WATER POLLUTION CONTROL RESEARCH SERIES 012020 EJI 07/71
Inorganic Chemicals
Industry Profile
ENVIRONMENTAL PROTECTION AGENCY • RESEARCH AND MONITORING
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes
the results and progress in the control and abatement
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Protection Agency, Room 801, Washington, B.C. 20^0.
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07/77
EPA Region Vlli LIBRARY
Denver, Colorado
INORGANIC CHEMICALS INDUSTRY
PROFILE (UPDATED)
Datagraphics Incorporated
Pittsburgh, Pennsylvania
of an original study by
Cyrus Wm. Rice & Company
Pittsburgh, Pennsylvania
for
ENVIRONMENTAL PROTECTION AGENCY
Program #12020 EJI
July, 1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.75
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EPA Review Notice
This report has been reviewed by the
Office of Research and Monitoring of
the Environmental Protection Agency
and approved for publication. Appro-
val does not signify that the contents
necessarily reflect the views and
policies of the Environmental Protec-
tion Agency, nor does mention of trade
names or commercial products constitute
endorsement or recommendation for use.
ii
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ABSTRACT
This report presents a description of the inorganic chemical
industry and the costs that the industry would incur in attaining
various levels of pollution abatement over the five-year period
through 1974. For the study purposes, the inorganic chemical
industry has been defined as including establishments producing
alkalies and chlorine, industrial gases, inorganic pigments,
paints and allied products, fertilizers (excluding ammonia and
urea), inorganic insecticides and herbicides, explosives, and
other major industrial inorganic chemicals. The report presents
in considerable detail the description of the various production
processes, the waste treatment methods practiced, and the possible
impact that changes in processes might have on the volume and
character of the wastes produced.
Projections have been based upon the chemical industry data
in the 1963 and 1967 Census of Manufacturers, the 1967 Manufac-
turing Chemists Association survey, and the 1968 FWPCA study of
the organic chemicals industry. Costs of treatment are estimated
by year for the levels of treatment corresponding to 27% and 100%
removal of contaminants. Data from 59 inorganic chemical plants
were obtained as primary input to the study.
Key Words: Chemical wastes, treatment costs, economics, indus-
trial effluents, survey, inorganic chemicals.
ill
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TABLE OF CONTENTS
Page
**
I. Summary 1
II. Introduction 6
III. The Inorganic Chemical Industry 7
IV. Projected Industry Growth 14
V. Wastewater Characteristics 18
VI. Wastewater Treatment Methods 21
VII. Industrial Waste Treatment
Practices Data Form 30
VIII. Plant Survey Data 31
IX. Costs of Unit Wastewater
Treatment Methods 42
X. Costs Versus Effluent Quality
Relationships. 50
XI. Projected Industry Costs 52
XII. Qualitative Manpower Requirements 70
XIII. Quantitative Manpower Requirements .... 71
APPENDIX
A. Inorganic Chemical Industry Survey Data. . 72
B. Inorganic Chemical Industry
Product Profiles 74
C. Costs of Unit Wastewater
Treatment Practices 141
D. Bibliography 203
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LIST OF TABLES
Page
CHAPTER III - THE INORGANIC CHEMICAL INDUSTRY
Table I - Financial Ratios for the
Chemicals and Allied Products Industry. ... 9
Table II - Value of Estimated Inorganic
Chemical Shipments 10
CHAPTER IV - PROJECTED INDUSTRY GROWTH
Table I - Production of Inorganic Chemicals . . 15
Table II - Industry Segmental Growth Rates
Through 1979 16
Table III - Industry Growth Rates
Geographically Through 1975 16
CHAPTER V - WASTEWATER CHARACTERISTICS
Table I - Composition of Typical Clean
Water Effluent 19
CHAPTER VI - WASTEWATER TREATMENT METHODS
Table I - Water Discharge by SIC 25
Table II - Employment Distribution 26
Table III - Distribution of Water Use ..... 27
CHAPTER IX - COSTS OF UNIT WASTEWATER
TREATMENT METHODS
Table I - Treatment Level I, Neutralization
Costs Including Equalization and
Sludge Dewatering ............... 47
Table II - Treatment Level II, Demineralization
Costs Including Prefiltration and Brine
Disposal. ...... 48
vi
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LIST OF TABLES (cont.)
CHAPTER XI - PROJECTED INDUSTRY COSTS
Table I - Numbers of Inorganic Chemical Plants
by Water Intake Volume - 1963 52
Table II - Water Discharges from Large In-
organic Chemical Plants - 1968 52
Table III - Large Inorganic Chemical Plant Dis-
charges Other Than to Municipal Sewers -
1968 53
Table IV - Large Inorganic Chemical Plant In-
takes and Usage, by Purpose, 1968 54
Table V - The Inorganic Chemical Industry ... 55
Table VI - Numbers of Plants in the Inorganic
Chemical Industry 56
Table VII - Projected Production of Inorganic
Chemicals, 1968-1974 57
Table VIII - The Inorganic Chemical Industry,
1963-74 58
Table IX - Water Use Data, 1958-67 59
Table X - The Inorganic Chemical Industry,
1963-74 61
Table XI - 1967 MCA Survey Data, The
Chemical Industry ... 62
Table XII - Ranges of Chemical Plant
Production Capacities 63
Table XIII - Numbers of Plants in the
Chemical Industry, 1963 63
Table XIV - Chemical Industry Survey Data,
1967 64
Table XV - Chemical Plant Sizes and Dis-
charges, 1967 65
vii
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LIST OF TABLES (cent.)
Page
CHAPTER XI (cont.)
Table XVI - Chemical Industry Discharges,
1967 66
Table XVII - Chemical Industry Costs and
Manpower, 1969 66
Table XVIII - Cumulative Inorganic Chemical
Industry Capital Costs, 1969-1974 67
Table XIX - Cumulative Inorganic Chemical
Industry Capital Costs, 1969-1974 67
Table XX - Projected Annual Inorganic Chemical
Industry Operating Costs 68
Table XXI - Projected Annual Inorganic Chemical
Industry Operating Costs 68
APPENDIX A - INORGANIC CHEMICAL INDUSTRY
SURVEY DATA
Table I 73
APPENDIX C - COSTS OF UNIT WASTEWATER TREATMENT
PRACTICES
Table I 177
viii
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LIST OF FIGURES
CHAPTER III - THE INORGANIC CHEMICAL INDUSTRY
Figure 1 - Location of Major Inorganic
Chemical Plants, SIC Nos. 2812,
2816, 2819 13
CHAPTER VI - WASTEWATER TREATMENT METHODS
Figure 1 - Wastewater Treatment Sequence. ... 22
CHAPTER VIII - PLANT SURVEY DATA
Figure 1 - Total 1969 Production - Millions
of Tons/Year 33
Figure 2 - Production - Thousands of Tons/Year. 34
Figure 3 - Flow - MGD ............. 35
Figure 4 - Major Source of Water 36
Figure 5 - Basis of Treatment Decision 37
Figure 6 - Year of Construction 38
Figure 7 - States 39
Figure 8 - Industry Water Use Regions 40
Figure 9 - Operating Costs of Treatment
Facilities Versus Capital Costs 41
CHAPTER IX - COSTS OF UNIT WASTEWATER TREAT-
MENT METHODS
Figure 1 - Applicable Ranges of Demineralization
Units 43
Figure 2 - Schematic Layout of Treatment Plant
for Wastes from the Inorganic Chemical
Industry Showing Various Possible Com-
binations of Units 44
Figure 3 - Flow Sheet for Neutralization Plant. 45
ix
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LIST OF FIGURES (cont.)
APPENDIX B - INORGANIC CHEMICAL INDUSTRY
PRODUCT PROFILES
Figure 1 - Flowchart for Diaphragm Caustic
Soda and Chlorine Cell 78
Figure 2 - Flowchart of a Standard Medium-
Pressure Air-Separation Plant 83
Figure 3 - Flowchart for Titanium Dioxide ... 88
Figure 4 - Flowchart for Mixing of Paint. ... 89
Figure 5 - Ammonium Nitrate Plant Locations . . 94
Figure 6 - Flowchart for 60% Nitric Acid
from Ammonia 103
Figure 7 - Phosphoric Acid Plant Locations. . . 107
Figure 8 - Typical Flowchart for Sulfur-
Burning Contact Plant . 119
Figure 9 - Ammonium Phosphate Plant Locations . 126
Figure 10 - Estimated Number of Bulk Blend
Fertilizer Plants 130
Figure 11 - Estimated Number of Liquid Mixed
Fertilizer Plants 132
Figure 12 - Flowchart for Smokeless Powder. . . 139
APPENDIX C - COSTS OF UNIT WASTEWATER
TREATMENT PRACTICES
Figure 1 - Applicable Ranges of Demineral-
ization Units . ..... 143
Figure 2 - Schematic Layout of Treatment
Plant for Wastes from the Inorganic Chemical
Industry Showing Various Possible Combin-
ations of Units . . 144
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LIST OF FIGURES (cont.)
Page
APPENDIX C (cont.)
Figure 3 - Flow Sheet for Neutralization Plant. 146
Figure 4 - Cap. Cost of Neutralization Facili-
ties Excluding Sludge Treatment 147
Figure 5 - Cap. Cost Versus Acidity for 1 MGD
Plant 148
Figure 6 - Capital Cost of Equalization Basins. 149
Figure 7 - Thickener Parameters for Sludge
from Neutralization of Acidic Wastes 152
Figure 8 - Variation of KQ with Initial Solids
Concentration 153
Figure 9 - Capital Cost of Thickeners 156
Figure 10 - Operating Costs for Lime Neutral-
ization Including Sludge Dewatering by Vacuum
Filtration 158
Figure 11 - Cost of Filtration Through Sand
or Graded Media 160
Figure 12 - Annual Operating Cost of Deep
Well Injection Systems for Waste Disposal . . 162
Figure 13 - Capital Cost of Deep Well Injection
Systems for Waste Disposal 163
Figure 14 - Area of Membranes as a Function of
Production Rate 165
Figure 15 - Membrane Area Required Versus Feed
and Product Flows 166
Figure 16 - Power Consumption as a Function of
Production Rate 167
Figure 17 - Capital Cost as a Function of
Production Rate 168
Figure 18 - Capital Cost of Reverse Osmosis
Plant 170
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LIST OP FIGURES (cont.)
Page
APPENDIX C (cont.)
Figure 19 - Operating Cost for Reverse Osmosis
Plant 171
Figure 20 - Determination of Total Number of
Units Required for Treatment 173
Figure 21 - Relationship of Plate Area Required
for a Desired TDS Removal 174
Figure 22 - Relationship of Rectifier Size to
Specific TDS Removal Desired 175
Figure 23 - Capital Cost of Membranes, Spacers,
End Plates, and Electrodes 179
Figure 24 - Capital Cost Curves for DC Rectifier
for Electrodialysis 180
Figure 25 - Relationship of DC Energy Required
for a Desired TDS Removal 181
Figure 26 - Operating Cost of DC Energy Re-
quired for Specific TDS Removal 183
Figure 27 - Capital and Operating Costs for
Electrodialysis Based on Feed Flow to Plant
at 3000 ppm TDS 184
Figure 28 - Capital Cost of Ion Exchange Plant. 186
Figure 29 - Chemical Cost per Pound TDS
Removed by Ion Exchange 187
Figure 30 - Capital and Operating Cost for
Multiple Effect Evaporation 190
Figure 31 - Vapor Pressure of Water Versus
Temperature 192
Figure 32 - Evaporation Versus Vapor Pressure
Differential 193
xii
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LIST OF FIGURES (cont.)
Page
APPENDIX C (cont.)
Figure 33 - Area Versus Required Evaporation. . 194
Figure 34 - Capital Cost Relationship for
Lagoons 195
Figure 35 - Relative Rating Factors Versus Wet
Bulb Temperatures 200
Figure 36 - Cooling Towers 202
xiii
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CHAPTER I
SUMMARY
This report presents a description of the inorganic
chemical industry, and the costs that the industry would
incur in attaining various levels of pollution abatement
over a five year period through 1974. The cost estimates
have been based upon published data, general data derived
from information in the files of the Contractors on in-
dustrial waste treatment methods and costs, and specific
data from 59 inorganic chemical plants, some of which
were supplied by the Manufacturing Chemists Association.
(The data supplied by the M.C.A. were presented in such
a manner as to render impossible identification of pro-
prietary information relating to a specific plant's
construction, operation, maintenance, or production.)
The inorganic chemical industry has been defined for pur-
poses of this study as including establishments producing
alkalies and chlorine, industrial gases, inorganic pig-
ments, paints and allied products, fertilizers (excluding
ammonia and urea), inorganic insecticides and herbicides,
explosives, and other major industrial inorganic chemi-
cals. The complex relationship which exists between
various products and industries, however, make it
extremely difficult to arbitrarily associate certain
products with one category. The overall output of the
industry, since its products are used for a wide variety
of purposes well removed from the final consumer, depends
upon the level of total economic activity rather than
the economic activity in any one segment of the economy.
Since new mineral sources are discovered infrequently and
usually involve large development expenditures, wide
fluctuations in the gap between demand and readily avail-
able supply are quite common.
Total production in the inorganic chemical industry is
estimated to be 328.7 billion pounds in 1969 and projected
at 455.5 billion pounds in 1974. While certain segments
of the industry are growing as rapidly as 18% per year,
the historical situation is for a growth rate 1.5 to 2.0
times that of the gross national product. The overall
price index of inorganic chemicals, however, has fallen
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2.5 percent in the recent past. Thus, expenditures for
pollution control may be of greater relative significance
than in other industries where prevailing rising prices
can more readily absorb increased costs.
The regional growth rates reflect a continuing trend to
move production facilities closer to raw materials and
markets. The industry, as a whole, is thus tending to
concentrate in the Midwest and Southwest.
Inorganic chemical plants vary greatly in size, level of
technology, product mix, and age. The report presents in
considerable detail the description of the various
production processes, the waste treatment methods
practiced, and the possible impact that changes in
processes might have on the volume and cnaracter of the
wastes produced. A typical or average plant exists,
however, only in the statistical sense. The total costs
given in this report are for the construction and opera-
tion of waste treatment facilities for the industry as a
whole and cannot be used to determine costs for individual
plants. The costs given are for the waste treatment
facilities only. The costs entailed in process changes,
restriction of plant operations, sewer segregation,
particularly in older plants, are not included. Treat-
ment system construction and operating costs for a
particular plant can only be estimated by detailed
engineering studies.
Projections based upon the chemical industry data in the
1963 Census of Manufactures, the 1967 Manufacturing
Chemists Association survey, the 1968 FWPCA study of
the organic chemicals industry, and the costs of treat-
ment for the two levels of 27% and 100% removal of
contaminants show the following projected operating
costs and cumulative capital investment for wastewater
treatment.
PROJECTED CUMULATIVE INORGANIC CHEMICAL INDUSTRY CAPITAL
COSTS FOR WASTE TREATMENT, 1969-74
Costs in Millions of Current Dollars
I/
Removal 1969 1970 1971 1972 1973 1974
27 314.3 341.7 377.9 420.1 467.7 519.4
100 1898.8 2062.2 2281.9 2537.1 2823.5 3118.5
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PROJECTED INORGANIC CHEMICAL INDUSTRY ANNUAL OPERATING
COSTS FOR WASTE TREATMENT, 1969-74
Removal
27
100
Costs in Millions of Current Dollars =•'
I/
1969
86.1
165.4
1970
93.6
179.6
1971
103.5
198.7
1972
115.1
221.0
1973
128.1
245.9
1974
142.3
273.2
I/ Based on an average 3.6% annual increase in the price
level
Contaminated wastewater from the inorganic chemical indus-
try comes primarily from electrolysis and crystallization
brines, washings from filter cakes, spent acid and alka-
lies, and washings from raw materials. These wastewaters
are generally characterized by dissolved solids and sus-
pended solids. In addition to contaminated waste streams,
process cooling discharges occur, accounting for 40 to 80%
of the total discharge on the average. Treatment practi-
ces vary but involve in-plant segregation of contaminated
wastes from uncontaminated cooling waters.
Many waste treatment methods are available depending on
the degree of treatment required, however, equalization,
neutralization, sedimentation and lagooning processes
are most widely used. Biological treatment is not appli-
cable since the contaminants are primarily dissolved or
suspended inorganic materials. Plants with small dis-
charges tend to employ only equalization and neutraliza-
tion with total discharge to municipal sewer systems for
joint treatment. It is estimated that between 10 and 20%
of the process wastewater discharge from the industry is
to municipal systems (7.9% of the total discharge). No
significant percentage changes in this regard are
expected through 1974. The inorganic chemical industry
has generally found that in-plant, separate treatment has
economic advantages, particularly when significant quanti-
ties of wastewater are involved.
Data from 59 inorganic chemical plants were obtained
and formatted according to the Industrial Waste Treatment
Practices Data Form, which was developed for the study
"The Cost of Clean Water and Its Economic Impact, Volume
IV," United States Department of the Interior, January,
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1969. The data obtained are given in some detail in the
report in terms of bar graphs and various calculated
parameters relating wastewater volumes, plant production,
and costs.
Key parameters of interest regarding waste treatment costs
are the following:
Average capital cost $223/1000 gpd
Average operating cost/yr. $58.49/1000 gpd
Average wastewater flow 16.73 gpd/annual ton of pro-
duction
Average capital cost $3.74/annual ton of production
Average operating cost $0.98 per year/annual ton of
production
An examination of the survey data showed that the reported
bases of waste treatment decisions were generally least
cost, or minimum compliance with pollution control regula-
tions .
The costs of unit wastewater treatment methods were
developed and are presented in the report as a series
of mathematical models and cost function graphs. These
data were used to calculate capital costs of waste
treatment facilities versus two levels of pollutant
removal for a series of typical plants. Treatment Level
I was chosen to represent the average treatment employed
in the industry as a whole and is judged to be equivalent
to 27% removal of suspended and dissolved solids. Treat-
ment Level II represents complete removal of contaminants.
Only two levels were selected because the industrial
wastes are principally inorganic solids that respond only
to physical treatment processes. Because there are no
intervening technologies, intermediate levels of
efficiency are not distinguishable. The two levels then
may be viewed as a range bounded on the one side by the
current level of efficiency and on the other by universal
application of advanced treatment practices. An almost
infinite number of intermediate positions are possible for
the industry as a whole within the range, but only as the
treatment II technology is applied to individual units of
the population. Unlike the case of organic waste, there
is no series of technological plateaus through which the
whole population may progress.
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The following table summarizes the capital and operating
costs in 1969 dollars for the two levels of treatment
chosen:
Capital Cost Operating Cost
% Removal Contaminants $/1000 qpd C/1000 gal
27 (SS and Acidity) 300 26.0
100 (TDSJ ' 2185 51.5
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CHAPTER II
INTRODUCTION
This study was performed pursuant to Contract No. 14-12-
592 with the Federal Water Pollution Control Administra-
tion, United States Department of the Interior.
The primary objective of this study was to acquire data
and develop cost estimates on the waste treatment prac-
tices of selected industrial categories within the in-
organic chemicals industry over the 1970 to 1974 period.
A secondary objective of the study was to further test
and refine as necessary the generalized methodology for
establishing and projecting industry costs which was de-
veloped in the course of work under PWPCA Contract No.
14-12-435 "Projected Wastewater Treatment Costs in the
Organic Chemicals Industry." This report was transmitted
to the Congress in January, 1969 as The Cost of Clean
Water, Volume IV.
The information contained in this report is not intended
to reflect the cost or waste load situations for any
particular plant. A generalized framework for analyzing
waste treatment practices has been provided instead.
The data and conclusions should be useful to industry
and to government in their efforts to find and implement
the most efficient ways to reduce pollution of the
nation's water bodies.
The study utilized on subcontract the services of
Resource Engineering Associates, Inc., Stamford, Conn.,
Datagraphics, Inc, Allison Park, Pa., and Gurnham,
Bramer, and Associates, Inc., McMurray, Pa. Assistance
from the Manufacturing Chemists Association in supplying
data, comments, and suggestions is gratefully acknowledged,
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CHAPTER III
THE INORGANIC CHEMICAL INDUSTRY
The inorganic chemical industry is not easily definable
in terms of the Standard Industrial Classification (SIC)
numbers. However, for the purpose of this study, it was
necessary to define the industry as follows:
2812 - Alkalies and chlorine
2813 - Industrial gases (except for organic gases)
2816 - Inorganic pigments
2819 - Industrial inorganic chemicals, n.e.c.
2851 - Paints and allied products
2871 - Fertilizers (not including ammonia and urea)
2879 - Inorganic insecticides and herbicides
2892 - Explosives
The most important of the groups in terms of product value
may be noted as 2819, 2812, and 2871. However, it is not
sufficient to ignore such groups as 2813 which includes
the important production of nitrogen and oxygen, 2851
which includes the vital surface coatings industry, or
2816 which involves inorganic pigments such as titanium
oxide. The surface coatings industry is typical of the
relationship which exists between segments of the
inorganic industry and the organic chemical industry. The
solvents and film formers which are utilized within the
inorganic chemical industry for the production of surface
coatings are important products of the organic chemical
industry while inorganic pigments, primarily oxides and
salts of titanium, iron and other metals are products
which fall into the inorganic industry category. We have
defined the total product as being part of the inorganic
industry. However, it is obvious that the complex
relationships which exist between various products and
industries (necessary to the smooth functioning of our
technological state) make it extremely difficult, if not
impossible, to arbitrarily associate certain products
with one SIC category. Product profiles are given in
Appendix C, along with typical product process flow
sheets.
The overall output of industrial inorganic chemicals,
since they are utilized in a wide range of industries
and for a wide variety of purposes usually well removed
from the final consumer, depends upon the level of
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total economic activity rather than economic activity in
any specific segment of the economy.
Changes in consumer preferences or redistribution of in-
come and spending, such as changes in tax levels or
defense spending/ may affect product mixes, but do not
significantly affect total industry output. In general,
price competition and product substitution are not as
significant in the inorganic chemical industry as in the
organic chemical sector. However/ changes although slow
to come tend to be quite profound.
Supplies of raw materials frequently vary and, in the
case of certain materials, the industry may face serious
shortages until new raw material sources (usually ores
or brines) are developed. The widely fluctuating price
of sulfur over the past ten years is a classic case
resulting from supply fluctuations which can be matched
by mercury, potash and silver, among others. Since new
sources of minerals are found infrequently and usually
involve relatively large expenditures to develop, wide
fluctuations in the gap between demand and readily
available supply are quite common in the inorganic
chemical industry.
Industrial chemical industries are generally capital
intensive operations (with a few exceptions such as the
paint manufacturing industry), and are characterized by
high productivity ($75,000 annual output per production
worker), high wages, a low labor turnover, and a con-
tinuing demand for skilled labor. Most of the plants
operate continuous and must operate at 75 to 85 percent
of capacity to maintain adequate levels of efficiency
and profitability. Smaller plants generally operate
batch processes and, hence, tend to produce low volume,
high cost, specialized chemicals. Financial ratios for
the chemical and allied products industry are shown in
Table I.
8
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TABLE I
FINANCIAL RATIOS FOR THE CHEMICALS AND ALLIED PRODUCTS INDUSTRY
Ratio 1963 1965 1967 1968
Profits after taxes/sales (%) 7.5 7.9 6.9 6.8
Profits after taxes/net worth (%} 12.9 14.7 12.6 13.1
Capital expenditure/gross plant (%} 6.3 8.2 7.6 -
Depreciation/gross plant (%) 6.1 5.8 5.8 6.0
Depreciation/sales (%) 4.5 4.4 4.5 4.5
Sales/total assets 1.13 1.13 1.10 1.14
First half
SOURCE: U.S. Industrial Outlook, 1970, U.S. Department of Commerce
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Profits after taxes as a percentage of sales in the
inorganic chemical industry ranged from 6.5 in 1967 to
7.9 in 1964-65. By comparison, comparable profits
for all manufacturing industries were 5.0 in 1967 and
5.4 in 1968. It is important to note that while the
inorganic segment attracts less attention than the organic
sector, satisfactory profits are generally associated
with investment in this segment.
The estimated value of inorganic chemical shipments for
1969 and 1970 are shown in II.
TABLE II
VALUE OF ESTIMATED INORGANIC CHEMICAL SHIPMENTS
(1969-70)($ million)
SIC 1969 1970
2812 792 832
2813 653 715
2816 690 725
2819 4305 4500
2851 3459 3675
2871-72 1856 1904
2879 830 880
2892 517 533
SOURCE: U.S. Industrial Outlook, 1970, U.S.
Department of Commerce
Further comparisons within the inorganic chemical indus-
try show that the price index for the chemical industry
in mid-1969 was 96.7 on the basis of 1957-59 = 100. In
1968, the level was 98.8. The paint industry price
index was 114.4 in 1968 and 118.7 in 1969. The ferti-
lizer industry price level was 102.3 in 1968 and 88.8
in 1969. Several factors distinguish the inorganic
chemical industry and its relationship to waste manage-
ment. Among these are the following:
1. While certain segments of the industry are growing
rapidly, the more common situation is for a growth
rate at 1.5 to 2 times that of the gross national
product and several of the major chemicals have
growth curves which might be substituted for a
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historical projection of industrial growth in
general. This strong growth will affect the need
for pollution control facilities.
2. Capital investment is generally considerable and,
because of the nature of inorganic chemistry and
its long history of relatively unchanging practice,
rapid technological obsolescence does not occur.
Consequently, new capacity is not quickly built.
This industry moves more slowly to increase plant
capacity than the organic chemical industry
for example. Accordingly, the inorganic chemical
industry with its relatively aged plant in place
faces relatively high expenditures for added pollu-
tion control facilities.
3. The overall price index of chemicals, in contrast
with the general experience of American industry,
has fallen two to five percent in the recent past.
Thus, expenditures for pollution control may be of
greater relative significance than in other indus-
tries where prevailing rising prices can more
readily absorb increased costs.
4. Inorganic chemical plants tend to be located to
take advantage of such business factors as the
availability of raw materials, low cost power, or
markets. Considerations relating pollution con-
trol and plant location have been of minor
importance in the past.
5. Many facilities are old and completely depreciated.
Accordingly, there is little incentive to build
pollution control facilities to handle wastes from
an obsolete operation. Because of the nature of the
industry, obsolete units remain sufficiently profit-
able to continue in use.
6. Characteristically, inorganic chemicals are handled
in only two or three steps from raw material (brine
or ore, usually) to product for use by industry
elsewhere. While the inorganic chemical industry
includes a large number of products and processes
with the possibility of many different products at a
particular production site, there are a limited
number of products which comprise the bulk of the
11
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value of this industry's production; these are
discussed in detail in Appendix C to this report
along with the wastes generated by their production,
The location of this portion of the industry's
production is shown on Map A.
12
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LOCATION OF MAJOR INORGANIC CHEMICAL PLANTS
SIC NOS. 2812, 2816, 2819
t-1
UJ
• over 1000 employees
• 500-999 employees
• 250 -499 employees
This mop represents a compilation, in content and configuration, of the location of major inorganic chemical plant» classified by SIC 2812.
2816. and 2819. The source of this information was the book by Barry R. Lowson, Atlas of Industrial Wattr Ust - A Riport to flu
Woltr fttsourcts Council, Cornell Univertity Water Resource! Center. Ithace, New York, Publication No. 18, September , 1967. pp. 21,25
a 29.
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CHAPTER IV
PROJECTED INDUSTRY GROWTH
During the next decade, the inorganic chemical industry
will be characterized by new technology and many new
products. Many large volume chemicals are likely to
face changing markets as synthetic materials replace
natural products and one inorganic chemical is replaced
by another. Some of the processes that will bring changes
in inorganic chemicals utilization include hydrocracking
in gasoline refining, oxygen use in steelmaking and in
blast furnaces, holopulping to eliminate chemical markets
in papermaking, the use of hydrochloric acid in steel
pickling, the production of phosphoric acid from hydro-
chloric or nitric acid, the recovery of chlorine from
by-product hydrochloric acid, the recovery of sulfur com-
pounds from power plant flue gases, the use of oxygen in
sparging rivers, streams, and sewers as a pollution
abatement measure.
Inorganic chemicals represent a rapidly growing sector
of the chemical industry. In the 1963-69 period, the
production of inorganic chemicals as measured by the
U.S. Department of Commerce production index rose about
12% per year compounded, compared to a 7% rate for the
previous five years. Prices in the industry, however,
have risen only 5.3% per year during 1963-68 due to
both competitive pressures and to improved production
efficiencies.
Projected growth in the industry, for the purposes of
the present study, are best expressed in terms of the
volume of production based upon the tonnages of chemicals
produced. Growth estimates have been obtained from a
study by Resource Engineering Associates, Stamford,
Conn., utilizing an analysis which incorporates estimates
of overall employment, rate of growth of the economy,
and other economic parameters, as well as specific
characteristics of the industry and marketability pros-
pects for its products. These data are considered to
be the most reliable available and are tabulated in
Table I.
14
-------
TABLE I
PRODUCTION OF INORGANIC CHEMICALS
(millions of tons unless otherwise noted)
SIC
1968
1969
1970
1971
1972
1973
1974
Ul
2812
2813 y
2316
2819
2851
2871
2879
2892
24
365
1.20
70
843
41.50
0.20
250
25
420
1.25
72
899
41.80
0.20
264
26
495
1.29
74
944
42.25
0.19
274
28
595
1.37
77
1000
43.94
0.18
282
30
715
1.44
80
1060
46.14
0.18
293
32
850
1.51
84
1124
47.99
0.17
305
34
1000
1.59
88
1191
49.91
0.15
322
I/ High purity oxygen and nitrogen only (billions of cu«. ft.)
2/ Millions of dollars
3_/ Millions of gallons
-------
The above data are applicable to the inorganic chemical
industry as a whole, but rates of growth vary in the
various segments of the industry and from one geographi-
cal region to another. Expected rates of growth over
the next decade according to industry segment and
according to geographical region are given in Tables II
and III.
TABLE II
INDUSTRY SEGMENTAL GROWTH RATES THROUGH 1979
SIC No. Growth Rate (%/year)
2812 6
2813 18
2816 5
2819 4
2851 6
2871 4
2879 1
2892 4
SOURCE: REA Projections
The above growth rates are based upon volumes of produc-
tion and assume a real growth in the Gross National Product
of 3.5% per year.
TABLE III
INDUSTRY GROWTH RATES GEOGRAPHICALLY
THROUGH 1975
Region Growth Rate (%/year)
Northeast and Middle Atlantic 4
Southeast 6
Gulf Coast 5
North Central 10
Mid South 10
Mountain States 4
Pacific Coast 5
SOURCE: REA Projections
16
-------
The regional growth rates reflect the continuing trend
to move production facilities closer to raw materials
and markets. The industry will thus tend to concentrate
more'heavily in the Midwest and Southeast.
17
-------
CHAPTER V
WASTEWATER CHARACTERISTICS
Wastewater from inorganic chemical processing consists
both of contaminated and relatively clean effluent streams.
In general, the contaminated wastewaters are those taken
from processes while the cleaner wastewaters are those used
for indirect heat exchange, general washing, etc.
Contaminated Wastewaters
The major sources of contaminated wastewaters are as
follows:
1. Brines arising from electrolysis and crystallization
2. Filter cake washings
3. Waste acid and alkaline streams
4. Washing streams containing substantial amounts of
suspended particulate matter
These waters are generally characterized by dissolved
solids and suspended solids. Typical sources are
discussed in connection with the various processes
described in detail in Appendix C of this report.
Clean Wastewaters
Clean waters, which are basically uncontaminated and
can be discharged untreated, are not included in the
total flows given in wastewater totals. Cooling water
and steam condensates are the primary sources of such
water, and a typical breakdown is given in Table I.
Also included is an indication of potential pollutants
and associated sources and concentrations. Because
these clean wastewaters are relatively uncontaminated
and exert little pollutional effect (except thermal)
on the environment, care must be exercised to prevent
their contamination.
The thermal effects cannot be ignored. Effluent heat
loads can adversely affect the surface receiving
waters/ causing decreased oxygen solubility and greater
oxygen utilization. Both of these effects significantly
18
-------
TABLE I
COMPOSITION OF TYPICAL CLEAN WATER EFFLUENT
Water Sources
% of Total
Wastewater
Flow Range (gpm)
Potential Pollutant
Sources
Cooling Water
(excluding sea water)
40 - 80
100 - 10,000
(500 - 200,000
(gal. water ton
product)
Steam Equipment
10
50 -
1,000
Process leaks:
Bearings, exchangers
etc.
Water treatment
Scrubbed from air
through tower
Make-up water
Boiler blowdown
Waste condensate
-------
reduce the ability of the receiving water to assimilate
waste loads. Through the use of cooling towers, the
quantity of high temperature wastewaters discharged has
been greatly reduced.
The segregation of clean wastewater flows is widely
practiced throughout the inorganic chemical industry/ as
a result of overall wastewater treatment economics and
regulatory requirements. Although there is a limited
possibility that wastewater flows can be further
reduced by segregating additional clean waters, most
major clean waters are currently collected and either
recirculated or discharged separately in those in-
organic chemical plants with treatment facilities.
Thermal Pollutants
Many process facilities in the inorganic chemical industry
generate large amounts of thermal energy which must be
removed by the circulation of cooling waters or air.
Additional heat is released through the release of hot
brines from evaporators, etc. Of particular significance
are the gas producing plants because of their need to
discharge the thermal energy extracted from air or
natural gas during their compression and cooling to sub-
zero temperatures. In many cases, the problems of
thermal pollution are reduced through the use of cooling
towers. In the latter case, the blowdown from such re-
circulating systems may contain substantial amounts of
chemicals added to the cooling water such as chromates,
zinc, phosphates, bactericides, organics, etc., which
may constitute a pollution problem.
In the case of many industries, there is concerted
effort to produce by-product steam from excess thermal
energy. In the manufacture of sulfuric acid, for
example, by-product steam is important to process
economics. In many other cases, however, waste hot
brines and other similar waste flows are held in ponds
for cooling prior to discharge into surface waters.
20
-------
CHAPTER VI
WASTEWATER TREATMENT METHODS
A variety of sequences of wastewater treatment are avail-
able for wastes from inorganic chemical manufacture.
Their use depends on the nature of the waste and treatment
requirements. These sequences are indicated in Figure 1.
Three typical cases will be presented. These are:
I. Waste-containing dissolved and suspended solids
II. An excess thermal energy discharge
III. Waste-containing dissolved solids
Treatment Sequence I
In this case, the proposed treatment sequence might be:
Liquid 2-3-4-7-11-15 (Note that 8, 9, and 10 can
substitute for 7 and 11)
Solids 15-14-12-19
In this sequence, the waste flow is equalized and oil
is removed, clarification is used for suspended solids
removal, and the dissolved solids are concentrated and
sent to a deep well for disposal. The effluent dis-
tillate is then discharged or reused. The suspended
solids slurry will be thickened, centrifuged, and dis-
posed of in a lagoon. Alternately, chemical addition
could be used for dissolved solids removal if the dis-
solved ions have a common insoluble salt. Then the
dissolved ion problem has been converted to a suspended
solids problem and a suspended solids removal and disposal
sequence of 4-15-14-12 would be followed. It is also
possible to concentrate the dissolved ions by electro-
dialysis, or by ion exchange instead of distillation
and the sequence would be similar to that described
above.
The blowdown from the dissolved solids concentration
step instead of being disposed in a deep well may be
distilled to dryness, solar evaporated, or converted to
a saleable product.
21
-------
to
to
DILUTE
PRETREATMENT
. WASTE WATER
SUSPENDED
SOLID REMOVAL
DISSOLVED
SOLID REMOVAL
LIQUID DISPOSAL
SLUDGE TREATMENT
HEAT REMOVAL
FIGURE I
WASTEWATER TREATMENT SEQUENCE
-------
Treatment Sequence II
Here the proposed treatment sequence would be:
17-6-4-13
That is, a cooling tower (or a spray pond) would be
installed and the cooled effluent discharged or recycled.
If recycling is used, then the blowdown from the system
may be treated by chemical addition and clarification to
remove undesirable components (especially hexavalent
chrome and zinc added for corrosion control) prior to
discharge. The suspended matter would then go into a
suspended solids disposal sequence discussed above.
Treatment Sequence III
With a very light suspended solids load but a heavy dis-
solved solids load, the sequence (with excess acidity)
would be:
2-1-7-11-13
where neutralizing would be prescribed following equaliza-
tion. This would be followed by reverse osmosis (or
distillation, electrodialysis, ion exchange or chemical
addition depending upon the circumstances) and discharge.
The concentrate would be disposed of in a deep well or
evaporated to dryness.
At this point, it is important to note the existence of
two significant treatment sequences of general impor-
tance. They are:
Treatment Sequence
a) excessive acidity or alkalinity
streams 1
b) many high dissolved solids streams 2-5-11
The above two treatment sequences are commonly used in
many circumstances in this industry. These treatment
sequences, of course, do not represent all those used by
the industry but are considered to be the most prevalent.
23
-------
Joint Industrial Municipal Treatment
According to the U.S. Department of Commerce's 1968 publi-
cation/ Water Use in Industry, (the most recent available
report), a total of 1.251 trillion gallons of water
(excluding SIC 2879 Inorganic Insecticides and Herbicides)
were discharged from plants of this industry group. Of
this total, some 98.4 billion gallons, or 7.9%, were
discharged to municipal systems. These studies, which
are supported by others, indicate that there is tremen-
dous variation within groups. The study (see Table I)
indicates that the SIC groups 2812, 2819, 2871, and 2892
do not make significant use of municipal systems, un-
doubtedly because of the nature of their discharges (high
chlorides, conservative species, low or high pH) and their
volume as well as the location of the plants. SIC 2813
and 2851 make extensive use of municipal systems. The
data for 2813 were not available, but because of the
plant locations and the fact that the waters discharged
are primarily cooling waters, it is estimated that 40
percent goes into municipal systems. The data on SIC
2879 are inconclusive and that on 2816 indicate that a
significant though not necessarily major percentage of
the plants do use municipal facilities.
The data in Table I apply only to plants reporting water
use of at least 20 million gallons per year or having
more than 100 employees. The distribution of water use
by SIC categories and plant sizes is shown in Table II
for 1963, the latest available data. The distribution
of employees is shown in Table III.
24
-------
TABLE I
WATER DISCHARGE BY SIC (1)
to
en
Inorganic
Industry SIC
Alkalies 2812
Gases 2813
Pigments 2816
Chemicals 2819
Paints 2851
Fertilizers 2871
Herbicides 2879
Explosives 2892
Total Discharge
(billion gals/yr)
364.1
80.8
91.5
468.0
6.5
97.4
Not available
143.1
Discharge to
Municipal Systems
(billion gals/yr)
47.2
2.7
1.0
42.6
4.6
0.3
Not available
Less than 50
million gallons
Percent to
Municipal Sewers
13.0
3.3
1.1
9.1
70.8
0.3
0.0
(1) U.S. Census Bureau, Census of Manufactures (1968), Water Use in Manufacturing
-------
TABLE II
EMPLOYMENT DISTRIBUTION (1)
ro
Number of
Employees
1-4
5-9
10-19
20-49
50-99
100-249
250-499
500-999
1,000-2,499
2,500 and more
SIC
2812
3
1
-
5
5
12
6
6
6
—
2813
130
86
115
110
33
12
1
-
-
-
2816
14
13
11
22
11
12
11
1
3
-
2819
168
85
107
117
92
74
42
21
8
4
2851
468
242
311
350
171
113
36
8
2
—
2871
8
7
14
55
71
40
14
3
1
-
2879
106
62
61
66
23
19
4
2
1
-
2892
31
5
4
13
7
15
5
6
1
5
(1) U.S. Census Bureau, ibid
-------
to
Number of
Establishments
Reporting
Indicated
Water Use
(mil, gal/yr)
Less than 1
1-9
10-19
20-99
100+
TABLE III
DISTRIBUTION OF WATER USE - 1963
SIC
2812
4
2
1
2
29
2813
197
106
36
33
49
2816
32
13
4
7
20
2819
189
98
39
60
138
2851
981
162
28
38
15
2871
104
50
24
32
31
2879
218
23
2
7
3
2892
28
4
5
4
17
U.S. Census Bureau, 1963 Census of Manufacturers, Water Use in Manufacturing
-------
The smallest plants tend to discharge effluent to munici-
pal sewers but they also tend to discharge small volumes
of water. If we assume that they discharge all of their
effluent water to municipal sewers, the figures change as
shown below:
Percent to Municipal Sewers
SIC From Table IRecalculated
2812 13.0 13.0
2813 3.3 4.9
2816 1.1 1.3
2819 9,1 9.3
2851 70.8 100.0
2871 0.3 1.0
2892 0.0 Not available
Thus, the total discharge on a percentage basis is not
significantly changed and would approximate 8.2 percent
of the total.
It is significant to note that the total percentage, and
that within an SIC group, is not going to increase
significantly in the future. Spreading municipal systems
and increasing pressure on industry to treat its wastes
will be counter-balanced by restrictions on discharges
into municipal systems which will be especially true
with regard to discharges from the inorganic chemical
industry. It is likely that waste streams currently
being discharged into municipal systems from this indus-
try's establishments will be reduced because of increas-
ingly stringent sewer restrictions. The main point is
that there is not much point in co-treating a highly
conservative, dissolved solids waste stream in a facility
designed to treat non-conservative, suspended and
colloidal solids wastewaters.
Sewer restrictions which may bar or establish limita-
tions on chlorides, total dissolved solids, suspended
solids, heavy metals, color, pH, etc., are the princi-
pal barriers to the acceptance of wastewaters from this
industry into a municipal system. Economics rarely
play a role since almost any charge levied by a munici-
pality would be cheaper than known techniques for treat-
ing inorganic dissolved solids in most locations where
direct discharge to receiving streams is not permitted.
Rates vary from the infrequent zero cost to a rate on a
par with residential customers up through above average
costs based on surcharges or intentional industrial
burdens. Charges may run from $0.10-$1.00/1000 gallons
28
-------
with a level of $0.30-$0.40/1000 gallons at the 30-50
mgd treatment level believed to be average.
The chemical industry has generally found that in-plant,
separate treatment for neutralization and suspended solids
removal has economic advantages, particularly when
significant quantities of contaminated wastewaters are
involved. No significant percentage increase in the
amount of wastewaters treated in municipal systems is
expected in the near future. If complete, water renova-
tion of municipal wastewater becomes common, however,
then joint treatment for this industry's wastewater might
become more common and desirable.
29
-------
CHAPTER VII
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
The Industrial Waste Treatment Practices Data Form was
developed as a part of the study entitled "Projected
Wastewater Costs in the Organic Chemicals Industry"
under Federal Water Pollution Control Administration
Contract No. 14-12-435 and published as a part of "The
Cost of Clean Water and Its Economic Impact - Volume
IV," United States Department of the Interior, January,
1969, and further refined in a subsequent study entitled
"Inorganic Chemicals Industry Profile" under Federal
Water Pollution Control Administration Contract No. 14-
12-592 and published as a part of "The Economics of
Clean Water - Volume Three," United States Department
of the Interior, March, 1970.
30
-------
CHAPTER VIII
PLANT SURVEY DATA
The Industrial Waste Treatment Practices Data Form was
used to tabulate data from 59 inorganic chemical plants.
The basic data obtained are tabulated in Appendix B and
are portrayed in the bar graphs of Figures 1 to 9.
From those plants for which adequate information was
available, the following average statistics were calcu-
lated:
Average production = 280,734 tons per year
Water use per plant = 27,034,619 gpd
Wastewater discharge per plant = 4.697 mgd
Average treatment efficiency = 85%
Average capital costs of treatment facilities =
$1,048,578
Average operating costs of treatment facilities =
$274,730 per year
Generalizing the above data:
Average capital cost = $223/1000 gpd
Average operating cost = $58.49 per year/1000 gpd
Average wastewater flow = 16.73 gpd/annual ton of
production
Average capital cost = $3.74/annual ton of
production
Average operating cost = $0.98 per year/annual ton
of production
The generally fragmentary nature of the survey data is
indicative of the status of wastewater treatment in
this segment of the chemical industry. Wastewater
treatment practices tend to be those which reduce gross
pollutants such as acidity, oil, and suspended solids.
The refractory nature of the wastes from most of the
industry's processes would require more advanced treat-
ment technologies than have generally been applied.
The production, capital costs, and operating costs
data reported per plant are judged to be reliable.
Such data are easily obtained from plant records. The
data reported on wastewater flows, however, are not
sufficiently reliable to be used for projection calcula-
31
-------
tions; these data are in error in that contaminated
wastewater flows are not accurately differentiated from
cooling water effluents.
Even though an extensive correlation study was made,
no statistically significant relationships were found
among the various cost-related parameters. The relation-
ship indicated in Figure 10 showing operating costs of
treatment facilities per ton of annual production as a
function of capital costs of facilities per ton of annual
production is the most useful found; it can be used to
indicate at least order-of-magnitude variations.
Among the plants in the survey sample, production
capacities were generally low while wastewater volumes
reported tended to be high. Most of the plants employed
more than 100 persons and were less than 10 years old.
The plants were widespread geographically and, accord-
ingly, may be considered to be representative in this
regard. The bases of treatment decisions for these plants
were generally least cost or minimum compliance with
regulations. A few decisions were made on the basis of
a projected economic return and only one plant decision
was based on ultimate treatment.
32
-------
FIGURE I
a:
<
UJ
V)
2
o
u.
O
O
I-
o
3
a
o
a:
Q.
0>
O
-TOTAL PRODUCTION
-SURVEYED PRODUCTION
2813 2816 2819 2851 2871 2879
STANDARD INDUSTRIAL CATEGORY
2892
33
-------
FIGURE 2
10 15 20 30 40 50 60 70
PLANT FREQUENCY
80 85 90 95
98
34
-------
Ul
Tl
8
I
--
H
o
a
»
ra
OJ
Q01 Q05Q1 Q2Q512 5 10 20304050607080 90 95 9899 99B999 9999
PLANT FREQUENCY
-------
o
z
U
3
O
U
tr
I-
z
18
17
15
14
12
II
9
8
7
6
5
4
3
2
i-t——i • • • I i —ili'' i
FIGURE 4
HI
timMiMMttm
COOT
lo
o:
i^
:
MAJOR SOURCE OF WATER
36
-------
FIGURE 5
o
z
111
o
UJ
U.
H
<
0.
8
6
M
li:
::
•
{h;
= ? O :r
T-
-
m
rrrt
:
::
iiii
1
»-b~
Q.
°
:n i!:
m
11LL
1
i:tt
O
P
Oz>
O UJ
.
ffi
1
!i:
tffl
E US
141
u
o
• '
i:
.;.;
•
:
.
::::
tra
:
BASIS OF TREATMENT DECISION
37
-------
u
z
UJ
z>
a
UJ
cc
FIGURE 6
14
13
12
10
9
8
4
3
2
I
:4
I
!
1900-1920 1921-1930 1931-1940 1941-1950 1951-1960 1961-1969
YEAR OF CONSTRUCTION
38
-------
FIGURE 7
vo
UJ
3
O
LJ
CE
U.
STATES
-------
FIGURE 8
*».
o
o
UJ
a
UJ
o:
INDUSTRY WATER USE REGIONS
-------
o
I-
CE
UJ
Q.
tC.
<
UJ
ac
LJ
O.
(O
H
co
o
o
QL
UJ
Q.
O
FIGURE 9
OPERATING COSTS OF
TREATMENT FACILITIES
VERSUS
CAPITAL COSTS
20 30 40 50 60 70 80
CAPITAL COSTS ($ PER ANNUAL TON)
IOO
-------
CHAPTER IX
COSTS OF UNIT WASTEWATER TREATMENT METHODS
Introduction
The composition of wastes from the inorganic chemical indus-
try are very unpredictable, but the types of pollutant in
the waste can be classified under one of the following head-
ings:
1. Acidity or alkalinity
2. Suspended solids
3. Filterable solids
4. Dissolved solids
5. Temperature
Various combinations of the above types of pollution may
occur in an inorganic chemical waste. Care must be taken
when discussing these types of pollutants that the correct
references are used, e.g., the total dissolved solids (TDS)
referred to here refers to TDS after neutralization when
there is no excess acidity or alkalinity, since a large
amount of TDS may be removed or added in the process of
neutralization.
The ranges of the values for pollutants found from the
industry were as follows:
Process Water
Flow rate 0.5 mgd to 50 mgd
Acidity 200 mg/1 (as CaCO3) to 20,000 mg/1
Suspended solids 0-500 mg/1
Dissolved solids 1000-150,000 mg/1
Cooling Water
Flow rate Up to 150 mgd
Temperature range 140°F-180°F
It is evident from many studies of distribution of pollu-
tant concentration with flow rate that the combination of
high pollutant load with high flow rate is improbable.
Thus, generally with high process water flow rates such
as 50 mgd, the probability of having a TDS of 150,000 mg/1
is remote. For this reason, an envelope of extreme values
42
-------
•Cfc
u*
200,000
100,000
50,000
•DEEP WELL
FIGURE I
APPLICABLE RANGES OF
DEMORALIZATION UNITS
CO
o
-J
o
CO
o
-------
NO NEUTRALIZATION FOR DEEP WELL EVAPORATION
FILTRATE
OR
CENTRATE
ALTERNATIVE:
SETTLING POND
Vacuum Filter
or
Centrifuge
| Sludge |
DEEPWELL
OOO r»
OR DEMORALIZATION
DIRECT TO EVAPORATION OR CONTROLLED DISCHARGE
EVAPORATION
(alternative
to deep well)
REUSE OR
DISCHARGE
FIGURE 2
SCHEMATIC LAYOUT OF TREATMENT PLANT FOR WASTES FROM THE INORGANIC
CHEMICAL INDUSTRY SHOWING VARIOUS POSSIBLE COMBINATIONS OF UNITS
-------
lime
Lime storage
O Blower
/
Equalization Basin
filtrate
tn
5
UIIIIV
slakes
Mixing
Oxidation
Flocculation
Vacuum filter
or
Centrifuge
L
f
J
Sludge to
disposal
occasional
removal of
sludge after
drying
FIGURE 3
FLOW SHEET FOR NEUTRALIZATION PLANT
To stream or
demineralization
plant
Alternative
flow pattern
Sludge"
settling] •- To stream
pond
-------
of TDS and flow rate that have been considered for cost
calculations are shown in Figure 1. The following combina-
tions within the triangle and values of acidity were chosen
for this cost study:
Flow rate 0.5, 1.0, 10.0, 50.0 mgd
Acidity 500, 1000, 20,000 mg/1 (as CaCOa)
Suspended solids 100, 500 mg/1
TDS 3000, 30,000, 150,000 mg/1
The flow sheet suggested for analysis is shown in Figure
2. When neutralization of the acidity is not required, the
neutralization plant will be bypassed. At low acidities
and a low flow rate, it may be more economical to eliminate
neutralization if high TDS must be removed anyway. This
will depend on the cost structure of the various units, the
quantities of waste, the use to which product wastes may
be used, the economy of brine disposal versus solids dispo-
sal, and other such considerations.
The neutralization plant suggested for cost analysis is
shown in Figure 3, and discussed in Appendix E under
the heading of neutralization. The plant included aeration
flocculation to precipitate ferrous and other metal ions.
The costs are shown in Table I.
The removal of TDS in any of the five units, i.e., deep
well disposal, reverse osmosis, electrodialysis, distilla-
tion, or ion exchange might require filtration of the
liquid as a pretreatment.
All of the last four processes that were considered will
produce brine. The concentration of brine produced will
depend first, on the process used, but also on the cost
of brine disposal and on the possible market value of the
usable water produced.
For this study, it was assumed that all brine produced
will be disposed of in deep wells or at a similar cost.
Other disposal methods include disposition to the ocean,
solar evaporation ponds, and evaporation ponds that use
applied heat. The process used depends on the location
and the brine concentration, as well as the cost of brine
disposal. These factors are too unpredictable to be
included in a study and the costs are given based on the
above assumptions.
46
-------
TABLE I
TREATMENT LEVEL I
NEUTRALIZATION COSTS INCLUDING EQUALIZATION
AND SLUDGE DEWATERING
Operating Cost
<71000 gal
15
20
27
29
108
108
14.5
25
26
26
103
103
11
12.5
18
20
10.5
11
NOTE: Costs based on the sum of unit processes 1, 2,
3, and 4 in Figure 1.
Flow
mgd
0.5
0.5
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
1.0
1.0
10.0
10.0
10.0
10.0
50.0
50.0
Acidity
mg/1
500
500
1,000
1,000
20,000
20,000
500
500
1,000
1,000
20,000
20,000
500
500
1,000
1,000
500
500
SS
mg/1
100
500
100
500
100
500
100
500
100
500
100
500
100
500
100
500
100
500
Capital Cost
$1000
120.0
145.0
184.0
190.0
514.0
514.0
183.0
236.0
300.0
320.0
807.0
807.0
1,120.0
1,290.0
1,540.0
1,640.0
3,420
3,980
47
-------
TABLE II
TREATMENT LEVEL II
DEMINERALIZATION COSTS INCLUDING PREFILTRATION AND BRINE DISPOSAL
CAPITAL COSTS
OPERATING COST
00
Flow
mgd
0.5
0.5
0.5
1.0
10.0
10.0
50.0
TDS
mg/1
3,000
30,000
150,000
3,000
30,000
3,000
30,000
3,000
Total
Product
Water @
500 mg/1
mgd
0.35
0.25
0.47
0.45
0.167
-
0.25
-
-
-
0.75
0.50
0.95
-
0.9
0.33
0.50
7.5
5.0
8.0
9.5
3.3
0.50
45.0
45.0
Demineraliza-
Brine
Disposal
mgd
0.15
0.25
0.03
0.05
0.33
0.25
0.25
0.50
0.05
0.1
0.67
0.50
2.5
5.0
2.0
0.5
6.7
0.50
5.0
5.0
Filtra-
tion
$1000
66
66
66
66
66
66
66
_
66
66
-
102
102
102
102
-
102
102
102
450
450
450
450
-
450
450
1,350
1,350
tion
Process
No.
6
7
8
10.,
11^X
9
6
7
11
9
6
11
6
7
8
10
11
9
7
9
7
8
9
10
11
7
9
7
9
Brine
Disposal Total
Cost
$1000
430
640
455
1,700
40
806
430
784
40
806
430
40
290
1,120
896
3,020
100
1,610
1,340
1,610
6,700
6,400
9,070
14,800
410
8,400
9,070
29,100
34,700
Cost
$1000
_
360
398
190
-
388
412
397
397
431
360
370
447
430
740
925
646
430
-
1,200
925
925
925
Cost
+35*
670
1,439
1,240
2,551
40
1,701
670
1,704
40
1,713
670
40
529
2,185
1,929
4,700
75
2,810
2,550
2,892
10,651
10,496
13,724
21,160
410
13,567
14,100
42,356
49,920
Filtra-
tion («/
1000 gal)
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
7.0
7.0
7.0
7.0
-
7.0
7.0
7.0
3.0
3.0
3.0
3.0
-
3.0
3.0
2.0
2.0
Deminerali-
zation
(C/1000 gal)
35.0
40.0
65.0
25.0
5.0
98.0
35.0
75.0
5.0
98.0
25.6
31.0
54.0
33.3
85.0
50.0
85.0
18.5
38.0
38.0
30.0
5.0
25.0
38.0
15.0
22.0
Brine
(-J/1000
gal)
_
18.0
24.0
16.0
16.0
-
29.0
24.0
13.5
18.3
8.5
11.0
20.6
18.3
4.5
8.0
3.0
1.0
-
10.0
8.0
2.0
2.0
Total
Cost
(C/1000
gal)
43.5
66.5
97.5
49.5
5.0
122.5
43.5
112.5
5.0
130.5
43.5
5.0
51.5
79.3
48.8
5.0
103.0
77.6
110,3
26.0
49.0
44.0
34.0
5.0
38.0
49.0
19.0
26.0
- For evaporation ponds, consider only those states or areas where the evaporation rate is twice the average
annual rainfall. Consider land value a nominal $100/acre. Capital costs in thousand dollars.
-------
The literature was searched for the amount of brine pro-
duced by the desalting units under "normal" operating
conditions. Assumptions were made based on this informa-
tion and the quantities used are shown in Table II,
which presents the capital and operating costs for
various combinations of capacities and processes. Avail-
able data usually refers to brine production as a by-
product of potable water production and not of waste
treatment as such. For potable water production, the
disposal of brine is of secondary importance.
Where land is available and the evaporation rate exceeds
the average annual rainfall by a sufficient margin,
solar evaporation ponds will be an economical treatment
method that will not require pretreatment. Operating
costs will also be low.
In the regions of regular (as compared with seasonal)
rainfall, it may be more economical to store the waste
in lagoons and discharge to the stream only at
sufficiently high stream flow rates to provide the
necessary dilutions. This method is limited to a small
number of locations in the country. The size of the
ponds will be determined by the flow rate and variance
of the stream flow, the TDS content of the stream and
the later use of the stream. It is difficult to base
a cost function on these factors and for this reason,
only the method is shown.
Cooling water would normally need only to be cooled down
sufficiently so as not to raise the stream temperature
unduly. Cooling towers may be constructed based on the
mean low flow condition in summer or cooling ponds may
be used if land is cheap.
The calculated costs are summarized in two separate
tables mentioned in the foregoing. Table I considers
neutralization for Treatment Level I only, and Table II
considers the dissolved solids removal and brine dispo-
sal costs of waste treatment at Treatment Level II.
49
-------
CHAPTER X
COSTS VERSUS EFFLUENT QUALITY RELATIONSHIPS
The data from the survey of 59 plants was not
sufficiently complete in regard to effluent quality to
construct any statistically significant relationship
between numbers of plants, and effluent quality
parameters such as acidity, suspended solids and
dissolved solids.
The methods of treatment currently employed by the
inorganic chemical industry, as previously discussed,
are quite limited in number and/ in general, involve as
a group (1) equalization, (2) neutralization, (3) floccu-
lation, (4) sedimentation, and (5) sludge dewatering.
This combination then is judged to account for the typical
situation and to be equivalent to approximately 27% level
of treatment, the reported average industry level.
The nature of the waste substances, inorganic soluble
salts, and the treatment processes available to re-
duce or remove such salts is such that there are,
practically speaking, no intermediate levels of treatment.
That is to say, treatment for removal of dissolved salts,
if applied at all, produces a quality of effluent water
equivalent or better than plant influent supply water.
An increase in the level of treatment of inorganic chemi-
cal plant effluents thus goes in one step from the 27%
level involved in neutralization and suspended solids
removal to 100% removal of the contaminants. For design
purposes, demineralization effluent quality is set at
500 mg/1.
On the basis of the range of volumes of plant effluents
and the foregoing considerations of only two levels of
treatment, a series of likely design combinations was
constructed, one for each level and the capital and
operating costs determined. Table I in Chapter IX pre-
sented the cost data for Treatment Level I which, as
previously mentioned, is judged equivalent to 27% removal.
Table II in Chapter IX presented the cost data for
Treatment Level II which represents 100% removal with
ultimate disposal of the residues. Figure 2 in Chapter
IX is a schematic diagram showing the generalized layout
for treatment of water from the inorganic chemical
industry. The numbers identifying each unit process
50
-------
correspond to the unit process numbers in Tables I and II.
Note from Figure 2 in Chapter IX that the brine from the
demineralization processes is taken to deep well disposal
or to solar evaporation alternatively. Figure 1 in Chapter
IX shows the applicable ranges of the alternative de-
mineralization units employed in the construction of Table
II data.
An examination of the information shown in the afore-
mentioned Tables I and II of Chapter IX, coupled with a
judgment as to the typical level of wastes to be
encountered/ leads to the selection of 1000 ppm acidity
and 100 ppm suspended solids as representative of present
practice to establish the basis of industry cost pro-
jections covered in Chapter XI for Treatment Level I.
Similarly, 3000 ppm TDS is judged representative of wastes
for application of Treatment Level II. In this latter
connection, the capital and operating costs for deminerali-
zation process No. 7 reverse osmosis, were chosen for
projection purposes even though simple deep well disposal
is clearly lower in both costs.
It is believed that any generalization developed based
upon wide use of large volume deep well disposal for
Treatment Level II would be misleading since such general
application of deep wells is considered impractical.
51
-------
CHAPTER XI
PROJECTED INDUSTRY COSTS
According to the U.S. Census Bureau's 1963 publication,
Water Use in Manufacturing, inorganic chemical plants
reported annual water intake volumes as shown in Table
I. These are the latest available data.
TABLE I
NUMBERS OF INORGANIC CHEMICAL PLANTS BY
WATER INTAKE VOLUME-1963 (1)
INTAKE VOLUMES
millions of gallons per year
SIC less more
No. Total than 1 1-9 10-19 20-99 than 100
2812 38 4 21 2 29
2813 421 197 106 36 33 49
2816 76 32 13 4 7 20
2819 524 189 98 39 60 138
2851 1224 981 162 28 38 15
2871 241 104 50 24 32 31
2879 253 218 23 2 7 3
2892 58 28 4 5 4 17
TOTAL J835 T753 4~58" I3T T8~3 3~0~2
(1) U.S. Census Bureau, Census of Manufactures-1963,
"Water Use in Manufacturing"
Water discharges from large plants (intakes of more than
20 million gallons per year) are given in Table II.
TABLE II
WATER DISCHARGES FROM LARGE INORGANIC
CHEMICAL PLANTS-1968 (1)
Discharge to
SIC Total Discharge Municipal Sewers Percent to
No. (109 gal/yr) (109 gal/yr) Sewers
2812 364.! 47.2 13.0
2813 8o.8 2.7 3.3
52
-------
TABLE II (cont.)
SIC
No.
2816
2819
2851
2871
2879
2892
Total Discharge
(109 gal/yr)
91.5
468.0
6.5
97.4
Not available
143.1
Discharge to
Municipal Sewers
(109 gal/yr)
1.0
42.6
4.6
0.3
Not available
<50 million gal.
Percent to
Sewers
1.1
9.1
70.8
0.3
0.0
(1) U.S. Census Bureau, Census of Manufactures-1968,
"Water Use in Manufacturing"
Assuming that all plants having intakes of less than 20
million gallons per year discharge to municipal sewers,
the total industry discharge to municipal sewers in
1963 is estimated to have been 48.0 billion gallons.
Discharges from large plants to other than municipal
sewers are given in Table III.
TABLE III
LARGE INORGANIC CHEMICAL PLANT DISCHARGES
OTHER THAN TO MUNICIPAL SEWERS-1968 (1)
No. Of
Plants
2812 31
2813 65
2816 24
2819 223
2851 32
2871 42
2879 Not available
2892 21
TOTAL 438
Discharge
1Q9 gal/yr
316.9
.1
,5
78,
90,
425.4
1.9
97.1
Not available
143.1
1153.1
Average Discharge
1Q9 gal/yr
10.22
1.20
3.77
1.91
0.06
2.31
6.81
2.63
(1) U.S. Census Bureau, ibid
53
-------
Water intakes and usages by purpose are given in Table
IV.
TABLE IV
LARGE INORGANIC CHEMICAL PLANT INTAKES
AND USAGE, BY PURPOSE, 1968 (1)
2812
2813
2816
2819
2851
2871
2879
2892
TOTAL
Billions of Gallons per
Total
Intake
386.4
92.3
95.4
514.8
6.8
113.7
152.3
1361.7
Process
18.9
5.3
21.2
75.2
2.7
24.2
28.0
175.5
Cooling
Other
361.0 6.5
86.5 0.6
68.5 5.7
404.5 35.2
2.9 1.3
64.5 24.9
116.2 8.2
1104.1
82.4
Year
Gross
Use
574.3
193.7
125.8
1432.0
9.8
474.1
186.8
2996.5
Use
Rate
1.49
2.10
1.32
2.78
1.44
4.17
1.23
2.20
(1) U.S. Census Bureau, ibid
Assuming that contaminated wastewaters will be equivalent
to that withdrawn for process and other non-cooling
purposes, and that percentage disappearances are constant
for all purposes, the total of such wastewaters for large
plants in the industry in 1968 is estimated to have been
237.5 billion gallons to other than municipal sewers.
The average contaminated wastewater discharge from large
plants to other than municipal sewers is thus estimated
to have been 1.485 mgd. The average discharge to munici-
pal sewers from large plants is estimated to have been
0.616 mgd.
Numbers of plants, values of shipments, and price indexes
for the inorganic chemical industry in 1958, 63, 66, 67,
68 and 69 are given in Table V.
54
-------
TABLE V
THE INORGANIC CHEMICAL INDUSTRY
SIC
No.
2812
2813
2816
2819
2851
2871
2879
2892
2812
2813
2816
2819
2851
2871
2879
2892
2812
2813
2816
2819
2851
2871
2879
2892
2812
2813
2816
2819
2851
2871
2879
2892
2812
2813
2816
2819
2851
2871
2879
2892
Yr.
58
58
58
58
58
58
58
58
63
63
63
63
63
63
63
63
66
66
66
66
66
66
66
66
67
67
67
67
67
67
67
67
68
68
68
68
68
68
68
68
No. of
Plants Value of
Total +20 Emp. ($1000)
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
37
460
97
678
1,779
279
329
67
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
44
507
98
718
1,701
213
344
92
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
32
178
57
301
600
207
101
58
34
148
52
326
650
198
108
47
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
40
156
60
358
680
184
115
52
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
425,431
262,581
412,011
2,146,254
1,753,923
611,103
347,628
169,699
652,120
425,388
484,768
3,493,870
2,456,361
863,701
476,661
283,298
782,661
549,687
581,774
3,845,232
2,970,403
1,183,321
692,741
469,413
719,800
588,700
549,300
4,248,400
2,911,400
1,196,900
817,000
647,000
754,000
613,000
650,000
4,200,000
3, 221,000
1,091,820
869,288
667,057
Shipments Price Index
($1000- '58) '57-59=100
425,431
262,581
412,011
2,146,254
1,753,923
611,103
347,628
169,699
687,890
448,722
532,127
3,685,517
2,696,335
864,566
477,138
286,160
817,828
574,386
645,698
4,018,006
3,296,785
1,133,449
663,545
468,009
741,298
606,282
602,303
4,375,283
3,192,325
1,168,848
797,852
615,019
766,260
622,967
704,989
4,268,293
3,493,492
1,088,554
866,688
606,415
100.0
100 . 0
100.0
100.0
100.0
100.0
100.0
100.0
94.8
94.8
91.1
94.8
91.1
99.9
99.9
99.0
95.7
95.7
90.1
95.7
90.1
104.4
104.4
100.3
97.1
97.1
91.2
97.1
91.2
102.4
102.4
105.2
98.4
98.4
92.2
98.4
92.2
100.3
100.3
110.0
55
-------
TABLE V (Continued)
2812
2813
2816
2819
2851
2871
2879
2892
No. of Plants Value of Shipments Price Index
Yr. Total +20 Emp. ($1000) ($1000- ~58)'57-59=100
69
69
69
69
69
69
69
69
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
792
653
690
4,305
3,459
1,149
924
687
,000
,000
,000
,000
,000
,686
,922
,736
804
663
748
4,375
3,751
1,146
922
625
,878
,618
,373
,000
,627
,247
,156
,215
98.4
98.4
92.2
98.4
92.2
100.
100.
3
3
110.0
Using the data in Table V and assuming that (1) the num-
ber of plants having water intakes of over 20 million
gallons, (2) those having more than 20 employees, and
(3) the total number of plants will remain in the 1963-67
ratio, numbers of plants are estimated by year in Table
VI.
TABLE VI
NUMBERS OF PLANTS IN THE INORGANIC
CHEMICAL INDUSTRY
Val. of
Ship
Year ($1000-'58)
1958 6,128,630
1963 9,669,455
1966 11,617,706
1967 12,099,210
1968 12,417,658
1969 13,037,114
No. of
Plants
(more than
20 Emp.)
1,534
1,563
1,617
1,645
1,672
1,699
No. of
Plants
(more than
20 mil.gal/yr)
476
485
501
510
518
527
No. of
Plants
(Total)
3,656
3,726
3,853
3,717
3,778
3,839
56
-------
In Table VII, productions of inorganic chemicals are
given for 1968 and projected by year through 1974.
TABLE VII
PROJECTED PRODUCTION OF INORGANIC CHEMICALS, 1968-1974
(millions of tons)
SIC
No. 1968 1969 1970 1971 1972 1973 1974
2812 ,
2813 ±f
2816
2819 .
2851 -'
2871
2879
2892 ±f
24
17,5
1.20
70
3.51
41.5
0.20
0.98
25
20.1
1.25
72
3.74
41.0
0.20
1.04
26
23.7
1.29
74
3.93
42.3
0.19
1.08
28
28.5
1.37
77
4.16
43.9
0.18
1.11
30
34.3
1.44
80
4.41
46.1
0.18
1.15
32
40.8
1.51
84
4.68
48.0
0.17
1.20
34
47.9
1.59
88
4.96
49.9
0.15
1.27
From Chemical and Engineering News 1968 production and
Resource Engineering Associates projections
.27 From Resource Engineering Associates projection and
sp. gr.=1.0
3/ From 1963 production and values and Resource
Engineering Associates projections
Production in the industry, numbers of plants, and waste
discharges are projected from the above data in Table
VIII. Numbers of plants were estimated by a detailed
analysis of the total industry production and the ratios
of plant sizes and SIC distributions in 1963. These
estimates were updated according to the data of the 1967
Census of Manufactures. Eighty five percent of the total
production is assumed to have been produced in large
plants, as is indicated by the plant capacity data in
Appendix A.
57
-------
TABLE VIII
THE INORGANIC CHEMICAL INDUSTRY, 1963-74 I/
1963
1968
1969
1970
1971
1972
I/ Based upon 1963 and 1968 water use data and projected production
2/ <20 million gallons per year
3/ >20 million gallons per year
1973
1974
No. of Plants, Total
No. of Small Plants 2/
No. of Large Plants 3/
Production Total
(billion Ibs)
Production, Large Plants
(billion Ibs)
Production, Small Plants
(billion Ibs)
in Municipal Sewer Discharges
00 (billion gal)
Large Plants (billion gal)
Small Plants (billion gal)
Wastewater, Not to Sewers,
Large Plants (bil. gal)
Cooling Hater, Not to Sewers,
Large Plants (bil. gal)
Gross Hater use. Large Plants
(billion gal)
Value of Shipments, Total
(bil. 1958 $)
3458
3012
446
~
-
™
59.0
53.7
5.3
211.8
922.9
2466.0
9.669
3514
3036
478
317.8
270.1
47.1
108.1
98.4
9.7
257.9
1104.1
2996.5
12.418
3574
3088
486
328.7
279.4
49.3
112.2
102.1
10.1
267.7
1145.6
3110.4
13.037
3597
3109
488
345.0
293.3
51.7
117.6
106.9
10.7
280.5
1200.9
3262.2
-
3631
3139
492
368.4
313.1
55.3
125.3
113.9
11.4
298.9
1279.8
3480.1
-
3670
3173
497
395.2
355.9
59.3
134.1
121.9
12.2
320.1
1370.9
3730.3
-
3711
3209
502
424.7
361.0
63.7
143.8
130.7
13.1
343.5
1468.5
4006.0
-
3755
3247
508
455.5
387.2
68.3
154.0
139.9
14.1
367.9
1572.5
4294.0
-
-------
The data in Table VIII are based upon the water uses
reported in 1963 and 1967/ and discharges are estimated
from gross water uses based upon projected production.
In 1968, large plants in the inorganic chemical industry
used (including recirculation) 2996 billion gallons of
water for all purposes and discharged 1362 billion gal-
lons, taking in 1362 billion gallons. The entire chemical
industry (SIC 28) reported a use of 9416 billion gallons
that year; the inorganic chemical industry thus used
about 31.8% of the total, slightly less than the 32.5%
as earlier reported. A 1967 survey of the chemical
industry by the Manufacturing Chemists Association (2)
indicated a gross water use of 8340 billion gallons that
year. These data and the data in Table VIII indicate
water uses in the inorganic chemical industry of 2711 and
2890 billion gallons per year, respectively. Inorganic
chemicals have shown a long term decrease in percentage
of the overall chemical market from 49.5% in 1958 to 40%
in 1968.
Data from the 1958, 1963, and 1967 Census of Manufactures
and from the 1967 MCA survey are shown in Table IX. These
data generally apply to large plants in the chemical
industry.
(2) "Toward a Clean Environment," Manufacturing Chemists
Association, 1967.
TABLE IX
WATER USE DATA, 1958-67
1958 I/ 1963 I/ 1967 2_/ 1968 3_/
CHEMICALS & ALLIED PRODUCTS:
Intake, bil. gal. 3240 3889 4269 4476.2
Gross Use, bil. gal. 5225 7577 8340 9415.8
Discharges, bil. gal. 3061 3662 4085 4175.1
Use Rate 1.61 1.95 1.95 2.104
Discharges as % of Use 58.5 48.3 48.9 44.3
59
-------
TABLE IX (Continued)
INORGANIC CHEMICALS:
Intake, bil. gal.
Gross Use, bil. gal.
Discharges, bil. gal.
Use Rate
Discharges as % of Use
I/
1958 I/ 1963 I/ 1967 2_/ 1968 3_/
1287
2466
1134.7
1
92
46.0
1361.7
2996.5
1153.0
2.20
38.5
_ U.S. Bureau of Census, 1963 Census of Manufactures,
Water Use in Manufacturing
2/ Ref (2) MCA Survey, ibid
3_/ "Water Use in Manufacturing," Census of Manufactures
Table X shows projections of production and discharges
which incorporate all of the above data from Tables VIII
and IX.
Data from the 1967 MCA survey of the chemical industry
are given in Table XI and ranges of plant capacities
in the inorganic chemical industry are shown in Table XII.
Table XII indicates an average plant capacity of 0.783
billion pounds per year and a median capacity of 0.319
billion pounds per year. This compares favorably with the
1968 average capacity in Table X of 0.565 billion pounds
per year. The data in Table XI indicate an average dis-
charge from large plants of wastewater to other than
municipal sewers of 0.657 billion gallons per year per
plant in 1967 for the chemical industry as a whole.
60
-------
TABLE X
THE INORGANIC CHEMICAL INDUSTRY, 1963-74 I/
1963 1968 1969 1970 1971 1972 1973 1974
Large Plants, Average Data:
Production, bil Ibs/yr/plant - 0.565 0.575 0.601 0.636 0.676 0.719 0.762
Wastewater, bil gals/yr/plant 0.475 0.539 0.551 0.575 0.608 0.644 0.684 0.724
I/ Ref (1) U.S. Census Bureau, ibid
Ref (2) Manufacturing Chemists Association 1967 Survey, ibid
-------
TABLE XI
1967 MCA SURVEY DATA
THE CHEMICAL INDUSTRY (2)
No. of Plants
Capital Investment in Wastewater
Treatment through 1966
Capital Investment in Wastewater
Treatment, 1962-1966
Capital Investment in Wastewater
Treatment, 1967-1971
Annual Operating Cost, 1967
Water Withdrawals
Water Used
Discharge to Surface Waters:
Cooling Water
Process Wastewater
Discharge to Public Sewers:
Cooling Water
Process Wastewater
Inorganic Waste Discharges:
To Surface Waters:
Dissolved
Undissolved
To Public Sewers:
Dissolved
Undissolved
Total Discharged
Total Discharged with No
Treatment
987
$385,268,000
$140,640,000
$235,700,000
$59,638,000
11.696 bil. gal/day
22.848 bil. gal/day
9.224 bil. gal/day
1.777 bil. gal/day
0.078 bil. gal/day
0.114 bil. gal/day
135.3 mil. Ibs/day
11.65 mil. Ibs/day
2.156 mil. Ibs/day
0.192 mil. Ibs/day
149.3 mil. Ibs/day
205.1 mil. Ibs/day
(2) Manufacturing Chemists Association 1967 Survey,
ibid
62
-------
TABLE XII
RANGES OF CHEMICAL PLANT PRODUCTION CAPACITIES -'
Capacity Range,
Product tons/day
Caustic Potash 13.7 - 98.6
Caustic Soda 300 - 7800
Chlorine 180 - 7050
Soda Ash 205 - 10274
Titanium Dioxide 49.3 - 474
Ammonium Nitrate 30.1 - 1164
Nitric Acid 43.8 - 1096
Phosphoric Acid 47.4 - 1342
Phosphorous 16.4 - 389
Sodium Dichromate 41.1 - 247
Sodium Sulfate 21.9 - 753
Superphosphate 63.0 - 959
Ammonium Phosphate 19.2 - 630
Potash 27.4 - 1699
Calcium Carbide 54.8 - 822
Hydrofluoric Acid 27.4 - 137
Sodium Sulfite 8.2 - 397
—' Industry Product Profiles, Appendix C
Numbers of plants in the chemicals and allied products
industries in 1963 are shown in Table XIII by industry
segments and by intake water volumes.
TABLE XIII
NUMBERS OF PLANTS IN THE CHEMICAL INDUSTRY, 1963
Large Plants Small Plants
(more than 20 (less than 20
mil, gal) mil, gal)
Industry Total i/ 1129 6382
Organic Chemicals
Industry 2/ 211 550
Inorganic Chemicals
Industry V 446 2187
Other Industry Segments 472 3645
63
-------
_!/ 1963 Census of Manufactures
2/ Ref (3) FWPCA Organic Chemicals Industry, ibid
3/ Present study
Data from the 1967 survey of the chemical industry by
the Manufacturing Chemists Association as shown in Table
XI are extended on an annual basis and given in Table
XIV.
TABLE XIV
CHEMICAL INDUSTRY SURVEY DATA, 1967 (2)
No. of Plants
Total Employment
Capital Investment in Wastewater
Treatment through 1966
Capital Investment in Wastewater
Treatment, 1962-1966
Capital Investment in Wastewater
Treatment Projected, 1967-1971
Annual Operating Cost, 1967
Annual Manpower Requirements, 1967
Annual Water Intake, bil. gal.
Annual Water Use, bil. gal
Use Rate
Plant Effluents:
Cooling Water, to Public Sewers,
bil. gal
Process Wastewater, to Public
Sewer, bil. gal.
Cooling Water, to Surface Waters,
bil. gal.
Process Wastewater, to Surface
Waters, bill. gal.
Total Effluents, bil. gal
Contaminants in Effluents to
Surface Waters:
Dissolved Inorganics, mil. Ibs.
Undissolved Inorganics, mil. Ibs.
Dissolved Organics, mil. Ibs.
Undissolved Organics, mil. Ibs.
Contaminants in Effluents to
Public Sewers:
Dissolved Inorganics, mil. Ibs.
Undissolved Inorganics, mil. Ibs.
Dissolved Organics, mil. Ibs.
Undissolved Organics, mil. Ibs.
987
393,657
$385,268,000
$140,640,000
$235,700,000
$59,638,000
2096.1 man-years
4269
8340
1.95
28.33
41.65
3367
648.6
4085
49370
4252
1284
155.5
786.9
70.1
292
74.8
64
-------
TABLE XIV (cont.)
Total Contaminants Produced:
Inorganics, mil. Ibs. 74857
Organics, mil. Ibs. 4191
(2) MCA 1967 Survey, ibid
The chemical industry, other than those segments defined
as "inorganic chemicals" and as "organic chemicals,"
includes operations producing inorganic and organic
compounds which appear in effluents. Assuming (1) that
process wastewaters from the inorganic chemical industry
contain only inorganic contaminants, (2) that process
wastewaters from the organic chemical industry contain
only organic contaminants, and (3) that effluents from
other segments contain proportionate amounts of each
wastewater volume, the characteristics of the industry's
discharge are estimated below in Table XVI from the 1967
MCA survey, the 1963 census data, the 1969 FWPCA study
of the organic chemicals industry, and the 1967 census data,
Table XV shows the estimated numbers of plants and
wastewater discharges in the chemical industry in 1967,
based upon the above three data sources.
TABLE XV
CHEMICAL PLANT SIZES AND DISCHARGES-1967
Industry Segment
Inorganic Organic Other Total
Numbers of Plants:
Total 3454 833 3542 7829
Large (>20 mgy) 470 231 485 1186
Small (<20 mgy) 2974 602 3067 6643
Wastewater, Large Plants:
Not to Sewers (bil. gal) 248 333 148 779
Discharge to Sewers
(bil. gal). 104 78.2 39.3 221.5
65
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TABLE XVI
CHEMICAL INDUSTRY DISCHARGES-1967
Industry Segment Discharges
Inorganic Organic Other Total
Discharges to Public Sewers:
Inorganics (mil. Ibs) 989.0 - 41.0 1030
Organics (mil. Ibs) - 304.5 136.5 441
Discharges to Surface Waters:
Inorganics (mil. Ibs) 48498 - 14925 63423
Organics (mil. Ibs) - 1474 256 1730
Using the data in Tables XV and XVI and the MCA survey
data, prorating costs and manpower requirements on the
basis of wastewater discharges and relative contaminant
removals, the data in Table XVII are estimated for large
plants in the chemical industry in 1969.
TABLE XVII
CHEMICAL INDUSTRY COSTS AND MANPOWER-1969
Industry Segment
Inorganic Organic Other Total
Investment, mil. $ 122.488 399.773 110.291 632.552
Operating Costs,
mil. $/yr. 18.960 61.880 17.072 97.912
Manpower Use,
raan-years/yr. 666 2175 601 3442
Assuming, as discussed in Chapter X, that the average
plant in the industry produces wastewaters containing 100
ppm suspended solids, 1000 ppm acidity and 3000 ppm
dissolved solids, and that present practice as defined by
the MCA survey (27% removal of contaminants) is achieved
by neutralization with equalization and sludge dewatering,
the following unit costs are as shown in Chapter IX for
the typical plant. Reverse osmosis is the method of
choice for demineralization (100% removal of contaminants)
as indicated by reasonable capital and operating costs.
Deep well disposal and evaporation ponds, although lower
in cost/ are not always applicable due to local conditions
and, hence, were not shown.
66
-------
Capital Costs
% Removal Contaminants $/1000 gpd
27 (SS and Acidity)
100 (TDS)
300
2185
Operating Costs
C/1000 gal
26.0
51.5
Assume also that the capital costs involved in discharg-
ing to public sewers are those entailed in removing
suspended solids and neutralizing acidity. Therefore,
based upon the flows shown in Table X and the above
assumptions on unit capital costs, the capital costs for
the inorganic chemicals industry are estimated as shown
in Table XVIII and XIX. The capital costs for the 27%
removal level shown in 1969 thus represent the in place
capital for the existing levels of treatment in the in-
organic chemical industry in 1969 dollars.
TABLE XVIII
CUMULATIVE INORGANIC CHEMICAL INDUSTRY CAPITAL COSTS,
1969-1974
Costs in Millions of 1969 Dollars
Removal 1969
27
100
1970
1971
1972
1973
1974
314.3 329.8 352.2 377.8
1898.8 1992.4 2127.6 2281.7
405.9 435.4
2451.8 2632.4
In terms of current dollars, and using an average of 3.6%
annual increase in the price level, total industry capital
costs are projected in Table XIX.
TABLE XIX
CUMULATIVE INORGANIC CHEMICAL INDUSTRY CAPITAL COSTS,
1969-1974
Costs in Millions of Current Dollars
Removal 1969
1970
1971
1972
1973
1974
27
100
314.3 341.7 377.9 420.1 467.7 519.4
1898.8 2062.2 2281,9 2537.1 2823.5 3118.5
67
-------
It should be underscored that the capital costs shown in
Table XVIII and in Table XIX for 3.969 are in terms of
1969 dollars. The capital costs for the chemical
industry shown in Table XVII are in terms of sums spent
over perhaps the preceding 30 years. Allowing for price
increases over such a period of time, the costs shown in
Table XVII for the inorganic segment of the industry
compare well with that portion of the 1969 costs in Table
XVIII for the 27% level of treatment attributable to
large plants. Assuming that the operating costs
associated with discharges to municipal sewers at 10
cents per 1000 gpd, projected industry operating costs
are given in Table XX in 1969 dollars and in Table
XXI in current dollars.
TABLE XX
PROJECTED ANNUAL INORGANIC CHEMICAL
INDUSTRY OPERATING COSTS
Costs in Millions of 1969 Dollars
Removal 1969
27
100
86.1
165.4
1970
90.3
173.4
1971
96.5
185.1
1972
103.5
198.7
1973
111.2
213.4
1974
119.3
228.9
TABLE XXI
PROJECTED ANNUAL INORGANIC CHEMICAL
INDUSTRY OPERATING COSTS
Costs in Millions of Current Dollars
Removal 1969
27
100
86.1
165.4
1970
93.6
179.6
1971
103.5
198.7
1972
115.1
221.0
1973
128.1
245.9
1974
142.3
273.2
The plant survey data shown in Chapter VIII, based upon
costs per unit of wastewater flow, indicate that the
industry costs to achieve 85% removal of contaminants
other than dissolved solids in large plants in 1969 are
as follows:
68
-------
In place capital costs =
$223 x 1,131,520 (1000 gpd) = $252,328,960
In place operating costs =
$58.49 x 1,131,520 (1000 gpd) = $ 66,182,605/year
Addition of the costs associated with discharges to
municipal sewers by small plants show that the total
industry costs for the level of treatment described can
be estimated as follows:
In place capital costs =
259.5 million dollars
In place operating costs -
67.0 million dollars per year
The above costs would represent an overall removal of
wastewater contaminants of approximately 23%, i.e.,
85% removal of contaminants constituting 27% of the
total in the wastewaters. Comparison of these figures
with those in Tables XVIII and XX shows good agreement
and tend to support the projections made.
69
-------
CHAPTER XII
QUALITATIVE MANPOWER REQUIREMENTS
Information regarding qualitative manpower requirements
can be found in Chapter XII, pages 76-96 of the study
entitled "Inorganic Chemicals Industry Profile," which
was completed under Federal Water Pollution Control Ad-
ministration Contract No. 14-12-592 and published as a
part of "The Economics of Clean Water - Volume Three,"
United States Department of the Interior, March 1970.
70
-------
CHAPTER XIII
QUANTITATIVE MANPOWER REQUIREMENTS
Information regarding quantitative manpower requirements
can be found in Chapter XIII, pages 97-121 of the study
entitled "Inorganic Chemicals Industry Profile," which
was completed under Federal Water Pollution Control Ad-
ministration Contract No. 14-12-592 and published as a
part of "The Economics of Clean Water - Volume Three,"
United States Department of the Interior, March 1970.
71
-------
APPENDIX A
INORGANIC CHEMICAL INDUSTRY SURVEY DATA
72
-------
TABLE I
•J
u>
Plant
Number
00013
00016
00017
00018
00026
00027
00030
00033
00034
00037
00040
00042
00050
00051
00052
00053
00054
00055
00056
00057
00058
00059
00060
00061
00062
00063
00064
Critical
Pollutant
SO4
Acidity
Acidity
—
Acidity
—
ss
Cl
ss
Cl
Oil
-
Temp.
SS
SS
SS
BOO
BOD
SS
-
—
SS
BOD
-
—
BOD
Acidity
Efficiency
99
99
99.5
98
73
95
95
90
45
99.8
0
90
50
99
0
70
Capital Operating
Cost Per Cost Per
1000 GPD 1000 GPD
1736.11
2083.33
1666.67
6.92
260.41
1.06
1.29
411.37
20.83
83.33
1500.00
152.17
583.33
116.66
12.00
0.00
5.00
387.10
307.69
0.00
1.67
300.00
1.04
0.10
1.28
140.27
5.55
600.00
1.04
166.66
36.66
1.00
0.00
2.50
32.26
116.92
0.00
0.35
Capital
Cost Per
Ton/Year
2.66
3.62
57.80
1.28
2.17
22.00
1.42
4.15
1.74
8.82
1.44
0.44
87.50
7,
6,
.00
.00
0.00
10.00
0.41
0.31
0.00
0.01
Operating
Cost Per
Ton/Year
-
—
—
10.40
0.19
-
—
—
-
2.00
0.21
1.42
—
5.88
0.58
<0.01
25.00
2.20
0.50
0.00
5.00
0.03
0.12
0.00
<0.01
-
Wastewater
GPD/Ton/
Year
1.53
1.74
18.33
34.68
185.70
336.00
7.21
8.34
7.22
20736.00
166.66
10.09
83.33
105.88
0.96
2.90
150.00
60.00
500.00
40000.00
2000.00
1.07
1.00
42.42
6.48
64.11
NOTES: The following abbreviations are used:
BOD
SS
Cl
Biochemical Oxygen Demand
Suspended Solids
Chlorides
Temp.
SO4
Temperature
Sulfates
-------
APPENDIX B
INORGANIC CHEMICAL INDUSTRY
PRODUCT PROFILES
Individual Product Profiles
Flowchart of a Standard Medium-Pressure Air-Separation
Plant
Flowchart for Diaphragm Caustic Soda and Chlorine Cell
Flowchart for 60% Nitric Acid from Ammonia
Typical Flowchart for Sulfur-Burning Contact Plant
Flowchart for Smokeless Powder
Flowchart for Mixing of Paint
Flowchart for Titanium Dioxide
Sources of Data:
Chemical Profiles
Oil, Paint and Drug Reporter
"Future Inorganic Chemical Growth Patterns"
R. N. Rickles, Noyes Development
Chemical Week
Bureau of the Census
TVA
74
-------
SIC 2812 (ALKALIES AND CHLORINE)
Caustic Potash
Producer Capacity —'
Allied, Syracuse, N.Y. 30,000
Diamond, Delaware City, Del. 12,500
Diamond, Muscle Shoals, Ala. 22,000
Dow, Pittsburg, Calif. 10,000
FMC, South Charleston, W. Va. 10,000
Hooker, Niagara Falls, N.Y. 36,000
IMC, Niagara Falls, N.Y. 22,000
Monsanto, Anniston, Ala. 25,000
Monsanto, East St. Louis, 111. 29,000
Pennsalt, Calvert City, Ky. 5,000
PPG, Corpus Christi, Tex. 5,000
PPG, New Martinsvilie, W. Va. 10,000
Total 216,500
!/ 1000's of tons/year (90% basis)
Production: 1969: 180,000 tons (90% basis)
1974: 216,000 tons (90% basis)
Uses; Soaps and detergents (including use as tetra-
potassium pyrophosphate), potassium carbonate
and other potassium chemicals.
Processes: By the electrolysis of potassium chloride
Waste Problems: No major change is expected.
See chlorine.
Caustic Soda
Producer Capacity —'
Alcoa 450
Allied 1,200
Diamond 2,030
Dow 7,800
FMC 850
GAF 525
Goodrich 575
Hooker 1,780
75
-------
Caustic Soda (cont.)
Producer
Kaiser
Monsanto
Olin
Pennsalt
PPG Industries
Shell
Stauffer
Vulcan
Weyerhaeuser
Wyandotte
Others
Capacity —'
600
350
1,870
1,100
2,860
275
913
330
300
1,870
1,070
Total
26,748
JL/ tons/day
Production:
1969:
1974:
8,500,000 tons/year
11,500,000 tons/year
Uses; Chemicals, pulp and paper, aluminum, rayon,
textiles, petroleum refining, soap and detergents,
cellophane.
Processes; Caustic soda is manufactured primarily
from salt in electrolytic cells. A full discussion
is included under chlorine.
Waste Problems: See chlorine.
Chlorine
Alcoa
Allied
Diamond
Dow
DuPont
Ethyl
FMC
Frontier
GAP
Goodrich
Hooker
Producer
Capacity —'
415
1,100
1,850
7,050
180
625
765
415
475
520
1,800
76
-------
Chlorine (cont.)
Producer Capacity =/
IMC 180
Kaiser 500
Monsanto 310
Olin 1,700
Pennsalt 1,000
PPG Industries 2,600
Shell 200
Stauffer 700
Vulcan 300
Wyandotte 1,700
Other 1,300
Total 25,685
I/ tons/day
Production; 1969: 8.6 million tons/year
1974: 12.0 million tons/year
Uses; Organic chemicals, inorganic chemicals, paper
industry, cyclic intermediates, sanitation, anti-
freeze, chlorofluoro carbons, plastics.
Processes; Chlorine and caustic soda are produced
by the electrolysis of brine. As an alternative,
caustic potash may be produced by the electrolysis
of potash. Other sources of chlorine are from the
manufacture of hydrochloric acid and sodium.
Neither method is important.
Two basic methods are involved. The production is
divided between the diaphragm and mercury cells and
there is no expected change in the distribution.
In a typical diaphragm cell, the nearly saturated
brine solution at 60-70°C is fed to the anolyte
which flows through the diaphragm to the catholyte
where the caustic is formed. Chlorine is formed at
the anode.
In the mercury cell, mercury flowing along the
bottom of a steel trough forms the cathode. The
anodes are horizontal graphite plates. Brine at
290 gms/liter is fed to the cell. A sodium
amalgam is formed with the mercury at the cathode
and is decomposed external to the cell by the
addition of water. Hydrogen is produced as a by-
product of this latter action.
77
-------
FIGURE 1
BRINE
HEATER
ELECTROLYTIC
CELL -I
MULTIPLE
EVAPORATORS
CHEMICALS
BRINE
STEAM
BRINE PURIFICATION
Ca,Mg OUT
CO
*#
##
DRYING TOWER
fWET CHLORINE
BRINE
HEATER
nnnnnj
STEAM
N
:
) CH
\ nn
1
1
LORtNE
m Eft
r
L
HYDROGEN OUT
REFRIGERATION MACH.}
SOME H20 OUT
-CAUSTIC FOR
SPECIAL PURIFICATION
CRYSTALLIZER
'CENTRIFUGAL
FILTER
WASH
SALT TO
BR INE
LIQUEFIED
CHLORINE
SALT OUT
FINAL EVAPORATION
WEAK
CAUSTIC
STORAGE
CAUSTIC NOT SPECIALLY
PURIFIED
LIQUID
CAUSTIC
SALES
DRUMS FLAKES
FOR SALE
FLOWCHART FOR DIAPHRAGM CAUSTIC SODA AND CHLORINE CELL
This flow chart is selectively reproduced in content and configuration from Figure 13.7
in the book by R. Norn's Shreve, Chemical Process Industries, Third Edition, New
York, Me Grow - Hill Book Company, 1967, p. 236
-------
Brine purification is necessary to produce a high
grade caustic in the diaphragm process. Calcium,
iron magnesium and sulfate ions are precipitated.
In the diaphragm process, the cell liquor, contain-
ing 50% of the sodium chloride, is concentrated.
The salt precipitates and is reused following wash-
ing. Special purification of the caustic may be
necessary and this usually produces considerable
sludge.
It is necessary to dry the chlorine, and this is
accomplished by contact with a concentrated
sulfuric stream.
The mercury cell produces, without all of the major
purification problems, a high purity caustic and
chlorine. This eliminates the major waste problems
except those arising from chlorine drying.
No significant change is expected in this process.
Waste Problems; The waste problem common to both
systems is the waste sulfuric acid stream which
amounts to about 1,000,000 gpd/100 tons/day of
chlorine. Such a stream (1,000,000 gpd) would
contain about 2000 pounds of sulfuric acid and 200
pounds of chlorine. Regeneration of this stream
is quite possible by evaporation and steam
stripping of the chlorine. This would permit use
of the chlorine for sterilization purposes.
Other wastes arise from the discharge of waste
brine as a slipstream. This may amount to 1-5%
of total brine throughput. Improved brine puri-
fication techniques could reduce these practices.
The waste brine could be utilized in a small
mercury cell to produce chlorine or for the
regeneration of ion exchange systems. The waste
brine from a mercury cell contains some mercury
which requires physical separation for removal.
Economics usually justifies removal.
The sludges collected from the purification of
brine also create a problem, and current techniques
involve land disposal or discharge to a water
body. No major processing changes are anticipated.
79
-------
Soda Ash
Producer Capacity I
Allied, Baton Rouge, La. (S) 785,000
Allied, Green River, Wyo. (N) 550,000
Allied, Syracuse, N.Y. (S) 1,000,000
American Potash, Trona, Calif. (N) 160,000
Diamond Shamrock, Painesville, O. (S) 800,000
Dow, Freeport, Tex. (S) 75,000
FMC, Green River, Wyo. (N) 1,250,000
Olin, Lake Charles, La. (S) 3,750,000
Olin, Saltville, Va. (S) 400,000
PPG, Barberton, O. (S) 600,000
PPG, Corpus Christi, Tex. (S) 240,000
Stauffer, Green River, Wyo. (N) 800,000
Stauffer, Westend, Calif. (N) 160,000
Wyandotte, Wyandotte, Mich. (S) 800,000
Total 7,995,000
V tons/year (S) synthetic; (N) natural
Production; 1969: 7,000,000 tons
1974: 9,000,000 tons
Uses; Glass, chemicals, pulp and paper/ soap and
detergents, aluminum, water treatment.
Processes: About 30% of the current production of
soda ash is obtained naturally through the mining
of trona (sodium sesquicarbonate). Some amount is
recovered through the calcination of natural
alkali brines in California. Neither technique
produces significant quantities of waste. The
mining operation does produce the usual solid waste
problems and any brine operation produces a waste
brine solution. The location of these areas makes
their impact upon the environment relatively
insignificant.
The Solvay process uses brine, limestone and coke
or gas as the raw material. Brine is purified as
previously noted (see chlorine). Ammonia is
dissolved in the purified brine and this solution
is carbonated with carbon dioxide produce by the
80
-------
decarbonation of limestone by calcining the stone
mixed with coke. This produces a moist sodium
bicarbonate which is calcined to soda ash. The
ammonia is recovered from the filtrate (sodium
bicarbonate unit) by addition of quick lime to the
system. The ammonia and carbon dioxide are
recovered and recycled.
The recovery of ammonia produces a waste stream
(1-2000 gals/ton) which contains ammonia (2-4 kgms
of (NH4)2 804 per ton of 58% soda ash) and sub-
stantial amounts of calcium chloride (0.3 tons/ton
of 58% Na2) and some calcium sulfate and calcium
carbonate. While some calcium chloride is
recovered by distillation, this practice is not
sufficiently prevalent to prevent it from being a
major pollution problem.
Since calcination involves dust control, there is
the likelihood of a discharge containing a large
concentration of suspended solids from a scrubber
or where water is used for conveying fly ash.
It is expected that more natural soda ash will be
utilized, but no major changes in the manufacture
of soda ash by the Solvay process are anticipated.
81
-------
SIC 2813 (INDUSTRIAL GASES, EXCEPT FOR ORGANIC GASES)
Nitrogen
Producers; The number of nitrogen and oxygen produc-
ing plants is quite large and capacities of either
individual plants or companies are not available.
These plan to be generally located in areas of high
user demand.
Major producers are:
Air Products and Chemicals - 20% of market
Airco - 20% of market
Big Three Industrial Gas
Burdett Oxygen
Chemetron - National Cylinder Gas
Union Carbide - Linde Division - 40% of market
Production; 1969: 130,000 million cubic feet
1974: 370,000 million cubic feet
Uses: Chemical and drug production, steel and metal
production, electronics, aerospace, cryogenics.
Processes; Both oxygen and nitrogen are produced
primarily through the medium pressure liquification
and rectification of air. The process can produce
a variety of products including high purity oxygen
and nitrogen and low purity oxygen. The process
naturally has many variations, but it is expected
that there will be no substantial changes in the
method of production.
Waste Problems; The major problem associated with
this process is related to the discharge, with the
cooling waters, of waste compressor oils. The
quantity of such oils may vary greatly from plant
to plant depending on compressor type, size, and
age. In-plant control is not only possible, but
feasible. This is best done by skimming in the
sumps.
Oxygen
Producers; See nitrogen.
82
-------
NITROGEN
CO
u»
OXYGEN
WASTE
COMPRESSOR
DRIER
C02 SCRUBBER
FIGURE
EXCHANGERS
SUBCOOLER
EXPANDER
^LOW-PRESSURE
^COLUMN
^VAPORIZER
FILTERS^
AUXILIARY
VAPORIZER
HIGH
PRESSURE
COLUMN
OXYGEN
SEPARATOR
FLOWCHART OF A STANDARD MEDIUM-PRESSURE AIR-SEPARATION PLANT
This flow chart is selectively reproduced in content and configuration from Figure 7.7 in
the book by R. Norris Shreve, Chemical Process Industries, Third Edition, New York,
Me Grow - Hill Book Company, 1967, p. 109
-------
Production; High Purity (99.5-100%)
1969: 260,000 million cubic feet
1974: 520,000 million cubic feet
Low Purity
1969: 1,900,000 tons
1974: 3,800,000 tons
Uses_: Chemical production, steel production, medi-
cal.
Processes; See nitrogen.
Waste Problems; See nitrogen.
84
-------
SIC 2816 (INORGANIC PIGMENTS)
Barites
Producers; Produced by:
Chemical Products Corporation, Cartersville, Ga.
Chicago Copper and Chemical Corporation, Blue
Island, 111.
The Great Western Sugar Corporation, Johnstown,
Colo.
Holland-Suco Color Corporation, Huntington, W. Va.
FMC, Modesto, Calif.
Mallinckrodt Chemical, St. Louis, Mo.
Ozark Smelting and Mining, Coffeyville, Kan.
PPG, New Martinsville, W. Va.
Capacities are not available.
Production; 1969: 950,000 tons
1974: 1,300,000 tons
Uses; White pigment.
Processes; Barites is recovered as a mineral which
may be converted to a soluble salt, such as the
chloride or the sulfide, by thermal reduction. The
sulfate is then produced by the addition of a
sulfate such as sodium sulfate. The resulting
filtrate is a solution of the resulting chloride
(usually sodium) on an equivalent mole basis.
Thus, the discharge will be a brine solution. No
major process change may be expected in the near
future and no process improvement is considered
likely.
Calcium Carbonate
Producers; Produced by:
Allied, Baton Rouge, La.
Allied, Green River, Wyo.
Allied, Syracuse, N.Y.
American Potash, Trona, Calif.
Diamond Shamrock, Painesville, 0.
Dow, Freeport, Tex.
FMC, Green ftiver, Wyo.
85
-------
Olin, Lake Charles, La.
Olin, Saltville, Va.
PPG, Barberton, 0.
PPG, Corpus Christi, Tex.
Stauffer, Green River, Wyo.
Stauffer, Westend, Calif.
Wyandotte, Wyandotte, Mich.
Capacities are not available.
Production; 1969: 180,000 tons (estimated)
1974: 240,000 tons
Uses; Pigment, filler, neutralization, soaps, abra-
sives, agriculture.
Processes; Whiting is used as a filler and pigment.
It is prepared by wet grinding and levigating
natural chalk. This process produces a waste which
contains large amounts of suspended solids.
Artificial whiting arises through the reaction of
calcium chloride with sodium carbonate forming a
milk of lime suspension. The filtrate from this
suspension is high in suspended solids. Use of
polyelectrolytes will increase recovery of this
product.
Iron Oxide Pigments
Producers; Not available
Production;
1969: Natural Brown Iron Oxides
Umbers
Red Iron Oxides
Sienna
Yellow Ocher
Sienna
Subtotal
Manufactured Black
Brown
Red
Yellow
Subtotal
Total
13,000 tons
5,000 tons
35,000 tons
1,000 tons
5,000 tons
1,000 tons
60,000 tons
4,000 tons
5,000 tons
32,000 tons
24,000 tons
65,000 tons
125,000 tons
86
-------
1974: 160,000 tons
Processes and Waste Problems; These products are made
in dry thermal processes or are produced from natural
clays, etc. Therefore, except for waste slurries
and equipment washouts, no serious waste problems
exist. The discharge of highly colored turbid solu-
tions from clay-mining sites is most serious
locally.
Titanium Dioxide
Producer
American Potash, Hamilton, Miss. (C)
Cabot, Ashtabula, O. (C)
Cyanamid, Piney River, Va. (S)
Cyanamid, Savannah, Ga. (C,S)
DuPont, Antioch, Calif. (C)
DuPont, Baltimore, Md. (S)
DuPont, Edge Moor1, Del. (C,S)
DuPont, New Johnsonville, Tenn. (C)
Glidden, Baltimore, Md. (S)
National Lead, Sayreville, N. J. (C,S)
National Lead, St. Louis, Mo. (S)
New Jersey Zinc, Gloucester City,
N. J. (S)
PPG, Natrium, W. Va. (C)
S. Williams
Total
Capacity —
30,000
20,000
18,000
92,000
27,000
40,000
100,000
68,000
56,000
173,000
108,000
46,000
18,000
25,000
821,000
I/ tons/year (C) chloride process; (S) sulfate process
Production:
1969: 650,000 tons
1974: 800,000 tons
Uses; Varnish and lacquer, paint, floor coverings,
rubber, coated fabrics, printing ink.
Processes; Titanium dioxide is produced by either of
two processes. The older process is the digestion
of ilraenite ore in sulfuric acid. The heat of the
reaction evaporates the water. Water is added
dissolving the titanium and iron sulfates. The
ferric ions are reduced with scrap and the solution
is clarified. Fifty percent of the iron is re-
87
-------
FIGURE 3
oo
00
GROUND
ILMENITE
ORE
STRONG
H2S04
HYDR
PREC
i
2 THICKENERS-
WAT CD
*
0) DIGE
(2)DISS
(3) RED!
«
*"" 1 'J//'*J
>^ 1
1
rmi
STEAM
RESIDUE
TO
POSSIBLE
RECOVERY
EVAPORATOR
CRYSTALLIZER
| ^CENTRIFUGAL
FERROUS
SULFATE
SEPTAHYDRATE
6
s
X
1 1
i
/-
FILTRATE
TO H2S04
AND FeS04
RECOVERY
TITANIUM'
HYDRATE
WATER
fl
TO STACK OR PRECIPITATOR
OIL-FIRED KILN
DISPERSING
AGENTS
{WATER
•i'
HYDRO-
SEPARATOR'
•• 1 A 1
I fJfJffJ/fffl/'Fff{ftf**ftffff
REPULPER
REAGENT
FOR pH
CONTROL
CLARIFYING FILTER
FILTRATE TO |
SETTLING
FOR Ti02
RECOVERY
STEAM ROTARY
DRYER^
AIR SEPARATION
PULVERIZER
FLOWCHART FOR TITANIUM DIOXIDE
This flow chart is selectively reproduced in content and configuration from Figure 24-9
in the book by R. Norris Shreve, Chemical Process Industries, Third Edition, New York,
Me Grow-Hill Book Company, 1967, p. 438
-------
FIGURE 4
oo
TINTING
a
THINNING
TANK
PLATFORM
SCALE
LABELING
MACHINE
FILLING, p MACHINE
Jini
(T
nnnnnn
1
BELT CONVEYOR
t
CARTON
PACKAGING * -NIPPING
GRINDING MILLS
FLOWCHART FOR MIXING OF PAINT
This flow chort is selectively reproduced in content and configuration from Figure 24.1 in
the book by R. Norn's Shreve, Chemical Process /ne'ui.-trfes, Third Edition, New York,
Me Grow-Hill Book Company, 1967, p. 428
-------
moved by crystallization of ferrous sulfate. The
titanyl sulfate is hydrolyzed and crystallized and
filtered and washed.
The newer chloride process involves the oxidation
in a flame of titanium chloride produced by the
chlorination, in the presence of coke of rutile
ore or slag. Chlorine is recovered. The chloride
process is expected to become the more standard
one if supplies of rutile and slag hold out.
Waste Problems: The sulfate process generates
considerable quantities of wastewater effluents.
The principal sources are the wash waters from
the washing of the titania and the overflow from
the thickeners earlier in the process. Both steps
are necessary but it seems likely that some
reuse of the wash waters can be provided for.
Zinc Oxide
Producers; Major producers are:
American Zinc
Eagle Picher
New Jersey Zinc
St. Joseph Lead
Capacities are not available.
Production; 1969: 195,000 tons
1974: 220,000 tons
Processes; The American process produces zinc oxide
directly from ore franklinite. The ore is mixed
with coal and heated. The zinc oxide is reduced
to zinc which is then oxidized to zinc oxide in
cyclones and bag filters without wet wastes.
The French process involves the vaporization of zinc
in a retort with indirect heat and carbon monoxide
gas. The zinc and carbon monoxide are oxidized to
carbon dioxide and zinc oxide. The process is dry.
The Electrothermic process is similar to the
American process except that the furnace is
electrically heated.
90
-------
Aluminum Sulfate
Producers; Allied
American Cyanamid
DuPont
Essex
Monsanto
Olin
Stauffer
Production; 1969: 1,090,107 tons
1974: 1,250,000 tons
Uses: Water treatment, paper sizing, dye industry.
Production; Aluminum sulfate, while commonly called
alum, Is" not a true alum. True alums are a double
sulfate of aluminum or chromium and a monovalent
metal or radical.
Aluminum sulfate is made by the reaction of 60 Be1
sulfuric acid with bauxite following grinding.
The liquor is treated by the addition of barium
sulfide to remove iron and is then clarified and
solidified. Production means are not likely to
change in the near future.
Waste Problems; The major wastes are slurries of
solids collected in the thickener decanters.
These solids can easily be collected and con-
trolled. No major change in the amount of wastes
is expected.
91
-------
Ammonium Nitrate
AMMONIUM NITRATE PLANTS
UNITED STATES
Company
Agway, Inc.
Allied Chemical Corp.
American Cyanamid Co,
Apache Powder Co.
Arkla Chemical
Armour Agricultural
Chemical Company
Calumet Nitrogen Co.
Carolina Nitrogen Co.
Central Nitrogen Co.
Cherokee Nitrogen Co.
Chevron Chemical Co.
Columbia Nitrogen Co.
Cominco American, Inc.
Commercial Solvents
Corporation
Escambia Chemical
Corporation
Farmers Chemical
Association
Farmland Industries
Fel-Tex, Inc.
Gulf Oil Corp.
Hawkeye Chemical Co.
Hercules, Inc.
Location
Olean, N.Y.
Geismar, La.
Hopewell, Va.
Omaha, Nebr.
South Point, O.
Hannibal, Mo.
Benson, Ariz.
Helena, Ark.
Cherokee, Ala.
Crystal City, Mo.
Hammond, Ind.
Wilmington, N.C.
Terre Haute, Ind.
Pryor, Okla.
Fort Madison, Iowa
Kennewick, Wash.
Richmond, Calif.
Augusta, Ga.
Beatrice, Nebr.
Marion, 111.
Sterlington, La.
Pace, Fla.
Tyner, Tenn.
Lawrence, Kans.
Fremont, Nebr.
Henderson, Ky.
Pittsburg, Kans.
Vicksburg, Miss.
Clinton, Iowa
Donora, Pa.
Hercules, Calif.
Louisiana, Mo.
Capacity-
1966
(thousand
tons)
105
385
400
98
235
140
30
150
128
111
55
161
134
45
70
61
55
208
200
148
100
180
208
34
105
360
43
153
• • •
140
425
92
-------
Ammonium Nitrate (cont.)
Company
Location
Illinois Nitrogen, Inc.
Kaiser Chemical Co.
Ketona Chemical Corp,
Mississippi Chemical
Corporation
Mobil Chemical Co.
Monsanto Co.
Nipak, Inc.
Nitram, Inc.
Nitrin, Inc.
Northern Chemical
Industries
Olin Mathieson
Chemical Co.
Phillips Chemical Co.
St. Paul Ammonia Corp.
Smith Chemical Co.
Solar Nitrogen
Chemicals Co.
Terra Chemicals
International
Texaco, Inc.
Union Oil of Calif.
U.S. industrial
Chemicals Co.
U.S. Steel Corp.
Valley Nitrogen
Producers
Wycon Chemical Co.
Marseilles, 111.
Bainbridge, Ga.
North Bend, Ohio
Savannah, Ga.
Tampa, Fla.
Ketona, Ala.
Yazoo City, Miss.
Beaumont, Tex.
El Dorado, Ark.
Luling, La.
Kerens, Tex.
Tampa, Fla.
Cordova, 111.
Searsport, Maine
E. Alton, 111.
Beatrice, Nebr.
Etter, Tex.
Kennewi ck, Wash.
Pine Bend, Minn.
Douglas, Ga.
Joplin, Mo.
Lima, Ohio
Port Neal, Iowa
Lockport, 111.
Brea, Calif.
Tuscola, 111.
Geneva, Utah
El Centro, Calif.
Helm, Calif.
Cheyenne, Wyo.
Total
Capacity-
1966
(thousand
tons)
132
50
95
198
54
39
296
200
280
290
56
140
110
25
50
11
240
20
88
110
75
145
95
60
88
90
88
35
37
7,874
Source: TVA
93
-------
AMMONIUM NITRATE PLANT LOCATIONS
FIGURE 5
VD
A NEW PLANT
-------
Production; 1969: 5,200,000 tons
1974: 6,300,000 tons
Uses_: Fertilizer, explosives.
Processes; While some ammonium nitrate is manu-
factured by the old batch method, the vast
majority is manufactured by one of a variety of
continuous processes. All processes involve
the direct contact of preheated ammonia and
nitric acid, separation of the gaseous water,
and prilling or flaking by melting. While
various modifications are continuously being
brought into use, no basic changes are expected.
Waste Problems; Washdown produces substantial
amounts of nitrogen rich wastewaters. Additional
amounts are associated with scrubber blowdowns
and from cooling water. Improved plant mainten-
ance would assist in controlling this problem.
Ammonium Sulfate
Producers; A detailed list is not available because
of the large number of by-product producers, but
producers include:
Alabama By-Products Interlake Steel
Allied Chemical Olin
American Cyanamid Phillips
Bethlehem Steel Shell
C. F. & I Steel Simplot
Chevron Sinclair
Columbia Nitrogen Sunray
DuPont U. S. Pipe
Graver U. S. Steel
Inland Steel
Production; 1969; 2,715,000 tons
1974; 3,000,000 tons
Uses: Fertilizer
95
-------
Processes; About 35% of the production is associated
with the direct reaction of ammonium salts such as
the carbonate with sulfuric acid. Some is made by
the use of gypsum in place of the sulfuric acid.
Major discharges involve solid slurries of by-
product materials.
Major amounts of ammonium sulfate are made during
the recovery of ammonia from coke oven gas. About
40% of the total production is involved with the
actual recovery of by-product ammonia from a
variety of other processes. A plant in California
is being built based on the reaction of gypsum and
ammonia. To summarize, most of the ammonium sul-
fate produced in this country is a result of
attempts to control atmospheric pollution. No
change in production pattern is expected to occur.
Waste Problems; As indicated above, no major waste
problem exists.
Calcium Carbide
Producer Capacity —
Airco, Calvert City, Ky. 300,000
Airco, Keokuk, Iowa 36,000
Airco, Louisville, Ky. 150,000
Midwest Carbide, Keokuk, Iowa 50,000
Midwest Carbide, Pryor, Okla. 30,000
Pacific Carbide, Portland, Ore. 20,000
Union Carbide, Ashtabula, Ohio 228,000
Union Carbide, Niagara Falls, N. Y. 210,000
Union Carbide, Portland, Ore. 32,000
Union Carbide, Sheffield, Ala. 60,000
Total 1,116,000
I/ tons/year
Production; 1969; 920,000 tons
1974: 900,000 tons
Uses; Production of acetylene.
Processes; Calcium carbide is prepared from quicklime
and carbon (usually coke, petroleum coke or anthra-
96
-------
cite) at 2000-2200°C in a furnace related to the
familiar arc furnace. No major process change is
expected but the use of carbide-based acetylene is
expected to be reduced in the future.
Waste Problems; Since the process is not a wet
process, the only major discharges are associated
with wastewaters used to scrub furnace and kiln
effluents.
Hydrochloric Acid
Producers; Most HC1 is produced as a by-product from
the production of carbon tetrachloride and other
chlorinated hydrocarbons, PVC, ethylene oxide, and
phenol. (See "Projected Wastewater Treatment Costs
in the Organic Chemicals Industry," Department of
the Interior.) Major producers of anhydrous HC1
are:
Detrex Morton
Diamond Shamrock Shell
Dow Stauffer
Hooker Vulcan
Montrose
Major producers of aqueous HC1 are:
Allied Hooker Pennsalt
Arkla Mobay PCA
Baker Monsanto Reichhold
Cabot Mont Shell
Detrex Morton Stauffer
Diamond Shamrock Olin Velsicol
Dow PPG Vulcan
DuPont Pearsall Wyandotte
GAF
Production: 1969: 1,800,000 tons
1974: 2,200,000 tons
Uses: Oil well activation, chemical production, steel
pickling, monosodium glutamate and starch hydrolysis,
metal cleaning.
97
-------
Processes: The major portion of HC1 currently produced
(85%) is a by-product of the chlorination of hydro-
carbons. However, it is expected that the amount of
by-product HC1 available will be greatly decreased
in the future for several reasons. These include:
1. The practice of oxychlorination is increasing
rapidly and this, in a balanced system, can
eliminate the presence of waste HC1.
2. Most vinyl chloride plants employ oxychlorina-
tion and do not produce major amounts of waste
acid.
3. A new process, based on a modification of the
old Deacon process, as developed by Kellogg,
is expected to produce large amounts of chlorine
(note impact on chlorine under #2812) and con-
sume substantial amounts of by-product acid.
There are sufficient amounts of waste acids avail-
able so that the short term supply will not be a
problem.
Three other sources of supply are as follows:
1. Direct burning of chlorine in a small excess of
hydrogen. This is followed by the adsorption
of HC1 in water, followed by stripping to pro-
duce a high purity HC1.
2. The reaction of salt and sulfuric acid in a
high temperature furnace. Sodium sulfate is
formed as a by-product. Adsorption of the acid
in water takes place with removal of salt and
acid in a coke tower.
3. A Hargreaves-type operation which involves the
reaction of salt, sulfur dioxide, oxygen and
water to form sodium sulfate and acid. (This
process is used by only one plant.)
Waste Problems; In the salt acid reaction, the wash-
ing out of the coke tower produces a waste stream
of acid and salt. Improved furnace design would
cut down on the amount of carryover.
98
-------
In the salt-acid process, as in the Hargreaves
reaction/ a stream of weak sulfuric amounting to
50-90 Ibs/ton 20° Be1 hydrochloric acid is pro-
duced.
Weak hydrochloric acid is also wasted from the
system.
Hydrofluoric Acid
Producer Capacity I/
Alcoa, Point Comfort, Tex. 25,000
Allied, Baton Rouge, La. 15,000
Allied, Geismar, La. 15,000
Allied, Nitro, W. Va. 20,000
Allied, North Claymont, Del. 25,000
Allied, Port Chicago, Calif. 12,000
DuPont, Deepwater Point, N. J. 15,000
DuPont, Strang, Tex. 50,000
Essex, Paulsboro, N. J. 11,000
Harshaw, Cleveland, Ohio 10,000
Kaiser, Gramercy, La. 15,000
Olin, Joliet, 111. 12,000
Pennsalt, Calvert City, Ky. 18,000
Reynolds, Bauxite, Ark. 40,000
Stauffer, Houston, Tex. 18,000
Total 301,000
I/ tons/year
Production; 1969: 310,000 tons
1974: 420,000 tons
Uses; Fluorocarbons, aluminum, petroleum alkylation,
stainless steel pickling, AEC work.
Processes; HF is prepared by heating, in kilns, the
ore-fluorspar (CaF2) with sulfuric acid. The
gaseous HF is either absorbed in water or liquified,
employing refrigeration to obtain the anhydrous
product.
Waste Problems: Not significant except in washout
where fluoride concentrations can be a serious prob-
lem.
99
-------
Hydrogen Peroxide
Producer Capacity —'
Allied, Syracuse, N. Y. 4,000
DuPont, Memphis, Tenn. 25,000
FMC, Buffalo, N. Y. 6,000
FMC, South Charleston, W. Va. 8,000
FMC, Vancouver, Wash. 6,000
Pennsalt, Wyandotte, Mich. 1,750
Pittsburgh Plate, Barberton, Ohio 3,750
Shell, Norco, La. 17,000
Total 71,500
I/ tons/year
Production; 1969: 70,000 tons
1974: 100,000 tons
Uses; Textiles, paper and pulp, plasticizers, chemi-
cals .
Processes: Hydrogen peroxide is manufactured by one
electrolytic and two organic oxidation processes.
Sulfuric acid is electrolyzed to peracid (H2S2O8)
which hydrolyzes to sulfuric acid and peroxide.
The organic processes center on 2-ethylanthraquinone
which is oxidized to produce peroxide and recycle-
able quinone and isopropyl alcohol. The latter are
oxidized at modest temperatures and pressures to
peroxide and acetone.
Waste Problems; The electrolytic process produces a
stream of dilute sulfuric acid. The organic based
processes will probably produce a waste stream from
the distillation column.
Lime
Producers: There are some 210 lime producing plants
located wherever there are significant limestone
deposits. This list is too exhaustive for display
here. Refer to "Minerals Yearbook," U. S. Bureau
of Mines, for a complete listing.
100
-------
Production; 1969:
1974:
Quicklime - 14,000,000 tons
Hydrated - 3,000,000 tons
Total - 19,000,000 tons
Uses; Agriculture, chemical manufacture, pulp manu-
facture, tanning, steel and cement manufacture,
water treatment, soap manufacturing, construction.
Processes: Thermal decarbonation of limestone or
calcium carbonate sludge usually in a shaft kiln
or a rotary kiln but also in a fluidized bed kiln.
Waste Problems; These generally arise if solids cap-
ture is by wet scrubbing. Conversion to a dry
capture system such as bag filters would eliminate
the problem.
Nitric Acid
Producers:
Company
Agway
Allied
American Cyanamid
Ark la
Armour
Atlas
Celanese
Central Farmers
Central Nitrogen
Plant Location
Clean, N.Y.
Buffalo, N.Y.
Geismar, La.
Hopewell, Va.
La Platte, Nebr.
Newell, Pa.
South Point, O.
Bound Brook, N.J.
Hannibal, Mo.
Willow Island, W. Va,
Helena, Ark.
Cherokee, Ala.
Crystal City, Mo.
Joplin, Mo.
Tamaqua, Pa.
Bay City, Tex.
Fremont, Nebr.
Terre Haute, Ind.
Estimated capacity
C68) (1,000 tons/
year)
Plant
60
25
200
250
90
60
240
25
110
27
90
110
100
122
24
77
31
133
Co. Total
60
865
162
90
210
146
77
31
133
101
-------
Nitric Acid (cont.)
Company
Plant Location
Cherokee
Chevron
Collier
Columbia Nitrogen
Cominco
Commercial Sol-
vents
Cooperative Farm
Chems.
DuPont
El Paso
Escambia
Farmers' Chemical
Grace
Gulf
Hawkeye
Hercules
Estimated capacity
('68) (1,000 tons/
year)
PlantCo. Total
Prior, Okla.
Ft. Madison, La,
Kennewick, Wash,
Richmond, Calif.
Brea, Calif.
Augusta, Ga.
Beatrice, Nebr.
Marion, 111.
Sterlington, La.
Lawrence, Kans.
Barksdale, Wis.
Belle, W. Va.
Birmingham, Ala.
DuPont, Wash.
Gibbstown, N.J.
Louviers, Colo.
Old Hickory, Tenn,
Orange, Tex.
Victoria, Tex.
Seneca, 111.
Wabash, Ind.
Odessa, Tex.
Pensacola, Fla.
Tyner, Tenn.
WiImington, N. C.
Henderson, Ky.
Pittsburg, Kans.
Vicksburg, Miss.
Clinton, La.
Bessemer, Ala.
Hercules, Cali f.
Kenvil, N.J.
Louisiana, Mo.
Parling, N.J.
Donora, Pa.
Illinois Nitrogen Marseilles, 111.
65
94
130
85
47
162
135
50
163
485
20
82
20
20
350
15
44
180
120
215
150
63
90
170
164
85
281
85
125
20
65
16
400
53
120
120
65
309
47
162
135
213
485
1,216
63
90
170
164
451
125
674
120
102
-------
FIGURE 6
STEAM
AMMONIA
ABSORPTION
COLUMN
AIR
INTAKE
FILTER
O
OJ
CONDENSED STEAM
MAKE UP WATER
ABS. COL.
FEED TANK
VAPORIZER
•^
AMMONIA
SOLENOID
VALVEv
ABS. COL.
FEED PUMP
COOLING
WATER
MIST
SEPARATOR
GAS
, ,MIXER
COOLING
COOLER
CONDENSER
'AMMONIA
IFEEDER
i
PLATINUM
FILTER
WASTE
HEAT
BOILER
•IRQ r
COOLING
WATER
HNOS TO
STORAGE
COMPRESSOR I
(ELECTRIC MOTOR)!
EXPANDER
COOLING WATER
RETURN PUMP
BLEACHING AIR
SOLENOID VALVE
'TERMINAL BOX
FLOWCHART FOR 60% NITRIC ACID FROM AMMONIA
This flow chart is selectively reproduced in content and configuration from Figure 16.9
in the book by R. Norris Shreve, Chemical Process Industries, Third Edition, New
York, Me Grow-Hill Book Company, 1967, p. 3IS
-------
Nitric Acid (cont.)
Company
Kaiser
Ketona
Miscoa
Mob ay
Mobil
Monsanto
Nipak
Nitram
Nitrin
Northern Chemi-
cal Industries
Olin Mathieson
Phillips Chemical
St. Paul Ammonia
Plant Location
Bainbridge, Ga.
North Bend, 0.
Savannah, Ga.
Tampa, Fla.
Ketona, Ala.
Yazoo City, Miss.
New Martinsville,
W. Va.
Beaumont, Tex.
El Dorado, Ark.
Luling, La.
Pensacola, Fla.
Kerens, Tex.
Tampa, Fla.
Cordova, 111.
Searsport, Maine
Lake Charles, La.
Kennewi ck, Wash.
Beatri ce, Nebr.
Etter, Tex.
Pasadena, Tex.
Pine Bend, Minn.
Estimated capacity
{'68) (1,000 tons/
year)
Plant Co. Total
47
84
162
42
36
388
50
154
275
270
258
50
120
95
25
95
43
9
164
13
100
335
36
388
50
154
803
50
120
95
25
95
100
Production:
1969: 6,140,000 tons
1974: 7,000,000 tons
Uses: Fertilizers, chemicals, photoengravings,
explosives.
Processes; Nitric acid is produced by the catalytic
air oxidation of ammonia. Nitric oxide is absorbed
in water and oxidized. Higher strength nitric acid
is produced by breaking the azeotrope with either
sulfuric acid or magnesium nitrate. No significant
changes are expected in the production of nitric
acid.
104
-------
Waste Problems: Major problems are associated with
cooling water blowdown and area washdown which may
contain troublesome amounts of nitric acid.
•Phosphoric Acid
Producers
Location
Allied Chemical
American Agricul-
tural Chem.
American Cyanamid
American Potash
Arkla Chemical
Armour Agricul-
tural
Borden
Bunker Hill
Central Phos-
phates
Coastal Chemical
Consumers Co^
operative
Des Plaines
Chemical
El Paso Natural
Gas
Farmers Chemical
Freeport Sulfur
W. R. Grace
National Phos-
phate
IMC
New Jersey Zinc
Nipak
NW Cooperative
Mills
E. St. Louis, 111
N. Claymont, Del.
Geismar, La.
Pierce, La.
Brewster, Fla.
Trona, Calif.
Helena, Ark.
Bartow, Fla.
Ft. Meade, Fla.
Piney Point, Fla.
Streator, 111.
Texas City, Tex.
Kellogg, Ida.
Plant City, Fla.
Pascagoula, Miss.
Pierce, Fla.
Morris, 111.
Conda, Ida.
Joplin, Mo.
Uncle Sam, La.
Bartow, Fla.
Joplin, Mo.
Taft, La.
Marseilles, 111.
Bonnie, Fla.
Depue, 111.
Tulsa, Okla.
Pine Bend, Minn.
Capacity (tons
100% P205/yr)
36,200
36,200
159,300
216,000
148,800
Not Available
50,000
85,000
188,000
165,000
24,000
60,000
24,500
200,000
175,900
200,000
50,000
100,000
55,000
540,000
415,000
35,000
207,000
103,500
500,000
150,000
21,000
32,000
105
-------
Phosphoric Acid (cont._)
Producers
Location
Occidental
Petroleum
Best Fertilizer
Olin Mathieson
Phosphate Chemi-
cals
F. S. Royster
Guano
J. R. Simplot
Mobil Chemical
Western Phos-
phates
Swift
Tennessee Corp.
TGS
U.S. Industrial
Chemicals
Valley Nitrogen
Western States
Chem.
Hamilton Co., Fla.
Lathrop, Calif.
Joliet, 111.
Pasadena, Tex.
Pasadena, Tex.
Mulberry, Fla.
Pocatello, Ida.
Nichols, Fla.
Garfield, Utah
Agricola, Fla.
E. Tampa, Fla.
Aurora, N. C.
Tuscola, 111.
Helm, Calif.
Capacity (tons
100% P205/yr)
207,000
17,300
127,000
217,500
50,000
130,000
265,000
125,000
70,000
126,300
490,000
347,000
40,000
50,000
Point Chicago, Calif. 90,000
Total 5,807,500
1969: 4,926,000 tons (100% P205)
1974: 5,900,000 tons (100%
Production:
Uses: Fertilizer, detergents, food.
Processes: Phosphoric acid is produced by two methods.
One method involves the hydrolysis of phosphorous and
will be discussed under phosphorous. The most common
approach is responsible for some 80% of the total
production; this is from the acidulation of phosphate
rock. Usually the acidulation involves the use of
sulfuric acid. The acid is concentrated while the
by-product, gypsum, is filtered and washed.
106
-------
PHOSPHORIC ACID PLANT LOCATIONS
FIGURE 7
FURNACE PHOSPHORIC ACID
WET PROCESS PHOSPHORIC ACID
NEW WET PROCESS PHOSPHORIC ACID PLANT
-------
Alternative routes involve the use of nitric or
hydrochloric in place of sulfuric. This approach
is not likely to make any impact on acid production
The swing towards production of a more usable by-
product in the form of the hemihydrate will have a
major impact upon waste treatment. On the other
hand, increasing pressure relative to air pollution
will increase the removal of fluorides and thereby
increase waste streams.
Wajste Problems; Waste arises from at least four
sources in the process. The primary source is the
waste gypsum from the acidulation. This semi-solid
waste may contain quantities of phosphoric and
sulfuric acid. The development of techniques for
utilizing the waste product should greatly reduce
the magnitude of the problem.
The second source is the water from the scrubbers
which contain large amounts of acid fluorides.
By-product use would appear to be the answer here,
as well. Increasing amounts are utilized as a
source for fluoride chemicals.
This third waste source is the sludge of aluminum
and iron phosphate sludge produced by the post
precipitation of the acid. This may amount to
1-5% of production.
A fourth source involves the tailings from the rock
beneficiation. No change in these waste sources is
anticipated.
Phosphorus
Capacity
Producers Location (tons/year)
Continental Oil Pierce, Fla. 30,000
El Paso, George-
town, Ida. 21,000
FMC Pocatello, Idaho 142,000
Hooker Columbia, Tenn. 68,500
Mobil (V-C) Charleston, S. C. 10,000
Mobil (V-C) Mt. Pleasant, Tenn. 20,000
Mobil (V-C) Nichols, Fla. 6,000
108
-------
Phosphorus (cont.)
Capacity
Producers Location (tons/year)
Monsanto Columbia, Tenn. 110,000
Monsanto Soda Springs, Idaho 120,000
Stauffer Mt. Pleasant, Tenn. 80,000
Stauffer Silver Bow, Mont. 30,000
Stauffer Tarpon Springs, Fla. 12,500
TVA Wilson Dam, Ala. 110,000
Total 760,000
Production: 1969: 610,000 tons
1974: 740,000 tons
Uses; Sodium tripolyphosphate, phosphoric acid,
other sodium phosphates, calcium phosphates,
tetrapotassium pyrophosphate, sodium metaphosphate.
Processes; Phosphate rock is mixed with sand and coke,
sintered and introduced into an electric furnace.
After heating at elevated temperature, slag and
ferrophosphorous is drawn off. Phosphorous vapor is
drawn off and condensed. Phosphorous is oxidized to
^2^5 which is cooled and hydrated, filtered and
purified.
Waste Problems: A stream containing a significant
amount of phosphorous (1% of production) is known as
"phossy" water. The phosphorous may be settled,
thickened and recycled. The filtration of the acid
also produces a waste sludge of acid which causes a
disposal problem. No major processing changes are
anticipated.
TKPP
Producer Location Capacity =/
FMC Carteret, N. J. 10,000
FMC Newark, Calif. 2,500
Hooker Jeffersonville, Ind. 5,000
Mobil (V-C) Fernald, Ohio 12,000
Monsanto Carondelet, Mo. 15,000
109
-------
TKPP (cont.)
Producer Location Capacity —'
Olin Joliet, 111. 5,000
Stauffer Chicago Heights, 111. 7,500
Stauffer South Gate, Calif. 2,500
Total 59,500
I/ tons/year
Production: 1969: 48,500 tons
1974: 60,000 tons
Uses; Liquid detergent builder.
Procejssgs t TKPP is prepared by the reaction of phos-
phoric acid and potassium carbonate to produce
dipotassium-phosphate which is calcined to TKPP.
Waste Problems: Not significant.
Sodium Metal
Producers Location Capacity —'
DuPont Memphis, Tenn. 70
Niagara Falls, N.Y. 84
Ethyl Baton Rouge, La. 90
Houston, Tex. 60
National
Distillers Ashtabula, Ohio 56
Total J60"
I/ million Ibs/year
Production; 1969: 165,000 tons
1974: 200,000 tons
Uses; Tetraethyl and tetramethyl lead, potassium,
sodium peroxide, sodium cyanide.
Processes; Electrolysis of fused sodium chloride.
The crude sodium is filtered at 105-110°C.
110
-------
Waste Problems: Since the process is run dry, waste
problems are limited to washouts, spills and filter
cake discharge.
Sodium Bicarbonate
Producer Location Capacity —'
Church & Dwight Syracuse, N. Y. 100,000
Church & Dwight Green River, Wyo. 40,000
Diamond Painesville, Ohio 28,000
Olin Saltville, Va. 23,000
PPG Barberton, Ohio 40,000
Wyandotte Wyandotte, Mich. 30,000
Total 261,000
I/ tons/year
Production; 1969: 205,000 tons
1974: 235,000 tons
Use s; Food, chemicals, drugs, fire extinguishant,
soap and detergents, leather, textile, and paper.
Processee?; Sodium bicarbonate is not made by refining
the crude sodium bicarbonate from the Solvay process,
A saturated solution of soda ash (natural or
synthetic) is prepared and is carbonated with CO2 in
a tower. The suspension is filtered, washed,
centrifuged and dried.
Waste Problems; Major problem is the blowdown of the
filter cake and filter cake washups. No significant
process changes are expected and no change in the
nature of pollutional problems seems likely.
Sodium Bichromate
Producer Location Capacity =/
Allied Baltimore, Md. 90,000
Diamond Shamrock Kearny, N.J. 15,000
Diamond Shamrock Painesville, Ohio 50,000
Hercules Glen Falls, N.Y. 16,000
Pittsburgh Plate Corpus Christi, Tex. 35,000
Total 206,000
I/ tons/year
111
-------
Production: 1969: 150,000 tons
1974: 165,000 tons
Uses; Pigments, leather tanning, chromic acid, metal
treatment, textiles and dyes.
Processes; The raw material is a chromium iron oxide
containing about 50% Cr2O3. The ore is ground to
200 mesh, mixed with limestone and soda ash and
heated to 2200°F in a strongly oxidizing atmosphere.
The mass is leached with hot water to remove the
soluble sodium chromate. The solution is acidified
to convert the chromate to dichromate. The sodium
sulfate crystallizes out and the solution is sent
to crystallizers to recover the dichromate. No
process changes are expected.
Was te Problems: The solution coming off the
crystalTizer s contains about 0.1 ton of Na2S04 per
ton of sodium dichromate and minor amounts of
sodium dichromate and chromate. Use of ion exchange
and other concentrating systems could permit re-
covery from this system.
Sodium Chloride .
Producers Capacity —^
Morton 6
International 4
Diamond Crystal 2.5
Leslie 1.5
Other salt companies 5
Total noncaptive capacity 19
Captive to chemical companies 22
Total salt and brine 41
I/ million tons/year
Production; 1969: 43,000,000 tons
1974: 57,000,000 tons
Uses: Production of chlorine, caustic, soda ash, other
chemicals, highway use, food, feed, water condition-
ing.
112
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Processes; Salt is obtained in three fashions: one
by solar evaporation of sea water or western lake
brines; another from well brine and a third by the
mining of rock salt. It is necessary to remove
calcium and magnesium chlorides, usually by under-
taking evaporative concentration followed by filtra-
tion of the precipitated salts of Mg and Ca. The
process may undergo some modification but major
changes are not likely.
Waste Problems; Wastewater results from two sources.
One is the deposits of calcium and magnesium salts
which are removed in the process. This slurry can
amount to 3-5% of the total process flow.
The second source is the slip stream removed to
control impurities in any recycling system such as
the Alberger method. Use of a concentrating or an
ion control system may be effective in controlling
this problem internally.
Sodium Silicate
Producer Capacity —
Allied 105,000
Amerace 25,000
Chemical Products 10,000
Diamond 230,000
DuPont 150,000
Grace 65,000
Philadelphia Quartz 225,000
Philadelphia Quartz (Calif.) 35,000
Pittsburgh Plate 60,000
Proctor & Gamble 20,000
Twin Chemical 15,000
Total 940,000
I/ tons/year
Production; 1969: 640,000 tons
1974: 750,000 tons
Uses; Catalysts and silica gels, soaps and detergents,
boxboard adhesives, pigments, water, paper and ore
treatment.
113
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Processes: Sodium silicates are prepared by fusing
sodium carbonate and silica sand in a glass melting
furnace at about 1300°C. If the product is to be
sold as a solution/ it is dissolved by steam
injection. No process change is anticipated.
Waste Prob1ems: None except washdown.
Sodium Sulfite
Producer
Allied
Allied
Koppers
Monsanto
Reichhold
Stauffer
I/ tons/year
Location
El Segundo, Calif.
N. Claymont, Del.
Petrolia/ Pa.
Monsanto, TiJ..
Tuscaloosa, Ala.
South Gate, Calif.
Total
Capacity —'
5,000
10,000
25,000
62,500
145,000
3,000
250,500
Production:
1969: 230,000 tons
1974: 240,000 tons
Processes; Direct contact between SO2 and soda ash
followed by boiling off of C02- Sesqihydrate is
precipitated. Another source is as a by-product in
the preparation of phenol by the fusion of sodium
benzene sulfonate with caustic (See "Waste Water
Treatment Costs in the Organic Chemical Industry,"
U. S. Department of the Interior).
Uses; Sulfite pulping, water treatment, photo grade.
Waste Problems; The waste solution contains a
saturated solution of sulfite which has an
immediate oxygen demand if released to the river.
Additional recycling and reuse is possible and,
if practiced, dumping may be eliminated.
114
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Sodium Sulfate
Producer Capacity —'
Allied (B) 45,000
American Cyanamid (0) 13,000
American Enka (R) 56,000
American Potash (N) 250,000
Beaunit (R) 42,000
Climax Chemical (M) 35,000
Diamond Shamrock (B) 50,000
DuPont (M) 30,000
FMC (R) 275,000
Hercules (B,M) 25,000
Huber (0) 8,000
Industrial Rayon (R) 36,000
Koppers (0) 15,000
Lithium Corporation (0) 15,000
Monsanto (0) 35,000
Morton Chemical (M) 120,000
Ozark-Mahoning (N) 200,000
Stauffer (N,0) 200,000
U. S. Borax (0) 30,000
Miscellaneous 25,000
Total 1,505,000
I/ tons/year
B-Bichromate; 0-Other; R-Rayon or Cellophane;
N-Natural; M-Mannheim or Hargreaves
Production; 1969: 1,500,000 tons/year
1974: 1,800,000 tons/year
Uses; Sulfate pulping, detergents, glass.
Processes; Much of the sodium sulfate is from by-
product sources discussed elsewhere. Glauber's
salt (Na2SO4.1OH2O) is made by dissolving salt cake
in mother liquor, adding of CaCl2 and lime. The
Mg, Ca and Fe are permitted to settle and the mud
washed. Crystallization takes place in pans and
anhydrous sodium sulfate is prepared by dehydrating
Glauber's salt. No new sources or processes are
anticipated.
Waste Problems; Disposal of the mud is the primary
problem and in-plant control would have little
impact on this problem.
115
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Sodium Tripolyphpsphate
Producer
Allied
AAC
FMC
PMC
FMC
FMC
Hooker
Hooker
Hooker
Monsanto
Monsanto
Monsanto
Monsanto
Monsanto
Olin
Stauffer
Stauffer
Stauffer
Stauffer
Virginia-Carolina
Location
I/ tons/year
Production:
N. Claymont, Del.
Carteret, N. J.
Carteret, N. J.
Green River, Wyo.
Lawrence, Kans.
Newark, Calif.
Adams, Mass.
Dallas, Tex.
Jeffersonville, Ind.
Augusta, Ga.
Carondelet, Mo.
Kearny, N. J.
Long Beach, Calif.
Trenton, Mich.
Joliet, 111.
Chicago, 111.
Chicago Heights, 111,
Morrisville, Pa.
South Gate, Calif.
Fernald, Ohio
Total
Capacity ±/
1969: 1,200,000 tons
1974: 1,600,000 tons
30
40
150
50
75
50
25
25
75
25
100
75
25
75
140
40
25
75
50
50
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
1,200,000
Uses: Detergents.
Processes; The sodium phosphates are made primarily
from furnace acid and soda ash which are reacted
in a mix tank and dried in a rotary or spray drier
and dehydrated in a calciner. This is followed by
annealing and cooling in a tempering unit.
Water Problems; Scrubber waters and vessel washouts
are major sources of polluted wastewaters.
116
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SIC 2819 (INDUSTRIAL INORGANIC CHEMICALS)
Aluminum Chloride Anhydrous
Producer Capacity ~
Allied, Elberta, N. Y. 9,000
Dow, Freeport, Texas 5,000
Hercules Alelor, Ravenna, Ohio 2,400
Pearsall, LaPorte, Texas 4,000
Pearsall, Phillipsburg, N. J. 6,000
Stauffer, Baton Rouge, La. 8,000
Stauffer, Elkton, Md. 8,000
Van de Mark, Lockport, N. Y. 2,500
Total 44,900
I/ tons/year
Production; 1969: 34,000 tons
1974: 44,000 tons
Uses: Ethylbenzene catalyst, dyestuffs, detergent
alkylate, ethyl chloride, Pharmaceuticals.
Processes; The reaction involves the direct contact
of chlorine vapor with molten aluminum. Chlorine
is fed below the surface of the aluminum and the
product sublimes and is collected by condensing.
No change is expected in processing methods.
Waste Problems; The major discharge is a chlorine
containing wastewater which could be utilized as a
treatment chemical. Recovery of the chlorine by
rectification is feasible.
Sulfuric Acid
New Plants Built Since 1966 Include The Following:
Producer Location Capacity —'
Acid, Inc. Bonnie, Fla. 2,000,000
Arkla Chemical Helena, Ark. 180,000
American Cyanamid Linden, N. J. 250,000
117
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Sulfuric Acid (cont.)
Producer
American Oil Co.
Allied
American Smelting &
Refining Co.
American Zinc
Borden Chemical
Bunker Hill
DuPont
Freeport Sulfur
W. R. Grace
Kennecott Copper
Mo. Lead Smelting
National Zinc
Olin
Sinclair
Stauffer
Stauffer
Tennessee Corp.
Texaco
Texas Gulf Sulfur
I/ tons/year
Location
Texas City/ Tex.
Geismar, La.
Haydon, Ariz.
Monsanto, 111.
Columbus, Ohio
Plant City, Fla.
Kellogg, Idaho
Burnside, La.
Memphis, Tenn.
Uncle Sam, La.
Bartow, Fla.
Hayden, Ariz.
Salt Lake City, Utah
Iron Co. , Mo.
Bartlesville, Okla.
Shreveport, La.
Ft. Madison, Iowa
Houston, Texas
Martinez, Calif.
Augusta, Ga.
Port Arthur, Tex.
Lee Creek, N. C.
Total
Capacity —'
150,000
720,000
250
146
64
385
100
540
75
1,725
385
270
505
75
100
125
540
720
360
135
92
1,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
,000
10,892,000
Major merchant producers include:
Stauffer Chemical
Allied Chemical
DuPont
American Cyanamid
Tennessee Corporation
Production:
1969: 28,000,000 tons
1974: 34,000,000 tons
Uses; Fertilizer, chemical production, iron and steel
pickling, food, petroleum products, metallurgy,
TiO2 production, (NH4)2 804, alum, rayon.
Processes; Two processes have been used for the
production of sulfuric acid - the chamber process
and the contact process. Since no new chamber
processes have been built for perhaps 30 years, the
118
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FIGURE 8
AIR INTAKE
SILENCER
OR FILTER
EXIT GAS
STACK
98-99% »
ACID TO
STORAGE
ABSORBING
TOWER
MELTER -
SETTLER
CIRCULATING
TANK
••-OLEUM TO
STORAGE
OLEUM PUMP
VOLEUM COOLER
TYPICAL FLOWCHART FOR SULFUR-BURNING CONTACT PLANT
This flow chart is selectively reproduced in content and configuration from Figure 19.4
in the book by R. Morris Shrewe, Chemical Process Industries, Third Edition, New York
Me Graw-Hill Book Company, 1967, p. 330 '
-------
following discussion will center on the contact
process. In this process, either sulfur or SC>2 may
be the starting point. If sulfur is the starting
point, it is melted and burnt with air to SO2. The
S02 must be filtered and converted catalytically to
803. 503 is absorbed in strong sulfuric acid.
Present process changes are directed towards the
improvement in conversion and recovery because of
the air pollution problem.
Waste Problems; Primarily from vessel cleanout, and
slab washdown as well as discharge of cooling
waters.
120
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SIC 2851 (PAINTS AND ALLIED PRODUCTS)
Paints, and Allied Products
Producers; There are several hundred paint companies
with several thousand paint plants scattered through-
out the country. Paint production tends to be a
local product because of the high transportation
charges. However, Ohio, Illinois, New Jersey and
California are major paint-producing centers.
Among the leading concerns are the following:
DuPont
National Lead
Sherwin-Williams
Glidden
Moore
Devoe and Reynolds-Celanese
Production;
Paint and Varnishes, Total
Trade Sales
Paint and Varnish
Lacquer
Trade Sales, Total
industrial Product Finishes
Paint and Varnish
Lacquer
Industrial Product
Finishes, Total
1969 (gal)
904,000,000
438,000,000
11,000,000
449,000,000
360,000,000
95,000,000
455,000,000
PPG
DeSoto
Mobil
Inmont
Cook
1974 (gal)
1,196,000,000
587,000,000
15,000,000
602,000,000
482,000,000
112,000,000
5947000,000
Processes; The manufacture of paints involves
primarily mixing in tanks although grinding mills,
sand mills, high-speed stone mills and high-speed
agitators are being increasingly used in these
systems. The process is batch type. Finally, color
may be added in a tinting and thinning tank before
packaging.
Varnish is a solution of a resin in a drying oil
or solvent (shellac). This is accomplished by
mixing; in some cases, by heating. Finally, the
final product is clarified by filtration or
121
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centrifugation followed by aging in large tanks
to precipitate grit particles.
There has been little change in the manufacture
of paints for a century or more and none is
expected.
Waste Problems; The major problems arise from tank
washings and dumpings. The presence of latex is
a specially difficult problem but collection and
recycle of the latex is completely possible as is
the multiple reuse of wash waters.
122
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SIC 2871 (FERTILIZERS)
Fertilizers
Producers: Fertilizers are generally made by a large
number of production facilities located throughout
the country. The basic ingredients include: potash,
ammonia, ammonium sulfate, ammonium nitrate,
ammonium phosphates, plus other phosphate products
all of which are prepared in a limited number of
large production facilities. Most of these have
already been discussed under SIC 2819 but several
including potash, super phosphate, triple super
and mixed fertilizers will be discussed in this
section.
CONCENTRATED SUPER-PHOSPHATE PLANTS
UNITED STATES
Company
American Cyanaraid
Armour Agr. Cheru. Co.
Borden Chem. Co.
Central Phosphates
Cities Service Oil
Coastal Chemical
Continental Oil
El Paso Natural Gas
Farmland Industries
W. R. Grace & Co.
Int. Minerals & Chem.
Kerr-McGee
Mobil Chemical
Occidental Agrilcul.
Phillips Chemical
F. S. Royster Guano
J. R. Simplot
Stauffer Chemical
Swift & Company
Tenn. Valley Authority
Texas Gulf Sulfur
Location
Brewster, Fla.
Ft. Meade, Fla.
Port Mantee, Fla.
Plant City, Fla.
Tampa, Fla.
Pascagoula, Miss.
Pierce, Fla.
Georgetown, Idaho
Lakeland, Fla.
Joplin, Mo.
Ridgewood, Fla.
Bonnie, Fla.
Baltimore, Md.
Nichols, Fla.
White Springs, Fla.
Pasadena, Tex.
Mulberry, Fla.
Pocatello, Idaho
Garfield, Utah
Tacoma, Washington
Agricola, Fla.
Muscle Shoals, Ala.
Lee Creek, N. C.
Total
Capacity
Cthou. tons)
180
113
33
155
165 I/
135 y
180
55
36
32
350
203
• • •
130
188
45 y
170
92
45
23
77 2/
27 ±/
167
I/
2,601
Idle facilities
High- analysis 54% P2Os material
123
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AMMONIUM AND DIAMMONIUM PHOSPHATE PLANTS
UNITED STATES
Company
Location
AFC, Inc.
Allied Chemical
American Cyanamid
Arizona Agrochemical
Arkla Chemical
Armour Agri. Chem.
Borden Chemical
Bunker Hill
Central Phosphates
Chevron Chemical
Cities Service Oil
Coastal Chemical
Colorado Fuel & Iron
Continental Oil
Des Plaines Chemical
Dominguez Fertilizer
El Paso Nat. Gas
Farmland Industries
Ford Motor
W. R. Grace
Hooker Chemical
Int. Min. & Chem.
Kaiser Steel
Mobil Chemical
Monsanto
Nat. Dist. & Chem.
N. J. Zinc
Nipak/ Inc.
NW Coop. Mills
Occidental Agri.
Edison, Calif.
Geismar, La.
Brewster, Fla.
Chandler, Ariz.
Helena, Ark.
Bartow, Fla.
Cherokee, Ala.
Port Manatee, Fla.
Streator, 111.
Texas City, Tex.
Kellogg, Idaho
Plant City, Fla.
Ft. Madison, Iowa
Kennewick, Wash.
Richmond, Cali f.
Tampa, Fla.
Pascagoula, Miss.
Pueblo, Colo.
Pierce, Fla.
Morris, 111.
Long Beach, Calif.
Soda Springs, Idaho
Lakeland, Fla.
Joplin, Mo.
Dearborn, Mich.
Henry, 111.
Joplin, Mo.
Ridgewood, Fla.
Marseilles, 111.
Taft, La.
Bonnie, Fla.
Fontana, Calif.
Nichols, Fla.
Luling, La.
Danville, 111.
Depue, 111.
Kerens, Tex.
Tulsa, Okla.
Pine Bend, Minn.
White Springs, Fla.
Lathrop, Calif.
Plainview, Tex.
Capacity
(thousand
tons/year)
28
91
18
15
75
85
25
45
15
NK y
NK y
NK I/
NK V
179
120
7 ±/
46
34
15
30
147
67 ,
10 I/
100
20
174
69
175
230
15
77
120
15
124
46
20
69
115
10
9
124
-------
AMMONIUM AND DIAMMONIUM PHOSPHATE PLANTS (cent.)
Company
Olin Mathieson Chem.
Phosphate Chemicals
F. S. Royster Guano
Shell Chemical
J. R. Simplot
Stauffer Chemical
Swift
Tennessee Farmers
Tennessee Valley Auth.
Texas Gulf Sulfur
Union Oil of Calif.
Valley Nitrogen Prod.
Western States Chem.
Location
Pasadena, Tex.
Houston, Tex.
Mulberry, Fla.
Pittsburg, Calif.
Pocatello, Idaho
Garfield, Utah
Agricola, Fla.
Sheffield, Ala.
Muscle Shoals, Ala.
Lee Creek, N. C.
Brea, Calif.
Helm, Calif.
Capacity
(thousand
tons/year)
200
69
Nichols, Calif.
Total
I/ Nitric phosphate process
£/ Diammonium phosphate 21-53-0 analysis
91
80
69
NK V
15 2/
105
12
35
NK V
3,169
125
-------
AMMONIUM PHOSPHATE PLANT LOCATIONS
FIGURE 9
to
A NEW PLANT
-------
PHOSPHATE ROCK MINES
UNITED STATES
Company
Location
American Cyanamid
Armour Agr. Chem.
Armour Agr. Chem. &
Freeport Sulfur
Borden Chemical
Cities Service
Continental Oil
W. R. Grace
Int. Min. & Chem.
Kerr-McGee, Inc.
Mobil Chemical
Occidental Agril.
Swift & Co.
Texas Gulf Sulfur
Armour Agril. Chem.
Hooker Chemical
Mobil Chemical
Monsanto
Presnell Phosphate
Stauffer Chemical
Tennessee Valley Auth,
Florida
Brewster
Amour
Lake Hancock
Ft. Meade
Teneroc
Ft. Meade
Pierce
Bonny Lake
Bonnie
Kingsford
Brewster
Ft. Meade
White Springs
Watson
Silver City
North Carolina
Lee Creek
Tennessee
Columbia
Columbia
Mt. Pleasant
Columbia
Columbia
Mt. Pleasant
Knob Creek
Franklin
Capacity
(thousand
short tons)
3,650
1,500
2,000
1,500
2,000
6,500
1,550
6,000
2,000
1,500
5,700
3,000
2,325
3,000
90
750
200
1,000
700
600
200
Cominco Ltd.
El Paso Nat. Gas
Monsanto
Mountain Fuel Supply
New Idria Mining
& Chemical
George Relyea
J. R. Siraplot
Western States
Garrison,Mont.
Phillipsburg, Mont.
Soda Springs, Idaho
Ballard, Idaho
Soda Springs, Idaho
Bakersfield, Calif.
Garrison, Mont.
Fort Hall, Idaho
Soda Springs, Idaho
1,050
400
500
NK
NK
100
1,600
127
-------
PHOSPHATE ROCK MINES (cont.)
Capacity
(thousand
Company Location short tons)
Stauffer Chemical Hot Springs, Idaho
Montpelier, Idaho
Cherokee, Utah 400
Vernal, Utah 200
Leefe, Wyo. 350
Melrose, Mont. 600
Total United States 51,165
128
-------
ESTIMATED NUMBER OF BULK BLEND PLANTS IN THE
UNITED STATES
State
Maine
New Hampshire
Vermont
Massachusetts
Rhode Island
Connecticut
NEW ENGLAND
New York
New Jersey
Pennsylvania
Delaware
Maryland
West Virginia
MIDDLE ATLANTIC
Virginia
North Carolina
South Carolina
Georgia
Florida
SOUTH ATLANTIC
Ohio
Indiana
Illinois
Michigan
Wisconsin
No. of
Plants
1966
3
1
3
5
5
21
39
20
44
7
26
_ 1
137
255
100
235
428
55
82
EAST NORTH CENTRAL 900
Minnesota
Iowa
Missouri
North Dakota
South Dakota
Nebraska
Kansas
WEST NORTH
CENTRAL
State
Kentucky
Tennessee
Alabama
Mississippi
EAST SOUTH CENTRAL
Arkansas
Louisiana
Oklahoma
Texas
WEST SOUTH CENTRAL
Montana
Idaho
Wyoming
Colorado
New Mexico
Arizona
Utah
Nevada
No. of
Plants
1966
35
17
37
18
107
50
23
56
125
254
11
43
29
53
15
13
27
— _
MOUNTAIN
Washington
Oregon
California
PACIFIC
191
174
Total Continental
U.S. 37149
Hawaii 4
TOTAL U.S.
3,153
1,110
129
-------
ESTIMATED NUMBER OF BULK BLEND FERTILIZER PLANTS
FIGURE 10
137 a MIDDLE
ATLANTIC
OJ
o
HAWAII - 4
WEST NORTH EA'"ST
CENTRALS CENTRAL
MOUNTAIN
x-^"-
191
AST
clNTRAL— ATLANTIC
WEST SOUTH
CENTRAL
NEW
ENGLAND
TOTAL - 3, 153
-------
ESTIMATED NUMBER OF LIQUID MIX PLANTS IN THE
UNITED STATES
State
Maine
New Hampshire
Vermont
Massachusetts
Rhode Island
Connecticut
NEW ENGLAND
New York
New Jersey
Pennsylvania
Delaware
Maryland
West Virginia
MIDDLE ATLANTIC
Virginia
North Carolina
South Carolina
Georgia
Florida
SOUTH ATLANTIC
Ohio
Indiana
Illinois
Michigan
Wisconsin
Minnesota
Iowa
Missouri
North Dakota
South Dakota
Nebraska
Kansas
WEST NORTH
CENTRAL
No. of
Plants
1966
2
4
6
5
8
1
6
26
11
11
7
12
2T_
68
29
129
154
12
15
EAST NORTH CENTRAL 339
41
85
63
5
7
49
125
375
State
Kentucky
Tennessee
Alabama
Mississippi
EAST SOUTH CENTRAL
Arkansas
Louisiana
Oklahoma
Texas
WEST SOUTH CENTRAL
Montana
Idaho
Wyoming
Colorado
New Mexico
Arizona
Utah
Nevada
MOUNTAIN
Washington
Oregon
California
PACIFIC
Total Continental
U.S. 1
Hawaii
No. of
Plants
1966
7
3
6
35
19
15
24
67
125
4
24
5
16
1
19
1
_2
72
55
17
109
181
,229
2
TOTAL U.S.
1,231
131
-------
ESTIMATED NUMBER OF LIQUID MIXED FERTILIZER PLANTS
FIGURE 11
U)
NJ
HAWAII - 2
MIDDLE
ATLANTIC
WESTITORTH
CENTRAL
LLNIKAL
MOUNTAIN
AST
SOUTH
CENTRAL
SOUTH
ATLANTIC
WEST SOUTH
CENTRAL
NEW
ENGLAND
TOTAL - 1,231
-------
Production; (100% APA)
Other
Normal Triple Ammonium Phosphatic
Super Super Phosphates Fertilizer
1969 913,000 1,390,000 1,651,000
1974 900,000 1,800,000 2,200,000
Processes; Superphosphate is solubilized phosphate
rock in which the rock is acidulized with sufficient
acid to convert the rock to monocalcium phosphate
and gypsum. No separation is made. The waste
products and processes except for the gypsum are
similar to those generated in the production of
phosphoric acid.
Concentrated superphosphate is produced by the
reaction of phosphoric acid with phosphate rock
producing Ca (H2P04)2« No gypsum is produced.
The reaction takes place in a rotating granulator.
The major waste products are the scrubber waters
from the granulator and subsequent cooler exhaust
gas scrubbers which contain some phosphoric and
considerable amounts of silico fluorides for which
a considerable market exists. The condensate from
the acid preheater can be used for scrubber water
to close loop the system. Normal super production
is being superseded by triple production.
Phosphate rock handling results in a heavily turbid
water flow. Solids settling is usually practiced.
Ammonium phosphate is produced by the direct contact
of phosphoric acid and ammonia. Vessel washout is
the major pollutional source.
Liquid mix an,d dry mix plants involve the blending
of fertilizer base materials such as superphosphate,
urea, ammonium nitrate, ammonium phosphate and
potash thereby producing the final product. Vessel
washout is the major pollutional problem.
Potash is produced from sedimentary deposits of
syluinite (a mixture of K Cl and Na Cl) and lang-
beinite (K2S04*2MgS04), primarily. Langbeinite is
processed to produce potassium sulfate. The Trona,
133
-------
California, salts are another important salt.
Solar evaporation at Great Salt Lake is also
practiced. The biggest single source of new potash
is the deep deposit in Saskatchewan, Canada which
will be developed by conventional and solution
mining.
Some of the potash is produced by fractional
crystallization but the syluinite deposits are
handled by either soap flotation or fractional
solution. In both processes, slimes and reject
salt solutions are present to create pollution
problems. The reject salt solutions may contain
small amounts of flotation agents such as starch
and amines. It is possible through the careful
use and selection of these agents to minimize
losses. Reuse and recovery of the slimes and salt
solutions may be practiced. Of course, since
great stretches of land are available, disposal is
not generally a problem. In Europe, the great
potash mines of the Alsace are one of the main
polluters of the Rhine. Recovery of the salt is
totally feasible. The present trend is towards
partial solution of KC1 as practiced in Canada
since this area will be the major source in
the next decade.
Complex fertilizer is prepared by reaction of
ammonia, phosphoric acid, nitric acid and phosphate
rock in acidulation tanks. The final slurry is
mixed with potassium chloride (potash). The
product may be spherodized, granulated or coated.
A dust collector is used to recover fines.
Generally, the entire system is kept dry for process
reasons but vessel and slab washdowns produce waste-
water problems. Fluorine in fume scrubbing water
may be a problem.
TVA has been successful in developing direct
ammination and acidulation processes aimed at pro-
ducing higher concentration fertilizers. Most of
these processes are carried out dry, but this is
not the universal practice and those processes
carried out in a wet state create steady waste
streams. The trend towards high analysis ferti-
lizer is expected to continue in the future.
134
-------
POTASH PLANTS
UNITED STATES AND CANADA
Company
Location
American Metal
Climax
Am. Potash & Chem,
U.S. Borax & Chem.
Agri. Minerals
Dow Chemical
N. Am. Cement
Int. Min. & Chem.
Calium Chemicals
Potash Corp. of Am.
U.S. Borax & Chem.
United States
Carlsbad, N. M.
Trona, Calif.
Carlsbad, N. M.
Carlsbad, N. M.
Wendover, Utah
Carlsbad, N. M.
Ogden, Utah
Carlsbad, N. M.
Carlsbad, N. M.
Moab, Utah
Carlsbad, N. M.
Davenport, Calif.
Midland, Mich.
Security, Md.
Total
Canada
Lanigan, Sask,
Delisle, Sask.
Saskatoon, Sask.
Esterhazy, Sask.
Belle Plaine, Sask.
Viscount, Sask.
Lake Patience, Sask.
Saskatoon, Sask,
Total
Total North America
1969 Capacity
(thou. tons)
600
235
450
450
66
300
270
350
620
350
550
10
4,251
600
600
600
2,460
360
720
430
900
6,670
107921
135
-------
SIC 2879 (INORGANIC PESTICIDES)
Inorganic Pesticides
Producers: Data not available
Production; (tons/year) 1969 1974
Arsenic compounds 6,000 5,000
Sulfur 210,000 150,000
Processes and Waste Problems; In general, inorganic
compounds have been replaced by organic compounds.
The major inorganic pesticides are the following:
lead arsenate
sulfur
carbon bisulfide
hydrogen cyanide
fluorine
lime-sulfurs
Bordeaux mixture
mercury chlorides
sodium chlorate
sodium arsenite
ammonium sulfamate
This review does not consider the organophosphorous
compounds which are gaining major importance in the
industry. Neither will this review detail many of
the above listed chemicals because their use in this
particular application is minor compared to other
uses for them.
Lead arsenate is prepared from lead oxide which is
dissolved in acetic and nitric acid and arsenic
acid is added. Lead arsenate is removed by filtra-
tion. The mixture of nitric and acetic acid is
reused three times. Thus, 0.15 pounds of nitric
acid per pound of product and a similar amount of
acetic acid is discarded or must be treated and
recycled. It is obvious that recycle would result
in greatly reduced waste problems.
Sulfur is made by milling sulfur to 325 mesh,
emulsifying molten sulfur, heating mixtures of
136
-------
sulfur with bentonite and using flotation sulfur
obtained from the recovery of the element from
hydrogen sulfide from gases. Washout streams con-
taining fine sulfur particles can be recovered.
Lime-sulfur is prepared by boiling a mixture of
lime, sulfur and water to a dry mixture.
Bordeaux mixture is prepared by mixing copper
sulfate, lime and water. Both lime sulfur and
Bordeaux mixture are generally prepared in the
field and wastewater problems are not significant,
Mercury chlorides are prepared in the following
fashion.Mercuric chloride is prepared by the
direct reaction of mercury and chlorine and
mercurous chloride is made by reducing mercuric
chloride with mercury. Wastewater problems
result from vessel washout.
Considering the fading nature of the industry, no
process changes are expected.
137
-------
SIC 2892 (EXPLOSIVES)
Explosives
Producer: Data not available
Production; 1969: {$) 264,000,000
1974: ($) 322,000,000
(weight data not available)
Processes and Waste Problems; Nitrocellulose is
prepared first by boiling cotton linters in dilute
caustic and bleaching with chlorate. The cotton
is then dried and nitrification with nitric acid
and sulfuric acid takes place in a nitrator.
The charge is dropped into a centrifuge for drying.
Two waste problems exist. The kiering caustic
solution must be dumped from time to time and this
is a serious waste load. Regeneration of the
caustic solution by dialysis or other membrane
processes is possible but not practical.
The waste acid amounts to 0.5 pounds of sulfuric
and 0.35 pounds of nitric. Some of this acid is
sent for concentration, some is sold and the
remainder is discharged. Reuse of this acid should
be possible if careful measures are taken.
Naturally, washouts of vessels and slabs can also
produce major waste treatment problems.
Smokeless powder is washed and beaten to remove
free acid and destroy any unstable sulfate esters
that may have been formed. The final product is
colloidized by mixing with alcohol, ether,
diphenylamine and other modifying agents. Again,
the washing of the nitro cellulose produces a
waste containing sulfuric and nitric acid which can
be reclaimed in a fortifying plant.
TNT is produced by the three stage nitrification
of toluene followed by soda ash and sodium sulfate
washes. The wash water contains considerable
amounts of alkalies and sodium dinitrosulfanates.
138
-------
M
U)
VO
DEHYDRATING
PRESS
FIGURE 12
WATER-WET
NITROCELLULOSE
12.5-12.7% N2
ETHYL
ALCOHOL
ETHYL
ETHER
1
— <
^
DIPHENYLAMINE
OR OTHER
STABILIZER
GRAINING
PRESS
BLENDING
TOWER
DOUBLE -ARM
MIXER
BLOCKING
PRESSES
SOLVENT DRYER
U P U n
WARM AIR HOT COLL
COIL COIL
MIXED SOLVENTS
AND WATER
* NOTE: ASTERISKS DENOTE EQUIPMENT CONNECTED TO SOLVENT RECOVERY SYSTEM
FLOWCHART FOR SMOKELESS POWDER
This flow chort is selectively reproduced in content and configuration from Figure 22.4
in the book by R. Norris Shreve, Chemical Process Industries, Third Edition, New York,
Me Graw-Hill Book Company, 1967, p. 390
-------
Ammonium nitrate - Fuel oil (AN) are produced by
mixing and shaping of the two ingredients. A
major waste source is from the washing of the
equipment, thereby producing a waste stream con-
taining oil and a high nitrogen content.
Nitroglycerin and dynamite. Nitration of the
glycerin takes place in the presence of sulfuric
acid. The nitroglycerin is separated from the
spent acids and washed several times. The spent
acid is recycled and fortified. About 80 pounds
of sulfuric and 160 pounds of nitric are wasted
from the system per ton of nitroglycerine.
Dynamite is made by adsorbing nitroglycerine on
agents such as wood flour, ammonium nitrate or
sodium nitrate. Nonfreezing dynamite can be
made by the addition of ethylene glycol dinitrate
to lower the freezing point of nitroglycerine.
A typical waste from a dynamite-nitroglycerine
facility has the following composition: pH-7,
COD-350 ppm, TDS-10,800 ppm, SS-40, sodium-150,
ammonia-nitrogen-1270 ppm, nitrate nitrogen-550
ppm, sulfates-1000 ppm.
140
-------
APPENDIX C
COSTS OF UNIT WASTEWATER TREATMENT PRACTICES
Neutralization
Deep Well Disposal
Reverse Osmosis
Electrodialysis
Ion Exchange
Multiple Effect Evaporation
Solar Evaporation
Cooling Towers
141
-------
COSTS OF UNIT WASTEWATER TREATMENT PRACTICES
An envelope of extreme values of TDS and flow rate that
have been considered for the subsequent cost calculations
are shown in Figure 1. The following are the combina-
tions within the triangle of flow, acidity, suspended and
dissolved solids chosen for the study:
Flow rate 0.5, 1.0, 10.O/ 50.0 mgd
Acidity 500, 1000, 20,000 mg/1 (as CaC03)
Suspended solids 100, 500 mg/1
TDS 3000, 30,000, 150,000 mg/1
The flow sheet used for the cost calculations is shown in
Figure 2. When neutralization is not required, the
neutralization portion will be bypassed.
142
-------
200,000
100,000
50,000
•DEEP WELL
FIGURE I
APPLICABLE RANGES OF
DEMINERALIZATION UNITS
CO
0
o
en
-i 10,000 ii
CO
5
5,000
DISPOSAL
VAPOR AT ION
ENVELOPE OF TDS
COMBINATION
il^REVERSE OSMOSIS
DISTILLATION
ICTRODIALYSIS
I.O 5.0 10.0
PLANT CAPACITY ( MGD)
50.0 100.0
-------
NO NEUTRALIZATION FOR DEEP WELL EVAPORATION
DEEPWELL
OOO
Reverse
Osmosis
OR DEMINERALIZATION
Mixed
Media
Filter
Primary
Sediment
Equalization
Flocculation
Electrodialysls
Neutralization
ALTERNATIVE:
SETTLING POND
EVAPORATION
FILTRATE
OR
CENTRATE
(alternative
to deep well)
Vacuum Filter
or
Centrifuge
Ion Exchange
Evaporation
REUSE OR
DISCHARGE
DIRECT TO EVAPORATION OR CONTROLLED DISCHARGE
FIGURE 2
SCHEMATIC LAYOUT OF TREATMENT PLANT FOR WASTES FROM THE INORGANIC
CHEMICAL INDUSTRY SHOWING VARIOUS POSSIBLE COMBINATIONS OF UNITS
-------
NEUTRALIZATION
Neutralization of inorganic industrial wastes usually
implies the use of some form of lime for the neutralization
of acidic wastes or sulfuric acid for the neutralization of
alkaline wastes. Acidic wastes are more prevalent and
neutralization presents more of a problem with such wastes.
All forms of inexpensive neutralizing material produces
sludge which is difficult to dewater. For large scale
Plants, economy requires the use of some form of lime or
limestone for treatment. Hydrated lime has been used
extensively for neutralization of acidic wastes but recent
studies (1) seem to indicate that greater economy could
be achieved by the use of limestone, both from the view-
point of lower cost of the alkali combined with a lower
cost of sludge dewatering (2). Few cost figures are
available for limestone treatment facilities, and for the
Purpose of this study, only hydrated lime treatment will
be considered.
Neutralization with lime combined with aeration will remove
iron as a necessary consequence since the solubility of
ferric ions decreases rapidly above a pH of 3.0. Mangan-
ese, alumina, and silica, as well as many of the heavy
toetal ions, also are removed by lime neutralization result-
ing in a decrease in total hardness.
The capital costs were calculated for a flow sheet shown
in Figure 3. Equalization capacity is required to supply
a constant flow of waste to the flash mixer. Lime from
the lime storage tank is fed into the slaker together with
some clarified effluent. Lime slurry from the slaker is
added to the waste stream in a flash mixer. After flash
fixing, the mixture is flocculated and aerated. Next the
^aste is thickened in a clarifier-thickener or in a
sludge settling pond. The underflow from the thickeners
with 2% to 3% solids may be passed on to a vacuum filter
Mihok, E. A., et al "Mine Water Research-The Lime-
stone Neutralization Process, U.S. Bureau of Mines
R.I. 7191, September, 1968.
Rice & Company, "Engineering Economic Studies of
Mine Drainage Control Techniques," Appendix B to
Acid Mine Drainage in Appalachia, A Report by the
Appalachian Regional Commission.
145
-------
lime
— ""^ Lime storage
i .
Lime >
slakes
"} Blower
» Eaualiiatinn Rnsin PI Oxidation
flash Mi
filtrate
Vacuum filter
Centrifuge
*
Flocculation
xmg
k
'I
1
1
1
^ /ClarifieA 1
i VThlckenery
: ^
i
^/
1 —
1
1
-1
To stream or
demineralization
plant
Sludge to
disposal
occasional.
removal of
sludge after
drying
FIGURE 3
FLOW SHEET FOR NEUTRALIZATION PLANT
[Alternative
flow pattern
/Slu dge
(settling)
pond
To stream
-------
1000
FIG. 4
CAP COST OF NEUTRALIZATION
FACILITIES EXCLUDING
SLUDGE TREATMENT
o
o
o
(A
O
O
0.
<
o
100
FROM RICE REPORT (2)
FROM BARNARD THESIS(4)
10
J—I I I I I
_L
1.0 10.0
PLANT CAPACITY MGD
-------
HYDRATED LIME TREATMENT PLANT
FIGURE 5
CAR COST VS ACIDITY FOR I M6D PLANT (INCLUDING SLUDGE DISPOSAL)
(FROM OPERATION YELLOWBOY) (2)
10,000
O
O
O
00
K-
co
o
o 1000
o:
o
000
iii
100
1000 10,000
ACIDITY, ppm (AS CaC03)
100,000
-------
o
o
o
vo
CO
o
o
Q.
<
O
1000
100
40-
X
1.0
10.0
50.0
VOLUME OF BASIN (IN MILLION GAL.)
FIG. 6 CAPITAL COST OF EQUALIZATION BASINS REF. (3)
-------
or a centrifuge for dewatering or may be discharged to a
dewatering pond. Sludge will be dewatered mechanically
to approximately 20% solids at which consistency it can be
trucked to disposal. If abundant land is available, the
waste will be discharged from the flocculator directly into
a settling pond. If land is scarce but available within
pumping distance, only the thickened sludge will be settled
in a pond.
Costs for hydrated lime treatment of acid drainage includ-
ing sludge disposal by thickening and disposal of the
slurry in ponds are presented in a report on the economics
of acid mine drainage (2). These cost curves show a
decrease in the unit capital cost of neutralization
facilities with increase of acidity, but no such decrease
in unit cost with increase in the volume of waste treated
daily. This is contrary to previous findings (4) that
the overall cost increase is proportional to flow rate to
the power of 0.83 (see Figure 4). Combining these two
values, the general overall cost for neutralization,
thickening and sludge holding ponds can then be expressed
as:
Capital Cost (in $1000}=172 Q0.83A0.79 (gee Figure 5)
where
Q = flow rate in mgd
A = acidity in mg/1
From available cost curves for (1) the equalization basin,
(2) lime plant, mixes and flocculator (3) the clarifier
thickener and (4) the vacuum filter or centrifuge, it was
also possible to synthesize the cost for full sludge de-
watering.
The cost curve for equalization basins (shown in Figure 6)
is based on findings by Chow (3) and additional costs
determined by Barnard (4).
(2) Rice, ibid
(3) Chow, C. S., Malina, J. F. and Eckenfelder, W. W.,
"Effluent Quality and Treatment Economics," Report
published by the Center for Research in Water Re-
sources Technical Report EHE 07-6801, CRWR 28,
The University of Texas at Austin.
(4) Barnard, J. L., "Treatment Cost Relationships for
Wastes from the Organic Chemical Industry," M.S.
Thesis, The University of Texas at Austin, June, 1969
150
-------
The cost curve for the lime plant mixer and flocculator is
based on costs extracted by Barnard (4) and additional
costs obtained from Operation Yellow Boy (2). These
curves shown little variation with acidity which influences
mainly the sludge handling units, but they are dependent
on the plant size.
Costs for the clarifier thickener were based mainly on
flow since clarification and thickening is combined into
one unit. Clarification requires a minimum overflow rate
for effluent control and this will determine the size of
the unit. The amount of thickening obtained is then
calculated from zone settling considerations to determine
the consistency of the thickener underflow. Costs were
obtained from the Mine Drainage Report (2) and calculated
from parameters obtained from a laboratory study of
neutralized acid wastes.
The size of the clarifier itself is based on an overflow
rate of 700 gpd/ft2. in order to produce an effluent
suitable for further use or treatment, it will be
necessary to use polymers to reduce the suspended solids
in the effluent and to filter the effluent. The thickener
design was based on values from laboratory studies (5) as
shown in Figures 7 and 8.
The design is based on the following mathematical model
by Edde and Eckenfelder (6):
Cu _ = kB
Ci (ML)n
where
Cu = solids concentration of the underflow in mg/1
Ci - influent solids concentration in mg/1
ks = constant depending on Ci as shown in Figure 8
ML = mass loading in Ibs. solids per day/sq. ft. of
tank surface
(2) Rice, ibid
(4) Barnard, ibid
(5) Atlas Chemicals, Marshall, Texas, Private Report.
(6) Edde, H., and Eckenfelder, W. W., "Theoretical Concept
of Gravity Sludge Thickening," Presented at 40th
Annual Conference of the Water Pollution Control
Federation, New York, New York, October 8, 1967.
151
-------
Ul
10
30
20
to
016
FIG.7 THICKENER PARAMETERS FOR SLUDGE
FROM NEUTRALIZATION OF ACIDIC WASTES
i i
1111
10
20 3O 40 50 60 7O
MASS LOADING (Ibs/ft2-day)
REFC5)
-------
Ul
U)
m
7O
fin
Ov
f>O
40
3O
•j\j
?0
in
1 w
O
\
\
Fl
G. 8
VARIATION OF KB WITH INITIAL
SOLIDS CONCENTRATION
F
V
y
X
^
EF(5)
"^-^
*
8
10
12
INITIAL SOLIDS CONCENTRATION Cj (lOOOmg/l)
-------
This model will be applied to determine the underflow solids
discharged to the vacuum filter or centrifuge.
Sludge Dewatering
The cost functions used for the calculation of costs for
vacuum filters and centrifuges are based on those applied
by Quirck (7) for industrial wastes. The unit capacity
or loading factor for vacuum filters, expressed as Ib.
solids per hour through one square foot Ibs/hr will be
(sq. ft.J
determined from experimentally determined values (5). The
cost function for centrifuges gives:
Capital Cost ($)n=4n
15,700 x (HP) U**U (adjusted to ENR 1285)
The required horsepower is based on 1 HP per 1 gpm of
sludge dewatered. Cost function for vacuum filters.
Capital Cost ($) =
4820 x (area) 0«58 where the area of filter is deter-
mined by load factor.
Example of Cost Calculation for Plant Using Mechanical
Dewatering
Flow rate 1.0 mgd
Acidity 2000 mg/1 as CaCC-3
Suspended solids 200 mg/1
Precipitable metal
salts 200 mg/1
The basicity of hydrated lime (2) is 0.71. For every 1 gm
acidity neutralized 0.76 gm of lime is used to produce
OTTT
1.36 of CaSO4. The basicity factor of 0.71 is probably
due to some unreactive part of the lime that will end up
with the sludge. Assuming that the main product of
(2) Rice, ibid
(5) Atlas Chemicals, ibid
(7) Quirck, T. P., "Application of Computerized Analysis
to Comparative Costs of Sludge Dewatering by Vacuum
Filter and Centrifuge," Report Quirck, Lawler and
Matusky Engineers, New York.
154
-------
neutralization is CaSC>4, the concentration of the salt in
the effluent will be determined by the solubility
product. (Ca+4~) (SOj) = 10 x 10~6, thus the molar concen-
ration of CaS04 in solution would be 0.00315 molar or
428 mg/1. Metal precipitates will add to the sludge as
will initial suspended solids. These values are normally
not high. Where suspended solids are high, they will be
dealt with separately under the cost function. As some
metals will precipitate during neutralization, these will
be added to the total acidity for the purpose of this
study.
Thus, total sludge produced given by sludge (mg/1) =
1.36 x acidity
+0.31 x acidity for unreactive lime constituents
+15% of acidity for metal ppts
-428 mg/1
=1.36 x 2000 + 0.31 x 2000 + 0.15 x 2000 - 428 =
3400 mg/1
Assume sludge production 1.7 x acidity.
Equalization for 6 hours, i.e., basin size 0.25 MG
From cost curve, Capital Cost = $20,000
Neutralization installation
From Figure 4 Capital Cost = $54,000
Thickener - clarifier
Prom Figure 9 Capital Cost = $110,000
Assume
Underflow solids concentration 2% solids
Volume of sludge produced = 3400 x 8.33 = 170,000 gal/day
0.02 x 8.13
Vacuum filter Lf = 2.5 Ibs/day based on Ref (7)
sq. ft.
Filter area = 3400 x 8.33
2.5 x 16
= 710 sq. ft. for 16 hrs/day operation
Capital Cost = $4820 x (710)°-58
= $216,000
Capital Cost of Centrifuge
Sludge volume = 170,000 gpd
=142 gpm for a 20 hour day
155
-------
UI
en
O
O
O
O
o
ouu
500
400
300
ZOO
100
50
40
30
20
0.
FIG. 9 CAPITAL COST OF THICKENERS ^ ^
-
^
/
' 9
REF (2)
X
X
X
fX
x
- ••
X
f
>
r j -
X
X
1 1 1 1
1 0.5 1.0 2.0 3.0 4JO 5.0 10 O
PLANT SIZE (MGD)
-------
which requires 142 HP
Capital Cost = $15,700 x (142)°-40
= $114,000
The cost of the vacuum filter is much higher than for the
centrifuge but there will be a substantial saving in the
operating cost as little chemicals will be required to
achieve the desired results. The capital cost for vacuum
filtration will be used here.
Total cost (excluding trucking)
Equalization 20,000
Neutralization 54,000
Thickener clarifier 110,000
Vacuum filter 216,000
400,000
Add 35% for site preparation
pipework, etc. 140,000
$540,000
Calculating a range of values for flow Q from 0.5 to 50
mgd and for acidity A from 500 mg/1 to 10,000 mg/1, the
following cost model was found:
Capital Cost (in $1000) = 300 x Q0.71A0.34
The acidity seems to be less of a factor in this model
but only because trucking or other disposal of the filter
cake has been included in the total calculated costs.
Also, the operating cost will be much higher than for
lagooning of the sludge. Although the capital costs
will be lower, the total annual cost for mechanically
dewatered sludge will be high.
Operating costs were determined from the acid mine drain-
age report without sludge disposal and the operating costs
of vacuum filters were added to that. The resultant
curves are shown in Figure 10.
Suspended Solids
The sludge produced from the lime neutralization process
has more definite properties than the sludge produced by
the settling of other suspended matter. It was assumed
that at worst the suspended solids will have the same
properties and for this reason, it was lumped together
with acidity in the calculation of total costs.
157
-------
U1
CO
4\J\J
J
O
^^ a f\
o ^o
. ^
-». 60
— 50
K 40
U>
8 30
Z 20
1- 20
<
o:
UJ
0.
o
10
l(
OPERATING COS
(COST
TS FROM RICE REPORT (2)
5 FOR DEWATERING ADDE
/>
^
^^
^x* ^
/ ^
s/
f
I i l
.
/•v
tf. W^^
Oi^"^ C
X ^$$
\9^"^
i i i r
r^
^rV*
ptf"*"
t**
i t
)0 500 1,000 5000 10,000
NET ACIDITY mg/L
FIGURE 10
OPERATING COSTS FOR LIME NEUTRALIZATION INCLUDING
SLUDGE DEWATERING BY VACUUM FILTRATION
-------
Filtration
The cost values used for filtration were obtained from
Smith's (8) curves and they are reproduced in Figure 11,
The capital costs and operating costs were calculated
at ENR index 1285.
(8) Smith, R., "Cost of Conventional and Advanced Treat-
ment of Wastewater, Journal Water Pollution Control
Federation, Vol. 40, 69, September, 1968.~~
159
-------
2000
1000
O
O
O
CO 100
(0
O
u
£
OL
<
u
0.01
1.0 10.0 50.0
DESIGN CAPACITY (MOD)
FIGURE II. COST OF FILTRATION THROUGH SAND OR GRADED MEDIA
AFTER SMITH (8)
-------
DEEP WELL DISPOSAL
The capital cost and operating cost for deep well injection
systems are presented in the attached Figures 12 and 13.
These costs are presented for different flow rates as well
as casing head pressures. The capital costs are expressed
in terms of total capital investment and the operating
cost is expressed on an annual basis. In order to develop
usable curves, it is necessary to select typical geologi-
cal and hydraulic systems (9). Therefore, the following
items were constant:
Depth
Effective Thickness
Porosity
Permeability
Reservoir Pressure of the Disposal Horizon
The diameter of the injection stream was also held constant
and for this particular example was seven inches. The
geological characteristics assumed were based on evaluation
of existing data and are valued to represent the conditions
at more than 50 percent of the existing installations. The
operating costs are based on a power cost of 0.005 dollars
per kilowatt hour, an interest rate of five percent and a
payout period of 20 years.
The ENR building cost index of 700 was used for estimating
the capital cost. These cost flows include minimal ser-
vice treatment. If service treatment greater than filtra-
tion is required, the cost of the additional unit process
must be added to the capital and operating cost shown in
Figures 12 and 13.
In order to convert costs to 1969 values with ENR index
1285, the values from the curve were multiplied by 1.84.
(9) Moseley, J. C., and J. F. Malina, Jr., "Relationships
Between Selected Physical Parameters and Cost
Responses for the Deep-Well Disposal of Aqueous Indus-
trial Wastes," Report published by the Center for
Research in Water Resources, Technical Report, EHE-
07-6801, CRWR-28, The University of Texas at Austin,
(August, 1968).
161
-------
100
90
80
— 70
tr
<
UJ
o
o
o
o
60
Q. 50
O
40
30
INJECTION
PRESSURE
0.2 0.4 0.6 0.8
FLOW RATE (MOD)
1400 psi
1000 psi
600 psi
0 psi
1.0
FIG. 12
ANNUAL OPERATING COST OF DEEP WELL
INJECTION SYSTEMS FOR WASTE DISPOSAL
162
-------
280
~ 260
O
O
O
240
220
200
ISO
(0
O
O
g
0.
<
O
0,2
0.4
0.6
0.8
FLOW RATE (MGD)
INJECTION
PRESSURE
1400 psi
1000 psi
600 psi
0 psi
1,0
FIGURE 13
CAPITAL COST OF DEEP WELL
INJECTION SYSTEMS FOR
WASTE DISPOSAL
163
-------
REVERSE OSMOSIS
The curves actually used for cost calculation were obtained
from the Acid Mine Drainage Report (2) and they are repro-
duced in Figures 14-17. The pretreatment and brine disposal
required was considered separately. These curves gave
generalized cost figures. If more accurate assessments
are required, one can calculate the yield and the actual
membrane size required. This is demonstrated below. For
a high total dissolved solids content, it is necessary to
make an assumption as to the number of units required to
produce the desired effluent. Also, the feasibility of
rejection of brine at certain levels should be considered.
From the viewpoint of producing palatable water only, one
may reject a large quantity of brine for every unit of
water produced if brine disposal presents no problem. How-
ever, when brine disposal does present a problem, the
amount produced must be minimized. For disposal for treat-
ment purposes, both the value of the water produced and the
cost of brine disposal will determine the degree to which
the concentration of the brine must be increased or, con-
versely, the total volume of the brine decreased.
The curves (Figures 14-16) were plotted from actual data
of pilot and demonstration plants. The membrane area
required depends on many factors including: membrane
characteristics (salt rejection, porosity, etc.), applied
pressure, water characteristics, and the feed flow.
The capital costs quoted here are for the entire plant
including installation. However, the operating costs
are for power consumption only. Membrane replacement
costs have been estimated at $0.35/1000 gal. of product
flow. The estimated overall projected figure would be
.35 + .98 = $1.33/1000 gal of treated water (10). This
is a very conservative estimate and does not consider
future improvements in membrane technology.
The operating costs do not include pretreatment to remove
undesirable pollutants such as iron, manganese, organics,
etc., and do not consider ultimate disposal of the brine.
(2) Rice, ibid
(10) Spiegler, K. S., Principles of Desalination, Academic
Press, (1966).
164
-------
o\
Ul
CM
I-'
u.
o
0
UJ
UJ
u_
Ul
(E
10,000
0.30
J_
FIG. 14
AREA OF MEMBRANES AS
A FUNCTION OF
PRODUCTION RATE
REF: "SALINE WATER
CONVERSION REPORT;*
U.S. DEPT. OF SALINE
WATER (1967)
0.40 o;so
PRODUCTION FLOW/ FEED FLOW
0,60
-------
en
-------
o\
O
O
O
O
I-
v>
z
O
O
DC
Ul
O
Q_
w
90
80
70
6O
50
40
30
20
-
••*
^>
•
N
<
S
(
»
*v
\
\
FIG. 16
pnu/pp
AQ A pi
PRODUC
REF (1C
\
CONSUMPTION
JNCTION OF
TION RATE.
» SPIEGLER, ibid
5 6 7 8 9 10
20
30 40
PRODUCTION RATE (gpd/ft.2)
-------
FIG. 17
CAPITAL COST AS A FUNCTION
OF PRODUCTION RATE
REF. (10) SPIEGLER,ibid
3.O
2,0
•o
&
o»
4fe
~1.0
1-
en
O
o
^0.5
H
a.
<
o
0.3
0.2
O.I
-
-
i
\
\
\
\
i i i i
\
\
S ©
\
\
PROD. RATE (gpd/ft2)
168
-------
The latter was considered separately for calculating the
cost of treatment.
Most work with reverse osmosis has been concerned with
TDS levels of 1000-5000 mg/1. Thus, the plots presented
are based on these ranges. Higher levels of TDS would
probably require much more specific surface for equivalent
removals, thus increasing capital expenditures. Also,
maintenance costs would be increased due to increased
scaling, etc.
I. REQUIRED DATA: Plant Flow, Removal Desired Produc-
tion Flow (amount of plant flow to be recovered
through membrane)
If plant flow = 1 mgd and a recovery factor of 60%
is desired, then the production flow = 600,000
gpd - 0.60 mgd waste flow = 0.40 mgd
At influent concentration of 5000 mg/1 TDS and a
desired effluent of 500 mg/1, the desired removal
or fractional "cut" would be 0.90.
II. SIZE OF PLANT AND POWER CONSUMPTION
Product flow = 0.60 mgd
Prod/Feed = 0.60
From Figure 14: Area/Feed flow = 102,000 ft2/mgd
.-. Total Area = 102,000 ft2
check: From Figure 15: @ Prod. Flow - 600,000 gpd,
Area = 102,000 ft2
Production rate = 600,000/100,000 =6.0 gpd/ft2
From Figure 16: Power = 44 KW-hr/k gal = 44,000
KW - hr/day
III. COSTS
Capital Cost
Production rate =5.0 gpd/ft2
.'.From Figure 17:
Capital Cost =1.20 $/gpd + 106 gpd
Operating Cost
Power Consumption = 44,000 kw-hr/day (Figure 16)
.*.@ $0.015/kw-hr
Power Cost = $660/day
169
-------
10.0
CO
o
1.0
FIGURE 18
CAPITAL COST OF REVERSE OSMOSIS
PLANT
REF (2) RICE, ibid
CO
O
O
CL
<
O
i t i i i i i
i 111(11
0.1
i.o
IOJO
PLANT CAPACITY
(MOD)
30.0
-------
10.0
O
O
O
o
o
o
z
cc.
Ill
a.
o
s
Ul
UJ
CO
TIG. I9
OPERATING COST FOR REVERSE OSMOSIS PLANT
REF(2) RICE, ibid
i.O 10
TREATMENT PLANT CAPACITY
(MGD)
-------
ELECTRODIALYSIS
Cost figures for electrodialysis were difficult to obtain
because this method is mostly used where brine disposal
does not represent a problem or very high concentrations
of effluent brine or not necessarily required. As a
treatment method to concentrate and thus reduce the volume
of brine produced, a slightly increased number of cells
will have to be used and a proper balance between brine
produced and usable water production will depend on the
need or cost of the clean water as well as the cost of
brine removal. To get some idea of the number of units
required to concentrate waste streams and produce a
product effluent of less than 500 mg/1 total dissolved
solids, a study was made of existing data (11) to produce
the set of curves in Figure 20. This will give some
idea of the number of units required and the relative
amounts of effluent and brine produced. With recircula-
tion of the waste through the cells the concentration
in each cell will reach an equilibrium value which is
not easy to calculate. Certain values were assumed and
the units calculated according to this. Using basic
design parameters, the size of the plant was calculated
for waste with varying values of total dissolved solids.
These values were then used for calculating the final
capital costs. From Figure 22, the volume of brine was
calculated and the cost of disposal of the brine was
added to the cost of treatment.
Design Equations
I. nAp = 1000 Fd F(2K2Cdif +
CE (i/Cd)0(2K2Cdi (1-f) + K!Y)
nAp = effective transfer area, cm^ (n=number of
individual cell pairs)
f = fraction of total cut through filter (the TDS
removal factor) (measure of approach to
polarization and film diffusion limitations)
should stay less than 0.5
(11) Electrodialysis in Advanced Waste Treatment, FWPCA
Publ. No. WP-20-AWTR-8. Water Pollution Control
Research Service (1967).
172
-------
W
9000 6000 4900 3300 2200
I5OO
1000 50C
APPROXIMATE UNIT OPERATIONAL LEVELS
FIGURE 20 'N m9/l TDS'
DETERMINATION OF TOTAL NUMBER OF UNITS REQUIRED FOR
TREATMENT
-------
10,000
-4
*>.
500.
0.0
1,000
50,000 IDS
10,000 IDS
DS
F1G.2I
RELATIONSHIP OF PLATE
AREA REQUIRED FOR A
DESIRED TDS REMOVAL
(ELECTRODIALYSIS)
REF. (H)
0.)
0.2 0.3 0.4
TOTAL CUT f
0-5
0.6
-------
100,000
10,000
UJ
N
cc
UJ
C
1,000
100
O.I
100,000 IDS
50,000 TDS
FIG. 22
RELATIONSHIP OF
RECTIFIER SIZE TO
SPECIFIC TDS REMOVAL
DESIRED
(ELECTRODIALYSIS)
REE (II)
0.2 0.3 0.4
TOTAL CUT, f
10,000
1,000 T
TDS
DS
0.5 0.6
175
-------
i = Cde)/Cdi
Faraday's constant, 96,500 coulombs/equivalent
current density, ma/cm^
influent dilute stream flow rate, liters/sec
influent dilute stream concentration, equiva-
lent/liter
Cci = concentrated stream concentration equivalent/
liter
kl,k2 = constants depending on various membranes,
solutions, and temperature parameters
ki/ca = a solution resistance term
k2 = a membrane resistance term
Y = 1 + (l^f-)g. (i/Cd) = a measure of approach
(gf+1) ° polarization. Thus,
there is an upper
limit to this ratio.
z = in
(l-gf)
g - Cdi/Cci
CE = current efficiency
II. Vp = Ji/Cd)o
Vp = potential drop across membranes, volts
I = Fd F f Cdi
nCE
DC power requirement = P = (Vpl) in kva
176
-------
TABLE I
SUMMARY
Influent
TDS
1,000
10,000
50,000
100,000
f
0.50
.35
.25
.10
0.50
.35
.25
.10
0.50
.20
.10
0.50
.35
.25
.10
Plate Area
(ft2)
5,180
3,110
2,038
731
6,120
3,440
2,177
742
6,560
1,678
745
6,640
3,585
2,270
747
DC Energy
(kw-hr)
988
742
553
235
26,200
21,600
17,800
8,220
494,000
307,000
171,000
1,890,000
1,710,000
1,450,000
649,000
ED Unit
Cost $
45,380
27,160
17,830
6,400
53,600
30,140
19,040
6,480
57,450
14,690
6,503
58,150
31,410
19,860
6,531
Rectifier
Cost
2,500
1,875
1,400
595
66,100
54,600
45,000
20,800
1,250,000
776,000
431,000
4,770,000
4,330,000
3,550,000
1,641,000
Operating
Cost
DC Energy
Cost $/MGD
9.88
7.42
5.53
2.35
262
216
178
82
4,940
3,070
1,710
18,900
17,100
14,050
6,490
-------
Example: 10 mgd plant
TDS = 1000 mg/1
Normality = 0.01 equiv./liter
Allowable effluent concentration =600 mg/1
.*. f = 1000 - 600/1000 = 0.40
Capital Considerations
From Figure 21: Area of plates
= 3,700 ft2/mgd + 10 mgd
= 37,000 ft2 total
From Figure 22: Rectifier size
= 30.25 ku-a/mgd + 10 = 302.5 ku-a
From Figure 23: Capital cost of plates, spacers, membranes
and electrodes
= 31.500/mgd
= $315.000 total
From Figure 24: Capital cost of rectifier
= $2100/mgd + 10 mgd
= $21,000 total
Capital Cost = $315,000 + $21,000 = $336,000
Stack hardware = $500/mgd = 5,000
10% installation = 0.10 (341,000) = 3,410
Auxiliary equip, (installed @ 40%)
pumps, valves and fittings,
control panels, acid tanks,
conduct = 20.000/mgd = 200,000
(10% miscellaneous included)
Total ±f $544,400
I/ exclusive of building, spare parts, etc.
Operating Condi tions
From Figure 25: DC Energy Requirements
=840 kw-hrs/mgd
= 8400 kw-hrs
178
-------
h-
(O
o
o
5Z
<
o
IOO.OOO
FIGURE 23
50,000
40,000
30,000
20,000
10,000
5000
. CAPITAL CO
- SPACERS, Et
- ELECTRODE*
- REF. (II)
: |
/
*
ST OF
/
^--100,
• CO
• 5O,
i f\
1 Oi
lOrtft '
000 T
000 T
000 T
ros
)S
OS
DS
0.0
O.I
0.2
0.3
0.4
0.5
0.6
TOTAL CUT f
-------
10,000,000
1,000,000
V)
o
o
100,000
a.
o
ae
111
U
UJ
£C
10,000
1,000
0.0
FIG. 24
CAPITAL COST CURVES
-FOR DC RECTIFIER FOR—
ELECTRODIALYSIS REF(H)
100,000 TDS
0.2 0.3 O.4
TOTAL CUT, f
50,000 TPS
10,000 TDS
1,000 TDS
0.5
0.6
180
-------
tOOOO.OOOr
1,000,000
100,000
o
en
UJ
UJ
o
Q
(0,000
1,000
0.0
ai
•100,000 IDS
5QOOOTDS
FIGURE 25
RELATIONSHIP OF DC ENERGY
REQUIRED FOR A DESIRED -
IDS REMOVAL
(ELECTRODIALYSIS) REF (II)
0.2 03 0.4 0.5
TOTAL CUT, f
0.6
181
-------
From Figure 26: DC Energy Operating Costs @ $0.01/kw-hrs
~ 8.40/mgd
Total I/ = $8.40/day
Costs for 0.5 mgd wastewater at 3000 mg/1 total dissolved
solids.
From Figure 20, the following units would be required to
deliver equal volumes of product water at 500 mg/1 total
dissolved solids and brine at 10/000 mg/1.
Approximate
Feed
Concentration
3,000
2,200
1,500
1,000
4,900
6,000
# Units/
mgd
2.8
2.0
1.4
0.7
1.8
1.0
Cost/
Unit
58,000
52,000
50,000
47,000
70,000
78,000
Plus 25% for pumps
Total
Cost
81,000
52,000
35,000
16,000
63,000
78,000
325,000
81,000
406,000
These costs were obtained from costs calculated from the
fundamental design equations. Similar costs evaluated
for other points and those were plotted on Figure 27.
Values for operating costs were calculated as shown in the
Appendix and the values also are shown in Figure 27. One
value obtained from Ref. (12) is shown to be within the
calculated range of operating costs.
I/ Must include maintenance costs:
Membrane replacement = 4 sets/25 years
Spacer replacement = 4 sets/25 years
Anode maintenance - $200/stack year
Other maintenance = 1-1/2% of capital investment/year
Labor = 2 man-hrs./day plus 100 man-hrs. per stack year
Other operating costs would be acid or alkali additions
to maintain a suitable pH.
(12) Lacey, R. E. , Lang, E. W., and Huffman, E. L.,
"Economics of Demineralization by Electrodialysis,"
Saline Water Concession II. Advances in Chemistry
Series 38. American Chemical Society, 1155 16th St.,
N.W., Washington, D.C., 1963.
182
-------
100,000
FIGURE 26
OPERATING COST OF DC ENERGY
REQUIRED FOR SPECIFIC
TDS REMOVAL
(ELECTRODIALYSIS) REF. (II)
10,000
TOTAL CUT, f
183
-------
FIGURE 27
CAPITAL AND OPERATING COSTS FOR
ELECTRODIALYSIS BASED ON FEED FLOW
TO PLANT AT 3000 ppm T. D.S.
10.0
CD
CO
o
o
10
a.
<
o
O.I
O.I
100.0 ^
o
o
o
V)
CO
o
o
o
10.0 =
o:
UJ
a.
o
B COSTS AS CALCULATED
* FROM REFEREN
LACEY, ibid
1.0 10.0 20.0
PLANT SIZE (MGD)
184
-------
ION EXCHANGE
The cost of ion exchange plants is dependent on the total
volume of waste treated but also to a large extent on the
total amount of dissolved solids removed or exchanged since
the flow rate through the media remains fairly constant.
The regenerant chemical cost will also be in direct propor-
tion to the rate of electrolyte removal. The water used
for the wash cycle may for the purpose of treatment, be
returned to the filter and recycled and will thus be added
to the waste stream. The waste stream will be very concen-
trated and provide a possibility of recovery of chemicals
if such chemicals have any commercial values.
The cost curves in Figure 28 were obtained from the Acid
Mine Drainage Report (2) for the Nalco process for an
influent TDS of 1500 mg/1. The curve for the Desal Process
was obtained from Kunin, et al (13).
The No. 3 curve in Figure 28 was calculated on the basis
of the increased capacity required for the increased ion
concentration in the waste.
Operating costs for ion exchange were obtained from various
sources and pieced together to give a reasonable estimate
of the total operating costs. Costs for chemicals used
per Ib. of TDS removed varies with the initial concentra-
tion of the solids in the influent. The curve in Figure
29 was drawn from the following information:
Influent TDS Chemical Cost per Pound
(mg/1) TDS Removed
200 10.2 Ref (14)
354 4.05 Ref (14)
1000 2.0 Ref (15)
(2) Rice/ ibid
(13) Kunin, R. , et al "Desal Process-Economic Exchange
System for Treating Brackish and Acid Mine Drainage
Waters and Waste Effluents," Chemical Engineering
Progress Symposium Series No. 90, Vol. 64, AICHE,
1968.
(14) Levendusky, et al "An Innovation in Ion Exchange,"
Industrial Water Engineering, Vol. 2, 11, Nov., 1965.
(15) Lyons, D., M.S. Thesis, University of Texas at Aus-
tin, 1969.
185
-------
10.0-
CO
a\
LO-
O
o
-I
£
Q.
<
O
0.1-
O.I
I I I I I I I
DE
SAL PROCESS REF. (13)
ID NALCO PROCESS REF. (14)
(D ESTIMATED
I I
i l I I i I I
1.0 10.0
PLANT CAPACITY (MGD)
FIGURE 28 CAPITAL COST OF ION EXCHANGE PLANT
-------
10
»»••
00 9
8
7
6
5
4
O
UJ
1
UJ
£E
CO
O
I-
»
CD
_I
o:
UJ
o.
o
O 3
O
1000
2000
3000
INFLUENT DISSOLVED SOLIDS
(mg/l)
FIG. 29 CHEMICAL COST PER POUND TDS REMOVED
BY ION EXCHANGE
187
-------
The total operating cost for an influent TDS of 3000 mg/1
was calculated as follows:
For 0.5 mgd - 2500 rag/1 removed for effluent concentra-
tion of 500 mg/1
Chemical Costs:
0.001 x 1.5 x 2500 x 8.33 = 31.2C/1000 gal.
Other Costs
Labor
Material
Chemicals
Utilities
For 1.0 mgd
Labor
Material
Chemicals
Utilities
For 10.0 mgd
Labor
Material
Chemicals
Utilities
1.1
1.4
31.2
1.3
3T70 $/1000 gal.
0.9
1.2
30.0
1.2
33.3 C/1000 gal.
0.1
0.9
27.0
1.0
'.6 C/1000 gal.
188
-------
MULTIPLE EFFECT EVAPORATION
The capital and operating costs for multiple effect
evaporation was obtained from the report "Cost of Purify-
ing Municipal Wastewater by Distillation." Environmental
Health Series, Report No. AWTR-6, U.S. Department of HEW
(1963). The costs were based on product water and from the
above report, it appears that approximately 10% brine is
produced. Few operating costs were available. Additional
points were obtained from a report in the 1965 report
"Saline Water Conversion Report," U.S. Department of the
Interior, Office of Saline Water.
The capital and operating costs are shown in Figure 30.
189
-------
vo
o
o
o
o
0.05
12
(O
o
o
CD
o:
UJ
Q.
o
10.0 100.0
PLANT SIZE MGD (PRODUCT WATER)
0.02
FIGURE 30
CAPITAL AND OPERATING COST FOR MULTIPLE
EFFECT EVAPORATION (DISTILLATION)
-------
SOLAR EVAPORATION
Pond evaporation would only be considered in areas where
the land is cheap and the net evaporation exceeds the net
rainfall by a sufficient margin so as to keep the
evaporation ponds within reasonable limits. An example
of such a calculation is given below. No areas of pond
required are calculated and land value is assumed to be
a minimal $100/acre. The costs for construction of the
ponds shown in the curve in Figure 34 does not include the
cost of land.
Example:
Industry located in Austin, Texas
Discharge -0.1 mgd high solids. T° @ 140°F
METHOD 1 - Average conditions (long term) (Empirical
approach)
Determine annual precip. from U.S. Weather Bureau data -
32"
Determine annual lake evaporation from U.S. Weather
Bureau = 60"
Net evaporation - 60-32 = 28"/yr or .0735"/day
From Figure 33 enter @ evaporation/day = .074
Read chart @ acres/mgd = 520
Average required = .1 x 520 = 52 acre
(values are 50% occurrence values).
METHOD II - short term conditions - (Rational Approach)
(1) from local weather bureau, or compiled data (17)
Determine (95% occurrence value)
(16) The Nation's Water Resources, USGPO, Washington, D.C.,
1968, Part 1.
(17) Evaluated Weather Data for Cooling Equipment, Flow
Products Company, Santa Rosa, Calif. (1958)
191
-------
\o
ro
COX CHART
REF(I8) HIMELBLAU, ibid
VAPOR PRESSURE OF WATER VS TEMPERATURE
0.10
1.0 10.0
VAPOR PRESSURE, INCHES Hg
(TO
FIGURE 31
-------
10.0
vo
>-
<
Q
o
Q.
§
Id O.I
CO
UJ
o
z
O.oi
O.I
EVAPORATION
VS
VAPOR PRESSURE
DIFFERENTIAL REF(I7)
where O 0.55W
and W= wind velocity,
mph
L Jl^
>:
<
a:
o
Q.
100
en
LJ
1,0 10
VAPOR PRESSURE DIFF, Ae (inches Hg)
10
IOO
FIGURE 32
-------
10,000
1.0
INCHES WATER
EVAPORATION
1000
vo
*>.
O
CD
CO
UJ
tt
O
IOO
101
0.01
10.0
PER DAY
FIGURE 33
AREA VS
REQUIRED EVAPORATION
REF. (17)
100.0
~qio
\
o
(D
a
O.I
U I
0.10 1.00
INCHES WATER EVAPORATION /DAY
10.0
-------
10 20
SURFACE AREA (IN ACRES)
FIGURE 34
CAPITAL COST RELATIONSHIP FOR
LAGOONS REF (4)
30
195
-------
(a) temperature range
wet bulb temp 77° (Figure 19, Ref. 17)
dry bulb temp 95° (Figure 75, Ref. 17)
(b) wind speed - 15 mph (Figure 73, Ref. 17)
(c) relative humidity - 45% (psychrometric chart
Figure 69, Ref. 18)
(2) From Figure 31
Determine vapor pressures
water @ 140° = 5.8"
Atmosphere @ 95°F = 1.67 x .45 = .75
= 5.8 - .75 = 5.05
From Figure 32 Evap. = 5.8"/day
(3) From Figure 33 @ 5. 8 "/day evap.
read acres/mgd = 6.8 acre/mgd
@ .1 mgd - require .68 acre
Controlled Discharge (19)
Example :
Industry flow @ 200 mgd 308 cfm
Cone @ 1000 TDS = Ci
Stream flow @ 1200 cfs (775 mgd) mean annual flow = SF
Cone @ 100 ppm TDS - Cs
Coefficient variation @
Allowable stream concentration 500 ppm TDS = Ca
Based upon concentration factor -
allowable ratio = II? = Ca-Cs
SF Ci-Ca
or, IF = 500-100 = 400 = .8
SF 1000-500 5"00i
(17) Flow Products Co., ibid
(18) Himelblau, D. M., "Basic Principles and Calculations
in Chemical Engineering," Prentice Hall, Inc.,
England, New Jersey, 1967.
(19) Industrial Waste Guide on Thermal Pollution, U.S.
Department of the Interior, FWPCA, Pacific Northwest
Laboratory, Corvallis, Oregon, September, 1968.
196
-------
. *. @ any time, industrial flow can be 80% of stream
flow or, stream flow must be 125% waste flow
From flow duration curve (USGS)
(1) determine 84% occurrence value and 16% occurrence
value
(2) calculate average ratio between these values and
50% occurrence value (Mode) ; this is Sigma (G) or
standard geometric deviation.
(3) Determine coefficient of variation = sigitia
mode
(refer to fraction of flow duration curve)
Example - 50% value - 1200 cfm
85% value - 7100 cfm
16% value - 280 cfm
= 7100 =5,9 1200 = 4.3, G Avg =5.1
~~~
plotting geometric normal distribution
low (16%) @ 1200 +- 5.1 = 234 high (84%) @ 1200 x 5.1
6120
Coef of variation = 280 = .233
1200
or
1200 = .17
7100.
average = .23 + .17 * .20
Entering draft/storage @ ratio industry flow to stream
flow
IF/SF = 200/775 = .257
and cost of variability @ .25
Storage factor = .063 MAG
.063 x 775 mgd = 488 MG
Storage required
488 mgd x 365 days = 17,800 MG or 89 days
(4) from flow duration curve, flow of 318 cfra would be
exceeded approximately 80% of the time
(5) allowing for dilution factor storage must be
minimal by 25% or 17,800 mg x 125% = 22,300 MG
197
-------
Note: No consideration of rainfall and evaporation has
been made; each individual application should consider
these factors separately.
Cooling Ponds
Temperature drop through a pond
(1) To = {Ti-E)e"a +E
where
To = outlet temperature °F
Ti = inlet temperature °F
(2) a1 = KA
pCpQi
where
a* - decay e ? -1
K = energy exchange coef. (BTU ft day )
A = pond area (ft2)
P = water density (62.4# ft"3)
Cp = specific heat function (1BTU lb""1°F"1}
Qi = influent flow (ft3 day"~i)
E = equilibrium
Solving for K = 157 + (0.26 + B) (bW)
where
W = wind speed in mph
b = experimental evaporation coef.
B = proportionality coefficient
from E(°F) B(mmHg-J-)
50-60 0.405
60-70 0.555
70-80 0.744
80-90 0.990
Example
Assume b = 12
K = 118
To = 80°F
E = 769 °F
from eq. (1)
80 = (93-769)e~a< + 76.9
e-a< = 0.193
a1 = 1.65
Eq. (2)
a1 = 118A
(62.4)(ir(1500)(24)(3600)
a1 = (1.46 x 10-8) A=1.65
A = 11.3 x 10? ft2
A = 2590 acres
198
-------
COOLING TOWERS
Parameter affecting cooling tower costs are (Ref. 20)
(1) Wet bulb temperature - WBT
(2) Approach (CWT-WBT) = A
(3) Range (HWT-CWT) = R
where :
CWT is cooled water temperature
HWT is hot water temperature °F
WBT is web bulb temperature
Example :
An industry is located on a stream having an average dry
weather flow of 1 cfm and a dry weather temperature averag-
ing 70 °F. Industrial discharge totals 400 gpm at 110 °F.
Local regulations limit temperature rise to 10 °F.
By dilution alone, allowable discharge temperature can be
computed by the relationship:
TM = Ti Qi + Ts Qs where
Qi + Qs
or,
Ti = Tm (Qi + Qs) - TsQs
Qi
so, allowable discharge temp.
Ti = 80(400 -I- 450) - 70 (450) = 91°
and the cooling tower must lower the water temperature
from 110°F to 91°F, or a range of approximately 20°. From
local data (U.S. Weather Bureau) the average wet bulb
temperature is 70° giving an approach of approximately
20°
Entering Figure 35 @ range of 20°, approach of 20°, and
WBT of 70° - the relative rating factor of .8.
Using a cost factor of $10.00 per gpm (Ref. 20 + cost
index increase)
The capital cost in 1000 x 400 gpm x .8 = $3,200
(20) Cootner, P. H., Lof, Go. O.7 "Water Demand for Stream
Electric Generation," John Hopkins Press, Baltimore,
Maryland, 1965, p. 69.
199
-------
cc
o
3.0
2.0
1.0
O 3 -
°*9o.e
0.7
0.6
05
04
3.0
2.0
no1'0
0>lT
0.7
0,6
0.5
4.0
3.0
2.0
nj.o
03 —
n fl
07
OA
0.5
-
«
^
*^
•>,
•»»
•^^
•N^
*^^
"^
^^
^*.
^^•^^
"""te
^^.
" ^
"**—,,
^^
"*!•»._.,
^-^
•^»^^^
APPI
^VAL
^**^v
*^,
APPR
"^VA
"^^^
^ —
"v^_
'
^OAC
UES
H "
^^*»
~^»
^^
OA&ir
LUES
^
k-v*>.
^--,
APP
^»^^
*-,
^^N
**-.
^**^
^
*»-
^s
"^
^
ROA(
ALUI
•**^^
•^^
WPL
R
V
•^^
^**^
•*^
^,
*^^^
*^^
*-^_
**-,_
:H •
s
^^^
~*»,^_
^
r
FIG. 35
ELATIVE
/ET BUL
"5°
I A
IU
-I'S0
*-^
•*^.
••^
^
•**
F
: R/S
V
.B 1
'ID- f
RANGE
5°F
l?^~
\*\°
ID
20°
5°F
o°-
5*
20°
TING FACTORS
s
'EMPERATURES
iKotr
DAKIAT
-20°F
RANGE
UJ
>
UJ
CL
50 55 00 63 70 75 80 85 90 95 100
WET BULB TEMPERATURE °F
200
-------
Operating Cost
Cooling tower operating costs
Losses = 0.00112 R
Chemical = .033 Y + 17
C
Acquisition = Wa
Power = (0.14K + 0.005A)p
where:
R - range, °P
Y = alkalinity, ppm CaCOs
C = concentration factor
Wa = cost of water/1000 gal.
K - Relative factor
P = Power costs in C/KWH
A = pumping head in
Total operating costs - (C/1000 gal)
when C=l, assuming Wa=10<:/1000 gal, power @ 1C/KWH and
allowing 0.5 KWH consumption for lifting 1000 gallon
100 feet (approximatey 85% efficiency).
Operating Cost » 0.00112 R (.033 Y + 17) + 10 + (.14K +
.005A)
Example using graph in Figure 36:
Cooling tower operating under @ 20° range with a rela-
tive rating factor of 1.0, alkalinity of 1000, and
assuming 100 foot operating head, cost/1000 gal= 2$,
assume 100,000 gpd flow, then operating cost - 2£ x
100 * $200/day.
201
-------
ro
o
to
O
O
O
t-
U)
O
O
z
K-
<
cr
LU
Q_
o
5.0
4.0
2.0
0.6
0.5
FIG. 36
COOLING TOWERS
JRANGE
JJANGE.
10_ ALKjgQgi^
0.0
0.5
1.0 1.5 2.0 2.5
RELATIVE RATING FACTOR, K
-------
APPENDIX D
BIBLIOGRAPHY
203
-------
BIBLIOGRAPHY
1. Lawson, Barry L., "Atlas of Industrial Water Use,"
Cornell University, Water Resources Center, Publica-
tion No. 18, September, 1967, 47 pages.
2. Grant, H. 0., "Pollution Control in a Phosphoric Acid
Plant," Chemical Engineering Progress, Vol. 60, No.
1, January, 1964, pp. 53-55.
3. "Pollution-Causes, Costs, Controls," Chemical and
Engineering News, Vol. 47, No. 24, June^ 97 T9 69,
pp. 33-68.
4. "Toward a Clean Environment," Manufacturing Chemists
Association, 1967, 24 pages.
5. Sener, Ismail, "What Value Water"? Industrial
Development, October, 1968, pp. 13-16"^
6. "Phosphate-Florida's Hidden Blessing," Florida
Phosphate Council, 1966, 30 pages.
7. "Waste Control at Dow-Midland," The Dow Chemical
Company, 1968, 20 pages.
8. Davis, C. H., Meline, R. S., Graham, G. H., Jr./
"Plant Production of Nitric Phosphates by the TVA
Mixed Acid Process," American Institute of Chemical
Engineers, 63rd National Meeting, February 18-21,
1968, Preprint 15C, 26 pages.
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10. "U.S. Industrial Outlook-1967," U.S. Department of
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July, 1969, pp. 26-29.
204
-------
BIBLIOGRAPHY (cont.)
12. "Water Use in the Chemical Industry," ORSANCO's Chemi-
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December, 1967, pp. 16-20.
13. Cecil, Lawrence K., "Water Reuse and Disposal/1
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205
-------
BIBLIOGRAPHY (cont.)
Waste Conference, Purdue University, May 4, 5, and
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26. "A Study to Determine the Costs of Water in Industrial
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29. Chopey, N. P., "Fresh Ideas Improve Urea Process,"
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32. Labine, R. A., "Converting Waste Sludge Acid to
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35. Spealman, Max L., "New Route to Chlorine and Salt-
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206
-------
BIBLIOGRAPHY (cont.)
37. Rogers, W. R. and Muller, K., "Hydrofluoric Acid
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38. "A Giant Goes into Action," Chemical Week, Vol. 103,
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Vol. 47, No. 4, April, 1955, pp. 672-683.
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. 2010-
10, October, 1954, pp. 2010-2022.
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207
-------
BIBLIOGRAPHY (cont.)
48. Dorsey, J. J., Jr. and Kaufman, J. T., "Stengel
Process Ammonium Nitrate," Industrial and Engineering
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BIBLIOGRAPHY (cont.)
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211
* U. S. GOVERNMENT PRINTING OFFICE : 19TO O - 384-038
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1
Accession Number
w
5
Q Subject Field & Group
05D
SELECTED WATER RESOURCES ABSTRACTS •
INPUT TRANSACTION FORM
Organization
Pittsburgh, Pennsylvania
Title
Inorganic Chemicals Industry Profile( Updated)
] Q Authors)
16
Project Designation
EPA Project 12020 EJI
O1 Note
Citation
23
Descriptors (Starred First)
^Chemical Wastes, "^Economics, Industrial Wastes
25
Identifiers (Starred First)
^Inorganic Chemicals, ^Treatment Costs, Survey
27
Abstract
This report presents a description of the inorganic chemical industry and the costs
"that the industry would incur in attaining various levels of pollution abatement over the
five-year period through 1974. For the study purposes, the inorganic chemical industry
has been defined as including establishments producing alkalies and chlorine, industrial
gases, inorganic pigments, paints and allied products, fertilizers (excluding ammonia and
^ea), inorganic insecticides and herbicides, explosives, and other major industrial in-
organic chemicals. The report presents in considerable detail the description of the
Carious production processes, the waste treatment methods practiced, and the possible
impact that changes in processes might have on the volume and character of the wastes
Produced.
have been based upon the chemical industry data in the 1963 and 1967 Census of
toanuf acturers, the 1967 Manufacturing Chemists Association survey, and the 1968 FWPCA study
°f the organic chemicals industry. Costs of treatment are estimated by year for the
levels of treatment corresponding to 21% and 100# removal of contaminants. Data from
59 inorganic chemical plants were obtained as primary input to the study.
Dr. Henry C. Bramer
Institution
Datagraphics, Incorporated
WR;102 (REV. JULY 1969)
WRSIC
SEND. WITH COPY OF DOCUMENT. TOl WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 20240
* 5POI 1970-389-830
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