process) - Thermal-process acid is used primarily in the
manufacture of industrial phosphates; usage has been con-
fined to products other than fertilizers.
(10) Combustion Chamber - Liquid phosphorus is pumped to the
chamber where it is burned in air at temperatures of 1650 to
1930°C to produce P2°5' The resultin9 mixture of phosphorus
pentoxide vapor and excess air passes from the combustion
tower into a gas cooler. About 75 percent of the P^O,.
collects in the circulating acid in the combustion tower/
and 25 percent is recovered in a waste gas purification
unit. If the combustion chamber is made of stainless steel,
the weak phosphoric acid is drawn into the chamber to
relieve the excess heat.
The emission gases, mainly P2°5' N2' °2' steain' No '
and excess air, are drawn into a gas cooler. They may
include phosphine (Ph.,), a highly toxic gas formed by
hydrolysis of metallic phosphides present as impurities in
phosphorus carriers and storage. If excess air is used, a
dense fume containing phosphorus pentoxide (Pir.) is
6-18
-------
formed. Particles in these fumes are submicron in size and
the fumes are 100 percent opaque.
The yellow phosphorus raw material is highly toxic.
Because it ignites spontaneously in the presence of atmo-
spheric air, special facilities are required for handling.
It is always shipped in tank cars and stored under water to
prevent combustion.
Phosphorus is transferred from the feed tank to the
combustion chamber by a pump at feed rates of 3.8 to 19
18
liters per minute.
19
(11) Gas Cooler - In some plants gases from the combustion
chamber are drawn into a gas cooler and cooled from 785°C to
180°C by water through internal sprays. The cool gases are
passed to a hydrator. No pollutants are emitted.
(12) Hydrator - In the hydrator the P2°5 vaP°rs are converted to
H^PO. by contact with recycled weak phosphoric acid. This
circulating acid also removes heat and collects the acid
mist formed. Water is sprayed countercurrently from the
top. The acid is precipitated, separated, and stored.
Table 6.11 gives a typical analysis of acid produced by the
thermal process. Arsenic will appear in the product if it
is present in the raw material.
.,5
Table 6.11 Typical Analysis of a Commercial Food-Grade Phosphoric Acid
H3P
-------
Since economical operation of the process depends upon
the agglomeration of mist particles and subsequent sep-
aration from the gas stream, almost all plants are equipped
with emission controls. Since the substances are highly
corrosive, the operation requires special materials of
14
construction.
The hydrator is the principal emission source in the
thermal process. The emissions contain phosphoric acid mist
in the form of orthophosphoric acid (H PO.); particle sizes
range from 0.4 to 2.6 microns. Emissions also contain 10 to
60 percent water vapor, depending upon the operating con-
1 fl
ditions.
Median particle size is reported as 1.6 microns, with
14
13 percent being less than 1 micron in diameter.
A typical flow rate of phosphoric acid mist is about
7.08 x 10 cm /sec. The mist particles, which contain 77
percent H3PO. with 2.3 pH, are present at a temperature of
80°C. Gas velocities range from 61 to 244 cm/sec, and
temperatures from 66 to 149°C. Concentration of mist varies
from 0.11 to 0.8 x 10~6 gm/cm3.11
6.4.5 Superphosphoric Acid (SPA) Prpductign.
Production of SPA from wet-process phosphoric acid
basically involves the removal of free and bonded water by
evaporation; in production from furnace acid, the acid is
concentrated by recycling to the hydrator.
6.4.5.1 Superphosphoric Acid from Wet-Process Phosphoric
(13) Acid - The 54 percent acid is evaporated in (1) a falling
film evaporator or (2) a forced circulation evaporator.
6-20
-------
The 54 percent phosphoric acid is pumped into an oil-
or natural-gas-fired evaporator, where an acid vapor is
produced by boiling and is discharged to a condenser. Table
6.12 gives a typical plant analysis of the phosphoric acid
feed and superphosphoric acid product.
(14) 6.4.5.2 Superphosphoric Acid from Furnace Acid - Usually,
superphosphoric acid is produced at a conventional furnace
acid plant with some alterations or additions.
In cooling of the combustion chamber gases, much less
water is sprayed than in production of simple phosphoric
acid. The combustion gases enter the hydrator and rise
against water and dilute acid. Roughly half the P2°5 dr°Ps
out as superphosphoric acid. The rest leaves overhead as a
mist and is collected as less concentrated (dilute) acid.
The dilute acid is sprayed back into the hydrator.
The superphosphoric acid then flows to a stainless
steel storage tank. A stream of acid is withdrawn for
recycling and pumped to the hydrator. Emissions are the
same as those from phosphoric acid production.
6.4.6 Normal Superphosphate
Normal superphosphates, the first commercial phosphate
fertilizer, contains 16 to 21 percent phosphoric anhydride
(P_G5). Superphosphate plants in the United States are
numerous. The only processes are mixing and den curing.
(15) Mixing and Den Curing - The phosphate rock is mixed with
sulfuric acid in a cone mixer and discharged to a den, where
6-21
-------
Table 6.12 ANALYSIS OF TYPICAL STREAMS
21
Item
Total V2°5
Ortho P2°5
Conversion
Fe2°3
A1203
MgO
so3
F
CaO
K2°
Na2°
Si02
Solids
Specific Gravity
(60 F.)
Phosphoric
acid feed,
54.2
100.0
0
1.0
1.9
0.3
2.6
1.0
0.01
0.09
0.03
0.015
1.50
1.7
Superphosphoric
acid product,
72.49
31.37
56.7
1.33
2.47
0.40
1.90
0.30
-
-
-
-
0.37
2.08
6-22
-------
it is held for sufficient time to allow the slurry mixture
to set into a solid porous form. It is then stored for the
acidulation process to go to completion. Most of the plants
in the United States use batch methods/ although both batch
and continuous dens are in use. The ratio of acid to rock
in feed to the mixer is about 60 grams of (100 percent)
sulfuric acid per 100 grams rock (containing about 33
percent P^O,.) . The resulting superphosphate contains phos-
phoric anhydrite of 16 to 21 percent P20c and calcium
sulfate of the reaction. About 0.18 KWH of electric power
22
is required to produce 1 metric ton of superphosphate.
Gases released from the acidulation of phosphate rock
contain silicon tetrafluoride, carbon dioxide, steam, sulfur
dioxide, and particulate. Total fluoride content of stack
gases including particulate fluorides is 0.075 gm/kg (0.15
Ib/ton) of fertilizer produced.
Cranes and draglines are used for removing superphos-
phate from the den.
(16) Granulator and Dryer - The cured product is granulated by
adding ammonia, sulfuric acid, triple superphosphate, or
potash, then dried in dryers fired by oil or natural gas.
The product is then cooled and bagged for market.
Emissions include ammonia, SiF., HF, NH.C1, and fer-
tilizer dust from the granulator; ammonia, fertilizer dust
and fuel combustion products from the dryer. The cooling
operations produce particulate. Grinding and drying produce
4.5 grams of particulate per kilogram (9 Ib/ton) of phosphate.
6-23
-------
6.4.7 Triple Superphosphate Production
Triple superphosphate is a highly concentrated fer-
tilizer containing 44 to 51 percent available P?0cf nearly 3
times the amount in regular superphosphate. It is made by
the action of phosphoric acid on phosphate rock. The re-
sulting product is cured in a den for 1 or 2 weeks. The
processes of manufacture are granulating, cooling, and
finishing.
(17) Granulator - Metered amounts of the ground phosphate rock
and phosphoric acid are fed continuously to the granulator,
where reaction and granulation take place. Fine particles
of the product are recycled to the granulator.
Following are typical input rates for production of 1
ton of triple phosphate of 46 percent P2°5: Pn°sPhate rock
(75 B.P.L.) 386 kilograms; phosphoric acid (45 percent P2°5^
535 kilograms, fuel 35,280 kcal; and power 35 KWH-hr.22
Exhaust gases contain particulate, HF, and SiF.. Rate of
the fluoride emission is about 0.5 gram fluoride per kilo-
Q
gram (0.10 lb/ton) of product.
(18) Cooler - The granules are fed to a cooler where they are
cooled. The fines are screened from the product and re-
cycled to the granulator.
Dust from exhaust gases is recovered and also recycled
to the granulator.
(19) Finishing Operations - The product is stored in bulk to cure
for 1 to 2 weeks, during which time the granules increase in
physical strength. The product is bagged and shipped to
market.
6-24
-------
6.4.8 Diammonium Phosphate Production
(20) Reaction - Phosphoric acid is reacted with ammonia in the
presence of sulfuric acid to produce diammonium phosphate.
The sulfuric acid controls the composition of the final
product.
(21) Granulator and Dryer - The product of reaction is mixed with
more ammonia to produce phosphate granules. The operation
emits particulate and large quantities of ammonia. The
residual ammonia is recovered by treating the exhaust gases
in scrubbers. The granules are dried in an oil- or gas-
fired dryer, which emits fluorides, ammonia, and particulate
matter. The granules are screened. The oversize product is
ground and recycled to the ammoniator along with the fines
for product control. The diammonium phosphate is cooled
before storing. Ammonia and particulate matter are emitted.
The granulator emits about 1 gram (2 Ib/ton) of particulate
and the dryer and cooler emit approximately 40 grams/kg (80
Q
lb/ton) of particulate matter.
6.4.9 Nitrogen Fertilizers
The major nitrogen fertilizers are ammonium phosphate
nitrate, ammonium nitrate sulfate, and nitric phosphate, all
of which contain ammonium nitrate. Processes are mixer,
neutralizer , and concentrator.
(22) Mixer - For production of ammonium phosphate nitrate, nitric
acid, phosphoric acid, sulfuric acid, and ammonia are mixed.
For other products, no phosphoric acid is used. Exhaust
6-25
-------
gases from the mixer contain ammonia and particulate matter.
(23) Neutralizer and Concentrator - The acids are neutralized
with excess ammonia, granulated, dried, cooled, and con-
ditioned before storing. Exhausts contain particulate and
combustion products resulting from burning of oil or gas in
the dryer.
Very few plants produce nitric phosphate in the United
States.
In addition to the fertilizers described here, many
other phosphate-containing fertilizers are produced.
Important among them are sodium polyphosphates and po-
tassium phosphates. Emissions are about 1.38 grams of dust
per kilogram (2.75 Ib/ton) of product and 1.78 grams of
23
ammonia per kilogram (3.55 Ib/ton) of product.
Table 6.13 gives data on fluorine emissions from
various processes of the phosphate rock industry.
6.5 MAJOR POLLUTANT SOURCES
Many processes in the phosphate rock industry are
responsible for release of particulate and gases, some of
which are toxic in nature and almost all companies apply
some degree of emissions control. The following are the
most significant sources of emission.
0 Phosphate Mining and Washing Operations - Phosphate
mining and washing generate an equivalent amount of phos-
phate-bearing slimes to the amount of ore mined. These
slimes contain about 3 to 5 percent of very fine clay. This
6-26
-------
problem exists only in central Florida where 80 percent of
U.S. phosphate is produced. At present the slimes are
impounded in special ponds. Since these slimes exist in the
ponds for 10 to 25 years there is always a potential for
surface and ground water pollution.
0 Hydrator (Phosphoric Acid Production by Thermal Process)
Primary pollutant is acid mist which is discharged at a rate
of 67.5 grams per kilogram (135 Ib/ton) of P-jO produced.
^ l>
Many industries control the emissions using equipment with
99.5 percent efficiency. Still the hydrator is the prin-
cipal emission source in the thermal process. The acid mist
is present in the form of orthophosphoric acid (H PO.);
particle size ranges from 0.4 to 2.6 microns. A typical
flow rate for the offgas is 7.08 x 10 cm /sec.
0 Reactor (Phosphoric Acid Production by Wet Process) -
Primary air pollutants are rock dust, fluorides, carbon
dioxide, silicon tetrafluoride, hydrogen fluoride, and
phosphoric acid mist. Most modern wet-process phosphoric
acid plants provide a complete collection system through one
scrubber. Emissions from a system of this type are 0.025 to
0.05 gram fluorine per kilogram (0.05 to 0.1 Ib/ton) of P2°c
produced.
0 Dryer and Cooler (Diammonium Phosphate Production) -
The emission factor is 97.5 grams per kilogram (195 Ib/ton)
of product. Emissions include ammonia and fluorides. In
1970, after controlling 90 percent of emissions, about 145,200
metric tons were emitted from treating 16.33 million metric
tons.
6-27
-------
Table 6.13 FLUORINE EMISSIONS FROM VARIOUS PROCESSES
10
Process
Calcining phosphate rock
(benef iciation )
Calcining phosphate rock
(def luorination)
Calcining phosphate rock
(def luorination)
Nodulizing phosphate rock
Sintering phosphate rock
Calcining phosphate rock
Calcining phosphate rock
Defluorinating molten
phosphate rock
Process
materials
Phosphate
Rock
Phosphate
rock
Phosphate
rock, sil-
ica
Phosphate
rock
Phosphate
rock
Phosphate
rock
briquettes
Phosphate
rock
pellets
Phosphate
rock, sil-
ica
Process
equipment
Rotary kiln
Rotary kiln
Rotary kiln
Rotarv kiln
Dwight-Lloyd
machine
Rotary kiln
Shaft kiln
Rotary kiln
Electric
furnace
Fuel
used
Oil
Oil
Oil
Oil
Coal
CO gas
Coke
Oil
Coal
CO gas
CO gas
Propane-
butane
Oil
Water
vapor
in gases,
%
8-10
13
20*
4-12
4-12*
4*
8-12*
8-12*
Low
Maximum
tempera-
ture
°c
1090
820
1400-1450
1480-1590
1200-1480
1400*
1000-1040
1090-1200
1150-1180
1600
Percent
of input
fluorine
emitted
3
Almost nil
50-70
75
98
20-45
30
35-40
Almost nil
14
14
28
Small
en
I
SJ
CD
* Values estimated.
-------
Table 6.13 (continued)-. FLUORINE EMISSIONS FROM VARIOUS PROCESSES
Process
Defluorinating molten
phosphate rock
(cont'd. )
Phosphoric acid
manufacture
Elemental phosphorus
manufacture
Process
materials
Phosphate
rock, sil-
ica
Phosphate
rock, coke
Phosphate
rock, sil-
ica
Phosphate
rock, sil-
ica coke
Process
equipment
Hearth
Furnace
Electric
furnace
(for melt-
ing)
Hearth
furnace
(for de-
fluori-
nation)
Shaft
furnace
Electric
furnace
Blast
furnace
Electric
furnace
Fuel
used
Oil
Oil
CO gas
Oil
Coke
Water
vapor
in gases,
%
8-12*
12
12
4
12-14
Low
Very
Low
Maximum
tempera-
ture
°C
1500-1550
1550-1600
1600
1430-1540
1430-1540
1480*
1740-1850
1470*
Percent
of input
fluorine
emitted
84-95
90
92-96
70
90 or
greater
35
25
20-30
52
30
9.6
* Values estimated.
-------
Table 6.13 (continued). FLUORINE EMISSIONS FROM VARIOUS PROCESSES
Process
Calcium-magnesium
phosphate manufacture
Manufacture of calcium
meta-phosphate
Defluorination of
superphosphate
Manufacture of
superphosphate
Process
materials
Phosphate
rock,
olivine
Phosphate
rock,
olivine,
silica
Phosphate
rock,
olivine
Triple
super-
phosphate
Phosphate
rock , sul-
fur ic
acid
Process
equipment
Electric
furnace
Electric
furnace
Electric
furnace
Combustion
chamber and
absorp,
tower
Rotary kiln
Mixer and
den
Fuel
used
White
phos-
phorous
Oil
Water
vapor
in gases,
%
Low
Low
Very
Low
10-14
5.2-9.8
18-20
Maximum
tempera-
ture,
°C
1450-1550
1450-1550
1500-1600
1100
370-390
100-115
Percent
of input
fluorine
emitted
27-33
11
27-57
10-20
80-85
78-82
16-42
30-35
I
U)
O
-------
REFERENCES FOR CHAPTER 6
1. Lewis, R.W. Phosphorus. In: Mineral Facts and Prob-
lems. Bureau of Mines Bulletin Number 650. United
States Department of the Interior. Washington, D.C.
1970.
2. Lewis, R.W., and W. F. Stowasser. Phosphate Rock. In:
Minerals Yearbook. U.S. Bureau of Mines. 1971.
3. Engineering and Mining Journal. March 1974.
4. Cathcart, J.B. Economic Geology of the Chicora Quad-
rangle, Florida. U.S. Department of Interior, Washing-
ton, D.C. Geological Survey Bulletin No. 1162-A.
1963.
5. Kirk-Othmer. Encyclopedia of Chemical Technology. New
York, John Wiley and Sons, Second Edition. 1967.
6. Waggaman, W.H., and E.R. Ruhlman. Conservation Prob-
lems of the Phosphate Industry. Industrial and Engi-
neering Chemistry. Vol. 48, No. 3. March 1956.
7. Typer, P.M., and W. H. Waggaman. Phosphatic Slime. A
Potential Mineral Asset. Industrial and Engineering
Chemistry. Vol. 46, No. 5. May 1954,
8. Gary. J.H., F.L. Field, and E.G. Davis. Chemical and
Physical Beneficiation of Florida Phosphate Slimes.
U.S. Department of the Interior. Washington, D.C.
Bureau of Mines Report of Investigation Number 6163.
1963.
9. Compilation of Air Pollutant Emission Factors. En-
vironmental Protection Agency, Raleigh, North Carolina.
Publication Number AP-42. April 1973.
10. Semrau, K.T. Emission of Fluorides from Industrial
Processes. Journal of Air Pollution Control Asso-
ciation. August 1957.
6-31
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11. Oglesby, Sabert, Jr. A Manual of Electrostatic Pre-
cipitator Technology. Southern Research Institute.
Alabama 35205. CPA Contract Number 22-69-73.
12. Bryant, H.S., N.G. Holloway and A.D. Silber. Phos-
phorus Plant Design. New Trends. Industrial and
Engineering Chemistry. Vol. 62, No. 4. April 1970.
13. Manufacturing Chemists' Association, Inc. and Public
Health Service. Atmospheric Emissions from Wet-Process
Phosphoric Acid Manufacture. U.S. Department of
Health, Education and Welfare. Publication Number AP-
57. April 1970.
14. Lund, H.F. Industrial Pollution Control Handbook. New
York. McGraw Hill Book Company, 1971.
15. Cross, F.L., and Roger W. Ross. New Developments in
Fluoride Emissions from Phosphate Processing Plants.
Journal of Air Pollution Control Association, January
1969. Vol. 19, No. 6.
16. Phosphate Plant Waste Looms as Hydrofluoric Acid
Source. Chemical Engineering, May 4, 1970.
17. Danielson, J.A. Air Pollution Engineering Manual. Air
Pollution Control District. County of Los Angeles, May
1973.
18. Manufacturing Chemists' Association, Inc. and Public
Health Service. Atmospheric Emissions from Thermal -
Process Phosphoric Acid Manufacture. U.S. Department
of Health, Education and Welfare. Publication Number
48. October 1968.
19. Noyes, Robert. Phosphoric Acid by Wet Process.
20. Rea, R.D. Plume Free Stacks Achieved in H^PO. Pro-
duction. Chemical Processing. January 1971.
21. Stern, D.R., and J. D. Ellis. Processing Problems Pared
for Superphosphoric Acid. Chemical Engineering. March
23, 1970.
22. Shreve, R.N. Chemical Engineering Series. New York.
McGraw Hill Book Company, 3rd Edition. 1967.
23. Information provided by Tennessee Valley Authority.
Muscle Shoals, Alabama 35660.
6-32
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7.0 POTASH
7.1 INDUSTRY BACKGROUND1
Approximately 50 percent of the nation's supply of
potash is produced domestically. The remainder is imported,
mainly from Canada, and also from West Germany, France,
Italy, and Spain.
Agriculture is the major consumer, accounting for
approximatley 95 percent of the total consumption. The
remainder is consumed in the manufacture of dyes, deter-
gents, soaps, glass, and analytical reagents. The future
for potassium, both in the United States and the rest of the
world, depends upon agriculture.
Brines and bedded deposits are the two types of do-
mestic sources of potash. The bedded deposits in New Mexico
produce approximately 84 percent of the nation's domestic
supply. The potash ores in these areas, which contain 20 to
25 percent KpO, are gradually depleting and are estimated to
provide only a 10-year supply. Other states producing
potash are Utah and California.
In 1970 there were seven producers near Carlsbad, New
Mexico, one in Utah, and one in California. Six of the New
Mexico producers have holdings in Canadian potash deposits.
7-1
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The cost of transporting potash from refineries to
consumer areas is a major expense of the industry. The
possibility of transporting potash from Canada to Chicago
through pipelines was investigated several years ago.
Currently, the U.S. Bureau of Mines is engaged in
research programs to improve potash ore processing and to
develop a modified flotation process for the economic re-
covery of potassium minerals from the high-clay minerals and
complex ores of New Mexico.
Potassium-bearing lands, including the brine deposits
in California and Utah, are owned mainly by state or the
federal government and are leased by individual firms.
New technological developments have changed production
techniques. Drilling and blasting techniques have been
replaced by continuous borer mining. The magnitude of
operations has also increased markedly. Before I960, plant
production ranged from 91,000 to 454,000 metric tons per
year. Today plants with yearly outputs of less than 1
2
million metric tons per year are the exception.
World demand for potash by the year 2000 could be three
2
to five times today's demand.
Table G-l in Appendix G lists companies and their
production.
7.2 RAW MATERIALS
The term "potash" is applied to potassium compounds or
any of the potassium-containing minerals. Much of the
potash occurs in chemical compounds that have no present
7-2
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economic value. Potash is found throughout the world in
soluble and insoluble forms. Only the soluble forms are
economically attractive to process, primarily as chlorides
and sulfates; potassium chloride is by far the most im-
portant potash salt. Sylvinite ore, a mechanical mixture of
sylvite (KCl) and halite (NaCl), is a natural ore for po-
tassium. Table 7.1 lists all potash minerals and their
composition. Tables 7.2 and 7.3 show the chemical compo-
sition of potash ores in several areas of the United States.
7.2.1 Description of the Typical Potash Ores
Sylvite is the principal and most important potash ore
because of its availability and high K^O content. It is
usually found mixed with sodium chloride. A typical anal-
ysis is sylvite (KCl) 23 percent, halite (NaCl) 73 percent,
and other, 4 percent. The color ranges from clear to brick
red, and the content also varies considerably. This ore is
found in commercial grades near Carlsbad, New Mexico. For
the last four decades, vast tonnages of high-grade, low-
clay-content ores have been mined; however, these deposits
are rapidly diminishing, leaving high-clay, low-grade re-
serves of over 667 million metric tons.
Langbeinite (K2S042MgSO.) is theoretically composed of
42.1 percent potassium sulfate (K2SO.) and 57.9 percent
magnesium sulfate (MgSO,). Its color varies from clear to
gray.
Polyhalite (K2SO.-MgSO^2CaS04«2H20) occurs in various
colors: white, light and dark gray, salmon, orange, brown,
7-3
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Table 7.1 POTASH MINERALS'
Type of ore
Chlorides
Chloride-
Sulfates
Sulfates
Nitrates
Silicates
Micas
Miner ological
name
Sylvite
Carnallite
Kainite
Alunite
Polyhalite
Langbeinite
Leonite
Syngenite
Krugite
Apthitalite
Picromerite
Kalinite
Niter
Leucite
Feldspars :
Orthoclase
Anorthoclase
Muscovite
Biotite
Phogopite
Lepidolite
Zinnwaldite
Roscoelite
Glauconite
Carnotite
Nephelite
Composition
KC1
KC1 .MgCl2.6H20
MgSO4.KCl.3H20
K2(A1(OH)2(6)S04)4
K2SO4 .MgS04 . 2CaS04 . 2H20
K2S04. 2MgSO.
K2SO .MgS04 -4H20
K2S04.CaS04.H20
K2S04 .MgS04 . 4CaS04 . 2H20
(K,Na) 2S04
K2S04.MgS04.6H20
K2S04 .A12 (S04) 3 ,24H20
KN03
KAl{SiO3) 2
KAlSi-,Og
(Na,K)AlSx3Og
H2KA13 (SiO4)3
(H,K)2(Mg,Fe)2Al2(Si04)3
(H,K,Mg,F) 3Mg3Al(Si04) 3
H,Li(Al,OHfF2)Al(Si03)3
H2K4Li4Fe3AlgFgSi14042
HgK(Mg/Fe) (Al,V)4(Si03)12
KFeSi206.nH20
K-iO . 2U-,On . V00r . 3H_0
223 25 2
K2Na6A18Sl9°34
Equivale
K20 cont
in perce
63.1
17.0
18.9
11.4
15.5
22.6
25.5
28.8
10.7
42.5
23.3
9.9
46.5
21.4
16.8
2.4-12.0
11.8
6.2-10.1
7.8-10.3
10.7-12.3
10.6
7.6-10.3
2.3- 8.5
10. 3-11.2
0.8- 7.1
7-4
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Table 7.2 COMPOSITION OP POTASH
Area
Carlsbad - New Mexico
Eddy County - New Mexico
Bonneville Brine
Utah
Composition in
Polyhali te
K2S04
MgS04
CaS04
Anhydrite
CaS04
NaCl
H2°
Fe2°3
MgC03
Total Mineral
Polyhalite
Halite
Anhydrite
Others
Langbenite
K2°
MgO
so3
Na20
Insoluble in
water
NaCl
KC1
MgCl2
MgS04
CaS04
LiCl
Percentage
21.93
15.15
34.29
8.17
12.91
4.53
2.29
0.73
75.9
12.9
8.2
3.0
22.37
19.15
57.44
0.48
C.05
18 - 24.
0.8 - 1.
0.9 - 1.
0.2 - 0.
0.3 - 0.
0.03 - 0.
0
2
2
3
4
04
7-5
-------
and shades of red. Polyhalite contains potassium oxide
(K2O) 15.6 percent; magnesium oxide (MgO) 6.6 percent;
calcium oxide (CaO) 18.6 percent; sulfur trioxide (S0_) 53.2
percent; and water (H-O) 6.0 percent.
Table 7.3 TYPICAL MINEROLOGICAL ANALYSIS OF
POTASH ORE OF CARLSBAD-NEW MEXICO
Component
Sylvite
Halite
Langbeinite
Kainite
Leonite
Kieserite
Carnallite
Polyhalite
Anhydrite
Insolubles
Percentage
(range)
23-28
71
Trace-2
0.1-0.5
Trace-0.1
Trace-1.0
0.15
0.5-1.5
7.3 PRODUCTS
Four potassium salts are produced in the United States
for use as fertilizers: potassium chloride, potassium sulfate,
potassium magnesium sulfate, and potassium nitrate. The
chloride is available in four grades, standard, coarse,
granular, and soluble, each containing a minimum of 60
percent K~O. A chemical-grade, or refined, potassium
chloride, that is produced in the United States contains
7-6
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99.9 percent KC1. A small quantity of fertilizer with 20 to
22 percent K20 content is also made for special uses. The
potassium sulfate contains a minimum of 50 percent K-O.
The potassium magnesium sulfate contains 22 percent potas-
sium oxide equivalent and 18 percent magnesium oxide.
Potassium nitrate is manufactured from chloride by only one
firm (South West Potash Company), at Vicksburg, Mississippi.
Potassium nitrate is mostly imported from Chile, along with
potassium-sodium nitrate mixtures.
Ore mined in Carlsbad, New Mexico, contains small
quantities of cesium and rubidium, but presently they are
not recovered. Small quantities of magnesium oxide and
rubidium chloride are recovered as by-products with langbein-
ite.
7.4 PROCESS DESCRIPTION
Potash is recovered from bedded deposits and brine
solutions. This section describes only the processing of
potash from bedded deposits.
7.4.1 Mining
(1*) Potash ores are usually processed in refineries adjacent to
the mines. The bedded deposits of New Mexico and Utah are
all mined underground. The ore is mined through shafts in a
manner similar to that used for coal. In mining of lang-
beinite, 15 to 20 percent of the material is classed as
waste and left in the mine. This material is loaded onto
shuttle cars and transported to an abandoned part of the
mine.
* Numbers refer to corresponding processes in Figure 7.1.
7-7
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rtiitsiii enotn: n
lltllllM HETItl
nussiui c
fllCTIOmi CITCTtUIIIItl
MillOt
rO-
PltlSSIOM IIIFlU
PIM.ICMOI
NIISSIUK UltUI!
PI1DIICTIU
if" ,
IHEHO.
Figure 7.1 Potash industry
7-8
-------
Ore is moved from the face to mine cars by caterpillar-
mounted conveyor-type loaders and rubber-tired double-trolly
shuttle cars. Main haulage is by trolley locomotives on
rails. The refining of mined ores for different potassium
salts is described in the following sections. Figure 7.1
shows the processing steps.
7.4.2 Potassium Chloride Production
The main source of potassium chloride is sylvite, which
is processed by two basic methods: flotation and fractional
crystallization.
7.4.2.1 Flotation Method - Most of the potash in the United
States is recovered by flotation. In general, potash is
manufactured by mixing the ore with a recycled brine solu-
tion, disliming it to remove clay impurities, and then
conditioning it by using flotation reagents to remove other
impurities, including sodium chloride. This process con-
sists of the following steps:
(2) Crusher and Screen - Crushing and screening are required to
unlock potassium chloride crystals. Since the flotation
action is affected by the surface/weight ratio of the ore
particles, very efficient crushing is required. The ore is
crushed either at the mine site or at the refinery plant.
After crushing and screening, the material is sent to
scrubbing units. A portion of the crushed and screened ore
is taken off for direct shipment to market as fertilizer.
About 12.5 grams of particulate of the same composition as
the ore may be emitted from processing one kilogram (25
Ib/ton) of ore.
7-9
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(3) Scrubber and Settler - The finely crushed material is
scrubbed with recycled saturated brine to prepare a solution
from which the product is concentrated. The scrubbed
material is introduced to classifiers, with the addition of
more recycled brine. The overflow brine is transferred to a
thickener for removal of clay. Then the clear brine solu-
tion is recycled to the scrubber. Since scrubbing and
settling are wet operations, there are no atmospheric emis-
sions. However waste clay is produced which is disposed of
in a dump.
(4) Flotation - Any of the remaining clay from the ore slurry is
neutralized by adding a depressant, such as starch. Then,
an aliphatic amine collector is added to selectively coat
one of the constituents (KC1 or NaCl), generally the KC1 of
the ore. Air is bubbled through the slurry to lift and
float the coated particles; uncoated particles sink to the
bottom. The cleaner concentrate floating on the surface is
separated and treated further. The bottoms material can be
processed further in a thickener to recover NaCl.
The tailings containing sodium chloride salt are sent
to a large disposal area, always located close to the re-
finery. These areas, covered with tailing salts, are in-
capable of supporting plant life. Because these refineries
are located in sparsely populated areas, the tailings have
not been considered an environmental pollution problem.
Typical analysis of a flotation grade of potassium chloride
is given in Table 7.4.
7-10
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Table 7.4 TYPICAL ANALYSIS OF FLOTATION GRADE
OF POTASSIUM CHLORIDE6
Assay
Na
Ca
Mg
Fe
Al
so4
Water insoluble
HC1 insoluble
H20
%
1.0
0.05
0.1
0.05
0.03
0.3
0.5
0.3
0.3
(5) Centrifugation and Classification - The concentrate from the
flotation unit is centrifuged to minimize brine losses.
Then the solid mass produced is classified. The underflow,
which is standard potash with 60 percent K^O content, is
sent to a drier. The overflow material, which is granular-
grade potash, is dissolved and recrystallized to produce a
chemical grade of potassium chloride (99.9%). The remainder
is sent to the drier.
(6) Dryers - After classification, the standard and granular
products are dried and cooled before storing for market.
The dryers are heated by oil or natural gas. Par-
ticulates are emitted from the dryer but emission rate data
are not available.
(7) Thickener - The overflow of scrubber-classifiers is trans-
ferred to a thickener, where clay is separated and the clear
7-11
-------
brine solution is recycled to the scrubber. The slurry
tailings from the flotation cells, are dewatered in thick-
eners, from which the overflow is sent to brine storage and
the underflow to the centrifuger. The centrifuged product,
NaCl, is stored. No pollutants are known to be emitted.
7.4.2.2 Fractional crystallization method - This method is
based on solubility/temperature relationships of two main
ore constituents; potassium and sodium chlorides. In solu-
tions saturated with both salts, the solubility of potassium
chloride increases rapidly with the temperature, while that
of sodium chloride remains constant.
(8) Hot Leach - Hot recycled brine, which is nearly saturated
with NaCl, is fed to the system, in which the crushed ore is
carried countercurrent to the hot brine flow. The KC1 and a
small portion of NaCl are dissolved, leaving the bulk of
NaCl solids unaffected. The pulp is dewatered in a clas-
sifier and centrifuged. The solids are rejected. The hot
brine is sent for further treatment. Except for the solid
tailings of NaCl, there are no known emissions.
(9) Classifier - The hot brine is classified to remove clay and
slimes in an insulated thickener. The underflow is re-
jected. Further treatment in a second thickener removes the
sodium chloride, which is separated by centrifugation.
Large volumes of mud-contaminated clay and sodium chloride
from the underflow are dumped into the waste area refinery
unit. To minimize losses of KCl, the wash liquor from the
centrifuger is recycled to the thickener. The cleaner, hot
saturated brine is pumped to a vacuum cooler crystallizer.
7-12
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(10) Vacuum Cooler Crystallizer - Most of the hot, saturated
brine is evaporated, leaving a concentrated brine containing
KC1 crystals. The evaporate is condensed and returned to
leach tanks as mother liquor. The remaining brine con-
taining crystals is centrifuged to separate the crystals.
The wash liquor is added to the crystallizer.
Particulate, with the composition of the mother liquor,
may be evolved.
(11) Dryer - The final product, potassium chloride, is dried in
an oil- or gas-fired dryer and stored.
Particulate may be emitted and may not exceed 5 grams
per kilogram (10 Ib/ton) of crystals. The degree of control
should be high since the material is valuable.
7.4.3 Potassium Sulphate Production
The product of 90 to 95 percent potassium sulfate is
prepared by hydrating a pulverized langbeinite ore and
combining it with sylvite, to eliminate magnesium by pre-
cipitation. The processes involved are described in the
following sections.
7.4.3.1 Beneficiation - The beneficiation of the langbeinite
ore, which includes crushing and washing, presents no known
serious pollution problem.
(12) Crushing - Mine-run ore is dry-ground in a mill operating in
closed circuit, with vibrating screens. Mostly hammer mills
are used. About 15 grams of particulate per kilogram (30
Ib/ton) of ore is emitted to the atmosphere.
7-13
-------
(13) Washing - The crushed ore is introduced into a wash unit.
The chloride gangue salts are dissolved from the ore by wash
water by means of solubility differences. A continuous
countercurrent washing process gives maximum solution of the
gangue salts in minimum contact time.
The finished langbeinite, which is 96 percent J^SO,-
2MgSO., is marketed as potassium magnesium sulfate or
further processed for potassium sulfate by a base exchange
process.
The overflow containing gangue is sent to a waste
disposal area.
(14) 7.4.3.2 Production - Hydrator - The finely pulverized
langbeinite is agitated with potassium sulfate mother
liquor, to produce schoenite (K^SO.-MgSO.6H2O) or leonite
(K-SO,' MgSO.4H_0), the product determined by temperature
and by magnesium chloride content of the waste liquor. The
products of hydration are transferred to a centrifuge, where
the cake product (leonite) is separated from the liquid.
The solid cake is further treated and the wash liquor is
rejected or evaporated to recover chlorides. The progress
of the reaction can be estimated by examining typical com-
positions of mother liquor and waste liquor at 25°C, as
indicated in Table 7.5.
(15) Reactors - The solid cake is mixed and agitated at carefully
controlled temperatures with sylvite and water to produce
potassium sulfate as a solid and a mother liquor for use in
the hydrator. Temperature strongly influences yield in this
7-14
-------
reaction. Solubility of the potassium rises rapidly, and
the yield decreases, with increase in operating temperature.
The optimum temperature is 25°C. The reaction product is
treated in a centrifuger to separate the solid product from
the mother liquor. The solid product is sent to a dryer,
and the mother liquor is recycled directly to the hydrator.
The emissions are negligible.
Table 7.5 A TYPICAL ANALYSIS OF MOTHER LIQUOR
AND WASTE LIQUOR FROM HYDRATOR7
Stable solid
- phases, %
MgCl2
KC1
MgS04
H2°
Mother liquor
schoenite,K2SO.,KCl
7.98
14.87
5.28
71.87
Waste liquor
schoenite
14.82
9.84
5.26
70,08
(16) Dryer - The potassium sulfate product is dried in a kiln
heated by oil or gas. Twenty-five to 30 grams of partic-
ulate may be evolved per kilogram (50 to 60 Ib/ton) of
product.
(17) Evaporator and Cooler - The mother liquor from the hydrator
is evaporated to a point where, on cooling to 30°C, the
liquor is saturated with sodium chloride and the mixed salts
are separated. These mixed salts (predominatly potassium
chloride, with some leonite), are suitable for production of
potassium sulfate and are returned to the reaction tanks.
7-15
-------
The liquid containing sodium chloride is rejected. Par-
ticulates are emitted but emission rate data are not avail-
able.
p
7.4.4 Potassium Nitrate Production
Only one plant in the United States produces potassium
nitrate by reacting potassium chloride and nitric acid. The
process also recovers 99.5 percent of the liberated chlorine.
The sequence is described in the following section.
(18) Reactor - The potassium chloride is reacted in an agitated
tank, with 65 percent nitric acid vapor, to produce po-
tassium nitrate by the reaction: 3KC1 + 4HNO 3KNO +
J J
NOC1 + Cl- + 2H_O. The nitrosylchloride (NOC1) and chlo-
rine, present in a gaseous phase, are sent to a gas reaction
column. The product, which is a solution of HNO- and KNO_,
is passed to an adjacent column. The hot nitric acid vapors
are introduced into the column, to effectively strip the
solution of chloride and chlorine, to a concentration of
0.004 percent chlorine or lower. This stripping action is
required to protect the stainless steel equipment in which the
solution is subsequently processed. The gases emitted may
contain chlorine, nitrosylchloride, and nitrylchloride.
(19) Gas Reaction Column - The gases from the reactor are intro-
duced into the column, where 81 percent HNO in vapor form
and recycled gases containing NOC1, NO2C1, N2°4' C12 and
BrCl are added. Most of the NOC1 is converted to N02. The
overflow gases containing chloride {Cl~), nitrosylchloride
(NOC1), and nitrylchloride (NO-Cl) are liquefied by con-
7-16
-------
densation. The amount of bromine impurities in the KC1 may
present themselves in the overflow as BrCl.
Composition of the effluent from the column may include
all the overflow gases.
(20) Fractionating Column - The liquefied gases are fractionated;
first to separate 99.5 percent chlorine, then nitrogen
tetroxide. The chlorine is stored and the N20 (99.5%) is
used in HNO_ absorption towers to convert 55 percent nitric
acid to 65 percent HNO_. The remaining gases are recycled
to the gas reaction column.
(21) Water Stripping Column - The solution containing KNO_ and
55 percent HNO_, in the ratio of approximately 1:4, is
introduced into the column, where 65 percent HNO, is sep-
arated in vapor form from the concentrated solution of
KNC- in HNO_. Later, nitric acid is condensed and recycled
to reactor tanks. The KNC> solution (90 parts per 100 parts
of 82% HNO_), is introduced to the vacuum crystallizer.
Nitric acid mist is emitted.
(22) Vacuum Crystallizer - The crystallizer produces large
crystals of technical grade (99.3%) KN03, which are cen-
trifuged, and 81 percent HN03, which is recycled to the gas
reaction column.
(23) Dryer - The final potassium nitrate product is passed
through a direct-fired dryer, cooled, and stored. Oil or
gaseous fuel is used. Particulate is emitted and may not
exceed 5 grams per kilogram (10 Ib/ton) of product.
7-17
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7.5 MAJOR POLLUTANT SOURCES
About 84 percent potash is produced in a low populated
area of 142 square kilometers (55 square miles) at Carlsbad,
New Mexico. Disposal areas where large amounts of sodium
chloride tailings are dumped become incapable of supporting
any plant life.
Potash plants in Utah are similarly located, but care
must be taken to prevent pollution of the Colorado River.
7-18
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REFERENCES FOR CHAPTER 7
1. Lewis, R.W. Potassium, In: Mineral Facts and Problems,
U.S. Department of the Interior, Washington, D.C.
Bulletin No. 650. 1970.
2. Mitchell, J.B. Population, Politics and Potash.
Mining Engineering. May 1972.
3. Johnson, A.B. and others. Beneficiation of High Clay
Potash Ore by Flotation. Bureau of Mines, Technical
Progress Report. No. 41. September 1971.
4. Industrial Minerals and Rocks. Seeley W. Mudd Series.
New York, American Institute of Mining, Metallurgical
and Petroleum Engineers, 1960.
5. Johnson, B. U.S. Bureau of Mines Information Circular,
No. 7277. April 1944.
6. Kirk and Othmer. Encyclopedia of Chemical Technology.
New York, New York. 1968.
7. Harley, G.T., and G. E. Atwood. Langbeinite... Mining
and Processing. Industrial and Engineering Chemistry.
Vol. 39. January 1947.
8. Spealman, M.L. New Route to Chlorine and Saltpeter.
Chemical Engineering. November 8, 1965.
7-19
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8.0 BORON COMPOUNDS
8.1 INDUSTRY BACKGROUND1'2'3
Boron is used mainly in the form of its many compounds,
of which borax (sodium borates) and boric acid are the most
common. Uses of boron compounds in the order of decreasing
importance include production of glasses, enamels, soaps and
detergents, agricultural chemicals, fluxes for metal work-
ing, abrasives, medicines, Pharmaceuticals, and many mis-
cellaneous applications.
The United States is the world's largest producer of
boron compounds, supplying 71 percent of the total demand,
and the largest consumer, requiring 36 percent of the total
demand. In 1971, the United States produced 949,800 metric
tons of boron compounds of which about one-haIf was ex-
ported. The United States imported only 6350 metric tons of
boron compounds (colemanite) during the same period.
Five companies account for most of the boron compounds
produced in the United States. All are located in California,
which provides the entire domestic production of boron
minerals. Three are located on Searles Lake in San Bernardino
County, producing boron compounds as coproducts from the
brines of the lake. The largest producer is located in Kern
8-1
-------
County, and the other source is in the Furnace Creek dis-
trict of Inyo County. At this location the boron is mined
from deposits. Table H-l in Appendix H lists the principal
producers and their capacities.
Research continues on new uses of boron compounds.
Possible applications include the use of boron as rein-
forcement in aircraft structures and the use of colemanite
as a substitute for fluorspar in the EOF steel-making pro-
cesses .
8.2 RAW MATERIALS
Elemental boron is a black or brownish powder in the
amorphous form and a black, hard, brittle solid in the
crystalline form. The elemental form is not encountered in
nature. Boron usually occurs as a hydrated borate or as
borax in brines. Compositions of the various boron minerals
are summarized in Table 8.1.
2
Table 8.1 PRINCIPAL BORON-CONTAINING MINERALS
Mineral
Composition
Borax (tincal)
Kernite (rasorite)
Colemanite (borocalcite)
Ulexite (boronatrocalcite)
Ca0B,.01 -5H00
2. D 11 2.
CaNaBr-0 -BIUO
59
Priceite (pandermite)
Boracite (stassfurtite)
Sassolite (natural boric acid)
A description of the more important minerals follows,
8-2
-------
Borax (sodium tetraborate decahydrate) - composed of 36.6
percent B20_, 16.2 percent Na,,0, and 47.2 percent H-O.
Calcining increases the B-0, content to 69.2 percent. Borax
occurs in the Kern County deposits and in solution in
Searles Lake.
Kernite {sodium tetraborate tetrahydrate) - composed of 51.1
percent B_0_, 22.6 percent Na»0, and 26.3 percent H_O.
Calcining increases the B-0 content to 69.2 percent.
Kernite occurs mainly in the Kern County deposits.
Colemanite (calcium borate penthydrate) - composed of 50.9
percent B203, 27.2 percent CaO, and 21.9 percent H2O.
Calcining produces 65.2 percent B-O-. Colemanite occurs in
the deposits in Inyo County.
8.3 PRODUCTS
The primary commercial compounds of boron are sodium
tetraborate decahydrate, sodium tetraborate pentahydrate,
anhydrous sodium tetraborate, boric acid, and boric oxide.
By-products produced along with boron compounds include
sodium sulfate, potassium, lithium, and bromine.
8.4 PROCESS DESCRIPTION
Figure 8.1 illustrates the process steps in production
of boron compounds. Processing of brines is not considered
in this report. In the production of borox, boric acid, and
boric oxide, the emission potential varies widely from plant
to plant. Reference 5 gives a range of particulate emis-
sions from 0.1 to 20 grams per kilogram (0.2 to 40 Ib/ton)
of product.
8-3
-------
8.4.1 Mining
(1*) Borates are mined by the open-pit method. A typical anal-
ysis of California borate ore is presented in Table 8.2.
Table 8.2 ANALYSIS OF BORATE ORE FROM
KRAMER DISTRICT (CALIFORNIA)
Component
CaO
Na2°
B2°3
H20
Insoluble
sio2
A12°3
Ulexite, %
13.85
7.65
42.95
35.45
0.10
-
-
Kramer ite*, %
15.11
8.65
49.30
25.52
1.74
0.57
0.42
Borax, containing
32% H20, %
-
21.40
47.26
31.01
0.25
-
-
* "Kramerite" formula is same as ulexite, except it contains
five water molecules.
The mining operation is a source of atmospheric emis-
sions in the form of particles of the same composition as
the ore being mined. The range of particle size is 0.5 to
20 microns. Emissions amount to about 0.5 gram per kilogram
(1 Ib/ton) of ore mined. The ore is extracted by use of
explosives and electric shovels and is removed from the pit
by belt conveyors and trucks.
8.4.2 Beneficiation
The ore is beneficiated to concentrate the borate
component. Several steps are involved in the concentration
process.
* Numbers refer to corresponding processes in Figure 8.1.
8-4
-------
BORAX PRODUCTION
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_ J
BORIC ACID PRODUCTION
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Figure 8.1 Boron industry
-------
(2) Blending and Crushing - The lumps of ore are crushed to a
size that is easy to process and gives a good yield of
borates. The ore is also blended to give a fairly con-
sistent borate content in the feed.
Crushing causes some emission of particulates to the
atmosphere. Composition of the particles is similar to that
of the borate ore.
(3) Mixing and Filtration - The crushed ore is mixed with a weak
borax solution or mother liquor returning from the crys-
tallizers and centrifuges and then heated and agitated to
dissolve the borates. The solution is kept near boiling
temperature to dissolve the maximum amount of borax. In-
soluble rocks, clays, and other materials are separated by
means of screens, sedimentation, and/or filtration. The
residual muddy solution contains fine gangue materials.
The screened material is dumped on the tailings pile
and may present potential problems of fugitive dust and solid
waste disposal.
(4) Thickeners - The muddy solution is run through a series of
thickeners and filters to remove the remaining impurities.
The temperature of the solution is maintained at 93°C to
ensure maximum recovery of the borax.
Again the impurities are dumped on the tailings pile as
solid waste.
8.4.3 Borax Production
Concentrated liquor from the beneficiation process may
be treated in several ways depending upon the product desired,
8-6
-------
Production of borax pentahydrate and borax decahydrate
entails the following processes.
(5) Crystallizer and Centrifuge - As the hot solution is cooled
in the crystallizer, borax crystals grow and settle to the
bottom. Excess water is evaporated by applying a vacuum.
The crystals are separated from the remaining solution in
the centrifuge. This solution is recirculated to the mixer
(Process 3 in Figure 8.1).
The only emission from this process is water vapor.
(6) Dryer - Borax crystals from the centrifuge are moist. The
moisture is removed by passing the crystals through a steam-
heated dryer. The product from the dryer is refined borax
in the form of borax pentahydrate and borax decahydrate.
Emissions from the dryer include borax particulates and
water vapor. The particulates amount to about 14 grams per
kilogram (28 Ib/ton) of borax processed. Borax is moder-
ately toxic.
8.4.4 Anhydrous Borax Production
Borax decahydrate may be further processed to obtain
anhydrous borax.
(7) Calciner and Fusion Furnace - The dry borax decahydrate or
wet borax decahydrate from the centrifuge is partially
dehydrated in the calciner. The effluent gases are usually
treated in a cyclone followed by a wet scrubber. Dust
collected in the cyclone is added to the calciner discharge,
and water from the scrubber is recycled through the borax
refining process. The calcined borax next enters a fusion
8-7
-------
furnace, where it becomes molten. The furnace is usually
gas-fired.
Although the calciner generates dust, emissions to the
atmosphere are controlled by the cyclone and wet scrubber.
Slag formed in the calciner is discarded to the tail-
ings pile.
Combustion products from the furnace are the only
significant emissions.
(8) Molding, Crushing and Screening - The molten anhydrous borax
is subjected to a number of finishing operations depending
upon the desired physical characteristics. If the crys-
talline form is desired, the molten borax is cooled in
molds, then crushed and screened to the desired size. If
the amorphous form is desired, the molten anhydrous borax is
run between water-cooled rolls, then crushed and screened to
the desired size.
In both cases, the crushing and screening process
creates particulate emissions. The particles are essen-
tially pure borax, which is considered moderately toxic.
8.4.5 Boric Acid Production
Boric acid is manufactured from the concentrated borax
solution. The processes are described below.
(9) Reactor - The concentrated borax solution is charged into a
reaction vessel along with sulfuric acid, sulfur dioxide,
and sodium sulfate. The subsequent reaction produces a
combination of boric acid in solution and sodium sulfate
crystals.
8-8
-------
The temperature is kept at 100°C to hold the boric acid
in solution. The process has no known pollution potential.
(10) Centrifuge, Crystallizer - The solution from the reactor is
centrifuged to collect the sodium sulfate crystals. The
remaining solution is cooled to 40°C to precipitate most of
the boric acid. The boric acid is recovered in a centri-
fuge, and the excess solution is recycled to the mixer
(Process 3 in Figure 8.1).
This process has no known pollution potential.
(11) Dryers - The wet boric acid crystals and the sodium sulfate
by-product are dried in separate dryers. Some boric acid
and sodium sulfate are emitted as particulate from these
dryers but emission rate data are not available.
8.4.6 Boric Oxide Production
(12) Heating Vessels - Boric oxide may be produced by heating
boric acid. One method entails heating finely ground boric
acid slowly to 260°C in a vacuum and holding for 6 hours. A
second method involves heating boric acid in a loosely
covered container for several days.
Both processes emit small amounts of boric oxide, which
is moderately toxic.
8.5 MAJOR POLLUTANT SOURCES
The pollution problems caused by the entire boron
mineral industry are minor in comparison to other non-
metallic processing industries. The emission potential from
borax, boric acid and boric oxide producing plants, varies
8-9
-------
from plant to plant. Tailing materials from filter and
thickener operations in the industry are potential solid
waste problems. The dryers, calciners, and fusion furnaces
emit particulate which can be classified as moderately
toxic.
8-10
-------
REFERENCES FOR CHAPTER 8
1. Wang, K.P. Boron. In: Minerals Yearbook, U.S. Bureau
of Mines. 1971.
2. MacMillan, R.T. Boron. In: Mineral Facts and Prob-
lems. Bureau of Mines Bulletin 650. U.S. Department
of the Interior, Washington, D.C. 1970.
3. Kirk-Othmer, Encyclopedia of Chemical Technology. John
Wiley and Sons, Inc, Second Edition, New York, 1967.
4. Smith, N.C. Borax and Borates. In: Industrial Min-
erals and Rocks. The American Institute of Mining,
Metallurgical and Petroleum Engineers. New York.
1960.
5. Davis, W.E. National Inventory of Sources and Emis-
sions. Barium, Boron, Copper, Selenium and Zinc.
Section II. Boron. May 1972.
6. Shreve, R.N. Chemical Process Industries. McGraw-
Hill, Inc. New York. 1967.
8-11
-------
9,0 MICA INDUSTRY
1234
9.1 INDUSTRY BACKGROUND ' ' '
Mica, a group of minerals of which muscovite and
phlogopite are the most common, is generally classified as
sheet mica or scrap mica. Sheet mica (including block,
film, and splittings) can be formed into desired shapes for
industrial use and is precisely defined by ASTM specifica-
tion D351-60T; scrap (or flake) mica is any mica that does
not meet the standards of sheet mica. Most scrap mica is
made into ground mica. Recently synthetic micas, the most
common of which is fluorophlogopite, have become commer-
cially available at relatively low cost and in high purity.
Raw materials for synthesis of these compounds are abundant,
and they can be produced in any desired quantity at ambient
pressures. These compounds can be treated by isomorphic
substitution to create varieties with unusual properties,
and usage of the synthetic micas is expected to increase.
Because the process requires much skilled hand labor,
very little sheet mica is produced in the U.S. (none in
1970, 7.7 metric tons in 1971). U.S. producers sold or used
115,200 metric tons of scrap and flake mica in 1971.
Since most mica deposits average from 5 to 18 percent re-
9-1
-------
coverable muscovite, producing this amount requires 0.45 to
2.27 million metric tons of ore.
Over half of the scrap and flake mica produced in 1971
came from North Carolina, most from the Spruce Pine, Franklin-
Sylva, and Shelby districts. Another 2 percent came from
Connecticut, and the remainder came from Alabama, Arizona,
Colorado, Georgia, New Mexico, Pennsylvania, South Carolina,
and South Dakota. Producers usually have integrated plants
for mining, beneficiation, and grinding scrap mica. Table
1-1 in Appendix I, lists producers of mica in the United
States.
The sheet mica used in the U.S. comes from India and
the Malagasy Republic. In 1971, 640 metric tons of sheet
mica were imported into this country, most of it for use by
the electrical industry. Since essentially all of the
sheet mica used in the U.S. is imported and processed by the
ultimate user, this report is concerned primarily with the
scrap mica industry.
Mica production in the U.S. has been fairly steady in
recent years. Production of sheet mica from 1967 to 1971
has been no higher than 9 metric tons per year. Production
of scrap and flake mica during that time ranged from 107,500
metric tons in 1967 to 120,600 metric tons in 1969.
Prior to the 1950's, most mica was processed by washer
plants. With the development of a process using a Humphrey's
spiral, mica recovery rates increased from approximately 50
percent to 80 percent. In more recent years the Bureau of
9-2
-------
Mines has developed a flotation process, which has been
proven in the laboratory but is not yet used on a large
scale.
9.2 RAW MATERIALS
Although a small amount of scrap mica is obtained as
the by-produc.t of mining, trimming, and fabricating sheet
mica, the raw material for either washer plants or Humphrey's
spirals is mica ore. Mica is commonly found in many meta-
morphic and igneous rocks and in quartz, feldspar, pyrite,
carbonates, and other minerals. Wherever possible, weath-
ered deposits are selected for mining. Since production of
ground mica is an integrated industry from mining through
grinding, the location of ore bodies can be presumed to be
the same as the location of the grinding mills listed in
Table 1-2 of Appendix I.
9.3 PRODUCTS
The largest use of dry-ground mica is in production of
rolled roofing and asphalt shingles. Wet-ground mica is
used largely as a pigment extruder in the production of
paint, and also in making wallpaper and rubber goods.
9.4 PROCESS DESCRIPTION4'5'6
Figure 9.1 illustrates the processes in the mica
industry. The ore is mined and beneficiated. The indi-
vidual operations are described in the following sections.
9.4.1 Mining
(1*) Dry Mining - Mica mining is an open-pit process. Bulldozers
or draglines remove the overburden ahead of the face.
* Numbers refer to corresponding processes in Figure 9.1.
9-3
-------
BENEFICIATION
GRINDING
CO
I
Htoa
»U
4.:
-------
Power-driven equipment such as power shovels, drag pans,
trucks, and bulldozers then remove the ore from the deposit
and transport it to beneficiation plants.
Fugitive dust is the principal pollutant discharged
from this type of mining. The dust contains, among other
minerals, mica (with a TLV of 706 particles per cubic
centimeter) and quartz (with a TLV of ^ '6 . , million
% quartz T JLU
particles per cubic meter).
Strip mining can increase soil erosion and lead to high
concentrations of particulates in run-off water. Removal of
large amounts of overburden and the subsequent disruption of
large areas of land are potential solid waste problems.
Since mica is usually mined near processing plants,
transportation problems are minimal. If the ore is trucked,
however, the trucking operation can cause additional fugi-
tive dust emissions. Exhaust emissions from dieselized
mining and hauling equipment, and noise from the blasting,
mining and transport of the ore may also create significant
environmental impact.
(2) Hydraulic Mining - In the hydraulic process water is di-
rected under pressure against the face. The ore is broken
up by the force of the water, washed from the face into a
sump, and then flumed or pumped to the processing plant.
Hydraulic mining offers the advantages of low investment and
operating costs. The principal limitation is that the
ambient temperature cannot be below the freezing point of
water.
9-5
-------
Wet mining entails few fugitive dust problems but can
generate high solids concentration in the run-off water.
Solid waste problems are similar to those encountered in dry
mining operations.
In an efficient hydraulic mining operation the process-
ing plant must be close to the mine to permit convenient
transportation of the ore slurry. This eliminates fugitive
dust and other emissions generated in transportation.
Because the ore deposit must be large enough to supply the
beneficiation plant for at least 2 years, most mica ore is
mined by the dry method. Some mines combine the two
methods.
9.4.2 Beneficiation
(3) Washer Plant - Mica ore is upgraded to a 95 to 98 percent
mica content by washer plants, which depend on differential
crushing and screening to separate the mica from the gangue.
Mica, being more flexible than quartz, pyrite, feldspar,
carbonates, and other minerals with which it is found, forms
flat plates in a crusher where other minerals are pulver-
ized. The mica remains long enough to be caught on the
trommel screens, but the unwanted material passes through
and is discarded. This process requires large amounts of
water and recovers only about 50 percent of the mica from
the ore. Operation is at ambient conditions.
The dust emitted into the air from the crushing oper-
ation is similar to that created in mining.
9-6
-------
Water may be contaminated by particulates from the
gangue. For several years mineral wastes from the Spruce
Pine district in western North Carolina were allowed to flow
into the power plant reservoir at Greenville, Tennessee.
These mineral wastes, along with normal products of erosion
and organic matter, filled the reservoir to a point where
storage of flood water was no longer significant and power
generation was of marginal value.
Approximately 90 percent of the ore processed by this
method is discarded; disposal of this material can create
serious problems.
A small amount of scrap and flake mica is shipped to
companies for use in making mica paper or built-up mica,
generally for electrical insulators. Most scrap and flake
mica is used to produce ground mica. Grinding is performed
at the beneficiation plant, so transportation is not re-
quired.
(4) Humphrey's Spirals - Humphrey's spirals recover approxi-
mately 80 percent of the mica from the ore. In this method
of concentration, the ore is ground and then sent through
the spiral where the mica is washed away from the gangue by
differences in specific gravity. This process also requires
large amounts of water.
Emissions from a Humphrey's spiral beneficiation plant
are similar to those from a washer plant except that a
deflocculating agent used in the process constitutes an
9-7
-------
additional water contaminant. Operating conditions and
energy requirements for pumping, crushing, and drying are
similar to those for a washer plant.
(5) Flotation - The Bureau of Mines has recently developed a
flotation method to concentrate mica, but the method is not
yet economically feasible. A small amount of mica is
obtained, however, as a by-product of flotation of feldspar
ore.
The amounts of energy required for concentration by
flotation are not significantly different from those for
other beneficiation methods. Chemicals used in flotation,
however, could increase waste water contaminants including
inorganic salts, fatty acids, amines, excess heat, and
alkalinity.
(6) Drying - The final beneficiation process is drying. Even if
the mica is to go to a wet-grinding operation, it is dried
to remove the quartz which tends to cling to wet mica.
Drying requires large amounts of heat; air contaminants
include hydrocarbons, sulfur oxides, and other pollutants
that depend on the source of heat for the dryers.
9.4.3 Grinding
(7) Dry Grinding - Dry grinding of scrap and flake mica is done
with buhr mills, rod mills, high-speed hammer mills, cage
disintegrators, or attrition mills. Dry, screened mica is
fed into the mill, where it is crushed and discharged into
an air separator, which returns the oversize particles for
9-8
-------
additional crushing. Various sized fractions are bagged for
marketing.
Particulate emissions from the grinding and bagging
activities are probable sources of atmospheric pollution.
Wet Grinding - Done with a mica-on-wood grinding action and
enough water to preserve a paste consistency, wet grinding
is usually performed in chaser mills. Water is separated
from the final product by settling, pressing, or centri-
fuging.
Water discharged from these plants may contain
suspended solids and heat.
(9) Drying - After wet-ground mica is drained or pressed to
remove most of the water, it is put in steam-heated kettles
or rotary dryers, heated to drive off traces of water, then
sized and bagged for marketing. As in other drying pro-
cesses, gaseous pollutants result from heating, the most
probable emissions being hydrocarbons and sulfur oxides.
Particulates may be emitted from the bagging step but are
usually well controlled.
(10) Micronizing - Superheated steam from high-pressure jets
breaks the mica into fine fragments, yielding mica particles
in the 5 to 20 micron size range. Production of the steam
requires large amounts of energy. The process occurs at
ambient pressure.
Water pollutants may be discharged with condensate;
fugitive dust and solid waste problems seem unlikely.
9-9
-------
After grinding, the product is bagged and shipped to
the consumer.
9.5 MAJOR POLLUTANT SOURCES
Since very little mica is mined in the U.S., environ-
mental problems do not arise from large amounts of solid
waste generated from the mining of mica. Disposal of re-
jected fine mica and other waste rock generated by bene-
ficiation of the host rock is an environmental problem.
9-10
-------
REFERENCES FOR CHAPTER 9
1) Petkof, Benjamin. Mica. In: Minerals Year Book, Volume
1. Bureau of Mines. 1971.
2) Readling, Charles L. Mica. In: Minerals Year Book,
Volume I-II. Bureau of Mines. 1969.
3) Petkof, Benjamin. Mica. In: Minerals Year Book, Volume
I-II. Bureau of Mines. 1967.
4) Lesure, Frank G. Mica. In: United States Mineral
Resources. Geological Survey Professional Paper 820.
U.S. Department of the Interior.
5) Kirk-Othmer. Encyclopedia of Chemical Technology.
Wiley and Sons, Inc., New York. 1967.
6) Industrial Minerals and Rocks. Seeley W. Mudd Series.
American Institute of Mining, Metallurgical, and
Petroleum Engineers. New York. 1960.
9-11
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10.0 FLUORSPAR
10.1 INDUSTRY BACKGROUND1'2
In the United States, fluorspar is used as a flux in
open-hearth steel furnaces; in aluminum refining; in the
smelting of copper, silver, gold, and lead; and in the
manufacture of hydrofluoric acid. Fluorspar is natural
calcium fluoride (CaF-), occurring as a gangue associated
with metallic ores such as lead, zinc, and silver, and with
quartz, calcite, dolomite, or barite.
The steel industry is the major consumer of fluorspar
in the U.S., consuming 43 percent of total U.S. production
in 1971. The chemical industry consumed another 37 percent,
mainly in the manufacture of hydrofluoric acid (HF). The
aluminum industry accounted for 15 percent, and the re-
maining 5 percent went to other uses. New uses are being
discovered constantly; these include applications in medi-
cine, in propulsion motors for a nonpolluting automobile, in
fluorocarbon paint to resist fires, in new polymerization
catalysts, in electrochemical cells, and in new fluorinating
agents.
In 1971, 246,800 metric tons of fluorspar were mined
and processed in the United States. This represents 5
10-1
-------
percent of the world's output. In 1971, the U.S. consumed
1,220,000 metric tons, or 26 percent of the world's output.
Of the 972,900 metric tons imported into the U.S., Mexico
supplied 79 percent.
Illinois mines are the major producers of fluorspar in
the U.S., accounting for 51 percent of the U.S. shipments in
1971. Other states producing fluorspar are Colorado,
Montana, Nevada, New Mexico, Idaho, Utah, Arizona, and
Kentucky. Twenty-eight mines are in operation, controlled
by 22 companies. Table J-l in Appendix J lists the principal
producing mines.
Based on the present ratio of domestic production to
demand, the currently known U.S. resources of fluorspar will
be depleted in 20 to 25 years. It is believed, however,
that as known reserves are depleted, advancing technology
will allow better exploration and more efficient recovery of
fluorspar deposits, but at proportionate price increases.
This trend is evident now, as today's rising prices en-
courage many companies to spend considerable amounts of
money and time in exploration for new deposits.
10.2 RAW MATERIALS
Fluorspar is weakly radioactive and is a moderately
hard, glassy mineral occurring in a variety of colors.
Fluorspar ore is the only material needed for pro-
duction of the principal grades of fluorspar. The ore from
different states is described below.
10-2
-------
3
Illinois-Kentucky - One of the most important fluorspar
deposits in the world occurs in the southeastern part of
Illinois and western Kentucky. The Illinois portion lies in
Hardin and Pope counties; the Kentucky segment lies in six
counties, the principal producing areas being in Crittenden
and Livingston counties. Fluorspar occurs as veins with
thickness ranging from a film to more than 9.14 meters. Al-
though chiefly associated with limestone and sandstone, it
is sometimes associated with galena, sphalerite, calcitef
and barite.
4
Colorado - The mineral occurs in beds or veins in granite
or volcanic rocks, which are highly acidic with high silica
and low calcium content.
The fluorspar deposits are found mainly in a belt
roughly paralleling the eastern side of the Front Range.
Several productive areas also occur in the southern and
southwestern parts of the state, and a few deposits of no
economic significance are scattered throughout the moun-
tains.
New Mexico - The known fluorspar deposits are in the moun-
tain regions. The deposits occur in fissures and fault
breccia, and in cavities of less fractured rock. Most
deposits occur in groups of veins or masses, but a few do
occur singly. The deposits may contain one or more ore
bodies, which commonly constitute only a small part of the
entire deposit.
10-3
-------
Nevada - The deposits are in the Spor mountain region and
occur in sedimentary rock.
Idaho - The deposits are in Lenhi County. They range in
size from isolated veinlets to large ore bodies as much as
several hundred feet long and up to 20 feet wide. The
fluorspar is usually associated with calcite and barite.
7
Utah - Deposits occur in Beaver, Jaub, and Joole counties.
The ore is found chiefly in veins and faults. Most deposits
are epithermal, formed by the filling of fault fissures and
interstices in fault breccia. The Jaub county deposits have
an abnormally high uranium content.
Montana - The ore occurs in granite. Fluorspar associated
with metalliferous deposits also has been found in some
localities.
Arizona - Fluorspar is a common gangue mineral in veins, but
very few deposits have yielded fluorspar on a commercial
basis.
Table 10.1 presents an analysis of 18 fluorspar ores
from various mines. Table 10.2 gives a spectrographic
analysis of several additional fluorspar ores.
10.3 PRODUCTS
Three grades of fluorspar are produced: metallurgical
grades contain 60, 70, and 72.5 percent effective calcium
fluoride (CaF2); ceramic grades range from 85 to 96 percent
CaF_; and acid grades contain greater than 97 percent CaF2.
The main by-products of the fluorspar industry are zinc
and lead. Small quantities of silver, cadmium, germanium,
and stone are also produced.
10-4
-------
Table 10.1 ANALYSIS OF FLUORSPAR
Composition
CaF2
sio2
Fc203 & A1203
CaCOj
BaS04
Zn
Pb
Ag
Au
1,2,3,4:
5,6,7,8,9:
10,11-.
12,13,14,15,16:
17:
18:
1 2
36.7 63.6
24.9
2.5
32.5
0.01
345
2.39 78.97 34.12
IS. 29 22.70
4.19 16.21
1.13 26.47
-
2.17
6
72.73
27.72
8.14
11.41
-
1.75
0.22
7 8 9 10 11 12 13
21.43 13.40 4.29 2.38 45.76 73.94 54.21
25.86 68.20 35.32 42.70 8.90 7.0 17.74
22.51 12.34 18.50
30.20 6.06 41.89 - 26.12
-
1.26 0.77 18.00 2.31
5.01 0.53
1,1
0.02
14 15 16 17 18
47.26 39.87 55.39 18.10 59.54
26.8 1.68 21.98 9. 59 38.67
0.80
54.42 20.81 0.50 0.57
0.12 1.58 1.79
2.1 Trace 0.10
0.005 Trace Trace
Knox & Yingling Cluorite mines, Hardin Co., 111. (at different depths of different holes).
Ridge clay Lickfault, Livingston Co., Kentucky (at different level at the same deposit).
Columbia mine, Kentucky (at different locations) .
Fluorspar from Montana.
Meyers Cove, Lemhi County, Idaho.
Blackbird Mine, Hew Mexico.
-------
O
t
Table 10.2 SPECTROGRAPHIC ANALYSIS OF FLUORITE FROM ILLINOIS AND KENTUCKY
(parts per million)
Sample Location
Oxford Mine, 111.
Early yellow
Oxford Mine, 111.
Early colorless
Rose Mine, Hicksdome, 111.
Colorless
Green
Oxford Mine, 111.
Blue
Deardorf Mine, 111.
Early purple
Late purple
Lone Oak, Mercer Co.,
Early colorless
Late purple
Volga, Clayton Co., Iowa
Colorless
Type of
Analysis
SQ
SQ
Q
Q
Q
SQ
SQ
SQ
SQ
As
nd
nd
nd
nd
nd
nd
nd
Mn
nd
nd
nd
nd
nd
0.0002
0.0007
Ti
nd
nd
nd
nd
10
0.02
nd
Ba
20
nd
7
7
50
nd
Na
nd
nd
0.0370
0.0280
0.0310
nd
Fe
nd
nd
0.01
0.006
0.0002
nd
nd
0.0030
0.0150
nd
Cu
nd
nd
0.0002
0.0002
0.0002
nd
4
0.0001
0.0015
nd
Sr
300
0.0050
0.0034
0.0037
0.0026
0.005
0.007
0.05
1.5
0.007
Y
70
0.2002
0.004
0.004
<0.02
0.002
0.002
0.0015
0.0015
nd
SQ: Semi-quantitative, Q: Quantitative, nds below the limit of detection.
-------
10.4 PROCESS DESCRIPTION
Figure 3.0.1 illustrates the steps involved in producing
fluorspar. The ores are mined, beneficiated, and agglomerated
to meet specifications depending upon the ultimate use. The
individual processes and their emission potentials are
described in the following sections.
10.4.1 Mining9
(1*) Mining is done by metal-mining practices, usually by top-
slicing, cut-and-fill, and shrinkage and open stopping.
Bedded deposits are usually worked by the room-and-pillar
system. Mining is done by shafts, drifts, and open cuts.
Mines range in size from small operations with mostly hand-
operated equipment to large operations extensively mecha-
nized with diesel-powered hauling and loading equipment.
Fugitive dust emitted in mining has essentially the
same composition as the ore being mined.
Water from subsurface mining operations usually is
polluted with finely crushed rock as well as some oil,
hydraulic fluid, gasoline, and other materials commonly used
in the underground operations.
10.4.2 Beneficiation9 *1Q'll
Fluorspar ore, as mined, is generally intermixed with
other rocks and clays, which must be removed before com-
mercial distribution. The amount of refining depends upon
properties of the ore and the grade of fluorspar desired.
Following are descriptions of the typical processes in-
volved.
* Numbers refer to corresponding processes in Figure 10.1.
10-7
-------
o
I
CO
[DEPRESSANT
JflOCCUlANTS
FROTHING AGENTS
£AH«
FUEL
lAlR
6
IHICKE1F.R
Cfi
-II-
8
GRINQI'IG
£
[BINDING
JAGENT
LUEL ?
PRODUCT
«IAUURGICAl-
GRAOE FLUORSPAR
Figure 10.1 Fluorspar industry
OACIO-GR,
CfRAHIC-
GRADE FLUORSPAR
GRAOF. FLUORSPAR
»CGLOK£ RAT 10.1
K)
PBOOUCI
HCTAILURG1CAL-
GRADC FLUORSPAR
-------
(2) Washing - A log washer or trommel screen removes any clays
associated with the ore. The raw ore is subjected to water
sprays as it travels up the log pulper, washing away the
clay and leaving the heavier rock. The rock is usually
screened to remove the larger lumps.
The liquid effluent from the washing operation contains
a heavy concentration of suspended solids and may also
contain a small quantity of dissolved salts.
Oversized material from screening is usually crushed or
deposited on a tailings pile by belt conveyors and/or a
bulldozer. Tailings are a solid waste problem.
(3) Heavy Media Separation - The ore minerals are separated from
waste in a cone containing a suspension of finely ground
ferrosilicon. The ratio of ferrosilicon to water is ad-
justed to give the suspension a specific gravity of 2.55 to
2.62 at the top of the cone, and 2.85 to 3.1 at the bottom.
Crude ore is introduced at the top of the cone. Heavy
minerals, such as fluorspar and metal sulfides, sink and are
recovered at the bottom of the cone. Light minerals float
and are carried away with the overflow. Ferrosilicon is
recovered magnetically and returned to the process.
The overflow water, containing light minerals, is a
possible pollution problem.
(4) Crushing and Screening - The ore is fed through a crushing
system for reduction to the desired fineness. Metallurgical
grades require sizes between 0.95 centimeter and 3.8 cen-
timeters. If the raw fluorspar ore is of metallurgical
10-9
-------
grade, it is crushed and screened to the proper size with no
previous refinement. To produce acid and ceramic grade
fluorspar the crushed and sized ore is fed to a ball mill in
conjunction with a cross-flow or spiral classifier. This
operation reduces the size to between 35 and 200 mesh. The
resultant "pulp" is maintained at greater than 60 percent
solids.
Virtually no air pollution results from the crushing
and screening operation if the ore is wet. Particulate is
evolved if the ore is dry, which may occur in production of
metallurgical-grade fluorspar. The particles emitted are of
the same composition as the raw ore (Tables 10.1 and 10.2).
For dry crushing and screening the particulate emission is
approximately 1 gram per kilogram (2 Ib/ton) of ore processed.
Water pollution is created in the form of suspended
solids in the classifier overflow. The concentration is
usually between 15 and 17 percent solids. A typical size
analysis of the suspended solids is given in Table 10.3.
Table 10.3 REPRESENTATIVE SCREEN ANALYSIS
OP CLASSIFIER OVERFLOW10
Sorcco Bite, Meih Pot
On 20 0.08
On 60 0.26
On 100 0.21
On ISO 3.17
On SCO 13,18
-ZOO 83.08
This process generates no significant solid waste.
Flotation - Further purification is achieved by treating the
ore minerals in flotation units by use of agitated water
baths to which are added frothing agents and reagents that
10-10
-------
selectively coat the minerals. The sequence of reagents and
flotation procedures varies according to the composition of
the ore and preferences of the mill operator.
Typical reagents are xanthates, acids, or sulfates.
The temperature of the water supplied to flotation
cells is usually around 38°C. This temperature is main-
tained throughout the system by injection of steam at
various points.
Tailings from the flotation operation are usually in
the form of a pulp containing 11 percent solids; thus they
present both water pollution and solid waste disposal
problems. The water contains all of the various reagents
added to the system along with the ore minerals. These
materials are not necessarily toxic/ but cause excessive
growth of algae and bacteria.
Settling ponds may remove most of the suspended solids,
but the organic reagents are still present in the effluent.
Fluorine is also present in the waste water in concentra-
tions that exceed those of normal surface waters.
(6) Filter and Dryer - The "pulp" from the flotation cells
usually contains between 20 and 40 percent solids. The
concentration is increased to about 60 percent solids in a
thickener. The moisture is further reduced with a filter.
The filter liquid is sent to a disposal area and the cake is
further treated.
(7) Dryer - The resulting filter cake may contain as low as 6
percent moisture, and is dried to less than 0.5 percent moisture
10-11
-------
in a rotary dryer at a temperature around 2609C. The dryer
can be oil- or gas-fired.
Without controls, the dryer can emit particulate with a
composition like that of the fluorspar product. A typical
analysis of acid-grade fluorspar appears in Table 10.4. The
amount of particulate emitted without controls is around 5
to 7.5 grams per kilogram (10 to 15 Ib/ton) of concentrate
processed, varying considerably according to the fineness of
the particles in the concentrate.
Table 10.4 ANALYSIS OF ACID FLUORSPAR CONCENTRATE10
Screen analysis 91.99 ( 300 mesh)
tnlclum fluoride 97.02
Calcium carbonate 1.89
Silica 0.94
R,0j 0.53
Sulphur 0.08
The remaining reagent is also emitted as vapor from the
dryer. The amount and composition depend upon the reagents
used and the percent moisture in.the filter cake.
Overflow from the thickener and the filter may contain
the flotation reagents and some dissolved minerals. Again,
the fluorine concentration is abnormally high.
No solid waste is generated in this process.
Grinding - After drying, the fluorspar concentrate is ground
to minus 325 mesh. Screw conveyors and elevators transport
the product to storage bins for subsequent shipment. En-
closed hopper cars are usually used to ship the product.
Particulates emitted in this operation have the com-
position similar to that of the fluorspar concentrate (Table
10-12
-------
10.4). Because the particles are small, the quantity of
emissions could be as much as 12.5 grams per kilogram (25
Ib/ton) of fluorspar produced.
8 n
(9) Agglomeration ' - Many fluorspar flotation plants are now
supplemented by pelletizing equipment. This equipment
allows the recovery of fine-grained flotation concentrates
of metallurgical quality by conversion to strong, weather-
proof agglomerates suitable for automatic feeding into steel
furnaces.
One type of equipment produces a spherical pellet in a
2.44-meter diameter rotating disc-type pelletizer. Dry feed
is mixed with a binder solution of sodium silicate with an
undisclosed additive. The "green" pellets are fed into a
long Porbeck baking oven and subjected to temperatures of
371 to 399°C for 20 to 30 minutes. The pellets withstand
outdoor exposures including freezing and thawing, and show
less dusting than natural gravel spar when exposed to
thermal shock in the steel furnace.
The main emission source in this operation is the
baking oven. Most of the emissions are vapors from the
sodium silicate solution. Essentially all of the binder
solution is emitted as vapors. A small amount of particu-
late is exhausted from the oven.
10.5 MAJOR POLLUTANT SOURCES
Fluorspar mining and milling produces no unusual
environmental hazards. However, insufficient ventilation at
10-13
-------
the Barnett Mine, Illinois on April 12, 1971 caused the
death of seven miners due to an accumulation of hydrogen
sulfide gas at deep levels -of the mine.
10-14
-------
REFERENCES FOR CHAPTER 10
1. MacMillan, R.T. Fluorine. In: Mineral Facts and
Problems. Bureau of Mines Bulletin No. 650. United
States Department of the Interior. Washington, D.C.
1970.
2. Wood, H.B. Fluorspar and Cryolite. In: Minerals Year
Book. U.S. Bureau of Mines. 1971.
3. Boston, Edron Sutherland. The Fluorspar Deposits of
Hardin and Pope Counties. Illinois State Geological
Survey. Bulletin No. 58. 1931.
4. Aurand, H.A. Fluorspar Deposits of Colorado. Colorado
Geological Survey. Bulletin No. 18. 1920.
5. Rothrock, H.E. and C.H. Johnson. Fluorspar Resources
of New Mexico. New Mexico Bureau of Mines and Minerals
Resources. Bulletin No. 21, 1946.
6. Cox, D.C. U.S. Geological Survey. 1015A, 1955.
7. Stoatz, M.H. and F.W. Osterwald. U.S. Geological
Survey. B-1069, 1959.
8. Economic Geology. Volume 63, No. 6, Page 655.
9. Kirk-Othmer. Encyclopedia of Chemical Technology. New
York. John Wiley & Sons, Inc., 1966.
10. West, L. and R.R. Walden. Milling Kentucky Fluorspar
Tailings. Mining Engineering 542-544, May 1954.
11. Maier, F.J. and E. Bellack. Fluorspar for Fluorida-
tion. Journal of the American Water Works Association.
January 1957.
12. Lindsay, G.C. Metal Mining and Processing. Volume 2,
26-28, 1965.
10-15
-------
11.0 RECOMMENDATIONS
The purpose of this study was to assemble production
data for nonmetallic minerals and descriptive data on
processes and emissions for selected industries. In pre-
vious chapters we have described background of industry,
availability of raw materials, products and their compo-
sition, processes, and significant emission sources. In
this chapter those processes are identified that should be
further evaluated because of their potential for emissions of
hazardous pollutants or fugitive dust.
These processes are:
0 Kilns (Cement Industry)
0 Kilns (Lime Industry)
0 Phosphate Rock Mining and Washing
0 Clay Mining
0 Hydrator (Thermal Phosphoric Acid Production)
0 Reactor (Wet-Process Phosphoric Acid Production)
KILNS (CEMENT INDUSTRY)
Cement kilns emit (uncontrolled) about 83.5 grams of
particulate per kilogram (176 Ib/ton) of cement processed.
Elements present in the particulate include Be, Cd, Cr, Cu,
11-1
-------
Fe, Mm, Ni, Pb, Sb, Sr , and V. Most of the particulate is
smaller than 10 microns in size. The effluent gas rate is
approximately 5319 grams per kilogram (2000 Ib/bbl) of
cement at about 760°C. The gas stream also contains alkali
sulfates, alkali chlorides, calcium fluoride , and fuel com-
bustion products. Cement plants may also release appre-
ciable amounts of mercury to the atmosphere.
KILNS (LIME INDUSTRY)
Lime kilns emit approximately 90 grams of particulate
per kilogram (180 Ib/ton) of lime. The particulate contains
raw limestone, calcined lime dust, fly ash, tar, and un-
burned carbon. Thirty percent of the emitted particulate is
below 5 microns in diameter and 10 percent is below 2
microns. The gaseous effluent is usually between 427 and
982°C and contains sulfur dioxide and sulfur trioxide if
fuel oil or coal are used.
PHOSPHATE ROCK MINING AND WASHING
In preparation of Florida pebble phosphate, approxi-
mately one ton of slime is produced for each ton of phos-
phate fertilizer produced. This waste, which is mainly
phosphate-clay-bearing slimes, contains about 3 to 5 percent
of very fine clay. These slimes are impounded by dikes or
earth dams in special ponds in which the solid material
settles. As of November 1973, some 162 million square
meters (40,000 acres) of active and inactive settling areas
existed. It is estimated that about 10 million square
11-2
-------
meters (2500 acres) of new settling pond areas are estab-
lished each year.
Earth dams have been known to fail. Recently, on
December 3, 1971, 1.8 million metric tons of slime cascaded
into the Peace River in Florida when a dam failed. (Since
1942/ about 20 dam failures have occurred releasing large
amounts of phosphate slimes). Since these slime ponds exist
for 10 to 25 years, there is always a potential for water
pollution. Table 6.6 presents the composition of slimes.
CLAY MINING
A large number of mines are located in heavily popu-
lated areas and cause some environmental problems. A con-
siderable amount of dust is generated which, although it may
not create any hazardous effects, does produce nuisance
problems. Clay dust problems are very significant in
Georgia's urban areas.
Approximately 27.2 million metric tons of waste mate-
rial are discharged annually from mining kaolin in Georgia,
1.8 million metric tons from mining fuller's earth along the
Georgia-Florida border, and 4.54 million metric tons from
mining bentonite in Wyoming.
Water pollution is also a problem in mining clay.
HYDRATOR (THERMAL PHOSPHORIC ACID PRODUCTION)
Phosphoric acid mist is discharged at an uncontrolled
rate of about 67.5 grams per kilogram (135 Ib/ton) of P2°5
produced. Many industries control the emissions using
11-3
-------
equipment with 99.5 percent efficiency. The acid mist particles
in the form of orthophosphoric acid (H PO.) range in size-from
0.4 to 2.6 microns. A typical effluent flow rate from the
hydrator is about 0.708 x 10 cm3/sec.
REACTOR (WET-PROCESS PHOSPHORIC ACID PRODUCTION)
The primary air pollutants are rock dust fluorides,
carbon dioxide, silicon tetrafluoride, hydrogen fluoride, and
phosphoric acid mist. Most modern wet phosphoric acid
plants use a scrubber. Emissions from a system of this type
are 0.025 to 0.05 gram fluorine per kilogram (0.50 to 0.1
Ib/ton) of P2°5 Produced. Fluoride emissions are toxic.
The next study phase should consist of obtaining de-
tailed information for each of these processes on the emis-
sion characteristics and the approximate degree of emissions
control. This phase would entail several plant inspections
of each process and discussions with appropriate personnel
from the industry, their design/process engineers, and
emission control equipment manufacturers. Emission source
tests may also be required for several processes to obtain
necessary data on emission particle size distribution and
composition.
A consistent quantitative procedure of ranking these
processes should then be used to identify the most sig-
nificant sources. This procedure should encompass the
qualitative factors, listed above, which were used in the
initial selection. For example, such a procedure might
11-4
-------
include determination of the "area of significant pollution
impact;" such an area could be estimated by considering
probable distance of significant pollutant transport coupled
with probable health impact. Health impact determinations
should be based upon consideration of the particle size
distribution and particle composition. Such a study should
be a cooperative effort with EPA's Health Effects Research
Laboratory. Once the "significant impact area" is deter-
mined, the population living or working within such areas
could be determined and an emissions control priority
established for all processes, not only for the significant
sources identified by this study but for those identified in
parallel studies.
11-5
-------
APPENDIX A*
PRODUCTION AND CONSUMPTION STATISTICS
* A table for conversion of English to metric units of
measurement is given on Page A-2.
A-l
-------
Table A-l FACTORS FOR CONVERSION OF ENGLISH TO METRIC UNITS
Multiply
(English unit)
By
To obtain
(Metric unit)
Atmosphere 760.0
BTU (British Thermal Unit) 252.0
Cubic foot 28.32
Foot 30.48
Gallon (US) 3.785
Grain 0.065
Horsepower 0.7457
Ounce (avoirdupois) 28.35
Ounce (fluid) 29.57
Pound 453.6
Ton (long) 1016
Ton (short) 907.0
Watt 0.0143
millimeter of mercury
gram calorie
liter
centimeter
liter
gram
kilowatt
gram
milliliter
gram
kilogram
kilogram
kilo calorie/minute
A-2
-------
>
TRIPOLI
75,134
Sp. SILICA-
STONE
2,349
GARNET
18,984
ENERGY
1,586
ARTIFICIAL
ABRASIVES
472,299
TOTAL:
MATERIAL
MINED
570,352
IMPORTS
EXPORTS
PROCESSED
RE-EXPORTS
*
USES-
ABRASIVE
APPLICATIONS
AND AS A
FILLER
Quantities are expressed in short ton units,
*Data not available.
Figure A-l Abrasive materials production and consumption statistics (1971)
-------
MINED
130,882
PROCESSED
812,249
USES:
ASBESTOS CEMENT,
PIPE AND
BUILDING PRODUCTS
25%
FLOOR TILE
18%
FELTS AND PAPERS
14%
FRICTION
PRODUCTS
10%
TEXTILES
3%
PACKING AND
GASKETS
3%
SPRAYED
INSULATION
2%
MISCELLANEOUS
25%
Quantities are expressed in short tons.
Figure A-2 Asbestos production and
consumption statistics (1971) .
A-4
-------
MINED
1,047,000
IMPORTS
7,000
EXPORTS
523,000
PROCESSED
1,054,000
Quantities are expressed in
short tons.
CONSUMED - 531,000
USES:
HEAT RESISTANCE
GLASS
15%
INSULATION GLASS
FIBER
15%
TEXTILE GLASS
FIBER
15%
HOUSEHOLD AND
INDUSTRIAL
APPLIANCES
10%
SOAP AND CLEANSER
15%
AGRICULTURAL
PRODUCTS
10%
MISCELLANEOUS*
20%
*Abrasion resistance parts, catalyst in silicon production,
extinguishing agent for magnesium fires, plasticizers, adhe-
sive additives for latex paint, and dyeing leather textiles
Figure A-3 Boron production and
consumption statistics (1971) .
A-5
-------
PRODUCED
78,325,688
IMPORTS
3,087,336
EXPORTS
124,644
PROCESSED
81,288,380
USES:
READY-MIX
MANUFACTURING
63.1%
CONC. PRODUCT
MANUFACTURING
13.4%
HIGHWAY
CONSTRUCTION
9.4%
BUILDING MATERIAL
DEALERS
8.5%
MISCELLANEOUS
5.6%
Quantities are expressed in short tons.
Figure A-4 Cement production and
consumption statistics (1971).
A-6
-------
PRODUCED
56,666,000
IMPORTS
64,000
PROCESSED
56,730,000
EXPORTS
1,973,000
CONSUMED
54,757,000
BUILDING BRICK,
SEWER PIPE,
DRAIN TILE
40%
PORTLAND CEMENT
& CLINKER
20%
LIGHT WEIGHT
AGGREGATE
18%
MISCELLANEOUS*
22%
*Miscellaneous uses include:
Absorbent uses
Drilling mud
Floor and wall tile
Palletizing iron ore
Pottery
1% of total
12%
8%
-%
1%
Quantities are expressed in short tons
Figure A-5 Clay production and
consumption statistics (1971) .
A-7
-------
PROCESSED
535,450
USES:
FILTRATION
59%
INSULATION
3%
MISCELLANEOUS
INCLUDES
FILTERS
38%
All quantities are expressed in short tons.
*Imports: Same part of it is processed material.
Figure A-6 Diatomite production and
consumption statistics (1971).
A-8
-------
PROCESSED
663,343
GLASS MAKING
51%
POTTERY,
ENAMEL, ETC,
49%
Quantities are expressed in long tons
Figure A-7 Feldspar production and
consumption statistics (1971).
A-9
-------
IMPORTED
1,072,408
EXPORTED
12,491
CONSUMED
1,874,960
USES -'
IRON & STEEL
43%
CHEMICAL
INDUSTRY
37%
ALUMINUM
INDUSTRY
15%
MISCELLANEOUS
GLASS,
CERAMICS
5%
All quantities are expressed in short tons.
Figure A-8 Fluorspar production and
consumption statistics (1971) .
A-10
-------
PRODUCTION
W
IMPORTED
57,755
PROCESSED
N/A
EXPORTED
5,733
CONSUMED
39,172
BEARINGS
W
BRAKE LININGS
1,313
CARBON BRUSHES
380
CRUCIBLES,
RETORTS, ETC,
3,746
FOUNDRY
FACINGS
6,517
LUBRICANTS
2,843
PACKINGS
370
PENCILS
1,748
STEEL MAKING
4,358
All quantities are expressed in
short tons.
W: Information is withheld.
N/A: Not available.
Figure A-9 Natural graphite production and
consumption statistics (1971).
MISCELLANEOUS
17,706
A-ll
-------
CRUDE
GYPSUM
10,418,000
IMPORTS
6,094,000
PROCESSED
16,471,000
EXPORTS
41,000
INDUSTRIAL
263,000
BUILDING
1,016,000
PREFABRICATED
PRODUCTS
11,112,000
PORTLAND
CEMENT
RETARDER
3,386,000
AGRICULTURAL
GYPSUM
1,124,000
FILTER AND
UNCLASSIFIED
113,000
All quantities expressed in short tons.
Figure A-10 Gypsum production and
consumption statistics (1971).
A-12
-------
PRODUCTION
W
IMPORTS
1,179
PROCESSED
EXPORTS
24,024
USES :
MOSTLY FOR
REFRACTORIES
Quantities are expressed in short tons.
W: Specific kyanite production statistics are withheld,
Figure A-ll Kyanite and related minerals production
and consumption statistics (1971).
A-13
-------
MINERAL
19,591,000
IMPORTS
242,000
PROCESSED
19,833,000
EXPORTS
66,000
CONSUMED
19,767,000
AGRICULTURE
80,000
CONSTRUCTION
1,085,000
CHEMICAL
INDUSTRY
17,000,000
REFRACTORY
DOLOMITE
1,007,000
Quantities are given in short tons.
Figure A-12 Lime production and
consumption statistics (1971).
A-14
-------
UNCUT, PUNCH,
AND CIRCLE
MICA
17,005
SCRAP AND
FLAKE MICA
127,084
GROUND MICA
239,208,000
TOTAL
MINERAL
239,352,089
IMPORTS
13,103
EXPORTS
15,182
PROCESSED
239,336,907
N/A: Not available.
Quantities are given in short tons
CONSUMED
239,350,000
HI
USES OF GROUND MICA
ROOFING
17,835
WALLPAPER
N/A
RUSSER
5,284
PAINT
26,807
PLASTIC
479
WELDING RODS
N/A
JOINT CEMENT
45,230
ASHES
23,969
Figure A-13 Mica production and
consumption statistics (1971).
A-15
-------
PROCESSED
898,831
USES:
SOIL IMPROVEMENT 85%
OTHER
15%
Quantities are expressed in short tons.
Figure A-14 Peat production and
consumption statistics (1971).
A-16
-------
CONSUMED
(EXPANDED
MATERIAL)
432,000
USES:
FILTER - AID
14%
PLASTER
AGGREGATE
10%
CONCRETE
AGGREGATE
10%
MISCELLANEOUS
61%
HORTICULTURAL
AGGREGATE
3%
LOW TEMPERATURE
INSULATION
2%
All quantities are expressed in short tons.
Figure A-15 Perlite production and
consumption statistics (1971) .
A-17
-------
MINED*
127,752,000
IMPORTS
84,000
PROCESSED
127,836,000
EXPORTS
12,587,000
APPARENT
CONSUMPTION
27,788,000
PHOSPHORIC
ACID
15,407,000
ELEC. FURNACE
PHOSPHOROUS
5,516,000
TRIPLE SUPER-
PHOSPHATE
2,331,000
ORDINARY
SUPERPHOSPHATE
3,463,000
OTHER:
FERTILIZER,
FEED, ETC.
907,000
All quantities are expressed in short tons.
* Marketable product - produced = 38,886,000
Figure A-16 Phosphate rock production
and consumption statistics (1971) .
A-18
-------
MINED
4,578,000*
IMPORTED
4,672,000
EXPORTED
1,033,000
PROCESSED
9,250,000
CONSUMED
8,217,000
AGRICULTURAL
95%
CHEMICAL
5%
SOAP AND
DETERGENTS
35%
GLASS AND
CERAMICS
25%
TEXTILES
AND DYES
20%
All quantities are expressed
in short tons.
CHEMICALS
AND DRUGS
13%
MISC. 7%
* Sold by producers: 4,543,000
Figure A-17 Potash production and
consumption statistics (1971).
A-19
-------
PRODUCED
3,316,000
PROCESSED
3,716,000
IMPORTS
400,000
ROAD
CONSTRUCTION
48%
CONCRETE MIX
32%
RAILROAD
BALLAST
13%
ABRASIVE
MATERIAL AND
MISCELLANEOUS
7%
Quantities are expressed in short tons.
Figure A-18 Pumice production and
cpnsumption statistics (1971).
A-20
-------
>
EVAPORATED
SALT
5,928,000
USES:
ROCK SALT
13,700,000
SALT IN
BRINE
24,449,000
TOTAL SALT
PRODUCTION
44,077,000
IMPORTS
3,855,000
PROCESSED
47,932,000
EXPORTS
670,000
CONSUMED
47,262,000
Quantities are expressed in short tons.
CHLORINE MANUFACTURING
19,621,000
SODA ASH
6,358,000
SOAP
27,000
ALL OTHER CHEMICALS
1,259,000
TEXTILE
193,000
MEAT PACKERS AND TANNERS
653,000
FOOD CANNING, ETC.
1,012,000
FISHING
37,000
WATER SOFTENER
680,000
GROCERY STORES
1,236,000
STATE, COUNTY, ETC.
7,905
MISCELLANEOUS
BALANCE
Figure A-19 Salt
TOTAL: 44,283,000
production and consumption statistics (1971).
-------
SAND
PRODUCED
400,759,000
GRAVEL
PRODUCED
518,834,000
TOTAL
PRODUCTION
919,593,000
PROCESSED
919,593,000
USES:
CONSTRUCTION SAND
GRAVEL
INDUSTRIAL SAND,
UNGROUND
INDUSTRIAL SAND,
GROUND
MISCELLANEOUS -
GRAVEL
TOTAL:
374,594,000
508,699,000
24,248,000
1,911,000
10,141,000
919,593,000
Quantities are expressed in short tons.
Figure A-20 Sand and gravel production and
consumption statistics (1971).
A-22
-------
CRUDE
(SALT CAKE)
236,000
ANHYDROUS
33,000
PROCESSED
1,006,000
USES:
KRAFT PAPER
67%
GLASS, CERAMICS
AND TEXTILES
33%
Quantities are expressed in short tons.
Figure A-21 Sodium sulfate production and
consumption statistics (1971) .
A-23
-------
PRODUCED
7,153,000
PROCESSED
7,153,000
USES :
EXPORTS
437,000
GLASS MAKING
40%
CHEMICALS
23%
PULP AND PAPER
6%
MISCELLANEOUS
31%
Quantities are expressed in short tons.
Figure A-22 Sodium carbonate production
and consumption statistics (1971).
A-24
-------
?
to
Ul
PRODUCTION
OF NATIVE
SULFUR ORE
7,025,000
RECOVERED
ELEMENTAL
SULFUR
1,595,000
BYPRODUCT
SULFUR 1C ACID
(100% BASIS)
PRODUCED AT
Cu, Zn & ?b PLANTS
1,585,000
SULFUR
CONTENT
7,025,000
SULFUR
CONTENT
1,586,000
SULFUR
CONTENT
518,000
1
^
TOTAL
SULFUR
CONTENT
9,129,000
PYRITES
316,000
OTHER
FOR.MS
127,000
1
J 1
TOTAL SULFUR
CONTENT FOR
PROCESSING
10,999,000
IMPORTS
(PYRITES &
SULFUR)
1,427,000
EXPORTS .
(SULFUR)
1,536,000
. T
o stocks 283,000
i
AVAILABLE
FOR USES
(CONSUMPTION)
9,180,000
r
FOR
MANUFACTURING
OE FERTILIZERS
50%
PLASTICS, PAPER
PRODUCTS, PAINTS,
EXPLOSIVES, ETC,
24%
MISCELLANEOUS
USES
26%
All quantities are expressed in long ton units.
Figure A-23 Sulfur and pyrites production and consumption statistics (1971).
-------
PROCESSED
USES:
CONSTRUCTION
OF BUILDINGS, ETC,
* Data are expressed as dollars worth.
All quantities are expressed in short tons.
Figure A-24 Stone production and
consumption statistics (1971).
A-26
-------
MINED
1,037,000
IMPORTED
17,000
PROCESSED
1,054,000
EXPORTED
136,000
USES:
CERAMIC
270,358
PAINT
155,140
INSECTICIDES
63,381
PAPER
52,886
ROOFING
35,189
RUBBER
27,098
TOILET
PREPARATIONS
31,249
TEXTILE
4,985
OTHER
277,714
All quantities are expressed in short tons.
Figure A-25 Talc, soapstone, etc. (pyrophyllite)
production and consumption statistics (1971) .
A-27
-------
USES:
PLASTER AND CONCRETE
AGGREGATE
40%
INSULATION
38%
HORTICULTURE,
SOIL CONDITIONING,
ETC.
15%
MISCELLANEOUS
7%
All quantities are expressed in short tons.
Figure A-26 Vermiculite production and
consumption statistics (1971) .
A-28
-------
APPENDIX B
CEMENT PRODUCTION STATISTICS
B-l
-------
Table B-l
PRINCIPAL PRODUCERS OF CEMENT IN THE UNITED STATES
Company
to
American Cement Corp.
Calaveras Cement Co.
California Portland Cement
Co.
Ideal Cement Co.
Kaiser Cement & Gypsum Corp.
Monolitti Portland Cement Co.
Pacific Cement & Aggregates
Pacific Western Industries
Southwestern Portland Cement
Co.
Allentcwn Portland Cement Co.
County
Riverside & San
Bernardino, Calif.
Calaveras & Shasta, Cal.
Kern & San Bernardino,
Calif.
San Benito & San Mateo,
Calif.
San Bernardino & Santa
Clara, Calif.
Kern, Calif.
Santa Cruz, Calif.
Kern, Calif.
San Bernardino, Calif,
Berks, Pen P..
Type of Activity
Dry process and portland
cement process
Wet & dry process,
Portland cement plant
Dry process and portland
cement plant
Wet process and portland
cement plant
Wet process and portland
cement plant
Wet process and portland
cement plant
Dry process and portland
cement plant
Dry process and portland
cement plant
Wet & dry process, port-
land cement plant
Plant
-------
Table B-l (continued).
PRINCIPAL PRODUCERS OF CEMENT IN THE UNITED STATES
Company
County
Type of Activity
Allentown Portland Cement
Co.
Bessemer Cement Co.
Coplay Cement Manufacturing
Co.
Dragen Cement Co.
Coplay Cement Manufacturing
Co.
Green Bag Cement Co.
Hercules Cement Co.
Keystone Portland Cement
Co.
Lonestar Cement Corp.
Medusa Portland Cement Co.
Medusa Portland Cement Co.
National Portland Cement Co.
Penn-Dixie Cement Corp.
Universal Atlas Cement
Alpha Portland Cement Co.
Capitol Aggregates, Inc.
Montgomery/ Penn.
Lawrence, Penn.
Lehigh, Penn.
Northampton, Penn.
Northampton, Penn.
Allegheny, Penn.
Northampton, Penn.
Northampton, Penn.
Northampton, Penn.
Lawrence, Penn.
York, Penn.
Northampton, Penn.
Butler, Penn.
Lehigh, Penn.
Orange, Texas
Bexar, Texas
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Quarry & Plant
Plant
-------
Table B-l (continued). PRINCIPAL PRODUCERS OF CEMENT IN THE UNITED STATES
Company
to
i
Centex Cement Corporation
General Portland Cement Co.
Gifford-Hill & Co., Inc.
Gulf Coast Portland Cement
Co.
Ideal Cement Co.
Kaiser Cement & Gypsum Corp,
Lone Star Cement Corporation
San Antonio Portland Cement
Co.
Southwestern Portland Cement
Co.
Texas Industries, Inc.
Universal Atlas Cement Div.,
United States Steel Corp.
Aetna Portland Cement Co.
Div. of Martin Marietta Corp,
Dundee Cement Co.
Huron Cement Co., Div. of
National Gypsum Co.
County
Nueces, Texas
Dallas, Harris, & Tarrant,
Texas
Ellis, Texas
Harris, Texas
Harris, Texas
Bexar, Texas
Harris & Nolan, Texas
Bexar, Texas
Elliss El Paso, Texas
Ellis, Texas
McLennan, Texas
Bay, Michigan
Monroe, Michigan
Alpena, Michigan
Type of Activity
Quarry & Plant
Quarry & Plant
Quarry & Plant
Quarry & Plant
Quarry & Plant
Plant
Quarry & Plant
Quarry & Plant
Quarry & Plant
Quarry & Plant
Quarry & Plant
Wet process
Wet process
Dry process
-------
Table B-l (continued). PRINCIPAL PRODUCERS OF CEMENT IN THE UNITED STATES
Company
Medusa Portland Cement Co.
Peerless Cement Co.r Div. of
American Cement Corp.
Port Huron plant
Brennan Ave. plant
Jefferson Ave. plant
Penn.- Dixie Cement Corp.
Wyandotte Chemicals Corp.
County
Charlevoix, Michigan
St. Clair, Michigan
Wayne, Michigan
Wayne, Michigan
Emmet, Michigan
Wayne, Michigan
Type of Activity
Wet process
Wet process
Wet process
Wet process
Wet process
Wet process
i
ui
-------
Table B-2 PRODUCTION OF CEMENT IN UNITED STATES, BY STATES,
1971
State
Alabama
California
Florida
Georgia
Hawaii
Illinois
Indiana
Iowa
a
Kansas
Michigan
Missouri
Ohio
Pennsylvania
Tennessee
Texas
Washington
Amount in Thousands S. Tons Mined
Portland
12,149
48,493
11,581
6,458
1,993
7,578
W
12,726
9,208
32,489
24,017
15,411
41,753
9,110
38,287
W
Masonry
2,493
-
1,283
448
79
522
W
473
355
1,704
518
1,010
2,994
1,135
1,209
W
a) Excludes certain cements, included with value of items
that cannot be disclosed.
W Information withheld.
B-6
-------
APPENDIX C
CLAY PRODUCTION STATISTICS
C-l
-------
Table C-l PRINCIPAL PRODUCERS OF CLAY IN THE UNITED STATES
Company
o
i
Cairo Production Co.
Englehard Minerals &
Chemicals Corp.
Georgia, Tennessee Mining
& Chemical Co.
Thor Mining Co.
Waverly Mining Products
American Industrial Clay
Co. of Sandersville
Eaglehard Minerals &
Chemical Corp.
Freeport Kaolin Co.
Georgia Kaolin Co.
J. M. Huber Corp.
Burns Brick Co.
Chattahoochee Brick Co.
Cherokee Brick & Tile Co.
Merry Brothers Brick &
Tile Co.
Southern Cement Co., Div.
of Martin Mariella Corp.
Acne Brick Co.
County
Thomas, Georgia
Decatur, Georgia
Jefferson, Georgia
Thomas, Georgia
Thomas, Georgia
McDuffie & Washington,
Georgia
Washington & Wilkinson,
Georgia
Twiggs, Georgia
Twiggs, Georgia
Twiggs & Warren, Ga.
Bibb, Georgia
Floyd, Fulton & Polk, Ga.
Bibb, Georgia
Richmond, Georgia
Jasper, Georgia
Denton, Guadalupe.
Henderson, Nacogd -.ches,
Parker, Wise, To::,.:.-:
Type of
Mineral Produced
Fuller's earth
Fuller's earth
Fuller's earth
Fuller's earth
Fuller's earth
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Miscellaneous
Clays & shale
-------
Table C-l (continued).PRINCIPAL PRODUCERS OF CLAY IN THE UNITED STATES
Company
o
i
co
Alpha Portland Cement Co.
Dresser Minerals
Elgin Butler Brick Co.
Featherlite Corp.
General Portland Cement
General Refractories Co.
Gulf Coast Portland Cement
Co., Div. of McDonough
Henderson Clay Products Co.
Ideal Cement Co., Div. of
Ideal-Basic Industries Inc.
Lone Star Cement Corp.
The Millwhite Co., Inc.
Reliance Clay Products Co.
Southern Clay Products Inc.
Texas Clay Products Inc.
Texas Industries Inc.
AFC Corporation
The Belden Brick Co.
County
Orange, Texas
Angelina & Limestone,
Texas
Bastrop, Texas
Bexar & Eastland, Texas
Dallas, Harris, Lime-
stone, Texas
Cherokee, Texas
Chambers, Texas
Rusk, Texas
Galveston, Texas
Fisher & Harris, Texas
Fayette & Walker, Texas
Ellis, Palo Pinto,
and Smith, Texas
Cherokee & Genzales,
Texas
Henderson, Texas
Dallas, Eastland, Ellis,
& Fort Bend, Texas
Mahoning, Ohio
Stark & Tuscarawas, Ohio
Type of
Mineral Produced
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Clays & shale
Fire clay
Fire clay & shale
-------
Table C-2 PRODUCTION OF CLAYS IN THE UNITED STATES,
BY STATE, 1971
State
Georgia
Texas
Ohio
N. Carolina
Alabama
Arizona
Arkansas
California
Colorado
Connection tt
Delaware
Florida
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Minnesota
Mississippi
Missouri
Montana
Nebraska
New Hampshire
New Jersey
New Mexico
New York
Oklahoma
Oregon
Quantity in S. Tons
5,111,000
4,687,000
4,750,000
3,310,000 a
2,793,000
77,000
919,000 a
2,755,000 a
616,000 a
195,000
12,000
808,000 a
3,000
12,000 3
2,327,000 a
1,550,000
1,264,000
932,000
l,219,000'a
863,000
42,000 a
1,078,000 a
257,000
240,000 a
1,693,000
2,433,000
30,000
28,000
41,000
373,000
66,000
1,675,000
726,000 3
a
213,000
C-4
-------
Table C-2 (continued). PRODUCTION OF 'CLAYS' IN THE UNITED STATES,
BY STATE, 1971
State
Pennsylvania
South Carolina
South Dakota
Tennessee
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Quantity in S. Tons
3,034,000
1,936,000
226,000
1,562,000 a
160,000 a
1,462,000
255,000 a
193,000 a
17,000
1,828,000
a) Excludes certain clays, including value of items
that cannot be disclosed.
C-5
-------
APPENDIX D
GYPSUM PRODUCTION STATISTCS
D-l
-------
Table D-l PRINCIPAL PRODUCERS OF GYPSUM IN THE UNITED STATES
Company
a
i
Georgia-Pacific Corp.
Grand Rapids Gypsum Co.
Michigan Gypsum Co.
National Gypsum Co.
United States Gypsum Co.
United States Gypsum Co.
H. M. Holloway, Inc.
Temblor Gypsum Co.
United States Gypsum Co.
The Celotex Corp.
The Flintkote Co.
Georgia-Pacific Corp.
National Gypsum Co.
United States Gypsum Co.
United States Gypsum Co.
The Celotex Corp.
County
Kent, Michigan
Kent, Michigan
losco, Michigan
losco, Michigan
losco, Michigan
Wayne, Michigan
Kern, Calif.
Kern, Calif.
Imperial, Calif.
Fisher, Texas
Nolan, Texas
Hardeman, Texas
Fisher, Texas
Nolan, Texas
Harris, Texas
Webster, Iowa
Activity
Underground mine, cal-
cining, and board plant
Underground mine, cal-
cining, and board plant
Opem-pit mine
Open-pit mine, calcining,
and board plant
Open-pit mine
Calcining and board plant
Open-pit mine
Open-pit mine
Open-pit mine and calcining
plant
Open-pit mine and calcining
plant
Open-pit mine and calcining
plant
Open-pit mine and calcining
plant
Open-pit mine and calcining
plant
Open-pit mine and calcining
plant
Plant
Open-pit mine, calcining,
and board plant
-------
Table D-l (continued). PRINCIPAL PRODUCERS OF GYPSUM IN THE UNITED STATES
Company
o
i
u>
Georgia-Pacific Corp.
National Gypsum Co.
United States Gypsum Co,
United States Gypsum Co.
Arizona Gypsum Corp.
Verde Division
Winkelman Division
National Gypsum Co.
Dulin Bauxite Co., Inc.
Weyerhaesur Co.
Johns-Manville Products
Corp.
National Gypsum Co.
United States Gypsum Co.
Georgia-Pacific Corp.
National Gypsum Co.
National Gypsum Co.
United States Gypsum Co.
Winn Rock, Inc.
United States Gypsum Co.
County
Webster, Iowa
Webster, Iowa
Webster, Iowa
Des Moines, Iowa
Yavapai, Arizona
Pinal, Arizona
Pinal, Arizona
Pike, Arkansas
Howard, Arkansas
Fremont, Colorado
Martin, Indiana
Lake & Martin, Ind.
Marshall, Kansas
Barber, Kansas
Jefferson, Louisiana
New Orleans, Louisiana
Winn, Louisiana
Fergus, Montana
Activity
Open-pit mine, calcining,
and board plant
Open-pit mine, calcining,
and board plant
Open-pit mine, calcining,
and board plant
Underground mine, calcin-
ing and board plant
Open-pit mine and plant
Open-pit mine and plant
Open-pit mine and plant
Mine and plant
Mine and plant
Open-pit mine and wall-
board plant
Underground mine and cal-
cining plant
Underground mine and 2
calcining plants
Quarry and plant
Quarry and plant
Calcining plant
Calcining plant
Quarry and plant
Underground mine and cal-
cining plant
-------
Table D-l (continued)
PRINCIPAL PRODUCERS OF GYP-SUM IN THii UNITED STATES
Company
O
i
The Flintkote Co.
Johns-Manville Products
Corp.
United States Gypsum Co.
White Mesa Gypsum Co.
Georgia-Pacific Corp.
Georgia-Pacific Corp.
National Gypsum Co.
United States Gypsum Co.
United States Gypsum Co.
National Gypsum Co.
The Celotex Corp.
(Crude gypsum)
United States Gypsum Co.
(Crude gypsum)
National Gypsum Co.
(Calcined gypsum)
Republic Gypsum Co.
United States Gypsum Co.
Universal Atlas Cement
South Dakota Cement Comm,
County
Clark, Nevada
Clark, Nevada
Pershing, Nevada
Sandoval, N. Mexico
Erie, N. Y.
Westchester, N. Y.
Erie, New York
Genesee, New York
Richmond & Rockland,
N. Y.
Bronx, New York
Ottawa, Ohio
Ottawa, Ohio
Lorain, Ohio
Jackson, Okla.
Elaine, Okla.
Elaine, Okla.
Meade, S. Dakota
Activity
Open-pit mine
Open-pit mine
Open-pit mine
Open-pit mine
Underground mine and cal-
cining plant
Calcining plant
Underground mine and cal-
cining plant
Underground mine and cal-
cining plant
Calcining plant
Calcining plant
Pit
Underground
Plant
Quarry and plant
Quarry and plant
Quarry
Open pit mine
-------
Table D-l (continued). PRINCIPAL PRODUCERS OF GYPSUM IN THE UNITED STATES
Company
County
Activity
Georgia-Pacific Corp.
United States Gypsum Co.
United States Gypsum Co.
United States Gypsum Co.
Kaiser Gypsum Co.
Big Horn Gypsum Co.
Sevier, Utah
Sevier, Utah
Chesapeake, Va.
(Process imported gyp.)
Washington, Virginia
King, Washington
Park, Wyoming
Open-pit mine and calcin-
ing plant
Open-pit mine and calcin-
ing plant
Plant
Mine and plant
Plant
Open-pit mine and wall-
board plant
-------
Table D-2 PRINCIPAL GYPSUM PRODUCING STATES
IN THE UNITED STATES, 1971
State
Michigan
California
Texas
Iowa
Quantity (short
1,433,000
1,352,000
If303,000
1,154,000
tons)
Other producing states:
Arizona W
Arkansas W
Colorado W
Indiana W
Kansas W
Louisiana W
Montana W
Nevada 695,000
New Mexico W
New York 415,000
Ohio W
Oklahoma 1,022,000
South Dakota 21,000
Utah W
Virginia W
Washington W
Wyoming 232,000
D-6
-------
APPENDIX E
LIME PRODUCTION STATISTICS
E-l
-------
Table E-l PRINCIPAL PRODUCERS OF LIME IN THE UNITED STATES
Company
County & State
Type ot
Activitv
Basic Incorporated
Cuyahoga Lime Company
Diamond Shamrock Chemical Co.
The National Lime & Stone Co.
Huron Lime Co.
Ohio Lime Co.
Charles Pfizer & Co., Inc.
PPG Industries, Inc.
Republic Steel Corp.
Standard Lime & Refractories
Co.
Union Carbide Corp.
United States Gypsum Co.
U. S. Steel Corp.
The J. E. Baker Co.
Mercer Lime & Stone Co.
National Gypsum Co.
Standard Lime & Refractories
Co.
Warner Co.
Detroit Lime Co.
The Dow Chemical Co.
Marblehead Lime Co.
Seneca, Ohio
Cuyahoga, Ohio
Lake, Ohio
Wyandot, Ohio
Erie, Ohio
Sandusky, Ohio
Summit, Ohio
Lake, Ohio
Sandusky, Ohio
Ashtabula, Ohio
Ottawa, Ohio
Lorain, Ohio
York, Penn.
Butler, Penn.
Centre, Penn.
Centre, Penn..
Centre & Chester, Pa,
Wayne, Michigan
Mason, Michigan
Wayne, Michigan
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Quick lime,
shaft,
rotary kilns
Quick lime,
kiln & hydra-
tor
Quick lime &
kiln
E-2
-------
Table E-l (Cont'd.)PRINCIPAL PRODUCERS OF LIME
BY STATE, 1971
Company
County & State
Type of
Activity
Wyandotte Chemical Corp,
Aluminum Co. of America
Armco Steel Corp.
Austin White Lime Co.
Champion Papers, Inc.
The Dow Chemical Co.
Eastex, Inc.
McDonough Bros., Inc.
PPG Industries, Inc.
Round Rock Lime Co.
Texas Lime Co.
United States Gypsum Co.
Alabaster Lime Co.
Cheney Lime & Cement Co.
Longview Lime Co.
Southern Cement Co.
United States Gypsum Co,
Wayne, Michigan
Calhoun, Texas
Harris, Texas
Travis, Texas
Harris, Texas
Brazoria, Texas
Jasper, Texas
Bexar, Texas
Nueces, Texas
Hill & Williamson,
Texas
Johnson, Texas
Comal & Harris, Texas
Shelby, Alabama
Shelby, Alabama
Shelby, Alabama
Shelby, Alabama
Shelby, Alabama
Quick lime
& kiln
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Plant
Lime kiln
Lime kiln
Lime kiln
Lime kiln
Lime kiln
E-3
-------
Table E-2
PRODUCTION OF LIMP. TM THE UNITED STATES,
BY STATE, 1971
State
Ohio
Pennsylvania
Michigan
Texas
Alabama
Arizona
Arkansas
California
Colorado
Florida
Hawaii
Kansas
Louisiana
Massachusetts
Montana
Nebraska
New Mexico
New York
Oregon
Utah
Vermont
Virginia
West Virginia
Wisconsin
Wyoming
Quantity
(in s. . tons)
3,701,000
1,702,000
1,630,000
1,564,000
773,000
260,000
206,000
568,000
125,000
125,000
8,000
W
781,000
198,000
179,000
148,000
27,000
1,086,000
120,000
174,000
W
919,000
207,000
224,000
W
No. of Plants
10
5
7
3
15
11
3
2
1
4
2
4
4
1
3
3
6
W
8
3
6
3
W: Withheld
E-4
-------
Table E-3 LIME PRODUCED IN THE UNITED STATES, BY SIZE OF PLANT
(thousand short tons)
1,
Size of Plant
Less than 10,000 tons
10,000 to 25,000 tons
25,000 to 50,000 tons
50,000 to 100,000 tons
100,000 to 200,000 tons
200,000 to 400,000 tons
More than 400,000 tons
Total
1971
Plants
30
37
37
26
25
26
7
188
Quantity
138
590
1,404
1,775
3,805
7,215
4,708
19,635
Percent
of Total
1
3
7
9
19
37
24
100
1) Excludes regenerated lime. Includes Puerto Rico.
E-5
-------
APPENDIX F
PHOSPHATE INDUSTRY STATISTICS
F-l
-------
Table F-l
PRINCIPAL PHOSPHATE ROCK PRODUCING COMPANIES
IN THE UNITED STATES
Company
County & State
Agrico Chemical Co.
American Cyanamid Co.
International Minerals &
Chemical Corp.
Mobil Chemical Co.
U. S. S. Agri-Chemicals,
Inc.
Howard Phosphate Co.
Kellog Co.
Loncala Phosphate Co.
Soil Builders, Inc.
Sun Phosphate Co.
Monsanto Co.
J. R. Simplot Co.
Stauffer Chemical Co.
Hooker Chemical Corp.
Monsanto Co.
Stauffer Chemical Co.
Tennessee Valley Authority
M. C. West, Inc.
Texas Gulf Sulphur Co.
Monsanto Co.
Cuyama Phosphate Corp.
Cominco American, Inc.
A. G. Jackson
Stauffer Chemical Co.
Stauffer Chemical Co.
Stauffer Chemical Co.
of Wyoming
Polk, Florida
Hillsborough & Polk, Fla,
Polk, Florida
Hamilton, Florida
Polk, Florida
Citrus, Florida
Citrus, Florida
Marian & Gilchrist, Fla.
Citrus, Florida
Citrus, Florida
Caribou, Idaho
Bingham & Caribou, Idaho
Caribou, Idaho
Hickman & Maury, Tenn.
Davidson, Gibs, Hickman,
Maury & Williamson,
Tenn.
Maury, Tennessee
Maury & Williamson, Tenn.
Hickman, Tennessee
Beaufort, N. C.
Limestone, Alabama
Santa Barbara, Calif.
Powell, Montana
Powell, Montana
Silver Bow, Montana
Rich & Uintah, Utah
Lincoln, Wyoming
F-2
-------
Table P-2 NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
ALABAMA
Al i cavil! e
Bessemer
Birmingham
Cu ] 1 man
Decatur
Dothan
Dothan
Florence
Montgomery
Selma
ARKANSAS
North Little Rock
Texarkana
CALIFORNIA
Bena
Lathrop
Los Angeles
SMSA
..
Birmingham
Birmingham
Montgomery
Little "Rock-N. Little Rock
Texarkana
Bakersfield
Stockton
Los Angeles-Long Beach
Company
Valley Fertilizer Co.
F.S. Royster Guano Co.
Mobil Chemical Co.
International Minerals & Chemical Corp.
Alabama Farmers Cooperative, Inc.
The Home Guano Co.
Mobil Chemical Co.
International Minerals & Chemical Corp.
Capital Fertilizer Co.
Centrala Farmers Cooperative, Inc.
Olin Mathieson Chemical Co.
International Minerals & Chemical Corp.
AFC, Inc.
Best Fertilizers Co.
Stauffer Chemical Co.
Capacity,
tons per year
15,000
50,000
-
-
50,000
40,000
-
-
-
20,000
-
20 T/hr
_
_
U)
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
Citv
CALIFORNIA (cont.)
Nichols
FLORIDA
Bartow
Jacksonville
Jacksonville
Nichols
Pensacola
Pierce
Tampa
Tampa
GEORGIA
Albany
Albany
Americus
Athens
Atlanta
Augusta
Columbus
Cordele
East Point
East Point
Macon
SMSA
San Francisco-Oakland
Jacksonville
Jacksonville
--
Pensacola
Tampa-St. Petersburg
Tampa-St. Petersburg
Albany
Albany
Atlanta
Augusta
Columbus
Atlanta
Atlanta
Macon
Company
Western States Chemical Co.
W.R. Grace & Co.
Armour Agric. Chemical
Wilson & Toomer Fertilizer Co.
Mobil Chemical Co.
Agrico Chemical Co.
Agrico Chemical Co.
Tennessee Corp.
W.R. Grace & Co.
Armour Agric. Chemical
Swift & Co.
International Minerals & Chemical Corp.
F.S. Royster Guano Co.
Swift & Co.
Etheridge Fertilizer Co.
Armour Agric. Chemical
Cotton Producers Assn.
International Minerals & Chem.
Tennessee Corp.
Cotton States Fertilizer Co.
Capacity,
tons per year
60,000
.
_
125,000
-
-
-
-
-
-
-
75,000
-
25,000
-
100,000
-
25,000
40,000
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
GEORGIA (cont.)
Macon
Moul trie
Pel ham
Savannah
Savannah
Savannah
Tifton
Valdosta
ILLINOIS
Ashkum
Calumet City
Chicago Heights
Chicago Heights
E. St. Louis
E. St. Louis
E. St. Louis
Granite City
Morris
National Stock
Yards
SMSA
Macon
--
Savannah
Savannah
Savannah
--
--
--
Chicago
Chicago
Chicago
St. Louis
St. Louis
St. Louis
St. Louis
--
St. Louis
Company
F.S. Royster Guano Co.
Smith Fertilizer & Chem. Co.
Pelham Phosphate Co.
Kaiser Agricultural Chemicals
Southern States Phosphate & Fertilizer Co.
Mobil Chemical Co.
International Minerals & Chem. Corp.
Georgia Fertilizer Co.
Occidental Agricultural Chemicals Corp.
Swift & Co.
Armour Agriculture Co.
International Minerals & Chemical Corp.
Armour Agricultural Co.
FS Services, Inc.
Mobil Chemical Co.
American Phosphate Co.
Gilchrist Plant Food Co.
Swift & Co.
Capacity,
tons per year
50,000
100,000
60,000
-
100,000
-
-
75,000
-
-
-
-
-
60,000
-
-
-
-
I
Ul
-------
Table F-2
(continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
INDIANA
Fort Wayne
Indianapolis
Indianapolis
Indianapolis
Indianapolis
Jeffersonville
Schererville
IOWA
Oubuque
Eagle Grove
Mason City
KENTUCKY
Danville
London
Russellville
Winchester
LOUISIANA
Baton Rouge
Bunkie
Lake Charles
New Orleans
Shreveport
SMSA
Fort Wayne
Indianapolis
Indianapolis
Indianapol is
Indianapol is
Louisville
Chicago
Dubuque
..
Louisville
Baton Rouge
Lake Charles
New Orleans
Shreveport
Company
Mobil Chemical Co.
F.S. Royster Guano Co.
Indiana Farm Bureau Cooperative Assoc., Inc.
International Minerals & Chemical Corp.
Smith-Douglass Div., Borden Chemical Co.
Indiana Farm Bureau Cooperative Assoc., Inc.
Indiana Farm Bureau Cooperative Assoc., Inc.
Mobil Chemical Co.
Farmland Industries, Inc.
International Minerals & Chemical Corp.
Cardinal Chemical Co.
Agrico Chemical Co.
Commonwealth Fertilizer Co., Inc.
Cooperative Fertilizer Serv. of Richmond, Va.
Louisiana Agricultural Supply Co., Inc.
Bunkie Phosphate Co., Inc.
Kelly-Weber & Co. , Inc.
USS Agri-Chemicals, Inc., U.S. Steel Corp.
Mobil Chemical Co.
Capacity,
tons per year
.
90,000
90,000
-
-
40,000
60,000
-
25,000
-
20 T/hr
-
25,000
20,000
25,000
15,000
30,000
4 T/batch
-
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
MAINE
Searsport
MARYLAND
Baltimore
Baltimore
Baltimore
MASSACHUSETTS
Lowel 1
MICHIGAN
Saginaw
Saginaw
Saginaw
MINNESOTA
Winona
MISSISSIPPI
Canton
Hattiesburg
Jackson
Jackson
SMSA
--
Baltimore
Baltimore
Bal timore
Boston
Saginaw
Saginaw
Saginaw
_-
..
--
Jackson
Jackson
Company
W.R. Grace & Co. --Northern Chemical
Industries, Inc.
Agrico Chemical Co.
Kerr-McGee Chemical Co.
F.S. Royster Guano Co.
Lowell Rendering Co.
Agrico Chemical Co.
Farm Bureau Services, Inc.
Smith-Douglass Div., Borden Chemical Co.
Cenex
Coastal Chemical Corp.
Coastal Chemical Corp.
F.S. Royster Guano Co.
Mobil Chemical Co.
Capacity,
tons per year
-
-
100,000
20,000
50,000
-
50,000
40,000
40,000
50,000
-
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
SMSA
Company
Capacity,
tons per year
i
00
MISSISSIPPI (cont.)
Marks
Meridian
New Albany
MISSOURI
Joplin
Maryland Heights
St. Joseph
Springfield
NEW JERSEY
Carteret
NEW YORK
Buffalo
Buffalo
NORTH CAROLINA
Acme
Charlotte
Greensboro
Greensboro
Greensboro
St. Louis
St. Joseph
Springfield
Buffalo
Buffalo
Charlotte
Greensboro-Winston-Sal em-High Point
Greensboro-Wins ton-Sal eiP-Hign Point
Greensboro-Vlinston-Salem-High Point
Riverside Fertilizer Co.
Coastal Chemical Corp.
Coastal Chemical Corp.
W.R. Grace & Co.
M.F.A. Plant Food Div., Missouri
Farmers Assoc.
Farmland Industries, Inc.
M.F.A. Plant Food Div., Missouri
Farmers Assoc.
Agrico Chemical Co.
Agrico Chemical Co.
International Minerals & Chemical Corp.
Acme Fertilizer
F.S. Royster Guano Co.
Agrico Chemical Co.
Armour Agricultural Chemical
Swift & Co.
10 T/hr
40,000
50,000
50,000
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
NORTH CAROLINA (co
Laurinburg
Navassa
Riegelwood
Selma
Waynesville
Wilmington
Wilmington
Wins ton-Sal em
OHIO
Ca i ro
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Cleveland
Cleveland
Columbus
Columbus
Dayton
Toledo
Washington Court;
House
SMSA
nt.)
Wi Imington
--
--
--
Wilmington
Wilmington
Greensboro-Wins ton-Sal em-High Point
--
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Cleveland
Cleveland
Columbus
Columbus
Dayton
Toledo
Company
Dixie Guano Co.
Armour Agricultural Chemical
Kaiser Agricul tural Chemicals
Mooil Chemical Co.
Western Carolina Phosphate Co.
Mobil Chemical Co.
Swift & Co.
International Minerals & Chemical Corp.
Agrico Chemical Co.
Agrico Chemical Co.
Armour Agricul tural Chemical
International Minerals & Chemical Corp.
Mobil Chemical Co.
Tennessee Corp.
Agrico Chemical Co.
Swift & Co.
Federal Chemical Co.
Smith-Douglass Div., Borden Chemical Co.
Capacity,
tons per year
15 T/hr
-
-
-
30,000
-
-
-
-
-
-
-
-
100,000
-
-
-
-
Farm Bureau Cooperative Fertilizer Assoc., Inc. 20 T/hr
F.S. Royster Guano Co.
Agrico Chemical Co.
100,000
-
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
PENNSYLVANIA
Philadelphia
SOUTH CAROLINA
Anderson
Charleston
Charleston
Charleston
Charleston
Hartsville
Spartanburg
TENNESSEE
Knoxvi lie
La Vergre
Memphis
Mt. Pleasant
Mashvil le
Nashville
Tenco
TEXAS
Comanche
El Paso
Fort Worth
Galena Park
SMSA
Philadelphia
Charleston
Charleston
Charleston
Charleston
--
Knoxvi lie
--
Memphis
--
Nashville
Nashville
Knoxvi lie
El Paso
Fort Worth
Houston
Company
Kerr-McGee Chemical Co.
Anderson Fertilizer Co., Inc.
Agrico Chemical Co.
F.S. Royster Guano Co.
Mobil Chemical Co.
Planters Fertilizer & Phosphate Co.
International Minerals & Chemical Corp.
International Minerals & Chemical Corp.
Agrico Chemical Co.
Tennessee Farmers Cooperative
Mobil Chemical Co.
Mobil Chemical Co.
Armour Agricul tural Chemical
Federal Chemical Co.
Tennessee Farmers Cooperative
Central Texas Fertilizer Co.
VJ.R. Grace & Co.
International Minerals & Chemical Corp.
American Plant Food Corp.
Capacity,
tons per year
-
50,000
-
40,000
-
100,000
-
_
30,000
-
-
-
-
30,000
15,000
-
-
-
I
II
o
-------
Table F-2 (continued). NORMAL SUPERPHOSPHATE PLANTS
Major Producers
1968
State
City
TEXAS (cont.)
Greenville
Littlefield
Littlefield
Pasadena
Plainview
UTAH
Midvale
VIRGINIA
Chesapeake
Norfol k
Norfolk
Norfolk
Richmond
Richmond
South Norfolk
WASHINGTON
Tacoma
WISCONSIN
Green Bay
Madison
Prairie DuChien
SMSA
--
Houston
Salt Lake City
Norfol k-Portsmouth
Norfolk-Portsmouth
Norfol k-Portsmouth
Norfolk-Portsmouth
Richmond
Richmond
Norfol k-Portsmoutn
Tacoma
Green Bay
Madison
--
Company
International Minerals & Chemical Corp.
Caprock Fertilizer Co.
Nipak
01 in Mathieson Chemical Co.
Best Fertilizers Co.
Mineral Fertilizer Co.
F.S. Royster Guano Co.
Farmers Guano Co.
Smith-Douglass Div.,. Borden Chemical Co.
W.R. Grace & Co.
Mobil Chemical Co.
Richmond Guano Co.
Swift & Co.
Stauffer Chemical Co.
Northwest Cooperative Mills
F.S. Royster Guano Co.
F.S. Services, Inc., Wisconsin Oiv.
Capacity,
tons oer vear
.
30,000
30,000
-
-
.25,000
100,000
-
60,000
-
-
60,000
20 T/hr
mf
30,000
80,000
120,000
-------
Table F-3 TRIPLE SUPERPHOSPHATE PLANTS
June 1968
State
City
CALIFORNIA
Bena
SMSA Comoanv
Bakersfield AFC, Inc.
Capaci ty
Tons Per Year
170,000
FLORIDA
Agricola
Bartow
Bartow
Brewster
Bartow & Fort Meade
Green Bay
i Mulberry
N Nichols
Piney Point
Plant City
South Pierce
Tampa
White Springs
IDAHO
Georgetown
Idaho Falls
Pocatello
Tampa-St. Petersburg
Tampa-St. Petersburg
MARYLAND
Baltimore
Baltimore
Swift and Co.
Davison Chemical (W. R. Grace)
International Minerals & Chemical
American Cyanamid
USS Chemicals, U.S. Steel Corp.
Farmland Industries
F. S. Royster Guano
Mobil Chemical
Bordon Chemical
Central Phosphates
Agrico Chemical (Conoco)
U.S. Phosphoric Products (Cities Service)
Occidental Agricultural
Central Farmers Fertilizers
J. R. Simplot Co.
J. R. Simplot Co.
Kerr-McGee Chemical
170,000
450,000
450,000
380,000
600,000
80,000
11Q.OOO
400,000
180,000
500,000
850,000
200,000
200,000
360,000
-------
Table F-3 (continued). TRIPLE SUPERPHOSPHATE PLANTS
June 1968
State
City SMSA
MISSISSIPPI
Pascagoula
MISSOURI
Joplin
NORTH CAROLINA
Aurora
UTAH
Garfield Salt Lake City
CO
Company
Coastal Chemical
Davison Chemical (W. R. Grace)
Texas Gulf Sulphur
Western Phosphates (Stauffer)
Capacity
Tons Per Year
300,000
35,000
308,000
75,000
-------
Table F-4 AMMONIUM PHOSPHATE FERTILIZER PLANTS (SOLID)
1968
i
M
State
City
ALABAMA
Cherokee
Midland City
Muscle Shoals
ARIZONA
Phoenix
ARKANSAS
Helena
CALIFORNIA
Bena
Dominguez
Fontana
Helm
Lathrop
Pittsburg
FLORIDA
Bartow
Bartow
Bonnie
Brewster
East Tampa
SMSA
Phoenix
__
Bakersfield
Los Angeles-Long Beach
San Bernardino-Riverside-Ontario
Fresno
Stockton
San Francisco-Oakland
<»
--
--
--
Tampa-St. Petersburg
Company
USS Agri-Chemicals, Inc., U.S. Steel Corp.
United Chemical Corp.
Tennessee Valley Authority
Arizona Agrochemical
Arkla Chemical
Agricultural Pert. Chem.
Western States Chemical
Kaiser Steel
Valley Nitrogen Producers
Best Fertilizers (Occidental)
Shell Chemical
W.R. Grace & Co.
USS Agri-Chemicals, Inc., U.S. Steel Corp.
International Minerals & Chemicals
American Cyanamid
U.S. Phosphoric Products
Capacity,
tons per year
180,000
240,000
27,000
-
290,000
90,000
50,000
28,000
100,000
-
10,000
200,000
-
350,000
200,000
225,000
-------
Table F-4 (continued). AMMONIUM PHOSPHATE FERTILIZER PLANTS (SOLID)
1968
State
City
FLORIDA (cont.)
Green Bay
Hul berry
Nichols
Piney Point
Plant City
South Pierce
White Springs
COLORADO
Pueblo
IDAHO
Kellogg
Kellogg
Pocatello
ILLINOIS
Chicago Heights
Danville
Depue
Henry
Joliet
Marseilles
Streater
SMSA
--
--
Tampa-St. Petersburg
__
__
Pueblo
..
--
Chicago
__
Chicago
--
Company
Farmland Industries
F.S. Royster Guano Co.
Mobil Chemical Co.
Borden Chemical Co.
Central Phosphates
Agrico Chemical Co. (Conoco)
Occidental Agricultural
Colorado Fuel and Iron
Bunker Hill
Victor Chemical
J.R. Simplot
Victor Chemical
U.S. Industrial Chemicals
New Jersey Zinc
W.R. Grace & Co.
01 in Mathieson Chemical
National Phosphate
Smith-Douglas Div., Borden Chemical Co.
Capacity,
tons per year
200,000
90,000
100,000
185,000
250,000
250,000
250,000
15,000
.
70,000
200,000
.
-
270,000
100,000
200,000
150,000
-
I
H
cn
-------
Table F-4 (continued). AMMONIUM PHOSPHATE FERTILIZER PLANTS (SOLID)
State
City SMSA
IOWA
Dubuque Dubuque
Fort Madison
LOUISIANA
Donaldsonville
Hahnville
Harvey New Orleans
Luling
MICHIGAN
Dearborn Detroit
MINNESOTA
Pine Bend Minneapolis-St. Paul
MISSISSIPPI
Pascagoula
MISSOURI
Joplin
Joplin
NORTH CAROLINA
Aurora
OKLAHOMA
Tulsa Tulsa
TEXAS
Houston Houston
Kerens
Company
01 in Mathieson Chemical
Chevron Chemical
Gulf Oil
National Phosphate
Swift & Co.
Monsanto
Ford Motor Co.
Northwest Co-op. Mills
Coastal Chemical
Farmers Chemical
W.R. Grace & Co.
Texas Gulf Sulphur
Nipak, Inc.
Phosphate Chemicals
Nipak, Inc.
Capacity,
tons per year
-
-
350,000
150,000
240,000
14,000
100,000
180,000
70,000
-
250,000
75,000
150,000
100,000
-------
Table F-4 (continued). AMMONIUM PHOSPHATE FERTILIZER PLANTS (SOLID)
1968
State
City
SMSA
Company
Capacity,
tons per year
TEXAS (cont.)
Pasadena
Plainview
Texas City
UTAH
Garfield
WASHINGTON
Kennewick
Houston
Galveston-Texas City
Salt Lake City
01 in Mathieson Chemical
Best Fertilizers (Occidental)
Smith-Douglass Div., Borden Chemical Co.
Western Phosphates
Chevron Chemical
600,000
i
»-»
-4
-------
Table F-5
FERTILIZER GRANULATION PLANTS
December 1967
State
City
ALABAMA
Bessemer
Birmingham
Columbia
Decatur
Decatur
Do than
Florence
Forkland
Hanceville
Montgomery
Montgomery
Montgomery
Montgomery
Sheffield
ARKANSAS
Little Rock
Texarkana
Walnut Ridge
CALIFORNIA
Antioch
Blythe
Compton
SMSA
Birmingham
Birmingham
Montgomery
Montgomery
Montgomery
Montgomery
Little Rock-North Little Rock
Texarkana
San Francisco-Oakland
San Bernardino -Riverside-Ontario
Los Angeles-Long Beach
Comoany
F. A. Royster Guano Co.
V-C Chemical Co. (Mobil)
Gulf Oil Co.
Ala. Farmers Co-op, Inc.
Coastal Chemical Corp.
V-C Chemical Co. (Mobil)
International Minerals & Chem.
Central a Farmers Co-op
The Cotton Producers Assn.
Capital Fertilizer Co.
V-C Chemical Co. (Mobil)
Tennessee Corp.
F. S. Royster Guano Co.
Tennessee Farmers Co-op
Southern Cotton Oil Oiv.
International Minerals & Chem. Corp.
Ark-Mo Plant Food Co.
Kerley Chem. Corp.
The Arical Co. , Inc.
Dominguez Fertilizers, Inc.
Capacity,
Tons per Year
50,000
-
-
50,000
40,000
-
-
50,000
50,000
25,000
-
40,000
-
-
-
100,000
100,000
-
50,000
I
M
00
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
CALIFORNIA (cont.)
Edison
Fresno
Lathrop
Los Angeles
Los Angeles
Los Angeles
Nichols
Richmond
Santa Rosa
COLORADO
Denver
Longmont
CONNECTICUT
Water bury
DELAWARE
Wilmington
FLORIDA
Bartow
Cottondale
Fort Pierce
Fort Pierce
Jacksonville
Jacksonville
Mulberry
SMSA
Bakersfield
Fresno
Stockton
Los Angeles-Long Beach
Los Angeles-Long Beach
Los Angeles-Long Beach
San Francisco-Oakland
San Francisco-Oakland
Denver
Denver
Waterbury
Wilmington
..
Jacksonville
Jacksonville
--
-
Company
AFC, Inc.
Niagara Chem. Div. (FMC)
Occidental Chemical Co.
Stauffer Chem. Co.
Swift & Co.
Wilbur-Ellis Co.
Western States Chem. Corp.
Stauffer Chem. Co.
Fersolin Corp.
'Bennett Chem. Co.
Farm Chemical Co.
Kerr-McGee Chemical Co.
Agway, Inc., Fertilizer Div.
Farmland Industries, Inc.
Cartledge Fertilizer Co.
Briggs Fertilizer Co.
W. R. Grace & Co.
Capacity
Tons per Year
100,000
-
90,OCC
-
-
25,000
60,000
50,000
8,000
10,000
150,000
_
25,000
50,000
-
-
USS Agri -Chemicals, Inc., Div. U.S. Steel Corp.
Wilson & Toomer Fertilizer Co.
International Minerals & Chemical
125,000
-
"3
M
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
FLORIDA (cont.)
Pensacola
Pensacola
Pensacola
Piney Point
Tampa
Winter Haven
GEORGIA
Al bany
Al bany
Albany
Americus
Athens
Augusta
Cordele
Doerun
Macon
Moultrie
Pel ham
Rome
Savannah
Savannah
Tifton
IDAHO
Conda
SMSA
Pensacola
Pensacola
Pensacola
Tampa-St. Petersburg
Albany
Albany
Albany
Augusta
Macon
Savannah
Savannah
Company
Agrico Chemical Co.
Merchants Fertilizer Co.
Kerr-McGee Chemical Corp.
The Borden Chemical Co.
Earl Harrell's Fertilizer Co.
Swift & Co.
USS Agri-Chemicals, Inc., Div. U.S. Steel Cc
Swift & Co.
V-C Chemical Co. (Mobil)
International Minerals & Chem. Corp.
F. S. Royster Guano Co.
International Minerals & Chem. Corp.
The Cotton Producers Assn.
Toney Brothers
F. S. Royster Guano Co.
C. 0. Smith Fertilizer & Chemical Co.
Pelham Phosphate Co.
V-C Chemical Co. (Mobil)
Southern Fertilizer & Chemical Co.
V-C Chemical Co. (Mobil)
Kerr-McGee Chemical Corp.
El Paso Prod. Co.
Capacity,
Tons per Year
4.
30,000
-
-
-
-
>rp.
-
-
-
-
100,000
-
-
100,000
60,000
150,000
-
30,000
125,000
i
to
o
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
Citv
IDAHO (cont.)
Pocatello
ILLINOIS
Allertown
Atlanta
Calumet City
Chicago
Chicago
Chicago Heights
Chicago Heights
Danville
Danville
Decatur
Depue
East St. Louis
East St. Louis
East St. Louis
East St. Louis
Effingham
Fulton
Henry
Meredosia
Morris
National Stock
Yards
Ridgway
Swan Creek
SMSA
..
Chicago
Chicago
Chicago
Chicago
Chicago
Decatur
St. Louis
St. Louis
St. Louis
St. Louis
St. Louis
~
Company
J. R. Simplot Co.
Allerton Supply Co.
Diamond Alkali Co.
Swift & Co.
American Fertilizer Co.
Gillette Inhibitor Co., Inc.
Capacity,
Tons per Year
300,000
15,000
-
-
-
6,000
USS Agri -Chemicals, Inc., Div. U.S. Steel Corp.
International Minerals & Chem. Corp.
Amer. Agric. Chem. Co. (Conoco)
U.S.I. Farm Chemicals
Perkinson Co.
New Jersey Zinc Co.
-
-
-
20,000
-
USS Agri-Chemicals, Inc., Div. U.S. Steel Corp.
Agri co Chem. Co. (Conoco)
Darling & Co.
V-C Chemical Co. (Mobil)
Effingham Equity, Inc.
Amer. Agric. Chem. Co.
W. R. Grace & Co.
A. B. Chrisman Fertilizer Co., Inc.
Gilchrist Plant Food Co.
Swift & Co.
Wabash Valley Service Co.
Sands Elevator
-
-
-
60,000
-
-
12,000
-
-
-
-
i
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
INDIANA
Bryant
Columbia City
Fairmount
Fort Wayne
Fulton
Indianapolis
Indianapolis
Indianapolis
Jasonville
Jeffersonville
Jeff ersonvi lie
New Albany
New Albany
Peru
Remington
Rushville
Rushville
Seymour
Vincennes
IOWA
Alleman
Auburn
Des Moines
Des Moines
Oes Moines
SMSA
..
Fort Wayne
Indianapolis
Indianapolis
Indianapolis
__
Louisville
Louisville
Louisville
Louisville
Des Moines
Des Moines
Des Moines
Des Moines
Company
Occidental Chemicals Co.
Ind. Farm Bureau Co-op
Occidental Chemicals Co.
V-C Chemical Co. (Mobil)
Occidental Agricultural Chemicals
Borden Chemical Co. - Smith-Douglass
International Minerals & Chem. Corp.
F. S. Royster Guano Co.
V-C Chemical Co. (Mobil)
Capacity,
Tons per Year
25 tons/hr
40,000
30 tons/hr
-
20 tons/hr
-
-
-
-
USS Agri-Chemicals, Inc., Div. U.S. Steel Corp.
Ind. Farm Bureau Co-op Assn., Inc.
W. R. Grace & Co.
Tennessee Corp,
Federal Fertilizer Sales Corp.
V-C Chemical Co. (Mobil)
Gulf Oil Corp. Chemicals
Kerr-McGee Chemical Corp.
Amer. Agric. Chem. Co. (Conoco)
Federal Fertilizer Sales Corp.
Farmland Industries, Inc.
Brincks Farm Supply
FS Services, Inc.
National Fertilizer Co.
Ross Daniels, Inc.
40,000
_
-
35,000
-
-
-
-_
-
-
100 tons/hr
90,000
15,000
-
i
to
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
Stite
Citv
IOWA (cont.)
Dike
Dubuque
Eagle Grove
Esther-vine
Ft. Madison
Humboldt
Mason City
Mason City
Ottumwa
Ottumwa
Perry
Pleasantville
Spirit Lake
Spencer
Zearing
KANSAS
Chanute
Downs
Kansas City
Manhattan
Marysville
Olathe
Wankeeney
KENTUCKY
Cecil ia
SMSA
Dubuque
--
__
--
--
.._
--
Kansas City
~
Kansas City
--
Comoany
Allied Chemical Corp.
V-C Chemical Co. (Mobil)
Farmland Industries, Inc.
V-C Chemical Co. (Mobil)
Chevron Chemical Co.
Amer. Agric. Chem. Co. (Conoco)
International Minerals & Chem. Corp.
Swift & Co.
Super-Crop Plant Foods, Inc.
H. D. Sales, Inc.
W. R. Grace & Co.
Farm & Town Industries
Fanners Elevator Co.
American Cyanamid Co.
Zearing Fertilizer Co.
Mobil Chemical Co.
Huiting & Cary Fertilizer Service
Gulf Oil Corp.
Farmland Industries, Inc.
Burger Fertilizer Co.
Amer. Agric. Chem. Co. (Conoco)
Turman Chemical Co.
Gulf Oil Corp.
Capacity,
Tons per Year
-
-
25,000
-
-
-
-
-
_
-
-
-
-.
-
-
-
-
20 tons/hi
15,000
-
-
-
"3
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
KENTUCKY (contj
Henderson
Lexington
London
Louisville
Louisville
Maysville
Russelville
Shelbyville
LOUISIANA
Arcad i a
Baton Rouge
Bunkie
Harvey
Jonesville
Lake Charles
New Orleans
Ruston
Shrevepcrt
MAINE
Caribou
Detroit
Fort Kent
Greene
Presque Isle
SMSA
Evans vi lie
Lexington
Louisville
Louisville
Baton Rouge
New Orleans
--
Lake Charles
New Orleans
Shreveport
--
Comoany
Gulf Oil Corp.
Burley Belt Fertilizer Co.
Burley Belt Chemical Co.
North American Fertilizer Co.
F. S. Royster Guapo Co.
Ohio Valley Fertilizer, Inc.
Southern States Co-op, Inc.
Gro-Green Chem. Co., Inc.
Ruston Oil Mill & Fertilizer Co.
Louisiana Ag. Supply Co., Inc.
Guaranty Seed Co., Inc.
Swift & Co.
Brown Brothers
Kelly Weber & Co. , Inc.
Capacity,
Tons per Year
.
35,000
20 tons/hr
45,000
-
20,000
-
-
10 tons/hr
2.5,000
10,000
'-
-
30,000
USS Agri-Chemicals, Inc., Div. U.S. Steel Corp.
Ruston Oil Mill & Fertilizer Co.
V-C Chemical Co. (Mobil)
Aroostook Federation of Farmers
Agway, Inc.
Aroostook Federation of Farmers
Fedco Farm Service
Brockville Chemical Co.
-
-
25,000
25 j 000
20,000
-
16,000
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
MAINE (cont.)
Sandy Point
MARYLAND
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Cambridge
Hagerstown
Landover
Salisbury
White ford
MASSACHUSETTS
Cambridge
MICHIGAN
Kalamazoo
Lansing
Marshall
Niles
Owosso
Riga
Riga
SMSA
--
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Washington, D. C.
--
Boston
Kalamazoo
Lansing
Company
The Summers Fertilizer Co., Inc.
(Corenco Corp. }
Amer. Agric. Chem. Co.
Mobil Chemical Co.
Capaci ty,
Tons per Year
50,000
-
USS Agri -Chemicals, Inc., Div. U.S. Steel Corp.
Lebanon Chemical Corp.
F. S. Royster Guano Co.
Swift & Co.
Southern States Co-op
Kerr-McGee Chemical Corp.
Central Chem. Corp.
F. W. Bolgiano & Co.
W. B. Tilghman Co., Inc.
Miller Chem. & Fertilizer Corp.
Agway, Inc.
Farm Bureau Services, Inc.
W. R. Grace & Co.
Spieldenner Fertilizer Co.
Mi chi ana Chem. Co.
USS Agri-Chemicals, Inc., Div. U.S. Steel C
Anderson Fertilizers
The Borden Chemical Co.
-
-
-
80,000
-
-
10,000
20,000
15,000
50 ,000
40,000
-
-
30,000
3rp.
30 tons/hr
-
I
to
(Jl
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
MICHIGAN (cont.)
Saginaw
Saginaw
Saginaw
MINNESOTA
East Grand Forks
Fergus Falls
Little Falls
Madison
Minneapolis
Minneapolis
Rochester
St. Paul
South St. Paul
Walnut Grove
Winona
Winona
MISSISSIPPI
Jackson
Jackson
Jackson
Meridan
Meridan
Tupelo
SMSA
Saginaw
Saginaw
Saginaw
« <>
Minneapolis-St. Paul
Minneapolis-St. Paul
Minneapolis-St. Paul
Minneapolis-St. Paul
Jackson
Jackson
Jackson
--
Company
Amer. Ag. Chem. Co.
Farm Bureau Services, Inc.
The Borden Chemical Co. (Smith-Douglass Div.)
Northland Chem. Co., Inc.
Occidental Chemicals Corp.
Creamery Blending Inc.
Fieldcrest Fertilizer Co.
Howe, Inc.
Land 0' Lakes Creameries, Inc.
Rochester Fertilizer Co.
Minnesota Farm Bureau Service Co.
Cenex, Inc.
American Cyanamid Co.
USS Agri-Chemicals, Inc., Div. U.S. Steel Con
Cenex, Inc.
Delta Cotton Oil & Fertilizer Co.
F. S. Royster Guano Co.
V-C Chemical Co. (Mobil)
Coastal Chemical Corp. Plant #1
Coastal Chemical Corp. Plant ?2
International Minerals & Chemical
Capacity,
Tons per Year
50,000
-
10,000
60 tons/hr
_
15,000
30,000
50,000
15 tons/hr
60., 000
-
-
3.
-
25,000
-
-
-
10 tons/hr
-
I
to
-------
Table P-5 (continued) . FERTILIZER GRANULATION PLANTS
December 1967
State
City
MISSOURI
Edina
Sikeston
South St. Joseph
Westboro
NEBRASKA
Broken Bow
Cozad
Fairbury
Grand Island
Harvard
Hoi brook
Omaha
South Omaha
NEW JERSEY
Cavteret
Windsor
NEW YORK
Albany
Big Flats
Buffalo
Buffalo
Lyons
Lyons
Newark
SMSA
..
St. Joseph
--
..
--
--
Omaha
Omaha
..
Trenton
Al bany-Schenectady-Troy
Buffalo
Buffalo
Rochester
Rochester
Rochester
Company
Northeast Mo. Co-op Swervices
Gulf Oil Corp.
Farmland Industries, Inc.
Herrick Feed & Produce
Co-op Marketing Assn.
Cozad Elevator Inc.
National Fertilizer Co.
Gulf Oil Corp.
Farmers Union Co-op Elevator
Holbrook Non-Stock Co-op Co.
Federal Chemical Co.
Federal Chemical Co.
Amer. Ag. Chem. Co. (Conoco)
Capacity,
Tons per Year
-
25,000
10 tons/hr
20 tons/hr
25,000
25,000
-
-
-
-
USS Agri-Chemicals, Inc., Div. U.S. Steel Corp.
Agway, Inc.
Agway, Inc.
Amer. Ag. Chem. Co. (Conoco)
Inter. Minerals & Chem. Corp.
Agway, Inc.
F. S. Royster Guano Co.
Kerr-McGee Chemical Corp.
50,000
50,000
_
-
50,000
-
-
i
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
SMSA
Company
Capacity,
Tons per Year
i
to
CO
NEW YORK (cont.)
Riverhead
NORTH CAROLINA
Acme
Charlotte
Greensboro
Greensboro
Greensboro
Kins ton
Lumberton
Laurinburg
Selma
States vi He
Wilmington
Wilmington
Wilmington
Wilmington
Wilmington
Wilmington
Wins ton-Sal em
OHIO
Alliance
Andover
Bradner
Cairo
Chillicothe
New York
Charlotte
Greensboro-Winston-Sal em-High Point
Greensboro-Wi nston-Sal em-Hi gh Poi nt
Greensboro-Winston-Sal em-High Point
Wilmington
Wilmington
WiImington
Wilmington
Wilmington
Wilmington
Greensboro-Wins ton-Sal em-High Point
Canton
Toledo
Long Island Produce Co.
Acme Fertilizer Co.
F. S. Royster Guano Co.
Amer. Ag. Chem. Co.
USS Agri-Chemical, Inc., Div. U.S. Steel Corp
Swift & Co.
Borden Chemical Co., Smith-Douglass Div.
PCX, Inc.
Dixie Guano Co.
V-C Chemical Co. (Mobil)
W. R. Grace & Co.
USS Agri-Chemical, Inc., Div. U.S. Steel Corp
Swift & Co.
Borden Chemical Co., Smith-Douglass Div.
V-C Chemical Co. (Mobil)
W. R. Grace & Co.
F. W. Royster Guano Co.
International Minerals
W. R. Grace & Co.
Central Chem. Corp. of Ohio
F. S. Royster Guano
Amer. Ag. Chem. Co.
Scioto Farm Chem., Inc.
30,000
40,000
60,000
6,000
10,000
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
Citv
OHIO (cont.)
Cincinnati
Cincinnati
Cincinnati
Cleveland
Cleveland
Columbus
Columbus
Columbus
Dayton
Find lay
Fostoria
Greenville
Lima
Marion
Marysville
Mount Gilead
Napoleon
New Bremen
Orrville
Pi qua
St. Paris
Smithville
Toledo
Washington
Court House
SMSA
Cincinnati
Cincinnati
Cincinnati
Cleveland
Cleveland
Columbus
Columbus
Columbus
Dayton
--
Lima
__
Dayton
~
Toledo
Company
Capaci ty,
Tons per Year
USS Agri-Chemical, Inc., Div. U.S. Steel Corp.
Internat. Minerals & Chem. Corp.
V-C Chemical Co. (Mobil)
Amer. Ag. Chem. Co.
The Stadler Fertilizer Co.
Federal Chemical Co.
W. R. Grace & Co.
Smith-Douglass Co., Inc. (Borden Chemical)
Landmark Farm Bureau Co-op
W. R. Grace & Co.
Kerr-McGee Chemical Corp.
Swift & Co.
Mobil Chemical
Marion Plant Life Fertilizer Co.
Scott Chem. Plant, Inc.
Landmark Farm Bureau Co-op
Midwest Plant Food, Inc.
Occidental Chemical Co.
V-C Chemical Co. (Mobil)
F. S. Royster Co.
Occidental Chemicals Co.
Tyler Grain & Fertilizer Co.
F. S. Royster Co.
Amer. Ag. Chem. Co.
-
-
-
50,000
-
-
-
20 tons/hr
-
-
-
-
50,000
15,000
-
20,000
15,000
-
-
20,000
20 tons/hr
_
-
I
to
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
OKLAHOMA
Muskogee
Oklahoma City
Tulsa
PENNSYLVANIA
Allentown
Hanover
Kittanning
Lebanon
Philadelphia
York
SOUTH CAROLINA
Blackville
Charleston
Charleston
Charleston
Charleston
Charleston
Florence
Greenville
Hartsville
Jericho
Spartanburg
SOUTH DAKOTA
Alexandria
Howard
SMSA
Oklahoma City
Tulsa
Allentown-Bethlehem-Easton
York
Philadelphia
York
..
Charleston
Charleston
Charleston
Charleston
Charleston
Greenville
Charleston
Comoany
Farmland Industries, Inc.
American Cyanamid Co.
Nipak, Inc.
Robert A. Reichard, Inc.
Miller Chem. & Fertilizer Corp.
Agway, Inc.
Lebanon Chem. Corp.
Kerr-McGee Chemical Co.
Agway, Inc.
Brown Fertilizer Co., Inc.
Amer. Ag. Chemical Co. (Conoco)
W. R. Grace & Co.
Planters Fertilizer & Phosphate Co.
f, S. Royster Guano Co.
V-C Chemical Co. (Mobil )
F. S. Royster Guano
V-C Chemical Co. (Mobil)
Internat. Minerals & Chem. Corp.
Kerr-McGee Chemical Corp.
Internet. Minerals & Chem. Corp.
Farmers Union Oil Co.
Peavey Co., Producer Service
Capacity,
Tons per Year
30,000
-
75,000
20,000
15,000
40,000
-
-
50,000
8,000
-
-
100,000
_
-
_
-
_
100,000
-
-
I
U)
o
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
TENNESSEE
Chattanooga
Humboldt
Memphis
Memphis
Mt. Pleasant
Nashville
Nashville
Nashville
TEXAS
Bonham
Bonham
Comanche
Dalhart
Dallas
Dallas
Dallas
Fort Worth
Freeport
Houston
Houston
Jacksonville
Keller
Littlefield
Nacogdoches
Pasadena
SMSA
Chattanooga
Memphis
Memphis
Nashville
Nashville
Nashville
Dallas
Dallas
Dallas
Fort Worth
Houston
Houston
Houston
Fort Worth
__
Houston
Comoany
A. D. Adair & McCarty Bros., Inc.
Federal Chemical Co.
USS Agri -Chemical, Inc., Div. U.S. Steel Corp.
V-C Chemical Co. (Mobil)
V-C Chemical Co. (Mobil)
USS Agri-Chemical, Inc., Div. U.S. Steel Corp.
Federal Chem. Co., Inc.
W. R. Grace & Co.
Hi-Yield Fertilizer Co.
The Fertilome People
Central Texas Fertilizer Co., Inc.
J. Eddie Jones Fertilizer Co.
USS Agri-Chemical, Inc., Div. U.S. Steel Corp.
Dallas Laboratories
Southwest Fertilizer Co.
Inter. Min. & Chem., Inc.
Red Barn Chem.., Inc.
USS Agri-Chemical, Inc., Div. U.S. Steel Corp.
Swift & Co.
Jacksonville Fertilizer Co.
Tacco Co.
Nipak, Inc.
Texas Farm Products Co.
01 in Mathieson Chem. Corp.
Capacity,
rons per Year
30,000
-
-
-
-
-
-
-
40,000
-
15,000
-
-
-
3,000
-
90,000
-
-
15,000
10,000
30,000
75,000
-
I
U)
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
Company
Capacity,
Tons per Year
i
CO
to
TEXAS (cont.)
Pittsburg
Plainview
Sulphur Springs
Sulphur Springs
Texarkana
Texarkana
Texas City
Tyler
UTAH
Midvale
VERMONT
Bradford
VIRGINIA
Alexandria
Chesapeake
Chesapeake
Chesapeake
Chesapeake
Chilhowie
Norfolk
Norfolk
Norfolk
Norfolk
Richmond
Texarkana
Texarkana
Galveston-Texas City
Tyler
Salt Lake City
Washington, D. C.
Norfolk-Portsmouth
Norfolk-Portsmouth
Norfolk-Portsmouth
Norfolk Portsmouth
Norfolk-Portsmouth
Norfolk-Portsmouth
Norfolk-Portsmouth
Norfolk-Portsmouth
Richmond
Nipak, Inc.
The Best Fertilizer Co. of Texas
Southern Farm Supply Assn.
Coastal Chemical Corp.
Farmers Fertilizer Co.
International Minerals & Chemicals
Smith-Douglass Co., Inc.
East Texas Products Co.
Mineral Fertilizer Co.
Kerr-McGee Chemical Corp.
Herbert Bryant, Inc.
W. R. Grace & Co.
Reliance Fertilizer & Lime Corn.
F. S. Royster Guano Co.
Southern States Co-op
The Vance Co., Inc.
Chas. W. Priddy & Co., Inc.
Smith-Douglass Co., Inc.
Weaver Fertilizer Co., Inc.
Swift & Co.
Richmond Guano Co.
50,000
20 tons/hr
25,000
25,000
80,000
20,000
65,000
60,000
60,000
-------
Table F-5 (continued). FERTILIZER GRANULATION PLANTS
December 1967
State
City
VIRGINIA (cont.)
Richmond
Suffolk
WASHINGTON
Burbank
Pasco
WISCONSIN
Cumberland
Green Bay
Green Bay
Hillsboro
Junea
Kenosha
Madison
Madison
Marshall
Prairie Du Chien
Stevens Point
Whitewater
WYOMING
Glenrock
Worland
SMSA
Ri chmond
Green Bay
Green Bay
Kenosha
Madison
Madison
Madison
Comoany
V-C Chemical Co. (Mobil)
V-C Chemical Co. (Mobil)
G-W Chemco, Inc.
G-W Chemco, Inc.
Cumberland Farmers Union Co-op
Northwest Co-op Mills
F. S. Services Inc.
Midwestern Farm Fertilizers
Western Dodge Co. Co-op
The N. S. Koos & Sons Co.
Swift & Co.
F. S. Royster Guano Co.
Dairyland Fertilizers, Inc.
Wisconsin Farmco Service Co-op
Midwestern Farm Fertilizers, Inc.
Federal Chemical Co.
American Humates, Inc.
Wyoming Pure Seed Growers, Inc.
Capacity,
Tons per year
-
20,000
-
-
25,000
20,000
'-
60,000
-
-
30,000
120,000
30,000
-
10,000
-
U)
-------
Table F-6
PHOSPHORIC ACID PLANTS (Wet Process)
June 1968
State
City
ARKANSAS
Helena
CALIFORNIA
Bena
Dominguez
Helm
Lathrop
Trona
DELAWARE
North Claymont
FLORIDA
Bonnie
Bartow
Bartow
Bartow
Brewster
Fort Meade
Green Bay
Hamilton
Mulberry
Nichols
SMSA
Bakersfield
Los Angeles-Long Beach
Fresno
Stockton
San Bernardino-Riverside-
Ontario
Wilmington
Fort Lauderdale-Hollywood
Company
Arkla Chemical Corp.
AFC, Inc.
Western States Corp.
Valley Nitrogen Products, Inc.
The Best Fertilizers Corporation
American Potash & Chemical Corp.
Allied Chemical Corp.
International Minerals & Chemical Corp.,
Agricultural Operations Div.
USS Agri-Chemicals, Inc., U.S. Steel Corp.
W. R. Grace and Co., Agricultural Products Div.
Swift and Co., Phosphate Center
American Cyanamid Co., Agricultural Div.
USS Agri-Chemical, Inc., U.S. Steel Corp.
Farmland Industries
Occidental Petroleum Co.
F. S. Royster Guano Co.
Mobil Chemical Co., Div. Mobil Oil Corp.
Capacity, P205
Tons per Year
-
20,000
12,000
49,000
18,000
5,000
33,000
500,000
275,000
165,000
90,000
200,000
165,000
110,000
550,000
25,000
230,000
I
00
-------
Table F-6 (continued). PHOSPHORIC ACID PLANTS (Wet Process)
June 1968
State
Citv
FLORIDA (cont.)
Pierce
Piney Point
Plant City
Plant City
South Pierce
Tampa
White Springs
IDAHO
Conda
Kellogg
Pocatello
ILLINOIS
Deoue
East St. Louis
Joliet
Marseilles
Morris
Streator
Tuscola
INDIANA
Gary
LOUISIANA
Covent
Donaldsonville
SMSA
..
--
Tampa-St. Petersburg
Tampa-St. Petersburg
Tampa-St. Petersburg
__
~
St. Louis
Chicago
--
--
Gary-Hammond-East Chicago
Company
Consumers Cooperative Association
Borden Chemical Co., Smith Douglass Div,
Borden Chemical Co., Smith Douglass Div.
Central Phosphates
Agrico Chemical Co., Div, Continental Oil Co.
U.S. Phosphoric Products, Oiv. Tennessee Corp.
Occidental Corp. of Florida
El Paso Products Co.
Collier Carbon and Chemical Co.
J. R. Simplot Co.
New Jersey Zinc Co.
Allied Chemical Corn.
01 in Mathieson Chemical Corp., Chemicajs Div.
Hooker Chemical Corp., Farm Chemicals Div.
Des Plaines Chemical Co.
Borden Chemical Co., Div. Smith-Douglass Co.
U.S. Industrial Chemicals Co.,
Div. National Distillers & Chemical Corp.
Mobil Chemical Co., Div. Mobil Oil Corp.
Freeport Chemical Co.
Gulf Oil Corp.
Capacity, PgOg
Tons per Year
75,000-100,000
140,000
-
100,000
227,500
360,000
250,000
90,000
33,000
270,000
130,000
50,000
125,000
200,000
90,000
33,000
30,000
30,000
600,000
-
i
CO
ui
-------
Table F-6 (continued). PHOSPHORIC ACID PLANTS (Wet Process)
June 1968
State
City
LOUISIANA (cont.
Geismar
Taft
MINNESOTA
Pine Bend
MISSISSIPPI
Pascaugoula
MISSOURI
Joplin
Joplin
NORTH CAROLINA
Aurora
OKLAHOMA
Tulsa
TEXAS
Houston
Pasadena
Pasadena
UTAH
Garfield
SMSA
)
Minneapolis-St. Paul
_.
..
--
Tulsa
Houston
Houston
Houston
Salt Lake City
Company
Allied Chemical Corp., Nitrogen Div.
Hooker Chemical Corp.
Cenex, Inc.
Coastal Chemical Corp.
Farmers Chemical Co,
W. R. Grace and Co.
Texas Gulf Sulfur Co.
Nipak, Inc.
Phosphates Chemicals, Inc.
01 in Mathieson Chemical Corp., Agricultural Div.
Phillips Chemical Co.
Stauffer Chemical Co., Fertilizer Div.
Capacity, P205
Tons per Year
180,000
100,000
54,000
50,000
50,000
50 ,000
375,000
30,000
100,000
200,000
50,000
100,000
I
u>
-------
Table F-7 PHOSPHORIC ACID AND SUPERPHOSPHORIC ACID PLANTS (Thermal Process)
June 1968
State
City
ALABAMA
Muscle Shoals
CALIFORNIA
Newark
Long Beach
Richmond
COLORADO
Pueblo
FLORIDA
Nichols
Pi erce
Tarpon Springs
KANSAS
Lawrence
MONTANA
Butte
NEW JERSEY
Carteret
Carteret
Kearny
NEW YORK
Niagara Falls
SMSA
--
San Francisco-Oakland
Los Angel es-Lonq Beach
San Francisco-Oakland
Pueblo
..
--
Tampa-St. Petersburg
--
__
..
--
Jersey City
Buffalo
Company
Tennessee Valley Authority
F M C Corp., Inorganic Chemical Div.
Monsanto Co.
Stauffer Chemical Co., Fertilizer Div.
CF&I Steel Corp. (idle)
Mobil Chemical Co., Div. Mobil Oil Corp.
Agrico Chemical Co., Div. Continental Oil Co.
Stauffer Chemical Co.
F M C Corp., Inorganic Chemical Div.
Stauffer Chemical Co.
Agrico Chemical Co., Div. Continental Oil Co.
F M C Corp., Inorganic Chemical Div.
Monsanto Co.
Hooker Chemical Corp., Industrial Chemical Div.
Phosphorus Production
or Burning Capacity,
Tons oer Year
37,600
.
_
-
_
6,000
40,000
15,000
-
30,000
40,000
-
-
6,000
I
UJ
-J
-------
Table F-7 (continued)
PHOSPHORIC ACID AND SUPERPHOSPHORIC ACID PLANTS (Thermal Process)
June 1968
State
C1 ty
OHIO
Fernald
Addyston
PENNSYLVANIA
Morn svi lie
SOUTH CAROLINA
Charleston
TENNESSEE
Columbia
Columbia
Columbia
Columbia
TEXAS
Brc.vnfield
Dallas
SMSA
Cincinnati
Cincinnati
Philadelphia
Charleston
--
__
__
Dallas
Company
Mobil Chemical Co., Div. Mobil Oil Corp.
Monsanto Co.
Stauffer Chemical Co.
Mobil Chemical Co., Div. Mobil Oil Corp.
Hooker Chemical Corp., Industrial Chemical Div.
Mobil Chemical Co., Div. Mobil Oil Corp.
Monsanto Company
Stauffer Chemical Co.
Goodpasture Grain and Milling Co.
Hooker Chemical Corp., Industrial Chemical Div.
Phospnorus Droduction
or Burnino Capaci ty,
To"- '>er Year
-
-
10,000
68,400
20,000
110,000
s:, ooo
19,000
-
I
w
oo
-------
APPENDIX G
POTASH PRODUCTION STATISTICS
G-l
-------
Table G-l PRINCIPAL PRODUCERS OF POTASH IN THE UNITED STATES
Company
Q
i
Amax Chemical Corp.
Duval Corp.
International Mineral &
Chemical Corp.
Kerr-McGee Chemical Corp.
National Potash Co.
Potash Co. of America
Southwest Potash Corp.
U. S. Borax & Chemical
Corp.
Kerr-McGee Chemical Corp.
American Potash & Chemical
Corp.
Kaiser Aluminum & Chemical
Corp.
Texas Gulf Sulphur Co.
Dow Chemical Co.
County & State
Eddy, New Mexico
Eddy, New Mexico
Eddy, New Mexico
Lea, New Mexico
Eddy, New Mexico
Eddy, New Mexico
Eddy, New Mexico
- New Mexico
San Bernardino, Cal.
Searles Lake, Cal.
Tooele, Utah
Grand, Utah
Michigan
Capacity
tons K-0/year
a
450,000
425,000
300,000
300,000
600,000
550,000
550,000
a
220,000
a
360,000
Produces a very
small quantity
a) Data not available.
-------
APPENDIX H
BORON PRODUCTION STATISTICS
H-l
-------
Table H-l PRINCIPAL PRODUCERS OF BORON IN THE UNITED STATES
Company
Location
Capacity
(tons per year 1971)
Method of
producing boron
K>
United States Borax and
Chemical Corporation
Tenneco Oil Company
American Potash and
Chemical Company
Hooker Chemical
Corporation
Stauffer Chemical
Company
Kern County
Inyo County
Searles Lake
(San Bernardino County)
Searles Lake
Searles Lake
500,000
150,000
100,000
65,000
30,000
Ore beneficiation
Ore beneficiatior
Processing lake
brines
Processing lake
brines
Processing lake
brines
-------
APPENDIX I
MICA INDUSTRY STATISTICS
1-1
-------
Table 1-1 MICA GRINDERS IN 1960 (5)
Location of Mill
State
Alabama
Arizona
California
Do
Colorado
Georgia
Do
Illinois
Massachusetts
New Hampshire
New Mexico
North Carolina
Do
Do
Do
Do
Do
North Carolina
Do
Do
Do
Do
Pennsylvania
South Carolina
Tennessee
Do
Texas
Virginia
County
Cleburne
Cochise
Maricopa
Imperial
Los Angeles
Larimer
Bartow
Hart
Cook
Middlesex
Merrimack
Taos
Avery
Buncombe
Cleveland
Macon
Mitchell
Do
Mitchell
Do
Do
Yancey
Do
York
Lancaster
Unicoi
Greene
Sullivan
Tarrant
Nearest Town
Heflin
Tombstone
Buckeye
Ogilby
Los Nietos
Fort Collins
Cartersville
Hartwell
Forest Park
Wilmington
Penacook
Ojo Caliente
Plumtreo
Biltmore
Kings Mountain
Franklin
Spruce Pine
Do
Spruce Pine
Do
Minpro
Burnsville
Newdale
Glenville
Kershaw
Erwin
Greenville
Kingsport
Fort Worth
Newport News
Method of
Grinding
Wet
X
X
X
X
X
X
X
X
Dry
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Company Name and Address
Dixie Mines, Inc., Box 365, Heflin, Ala.
James Steward Co., Tombstone, Ariz.
Buckeye Mica Co., Buckeye, Ariz.
C.O. Fiedler, Inc. 2221 East 37th St.,
Los Angeles 58, Calif.
Sunshine Mica Co., 440 Seaton St.
Los Angeles 13, Calif.
Jolex Mica1 Co., Fort Collins, Colo.
Thompson-Weinman & Co., Cartersville, Ga.
The Funkhouser Mills, Div. of the
Ruberoid Co., P.O. Box 569, Hagerstown, Md.
U.S. Mica Co., Inc., 26 6th St., Stamford, Conn.
Hayden Mica Co., Wilmington, Mass.
Concord Mica Corp., Concord, N.H.
Los Compadres Mica Co., Ojo Caliente, N. Mex.
David T. Vance, Plumtree, N.C.
Asheville Mica Co., P.O. Box 318, Newport
News, Va.
Kings Mountain Mica Co., Inc., Box 709, Kings
Mountain, N.C.
Franklin Mineral Prod. Co., Box 28, Franklin,
N.C.
DeWeld Mica Corp., Spruce Pine, N.C.
Diamond Mica Co., Spruce Pine, N.C.
The English Mica Co. , Ridgeway Center Bldg. ,
Stanford, Conn.
Harris Clay Co., Spruce Pine, N.C.
Lawson-Boone Mica Co., Minpro, N.C.
Hassett Mining Co., Burnsville, N.C.
Deneen Mica Co., Burnsville, N.C.
General Mining Assoc., 700 Cathedral St.,
Baltimore, Md.
Mineral Mining Corp., Kershaw, S.C.
International Minerals Chemical Corp., Old
Orchard Road, Skokie, 111.
Carolina-Southern Mining Co., Inc.,
Kingsport, Tenn.
Western Mica Corp., 101 South Meramec,
Clayton 5, Mo.
Richmond Mica Corp., 900 Jefferson Ave.,
Newport News, Va.
H
I
-------
APPENDIX J
FLUORSPAR INDUSTRY STATISTICS
J-l
-------
Table J.I PRINCIPAL PRODUCERS OF FLUORSPAR
Company
County, State
Type of
Activity
Minerva Co., Mining Div.
Minerva Oil Co., Crystal
Group
Minerva No. 1
Ozark-Mahoning Co.
Industrial Chemicals Div.
Allied Chemical Corp.
Ozark-Mahoning Co.
Calvert City Chemical Co.
Minerva Oil Co.
Kentucky Fluorspar Co.
Roberts Mining Co.
Hardin & Pope, 111,
Hardin, 111.
Hardin & Pope, 111.
Boulder, Colo.
Jackson, Colo.
Livingston, Ky.
Crittenden, Ky.
Crittenden, Ky.
Ravalli, Montana
Underground mine
& mill
Underground mine
& mill
Underground mine
& mill
Underground mine
& plant
Underground mine
& plant
Underground mine
& mill
Underground mine
Underground mine
& mill
Mine & plant
J-2
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT MO.
EPA-650/2-74-122
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Trace Pollutant Emissions from the Processing of
Non-Metallic Ores
5. REPORT DATE
November 1974
6. PERFORMING ORGANIZATION CODE
7. AUTHOHIS)
Vishnu Katari, Gerald Isaacs, and Timothy W. Devitt
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
PEDCo-Environmental Specialists, Inc.
Suite 13, Atkinson Square
Cincinnati, Ohio 45246
10. PROGRAM ELEMENT NO.
1AB015; ROAP 21AUZ-02a
II. CONTRACT/GRANT NO.
68-02-1321 (Task 4)
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final: Through 6/19/74
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
. ABSTRACT
repOr^ gives results of a. study to identify significant sources of emis-
sions of potentially hazardous trace pollutants from mining and processing of non-
metallic minerals. Based on a review of domestic ore processing data and consider-
ation of both the toxicity of potential pollutants and the significance of fugitive dust
emissions, the following nine industries were selected for further study: cement,
clay (including porcelain, refractory, and brick), gypsum, lime, phosphate rock
(including fertilizer), potash, boron, mica, and fluorspar. Provided for each of the
nine industries are process flow diagrams identifying major processes and material
flow, identification of sources of emissions of various pollutants, and process des-
criptions. The report recommends that five processes be further evaluated because
of their potential for emissions of hazardous pollutants or fugitive dust: kilns
(cement and lime industries), phosphate rock mining and washing, clay mining,
hydrator (thermal phosphoric acid production), and reactor (wet- process phosphoric
acid production).
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air Pollution
Hazardous Materials
Nonmetallif e rous
Minerals
Mining
Processing
Toxicity
Dust
Kilns
Phosphoric Acids
Reactors
Clays
Air Pollution Control
Stationary Sources
Trace Pollutants
Hydrators
13B , 06T
11G
13A
08G, 07B
081
13H, 11C
8. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
277
Unlimited
20. SECURITY CLASS (ThIs page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
J-3
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Office of Administration
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