&EPA
United States
Environmental Protection
Agency
Office of
Federal Activities
Washington, DC 20460
EPA 130/6-81-004
October 1981
Environmental
Impact Guidelines
For New Source
Non-Fertilizer Phosphate
Manufacturing Facilities
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EPA-130/6-81-004
October 1981
ENVIRONMENTAL IMPACT GUIDELINES
FOR NEW SOURCE
NON-FERTILIZER PHOSPHATE
MANUFACTURING FACILITIES
EPA Task Officer:
Frank Rusincovitch
US Environmental Protection Agency
Office of Federal Activities
Washington, D.C. 20460
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Preface
This document is one of a series of industry-specific Environmental Impact
Guidelines being developed by the Office of Federal Activities (OFA) for
use in EPA's Environmental Impact Statement preparation program for new
source.NPDES permits. It is to be used in conjunction with Environmental
Impact Assessment Guidelines for Selected New Source Industries, an OFA
publication that includes a description of impacts common to most industrial
sources.
The requirement for Federal agencies to assess the environmental impacts
of their proposed actions is included in Section 102 of the National
Environmental Policy Act of 1969 (NEPA), as amended. The stipulation that
EPA's issuance of a new source NPDES permit as an action subject to NEPA
is in Section 511(c)(l) of the Clean Water Act of 1977. EPA's regulations
for preparation of Environmental Impact Statements are in Part 6 of Title
40 of the Code of Federal Regulations; new source requirements are in
Subpart F of that Part.
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TABLE OF CONTENTS
LIST OF FIGURES iv
LIST OF TABLES vi
GLOSSARY viii
INTRODUCTION 1
1.0 OVERVIEW OF THE INDUSTRY 4
1.1 SUBCATEGORIZATION 6
1.2 PROCESSES 7
1.2.1 Major Processes of the Non-Fertilizer Phosphate Industry. 7
1.2.1.1 Phosphorus Production (Subcategory A) 10
1.2.1.2 Phosphorus Consuming (Subcategory B) 15
1.2.1.3 Phosphate Chemicals (Subcategory C) 23
1.2.1.4 Defluorinated Phosphate Rock (Subcategory D) 28
1.2.1.5 Defluorinated Phosphoric Acid (Subcategory E) 31
1.2.1.6 Sodium Phosphate from"Wet Process" Phosphoric Acid
(Subcategory F) 37
1.2.2 Auxiliary Processes 37
1.2.2.1 Phosphate Rock Mining and Processing 39
1.2.2.2 Production of "Wet Process" Phosphoric Acid 44
1.3 SIGNIFICANT ENVIRONMENTAL PROBLEMS 45
1.3.1 Location 47
1.3.2 Raw Materials 47
1.3.3 Process Related Problems 48
1.3.4 Pollution Control 50
1.4 TRENDS 57
1.4.1 Markets and Demands 57
1.4.2 Locational Changes 61
1.4.3 Trends in Raw Materials 61
1.4.4 Process Trends 64
1.4.5 Pollution Control Trends 64
1.5 REGUIAT IONS 66
1.5.1 Water Pollution Control Regulations 66
1.5.2 Air Pollution Control Regulations. 73
1.5.3 Solid Waste Regulations 80
1.5.4 Other Government Regulations 84
2.0 IMPACT IDENTIFICATION 90
2.1 PROCESS WASTES 90
2.1.1 Air Emissions 90
2.1.1.1 Phosphorus Production (Subcategory A) 91
2.1.1.2 Phosphorus Consuming (Subcategory B) 95
2.1.1.3 Phosphate Chemicals (Subcategory C) 97
2.1.1.4 Defluorinated Phosphate Rock (Subcategory D) 97
2.1.1.5 Defluorinated Phosphoric Acid (Subcategory E) 98
2.1.1.6 Sodium Phosphates (Subcategory F) 98
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TABLE OF CONTENTS (CONT.)
Page
2.1.2 Wastewater Characteristics 10°
2.1.2.1 Phosphorus Production (Subcategory A) 100
2.1.2.2 Phosphorus Consuming (Subcategory B) 103
2.1.2.3 Phosphate Chemicals (Subcategory C) 105
2.1.2.4 Defluorinated Phosphate Rock (Subcategory D) 105
2.1.2.5 Defluorinated Phosphoric Acid (Subcategory E) 108
2.1.2.6 Sodium Phosphates (Subcategory F) HI
2.1.3 Solid Waste Characteristics Ill
2.1.3.1 Phosphorus Production (Subcategory A) 113
2.1.3.2 Phosphorus Consuming (Subcategory B) 114
2.1.3.3 Phosphate Chemicals (Subcategory C) 115
2.1.3.4 Defluorinated Phosphate Rock (Subcategory D) 115
2.1.3.5 Defluorinated Phosphoric Acid (Subcategory E) 115
2.1.3.6 Sodium Phosphates (Subcategory F) 116
2.2 IMPACTS OF INDUSTRY WASTES. 116
2.2.1 Air Impacts 117
2.2.2 Water Impacts 118
2.2.3 Biological Impacts 121
2.2.3.1 Human Health Impacts 121
2.2.3.2 Ecological and Environmental Impacts 125
2.3 OTHER INDUSTRY IMPACTS 133
2.3.1 Aesthetics 133
2.3.2 Noise 134
2.3.3 Energy 135
2.3.3.1 Cogeneration 137
2.3.3.2 Energy Conservation 137
2.3.4 Socioeconomics 139
2.3.5 Raw Materials and Product Handling 142
2.3.6 Special Problems in Site Preparation and Facility
Cons truction 144
3.0 POLLUTION CONTROL TECHNOLOGY 147
3.1 STANDARDS OF PERFORMANCE TECHNOLOGY: AIR MISSIONS 147
3.1.1 Controllable Emissions 147
3.1.2 In-Process Emission Control Technologies 148
3.1.3 End-of-Process Emission Controls 149
3.1.3.1 Dry Collectors 149
3.1.3.2 Wet Scrubbers 151
3.2 STANDARDS OF PERFORMANCE TECHNOLOGY: WASTEWATER DISCHARGES. . 160
3.2.1 In-Process Controls 150
3.2.1.1 Waste Stream Segregation 161
3.2.1.2 Waste Recycle and Reuse 161
3.2.1.3 Water Reduction \\\ 162
3.2.1.4 Reduction of Spill and Runoff 162
3.2.1.5 Waste Stream Monitoring **] 162
3.2.2 Wastewater Treatment 163
3.2.2.1 Recycle of Wastewaters from the Defluorination of
Phosphoric Acid, Defluorination of Phosphate Rock
Subcategories 16 3
ii
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TABLE OF CONTENTS (CONT.)
3.2.2.2 Recycle of Scrubber Wastewaters from the Phosphorus
Production Subcategory 164
3.2.2.3 Recycle and Treatment of Phossy Water from the
Phosphorus Producing and Consuming Subcategories 165
3.2.2.4 Treatment and Recycle of Process Water from
Production of Anhydrous Phosphorus Derivatives. 165
3.2.2.5 Wastev«ater Treatment and Reduction in the Phosphate
Chemicals Subcategory 166
3.2.2.6 Sodium Wastewater Treatment for Production of
Phosphates from "Wet Process" Phosphoric Acid 167
3.2.3 Emergency Discharge of Recirculation Pond Effluent 167
3.2.4 Recirculation Pond Water Seepage Control 168
3.3 STATE OF THE ART TECHNOLOGY: SOLID WASTE 170
3.3.1 Recovery and Reuse 170
3.3.2 Solid Waste Storage and Disposal 175
3.3.3 Hazardous Wastes 175
4.0 EVALUATION OF AVAILABLE ALTERNATIVES 176
4.1 SITE ALTERNATIVES 176
4.2 ALTERNATIVE PROCESSES AND DESIGNS 179
4.2.1 Process Alternatives 180
4.2.2 Design Alternatives 181
4.3 NO-BUILD ALTERNATIVE 181
5.0 REFERENCES 183
5.1 REFERENCE LIST BY TOPIC 183
5.2 BIBLIOGRAPHY 190
iii
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LIST OF FIGURES
1. Overall material and product flow diagram for the non-fertilizer
phosphate industry 9
2. Standard process for production of elemental phosphorus... H
3. Standard process for production of "dry process" phosphoric acid 17
4. Standard process flow diagram for the manufacture of phosphorus
pentoxide 18
5. Standard process flow diagram for the manufacture of phosphorus
pentasulf ides 20
6. Standard process flow diagram for the manufacture of phosphorus
trichloride 21
7. Standard process flow diagram for the manufacture of phosphorus
oxychloride 22
8. Standard process flow diagram for the manufacture of sodium tri-
polyphosphate from "dry process" phosphoric acid 24
9. Standard process flow diagram for the manufacture of food grade
calcium phosphates from "dry process" phosphoric acid 26
10- Standard process flow diagram for the manufacture of animal feed
grade calcium phosphates from "wet process" phosphoric acid 27
11. Process flow diagram for the manufacture of defluorinated
phosphate rock by the fluid bed calcination process 30
12. Stauffer process for wet process superphosphoric (defluorinated)
acid , 32
13. Vacuum evaporation superphosphoric Cdefluorinated) acid process. 32
14. Process flow diagram for the manufacture of defluorinated
phosphoric acid by the submerged combustion process 35
15. Process flow diagram for the manufacture of defluorinated
phosphoric acid by the aeration process 36
16. Process flow diagram for the manufacture of sodium phosphates
from "wet process" phosphoric acid 38
17. Location of major phosphate rock deposits in the United States.. 40
18. Standard process flow diagram for the manufacture of 'Vet
process" phosphoric acid 46
19. 1975 phosphorus rock consumption pattern for various phosphorus
products 58
iv
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LIST OF FIGURES (CONT.)
Page
20. Raw emission types produced from phosphorus manufacture 92
21. Cyclone scrubber 150
22. Typical baghouse unit 152
23, Typical venturi scrubber unit 155
24 . Typical cyclonic spray scubber unit 156
25. Typical packed bed scrubber units 157
26. Typical layout for spray tower 159
27. Pond water treatment system 169
28. Recommended minimum cross section of dam.. . 171
29. Gypsum pond water seepage control 171
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LIST OF TABLES
Page
1. Subcategories of the non-fertilizer phosphate industry 8
2. Representative analysis of commercial phosphate .rock 41
3. Major waste streams of the phosphorus production subcategory.... 51
4. Major waste streams of the phosphorus consuming subcategory 52
5. Major waste streams of the phosphate chemicals subcategory 53
6. Major waste streams of the defluorinated phosphate rock
subcategory 54
7. Major waste streams of the defluorinated phosphoric acid
subcategory 55
8. Major waste streams of the sodium phosphate subcategory 56
9. Production of selected non-fertilizer phosphate chemicals 1973 -
1979 (quantity in 1,000 short tons, 100% basis) 60
10. Projections and forecasts for U.S. phosphate rock demand by end
use, 1975-2000 (thousand short tons) 60
11. Locational distribution of non-fertilizer phosphate chemical
plants in the United States 62
12. Standards of performance for new source wastewater effluents of
the non-fertilizer phosphate manufacturing point source category 68
13. National primary and secondary ambient air quality standards
(40 CFR Part 50) 74
14. Nondeterioration (PSD) increments for S02 and particulate matter
in areas with different air quality classifications 76
15. Typical permits, licenses, certifications, and approvals
required from Federal, state, regional, and local authorities
for construction and operation of a typical new source
facility 87
16. Average stack heights and controlled emission factors for "wet
process" phosphoric acid and superphosphoric acid plants 99
17. Water use and process waste generation for major operations in
the phosphorus production subcategory 104
18. Water use and process waste generation for production of major
products in the phosphorus consuming subcategory 106
vi
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LIST OF TABLES (CONT.)
Page
19. Water use and process waste generation for major products of
the phosphate chemicals subcategory 107
20. Water use and process waste generation for the defluorinated
phosphate rock subcategory 109
21. Water use and process waste generation for the defluorinated
phosphoric acid subcategory 110
22. Water use and process waste generation for the sodium
phosphates subcategory 112
23. The radioactive decay series for uranium 238 126
24. Process energy requirements of phosphorus and phosphate
chemical manufacturing operations 136
25. Treatment and disposal technologies for process solid wastes
of the phosphorus production subcategory 172
26. Treatment and disposal technologies for process solid wastes of
the phosphorus consuming and calcium phosphates subcategories.. 173
27. Treatment and disposal technologies for process solid wastes
from the defluorinated phosphate rock, defluorinated phosphoric
acid, and sodium phosphates subcategories 174
vii
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GLOSSARY
Adiabatic - A process in which no heat is transferred between the system and
its surroundings.
Apatite - A natural calcium phosphate usually containing fluorine which occurs
as phosphate rock.
Barn - A room- like condensation chamber for anhydrous phosphorus pentoxide.
Burden - The combined rock, coke, and silica feed to a phosphorus electric
furnace.
Calcination - Heating of a solid to a temperature below its melting point to
bring about a state of thermal decomposition or a phase transition other than
melting.
Calcium phosphates - Dicalcium - CaHPO 2HO or CaHPO ; Monocalcium - CaH (PO )
H0 or CaH (PO; Tricalcium - Ca (P0JH Mole ratio of CaO to P 3 to I.
4 - ^
DCP - Dicalcium Phosphate Dihydrate (CaHP H 0) .
4 2
Def luorinated phosphate rock - Apatite rock which has been treated to remove
fluorides. It contains 30 weight percent P?0,-» 0.2 weight percent fluoride.
Dry Process Phosphoric Acid - Phosphoric acid made from elemental phosphorus;
also called furnace acid.
Eut ect ic - The lowest or highest melting point of an alloy or solution of two
or more substances that is comprised of the same components.
Ferrophosphorus - A by-product iron-phosphorus alloy of phosphorus smelting,
typically containing 59 percent iron and 22 percent phosphorus.
Flux - A substance that promotes the fusing of minerals or metals or prevents
the formation of oxides* For example, in metal refining lime is added to the
furnace charge to absorb mineral impurities in the metal. A slag is formed
which floats on the bath and is run off.
Furnace Acid - Phosphoric acid made from elemental phosphorus. Also called
dry process phosphoric acid.
Gangue - The minerals and rock mined with a metallic ore but valueless in
themselves or used only as a by-product.
Gyp-pond - This term is widely used at fertilizer phosphate plants to indicate
the pond receiving wastewater and acting as a recirculation, cooling, and
water reuse pond. Many -plants have ponds with a variety of functions such as
receiving the calcium sulfate residue from acid treatment of rock, receiving
calcium fluoride from first stage of lime precipitation, receiving calcium
phosphate and calcium fluoride sediment from second stage of lime precipita-
tion, recirculation of stack washing and tail gas scrubber water and simul-
taneously removing heat and sediment, and deposition of troublesome
viii
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solids, as arsenic sulfide. Local authorities will have to determine specific
pond uses in order to establish essential solid waste control and groundwater
pollution control measures.
Hydrolysis - A chemical reaction in which water reacts with another substance
to form one or more new substances.
Immiscible - The property of one liquid being unable to mix or blend uniformly
with another.
_! - liter
Nodule - Semi-fused agglomerated and calcined phosphate rock particle.
Phossy water - Water from the phosphorus condenser or phosphorus storage that
is contaminated with colloidal phosphorus, fluosilicates, and dissolved solids.
Phosphorus nud - Sludge or emulsion of phosphorus, dust, and water.
Phosphorus Oxychloride - POC1
Phosphorus Pentasulfide - p?s,-
Phosphorus Pent oxide - P^Cv
Process water - Any water which, during the manufacturing process, comes into
direct contact with any raw material, intermediate, product, by-product, or
gas or liquid that has accumulated such constituents.
Slag - The fused agglomerate which separates in metal smelting and floats on
the surface of the molten metal. Formed by combination of flux with gangue of
ore, ash or fuel, and perhaps furnace lining. The slag is often the medium by
means of which impurities may be separated from metal, or in this case phosphorus.
Soda ash - Soda ash is the source of sodium in sodium phosphate and sodium
polyphosphate plants. Commercial grade contains 99 weight percent Na CO .
Sodium Phosphates - Sodium orthophosphates
Orthodisodium - NaH2HPOH4
Orthomonosodium - NaH PO
Orthotrisodium - Na PO
Viteous sodium 63-66 weight percent P«0 : 34-37
weight percent Na 0.
Sodium poly (pyro) phosphates
Sodium acid pyro - Na H P 0
Tetrasodium pyro - Na.P-O
Sodium tripoly - Na5 30^ '
Sump - A pit or reservoir serving as a receptacle for condensed phosphorus.
ix
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Welfare-related Pollutants - Pollutants for which adverse effects on human
health have not been demonstrated but which exhibit environmental effects.
Wet Process Phosphoric Acid - Phosphoric acid made from phosphate rock and
sulfuric acid.
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INTRODUCTION
The Clean Water Act requires that the United States Environmental Pro-
tection Agency (USEPA) establish standards of performance for categories of
new source industrial wastewater dischargers. Before the discharge of any
pollutant to the navigable waters of the United States from a new source in an
industrial category for which performance standards have been proposed, a new
source National Pollutant Discharge Elimination System (NPDES) permit must be
obtained from either USEPA or the state (whichever is the administering authority
for the state in which the discharge is proposed). The Clean Water Act also
requires that the issuance of a permit by USEPA for a new source discharge be
subject to the National Environmental Policy Act (NEPA), which may require
preparation of an Environmental Impact Statement (EIS) on the new source. The
procedure established by USEPA regulations (40 CFR 6 Subpart F) for applying
NEPA to the issuance of new source NPDES permits may require preparation of an
Environmental Information Document (EID) by the permit applicant. Each Elf) is
submitted to USEPA and reviewed to determine if there are potentially signif-
icant effects on the quality of the human environment resulting from construc-
tion and operation of the new source. If there are, USEPA publishes an EIS on
the action of issuing the permit.
The purpose of these guidelines is to provide industry-specific guidance
to USEPA personnel responsible for determining the scope and content of EIS's
and for reviewing them after submission to USEPA. It is to serve as supple-
mentary information to the previously published document, Environmenta1
Impact Assessment Guidelines for Selected New Source Industries (USEPA 1975),
which includes the general format for an EID and those impact assessment con-
siderations common to all or most industries. Both that document and these
guidelines should be used for development of an EID for a new source non-
fertilizer phosphate manufacturing facility.
[These guidelines provide the reader with an indication of the nature of
the potential impacts on the environment in the vicinity of the facility and
the surrounding region from construction and operation of non-fertilizer
phosphate manufacturing facilities.I In this capacity, the volume is intended
to assist USEPA personnel in the identification of those impact areas that
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should be addressed in an EID. In addition, the guidelines present (in
Chapter 1.0) a description of the industry; its principal processes; sig-
nificant environmental problems; and recent trends in location, raw materials.
processes, pollution control, and environmental impacts. This "Overview of
the Industry" is included to familiarize USEPA staff with existing conditions
in the industry.
Although this document may be transmitted to an applicant for infor-
mational purposes, it should not be construed as representing the procedural
requirements for obtaining an NPDES permit or as representing the applicant's
total responsibilities relating to the new source EIS program. In addition,
i
the content of an EID for a specific new source application is determined by
USEPA in accordance with Section 6.604(b) of Title 40 of the Code of Federal
Regulations and this document does not supersede any directive received by the
applicant from USEPA's official responsible for implementing that regulation.
These Guidelines are divided into five chapters. Chapter 1.0 is the
"Overview of the Industry," described above. Chapter 2.0, "Impact Identifica-
tion," discusses process-related wastes and the impacts that may occur during
construction and operation of the facility. Chapter 3.0, "Pollution Control
Technology," summarizes the technology for controlling environmental impacts.
Chapter 4.0, "Evaluation of Alternative," summarizes possible alternatives to
the proposed action and discusses their evaluation. Chapter 5.0 is a list of
references which are useful for additional or more detailed information.
The principal sources used in the preparation of this guidelines document
were the Development Document for Proposed Effluent Limitations Guidelines
and New Source Performance Standards for the Phosphorus-Derived Chemicals
Segment of the Phosphate Manufacturing Point Source Category (USEPA 1973) and
the Development Document for Effluent Limitations Guidelines and New Source
Performance Standards for the Other Non-Fertilizer Phosphate Chemicals
Segment of the Phosphate Manufacturing Point Source Category (USEPA 1976).
These development documents present evaluations of the industry intended to
identify appropriate control levels for water-borne pollutants as a basis for
establishing effluent limitations. They present a great deal of information
on the industry including process information and information on air emission
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controls and solid waste generation as they relate to contamination of liquid
wastes. These two documents are recommended as additional sources of infor-
mation on the Non-Fertilizer Phosphate Industry and may be obtained from the
Effluent Guidelines Division of USEPA.
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1.0 OVERVIEW OF THE INDUSTRY
Phosphorus, an essential nutrient for both plants and animals, also has
numerous uses in the manufacture of industrial chemicals. Phosphate or phos-
phorus-based chemicals are produced for use in agricultural fertilizers,
animal food supplements, human food supplements, metallurgical alloying mate-
rials, detergents, lubricating oils, and a variety of other uses. The phos-
phate industry can be divided into two major groups of related industries
based on their products: non-fertilizer and fertilizer phosphate. This
document deals with the group of industries producing elemental phosphorus,
phosphorus-derived chemicals, and other non-fertilizer phosphate chemicals.
Collectively these will be referred to as the non-fertilizer phosphate industry.
The phosphate fertilizer industry, by far the larger of the two groups, is
the subject of a companion document, Environmental Impact Guidelines for New
Source Phosphate Fertilizer Manufacturing Facilities.
The products of the non-fertilizer phosphate industry fall into two
distinctive categories: 1) elemental phosphorus and phosphorus-derived
chemicals, and 2) other non-fertilizer phosphate chemicals which are derived
primarily from fertilizer industry intermediates. These two categories are
included under Standard Industrial Classifications (SIC) 2819 (Industrial
Inorganic Chemicals) and 2874 (Phosphatic Fertilizers) respectively.
The non-fertilizer phosphate industry is difficult to characterize be-
cause its designation is based on the non-fertilizer use of its products
rather than on a similarity between its industrial processes and the facilities
required for the products' manufacture. This designation is further obscured
by the close association between producers of fertilizer and non-fertilizer
phosphate chemicals. In general, companies producing non-fertilizer phosphate
chemicals are large, integrated chemical or petrochemical companies with
diversified interests throughout the chemical industry (USEPA 1973b, USEPA
1974b). Most of these companies also have interests in the fertilizer in-
dustry and produce both fertilizer and non-fertilizer products. Many of the
plants producing non-fertilizer phosphate products are part of large integrated
chemical complexes which produce a wide variety of both fertilizer and non-
fertilizer phosphate chemicals while others are small operations producing
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only one or two products which are shipped to other plants for further pro-
cessing.
It is not uncommon for one company to be involved in all aspects of the
industry from ore extraction to production of finished products. Because
economics dictate that processing facilities which utilize bulky phosphate
rock be near their source of raw materials, it also is common for'a company to
have several operations in the mining area or even on one site (USEPA 1973a).
For example, a plant located at or near a phosphate rock mine site may be
involved in mining and preparing the rock, as well as producing a variety of
phosphate and non-phosphate fertilizer products and non-fertilizer phosphate
products on the same or nearby sites. The non-fertilizer phosphate production
at such a facility may be a small part of a much larger operation and, con-
sequently, the impacts of this operation may be difficult to distinguish from
those of other operations.
Due to the degree of integration and diversification among the companies
producing phosphate chemicals, it is necessary to view the non-fertilizer
phosphate industry in context with the related mining and fertilizer industries.
Not only are the industries related in terms of raw materials, processes, and
facilities, but they also may be located in close proximity to each other and
share common environmental problems. The major mining and manufacturing
operations related to production of phosphate chemicals and fertilizer are
briefly described in the following paragraphs to highlight the interrelation-
ships and distinctions among the various segments of the non-fertilizer
phosphate industry (USEPA 1980).
• Phosphate mining industry. This is a segment of the mining industry
which extracts phosphate ores and processes them to produce marketable
quality "phosphate rock." Most ores are sedimentary deposits of the
mineral fluorapatite and associated impurities, along with clays,
sands, or other rock matrix. These constituents usually must be
separated to concentrate the phosphate-bearing deposits which are
referred to as "phosphate rock," "phosrock," "phosphate rock con-
centrate," and "benefidated phosphate rock."
• Phosphate fertilizer industry. This industry uses phosphate rock from
the phosphate mining processes to manufacture phosphate fertilizer
chemicals.
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• Non-phosphate fertilizer industries. In reference to the phosphate
fertilizer industry, these industries include the "nitrogen" or
"nitrogenous" fertilizer industry and the "potassium" or "potash"
fertilizer industry. The products of the nitrogen and potash
fertilizer industries are usually considered "intermediate," to be
combined with other materials or processed further for specific
applications.
• Mixed (and blended) fertilizer industry. This is the industry which
actually produces most of the fertilizer materials commercially
marketed. Phosphate, nitrogen, and potassium fertilizer chemicals,
along with various fillers, coating agents, insecticides, and other
useful additives, are combined by this industry to produce popular
blends or formulations tailored to the needs of certain geographic
areas.
• Non-fertilizer phosphate industry. This category includes industries
involved in the manufacture of phosphorus-derived and non-fertilizer
phosphate chemicals that are widely used for purposes other than soil
fertilization. This broad industry category includes the production
of phosphorus and ferrophosphorus by smelting phosphate ore; pro-
duction of phosphoric acid, phosphorus pentoxide, phosphorus tri-
chloride, and phosphorus oxychloride directly from elemental phos-
phorus; production of sodium tripolyphosphate and animal feed grade
and human food grade calcium phosphate from phosphoric acid; defluor-
ination of phosphate rock by high temperature and other treatments;
defluorination of phosphoric acid; and purification of sodium phos-
phates from "wet process" phosphoric acid. These products are used in
applications such as human food additives, animal feed supplements,
plastics manufacture, metal treatment, detergent builders, and in-
cendiary chemicals.
Where requi'red to enhance the understanding of the non-fertilizer phos-
phate industry, the interrelationships of the above industry segments are
indicated in this document. In general, however, these Guidelines do not
address the other industry segments.
1.1 SUBCAIEGORIZATION
The non-fertilizer phosphate industry is difficult to identify and sub-
categorize because its various segments are grouped together as mich on the
basis of their lack of association with the fertilizer industry rather than
on the internal similarity between them.
The industry is generally divided into two categories: 1) elemental
phosphorus and phosphorus-derived chemicals, and 2) other non-fertilizer
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phosphate chemicals. Within these general categories, subcategories may be
identified by grouping particular manufacturing operations according to their
raw materials, products, processes, waste materials, and environmental prob-
lems. The industry has been subcategorized by USEPA according to these cri-
teria for the purpose of establishing effluent limitations guidelines and
standards pursuant to Section 304 of the Federal Water Pollution Control Act.
These subcategories are identified in Table 1 and will be used as the basis
for industry descriptions in this document.
Of the six subcategories, only phosphorus production and defluorinated
phosphate rock operations are likely to be found as completely separate facil-
ities. The others probably would be found associated with a larger industrial
complex manufacturing several products. The degree of integration and diver-
sification among the phosphate manufacturing facilities often makes it diffi-
cult to identify the subcategory to which a specific facility may belong. Any
new source facility should be examined carefully to determine the subcategory
or subcategories within which its manufacturing processes belong.
1.2 PROCESSES
1.2.1 Major Processes of the Non-Fertilizer Phosphate Industry
The major industrial processes of the non-fertilizer phosphate industry
include those for the production and use of elemental phosphorus and those for
the production of non-fertilizer products from phosphate rock and "wet process"
phosphoric acid. The general product manufacturing scheme for the industry is
depicted in Figure 1. The initial process for the production of phosphorus
and phosphorus-derived chemicals is the production of elemental phosphorus by
thermal reduction of phosphate rock in an electric arc furnace (USEPA 1973a).
Ferrophosphorus, commonly used in the metallurgical industry, is a direct
by-product of this phosphorus production process. Most of the elemental
phosphorus produced in this country is used to produce "dry process" or
"furnace grade" phosphoric acid. The remainder of the phosphorus either is
sold or used to produce chemicals such as phosphorus pentoxide, phosphorus
pentasulfide, phosphorus trichloride and phosphorus oxychloride. The "dry
process" phosphoric acid produced from phosphorus is of a much higher quality
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Table 1. Subcategories of the non-fertilizer phosphate industry.
A. Phosphorus Production facilities manufacture elemental phosphorus from
phosphate rock by thermal reduction of the rock with coke and silica in
an electric arc furnace.
B. Phosphorus Consuming facilities manufacture chemicals including "dry
process" phosphoric acid, phosphorus pentoxide, phosphorus trichloride,
phosphorus oxychloride, phosphorus pentasulfide, red phosphorus, and
various munitions from elemental phosphorus.
C. Phosphates facilities manufacture high quality phosphate products such as
sodium tripolyphosphate and food grade calcium phosphates from "dry
process" phosphoric acid.
D. Defluorinated Phosphate Rock facilities chemically or thermally remove
fluorine from phosphate rock for production of animal grade phosphate
food supplements.
E. Def luorinated Phosphoric Acid facilities, remove fluorine from "wet pro-
cess" phosphoric acid (a major intermediate of the fertilizer industry)
for use in the production of animal food grade calcium phosphates and
other chemicals.
F. Sodium Phosphates facilities produce high quality sodium phosphate chemi-
cals from "wet process" phosphoric acid (a major intermediate of the
fertilizer industry) rather than "dry process" phosphoric acid as done in
subcategory B.
Sources: US Environmental Protection Agency. 1973a. Development document
for proposed effluent limitations guidelines and new source per-
formance standards for the phosphorus derived chemicals segment of
the phosphate manufacturing point source category. Office of Air
and Water Programs, Washington DC, 159 p.
US Environmental Protection Agency. 1976a. Development document
for effluent limitations guidelines and new source performance
standards for the other non-fertilizer phosphate chemicals segment
of the phosphates manufacturing point source category. Office of
Water and Hazardous Materials, Washington DC, 105 p.
-------
Figure 1. Overall material and product flow diagram for the non-fertilizer
phosphate industry.
vo
Mixed Phosphate Rock
Electric
Furnace
Elemental
Phosphorus
Ferrophosphorus
"Wet" Process
(Acidulation)
Wet Process Acid
Batch Reactor
(Direct Union)
Phosphorus Trichloride
Combustion
Phosphorus Pentoxide
Batch Reactor
(Direct Union)
Phosphorus Pentasulfide
"Dry" or Furnace
Process
Phosphoric Acid (Dry)
Defluorination
Defluorinated Phosphoric Acid
Neutralization
Sodium Phosphates
Defluorination
Defluorinated Phosphate Rock
Batch Reactor
(Direct Union)
Phosphorus
Oxychloride
Neutralization
Calcium
Phosphates
Neutralization
Tripolyphosphates
Source: US Environmental Protection Agency. 1977b. Federal guidelines - state and local pretreatment programs,
Appendix 8, Volume III. Office of Water Program Operations, Washington DC, 475 p.
-------
than the "wet process" phosphoric acid of the fertilizer industry and is vised
largely by the food industry. Products made from "dry process" phosphoric
acid include animal and human food grade calcium phosphate, reagent grade
phosphate compounds, and sodium tripolyphosphate which is used in detergents
and water purification systems.
There is also a demand for phosphate products of adequate quality for
soap and animal feed but at a lower cost than those produced from "dry
process" acid. These products can be produced from lower grade phosphate
materials such as defluorinated phosphate rock and "wet process" phosphoric
acid by using appropriate purifying techniques. Defluorinated phosphate rock
produced by chemical and heat treatment of phosphate rock is utilized as an
animal feed ingredient. Phosphoric acid is defluorinated by evaporation or
stripping techniques and is mainly used in the production of animal feeds and
some high analysis and liquid fertilizers. With the use of appropriate puri-
fication steps, sodium phosphates can be produced from "wet process" acid and
used as intermediates in the production of soaps and detergents (USEPA 1976a).
These process descriptions are adopted from the development document for
effluent guidelines limitations and standards for the Industry (USEPA 1973a
and 1976a) unless otherwise noted. Following are general descriptions of the
processes used to manufacture non-fertilizer phosphate products.
1.2.1.1 Phosphorus Production (Subcategory A)
Elemental phosphorus is manufactured by the thermal reduction of phos-
phate rock with reducing carbon (coke) in an electric furnace. Silica in the
form of sand is used as a flux. As shown in Figure 2, the standard process
for phosphorus production consists of three major subprocesses: furnace
charge preparation, thermal reduction in the electric furnace, and product
recovery.
Furnace Charge Preparation
The phosphate rock or phosphate rock concentrate used for manufacturing
phosphorus is usually conditioned by an agglomeration process in order to
obtain a relatively porous furnace burden that will be retained in the furnace
10
-------
Figure 2. Standard process for production of elemental phosphorus,
BURN EXCESS
WASHED
ORES
ORE
BLENDER
SIZING
AND
CALCINING
KILN
SILICA
STORAGE
-^FERROPHOSPHORUS
r^FOR SALE
P,CO, DUST
ELECTROSTATIC
PRECIPITATOR
WASTE
V
TO FURTHER
SLAG PREPARATION
BEFORE SALE
^
DUST
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus~derived
chemicals segment of the phosphate manufacturing point source category. Office of Air
and Water Programs, Washington DC, 159 p.
-------
during puffs and blows. An agglomerated burden allows reaction gases to
escape from the furnace as it is being smelted and promotes more efficient
heat transfer throughout the furnace.
Relatively low grade phosphate rock such as that from western states may
contain high concentrations of clay or organic material and low concentrations
of phosphate reducing its value as a fertilizer material. However, this low
grade rock may be used to manufacture elemental phosphorus and phosphate chemi-
cals if properly conditioned.
Commonly used conditioning processes include nodulizing, pelletizing,
briquetting and compacting. Sintering may be used at a few existing furnaces
but probably would not be used at a new facility. Following pelletizing,
briquetting or compacting, the agglomerated burden may need to be calcined to
impart the necessary strength. Conditioning processes are described as fol-
lows:
Sintering is an operation in which fine ore is mixed with coke or coal
and burned on a moving grate under a strong draft. Heat from the
burning coke or coal fuses the phosphatic material into a uniform
mass. The sintered ore mixture is then crushed and screened for
calcining and smelting. Undersized particles are returned for re-
processing. This process in now considered to be outmoded and
probably would not be used at a new source facility.
Nodulizing involves heat fusing phosphate fines in a rotary kiln.
Tumbling in the kiln causes the material to cohere and form rounded
nodules suitable for smelting. Feed may be either relatively dry or a
wet slurry. The feed may be mixed using pug mixers; crane-bucket
mixing; pile building, blending, and reclaiming chaser mills; or
layering on conveyor belts. Processing includes rotary drying (dry
kiln), cooling of the kiln product (inclined grate cooler), crushing,
and screening. Mud rings which form on kiln walls near the discharge
end must be removed periodically with a boring bar.
Pelletizing involves grinding the phosphate to provide a large surface
area, adjusting the liquid phase by addition of water and tumbling the
material in a drum or pan. Agglomerates are held together by surface
tension forces. When the phosphate contains clay, grinding may be un-
necessary (Barber 1980b).
Briquetting involves plasticizing the mixture in an intensive mixture
followed by pressure molding into various shapes called briquets.
Optimum moisture for briquetting is provided by adding water to par-
12
-------
tially dried material. Usually clay present in low-grade phosphates
serves as a binder for briquetting, but when insufficient clay is
present a binder must be added (Barber 1980b).
• Compacting is similar to briquetting except that pressure is exerted
on the material by smooth rolls forming a sheet of material of the de-
sired thickness. The sheet of material is broken into chunks of the
desired size. Clay serves as the binder, although solids may be
agglomerated without a binder if high pressures are exerted by the
rolls (Barber 1980b).
• Calcining involves the drying and screening of pellets, briquettes,
or sheets and burning them in a rotary kiln just below the fusion
temperature to strengthen them. Equipment used for this process
includes drums, rotary driers, screens, and rotary kilns.
Thermal Reduction in the Electric Furnace
The prepared furnace burden is charged to a specially designed electric
arc furnace along with coke, the reducing agent, and sand, which serves as a
flux. Weighed quantities of each material are blended and intermittently fed
into the furnace by means of a common conveyor. Phosphate reduction in the
arc furnace requires tremendous energy input totaling 13,000 +_ 1,000 kwh of
electric energy per ton of phosphorus produced (Stinson 1976). The furnace is
water-cooled and has carbon-lined steel walls, a concrete or steel roof, and a
carbon crucible. Its operating temperature is in the range of 1400°-1550° C
(2252°-2822° F) (Barber 1980b).
The electrothermal reduction of phosphate rock produces a gaseous product
consisting of approximately 90% carbon monoxide (CO), 7% phosphorus, and 3%
other gases, primarily nitrogen, hydrogen, silicon tetrafluoride and dust.
Furnace off-gas is routed on for cleaning and product recovery in another part
of the plant. Ferrophosphorus, a by-product used by the metallurgical indus-
try, and waste slag are also produced. These molten materials are inter-
mittently tapped from one of two furnace tapholes in a molten state. Ferro-
phosphorus can be produced from the iron which naturally occurs in the phosphate
rock, but iron slugs sometimes are added to the furnace burden to increase
ferrophosphorus production. Slag consists mostly of calcium silicate and
calcium aliminate and contains most of the impurities found in the original
rock. Slag may be cooled with water or air but ferrophosphorus is strictly
air-cooled since it is highly reactive with water and will burn or explode.
13
-------
Product Recovery
The gaseous mixture from the electric furnace is treated in an electro-
static precipitator to remove dust (Barber 1980b). Phosphorus vapor in the
gas is condensed by adiabatic cooling with water sprays in an open chamber.
Water and liquid phosphorus drain to a sump under the chamber where relatively
pure liquid phosphorus settles to the bottom covered by a layer of water
containing suspended particles of liquid phosphorus. The water and phosphorus
mixture overflows into another compartment of the sump where additional liquid
phosphorus settles out as the bottom layer. An emulsion, called phosphorus
sludge, settles out as another layer, and the partially clarified (phossy)
water is the top layer. Finally, the water flows to another compartment from
which it is recycled to the condenser.
Uncondensed off-gases flow to a tubular condenser surrounded by cooling
water. The mixture of condensed phosphorus and water drains to the phosphorus
sludge compartment of the condenser sump. The gas is exhausted by a liquid-
piston type of rotary blower. Recycled condenser water is used in the exhauster.
Some phosphorus is collected by the exhauster, and the mixture of water and
phosphorus drains to the spray water compartment of the sump.
Phosphorus condensing arrangements have not been standarized in the
industry. Various combinations of spray and tubular condensers may be used.
The objectives are to cool the gas as ranch as possible and to minimize forma-
tion of phosphorus sludge during the condensing process. When the gas is
cooled to 50° to 55° C (122° to 131° F) by the condensing system, the opera-
tion is considered acceptable.
Phosphorus and phosphorus sludge are removed from the condenser sump by
submerged pumps. Phosphorus and phosphorus sludge are kept separate. The
phosphorus is a yellow liquid which will contain about 98 percent elemental
phosphorus, but the quality will increase as impurities rise to the top as a
sludge quality layer. Some producers filter phosphorus to obtain a higher
quality product. The sludge collected in the condenser sump contains about
one-third elemental phosphorus, one-third solid impurities, and one-third
water. Both phosphorus and phosphorus sludges are stored under water to pre-
vent burning, but in the case of phosphorus sludge the interface with water is
not easily determined.
14
-------
The exhaust gas contains about 92.3% CO, 4.6% H , 2.1% N , 0.5% CO , and
0.3% CH^ on a dry basis. The gas is saturated with both water and phosphorus
at the condenser exhaust temperature. It has a heating value of about 300 Btu
per cubic foot and may be burned in equipment such as dryers and kilns. The
gas is needed as fuel in dryers and kilns, and combustion in boilers is not
practiced. Without cleaning, combustion of the gas causes P 0 to be emitted
in the combustion gases.
Because liquid phosphorus autoignites on contact with warm air (93° C),
it must be covered with water at all times to maintain a seal from the atmos-
phere. The phosphorus is kept under water both in the sump pit of the con-
denser tower and in the product storage tanks, but must be kept above its
freezing point (44° C, 111° F) so that it can be removed. It must also be
transported under a water blanket. Elemental phosphorus is only slightly
soluble in water but the condenser water and water blanket pick up colloidal
phosphorus which is very difficult to remove or treat. Disposal of this
phosphorus-contaminated or "phossy" water is one of the industry's most serious
e nvi ro nme nt a1 pr oblems.
1.2.1.2 Phosphorus Consuming (Subcategory B)
Five major products are produced using elemental phosphorus from the
electric furnace: phosphoric acid ("dry process" or furnace grade), phospho-
rus pentoxide, phosphorus pentasulfide, phosphorus trichloride, and phosphorus
oxychloride. Various munitions are also produced from elemental phosphorus
including white phosphorus and nerve gases known as GB and VX. However, the
great majority (85%) of the industry's production of phosphorus is used to
manufacture "dry process" phosphoric acid. Smaller quantities of other pro-
ducts are produced using anhydrous processes. Because phosphorus is trans-
ported and stored under a water blanket, phossy water may be a raw waste
material at phosphorus-consuming plants as well as at phosphorus producing
plants. The standard procedure for transferring liquid phosphorus from a rail
car to the using plant's storage tank, however, is to pump the displaced
phossy water from the storage tank back into the emptying rail car. Instead
of being wasted at the phosphorus-using plant, the phossy water is shipped
back to the phosphorus-producing facility for treatment and/or reuse.
15
-------
Phosphoric Acid ("Dry Process")
In general, high quality "dry process" phosphoric acid is manufactured
by burning phosphorus in air to produce phosphorus pentoxide and absorbing it
in water to produce phosphoric acid (Figure 3). The following steps are
involved in this process (USEPA 1977c):
• Molten phosphorus is sprayed into a combustion chamber with air or air
and steam where it is burned. The combustion chamber is cooled by
running water over the surface or by running phosphoric acid down the
interior walls. The resulting gaseous mixture of phosphorus pentoxide
and nitrogen may be cooled in a heat exchanger before being forwarded
to the next process.
An alternative to this process may be practiced in those cases where
phosphorus is produced and consumed on the same site. The offgas from
the electric arc furnace may be forwarded directly to the combustion
chamber following cleaning where it is oxidized to phosphorus pent-
oxide (P 0 ) and carbon dioxide (CO ). This gas may then be cooled
and forwarded on for the production of phosphoric acid.
• Mixed P 0 /CO /N gases from off-gas combustion, or P_0 /N gases from
phosphorus combustion, are passed through an adsorption tower counter-
current to sprayed water. Acid mist is separated from the gas stream
by means of a scrubbing tower, a cyclone, or a glass-wool filter.
• Phosphoric acid from the hydrator/absorption unit is purified by the
addition of a soluble sulfide and silica and the filtration of the
resulting precipitants. Arsenic and lead are precipitated by treat-
ment with sulfide and silica is used to remove hydrofluoric acid.
Arsenic and lead are removed by filtration.
• "Dry process" phosphoric acid may also be produced by contacting the
combustion gases in the hydrator with dilute phosphoric acid rather
than with water.
Phosphorus Pentoxide
Phosphorus pentoxide (P?0c) is produced by the rapid condensation of dry
phosphorus combustion gases (Figure 4). The mixed P2°5/N2 &ses from the
combustion of elemental phosphorus are forwarded to an externally cooled
condensation chamber called a "barn." Solid phosphorus pentoxide condenses on
the walls and is scraped from the walls by moving chains. It is removed from
the hopper at the bottom of the "barn" by means of a screw conveyor.
16
-------
Figure 3. Standard process for production of "dry process" phosphoric acid.
VENT
JL
ELECTROSTATIC
PRECIPITATION
AIR
WATER
LIQUID
PHOSPHORUS'
GASES
COMBUSTION
FURNACE
P2°5
HYDRATION
_V
»DUST WASTE
NoSH
WATER
PURIFICATION
FILTRATION
I
PHOSPHORIC
ACID
STORAGE
WASTE
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus-derived
chemicals segment of the phosphate manufacturing point source category. Office of Air
and Water Programs, Washington DC, 159 p.
-------
Figure 4. Standard process flow diagram for the
manufacture of phosphorus pentoxide.
AIR
X
AIR FILTER
AIR DRYER
LIQUID PHOSPHORUS STORAGE
COMBUSTION
CHAMBER
BARN
oo
.PRODUCT
P2°5
WATER SEAL
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus-derived
chemicals segment of the phosphate manufacturing point source category. Office of Air
and Water Programs, Washington DC, 159 p.
-------
Phosphorus Pentasulfide
Phosphorus pentasulfide (P?S ) is produced by mixing liquid phosphorus
and liquid sulfur in a batch reactor (Figure 5). The reaction is highly
exothermic and since both reactants are extremely flammable at the reaction
temperature, the reactor must be constantly purged with nitrogen and the vent
line mast be water-sealed. The product is either casted and solidified
directly from the holding tank or purified by vacuum distillation before
casting. Since in its molten state P?S burns on contact with air, casting
fumes are produced which must be removed. However, once the P2sc *s solidi-
fied, it no longer produces fumes and can be handled and stored.
Phosphorus Trichloride
Highly corrosive phosphorus trichloride (PCI ) is produced in a water-
cooled, jacketed batch reactor (Figure 6). Liquid phosphorus is charged into
the reactor and gaseous chlorine is bubbled through it to produce phosphorus
trichloride. The product is refluxed through the reactor until all of the
phosphorus is consumed. The chlorine input nust be carefully controlled to
prevent production of phosphorus pentachloride. Following production of PCI ,
the product is batch distilled by the introduction of steam into the reactor
jacket. The distillate is then condensed and collected. A semi-continuous
variation of this process has also been developed.
Phosphorus Oxychloride
Phosphorus oxychloride (POC1 ) is manufactured by the reaction of phos-
phorus trichloride, chlorine, and solid phosphorus pentoxide in a jacketed
batch reactor (Figure 7). Liquid phosphorus trichloride is charged into the
reactor, solid phosphorus pentoxide is added, and chlorine is bubbled through
the mixture. Following reaction, steam is supplied to the reactor jacket,
water to the reflux condenser is shut off, and the product is distilled from
the reactor and collected. An alternate process also is in commercial use
which involves air oxidation of phosphorus trichloride to produce the oxy-
chloride form.
19
-------
Figure 5. Standard process flow diagram for the manufacture of phosphorus pentasulfides.
WATER VENT
t
SCRUBBER
SULFUR
STORAGE
TANK
N2 PURGE-
LIQUID
PHOSPHORUS
STORAGE
TANK
BATCH
REACTOR
HOLDING
TANK
> WASTE
CASTING
PRODUCT
STILL POT
CRUSHING
VENT
t
DUST
COLLECTOR
PRODUCT
WASTE
CONDENSER
WATER
SEAL
WENT
_y
A
COLD TRAP
HEAT
EXCHANGER
_y
VACUUM
PUMP
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus-derived
chemical segment of the phosphate manufacturing point source category. Office of Air and
Water Programs, Washington DC, 159 p.
-------
Figure 6. Standard process flow diagram for the manufacture of phosphorus trichloride.
CHLORINE
LIQUID
PHOSPHORUS
STORAGE
TANK
BATCH
REACTOR
REFLUX
CONDENSER
CONDENSER
HOLDING
TANK
WATER
TRANSFER
TO
CONTAINERS
VENT WATER
t
I
SCRUBBER
1
\l/
_y
-^PRODUCT
VENT
SCRUBBER
i
&STE
WASTE
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus-derived
chemicals segment of the phosphate manufacturing point source category. Office of Air and
Water Programs, Washington DC, 159 p.
-------
Figure 7. Standard process flow diagram for the manufacture of phosphorus oxychloride.
PCI3 P205 CI2
V V V
VENT WATER
t
SCRUBBER
WASTE
BATCH
REACTOR"
REFLUX
CONDENSER
V
CONDENSER
V
HOLDING
TANK
V
TRANSFER
TO
CONTAINERS
PRODUCT
VENT WATER
1
SCRUBBER
WASTE
Source:
US Environmental Protection Agency. 1973a. Develop-
ment document for proposed effluent limitations guide-
lines and new source performance standards for the
phosphorus ^derived ehemiealsTsegment of the phosphate
manufacturing point source category. Office of Air and
Water Programs, Washington DC, 159 p.
22
-------
1.2.1.3 Phosphate Chemicals (Subcategory C)
The products of this subcategory are primarily high quality sodium tri-
polyphosphate and high grade calcium phosphate for use in food or personal
products. The sodium phosphates produced from "dry process" acid are used
primarily in the manufacture of detergents due to their low coloration and
purity. Feed.grade and human food grade calcium phosphate are usually manu-
factured from "dry process" acid due to the obvious purity requirements of
these products.
Sodium Phosphates
A number of sodium phosphate compounds including tetrasodium pyrophos-
phate (Na P 0 ), sodium acid pyrophosphate (Na H P 0 ), and disodium ortho-
phosphate are made in small quantities, but the largest volume sodium phos-
phate products are sodium tripolyphosphate and sodium orthophoshpate. Sodium
tripolyphosphate is considered by some to be the ideal builder for use in
detergents and is the major product of this segment of the industry. It is a
water softener, emulsifier, soil dispersant, buffering agent and is non-
irritating (USDOC 1980). The process for the manufacture of sodium tripoly-
phosphate as shown in Figure 8 involves the neutralization of "dry process"
phosphoric acid with either soda ash (Na CO ) or a mixture of soda ash and
caustic soda (NaOH) followed by crystallization and calcination of the mono-
and disodium products to a condensed form. Sodium orthophosphate products are
made by slight variations of the same processes. These steps are described in
more detail below (USEPA 1977c):
• The manufacture of all sodium phosphate products begins as a common
process. Phosphoric acid is first neutralized in a batch reactor with
a slight excess of soda ash (Na.CO ) or a caustic and soda ash mixture.
This solution is then boiled with steam until all of the carbon dioxide
is driven off. The disodium orthophosphate (Na_HPO.) solution is then
filtered to remove silica, iron, and aluminum phosphates. The final
solution is then prepared by addition of phosphoric acid or acid and
caustic soda (NaOH) corresponding to the pH and composition of the
desired product.
• To produce monosodium orthophosphate the sodium phosphate solution is
diluted with HOPOA to Sive a solution corresponding to NAH PO and
evapo'rated to form the desired product in a dessicated, crystalline
form.
23
-------
Figure 8. Standard process flow diagram for the manufacture of
sodium tripolyphosphate from "dry process" phosphoric acid.
50%
CAUSTIC
TANK
PHOSPHORIC___±*.
ACID ^
STACK
4
DEMISTER
CO 2
RELEASE
TANK
V
SPRAY
DRYING
TOWER
CALCINER
PRODUCT
COOLER
(TEMPERING)
V
PRODUCT
MILLING
AND SIZING
SCRUBBER
A
FINES
WATER
DUST
COLLECTOR
Source:
PRODUCT
US Environmental Protection Agency. 1973a. Development
document for proposed effluent limitations guidelines
and new source performance standards for the phosphorus-
derived chemicals segment of the phosphate manufacturing
point source category. Office of Air and Water Programs,
Washington DC, 159 p.
24
-------
• To produce disodium orthophosphate (Na HPO ) the solution is crys-
talized and the crystals are separated by centrifugation. Process
solutions are returned to the neutralization stage and the crystals
are dried to Na0HP0.2H 0 or Na^HPO,.
242 24
• Sodium tripolyphosphate (Na P_0 „) is produced by the calcination of a
solution or mixture of mono- and disodium orthophosphate in a rotary
kiln. Following calcination, vitreous sodium tripolyphosphate is
annealed to prevent the phosphates from reverting to a different form.
• Vitreous sodium orthophosphate products are produced by feeding mono-
and disodium phosphate solutions into a furnace. A molten solid forms
which must be chilled and ground into the final product.
Calcium Phosphates
In general, non-fertilizer calcium phosphates are made by the neutral-
ization of phosphoric acid with lime. The processes for two of the major
products are indicated in Figures 9 and 10 which show the processes for various
human food grade calcium phosphates and animal feed grade calcium phosphates
respectively. Although the processes for production of all calcium phosphate
compounds are chemically similar, they differ in the amount and grade of lime
and phosphoric acid used and in the volume of process water required. "Dry
process" or furnace grade phosphoric acid must be used in the production of
human food grade calcium phosphates, while defluorinated "wet process" phos-
phoric acid is acceptable for animal feeds (USEPA 1977c).
Generalized descriptions of the processes for production of the various
calcium phosphate products are provided below (USEPA I977c):
• Monocalcium phosphate monohydrate (MCP) (CaH (PO ) H 0) is formed by
mixing an excess of 75% dry process phosphoric aciS with a lime slurry.
An excess of acid is maintained to prevent formation of dicalcium
phosphate. A small amount of steam is liberated from the process due
to heat of reaction.
• Anhydrous monocalcium phosphate (MFC) (CaH. (?(),)„) is produced by the
reaction of quicklime with dry process phosphoric acid at 140° C in a
batch mixer. At higher heat the water is driven off as it is produced.
A small amount of aluminum phosphate or potassium and sodium phosphates
are Included in the mix. After heat treatment, these additives form
protective coatings on the surface of the CaH (PO.) crystals.
25
-------
Figure 9. Standard process flow diagram for the manufacture of
food grade calcium phosphates from "dry process" phosphoric acid.
LIME
1
WATER
1
LIME PHOSPHORIC
SLURRY ACID
TANK TANK
\
/ V
V
y
MCP
MIX
TANK
\
f
SLURRY
HOLD
TANK
\/
HOT GAS
SPRAY
TOWER
>^
/
SIZING
V
PRODUCT
MCP
WATER VENT
1 t
\b 1
t^r
at
;RUBBER
WASTE
\
/
DCP
MIX
TANK
>
f
SLURRY
HOLD
TANK
>
f
CENTRIFUGE
WASTE
\
HOT GAS
* \b
KILN
MILL
WATER VENT
X t
sc
/
CYCLONE
\
/
TCP
MIX
TANK
\
/
SLURRY
HOLD
TANK
STEAM
1 V
VENT
/ t
DRUM
DRYER
\
/
SIZING
X
PRODUCT
TCP
4/ v
WASTE PRODUCT
DCP
Source: US Environmental Protection Agency. 1973a. Development document
for proposed effluent limitations guidelines and new source per-
formance standards for the phosphorus derived chemicals segment of
the phosphate manufacturing point source category. Office of Air
and Water Programs, Washington DC, 159 p.
26
-------
Figure 10.«• Standard process flow diagram for the manufacture of animal feed grade calcium
phosphates from "wet process" phosphoric acid.
to
PHOSPHORIC
ACID
I
XS1
WASTE
WATER VENT
t
AIR
Y
SILICA LIME
\l/ \b
A
DEFLUORINATtON
WATER
\|/ \
PUG
REAC
VENT WATER
A 1
f \ W \
SCRUBBER
--
MILL
TOR
VENT
> 4-
SCRUBBER
PYPI OWF > ^CRURRFR
/\
V
WASTE
ROTARY v x PRODUCT ^
> DRYbR > COOLER •>
PRODUCT
WASTE
Source: US Environmental Protection Agency. I9?3a. 'development document for pr^pos-ed effluent limi-
tations guidelines and new source performance standards for the phosphorus-derived
chemicals segment of the phosphate manufacturing point source category. Office of Air and
Water Programs, Washington DC, 159 p.
* Defluorination of phosphoric acid is a separate process described in Subcategory E.
-------
• Dicalcium phosphate dihydrate (DCP) (CaHPO 2H 0) is produced by mixing a
dilute lime slurry with dilute dry process phosphoric acid and dissi-
pating the heat of the reaction. An excess of water is used in this
process to assure a homogenous mixture and a correct stoichiometric
balance among the reactants. The product must be centrifuged to
remove excess water prior to drying.
• Dicalcium phosphate for animal feed is manufactured with purified wet
process phosphoric acid and powdered limestone in a pug mill reactor
without excess water since a higher concentration of mono- and tri-
calcium phosphates are acceptable in animal feed.
• Tricalcium phosphate (TCP) (Ca (PO ) ) is prepared by adding phosphoric
acid to a slurry containing an excess of lime to prevent formation of
DCP.
• Finishing operations Following the initial reaction, calcium phosphate
products are dried or further processed as follows (USEPA I977c).
Monocalcium phosphate monohydrate (CaH (PO,)_H 0) thick slurry is
usually dried in a spray tower or vacuum dryer. Anhydrous monocalcium
phosphate (CaH. (PO, ,. „) is heat-treated to change the protective coatings
(formed by aluminum phosphate or potassium plus sodium phosphate) from
orthophosphates to polyphosphates. Dicalcium phosphate dihydrate
(CaHOP 2H 0) must be dried in a tube dryer or kiln mill if powdered
limestone is the source of calcium in the compound. If quicklime is
used as the calcium source, no drying is necessary. Tricalcium phos-
phate slurry is filtered and dried.
1.2.1.4 Defluorinated Phosphate Rock (Subcategory D)
Apatite phosphate rock contains sufficient calcium and phosphorus to be a
useful animal feed supplement but the 3-4% fluorine that it contains must be
removed first to avoid its toxic effects. Three methods have been developed
for defluorinating phosphate rock commercially: 1) acidulation and heat
treatment of phosphate rock, 2) furnace volatilization of fluoride, and 3)
calcination of phosphate rock. Of these, calcination is the most commercially
favorable and is the process most commonly used. Details regarding these
processes are trade secrets and not generally available but they may be
described generally as follows (USEPA I976a):
Acidulation
Def luorinated phosphate rock may be produced by reacting phosphate rock
with sulfuric acid and heating the resultant superphosphate to volatilize the
28
-------
fluorine. This process is similar to the production of normal superphosphate
in the fertilizer industry. The phosphate product is in the form of tri-
calcium phosphate.
Furnace Volatilization
Fluorine may also be removed from phosphate rock by heating a rock and
silica mixture in an oil-fired shaft furnace to agglomerate the mixture and ,
drive off the fluorine. The hot mass is quenched with water as it is removed
from the furnace.
Calcination
The predominant commercial phosphate rock def luorination process in the
United States involves calcination of a phosphate rock/silica/soda ash/and
phosphoric acid mixture in a rotary kiln or fluid bed reactor (Figure 11).
The charge for the fluid bed reactor, the more widely used of the two reactors,
is a combination of phosphate rock silica, soda ash, and other defluorinating
agents which is treated with phosphoric acid and dried to form a nodular
charge. The nodular, predried charge is used to effect particle classifica-
tion in the bed and aid the loss of exhaust gases. Exhaust gases are cleaned
to remove dust and fluoride compounds 'evolved during calcination. The rotary
kiln may receive its charge either as a physical mixture or in a nodular form.
From the kiln or reactor, the defluorinated product is quickly quenched with
air or water, then crushed and sized. The rapid quenching following calcina-
tion maintains the tricalcium phosphate product in the more highly soluble
alpha form.
Critical operating criteria for this process include temperature, reten-
tion time, and water vapor content. Reaction temperatures are maintained in
the range of 1,205-1,360° C for 30 to 90 minutes with the fluid bed reactor
operating at the lower temperatures and requiring less time. Water vapor
content must also be maintained at a level sufficient to effect evolution of
fluorine. Dehydrated tricalcium phosphate is formed in the kiln. Gaseous
silicon fluoride is liberated during calcination and is hydrolyzed to silica
and hydrofluoric acid by the tail gas exhaust scrubber.
29
-------
Figure 11. Process flow diagram for the manufacture of defluorinated phosphate rock by
the fluid bed calcination process.
Phosphate
Rock
Make Up Water
To
Atmosphere
Non-Agglomerated ^
Feed
Fluidizing Gas
7
en
7
E
»•»•
fflu
i
ent Gas ^
£
Fluid
Bed
Reactor
—
— B»
T
vDu
*w
f~
/
ff
Cyclone
Scrubber
i
^
r
(jontami
Water
Recycle
Contaminated
Water to
Retention
Pond
Agglomerated and
Defluorinated
Phosphate
Product
Source: US Environmental Protection Agency. 1976a. Development document for effluent limitations guide-
lines and new source performance standards for the other non-fertiliser phosphate chemicals segment
of the phosphate manufacturing point source category. Office of Water and Hazardous Materials,
Washington DC, 105 p.
-------
1.2.1.5 Defluorinated Phosphoric Acid (Subcategory E)
Defluorinated phosphoric acid is used in the manufacturing of both dry
and liquid mixed fertilizers and in the production of dicalcium phosphate
animal feed supplements. However, the majority of the defluorinated phos-
phoric acid produced in this country is used in the manufacture of fertilizer
(USEPA 1976a).
There are three commercial methods for production of def luorinated acid.
The most common method is vacuum evaporation. Aeration and submerged combus-
tion also have been successfully used but submerged combustion is considered
outmoded and is not likely to be used in the future for new facilities.
Vacuum Evaporation
The defluorination of phosphoric acid by vacuum evaporation is an example
of crossover technology from the fertilizer industry. In fact, the same units
are used by the fertilizer industry for evaporating commercial wet process 54%
P 0 phosphoric acid to superphosphoric acid (68-72% P9°c) as are used for
def luorination of phosphoric acid. Approximately 86% of the def luorinated
phosphoric acid in the United States is produced by the fertilizer industry
(USEPA 1974b), but to the fertilizer industry def luorination is merely an
accessory (or additional) side benefit accomplished during superphosphoric
acid production. However, phosphoric acid is def luorinated specifically for
the production of non-fertilizer products in a few places.
In the vacuum evaporation process, water and other contaminants including
fluorine are evaporated from the acid using heat transfer surfaces and low
(vacuum) pressure. Two of the most popular variations of this process are the
Stauffer falling film evaporator and the Swenson forced circulation evaporator.
These two processes are described below and shown schematically in Figures 12
and 13 respectively.
In the Stauffer process, clarified 54% P^OC orthophosphoric acid is con-
tinuously fed to the evaporator recycle tank where it mixes with superphospho-
ric acid from the evaporator. Some of the mixture (approximately 1.2%) is
31
-------
WATCH
FALLINO FILM
EVAPORATOR
EVAPORATOR REC1RCULATION
RECYCLE PUMP
TANK
Figure 12. Stauffer process for wet process superphosphoric (deflourinated) acid.
Source: Barber, J.C. 1979. Falling film evaporator process. Adapted from
TVA file drawings. Florence AL.
TO AIR EJECTOR
ACIO STORAGE
Figure 13. Vacuum evaporation superphosphoric (deflourinated) acid.
Source: Adapted from Rushton, W.E. 1966. Swenson superphosphoric acid
process. Phosphorus and Potassium 23*13-16, 19.
32
-------
drawn off as product acid, but most (approximately 98.8%) is pumped to the top
of the evaporator and is distributed across the heat exchanger tube bundle.
The falling acid, heated by high-pressure steam condensing on the outside of
the tubes, evaporates. The vapors and dehydrated acid then enter the separa-
tor section where entrained acid mist is removed. Product acid flows to the
recycle tank, and the vapor is drawn off, condensed in a barometric condenser,
and delivered to a hot well. Noncondensables are removed by a two-stage steam
ejector and are vented to the hot well. Superphosphoric acid flows to the re-
cycle tank where it is mixed with more 54% P?0 orthophosphoric acid and re-
cycled or removed as product. The approximate recycle to feed acid ratio is
80:1. The product stream is cooled and stored before shipping. Both the hot
well and cooling tank are vented to a wet scrubbing system.
The Swenson process utilizes closed heat exchanger tubes filled with heat
exchanger f^uid to provide the heat of reaction. Feed acid (54% P2°s^ P1™1?6^
into the evaporating system mixes with recycled Superphosphoric acid. As the
acid leaves the exchanger tube bundle and enters the flash chamber, evapora-
tion begins. Vapors are removed by a barometric condenser. Condensed ma-
terials and noncondensed vapors are delivered to a hot well. Product acid
flows toward the bottom of the flash chamber where part (approximately 0.6%)
is removed to a cooling tank and the rest (99.4%) is recycled. An approximate
recycle to feed ratio is 150:1 (compared with 80:1 for the Stauffer process).
Cooling in both systems is accomplished by circulating water through
stainless steel tubes in the holding tank.
Impurities in "wet process" acid, such as iron and aluminum phosphates,
soluble gypsum, and fluosilicates, form supersaturated solutions in 54% P9°c
phosphoric acid and precipitate during storage. The precipitated impurities
are separated from the acid by settling and/or centrifugation and either sent
to the recirculation pond, processed into a low quality fertilizer, or re-
cycled to the evaporator feed tank (USEPA I979b).
33
-------
Submerged Combustion
Although this process is outmoded and an unlikely option for any new
facility, it is presented to give the reader an alternative perspective on the
process. The submerged combustion apparatus consists of a combustion chamber
with one or more gas or fuel oil burners mounted atop an acid vat called the
evaporator (See Figure 14). Heat is transferred by inserting the dip tubes
into the evaporator which bubble hot combustion gases through the acid and
strip hydrogen fluoride and silicon tetrafluoride from the solution. Acid
concentration is also achieved through evaporation of water. The production
of a continuous product stream is controlled by feed acid flow and the acid
temperature in the evaporator.
Gaseous emissions from this process are significant and require a series
of cleaning and adsorption steps to effect product recovery and control air
pollution. Entrained phosphoric acid first is recovered from the gas stream
and recirculated or returned to the product line. A multistage direct contact
condenser or a scrubber and gas filter is then used for removal of fluorides
before the tail gas is exhausted. Water may be used in all or only the final
stage of the condenser as a condensing and scrubbing medium.
Aeration
A relatively new method of defluorinated phosphoric acid production has
been introduced in which fluorine is stripped from the acid by aeration
(Figure 15). Small quantities of either diatomaceous silica or spray-dried
silica gel are mixed with commercial 54% p?0 phosphoric acid and heated.
Silica reacts with the small amount of hydrogen fluoride in the acid to
produce fluosilicic acid (H SiF.). When the mixture is heated, the
i o
fluosilicic acid breaks down to tetrafluorosilane (SiF.) which is stripped
from the acid by aeration. The gas evolved during aeration is kept above its
dew point and sent to a water scrubbing unit where the tetraf luorosilane is
removed from the tail gas before discharge.
34
-------
Figure 14. Process flow diagram for the manufacture of defluorinated
phosphoric acid by the submerged combustion process.
54% P205
Feed Acid
Gas
Air
To Cooling
Pond
Superphosphor ic
Acid
(To shipping)
Weak Acid
(To phos.
Acid
Plant)
Air cooler
j , And Sludge
J Product
Pump
Scrubber
Tank
Source: US Environmental Protection Agency. 1976a. Development document for effluent limitations guide-
lines and new source performance standards for the other non-fertilizer phosphate chemicals segment
of the phosphate manufacturing point source category. Office of Water and Hazardous Materials,
Washington DC, 105 p.
-------
Figure 15. Process flow diagram for the manufacture of defluorlnated
phosphoric acid by the aeration process.
Contaminated
Water
Process
Water
LO
Silica
54%
Phosphoric
To
Atmosphere
Scrubber
Fan
To
TTT
P205
Acid
Contaminated Water
Pond
Steam
Heat
Exchanger
^Condensate Return
Circulation Pump
Product to
Shipping
Source: US Environmental Protection Agency. 1976a. Development document for effluent limitations
guidelines and new source performance standards for the other non-fertilizer phosphate
rhemicals segment of the phosphate manufacturing point source category. Office of Water and
hazardous Materials, Washington DC, 105 p.
-------
1.2.1.6 Sodium Phosphate from "Wet Process" Phosphoric Acid (Subcategory F)
Most high grade sodium phosphate is made from dry process phosphoric acid
because of the purity and product color requirements of the industry. Although
limited in production to one plant at present, "wet process" acid can be
purified sufficiently to manufacture sodium phosphate for soap (Figure 16).
This process removes the more significant contaminants such as sulfuric acid,
sodium f luosilicate, iron phosphate, aluminum phosphate, and calcium sulfate—
as well as some of the minor impurities such as arsenic—and yields an accept-
able quality product.
In order to manufacture high quality sodium phosphates by this process,
the phosphoric acid must be prepared from phosphate rock which has been cal-
cined to remove organic impurities that would give the acid a greenish color
typical of "wet process" phosphoric acid. The nearly colorless "wet process"
acid is partially neutralized with partially recycled sodium phosphate liquor
to precipitate granular sodium f luosilicate which is sold as a by-product.
After filtration of the sodium fluosilicate, sodium sulfide and barium car-
bonate are added. The sodium sulfide precipitates the small amount of arsenic
found in wet process acid and the barium carbonate is added to remove excess
sulfate. The precipitates are filtered and disposed of. Because of its toxic
nature, arsenic sludge nust be disposed of in an approved hazardous waste
disposal site or reprocessed to recover the arsenic. A final neutralization
of the acid is performed by the addition of soda ash (Na CO ) to remove the
remaining impurities. This procedure produces a large volume of light sludge
containing iron phosphate, aluminum phosphate, and fluorine compounds.
Although difficult to separate, the solid impurities from this final neutral-
ization contain a relatively high concentration of phosphate and have some
commercial value. Monosodium phosphate is crystalized from the acid by con-
centrating the solution in an evaporator. Other sodium phosphate compounds
may be made from the monosodium phosphate with further dehydration, crystal-
lization, and neutralization as described under subcategory C.
1.2.2 Auxiliary Processes
The non-fertilizer phosphate industry is closely linked to the phosphate
raining and fertilizer industries. A brief background description of certain
37
-------
Figure 16. Process flow diagram for the manufacture of sodium phosphates from
"wet process" phosphoric acid.
Wet Process Phosphoric Acid
SODIUM PHOSPHATE PROCESS
PROM WET PROCESS
PHOSPHORIC ACID
CO
00
STORAGE-SETTLE
Na2HPO4
MOTHER LIQUOR
Water to Sewer
SALTING
EVAPORATO
ASjSj to Solid Waste Disposal
HIGH GRADE
HEUTRAL
PHOSPHATE
(FERTILIZER)
\
Na2co3 Vro WASTE
Na,P04/
Water to
Haste
TRI SODIUM PHOSPHATE
CRYSTAL
CRYSTALLIZERS
Water to Waste
5
r
1 SALTING
pVAPORATOR
\
CRYSTALI
MONO SODIUM
PHOSPHATE
SODIUM
META PHOSPHATE
Total contaminated
Effluent
DISODIUM PHOSPHATE
DOOHYDRATE OR
DISODIUM PHOSPHATE
CRYSTAL
Source: US Environmental Protection Agency. 1976a- Development document for effluent limitations guidelines
and new source performance standards for the other non-fertilizer phosphate chemicals segment
of the phosphate manufacturing point source category. Office of Water and Hazardous Materials
Washington DC, 105 p. '
-------
related operations from these industries is included in order to augment any
process and environmental related descriptions. More complete descriptions of
phosphate mining and production of "wet process" phosphoric acid are available
in a companion guidelines document (USEPA 1980).
1.2.2.1 Phosphate Rock Mining and Processing
The phosphate mining industry is not a part of the fertilizer or non-
fertilizer phosphate industries. Since most phosphate rock mined is used for
production' of fertilizer and other phosphate products, rather than being ex-
ported in raw form, most mining operations include phosphate processing in
their corporate activities. For example, of 34 major phosphate industry
operations in central Florida, 18 perform processing of phosphate fertilizer
or animal feed grade products (USEPA 1978a). Following is a brief description
of phosphate mining operations to provide the reader with an idea of the most
common procedures.
After any prospecting and mining claims are complete, the mining opera-
tion concentrates on matrix or ore extraction and beneficiation of the ore.
Extraction of the matrix or ore is done by different processes depending on
the location and characteristics of the deposits. Figure 17 is a map showing
the locations of the major phosphate deposits in the United States. Ore is
actually mined in'only four areas - Florida, North Carolina, Tennessee, and
several contiguous western states. The mineral content of the phosphate rock
varies considerably depending on the location and grade of the rock being
mined. Representative analysis of rock from several mining areas is given in
Table 2.
In Florida, which accounts for roughly 78% of the United States pro-
duction of phosphate rock, deposits are alluvial. The phosphate-rich beds are
composed of a loosely consolidated conglomerate of phosphate pebbles and
clays, known as matrix. The thin overburden deposits are unconsolidated
sediments. Mining is- conducted by stripping overburden from the matrix de-
posits by use of electrically driven "walking draglines" equipped with buckets
of 20 to 65 cubic yard capacities and booms of 165 to 275 feet in length
(USEPA 1978a). In successive moves of the draglines, matrix is removed and
39
-------
Figure 17. Location of major phosphate rock deposits
in the United States.
NUMEROUS SCATTERED FIELDS
OF PHOSPHATE ORES
Source: US Environmental Protection Agency. 1979d. Source
assessment, phosphate fertilizer industry. Office of
Energy, Minerals, and Industry, Research Triangle Park
NC. Prepared by Monsanto Research Corporation, Dayton
OH, 186 p.
40
-------
Table 2. Representative analysis of commercial phosphate rock.
Component
P2°5
CaO
MgO
A12°3
Fe2°3
Si02
so3
F
Cl
co2
Org. Carbon
Na,0
K20
H20
Zr.O
Location and 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
1.9
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 Grade
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
Phosphate Rock
32.2
46.0
0.2
1.0
0.8
7.5
1.7
3.4
0.02
2.1
1.8
0.5
0.4
0.4
2.5
Low Grade
Phosphate Rock
19.0
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
Source:
US Environmental Protection Agency. 1976e. (Draft) Air pollution emissions and control from
the manufacture of elemental phosphorus. Industrial Environmental Research Laboratory, Office
of Research and Development, Edison NJ, 32 p.
-------
spoil from succeeding cuts is sidecast. As the ore is removed it is stacked
in a sluice pit where hydraulic monitors (high-pressure water guns) slurry the
ore into pumps for transport by pipeline to the washing plant (USEPA 1978a).
In North Carolina the process is basically the same. The North Carolina
deposits occur in interbedded phosphatic clays, limestones, and sands
(USEPA 1971b). Hydraulic sluicing and transport are also used in North Caro-
lina where, as in Florida, level terrain and excellent pumping characteristics
make these methods feasible.
In Tennessee, the high grade brown rock deposits are a weathered phos-
phatic limestone that occurs in a north-south belt across the State (Figure 17).
Deposits are concentrated in small pockets of phosphate sands surrounded by
silica sands. Mining is done by open pit methods. In Tennessee (and the
western states also), however, overburden is removed well in advance of actual
mining operations (USEPA 1974a). Draglines and small power shovels are used
to mine the phosphate sand, which is hauled by truck or rail to the processing
plant. Much of the phosphate rock used to make elemental phosphorus is low
grade ore from Tennessee and the western states.
The phosphate deposits which are mined in the western states of Idaho,
Montana, Wyoming, and Utah account for 14% of United States production
(Harre 1976). Western deposits are "hard rock" (consolidated) layers, with
degree of hardness generally decreasing the farther north the location.
Conventional earth moving equipment is used to remove 5 to 50 feet of over-
burden. In Utah, the hard rock must be blasted with dynamite. In softer rock
areas, "rippers" are used, which are toothed machines that gouge and break the
rock from the surface. In Montana, two small underground mines are operated
using the room-and-pillar method, which is a kind of underground quarrying.
Western rock is usually transported by rail to processing plants.
Beneficiation is the upgrading of the ore by application of processes to
the mined matrix or ore to remove inert materials (such as silica sand) or
extremely fine materials that cannot be economically separated. Beneficiation
processes in Florida and North Carolina vary from plant to plant, depending on
grade, size, and ratio of pebbles to fines. A generalized procedure starts
42
-------
with washing. The matrix slurry (20% to 50% solids) is passed through a series
of screens, mills, and washers which break down the matrix to separate phosphate-
bearing pebbles from sand and clays. Coarse screening obtains a first fraction
of oversize phosphate ore. Further processing of the remaining matrix is done
by cyclones to remove very fine sands and colloidal size materials. These are
pumped to settling ponds and the remaining fraction undergoes a series of
flotations (with tailings going to settling ponds) and finally the ore is
dried. Some ore is ground and stored in silos, from which it is transferred
to railroad hopper cars for transport (USEPA 1978b).
Tennessee ores are beneficiated by a similar process, except that all
water is added at the beneficiation plant since matrix is received dry, and
cyclones are operated in a water medium rather than air. A further step for
most Tennessee ore is nodulizing in kilns, which prepares the ore for use in
electric arc furnaces for production of elemental phosphorus (USEPA 1978o).
Western ore beneficiation starts with crushing and/or scrubbing. Sub-
sequent sizing is done by further crushing, grinding, and size classification.
Very fine and colloidal size materials are discharged to a slime pond or
thickened for storage as a solid waste. The product is dried or may be cal-
cined before shipment as a product.
Calcining is an operation done on some phosphate rock such as that from
the west which has a high organic content or which will be used in processes
requiring a higher phosphate content. The rock is subjected to temperatures
of 650°-975° C (1202°-1787° F) in rotary drum calcining units (USEPA 1978a).
Organics are destroyed and tramp iron materials are removed magnetically.
Because of the high energy demands of calcining, it is not done as routinely
as it was in the past. Alternate methods can be used in some cases to remove
impurities in later processes.
The product of the above processes, ground beneficiated phosphate rock or
concentrate, is the raw material for a number of basic fertilizer and phospho-
rus chemical processes. Additional grinding may be performed after transport,
or farther along in the plant complex. The benef iciation process produces
slurry effluents that have caused notorious pollution problems in the past in
43
-------
the form of phosphatic clay slurries, or slime ponds. The magnitude of the
disposal problem is indicated by the fact that approximately one ton of slimes
(dry weight) is produced per ton of beneficiated phosphate rock (USEPA 1977a).
Just one of the larger mining operations in Florida produces 111.4 billion
gallons per year of slimes, with up to 45% by weight 0.5 microns in size.
These slimes are typically on 5% solids by weight (Hocking 1978). Florida
slimes are usually about 70% water after 15 or more years' dewatering and
therefore occupy more volume than the original matrix from which they were
derived (White et al. 1978). This constitutes one of the phosphate industry's
major pollution problems.
1.2.2.2 Production of "Wet Process" Phosphoric Acid
The products of the last two subcategories of the non-fertilizer phos-
phate industry, defluorinated phosphoric acid and sodium phosphates, are not
derived from elemental phosphorus as are the products of the first three.
These products are made from or with one of the major intermediate products of
the fertilizer industry, "wet process" phosphoric acid. "Wet process" acid is
also used in other subcategories of the non-fertilizer phosphate industry,
such as in the production of animal feed grade calcium phosphates and de-
fluorination of phosphate rock. Consequently, these processes share some
common technology and pollution problems with the fertilizer industry.
Therefore, a brief discussion of the production of "wet process" phosphoric
acid is presented to give the reader a complete picture of the industry. The.
reader is referred to the Environmental Impact Assessment Guidelines for
New Source Phosphate Fertilizer Manufacturing Facilities for a more detailed
description of the processes and environmental problems associated with "wet
process" phosphoric acid.
Phosphoric acid is the most important intermediate manufactured by the
phosphate fertilizer industry because it is a basic ingredient in every phos-
phate fertilizer product of the industry other than normal superphosphate and
salable phosphate rock. "Wet process" acid, also known as "merchant grade"
phosphoric acid, contains more impurities than does "dry process" acid since
it is made directly from the phosphate rock. All phosphate fertilizer pro-
duction from phosphoric acid in the United States uses "wet process" acid.
44
-------
The "wet process" is based on reaction of phosphate rock with a suitable
strong acid to produce phosphoric acid and an acid salt. Sulfuric acid is by
far the most widely used acid in the United States for manufacture of phos-
phoric acid (USEPA 1974a).
A flowsheet typical of the "wet process" for production of phosphoric
acid is shown in Figure 18. Ground benef iciated or concentrated phosphate
rock is fed continuously to a reaction system where it is mixed with .su If uric
acid. The sulfuric acid is diluted, sometimes with contaminated process
*
water, to a proper strength. Then, depending on process temperature and phos-
phate rock composition, the process is operated to ensure optimal dihydrate
crystallization. Some commercial processes also recycle some dilute phos-
phoric acid into the reaction system. Older plants may have one or more
digestion or attack tanks, but in more recent installations the reaction
system is a single, large compartmented tank. In this attack vessel, the rock
and acid react to form gypsum (CaSO ) and phosphoric acid (H PO .).
To obtain complete reaction, the rock-gypsum-acid slurry is recirculated
through the reaction vessel compartments. The reaction is carried out at
75° C for 3-8 hours depending on the particular process being used. Commer-
cial processes typically achieve 96+% efficiencies in extraction of P~0,- from
rock. The slurry flows from the reactor to a filter where the gypsum is
removed and the phosphoric acid is separated into two streams. One stream
containing 30-32% P 0 is taken off as the product while a weaker 20% P 0
stream is recycled to the reactor.
Major emissions, effluents, and solid wastes from "wet" phosphoric acid
production are hydrogen fluoride gas, sulfur oxides, particulates, acid mists,
contaminated cooling and scrubber water, and gypsum solids.
1.3 SIGNIFICANT ENVIRONMENTAL PROBLEMS
This section is an overview of the most significant environmental prob-
lems associated with the non-fertilizer phosphate industry. For any particu-
lar plant or subcategory some or all of these problems may be anticipated
depending on the processes employed and the product line produced. It is
45
-------
H2SV
PHOSPHATE
ROCK
WATER
-*»
VENT TO ATMOSPHERE
FLUORINE
SCRUBBER
-*• WASTE WATER
RECYCLE fFLUORIDE*
ACID J FUMES
DIGESTION TANK
ACID
CONCENTRATOR
WATER
SLURRY TANK
WATER
GYPSUM SLURRY
TO GYPSUM POND
** VENT TO ATMOSPHERE
FLUORINE
SCRUBBER
WASTE WATER
PHOSPHORIC
ACID PRODUCT
STORAGE
Figure 18. Standard process flow diagram for the manu-
facture of "wet process" phosphoric acid.
Source: US Environmental Protection Agency. 1971b. Inorganic fertilizer
and phosphate mining industries, water pollution and control.
Prepared by Battelle Memorial Institute, Richland WA, 225 p.
46
-------
emphasized that the problems discussed are the most significant, but not
necessarily the only problems associated with the industry. A more compre-
hensive treatment of industry impacts is developed in Section 2.0.
1.3.1 Location
Due to the economic structure of the industry, locational impacts have
been minimized. Segments of the industry which require the use of bulk raw
materials and generate significant quantities of pollutants have traditionally
been located near rural mine sites, while the producers of refined products
have been located near the more populated market areas. The relative iso-
lation of phosphorus producers has prevented their sizable emissions of fluo-
rides and particulates from severely affecting ambient air quality in popu-
lated areas but problems could develop if a plant were located in a highly
populated area with numerous other industries which also have large quantities
of emissions.
Some of the potential water quality impacts of a new source phosphate
facility are closely related to the rainfall, soils, and groundwater features
of the plant location. For defluorination plants, the ratio of rainfall to
evaporation is of concern in the maintenance of the water balance between the
plant and the recycle pond. Rainfall is also of concern for other plants
which practice retention or retention and treatment of contaminated runoff.
Also of interest to producers using recycle or retention ponds is the suit-
ability of the soil and subsurface geology for construction and maintenance of
dams around the recycle ponds. Unstable soils, steep topography, high ground-
water tables, or porous soils overlying a vulnerable source of potable ground-
water may limit the capacity of the plant to control its wastewater problems.
1.3.2 Raw Materials
Phosphate Rock
Beneficiated phosphate rock is the primary raw material used by the in-
dustry. The mining, benef iciation, and transportation of phosphate rock can
have significant impacts on the mining area due to the sheer magnitude of the
-------
operation. Beneficiated rock has generated serious environmental problems in
poorly controlled facilities. Dust can be a significant air contamination
problem at each point of transfer of the materials and in the grinding process
when dry grinding is used. Beneficiation of the phosphate rock also leads to
the production of large volumes of clay slimes which are very difficult to
dewater and may require large areas of land for storage. Mining impacts are
highlighted in Environmental Impact Guidelines for New Source Phosphate Fertilizer
Manufacturing Facilities.
Energy
3
Approximately 12,500 kwh of electricity and 12,000 ft of natural gas are
required to produce one ton of elemental phosphorus (USEPA 1973b). Smaller
but still significant energy requirements are associated with defluorination
of phosphate rock by calcination. This process requires as much as 5,000 ft
of natural gas per ton of defluorinated rock (USEPA 1974b). The energy re-
quirements of such manufacturing operations may not be significant in terms of
regional supplies but they could have a significant impact on the energy
resources of smaller communities.
1.3.3 Process Related Problems
Phossy Water
Water contaminated with colloidal phosphorus (phossy water) from con-
densation of furnace off-gas or use as an air seal in storage tanks presents
difficult problems for producers and consumers of elemental phosphorus, be-
cause it is toxic, highly reactive, and not amenable to treatment. Therefore,
systems for its segregation, recycle, and reuse are required wherever phossy
water is encountered. See Section 2.1.2.1 for a more detailed explanation of
this problem.
Fluorine
Significant gaseous emissions of fluorine and fluorine compounds are
evolved in the manufacture of phosphorus, def luorinated phosphate rock, and
48
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defluorinated phosphoric acid. Fluorides are transferred from the emission
stream to the wastewater and solid waste streams by pollution control equip-
ment. Large quantities are also found in the slag from phosphorus furnaces.
Dust and Particulates
Handling of bulk raw materials and products such as phosphate rock,
silica, calcium phosphates, and sodium phosphates creates problems with fugi-
tive dust around the plant site and transshipment areas. Particulates are
also generated by many of the industry's production processes and are dif-
ficult to control. Calciners, kilns, phosphorus furnaces, and dryers are the
most significant particulate sources.
Priority and Toxic Pollutants
Relatively large quantities of fluoride and small quantities of arsenic,
cadmium, chromium, zinc, vanadium, uranium, radium 226, radon 222, and other
trace elements are present in phosphate rock. These substances may appear in
varying concentrations in emissions, wastewater streams, solid wastes, and in
unrefined products. Most of these substances are found in small quantities
and do not appear to be of significance; however, arsenic, uranium, and radium
present special problems and make certain waste streams hazardous. Arsenic is
carried through the thermal reduction process and concentrates in the refined
phosphorus product. It must be removed during production of many phosphorus
derrived products such as sodium phosphates, calcium phosphates and many of
the anhydrous derivatives used for food and manufacturing purposes. Arsenic
is generally found as waste precipitates or residues from these processes;
consequently, these residues require special handling. Unlike arsenic, most
of the other contaminants remain in the slag. Due to the low level radiation,
phosphorus furnace slag is now considered a hazardous waste under RCRA and
must be handled accordingly.
Fluorides are present in large quantities in phosphate rock and are a
component of every waste stream. These compounds have not been demonstrated
to have an impact on public health and are considered welfare related pollut-
ants which must be controlled but are not generally considered hazardous.
49
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However, toxic fluoride compounds such as calcium fluoride from the cooling/
recirculation/scrubber pond may require special handling and disposal if
isolated.
Products
Several products of the industry are dangerous by their very nature and
are very carefully controlled by plant personnel due to fire, explosive, and
poisoning hazards. Both phosphorus and ferrophosphorus present potential fire
hazards. Phosphorus must be kept under a water blanket and ferrophosphorus
must be kept away from water to prevent explosion. As an indication of its
dangerous nature, white phosphorus is used in the manufacture of certain
incendiary munitions for the military.
Congress recently appropriated $3.15 million to begin construction of a
binary weapons plant at Pine Bluff, Arkansas. The weapons to be produced
there include two phosphorus based nerve gases referred to as GB and VX (Barber
1980b). Obviously these products are extremely dangerous and require maximum
security precautions.
1.3.4 Pollution Control
The major waste streams and associated pollutants from each subcategory
of the industry are identified in Tables 3-8. Most process emissions from the
industry are captured by air pollution control equipment, transferred to the
wastewater stream, and eventually precipitated to form a solid waste. Properly
controlled and contained, these pollutants present only minor problems but
poor maintenance, equipment failure, and poor housekeeping may result in their
release into the environment. The results of such problems can be relatively
low level or major catastrophic events. The lack of equipment maintenance,
build up of dust in the vent system, or the inadequate control and entrainment
of bulk materials may result in small increases in the emission of particulates
and fluorides or runoff of finely divided raw materials and products such as
calcium phosphates which are scattered around a plant site. On the other
hand, the lack of maintenance in combination with other factors such as poor
design or extraordinary rainfall could contribute to the catastrophic failure
50
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Table 3. Major waste streams o£ the phosphorus production subcategory.
Process
Furnace charge
preparation
Waste Stream
Combustion gases from dryers,
sintering grate nodulizing,
and calcining kilns;
Vent gas from travelling grates;
Solids material handling cast
from combustion gases;
Byproduct CO gas flares.
Significant Pollutants
Phosphate dust
Coke dust
Silica rock dust
P2°5
Fluorides
SOo
Electrothermal
reduction
Handling, proportioning, and
feeding of solid materials;
Furnace gases escaping through
feed bins;
Furnace gas leakages;
Byproduct CO gas flares;
Slag and ferrophosphorus tapping;
Solidified slag.
Fluorides
Radium 226
P2o5
CO
Phosphate dust
Coke dust
Silica rock dust
Product recovery
Condenser exhaust gas;
Precipitator dust;
Phosphorus and phosphorus sludge
storage;
Phosphorus sludge cleaning;
Water contaminated with
elemental phosphorus;
Slag crushing and handling.
Elemental phosphorus
Nutrients
P2°5
Lower oxides of phosphorus
Fluorides
Fluosilicates
Source: Barber, J.C. 1980b. Comments on document, "Environmental Impact Assessment
Guidelines for New Source Non-Fertilizer Phosphate Manufacturing Facilities."
51
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Table 4. Major waste streams of the phosphorus consuming subcategory.
Product
Waste
Stream
Significant
Pollutants
Phosphoric Acid
Phosphorus Pent oxide
Phosphorus
Pentasulfide
Phosphorus
Trichloride
Phosphorus
Oxy chloride
Phosphorus handling
Combustion gases
Filter solids
Phosphorus handling
Phosphorus handling
Distillation residues
Casting fumes
Phosphorus handling
Distillation residues
Distillation vapors
Distillation vapors
Phosphorus (phossy) water
£cid mist (H PC>4)
Arsenic sulride
Phosphorus (phossy) water
phosphorus (phossy) water
Arsenic pentasulfide
S°2' P2°5
Phosphorus (phossy) water
Arsenic trichloride
PC13
HC1, H PC-
Very small quantities generated.
Source: U.S. Environmental Protection Agency. 1973a. Development document for
proposed effluent limitations guidelines and new source performance
standards for the phosphorus derived chemicals segment of the phosphate
manufacturing point source category. Office of Air and Water Programs,
Washington DC, 159 p.
52
-------
Table 5. Major waste streams of the phosphate chemicals
subcategory.
Waste Significant
Process Stream Pollutants
Sodium tripolyphosphate White mud drying/ Silica, iron,
manufacture calcination emissions aluminum phos-
phates, particu-
lates
Calcium phosphates Filtrate from Calcium phosphates
manufacture dicalcium phosphate
dewatering
Drying emissions Particulates,
phosphates
Source: U.S. Environmental Protection Agency. 1973a. Development document for
proposed effluent limitations guidelines and new source performance
standards for the phosphorus-derived chemicals segment of the phosphate
manufacturing point source category. Office of Air and Water Programs,
Washington DC, 159 p.
53
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Table 6. Major waste streams of the defluorinated phosphate
rock subcategory.
Waste Significant
Process Stream Pollutants
Raw material handling Fugitive dust Dust
Calcination Effluent gases Fluorine
from reactor SO
and furnace firing particulates
Quenching Qienching water Phosphates, fluoride
trace pollutants.
Source: US Environmental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate
manufacturing point source category. Office of Water and Hazardous
Materials, Washington DC, 105 p.
54
-------
Table 7. Major waste streams of the defluorinated phosphoric
acid subcategory.
Process
Waste
Stream
Significant
Pollutants
Vacuum evaporation
Submerged combustion
Aeration
Evaporator gas stream
acid mist
condenser water
Fuel combustion
products
product gas stream
Process emissions
Acid mist, fluorides
fluorides, phosphates,
metals
fluorides
SO
Silicon tetrafluoride,
hydrogen fluoride, acid mists
Te traflu os ilene
Source: US Environmental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate manu-
facturing point source category. Office of Water and Hazardous Materials,
Washington DC, 105 p.
55
-------
Table 8. Major waste streams of the sodium phosphate
subcategory.
Waste Significant
Process Stream Pollutants
Calcination of phosphate Emissions Fluorine
rock Particulates
so2
Acidulation Emissions Acid mist
Solid waste Gypsum
Precipitation/ Solid waste Arsenic sulfide
Filtration
Neutralization Solid waste Iron & aluminum
Phosphates
Source: US Envirormental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate manu-
facturing point source category. Office of Water and Hazardous Materials,
Washington DC, 105 p.
56
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of a recirculation pond dam and the release of its highly polluted contents.
The process wastewater in these ponds has a low pH (less than 2.0) and con-
tains the entire range of pollutants generated by the industry. Even without
failure, seepage around a dam structure can introduce smaller quantities of
the same pollutants into receiving waters. Maintenance of such structures
should be carefully monitored.
1.4 TRENDS
Trends in the non-fertilizer phosphate industry are difficult to iden-
tify. The industry is highly fragmented consisting of several individual
groups of producers whose products and processes are relatively unrelated
except for the principal material, phosphate. Portions of this industry such
as defluorinated acid are more closely related to the fertilizer industry than
to other non-fertilizer phosphate segments, which creates a problem in ob-
taining unified projections. Finally, because non-fertilizer phosphate manu-
facture is not a growth industry its trends are slow to develop and obscured
by the trends of the phosphate industry as a whole.
1.4.1 Markets and Demands
Overall the phosphate industry produces a variety of intermediate products
for the agriculture, chemical, and food industries. As indicated in Figure 19,
approximately 82.6% (total agricultural use less defluorinated rock) of phos-
phate rock consumed in the United States during 1975 was used for fertilizer
production, while only 17.4% was used for non-fertilizer purposes. For the
non-fertilizer phosphate segment of the industry, the largest product is
furnace grade or "dry process" phosphoric acid which is used for the manufac-
ture of food additives (calcium phosphates) and household detergents (sodium
phosphates). Of the estimated 460,000 tons of phosphorus produced in 1979,
approximately 85% was used for production of furnace acid, while only 10% was
used for other products (Chemical and Engineering News 1980).
Unified forecasts of markets and demands for non-fertilizer phosphate
chemicals are incomplete at best. Growth forecasts for SIC 2819 (Industrial
Inorganic Chemicals, n.e.c.), which includes most segments of the industry,
57
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Figure 19. 1975 phosphate rock consumption pattern for various phosphorus
products.
PHOSPHATE ROCK MINED
31,029 x 103 metric tons/yr
INDUSTRIAL
4,933 x 103
metric tons/yr
15.9%
AGRICULTURE
26,096 x 103
metric tons/yr
84.1%
FERROPHOSPHORUS
404 x 103
metric tons/yr
1.3%
ELEMENTAL
PHOSPHORUS
4,530 x 103
metric tons/yr
14.6%
DEFLUORINATED NORMAL
ROCK SUPERPHOSPHATE
465 x 103 2,265 x 103
metric tons/yr metric tons/yr
1.5% 7.3%
WET PROCESS
PHOSPHORIC ACID
21,161 x 103
metric tons/yr
68.2%
oo
* 1
ANHYDROUS ELEMf
DERIVATIVES PHOSPJ
I 1
1 * *
:NTAL OTHER
[ORUS FURNACE 8,129 x 103
279 x 103 620 x Ifl3 PHOSPHORIC ACID metrlc tons/yr 1
metric tons/yr metric tons/yr 3>631 x 1(] 26.2% f
0.9% 2% metric tons/yr DICALCIUM
11.7% PHOSPHATE
| 1,117 x 103
* ' ]
SODIUM DICALCIUM
3,227
metric 1
10
TRIPOLYPHOSPHATE PHOSPHATE DIAMMONIUM
2,327 x 103 1,304 x 103 PHOSPHATE
metric tons/yr metric tons/yr 8,688 x 103
'•5* 4.iX metric tons/yr
28.0%
x X°3 2,204
:ons/yr .
metric
7
x 103
tons/yr
1%
Source:
TRIPLE
SUPERPHOSPHATE
5,431 x 103
metric tons/yr
17.5%
US Environmental Protection Agency. 1979d. Source assessment, phosphate
fertilizer industry. Office of Energy, Minerals and Industry, Research
Triangle Park NC. Prepared by Monsanto Research Corporation, Dayton OH,
186 p.
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indicate a 3.5% compound annual rate of real growth to 1984 (U.S. Dept. of
Commerce 1980). An examination of recent production trends for elemental
phosphorus, cadmium phosphate, and phosphorus trichloride, (Table 9) indicates
a slow, steady rate of growth for the industry. Production of sodium tripoly-
phosphate declined during the 1970's due to environmental concerns over the
use of phosphate detergent.
Projections of phosphate rock demand by end use for the year 2000, pre-
pared for the U.S. Bureau of Mines (Stowasser 1977), also forecast slow growth
rates for most segments of the industry (Table 10). Based on these projec-
tions, phosphate chemicals made for use in detergents will remain at present
levels of production. Non-phosphate chemicals such as alumino-silicates,
sodium nitrilotriacetate, and sodium nitrates are being examined as potential
replacements for phosphate based detergent building^ However, these substi-
tutes are plagued with problems of higher cost, lower effectiveness, or a
greater possibility for irritation (USDOC 1980). Phosphate chemicals manu-
factured for animal feed (def luorinated phosphate rock, dicalcium phosphate,
etc.) should increase by approximately 85% over 1975 levels by the year 2000.
The production of food grade phosphate chemicals are projected nearly to
double by 2000. These forecasts were based on several assumptions: 1) reduced
phosphorus content in detergents will be compensated by the growth in detergent
demand; and 2) both animal feed and food-grade phosphorus products will increase
in demand proportionally to population forecasts.
Foreign trade in non-fertilizer phosphate chemicals is quite small. In
1979 an estimated 171,436 short tons of phosphorus, calcium phosphates, sodium
tripolyphosphates, and other sodium phosphates valued at $88.6 million were
exported to foreign markets, which represents a small fraction (8%) of domes-
tic production. Most of the major industrialized countries, and some of the
developing nations, prefer to import the basic mineral products for processing
within their countries instead of importing finished products (USDOC 1980).
In summary, the future production levels of the various subcategories of
the non-fertilizer phosphate chemical industry, with the exception of sodium
tripolyphosphate, should increase at a slow, steady pace. Sodium tripoly-
phosphate, on the other hand, will level out at current levels of production
into the forseeable future.
59
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Table 9. Production of selected non-fertilizer phosphate chemicals,
1973-1979 (quantity in 1,000 short tons, 100% basis).
Elemental phosphorus
Calcium phosphate
Phosphorus trichloride
Sodium tripolyphosphate
1973
526
540
80
967
1974
524
611
75
903
1975
450
522
82
770
1976
437
656
83
724
1977
431
699
95
717
1978
441
766
100
735
19791
460
817
115
750
Estimated
Source: U.S. Department of Commerce. 1980. 1980 U.S. industrial outlook for
200 industries with projections for 1984. US Government Printing Office,
Washington DC, 515 p.
Table 10. Projections and forecasts for U.S. phosphates
rock demand by end use, 1975-2000 (thousand short tons).
2000
End Use
Detergents
Animal grade feed
Food products
1975
3,212
1,539
273
Low
3,200
2,400
400
High
3,200
3,400
600
Probable
3,200
2,800
500
Source: Adapted from Stowasser, W.F. 1977. Phosphate rock, the present and
future supply and demand. Letter from U.S. Bureau of Mines and R.E.
McNeill, US Environmental Protection Agency, Region IV.
60
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1.4.2 Locational Changes
The distribution of non-fertilizer phosphate chemical plants is indicated
in Table 11 by industry subcategory and by state. Florida, the nation's
leading producer of phosphate rock, contains the largest number of plants,
some of which are associated with the phosphate fertilizer industry.
Two predominate siting or locational patterns can be identified within
the industry. Facilities in the Phosphorus Production and Defluorinated
Phosphate Rock subcategories tend to locate relatively near to the source of
phosphate rock, which is mined in Florida, Idaho, Montana, North Carolina, and
Tennessee. Because these industries use large quantities of phosphate as a
raw material, transportation costs make it economically prohibitive to locate
these facilities elsewhere. The remaining four subcategory industry types
tend to locate closer to their market area. As an example, almost all of the
STPP (sodium tripolyphosphate) plants in the United States are located near
specific detergent manufacturing plants, the primary market for STPP (USEPA
1973b).
With some exceptions, new source non-fertilizer phosphate plants can be
expected to follow the existing locational trends discussed above. A poten-
tial exception to this is the relocation of several Tennessee phosphorus
producers to other phosphate mining locations. Projections indicate that
.production of phosphate rock in Tennessee will terminate and force the re-
location or permanant shutdown of that portion of the industry's phosphorus
production capacity (Stowasser 1977). Within the near future, however, the
likelihood of new production facilities is slim.
1.4.3 Trends in Raw Materials
The basic raw materials utilized in the various subcategories of the
non-fertilizer phosphate industry include phosphate rock, coke, silica,
electric energy, elemental phosphorus, dry process phosphoric acid, and wet
process phosphoric acid. The important trends pertaining to these raw mater-
ials are discussed below:
61
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N>
Table 11. Locational distribution of non-fertilizer phosphate
chemical plants in the United States.
CA FL GA IA ID IL IN KS IA MI MO MT NE NJ NY NC OH PA SC TN TX VT WY WV
Phosphorus
Production 22 1 3
Phosphorus
Consuming 4
Phosphate
Def luorinated
Rock
Def.
Acid
Sodium
Phosphate
Sources: US Environmental Protection Agency. 1973a. Development document for
proposed effluent limitations guidelines and new source performance
standards for the phosphor us-derived chemicals segment of the phosphate
manufacturing point source category. Office of Air and Water Programs,
Washington DC, 159 p.
US Environmental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate
manufacturing point source category. Office of Water and Hazardous
Materials, Washington DC, 105 p.
Revised per Barber 1980
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Phosphate Rock - the supply of domestically produced phosphate rock is
projected to increase until the year 2000 and then gradually decline. The
quality (P2°5 content) of domestic rock supplies will also decline as the
existing high-quality deposits are depleted (USEPA 1980).
Coke - the supply of metallurgical coke is inadequate. Some phosphorus
porducers use reformed coke and petroleum coke in addition to metallurgical
coke as a reducing carbon. Low-volatile bituminous coal is also being con-
sidered as a reducing carbon (Barber 1980b).
Silica - no changes in silica availability and use have been identified.
This mineral is easily obtained by the industry.
Elemental Phosphorus - produced within the industry, elemental phosphorus
is also a raw material for the phosphorus consuming subcategory. From 1978 to
1980, the price of elemental phosphorus has increased by approximately 9%
(Barber 1980a). Electric furnaces for phosphorus production are increasing in
size to achieve operating economies (USEPA 1973a).
"Dry Process" Phosphoric Acid - used as the raw material in most deter-
gent and food grade phosphates, this acid is increasing in price as the cost
of elemental phosphorus and energy increases. Additional production of the
acid may depend on the benefits of using highly concentrated (76% P70c) acid
for making fertilizers (Barber 1980b). This highly concentrated acid can be
made from dry process phosphoric acid whereas the maximum concentration that
can be achieved from merchant-grade, "wet process" acid is around 70% P~0,--
"Wet Process" Phosphoric Acid - no new production trends have been iden-
tified for this product which is used in the production of defluorinated
phosphoric acid and some sodium phosphates. However, a shortage of sulfur, a
basic raw material, may drive the price of wet process acid up during the
coming years (Giusti 1980).
Electric Energy - used to produce elemental phosphorus, the price of
electric energy has increased by 377% through the seventies (Barber 1980a).
High energy costs have forced the elemental phosphorus industry to shut down
smaller furnaces as a retrenchment step and switch production to the larger,
more efficient furnaces (USEPA 1973a).
63
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1.4.4 Process Trends
Processes in predominant use by non-fertilizer phosphate producers are
described in Section 1.2. Following are highlights of processes which have
been tried by the industry and appear to be gaining favor. There is also a
possibility of increasing crossover technology from the larger and faster
growing phosphate fertilizer industry affecting the processes implemented in
non-fertilizer phosphate facilities.
• Phosphorus production facilities have been built using progressively
larger furnaces to achieve a greater economy of scale. The average
furnace production of 15,000 tons of phosphorus/year in 1950 grew to
40,000 tons/year by 1970 (USEPA 1973a).
• Recycled "dry process" phosphoric acid from the product line and acid
mist control facilities can be used in the hydrator to obtain more
concentrated acid with less water use (USEPA 1973a).
• Defluorination of phosphate rock is accomplished more rapidly and at
lower temperature using a fluid bed reactor rather than a rotary kiln.
The use of fluid bed reactors is a long established trend and is
widely accepted in the industry (USEPA 1976a).
« Defluorinated phosphoric acid is produced largely by the fertilizer
industry as superphosphoric acid. The preferred process in the fer-
tilizer industry is vacuum evaporation due to its reduced tail gas
scrubbing requirements. Non-evaporative defluorination of phosphoric
acid using silica addition and aeration stripping may offer advantages
in the future due to lower energy requirements (USEPA 1976a).
1.4.5 Pollution Control Trends
Pollution control systems applicable to the industry are described in
Section 3.0. Following are highlights of pollution control technologies which
have been successfully implemented by the non-fertilizer phosphate industry
and appear to be gaining favor among producers. Also included are potential
crossover technologies that have been adopted by the fertilizer industry and
may also be applicable to similar situations in the non-fertilizer phosphate
indus try-
Treatment of final wastewater effluents is a relatively small segment of
the total pollution control effort of most plants because of the no discharge
64
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requirements placed on much of the industry. Housekeeping and operational and
design controls are the basis of an effective wastewater management program
and require the most emphasis if stringent pollution control requirements are
to be met. Internal water management control techniques may include:
• Prevention of cooling water contamination from contact with process
waste by prompt repair of leaks and equipment.
• Recycle and reuse of scrubber water after appropriate treatment.
• Containment of all spills and leaks by the use of dikes, pumps, and
catch basins.
• Reuse and recycle of phossy water.
• Containment and treatment of all contaminated runoff from specified
rainfall events by routing to the recirculation pond.
• Management of the overall plant water balance by integrated control of
plant processes.
• Recirculation of seepage from ponds.
• Prevention of pollutant introduction to wastewater streams by the use
of dry dust and particulate collectors such as baghouses.
• If discharge is necessary from recirculation or no-discharge facili-
ties, proper treatment by double liming should be practiced.
Emission control for air-borne pollutants is probably the industry's
single most rapidly changing area of technology. Controls which appear to be
widely accepted are:
• Cyclones for control of dust and large particulates.
• Baghouses for control of dust and smaller noncarbonaceous particu-
lates. (These may be preceded by a cyclone.)
• Electrostatic precipitators for control of fine particulates. .
• Wet scrubbing for control of fumes and combined fine particulate/fume
emission streams. Scrubber systems frequently used include:
1) Venturi scrubbers
2) Spray towers
3) Packed bed scrubbers
4) Cyclonic scrubbers
65
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• Forced air collection hood systems at critical operation points through-
out a plant to collect fumes from fugitive sources such as tap holes
and slag quenching areas in a phosphorus plant.
• Skirts around dry material transfer and handling systems and dry raw
material and product handling locations.
Trends have not yet developed in the handling of the hazardous waste
materials of the industry in accordance with the requirements of RCRA; how-
ever, rapid advances are expected in the near future.
Solid waste management programs currently in use by the industry include:
• Product recovery or reuse from solid wastes including dust and sludges
from air emission control equipment.
• Sale of waste materials such as arsenic trichloride still bottoms for
reprocessing.
• Pond storage of fluoride precipitates from emission and wastewater
treatment systems.
1.5 REGULATIONS
1.5.1 Water Pollution Control Regulations
The Federal Water Pollution Control Act (FWCA) Amendments of 1972 (P.L.
92-500) established two major interrelated procedures for controlling indus-
trial effluents from new sources, and specifically included phosphate manu-
facturing in the list of affected categories of sources. The principal
mechanism for discharge regulation is the NPDES permit. The other provision
is the New Source Performance Standard (NSPS). The Clean Water Act of 1977
(P.L. 95-217), which amends P.L. 92-500, made no change in these basic pro-
cedures.
The NPDES permit, authorized by Section 402 of FWPCA, prescribes 'the
conditions under which effluents may be discharged to surface waters. The
conditions applicable to new or expanded phosphate manufacturing facilities
will also be in accordance with New Source Performance Standards adopted by
USEPA pursuant to Section 306, and pretreatment standards promulgated to
66
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implement Section 307(b). Different standards will be applicable depending on
the subcategpry under consideration. Stricter effluent limitations may be
applied on a site-specific basis if required to achieve water quality stand-
ards.
The effluent NSPS promulgated for new sources in the Phosphate Manu-
facturing Point Source Category are listed in Table 12. With the exception of
the sodium phosphates subcategory, NSPS promulgated for the non-fertilizer
phosphate industry under 40 CFR 422 prohibit discharge of any process waste-
water pollutants to navigable waters except under emergency conditions. For
the phosphorus-producing, phosphorus-consuming, and phosphate subcategories
this limitation is straightforward. For the defluorinated phosphate rock and
defluorinated phosphoric acid subcategories, however, the basic no-discharge
NSPS limitation mast be qualified to reflect the problems associated with
maintenance of the critical water balance between the plant and the recircu-
lation pond during extremely wet weather. Recirculation ponds perform an
integral part in closed loop wastewater treatment and reuse schemes of most
phosphoric acid operations in the fertilizer industry and defluorinated rock
and acid operations in the non-fertilizer phosphate industry including cooling
and settling of calcium precipatates from treatment of wastewater with lime.
The pond typically provides sufficient treatment of process wastewater to
allow its resue as makeup water while also providing an evaporative surface
and waste flow buffering vessel to keep the operation hydraulically balanced
without discharge. Obviously, however, the pond has limited capacity and can
be overloaded by an unusually large rainfall. In such an event, provisions
must be made for treatment and discharge of recirculation pond effluents to
prevent dike overflow and damage to the pond. For this reason there are
several lengthy but specific footnotes to Table 12 outlining the conditions
under which effluents from the recirculation ponds may be discharged.
New sources that discharge wastewater to publicly owned treatment works
(POTW) are required to comply with USEPA's pretreatment regulations, issued in
the 26 June 1978, Federal Register (40 CFR 403). These regulations stipulate
that certain POTW's categorized by size and influent characteristics, develop
POTW Pretreatment Programs. These programs are intended to prevent the intro-
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Table 12. Standards of performance for new source wastewater
effluents of the non-fertilizer phosphate manufacturing point
source category (41 FR 25974, June 23, 1976).
Standards Category
Standards of Performance
for New Sources
Pre treatment
for New Sources
A. Phosphorus Production
B. Phosphorus Consuming
C. Phosphate
D. Def luorinated
Phosphate Rock
E. Def luorinated
Phosphoric Acid
F. Sodium Phosphates
no discharge of process
wastewater pollutants to
navigable waters
no discharge of process
wastewater pollutants to
navigable waters
no discharge of process
wastewater pollutants to
navigable waters.
no discharge of process
wastewater (1) pollutants to
navigable waters (3)
no discharge of process
wastewater (1) pollutants to
navigable waters (3)
(4)
(Note 2)
(Note 2)
(Note 2)
NA
NA
NA
(l)a The term "process wastewater" means any water which, during manufacturing
or processing, comes into direct contact with or results from the pro-
duction or use of any raw material, intermediate product, finished product,
by-product, or waste product. The term "process wastewater" does not
include contaminated non-process wastewater, as defined below.
b The term "contaminated non-process wastewater" means any water including
precipitation runoff, which during manufacturing or processing, comes
into incidental contact with any raw material, intermediate product,
finished product, by-product or waste product by means of (1) precipita-
tion runoff, (2) accidental spills, (3) accidental leaks caused by the
failure of process equipment and which are repaired or the discharge of
pollutants therefrom contained or terminated within the shortest reason-
able time which shall not exceed 24 hours after discovery or when discov-
ery should reasonably have been made, whichever is earliest, and (4)
discharges from safety equipment, and from equipment washings for the
purpose of safe entry, inspection and maintence; provided that all reason-
able measures have been taken to prevent, reduce, eliminate and control
to the maximum extent feasible such contact and provided further that all
reasonable measures have been taken that will mitigate the effects of
such contact once it has occurred.
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Table 12. Standards of performance for new source wastewater
effluents of the non-fertilizer phosphate manufacturing point
source category (continued).
c The term "25-year 24-hour rainfall event" means the maximum precipi-
tation event with a probable recurrence interval of once in 25 years as
defined by the National Weather Service in Technical Paper No. 40, "Rainfall
Frequency Atlas of the United States," May, 1961, and subsequent amendments
or equivalent regional or state rainfall probability information developed
therefrom (41 FR 25974, June 23, 1976).
(2) Pretreatment standards for new sources in this subcategory revoked by 43 FR
46020, October 5, 1978.
(3) The following standards of performance establish the quantity or quality of
pollutants or pollutant properties which may be discharged by a new source
subject to the provisions of this subpart: (40 CFR 422.45 422.55)
a Subject to the provisions of paragraphs (b) and (c) of this section, the
following limitations establish the quantity or quality of pollutants or
pollutant properties, controlled by this section, which may be discharged
by a point source subject to the provisions of this subpart after application
of standards of performance for new sources: there shall be no discharge
of process wastewater pollutants to navigable waters (41 FR 25974, June 23,
1976)
b Process wastewater pollutants from a calcium sulfate storage pile runoff
facility operated separately or in combination with a water recirculation
system designed, constructed, and operated to maintain a surge capacity
equal to the runoff from the 25-year, 24-hour rainfall event (see (1) c above)
may be discharged, after treatment to the standards set forth in paragraph (c)
below, whenever chronic or catastrophic precipitation events cause the water
level to rise into the surge capacity. Process wastewater must be treated and
discharged whenever the water level equals or exceeds the midpoint of the
surge capacity (41 FR 25974, June 23, 1976).
c The concentration of pollutants discharged in process wastewater pursuant
to the limitations of paragraph (b) shall not exceed the values listed
in the following table:
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Table 12. Standards of performance for new source wastewater
effluents of the non-fertilizer phosphate manufacturing point
source category (concluded).
Effluent Limitations (mg/1)
Ave r a ge of da ily
Effluent Maximum for values for 30 con-
Characteristic any one day secutive days shall
not exceed
Total Phosphorus (as P) 105 35
Fluoride 75 25
TSS 150 50
pH (standard units) 6-9.5
FR 25974, june 23, 1976)
(4)
Standards of Performance for New Source Manufacturers producing Sodium
Phosphates from 'Vet Process" Phosphoric Acid, 40 CFR 422.65. The following
limitations establish the quantity or quality of pollutants or pollutant
properties, controlled by this section, which may be discharged by a point
source subject to the provisions of this subpart after application of the
standards of performance for new sources:
[Metric units, kg/kkg* of product; English units,
lb/1,000 of product]
_ Effluent Limitations (mg/1)
Effluent Average of daily
Characteristic Maximum for values for 30
any one day consecutive days
shall not exceed -
TSS 0.35 0.13
Total Phosphorus (as P) 0.56 ' 0.28
Fluoride (as F) 0.21 0.11
pH Within the
range 6.0 to
9.5.
(41 FR 25974, June 23 1976) ~~
* kkg = thousand kilograms
70
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duction of pollutants by industrial users that would interfere with the opera-
tion of treatment works, would pass through treatment works, or would adversely
affect opportunities to recycle and reclaim wastewaters and sludges.
Regardless of specific limitations required by the Pretreatment Programs,
the regulations (40 GFR 403.5) state that the following may not be introduced
into a POTW:
• pollutants which create a fire or explosion hazard in the POTW;
• pollutants which will cause corrosive structural damage to the POTW,
but in no case discharges with pH lower than 5.0, unless the works is
specifically designed to accommodate such discharges;
• solid or viscous pollutants in amounts which cause obstruction to the
flow in sewers, or other interference with the operation of the POTW;
and
• any pollutant, including oxygen-demanding pollutants, released in a
discharge of such volume or strength as to cause interference in the
POTW.
In addition, there is a restriction on thermal discharges that became effec-
tive in June 1981.
With respect to the phosphate industry, pretreatment standards are not
well defined. Pretreatment standards for the first three subcategories dealing
with phosphorus-derived chemicals have been revoked as indicated in Table 12.
For the latter three subcategories dealing with other non-fertilizer phosphate
chemicals, new source pretreatment standards have not be promulgated.
NPDEf? permits also impose special conditions beyond the effluent limita-
tions stipulated, such as schedules of compliance and treatment standards.
Once plants are constructed in conformance with all applicable standards of
performance, they are relieved by Section 306(d) from meeting any more strin-
gent standards of performance for 10 years or during the period of deprecia-
tion or amortization, whichever ends first. However, this guarantee does not
extend to effluent standards for priority pollutants adopted under Section
307(a), which can be added to the processing plant's NPDES permit when they
are promulgated. These effluent standards will be promulgated if the finding
71
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is that an industry's effluents contain more than trace amounts of the pri-
ority pollutants under investigation by USEPA. A number of priority pollu-
tants are known to be present in phosphate industry wastes including cadmium,
chromium, zinc, and arsenic. P.L. 95-217 also expands Section 307(a) of P.L.
92-500 dealing with toxic standards or prohibitions on existing sources.
Thus, any evaluation of the impact of new or expanded phosphate plants should
include a verification on the status of applicable toxic effluent standards.
Many states have qualified, as permitted by P.L. 92-500, to administer
their own NPDES permit programs. The major difference in obtaining an NPDES
permit through approved state programs vis-a-vis the Federal NPDES permit
program is that the Act does not extend the NEPA environmental impact assess-
ment requirements to state programs. Because over half the States have en-
acted NEPA-type legislation, it is likely that new plants or major expansions
of existing plants will come under increased environmental review in the
future. Since the scope of the implementing regulations varies considerably,
current information on prevailing requirements should be obtained early in the
planning process from permitting authorities in the appropriate jurisdiction.
1.5.2 Air Pollution Control Regulations
New Source Performance Standards (NSPS)
National air pollution performance standards have not yet been promul-
gated for the non-fertilizer phosphate industry. In the absence of Federal
emission standards, air quality impacts are assessed based on ambient air
quality standards and applicable state and local standards.
National Ambient Air Quality Standards
National Ambient Air Quality Standards (NAAQS) (40 CFR 50) that specify
the minimum ambient air quality that must be maintained in the United States
are shown in Table 13. Standards designated as primary are those necessary to
protect the public health with an adequate margin of safety, and secondary
standards are those necessary to protect the public welfare from any known or
anticipated adverse effects of air pollution.
72
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A combined Federal/state regulatory program is designed to achieve the
objectives of the Clean Air Act and NAAQS. Each state must adopt and submit
to USEPA a State Implementation Plan (SIP) for maintaining and enforcing
primary and secondary air quality standards in Air Quality Control Regions.
USEPA either approves the state's SIP or proposes and implements an alternate
plan. The SIP's contain emission limits which may vary within a state due to
local factors such as concentrations of industry and population. Because
SIP's have been subject to frequent revision, it is best to verify the status
of the SIP requirements before applying them.
There are two alternate programs requiring preconstruction approval of
industrial air pollution abatement systems. These are the Prevention of
Significant Deterioration (PSD) Program which applies to areas in compliance
with NAAQS and the Nonattainment Program for areas which are in violation of
NAAQS.
Prevention of Significant Deterioration (PSD)
In 1974 USEPA issued regulations for the PSD Program under the 1970
version of the Clean Air Act (P.L. 90-604). These regulations established a
plan for protecting areas that possess air quality which is cleaner than that
dictated by the National Ambient Air Quality Standards. The PSD Program
components include:
• A classification system for areas of the country meeting NAAQS.
• Limitations on the increase in concentration of pollutants above
baseline conditions.
• Best Available Control Technology requirement for large sources.
• Preconstruction review and approval by permit of new source air pollu-
tion facility abatement programs.
Under USEPA's PSD regulatory plan, all areas of the nation are designated
as one of three classes. The plan permits specified numerical increments of
air pollution increases from major stationary sources for each class, up to a
level considered to be significant for that area. Class I provides extra-
ordinary protection from air quality deterioration and permits only minor
73
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Table 13. National primary and secondary ambient air
quality standards (40 CFR Part 50).
Carbon monoxide3
Hydrocarbons0
Nitrogen dioxide
Particulate
matter6
Sulfur dioxide
Lead
Ozone
Type of
Standard
Primary
Primary and
secondary
Primary and
secondary
Primary
Secondary
Primary
Secondary
Primary
Primary and
secondary
Averaging Frequency
Time Parameter
1 hr
8 hr
3 hr
(6 to 9
a.m. )
1 yr
24 hr
24 hr.
24 hr
24 hr.
24 hr
1 yr
3 hr
90 day
1 hr
Daily maximum3
Daily maximum3
Annual maximum'5
Arithmetic mean
Annual maximum*5
Annual geometric
Annual maximum*'
Annual geometric
Annual maximum*5
Arithmetic mean
Annual maximum*1
Concentration
ug/mj.
40,110
10,310
160
100
260
mean 75
150
mean 60^
365
80
1,300
ppm
35
9
0.24C
0.05
-
-
0.14
0.03
0.5
Quarterly maximum0 1.5
Daily maximum3
235
0.12
a. Expected exceedence less than or equal to one per year.
b. Not to be exceeded more than once per year.
c. As a guide in devising implementation plans for achieving oxidant standards.
d. As a guide to be used in assessing implementation plans for achieving the
annual maximum 24-hour standard.
e. Not to be exceed more than once per 90 days.
Source: Adapted from 40 CFR Part 50, and 45 FR 55065.
74
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increases in air pollution levels. Under this concept, virtually any increase
in air pollution in these pristine areas is considered significant. An ex-
ception may be granted to a source exceeding the Class I allowable increase on
these mandatory Class I areas if the Federal Land Manager certifies that the
facility will have no adverse impact on the air quality-related values of the
area, including visibility. Class II increments permit increases in air
pollution levels that would accompany well-control led growth. Class III
increments permit increases in air pollution levels up to the NAAQS. Accept-
able increases in pollutant concentrations over background for each of the
three PSD classes are shown in Table 14.
Sections 160 - 169 were added to the Act by the Clean Air Act Amendments
of 1977. These Amendments adopted the basic concept of the above administra-
tively developed procedure of allowing incremental increases in air pollutants
by class. Through these Amendments, Congress also provided a mechanism to
apply a practical adverse impact test which did not exist in the USEPA regula-
tions previously.
As indicated in Table 14, the PSD requirements of 1974 apply only to
two pollutants: total suspended particulates (TSP) and sulfur dioxide (S02>.
However, Section 166 requires USEPA to promulgate PSD regulations which
address nitrogen oxides, hydrocarbons, lead, carbon monoxide, and photo-
chemical oxidants, including use of increments or other effective control
strategies which, if taken as a whole, accomplish the purposes of PSD policy
set forth in Section 160.
The 1977 Amendments designate certain Federal lands as Class I, including
all international parks, national memorial parks, national wilderness areas
which exceed 5,000 acres, and national parks which exceed 6,000 acres. This
constitutes 158 areas which may not be redesignated to another class through
state or administrative action. The remaining areas of the country have been
initially designated Class II. Within this Class II category, certain Federal
lands over 10,000 acres (national primitive areas, national wild and scenic
75
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Table 14. Nondeterioration (PSD) increments for SO and participate matter
in areas with different air quality classifications.
Class-I Class-II Class3III Class I exception
Pollutant (ug/m ) (ug/m ) (ug/m ) (ug/m )
Particulate matter:
Annual geometric mean 5 19 37 19
24-hour maximum 10 37 75 37
Sulfur dioxide:
Annual arithemetic' mean 2 20 40 20
24-hour maximum 5* 91 182 91
3-hour maximum 25 512 700 325
*
A variance may be allowed to exceed each of these increments on 18 days
per year, subject to limiting 24-hour increments of 36 ug/m for low terrain
and 62 ug/m for high terrain and 3-hour increments of 130 ug/m for low
terrain and 221 ug/m for high terrain. To obtain such a variance requires
both State and Federal approval.
Source: Public Law 95-95. 1977. Clean Air Act Amendments of 1977, Part C,
Subpart 1, Section 163 (Passed August 1977).
76
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rivers, national wildlife refuges, national seashores and lakeshores, and new
national park and wilderness areas) established after 7 August 1977 will be
Class II "floor areas" ineligible for redesignation to Class III.
The general responsibility for redesignation of PSD areas lies with the
states. The Federal land Manager has an advisory role for redesignation to
the appropriate state and to Congress. Redesignation by Congress will require
the normal legislative process of committee hearings, floor debate* and action.
In order for a state to redesignate areas, the detailed process (outlined in
Section 164(b) of the 1977 Amendments) would include an analysis of the health,
environmental, economic, social, and energy effects of the proposed redesigna-
tion which would be discussed at a public hearing.
Federal regulations require that any new source of emissions that obtains
its permits after March 1, 1978, or has the potential for production of 250
tons/year (227 kkg) of any registered pollutant, before controls, must undergo
full PSD review and receive preconstruction approval. Full PSD review requires
analysis of effects of the source on air quality increments, application of
Best Available Technology, and a comprehensive monitoring program. Applicants
for construction permits must demonstrate by monitoring and submission of air
quality data that the new facility will not violate an applicable NSPS or
increment or any air quality standard.
Due to the nature of some subcategories of the non-fertilizer phosphate
industry such as phosphorus production and def luorination of phosphate rock
which handle large quantities of material and which require large quantities
of fuel for thermal processes, there may well be a need for full PSD review of
a new source facility. This may not be the case, however, if a smaller fa-
cility or less polluting facility is proposed. A small source of the desig-
nated pollutants (less than 50 tons/yr, 1,000 Ib/day, or 100 Ib/hr after
abatement) is required only to apply for and obtain a preconstruction permit
unless it would impact a Class I area. This may exempt many new source plants
from full PSD review.
77
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Nonattainment Areas
Even more stringent air quality regulations may be applied to new source
facilities or significantly modified existing facilities in areas where ambient
air quality standards are being exceeded (nonattainment areas). Permits will
be required for construction and operation of major new or modified sources
and applicants will be required to achieve the "lowest achievable emission
rate" (LAER) of any pollutant which exceeds the standards. This rate is
defined as a rate of emissions which reflects:
• the most stringent emission limitation in the applicable state imple-
mentation plan unless the applicant can demonstrate that such limita-
tions are not achievable; or
• the most stringent limitation which is actually achieved in practice
by similar facilities.
The Clean Air Act Amendments further require that the permit to construct
and operate such facilities may be issued only if:
• by the time the facility is to commence operation, total allowable
emissions from all existing and new sources in the Air Quality Control
Region, including the new or modified facility, will permit reasonable
further progress toward attainment of the applicable national ambient
air standard for the identified pollutant; or
• the emissions of such pollutant from the new or modified facility will
not cause the total emissions of the pollutant to exceed the allowance
permitted by the implementation plan for the pollutant from all new or
modified sources in the area.
The purpose of these requirements is to allow, under strict stipulations,
the economic benefits to a region from introduction of new industry or new
expansion of existing industry (new sources) to be obtained. The qualifying
condition is that the new action must be accomplished in such a way as to
assure progress toward compliance in the nonattainment area. Thus, permits
issued by USEPA or the approved state agency must require "offsets" in the
existing levels for pollutants which exceed Federal ambient air quality
standards.
78
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Emission Offsets
Offsets are enforceable reductions from the existing sources of air
pollutants which will be greater than the emissions of those pollutants antic-
ipated from the new source. A "new air quality benefit" must result from the
combined new project plus the offsets attained (44 FR 3284, Part IV.A.4 and 44
FR 3275). In addition, the quantity of offsets must match the new source
emissions on a "more than one-for-one" basis. The manner in which offsets may
be attained is not specified. Several possible approaches which have been
used include the following:
when the new source is an expansion of an existing facility, the owner
may install tighter controls on existing operations to achieve emis-
sions which may be lower than those otherwise required for the existing
sources;
when the new source is an entirely new plant under a new owner in the
nonattainment area, the applicant may reach an agreement with one or
more existing sources whereby they agree to apply stricter pollution
control measures, presumably in exchange for compensation by the new
source applicant;
in some instances, the applicant may purchase outright an existing
facility, especially an obsolete facility with high pollutant emis-
sions, and either clean it up or simply close it down;
in cases where the state and/or local government are extremely in-
terested in locating the new source industry in the area (for example,
due to the benefits to the local economy), they may assist the applicant
by either putting pressure on the existing sources to achieve stricter
pollution control standards or by public works actions such as paving
of roads in the area to help reduce background particulate emissions.
The amount of time required to process PSD applications could run to
several years in some controversial cases and adequate lead time for design,
for modeling of air quality effects, and for required monitoring (one year)
should be anticipated. USEPA is committed to a policy of expediting permit
application processing, public participation activities, and internal reviews
so that the entire PSD review process could theoretically be carried out
within 90 days after receipt of a complete and technically substantiated
application. This time, however, could be extended by state review pro-
cedures, litigation, or offset arrangements in a highly industrialized
nonattainment area. Hoffnagle and Dunlap (1978) emphasize that an industry
79
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should allow adequate time for the one-year baseline monitoring. Review and
approval by regulatory agencies of the design of the monitoring plan at the
earliest possible time can be a time saver. Total time involved in the PSD
process for the permit applicant may realistically range from 18-34 months, as
illustrated below (Hoffnagle and Dunlap 1978):
Activity
Specify monitoring required
Select vendors and contractors
Procure and install equipment
Conduct 1-yr baseline monitoring
Complete data analysis, modeling,
and permit application
Request special model (if
necessary) with agency hearing
and review
Hearings on application and ,
agency review
1.5.3 Solid Waste Regulations
Time for
Activity
(Months)
1-2
0-3
1-4
12
1-4
0-6
3-12
Cumulative
Time
(Months)
1-2
1-5
2-9
14-21
15-25
15-31
18-43
The Resource Conservation and Recovery Act (RCRA), P.L. 94-580, defines
"solid waste" as including solid, liquid, semisolid, or contained gaseous
materials. Regulations implementing Subtitle C of the Act (40 CFR Part 261)
provide that a solid waste is a hazardous waste if it is, or contains, a
hazardous waste listed in Subpart D of Part 261 or the waste exhibits any of
the characteristics defined in Subpart C. These characteristics include:
• Ignitability (flash point below 60° C (140° F)
• Corrosivity
• React ivi ty
• Toxicity
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Hazardous wastes are identified in 40 CFR 261 Subpart D. The hazardous
substances identified at this time in Subpart D do not include the major solid
wastes of the non-fertilizer phosphate industry. However, additions are
scheduled to be made to the list in the near future which will include solid
wastes of the non-fertilizer phosphate industry as well. The only solid waste
of the non-fertilizer phosphate industry that is definitely identified in
these proposed regulations is "slag and fluid bed prills from processing phos-
phate ore to produce elemental phosphorus." This does not eliminate the
possiblity of many other industry wastes having "hazardous" designations.
Wastes containing arsenic or cadmium, for example, may be considered hazardous
if the toxic materials can be leached out at concentrations of 5 mg/1 and
1 mg/1 respectively using the EP (Extraction Procedure) toxicity test. The
nature of the wastes to be generated by a particular new source non-fertilizer
phosphate plant will have to be carefully examined to determine the applica-
bility of the hazardous waste designation.
All new facilities that will generate, transport, treat, store, or dis-
pose of hazardous wastes must notify .USEPA of this occurrence and obtain a
USEPA identification number. Storage, treating, and disposal also require a
permit.
The determination of whether wastes generated or handled are hazardous is
the responsibility of the owner or operator of the generating or handling
facility. The first step is to consult the promulgated list (40 CFR 261 Subpart
D). Furnace slag from the production of elemental phosphorus, for example, is
listed as a hazardous waste. If the waste is not listed, the second step is
to determine whether the waste exhibits any of the hazardous characteristics
listed through analytical tests using procedures promulgated in the regula-
tions or by applying known information about the characteristics of the waste
based on process or materials used.
If it is determined that a hazardous waste is generated, it should be
quantified to determine applicability of the small generator exemption. This
cutoff point is 2,200 pounds per month, but it drops to 2.2 pounds for any
commercial product or manufacturing chemical intermediate having a generic
name listed in Section 261.33. Containers that have been used to contain less
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than 21 quarts of Section 261.33 materials and less than 22 pounds of liners
from such containers are also exempt. It is anticipated that this exemption
may be available to many very small plants with, for example, only one machine
tool and one small painting operation. However, as more information is ob-
tained on the behavior of substances in a disposal environment, the terms of
this exemption may be altered from time to time.
The hazardous waste management system is based on the use of a manifest
prepared by the generator describing and quantifying the waste and designating
a disposal, treatment, or storage facility permitted to receive the type waste
described to which the waste is to be delivered. One alternate site may be
designated. Copies of the manifest are turned over to the transporter and a
copy must be signed and returned to the generator each time the waste changes
hands. If the generator does not receive a copy from the designated receiving
facility or alternate within 35 days, he must track the fate of the waste
through the transporter and designated facility or facilities. If the mani-
fest copy is not received in 45 days, the generator must file an Exception
Report with USEPA or the cognizant state agency.
A copy of each manifest must be kept for three years or until a signed
copy is received from the designated receiving facility. In turn, the signed
copy must be kept for three years. The same retention period applies to each
Annual Report required whether disposal, storage, or treatment occurs on-site
or off-site.
The generator must also:
• package the waste in accordance with the applicable DOT regulations
under 49 CFR Parts 173, 178, and 179;
• label each package in accordance with DOT regulations under 49 CFR 172;
• mark each package in accordance with the applicable DOT regulations
under 49 CFR 172;
* mark each container of 110 gallons or less with the following DOT
(49 CFR 172) notice:
"Hazardous Waste - Federal Law Prohibits Improper Disposal.
If found, contact the nearest police or public safety authority
or the U.S. Environmental Protection Agency."
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• supply appropriate placards for the transporting vehicle in accordance
with DOT regulations under 49 CFR Part 172, Subpart F.
Waste in properly labelled and dated containers in compliance with the
regulations may be stored on the generator's premises for up to 90 days with-
out a storage permit. This is to permit time for accumulation for more economic
pickup or to find an available permitted disposal facility.
Due to the cost and stringent design and operating requirements for
permitted landfills, it is anticipated that most new generator plants will
utilize off-site disposal facilities. However, any companies desiring to
construct their own will be subject to 40 CFR Part 264.
Incineration is considered to be "treatment," and, as such, is also
subject to Part 264 as are chemical, physical, and biological treatment of
hazardous wastes, and a permit will be required. Totally enclosed treatment
systems—such as in-pipe treatment of acid and alkaline solutions—are not
subject to this part.
Although underground injection of wastes constitutes "disposal" as de-
fined by RCRA, this activity will be regulated by the underground injection
control (UIC) program adopted pursuant to the Safe Drinking Water Act (P.L.
93-523). The consolidated permit regulations (40 CFR Parts 122, 123, 124)
govern the procedural aspects of this program; the technical considerations
are contained in 40 CFR 146.
The disposal of innocuous solid wastes is subject to Subtitle D of RCRA
and the implementing regulations (40 CFR Part 256). Recovery or disposal in
an approved sanitary landfill will be required under a state program. Disposal
in open dumps is prohibited. All existing state regulations which do not meet
the requirements of Subtitle D are superseded.
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1.5.4 Other Government Regulations
There are various regulations other than pollution control that may apply
to the siting and operation of facilities. Some of these regulations require
that permits be obtained while others require only that the resource area in
question be examined during the review process for issuance of pollution con-
trol and other permits. It is advisable to contact the appropriate agency to
determine the applicability of a regulation to the project in question. Some
Federal regulations that may be pertinent to a proposed facility include, but
are not limited to, the following:
• Coastal Zone Management Act of 1972 (16 USC 1451 et seq.)
• Fish and Wildlife Coordination Act of 1974 (16 USC 661-666)
• National Environmental Policy Act of 1969 (42 USC 4321 et seq.)
• USDA Agriculture Conservation Service Watershed Memorandum 108 (1971)
• Wild and Scenic Rivers Act of 1969 (16 USC 1274 et seq.)
0 Flood Control Act of 1944
• Federal-Aid Highway Act, as amended (1970)
• Wilderness Act of 1964
• Endangered Species Preservation Act, as amended (1973)
(16 USC 1531 et seq.)
• National Historical Preservation Act of 1966 (16 USC 470 et seq.)
e Executive Order 11593 (Protection and Enhancement of Cultural Environ-
ment, 16 USC 470) (Sup. 13 May 1971)
• Archaeological and Historic Preservation Act of 1974 (16 USC 469 et
seq.)
• Procedures of the Council on Historic Preservation (1973) (39 FR 3367)
• Occupational Safety and Health Act of 1970
• Executive Order 11988 (Floodplain Management - replaced Executive
Order 11296 on 10 August 1966)
• Executive Order 11990 (Wetlands)
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• Energy Policy and Conservation Act of 1975
• Energy Conservation and Production Act of 1976
Particular emphasis should be placed on obtaining the services of a qualified
archaeologist to determine the potential for disturbance of an archaeological
site, such as an early Indian settlement or a prehistoric site. .Both the
applicant and the archaeologist should stay in contact with the State Historic
Preservation Officer (SHPO) throughout the entire process of siting the new
facility. The Ifetional Register of Historic Places also should be consulted
for historic sites such as battlefields.
The appropriate wildlife agency (state and Federal) should be" contacted
to ascertain that the natural habitat of a threatened or endangered species
will not be affected adversely; other resource agencies also should be con-
sulted to avoid or minimize impacts to areas that previously have been de-
termined to be sensitive or uniquely important (wetlands, floodplains, prime
farmlands, etc.).
From a health and safety standpoint, most industrial operations involve a
variety of potential hazards and to the extent that these hazards could affect
the health of plant employees, they may be characterized as potential environ-
mental impacts. Company policy should provide and maintain safe and healthful
conditions for employees and establish operating practices that will result in
safe working conditions and efficient operations. All proposed plans to
maximize health and safety should be described in the EID.
The plant must be designed and operated in compliance with the standards
of the U.S. Department of Labor, the Occupational Safety and Health Administra-
tion, and the appropriate state statutes relative to industrial safety. Close
coordination with local and/or regional planning and zoning commissions is
recommended to determine possible building or land use restrictions. State
and local regulations may exist that affect the facility, and the EID should
indicate that these have been considered.
85
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Table 15 presents a range of typical permits, licenses, certifications,
and approvals that could be required from local, regional, state, and Federal
officials for construction and operation of a major new source facility.
Although this list doubtless will vary between jurisdictions, it is intended
primarily to be illustrative. The new source NPDES permit review process
normally will be expedited by documenting in the EID all known permits,
licenses, and approvals that are needed to construct and operate the proposed
plant, and the status of each.
86
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Table 15. Typical permits, licenses, certifications, and
approvals required from Federal, state, regional, and
local authorities for construction and operation of a
typical new source facility.
Agency
• Local Planning Organization
(regional, county, city)
• Local Department of Public Works
• Local Beautif ication Board
• Local Department of Development
and Licensing
• State Planning Department
• State Fire Marshal
State Department of Environmental
Protection
Requirement
• Rezoning of plant site
• Approval of access road
right s-of-way
• Permit for filling or construc-
tion operations in floodplains
• Construction on public property
if required
• Building permit for each
structural component of
facility
• Use and occupancy permits
• Coastal zone construction
permit, if required
• Permit to store flammable
liquids
• Approval of facility for fire
protection
• Water use and discharge permits
• Test well permit
• Commercial well permit
• Permit for dewatering excavation
• Permit for fuel oil storage tanks
• Permit for solid waste disposal
• Dredging, filling, or construction
of intake structures
• Sedimentation control approval
87
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Table 15. Typical permits, licenses, certifications, and approvals (continued),
Agency
State Air Pollution Control
Department
State Board of Health
State Department of Highways
and Transportation
• US Environmental Protection
Agency (Regional Office)
Requirement
• Noise control approval
• State water quality certification
• Construction permit for combustion
equipment
• Permit for handling, treatment,
storage, or disposal of hazardous
wastes
• Registration of gaseous emissions
• Permit for construction of sta-
tionary source of air pollutants
• Permit for operation of stationary
new source
• Open burning of construction refuse
9 Review of indirect (mobile) emission
sources
• Permit to construct and operate ap-
proved sewage disposal and potable
water facilities
• Permit for consumptive use of
water, if applicable
• Permit for highway entrance of
plant access road
• Approval of public road improve-
ments
• Permits for oversize or overweight
vehicles
• National Pollutant Discharge
Elimination System (NPDES) permit
for wastewater discharge
• Prevention of Significant Deteriora-
tion of air quality (PSD) certifi-
cation prior to commencement of con-
struction activities
88
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Table 15. Typical permits, licenses, certifications, and approvals (continued)
Agency
US Army Corps of Engineers,
(District Office)
(COE, Washington Office)
Occupational Safety and Health
Admini s tra ti on
Requirement
• Spill Prevention, Control, and
Countemeasure (SPCC) plan
• Hazardous/toxic waste disposal
plan
• Permit to construct structures or
works* in navigable waters (Sec-
tion 10, Rivers and Harbors Act
of 1899)
• Permit to dispose of dredged or
fill materials in waters of the
US (including wetlands) (Sec-
tion 404)
• Permit to construct any dam or
dike in a navigable water of the
US (Section 9, Rivers and Har-
bors Act of 1899)
• Permit to ocean dump dredged
materials (Section 103, Ocean
Dumping Act)
• Permit to discharge refuse matter
into navigable waters of the US
or their tributaries (Section 13,
The Refuse Act of 1899)
• Test boring on Federal land
• Certification of safety and
health criteria for plan ope-
ration (noise in the work place,
etc.)
Structures may include piers, breakwaters, bulkheads, revements, and aids
to navigation; works may include dredging, stream channelization, excava-
tion, and filling.
89
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2.0 IMPACT IDENTIFICATION
This chapter presents an overview of the pollutants and impacts that
could be expected due to the construction and operation of a new source
non-fertilizer phosphate manufacturing facility and describes critical infor-
mation and analyses that should be included in an EID. Pollutant generation
and impacts have been quantified where possible to enhance the readers appre-
ciation of the magnitude of any impacts. In addition to quantifying air
emissions, wastewater discharges and solid wastes that may be generated by a
new source, this chapter presents a discussion of the fate of industry pol-
lutants in the environment. Impacts of the industry on energy and aesthetic
resources as well as noise and socioeconomic factors are also discussed.
Part 2.1 of this chapter provides identification of the major pollutants
associated with the industry and gives information on their sources and rates of
discharge where such information is available. Part 2.2 identifies factors
that should be included in an assessment of potential impacts as well as a
generic discussion of pollutant toxicity.
2.1 PROCESS WASTES
The EID should present a complete description of the source, quantity,
nature, treatment, and disposal of process wastes generated by the new source
non-fertilizer phosphate facility. Because these materials may contribute to
some of the most significant environmental impacts of the industry, a clear
presentation of their origin and fate is of critical importance to the overall
assessment of the consequences of operating a new source facility. Following
are major waste streams and typical associated pollutant generation factors
for the various subcategories of the non-fertilizer phosphate industry.
2.1.1 Air Emissions
Mass emission factors and air quality impact data for the non-fertilizer
phosphate industry are sketchy. A Source Assessment of the industry has not
been prepared by USEPA as of the publication of this document, and representa-
tive emission data are presently'available only for portions of the industry.
90
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In addition, the character of well studied emissions can vary significantly
depending on the mineral content of the phosphate rock being used for phos-
phorus production or phosphate rock defluorination. Variations of this nature
must be taken into account when quantifying projected raw emissions from the
new source phosphate facility. The sources of emissions for the industry have
been summarized in the following sections according to the process subcate-
gories described in Chapter 1.0. Emission data have been included where
available.
2.1.1.1 Phosphorus Production (Subcategory A)
The production of elemental phosphorus is a potentially significant air
pollution generator. Significant emissions are generated by all three of the
major operations: 1) furnace charge preparation, 2) electric arc furnace
reduction, and 3) phosphorus recovery and storage (Stinson 1976). The pol-
lutants generated during each of these operations are indicated in Figure 20.
Furnace Charge Preparation
Potential emission sources associated with furnace charge preparation
include:
raw material preparation and handling
drying
calcining
transportation and weighing
crushing and sizing
storage
Pollutant emissions due to raw material handling and preparation are
magnified by the bulk of materials required to produce elemental phosphorus.
This is illustrated by the following generalized materials balance for the
phosphorus production process (Stinson 1976):
91
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FEED PREPARATION
NO,
SOX/ H20, DUSTS
PHOSPHORUS COMPOUNDS
FLUORINE COMPOUNDS
SILICA + COKE FINES
ELECTRIC FURNACE REDUCTION
/ FEED
FURNACE
o5, co, co2,
^^v / **o / ^ ^ *"* /i J * ' v w v
A Z *r A A
PHOSPHORUS COMPOUNDS,
OTHER COMPOUNDS
RECOVERY AND STORAGE
DUSTS
P20 , CO, OTHER
PHOSPHORUS COMPOUND!
Figure 20. Raw emission types produced from phosphorus manufacture.
Source: Stinson, Mary, and F. Ellerbusch. 1976. Air pollution emissions
and control from the manufacture of elemental phosphorus. USEPA,
Industrial Env. Research Lab.,1 Office of Research and Development,
Edison NJ, 32 p,
92
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Input Output
9.5 kkg phosphate rock 1 kkg phosphorus
1.1 kkg coke 8.9 kkg slag
1.7 kkg silica 0.3 kkg ferrophosphorous
0.4 kkg coal 2.8 kkg carbon monoxide
0.1-0.2 kkg iron
Nearly 13 tons of raw material are required to produce one ton of elemental
phosphorus.
The drying and calcining operations liberate carbon dioxide, fluorides,
and particulates and are a more significant source than fugitive dust from raw
material piles. The quantity of these emissions, particularly for fluorine,
depends on the particular quality of rock and the furnace charge preparation
process being used. Of the fluorine present in phosphate rock, approximately
20% to 50% is released through nodulizing and 30% to 40% is released by sin-
tering (Stinson 1976).
Quantification of emissions from furnace charge preparation depends on
the quality of phosphate rock being processed. Phosphate ores with a high
ratio of fluoride to P«0 will evolve fluorine at a lower furnace temperature
than ores with lower ratios (Barber 1980b). Examples of typical phosphate
rock mineral analyses are shown in Table 2 of Section 1.2.2, "Auxiliary Pro-
cesses."
In addition to phosphate rock preparation, particulate emissions are
generated by the handling of coke and silica, and the crushing, sizing, and
storage of calcined furnace charge. Although the calcining kiln is heated
with carbon monoxide off-gas from the electric furnace, it does not provide
enough heat to run the agglomeration process. A supplemental fuel such as oil
or coal must be used also. Sulfur dioxide emissions from the operation of the
calcining kiln may be significant if not controlled.
Electrothermal Reduction
Potential emission sources associated with the electric arc furnace
include (Stinson 1976; Barber 1980b):
93
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• Particulates from conveying system and proportioning bins;
• CO from the furnace feed bins;
• Fumes and particulates from slag and ferrophosphorus tapping opera-
tions;
• Fumes from venting CO fumes;
• Fumes from slag and ferrophosphorus cooling operations; and
• Fumes and particulates from miscellaneous openings in the furnace roof
and gas offtake, rodout holes, electrode seals, and cracks in the
furnace.
Furnace feeding operations from the bins atop the furnace may evolve large
quantities of particulates. There is no seal between the bins and the furnace
so pressure fluctuations within the furnace may allow emission of carbon
monoxide (CO) and phosphorus (P.) or draw air into the furnace with the CO and
P, creating a potentially explosive situation.
When slag and ferrophosphorus are tapped from the furnace and cooled,
fumes consisting of phosphorus oxides, fluorides, particulates, and SO along
with small quantities of trace metals such as vanadium are emitted. The rate
of emissions from the tapping operation varies with their duration and fre-
quency. Fluoride, SO , and P?0,- fumes evolved during the slag cooling opera-
tion depend on the method of quenching. Air quenching tends to evolve less
fluorine than does water quenching (Stinson 1976). Ferrophosphorus is always
air quenched, since it is highly reactive in the presence of water. Most
fumes are controlled by the product recovery process and emission controls but
emissions may still be a problem due to small, uncontrolled sources.
Phosphorus Recovery
Potential emission sources from the recovery of phosphorus include:
• Handling phosphorus-laden dust from the electrostatic precipitator.
94
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• Contaminated carbon monoxide furnace fumes passed through the condenser.
• Fumes from phosphorus storage tank cleaning.
Approximately 125 kg dust/kkg P is collected in the electrostatic precipitator
and may contain as much as 1% phosphorus (Stinson 1976). Phosphorus pentoxide
(P 0 ) fumes may be evolved during the handling of precipitator dust or repair
of the precipitator itself. Condensed furnace off-gas may contain phosphorus,
silicon tetrafluoride, methane, and sulfur compounds in addition to carbon
monoxide. The carbon monoxide wastestrearn is used as a fuel for calcining or
localized heating, or may be flared. Condensed phosphorus is kept under a
water blanket and produces no emissions. However, P~0 may be evolved when
phosphorus residuals come into contact with the air during cleaning of the
phosphorus storage tanks.
2.1.1.2 Phosphorus Consuming (Subcategory B)
Emission problems of the phosphorus consuming processes vary widely.
However, most emissions are captured by wet scrubbing devices and are trans-
ferred to the wastewater stream. Because 80% of the elemental phosphorus
produced in the United States is used to manufacture "dry process" phosphoric
acid, emissions from this source potentially may be the most significant
overall (USEPA 1977d).
Phosphoric Acid
Potential emission sources associated with phosphoric acid production
include (USEPA 1974):
• Tail gas emissions containing acid mists.
• Phosphorus fumes from leaks in the combustion chamber or transporta-
tion systems.
Tail gas emissions may contain submicron particles of phosphoric acid. There
is also potential for phosphorus or toxic phosphoric emissions from fugitive
sources.
95
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Phosphorus Pent oxide
Potential emission sources from the manufacture of phosphorus pentoxide
may include (USEPA 1973a):
« Phosphorus fumes from leaks in the combustion chamber.
• P90c fumes from the condenser barn or transportation of product.
Phosphorus Pentasulfide
Potential emission sources from the manufacture of phosphorus penta-
sulfide may include (USEPA 1973a):
• Casting fumes from production of solid P2^s*
• Dust from crushing of solid P2J*5"
• Vented reaction gases from the batch reactor.
Phosphorus Trichloride
Potential emission sources from the manufacture of phosphorus trichloride
include (USEPA 1973a):
• Hydrochloric and phosphorus acid fumes from condenser scrubber.
• Acid fumes from PCI,, transfer and storage.
• Fugitive emissions from reactor cleaning.
Phosphorus Oxychloride
Potential emissions sources from the manufacture of phosphorus oxychloride
include (USEPA 1973a):
• Hydrochloric and phosphoric acid fumes from condenser scrubber.
96
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• Acid fumes from POC1 transfer and storage.
• Process vapors from the air oxidation variation of the POC1 process.
2.1.1.3 Phosphate Chemicals (Subcategory C)
Gaseous emissions are less of a problem for industrial phosphate productions
than for other subcategories. However, phosphate particulate emissions are
potentially significant due to product drying and handling procedures.
Sodium Tripolypho^phate
Potential emission sources from the manufacture of sodium tripolyphosphate
may include (USEPA 1973a):
• Sodium phosphate mists from evaporator.
• CO from the neutralization reaction.
• Dust and product fines from the spray drier and calciner.
Calcium Phosphates
Potential emission sources from the manufacture of calcium phosphates may
include (USEPA 1973a):
• Fines from the monocalcium phosphate spray drying tower.
• Fines from kiln drying of dicalcium phosphate.
• Fines from the drum drying of tricalcium phosphate.
2.1.1.4 Defluorinated Phosphate Rock (Subcategory D)
The processes associated with the def luorination of phosphate rock are
potentially significant emission generators. Large quantities of phosphate
rock and sodium compounds must be handled and the calcining operation produces
silicon fluoride and particulates (USEPA 1976a). Potential emission sources
from this process may include:
97
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• Dust from phosphate rock, silica or sodium carbonate handling, mixing,
and drying.
• Sulfur compounds from heating the kiln or fluid bed reactor.
• Fluorine compounds such as hydrofluoric acid from calcining off-gas.
• Dust from product handling consisting of tricalcium phosphate and
calcium silicates.
2.1.1.5 Defluorinated Phosphoric Acid (Subcategory E)
Information on the controlled emission of air pollutants from acid de-
fluorination facilities has not yet been compiled by USEPA. However, the
primary commercial method for defluorination of phosphoric acid is vacuum
evaporation which essentially is identical to the procedure and equipment used
for production of superphosphoric acid by the fertilizer industry. Informa-
tion on controlled emissions from superphosphoric acid plants is available
from the source assessment on the fertilizer industry (USEPA 1977d). Emis-
sions from superphosphoric acid plants may serve as an indication of 'the
levels that could be expected from a defluorination facility but these levels
may not necessarily be applicable. Emission factors for these plants are
presented in Table 16.
Typical data on the other two defluorination processes have not been
compiled. The aeration process is quite new and may become more favored in
the future, but the submerged combustion process has extensive emission
scrubbing requirements and is not expected to enjoy expanded use in the future
(USEPA 1977d).
2.1.1.6 Sodium Phosphates (Subcategory F)
Exact information is unavailable on emissions from the production of
sodium phosphates from "wet process" phosphoric acid due to the proprietary
nature of the process. Based on general descriptions of the process, emis-
sions may be expected from the following operations:
• Handling of dry raw materials.
98
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Table 16. Average stack heights and controlled emission factors for "wet process"
phosphoric acid and superphosphoric acid plants.
Emission Point
"Wet process" phosphoric acid:
Rock unloading
Rock transfer and conveying
Wet scrubber system:
Overall
With recovery of fluorine
Without recovery of fluorine
Gypsum pond
Stack
Height,
m
12
21
29
Emission Factor, g/kg P2°5
Total
Fluorine
0
0
0.010 + 47%
0.0059 + 61%
0.012 + 60%
0.025 to 2.5
avg 0.50
Particulate SO
X
0.15 + 250% 0
0.045 +_ 180% 0
0.054 +_ 164% 0.032 +_ 200%
a a
a a
0 0
Superphosphoric acid:
Wet scrubber
21
0.0073 + 71% 0.011 to 0.055
Insufficient data to determine the effect of fluorine recovery on other emissions
Accuracy based on standard deviation instead of "Student t" confidence limits due to
only two data points.
Source: US Environmental Protection Agency. 1977d. Source assessment: Phosphate fertilizer
industry - phosphoric acid and superphosphoric acid. Office of Research and Development,
Washington DC. Prepared by Monsanto Research Corporation, Dayton OH, 93 p.
-------
• Operation of calciners and dryers.
• Sulfur compound emissions from burning fuel for dryer heating.
2.1.2 Wastewater Characteristics
Wastewater generated by the various elements of the non-fertilizer phos-
phate industry generally contains high concentrations of phosphorus, fluorine,
and dissolved solids, and is highly acidic. To a large degree, these pol-
lutants are generated from the capture by various air pollution control de-
vices such as wet scrubbers on the various emission sources. Other major
sources of wastewater contamination include aqueous process solutions, slag
quenching, condenser- water, cooling water, and runoff.
Waste loads from the non-fertilizer phosphate industry have been charac-
terized in two reports prepared by USEPA in connection with development of
effluent limitations guidelines and standards (USEPA 1973a, I976a). Data were
collected from a number of plants representing a cross section of the manu-
facturers in each subcategory. Due to the age of the data and the increasing
emphasis on control of all waste materials, it is possible that a new source
facility would implement process changes and select equipment that would
reduce their raw waste load to levels even less than those indicated. In view
of this and the variability of pollutant generation for the various manufac-
turing processes, the nature of the wastewater for any new source phosphate
plant should be documented by the applicant and specifically related to the
particular processes and raw materials proposed.
2.1.2.1 Phosphorus Production (Subcategory A)
! Wastewater is generated during phosphorus manufacture from the following
sources (USEPA 1973a):
0 Calciner and phosphorus furnace fume scrubbers.
9 Phosphorus condenser (phossy water).
• Noncontact cooling water.
100
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• Phosphorus sludge.
• Slag quenching.
• Phosphorus storage and transportation water (phossy water).
• Calciner heat source scrubber.
Scrubber Liquor
Air pollution control equipment nay be the largest single source of
contaminated wastewater from a phosphorus plant. Scrubbers are used to con-
trol emissions from the calciner, dust from phosphate rock, coke and silica
feed and storage bins, condenser tailgas, and furnace taphole. These waste
streams contain suspended solids, phosphates, sulfates, and fluorides.
Fluorides are evolved as hydrogen fluoride or silicon tetrafluoride during
calcining and thermal reduction of the phosphate rock and are hydrolized to
hydrofluoride or fluosilicic acid in the scrubbers. Oxides of sulfur and
phosphorus evolved during thermal treatment of phosphate rock produce sulfuric
and phosphoric acid when hydrolized in the scrubber water. Suspended solids
are also found in the form of Fe?0 and SiO .
Phossy Water
Phossy water is produced both by the phosphorus recovery process con-
"denser and by the need to store and transport the highly reactive phosphorus
under a water blanket. Recycling of the phossy water is carried out to the
maximum degree possible but mineral contamination makes it difficult to
achieve total recycle. The problem with continuous recycle of phossy water
can be explained as follows (Barber 1980b):
In the phosphorus condensing system, furnace gases are contacted
with water as part of the adiabatic cooling for condensation of phos-
phorus. Some water is lost by vaporization into the dry gas stream.
However, water is used over and over in the condenser.v
In the phosphorus furnace about 9 percent of the fluorine in the
phosphate is violatilized and comes over in the gases; 91 percent is
combined in the slag. Some of the alkali metals—sodium and
potassium—are volatilized from the funace. As a result, sodium
fluosilicate and potassium fluosilicate salts accumulate in the re-
101
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circulated condenser water. Since these salts have low solubility in
water, saturation is reached by continuously recirculating the water and
the fluosilicates will precipitate as scales in pumps, exhaust blower,
spray nozzles, and piping causing stoppages and plant shutdowns. Con-
sequently, some of the recirculating water must be bled off and replaced
with fresh water to control the concentration of the scale-forming salts.
The phosphorus condensers may be constructed of mild steel or stain-
less steel. In the case of mild steel construction, the condenser water
must be neutralized to prevent corrosion. When the water is neutralized
with soda ash the scale-forming tendency is increased because the concen-
tration of sodium fluosilicate is increased. Neutralization with ammonia
is generally preferred because ammonium fluosilicate is more soluble than
the sodium and potassium salts. With stainless steel construction, neu-
tralization of the water is not required. The solubility of the fluo-
silicates is increased greater in acid solution than it is in neutralized
solution. Nevertheless, if the recirculating condenser water were recycled
indefinitely it would accumulate suspended solids and the viscosity would
increase to the point that it would become difficult to pump, the spray
nozzles would clog, and the system would loose its effectiveness for
cooling the furnace gas.
The condenser water can be clarified and recycled to the condensing
system. The elemental phosphorus content of the water is reduced from
1,770 ppm to 120 ppm by clarification. However, fluosilicates will
accumulate and form scales unless some of the clarified water is replaced
with fresh water. When condenser water is neutralized with ammonia to a
pH of 5.5 to 6.0, about 1,300 gallons of water must be bled off per ton of
phosphorus produced. The bleedoff rate is greater when soda ash is the
neutralizing agent and less with acid condenser water. The elemental
phosphorus content of the clarified water still exceeds the concentration
that can be safely discharged by several orders of magnitude.
Phosphorus Mud or Sludge
A colloidal mixture of dust and phosphorus is collected in the condenser
sump. The phosphorus sludge from the sump is stored in tanks to allow the
high quality phosphorus to settle out. The resulting sludge may be centri-
fuged or filtered to remove more of the phosphorus. ,The sludge may be dis-
tilled to remove even more of the phosphorus.
Slag Ojnenching
Although it is almost always evaporated and not discharged, slag quenching
water is of special concern due to the presence of uranium and its degradation
products in phosphate rock. These, along with most of the fluorine and a
102
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small quantity of the phosphate in the original rock, are concentrated in the
slag. Fluoride and sulfate concentrations averaging 170 and 1,000 mg/1 re-
spectively may be found in the quenching water (USEPA 1973a). Concentrations
of radioactive substances in quenching water are not likely to be high; how-
ever, the possibility exists that some radioactive substances may be picked up
during slag quenching.
Cooling Water
Non-contact cooling water constitutes the largest water use in the phos-
phorus production process. It remains relatively uncontaminated, however,
unless leaks or breaks develop in the system.
Typical raw wastewater characteristics for phosphorus producing facili-
ties are presented in Table 17.
2.1.2.2 Phosphorus Consuming (Subcategory B)
No process wastewater is generated by the various manufacturing processes
in the phosphorus consuming subcategory. However, contaminated water may
result from other plant operations as indicated below:
• Phosphorus transportation and storage.
• Wet scrubbing of tail gases.
• Equipment cleaning.
• Leaks and spills.
Water contaminated with elemental phosphorus (phossy water) may be en-
countered in the waste stream of a phosphorus consuming operation due to
spills or emergency conditions requiring a reactor dump. Due to its density
and extreme reactivity (autoignition at 93° C), phosphorus settles into low
spots in the sewer system and is dangerous to remove.
Hydrolysis of tail gases from the manufacture of phosphoric acid, phos-
phorus pentasulfide, phosphorus trichloride, and phosphorus oxychloride intro-
duces phosphoric, sulfuric, and hydrochloric acid into the waste streams.
Equipment cleaning may pick up reaction residues containing acid, phosphorus,
103
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Table 17. Water use and. process waste generation for major
operations in the phosphorus production subcategory.
Phosphorus
Calciner Condenser
Scrubber Plus other
Liquor Phossy Water
Waste water Quantity,
1/kkq 300,000
qal/ton 72,000
Raw Waste Load,
kq/kkq
TSS
P4
P04
SOI
F
Total Acidity
Total Alkalinity
Raw Waste Load,
Ib/ton
TSS
pa
PO4
SO4
F
Total Acidity
Total Alkalinity
Concentrations, mq/1
TSS
P4
PO4
S04
F ~"
Total Acidity
Total Alkalinity
8.5
2
36
22
60
17
V
4
72
44
120
28
»
7
120
73
200
100,000
24,000
13.5
9
22
27
27
18
44
54
135
90
220
270
Slaq
Quenchinq
Water
25,000
6,000
20.5
1
75
4.5
5.5
41
2
150
9
11
820
40
3,000
180
220
Composite
Waste
425,000
102,000
42.5
9
25
111
53.5
54.5
85
18
50
222
107
109
100
21
59
260
126
128
Note: Wastewater quantities and constituent concentrations are highly
variable, depending upon degree of recirculation, but the raw
waste loads should be representative.
Source: US Environmental Protection Agency. 1973a. Development document
for proposed effluent limitations guidelines and new source perfor-
mance standards for the phosphorus-derived chemicals segment of the
phosphate manufacturing point source category. Office of Air and
Water Programs, Washington DC:, 159 p.
104
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carbon, iron, sulfur, chlorine, and arsenic compounds. However, most of these
residues are removed as a solid waste rather than in the aqueous waste stream.
Typical raw wastewater characteristics for phosphorus consuming operations are
presented in Table 18.
2.1.2.3 Phosphate Chemicals (Subcategory C)
Contaminated wastewater is generated by the following sources during
manufacture of phosphate chemicals (USEPA 1973a):
• Wet scrubbing of product fines.
• Filtrate from dewatering of food grade calcium phosphates.
• Leaks, spills, and equipment cleaning.
• Water softening.
• Defluorination of wet process phosphoric acid.
Finely divided particles of product from the drying operations are re-
moved by wet scrubbing. Phosphoric acid mists also may be introduced into the
wastewater stream from emission control systems. An excess of process water
is used for the manufacture of dicalcium phosphate. The product slurry is
dewatered by filtration or centrifugation prior to drying, which leaves a con-
taminated filtrate or centrate. Makeup water for the neutralization step
requires softening, which produces a wastewater stream from regeneration of
the softener. Leaks, spills, and equipment cleaning also may contribute raw
material and product contaminants to the wastewater stream. When non-food
grade calcium phosphates are produced, an additional wastestream is created
from the defluorination of "wet process" phosphoric acid. This is discussed
under Subcategory E. Typical raw wastewater characteristics from production
of phosphate chemicals are presented in Table 19.
2.1.2.4 Defluorinated Phosphate Rock Subcategory (D)
Wastewater is generated during def luorination of phosphate rock from the
following sources (USEPA 1976a):
105
-------
o
CT>
Table 18. Water use and process waste generation for production
of major products of the phosphorus consuming subcategory.
Water or Waste Load Product
Phosphoric
Ac-id ("dry process")
Process Water Consumed
1/kkg Pdt.
gal/ ton Pdt.
Process Water Wasted: 1/kkg Pdt
gal/ ton Pdt.
Cooling Water Used: 1/kkg Pdt.
gal/ ton Pdt.
Phossy Water: P, cone, ppm
1/kkg P, consumed
kg/P, /kRg P, consumed
gal/ton P, consumed
Ib/ton P, consumed
Raw Waste Load, kg/kkg Pdt:
HC1
H SO
H0P00 + H0PO,
33 34
Raw Waste Load, Ib/ton Pdt.
HC1
H0SO,
2 3
Concentrations, mg/1: HC1
H SO
H.PO. + H PO,.
380
92
__
—
91,000
22,000
1,700
580
1
140
2
—
__
1
—
—
2
__
__
High
Phosphorus
Pentoxide
P2°5
~™~"
500
120
29,000
7,000
1,700
580
1
140
2
—
— _
0.25
——
—
0.5
—
""•""
470
Phosphorus
Pentasulfide
P2S5
30,000
7,200
16,600
4,000
1,700
580
1
140
2
— —
1
0.5
.-_
2
1
—
34
17
Phosphorus
Trichloride
3
5,000
1,200
54,000
13,000
1,700
580
1
140
2
3
—
2.5
6
— —
5
600
__
500
Phosphorus
Oxy chloride
poci3
~
2,500
600
50,000
12,000
—
—
^^
™*~
2
— _
0.5
4
— —
1
800
— —
200
'33
Source: U.S. Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus-derived
chemicals segment of the phosphate manufacturing point source category. Office of Air and
Water Programs, Washington DC, 159 p.
-------
Table 19. Water use and process waste generation for major
products of the phosphate chemicals subcategory.
Process Water Wasted:
1/kkg Pdt.
gal/ton Pdt.
Raw Waste Load,
TSS
Dissolved P04
HF, H2S1F6, H2S101
Raw Waste Load,
Ib/ton Pdt:
TSS
Dissolved P4_
HF, H2_SiF6_, H2Si0.3
Concentrations, mg/1:
TSS
Dissolved P04^
HF, H2SiF6_, H2SiO_3
TDS, mg/1
Sodium
Tripoly-
Phosphate
0
0
Food Grade
Calcium Phosphates
Particulate
Dewatering Scrubbing
2,100
500
50
15
100
30
24,000
7,000
7,000
2,100
500
50
15
100
30
24,000
7,000
7,000
Animal Feed
Calcium Phosphate
Acid Deflu- Particulate
orination Scrubbing
6,300
1,500
12
24
1,900
1,900
420
100
225
4
45
8
54,000
7,000
7,000
Source: U.S. Environmental Protection Agency. 1973a. Development document for proposed
effluent limitations guidelines and new source performance standards for the
phosphorus-derived chemicals segment of the phosphate manufacturing point source
category. Office of Air and Water Programs, Washington DC, 159 p.
-------
« Wet scrubbing of particulates and stack gases.
• Quenching water.
• Leaks and spills.
Particulates from handling of raw materials and hydrofluoric acid from
hydrolysis of silicon fluoride in the tail gas are introduced to the waste-
water stream by wet scrubbing. All process related water as well as cooling
water and runoff, in many cases, is routed through a cooling/recirculation
pond. Recirculated scrubber water is typically neutralized with lime before
being returned to the plant from the recirculation pond. Solubilized tri-
calcium phosphate may also be picked up in the wastewater stream if water is
used for quenching the def luorinated rock. Leaks, spills, and yard runoff
also are sources of contaminated wastewater. Typical water use and raw waste-
water characteristics from production of def luorinated phosphate rock are
presented in Table 20.
2.1.2.5 Def luorinated Phosphoric Acid (Subcategory E)
Wastewater is generated during the def luorination of phosphoric acid from
the following sources (USEPA 1976a):
e Wet scrubbing of stack and tail gases.
e Leaks, spills, and equipment cleaning.
Approximately 12 kg of fluosilicic (E^iF ) , hydrofluoric (HF) , and
silicic acid (H SiO ) per kkg of def luorinated phosphoric acid are dissolved
in the wastewater stream from emission control equipment (USEPA 1973a).
Phosphoric and sulfuric acids may also be entrained by the emission control
equipment during the def luorination process (USEPA 1976a). A small amount of
wastewater is also generated by leaks, spills, and equipment maintenance. It
should be kept in mind that all wastewater from this operation is recycled.
Sample raw wastewater characteristics for this process are presented in Table 21.
108
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Table 20. Water use and process waste generation for
the defluorinated phosphate rock subcategory.
Total Process Water
Makeup Water Required
Raw Waste Load
PH
Total suspended solids
Total Solids
Chloride (Cl)
Sulfate (S04)
Calcium (Ca)
Magnesium (Mg)
Aluminum (Al)
Iron (Fe)
Fluorine (F)
Arsenic (As)
Zinc (Zn)
Phosphorus (P)
BOD5
COD
Color
Turbidity
45,894 1/kkg
(11,000 gal/ton)
877 1/kkg
(210 gal/ton)
Concentration
1,65
(TSS) 16.00 mg/1
2,267.00 mg/1
101.00 mg/1
350.00 mg/1
40.00 mg/1
12.00 mg/1
58.00 mg/1
8.30 mg/1
1,930.00 mg/1
0.38 mg/1
5.20 mg/1
600.00 mg/1
3.00 mg/1
48.00 mg/1
#120 (after filter)
45.00 Jackson
Candle Units
Most defluorinated phosphate rock facilities operate on a complete recycle
basis with a net consumption of water.
Source: U.S. Environmental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate
manufacturing point source category. Office of Water and Hazardous
Materials, Washington DC, 105 p.
109
-------
Table 21. Water use and process waste generation for
the defluorinated phosphoric acid subcategory.
Total Process Water
Vacuum Evaporation Process
Submerged Combustion
Non-process water
Raw Waste
pH
Total suspended Solids
Total solids
Chloride (Cl)
Sulfate (804)
Calcium (Ca)
Magn es ium (Mg)
Aluminum (Al)
Iron (Fe)
Fluorine (F)
Arsenic (As)
Zinc (Zn)
Total Phosphorus (P)
BOD5
COD
Color
Turbidity
70,510 1/kkg
(16,900 gal/ton)
18,024 1/kkg
(4,320 gal/ton)
43 1/kkg
(14 gal/ton)
Concentration
1.29
30.00 mg/1
28,810.00 mg/1
65.00 mg/1
4,770.000 mg/1
1,700.00 mg/1
106.00 mg/1
260.00 mg/1
180.00 mg/1
967.00 mg/1
0.83 mg/1
5.30 mg/1
5,590.00 mg/1
15.00 mg/1
306.00 mg/1 2
#120 (after filter)
45 Jackson
Candle Units
Most phosphoric acid, defluorination facilities operate on a complete recycle
basis.
2
Unit of color - potassium chloroplatinate.
Source: U.S. Environmental Protection Agency. 1976a. Development document
for effluent limitations guidelines and new source performance standards
for the other non-fertilizer phosphate chemicals segment of the phosphate
manufacturing point source category. Office of Water and Hazardous
Materials, Washington DC, 105 p.
110
-------
2.1.2.6 Sodium Phosphates (Subcategory F)
Contaminated wastewater Is generated by the following sources during
manufacture of sodium phosphates from "wet process" phosphoric acid:
• Calciner and phosphoric acid emission controls.
• Neutralization precipitation and filtration operations.
• Leaks, spills, and equipment cleaning.
If the "wet process" phosphoric acid used in the manufacture of sodium
phosphates is produced on site, the phosphate rock is calcined to remove
organic impurities. Emission control equipment or the calciner and acidu-
lation equipment will introduce solids as well as acidic phosphorus, sulfur,
and fluorine compounds into the wastewater stream. Sodium phosphate solutions
are treated several times during the purification process to remove various
impurities such as fluorine, arsenic, iron, aluminum, and silica present in
the "wet process" acid. The precipitated impurities are removed at several
steps in the process and the filtrates or centrates are discharged to the
wastewater stream. A small amount of wastewater may also be generated by
leaks, spills, and general equipment maintenance. Raw wastewater charac-
teristics typical of sodium phosphate manufacture from "wet process" phos-
phoric acid are presented in Table 22. This wastewater mast be treated before
being discharged.
2.1.3 Solid Waste Characteristics
A variety of solid wastes are generated by non-fertilizer phosphate
manufacturing operations. The most significant sources are slag from phos-
phorus production, process residues and by-products, precipitates from
emission and water pollution control equipment, and general solid wastes from
plant maintenance and bulk materials handling. Some of these solid waste
materials may contain radioactive and toxic substances such as uranium,
radium, and arsenic and are considered hazardous. Due to the potentially
hazardous nature of many of the industry's raw materials and products, the
composition of all waste material must be carefully documented in the BID and
appropriate treatment and disposal measures must be identified.
Ill
-------
Table 22. Water use and process waste generation for
the sodium phosphates subcategory.
Total Water Supply
Effluent Wastewater Discharge
Raw Waste
Parameter
PH
Total Suspended Solids
Total Solids
Chloride (Cl)
Sulfate (SO )
Calcium (CaJ
Fluorine (F)
Total Phosphorus (P)
BOD
9,992 - 12,349 1/kkg
(2,395 - 2,960 gal/ton)
7,600 - 10,000 1/kkg
(1,830 - 2,400 gal/ton)
Temperature
Concentration
7.8
460 mg/1
2,100 mg/1
90 mg/1
240 mg/1
95 mg/1
15.0 mg/1
250 mg/1
31.0 mg/1
55.0 mg/1
78°F
Source: U.S. Environmental Protection Agency. 1976a. Development document for
effluent limitations guidelines and new source performance standards for
the other non-fertilizer phosphate chemicals segment of the phosphate
manufacturing point source category. Office of Water and Hazardous
Materials, Wahington DC, 105 p.
112
-------
Significant aspects of solid waste generation for each process sub-
category are highlighted in the following sections.
2.1.3.1 Phosphorus Production (Subcategory A)
Large quantities of solid waste and by-product materials are produced
during the manufacture of elemental phosphorus as indicated below (USEPA
1973a, Barber 1975):
Solid Waste or By-product /kkg Phosphorus Produced
Slag 8,900 kg/kkg (17,800 Ib/ton)
Ferrophosphorus 300 kg/kkg (600 Ib/ton) (By-product)
Dust 50-125 kg/kkg (250 Ib/ton) (By-product)
Phosphorus sludge 25 kg/kkg ( 50 Ig/ton) (By-product)
Slag is composed primarily of calcium silicate (CaSiCL) with small quantities
of other minerals as follows:
Typical Analysis of Phosphorus Furnace Slag (Barber 1975a)
Percent Concentration
Constituent (Dry Basis) (ppm)
CaO 44. 1
SiO 41.3
A10 8.8
P2°5
2.8
1.2
Na 0 0. 1-0.2
2
MgO 0.1-0.2
MnO 0.1-0.2
S 0.1-0.2
U* - 30-200
Ra* - 3-75
Th* - 10
113
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In the past, furnace slag has been sold as an aggregate or disposed of if no
market could be found for it. Under the new RCRA regulations, however, slag
will be classified as a hazardous waste due to the presence of significant
quantities of radioactive materials and will require special handling and
disposal (40 CFR 261.3). Ferrophosphorus is a valuable by-product consisting
of several iron-phosphorus compounds: Fe , P, Fe P, FeP, and Fep2' It is
carefully handled and sold to users in the metallurgy industry. Dust col-
lected by the electrostatic precipitators is made up of the following ma-
terials (USEPA 1977c).
P205 - 20-40%
K 0 - 12-16%
CaO - 6-16%
SiO - 18-30%
C - 1-4%
F - 1-6%
A small quantity of sludge containing 10% dust, 30% water, and 60% phosphorus
collects in the sump of the phosphorus condenser (USEPA 1973a). Sludge may be
reprocessed to recover or utilize its phosphorus content while dust is oxidized
to eliminate the residual phosphorus.
2.1.3.2 Phosphorus Consuming (Subcategory B)
Solid waste materials are generated as follows by the various processes
producing chemicals from elemental phosphorus (USEPA 1973a):
Process or Product Solid Waste/Unit Weight of Product
Phosphoric acid Arsenic sulfide 0.1 kg/kkg (0.2 Ib/ton)
"dry process" Filter acid 0.75 kg/kkg (1.5 Ib/ton)
P 0 Waste silica from air drying unit
P0S Residue 0.60 kg/kkg (0.3 Ib/ton)
'2 5
PS dust 1 kg/kkg (2 Ib/ton)
Arsenic pentasulfide 0.05 kg/kkg
(0.1 Ib/ton)
114
-------
Arsenic trichloride 0.05 kg/kkg (0.1 Ib/ton)
Still residue 0.05 kg/kkg (0.1 Ib/ton)
^
Still residue 0.05 kg/kkg (0.1 Ib/ton)
Arsenic is present in phosphate rock and is carried over with the phosphorus
in the thermal reduction process. Small amounts of arsenic and product re-
sidues are generated during manufacture of anhydrous phosphorus derivatives.
Although low in volume, these wastes are hazardous and require special
handling.
2.1.3.3 Phosphate Chemicals (Subcategory C)
Very little solid waste is produced by manufacturing processes in this
subcategory. Emissions of product fines from the drying operations generally
are recovered from the scrubber stream and added back to the product line.
Spilled material and floor sweepings are often used for making fertilizers. A
notable exception to this is in the manufacture of food grade calcium phos-
phates where purity requirements prohibit the use of sweepings in the product.
This amounts to approximately 10 kg of lime, grit, and calcium phosphate per
kkg of product (20 Ib/ton) (USEPA 1973a).
2.1.3.4 Defluorinated Phosphate Rock (Subcategory D)
A substantial quantity of solid waste is generated during the defluor-
ination of phosphate rock. Most of the solids accumulate in a clarifier or
the recycle pond due to settling and liming of the wet scrubber water (USEPA
1976a). Most of the precipitates occur in the form of calcium phosphates,
calcium sulfate, and calcium fluoride which is toxic and must be afforded
special handling. Other solid wastes from this subcategory include dust from
bulk materials and general plant waste such as string, bags, and boxes.
2.1.3.5 Defluorinated Phosphoric Acid (Subcategory E)
Solid waste production for defluorinated phosphoric acid operations is
similar to that for def luorinated phosphate rock. The largest source of solid
115
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waste is the liming of the pond wastewater stream prior to discharge to pro-
duce calcium precipitates. If the defluorinated acid process is operated in
conjunction with a "wet process" phosphoric acid plant as is typically the
case, a common recirculation pond may be used to contain both the gypsum
produced from the wet process acid and the calcium precipitates from the
superphosphoric or def luorinated phosphoric acid operation.
2.1.3.6 Sodium Phosphates (Subcategory F)
A number of by-products and solid wastes are produced by the manufacture
of sodium phosphates from "wet process" phosphoric acid as follows (USEPA
1976a):
• Fine solids may be captured during the rock calcining operation.
• Sodium fluosilicate is a by-product of the first neutralization step.
• Arsenic sulfate is precipitated from the acid.
• The second neutralization produces a voluminous sludge containing
iron, aluminum, fluorine, and phosphorus pentoxide which is reclaimed
as a fertilizer by-product.
• Fine solids may be captured during the handling of dry raw materials
and products.
2.2 IMPACTS OF INDUSTRY WASTES
The non-fertilizer phosphate industry generates wastes that would cause
severe, long-lasting impacts if introduced into the environment in the quanti-
ties and concentrations at which they are generated. The potential impacts of
each recognized pollutant on impacted receiving media (i.e. , air, water, land)
should be identified in the EID based on its projected rate of generation and
appropriate treatment. Because the industry generates wastes with relatively
similar properties, the impacts of industry wastes will be discussed according
to the pollutant characteristics rather than according to industry subcate-
gories.
116
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2.2.1 Air Impacts
Operations within this industry may generate emissions of the following
pollutants:
• Fluorine compounds.
• Acid mists.
• Particulates.
• Phosphorus compounds.
Sulfur dioxide and particulates also may be generated from fossil-fueled
calciner or dryer operations associated with several processes. The controls
for the sources, however, can mitigate the impacts of these emissions on air
quality and the environment. The potential impacts of these industry pollut-
ants on human health and the environment are identified in Section 2.2.3.
Because New Source Performance Standards for the industry emissions have
not been promulgated, industry impacts on air quality must be evaluated against
ambient air quality standards. Based on industry emissions, a large new
source facility may have to undergo the full PSD review and permit application
procedure. This must be determined by US EPA and the state on a case by case
basis, based on the estimates developed by the new source applicant in the
BID.
The assessment of air quality impacts for a new source non-fertilizer
phosphate facility may require the following measurements or studies for major
sources such as phosphorus furnaces or phosphate rock defluorination facil-
ities, but less stringent requirements may be applied to minor sources.
• Evaluation of emission rates from all potential contaminant sources
(mobile and stationary) within the facility during its construction
and operation.
• Discussion of the various available and proposed emission control
techniques should describe contingency plans to be used if pollution
control systems malfunction and the associated impacts.
117
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Where reliable representative data are not available, insurance of
accurate measurements of facility performance and emissions, as well
as ambient air quality and meteorology in the vicinity of the proposed
new source facility before and during operation. Long-term air quality
monitoring data may need to be obtained on the site to characterize
existing conditions adequately.
Atmospheric dispersion modeling to evaluate the short- and long-term
effects of facility emissions and other neighboring emission sources
on ambient air quality (cumulative and synergistic effects). A com-
plete discussion of available air quality modeling techniques can
be found in "Guideline on Air Quality Models," EPA-450/2-78-027
(USEPA 1978p) and in Section II.E. of a companion document to this
one, "Environmental Impact Assessment Guidelines For New Source
Fossil-Fueled Steam Electric Generating Stations" (USEPA 1979a).
Potential for atmospheric chemical reactions that may result from
plant emissions and produce new air contaminants.
Discussion of projected ambient air contaminant levels with respect to
Federal, state, and local ambient air standards and PSD increments.
2.2.2 Water Impacts
Many of the processes for the manufacture of phosphorus and non-fertili-
zer phosphate chemicals produce large quantities of highly contaminated
aqueous wastes containing the following pollutants:
• Phosphorus and phosphate compounds.
• Fluorine compounds.
• Suspended solids.
• High acidity (low pH).
Effluent guidelines established for these parameters are discussed in Section
1.5.1.1. Significant concentrations of other pollutants including trace
metals and toxic elements may also be present in industry wastewaters (USEPA
1973a, USEPA 1976a):
• Total dissolved solids.
• Temperature.
118
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• Sulfates.
• Chlorides.
• Cadmium.
• COD.
• Vanadium.
• Arsenic.
• Uranium.
• Radium 226.
These pollutants require monitoring, but specific effluent guidelines have not
been established. The new source applicant's EID should identify sources of
the above and any other pollutants, expected discharge quantities, and effec-
tiveness of proposed treatment technologies in controlling them. The appli-
cant should clearly identify wastewater streams as well as process streams,
because much of the industry's aqueous waste is reclaimed and reused within
production processes and is not discharged to surface waters. The potential
impacts of industry discharges on human health and the environment are iden-
tified in Section 2.2.3.
New source performance standards for the non-fertilizer phosphate industry
generally require "no discharge" of process waste for all subcategories except
production of sodium phosphates from "wet process" phosphoric acid. However,
wastewater from such sources as non-point plant runoff and non-contact process
equipment cooling may be discharged. In addition, provisions are made for
infrequent discharges of process wastewater from the recycle/reuse ponds
typically used by defluorinated phosphate rock and phosphoric acid facilities
as described in Section 1.5.1.1.
The assessment of water resource impacts for a new source non-fertilizer
phosphate facility will require an analysis to predict the potential effects
of any industry discharges on surface and groundwater resources. Such an
analysis will probably require the use of mathematical models to predict
in-stream concentrations. Two of the most widely used and accepted models
are:
119
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• DOSAG (and its modifications).
• QUAL series of models developed by the Texas Water Development Board
and modified by Water Resources Engineers, Inc.
These are steady-state, one-dimensional models useful in evaluating stream
impacts. While these models are most often used to predict the decay of
in-stream dissolved oxygen concentrations from discharges of organic wastes,
they are also useful in predicting the fate of conservative type pollutants
that are found in the phosphate industry's waste. The data required for these
models include:
DOSAG-I
• Flow rates for system inputs and withdrawals.
• Information on reaches, junctions, stretches, headwater reaches.
• Reaction coefficients.
• Concentration of inflows.
• Stream temperature.
QUAL-II
• Identification and description of stream reaches.
• Initial conditions.
• Hydraulic coefficients for determining velocity and depth.
• Reaction coefficients.
• Headwater data.
• Waste loadings and runoff conditions.
• If temperature is to be modeled, also requires sky cover, wet bulb/dry
bulb air temperature, atmospheric pressure, wind speed, evaporation
coefficient, and basin elevation.
Other models are available for non-steady state conditions and two dimensions,
as required for modeling estuaries, including:
120
-------
• RBCEIV and RECEIV II, developed by Raytheon for the USEPA Water Plan-
ning Division.
These models can evaluate both conservative (e.g., dissolved solids, metals)
and non-conservative materials subject to first order reaction kinetics (e.g.,
BOD, DO). The data required as input to both of these models include:
• Tidal variations.
• Water surface elevations, area, and depth.
• Bottom roughness coefficients.
• Meteorological data, including rainfall, evaporation, and wind velo-
city and direction.
• Downstream boundary conditions.
• Junction and channel data.
• Water temperature.
• Initial pollutant concentrations.
• Inflow data.
• Oxygen saturation and reaeration coefficients.
In addition, there are many available water quality models that were
developed in association with NPDES activities and the need for optimization of
waste load schemes for an entire river basin.
2.2.3 Biological Impacts
The biological environment may be affected by certain pollutants from the
various processes within the industry.
2.2.3.1 Human Health Impacts
The following listings summarize documented effects of primary*and secondary
pollutants on human health (USEPA 1974a).
121
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Fluorides
Fluorides are rare in natural surface waters, but may occur in detri-
mental concentrations in groundwaters. Ingestion of fluoride compounds can
result in:
• Lowering of tooth decay in children - 0.8 to 1.5 mg/1 fluoride ion in
drinking water.
• Mottling of tooth enamel in children, in quantities (varying with
individuals) above 0.9 - 1.0 mg/1.
• Endemic cumulative fluorosis and skeletal effects in adults, in
(varying) quantities above 3 or 4 mg/1.
• Death, or severe symptoms, in doses of 250-450 mg. Severe symptoms
are "diffuse abdominal pain; diarrhea and vomiting; excessive saliva-
tion, thirst, and perspiration; and painful spasms of the limbs"
(National Academy of Sciences 1971).
Experts disagree on how much airborne fluoride is dangerous, but believe that
levels equivalent to workplace heavy exposure would be required. Apparently
airborne fluorides are largely retained when ingested, but the dangers of
airborne fluorides include resettling and transport into drinking water or
vegetable food supplies (National Academy of Sciences 1971).
Total Suspended Solids (TSS)
Suspended solids include both organic and inorganic materials. Inorganic
components include sand, silt, clay, fine raw materials and products such as
phosphate rock particles, and certain insoluble products. The organic frac-
tion includes such materials as grease, oil, tar, fats, various fibers, sawdust,
and various materials from sewers. These solids may settle out rapidly and
bottom deposits are often a mixture of both organic and inorganic solids.
Besides the aesthetic displeasure associated with turbid waters or with bottom
sludges when the suspended solids settle out, they can cause untreated water
to be unpa^table and suspended particles can absorb pesticide and other
chemical impurities that might not be transported otherwise in the water.
122
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pH (Acidity/Alkalinity)
pH is a logarithmic expression of the concentration of hydrogen ions. At
pH 7, hydrogen and hydroxyl (OH~) ion concentrations in solution are essen-
tially equal and the water is neutral. Lower pH values indicate acidity and
higher values indicate alkalinity, in a nonlinear relationship. Extremes of
pH are harmful or fatal to aquatic life, and dangerous to humans, but human
contact with water of extremely high or low pH is usually avoidable:
• A deviation of 0.1 pH unit from 7.0 may result in eye irritation to
swimmers; appreciable deviations cause severe pain.
• By effects on plumbing fixtures, water lines, and water works struc-
tures, pH below 6.0 can cause high levels of iron, zinc, copper,
cadmium, and lead in drinking water.
Total Dissolved Solids (IDS)
In natural waters the dissolved solids consist mainly of carbonates,
chlorides, sulfates, phosphates, and possibly nitrates of calcium, magnesium,
sodium, and potassium, with traces of iron, manganese, and other substances.
Although IDS levels above 500 mg/1 in drinking water are progressively unpala-
table, levels of:
• 4,000 mg/1 are unfit for human use, except in hot climates where the
salt content may be tolerable.
• 5,000 mg/1 in drinking water causes bladder and intestinal irritation.
Cadmium
Cadmium in drinking water supplies is extremely hazardous to humans, and
conventional treatment as practiced in the United States does not remove it.
Cadmium is cumulative in the liver, kidneys, pancreas, and thyroid of humans
and other animals. Human health effects include:
• A severe bone and kidney syndrome reported in Japan, from ingestion of
as little as 600 mg/day.
123
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• As a cumulative toxicant, cadmium causes insidious chronic poisoning
in mammals and also fish and probably other animals.
• Organic compounds of cadmium may cause mutagenic or teratogenic (mon-
strous deformities) effects.
Phosphorus
Elemental phosphorus exists in three allotropic forms: white, red, and
black (CRC 1967). The white form produced by the phosphate industry is
highly reactive and is never found free in nature. It autoignites on contact
with air and will cause severe burns if handled.
• Ingested, a fatal dose is 50 mg.
3
• The maximum recommended allowable concentration in air is 0.1 mg/m .
Arsenic
Arsenic is found to a small extent in nature in the elemental form. It
occurs mostly as arsenites of metals or as mineral pyrites. If ingested,
arsenic compounds can be a sudden or a cumulative poison:
100 mg - severe poisoning.
• 130 mg - possibly fatal poisoning.
• Smaller doses can accumulate and be fatal - arsenic accumulates in the
body faster than it is excreted.
Uranium and Radium 226
Radioactive materials present a host of hazards through direct exposure
or by accumulation in the biological ecosystem. The effects of these pollu-
tants have been identified as follows (USEPA 1974a):
"Ionizing radiation, when absorbed in living tissue in quantities sub-
stantially above that of natural background levels, is recognized as in-
jurious. It is necessary, therefore, to prevent excessive levels of
radiation from reaching any living organism. Beyond the obvious fact
that radioactive wastes emit ionizing radiation, they are also similar in
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many respects to other chemical wastes. Man's senses cannot detect
radiation unless it is present in massive amounts.
"Radium-226 is one of the most hazardous radioisotopes of the uranium
decay scheme, when present in water. The human body preferentially
utilizes radium in lieu of calcium when present in food or drink. Plants
and animals concentrate radium, leading to a multiplier effect up the
food web.
"Radium-226 decays by alpha emission into radon-222, a radioactive gas
with a half life of 3.8 days. The decay products of radon-222, in turn,
are particulates which can be absorbed onto respirable particles of dust.
Radon and its decay products have short half lives and have been implicated
in an increased incidence of lung cancer in those workers exposed to high
levels (Bureau of Mines 1971). Heating or grinding of phosphate rock can
liberate radon and its progeny to the surrounding atmosphere."
It may be added that ionized, airborne radon progeny attach readily to
small dust particles that are easily lodged in the upper respiratory tract.
Once there, their short half-lives lead to decay before they can be cleared
from the lungs (Schiager 1978). The radioactive decay series for uranium and
its decay products is presented in Table 23.
Guidelines for radiation exposure cannot be defined in terms of threshold
values but it is agreed that exposure to radiation should be held to a minimum
and should be encountered at all only when the necessity is justified.
2.2.3.2 Ecological and Environmental Impacts
The effects of pollutants generated by the industry may have the follow-
ing impacts on the environment.
Phosphorus
Increases of phosphorus in surface waters have been linked to a wide
range of direct and indirect ecological disruptions. These include:
• Proliferation of nuisance water plants.
• Accelerated eutrophication of water bodies.
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Table 23. The radioactive decay series for uranium 238.
Nuclides
U-238
Th-Pa-U-234
Th-230
Ra-226
Rn-222
Po-218
Pb-Bi-Po-214
Pb-Bi-Po-210
Pb-206
Half-Life
4.51 X 109 yr
2.47 X 105 yr
8.00 X 104 yr
1.60 X 103 yr
3.82 day
3.05 rain
46.5 min
21 yr
Specific
Activity
(Ci/G)
3.3 X 10-7
1.9 X 10~2
0.99
1.5 X 105
2.8 X 108
Decay Energies
Q (Mev) Q (Mev)
Beta Alpha
4.27
2.48 4.86
4.77
4.87
5.59
6.11
4.32 7.84
1.22 5.41
Notes
Parent
Bone Seeker
Noble Gas
Short-Li ved
Radon Progeny
Stable
Series Totals:
8.02 + 43.7
51.72
Source: Schiager, Keith J. 1978. Radiation - a perspective. J!n Proceedings of
an Environmental Symposium, The Fertilizer Institute, New Orleans LA,
6, 7, and 8 March 1978.
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• Bioaccumulation and toxicity (of elemental P) for marine fish.
The plant overgrowth and eutrophication aspect of the effe.ctfj of increased
phosphorus availability have specific negative effects:
• Dangerous to swimming, boating, and water skiing.
• Interferes physically with sport fishing.
• Interferes with development of fish populations.
• Vile stenches and tastes associated with water.
• Ineffectuates standard water treatment processes.
• Aesthetic effects.
- reduced resort trade
- lowered property values
• Contact rashes to human skin.
• Improved breeding environment for flies.
Fluorides
The effects of fluorides on the animal environment are relat:eri to vegeta-
tive accumulations and surface water contamination. Effects include:
• Chronic fluoride poisoning of livestock when water contains 10-15 mg/1.
• Shorter-term fluoride poisoning of livestock when water nation contains
30-50 mg/1.
• Toxicity to fish in concentrations above 1.5 mg/1.
The effects of acute poisoning in livestock include (National V\cademy of
Sciences 1974):
• Res tie s su es s.
t Stiffness.
• Anorexia.
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• Reduced mill*, production.
• Nausea and 'vomiting.
• Incontinence of urine and feces.
• Necrosis o,f mucosa of digestive tract.
• Weakness and severe depression.
• Cardiac fad.lure.
Chronic toxicosis is not always distinguishable from acute symptoms, but also
iresults in (National Academy of Sciences 1974):
• Debilitati.ng osteoarthritis and lameness.
• Dental enamel lesions.
Although milk production in livestock is affected, fluoride transfer to the
milk i,s ve;ry slight. With poultry, however, a greater concentration of
fluoride does show up in the eggs.
juispended Solids
In the aquatic environment suspended solids cause a number of problems:
* Tui'bid waters decrease photosynthetic activity of aquatic plants.
« Sett ".led solids on stream or lake beds
- eliminate normal benthie species;
- reduce dissolved oxygen available in the area;
- stimulate populations of benthic sludgeworms and associated
organisms.
pH E'ffects
Extremes of rapid fluctuations in pH level can create problems to aquatic
organisms induct ing:
e Rapid dea th and associated rotting of fishkills, and generation of
algal
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Increased toxicity of other dissolved substances in the water, such as
- matalocyanide
- ammonia.
Dissolved Solids
Dissolved solids levels in water affect aquatic organisms and in general
make water troublesome for industrial uses and for irrigation. Effects on the
ecosystem include:
• Loss of habitat at 5,000 - 10,000 mg/1 for species of freshwater fish.
• Death to freshwater fish when salinity is changed rapidly.
• Increased toxicity of heavy metals and organic compounds to fish
and other aquatic life.
Temperature
Temperature is one of the most important and influential ecological water
quality characteristics. Temperature determines those species that may be
present; activates the hatching of young, regulates their activity, and stimu-
lates or suppresses their growth and development; attracts, and may kill when
the water becomes too hot or becomes chilled too suddenly. Colder water
generally suppresses development. Warmer water generally accelerates activity
and may be a primary cause of aquatic plant nuisances when other environmental
factors are suitable.
Temperature is a prime regulator of natural processes within the water
environment. It governs physiological functions in organisms and, acting
directly or indirectly in combination with other water quality constituents,
it affects aquatic life with each change. These effects include chemical
reaction rates, enzymatic functions, molecular movements, and molecular ex-
changes between membranes within and between the physiological systems and the
organs of an animal.
The specific mechanisms and results of elevated temperature extremes
include:
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• Higher chemical reaction rates.
• Decreased DO.
• Increased bacteria production.
• Spawning perturbations.
• Increases in predator, parasite, and competing species populations.
• Fish food alterations.
• Increased synergistic reactivity of pollutants.
• Increase in green and blue-green algae and decrease in number and
distribution of benthic organisms (food chain disruption).
• In the presence of sludge, increased gas formation and multiplication
of saprophytes and fungi.
Cadmium
Cadmium pollution problems are derived from direct toxicity and synergis-
tic actions with other metals. These include:
• Acute and chronic poisoning of aquatic and terrestrial species.
• Synergistically increases toxicity of copper and zinc
• Concentration of cadmium in marine organisms, particularly molluscs.
Chromium
The toxicity of chromium salts toward aquatic life varies widely with the
species, temperature, pH, valence of the chromium, and synergistic or antago-
nistic effects, especially that of hardness. Fish are relatively tolerant of
chromium salts, but fish food organisms and other lower forms of aquatic life
are extremely sensitive. Chromium also inhibits the growth of algae.
In some agricultural crops, chromium can cause reduced growth or death of
the crop. Adverse effects of low concentrations of chromium on corn, tobacco,
and sugar beets have been documented.
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Zinc
Zinc exhibits toxic effects on both freshwater and saltwater aquatic
organisms. The following effects have been observed:
• Concentrations of zinc in the range of 0.1 to 1.0 mg/1 in soft water
is lethal to fish.
• The presence of copper in the water increases the toxicity of zinc.
• The presence of calcium or hardness decreases the relative toxicity of
zinc.
• Invertebrate marine organisms are very sensitive to zinc. As little
as 30 ug/1 retards growth of the sea urchin.
• Long-term sub-lethal effects have been observed in the marine envi-
ronment.
• Zinc sulfate is lethal to many plants.
Vanadium
Vanadium and its compounds cause physiological disorders in mammals.
The major concern, however, is for effects in the aquatic ecosystem. The
following effects on aquatic species have been observed:
• The toxicity of vanadium varies inversely with the hardness of the
water.
• The common bluegill fish can be killed by 6 ppm in soft water and by
55 ppm in hard water.
• Other fish are similarly affected.
Arsenic
Arsenic ions and compounds can be lethal and harmful in both water and
soil environments. Typical effects are:
• An accumulative poison in oysters and shellfish.
• Arsenic trioxide is extremely harmful to some fish species (5.3 mg/1
for 8 days).
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• Arsenic trioxide is lethal to missels at 16 mg/1 in 3 to 16 days.
• Certain food crops are made unmarketable grown in water with 1 mg/1 of
arsenic
• Soils containing 4-12 mg/kg are unproductive.
Uranium and Radium 226
The life spans of many animal species are not long enough to show adverse
effects of low level radiation, but radionuclides tend to be accumulated in
the food chain so that the greatest danger is to species high on the food
chain. The potential effects for human health, or for economic disaster, are
severe when food species accumulate potentially dangerous levels of radio-
nuclides (resulting in a ban on production if controls are enforced). The
most significant pathway to humans is through the accumulative effects on fish
and shellfish, or through drinking water.
All of the factors noted above can affect the quantity and quality of
aquatic resources. Shifts in these resources caused by pollution will alter .
aquatic communities, but the magnitude and overall significance of such changes
will vary according to their specific agent. For example, industrial phosphate
wastes can stimulate growth of algae. However, such an increase in productivity
(eutrophication) leads to an overall decrease in water quality and species
diversity in the system as shown by many studies on lakes.
The effects of pollutional stress may be both immediate and delayed.
Organisms may be killed outright by the altered conditions of their habitat.
For example, fish kills can result when pH is reduced drastically or when
respiration is impaired because gill membranes are clogged by sediment and
suspended solids. A more subtle impact results from sub-lethal stress effects.
Weakened organisms may be unable to function efficiently and may succumb to
disease. The ability to avoid predators may be reduced, their reproduction
rates may be decreased, and their usefulness as a food supply diminished due
to concentration of toxic substances. Thus, both the acute and chronic effects
of pollution act to destabilize natural communities.
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2.3 OTHER INDUSTRY IMPACTS
The phosphate chemical industry can have significant impacts on public
health and the ecology if pollutants from the industry processes are uncon-
trolled. The industry can have other impacts that are not directly generated
by the chemical process. Wastes from the industry can also affect public
utilities and other pollution control systems. These potential impacts must
be addressed in the EID.
2.3.1 Aesthetics
If included as a part of an integrated phosphate complex, a new source
non-fertilizer phosphate facility could be associated with large and complex
operations occupying hundreds of acres. Rock storage and handling areas, haul
roads, rock conveyors, recycle ponds, solid waste storage piles, dust, ero-
sion, and sediment-laden streams can be aesthetically displeasing. Particu-
larly in rural and suburban areas, phosphate chemical manufacturing (and
possible associated mining activity) can represent a noticeable intrusion on
the landscape. Measures to minimize the aesthetic impacts of the project must
be developed during site selection, plant planning design, and construction.
The applicant should consider the following factors where feasible to reduce
potential aesthetic impacts: /
• Existing Nature of the Area. The topography and major land uses in
the area of the candidate sites are important. Topographic conditions
and existing trees and vegetational visual barriers can be used to
screen the operation from view. A lack of topographic relief and
vegetation would require other means of minimizing impact, such as
regrading or planting of vegetation buffers.
• Proximity of Parks and Other Areas Where People Congregate for
Recreation and Other Activities. The location of public use areas
should be mapped and presented in the EID. Representative views of
the plant site from observation points should be described. The
visual effects on these recreational areas should be described in the
EID in order to develop the appropriate mitigation measures.
• Transportation System. The visual impact of new access roads, rail
lines, haul roads, barge docking, pipelines, and storage facilities on
the landscape or waterfront should be considered. Locations, con-
struction methods and materials, and maintenance should be specified.
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2.3.2 Noise
The major sources of noise associated with phosphate chemical manufactur-
ing include:
• Plant construction equipment (bulldozers, graders).
• Raw material transport systems (haul roads, conveyors, loading
dozers) .
• Rock grinding and handling.
• Boilers and steam venting.
® Product transport systems (truck, railroad, and barge loading).
• Air pollution control equipment.
These activities can create significant ambient noise levels that may
decrease with increasing distance from the site. Noise can be attenuated
partially with thick stands of vegetation or other barriers (Bolt Beranek &
Newman 1973). Even at distances of 1,500 to 2,000 feet the increases in noise
levels due to manufacturing activities still may be noticeable. Sensitive
noise receptors within a half mile of a major manufacturing facility are of
potential concern and should be documented in the BID.
Noise also can create serious health hazards for exposed workers; there-
fore, the necessary source and operational control methods should be employed.
Such measures include:
9 Enclosed process machinery.
« Mufflers on engines.
• Lined ducts.
• Partial barriers.
• Vibration insulation.
• Imposed speed limits on vehicles.
• Scheduled equipment operations and maintenance.
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The USEPA has recommended a maximum 75 dBA, 8-hour exposure level to
protect workers from loss of hearing. A maximum 55 dBA background exposure
level is recommended to avoid annoyance during outdoor activity (USEPA 1974c).
A suitable methodology to evaluate noise generated from a proposed new source
facility would require the applicant to:
• Identify all noise-sensitive land uses and activities adjoining the
proposed plant site (e.g., schools, parks, hospitals, and businesses
in the urban environment; homes and wildlife sanctuaries in the rural
enviro nment).
• Measure the existing ambient noise levels of the areas adjoining the
site.
• Identify existing noise sources in the general area, such as traffic,
aircraft flyover, and other industry.
• Determine whether there are any state or local noise regulations that
apply to the site.
• Calculate the noise level of the phosphate facility processes, and
compare that value with the existing area noise levels and the appli-
cable noise regulations.
• Assess the impact of the operations's noise and, if required, deter-
mine noise abatement measures to minimize the impact (e.g., quieter
equipment, noise barriers, improved maintenance schedules).
2.3.3 Energy
Several of the products of the non-fertilizer phosphate industry, partic-
ularly elemental phosphorus, have high energy requirements as indicated in
Table 24. Increasing costs are forcing the industry to ever larger facilities
in order to achieve an acceptable economy of scale (USEPA 1973a). A new
source phosphorus producer or def luorinated phosphate rock producer could tax
local electric energy or natural gas supplies in some areas with their large
energy requirements. Such potential impacts as well as potential energy
conservation measures would be evaluated in any preliminary industrial plan-
ning report but potential conservation measures should be evaluated as well.
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Table 24. Process energy requirements of phosphorus
and phosphate chemical manufacturing operations.
Product
Phosphorus (P.)
Phosphoric acid (H PO )
Energy Requirements
Electricity
12,500 kwh/ton
60 kwh/ton P 0
Phosphorus pentoxide (P 0 )
Phosphorus pentasulfide (P9SS)
Phosphorus trichloride (PCI )
Phosphorus oxychloride (POC1 )
85 kwh/ton
7.8 kwh/ton
24.5 kwh/ton
25 kwh/ton
Dicalcium phosphate (feed grade) 18.2 kwh/ton
Dicalcium phosphate dihydrate 37 kwh/ton
Defluorinated phosphate rock - -
Defluorinated phosphoric acid 70 kwh/ton
Sodium phosphates (wet acid) 38.9 kwh/ton
Fuel
12,000 ft natural gas/ton
80 Ibs steam/ton
760 Ibs steam/ton
730 Ibs steam/ton
100,000 BTU/ton
1,100,000 BTU/ton
3
5,000 ft natural/gas/ton
3
1,800 ft natural gas/ton
13,900,000 BTU/ton
Sources;.: US Environmental Protection Agency. 1973b. Economic analysis of
proposed effluent guidelines, industrial phosphate industry.
Office of Planning and Evaluation, Washington DC.
US Environmental Protection Agency. 1974b. Economic analysis of
proposed effluent guidelines, non-fertilizer phosphate manufacturing
industry. Office of Planning and Evaluation, Washington DC.
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At a minimum, the applicant should provide the following information in
the BID:
• Total external energy demand for operation of th ie facility.
• Total energy generated on site.
• Energy requirements by type.
• Sources of energy off-site and alternatives.
• Use of electric generating capacity during non-peak hours
• Proposed measures to conserve or reduce energy demand and to increase
efficiency of operation.
2.3.3.1 Cogeneration
Cogeneration in industrial processes denotes any fontn of the simultaneous
production of electrical or mechanical energy and useful 1 thermal energy (usually
in the form of hot liquids or gases) (USDOE 1978).
Opportunities for Cogeneration should be identified a t any new source
operation. The Public Utility Regulatory Policies Act of H979 provides for
Federal Energy Regulatory Commission rules favoring cogener ation facilities,
and requiring utilities to buy or sell power from qualified cogenerators at
just and reasonable rates.
Extensive cogeneration is not practiced at most non-fen :ilizer phosphate
facilities; however, some internally generated energy sources are used. The
most notable example is the use of furnace off-gas from phospi horus production
to provide a portion of the heat required for agglomeration of the furnace
charge. Nonetheless, the BID should indicate the power demand; 3 of processes
to be used and assess the potential for excess steam capacity 1 Tor generation
of marketable or internally useable electric power.
2.3.3.2 Energy Conservation
Although the non-fertilizer phosphate industry is not erne of the major
energy consumers on a national scale, energy conservation pr'acticias are of
benefit to the producer, regional energy supplies, and the eiconomj ' as a whole.
The BID should identify opportunities for energy conservation at t.te new
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source manufacturing facility and indicate the costs and benefits of their
implementation. Examples of energy conservation measures that should be
considered include;
• Use of low tiemperature furnace charge agglomeration methods for phos-
phorus producers. This may include pulverization and combination of
furnace charf >e with clay binders followed by low-temperature calcina-
tion or forms ition of agglomerates using fertilizer industry techniques
such as "wet process" phosphoric acid sludge for a binder (Barber
1980a).
• Particulate collection systems are designed to provide optimum dust
pickup and transport velocities. Long and complicated ducts give rise
to duct stoppages' or expenditure of excessive energy to transport dust
at high enou gh velocity to prevent stoppages (Barber 1978).
• Baghouse col.lectors are used instead of scrubbers for particulate
collection when the particulates have low hygroscopicity and the gas
temperature does not exceed the limit for fabric filters. Baghouse
collectors • consume less energy than scrubbers unless gases have to be
heated to overcome the hygroscopicity problem. When the gases have to
be heated, energy for baghouses and scrubbers is about the same (Barber
1978).
• Phossy wati er effluent may be reused in the process or the effluent may
be sold as a fluid fertilizer. This saves energy for nutrient produc-
tion and eliminates a waste treatment facility (Barber 1978).
In addition, well -planned siting of the plant can greatly affect net energy
consumption of tt ie operations. The amount of energy consumed in transpor-
tation by the fo' ur major transportation modes is shown below in Btu's/ton-mile
(Achorn & Kimbrc mgh 1974):
Pipeline 450
Barge 500
Rail 700
Truck 2,500-2,800
These data in
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Finally, uranium production which can have significant effects on energy
supply should be considered if the facility has an associated phosphate rock
mine.
2.3.4 Socioeconomics
The introduction of a large new phosphate facility into a community may
cause land use, economic, and social changes. Therefore, it is necessary for
an applicant to understand the types of impacts of changes that may occur so
that they can be evaluated adequately. The importance of these changes usually
depends on the size of the existing community where the facility is located.
The significance of the changes caused by a facility of a given size normally
will be greater near a small rural community than near a large urban area.
This generally is due to the fact that a small rural community is likely to
have a nonmanufacturing economic base and a lower per capita income, fewer
social groups, a more limited socioeconomic infrastructure, and fewer leisure
pursuits than a large urban area. There are situations, however, in which the
changes in a small community may not be significant, and, conversely, in which
they may be considerable in an urban area. For example, a small community may
have had a manufacturing (or natural resource) economic base that has declined.
As a result, such a community may have a high incidence of unemployment in a
skilled labor force and a surplus of housing. Conversely, a rapidly growing
urban area may be severely strained to provide the labor force and services
required for a new phosphate facility.
The rate at which changes occur (regardless of the circumstances) also is
often an important determinant of the significance of the changes. The appli-
cant should distinguish clearly between those changes occasioned by the con-
struction of the facility, and those resulting from its operation. The former
changes could be substantial but usually are temporary; the latter may or may
not be substantial, but normally are more permanent in nature. The potential
impacts which should be evaluated include:
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• Increased consumption and rate of land development.
• Land use pattern and compatibility changes.
• Economic base multiplier effects.
• Population size and composition changes.
• Increased labor force participation and lower unemployment rates.
• Increased vehicular traffic and congestion.
• Loss of prime agricultural land and environmentally sensitive areas.
• Increased demand for comnunity facilities and services.
• Increased demand for water supply, sewage treatment, and solid waste
disposal facilities.
During the construction phase, the impact will be greater if the project
requires large numbers of construction workers to be brought in from outside
the comnunity than if local unemployed workers are available. The potential
impacts include:
• Creation of social tension.
• Short-term expansion of the local economy.
• Demand for increased police and fire protection, public utilities,
medical facilities, recreation facilities, and other public services.
a Increased demand for housing on a short-term basis.
• Strained economic budget in the comnunity where existing infrastruc-
ture becomes inadequate.
• Increased congestion from construction traffic.
Various methods of reducing the strain on the budget of the local comnunity
during the construction phase should be explored. For example, the company
itself may build the housing and recreation facilities and provide the utility
services and medical facilities for its imported construction force. Or the
company may prepay taxes, and the comnunity may agree to a corresponding
reduction in the property taxes paid later. Alternatively, the comnunity may
float a bond issue, taking advantage of its tax-exempt status, and the company
may agree to reimburse the comnunity as payments of principal and interest
become due.
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During operation, the more extreme adverse changes of the construction
phase are likely to disappear. Longer run changes may be profound, but less
extreme because they evolve over a longer period of time and may be both
beneficial and adverse.
The new source applicant should document fully in the EID the range of
potential impacts that are expected and demonstrate how possible adverse
changes will be handled. For example, an increased tax base generally is
regarded as a positive impact. The revenue from it usually is adequate t9
support the additional infrastructure required as the operating employees and
their families move into the community. The spending and responding of the
earnings of these employees has a multiplier effect on the local economy, as
do the interindustry linkages created by the new industry. Backward linkages
are those of the facility's suppliers. Forward linkages are those of the
facility's markets.
Socially, the community may benefit as the increased tax base permits the
provision of more diverse and higher quality services, and the variety of its
interests increases with growth in population. Conversely, the transformation
of a small comntinity into a larger comminity may be regarded as an adverse
change by some of the residents who choose to live in the comminity as well as
by those who grew up there and stayed because of its small town amenities.
The applicant also should consider the economic repercussions if, for
example, the quality of the air and water declines as a result of various
emissions from the phosphate facility. In some cases, other more traditional
sectors of economic activity may decline because labor is drawn away from them
into higher paying phosphate related or tertiary sector activities. As an
illustration, the fishing sector may decline if water pollution increases, or
if fishermen abandon the occupation in favor of employment at the phosphate
facility. Again, the tourist sector may decline if air and water pollution is
noticeable or if the landscape is degraded.
Thus, the applicant's framework for analyzing the socioeconomic impacts
of the location of a phosphate facility must be comprehensive. Most of the
changes described can and should be measured to assess fully the potential
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costs and benefits. The applicant should distinguish clearly between the
short-term (construction) and long-term (operation) changes, although some
changes may be common to both (e.g., the provision of infrastructure). The
significance of the changes depends not only on their absolute magnitude, but
on the rate at which they occur. The applicant should also develop and main-
tain close coordination with State, regional, and local planning and zoning
authorities to ensure full understanding of all existing and/or proposed land
use plans and other related regulations.
USEPA's Office of is developing a methodology to be
used to forecast the socioeconomic impacts of new source industries and the
environmental residuals associated with those impacts.
2.3.5 Raw Materials and Product Handling
In most instances potential major problems related to shipping, storing,
and handling of raw materials and products are well identified and systems are
in place or methods available to keep these problems in check.
Continuing use of phosphate rock as the industry's basic resource is
assured and any special problems should be discussed that cause impacts re-
lated to the mining area where the majority of the phosphate processing will
be conducted. Phosphate mining in North Carolina is carried on adjacent to
the Pamlico Estuary below the water table. Cofferdams and pumps are used to
expose phosphate deposits 100 feet deep. Even though the facility is well
managed, eutrophication in the estuary occurs as the result of phosphate laden
pumping waters being discharged to waters with significant nitrogen levels.
The wastes of phosphoric acid production also are disposed in this high
water level environment. Potential for leaching and for sedimentation and
contamination of surface waters is high, especially during hurricane condi-
tions.
In Florida, the significant special problems are related to new mining
areas. The richer deposits still unmined lie below deeper overburdens and
some deposits are in several layers. Higher volumes of overburdens must be
moved and replaced. The effects of this problem on phosphate processing are
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less limiting and can be useful as supplies of sands and tailings for gypsum
pond dewatering.
Effects of phosphate production on transportation facilities in new
source industries should be assessed. Florida, North Carolina, and Gulf Coast
facilities have good access to ocean, barge (river and intracoastal), pipe-
line, rail, and truck transportation. Similar advantages may not be enjoyed
by the western mining area; however, the BID should identify advantages of
alternate transportation modes. When properly controlled, pipeline and barge
transportation offers both environmental and economic advantages.
Since most facilities are near mines, stockpiles of phosphate rock are
not necessary. However, some phosphorus producers in the west stockpile huge
quantities of phosphate rock for winter operation or for mixture with local
ore to produce a better furnace charge. Facilities that purchase phosphate
rock should specify storage arrangements to prevent particulate air emissions
and rainfall runoff of waters contaminated with phosphorus and TSP. The BID
should state whether the storage area will be exposed to the weather and what
the impacts of fugitive particulate emissions and runoff waters would be.
Due to the fact that many of the non-fertilizer phosphate industry's
products are corrosive, highly reactive, toxic, flammable, or combinations of
these, their handling and transportation must be carefully controlled. Among
the industry's product handling problems are:
• ferrophosphorus
• elemental phosphorus
• phossy water
The handling of phosphorus and associated phossy water is one of the
industry's most pervasive problems. Phosphorus must always be stored under a
water blanket which always contains suspended colloidal phosphorus that is
very difficult to remove. In practice, phossy water is usually treated and
reused by phosphorus producing plants while phosphorus consuming plants col-
lect it from storage tanks or rail cars and send it back to the producing
plant for treatment (USEPA 1977c). The BID should identify the proposed means
for handling phossy water from any new source phosphorus producing or consuming
facility.
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By-product ferrophosphorus, like phosphorus, is highly reactive. However,
unlike phosphorus it is stable in air but explodes violently upon contact with
water. Safety precautions for handling ferrophosphorus should be identified
in the EID.
2.3.6 Special Problems in Site Preparation and Facility Construction
The environmental effects of site preparation and construction ,of new
phosphate manufacturing facilities are common to land disturbing activities on
construction sites in general. Erosion, dust, noise, vehicular traffic and
emissions, and some loss of wildlife habitats are to be expected and minimized
through good construction practices wherever possible. At present, however,
neither the quantities of the various pollutants resulting from site prepara-
tion and construction nor their effects on the integrity of aquatic and ter-
restrial ecosystems have been studied sufficiently to permit broad generaliza-
tions. Therefore, in addition to the impact assessment framework provided in
the USEPA document, Environmental Impact Assessment Guidelines for Selected
New Sources Industries, the permit applicant should tailor the conservation
practices to the site under consideration in order to account for and to
protect certain site-specific features that warrant special consideration
(e.g., critical habitats, archaeological/historical sites, high quality
streams, or other sensitive areas on the site). All mitigation/conservation
measures that are proposed should be discussed in the EID.
Erosion Control During Construction.
The major pollutant at a construction site is loosened soil that finds
its way into the. adjacent water bodies and becomes "sediment." Common re-
medial measures include, but are not limited to, proper planning at all stages
of development and application of modern control technology to minimize the
production of huge loads of sediment. Specific control measures include:
• Use of paved channels or pipelines to prevent surface erosion.
• Staging or phasing of clearing, grubbing, and excavation activities to
avoid high rainfall periods.
144
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• Use of storage ponds to serve as sediment traps where the overflow
may be carefully controlled.
• Use of mulch or seeding immediately following disturbance.
If the applicant chooses to establish temporary or permanent ground
cover, grasses normally are more valuable than shrubs or trees because of
their extensive root systems that entrap soil. Grasses may be planted by
seeding, sodding, plugging, or sprigging. During early growth, grasses should
be supplemented with mulches of wood chips, straw, and jute mats. Wood fiber
mulch has also been used as an antierosion technique. The mulch, prepared
commercially from waste wood products, is mixed into a slurry and sprayed
on the land with a hydroseeder.
Site Selection Factors
The EID should include information to indicate the capacity of the soils
and geology to accommodate production and waste storage. Problems which would
require special consideration include:
• Unstable soils.
• Steep topography.
• Presence of wetlands.
• Location relative to f loodplains.
• Permeability of soils.
• Erosion problems during construction and operation.
The applicant is responsible for assessing the effects of the proposed
facility on ground water quality and quantities. The areas of particular
relevance to the phosphate manufacturing industry are:
• Potential and effects of seepage of gypsum pond wastewaters into
aquifers.
• Potential for groundwater contamination from storage piles of raw
materials and waste gypsum.
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• Use of groundwater for process and make-up water.
In western states water supply can be a limiting factor. The BID should
evaluate effects of water consumption in terms of both groundwater and surface
water supplies in the region.
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3.0 POLLUTION CONTROL TECHNOLOGY
The new source industry must install and operate pollution control systems
that reduce the actual discharge of pollutants into the environment to levels
defined by the New Source Performance Standards (NSPS). The technologies
selected to attain these reduction levels are to be selected by the industry
and are not mandated by USEPA. However, this chapter describes the tech-
nologies used by USEPA in defining the levels that are appropriate for NSPS.
Where such technologies have not been identified by USEPA, state-of-the-nart
control techniques that could be evaluated by the applicant are discussed.
The permit applicant must demonstrate in the BID that NSPS will be met.
3.1 STANDARDS OF PERFORMANCE TECHNOLOGY; .AIR EMISSIONS
New Source Performance Standards (NSPS) for air emissions have not been
identified specifically by USEPA for non-fertilizer phosphate facilities;
therefore, the most recent applicable technology should be identified for
control of industry emissions. In general, emission control technologies may
be divided into groups consisting of in-process controls and end-of-process-
controls. A new source industry may use both types of controls.
3.1.1 Controllable Emissions
Major sources and types of emissions from the non-fertilizer phosphate
industry were identified in Section 2.1. The most significant pollutants from
the industry are particulates generated from raw materials handling, thermal
reactions, and the drying and handling of dry products; and fluorides removed
from phosphate rock and products. Smaller amounts of sulfur dioxide, phos-
phorus pentoxide (P_0 ), and acid mists also are emitted during manufacturing
operations. Due to the similarity between the emission problems faced by most
segments of the industry, air pollution abatement equipment tends to be similar.
In general, wet scrubbing systems are used on most emission sources because of
the presence of both particulates and hydrolyzable gas streams such as hydrogen
fluoride, and sodium tetrafluoride. In the past electrostatic precipitators
and baghouse filters have been successfully used where dry dust and particu-
lates alone are the problem. However, electrostatic precipitators and bag-
147
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houses have been greatly improved and are being examined as an alternative to
high energy wet scrubbers for dry, fine particulate control.
3.1.2 In-Process Emission Control Technologies
Many pollutants, particularly dust from raw materials handling, may be
eliminated or controlled at their source by containment. Large uncovered
stockpiles of raw materials kept on site may cause minor dust problems, but
the movement and processing of these materials represent more significant
emission sources. Some gaseous emission problems also may be reduced at their
source by modifications to the production process. Following are several
examples of in-process controls that may be applicable to control of emissions
from particular operations of the industry.
• Dust Control
Enclosed operation and baghouses are typical methods of control at
phosphate rock handling locations. Satisfactory control of dust
emissions from unloading hopper-bottom railroad cars or trucks at
phosphate fertilizer plants is achieved by the use of flexible skirts
around bases of the vehicles to contain dust and flexible-contact
hoods to channel emissions to baghouses.
Feed hoppers, storage bins, and conveyors usually are enclosed to
reduce particulate emissions and moisture contamination of phosphate
rock in the fertilizer industry. Similar control techniques also may
be applicable to raw materials handling for several categories of the
non-fertilizer phosphate industry. When transport of ground rock from
storage bin to feed hopper is accomplished by pneumatic conveyors, a
cyclone separator and baghouse may be located at the destination to
control bulk material and discharged dust (USEPA 1979a).
« Reduction of PCI and FOCI Emissions
Chlorides once dissolved in the wastewater stream are difficult to
remove, but reduction of emissions before they reach the scrubbers can
help eliminate this problem. PCI, and POC1 emissions from the reactor/
still can be reduced by maintaining a low vapor pressure using re-
frigerated condensers and demisters downstream of the reactor. Refrig-
erated condensers on storage vessels also can help reduce emissions
from that source by keeping the product in its liquid phase.
• Reduction of PpS Emissions
The major emissions from production of P2^s are t*ie ^umes from casting
molten P~S in air. These can be eliminated by either casting in a
vacuum or casting in an inert gas atmosphere.
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• Collection of Open Emissions
In the phosphorus production subcategory problems may be encountered
in controlling open process emission sources such as slag and ferro-
phosphorus tapping. Dense .clouds of corrosive, combustible gases
containing fine particulates, fluorine, sulfur, and phosphorus are
released during furnace tapping. Vacuum hood and duct systems are
usually installed to collect these fumes for treatment by a scrubber
system (Stinson 1976).
The most effective and probably most difficult in-process emission con-
trols to implement are process changes. Certain process variations offer
lower emissions or more easily controllable emissions as a significant side
benefit. In-process controls or modifications should be considered by the
applicant at every available opportunity to reduce emissions and reduce the
cost of treating them.
3.1.3 End-of-Process Emission Controls
End-of-process emission controls reduce industry emissions and may have
an important role in determining the wastewater and solid waste characteristics
of the industry. Basic air pollution control equipment that may have applica-
tion to the control of industry emissions includes dry collectors and scrubbers.
Several types are described in this section.
3.1.3.1 Dry Collectors
Dry collection devices are used primarily for removal of particulates;
however, they frequently are used as precleaning units for gas adsorption or
scrubbing units to remove larger particles. The most commonly used devices
are described below:
• Cyclone
A cyclone is essentially a type of gravity settler employing centri-
fugal force rather than gravitation for solids separation. The spinning
motion may be imparted to the carrier gas by tangential gas inlets,
vanes, or a fan (USDHEW 1969). The operation of one type of cyclone
is indicated in Figure 21. Most cyclones are capable of removing
particles ranging in size down to 15 to 40 microns. A cyclone may be
used ahead of a baghouse electrostatic precipitator or scrubber to
reduce the solids loading to that equipment.
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Dust laden air
Clean air"
Dust
caught in base
Figure 21. Cyclone scrubber.
Source: U.S. Environmental Protection Agency. 1978q. Environmental
pollution control, textile processing industry. Prepared by
the Torit Corporation.
150
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• Baghouses
Baghouses are essentially structures containing fabric bags which
remove particulates by direct filtration. A typical baghouse filter
is illustrated in Figure 22. The initial filtration efficiency and
pressure drop through a filter are low, but as a mat of dust collects
on the filter both the pressure drop and the efficiency increase.
Once established, the dust mat performs most of the filtration and
efficiencies of 99+% are achieved. Cleaning is accomplished by
mechanical vibration of the bag or reverse air flow. Baghouses are
not suitable for collection of small sized carbonaceous material such
as coke fines due to the potential fire hazards. More information is
available in the USEPA Air Pollution Engineering Manual (Danielson
1973).
Other filtration devices include fabric mist eliminators which remove
such pollutants as acid mists from emission streams. Droplets con-
dense on a fiber matrix and flow down to a collection point.
• Electrostatic Precipitators
Electrostatic precipitators are useful for control of acid mists and
small particle emissions; however, they are sensitive to variations in
the character of the gas stream and may not be equally effective on
all emissions. This device operates by first passing the emission
stream through an ionizing grid where the dust is given a positive
charge. These charged particles are then attracted to a negatively
charged plate where they are collected. Electrostatic precipitators
can be used for collection of dust down to the 0.1 micron range with
95-99% efficiency. These systems offer the advantage of low pressure
drop and a low power requirement but are quite large and require a
high initial investment. More information is available from the USEPA
Air Pollution Engineering Manual (Danielson 1973).
3.1.3.2 Wet Scrubbers
Most of the air pollutants produced by the non-fertilizer phosphate
industry are in combined streams consisting of both particulates and gases
such as fluorine. The ability of wet scrubbing systems to remove both fine
particulates and gaseous pollutants simultaneously has led to their predomi-
nance as an emission abatement technology in the industry. They can be used to
control explosive gases without a fire hazard or reduce the temperature of hot
gases by evaporation. They are also compact and have a well developed tech-
nology. Many scrubber designs also are able to utilize contaminated, recycled
water from the recycle pond as a scrubbing medium without serious problems.
This is important due to the no-discharge limitation placed on the industry by
NSPS.
151
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Figure 22. Typical baghouse unit.
Source: U.S. Environmental Protection Agency. 1978q. Environmental
pollution control, textile processing industry. Prepared by
the Torit Corporation.
152
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In general, the efficiency of a scrubber in removing parti-culate matter
is related to the energy input. Particle collection efficiency of a scrubber
is improved by increasing the relative velocity and decreasing the diameter of
the collecting media. This explains the energy/efficiency relationship of
scrubbers. Removal of a high percentage of particles requires removal of the
finest materials, which necessitates a large energy input to increase the
velocity and reduce the diameter of scrubber droplets. The relative energy
input in terms of pressure drop versus minimum particle size removed for
various types of scrubbers is indicated below:
Spray towers
Cyclone spray scrubbers
Impingement scrubbers
Packed- and fluidized-bed scrubbers
Orifice scrubbers
Ve ntu ri sc rub be rs
Fibrous-bed scrubbers
Pressure
drop, inches
of water
0.5-1.5
2-10
2-50
2-50
5-100
5-100
5-110
Minimum
particle size
(microns)
10
2-10
1-5
1-10
1
0.8
0.5
Source: Perry, Robert H., and Cecil H. Chilton (Eds.). 1973. Chemical
engineers handbook. 5th ed. McGraw Hill, New York NY.
Wet scrubbing systems also are used for removal of gaseous pollutants
from the emission stream. For the non-fertilizer phosphate industry this
typically involves hydrolyzing hydrogen fluoride, silicon tetrafluoride,
sulfur dioxide, or some other gaseous oxide to an acid in the scrubber media.
These are transferred to the new source wastewater streams and are significant
contributors to the industry's water pollution problems. The direct reuse of
scrubber water in treating emissions from phosphate rock calciners and de-
fluorination systems is limited by process requirements, but treated water
plus makeup may be relimed in the recirculation pond before being reused as a
scrubber medium. Many of the most common scrubber technologies are described
below. More information on scrubbers is available in the USEPA Scrubber
Handbook, Volumes I and II (Calvert et al. 1972).
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• Venturi Scrubbers
Venturi scrubbers are primarily high efficiency particulate collection
devices but they also are applicable to gas adsorption problems and
are in widespread use throughout the industry. They are particularly
well suited to treating emission streams containing large amounts of
solids or silicon tetrafluoride because of their high solids handling
capability and self-cleaning characteristics. Operational reliability
and low maintenance requirements are major reasons for the popularity
of this scrubber design (USEPA 1977d).
A venturi scrubber provides a high degree of gas-liquid mixing, but
the relatively short contact time and the concurrent flow of the
scrubbing liquid tend to limit its absorption capabilities. A typical
venturi scrubber unit is illustrated in Figure 23. When effluent
streams requiring a high degree of fluoride removal are treated,
Venturis are often used as the initial component in a multiple-
scrubber system.
• Cyclonic Spray
This scrubber atomizes the scrubbing liquid using the hydraulic
pressure developed by the liquid pump. The higher the pump pressure
the finer will be the spray droplet and the more effective the absorp-
tion of gaseous pollutants. This unit introduces the gases into a
well defined spray zone and assures complete coverage of waste gases.
The spray is removed from the gases by spinning. The cyclonic scrubber
requires a 2-6" WG pressure drop and liquid pressures of 50-150 psig.
They require between 4 and 8 gal/1,000 cfm. Because of the use of
spray nozzles, these units require fairly high quality scrubbing
liquid. The cyclonic scrubber has proven to be an excellent absorber
of gaseous contaminants such as fluoride (Hill 1976). A typical
cyclonic scrubber setup is illustrated in Figure 24.
• Impingement Scrubbers
These devices use a large number of small diameter orifices with
impingement target devices located downstream from the orifice holes.
Due to the use of small orifices and close tolerances, these units are
subject to plugging if there are other contaminants or reactants
within the scrubbing process. This limits their application in in-
stances where recycle water is used as a scrubbing medium (Hill 1976).
• Packed Scrubbers
The packed scrubber brings the liquid and gas into contact within the
zone of packed elements. The two basic principles employed in packed
scrubbing are the counterflow of gases flowing upward through the
packed bed section with the liquid being introduced above the packing
and flowing downward through the packing. The crossflow washer has a
horizontal gas flow through a packing with the water being introduced
normal to the gas flow. Typical examples of this type of scrubber are
illustrated in Figure 25. These units have proven to be the most
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Gas out
Gas in
Quench
spray
Slurry
inlet
Venturi
Effluent
drain
Figure 23. Typical venturi scrubber unit.
Source: US Environmental Protection Agency. 1978q..
Environmental pollution control, texitle processing
Indus try.
155
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Antispin vanes
Core buster disk
Tangential
gas inlet
Swinging
inlet damper
Damper
position
indicator
Spray
manifold
Water
outlet
Water
inlet
Figure 24. Typical cyclonic spray scrubber unit.
Source: US Environmental Protection Agency. 1978q
•Environmental pollution control, textile
processing industry.
156
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GAS OUTLET
LIQUID
DISTRIBUTION UNWETTED
PACKING HEADERS , SECTION FOR
SUPPORT^ / /' MIST ELIMINATION
GRID \ .' /
SUPPORT
GRID
FRONT
CLEANING
SPRAYS
, LUJJJlllLlT
/ ~~~~-~-~-~-~-
GAS INLET
s SUMP
MIST
ELIMINATOR
SECTION
LIQUID
INLET
'V WEIR
DISTRIBUTOR
PACKED
-SCRUBBING
SECTION
,. PACKING
SUPPORT
LIQUID
OUTLET
o. CROSS-FLOW SCRUBBER
b. COUNTERCURRENT-FLOW SCRUBBER
Figure 25. Typical packed bed scrubber units.
Source: US Department of Health, Education and Welfare,
1969. Control.techniques for particulate air
pollutants. National Air Pollution Control
Administration, Washington DC, 215 p.
157
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effective absorbers; however, they do have some problems in handling
gases containing particulates or contaminants that form precipitates
or reactants within the packing media (Hill 1976).
• Spray Tower Scrubber
Spray towers provide the interphase contacting necessary for gas
absorption by dispersing the scrubbing liquid in the gas phase in the
form of a fine spray. A typical layout for a spray tower is illus-
trated in Figure 26. Scrubbing liquid is sprayed into the gas stream
and droplets fall by gravity through an upward flow of gas. The spray
tower scrubber has the advantages of a very low pressure drop and an
inexpensive construction cost but entrainment of scrubbing mists in
the gas flow stream is a problem (USEPA 1977d).
0 Spray-Crossflow Packed Bed Scrubber
The spray-crossf low packed bed scrubber has been accepted for several
years by the fertilizer industry as the most satisfactory fluoride
control device available for wet process phosphoric acid plants (USEPA
1977d). This spray-crossf low packed bed scrubber consists of a spray
chamber and a packed bed separated by a series of irrigated baffles.
All internal parts of the scrubber are constructed of corrosion re-
sistant plastics or rubber-lined steel. General maintenance consists
of replacement of the packing once or twice a year. Both the spray
and the packed sections are equipped with a gas inlet. Effluent
streams with relatively high fluoride concentrations (particularly
those rich in silicon tetrafluoride) are treated in the spray chamber
before entering the packing. This preliminary scrubbing removes
silicon tetraf luoride, thereby reducing the danger of plugging the
bed. At the same time, it reduces the loading on the packed stage and
provides some solids handling capacity. Gases low in silicon tetra-
fluoride can be introduced directly to the packed section (USEPA
1977d). These systems may be found to be applicable to the significant
fluoride emission control problems of the defluorinated phosphate rock
and phosphorus production subcategories.
The effectiveness of a proposed control technique for a specific new
source facility must be documented, to include:
• Sources that will be controlled.
• Effectiveness of collection devices.
• Removal efficiency of control devices.
The applicant should address the specific nature of all emissions to identify
specific compounds that could be hazardous. These should be compared to the
pollutants and standards currently established by the National Emissions
158
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Figure 26. Typical layout for spray tower.
GAS IN
f//iw/av\
/' x/ x
' /\ \
,/V\
r /\ \
-MIST ELIMINATOR
GAS DISTRIBUTOR PLATE
Source: US Department of Health, Education, and Welfare,
1969. Control techniques for participate air
pollutants. National Air Pollution Control
Administration, Washington DC, 215 p.
159
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Standards for Hazardous Air Pollutants (NESHAP). As of November 1979, the
NESHAP program had established standards for these pollutants: asbestos,
beryllium, mercury, and vinyl chloride (USEPA 1979c). These emissions
normally are not associated with the non-fertilizer phosphate industry, but
the applicant must confirm this for the specific new source.
3.2 STANDARDS OF PERFORMANCE TECHNOLOGY; WASTEWATER DISCHARGES
For most new sources in the phosphate industry, NSPS will require no
discharge of process waste. To achieve this standard requires the conscious
design of the entire plant to recycle, reuse, and reduce the use of water at
every possible point. The BID should describe the integrated state-of-the-art
product ion/treatment system designed to achieve the no-discharge goal. A
detailed water balance should be developed showing the average and maximum
flow rates expected for all wastewater streams.
3.2.1 In-Process Controls
In-process controls are procedures to reduce pollution discharges at
their source, some of which result in product or by-product recovery, water
conservation, energy conservation, and greater production efficiency. Those
controls which are generally applicable include:
• Waste stream segregation.
• Water recycle and reuse.
• Reduction in water usage.
• Reduction of spill and runoff borne pollutants.
• Waste stream monitoring*
The application of in-rprocess pollution controls to the wastewater streams of
the industry are indicated in the following discussions.
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3.2.1.1 Waste Stream Segregation
Because concentrated waste streams are more economically and efficiently
treated than are large, dilute waste streams, it is advantageous to keep large
volume but uncontaminated streams (such as cooling water) segregated from con-
taminated streams which could cause the entire combined stream to require
treatment. A typical, generalized waste stream segregation scheme separates
the following four streams.
• Non-contact, uncontaminated cooling water.
• Contaminated process water.
• Contaminated auxiliary process streams.
• Plant sanitary waste.
The uncontaminated cooling water stream may be reused or discharged with
little or no treatment while the contaminated streams may be treated for
product recovery, by-product recovery, reuse, or discharge.
For the defluorinated rock and phosphoric acid segments of the industry,
cooling water, contaminated scrubber water, and contaminated runoff are not
segregated but collected in a common pond system for neutralization, cooling,
and solids separation. The quantity of water required for wet scrubbing is
withdrawn from the pond, treated, and returned to the plant for use. Cooling
water, which may not require treatment, is returned to the plant as needed.
3.2.1.2 Water Recycle and Reuse
Recycle and reuse are widely practiced in-process controls throughout the
industry. The most commonly reused waste streams include cooling water,
scrubber water, phosphorus seal (phossy) water, and quenching water. Process
related streams commonly must be treated before reuse but these treatment
practices do not result in waste discharges. The technologies available for
this treatment of recycle streams are discussed in the wastewater treatment
section.
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3.2.1.3 Water Reduction
A considerable savings in wastewater generation can be effected by the
use of dry dust collection devices such as cyclones and baghouses rather than
wet scrubbers. Useable product may be recovered while reducing an intermedia
transfer of waste. Plant cleanup practices also may be designed to maximize
water savings. For example, reactor washdown using fine spray rather than
high pressure fire hoses will save water and reduce the volume of cleanup
wastes generated.
3.2.1.4 Reduction of Spill and Runoff
The use of bulk raw materials and production of finely divided dry bulk
products by the industry makes site runoff a potentially significant source of
contaminated water. Fugitive raw material and product dust coating the plant
site can be transported by runoff to nearby waters. Leaks, spills, and pro-
cess upsets which are not properly contained also can contribute to the runoff
problem. Control of these pollution sources requires good housecleaning
practices, maintenance, and containment. The EID should identify a positive
plan for housecleaning to reduce the potential for contamination of runoff.
Provisions should be made in plant design for containment and treatment of
spills. Techniques for spill prevention and containment include:
• Use of corrosion resistant materials where needed.
* Regular repair and replacement of worn valves and pipes.
• Drip pans, canals, or sumps under process equipment.
• Dikes or containment vessels around reactors and storage vessels.
• Routing of plant runoff to the recycle containment pond.
3.2.1.5 Waste Stream Monitoring
Efficient and continuous monitoring is necessary to assure that accidents
are detected and that pollutants are segregated into the proper waste manage-
ment stream. Common techniques include:
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• In-line continuous monitoring of spent stream flow rates and pH to
warn operators of contamination and possible accidental discharge.
• Monitoring of selected streams for phosphorus, fluorine, total dis-
solved solids and suspended solids to identify long-term buildup of
pollutants and the potential need for water system blowdown and dis-
charge.
3.2.2 Wastewater Treatment
No discharge of process wastewater is allowed for most of the industry,
so much of the wastewater treatment technology is directed toward recycle and
reuse. Because a limited number of pollutants and problems characterize the
waste from the industry, treatment technologies tend to be similar for most
subcategories. This is illustrated in the control technologies described
below. Wastewater treatment technologies described in the BID should include
the source and nature of all wastewater in the plant, the processes for treat-
ment of recycled process water, and any wastewater discharge (i.e., process
wastewater, cooling water, runoff, or emergency discharge from the recycle
pond). The treatment technologies described must be demonstrated as capable
of meeting the stringent NSPS requirements for the industry.
3.2.2.1 Recycle of Wastewaters from the Defluorination of Phosphoric Acid,
Defluorination of Phosphate Rock Subcategories
These subcategories have similar wastewater treatment problems and employ
similar technologies. Wet scrubbers for control of emissions from defluorina-
tion of phosphate rock and phosphoric acid introduce large quantities of
fluorine and phosphorus compounds into the wastewater stream. Wet emission
control devices serving virtually all of the major processes for these in-
dustries also introduce highly acidic mineral wastes into the wastewater
stream. To meet the stringent no-discharge requirements of NSPS, these pro-
cess waste streams must be treated to the degree necessary to make the water
acceptable for reuse or recycle. The acids must be neutralized, equipment
fouling minerals removed, and suspended solids settled. The standard tech-
niques for treating these wastewaters are lime treatment and use of recircu-
lation (settling) ponds, which perform the following functions:
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• Neutralization of acid waste waters.
• Sedimentation of nuch of the original suspended solids in the waste
waters (silica, iron oxide, and others).
e Precipitation and sedimentation of much of the phosphates, fluorides,
and sulfates which were dissolved in the original wastewaters.
• Dissipation of the process heat to the atmosphere during the extended
residence in the settling ponds.
• Reduction in the wastewater quantity as a result of net evaporation
during the extended residence in the settling ponds.
• Where phossy water is combined with these other process waters, some
oxidation of the elemental phosphorus to phosphates is accomplished.
The limitations of these systems are that the ponds can overflow during ex-
cessively wet periods, and long detention times are required to remove the
lighter precipitates (e.g., lime precipitated phosphates). Mechanical clari-
fier systems can be used, but these require that large volumes of light,
poorly dewatering phosphorus sludge must be filtered mechanically and disposed
on a regular basis (USEPA 1976a).
3.2.2.2 Recycle of Scrubber Wastewaters from the Phosphorus Production
Subcategory
Similar technologies to those used by the defluorinated rock and acid
producers are employed for wastewater treatment and recycle by the phosphorus
production subcategory (although the ponds tend to be smaller). Highly acidic
scrubber wastewater contaminated with fluorine and phosphorus compounds is
routed to a recycle pond or tank where it is held for cooling and treatment.
Lime is added either to the pond or to a portion of the water as it is bled
off to a mechanical clarifier. Lime addition reduces the pH and precipitates
out mineral contaminants in the form of calcium salts (calcium fluorides,
calcium phosphate, calcium sulfates, etc.).
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3.2.2.3 Recycle and Treatment of Phossy Water from the Phosphorus
Pr odu ci ng and Consuming Subcat ego ries
Phossy water from the phosphorus condenser and phosphorus air seals
causes one of the industry's most dangerous and difficult waste management
problems. Phossy water always is recycled although it must be treated to
reduce the build-up of other undesirable dissolved solids. A portion of the
colloidal phosphorus may be flocculated and settled in a clarifier with the
effluent returned to the condenser or seals. Clarified effluent is then limed
to precipitate the phosphorus and fluorides and returned to the plant (USEPA
1973a). The underflow from the clarifier containing 25% solids by weight can
be treated by heating and distillation to recover the phosphorus. Wastewater
from the phosphorus recovery process can be recycled to the phossy water pond
(USEPA 1977c).
3.2.2.4 Treatment and Recycle of Process Water from Production of
Anhydrous Phosphorus Derivatives
Phosphorus Pent oxide
The single raw waste constituent is phosphoric acid from water tail
gas seals. Application of two standard techniques enables total recycle of
this wastewater (USEPA 1973a):
• Reduction in wastewater quantities by using dilute caustic or lime
slurry as tail gas liquor rather than pure water, increasing the
absorptive capacity for P°'
»
Lime treatment and sedimentation to neutralize and remove the
phosphate, permitting total recycle.
Phosphorus Pentasulfide
The sole source of process wastewater is the scrubber liquor for fumes
from casting liquid P2SS- One control technique would be the use of inert-
atmosphere casting or vacuum casting to completely eliminate the need for
165
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scrubbing. As an alternate to this approach, the application of three standard
techniques would permit total recycle of scrubber water (USEPA 1973a):
® Use of dilute caustic or lime slurry rather than pure water would
reduce the wastewater quantities by increasing the adsorptive capacity
for P-S and SO . :
• Both PS and SO are weakly absorbed by water and high flowrates are
required to control these emssions.
® Partial recycle of scrubber liquor from a sump would reduce the waste-
water quantity.
• Lime treatment and sedimentation to neutralize and remove phosphate,
sulfite, and sulfate would permit total recycle.
Phosphorus Trichloride and Phosphorus Qxychloride
The treatment problem which makes reuse difficult for these processes is
the difficulty of removing chlorides from the wastewater. Because chlorides
are not precipitated with lime, they build up in the process water when re-
cycled and require blowdown. Chlorides can be removed by reverse osmosis or
prevented from building up in the scrubber water by condensing product vapors
back into the product line before they reach the scrubber. The use of re-
frigerated condensers for emission control is described in Section 3.1. By
rigorously reducing wastewater from other sources such as tank washing, the
small amount of contaminated wastewater can be evaporated and the residue
disposed of with other solid waste (USEPA 1973a).
3.2.2.5 Wastewater Treatment and Reduction in the Phosphate Chemicals
Subcategory
Sodium Tripolyphosphate
All wastewater generated by production of STPP with dry process phos-
phoric acid is from wet scrubbing of dust from product drying .operations.
This wastewater may be reused in the neutralization step or as scrubber water
after treatment. The use of dry emission control techniques such as baghouses
could eliminate much of the process's water requirement (USEPA 1973a).
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Calcium Phosphates
Wastewater from the production of animal and human food grade calcium
phosphates result from wet scrubbing of dryer emissions and, in the case of
human food grade dicalcium phosphate, filtrate from the reaction slurry.
Complete recycle of the filtrate may be achieved by precipitation and vacuum
filtration of the slurry and disposal of the filter cake. Wet scrubbers may
be replaced by baghouses to eliminate the scrubber wastewater at its source
(US EPA 1973a).
3.2.2.6 Sodium Wastewater Treatment for Production of Phosphates from
"Wet Process" Phosphoric Acid
The rather complicated process of manufacturing purified sodium phosphates
from "wet process" phosphoric acid produces wastewater from filtration washes,
gas scrubber liquors, and leaks and spills. Periodic slugs of contaminated
site runoff also contribute to the wastewater load. Similar to the rest of
the industry, the heart of the wastewater treatment system for this process is
also a recirculation/treatment pond; however, the use of significant quantities
of water in the manufacturing process and the lack of large water losses from
cooling make the discharge of some wastewater a necessity. The recommended
treatment technology for this discharge is the double liming process described7
in Section 3.2.3 for emergency discharge of recirculation pond effluent.
3.2.3 Emergency Discharge of Recirculation Pond Effluent
The contaminated water stored in the recirculation pond must be treated
prior to any discharge necessitated by unusually high rainfall (which should
be in excess of the local 24-hour, 25-year frequency event). Once the storage
area approaches capacity it is necessary to begin treating the contaminated
water for subsequent discharge to natural drainage bodies.
Treatment must accomplish NSPS levels for phosphorus, fluorides, and
total suspended solids (TSS). In most cases pH also is'regulated by means of
the NPDES permit. "Double liming," or a two stage lime neutralization, is the
167
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standard of performance control technology for the fertilizer industry and is
also applicable to wastewater streams from large volume recycle systems in the
non-fertilizer phosphate industry (USEPA 1976a).
The first treatment stage provides sufficient chemical addition to in-
crease the pH of the contaminated water (containing up to 9,000 mg/1 F and up
to 6,500 mg/1 P) from the range of pH 1-2 to pH 3.5-4.0. The resultant treatment
effectiveness largely is dependent on constancy of the pH control. At a pH of
3.5 to 4.0, the fluorides will precipitate principally as calcium fluoride
(CaF ). This mixture is held in a quiescent area to allow the particulate
CaF to settle.
Equipment used for neutralization ranges from crude manual distribution
of lime with localized agitation to a well engineered lime control system with
a compartmented mixer. The quiescent areas may range from a pond to a con-
trolled settling rate thickener or settler. The partially neutralized water
(pH 3.0-3,5) after separation from the CaF should contain about 30-60 mg/1 F
and up to 5,500 mg/1 P. This water is again treated with lime to increase the
pH to 6.0 or above. At this pH level calcium compounds (primarily calcium
phosphates (CaHPO ) plus additional quantities of CaF ), precipitate from
solution. As before, this mixture is retained in a quiescent area to allow
the CaHPO. and minor amounts of CaF,, to settle.
4 2
The removal of phosphorus is strongly dependent upon the final pH level,
holding time, and quality of the neutralization facilities, particularly the
mixing efficiency. Figure 27 shows a sketch of a well designed "double lime"
treatment facility for a fertilizer plant gypsum pond. The same technology
is applicable to treatment of defluorinated phosphate rock or acid recircula-
tion pond overflows.
3.2.4 Recirculation Pond Water Seepage Control
The contaminated water storage areas (recirculation pond) are surrounded
by dikes except when mining pits are used. The base of these dikes is normally
natural soil from the immediate surroundings. When height of the retaining
dikes must be increased in the phosphate fertilizer industry, gypsum from
168
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L. P. STEAM
HOT WATER
TANK
FEEDER
71 Cl
MtLKOF
I LIME I I
STORAGE—*-
•»*-*-*-O
PhC
TO GYPSUM POND
CALCIUM PHOSPHATE
POND
CONTAMINATED (POND) WATER TREATMENT
Figure 27.
Source
Pond water treatment system.
TO RIVER OR '
PROCESS UNITS
US Environmental Protection Agency. 1974a.
Development document for effluent limitations
guidelines and new source performance standards
for the basic fertilizer chemicals segment of the
fertilizer manufacturing point source category.
Office of Air and Water Programs, Washington DC, 168p.
-------
inside the diked area is added to the top of the earthen base. Dikes in
Florida now extend 100-120 ft in vertical height and tend to have continual
seepage of contaminated water through them. The extent of this problem in the
non-fertilizer phosphate industry is not known but industry similarities make
seepage a possibility. To prevent pond seepage from reaching natural drainage
streams, it should be collected and returned to the pond.
Figures 28 and 29 illustrate the design and use of a seepage collection
ditch around the perimeter of the diked area. The ditch should be of suffi-
cient depth and size to collect contaminated water seepage and to permit
collection of seepage surface water from the immediate outer perimeter. This
is accomplished by erection of a small secondary dike. The secondary dike
also serves as a back-up or reserve dike in the event of a failure of the
major dike. The installation of a pump station at the collection point of the
seepage ditch is an essential part of the control system.
3.3 STATE OF THE ART TECHNOLOGY; SOLID WASTE
Solid waste control technologies practiced by the non-fertilizer phos-
phate industry include:
• Recovery and reuse.
• Pond storage.
• Landfilling.
Tables 25, 26 and 27 indicate solid waste management technologies that could
be used by manufacturers in the various subcategories.
3.3.1 Recovery and Reuse
Raw material and product recovery are significant solid waste management
strategies in this industry. The use of dry bulk raw materials and the pro-
duction of many fine-grained dry products provide opportunities for recovery
of valuable materials that would otherwise be wasted as dust. Recovery of
elemental phosphorus from phossy water is a necessity since this toxic, highly
170
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SLOPE NO GREATER
THAN 2:1
MINIMUM 6 m
TOP
OUTSIDE TOE
BERM\
DRAINAGE
DITCH
m MINIMUM
FREEBOARD,
MINIMUM 1.5m
i.
WATER LEVEL SLOPE N0 GREATER THAN 2:1
rINSIDE TOE
/BERM 8 m MINIMUM
BORROW PIT
CORE DITCH,
MINIMUM DEPTH 1 m
Figure 28. Recommended minimum cross section of dam.
Reprinted from Phosphoric Acid, Volume I, A.V. Slack, Editor, by permission of
Marcel Dekker, Inc., Year of first publication 1968.
SEEPAGE DITCH
RETURN TO GYPSUM
POND BY PUMP
OUTSIDE OF PLANT
^GYPSUM POND /PRIMARY
GYPSUM POND
BED
APPROXIMATELY
3 m WIDE BY
ABOUT 1 m DEEP
SEEPAGE
SEEPAGE
SEEPAGE
DITCH
'SURFACE DRAINAGE
DITCH EXTERNAL TO
THE PLANT
Figure 29. Gypsum pond water seepage control.
Source: Environmental Protection Agency. 1974a. Development document for efflu-
ent limitations guidelines and new source performance standards for the basic
fertilizer chemicals segment of the fertilizer manufacturing point source
category. Office of Air and Water Programs, Washington DC, 168 p.
171
-------
Table 25. Treatment and disposal technologies for process
solid wastes of the phosphorus production subcategory.
Solid Waste
Furnace Slag
Scrubber Precipitates
Calciner precipitator
dust
Phosphorus condenser
mud
Phossy water treatment
solids
Electrostatic pre-
cipitator dust
Fluorides, phosphates
metals, uranium
Fluorides, phosphates
Calcium floride
Phosphates
Phosphorous
Phosphorous
Phosphates
fluorides
Treatment
2
Cooling
detoxification
Liming, precipita-
tion evaporation
asphalting
Recovery
Recovery
Heat treatment and
distillation
Recovery
Disposal
Land disposal and
for road bed construction
Pond storage or
land disposal
Pond storage or
land disposal
Hazardous waste, must be handled, transported and disposed of according to 40 CFR 261.
2
Source: Abrams, E.F., G. Contos, and M. Drabkin, Versar-Inc. 1977. Alternatives for hazardous
waste management in the inorganic chemicals industry. Prepared for the Office of Solid
Waste, Hazardous Waste Management Division, US Environmental Protection Agency. Washington DC.
Source: Stinson, Mary K. and E.E. Berkan, Hazardous Waste Generation in the Inorganic Chemicals Industry."
Paper presented at the National Conference on Hazardous and Toxic Waste Management, June 3-5, 1980,
Newark, N.J.
3 Source: US Environmental Protection Agency. I973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus derived
chemicals segment of the phosphate manufacturing point source category. Office of
Air and Water Programs, Washington DC, 159 p.
-------
Table 26. Treatment and disposal technologies for process solid wastes
of the phosphorus consuming and calcium phosphates subcategories.
Solid Waste.
PS still residue
dust
Phosphoric acid
purification residue
Phosphoric acid
scrubber solution
precipitates
Phosphorus
trichloride
still bottoms
Food grade
calcium phosphates
sweepings
Contaminants
Arsenic pentasulfide
phosphorus
phosphorus sulfides
Phosphorus
phosphorus sulfides
Arsenic sulfides
Phosphorus,
fluorides
Arsenic trichloride
Lime, phosphates
Treatment
Butadiene
encapsulation,'
Recycle
1,2
Butadiene
encapsulation,
r
Neut raliza t ion*'
precipitation
1) distillation and
recovery
2) convert to less re-
active arsenic sulfides,
encapsulation
Disposal
Land disposal
Land disposal
Pond or land
disposal
Land disposal or
by-product sales
Land disposal
Unproven technologies: At the time at which these technologies were identified they had not been tested in the
suggested application.
Source: Abrams, E.F., G. Gontos and M. Drabkin, Versar, Inc. 1977. Alternatives
for hazardous waste management in the inorganic chemicals industry. Prepared
for the Office of Solid Waste, Hazardous Waste Management Division, U.S.
Environmental Protection Agency, Washington DC.
o
Source: US Environmental Protection Agency. 1973a. Development document for proposed effluent
limitations guidelines and new source performance standards for the phosphorus derived
Air and Water Programs, Washington DC, 159 p.
-------
Table 27. Treatment and disposal technologies for process solid wastes from the defluorinated
phosphate rock, defluorinated phosphoric acid, and sodium phosphates subcategories.
Solid Waste
Cont aminant s
Treatment
Disposal
Defluorination of
phosphate rock
Calciner dust
Wet scrubber
precipitates
Phosphates, fluorides
Calcium fluorides,
sulfates, and phosphates
Recycle
Lime precipitation
Pond storage
Defluorination of
phosphoric acid
Wet scrubber
precipitates
Calcium fluorides,
sulfates and phosphates
Lime precipitation
Pond storage
Sodium phosphates
Raw material and product
dust
Sodium fluosilicate
Arsenic sludge
Process sludge
Phosphates
Sodium fluosilicate
Arsenic sulfate
Iron, aluminum,
phosphates, fluoride
Reclaim
Encapsulation
Dewatering
By-product sales
Land disposal
By-product sales
Source: US Environmental Protection Agency. I976a. Development document for effluent limitations
guidelines and new source performance standards for the other non-fertilizer phosphate
segment of the phosphate manufacturing point source category. Office of Water and Hazardous
Materials, Washington DC, 105 p.
-------
reactive material cannot be allowed to come into contact with air. Some of the
more toxic, small volume wastes of the industry such as arsenic trichloride
have now become profitable to recover (Abrams et al. 1977). This type of
solid waste management is encouraged and should be fully explored in the EID.
3.3.2 Solid Waste Storage and Disposal
The largest volume of industry solid waste derives from precipitates from
the treatment of emission control scrubber water. These solids are collected
in a cooling/recirculation pond or dewatered and hauled to a landfill. Although
lime precipitated solids are largely insoluble, they may be toxic—as in the
case of calcium fluorides—and should be tested for potential leaching and
resultant contamination of groundwater. Other non-hazardous, solid plant
wastes including calcium phosphate sweepings and general trash may be land-
filled without difficulty.
3.3.3 Hazardous Wastes
Wastes such as electric furnace slag that are classified as hazardous
according to RCRA will require special handling and tracking as specified in
40 CFR Parts 264 and 265. The regulations urge that where practical, alter-
natives to disposal such as treatment, recovery, or destruction be considered.
The EID should identify the alternative means of hazardous waste management
evaluated in the project planning and demonstrate why the selected technology
was chosen. The chosen technology should be presented in detail showing how
much waste is to be generated, how it is to be handled, and its final dis-
position. If final disposal in a hazardous waste disposal site is chosen, the
EID should identify the means of transportation to the site, the suitability
of the site to accept the waste, and its capacity to accept the waste.
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4.0 EVALUATION OF AVAILABLE ALTERNATIVES
The alternatives section of the BID should address each reasonable alter-
native available for the new source phosphate facility. The purpose of this
analysis is to identify and evaluate alternate plans and actions that may
accomplish the desired goals of the project. These alternatives can include
process modifications, site relocations, project phasing, or project cancella-
tion.
For the alternatives to a proposed project to be identified and evaluated
properly, the impact assessment process should commence early in the planning
phase. In this manner, social, economic, and environmental factors against
which each alternative is to be judged can be established. Cost/benefit
analysis should not be the only means whereby alternatives are compared; the
environmental and social benefits of each alternative also must be considered.
In general, the complexity of the alternative analyses should be a function of
the magnitude and significance of the expected impacts of the proposed, pro-
*
cessing operations. A small processing facility located in an area with an
established industry of the same kind may have a relatively minimal impact on
a region and generally would require fewer alternatives to be presented in the
EID.
The public's attitude toward the proposed operation and its alternatives
also should be evaluated carefully. In this way key factors such as aesthetics,
community values, and land use can be assessed properly.
4.1 SITE ALTERNATIVES
As with all industries, the non-fertilizer phosphate industry locates
plants on the basis of several factors:
• Market demand for its products.
• Convenience to raw materials.
• Availability of an adequate labor force and water supply.
176
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Proximity to energy supplies and transportation.
Minimization of environmental problems.
A variety of sites initially should be considered by the applicant. The BID
should contain an analysis of each one, with the preferred alternative selected
on the basis of satisfying the project objectives with the least adverse
environmental impact.
Consultation with the appropriate resource agencies during the early
stages of site selection is recommended. Key agencies that can provide valu-
able technical assistance include:
• State, Regional, County, or Local Zoning or Planning Commissions.
These sources can describe land use programs and determine if vari-
ances would be required. Federal lands are under the authority of the
appropriate Federal land management agency (Bureau of Reclamation, US
Forest Service, National Park Service, etc.).
• State or Regional Water Resource Agencies. These sources can provide
information relative to water appropriations and water rights.
• Air Pollution Control Agencies. These sources can provide assistance
relative to air quality increments and other air-related standards and
regulations.
• The Soil Conservation Service and State Geological Surveys. These
sources can provide data and consultation on soil conditions and
geologic characteristics.
Further consideration should be given to any state siting laws. The appli-
cable regulations should be cited and any applicable constraints described.
The BID should include the potential site locations on maps, charts, or
diagrams that show the relevant site information. (A consistent identifica-
tion system for the alternative sites should be established and retained on
all graphic and text material.) These should display pertinent information
that includes, but is not limited to:
• Areas and sites considered by the applicant.
• Major centers of population density (urban, high, medium, low density,
or similar scale).
177
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• Waterbodies suitable for cooling water or effluent disposal.
• Railways, highways (existing and planned), and waterways suitable for
the transportation of materials.
• Important topographic features (such as mountains and marshes).
• Dedicated land use areas (parks, historic sites, wilderness areas,
testing grounds, airports, etc.).
• Other sensitive environmental areas.
Using the foregoing graphic materials, the applicant should provide a con-
densed description of the major considerations that led to the selection of
the final candidate areas, including:
• Proximity to markets and raw materials.
• Economic analyses with trade-offs.
• Adequacy of transportation systems.
• Environmental aspects, including the likelihood of floods.
• License or permit problems.
• Compatibility with existing land use planning programs.
• Current attitudes of interested citizens.
The EID should indicate the steps, factors, and criteria used to select
the proposed site. Quantification, although desirable, may not be possible
for all factors because of lack of adequate data. Under such circumstances,
qualitative and general comparative statements supported by documentation
may be used. Where possible, experience derived from operation of other
plants at the same site or at an environmentally similar site may be helpful
in appraising the nature of expected environmental impacts.
^
The factors considered in selecting each site, and especially those that
influenced a positive or negative decision on its suitability, should be
carefully documented in the permit applicant's EID. Adequate information on
the feasible alternatives to the proposed site is a necessary consideration in
issuing, conditioning, or denying an NPDES permit. Specifically, the ad-
178
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vantages and disadvantages of each alternative site must be catalogued with
due regard to preserving natural features sud) as wetlands and other sensitive
ecosystems and to minimizing significant adverse environmental impacts. The
applicant should ascertain that all impacts are evaluated as to their signif-
icance, magnitude, frequency of occurrence, cumulative effects, reversibility,
secondary or induced effects, and duration. Accidents or spills of hazardous
or toxic substances vis-a-vis site location should be addressed.
A proposed site may be controversial for a number of reasons:
• Impact on a unique, recreational, archaeological, or other important
natural or man-made resource area.
• Destruction of the rural or pristine character of an area.
• Conflict with the planned development for the area.
• Opposition by citizen groups.
• Unfavorable meteorological and climatological characteristics.
• Periodic flooding, hurricanes, earthquakes, or other natural disasters.
If the proposed site location proves undesirable, then alternative sites from
among those originally considered would be reevaluated, or new sites should be
identified and evaluated. Expansion at an existing site also could be a
possible alternative solution. Therefore, it is critical that a permit appli-
cant systematically identify and assess all feasible alternative site loca-
tions as early in the planning process as possible.
4.2 ALTERNATIVE PROCESSES AND DESIGNS
Typically the analysis of alternative processes and designs for a new
industrial facility are already complete and a design selected before an EID
is prepared. This selection process is primarily an economic one but it is
usually carried out in full awareness of environmental and energy constraints.
However, the industry should evaluate all feasible alternatives to ensure that
the most cost-effective and environmentally sound alternative is selected.
179
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Process selection is geared to maximizing production at the minimum cost.
For small operations with only an area or regional market this may be quite
different than for a plant designed for a large national or international
market. Within these production ranges the same economic concerns must be
dealt with, however. The rising cost of energy may push producers of calcium
and sodium phosphates toward the use of purified wet acid as a raw material
rather than "dry process" acid from energy intensive elemental phosphorus.
The cost of emission controls and energy may indicate that a chemical/aeration
method for defluorinating phosphoric acid is more favorable than the vacuum
condensation method. The BID should indicate the criteria and methodology
used to develop, screen, and select the processes and design of the new source
phosphate facility and justify the selection over others that may be more
advantageous in other respects.
4.2.1 Process Alternatives
Process alternatives are usually selected on the basis of the following:
• Product demand.
• Reliability of the process.
• Engineering feasibility.
• Economics.
• Availability of required raw materials.
• Environmental considerations.
Those alternatives that appear practical should be considered further on the
basis of criteria such as:
Land requirements of the processing facility, fuel storage facilities,
waste storage facilities, and exclusion areas.
Release to air of dust, sulfur dioxide, nitrogen oxides, and other
potential pollutants subject to Federal, state, or local limitations.
Releases to water of heat and chemicals subject to Federal, state, and
local regulations.
180
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• Effectiveness of pollution abatement technology.
• Water consumption rate.
• Energy consumption.
• Social impacts of increased traffic as materials are transported to
the site and wastes and products are transported from the site.
• Social effects, resulting from the influx of construction, operation,
and maintenance crews.
• Economics.
• Aesthetic considerations for each alternative process.
• Reliability and energy efficiency.
A tabular or matrix form of display often is helpful in comparing the
feasible alternatives. The EID should present clearly and systematically the
methodology used to identify, evaluate, and select the preferred process
alternative. Alternative processes which are not feasible should be dismissed
with an objective explanation of the reasons for rejection.
4.2.2 Design Alternatives
In order to properly present alternative facility designs available for
the project in the EID, the combination of component systems available for
selection should be analyzed and described for the following factors:
• Capital and operating costs.
• Environmental considerations.
• System reliability and safety.
All of these factors should be documented and quantified wherever possible.
4.3 NO-BUILD ALTERNATIVE
In all proposals for industrial development, the alternative of not
constructing the proposed new source facility must be considered. This analysis
is not unique to the development of phosphate manufacturing facilities (see
181
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Chapter IV, Alternatives to the Proposed New Source, in the USEPA document,
Environmental Impact Assessment Guidelines for Selected New Sources IndustriesA
October 1975). The key aspects of the no-build alternative should be identified
to include:
• Market Effect. Not constructing the facility may result in product
shortages.
• Industry Effect. Not constructing the facility may cause dated facil-
ities to be renovated.
• Technology Effect. Not constructing the facility may delay the need
for expanded capacity, which may allow time for improved technology to
be incorporated into the facility.
• Environmental Effect. Not building the facility might avoid adverse
environmental effects at the proposed site, but subsequently may cause
similar effects at a more sensitive site.
Other factors should be considered (e.g., specific environmental issues)
as appropriate for the situation leading to the proposed action.
182
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5.0 REFERENCES
The literature references in this section include cited references and
additional bibliographic references. The listings immediately below are short
form citations arranged according to topics. A complete listing of full
references, arranged alphabetically, follows the short form citations.
5.1 REFERENCE LIST BY TOPIC
General
Alsager 1978
Anonymous 19 7 6
Hooks 1978
Hurst 1961
Kirk-Othner Encyclopedia
of Chemical Technology 1969
Perry 1969
US EPA 1971
US EPA 1973a
USEPA 1974d
US EPA 1976a
USEPA 1976b
USEPA 1976d
USEPA 1977c
USEPA 1977d
USEPA 1978a
USEPA 1978b
USEPA 1978c
USEPA 1978d
USEPA 1978e
USEPA 1978f
USEPA 1978g
USEPA 1978h
USEPA 1978J
USEPA 1978o
USEPA 1979c
Van Wazer 1968
WAPORA 1979
Subca tego riza tion
Alsager 1978
Hooks 1978
USEPA 197la
USEPA 1971b
USEPA 1973a
USEPA 1974a
USEPA 1974d
USEPA 1975
.USEPA 1976a
USEPA 1977c
USEPA 1977d
USEPA 1974d
USEPA 1978J
183
-------
US EPA 1978o
US EPA 1979a
USEPA 1979c
WAPORA 1979
Processes and Trends
Achorn 1969
Albert son 1969
Anonymous 1952
Anonymous 19 6 4
Anonymous 1964
Anonymous 1965
Anonymous 1966
Anonymous 1971
Anonymous 19 73
Anonymous 1975
Anonymous 1977
Balay 1971
Banning 1975
Barber et al. 1960
Barber 1962
Blake 1974
Cammack 1955
Fleming 1969
Harre 1976
Hignett 1948
Jenkins et al. 1971
Long et al. 1956
Miyamoto 1975
Orckhov et al. 1976
Peterson et al. 1962
Ross 1975
Rushton 1966
Rushton and Smith 1964
Scott 1961
Scott et al. 1966
USDOC 1980
USEPA 1978a
Markets and Demands
Anonymous 1968
Anonymous 1975
Dell 1977
Dilworth 1964
Douglas 1977
Harre 1976
Miyamoto 1975
Stowasser 1977
USDOC 1980
USDOI, BOM 1977
USDOI, BOM 1979
184
-------
Pollution Control Technology
Abrams et al. 1977
Achorn et al. 1971
Barber 1968
Barber 1969
Barber 1970
Barber 197 6a
Barber 197 6b
Bargnan et al. 1971
Bourbon 1967
Calvert et al. 1972
Cammack 1955
Cochrane 1976
Convery 1970
Gulp 1969
Daniel son 1973
Drew Chem. Corp. 1977
Dunseth et al. 1971
Evers 1973
Gartrell 1966
Good 1968
Greer 1972
Hall 1969
Hill 1976
Kreissel 1971
Kumar 1973
Lehr 1978
Lombard! 1976
Long et al. 1971
McCollough 1976
Mint on 1972
Morgan 1972
Mori 1976
Nesbitt 1969
Palm 1978
Pflaum 1978
Rogers 1976
Rolater 1967
Sadels 1970
Sanders 1968
Sanjour 1978
Shindala 1972a
Shindala 1972b
Stinson 1976
Teller 1968
TRW Systems Group 1972a
TRW Systems Group 1972b
US Dept. of HEW 1969
US EPA 1971b
US EPA 1976b
USEPA 1978i
US EPA 1978k
185
-------
US EPA 19781
USEPA 1978m
US EPA 1978n
USEPA 1979b
Wheater 1972
Wukasch 1968
Industry Trends (location, raw materials, products)
Anonymous 1952
Anonymous 1964
Anonymous 1965
Anonymous 1966
Anonymous 1971
Anonymous 1973
Anonymous 1975
Anonymous 19 7 7
Barber 1962
Barber et al. 1960
Bernhart 1963
Blake 1974
Carothers 1963
Darden 1968
Dell 1977
Fleming 1969
Hignett 1948
Miyamoto 1975
Orckhov et al. 1976
Scott et al. 1966
Human Health
Balazova 19 71
Balazova et al. 1969
Balazova 1971
Call et al. 1965
Marci 1973
National Academy of Sciences 1971
Schiager 1978
US Bureau of Mines 1971
USEPA 1976
Water Quality
Aoyama 1973
Convey 1970
Drew Chem. Corp. 1977
Dunseth et al. 1971
Evers 1973
Goodman 1969
Greer 1972
Kumar 1973
Lehr 1978
Lombard! 1976
Long et al. 1971
Morgan 1972
Nesbitt 1969
Sadels 1970
Shindala 1972a
186
-------
Shindala 1972b
Taylor 1967
US EPA 1971b
USEPA 1973b
US EPA I974b
USEPA 1977a
US EPA I977b
USEPA 1978e
Wheater 1972
Air Quality
Adams et al. 1957
Balazova 1971
Balazova et al. 1969
Balazova 1971
Benedict et al. 1964
Bourbon 1967
Danielson 1973
Flagg 1978
Hendrickson 1961
Hodge 1970
Lombard i 1976
McCune 1971
McCune et al. 1964
National Academy of Sciences 1971
Navara 1968
Rippel 1970
Rippel 1971
Relates 1967
Stinson 1976
Suttie 1969
TRW Systems Group 1972a
TRW Systems Group 1972b
US Dept. of HEW 1969
US EPA 1974d
US EPA 1978d
USEPA 1978i
US EPA 1978k
Wheater 1972
Yang 1963
Solid Wastes
Abrams et al. 1977
Barber 1969
Barber 1975a
Barber 1975b
Bargman et al. 1971
Cheremisinoff et al. 1979
Dunseth et al. 1971
Good 1968
Goodman 1969
Palm 1978
187
-------
Socioeconomics/Land Use
Barber 1968
Barber 1975b
Cheremisinof f et al. 1979
Hocking 1978
Kumar 1973
Palm 1978
TRW Systems Group 1972a
TRW Systems Group 1972b
US EPA 1973b
USEPA 1974b
US EPA 1976b
USEPA 1978b
US EPA 1978c
USEPA 1978f
Ecology Impacts
Adams et al. 1957
Anonymous 1976
Aoyama 19 73
Balazova et al. 1969
Benedict et al 1964
Eisenbud 1973
Hocking 1978
McCune et al. 1964
McCune 1971
National Academy of Sciences 1971
Navara 1968
Palm 1978
Prister 1971
Rip pel 1970
Rip pel 1971
Schneider 1976
Suttie 1969
USEPA 1976b
USEPA 1976d
Yang 1963
Modeling of Impacts
Alsager 1978
Palm 1973a
Palm 1976b
Palm 1977c
Palm 1978
Palm 1978a
Palm 1978b
USEPA 1978g
USEPA 1978j
Noise and Vibration
USEPA 1974c
Bolt Beranek & Newman 1973
Regulations
Abrams et al. 1977
188
-------
Barber 1968
Barber 1975b
Danielson 1973
Hodge 1970
Hoffnagle 1978
Rich 1978
Schneider 1976
Suttie 1969
US EPA 1974c
US EPA 1979d
Energy
US EPA 1976c
White 1978
189
-------
5.2 BIBLIOGRAPHY
Abrams, E.F., G. Contos, and M. Drabkin, Versa-Inc. 1977. Alternatives for
hazardous waste management in the inorganic chemicals industry. Prepared
for the Office of Solid Waste, Hazardous Waste Management Division, US
Environmental Protection Agency, Washington DC.
Achorn, P.P., and J.S. Lewis, Jr. 1969. Use of superphosphoric acid in small
ammoniation-granulation plants. Croplife, p. 10-11, 15.
Achorn, P.P., H.L. Balay, E.D. Myers, and R.D. Grisso. 1971. A pollution
solution for granulation plants. Farm Chemistry 134(8):28-31.
Adams, D.F., J.W. Hendrix, and H.G. Applegate. 1957. Relationship among
exposure periods, foliar burn, and fluorine content of plants exposed to
hydrogen fluoride. Journal of Agricultural Food Chemistry 5:108-116.
Albertson, O.E. , and R.J. Sherwood. 1969. Phosphate extraction process.
Journal of the Water Pollution Control Federation 41(8): 1467-1490.
Allgood, H.Y. , F.E. Lancaster, Jr., J.A. McCollum and J.P. Simpson. 1967.
A high temperature superphosphoric acid plant. Industrial and Engineer-
ing Chemistry 59 (6): 19-29
Allgood, H.Y., F.E. Lancaster, Jr., R.D. Young and C.H. Davis. 1970. Design
of equipment to produce phosphoric acid from elemental phosphorus. Tenne
Valley Authority Bulletin, June 1970.
Alsager, Melvin D. 1978. Idaho phosphate environmental impact statement. _In
Proceedings of Environmental Symposium, The Fertilizer Institute, New
Orleans LA, p. 181-188.
Anonymous. 1952. New way to make dicalcium phosphate. Chemical Engineering
59:258-259.
. 1964. The electric phosphorus furnace. Phosphorus and
Potassium 11:19-
. 1965. Feasibility of a plasma fluidized bed for production
of elemental phosphorus. Phosphorus and Potassium 17:17.
. 1966. Gulf design's wet thermal superphosphoric acid proces
Phosphorus and Potassium 36:26-27.
1968. Elemental phosphorus developments. Phosphorus and
Potassium 36:16-19, 54.
1971. OxyNordac superphosphoric acid process. Phosphorus
and Potassium 51:33-34.
1973. Elemental phosphorus production-fluidized bed process
from Knapsack. Phosphorus and Potassium 64:44.
190
-------
1975. Large-scale uranium recovery from phosphoric acid
looks promising. Engineering and Mining Journal 11:32.
1976. Radioactivity in phosphates. Phosphorus and
Potassium 84:44-45.
Engineering News 55(1):7.
1977. Uranium recovery from phosphate rock. Chemical
1980. Phosphorus production. Chemical and Engineering
News, March 17, 1980:14.
Aoyama, I., and Y. Inoue. 1973. Estimation and evaluation of radioactive
contamination through a food web in an aquatic system. Journal of Radia-
tion Research 14(4):375-381.
Balay, H.L., and F.P. Achorn. 1971. Updated uses and handling of wet-process
superphosphoric acid. Fertilizer Solutions p. 15, 24, 26, 28, 30, March/
April.
Balazova, G. 1971. Long-term effect of fluoride emission upon children.
Fluoride Quarterly Report 4(2):85-88.
Balazova, G., P. Macuch, and A. Rippel. 1969. Effects of fluorine emissions
on the living organism (plants, animals). Fluoride Quarterly Report
2(l):33-36.
Banning, Lloyd H. 1975. Fluosilicic acid acidulation of phosphate rock.
Bureau of Mines, Albany Metallurgy Research Center. US Bureau of Mines,
Rl-8061.
Barber, J.C., Tennessee Valley Authority. 1968. The cost of pollution con-
trol. Chemical Engineering Progress 64(9):78-82.
. 1969. Waste effluent; treatment and reuse. Chemical Engi-
neering Progress 65(6):70-73.
. 1975a. Solid wastes from phosphorus production. Chapter
VII.2. _In_ Solid Wastes, C.L. Mantell (editor), John Wiley & Sons, Inc.,
18 p.
. 1975b. Storage and containment of phosphoric acid and
liquid fertilizer. Fertilizer Solutions 19(5):40, 42, 44, 46, 48.
1976a. Energy requirements for pollution abatement.
Chemical Engineering Progress, p. 42-46.
. 1976b. Reuse of wastes in the production of granular fer-
tilizers. In Proceedings of Environmental Symposium, The Fertilizer
Institute, New Orleans LA, p. 79-100.
1978. Environmental control in fertilizer production -
energy consumption and conservation. I_n_ Proceedings of Environmental
Symposium, The Fertilizer Institute, New Orleans LA, March 5-8, 1978, p.
79-100.
191
-------
1979. Falling film evaporator process,
. 1980a. Letter, James C. Barber, James C. Barber & Assoc-
iates, Chemical Consultants, to WAPORA, Inc., 20 June 1980, 10 p.
Barber, J.C. 1980b. Comments on document, "Environmental Impact Assessment
Guidelines for New Source Non-Fertilizer Phosphate Manufacturing Facili-
ties," 29 December 1980, Florence, AL.
Barber, J.C. 1980c. Energy conservation and pollution abatement at phosphorus
furnaces.
Barber, J.C., and E.G. Marks. 1962. Effects of various types of phosphate
charges on phosphorus furnace operations. TJI Proceeding of Electric
Furnace Conference 20:164-172.
Barber, J.C., E.G. Marks, and G.H. Megar, Tennessee Valley Authority. 1960.
Evaluation of reducing carbons for use in electric phosphorus furnaces.
Chemical Engineering Bulletin No. 3, 4. Wilson Dam AL, 53 p.
Barber, J.C., and T.D. Farr, Tennessee Valley Authority. 1970. Fluoride
recovery from phosphorus production. Chemical Engineering Progress 66
(ll):56-62.
Bargman, R. D., J.M. Betz, and W.F. Garber. 1971. Continuing studies in the
removal of phosphorus by the activated sludge process. T_n_ Water-1970, p.
117-121.
Benedict, Harris M., James M. Ross, and Robert W. Wade. 1964. The disposi-
tion of atmospheric fluorides by vegetation. Air and Water Pollution
Report 8(5):279-289-
Bernhart, D.N., and W.B. Chess. 1963. Determination of phosphate composition
of stock food calcium phosphate. Journal of Associated Official Agri-
cultural Chemists 46:312-315.
Blake, Henry E. , and B.D. Nash. 1974. Increasing fluosilicic acid evolution
from phosphate rock by digestion with phosphoric acid. RI-7980. US Bureau
of Mines, Albany Metallurgy Research Center.
Bolt Beranek & Newman, Inc. 1973. Fundamentals and abatement of highway
traffic noise. Prepared for the Office of Environmental Policy, Federal
Highway Administration, US Department of Transportation, Washington DC.
Variously paged.
Bourbon, P. 1967. Analytical problems posed by pollution by fluorine com-
pounds. Journal of Air Pollution Control Association 17(10):661-663.
Call, R. A., et al. 1965. Histological and chemical studies in man on ef-
fects of fluoride. Public Health Reports (U.S.) 80(6): 529-538.
Calvert, Seymour, Goldshmid Shuda, D. Leith, and Mehta Dilip. 1972. Scrubber
handbook, Vols. I & II. Prepared for US Environmental Protection Agency,
Washington DC.
192
-------
Cammack, H.Z., and G.L. Bridger. 1955. Recovery of uranium from slag from
the electric furnace production of phosphorus. ISC-638. U.S. Atomic
Energy Commission, 84 p.
Carothers, John N., and Hurka J. Rudolph, Jr. 1963. Low fluorine phosphates
from fluorine containing phosphate rock. U.S. Ratent 3,076,691; Appl.
Jan. 23, 1961. 4p.
Chemical Rubber Company (CRC). 1967. Handbook of chemistry and physics.
The Chemical Rubber Company, Cleveland OH.
Cheremisinoff, N.P., P.N. Cheremisinoff, F. Ellerbush, and A.J. Perna. 1979.
Industrial and hazardous wastes impoundment. Ann Arbor Science Publi-
shers, Inc., Ann Arbor MI, 475 p.
Cochrane, J.F. 1976. Scrubbers for calciners. J.n_ Proceedings of Environ-
mental Symposium, The Fertilizer Institute, New Orleans LA, p. 449-463.
Convery, J.J. 1970. Treatment techniques for removing phosphorus from muni-
cipal wastewaters (Water Pollution Control Series). Government Printing
Office, Washington DC, 38 p.
Gulp, R.L. 1969. Status of phosphorus removal. Public Works 100(10): 76-81.
Danielson, John A. (editor). 1973. Air pollution engineering manual. Pre-
pared for US Environnental Protection Agency, Research Triangle Park NC.
Darden, T. 1968. Elemental phosphorus production and use in fertilizer
manufacture. In Proceedings of the 18th Annual Meeting, Fertilizer
Industry Round Table, p. 54-58.
Dell, George J. 1977. Construction materials for phos-acid manufacture.
Chemical Engineering (April 10, 1967), p. 234, 236, 238, 240, and 242.
Dilworth, Ben C. , and Elbert J. Day. 1964. Phosphorus availability studies
with feed grade phosphates. Poultry Science 43(4):1039-1044.
Douglas, John, and J. Harold Parker. 1977- The phosphate industry rebounds.
Farm Chemicals 40(6):32-33, 36, 38.
Drew Chemical Corporation. 1977. Principles of industrial water treatment.
Boonton NJ, 310 p.
Dunseth, M.G., M.L. Salutsky, K.M. Ries, and J.J. Shapiro. 1971. Ultimate
disposal of phosphate from wastewater by recovery as fertilizer. US
Clearinghouse Federation of Science Technical Information, PB 196 739.
81 p.
Eisenbud, M. x 1973. Food chain from soil to man. In Environmental Radio-
activity, Academic Press, Inc., New York NY, p. 118-136.
Evers, R.H. 1973. Advanced wastewater treatment techniques for removing
nitrogen and phosphorus. Water Sewage Works, p. 15-16, 18-19, 134,
136-137.
193
-------
Flagg, Robert B. 1978. Fugitive emission monitoring. Jtn Proceedings of
Environmental Symposium, The Fertilizer Institute, New Orleans LA, p.
211-216.
Fleming, J.D. 1969. Polyphosphates are revolutionizing fertilizers. Part I:
What polyphosphates are. Farm Chemistry 132:30-36.
Gartrell, F.E. , and J.C. Barber, Tennessee Valley Authority. 1966. Pollution
control interrelationships. Chemical Engineering Progress 62(10):44-47-
Giusti, Gino P. 1980. Sulfur - the essential ingredient. Fertilizer Pro-
gress 11(4).
Good, P.C., and J.E. Tress. 1968. Recovery of hydrofluoric acid from waste
fluorosilicic acid, preliminary studies. RI 7213. US Bureau of Mines.
Goodman, B.L., and K.A. Mikkelson. 1969. Advanced wastewater treatment;
removing phosphorus and suspended solids. Chemical Engineering 77:75-83.
Greer, D.E., and C.D. Ziebell. 1972. Biological removal of phosphates from
water. Journal of Water Pollution Control Federation 44(12):2342-2348.
Harre, Edwin E. 1976. What's ahead in fertilizer supply-demand. In_ Tennessee
Valley Authority, Proceedings of TVA Fertilizer Conference, July 1976,
Cincinnati OH. National Fertilizer Development Center, Muscle Shoals AL,
p. 18-24.
Hall, M.W., and R.S. Engelbrecht. 1969. Phosphorus removal—past, present
and future. Water Wastes Engineering 6(8):50-53.
Hendrickson, E.R. 1961. Dispersion and effects of airborne fluorides in
central Florida. Journal of the Air Pollution Control Association
ll(5):220-225.
Hignett, T.P. 1948. Development of blast furnace process for production of
phosphoric acid. I,II,III. Chemical Engineering Progress 44:753-764;
821-832; 895-904.
Hill, L.J. 1976. Removing gaseous pollutants from phosphate fertilizer
operations. JLn_ proceedings of Environmental Symposium, The Fertilizer
Institute, New Orleans LA, p. 421-436.
Hocking, H. Treve. 1978. Reclamation - an overview. In Proceedings of
Environmental Symposium, The Fertilizer Institute, New Orleans LA, p.
409-418.
Hodge, H.C., and F.A. Smith. 1970. Air quality criteria for the effects of
fluorides on man. Journal of Air Pollution Control Association 20(4):
226-232.
Hoffnagle, Gale, and R. Dunlap. 1978. Industrial expansion and the 1977
Clean Air Act Amendments. Pollution Engineering 10(12):36-43.
194
-------
Hooks, Homer. 1978. EPA's area-wide environmental impact statement on Florida
phosphate. In proceedings of Environmental Symposium, The Fertilizer
Institute, New Orleans LA, p. 189-198.
Hurst, T.L. 1961. Chapter 18. _In Phosphorus and Its Compounds, J.R. Van
Wazer, ed., Interscience Publishers, Inc., New York NY, 2:1209-1213.
Jenkins, D. , J.F. Ferguson, and A.B. Menar. 1971. Chemical processes for
phosphate removal. Water Resources 5(7):369-389.
Kirk-Othner Encyclopedia of Chemical Technology. 1969. Second Edition,
Volume 18. John Wiley and Sons, Inc., New York NY, p. 95-96.
Kreissl, J.F. 1971. Phosphorus removal practice. US National Technical
Information Service. PB214 059/8. 30 p.
Kumar, J.J. , and N.L. Clesceri. 1973. Phosphorus removal from waste waters:
A cost analysis. Water Sewage Works 120(3):82, 86, 88-91.
Lehr, James R. 1978. Fluorine chemical redistribution in relation to gypsum
storage pond systems. In Proceedings of Environmental Symposium, The
Fertilizer Institute, New Orleans LA., p. 277-312.
Lombard!, C.E. , and A.J. Teller. 1976. Scrubbing fluoride emissions. _In_
Proceedings of Environmental Symposium, The Fertilizer Institute, New
Orleans LA, p. 437-448.
Long, D.A. , J.B. Nesbitt, and R.R. Kountz. 1971. Soluble phosphorus removal
in the activated sludge process. I. Chemical-biological process perfor-
mance (Water Pollution Control Research Series). Government Printing
Office, Washington DC, 119 p.
Long, T.A., A.D. Tillman, A.B. Nelson, B. Davis, and W.D. Gallup. 1956.
Dicalcium phosphate and soft phosphate with colloidal clay as sources of
phosphorus for beef heifers. Journal of Animal Science 15:1112-1118.
Louria, Donald B., Morris M. Joselow and Ann A. Browder. 1972. The human tox-
icity of certain trace elements. Annals of Internal Medicine 76:307-319.
McCollough, John F., Tennessee Valley Authority. 1976. Phosphoric acid
purification: Comparing the process choices. Chemical Engineering
83(26):101-103.
McCuhe, D.C., Leonard H. Weinstein, Jay S. Jacobson, and A.E. Hitchcock.
1964. Some effects of atmospheric fluoride on plant metabolism. Journal
of the Air Pollution Control Association 14(11): 465-468.
McCune, Delbert C. , and Leonard H. Weinstein. 1971. Metabolic effects of
atmospheric fluorides on plants. Environmental Pollution 1:169-174.
Marci, A.N. 1973. Environmental radioactive pollution and man. J-n Radio-
ecology, V.M. Klechkouskii (editor), John Wiley and Sons, Inc., New York
NY, p. 141-156.
195
-------
Minton, G.R., and D.A. Carlson. 1972. Combined biological-chemical phos-
phorus removal. Journal of the Water Pollution Control Federation
44(9): 1736-1755.
Miyamoto, Mitsuga. 1975. New Nissan process for concentrated phosphoric acid
and current trends in phosphoric acid manufacture. Chemical Economy and
Engineering Review 7(5):20-27.
Morgan, W.E. , and E.G. Fruh. 1972. An investigation of phosphorus removal
mechanisms in activated sludge systems (Environmental Protection Tech-
nology Series). Government Printing Office, Washington DC, 137 p.
Mori, Masasi. 1976. Recovery of phosphorus pentoxide from wastewaters by
adding lime. Jn Sekko to Sekkai, Volume 142, p. 111-113.
National Academy of Sciences. 1971. Biologic effects of atmospheric pollu-
tants: Fluorides. Washington DC, 295 p.
. 1974. Effects of fluorides in animals. 70 p.
Navara, J. , and A. Holub. 1968. The effect of fluoride upon plants (pathology)
Fluoride Quarterly Report 1:38-40.
Nesbitt, J.B. 1969. Phosphorus removal, state-of-the-art. Journal of Water
Pollution Control Federation 41(5)(Pt.l):701-713.
Onstott, E.I., W.S. Gregory, E.F. Thode, and K.L. Roman. 1973. Electro-
precipitation of phosphate from sewage. Journal of Environmental Engi-
neering Division, American Society of Civil Engineers 99(6): 897-907.
Orekhov, I.I. , V.P. Sverdlova, G.L. Slobodkiva, and S.B. Kopileva. 1976.
Production of concentrated phosphoric acid solutions. The Soviet Chem-
ical Industry 8(1):27-28.
Palm, Gordon F., and Anwar E.Z. Wissu. 1978. Environmental aspects of waste
disposal in the phosphate industry. In Proceedings of Environmental
Symposium, The Fertilizer Institute, New Orleans LA, p. 347-370.
Perry, John H. (editor). 1969. Chemical engineer's handbook. McGraw-Hill,
New York NY, p. 8-1 - 8-49.
Pflaum, Craig A. 1978. Practical design of cross-flow scrubbers in the phos-
phate industry, jn Proceedings of Environmental Symposium, The Ferti-
lizer Institute, New Orleans LA, p. 233-244.
Peterson, A.W. , D.L. Hacking, and D.E. Turner. 1962. Manufacture and use of
superphosphoric acid from wet-process acid. Presented at the 142nd ACS
Meeting, Sept. 9-14, Atlantic City NJ.
Prister, B.S. 1971. Behavior of uranium in the biological chain. Nuclear
Science Abstracts 25(22): 5109.
Rich, John B. 1978. Implementation of the Toxic Substances Control Act. In_
Proceedings of Environmental Syposium, The Fertilizer Institute, New
Orleans LA, p. 153-178.
196
-------
Rippel, A. 1970. Long-term effect of fluoride emissions on vegetation.
Fluoride Quarterly Report 3(1):18-21.
1971. Effect of fluoride emission on animal products.
Fluoride 4(2):89-92.
Rodgers, J. 1976. Scrubbing particulate emissions. ^n_ Proceedings of Envi-
ronmental Symposium, The Fertilizer Institute, New Orleans LA, p. 411-419.
Rolater, F.G. 1967. Phosphorus furnace fume control. Journal of Metals
19(ll):36-37.
Ross, R.C. 1975. Uranium recovery from phosphoric acid nears reality as a
commercial uranium source. Engineering/Mining Journal 176(12):80-85.
Rushton, W.E. 1966. Swenson superphosphoric acid process. Phosphorus and
Potassium 23:13-16, 19.
Rushton, W.E. , and J.L. Smith. 1964. Superphosphoric acid from wet process
phosphoric acid. Chemical Engineering Progress 60(7):97-99.
Sadels, S.E. 1970. An electrochemical method for removal of phosphates from
wastewaters (Water Pollution Control Research Series). Government Printing
Office, Washington DC, 47 p.
Sanders, M.D. 1968. Recovery of fluorides as by-products. In Phosphoric
Acid, Marcel Dekker Publishers, New York NY, p. 765-777-
Sanjour, William. 1978. Hazardous waste management regulations. In Proceed-
ings of Environmental symposium, The Fertilizer Institute, New Orleans
LA, p. 149-152.
Schiager, Keith J. 1978. Radiation a perspective. In Proceedings of an
Environmental Symposium, The Fertilizer Institute, New Orleans LA, 6, 7,
8 March 1978.
Schneider, W.J. 1976. The Idaho phosphate EIS. Jn Proceedings of Environ-
mental Symposium, The Fertilizer Institute, New Orleans LA, p. 301-308.
Scott, W.C., and J.A. Wilbanks. 1961. Producing 11-30-0 grade liquid fertilizer
from superphosphoric acid and ammonia. Agricultural Chemistry 16:16-18,
93-94.
Scott, W.C., G.G. Patterson, and A.B. Phillips. 1966. New developments in
pilot-plant production of highly concentrated wet-process phosphoric
acid. Commercial Fertilizer 113:32-33, 36-37, 52-53.
Shindala, A. 1972a. Nitrogen and phosphorus removal from wastewaters—Part
1: Water Sewage Works 119(6):66-71.
I972b. Nitrogen and phosphorus removal from wastewaters—
Part 2: chemical-biological. Water Sewage Works 119 (7) :60-67.
197
-------
Stinson, Mary, and F. Ellerbusch. 1976. Air pollution emissions and control
from the manufacture of elemental phosphorus (Draft). US Environmental
Protection Agency, Industrial Environmental Research Laboratory, Office
of Research and Development, Edison NJ, 32 p.
Stowasser, W.F. 1977. Phosphate rock, the present and future supply and
demand. Letter from US Bureau of Mines to R.E. McNeill, US Environmental
Protection Agency, Region IV.
Suttie, J.W. 1969. Air quality standards for the protection of farm animals
from fluorides. Journal of the Air Pollution Control Association 19(4):
239-242.
Taylor, A.W. 1967. Phosphorus and water pollution. Journal of Soil and
Water Conservation 22:228-231.
Teller, A.J., and D. Reeve. 1968. Scrubbing of gaseous effluents, jn Phos-
phoric Acid, Marcel Dekker Publishers, New York NY, p. 741-751.
TEW Systems Group. 19 72a. Engineering and cost-effective ness study of fluo-
ride emissions control, Volume I. APTD-0945. McLean VA.
. 1972b. Engineering and cost effectiveness study of
fluoride emissions control, Volume 2. McLean VA.
US Department of Commerce. 1980. 1980 U.S. industrial outlook for 200
industries with projections for 1984. US Government Printing Office,
Washington DC, 515 p.
US Department of Energy. 1978. Cogeneration: technical concepts, trends,
prospects. Division of Fossil Fuel Utilization, Washington DC, 41 p.
US Department of Health, Education & Welfare. 1969. Control techniques
for particulate air pollutants. National Air Pollution Control Adminis-
tration, Washington DC.
US Department of the Interior, Bureau of Mines. 1977. Phosphate rock, the
present and future supply and demand. 10 p.
. 1979. Mineral industry survey, phosphate rock - 1978.
Washington DC, 6 p.
US Environmental Protection Agency. 1971a. Background information for
proposed new source performance standards. Office of Air Programs,
Research Triangle Park NC.
1971b. Inorganic fertilizer and phosphate mining indus-
tries, water pollution and control. Prepared by Battelle Memorial Insti-
tute, Richland WA, 225 p.
____^_ . 1973a. Development document for proposed effluent limi-
tations guidelines and new source performance standards for the phos-
phorus-derived chemicals segment of the phosphate manufacturing point
source category. Office of Air and Water Programs, Washington DC, 159 p.
198
-------
_. 1973b. Economic analysis of proposed effluent guidelines,
the industrial phosphate industry. Office of Planning and Evaluation,
Washington DC.
• 1974a. Development document for effluent limitations
guidelines and new source performance standards for the basic fertilizer
chemicals segment of the fertilizer manufacturing point source category.
Office of Air and Water Programs, Washington DC, 168 p.
• 1974b. Economic analysis of proposed effluent guidelines,
non-fertilizer phosphate manufacturing industry. Office of Planning and
Evaluation, Washington DC.
• 1974c. Information on levels of environmental noise re-
quisite to protect the public health and welfare with an adequate margin
of safety. Office of Noise Abatement and Control, Arlington VA, vari-
ously paged, 159 p.
. 1974d. Trace pollutant emissions from the processing of
non-metallic ores. 650/2-74/122. Washington DC.
. 1975. Environmental impact assessment guidelines for
selected new source industries. Office of Federal Activities, Washington
DC, 35 p. plus appendices.
. 1976a. Development document for effluent limitations
guidelines and new source performance standards for the other non-ferti-
lizer phosphate chemicals segment of the phosphate manufacturing point
source category. Office of Water and Hazardous Materials, Washington DC,
105 p.
. 1976b. Disposal of hazardous wastes, manual on hazardous
substances in special wastes. Washington DC, p. 369-379.
. 1976c. "Executive Summary," Environmental considerations of
selected energy conserving manufacturing process options, Volume 13:
Elemental phosphorus and phosphoric acid industry report. Office of
Research and Development, Cincinnati OH, 96 p.
1976d. Quality criteria for water. Washington DC, 501 p.
1976e. (Draft) Air pollution emissions and control from the
manufacture of elemental phosphorus. Industrial Environmental Research
Laboratory, Office of Research and Development, Edison NJ, 32 p.
1977a. Effects of phosphate mineralization and the phos-
phate industry on radium-226 in ground waters of central Florida. Office
of Radiation Programs, Las Vegas NV, 125 p.
1977b. Federal guidelines - state and local pretreatment
programs, Volume III. Office of Water Program Operations, Washington DC,
475 p.
199
-------
. 1977c. Industrial process profiles for environmental use,
Chapter 22: the phosphate rock and basic fertilizer industry. Office of
Research and Development, Cincinnati OH. Prepared by Dow Chemical Co.,
Freeport TX, and Radian Corp., Austin TX, 202 p.
. 1977d. Source assessment: phosphate fertilizer industry
phosphoric acid and superphosphoric acid. Office of Research and Develop-
ment, Washington DC. Prepared by Monsanto Research Corporation, Dayton
OH, 93 p.
. 1978a. Central Florida phosphate industry areawide impact
assessment program, Volume 1: Program and industry description. Per-
formed by Texas Instruments, Inc., Dallas TX, 93 p.
. 1978b. Central Florida phosphate industry areawide impact
assessment program, Volume 2: Environmental permits and approvals re-
lating to phosphate mining and fertilizer manufacturing in Florida.
Performed by Texas Instruments, Inc., Dallas TX, 85 p.
. 1978c. Central Florida phosphate industry areawide impact
assessment program. Volume 3: Socioeconomics. Performed by Texas Instru-
ments, Inc., Dallas TX, 221 p.
. 1978d. Central Florida phosphate industry areawide impact
assessment program; Volume 4: Atmosphere. Performed by Texas Instru-
ments, Inc., Dallas TX, 146 p.
. 1978e. Central Florida phosphate industry areawide impact
assessment program, Volume 5: Water. Performed by Texas Instruments,
Inc. , Dallas TX, 309 p.
. 1978f. Central Florida phosphate industry areawide impact
assessment program, Volume 6: Land. Performed by Texas Instruments,
Inc., Dallas TX, 221 p.
. 1978g. Central Florida phosphate industry areawide impact
assessment program, Volume 7: Alternative effects assessment. Performed
by Texas Instruments, Inc., Dallas TX, 330 p.
. 1978h. Draft areawide environmental impact statement,
Central Florida phosphate industry. Variously paged, 187 p.
1978i. Evaluation of emissions and control techniques for
reducing fluoride emissions from gypsum ponds in the phosphoric acid
industry. Office of Energy, Minerals, and Industry, Research Triangle
Park NC. Prepared by Environmental Science and Engineering, Inc., Gaines-
ville FL, 210 p.
. 1978j. Final areawide environmental impact statement,
Central Florida phosphate industry, Volume 1. EPA 904/9-78-026a. Atlanta
GA, 80 p.
200
-------
• 1978k. OAQPS guideline series - Air pollutant control
techniques for phosphate rock processing industry. Office of Air Quality
Planning and Standards, Research Triangle Park NC. Prepared by PEDCo
Environmental, Inc., Cincinnati OH, 300 p.
• 19781. Particulate control highlights: fine particle scrub-
ber research. Office of Research and Development, Washington DC. Pre-
pared by S. Calvert and R. Parker, A.P.T., Inc., San Diego CA, 12 p.
• 1978m. Particulate control highlights: performance and
design model for scrubbers. Office of Research and Development, Wash-
ington DC. Prepared by S. Yung and S. Clavert, A.P.T. , Inc., San Diego
CA, 19 p.
1978n. Particulate control highlights: research on fabric
filtration technology. Office of Research and Development, Washington
DC. Prepared by R. Dennis and N.F. Surprenant, GCA Corporation, Bedford
MA, 15 p.
• 1978o. Source assessment: chemical and fertilizer mineral
industry state-of-the-art. Office of Research and Development, Cincin-
nati OH. Prepared by Monsanto Research Corporation, Dayton OH, 122 p.
. 1978p. Guideline on air quality models. OAQPS Guideline
Series, Office of Air Quality Planning and Standards, Research Triangle
Park NC.
. 1978q. Environmental pollution control, textile processing
industry.
. 1979a. Environmental impact assessment guidelines for new
source fossil-fueled steam electric generating stations. Office of
Environmental Review, Washington DC, 144 p.
•
. 1979b. Evaluation of control technology for the phosphate
fertilizer industry, final draft report. Industrial Environmental Re-
search Laboratory, Research Triangle Park NC. Prepared by TRC (The
Research Corporation of New England), Wethersfield CT.
1979c. A handbook of key Federal regulations and criteria
for multimedia environmental control. Office of Energy, Minerals, and
Industry, Research Triangle Park NC.
1979d. Source assessment, phosphate fertilizer industry.
Office of Energy, Minerals and Industry, Research Triangle Park NC.
Prepared by Monsanto Research Corporation, Dayton OH, 186 p.
Van Wazer, J.R. 1968. Phosphoric acids and phosphates. In Kirk-Othner
Encyclopedia of Chemical Technology, 2nd Edition. John Wiley and Sons,
Inc., New York NY. 15:257-261.
WAPORA. 1979b. Environmental impact guidelines for new source phosphate
fertilizer manufacturing facilities, final report. Prepared for Office
of Environmental Review, US Environmental Protection Agency, Washington
DC. 210 p.
201
-------
Wheater, D.W.F. 1972. Phosphorus removal from sewage. Process Biochemical
7(6): 17-19, 26.
White, Bill. 1978. Energy, food, and fertilizers. Fertilizer Progress,
July-August, 5 p.
White, J.C., T.N. Goff and P.C. Good. 1978. Continuous-circuit preparation
of phosphoric acid from Florida phosphate matrix. US Department of the
Interior, Bureau of Mines, Report of Investigations 8326, Washington DC,
22 p.
Wukasch, R. F. 1968. New phosphate removal process. Water Wastes Engineering
5 (9): 58-60.
Yang, S.F., and G.W. Miller. 1963. Biochemical studies on the effect of
fluoride on higher plants. I. Metabolism of carbohydrates, organic
acids, and amino acids. II. The effect of fluoride on sue rose-synthe-
sizing enzymes from higher plants. III. The effect of fluoride on dark
carbon dioxide fixation. Journal of Biochemistry 88(3) :505-522.
Zitko, V., D.E. Aiken, S.N. Tibbo, K.W.T. Besch, and J.M. Anderson. 1970.
Toxicity of yellow phosphorus to herring (Clupea harengus), Atlantic
salmon (Salmosalar), lobster (Homarus americamus), and beach flea
(Gammarus oceanicus)." Journal of Fisheries Research Board Canada 27,
No. 1, 21-29 (1970).
202
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1. REPORT NOT
_EPA-130/6-81-004
TECHNICAL REPORT DATA
(f lease read instructions on the reverse before completing) •
|3. RECIPIENT'S ACCESSION NO.
2.
4. TITLE AND SUBTITLE
Environmental Impact Guidelines for New Source
Non-fertilizer Phosphate Manufacturing
5. REPORT DATE
1981
6. PERFORMING ORGANIZATION CODE
7. AUTHOFUS)' ~~ ~
Ronald B. McNeil, Mark Cameron, Robert P. Stevens
and James C. Barber
8. PERFORMING ORGANIZATION REPORT NO.
613/A
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Wapora, Inc.
6900 Wisconsin Ave., N.W.
Washington, D.C. 20015
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-4157
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Federal Activities
401 M Street S.W.
Washington. D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/100/102
15. SUPPLEMENTARY NOTES
EPA Task Officer is Frank Rusincovitch, (202)7559368
16. ABSTRACT
This guideline document has been prepared to augment the information previously
released by the Office of Federal Activities entitled Environmental Impact
Assessment Guidelines for Selected New Source Industries. Its purpose is to
provide guidance for the preparation and/or review of environmental documents
(Environmental Information Document or Environmental Impact Statement) which
EPA may require under the authority of the National Environmental Policy Act
(NEPA) as part of the new source (NPDES) permit application review process.
This document has been prepared in six sections; organized in a manner to
facilitate analysis of the various facets of the environmental review process,
The initial section includes a broad overview of the industry intended to
familiarize the audience with the processes, trends, impacts and applicable
pollution regulations commonly encountered in the non-fertilizer phosphate
industry. Succeeding sections provide a comprehensive identification and
analysis of potential environmental impacts, pollution control technologies
available to meet Federal standards, and other controlable impacts. The document
concludes with two sections: available alternatives, and a comprehensive
listing of references for further reading.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Non-fertilizer Phosphate Plant
Water Pollution
Environmental Impact
Assessment
10A
13B
18, DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report}
Unclassified
PAGES
202
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
4U.S. GOVERNMENT PRINTING OFFICE: 1981 341-082/258 1-3
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