United States Office of Water & SW 180c
Environmental Protection Waste Management October 1979
Agency Washington DC 20460
ft*
vvEPA Assessment of Solid Waste
Management Problems
and Practices in the Inorganic
ENVIRONMENTAL
Chemicals Industry pSSr
DALL* •. TEXAS
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Prepublication issue for EPA libraries
and State Solid Waste Management Agencies
ASSESSMENT OF SOLID WASTE MANAGEMENT PROBLEMS
AND PRACTICES IN THE INORGANIC CHEMICALS INDUSTRY
This veport (Sf»'-180o) describes inovk performed
for the Office of Solid Waste under contract no. 68-03-2604
and is reproduced as received from the contractor.
The findings should be attributed to the contractor
and not to the Office of Solid Waste.
Copies will be available from the
National Technical Information Service
U.S. Department of Commerce
Springfield, VA 22161
U.S. ENVIRONMENTAL PROTECTION AGENCY
1979
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This report was prepared by V.ersar, Inc., Springfield, Virginia,under
contract number 68-03-2604.
Publication does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor
does mention of commercial products constitute endorsement by the
U.S. Government.
An environmental protection publication (SW-180c ) in the solid waste
management series.
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CONTENTS
Figures vii
Tables ix
Acknowledgments x
I. EXECUTIVE SUMMARY 1
Introduction 1
Industry Description 2
Program Methodology 14
II. INDUSTRY CHARACTERISTICS 16
III. SELECTION OF MAJOR WASTE SOURCES 36
IV. ANALYSIS OF MAJOR WASTE SOURCES 46
Potash 46
Alumina 49
Phosphorus 52
Natural Soda Ash 54
Hydrated Lime 56
Hydrofluoric Acid 56
Borax from Ore 60
Solvay Process Soda Ash 60
Titania - Sulfate Process 63
Sodium Chromate and Dichromate 66
Iron Oxide Pigments . 68
Lithium Carbonate . 70
Titania - Chloride Process 72
Aluminum Sulfate 75
Chlor-Alkali - Diaphragm Cell Process 77
Chlor-Alkali - Mercury Cell Process 80
Zinc Oxide 84
Antimony Oxide 87
Barium Sulfate 89
Manganese Sulfate 91
Vanadium Pentoxide 91
Calcium Phosphate (Food Grade) 93
Calcium Carbide 98
Sodium Hypophosphite 100
Barium Carbonate and Strontium Carbonate 102
Sodium 106
iii
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CONTENTS
(continued)
Sodium Chlorate 109
Chrome Yellow 112
Potassium Permanganate 112
V. CURRENT DISPOSAL PRACTICES 116
Current Disposal Practices by Industry Group 116
Chlor-Alkali - Diaphragm Cell 116
Chlor-Alkali - Mercury Cell 117
Solvay Soda Ash 117
Natural Soda Ash 118
Titanium Dioxide - Sulfate Process 118
Titanium Dioxide - Chloride Process 118
Antimony Oxide 119
Barium Sulfate 119
Zinc Oxide 120
Chrome Yellow 120
Iron Oxide 120
Hydrofluoric Acid 121
Lime 121
Alumina 122
Aluminum Sulfate 123
Sodium 123
Sodium Chlorate 123
Sodium Hypophosphite 124
Potash 124
Potassium Permanganate 124
Barium and Strontium Carbonates 124
Borax 125
Calcium Carbide 125
Calcium Phosphate 126
Sodium Dichromate 126
Lithium Carbonate 126
Manganese Sulfate 127
Phosphorus 127
Sodium Silicofluoride 128
Vanadium Pentoxide 128
VI. RCPA 4004 COMPLIANCE COSTS 129
COST METHODOLOGY 130
Data Sources 130
Presentation of Costs 130
iv
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CONTENTS
(can. tinned)
Cost Assumptions 130
Price Impacts 131
COMPLIANCE COSTS 133
CMorine/Caustic Soda (Diaphragm Cell) ,. 134
Chlorine/Caustic Soda (Mercury Cell) 134
Potassium Chloride 135
Potassium Sulfate 135
Alumina 136
Phosphorus 137
Natural Soda Ash 137
Lime 138
Hydrofluoric Acid 133
Borax 140
Solvay Process Soda Ash 140
Titanium Dioxide (Sulfate Process) 140
Sodium Dichromate 140
Iron Oxide 140
Lithium Carbonate 141
Titanium Dioxide (Chloride Process) 141
Aluminum Sulfate 141
Zinc Oxide 142
Antimony Oxide 142
Barium Sulfate 142
Manganese Sulfate 142
Vanadium Pentoxide 143
Calcium Phosphate 143
Sodium Hypophosphite 144
Barium Carbonate 144
Strontium Carbonate 144
Sodium 145
Sodium Chlorate 145
Chrome Yellow 145
Potassium Permanganate 145
Calcium Carbide 145
VII. WASTE HANDLING ALTERNATIVES AND RECOVERY OPTIONS 147
Potash 147
Alumina 147
Phosphorus 147
Line 148
Hydrofluoric Acid 148
v
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CONTENTS
(continued)
Titanium Dioxide 148
Chlor-Alkali 149
Sodium 149
Calcium Carbide 149
Chlorates 150
Chrome Yellow 150
NEW TRENDS IN THE INDUSTRY 150
VEIL REFERENCES 151
VI
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FIGURES
Number Page
1 States containing plants with high RCRA impact ^
2 Potassium chloride manufacture from sylvite ore 47
3 Potassium sulfate manufacture 48
4 Alumina manufacture from bauxite 50
5 Phosphorus flow diagram (electric furnace process) .... 51
6 Sodium carbonate from trona ore sesqui-carbonate
process 55
7 Calcium oxide (lime) manufacture 57
8 Hydrofluoric acid manufacture 58
9 Borax manufacture fron ore 61
10 Sodium carbonate manufacture by the Solvay process .... 62
11 Titanium dioxide manufacture by the sulfate process .... 64
12 Sodium dichromate manufacture 67
13 Iron oxide pigments manufacture 69
14 Lithium carbonate manufacture 71
15 Titanium dioxide manufacture by the chloride process
using 95% ore or 65% ore 73
16 Aluminum sulfate manufacture 76
17 Chlor-alkali manufacture diaphragm cell process 78
18 Chlor-alkali manufacture mercury cell process 83
19 Zinc oxide manufacture by the American process 86
20 Antimony oxide manufacture 88
vii
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FIGURES
(con tinned)
Number Page
21 Barium sulfate manufacture from barite ore 90
22 Manganese sulfate manufacture 92
23 Vanadates manufacture from Idaho ferro phosphorus 94
24 Standard process for food-grade calcium phosphates .... 96
25 Manufacture of food grade dicalcium phosphate 97
26 Open furnace calcium carbide manufacture 99
27 Process for manufacture of sodium hypophosphite 101
28 Barium carbonate manufacture 103
29 Strontium carbonate manufacture 105
30 Sodium and chlorine manufacture Downs cell process .... 107
31 Sodium chlorate manufacture 110
32 Chrome yellow manufacture 113
33 Potassium permanganate production 114
Vlll
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TABLES
Nuntoer Page
1 Amounts of Waste Generated by Industry Categories 5
2 Estimated Compliance Costs for Non-Hazardous Wastes .... 11
3 Inorganic Chemicals Industry Characterization 17
4 Land-Destined Waste Characterization of the Inorganic
Chemicals Industry 39
5 Distribution of Estimated Amounts of Land-Destined
Wastes Generated by the Diaphragm Cell Process
(kkg/year) 81
6 Distribution of Estimated Land-Destined Wastes Generated
by the Mercury Cell Process 85
7 Distribution of Estimated Wastes Generated by Sodium
Chlorate Manufacture Ill
ix
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ACKNOWLEDGMENTS
The work reported herein was accomplished as Task 2 under EPA Contract
No. 68-03-2604 with the joint sponsorship of the lERL-Ci, Industrial
Pollution Control Division and the Office of Solid Waste, Land Disposal
Division. The EPA Technical Project Monitors were Mary K. Stinson (IERL)
and Jon Perry (OSW).
Mr. Edwin F. Abrains/ an Operations Manager at Versar, Inc., was Program
Manager. Mr. Edwin F. Rissmann, the Principal Investigator, was assisted by
Peter LeBoff, Economist, and Garry Brooks, Environmental Scientist.
Versar would like to acknowledge the cooperation of the many chemical
corporations that contributed to this study. Their assistance was invaluable.
x
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I. EXECUTIVE SUMMARY
Introduction
The disposal of industrial wastes in landfills and permanent lagoons
in an environmentally sound manner is an area of increasing concern. The
adverse environmental and economic effects of disposal facilities which
are improperly located, designed, and managed will continue to increase
unless sound control practices are instituted and followed. The severity of
the problems associated with industrial solid waste disposal results from
several factors. First, more wastes are being disposed of on the land as
a result of population increases, economic and industrial growth, and
affluence. In addition, new regulations are causing increased generation of
solid wastes by requiring more stringent control of air and water pollutants.
To adequately determine the magnitude of these problems of industrial
solid waste disposal requires background information with which to
identify and define the specific solid waste problems of various industries.
This report addresses solid waste generation and management relative to
the inorganic chemicals industry. This study is one of a series of
assessments of industrial solid waste being conducted for the EPA Office of
Solid Waste (OSW) to provide support for implementation of P.L. 94-580,
the Resource Conservation and Recovery Act of 1976 (RCRA).
The Resource Conservation and Recovery Act of 1976 is an amendment to
a prior statute, the Solid Waste Disposal Act of 1965. The main purpose of
this act is to ensure that solid wastes are managed so as to prevent
damage to public health and the environment. The act addresses hazardous
wastes (Subtitle C) and non-hazardous wastes (Subtitle D). Although this
study is concerned with Subtitle D, and emphasizes non-hazardous wastes,
it addresses all of the solid wastes associated with the inorganic chemicals
industry. Definition of hazardous and non-hazardous wastes for this
study is based on proposed lists given in the Federal Register of December
18, 1978. It is important to note that the final regulations and guide-
lines may be different from those on which the 1978 list is based.
The RCRA requires that EPA provide criteria to be used by the states
in identifying practices that constitute the open dumping of solid wastes.
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It also requires that EPA provide criteria for determining which solid waste
disposal facilities do and which do not "pose a reasonable probability of
adverse effects on health or the environment." As part of a broad-based
effort undertaken to fulfill these requirements, EPA has commissioned this
study of solid waste disposal in the inorganic chemicals industry. The
study consisted of the following subtasks:
1. Industry Characterization - discussed in Section II.
2. Selection of Major Waste Sources - discussed in Section III.
3. Analysis of Selected Waste Sources - discussed in Section IV.
4. Treatment and Disposal Practices - discussed in Section V.
5. RCRA. Compliance Costs - discussed in Section VI.
6. Identification of Waste Handling Alternatives and Recovery Options -
discussed in Section VII.
This report provides (1) a data base on the type and quantity of wastes
generated and the treatment and disposal techniques now applied for their
control; (2) the background information needed to develop a long-term
strategy for Federal policies concerning solid wastes from inorganic
chemical industries; (3) information concerning the costs to industry of
meeting ECRA requirements, specifically Section 4004. The RCRA induced
costs are the additional costs above current costs of solid waste control
that will be incurred in bringing existing utilities into compliance with
RCRA requirements.
Industry Description
The inorganic chemicals industry is one of a number of sub-industries
comprising the broad chemicals industry. In its industrial classification,
the Bureau of Census has grouped the inorganic chemicals industry under the
Standard Industrial Classification (SIC) 281. The industry manufactures a
wide variety of chemicals and chemical products from inorganic compounds.
Inorganic compounds are those compounds usually not containing carbon and
are derived from atmospheric gases, minerals, water, and other matter that
is never, of itself, a part of living organisms.
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Types of Industries—
There are four major subcategories under the SIC 281 classification:
the chlor-alkali (SIC 2812) manufacturers that produce such comtnodities as
chlorine, caustic soda, potassium hydroxide, and soda ash; the industrial
gases (SIC 2813) manufacturers that produce such commodities as oxygen,
nitrogen, hydrogen, carbon dioxide and acetylene; the inorganic pigments
(SIC 2816) manufacturers that produce such commodities as titanium dioxide,
chrome pigments and iron blues; and the manufacturers of the industrial
inorganic chemicals not elsewhere classified (SIC 2819) that produce a
diversity of commodities such as sulfuric acid, hydrofluoric acid, alum,
sodium sulfide, and phosphorus.
The uses of inorganic chemicals are varied, ranging from pigment bases
for paints to scouring agents for toothpaste. Sulfuric acid, the largest
volume inorganic chemical produced in the United States, is used primarily
in the manufacture of phosphoric fertilizers and inorganic pigments.
The companies which produce industrial chemicals range from small
independent companies with one or two products to multi-plant corporations
employing thousands of people and making thousands of products. The
market is dominated by a relatively small number of large, diversified
companies. Among the reasons for this dominance by a relatively few
companies are economies of scale, growth by acquisition, and the trend
toward greater horizontal and vertical integration.
Industry Distribution—
The inorganic chemical production facilities are concentrated in certain
areas of the country rather than randomly distributed throughout the nation.
Most facilities are generally capital intensive skilled labor operations
located in the East Coast (Delaware, New Jersey), Gulf Coast (Texas,
Louisiana),_ or West Coast (California). Inorganic chemical plants are
located near coastal areas because raw materials for use in the manufacturing
of inorganic chemicals depend to a large extent on water transportation
since they are not readily transported by pipeline.
The ages of plants in the inorganic chemicals industry range from five
to 30 years. The production process is typically continuous, rather than
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batch, and operating levels of 70 to 85 percent of capacity nust generally
be achieved to assure efficiency and profitability.
Since major technological developments tend to take place infrequently,
new facilities are built only when market demand justifies capacity
expansions. In sectors of the industry where demand growth is low, virtually
all of the plants in the sector may have been built prior to 1970, with a
significant number built before 1940. Accordingly, many existing production
facilities were built with little regard (by today's standards) for
engineering and siting considerations relating to pollution control.
Waste Description—
The inorganic chemicals industry ranks third among U.S. industries in
the generation of land destined wastes. Currently, it is estimated that
the industry generates about 34 million metric tons of wastes per year
(dry basis), of which 8 million are classified as hazardous.
Land destined wastes from the inorganic chemicals industry originates
either directly from the manufacturing processes or from air or water
effluent treatment.
Waste Volume and Type—
Within the four subcategories under SIC classification 281 (chlor-alkali,
gases, pigments, and other inorganic chemicals) there are over 100 individual
products. Of these, 31 product areas each generate 1,000 metric tons or
more of land-destined waste per year. Twenty-three of the 31 industry seg-
ments generate an estimated combined total of 22 million metric tons of non-
hazardous waste per year. Fourteen of the 31 industry segments generate
about 8 million metric tons of hazardous wastes per year. These figures
represent over 80 percent of all solid waste generated by the inorganic
chemicals industry. Table 1 lists the 31 industry categories, including
number of plants, and type and volume of wastes.
Disposal Practices—
Waste from inorganic chemicals manufacturing is generally disposed of
by landfilling, settling in lagoons or ponds, and ocean dumping. Ocean
dumping, a common practice at one time, is currently limited to two
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titanium dioxide plants on the East Coast. These two plants are ocean
dumping small amounts of ferrous sulfate.
Lagoons are the primary method in which wastes are managed in the
inorganic chemical industry. This type of waste storage or disposal lends
itself to the industry because of the large amounts of waste slurries that
are generated. At one time, numerous chemical industries discharged their
waste slurries into bodies of water; however, because of EPA effluent
guidelines, this practice has been mostly eliminated. The large volumes
of waste that were previously discharged into waterways are now being put
into lagoons or ponds.
Impact of Resource Conservation and Recovery Act - Section 4004—
The problems that the inorganic chemicals industry faces with the
disposal of their non-hazardous wastes can be related to volume and site
location. Generally those industries that manufacture chemicals or chemical
products from ores have more severe problems. Of the 23 industry categories
generating primarily non-hazardous wastes, only the alumina industry will
bear a significant impact from the RCPA Section 4004 regulations proposed on
February 6, 1978 (see Table 2). The alumina industry will be affected
because of the large volumes of wet waste generated and potential number of
sites located near wetland areas. There are 10 alumina plants in the
United States, four of which have disposal lagoons located near wetland
areas. These sites are Mobile, Alabama; Point Comfort, Texas; Gramercy,
Louisiana; and Burnside, Louisiana, tiider the proposed wetland provisions
of RCRA 4004, these plants would probably have to locate future disposal
sites a considerable distance from plant sites to avoid the use of wetland
areas for disposal.
Most of the 31 industry segments that were addressed will be affected
to some degree by RCRA 4004; however, their projected costs of compliance
would be small compared to the projected costs for the alumina and
phosphorus industries.
Another industry (acetylene gas) also has the problem of having a large
stockpile of non-hazardous waste generated over many years. There are two
plants in the thited States that produce acetylene from calcium carbide, a
10
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process which produces a calcium waste. Both plants sell all the waste that
is generated. However, one plant at Louisville, Kentucky, has an estimated
450,000 metric tons of stockpiled waste. The potential problem associated
with this waste is the leaching of materials into the ground water, causing
excess hardness in the water. Figure 1 shows the general location of plants
in the United States that will be significantly impacted by RCRA 3004 and
4004 regulations.
Impact of Air and Water Regulations on Future Waste Generation—
Generally future waste volumes generated as a result of full implementa-
tion of the Clean Air Act and the Clean Water Act will be insignificant
compared to volumes presently being generated by the inorganic chemicals
industry.
The titanium dioxide industry is the only major inorganic chemical
industry which may face a major impact from RCRA because of the Clean
Water Act. In 1980, at which time EPA effluent discharge standards are
expected to be fully implemented, two titanium plants using the sulfate
process will have to neutralize their effluent discharge from disposal
lagoons. This action will approximately double the amount of land-destined
waste now being generated by the titanium dioxide industry.
Resource Recovery—
The inorganic chemicals industry as a whole generates wastes that have
potential market value. However, the amount of waste that is currently
being sold or reused is generally small compared to the volumes of waste
that are being generated. An exception is the phosphorus industry, which
sells over sixty percent of its waste slag. The sales are mostly to the
road building industry.
In the titanium dioxide industry, small amounts of ferric chloride
and gypsum waste are being sold. A number of titanium dioxide companies
are actively looking for markets for their gypsum waste. DuPont and
Allied sell some gypsum for hydrofluoric acid production to wallboard
manufacturers and construction firms and are currently looking for other
markets.
12
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The waste generated by the alumina industry (red muds) contain large
quantities of iron oxide which has a potential market value. However, very
little of the iron oxide is being utilized because of the small amounts of
titanium it contains. The titanium present in the iron oxide interferes
with the steel making process. The economics of removing the titanium from
the iron oxide does not appear to be an economically feasible alternative
at present market conditions.
The waste sodium chloride generated as a result of potassium chloride
production can be utilized as a table salt. However, to be sold as table
salt, it would have to be further refined to remove impurities. The costs
associated with removing the impurities and transportation to markets
result in an alternative which is not currently feasible.
In summary, poor economics and the lack of markets are the main factors
that impede waste recovery efforts by the inorganic chemicals industry.
Program Methodology
Extensive use was made of contractor files from past studies on the
inorganic chemicals industry. All of the data were reviewed to develop an
initial industry characterization and to identify those product and process
segments requiring special attention. The in-house files also served to
identify specific plants likely to be highly impacted by the projected RCRA
regulations.
After this review, contacts were established with over 100 individual
corporations and three trade associations to determine process changes
which have recently occurred, process information not already on file, and
projected compliance cost information for the major waste sources selected.
As these data were received, it became obvious that several waste
sources could be deleted from this study. Pecent process and waste
management practice changes have resulted in significant reductions of
several waste streams. For the other waste sources, process and cost
information was analyzed to determine amounts of waste generated, their
current disposition, and the projected economic impacts. Six industry
segments were identified as being highly impacted by the proposed PCRA
14
-------
regulations. Detailed economic analyses were then performed to determine
the total compliance costs (1978 dollars) including initial capital outlays,
interest charges, and operating expenses, and the effects of these costs on
product prices, production, and employment levels.
The data were analyzed on a plant-by-plant basis, because compliance
cost estimates varied considerably from site to site. Factors causing this
variation were amounts of stored waste inventories, distance from acceptable
disposal sites, and the chemical and physical properties of the wastes. To
ensure uniformity of industry cost estimates for compliance with FCRA, the
following assumptions were used:
Waste Stream Type
Assumption
Landfill site covering
Installation of three monitoring wells
Leachate control
Monitoring frequency
Monitoring duration
Hazardous
yes
yes
yes
monthly
20 years
after
closure
Non-Hazardous
yes
yes
no, except where
noted
quarterly
life of site
The averages of various cost estimates provided by the industry and
confirmed by Versar were:
Well installation $10,000 each
Landfill construction (including land) $20,000/acre
Quarterly monitoring $4,000/year
Monthly monitoring $10,000/year
Finally, based on the data received from the industry and literature
sources, waste recovery and reuse options were identified for several
current waste streams. Resource recovery and reuse options for specific
waste streams were discussed with the industry to determine limitations on
the applicability of such options.
15
-------
IE. INDUSTRY CHARACTERIZATION
This section of the report characterizes the inorganic chemicals
industry by SIC code with respect to number of plants, plant capacities,
location of plants, products, and general economic status.
Information was obtained from the 1977 Directory of Chemical Producers,
Stanford Research Institute1 and the Census of Manufactures and is summarized
in Table 3. This table also provides some information on the overall
economic outlook of major product segments. More detailed information on
specific chemicals, likely to be significantly impacted by solid waste
handling regulations, are given in Section V of this report.
16
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III. SELECTION OF MAJOR WASTE SOURCES
The primary objective of this study was to determine the cost of
compliance to RCRA, Section 4004, for the inorganic chemicals industry. The
logical assumption is that those processes generating the largest volumes of
land-destined wastes would be impacted the most.
Table 4, at the end of this chapter, lists the land-destined hazardous
and non-hazardous wastes generated by this industry. This table was
prepared to aid in the selection of major waste sources. These data were
obtained by the following methods:
(1) Production information was obtained from the U.S. Bureau of the
Census data,2 Minerals Yearbook,3 in-house files on past programs relating
to the inorganic chemicals industry and estimates based on producer contacts
or contractor knowledge.
(2) The amounts of solid wastes generated for each process per ton of
product produced were obtained from previous contractor studies of hazardous
solid waste handling practices in the inorganic chemicals industry1* and from
a recent contractor multi-media assessment of the inorganic chemicals
industry.5 Where ranges of waste loads are listed, maximum values were
usually chosen as the worst case. In cases where process information was
unavailable, estimates of waste quantities were made based on raw material
purities and process chemistry. It should be noted that, in the manufacture
of several chemicals, waste loadings were assumed to exist for all plants,
even though only a few producing facilities might have such wastes.
Examples of this are heavy metal salts (i.e., nickel sulfate and iron
chloride) which can be made from either pure or impure raw materials.
Major waste sources were selected from Table 4 as those processes
generating more than 1,000 metric tons of land-destined waste per year. This
value was chosen after examination of the data and consultation with the EPA
Technical Project Monitors. Based on this rationale, 40 processes were
selected as major waste sources. These processes are noted in Table 4.
Additional contacts with industry during this study led to the deletion
of ten processes fron the major waste source list. The ten processes and
the reasons for their deletion are listed below:
36
-------
(1) Sodium Silicate - Contacts with all producers revealed that about
90 percent of the generated solid wastes are currently recycled to the
process. Only about 600 metric tons per year of solid wastes are discarded.
(2) Nickel Sulfate - Of the eight plants producing this chemical, only
three use inpure materials and generate solid wastes. These three facilities
combined generate only 200 metric tons per year of waste.
(3) Iron Blue - Contacts with the industry revealed that there are only
two current producers who generate a combined total of only 400 metric tons
per year of waste.
(4) Magnesium Carbonate - The process originally evaluated is no longer
in use. According to several industry contacts, all current magnesium
carbonate production is from soda ash and magnesium chloride. This new
process generates no solid waste.
(5) Potassium Nitrate - Industry contacts have revealed that all
current production of this chemical is by the Vicksburg process, which
generates no solid waste. The old process is no longer used.
(6) Sodium Borohydride - The only U.S. producer of this chemical claimed
that hazardous sodium sludge waste is currently reprocessed to recover sodium
values. There is no waste requiring disposal.
(7) Ferric Chloride - All U.S. producers revealed that only three
facilities have product purification sludge wastes. These three sites
generate a combined total of 600 metric tons of waste per year.
(8) Potassium Dichromate - The only U.S. producer claimed that this
chemical is produced in batch quantities a few times per year. The amount
of solid waste requiring disposal is only about 500 metric tons per year.
(9) Acetylene from Calcium Carbide - At present, only one firm still
produces acetylene by this process at two locations. At one, the lime waste
is sold to a public utility for use in its wet scrubbers. At the other
site, all waste is sold to several local chemical and metallurgical firms
for use as a neutralization agent for acidic wastewater. There is,
however, a backlog of lime waste at one plant from past years when
production rates were higher. This problem is discussed in more detail in
the section of this report dealing with calcium carbide wastes.
37
-------
(10) Sodium Silicofluoride - Except for one plant, the industry combines
this process waste with waste from wet process phosphoric acid manufacture.
All but one of the production sites are fertilizer plants. Industry suggested
that production of this chemical at fertilizer plants be considered as part
of that industry. Usually the fertilizer industry does not segregate its
waste.
The remaining major waste sources are listed below in the order of
decreasing quantities of waste generated:
1. Potash (potassium chloride
and sulfate) from ore
2. Alumina
3. Phosphorus
4. Natural soda ash
5. Hydrated lime
6. Hydrofluoric acid
7. Borax from ore
8. Solvay process soda ash
9. Titania - sulfate process
10. Sodium chromate and dichromate
11. Iron oxide pigments
12. Lithium carbonate
13. Titania - chloride process
14. Aluminum sulf ate
15. Chlor-alkali - diaphragm and
mercury cell processes
16. Zinc oxide from ore
These processes and the impact of PCPA Sections 3004 and 4004 on them
are discussed in the following sections of this report.
17. Antimony oxide from ore
18. Barium sulfate from ore
19. Manganese sulfate
20. Vanadium pentoxide
21. Calcium phosphate (food grade)
22. Calcium carbide - open furnace
process
23. Sodium hypophosphite
24. Barium carbonate
25. Sodium
26. Sodium chlorate
27. Strontium carbonate
28. Chrome yellow
29. Potassium permanganate
38
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IV. ANALYSIS OF MAJOR WASTE SOURCES
This section examines the major waste sources selected in Section III.
This examination includes a description of the process and a description
and quantification of the wastes generated both on an aggregate basis and
by locality. The sources are discussed in the order of decreasing waste
generation rates.
Potash
The potash industry involves the production of two chemicals - potassium
chloride (KCl) and potassium sulfate (KzSO.*). They are combined because both
chemicals are produced at most potash facilities.
Potassium chloride is produced by two methods: (1) recovery from brines
and (2) from mined sylvite ore. The first process generates no solid wastes
because the spent brines are returned to their source. This process is used
at two sites, one in California and the other in Utah. The second process,
which is used at seven New Mexico facilities and one plant in Utah is shown
in Figure 2. Sylvite ore is crushed, ground and separated from waste clay
slimes and salt. These wastes exit the process as a waterborne stream and
are sent to evaporation ponds. The upgraded ore is subjected to a flotation
operation, where the KCl is separated from any residual salt. The KCl is
recovered from the flotation step, dewatered, and dried. The brine and salt
tailings wastes are sent to evaporation ponds on-site.
The wastes from this process are as follows:
(1) Clay and slimes - about 75 kg/kkg of product.
(2) Waste salt - 3,900 - 6,600 kg/kkg of product.
Potassium sulfate is also produced by more than one method. Some
material is recovered from natural brines at two sites. No solid waste is
generated by this process. Some is produced as a co-product of beet sugar
production. Again, no solid waste is generated. Some is produced from KCl
by the Hargreaves process at two sites with no solid waste generated.
At one plant, potassium sulfate is produced from langbeinite ore as
shown in Figure 3. After crushing, drying and removing sodium chloride, the
ore is reacted in solution with KCl to produce KzSOi*. The product is separated
46
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by filtration and is dried, sized, and shipped. The waste solutions,
containing sodium and magnesium sulfates are discarded in an on-site evapora-
tion pond. The wastes fron this process amount to about 2.4 kkg of salt and
mud per kkg of product.
The distribution of KC1 production wastes is given below:
State
New Mexico
Utah
Number
of Plants
7
1
Capacity
(kkg/yr)
2,315,000
136,000
Estimated Amount of
Solid Waste Generated (kkg/yr)
11,575,000
680,000
Rounded Totals 8 2,500,000 12,000,000
All land destined wastes from KaSOi* production are in New Mexico. The
generation rate of these wastes averages 600,000 metric tons per year. These
wastes are disposed of in the same evaporation ponds used for the potassium
chloride production wastes.
Alumina
Alumina is produced from bauxite ore by the Bayer Process as shown in
Figure 4. Bauxite ore is ground, mixed with aqueous caustic soda, and the
mixture is heated under pressure to dissolve the alumina content of the ore.
The heated solution is then cooled, thickened and filtered to remove insoluble
material (red mud). After this, the solution of sodium aluminate is further
cooled and seeded to precipitate hydrated alumina. This material is recc**ered
by filtration and calcined to alumina. The caustic soda solution separated
by filtration is reconcentrated and recycled to the initial digestion step.
Wastes from the process are waterborne and consist mostly of red mud,
unrecovered alumina, limestone, other insolubles, and small amounts of
caustic soda.
Settling of these wastes in large lagoons generates large quantities
of waste muds. The approximate compositions of red muds obtained from three
different types of bauxite are listed below:
49
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Weight Percent of Component in Red Mod
Component
Fe203
A1203
Si02
Ti02
CaO
Na20
Loss on
Ignition
Surinam
Bauxite
30-40
16-20
11-14
10-11
5-6
6-8
10.7-11.4
Arkansas
Bauxite
55-60
12-15
4-5
4-5
5-10
2
5-10
Jamaica
Bauxite
50-54
11-13
2.5-6
trace
6.5-8.5
1.5-5.0
10-13
The major constituents of red muds from the three most commonly used
ores are iron oxides, alumina, silica and titania. Also these muds contain
from 1.5 to 8 percent alkaline sodium salts and minor amounts of gallium,
nickel, chromium and other trace impurities in the raw ores used.
These wastes dry very slowly and require large amounts of land for
their disposal and dewatering.
The distribution of these wastes, on a state-by-state basis, is given
below:
Alumina Production Estimated Amount of Solid Number of
State Capacity (kkg/yr) Waste Generated (kkg/yr) Plants
Alabama
Arkansas
Louisiana
Texas
Virgin Islands
Rounded Totals
Phosphorus
934,000
1,060,000
2,230,000
2,490,000
330,000
7,000,000
1,010,000
1,145,000
2,410,000
2,690,000
360,000
7,600,000
1
2
4
2
1
10
Elemental phosphorus (PO is produced by a thermal process shown in
Figure 5. Phosphate rock ore is dried, calcined, blended with coke and silica,
and fed to an electric furnace. The three raw materials react to form phos-
phorus vapors, slag, and ferro phosphorus. The carbon monoxide and phosphorus
vapors are passed through electrostatic precipitators to remove furnace dusts
52
-------
and are condensed in a stream of water. The water-phosphorus mixture is
settled to recover the phosphorus. The carbon monoxide is flared prior to
release to the atmosphere.
There are several wastes from this process. These are:
(1) Particulate emissions from the initial ore drying and calcination
steps. These amount to about 300 kg/kkg of product and are removed from
vent gases by either dry collection methods or wet scrubbing. Where dry
collection is practiced, the particulates are recycled. They are stored
at the bottom of settling lagoons where wet scrubbing is employed.
(2) Slag and ferro phosphorus from the furnace. These are removed from
the furnace, quenched, and crushed. The ferro-phosphorus is normally sold as
a co-product and the slag, amounting to about 9,300 kg per kkg of product,
is sometimes sold as a crushed stone substitute when markets are available.
If markets are not available, the material is land stored. The slag contains
calcium oxide, silica, alumina, phosphate, a small amount of calcium fluoride
and traces of heavy metals present in the raw ore, including uranium. This
waste has been listed as hazardous by the EPA.
(3) Phossy dusts from the electrostatic precipitators. This is dust
that has been in contact with elemental phosphorus. It is periodically
recovered and added to phossy water wastes or oxidized to phosphate or
retorted to recover elemental phosphorus. Dust waste loads average 1 kg per
kkg of phosphorus product. They are considered hazardous because of the
toxicity of elemental phosphorus and the high reactivity of phosphorus with
oxygen.
(4) Phossy Water. Water used to condense the phosphorus, after
recovery and separation of the Pit product, still contains from 2 to 18 kg
per kkg of Pi* product of elemental phosphorus. This water is usually
impounded in lined lagoons and reused for the same purpose. It is totally
isolated from other plant wastewater streams and never intentionally dis-
charged. With time, elemental phosphorus accumulates in these ponds. This
situation is handled by the industry either by the use of flocculants in
the process to recover a maximum amount of product and minimize the Pi» con-
53
-------
tent of the phossy water, or by use of sodium hypochlorite and lime addition
to the ponds to oxidize the phosphorus. This treatment is usually followed
by periodically retorting the settled solids in the phossy water lagoons to
recover phosphorus. Ihe first technique is used in at least three plants and
at least two plants are using the second technique. Residual solids from the
retorting operations are then reused in the process in place of phosphate ore.
The distribution of non-hazardous and hazardous waste generation is:
State
Florida
Idaho
Montana
Number
of Plants
3
2
1
Tennessee 3
Rounded
Totals 9
Production
Capacity
(kkg/yr)
44,000
210,000
36,000
200,000
490,000
Estimated Amount
of Non-Hazardous
Waste Generated*
(kkg/yr)
13,400
63,000
11,600
60,000
148,000
Estimated Amount
of Hazardous
Waste Generated-;-
(including slag)
(kka/vr)
409,480
1,955,300
334,390
1,862,200
4,561,000
* For the purposes of this study, the fluoride containing calcination
dusts were considered non-hazardous.
+ All wastes containing elemental phosphorus were considered as hazardous.
Natural Soda Ash
Natural soda ash is produced by two processes, both of which generate
about the same waste loads. In the sesquicarbonate process, mineral trona
ore is crushed and then dissolved in hot water. The resulting solution is
clarified, treated with activated carbon to remove traces of organic materials
and then filtered. The clean filtrate is evaporated to recover solid sodium
sesquicarbonate which is calcined to soda ash.
In the -monohydrate process, mineral trona ore is crushed, calcined, and
dissolved in water. The resulting solution is clarified, filtered, and
evaporated stepwise to recover a solid material which is then calcined to
recover a soda ash product. Process diagrams for these two operations are
given in Figure 6. Process wastes, aside from the carbon dioxide liberated
to the atmosphere, consist of ore residues, spent carbon, filter aids, and
unrecovered soda ash. The amounts of these materials appear in the mass-
54
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balanced flow diagrams on Figure 6. All solid and waterborne wastes are
fed to evaporation ponds. The total production by these processes occurs
in Sweetwater County, Wyoming, at four plant sites. The total estimated
amount of solid wastes generated per year is 1,200,000 metric tons, based
on U.S. Census 1976 production figures for natural soda ash.2
Hydrated Lime
Lime is produced by the calcination of limestone as shown in Figure 7.
The limestone is ground, mixed, weighed, and fed to kilns where it is heated.
Carbon dioxide gas is liberated during the decomposition. The only process
emissions other than carbon dioxide are airborne emissions of lime and lime-
stone particulates. These are removed from process vent gases by either dry
collection or wet scrubbing methods. The amount of these particulates is
estimated at 90 kg per kkg of product.
The 20,000,000 metric tons of lime produced in the United States in
1977 were generated at 180* facilities located throughout the country.
Neither plant capacities nor complete lists of producers of all types of
lime are available. Many lime plants are captive to chemical, cement and
other industries and are not listed in producer directories. Therefore, a
detailed distribution by state of these wastes is not possible. However, an
estimated 1.9 million metric tons of lime wastes are generated nationwide.
Hydrofluoric Acid
The process for the production of hydrofluoric acid is shown in Figure 8.
After calcium fluoride (fluorspar ore) is dried, it is reacted with dry
sulfuric acid to yield hydrogen fluoride (HF) and calcium sulfate. The
hydrogen fluoride gas is then cooled and condensed. The crude HF is purified
by distillation and is stripped of residual sulfuric acid. The calcium
sulfate is sluiced to settling ponds for treatment and eventual disposal.
There are several waste streams fron this process:
* Total number of plants estimated by the National Lime Association.
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(1) Calcium sulfate sluice - about 3,600 kg are generated per kkg of
product. About 120 kg of unreacted sulfuric acid per kkg and 60 kg of
unreacted ore per kkg are also present in the sluice which is sent to
treatment ponds where lime is added to neutralize residual acid. The solids
are periodically removed from the settling ponds and landfilled.
(2) Tail gases from the initial purification and condensation of crude
hydrogen fluoride contain about 12.5 kg per kkg of product of hydrofluo-
silicic acid (HaSiFe) along with lesser amounts of S02 and unrecovered HF.
These gaseous wastes are passed through a recirculating sulfuric acid scrubber
to recover residual acid. The recovered acid is recycled and added to fresh
acid at the start of the process.
(3) Scrubber water - After sulfuric acid treatment, the tail gases are
wet scrubbed with water which creates a waterborne waste stream. After
neutralization with lime, this waste stream generates about 40 kg per kkg
of product of waste solids consisting of calcium fluoride, silica and calcium
sulfate for landfilling.
(4) Product purification waste - Between 1 and 5 kg of unconverted sulfur
acid per kkg of product is removed from the HF and is neutralized with lime
which produces more calcium sulfate to be landfilled.
The distribution of all waste generated is given below:
Estimated amount of
Waste Generated at
Total Capacity
State (kkg/yr)
California
Delaware
Kentucky
Louisiana
New Jersey
Ohio
Pennsylvania
Texas
West Virginia
Rounded Totals
10,900
22,500
22,500
104,700
10,000
16,400
4,400
157,000
13,500
350,000
100% Capacity
(kkg/yr)
40,000
82,800
82,800
385,300
36,800
60,300
16,200
577,800
49,700
1,300,000
Number of
Plants
1
1
1
3
1
1
1
3
1
13
59
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Borax from Ore
Borax is produced by two methods in the United States: (1) by extraction
from Searles Lake brines and (2) by extraction from ore.
The first of these methods generates no solid waste. In the second
process, as shown in Figure 9, ore is crushed and dissolved in water. The
ore insolubles are separated by filtration and the solution is evaporated
to recover the product, sodium tetraborate pentahydrate. The only process
waste from these operations is about 800 kg per kkg of product of ore
residues. At the only site using this process, the waste is stored in lined
ponds. This waste is considered to be potentially hazardous because it
contains a small amount of natural arsenic sulfide "realgar" (AsS2) that was
present in the ore before mining. The amount of arsenic present in the
residues is about 0.08 percent.
All this waste is generated in California. The generation rate of ore
residue waste is estimated at 510,000 metric tons per year.
Solvay Process Soda Ash
Soda ash is produced by toro methods - from salt and limestone by the
Solvay Process and by refining of natural trona ores. In the Solvay Process,
sodium chloride brine is purified to remove calcium and magnesium salts as
calcium carbonate and magnesium hydroxide. The purified brine is reacted with
ammonia and carbon dioxide which is produced on-site by limestone calcination.
Sodium bicarbonate precipitates from the brine and is recovered and calcined
to produce soda ash. The spent brine is then reacted with the lime generated
from the limestone calcination to recover ammonia values. The ammonia is
recycled and the waste brine, now containing mostly calcium chloride, is
discharged as a waterborne waste. A mass-balanced process diagram appears
as Figure 10.
The wastes from these operations are generally combined before treatment,
which consists of suspended solids settling and neutralization of wastewater.
The average compositions of the effluent and solid wastes from, these operations
are listed below5:
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Amount Discharged (kg/kkg
of soda ash produced)
Waterborne
Calcium chloride l,10c
Sodium chloride 510
Suspended solids 3
Calcium sulfite 30
Ammonia (as NHi»Cl) 0.15
Amount Discharged (kg/kkg
of soda ash produced)
Solid Wastes
Magnesium hydroxide 75-150
Calcium carbonate 50-200
Silica (from impure limestone) 60
Generally, the solid wastes are allowed to remain in settling lagoons.
As the lagoons are filled, new ones are dug and the old sites are drained
and restored. There are no hazardous constituents in these solid wastes.
The amounts of these wastes are expected to decrease in the future. The
number of Solvay plants since 1969 have decreased from 7 to 1. Effective
January 1, 1979, the only Solvay plant still operating was in Syracuse,
New York. This plant generates about 260,000 metric tons per year of land-
destined wastes.
Titania - Sulfate Process
Titanium dioxide is produced by two methods - the sulfate and chloride
processes. In the sulfate process, as shown in Figure 11, ilmenite ore, scrap
iron, and sulfuric acid are mixed and reacted to yield ferrous sulf ate and
titanyl sulf ate. After reaction, the resulting liquor is filtered to remove
undigested ore residues and cooled to crystallized ferrous sulfate. This
material is recovered by centrifugation and is either sold or disposed of as a
waste.
The purified titanyl sulfate solution is hydrolyzed to titania and
recovered by filtration. The spent liquor from the filtration step is dis-
carded as a waterborne waste. The recovered titania is repulped, washed,
recovered again by filtration, calcined and then wet or dry treated and ground
to produce a finished product.
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The mass-balanced process flew diagram shows the major wastes generated
by the sulfate process as follows:
(1) Undigested ore residues. The composition of these residues varies
slightly with the ilmenite ore used. A typical composition is listed on
the process flow diagram. The residues usually contain silica, alumina,
unreacted scrap iron, and minor amounts of cobalt, chromium, and other heavy
metal oxides and silicates. These wastes are normally landfilled.
(2) Ferrous sulfate. This material is either sold, if markets are
available, or is discharged or ocean dumped at 3 of 4 operating plants.
Cnly one plant currently produces complete neutralization of all wastes to
gypsum and metal oxides/hydroxides.
(3) Strong acid wastes from the titanyl sulfate hydrolysis and crude
titania recovery steps. At two plants, these wastes are discharged to the
environment. At another site, partial neutralization is currently used and
at a fourth site, complete neutralization is practiced. These wastes consist
of 15-30 percent sulfuric acid solutions containing dissolved ferrous sulfate
and the sulfates of magnesium, manganese, vanadium and other heavy metals.
Minor amounts of dissolved phosphates from the ores may also be present.
(4) Weak acid waste. This originates from washing the recovered titania
and consists of about two percent sulfuric acid solution containing small
amounts of the same heavy metal sulfates present in the strong acid waste.
This waste stream is usually neutralized prior to discharge and the sludges
generated are landfilled.
(5) Other wastewater. Additional process wastes include scrubber water
from product calcining and wash water from finishing operations. These contain
small amounts of sodium sulfate, sulfuric acid and unrecovered titania. These
waterborne wastes are usually neutralized and settled prior to discharge.
Disposal methods for the wastes produced by this process are undergoing
rapid changes because of the phasing out of ocean disposal and enforcement
of water pollution regulations. At present, one plant is fully neutralizing
its wastes and another is using partial neutralization. However, contacts
with the industry have revealed that within 5 years all plants will be using
full neutralization. A distribution of wastes generated on a state-by-state
basis is given below. Also listed are the estimated amounts of ferrous
65
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sulfate currently sold. Assuming full neutralization by the industry, over
1.2 million tens of solid waste will be generated by this process per year.
State
Georgia
Maryland
New Jersey
Totals
Waste Generated
and Unsold (kkg/yr)
290,000
295,000
629,000
1,214,000
Amount currently
sold (as FeSOO*
25,000
0
100,000
125,000
Number of
Plants
1
1
2
4
* Based on plant capacities for FeSOi* production.:
Sodium Oironate and Dichronate
This product is produced at three plants using the process shown in
Figure 12. Chromite ore is dried, ground, mixed with limestone and soda
ash, and placed in a kiln. The reacted solid mixture is then leached with
hot water and the resulting solution is filtered to remove insoluble ore
residues. The filtrate is acidified with sulfuric acid and refiltered to
remove any calcium sulfate that may have precipitated. Soda ash is added
and the solution is filtered again to recover a sodium sulfate co-product.
The filtrate is reacidified, evaporated, and centrifuged to recover sodium
dichromate crystals which are dried and packaged.
The wastes from this process are care residues and insoluble calcium
salts. They are removed from the process and slurried to wastewater treat-
ment ponds. After treatment to reduce hexavalent chromium to trivalent
chromium, the solids are landfilled. These wastes contain ore residuals
(iron, aluminum and calcium salts, and small amounts of chromium).
The distribution of waste generation for this process is:
Estimated Dichromate Estimated Amount of Solid
State Production Capacity (kkg/yr) Waste Generated (kkg/yr)
Maryland
North Carolina
Texas
Rounded Totals
70,000
70,000
30,000
170,000
56,700
56,700
24,300
140,000
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Iron Oxide Pigments
Pigment grade iron oxides are produced by ta«ro processes, both of which
are generally employed at the same production sites (see Figure 13). In the
dry process, ferrous sulfate is decomposed and oxidized by heating in air to
yield ferric oxide, sulfur dioxide and sulfur trioxide. The gases are either
reacted with caustic soda creating a waterborne waste or, at a few sites,
are converted to sulfuric acid.
In the wet process, sulfuric acid is reacted with pickle liquor or
upgraded iron ore. After reaction, the residues are separated by filtration
and the resulting ferrous sulfate solution is neutralized with caustic soda
to yield a hydrated ferrous oxide. This material is oxidized to ferric oxide,
recovered by filtration, dried, and calcined to the final product.
Wastes from the two processes are as follows:
Dry Process—
(1) Sulfur dioxide and sulfur trioxide. About 1,000 kg per kkg of
product are generated from ferrous sulfate calcination. The gases are either
converted to sulfuric acid on-site or wet scrubbed with a caustic solution.
(2) Scrubbing creates a waterborne waste containing about 1,800 kg of
sodium sulfate per kkg of product. Small amounts (5-10 kg per kkg of
product) of iron oxides are separated from this wastewater stream by settling
prior to discharge and landfilled.
Wet Process—
(1) Ore or pickle liquor residues of about 250 kg per kkg of product
are generated. These are washed and landfilled.
(2) Wastewater containing about 2,400 kg per kkg of product of sodium
sulfate and about 5-10 kg per kkg of product of unrecovered iron oxides is
settled prior to discharge and the solids are landfilled along with the ore
residues.
At present, there are eleven facilities producing iron oxide pigments
in the United States. These are listed as follows:
68
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Comments
At this plant waste S02 from dry process
is converted to H2SO.I
generated is converted to
Eastern Pennsylvania
East St. Louis, Illinois
Emeryville, California
Wyandotte, Michigan
Trenton, New Jersey
Monmouth Junction, New
Jersey
St. Louis, Missouri
Huntington, West Virginia
Newark, New Jersey
Pulaski, Virginia
Valparaiso, Indiana
Plant capacity information has not been published and this information
is regarded as confidential by the industry. Based on the waste load
information provided by several plants and the total annual production of
77,000 metric tons,3 we estimate the amount of land-destined waste from this
industry to be about 15,000 kkg per year.
Lithium Carbonate
This chemical is produced from two types of raw materials: (1) natural
brines and (2) spodumene ore.1* Brine extraction operations, conducted in
Nevada and California, return depleted brine to their sources and generate
little or no solid waste. The spodumene ore process, however, generates
large amounts of waste solids as shown in Figure 14. Spodumene ore is milled
and then roasted with sulfuric acid to convert many of the materials present
to their corresponding sulfates. The reacted ore is leached with water,
and the leachate is filtered to remove ore residues. The solution is then
reacted with calcium carbonate and filtered again to remove waste gypsum.
After this, the filtrate is reacidified, refiltered with carbon and partially
evaporated. The concentrated solution is reneutralized with soda ash and
further evaporated to form lithium carbonate crystals which are recovered
by filtration, dried, and packaged. The spent solution is then evaporated
to dryness to recover a sodium sulfate co-product.
Wastes from this process include the following:
70
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(1) Waste ore residues. About LO kkg of these are produced per metric
ton of product. These consist of mostly alumina, silica, and other acid
insoluble materials.
(2) Waste gypsum and calcium carbonate from various process neutraliza-
tion steps. These amount to about 440 kg per kkg of product.
(3) Waste carbon from solution filtration, about 10 kg per kkg of
product.
(4) Waterbome wastes containing about 180 kg per kkg of product of
lithium sulfate and small amounts of sodium sulfate.
All the above exit the process in wastewater streams. The first three
are usually settled from the wastewater prior to discharge.
Lithium carbonate produced fron spcdumene ore is manufactured by two
facilities in North Carolina. Total production is estimated at about
25,000 metric tons per year and the rate of solid waste generation is
estimated at 260,000 metric tons per year.
Titania - Chloride Process
Titanium dioxide (Ti02) is also produced by the chloride process which
is shown in Figure 15. Coke, chlorine and either rutile or ilmenite ore are
reacted to yield titanium tetrachloride (TiCU) and a variety of other metal
chlorides. This mixture of chlorides is separated by fractional distilla-
tion and condensation. The waste from these purification operations consists
of small amounts of unreacted ore and coke and variable amounts of iron and
other metal oxides and chlorides, depending on the ore quality used. When
high grade ore (rutile) is used, these waterborne wastes are usually
neutralized prior to discharge and the sludges are landfilled. When low
grade ore (ilmenite) is used, the waterborne purification wastes currently
are either disposed of by deep well injection or ocean dumping.
After purification, the TiCli* intermediate is reacted with oxygen to
generate TiC>2. The chlorine produced by this operation is recycled to the
chlorination step in the process. The TiOa is washed, treated, milled, and
packaged.
72
-------
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Wastes from the process consist of the following:
(1) Purification wastes from the TiCU intermediate purification. These
wastes initially leave the process in waterborne form. Neutralization of
these waterborne wastes generates sludge which is landfilled. The amounts
are shown in Figure 15.
(2) Vent gases from the TiCli, purification. These consist of CO and COa
and are vented after being wet scrubbed to remove traces of free chlorine.
(3) Scrubber water normally contains small amounts of TlCU and hydrogen
chloride as shown in Figure 15.
(4) Other waterfaorre wastes - small amounts from the TiOa finishing
operation. They contain unrecovered T1O2 and small amounts of dissolved
salt and sodium sulfite. These wastes are settled and the solids are land-
filled.
Some changes in waste loads are expected where low grade ore is used.
Cue facility, currently using ocean disposal, is converting to partial
sale of a recovered 30 percent ferric chloride solution and neutralization
and landfilling of the remaining wastes. The other plant using low grade
ore disposes of all wastes by deep well injection.
The estimated amounts of land-destined wastes projected from this pro-
cess on a state-by-state basis are shown below. Apparently/ about 800,000
metric tons of waste per year are expected if full neutralization is
adopted by all facilities.
State
California
Delaware
Georgia
Maryland
Mississippi
Ohio
Tennessee
Totals
Total Amount of Wastes
Ore Used Generated (kkq/yr)*
Rutile
Ilmenite
Rutile
Rutile
Rutile
Rutile
Ilmenite
1,500
337,000t
2,000
1,800
2,500
9,700
461,000
811,500
Number of
Plants
1
1
1
1
1
2
1
8
* Based on plant capacity data.1
t Of this quantity, as much as 150,000 tons per year may be sold as FeCl3.
74
-------
Aluminum Sulf ate
Aluminum sulfate (alum) is produced from sulfuric acid and bauxite by
the process shown in Figure 16. Bauxite ore, sulfuric acid and water are
mixed and reacted in a digestion tank. The resulting solution is settled
and filtered to remove insoluble materials. The solution is either marketed
as such or evaporated to yield a solid product.
The waste from the process consists of ore insolubles which are sluiced
from the reaction tank. Settling of this waste generates 105 kg per kkg
of product of rauds requiring land disposal. The primary constituents of
the muds are alumina, titania, silica, and iron oxide.
A state-by-state distribution of the amounts of wastes generated from
this process could not be developed. There are insufficient published data
on alum plant capacities. The number of alum plants by state, according to
the 1976 Census Bureau report2 is as follows:
State Number of Plants State Number of Plants
Alabama
Arkansas
California
Colorado
Delaware
Florida
Georgia
Illinois
Louisiana
Maine
Maryland
Massachusetts
Michigan
Total 67 plants
Based on a total production of 1.12 million metric tons in 1976, the
estimated amount of solid waste generated by this process per year is
120,000 metric tons.
75
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Minnesota
Mississippi
New Jersey
North Carolina
Chio
Oregon
Pennsylvania
South Carolina
Tennessee
Texas
Virginia
Washington
Wisconsin
2
2
3
1
4
1
2
1
4
1
3
4
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Chlor-Alkali - Diaphragm Cell Process
Chlorine and sodium hydroxide are produced by two electrolytic processes:
the diaphragm cell and the mercury cell. In the diaphragm cell shown in
Figure 17, saturated sodium chloride brine, containing minor amounts of
dissolved magnesium and calcium salts, is treated with sodium hydroxide
and/or soda ash to remove these impurities by precipitating calcium carbonate
and magnesium hydroxide. When the sulfate content of the brine exceeds 600
ppm, barium chloride is also added to remove sulfate as barium sulfate.
This sulfate removal process is usually required only for brine obtained
from the Texas-Louisiana coastal salt dome. Cn the other hand, removal of
calcium and magnesium ions is universally required.
The brine muds resulting from this chemical treatment average about
15 kg per kkg of chlorine produced and are disposed of either on site in
settling lagoons or off site in landfills.
The purified brine is first acidified with hydrochloric acid and then
pumped to the electrolytic cells where the anode and cathode are separated
by asbestos diaphragms. Chlorine is liberated at the anode and hydrogen gas
and sodium hydroxide (caustic soda) are formed at the cathode. The hydrogen
is usually conpressed, cooled, dried and either used on the plant site or sold.
The chlorine is cooled, dried with 98 percent sulfuric acid and then purified
to remove traces of chlorinated organics and nitrogen trichloride (formed
from traces of aninDnium salts in the brine). After purification, the
chlorine is compressed and sold.
The caustic soda exits the electrolytic cells with unconverted brine.
This material is evaporated to 50 percent caustic soda to precipitate un-
converted sodium chloride, which is either recovered and reused or discarded
as a waterborne waste. Most caustic soda is sold as a 50 percent solution;
however, solutions can be further evaporated to produce a solid sodium
hydroxide co-product.
The diaphragm cell is also used to produce potassium hydroxide (caustic
potash). In such cases, potassium chloride is used as a feed material
instead of sodium chloride. However, the process and wastes are very similar.
Figure 17 shows the diaphragm cell process diagram and mass balance.
The wastes from the process are as follows:
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(1) Brine muds are generated in amounts of up to 30 kg per kkg of
product. These muds contain magnesium hydroxide, calcium carbonate, and
in sons cases, barium sulfate. The amounts of these precipitates are
dependent on the purity of.the salt used. For plants using pre-purified
(i.e., chemical grade, evaporated salt) the amounts are very small (i.e.,
about 0.7 kg per kkg). Most, if not all, western plants use pre-purified
salt. For plants using salt from the Texas-Louisiana salt done, which
accounts for over 55 percent of the total U.S. production, the amounts are
about 10 kg per kkg of product. Barium is used in several of these plants
for sulfate removal and these muds will contain over 40 percent calcium
carbonate and magnesium hydroxide and up to 60 percent barium sulfate. For
other salt sources, the average values are about 30 kg per kkg of product
and these muds contain primarily calcium carbonate and magnesium hydroxide.6 '29
(2) Carbon and rubble - the amounts range up to 3 kg per kkg of product.
Waste carbon is present only at six facilities where they use carbon anodes.
The other plants use dimensionally stable metal anodes (DSA).
(3) Waterborne wastes containing 35-265 kg per kkg of salt, 15 kg per
kkg of caustic soda, small amounts of suspended solids and sulfates. Lead
salts are also present in these wastes at six plants. Waterborne wastes
are due to purges to eliminate sulfates from the system in plants not using
barium salts.
(4) Spent sulfuric acid - about 12 kg per kkg of chlorine product.
This waste is generated fron the drying of chlorine.
(5) Chlorinated hydrocarbons - Purification wastes contain up to 1 kg
per kkg of chlorine product. This waste no longer occurs at most plants
in the United States. Most plants now use DSA or cobalt oxide based
electrodes which do not yield lead or chlorinated hydrocarbon wastes.
Nitrogen trichloride, removed from the chlorine during purification, is
converted to nitrogen and chlorine, and the chlorine is added to the
product.8
(6) Scrubbing wastes created by wet scrubbing of process tail gases
to reduce chlorine emissions. These amount to 1 kg per kkg of product and
are waterborne. They contain dissolved sodium hypochlorite and sodium
carbonate or bicarbonate. At one site, this wastewater stream is processed
to decompose catalytically the hypochlorite to sodium chloride and oxygen.7
79
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(7) Asbestos - waste asbestos is generated in rebuilding of the elec-
trolytic cells. For newer cells, the asbestos diaphragm and its holders
are removed from the cells and containerized for burial. For some older
cells, such as those using the graphite electrodes, the asbestos is washed
from the diaphragm, recovered from the water and then containerized and
buried. This latter approach can lead to wastewater containing asbestos.
The amounts and types of land-destined wastes are unlikely to undergo
radical changes in the next few years because capacity expansion is ex-
pected to be only a few percent per year. The formation of chlorinated
hydrocarbon, lead, and graphite wastes, however, is expected to fall to
negligible values in the next few years as the remaining lead-graphite anodes
are replaced by metal anodes. One major corporation, which until recently
used graphite electrodes, has released R&D studies on the use of alternate
types of metal electrodes and has recently installed them.9 Six small plants
still using carbon electrodes are considering possible changeovers. They
handle electrode wastes as follows: at least four do not remove the
chlorinated hydrocarbons from the product, one plant disposes of all wastes
by deep well injection; the fate of these wastes at the sixth site is
unknown. These six plants account for less than 10 percent of production of
chlorine by diaphragm cells.
Table 5 shows the estimated amounts of land-destined waste generated
on a state-by-state and national basis from diaphragm cell operations. These
numbers were derived from current plant capacity data1 using a production to
capacity ratio of 0.9. Cumulative solid wastes for this process are:
brine muds 78,158 kkg/yr | 95,665 kkg/yr
carbon and cell 17,507 kkg/yr ( non-hazardous waste
rubble
asbestos 2,641 kkg/yr potentially hazardous waste
Chlor-Alkali - Mercury Cell Process
In the mercury cell process, chlorine and caustic soda or caustic
potash are produced by the electrolysis of sodium or potassium chloride
solutions. The raw salt (or brine) is pre-purified by addition of caustic
soda, soda ash, and at one plant, barium chloride. Calcium carbonate,
80
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TABLE 5.
DISTRIBUTION OF ESTIMATED AMOUNTS OF IAND-DESTINED
WASTES GENERATED BY THE DIAPHRAGM CELT. PROCESS (KKG/YR)
State
Alabama
California
Georgia
Indiana
Kansas
Louisiana
Michigan
New York
Nevada
North Carolina
Ohio
Oregon
Tennessee
Texas
Virginia
Washington
West Virginia
Wisconsin
Actual Totals
Bounded Totals
Brine Muds
(Non-Hazardous)
1,500
157
810
800
3,780
18,160
11,670
2,190
76
540
3,000
70
750
25,800
840
175
7,800
50
78,158 kkg/yr
78,000 kkg/yr
Carbon and Rubble
(Non-Hazardous)
161
78
81
75
378
6,000
117
219
300
54
300
300
75
7,800
84
700
780
5
17,507 kkg/yr
18,000 kkg/yr
Asbestos (Poten-
tially Hazardous)
20
80
10
9
40
720
160
28
32
7
40
280
10
1,000
11
90
103
1
2,641
2,600
kkg/yr
kkg/yr
81
-------
magnesium hydroxide and barium sulfate are precipitated from the brine and
removed as solid waste. The mass-balanced process diagram is shown in
Figure 18. Chlorine is formed at the anode and a sodium- (or potassium-)
mercury amalgam is formed at the cathode. The chlorine is cooled, dried
with sulfuric acid, purified, compressed and marketed. The sodiuttMtercury
amalgam is reacted with water to yield a 50 percent caustic solution and
to regenerate the mercury. The mercury is returned to the electrolytic
cells and the 50 percent caustic is either sold as such or evaporated to
recover a solid product. Spent brines from the electrolysis step are usually
recycled to the salt saturation step (if brine is not used) or brine purifi-
cation step in the process.
Ihe wastes from the process are as follows:
(1) Brine purification muds - The amount of these, as was discussed for
the diaphragm cell, is dependent on the purity of salt used, but they
average about 15 kg per kkg of chlorine for this process. These muds
normally contain calcium carbonate, magnesium hydroxide and barium sulf ate.
However, treatment of recycled brines to remove mercury or contact with other
mercury-bearing waste results in brine muds which are contaminated with minor
amounts of mercury sulfide and elemental mercury. Thus, for plants where
salt purification is segregated from mercury containing streams, brine muds
are non-hazardous. On the other hand, where no segregation of waste streams
is practiced, brine muds are hazardous. About 3/4 of the brine muds
generated do contain some mercury.
(2) Cell rubble, filter aids, and mercury sulfide from treatment of cell
area drainages. These average 2 kg per kkg of product.
(3) Waterfaorne wastes from chlorine drying and purification and from
scrubbing of process tail gases. These wastes, containing spent sodium
chloride and sodium sulf ate, are also treated to remove mercury. The amounts
of these wastes average 88 kg per kkg of product chlorine.
(4) Chlorinated hydrocarbon wastes generated by chlorine purification
are negligible because of the almost universal adoption of dimensionally
stable anodes. No mercury cell plants were found that still use graphite
anodes.
82
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For the land-destined wastes generated by this process, few major
changes are expected over the next few years. However, high costs for
wastewater treatment and compliance with OSHA regulations may cause some
changeover to the diaphragm cell process at a few sites. The state-by-
state distribution of wastes generated by the mercury cell process is given
in Table 6. The estimated amounts of hazardous and non-hazardous wastes
generated are:
39,000 kkg/yr potentially hazardous mercury containing wastes
15,000 kkg/yr non-hazardous brine muds (from six mixed cell plants
that segregate their wastes)
Comparison of these figures with those from the diaphragm cell shows
that:
(1) Although the mercury cell and diaphragm cell processes produce 23
and 72 percent, respectively, of the total U.S. chlorine production, the
amounts of brine waste differ by only a factor of two. This reflects greater
use of the diaphragm cell process in Gulf Coast and West Coast areas where
relatively high purity salt is available locally. According to the U.S.
Census,2 61 percent of total U.S. production in 1976 was from Louisiana and
Texas. Most of this production came from diaphragm cell operations.
(2) There is a need for segregation of mercury containing waste streams,
particularly if lower purity salt is used, to minimize the amount of brine
mud contaminated by mercury.
Zinc Oxide
This material is produced by four methods:
(1) By the French process from zinc metal and oxygen;
(2) As a by-product of sodium hydrosulfite production;
(3) By up-grading crude zinc oxide recovered by smelters; and
(4) By the American process.
The first three of these processes generate insignificant amounts of
land-destined wastes. In the American process, as shown in Figure 19, zinc
ore is wet milled to remove gangue wastes. The upgraded ore is then roasted
to convert zinc sulfide to zinc oxide and sulfur dioxide. The zinc oxide
84
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TABLE 6. DISTRIBUTION OF ESTIMATED LAND-DESTINED WASTES
GENERATED BY THE MERCURY CELL PROCESS
Concentrated
Mercury
Brine Muds Bearing Wastes
State (kkg/yr) * (kkg/yr)
Alabama
Delaware
Georgia
Illinois
Kentucky
Louisiana
Maine
New Jersey
New York
No. Carolina
Ohio
Tennessee
Texas
Washington
West Virginia
Wisconsin
Puerto Rico
actual Totals
^tounded Totals
4,100
2,150
1,700
1,050
3,650
8,560
400
2,320
4,950
40
400
5,520
4,420
60
9,500
150
148
49, 118 kkg/yr
49,000 kkg/yr
500
200
400
70
360
1,720
128
230
330
120
80
370
880
140
630
10
300
6,468 kkg/yr
6,500 kkg/yr
Number
of
Plants
4
1
2
1
2
3
1
1
3
1
1
1
2
1
2
1
1
28
Number of Plants
Known to Segregate
Brine Muds or Use
Uparaded Salt
4
2
2
1
1
1
1
1
1
14
* The majority of these wastes are hazardous because of non-segregation of
brine purification facilities at 22 mercury cell plants. The other
six mixed cell plants usually segregate their brine muds.
85
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and sulfur dioxide exit the roaster in the gas phase. The gas stream is
cooled and dry bag collectors are used to recover the zinc oxide. The
sulfur dioxide is fed to a sulfuric acid plant on-site. The recovered zinc
oxide is then sintered, mixed with coke and fed to hearth reduction furnaces
where the oxide is reduced to elemental zinc. The elemental zinc vapors,
emerging from the furnace, are reacted with air to form a purified zinc
oxide. This material is recovered by dry collection methods and packaged.
The following are the wastes from the American process:
(1) Ore residues from the milling and roasting operations. These
amount to 450-4,800 kg per kkg of product and are land disposed. The wide
variations in amounts of residue are due to different compositions of ore
used.
(2) Sulfur dioxide from ore roasting - at the three plants using this
process, the sulfur dioxide is used as feed for on-site sulfuric acid plants.
(3) Dusts from the sintering operation amount to 2 kg per kkg of
product and are recovered by dry collection methods to recover cadmium
values.
(4) Residue from the hearth reduction step which consists of lead
compounds. The amount of residue averages 2.5 kg per kkg of product and is
recovered for its lead value.
The 'three facilities using this process are located in Ohio, Illinois,
and Pennsylvania.
According to the industry, about 125,000 metric tons per year of
zinc oxide are produced by the American process. The unpublished capacities
of these plants are estimated to be approximately the same. On the basis
of this production rate, the total amount of waste generated is 325,000 kkg
per year.
Antimony Oxide
This pigment product is produced from ore as shown in Figure 20. Crude
antimony ore, containing about 25 percent antimony sulfide, is roasted
with oxygen. Antimony oxide is formed in the vapor state and is condensed
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and collected in a dry bag collector. Wastes from this process consist of
the following:
(1) Slag from the roasting operation - This material contains other
heavy metal values (including silver) and is generally not discarded. Most
plants sell this material to other processors for silver and other metals
recovery. About 3,500 kg of slag are generated per kkg of product.
(2) Flue gases from ore roasting contain considerable amounts of
which is either used for sulfuric acid production on-site or neutralized
by wet lime scrubbing.
(3) The waterborne waste stream from scrubbing is settled prior to
discharge and the recovered sludge is generally landfilled. About 360 kg
of sludge is generated per kkg of product. This sludge can contain small
amounts of unrecovered antimony oxide.
The distribution of waste generation is as follows:
Amount of Solid
Estimated Capacity Waste Generated Number of
State (kkg/yr) (kkg/yr) Plants
Maryland
New Jersey
Ohio
Texas
360
4,500
2,250
900
130 -slag sold
1,620 -slag sold
810 -slag sold
3,500 -including
1
1
1
1
slag
Total 8,010 6,060 4
Barium Sulfate
Most of the chemical grade barium sulfate produced is manufactured by
reaction of barium carbonate with sulfuric acid. This process produces no
land-destined wastes. One plant, however, uses a process which involves
upgrading of 95 percent barite ore by a wet leaching method. This process
is shown in Figure 21. At that plant, 95 percent barite ore is ground and
leached with 20 percent sulfuric acid to dissolve iron and other metallic
salt impurities present. After leaching, the purified barium sulfate is
recovered by filtration, washed free of sulfuric acid and then further
ground and packaged. The wastewater from sulfuric acid leaching and
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product washing is neutralized with lime prior to discharge. This generates
about 120 kg per kkg of product of sludge containing iron oxide and calcium
sulfate. This plant is located in St. Louis, Missouri, and it is estimated
that the amount of waste generated by the process is less than 35,000 kkg
per year. Plant capacity is not available.
Manganese Sulfate
Manganese sulfate (MnSO*) is produced by two processes at three locations.
At two sites, manganese ore, coke and sulfuric acid are reacted to form a low
grade product containing 27 percent MnSOjj . All solid wastes at the two
locations are sold with the product for agricultural purposes.
At the one remaining site, the process shown in Figure 22 is used.
Manganese ore, aniline and sulfuric acid are reacted to form hydroquinone,
arrroonium sulfate, and manganese sulfate. The hydroquinone is recovered by
steam distillation and the remaining solution is filtered to remove ore
residues. The filtrate is partially evaporated to crystallize MnSO^ which
is recovered by centrifugation and dried.
There are two waste streams from this process:
(1) Ore residues consisting of acid insoluble materials such as silica.
These range from 130 to 1,000 kg per kkg of product and are landfilled after
washing.
(2) Waste process solutions from the final centrifugation step. These
contain 30-600 kg of annonium sulfate per kkg of product along with smaller
amounts of unrecovered manganese sulfate. Treatment of this wastewater
generates from 100 to 660 kg per kkg of product of waste solids consisting
of manganese oxides and calcium sulfate. These wastes are also landfilled.
These wastes are generated only in Tennessee. The estimated solid waste
generation rate for this process is 32,500 kkg per year.
Vanadium Pentoxide
Vanadium pentoxide (VzOs) is produced in the United States either by
reprocessing of spent catalysts or from ferrophosphorus produced from Idaho
phosphate rock. Production of VaOs from spent catalysts generates little
solid waste and is practiced at only two sites with minor combined production.
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is produced from Idaho ferrophosphorus by the process shewn in
Figure 23. The ferrophosphorus, containing six to 8 percent vanadium, is
ground, mixed with soda ash and sodium chloride, and then calcined in air.
This procedure converts the ferrophosphorus alloy to a mixture of iron oxide,
iron phosphate and sodium metavanadate . The mixture is removed from the
kilns and leached with water to recover the salt and sodium metavanadate.
The iron oxides and phosphates are separated by filtration and discarded.
The filtrate is acidified with sulfuric acid to precipitate V205 .
The precipitate is recovered by filtration and redissolved in an ammonium
hydroxide solution. This solution is then mixed with a proprietary alkyl-
amine solvent which extracts the ammonium metavanadate from the aqueous
phase. This solvent is evaporated, to recover a purified ammonium
metavanadate, and condensed for reuse.
The pure vanadate is redissolved in water and the solution is reacted
with sulfuric acid to precipitate V205 which is recovered, dried, and
packaged.
There are several waste streams from this process as follows:
Estimated Amount
Waste _ Process Source Type Waste Generated (kq/kkg)
Iron oxides and leaching of calcined solid 11,800
phosphates raw material
Sodium chloride and second filtration waterborne 10,700
sodium sulfate
Ammonium hydroxide extraction waterborne 0-2
Ammonium sulfate final purification waterborne 730
At the one plant producing VaOs by this method, all wastes are fed to a
lined evaporation pond. All production occurs in Idaho and the waste
generation rate is estimated at 29,000 kkg per year.
Calcium Phosphate (Food Grade)
Food grade calcium phosphates are made by the neutralization of furnace
phosphoric acid with hydrated lime. The processes for manufacturing the
different calcium phosphates differ from one another principally in the
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amount and type of lime used and the amount of process water used. A
schematic process flow diagram for the manufacture of mono-, di- and tri-
calcium phosphates, respectively, is shown in Figure 24. The reaction to
form monocalcium phosphate (MCP) is:
2H3PCV + Ca(OH)2 * Cad^POJa'H'O + H20
An excess of phosphoric acid maintained during the batch addition cycle
inhibits the formation of dicalcium phosphate. A minimum quantity of process
water is used. The heat of the reaction liberates some water as steam in
the reactor, and the remaining water is evaporated in a vacuum drier, a
steam heated drum drier, or a spray drier. The anhydrous MCP is produced by
using CaO (quicklime) and in carrying out the reaction at 140 °C (310°F)
so that water is driven off as it is produced. Drying at higher temperatures
than 140°C results in product degradation.
Relatively pure food grade tricalcium phosphate (TCP) is made in a
similar manner to MCP, except that an excess of lime slurry, maintained
during the batch addition cycle, inhibits formation of dicalcium phosphate:
+ 3Ca(OH)2 •*• Ca3(P0lt)2 + 6H20
Like MCP, the TCP is dried in equipment designed to prevent excessive
product temperatures from developing.
Relatively pure, food grade dicalcium phosphate (DCP) is made in batch
stirred reactors, but with much more process water than for either MCP or
TCP:
Ca(OH)2 •»• CaHPCV2H20
The stoichiometry for DCP manufacture is critical; any excess
during the batch addition cycle would result in some MCP and any excess
Ca(OH)2 would result in seme TCP. The excess water in the DCP reactor is
to ensure homogeneity so that the local stoichiometry is as balanced as
the overall reactor stoichiometry (see Figure 25) .
As a result of the excess water used, the reaction mixture is a
pumpable slurry as opposed to the pasty consistency of MCP and TCP. The
DCP is mechanically dewatered before drying.
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Wastes fron all three product lines consist initially of waterborne
phosphates. Treatment of these wastes with lime generates calcium
phosphate sludges requiring land disposal. The average amount of these
varies slightly with product. All plants produce at least two of
the three product lines. Average waste load of wastewater treatment sludge
from all three product areas is estimated at 135 kg per kkg of product.
The distribution of waste generation is as follows:
Production Capacity Estimated Amount of Solid
State (kkg/yr) Waste Generated^ (kkg/yr)
Florida
Illinois
Iowa
Massachusetts
Missouri
Nebraska
New Jersey
Tennessee
430,000
45,000
170,000
4,500
180,000
69,000
6,200
18,000
58,000
6,100
23,000
600
24,300
9,300
800
2,400
Pounded Totals 820,000 120,000
Calcium Carbide
The open furnace process for calcium carbide is shewn in Figure 26.
Coke is dried and fed to a furnace along with lime and then the mixture is
heated to form calcium carbide. The product is recovered from the furnace,
cooled, crushed, screened, and packaged. There are several waste sources
in this process. These are:
(1) Particulate emissions from the coke drying. These amount to
about 50 kg per kkg of product. Dry collection methods are generally used
to recover these materials for reuse.
(2) Particulate emissions from the electric furnace. These consist
mostly of unreacted lime and coke and are collected primarily by dry
methods and reused. About 440 kg per kkg of product of carbon monoxide
is also vented from this source.
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(3) Particulate emissions from product screening and packaging. These
consist of mostly line and coke and are either recycled or landfilled.
The distribution of waste generation from calcium carbide production
is:
Production Capacity Estimated Amounts of Solid
State
Kentucky
Iowa
Ohio
Oklahoma
Oregon
Rounded Totals
(kkg/yr)
136,000
27,000
207,000
45,500
32,000
450,000
Waste Generated
36,700
7,300
55,900
12,200
8,600
120,000
(kkg/yr)
Not all 120,000 kkg per year is destined for land disposal. An estimate
of the percentage of the total going to landfills is eight percent.
Sodium Hypophosphite
Sodium hypophosphite is produced at two plants in the United States
using the process shown in Figure 27. Caustic soda, lime and elemental
phosphorus are reacted in a hot aqueous solution to yield calcium and sodium
hypophosphites, calcium phosphite and phosphine (PHs). The phosphine
liberated is burned to phosphorus pentoxide which is absorbed in -water to
produce phosphoric acid for other plant uses. The solution of sodium and
calcium hypophosphites is filtered to remove the solid calcium phosphate,
and then is reacted with sodium bicarbonate to convert the calcium hypo-
phosphite to the sodium salt and calcium carbonate. The solution is
filtered again to remove calcium carbonate and then evaporated to recover
the sodium hypophosphite product.
There are two waste streams generated by this process. These are
as follows:
(1) Phosphine emissions - about 200 kg per kkg of product. This air-
borne emission is normally converted to phosphoric acid for on-site use.
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(2) Product purificaticn wastes - about 630 kg of calcium phosphite
and 190 kg of calcium carbonate are generated per kkg of product. These
non-hazardous solid wastes are combined before landfilling.
Sodium hypophosphite is produced at only two sites in two states:
Tennessee and New York. Total estimated capacity for the two operations is
3,000 metric tons per year and the total amount of land-destined waste
generated is estimated at 2,500 metric tons per year.
Barium Carbonate and Strontium Carbonate
Barium and strontium carbonates (BaC03 and SrC03) are combiiied because
both chemicals are produced at the same sites using similar processes.
Figure 28 shows the process for barium carbonate.
Barite ore and coke are reacted in a kiln. Barium sulfide is produced
along with carbon dioxide (002) and some sulfur dioxide (S02)• The reaction
product from the kiln is leached with water to recover barium sulfide. The
insoluble ore residues are then discarded and the barium sulfide solution
is reacted with soda ash to precipitate barium carbonate. This product is
recovered by filtration, washed, and dried. The solution, after removal
of barium carbonate, is then generally filtered to recover a sodium sulfide
(Na2S) co-product.
Sometimes carbon dioxide is used in place of soda ash. This results
in a hydrogen sulfide (H2S) co-product which is either recovered for sale
or used on-site to manufacture other sulfide chemicals.
The wastes from barium carbonate manufacture are the following:
Amount
Waste
Ore residue
C02 and S02
H2S
Na2S
Sulfides and
Process Source
reaction kilns
reaction kilns
reactor (if C02 used)
reactor (if soda ash
used)
filtration and washing
Type Emission
solid
gaseous
co-product
co-product
waterborne
(kg/kkg
100-200
450 C02
170
390
12-47
of BaC03)
, 0-12 S02
barium
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The ore residue is the principal land-destined waste. Sane additional
wastes are generated by wastewater treatment and they are combined with the
ore residue before disposal.
Figure 29 shows the process for strontium carbonate manufacture. The
ore (Celestite) is reacted with coke to yield strontium sulfide which is
separated from the ore residues by leaching with water and filtration. The
ore residues are discarded and the strontium sulfide solution is reacted
with soda ash to precipitate strontium carbonate. This product is collected
by filtration, washed, and dried. The solution is further processed to
recover a sodium sulfide co-product.
As with barium carbonate manufacture, COz is sometimes used in place
of soda ash. Again, EzS is generated in the reactor as a co-product and is
used on-site to produce other sulfide chemicals. The rest of the process
is the same as for BaC03.
The wastes generated from SrC03 production are listed below:
Amount (kg/
Waste
Ore residue
COz and SOz
E2S
Na2S
Wash water
Process Source
kiln
kiln
reactor
reactor
final filtration
Type Emission
solid
gaseous
co-product
co-product
waterborne
kkg SrC03)
100-200
600 C02
0-18 S02
0-230
0-530
5-31
and washing
The ore residue is land disposed along with an additional amount (up
to 30 kg per kkg of SrCOa) of barium and strontium containing solids which
are generated after wastewater treatment.
For barium carbonate production, the distribution of waste generation
is:
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State
California
Georgia
Kansas
Texas
Pounded Totals
Number of
Plants
1
1
1
1
4
Published
Capacity
(kkg/yr) 1
27,300
13,500
10,800
5,000*
57,000
Amount of Land-
Destined Waste
(kkg/yr)
16,000**
2,000
1,600
500*
20,000
* Contractor estimates.
** Includes ore beneficiation wastes.
The Texas operation is considerably different from the others. At that
plant, the barium carbonate is produced for captive use for brine purifica-
tion at three chlor-alkali plants. The barium sulfate from brine purifica-
tion is apparently returned to the plant for reconversion to the carbonate.
This would account for the relatively low waste loads in Texas.
For strontium carbonate production, the distribution of waste generation
is:
State
California
Georgia
Totals
Sodium
Number of
Plants
1
1
2
Published
Capacity
(kkg/yr) l
9,100
900
10,000
Estimated Amount
of Land-Destined
Waste (kkg/yr)
4,900
300
5,200
Metallic sodium is produced by the Downs cell process as shown in Figure
30. Raw sodium chloride brine is treated with soda ash and barium chloride
to precipitate magnesium hydroxide, calcium carbonate and barium sulfate.
These wastes are removed by filtration and the purified brine is evaporated
to recover dry salt. The salt is blended with calcium chloride to form
a low melting eutectic and the mixture is melted and electrolyzed to produce
sodium and chlorine. The sodium leaves the cell as a liquid and is cooled,
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filtered to remove a sodium calcium sludge, and is prepared for shipment.
The chlorine is dried with sulfuric acid and then compressed, further
purified if required, and readied for market.
The wastes from these operations are as follows:
(1) Brine purification sludge - this averages about 9 kg per kkg of
product and consists of barium sulfate, magnesium hydroxide and calcium
carbonate. It is usually landfilled.
(2) Waterborne wastes from brine purification - contains 40-90 kg
per kkg of product of sodium chloride.
(3) Cell wastes - primarily waste salt, carbon and cell rubble
contaminated with traces of sodium. These materials are weathered to
oxidize the sodium present prior to disposal. The amount of this waste
averages about 10 kg per kkg of product.
(4) Sodium-calcium sludges from sodium purification - All three
manufacturers process these wastes to convert them to sodium and calcium
chlorides for recycle to the process.
(5) Waste sulfuric acid from chlorine drying - about 5 to 12 kg are
generated per kkg of product. It is neutralized prior to discharge.
(6) Scrubber waste - Tail gases are wet scrubbed with lime or caustic
soda solution which creates a waterborne waste. About 2.5 kg per kkg of
product of chlorides and hypochlorites are formed by the scrubbing of tail
gases.
The geographical distribution of sodium production wastes is as
follows:
State
Louisiana
New York
Ohio
Tennessee
Texas
Totals
Published
Capacity
(kkg/yr) 1
41,000
51,400
33,600
20,000
27,000
173,000
Estimated Amount of
Land-Destined Waste
Generated (kkg/yr)
820
1,030
670
400
540
3,460
108
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These land-destined wastes should be non-hazardous. The hazardous
wastes (sodium-calcium sludges) are reprocessed on-site by all the producers.
Sodium Chlorate
The manufacture of sodium chlorate starts with the purification of
sodium chloride solution by the addition of soda ash as shown in Figure 31.
Magnesium hydroxide and calcium carbonate are precipitated and removed by
filtration. The sodium chloride solution is acidified by addition of
hydrochloric acid. In some plants, sodium dichromate is added prior to
electrolysis. The brine is then electrolyzed to produce a sodium chlorate
solution. In five plants, barium chlorate is added to recover chromates as
barium chromate. The purified sodium chlorate solution is partially
evaporated and fed to crystallizers where the product is recovered by
filtration and dried. The liquor is recycled to the brine purification step
of the process. The use of chromates and barium salts in this process is
dependent on the electrodes used in the electrolytic cells. When platinum
electrodes are employed, chromates are never used. When graphite electrodes
are employed, chromates are generally used.
The wastes from this process are the following:
(1) Salt purification muds - these consist of calcium carbonate and
magnesium hydroxide and are generated only if impure salt is used as a feed
material. The amounts of these range from 0-15 kg per kkg of product.
(2) Spent graphite electrodes and barium dichromate wastes are present
only if graphite electrodes are used. The amounts generated average 25 and
6 kg per kkg of product, respectively. The chromate wastes are potentially
hazardous.
Of the 12 plants in the industry, seven currently use platinum electrodes
and five still enploy the older graphite electrode technology. Three of
these five are currently converting step-wise to the newer technology.
A distribution of wastes generated on a state-by-state basis is given
in Table 7.
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TABLE 7. DISTRIBUTION OF ESTIMATED WASTES GENERATED BY SODIUM
CHLORATE MANUFACTORE*
State
Alabama
Georgia
Kentucky
Louisiana
Mississippi
Nevada
New York
North Carolina
Oregon
Washington
Rounded Totals
Production
Capacity
(kkg/yr)
3,600
7,300
38,000
40,500
90,000
34,500
12,000
6,400
18,000
3,600
254,000
Number of
Plants
1
1
1
1
2
2
1
1
1
1
12
Amount of Amount of
Non-Hazardous Hazardous
Waste Generated Waste Generated
(kkg/yr) (kkg/yr)
None
200
1,000
600
725
640
125
None
None
100
3,800
None
None
None
270
400
None
80
None
None
24
800
* Waste information for this table was obtained from data provided by all
seven producers.
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Chroma Yellow
This pigment, as shewn in Figure 32 is produced in batches. Lead
nitrate or acetate and sodium chronvate solutions are prepared. These
solutions are mixed and the product lead chromate (chrome yellow) precipitates
from solution. It is then recovered by filtration, washed, dried, milled
and packaged. The processing solutions, containing unreacted lead, chromates,
and unrecovered pigments are usually treated prior to discharge. This
generates sludges containing lead chromate and chromium and lead oxides
and hydroxides which are landfilled. The amounts of these sludges average
50-70 kg per kkg of product and their approximate compositions are listed
in Figure 32.
The distribution of waste generators is as follows:
Plant Location
New York
New Jersey
West Virginia
Kentucky
Ohio
Illinois
Wisconsin
Estimated Amount
Capacity of Sludges Generated Number of
(kkg/yr) (kkg/yr) Plants
>19,000
not available
2,500
2,500
700
not available
not available
1,280
140
300
300
42
140
140
3
1
1
1
1
1
1
Totals 33,000 2,340 9
These wastes are potentially hazardous because of their lead and
chromate contents.
Potassium Permanganate
Potassium permanganate is made by the process shown in Figure 33.
Manganese ore, water and potassium hydroxide are reacted in a kiln with
oxygen to yield potassium manganate. This material is then leached from
the ore with water. The resulting solution/ore mixture is separated by
filtration and the ore residue is discarded. The filtrate is electrolyzed
to convert the manganate to permanganate. The permanganate solution is
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partially evaporated which causes crystallization of potassium permanganate.
The crystals are recovered by filtration and dried. The filtrate is
recycled to the electrolysis cells.
There are two sources of wastes from this process:
(1) Ore residues from the leaching and filtration step. These amount
to 140 kg per kkg of product and consist of silica, alumina and other
insoluble materials. These are landfilled.
(2) Waterborne wastes from the barometric condensers used on the
evaporators - this waste stream contains potassium manganate and permanganate
and small amounts of KOH in solution. Treatment of this waste stream
generates about 2.5 kg per kkg of product of manganese oxides which are
combined with the ore residue wastes for disposal.
The only plant producing this chemical is in Illinois. The rate of
solid waste generation at this site is estimated at 1,450 metric tons per
year.
115
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V. CURRENT DISPOSAL PRACTICES
This section is a discussion of the present disposal practices employed
by the major waste sources identified and characterized in previous sections.
Current Disposal Practices by Industry Group
Chlor-Alkali - Diaphragm Cell—
The wastes from diaphragm cell operations are brine muds, cell rubble,
spent electrodes, and asbestos.
The brine muds are usually disposed of by lagooning. As lagoons are filled,
new lagoons are dug if space is available, and the old ones are then drained,
covered and restored. If space is unavailable, the muds are periodically removed
from the lagoons and trucked to off-site disposal sites. Vfe estimate that at
least half the plants will eventually use off-site disposal for these muds. At
a few sites, the brine muds from the process are sent directly to off-site dis-
posal sites. Four of the 32 plants are located in areas where space is limited.
At least one plant disposes of its brine mud by deep well injection.30
Apparently one plant alone separates its brine purification process
into steps so that the recovery of barium sulfate is isolated. This is an
area where a waste material could be recovered for processing into other
barium chemicals.
Cell rubble and spent electrodes are usually landfilled on-site. The
asbestos wastes produced by the industry are normally handled wet and buried
in sealed, marked containers. At least 50 percent of the burial sites are
estimated to be on plant property. Lined sites for asbestos burial are not
generally used because the industry feels there is no danger of leachate
from the sealed containers.
Six plants still using lead graphite anodes also dispose of their lead-
bearing wastes in the plant lagoons. At most of these sites, these wastes
are mixed with brine mud wastes prior to storage.
Most of the 26 plants using the newer metal anodes, however, no longer
have any lead-bearing wastes on their premises. These wastes were either
correctly land disposed in the past or have already been removed by
contractors.
116
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Three of the 32 diaphragm cell plants are located in Louisiana near
wetlands areas. Another plant in Georgia may also be in a wetlands region.
At least one of these plants uses off-site disposal for its wastes.
Chlor-Alkali - Marcury Cell—
The mercury cell process industry generates about 15,000 kkg per year
of non-contaminated brine muds and 40,000 kkg per year of mercury-containing
wastes. Percentages of mercury in the brine muds prior to treatment range
from 5 x 10"1* up to 0.10.
The non-hazardous brine muds are disposed of in the same manner as
described for the diaphragm cell plants (i.e., lagoon storage and off-
site burial). About half the plants dispose of these wastes off-site.
The wastes contaminated with mercury are handled as follows:
- 12 plants store muds in lagoons
- 1 plant uses a lined lagoon
- 12 plants use off-site landfills
- 1 plant uses deep well injection (monitored)
- 4 retort brine muds before disposal to recover mercury
- 2 treat muds with hypochlorite
- 11 plants retort or chemically treat concentrated wastes
- 6 plants pond concentrated wastes after treating
- 15 plants dispose of concentrated wastes in secure, monitored
landfills
Five mercury cell plants are located near wetlands areas. These
include two in Louisiana and one each in Delaware, Georgia and Texas.
Three plants are in urban areas where additional land is unavailable.
Solvay Soda Ash—
About 260,000 metric tons per year of brine muds are generated by the
one plant still using the Solvay process. These wastes are currently
lagconed on-site and as the lagoons are filled new ones are constructed.
The used lagoons are drained and the land is restored. The plant expects to
continue this on-site disposal practice and already has monitoring wells
on-site to comply with current state regulations. However, the corporation
also operates a mercury cell chlor-alkali facility on the plant site and
the brine muds from the Solvay process may be contaminated with mercury
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from earlier years of operation. Therefore, leachate control and treatment
systems may have to be installed at about 10 restored pond areas.
Natural Soda Ash—
It was estimated that about 1,200,000 metric tons per year of ore
residues and unrecovered trona are being land disposed at four sites in
Wyoming. These plants currently use evaporation ponds for waste disposal.
Reclamation of the disposal areas is already required by Wyoming law. At
least two sites currently have and use monitoring wells.
Titanium Dioxide - Sulfate Process—
The four sulfate process plants currently dispose of their wastes as
follows:
- One plant practices full neutralization with on-site storage of
generated gypsum. A small amount of ferrous sulfate is recovered for sale.
- One plant ocean barges most of its wastes and recovers about 25
percent of the generated ferrous sulfate for sale. This plant expects that
it will have to install neutralization facilities in the next few years
because of the phasing out of ocean barging.
- One plant discharges its wastes directly to a river, but is
installing neutralization facilities.
- One site partially neutralizes its wastes, landfills the generated
gypsum off-site, discharges part of the remaining waterborne waste, and
landfills some ferrous sulfate off-site. This plant probably will have to
install full neutralization facilities.
No plants are located in environmentally sensitive areas, but three are
located in urban areas where land for on-site disposal is unavailable.
Titanium Dioxide - Chloride Process—
The current practices for waste treatment and disposal in this industry
are as follows:
- One plant disposes of neutralization wastes on-site and uses
monitoring wells (lined site).
- Two plants share a common off-site disposal area which has no
monitoring wells (unlined site).
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- One facility disposes of most wastes by deep well injection with
monitoring of the disposal site.
- One facility sells some waste ferric chloride and disposes of the
remaining wastes by ocean barging.
- One plant uses an unlined off-site landfill.
- Two facilities combine their wastewater with that from titanium
dioxide, sulfate process operations. One neutralizes all wastewater prior
to discharge and uses on-site disposal of solids. The other plant neutral-
izes only part of its wastewater.
These plants are not in environmentally sensitive areas.
Antimony Oxide—
The production of this chemical generates 6,000 metric tons per -year
of land-destined wastes. Approximately 3,000 kkg per year are scrubber
wastes and an equal volume is slag. Three of the four plants sell their
slag for reclamation of silver and other metals. The other plant obtains
its raw material from a uranium producer who has already extracted other
metal values. Because the spent slag at this site contains low levels of
radioactivity, it is land disposed at a special hazardous waste disposal
area off-site. The slag generated by the other producers is not radioactive.
All four plants use off-site disposal for the scrubber wastes.
Three plants are in urban areas and none is in an environmentally
sensitive region.
Barium Sulfate—
Only one plant will be generating land-destined wastes because of water
pollution regulations that will require neutralization of its waste stream.
Once this occurs, off-site disposal of the iron oxide and gypsum wastes
generated will be required. There is no room for on-site disposal at this
plant.
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Zinc Oxide—
The current disposal method at all three American process plants is
on-site storage of slag wastes. This practice over the years has resulted
in slag pi3es containing over 1.8 million metric tons of waste at one site
alone. The other two sites are about the same age and their slag piles are
estimated to contain similar quantities of material.
These slags contain small amounts of unsmelted material and some free
carbon. At one site, zinc and cadmium were detected in the leachate frcm
the waste piles. These materials are potentially hazardous.
These plants are not in environmentally sensitive areas.
Chrome Yellow—
Chrome yellow is produced at nine locations in the United States. The
solid wastes are produced from wastewater treatment to remove lead and
chromates.
Two plants use their own disposal facilities, one on site and the
other off site. Both sites are lined and equipped with leachate control
systems and monitoring wells. These sites are already in compliance with
projected hazardous waste disposal regulations.
The remaining seven plants use off-site contractor disposal. At least
three plants currently use acceptable disposal sites. The remaining four
facilities are uncertain as to the adequacy of present disposal areas.
Two plants have reported seme recovery of materials from wastewater
treatment and subsequent sale as offgrade products.
None of the plants is located in an environmentally sensitive area and
seven of the plants are in urban locations.
Iron Oxide—
Ten plants currently produce iron oxide products. The 15,000 metric
tens of waste which they generate annually are landfilled. Seven facilities
employ contractors who dispose of wastes off site, at locations which may
or may not have monitoring wells.
None of the facilities is in an environmentally sensitive area and
seven are located in urban or suburban locations.
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Hydrofluoric Acid—
Production of hydrofluoric acid generates a gypsum co-product which is
contaminated with small amounts of unreacted calcium fluoride. At the 13
plants producing this chemical, the current practices are as follows:
(1) TWo plants, with a combined production capacity of 36,000 kkg per
year, sell all their wastes for use as construction material or soil
stabilizer. Neither of these plants is in an urban location nor in an
environmentally sensitive area.
(2) Che plant, with a capacity of 45,000 kkg per year, uses all waste
for on-site construction purposes. At that site, which is near a wetlands
area, local construction material is not easily available. The waste is
used for levee construction and maintenance.
(3) Five plants use off-site landfill disposal and one plant landfills
on site.
(4) Four plants currently store all wastes on site in piles or lagoons.
Three of these plants combine these wastes with those from aluminum fluoride
production prior to storage.
Cne plant is unusual in that the waste gypsum produced is slightly
acidic because of only partial neutralization of the recycled solid
wastewater transport system used. All other facilities fully neutralize
their wastes prior to disposal. The gypsum precipitated from acid waters
at this plant is CaSCV^HaO instead of the dihydrate CaSCV2H20 normally
produced by full neutralization. Runoff water from these waste gypsum piles
is weakly acidic. However, this water is collected on site and either reused
or neutralized prior to discharge. This plant mixes wastes from an on-site
aluminum fluoride process with the hydrofluoric acid gypsum wastes.
Of the 13 plants, three are located near but not in wetlands areas and
two of these are presently using on-site storage.
Lime—
The wastes from the 180 plants in this industry consist of underburned
lime dusts which are collected by wet or dry methods from process vent gases.
About 30 plants either reprocess this material or sell it as off-grade
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material. The remaining 150 plants landfill these wastes either at the
plant or at the limestone mining site. The amounts landfilled on- or off-
site are about equal. None of these landfill sites is laiown to have
monitoring wells. Fewer than six lime plants are located near wetlands areas.
Alumina—
This product is manufactured from bauxite at ten facilities in the
United States. The waste muds from the process are pumped to settling
lagoons where they are allowed to accumulate. As the lagoons are filled,
new ones are dug. The old lagoons are allowed to slowly drain. All other
miscellaneous wastes are disposed of at the plant sites.
Large areas of land are required for mud storage. Current industry
practice does not include restoration of filled mud lagoons. At eight of
the ten sites, the mud lagoons are adjacent to the plant site. At two
locations, however, the muds are pumped several miles to disposal lagoons.
The muds leaving the process average 10 percent solids content. After
deposition in the lagoons and proper drainage, however, their solids con-
tent increases to approximately 50 percent. Removal of additional water
occurs very slowly and several years may be required for significant in-
creases in solids content. Only at this time can proper land reclama-
tion be practiced. The residual alkali content of the muds makes restoration
of the lagooning areas more expensive. Eight of the 10 plants use clay-lined
lagoons for mud storage.
Eight plants are located on the Gulf Coast. The other two are in
Arkansas, near bauxite deposits. The Gulf Coast plants were originally
located there for two reasons: (1) most of the bauxite used is transported
by ship from Jamaica, Surinam, West Africa or South America and (2) caustic
soda and natural gas (for fuel) are both readily available on the Gulf
Coast. One plant in Louisiana and one plant in Alabama are near but not
in wetlands areas. In addition, two other sites in Texas are near wetlands
and could also be impacted by wetlands regulations in future times as more
land is required.
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Aluminum Sulfate —
According to Census data,2 there are 67 plants manufacturing this
product. Most plants are located in rural areas where land is readily
available. The general waste disposal practice is for periodic removal
of the mud wastes from settling lagoons and landfill on-site. A few plants
near urban areas may employ off -site disposal. The number of such plants
is estiitated at less than ten.
Only two or three of these plants in Southern Alabama and Southern
Louisiana are in wetlands areas.
Sodium —
The production of sodium generates two waste streams requiring land
disposal. These are brine purification muds containing CaCOs, Mg(OH)a, and
; and cell rubble and spent graphite electrodes.
The general industry disposal practice is to landfill these wastes on
site. Only one plant uses an off -site disposal area. None of the five
plants is in an environmentally sensitive area.
Sodium Chlorate —
This product is produced at 12 locations in the United States using
technology which is undergoing rapid change. The seven plants using the
latest technology have only brine purification muds as wastes, if impure
salt is used. The five plants using old technology, however, have wastes
consisting of barium chromate and spent graphite anodes. The barium
chromate wastes are potentially hazardous.
Five of the seven modern technology plants reported no wastes requiring
disposal. The other two plants landfill their brine muds. One uses a
lined evaporation pond with on-site monitoring. The other combines these
wastes with gypsum and other non-hazardous process wastes prior to off-site
landfilling.
Two of the five plants using older technology landfill their wastes
off site. The other three landfill on site. One plant recovers and reuses
its barium chromate and land disposes only the graphite anodes along with
non-hazardous diaphragm cell chlor-alkali wastes.
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At least three plants use hazardous waste disposal sites that are in
compliance with projected ECRA regulations. The status of one wetlands
area plant is uncertain.
Sodium Hypophosphite—
Sodium hypophosphite is produced at only two locations, neither of
which is in an environmentally sensitive area. The solid wastes generated
at both plants are recovered and buried off site with other non-hazardous
wastes generated from other processes.
Potash—
The wastes from production of KC1 and K2SOu from ore are initially
waterborne. These wastes are all fed to evaporation ponds at the eight
sites. Over the years, the amount of waste salt and clay deposited in
these ponds has grown to an estimated 450 million iratric tons. All produc-
tion occurs in New Mexico and Utah. Both areas are arid regions where the
disturbed land has no agricultural value. Both areas are situated atop
salt domes so that the local ground water is saturated with salt. The
evaporation ponds are located sufficiently far from rivers and streams to
preclude the chance of salt contamination. Thus, the environmental effects
on these eight sites are minimal.
Potassium Permanganate—
Potassium permanganate is produced at only one site. The ore residues
and wastewater treatment sludges are combined and landfilled in an off-site
disposal area. The site is monitored and the wastes are considered non-
hazardous. The disposal site and plant are not in environmentally sensitive
areas.
Barium and Strontium Carbonates—
These two chemicals are produced by similar processes in the same
plants. The wastes fron the two operations are generally combined prior to
disposal. Both processes generate ore residues, containing small amounts
of potentially soluble barium or strontium and sulfides, and wet scrubber
residues containing mostly calcium sulfate. These two wastes are combined
prior to landfilling.
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There are four plants manufacturing one or both of these chemicals.
None of these is in an environmentally sensitive area.
One plant already disposes of the potentially hazardous waste at a
secure off-site landfill site in accordance with state hazardous regulations.
Another plant stores these wastes at the plant site and has land
available on site.
A third plant has been landf illing these wastes off-site in an unlined
landfill for the past ten years.
The fourth plant is captive to a chlor-alkali complex and supplies the
barium carbonate solely for use in brine purification. Much of this plant's
feed material is probably the barium sulfate formed by brine purification
with the result that the amount of ore residues generated is minimal. This
plant landfills its wastes off site in a secure area.
Borax—
Borax is produced from ore at only one site in the United States. The
spent ore residues are permanently stored in lined lagoons with the
surrounding area being monitored for leachate. As these ore residues contain
small amounts of natural arsenic minerals, they are potentially hazardous.
The production site is located in the MDJave Desert area of California.
Calcium Carbide—
The wastes from calcium carbide manufacture at five plants are
handled as follows:
Four plants either sell or reuse all solid wastes. Three facilities
sell the material as a low grade neutralization agent. Cue plant, located
in a ferroalloy complex, uses this material for neutralization of acidic
waterborne wastes from other operations.
Cne facility reported an unusual situation in that coal is used in
their process in place of high grade coke, generating a furnace slag not
present as a waste at the other plants. About 8,300 kkg per year of slag
and other wastes are generated which are currently land stored at the plant
site.
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One facility which currently sells its wastes, has over 450,000 metric
tons of stored line on the premises. This line is from previous years of
acetylene production and the plant feels it nay be salable over a period of
years. Ihe salability of this material is questionable.
None of these plants is in an environmentally sensitive area.
Calcium Phosphate—
For the solid wastes from calcium phosphate manufacture, landfilling
is the only reported method of disposal. At least three facilities use
off-site disposal. Most of the other plants are located in rural areas
and it would be expected that their waste disposal would be on-site. None
of the landfill sites had monitoring wells. There are no plants in
environmentally sensitive areas.
Sodium Dichromate—
The solid wastes, usually consisting of ore residues and wastewater
treatment generated muds, are landfilled. Chemical treatment with ferrous
chloride or sodium sulfide is used at two plants to reduce hexavalent
chromium to the trivalent form prior to disposal. The third plant thoroughly
washes its waste solids to remove soluble chromates before disposal.
One plant uses a lined on-site disposal area which is projected to meet
all PCRA hazardous waste disposal criteria. Another plant currently disposes
of its wastes in an unlined quarry near the plant site. Wastes have been
deposited in this quarry for the last six years.
The third plant has used outside contractors for waste disposal, but is
presently having problems finding suitable locations for its wastes.
None of the plants is in an environmentally sensitive area.
Lithium Carbonate—
There are two plants producing lithium carbonate. Ore plant stores
its solid wastes in a 60-acre ravine. The second facility also land stores
some of its wastes, however, it has landfilled most on site and has restored
the disturbed area. Neither plant is in an environmentally sensitive area
and one already has monitoring wells.
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Manganese Sulfate—
The one plant manufacturing manganese sulfate by the hydroquinone
process currently stores its wastes in an on-site lagoon. The plant is
not in an environmentally sensitive area and has the area for future lagoon
construction.
Phosphorus—
The handling practices for the wastes generated by phosphorus pro-
duction are as follows:
Slag is entirely sold at the six eastern plants for use as a crushed
stone substitute in roadbed construction. Only 60 percent of this material
is sold at the three western plants. The rest is stockpiled. Inventory
stockpiles from past years of production total about 18,000,000 metric tons
for the three western sites.
Particulates recovered from ore drying and preparation by dry collection
methods are generally landfilled on-site. Seven plants, however, do not
have monitoring wells at the landfill sites.
*
Phossy dusts, recovered by dry collection methods from phosphorus-
containing gas streams, are combined with the phossy water at most plants;
retorted to recover phosphorus at one plant which landfills the residues
on-site in a lined and monitored area; and collected, drummed, and stored
by another plant for future off-site disposal at a hazardous waste disposal
site. The phossy water is fed to lined lagoons for settling of suspended
phosphorus and is then reused in the process to condense and collect phos-
phorus. At sane sites, waste phosphorus accumulates at the bottom of these
ponds. Two plants currently recover the phosphorus periodically by retort-
ing and then landfill the residues in a lined and monitored area. Two
other plants have used in-process control technology to reduce the amounts
of phosphorus going to the ponds. One of these two plants also uses a
proprietary scheme for phosphorus recovery from these wastes.
None of these plants is located in either urban or environmentally
sensitive areas.
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Sodium Silicofluoride—
At the one plant studied in this program, all waterborne wastes are
disposed of by deep well injection. The plant is not located in an
environmentally sensitive area.
Vanadium Pentoxide—
At the only plant producing vanadium pentoxide, all solid and waterborne
wastes are fed to a lined evaporation pond. Space is available on site for
additional pond construction and corporate plans call for covering and
restoration of the original pond site, once the pond is filled. The plant
is located in an arid area in eastern Idaho.
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VI. ,!OA 4004 COMPLIANCE COSTS
This chapter provides an estimate of the additional capital and operating
costs the inorganic chemicals industry is likely to incur in complying with
section 4004 of RCRA. Cost estimates for recent State and other Federal
regulations are also presented. The scope has been limited to the manufacture
of 31 inorganic chemicals whose processes generate over 1,000 metric tons
per year of land-destined wastes. Other inorganic chemicals manufacturing
processes generate less significant quantities of land-destined waste which-
are generally contractor hauled. The impact of ECRA 4004 on these producers
will be minimal and therefore, is not discussed.
Table 1 in the Executive Summary of this report gives a comprehensive
overview of the 31 inorganic chemical product areas, indicating amounts of
non-hazardous wastes generated by each and the current status of disposal
methods, monitoring and reclamation. Table 2 summarizes the estimated
compliance costs for non-hazardous wastes.
The costing methodology section of this chapter describes the sources
of data and assumptions made to arrive at the estimated costs. The inorganic
chemicals industry is both complex and highly diversified; therefore, cost
information has to be obtained on a plant-by-plant and product-by-product
basis through contacts with corporation offices and on-site visits. Figures
used represent the most accurate averaging of costs on an industry-wide basis,
except where noted.
The compliance costs section of this chapter discusses disposal control
mechanisms which must be implemented to achieve compliance with RCRA. 4004
criteria and with other overlapping Federal and State regulations, and
provides estimates of the costs associated with compliance. These costs
are based on Versar's estimates of what is needed to upgrade current
practices. These estimates have not been endorsed by EPA and other control
mechanisms not discussed here may also be required or used. Nbn-KCRA
Federal regulations apply to such statutes as the Clean Water Act of 1977,
which covers surface waters and wetlands when an NPDES permit is denied.
State regulations refer to recent State ground-water regulations. All RCRA
4004-induced costs must be considered supplemental to other compliance costs
incurred.
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COST METKDDOLOGY
Data Sources
Compliance cost information was obtained directly from the inorganic
chemicals industry on a site-by-site and product-by-product basis. This
approach was necessitated by the complexity of the industry and the diversity
of products involved. Indus try-furnished costs were subjected to an in-
depth review and, when costs varied excessively from published data, they were
examined to determine if unusual factors were present. Follow-up visits to
several plants and corporation headquarters were then made to verify information
received.
Presentation of Costs
Compliance costs are divided into capital costs and annual operating/
maintenance costs and are expressed in 1978 dollars. Capital costs are then
amortized and combined with operating/maintenance costs to determine the total
annualized costs associated with compliance requirements. When it appeared
that compliance would have a significant economic impact on an industry
segment, costs were further broken down to derive estimates per ton of product
and to project possible price increases.
Cost Assumptions
Capital Costs
For most segments of the industry , the major capital cost expenditure is
the installation of three monitoring wells for each site. Industry estimates
for geological studies, equipment purchases, cost of borrowed capital at 12
percent interest, and actual installation ranged from $5,000 to $20,000 per well.
We averaged industry projections and assumed a cost of $10,000.
Several segments of the industry will incur capital costs for purchasing
or upgrading waste disposal areas. Following are industry estimates and the
figures we have derived as the most accurate averages:
• Cost of land
Industry estimates : $1,000 - $10,000 per acre
Our estimate: $5,000 per acre
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• Uhlined landfill construction costs
Industry estimates: $10,000 - $25,000 per acre
Our estimate: $20,000 per acre
• Amount of waste buried per acre
Industry estimates: 8,000 - 30,000 tons
Our estimate: 10,000 tons (including area for active landfill
operation, perimeter construction, fencing, monitoring
sites, etc.)
Annual Operating/Maintenance Costs
• Monitoring—These costs averaged $4,000 per year industry-wide for
quarterly monitoring. Vie also assume that each well will depreciate by $1,000
or 10 percent annually.
• Site closure costs—For most segments of this industry, closure costs
are merely those for monitoring during the site closure period. Monitoring
costs are assessed, as explained above , at $4,000 per site per year.
Land reclamation costs
Projections were uniformly about $1,500 per acre except for alumina.
These costs include those for site covering with topsoil and revegetation.
Because of the alkaline nature of alumina wastes, disposal sites must be
specially treated and will thus be more expensive. Costs for reclamation of
already disturbed areas are treated as capital costs. Costs for future
reclamation are treated on an annualized basis.
Current waste disposal costs are not emphasized because the objective
of this study is to determine incremental costs for compliance with RCRA. The
industry has reported that costs for on-site landfilling of non-hazardous
solid wastes range from $1.35 to $2.00 per ton. Off-site disposal costs are
as high as $&. 00 per ton, depending on the distance to be transported.
Price Impacts
The projected compliance costs for many of the chemical products were
not significant (i.e., amounted to less than one percent of the product
selling price on a per tonnage basis). For two of the chemical products
(alumina and hydrofluoric acid) compliance costs were large enough to
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justify a more detailed assessment. For each of these products, estimated
compliance costs per metric ton were developed. Capital cost estimates
include 12 percent interest charges and, in those cases where compliance costs
per ton of product exceeded one percent of the product selling price, the
capital costs were allocated over a 10-year capital recovery period. (One
exception where costs exceeded one percent but were not allocated over a
ten-year period was one hydrofluoric add plant that will incur environmental
costs of approximately 1.8 percent of the product price in the first year.
This cost was not spread out over a ten year period to allow comparison with
other similar hydrofluoric acid plants).
It must be emphasized that within each product category, compliance
costs will vary from site to site and will also vary over time as waste
inventory problems are eliminated. Tb give a realistic picture of compliance
costs, plants in each product area were grouped according to the level of
impact. Actual price increases will, of course, depend on actual compliance
costs at each site. To give an estimate of the magnitude of these price
increases, compliance costs per metric ton of product were estimated as a
percentage of the selling price of the chemical products. It is assumed that
all compliance costs will be passed on to consumers. Following are ranges of
potential increases for the most heavily impacted products:
Range of potential price increase
Product (as a percent of present product selling price)
Alumina 0.3 % - 1.6 %
Hydrofluoric acid 0.0 % - 1.8 %
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COMPLIANCE COSTS
In this section the estimated compliance costs presented in Table 2 are
disaggregated and attributed on a chemical-by-chemical basis to three criteria:
• State ground water protection regulations
• RCRA. 4004 (relating to ground water protection)
• State surface water regulations
These criteria and associated costs will be discussed in detail. Other
RCRA criteria listed below, do not have a cost impact on the inorganic chemicals
industry.
• Floodplains and wetlands regulations - NO inorganic chemical plants are
located in swamps or marsh areas. In addition, those that are
situated near rivers are already adequately protected from potential
flooding by levees.
• Critical habitat regulations - NO plants are located near critical
habitats.
• Air regulations - No hazardous gases result from the burial of
non-hazardous wastes. Fugitive dusts, however, could result from
open land storage of wastes and will be discussed for relevant cases.
• Disease vector regulations - No bacterial wastes are involved.
• Safety regulations - No explosive gas, toxic gas, bird sanctuary,
access, or fire-related problems are involved.
In the following discussion, the criteria that result in compliance costs
will be addressed on a chemical-by-chemical basis. As shown in Table 2,
these costs are divided between "State and other Federal-induced costs" and
"RCRA 4004 compliance costs". The State and other Federal-induced costs are
attributable to State regulations concerning ground water protection. Within
this category, the capital costs are for construction of monitoring wells
(three per site at $10,000 each), and the annual operating costs are for well
depreciation, quarterly monitoring, and analysis. The only other costs
incurred under this category are for compliance with State surface water
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regulations in the case of calcium carbide (see calcium carbide discussion
below).
The RCRA 4004 compliance costs are for ground water protection.
Specifically, this category covers landfill, burial, and reclamation costs
as well as monitoring wells for facilities in states which do not have
ground water related criteria.
Chlorine/Caustic Soda (Diaphragm Cell)
The major costs involve installation of monitoring wells for ground water
protection. Most wells are required by recently enacted State regulations.
The remainder are required by RCRA ground water criteria for plants in 13
States which do not have ground water regulations comparable to RCRA. In
addition to ground water protection, some additional site improvements will
be required to conform to RCRA closure requirements and surface water protection.
Compliance Costs—
State and other Federal-induced costs;
Capital: $900,000 for 90 monitoring wells at 30 plants.
Operating: $210,000 annual cost, including $4,000 for monitoring and
$3,000 for well depreciation at each of the 30 plants.
RCRA 4004-induced.costs;
Capital: $420,000. Most of this cost ($360,000) is for disposal of
brine mud and rubble inventories and for land reclamation at
a few sites. The remainder ($60,000) is for six monitoring
wells at two sites in States which do not have ground water
regulations.
Operating: $14,000, including $4,000 for monitoring and $3,000 for well
depreciation for each of two plants mentioned above.
Chlorine/Caustic Soda (Mercury Cell)
The major improvement required is installation of monitoring wells for
ground water protection to meet State regulations. Non-hazardous wastes are
generated at only six plants. All wastes from the remaining plants are
hazardous.
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Compliance Costs—
State and other Federal-induced costs;
Capital: $180,000 is for 18 monitoring wells at six plants.
Operating: $42,000 annual cost including $4,000 for monitoring
and $3,000 for well depreciation at each of the six plants.
RCRA 4004-induced costs;
Capital: $80,000 for closure expenses at six plants reclamation of
lagoon disposal areas.
Operating: No costs.
Potassium Chloride
Only monitoring wells for ground water protection will be required.
At seven of the eight sites, these are required by recent State regulations.
The costs at the remaining site are directly attributable to the RCRA ground
water criteria.
State and other Federal-induced costs;
Capital: $210,000 is for 21 monitoring wells at seven plants.
Operating: $49,000 including $4,000 for monitoring and $3,000 for well
depreciation at each of the seven plants.
RCRA 4004-induced costs:
Capital: $30,000 is for three monitoring wells at one site.
Operating: $7,000, including $4,000 for monitoring and $3,000 for well
depreciation at the one site mentioned above.
Potassium Sulfate
Potassium sulfate is produced at one facility which also produces
potassium chloride. Wastes are combined prior to disposal. Compliance costs
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for potassium chloride, given above, therefore include those for potassium
sulfate.
Alumina
Significant upgrading of waste handling and disposal procedures will be
required to meet both RCRA criteria and State and other Federal regulations.
Recently enacted State ground water protection regulations will necessitate
monitoring well installation and use at several facilities. In addition,
major site changes may be required at two locations to replace unlined waste
disposal ponds to conform with RCRA-specified criteria for ground and surface
water protection. Ihis may require construction of new lined lagoon
facilities and draining and restoration of the current lagoon systems.
No plants reclaim waste disposal ponds when filled. Reclamation of these areas
will be required to fulfill the site closure requirements specified by RCRA.
No disposal site areas currently have leachate control systems intact under
the disposal pond areas; however, eight of the 10 plants do have pond linings
of sufficient thickness to preclude any leachate problems.
Compliance Costs—
State and other Federal-induced costs;
Capital: $270,000 for 27 monitoring wells at nine plants. (One plant
already has monitoring wells).
Operating: $63,000 including $4,000 for monitoring and $3,000 for well
depreciation at each of the nine plants.
RCRA 4004-induced costs:
Capital: $41,300,000 for restoration of existing unlined ponds,
construction of new ponds, and closure expenses. Specifically,
this cost represents what is needed to reclaim 7,000 acres of
lagoon area in present use at 10 sites and for construction
of new lined lagoon facilities at two locations. Eight locations
presently use clay-lined lagoons; the other two do not.
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Operating: $6,000,000 for site restoration at all 10 plant locations
and for lining expenses at two plants.
Phosphorus
This is another product category where significant upgrading of current
disposal practices nay be required to meet RCRA and other State and Federal
regulations. At roost plants, monitoring wells will be required at disposal
sites to meet recent State ground water regulations.
Compliance Costs—
State and other Federal-induced costs;
Capital: $270,000 for 27 monitoring wells at nine plants.
Operating: $63,000, including $4,000 for monitoring and $3,000 for well
depreciation for each of the nine plants.
BORA 4004-induced costs;
Capital: No cost.
Operating: No cost.
Natural Soda Ash
Installation of monitoring wells to meet recent State ground water
regulations at two locations is the only disposal site upgrading required
for this industry category. All plants are located in Wyoming, viiich has had
land reclamation laws in effect for many years.
Compliance Costs
State and other Federal-induced costs:
Capital: $60,000 for six monitoring wells at two plants.
(Iwo other plants already have monitoring wells).
Operating: $12,000, including $4,000 for monitoring and $3,000 for well
depreciation at each of two sites.
RCRA 4004-induced costs;
Capital: No cost.
Operating: No cost.
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Lime
Many sites will be required to install monitoring wells to comply with
State ground water regulations. In addition, a few plants in States without
ground water regulations will also require these wells to meet RCRA. ground
water criteria.
Compliance Costs—
State and other Federal-induced costs:
Capital: $4,200,000 for 420 monitoring wells at 140 plants. (About
30 plants either reprocess lime dust or sell it as off-grade
material.)
Operating: $980,000 including $4,000 for monitoring and $3,000 for well
depreciation at each of the 140 plants noted above.
RCRA 4004-induced costs;
Capital: $300,000 for 30 monitoring wells at 10 sites in the States
which do not have ground water regulations.
Operating: $70,000, including $4,000 for nDnitoring and $3,000 for well
depreciation at each of the 10 sites mentioned above.
Hydrofluoric Acid
The costs for this category will be presented differently because of
special considerations involved for some sites. The estimated compliance
costs can be disaggregated as follows:
• Three plants which sell all of their waste gypsum will have no capital
or operating costs.
• The remaining ten plants will each require three monitoring wells
to meet recent state ground water regulations. These requirements
will cost the industry $300,000 in capital expenses and $70,000 in
annual operating costs for monitoring and 10 percent well depreciation
expenses. Four of these plants will also incur the following added
expenses:
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—Two facilities will incur a combined annual expense of $48,900 for
reclamation of lagoon storage areas to comply with PCRA site
closure requirements.
—One facility will incur similar closure costs distributed as follows:
$60,000 tq cover 40 acres of waste gypsum piles already located
on the premises and,
Up to $30,000 annual land reclamation expense to cover land-
stored gypsum piles to be created during future years of
operation
—One facility which land stores its wastes will also incur site
closure expense. About $135,000 will be needed for covering and
seeding of stored waste piles from earlier years of operation and
$30,000 annual land reclamation expenses will be incurred to cover
land-stored gypsum piles in future years of operation.
This last plant is unusual in that the gypsum is recovered from the
process wastewater as anhydrite instead of dihydrate material. This novel
recovery system was installed by the plant as part of an effort to develop
a marketable gypsum co-product. Runoff waters from the recent waste piles at
the site are weakly acidic, unlike other sites. However, the waste piles
are located on top of a clay base, and all runoff from the piles goes
to the plant wastewater treatment system before release. If the system
has to be modified to eliminate runoff water acidity, additional capital costs
of $40,000 to $6 million will be incurred. The former figure represents the
cost of additional lime feeding equipment alone and the latter the cost of
reworking the entire plant lagoon system. Increased annual operating expenses
for the latter situation would involve $360,000 for lime, plus as much as
$1.2 million for increased maintenance, pumping costs, and interest charges.
As all runoff and drainage water from the waste piles is already treated and
as the entire waste handling system is already clay-lined, these additional
expenses would buy little environmental improvement and it is doubtful that
they will be required.
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In summary, aside from costs to meet state ground water monitoring
requirements, the only added expenses likely to be required by this industry
segment are:
$48,900 annualized expenses for lagoon reclamation at two locations, and
$195,000 capital costs for inventory coverage and $60,000 annual expense
for waste covering at another two locations.
Borax
No costs. All wastes from this category are considered hazardous.
Solvay Process Soda Ash
No costs. The sole facility in this category already meets all of the
RCRA and other State and Federal regulations for its non-hazardous wastes.
Titanium Dioxide (Sulfate Process)
No costs. All wastes from this category are considered hazardous.
Sodium Dichromate
No costs. All wastes from this category are considered hazardous.
Iron Oxide
Monitoring wells will have to be installed at most disposal sites. At
all but one site,, wells are required by recent State regulations. The remaining
site will also require the monitoring wells to comply with RCRA ground water
regulations.
Compliance Costs—
State and other Federal-induced costs;
Capital: $270,000 for 27 monitoring wells at nine plants.
Operating: $63,000, including $4,000 for monitoring and $3,000 for well
depreciation at each of the nine plants.
RCRA 4004-induced costs;
Capital: $30,000 for three monitoring wells at one site where title State
does not have ground water regulations.
Operating: $7,000 including $4,000 for monitoring and $3,000 for well
depreciation at the one site mentioned above.
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Lithiun Carbonate
There are two facilities in this production category. One will require
nonitoring wells to meet recent State ground water regulations. Both plant
disposal areas will require land reclamation to conform with PCRA. closure
criteria.
Compliance Costs—
State and other Federal-induced costs;
Capital: $30,000 for three monitoring wells at one plant.
Operating: $7,000 including $4,000 for monitoring and $3,000 for well
depreciation at one plant.
PCRA 4004-induced costs;
Capital: $72,000, for land reclamation of existing stored waste areas at
two plants.
Operating: $8,000, annualized cost for land reclamation of future waste
disposal sites.
Titanium Dioxide (Chloride Process)
No costs. All wastes from this category are considered hazardous.
Aluninun Sulfate
Monitoring wells will have to be installed at most active disposal sites.
Most of these are required to meet recent State ground water regulations.
A few will be required to meet RCRA criteria in States with no ground water
regulations.
Compliance Costs—
State and other Federal-induced costs;
Capital: $1,920,000 for 192 monitoring wells at 64 plants.
Operating: $450,000, including $4,000 for monitoring and $3,000 for well
depreciation at 64 plants.
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RCRA 4004-induced posts;
Capital: $90,000 for nine monitoring wells at three plants in a State
with no ground water regulations.
Operating: $21,000, including $4,000 for monitoring and $3,000 for well
depreciation at the three plant sites noted above.
Zinc Oxide
No costs. All wastes from this category are considered hazardous.
Antimony Oxide
.Monitoring wells will have to be installed at four disposal sites to
meet recent State ground water regulations.
Compliance Costs—
State and other Federal-induced costs;
Capital: $120,000 for 12 monitoring wells at four plant sites.
Operating: $28,000 including $4,000 for monitoring and $3,000 for well
depreciation at each of the four plant sites.
RCPA 4004-induced costs:
No costs.
Barium Sulfate
The one facility which will generate solid wastes in this production
category plans to use commercial contractors to handle all waste disposal.
It is assumed that the waste disposal site chosen already meets all regulations
and that no additional costs will result. The plant presently discharges its
wastes in waterbome form.
Manganese Sulfate
The one facility generating land-destined wastes in this category will
require monitoring wells to comply with recent State ground water regulations.
Lagoon restoration will also be required to meet RCRA closure criteria.
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Conplianoe Costs—
State and other Federal-induced oosts;
Capital: .$30,000 for three monitoring wells at one plant.
Operating $7,000. This cost includes $4,000 for monitoring and $3,000
for wall depreciation at one plant.
PCRA 4004-induced costs;
Capital: $60,000 for pond area reclamation at one plant.
Operating: $5,000. Annualized cost for reclamation at one site.
Vanadium Pentoxide
The one facility producing this material from Idaho ferro-phosphorus
will require monitoring wells to meet recent State ground water regulations.
Reclamation of the currently used disposal lagoons will also be needed to
meet RCRA. closure requirements.
Compliance Costs—
State and other Federal-induced costs;
Capital: $30,000 for three monitoring wells at one plant.
Operating: $7,000 including $4,000 for monitoring and $3,000 for well
depreciation at one plant site.
RCRA 4004-induced costs;
Capital: No Costs.
Operating: $3,000 for annual site restoration.
Calcium Phosphate
Most disposal sites will require monitoring wells to meet recent State
ground water regulations. One disposal location is located in a State without
such requirements and will need wells to meet RCRA ground water criteria.
Compliance Costs—
State and other Federal-induced costs;
Capital: $360,000 for 36 monitoring wells at 12 plants.
Operating: $84,000 including $4,000 for monitoring and $3,000 for well
depreciation at 12 plants.
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RCRA. 4004- induced costs;
Capital $30,000 for three monitoring wells at one plant.
Operating: $7,000 including $4,000 for monitoring and $3,000 for well
depreciation at one plant.
Sodium Hypophosphite
There are two disposal sites used for the wastes from this product
category. Both sites are already in compliance with all RCRA criteria,
including closure requirements.
Compliance Costs —
State and other Federal-induced costs:
Capital: $10,000. The solid wastes generated at the two plants that
produce sodium hypophosphite are received and buried off site
with other non-hazardous wastes generated from other processes.
It is assumed that about 17 percent of the well and monitoring
costs will be borne by this category. (The $10,000 cost is
approximately 17 percent of the total $60,000 cost for six
monitoring wells at the two plants inwlved. )
Operating: $2,500. This represents approximately 17 percent of the total
$15,000 monitoring and well depreciation expenses at the two
plants.
4004-induoed costs;
No costs.
Barium Carbonate
No costs. All wastes from this category are considered hazardous.
Strontium Carbonate
No costs. The wastes from this production category are in all cases raised
with those from barium carbonate production prior to disposal. As a result,
the mixed wastes can be considered hazardous.
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Sodium
Four of the five landfill locations used for burial of these wastes
will require monitoring wells to meet recent State ground water regulations.
All sites are already in compliance with the other PCPA. related regulations.
Compliance Costs—
State and other Federal-induced costs;
Capital: $120,000 for 12 monitoring wells at four plants. (The waste
at the fifth plant is combined with the waste from a diaphragm
cell chlor-alkali plant, and its cost is attributed to the
chlorine plant.)
Operating: $28,000 including $4,000 for monitoring and $3,000 for well
depreciation at each of the four plants.
PCRA 4004-induced costs:
No costs.
Sodium Chlorate
No additional disposal site upgrading is necessary for the non-hazardous
wastes from this production category. All non-hazardous wastes are currently
landfilled at locations which were examined under other product categories
(mostly chlorine/caustic soda diaphragm cell).
Chrome Yellow
No costs. All wastes from this category are considered hazardous.
Potassium Permanganate
No costs. The one landfill used for wastes from this production category
is already in compliance with all RCRA and other Federal and State regulations.
Calcium Carbide
There is only one site in this production category which may have non-
hazardous wastes requiring disposal. This plant has about 450,000 metric tons
of by-product lime from earlier years of acetylene manufacture land-stored
on its premises. Contacts with the plant have established that some or all
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of this material may be salable over an unspecified period of time. For this
material, there are two options:
Option 1: $3,300,000. This option assumes that the lime inventory
cannot be sold and that the producer will use a private
contractor for disposing wastes at a landfill several miles
from the plant. It can be viewed as a one-time capital
expense since the producer is able to sell all wastes from
current production. The cost ($4.45/metric ton of waste)
includes loading, transportation, waste burial, contingencies
and a 12 percent cost of capital.
Option 2: $3,000,000 This option assumes that the waste inventory can
be sold over a period of time. The $3.0 million is estimated
as the cost for construction of an enclosure, including
loading facilities and 12 percent cost of capital, to prevent
rainwater contact with the waste lime piles. It is presumed
that loading facilities will be required if the lime is
marketed. (The $3.0 million cost was derived from that
received from a Kansas salt facility for construction of a
similar structure for storage of about the same quantity of
material to prevent runoff problems. Figures were provided
in 1976 dollars and updated to 1978 dollars.) No credit is
assumed for sale of the lime.
This cost can be viewed as a capital expenditure. Operating
costs cannot be estimated because it is uncertain how long the
inventory will have to be stored. Under either option, the
costs are attributable to State surface water regulations;
there are no RCRA 4004-induced costs.
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VII. WASTE HANDLING ALTERNATIVES AND RECOVER* OPTIONS
One of the objectives of this study was to identify waste handling
alternatives and resource recovery options that are being used or could
be used by the inorganic chemicals industry. This includes process changes
which would reduce the volume of wastes generated and/or alter its form so
as to reduce adverse impacts on the environment, and enhance resource
conservation and resource recovery. During our industry contacts, we
solicited information about industry's plans or existing practices for waste
handling alternatives and resource recovery options. The following were
identified:
Potash
Small amounts of the wastes from potash have been sold locally for road
salt and cattle salt applications. However, significant sales of the salt
wastes are not practical because large markets are too far away from the
plants and transportation costs would be prohibitive.
Alumina
Kaiser Aluminum has had an in-house program to develop methods for
recovery of iron and residual alumina from the red mud wastes. To date,
none of the methods has shown promise.
Kaiser also noted that more widespread use of high quality Surinam
bauxite would reduce the volume of wastes generated. Use of the alternative
raw material would be costly, though, and involve several million dollars
in plant modifications.
Phosphorus
The phosphorus plants in the east have been able to sell all their slag
wastes for use as a crushed stone substitute in roadbed construction.
Because of limited markets, the western plants can sell only about two-
thirds of the slag they generate. The rest is stockpiled. Transportation
costs limit more widespread sale of these materials.
Over the last several years, recovery of elemental phosphorus from
phossy waste has been practiced at two of the plants. Significant amounts
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of phosphorus nay be available for recovery from phossy water ponds at the
seven other plants. Industry plans call for increased use of this technology
in the near future. At least three other facilities are installing recovery
systems.
Lima
About 25 percent of the lime dusts are recycled in the production process
or sold as an off-grade product. Product applications include the following:
• Raw materials usage (in cement manufacturing).
• Agricultural lime.
• Waste acid neutralization.
• Flue gas desulfurization.
The sale of lime dusts for such uses is limited by local demand and
requires further study.
Hydrofluoric Acid
Approximately 25 percent of the gypsum wastes are sold for use as a soil
conditioner or construction material. The market for these applications is
limited by local demand.
Titanium Dioxide
Sulfate Process—
Two plants sell a fraction of their waste ferrous sulfate; one sells
25 percent and the other, 10 percent. The demand for ferrous sulfate is
limited and whatever is sold competes with that generated as a steel industry
waste.
A possible market exists for the waste gypsum; however, it would have
to compete with the gypsum generated as a waste in many other chemical
processes. •
Another possibility is the sale of iron oxides for use in colored cement;
the market for this application is very limited.
Chloride Process—
Some of the ferric chloride wastes are sold. One plant already has
40 percent of this market, though, and expanded sales are not expected. The
very limited market for iron oxide as a cement color also applies here.
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Chlor-AUcali
Diaphragm Cell—
The use of barium for sulfate removal as a separate step in brine
purification could allow for barium sulfate recovery and reuse. One
plant in Texas is already doing this and uses the barium sulfate as a raw
material for its on-site barium carbonate plant.
A possible use of the alkaline brine mud waste would be as a
neutralization agent for acid wastes at nearby plants.
Use of metal anodes at the six plants still using lead graphite
electrodes would eliminate the remaining lead wastes from the industry.
This change is expected to occur for energy related reasons.
Mercury Cell—
One waste handling alternative is a process change involving the
segregation of brine purification from the rest of the process; this would
reduce the quantity of mercury bearing wastes and the costs of disposal.
However, an energy penalty of 5 x 105 kcal (2 x 106 BTU) or $3.30 per kkg
($3.00 per ton) of chlorine product would be incurred because of this change.
The energy is required to evaporate the brine for recovery of salt for pro-
cess use.
Another waste handling alternative is a major process change requiring
conversion to diaphragm cells. One plant in Louisiana, with a published
capacity of 500,000 kkg (548,000 tons) per year, is currently undergoing
this type of conversion.
Sodium
The option to recover barium sulfate in a separate brine purification
step is also available for this industry as it was for diaphragm cell
chlor-alkali plants. This material could then be sold as a feed for barium
carbonate plants. Another possible option is to use the alkaline brine mud
wastes as a neutralization agent for other acidic wastes.
Calcium Carbide
At four of the five calcium carbide plants, the solid wastes are sold
as a low-grade lime. There is no market for the wastes from the fifth plant
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at the present tine because of the special problems associated with the type
of furnace in use. However, the installation of a new furnace would allow
it to market its wastes.
Chlorates
The chlorate wastes can be eliminated by using platinum electrodes in
the production process. Seven of the twelve plants are already using
platinum electrodes.
Chrone Yellow
IXbre efficient recovery of the product in the manufacturing process
would reduce the amount of wastes generated. One plant is currently
accomplishing this by using an improved filtration system.
NEW TRENDS IN THE INDUSTRY
Although most process technology used in the inorganic chemicals
industry is undergoing little change, an exception has been noted with
respect to the electrolytic industries. In the chlor-alkali area, coated
metal anodes have mostly replaced the old lead-graphite electrodes,
eliminating all of the lead and most of the chlorinated hydrocarbon wastes.
These metal anodes were utilized mainly because of their improved electro-
chemical characteristics which result in significant reductions in power
consumption by the industry. At present, two types of coated metal anodes
are known to be in use. The dimensionally stable anode (DSA) employs
a ruthenium dioxide coated titanium electrode. The other anode, in use
by one company, uses cobalt oxide coated titanium.
In the chlorates manufacturing industry, platinum coated electrodes
have largely replaced lead-graphite electrodes. Again, this results in
substantial power savings and waste reduction.
The electrolytic industries are undergoing rapid change as newer cell
designs and electrode materials are coming into widespread use. New
processes for the chlor-alkali industry, such as the membrane cell, are
currently undergoing development and may be commercialized within the next
decade. If this occurs, further declines in hazardous waste generation
will be experienced and the chlor-alkali area may cease to be an area of
major environmental concern.
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15. "Phosphate": Minerals Commodity Profiles (MCP-2). Bureau of Mines, U.S.
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30. LaGess, T.F. "Disposal of Brine Treating Solid Wastes by Recycling
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ya 1856
SW-180C
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*U8. GOVERNMENT PRINTING OFFICE: 1979 620-007/6315 1-3
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