PROJECTED WASTEWATER
in the
ORGANIC CHEMICALS
INDUSTRY
A study conducted by:
Cyrus Wm. Rice and Company
Pittsburgh, Pennsylvania
In cooperation with
W. Wesley Eckenfelder, Jr. and Associates
Austin, Texas
Roy F. Western, Inc.
West Chester, Pennsylvania
Resource Engineering Associates, Inc.
Stamford, Connecticut
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PROJECTED WASTEWATER TREATMENT COSTS
IN THE ORGANIC CHEMICALS INDUSTRY
A Study Conducted By:
CYRUS WM. RICE AND COMPANY
PITTSBURGH, PENNSYLVANIA
In Cooperation With
W. WESLEY ECKENFELDER, JR. AND ASSOCIATES
AUSTIN, TEXAS
ROY F. WESTON, INC.
WEST CHESTER, PENNSYLVANIA
RESOURCE ENGINEERING ASSOCIATES, INC
STAMFORD, CONNECTICUT
Prepared under contract with the
federal Water Pollution Control Administration
U.S. Dept. of the Inferior
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TABLE OF CONTENTS
Page
-M W
I. Summary 3
II. Introduction 10
III. The Organic Chemicals Industry 11
IV. Projected Industry Growth 19
V. Wastewater Characteristics 21
VI. Wastewater Treatment Methods 27
VII. Industrial Waste Treatment Practices Data Form 33
VIII. Plant Survey Data 34
IX. Costs of Unit Wastewater Treatment Methods 49
X. Costs Versus Effluent Quality Relationships 60
XI. Projected Industry Costs 88
XII. Methodology for Wastewater Treatment Costs
Determination 103
XIII. Appendicies:
A. Industrial Waste Treatment Practices Data Form....107
B. Organic Chemicals Industry Survey Data 117
C. Petrochemical Industry Product Profiles 122
D. Costs of Unit Wastewater Treatment Practices 168
XIV. Bibliography 184
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I. SUMMARY
This report presents an estimate of the costs that would be incurred
by the organic chemicals industry in attaining various levels of
pollution abatement over a five-year period and gives a generalized
methodology by which similar continuing estimates can be made for
other water-using industries. Cost estimates have been based upon
published data, general data derived from information in the files
of the Contractors on industrial waste treatment methods and costs,
and specific data from 53 organic chemicals plants; the latter
specific data were used to verify the applicability and accuracy of
the former and al'so to develop and test the generalized methodology.
It should be emphasized that the total costs given in this report are
for the construction and operation of waste treatment facilities for
the industry as a whole and cannot be used to determine costs for
individual plants. Organic chemicals plants vary greatly in size,
level of technology, product mix, etc., and a "typical" or "average"
plant exists only in a statistical sense. The costs given are, in
general, for waste treatment facilities only, i.e., for "battery
limit" industrial waste treatment plants. The costs entailed in
process changes, disruption of plant operations, sewer segregation,
monitoring and reporting waste treatment efficiency, etc., particu-
larly in older plants, are not included. Such costs are practi-
cally impossible to estimate in the aggregate and may add 40 percent
or more to the installed costs of facilities. Total costs for
particular plants can only be estimated by detailed engineering
studies; the unit costs in this report should be of value to
engineers in making such estimates.
INDUSTRY PROJECTIONS
The following data are estimated for the organic chemicals industry
for the years 1969 and 1973, based upon the methods and assumptions
detailed in the report.
Number of Large Plants
Production in Large Plants (109#)
Total Industry Production (109#)
Waste Water Volumes:
Large Plants (109 gpy) 287 323
Large Plants (gpd/ton/yr") 12.2 9.23
Municipal Discharges (109 gpy) 94.9 141
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The data indicate that the average large plant can be expected to
treat 3.2 mgd of wastewater during the five-year period 1969-1973.
The capital costs for such an average plant are given below versus
the level of treatment attained, in 1968 dollars.
Level
Removal Critical Pollutants $/1000 gpd Cost (5.2 mgd)
1
2
3
4
5
6
BOD
Removal
10%
83%
98%
99%
100%
COD
of Gross
10%
13%
30%
33%
100%
SS_
Pollutants
65%
71%
89%
99%
100%
147
176
250
700
751
1648
$ 470,400
563,200
800,000
2,240,000
2,403,200
5,273,600
On the basis of the above costs in the average large plant, the esti-
mated numbers of large plants, the total estimated discharges to
municipal sewers, and the assumption that the capital costs
associated with the latter disposal means are those entailed in
Level 1 treatment, capital costs are estimated as follow for the
entire industry in terms of current dollars, using the ENR Construc-
tion Cost Index to adjust 1968 prices.
Treatment Level
1
2
3
4
5
6
Industry Capital Costs (Millions of Dollars)
1969
158.9
182.5
242.6
608.1
649.6
1378.1
1970
172.6
197.8
261.8
561.2
695.3
1471.4
1971
188.3
215.1
283.6
699.9
747.1
1576.9
1972
204.8
233.4
306.5
751.1
801.6
1687.7
1973
222.6
253.2
331.2
805.3
859.1
1804.2
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Estimated operating costs in the average large plant are given below
versus level of treatment in 1968 dollars. These costs are based
upon data obtained from the sample plants and from published
operating cost data.
Level Removal Critical Pollutants $/yr/100 gpd $/yr (5.2 mgd)
1
2
3
4
5
6
BOD
Removal
10%
83%
98%
99%
100%
COD
of Gross
10%
13%
30%
33%
100%
§§.
Pollutants
65%
71%
89%
99%
100%r
7
8.5
13
105
120
350
22,400
27,200
41,600
336,000
384,000
1,120,000
Assuming that the operating costs associated with the discharge of
industrial wastes to municipal sewers are 10 cents per 1000 gpd, the
total operating costs for the industry are given below in current
dollars, using the ENR Construction Cost Index to adjust 1968
prices.
Industry Operating Costs (Millions of Dollars)
Treatment Level
1
2
3
4
5
6
1969
15.5
16.8
20.4
95.1
107.3
294.1
1970
17.3
18.7
22.5
102.1
115.1
314.1
1971
19.5
20.9
25.0
110.2
124.0
356.8
1972
21.9
23.4
27.8
119.4
134.3
363.2
1973
24.4
25.9
30.7
128.3
144.2
388.2
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THE ORGANIC CHEMICALS INDUSTRY
The important products of the organic chemicals industry are miscel-
laneous cyclic and acyclic organic chemicals and chemical products,
flavor and perfume materials, rubber-processing chemicals, plasti-
cizers, pesticides, and other synthetic organic chemicals. Of total
shipments in 1967, 75 percent were miscellaneous acyclic chemicals,
a large number of which are generally designated as petrochemicals.
The expansion of the petroleum industry into chemical production is
of particular significance insofar as the growth and complexity of
the organic chemicals industry is concerned.
Total sales in the organic chemicals industry are estimated to be
11.9 billion dollars in 1969 and 15.6 billion dollars in 1973.
Production is estimated at 135.6 billion pounds in 1969, increasing
to 201.6 billion pounds in 1973. Growth in the industry is not
expected to be uniform either among the various segments of the
industry or among the various geographical areas in which the
industry operates.
Organic chemicals industry pollutants originate from the incomplete
removal of principal products or raw materials from reactions, in
the production of non-recoverable or useless by-products, from
equipment cleaning operations, and from such water uses as cooling
and steam production. Wastewater generation in the industry per
unit of product varies so widely that an average value has little
meaning except in a statistical sense; wastewater generation varies
from less than 100 gallons per ton of product to more than 100,000
gallons per ton of product. The principal contaminants in the
industry's wastewaters are BOD, COD, oil, suspended solids, acidity,
heavy metals, color, taste-and-odor-producing compounds, and
residual organic products and by-products.
The production of organic chemicals results in many types of con-
taminated wastewaters, and the treatment methods employed cover
the range of known practical techniques. In-plant control is the
first step in instituting treatment practices. Such controls
include the salvage of unreacted chemicals, recovery of by-products,
multiple reuse of water, good housekeeping techniques to reduce
leaks and spills, and changes in processing methods. These controls
can result in reducing the concentrations of almost all potential
pollutants and can, most importantly, reduce the volumes of waste-
waters requiring treatment. Physical treatment methods such as
sedimentation or flotation are used primarily to remove coarse
suspended matter and floating oils and scums. Filtration is used
as a form of tertiary treatment for reuse or as a pretreatment
for deep-well injection. Chemical treatment is used primarily as
a pretreatment prior to sedimentation, filtration, or biological
treatment. Biological treatment is most widely used in the
industry due to the nature of the wastes, that is, their general
susceptibility to biodegradation as evidenced by relatively high
BOD values.
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Joint industrial-municipal treatment has proved to be very effective
in treating organic chemical wastewaters, particularly for smaller
chemical plants located near large municipal treatment systems.
Treatment costs play an important role in governing the expansion of
joint treatment participation. Rates established by municipalities
vary extremely. Where the municipal system is small and additional
contributors would overload the treatment plant, the high rates are
imposed to discourage industrial contributors.
The chemical industry has generally found that in-plant, separate
treatment has economic advantages, particularly when significant
quantities of contaminated wastewater are involved. No significant
percentage increase is expected in the amount of organic chemical
wastewaters that will be treated in joint systems in the near
future. On the basis of an annual production of about 71 billion
pounds by the organic chemicals industry in 1963, municipal
discharges might be expected to be about 1400 gallons per ton of
production for the industry as a whole.
DATA ACQUISITION AND METHODOLOGY
Data from 53 organic chemicals plants were obtained and formatted
according to the Industrial Waste Treatment Practices Data Form,
which was developed in the course of this study and is described in
the report. This form may be used for the acquisition of data upon
which the cost-effectiveness of industrial waste treatment practices
can be determined in general. Although the form has utility in
tabulating data for a single plant or firm, the prime purpose is to
format data for analysis in terms of general industry practices.
Data formatted in this system can be retrieved according to selected
parameters, and can be readily sorted and printed out according to
selected parameters, and can be readily analyzed and correlated by
machine computation.
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. It is of particular signifi-
cance that the distributions of wastewater volume and annual produc-
tion are markedly skewed in opposite directions and, although most
of the plants surveyed were judged to be medium or large in terms of
production, employment was relatively low in most cases. The level
of technology in the surveyed plants was generally judged to be
average or advanced, although the median age of the plants was 18
years. The explanation of such an apparent anomaly lies in the
relatively short lives of chemical processes and equipment; replace-
ment equipment and new processes installed in even the older plants
tend to be of modern design.
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The most frequently reported basis for action decisions by plants
was that the legal requirement existed, although legal actions and
public opinion cases were both mentioned. The particular treatment
decision was based upon least total cost most often; least total
cost generally means the least capital and operating costs over an
arbitrary time period and is not evaluated in any sophisticated
sense such as would be involved in considering savings in water use,
etc.
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 then used to calculate capital
costs of waste treatment facilities versus degree of pollutant
removals attainable for 20 typical plants. Both the unit cost data
and the design criteria for the example plants were checked for
reliability and likelihood on the basis of the 53-plant data.
Analysis of the available data indicated that estimates of industry-
wide costs in the organic chemicals industry would best be made on
the basis of estimated costs per plant and estimated numbers of
plants. Alternative calculations could have been made on the basis
of estimated costs per unit volume of wastewater and estimated
wastewater volumes. Cost estimates are based, additionally, upon
the assumption that wastewater generation per unit of production
will decrease as wastewater treatment facilities are installed and
that the costs involved in discharging to municipal sewers are
those of in-plant removal of gross pollutants plus a surcharge of
10 cents per 1000 gpd.
METHODOLOGY FOR WASTEWATER TREATMENT COSTS DETERMINATION
The methods which have been developed and used in this study of the
organic chemicals industry can be utilized to determine wastewater
treatment costs for other industries. The methodology is intended to
be used in establishing and projecting costs for an industry or for
groups of industries, rather than for individual plants. Costs
estimates for individual plants are readily calculable by conven-
tional engineering techniques to almost any degree of precision
desired, depending upon the effort to be expended and the intended
uses of the information. Costs for an industry could, of course,
be determined precisely by calculating the costs of treatment
facilities for each individual plant in an industry and totaling
these costs. Alternatives to this obviously impractical method are
to estimate the number of plants involved and multiply by the
"average" cost per plant or to estimate the volume of wastewater
involved and multiply by the "average" cost per unit volume of
wastewater; such alternative methods are practical and offer a
degree of accuracy sufficient for purposes of industry-wide plan-
ning and economic impact studies. The suggested methods for
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determining the total costs to an industry of attaining specified
degrees of wastewater effluent quality over a time period are
outlined in the report, as a series of steps as follows:
1. Characterization of the Industry
2. Projection of Industry Growth
3. Characterization of Wastewaters
4. Wastewater Treatment Methods Determinations
5. Sample Plant Data Acquisition
6. Sample Data Analysis
7. Unit Wastewater Treatment Methods Costing
8. Determination of Cost vs. Effluent Quality Relationships
9. Projection of Industry Wastewater Generation
10. Project of Industry Costs
Guidelines have been established for the use of this methodology
and its use has been demonstrated in the.organic chemicals
industry. Each industry has its own peculiar characteristics
and care must be taken that these are recognized in applying any
general schemes; for example, in the present study production-
related parameters were shown to be of prime importance, a
reliable estimate of numbers of plants was available, and the
"average" plant costs were closely estimated by two alternative
techniques. In another industry the most likely set of data
might well be different.
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II. INTRODUCTION
This study was performed pursuant to Contract No. 14-12-435, with
the Federal Water Pollution Control Administration, Department
of the Interior, and is a part of the National Requirements and
Cost Estimate Study required by the Federal Water Pollution Control
Act as amended.
The objectives of this study have been to develop estimates of the
costs to the organic chemicals industry of attaining, in a five-
year period, (a) State water quality standards and (b) specific
levels of removal of significant pollutants; and further to develop
a generalized methodology by which similar continuing estimates can
be made for other water-using industries.
These objectives have been accomplished by using data from 53
organic chemicals plants to estimate and predict present and future
treatment methods and costs in the industry and to develop and test
the generalized methodology.
The chemical industry has already expended much money and effort in
wastewater treatment facilities and in seeking new solutions in
pollution control. These efforts, however, have not been uniformly
distributed among either the individual plants or among the various
geographical areas in which chemical plants are operated.
The effectiveness of installed wastewater treatment facilities has
also not been uniform; some plants have wholly adequate facilities
to meet present and projected effluent quality requirements, but
many other plants have only marginal or inadequate facilities.
The information given in this report is not intended to reflect
the cost or wasteload situation for any particular plant. However,
a generalized framework has been provided for analyzing waste
treatment practices and it is hoped that the data given will be
useful in industry's efforts to find and implement the most
efficient ways to reduce wastewaters and resulting stream pollu-
tion.
The comments and suggestions received from members of the Water Re-
sources Committee of the Manufacturing Chemists' Association are
gratefully acknowledged.
10
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III. THE ORGANIC CHEMICALS INDUSTRY
The organic chemicals industry is not readily definable in terms
of the Standard Industrial Classification (SIC) numbers. Present
classifications, based upon 1967 revisions, include SIC 2815
(TTyclic Intermediates, Dyes, Organic Pigments (lakes and toners),
and Cyclic (coal tar) crudesj; SIC 2818 (Organic Chemicals, not
elsewhere classified); portions of SIC 2813 (industrial gases);
portions of SIC 2879 (agricultural chemicals not elsewhere
classified); and portions of SIC 2871 (fertilizers). On the basis
of the older SIC numbers the industry included portions of SIC
2811 (fertilizers) and included SIC 2814 [Cyclic (coal tar)
crudesj. For the purposes of this study, organic gases only were
included from SIC 2813 and ammonia and urea only from the Ferti-
lizer Industry (SIC 2879 and 2871, or the revised SIC 2811).
The important products of the organic chemicals industry are
miscellaneous cyclic and acyclic organic chemicals and chemical
products, flavor and perfume materials, rubber-processing
chemicals, plasticizers, pesticides, and other synthetic organic
chemicals. The organic chemicals industry ordinarily includes
production of monomers, but does not include production of
polymers or plastics and synthetic fibers. Of total shipments
in 1967, 75 percent were miscellaneous acyclic chemicals, a
large number of which are generally designated as petrochemicals.
The expansion of the petroleum industry into chemical production
is of particular significance. Detailed descriptions of the
principal products of the petrochemical industry are contained
in Appendix C.
The overall output of industrial chemicals depends primarily
on total economic activity rather than on any specific segments
of the economy. Changes in consumer preferences or redistribu-
tions of income and spending such as tax increases with increased
defense spending affect product mixes, but do not significantly
affect the total output of the industry. There is some price
competition among industrial chemicals which are possible
substitutes; the demand is primarily derived from the demand for
other goods using industrial chemicals in their manufacture.
Non-price competition, particularly in the development of new or
improved chemicals, is the dominant form of competition in the
industry.
Raw materials for industrial chemicals have been readily available
and at rather stable prices. Future raw materials shortages may
develop in the organic chemicals industry as petroleum fractions
are diverted to produce higher value products such as fuel oil
and gasoline. Industrial chemical industries are generally
capital-intensive operations with high productivity ($75,000 annual
output per-production worker), high wages, a low labor turnover,
and a demand for skilled labor. Most of the large plants operate
11
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continuous processes and must operate at a high percentage of
capacity to maintain acceptable efficiency levels and profit-
ability. Smaller plants generally operate batch processes and
produce low-volume, high-cost, specialized chemicals. Financial
ratios for the Industrial Chemicals Industry are shown in
Table I.
TABLE I
FINANCIAL RATIOS FOR THE INDUSTRIAL CHEMICALS INDUSTRY
Ratio 1965 1964 1965 1966 1967(1)
Profits after taxes/sales (%) 7.5 7.9 7.9 7.8
Profits after taxes/net worth (%) 12.9 14.3 14.7 14.7
Capital Expenditures/gross
plant (%) 6.7 7.3 8.6 8.7
Depreciation/gross plant (!) 6.1 5.8 5.8 5.8
Depreciation/sales (%) 4.5 4.4 4.4 4.4
Sales/total assets 1.1 1.1 1.1 1.1
7.0
SOURCE: U. S. Industrial Outlook 1968, U. S. Dept. of Commerce
(1) First half
By comparison, profits after taxes as percentages of sales for
all manufacturing industries were 5.6 in 1966 and 5.0 in 1967.
Estimated values of shipments in the Industrial Chemicals Industry
for 1968 are shown in Table II.
TABLE II
VALUES OF.SHIPMENTS IN THE INDUSTRIAL CHEMICALS INDUSTRY - 1968
Industry Group SIC Value of Shipments ($106)
Alkalies and Chlorine 2812
Industrial Gases 2813
Intermediates, Dyes, Crudes 2815
Inorganic Pigments 2816
Organic Chemicals, n.e.c. 2818
Inorganic Chemicals, n.e.c. 2819
Total 281
880
620
1,770
630
7,700
4,300
15,900
SOURCE: U. S. Industrial Outlook 1968, U. S. Dept. ofCommerce
Organic chemicals thus constitute about 601 of the entire Indus-
trial Chemicals Group in terms of value of shipments. The
Industrial Chemicals Industry in 1966 had a total value added of
$7,700 million dollars and shipments valued at $13,857 million
dollars. The price index for the industry in 1966 was 95.7 on
the basis of 1957-59 = 100.
12
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Several factors which characterize the organic chemicals industry,
particularly the petrochemical industry, bear significant re-
lationships to waste management problems in the industry:
(a) The industry is characterized by a rapid growth pattern.
It is anticipated that the petrochemical industry will
expand (on a volume basis) at the annual rate of 8-121.
Pollution control problems will, of course, be increased
in some relation to increased production capacity.
(b) The industry is characterized by low capital investment
per dollar of sales together with a low labor rate per
dollar of sales; additional investments and labor expen-
ditures for pollution control thus tend to appear rela-
tively high when expressed in terms of sales dollars and
compared with expenditures for production facilities.
(c) Rapid technological obsolesence is a constant factor in the
industry. This is in part a reflection of the relative
immaturity of the industry as well as the large number of
chemical reaction combinations available in preparative
organic chemistry. Wastewater treatment facilities must,
therefore, be relatively flexible to accommodate frequent
changes in production methods.
(d) The overall price index of chemicals, in contrast with the
general experience of American industry, has fallen 3-6%
in the recent past. Expenditures for pollution control are
of greater significance than in some other industries
where increasing prices can absorb increased costs.
(e) The industry has considerable spare production capacity
because of the interchangeability of processing units,
the availability, during periods of materials shortages,
of obsolete or retired units, and because of the various
alternative sources of many basic chemicals. Wastewater
treatment facilities must accommodate all of the likely
production methods and be sized on the basis of plant
capacities.
(f) The petrochemical industry is characterized by complicated
interrelationships between processes wherein (see Figure
1-3) petrochemicals travel through a variety of stages
(usually at least 2-3) before arriving at a point where
the product has consumer identity. For example
(1) Naphtha is thermally treated to produce ethylene
(2) Ethylene is reacted with chlorine to form ethylene
di chloride
(3) Ethylene dichloride is cracked to produce vinyl
chloride
(4) Vinyl chloride is polymerized to produce polyvinyl-
chloride
13
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ETHYLENE
GLYCOL
POLYESTER
ACRYLO
NITRILE
VINYL
ACETATE
VINYL
CHLORIDE
ETHYLEN
OXIDE
POLY-
ETHYLENE
POLY-
STYRENE
ETHYL
BENZENE
POLY-
PROPYLENE
BASIC
FEEDSTOCKS
GLYCERINE h-
DIRECT
t OXIDATION
ISO-
PROPANOL
ACETAL
DEHYDE
PROPYLENE
OXIDE
AND
GLYCOL
ACIDS
ALCOHOLS
ALDEHYDES
ACRYLATES
ACETIC
ACID
CELLULOSE
ACETATE
POLYESTER
Figure 1 - OLEFINS AND ACETYLENE
-------
PARA-
IXYLENE,
,TNT
NYLON
TOLUENE
MIXED
.XYLENES
ORTHO-
,XYLENE
POLYESTERS
CYCLO-
iHEXANE;
0V
REFINERY
REFORMATS
AND OTHER
.FEEDSTOCKS
PHTHALIC
ANHYDRIDE
RESINS
ETHYL
BENZENE,
-MSTYRENE
DETERGENT]
ALKLYLATEJ
DDT
-HCUMENE
ANILINE,
ACETONE
[C6H5OH
Figure 2 - AROMATICS
BISPHENOL1
A
URETHANES
-------
AMMONIUM
NITRATE
PETROLEUM
SOURCES
PENTA-
ERYTHRITILE
MISCELLANEOUS
ORGANIC CHEMICALS
-------
The organic chemicals industry is confusing to one not well versed
in the nature of the industry. This is due to the number of
products and processes utilized in the industry and at any particu-
lar production site. However, there exist a limited number of
processes which account for a significant portion of the industry
and an understanding of these processes is important in any
evaluation of the industry. The processes are described in detail,
by product, in Appendix C.
The geographical distribution of major organic chemical plants in
the United States is shown in Map A.
17
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LOCATION OF MAJOR ORGANIC CHEMICAL PLANTS MAP A
00
over IOOO employees
500-999 employees
250-499 employees
SCALE IN MILES
0 100 200 300
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IV. PROJECTED INDUSTRY GROWTH
Projected growth in the organic chemicals industry, for the
purpose of the present study, is best expressed in terms of
production based upon the tonnage of chemicals produced.
Growth estimates have been obtained from Chemical and Engi-
ne ering^ News^ a publication of the American Chemical Society.
The dataware obtained from a sophisticated analysis which in-
corporates estimates of overall employment, rate of growth of
the economy, etc. as well as specific characteristics of the
industry and marketability prospects for its products. These
data are considered to be the most reliable available.
TABLE III
PROJECTED PRODUCTION AND SALES OF ORGANIC CHEMICALS
Year
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
Sales
109 Dollars
8.46
9.0
9.9
10.5
11.2
11.9
12.7
13.7
14.6
15.6
Production
1Q9 Pounds
78.7
88.9
100.6
111.7
122.4
135.6
150.4
166.9
183.5
201.6
Sales
109 Pounds
42.8
46.8
52.7
56.6
61.6
67.1
73.2
79.9
86.9
94.3
SOURCE:INDUSTRIAL AND ENGINEERING NEWS, private communication
The above data are applicable to the total organic chemicals
industry. Rates of growth in various segments of the industry
vary considerably, as do the rates of growth by geographical
regions. Expected rates of growth over the next decade accor-
ding to industry segments and geographical distribution are
given in tables IV and V.
19
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TABLE IV
PROJECTED GROWTH RATES IN VARIOUS INDUSTRY SEGMENTS THRU 1975
Industry Segment Growth Rate (% per year)
Urea and Ammonia 9
Petrochemicals 9
Industrial Gases 5
Cyclic Intermediates, etc. 6
Misc. Organic Chemicals 10
SOURCE:REA Projections
These growth patterns are on a volume of production basis and
assume a real growth in the Gross National Product of 3.5% per
year. Growth in the petrochemicals industry will be sparked by
increased demands for fibers, coatings, plastics, and elastomers.
The growth in cyclic intermediates is expected to be due pri-
marily to increased production of ethylbenzene, styrene, and
phenol; high growth rates are not expected in dyes and coal-based
materials.
TABLE V
INDUSTRY GROWTH RATES BY GEOGRAPHICAL AREAS THRU 1975
Area Growth Rate (% per year)
Northeast and Middle Atlantic 5
Southeast 10
Puerto Rico and Virgin Islands 10
Gulf Coast 15
North Central States 5
Mid South 5
Pacific Coast and Alaska 25
SOURCE:REA Projections!
These growth rates reflect the general tendency for the petro-
chemicals industry to gravitate toward the petroleum production
areas such as the Gulf Coast. Growth in the Southeast reflects
growth of the fiber industry as does that in Puerto Rico and the
Virgin Islands. Growth on the Pacific Coast reflects the large
petroleum discoveries in Alaska.
20
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V. WASTEWATER CHARACTERISTICS
Wastewaters from organic chemicals processing consist of contami-
nated and of relatively clean effluent streams. In general, the
contaminated wastewaters are those which are used in direct
contact with products or by-products in reactions, separation
processes, vessel cleanouts, etc. The cleaner wastewaters are
those used for indirect heat exchange, general washing, etc.
Contaminated Wastewaters
The sources of contaminated wastewaters from petrochemical opera-
tions are three-fold. First, wastes containing a principal raw
material or product arise during the stripping of the product from
a solution. Incomplete removal is a fundamental requirement of
any equilibrium process. However, use of more expensive or
additional separation equipment may result in reduction of
effluents. By-products produced during reactions constitute a
second source of wastewaters. Many petrochemical reactions take
place under extreme conditions where the vagaries of organic
chemistry result in the production of chemicals other than those
specifically desired. Often markets cannot be found for these
chemicals or they cannot be reasonably recovered and are discarded
to the waste stream. New production methods are directed toward
increases in yields, and reductions in by-products; accordingly
new technology often results in a decrease in this source of
waste. Spills, slab washdowns, and vessel cleanouts comprise a
third category of effluents and these are generally not controll-
able by means of process modifications; changes in catalyst
concentrations and increases in yields, however, reduce the
amount of pollutants from this source and result in some changes
in the character of the waste. Some typical contaminated
wastewaters associated with general processing are shown in
Table VI.
It is difficult to pinpoint wastewater characteristics and quanti-
ties according to the primary organic chemical industry, but
Table VII presents a partial list of the characteristics associated
with specific chemical wastewaters. Dividing the industry into
six major product groupings,examples are given for each group:
flow is given in terms of volume of wastewater generated per ton
of product produced, while characteristics are given in concentra-
tions, mg/1. All values are expressed in terms of approximate
ranges. The characteristics given are for plants producing the
indicated products and are not necessarily additive in cases
where one product shown is produced from another.
Because of the limited data available, the numerous alternative
processes for producing the same product, and the variabilities
resulting from multi-product facilities, no attempt has been
made to define the production or technology levels of the total
21
-------
TABLE VI
TYPICAL PROCESS GENERATION OF CONTAMINATED WASTEWATERS
Operation
Sources
Typical Pollutants
Process units
Specific Syntheses
Specific treating
operations
Overhead water from distillation,
cracking, coking, etc.
Alkylation and polymerization
processes
Hydrodesulfurization and reforming
processes
Specific process for specific compound
Sweetening, stripping, filtering
Low molecular weight hydrocarbons,
coke, gums, organic acid, soaps,
salts, phenols and phenolates,
cyanides ammonia
Acid sludges, spent acids, caustics,
oil, bauxite and catalyst fines,
corrosion products, hydrogen sulfide
Hydrogen sulfide and miscellaneous
gases (hydrogen) coke, gums,
catalyst fines
Acrylonitrile, polyacrylonitrile,
acrylic acid acrolein, acetaldehyde,
acetonitrile, hydrogen cyanide, etc.
Hydrogen sulfide, mercaptans, amine,
sulfonates, acids, bases, miscella-
neous nitrogen and sulfur compounds,
ammonia, cyanides, furfural inor-
ganic salts and oxides suspended
solids
-------
plant or individual processing equipment. Other variations in
characteristics and the quantity of the wastewater flow resulting
from recirculation, reuse, and by-product recovery capabilities
can significantly alter these factors, even in plants producing
the same products and having similar capacities. Where significant
amounts of heavy metals or other substances are associated with the
wastewaters, these have been indicated.
Generally, the production of primary petrochemicals and polymers
generate the smallest quantities of wastewater with flows in-
creasing as the degree of processing progresses. Concentrations
of contaminants follow approximately the same pattern with some
exceptions. Of those listed, the largest amount of wastewater
results from the production of dyes and pigments because of the
multi-stage, small-batch operations which are very prevalent in
this industry.
It is important to note the staging of the petrochemical industry.
The basic raw materials for the industry are natural gas, refinery
gases and liquid fractions. Of key interest in the industry are
the so-called secondary raw materials; these material (and their
sources) are shown below:
Secondary Raw Material
Acetylene
Methane
Higher Paraffins
Ethylene
Propylene
C^ Hydrocarbons
Higher Olefins
Aromatics
Carbon Monoxide
Hydrogen
Source
Cracking or partial oxidation of
either methane in natural gas or
of higher paraffins
Natural gas
Refinery gas streams or natural gas
Refinery gas streams, pyrolysis of
propane and ethane or by thermal
cracking of liquid hydrocarbons
Refinery gas streams or by thermal
cracking of liquid hydrocarbons
Refinery gas streams or by thermal
cracking of liquid hydrocarbons
Waxcracking
Liquid petroleum fraction recovery,
dehydrogenation, hydrogenation
Partial oxidation of hydrocarbons
Partial oxidation of hydrocarbons
23
-------
From these basic raw materials the industry has created the
variety of intermediates that are finally converted to plastics,
elastomers, resins, solvents and other materials. The major
chemicals which have been surveyed in this report may be
listed as primary, secondary or tertiary intermediates or as
primary polymers. This interrelation between chemicals is a
typical feature of the petrochemical industry and this is
illustrated in the several charts (Figures 1, 2 and 3) which
show the intricate relationship between the chemicals.
Appendix C contains an individual listing of 29 different
petrochemical products together with associated descriptions
of raw materials, processing waste generation and elimination
aspects, and anticipated five-year growth projections for each
product.
Clean Wastewaters
Clean waters, which are basically uncontaminated and can be
discharged untreated, are not included in the total flows
given in Table VII. Cooling water and steam condensates are
the primary sources of such water, and a typical breakdown
is given in Table VIII. Also included is an indication of
potential pollutants and associated sources and concentrations.
Although these clean wastewaters are relatively uncontaminated
and exert little pollutional effect (except thermal) on the
environment, care must be exercised to prevent contamination
of these streams.
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
significantly 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, because the cooled water can be recirculated
in-plant. For the chemical industry, the thermal load exerted
by the effluent from the secondary treatment facilities is
generally restricted by the maximum temperature limitations of
the biological treatment system and is thus of less concern.
The segregation of clean wastewater flows is widely practiced
throughout the organic 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 re-
circulated or discharged separately in those organic chemical
plants with secondary treatment facilities.
24
-------
TABLE VII
WASTEWATER CHARACTERISTICS ASSOCIATED WITH SOME CHEMICAL PRODUCTS
Primary Petrochemicals
Ethylene
Propylene
Primary Intermediates
Toluene
Xylene
Ammonia
Methanol
Ethanol
Buthanol
Ethyl Benzene
Chlorinate Hydrocarbons
Secondary Intermediates
Phenol, Cumene
Acetone
Glycerin, Glycols
Urea
Acetic Anhydride
Terephtalic Acid
Acrylates
Acrilonitrile
Butadiene
Styrene
Vinyl Chloride
Primary Polymers
Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Cellulose Acetate
Butyl Rubber
Dyes and Pigments
Miscellaneous Organics
Isocyanate
Phenyl Glycine
Parathion
Tributyl Phosphate
Flow
gal/ton
50-
100-
300-
200-
300-
300-
300-
200-
300-
50-
500-
500-
1,000-
100-
1,000-
1,000-
1,000-
1,000-
100-
1,000-
10-
400-
400-
500-
1,500-
10-
2,000-
1,500
2,000
3,000
3,000
3,000
3,000
4,000
2,000
3,000
1,000
2,500
1,500
5,000
2,000
8,000
3,000
3,000
10,000
2,000
10,000
200
1,600
1,600
1,000
3,000
200
6,000
50,000-250,000
5,000- 10,000
5,000- 10,000
3,000- 8,000
1,000- 4,000
BOD
1
1
1
mg
100-
100-
300-
500-
25-
300-
300-
500-
500-
50-
,200-
,000-
500-
50-
300-
,000-
500-
200-
25-
300-
200-
/t
1
1
2
4
1
3
4
3
10
5
3
5
3
5
3
2
COD
mg/L
,000
,000
,500
,000
100
,000
,000
,000
,000
150
,000
,000
,500
300
,000
,000
,000
700
200
,000
,000
1
1
1
1
1
2
2
1
2
2
1
500-
500-
,000-
,000-
50-
500-
,000-
,000-
,000-
100-
,000-
,000-
,000-
100-
500-
,000-
,000-
500-
100-
,000-
500-
3
3
5
8
2
4
8
7
15
10
7
8
4
15
1
6
5
,000
,000
,000
,000
250
,000
,000
,000
,000
500
,000
,000
,000
500
,000
,000
,000
,500
400
,000
,000
Other Characteristics
phenol, pH, oil
phenol, pH
oil, nitrogen
oil
oil, solids
heavy metals
heavy metals
pH, oil, solids
phenol, solids
pH
heavy metals
solids, color, cyanide
color, cyanide, pH
oil, solids
50-
500-
800-
2
2
500
,000
,000
1
1
1
2
200-
200-
,000-
,000-
,000-
,500-
4
4
3
2
5
5
,000 solids
,000
,000 solids
,000
,000
,000
200- 400 500- 2,000 heavy metals, color,
solids, pH
1,000- 2,500 4,000- 8,000 nitrogen
1,000- 2,500 4,000- 8,000 phenol
1,500- 3,500 3,000- 6,000 solids, pH
500- 2,000 1,000- 3,000 phosphorus
SOURCE: Roy F. Western and REA
25
-------
TABLE VIII COMPOSITION OF TYPICAL CLEAN WATER EFFLUENT
% of Total POTENTIAL POLLUTANTS
Water Sources Waste Water Flow Range (GPM) Sources
Type
Cooling Water
(excluding sea
water)
40-80
100-10,000
(500-200,000
gal. water ton
product)
Process leaks:
Bearings, exchangers,
etc.
Water treatment
Steam
Equipment
10
50-1,000
Scrubbed from air
through tower
Make-up Water
Boiler Blowdown
Waste Condensate
Concentration
Range (ppm)
1- 1000
Extractables
Mercaptans
sulfides
Phenols
Cyanide
Mies. N. compounds
Acids
Chrornate
Phosphate
Heavy metals
Fluoride
Sulfate
Biocides, algacides
Misc. organics
Hydrogen sulfide
Sulfur dioxide
Oxides of nitrogen
Ammonia
Particulates
Total dissolved solids 100-5000
Particulates 0-100
Phosphates 0-5
Fluoride 0-2
Total dissolved solids 500-10,000
Particulates 5-300
Extractables 0-10
Phosphate 1-50
Sulfite 0-50
Sulfide 0-5
Misc. organic compounds 0-200
Misc. N compounds 1-100
Heavy metals 0-10
Alkalinity 50-400
Extractables 0-100
Ammonia 0-10
0-1000, but
usually less
than 1 ppm
0-60
0-60
0-30
0-30
100-10,000
0-50
0-100
0- 1000
0-300
SOURCE: Freedman. A. J - . et~ al. . Natl . Petroleum Refiners Assoc.. Tech. GC-67-19 . 1967
-------
VI. WASTEWATER TREATMENT METHODS
The production of organic chemicals results in many types of
contaminated wastewaters, and the treatment methods employed
cover the range of known practical techniques. In-plant con-
trol is the first step in instituting treatment practices.
Such controls include the salvage of unreacted chemicals, re-
covery of by-products, multiple reuse of water, good housekeeping
techniques to reduce leaks and spills, and changes in processing
methods. These controls can result in reducing the concentra-
tions of almost all potential pollutants and can, most impor-
tantly, reduce the volumes of wastewaters requiring treatment.
Physical treatment methods such as sedimentation or flotation
are used primarily to remove coarse suspended matter and floating
oils and scums. Filtration is used as a form of tertiary treat-
ment for reuse or as a pretreatment for deep-well injection.
Chemical treatment is used primarily as a pretreatment prior to
sedimentation, filtration, or biological treatment. Biological
treatment is most widely used in the industry due to the nature
of the wastes, that is, their general susceptibility to biode-
gradation as evidenced by relatively high BOD values.
A general treatment process sequence substitution diagram is
given in Figure 4.
This generalized diagram is broken up into two general treatment
trains, one for "dilute" and the other for "concentrated" waste-
water streams. Although this distinction is very arbitrary and
in many smaller plants all contaminated streams are collected for
joint treatment, the primary application is to larger plants where
treatment economics justify segregation and individual disposal.
The generalized diagram does not include all possible treatment
unit processes; only those widely prevalent or often considered
in the organic chemicals industry are included. The specific unit
processes employed and the removal efficiencies obtainable in any
given treatment system vary with the nature and flow of the waste-
water stream.
Example of Conventional Activated Sludge System
[Process Sequence:4-7-9-13-18-20-21-24-28 J
The use of activated sludge to remove soluble biodegradable or-
ganic matter probably is the predominant treatment process.
Many plants utilize such systems and report performances of 88
percent BODs removal. When using the activated sludge process,
the wasted sludge is first aerobically digested, then thickened,
dewatered by vacuum filtration, and disposed to landfill.
27
-------
Figure 4
Chemical Industry
Wastewater Treatment Sequence/Processes Substitution Diagram
Pretreatment
Dilute Wastewater
1 L
^
Screening &
Grit Removal
Equal Izatlon
& Storage
Oil Separation^
Primary Treatment
Chemical
' 4 Neutralization ^
4
i »
4 Chemical Addition
& Coagulation
5
Physical
']Gas Flotation^
1
, 6
*(SedlmentatlonH
7
Secondary Treatment
Dissolved To
Suspended Transfer
1 Activated Sludge |*
9
£ on tact Stabilization!*
'\ Trickling Filter \*
*\ Aerated Lagoon [*»
Suspended Solids
Removal
1 T
*-)Sedlment«tlonlJ ,
10
11
12
13
1
Tertiary
Treatment
_ Coagulation
& Sedimentation
i
L Filtration
-(Carbon Adsorption
,
,
*-| Ion Exchange
«
«
*
J
.Sludge
Treatment
14
15
16
17
Digestion or
Wet Combustion
'Sludge
Disposal
18
Liquid
Disposal
^ Control led <
Transported Disc
I Ocean Olspos<
Surface Appl Icat
Ground Water Set
«| Peep Wet 1 Injei
1 Evaporation 4
Waters]
ts)
00
Incineration
[26
27
]28
29
31
, Sludges
19
Cent rlf Cation
Land Fill | 24
20 '4 Thickening
21 ''-(vacuum Flltratlonj*
cean Disposal| 25
22*-
Lagoon Ing or
r
2
Equal Izatlon
& Storage
4
"] 4-) Neutralization |-| ,
1 ' "1
(Sedimentation t
4
lj Filtration ^
8
Drying Beds \ p
~ni
Deep Well Injection [ 3Q
Incineration
J31
Concentrated Organic
Wastewater
-------
Example of System Employing Contact-Stabilization
(Process Sequence:2-3-4-10-13-19-23-27)
Contact-stabilization systems are not widely used, but this
method has promise of greater application in the very near
future, because it offers some economic advantages over con-
ventional activated sludge treatment. For sludge removal,
this system employs centrifugation and incineration.
Example of Aerated Lagoon System
(Process Sequence:1-2-7-11-24-26)
Where applicable, an aerated lagoon system can prove to be
quite economical. Many plants employ such a system. However,
the solids that build up in both the settling pond and the
aerated lagoon have to be manually removed.
Example of Deep-Well Disposal
(Process Sequence:1-2-8-30)
In the areas where suitable geological formations are available
and where regulations permit, deep-well injection is a suitable
means of ultimate disposal of wastes. Filtration and other
pretreatment are often required to prevent plugging the forma-
tion. This technique is rather widely used in the industry.
Figure 5 shows a flow diagram for a typical wastewater treat-
ment system presently handling the effluent from a large multi-
product organic chemical plant.
JOINT INDUSTRIAL-MUNICIPAL TREATMENT
According to the Census of Manufactures (1963) 45 billion gallons
per year of water from the chemicals industry is discharged to
municipal sewers out of a total of 1.8 trillion gallons taken
in or about 2.41. These data are supported by other studies by
chemical industry groups, but apply to plants reporting water
use of at least 20 million gallons per year or having more than
100 employees. The employment distributions in 641 organic
chemical plants in 1963 is shown in Table IX.
29
-------
Figure 5
FLOW DIAGRAM OF
WASTEWATER TREATMENT FACILITIES
IN-PLANT SEPARATION
REMAINING
PROCESS
WASTEWATERS
v
HIGH BTU VALUE CONCENTRATED PROCESS WASTEWATERS
LOW BTU VALUE CONCENTRATED PROCESS WASTEWATERS
ALTERNATIVE
STORAGE TANK
TO DEEP WELL
TO RIVER
STORAGE TANK
EQUALIZATION BASIN
INCINERATOR
-------
TABLE IX
SIZE OF CHEMICAL PLANTS BY EMPLOYMENT
No. of Plants Employment
162 1-4
58 5-9
79 10-19
104 20-49
68 50-99
79 100-200
38 250-499
29 500-999
17 1000-2499
7 2500+
SOURCE:Census of Manufactures,
The smallest plants tend to be in or near urban centers and
discharge their wastewaters to municipal sewers; these same
plants, however, tend to be users of relatively little water.
Plants in the organic chemicals industry are distributed ac-
cording to total water intake as shown in Table X, based upon
a total of 561 plants surveyed in 1963.
TABLE X
WATER INTAKES OF ORGANIC CHEMICALS PLANTS
No. of Plants Water Intake, million gals, per year
260 less than 1
63 1-9
27 10-19
60 20-99
151 more than 100
SOURCE:Census of Manufactures,
From these data it can be seen that many chemical plants are
not included in the calculation of the 2.4% discharge to
municipal sewers, but that these small plants individually
use relatively little water. If it were assumed that all of the
organic chemicals plants taking in less than 20 million gallons
of water per year discharge all of their intake water to
sewers, a total of about 49.8 billion gallons per year of
wastewater might be expected to have been discharged to munic-
ipal sewers by the organic chemical industry in 1963. This
figure is based upon the assumption that municipal sewer
discharges by the large plants consist mainly of contaminated
wastewaters and that discharges from the smaller plants are
31
-------
entirely process water, presumed to be contaminated, and that
SIC 2515 and 2818 account for 92.5% of the organic chemical
industry.
On the basis of an annual production of about 71 billion pounds
by the organic chemicals industry in 1963, municipal discharges
might be expected to be about 1400 gallons per ton of production
for the industry as a whole.
Treatment costs play an important role in governing the expansion
of joint treatment participation. Rates established by munici-
palities vary widely. Where the municipal system is small and
additional contributors would overload the treatment plant, high
rates are imposed to discourage industrial contributors. Examples
of low, average, and high rates are given as follows:
1. Low - A major Atlantic coastal city applies the
same rates to any industrial discharge as they
do to domestic customers. This rate is based
on 51 percent of the water charge, which cur-
rently amounts to about $0.09/1,000 gallons.
However, the wastewater characteristics have
to be ascertained and acceptable for treatment
prior to acceptance. Furthermore, the city can
establish specific pretreatment requirements
before accepting the wastewater for treatment
in the municipal system.
2. Average - A small municipality in a North Atlantic
State, with a 30 mgd treatment plant, charges the
organic chemicals industry $0.40/1,000 gallons for
a 0.75 mgd discharge.
3. High - In another North Atlantic State, the cur-
rent industrial charge rate specified by the munic-
ipal regulations is $0.70/1,000 gallons for flows
less than 0.03 mgd decreasing to $0.44/1,000 gal-
lons for flows exceeding 0.57 mgd. In addition,
there is a surcharge of $0.20/lb BODs over 250 mg/1,
$0.15/lb suspended solids over 300 mg/1, and
$0.15/lb of chlorine demand above 5 mg/1.
4. In a major Midwestern city there is no charge for
industrial wastes discharged to the municipal
sewers; however, the wastewaters must have a degree
of pretreatment as defined in the city ordnances.
The chemical industry has generally found that in-plant, sepa-
rate treatment has economic advantages, particularly when sig-
nificant quantities of contaminated wastewater are involved.
No significant percentage increase is expected in the amount of
organic chemical wastewaters that will be treated in joint sys-
tems in the near future.
32
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VII. INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
An important objective of this study has been to develop a
generalized methodology for the determination of the cost-
effectiveness of industrial waste treatment practices. The
first requirement of any such generally applicable method is
to format the input data in a uniform and consistent manner
and to insure the adequacy of these data at an early stage,
preferably at the actual time of acquisition. The data form
presented here satisfies these primary requirements and was
used in acquiring data from 53 organic chemicals plants;
these data constitute one basis for this report.
The Industrial Waste Treatment Practices Data Form may be
used for the acquisition of data upon which the cost-effec-
tiveness of industrial waste treatment practices can be deter-
mined in general. Although the form has utility in tabulating
data for a single plant or firm, the prime purpose is to format
data for analysis in terms of general industry practices. The
form is designed on the basis of the Defense Intelligence
Agency's Formmatted File System, a punched-card system utilizing
aperture cards for document incorporation. The system is capable
of accepting subsequent additions of new data at points within
the file and is readily revised within the file. Data formmatted
in this system can be retrieved according to selected parameters,
can be readily sorted and printed out according to selected pa-
rameters, and can be readily analyzed and correlated by machine
computation.
The Industrial Waste Treatment Practices Data Form consists of
nine or more data sheets corresponding to nine types of punched-
cards; there is one each of cards 1, 2, and 5 for each form and
provision for multiple cards 3, 4, 6, 7, 8 and 9 for each form.
Data may be tabulated by a mark (X) within a labeled field, in
terms of quantitative measures in indicated and/or coded units,
or in terms of coded, qualitative information.
The nine data sheets comprising the Industrial Waste Treatment
Practices Data Form are shown in Appendix A.
33
-------
VIII. PLANT SURVEY DATA
The Industrial Waste Treatment Practices Data Form was used
to tabulate data from 53 organic chemicals plants. Complete
information was not obtainable for each plant, but all infor-
mation obtained was used to the extent possible. This
information was largely obtained from confidential reports,
private communications, and pertinent literature.
Data on 37 plants for which adequate information was obtained
are given in Appendix B in terms of the following parameters:
Capital Costs of Treatment Facilities ($/1000 gpd)
(X2) Operating Costs of Treatment Facilities ($/yr/1000 gpd)
Efficiency of Critical Pollutant Removal (%)
(X4) Capital Costs of Treatment Facilities ($/ton of Annual
Production)
(Xs) Operating Costs of Treatment Facilities ($/yr/ton of
Annual Production)
(X6) Volume of Wastewater (gpd/ton of Annual Production)
In Table XI the characteristics of the wastewaters from the 53
plants surveyed are shown in terms of the effluent volume and
the concentrations of BOD, COD, and suspended solids; the iden-
tification numbers generally correspond with the plant numbers
used throughout this report. In Table XII the frequencies of
certain wastewater treatment methods and of sludge treatment
are shown for 41 of the plants surveyed.
The bar graphs in Figures 6 through 10 show distributions of
various parameters for the plants surveyed. It is of particular
significance that the distributions of wastewater volume and an-
nual production are markedly skewed in the opposite directions
and, although most of the plants surveyed were judged to be medium
or large in terms of production, employment was relatively low in
most cases. The level of technology in the surveyed plants was
generally judged to be average or advanced, although the median
age of the plants was 18 years. The explanation of such an appa-
rent anomaly lies in the relatively short lives of chemical
processes and equipment; replacement equipment and new processes
installed in even the older plants tend to be of modern design.
34
-------
TABLE XI
CHEMICAL WASTE CHARACTERISTICS
Identi-
fication
Number Principal Products
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Phthalic anhydride, maleic anhy-
dride Plasticizers, H2S04
Chemical warfare gas , chromium
plating
Terephthalic acid, isophthelic
acid, dimethyl tenaphthalate
Butadiene, Styrene, Polyethy-
lene, Olefins
Phenol, Ethylene
Acrylonitrile
Fatty acids, esters, glycerol
Regenerated cellulose
Acetylene
Dyes, pigments, inks
Azo § Anthraquinine dyes
Anthraquinine vat dyes
Ethylene, Alcohols, Phenol
Benzene, Ethylene, Butyl Rubber,
Butadiene, Xylene, Isoprene
Acrylonitrile, Acetonitrile,
Hydrogen Cyanide
Terephthalic Acid
Glycerine, Various Glycols
Methyl § Ethyl parathion
Methyl isocyanate, Phosgene
Diphenol Glycine
Urea, Ammonia, Nitric acid,
NH4N03
Q
(mjjd)
0.002
0.001
5.36
1.68
2.0
0.302
0.10
1.41
-
0.452
0.94
5.0
5.9
14.7
3.9
0.335
0.49
0.075
0.543
0.65
BOD5 COD
(mjz/1) (rng/1)
200
200 1100
9800
-
300 1200
1200
10,000 14,000
-
-
227
352 1760
300 1160
1700 3600
91 273
390 830
4160
2810
3100 5000
1146 3420
105 140
ss
(rng/1)
24
.
10,600
.
300
239
-
-
-
93
152
-
610
-
106
-
-
80
-
35
-------
Identi-
fication
Number
Principal Products
TABLE XI - Continued
Q
BOD5
(»g/D
mg/11 Cmg/1)
22 Butadiene, styrene, propylene,
polyolefin, adipic acid
23 Butadiene, alkylate, methylethyl
ketone, styrene, maleic anhy-
dride
24 Butadiene, Maleic acid, Fumeric
acid, Tetrahydrophthalic
anhydride
25 Diphenol carbonate, D-nitro-
phenol, benzene, Quinolin,
H2S04» Tear gas, Ditnitro
benzoic acid
26 Organo-phosphates, Esters, Re-
sins Phosphorous chlorides
27 Phenols
28 500 Different products
30 Organic § Inorganic Chemicals
31 Phenols
32 Additives for lubricating oils
33 Polyethylene, ethylene oxide,
ethand polypropylene
34 -Acrylates, Insecticides, en-
zymes, Formaldehydes, Amines
35 Ethylene, propylene, butadiene,
crude benzene, toluene
36 Acids, Formaldehyde, acetone,
methanol, ketones, nitric acid,
nylon salt, vinyl acetate
acetaldehyde
37 Isocynates, Polyols, Urethane
Foam
38 Acetaldehyde
1.38 5630 1230
2.0 1870
3.605 959 1525
0.098 650 1380
1.2
0.215
3.2
2.1
0.22
0.20
2.1
1.06
0.228
3.46
0.57
1.15
845
6600
360
100
6600
465
1385
1960
500
530
421
20,000
2040
13,200
500
-
13,200
1050
2842
2660
-
10,131
1201
50,001
225
10
322
673
250
80
160
50
36
-------
TABLE XI - Continued
Identi-
fication
Number
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
Principal Products
Acrylanitrile, phenol, Butadiene
Ethylene, Propylene, Toulene,
xylene
Acids, Formaldehyde, Acetone,
methanol, ketones, alcohols,
acetaldehyde
(mRd)
1.817
0.43
1.15
Petrochemicals 15.2
Acrylonitrile, butadiene, styrene
impact polystyrene, crystal
polys trene
Ethylene, Propylene, Butadiene
alpha-olefins, polyethylenes
Organic chemicals
Pharmaceuticals (Dallas WPCF 66)
Organic Chemicals
2,4,5-T
2-4-D
Butadiene
Organic Chemicals
Olefins
Adipic acid
Hexamethylenediamine
Petro Chemicals
Petro Chemicals
»
0.085
0.750
1.4
0.037
0.077
0.005
0.005
0.288
0.288
0.288
0.13
0.13
0.02
0.17
BOD5
(mjz/1)
1300
15,000
177
200
155
2000
14,000
850
15,000
15,000
-
-
-
-
-
-
24,000
COD
(mg/1)
29,100
1500
30,000
-
380
4800
-
1700
21,000
23,000
350
750
320
35,000
113,000
40,000
39,000
SS
(mg/1)
-
.
-
60
120
900
500
300
700
348
300
120
400
180
1200
30
-
37
-------
TABLE XII
REPORTED UNIT PROCESS BREAK-DOWNS
Plant
No.
1
5
6
T A
10
1 O
ll
1 f
13
1 &
14
15
1 £.
lo
17
18
19
20
22
23
24
25
26
27
28
29
30
31
32
34
T C
35
T £.
3o
T t
37
7 O
38
39
4 /\
40
^
41
Oil
Sep.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Coag. -
Eq. Sed. Neut.
X
X X
X X
X
X
X
X
X
X
X X
X
X X
X X
X
X X
X X
X X
X
X
X X
X X
X
X
X
X
X
X X
X
Sludge treatment
A.L. A.S. yes no Products
x x Dye chem.
x x Dye chem.
x Dye chem.
x x Petro chem.
x x Petro. chem.
x Org. chem.
Org. chem.
x x Org. chem.
Org. chem.
Org. chem.
x x Org. chem.
x x Org. chem.
Org. §inor. chem.
Petro chem.
x x Org. Sinor. chem.
x x Petro chem.
x monome rs -po lyme r
Petro chem.
Petro chem.
Org. chem.
x chem.
xx x Petro chem.
Petro chem.
x x Phenol
x x Misc. chem.
x x Petro chem.
Petro. chem.
x Petro. chem.
x Petro. chem.
x Misc. chem.
Petro. chem.
x x cyclic chem.
Org. chem.
x x Org. chem.
Cyclic chem.
Petro chem.
x Org. chem.
Org. chem.
Org. chem.
Number industries reporting specified unit processes:
20 8 18 13 9 15 8
38
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SIZE OF PLANT IN THE INDUSTRY
41
-------
LEAST
TOTAL
COST
Figure 9 [
z«0
uJ
r>
o
uj 8
o
UJ
DC 5
1911- 1920
-1940 1941-1950 1951-1960 1961-1968
YEAR OF CONSTRUCTION
42
-------
18
17
16
15
14
13
12
Figure 10
o
LJ
tr
L. 10
< 9
_i
0.
8
7
6
5
4
3
2
.1 rrj j; 1_
LAW
111
PUBLIC
OPINION
LEGAL 1
ACTION
BASIS OF ACTION DECISION
43
-------
The most frequently reported basis for an action decision by
the plant was that the legal requirement existed, although
legal actions and public opinion cases were both mentioned.
The particular treatment decision was based upon least total
cost most often; least total cost generally means the least
capital and operating costs over an arbitrary time period and
is not evaluated in any sophisticated sense such as would be
involved in considering savings in water use, etc.
According to the 1963 Census of Manufactures, Water Use in
Manufacturing, 195 plants in SIC categories 2815 and 2818 took
in for process use a total of 323 billion gallons of waste-
water in 1964, an average of 1.66 billion gallons per year per
plant, indicating an average wastewater flow of 4,564,000 gpd
per plant. These data apply to the generally larger plants in
these industries.
In 1963 there were a total of 641 plants in the organic chem-
icals industry. The 1963 production in the industry was about
71 billion pounds. These data indicate an overall average
production in the industry of 110.76 million pounds or about
55,000 tons per year per plant. This figure has no meaning in
any real sense because of the preponderant number of very small
plants, and should be used, if at all, with caution.
There were 211 organic chemical plants having water intakes of
more than 20 million gallons per year according to the 1963
census data. These are the larger plants which might be expec-
ted to average the above wastewater flow of 4,564,000 gpd. The
industry survey data appended to the report covers 34 individual
products which accounted for 117.187 billion pounds out of a
total of 122.38 billion pounds (or about 95%) of organic chemi-
cals produced in 1968; 238 plants are indicated to have accounted
for this production, or an average plant production of 257,100
tons per year. The data of that survey also indicate an average
capacity per product in individual plants of 231 million pounds
per year (i.e., the total production of a product divided by the
number of plants in which it is produced).
The data of this study, based upon 24 pl'ants for which production
and wastewater flows were determined, indicate an average flow of
2,318,692 gpd per plant, an average capacity of 306,097 tons/year,
and an average capacity per product in individual plants of 267
million pounds per year. Considering that these parameters varied
by several orders of magnitude within the sample, the sample can
be considered to be a fair representation of the industry.
The distributions of plants by state and by capacities per
product in individual plants for the entire industry and
for the sample data are shown in Figures 11 and 12; again
the sample is considered to be a fair representation of the
industry.
44
-------
o
z
!u
o
UJ
K
65
60
55
50
45
40
35
30
25
20
15
10
5
Figure 11
= f~ 1~ TOTAL ORGANIC
1 ' CHEMICAL PLANTS
- ORGANIC CHEMICAL
PLANTS SURVEYED
4
STATES
-------
CO
3
1
f-
DL
tr
Q-
o
o
O
O
§
CL
UJ
O
<
Dt
UJ
II- TOTAL PLANTS
- PLANTS SURVEYED
-------
The survey data were examined for significant relationships
between the various parameters of plant operation and/or
waste treatment practices by means of multiple regression
analyses made using both the absolute values of the variables
and the logarithm of each variable. The results of the re-
gression analyses are discussed below with the intent of in-
dicating which relationships are of significance.
Data for 18 plants were analyzed in terms of the calculated
parameters X-^, ^2, Xj, X4 , Xs, X£ defined previously. Two
statistically significant relationships were found at the
0.900 level of significance.
The capital costs of waste treatment facilities in a plant
were found to be a logarithmic function of the wastewater
volume; the regression equation is:
log(X4) = 1.1145 + 1.1559 log (Xg) (1)
where: X4 = Capital Costs of Treatment Facilities
($/ton of Annual Production)
X5 = Volume of Wastewater (gpd/ton of Annual Production)
Of the variation in X4, 80% is explained by Xg alone (R2 =
0.7993) and the variance of X4 is reduced by an order of magnitude
(Sy = 2.3054; SE = 1.0690) .
Operating costs of treatment facilities in a plant were found to
be a logarithmic function of capital costs of treatment facili-
ties; the regression equation is:
log(X5) = 1.8977 + 0.9293 log (X4) (2)
where: Xs = Operating Costs of Treatment Facilities
($/yr/Ton of Annual Production)
*y
Of the variation in X5, 78% is explained by X4 (R^ = 0.7826)
and the variance in Xs is reduced by an order of magnitude
(Sy = 2.2765; SE = 1.0964).
Using all of the data available as appropriate, no statistically
significant relationships were found between the efficiencies of
critical pollutant removal and the other parameters. At a low
level of significance, however, the capital costs of treatment
facilities were indicated to be the major determinant of removal
efficiencies .
47
-------
With the data of 40 unit treatment operations no significant re-
lationships were found between efficiencies of critical pollutant
removals and costs per unit volume of wastewater.
Unit operating costs were found to be related to unit capital
costs for individual systems at the 0.900 level of significance
according to the following regression equation:
X2 = -76.7181 + 0.2611
(3)
where: Xj^ = Capital Costs of Treatment Facilities ($/1000 gpd)
Xo = Operating Costs of Treatment Facilities
($/yr/1000 gpd)
Of the variation in X2, 92% is explained by Xi (R2 = 0.9241)
and the variance in X2 is reduced by more than 701
(Sy = 1544; SE = 431).
48
-------
IX. COSTS OF UNIT WASTEWATER TREATMENT METHODS
There are several processes which have been and are being
applied to the treatment of wastewaters from the chemical in-
dustry. One of several biological treatment processes or a
combination of processes will effect removal of the degradable
organic compounds present in the waste. Anaerobic lagoons
have been used where large land areas are available and will
provide removals to BOD levels in the order of 100 mg/1.
Aerated lagoons will reduce the BOD to levels in the order of
50 mg/1 (depending on the temperature, the effluent BOD usually
increasing during low temperature operation). The activated
sludge process will provide high degree efficiency, with efflu-
ent BOD values of less than 25 mg/1.
In order to insure optimal and consistent secondary treatment
performance, several pretreatment steps are frequently required.
These include oil separation, neutralization and, in the case of
high load variations, equalization. In cases where high concen-
trations of suspended solids are present in the waste, primary
sedimentation is provided.
Figure 13 shows the processes most commonly employed for the
treatment of chemical industry wastes. The treatment sequence
has been broken down into pretreatment or primary treatment,
secondary or biological treatment, tertiary treatment, and sludge
handling and disposal.
For purposes of developing the cost-effluent quality relation-
ships the effluent characteristics for the principal pollutional
parameters have been estimated for each of the unit processes
and are shown in Figure 13. No change in effluent characteristic
(BOD, COD, S.S.) is attributed to neutralization or equalization.
Primary sedimentation has been estimated to yield 65 percent and
10 percent removal of BOD and suspended solids respectively.
The effluent BOD from the anaerobic lagoon, the aerated lagoon
and the activated sludge process is estimated at 200, 100, and
25 mg/1, respectively. (This assumes average operating conditions
at ambient temperature).
For each stage of the process, the effluent COD has been estimated
from the relationship CODEFF = CODINF - BOD5 removed/0.75
(It should be noted that the accumulation of non-biodegrad-
able COD during the biological oxidation process has not been
included).
The effluent characteristics for the tertiary treatment pro-
cesses have been estimated from laboratory and field results
on both municipal sewage and industrial wastewaters.
49
-------
Figure 13
WASTEWATER TREATMENT PROCESSES 8 MODELS
PRE OR PRIMARY TREATMENT
en
O
»EUt«LIZ«riON
OIL
ICNMTKM
All
st«i»rm«
IK
FLOT»TIO«
co»«UL»Tion
t
BIOLOGICAL TREATMENT
INFLUENT CHARACTERISTICS SUSPENDED SOLIDS < 125 PPM, ALKALINITY <0.5I Ib/ Ib BOO, SULFIOES <250 PPM. OIL tt GREASE < 50 PPM.
600 VARIATIONS !* 3-1 (Ib/dfl). 4-hr COMPOSITE 1
4CIIVJTED JLUOiE
^1 . I
* !!,»
»«t tlVSSI «$,«,
It O,/ OKI n'S, «»'»,
"(I
EFFLUENT CHARACTERISTICS'
SOLUAILE BOD lul/ll 10 -JO
TOUl BOO <»t/V) 15-!)
SUSPENDED SOLIDS l*|/l| < 10
COD I HI/I) (*_
10 - (0
tO- 40
< 70
(-1
mmocEii lit)
fHOJfHOHUJ Ilk)
TERTIARY TREATMENT
(OEPEHD5 OK DE5I6II HETEKriOH)
I PERIODS I TEHPCMTURE ]
SO-tOOIFUHCTIOH Of N«E« LEVEL!
-COO,.- (lOOgm
(-1
»«M«0«lt U«00«S
3 T7F,
FOR POK05 III StUltJ
> 100
100
< 100
l-l
CARIO*
tOSORPTIOH
CO>CVL
-------
Where available and applicable, mathematical models have been
developed for specific processes. These are shown in Figure
13. The average coefficients for these models are summarized
in Table XIII and the ranges of values obtained from 14 differ-
ent chemical wastes receiving biological treatment are given.
A definition of the symbols used in Figure 13 is detailed in
Table XIV.
The mathematical models shown in Figure 13 and the average
coefficients shown in Table XIII have been used to develop the
treatment plant sizes for the cost vs effluent quality study
discussed later in this report.
COST FUNCTIONS
The total cost functions and the unit cost functions which were
developed are based on data reported for actual organic chemical
plants which treat wastewater. The cost data were derived from
information reported in the "Industrial Waste Profiles - The Cost
of Clean Water," in published and private reports, and from
private communications. All the cost data have been adjusted to
1968 costs using the Engineering News Record (ENR) Construction
Cost Index.
The total capital cost functions for activated sludge treatment
plants are graphically related to wastewater flow in Figures 14
and 15 and to incoming BOD in Figures 16 and 17.
The systems which were considered included pretreatment or pri-
mary treatment, the activated sludge aeration basin(s) and
equipment, and final clarifier(s). However, in one system
sludge treatment was included and the other system included la-
gooning of the sludge. The data in Figures 14 and 16 are for
eight activated sludge plants with sludge treatment and the data
for fourteen activated sludge plants without sludge treatment
are presented in Figures 15 and 17. There is a better relation-
ship between total capital cost and flow than between cost and
BOD for both systems.
A mathematical expression of the relationship between total capi-
tal cost and the flow and BOD is presented in Table XV. The
constants and exponents which are also reported in Table XV were
evaluated by means of a regression analysis of the data presented
in Figures 14-17 inclusive. The results of the regression analyses
indicate that for the system without sludge treatment the waste -
water flow and incoming BOD concentration seem to have an equal
effect on the total capital cost. However, in the system with
sludge treatment the wastewater flow seems to have a more marked
effect on the total capital cost than does the incoming BOD
concentration.
The total capital cost function presented in Table XV is appli-
cable only over the range of data used in the regression anal-
51
-------
TABLE XIII
COEFFICIENTS AND CONSTANTS FOR BIOLOGICAL TREATMENT
OF WASTES FROM THE CHEMICAL INDUSTRY
Activated Sludge
Range of Values
(1 standard deviation)
k (1/mg-hr)
a
a1
b (day'1)
b1 (day'1)
8
F (Ib BOD/lbMLVSS/day)
Aerated Lagoon
K (day"1)
X (mg/1)
9V
Anaerobic Lagoons
K (day'1)
K_ (day'1)
9e
TricKling Filter
K1 - kxAm
n v
e
Gravity Thickeners
B
n
M.L. (Ib/sq ft/day)
C (percent solids)
0.00012
0.31
0.31
0.02
0.10
1.0
0.4
0.5
50.
1.085 -
0.030
0.07
1.08
0.24
0.4
1.035
4.
0.25
4.
3.
*K reaction rate for equation se =
K reaction rate constant
So
for equation
- 0.00076
- 0.72
- 0.76
- 0.18
- 0.24
- 1.04
- 0.0
1.0
ISO.
1.1
- 0.055
- 0.13
- 1.09
- 1.25
- 0.5
- 1.08
- 16.
- 1.8
- 12
- 5.
1
1+Kt
se = e
S
0
K1 based on loading in MGAD
Vacuum Filtration
m
n
s
Cake Moisture (% by wt)
Loading Ranges
(Ib solids/sq ft/hr)
Aerobic Digestion
Retention time (days)
Carbon Adsorption
Ibs COD/lb Carbon
Filtration
gpm/ft2
Primary Sedimentation
Overflow rate
(gal/day/ft2)
Secondary Sedimentation
0.5
0.5
0.72
72.
3.
10.
0.3
5.
500
- 0.71
- 0.70
- 0.88
- 79.
7.
- 24.
- 0.6
- 10.
1000.
- K
e
Average
0.00024
0.52
0.53
0.07
0.17
1.03
0.5
0.75
100.
0.042
0.10
1.085
(applicable to single ponds)
(applicable to series of ponds)
5.
15.
0.5
Overflow rate
(gal/day/ft2)
500.
700.
750.
600.
-------
TABLE XIV - LIST OF SYMBOLS
X , X , X Average, degradable fraction, and volatile fraction
a d v of the mass of the biological cells (Ibs)
x , x , x Average, degradable, and volatile biological solids
" concentration in aeration basin (mg/1)
AXy Cell or sludge yield (Ibs/day)
S , S Substrate (expressed as BOD or COD) applied or removed
a r (Ibs/day)
SQ, s Influent and effluent substrate concentration (mg/1)
K, K , K, Substrate removal rate coefficients and biological
sludge oxidation rate (day' )
K* Substrate removal rate for trickling filter
k Substrate removal rate coefficient (liter/mg-hr)
9 Temperature coefficient for the rate constant k or K
T Temperature (°C)
a Fraction of substrate removed, used for cell synthesis
a* Oxygen utilization coefficient for cell synthesis
b Cell auto-oxidation rate coefficient (day"1)
b' Oxygen utilization rate for endogenous respiration (day ~ )
t Time, retention time or cycle time (minutes, hours or days)
A Specific surface area of volatile media for trickling filters
F Food to micro-organism ratio (Ib BOD/lb MLVSS/day)
V Volatile fraction of biological sludge
f Degradable fraction of volatile solids
SS Suspended Solids (mg/1)
BOD Biochemical Oxygen Demand, S days at 20°C (mg/1)
BODU Biochemical Oxygen Demand, ultimate at 20°C (mg/1)
COD Chemical Oxygen Demand (mg/1)
TDS Total Dissolved Solids, inorganic (mg/1)
mg/1 Milligrams per liter
SRT Solids Retention Time
PQ Amount of phosphorous in influent (Ib)
N Amount of nitrogen in influent (Ib)
L Vacuum Filter Loading (Ib per sq ft per hour)
Cu Underflow concentration of solids from thickener (t solids)
C Overflow concentration from sludge thickener (I solids)
ML Mass Loading for sludge thickener (Ibs per sq ft per hr)
B Constant for sludge thickener
D Depth (ft)
P Vacuum pressure for vacuum filtration (inches Hg)
s Coefficient of compressibility of filter cake
c Weight of solids per unit volume of filtrate (gm/ml)
u Kinematic viscosity of the liquid (centipoise)
RO Specific resistance of the filter media (secz/gm)-
m,n Exponents, constant for specific type of sludge
F0 Overflow concentration for flotation process (t solids)
F Underflow concentration for the flotation process (t)
Q Flow rate (MGD, gpm, etc.)
53
-------
Figure 14
TOTAL CAPITAL COST RELATIONSHIP OF
ACTIVATED SLUDGE PLANTS WITH SLUDGE TREATMENT
FLOW- MGD
54
-------
Figure 15
TOTAL CAPITAL COST OF
ACTIVATED SLUDGE PLANTS WITHOUT SLUDGE TREATMENT
10.0
FLOW-MGD
55
-------
Figure 16
TOTAL CAPITAL COST OF
ACTIVATED SLUDGE WITH SLUDGE TREATMENT
BOD - mg / I
56
-------
Figure 17
TOTAL CAPITAL COST OF
ACTIVATED SLUDGE PLANTS WITHOUT SLUDGE TREATMENT
fO
10
BOD - mg/I
57
-------
yses. The flow range over which the relationship can be applied
is 30,000 gallons per day to 15 million gallons per day and the
BOD range is 150 mg/1 to 6000 mg/1.
The unit cost functions for the various unit processes are graph-
ically presented in Appendix D. The treatment processes and cost
function relationship, for which data are available are summarized
in Table XVI. The range of applicability of the unit cost function
for each of the processes presented are illustrated by the extent
of the curve(s) in Appendix D. One should be careful not to attempt
to apply these unit cost functions beyond the range of the data
presented.
TABLE XV
MATHEMATICAL MODEL OF WASTE TREATMENT COSTS, USING THE
COST OF EXISTING FACILITIES
C = K Qm Sn
o
where C - Capital cost in $1,000 (1968 replacement value
K = Constant
Q = Flow in MGD
S0 = BOD of waste in mg/1
Activated sludge without sludge treatment
90% confidence limits
Activated sludge with sludge treatment
90% confidence limits
K
62.0
14.1-270
433
85-2200
m
0.44
±0.14
0.71
±0.20
n
0.41
±0.23
0.17
±0.23
The total capital cost for a particular treatment system may
be calculated by adding the unit cost of each process included
in the system and to this total add 35 percent to cover the
costs of piping, pumping, engineering and other contingencies.
The percentage was derived by comparing the total reported
capital cost of an existing plant with the total capital cost
which was calculated by adding the unit costs of each unit
process.
The difference between these total costs was considered to in-
clude the miscellaneous cost mentioned above and was expressed
in terms of a percentage of the total capital cost.
The costs of deep well disposal present particularly unique prob-
lems. The cost function for deep well disposal is affected
markedly by a number of variables, therefore, a simple two-
dimensional graphical presentation will not provide a relationship
which can be generally applied to all disposal well systems.
The variables which are significant include:
58
-------
a. Flow rate
b. Required surface pretreatment
c. Diameter and number of the well and
d. Operating casing head pressure
Geological characteristics including type of formation, permeability
and porosity are other factors which can affect the total capital
cost.
The operating costs for disposal wells are primarily a function of
the operating well head pressure which in turn is affected by the
formation properties. The flow rate is related to some extent to
the operating pressure especially in the case where the friction
loss is high. The friction loss can be significant in a multiple
well system in which a distribution system is employed. The cost
of surface pretreatment will also add to the operating costs.
TABLE XVI
SUMMARY OF BASES FOR UNIT COST FUNCTIONS
Pre or Primary Treatment
Equalization
Neutralization
Oil Separation
Sedimentation
Biological Treatment
Lagoons
Aerated Lagoons
Activated Sludge
Aeration basin
Final Clarifier
Tertiary Treatment
Filtration
Ion Exchange
Adsorption (carbon)
Sludge jlandling and Disposal
Total sludge disposal
Thickening
Flotation thickening
Vacuum Filtration
Ultimate Disposal
Deep Well Injection
Cost vs. volume (Gal)
Cost vs. flow rate (MGD)
Cost/MGD vs. flow Rate (MGD)
Cost vs. Surface Area (Sq Ft)
Cost vs. Surface Area (Acre)
Cost vs. volume (MG)
Cost vs. volume (MG)
Cost vs. Surface Area (Sq Ft)
Cost vs.
Cost vs.
Cost vs.
flow rate (MGD)
flow rate (MGD)
flow rate (MGD)
Cost vs. flow rate (MGD)
Cost vs. volume of thickener (gal)
Cost/MGD vs. flow rate MGD
Cost vs. area of filter (Sq Ft)
Cost vs. flow rate (MGD)
59
-------
X. COST VS EFFLUENT QUALITY RELATIONSHIPS
In order to establish a realistic basis for establishing treat-
ment plant design criteria, the data of the 53 plants surveyed
were portrayed in terms of statistical probabilities of COD,
BOD, and suspended solids concentrations as shown in Figures 18
and 19 and in a graphical illustration of wastewater flow and
BOD concentration as shown in Figure 20. These data were used
to construct the twenty likely design combinations given in
Table XVII.
TABLE XVII
PLANT SIZE AND WASTEWATER CHARACTERISTICS - BASIS FOR DESIGN
Combina-
tion
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Plant Design
Flow (mgd)
10.0
10.0
10.0
10.0
5.0
5.0
5.0
5.0
1.0
1.0
1.0
1.0
1.0
1.0
0.5
0.5
0.5
0.5
0.5
0.5
BOD
(mg/1)
500
500
200
200
2000
2000
500
500
3000
3000
1000
1000
500
500
3000
3000
1000
1000
500
500
COD
Cmg/1)
1200
1200
550
550
5000
5000
1200
1200
8000
8000
3000
3000
1200
1200
8000
8000
3000
3000
1200
1200
ss
Cmg/1)
100
500
100
500
100
500
100
500
100
500
100
500
100
500
100
500
100
500
100
500
The cost vs effluent quality relationships have been developed
using BOD, COD, suspended solids and total dissolved inorganic
solids as quality parameters. Nitrogen and phosphorous have
not been included since in the majority of cases, these are
present in insufficient concentrations and must be added as nu-
trient supplements. Constituents such as color represent
specific cases and have, therefore, not been included in the
general correlations. The range of treatment plant sizes and
wastewater composition selected has been discussed and is
based upon current production in the chemical industry.
60
-------
.5 2%
10 15 20
30
PERCENTAGE
40 50 60
70 80 85 90
95
98%
IV
9
e
7
6
S
i
3
I04'
9
8
7
E
5
3
2
I0*i
9
7.
G
5
4
3
i
I02i
=
o
z
o
O
o
: cc
: o
Q
O
=
3
1
y
I
*
2
'
/
*
/
0
\
3.5
Figure l!
CHEMICAL WAS'
CHARACTERIZ
-1 -1 j ;4±j 4- -4-
h-"^- '4^!IIJ II 1 1||
r^~ : | - -4 :-^"|' ']<':£$
< :/l | h: rif-^
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LI' U It
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( l '
- jSiy;;|;^^iki
e. X 1 ; ' ' ] ' i ! ' , ;, , ,
2
Jt
£_
1
/
1
4.0 4.5 5.0
PROBITS
EWATER
ATION
:::::::::::: :::::::;:::::i;;zi ?'- I
1 III Illlllll Illiiii y
::::::::::::T!::|^:::::i:::|_
i / i
* _' /- = = ! = = = |=:
5:
fin
i
Ds=|4ssS^^
!imni!!nl|i;iiiiiimii(
e444-^-H-7T-fH :: =
.-
-j
1 1 1 1 1
5.5 6.0 6.5 7.0
61
-------
10 15 20
30
PERCENTAGE
40 50 60
7C
80 85 90
>000
1000
900
800
700
600
500
400
300
200
100
90
80
70
60
50
40
30
20
Fig
^tt|= CHEMICAL \
CHARACTE
----- . -- "Tl
S -* ^"tT~~ "^ *^~'3^* =^ U4~
1 c ! i ' : | ' ' ' ; TT- ' r- " j
p= W rprr-rrr r- T -rftrti TT=-T-
i _j; -j- j+r-j )- r ]--qy|
(o :::::: ^ Hftr-j jjjffi
=
-
10-*
p
. . t
z
lu ' '
o- ... . .., :; ..^
OT J /
CO . i i . . : =±=g=jj^^j i . ! ! 1 ' i j TT j: _
* . _ _ . | ^ ~ i 1 I IL Mr ' ^
I 1 I I 1 1 1 1 1 1
are 19 ^,= ^=====1=
VASTEWATER ^d==^===
:RIZATION
4. 4 j U. 4-i--- J ''' -H I --U i j...
[..,. ) ; i-p . ; ; . ; - *., . . \Jf\ 1 , : I ,
= =- V ^^ ^^ ^^ =^f -^=^ \ ! I
: | i
, . . . . . . . ... _
USPENDED SOLIDS "
; i^i ;; j ;'" "T~T" ~^ [ j -- - - -i ^- - -
^ . .. . .... rn4~ ' ' - ' ij~i i ~~"~ ' ' ! i ! ' - :~" j "~~ r
p~* T7T~ ~TT^ "i Tlt~j i 1 1
i
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^^
l i III
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:
-
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4.0
4.5
5.0
PROBITS
5.5
6.0
65
7.0
-------
EEEEE|7 ;|E|E
FEE: [±j±:
HN! '6 !Bi
'lip i i i
:± £-!--
j QiEf4 ^:
o
i 2::EjB JEJEEE!
;3:-sa
---1 1 T+V
iliyl
feiJfe
|||
JEEE :Eg| ::| :::::::::::i:::::EEEEEEEEE|EE|EEE|EEEEEEEE|E
:::: lulJill IliUul 14 141 IlllJ 1 II [1 1 1 1 1 1 -I+-U 1
.... Figure 20
:::: ::::::f:E FLOW ~ BOD RELATIONSHIP F<
IE CHEMICAL WASTEWATER TREA'
| A = WASTE STREAMS WHIG
BIOLOGICAL TREATMEN
;j EEEEE = PLANTS WHICH HAVE N
" -- -------- ----*"- BIOLOGICAL TREATMEN
~Hl~Ttj r | ' i i -i--*-1 i 1 r r -r-
^ -i- ii T-~--|-X- T :::
-j uj_ . j j j . j -
EE| pEEEEEE:
*c: ;||EE|Ef^:^^tj:g: || :^||: ^&M\ I ;;
-BOD - mg / 1 X 1C-"3
DR EXISTING
'MENT PLANTS ]
H RECEIVE
T
0
T Mm
: x: ::: :EEx : : : : :::: : t ~:xr:::
:::::::::: : : : :: :::: : C ::::::::
_ I T- III-! '.'.'. III..I- -
;^n:EE: : : E ::: :::::::::::: : :::: :: :
;E38E ; s pot ; jii ;:
-------
The generalized wastewater treatment processes and alternates
are shown in Figure 21. This flow sheet was selected as il-
lustrative of common practice in wastewater treatment plants
in the organic chemical industry today and according to pro-
jections of what might be required in the near future.
Design Eases For The Process Calculations
1. Sedimentation
Sedimentation is provided when the suspended solids
concentration exceeded 125 mg/1. An overflow rate of 750
gpd/ft^ is used to effect a suspended solids removal of 65%.
The percent removal of BOD and COD in sedimentation has been
taken as 101 for each.
2. Anaerobic Lagoon
This process is used when the BOD of the wastes ex-
ceeds 500 mg/1 and it is not preceded by sedimentation. The
obtainable effluent BOD and SS concentrations are 200 mg/1 and
50 mg/1 respectively. Reaction rate constant K (200°C) was
taken at 0.42 and the basin volume was computed from the rela-
tionship between the effluent BOD and reaction rate.
Se 1
So = 1 + Kt
The effluent COD was computed from the relationship CODOTTT =
CODIN - BODremoved/0.75
3. Aerated Lagoon
Sedimentation is not provided preceding aerated
lagoon process. A reaction rate constant of 0.75 (K at 20°C)
has been taken and the basin volume is computed from the re-
lationship between effluent BOD and reaction rate constant.
The effluent BOD and SS solids are expected to be 100 mg/1
each.
4. Activated Sludge
This process is preceded by sedimentation. A
reaction rate (k at 20°C) of 0.00024 1/mgVSS-hr and the
MLVSS concentration of 2500 mg/1 have been taken. Sludge
synthesis coefficient and the endogenous respiration rate
are taken at 0.52 and 0.07 respectively for the purpose of
excess sludge computations. 80% of the excess sludge is
assumed to be volatile. Also 80% of the suspended solids
entering the activated sludge process is assumed to form an
excess sludge. A typical overflow rate of 600 gpd/ft2 is
taken for final clarification. The effluent BOD and SS of
this process are expected to be 25 and 20 mg/1 respectively.
64
-------
SLUDGE HANDLING
Aerobic
Digestion
en
10% COD Removal
10% BOD Removal
65% S.S. Removal
O.R.= 750 gpd/ft2
BOD 25 mg/l BOD 15mg/l BOD Img/l TDS influent =
COD calculate COD calculate COD 5mg/l 2000 mg/l
tS.S. 20mg/l ,tS.S.
-------
5. Adsorption
The cost of this process is computed from the
cost curves available for municipal waste. The flows are cor-
rected for this purpose as follows:
Corrected flow - MGD X CODIND x g 75
CODMUN
6. Ion Exchange
The flows are corrected as below to obtain the cost
figures from the cost curve of domestic waste:
Corrected Flow = MGD total Dissolved Solids x 0.75
removed
350
7. Aerobic Digestion
Only excess activated sludge is treated in this
process. The feed concentration of the sludge is taken at 1%.
Also with a 15 day detention period, 50% reduction of VSS is
expected.
8. Flotation Thickening
The primary sludge and the aerobically digested
excess activated sludge are thickened by flotation. Flota-
tion area is estimated at 4 lbs/ft^/hr. The effluent sus-
pended solids are taken as 30 mg/1.
9. Vacuum Filtration
The thickened sludge is filtered to produce filter
cakes at high solids concentration and the filter area is es-
timated at 8 Ibs/ft2/day.
The capital costs were developed f,rom the sum of
the unit process costs plus 35 percent to include the cost of
engineering, miscellaneous piping and other appertances and
are related to effluent quality in Figures 22-41 for the various
size selections.
For the purpose of these cost determinations, it was assumed
that every selected combination of flow and wastewater charac-
teristics will receive identical treatment, except where im-
practicable. For example, all waste will pass through the oil
separator, neutralization tank, equalization tank (except when
followed by lagoons), primary sedimentation (except when sus-
pended solid concentrations are less than 175 mg/1), activated
66
-------
sludge, sand filtration, carbon adsorption, and ion exchange.
The excess activated sludge is aerobically digested, mixed with
the primary sludge when applicable, and subsequently thickened
and vacuum filtered. The cost of sludge treatment, which does
not include incineration, barging, or hauling, is included in
the cost of the activated sludge unit.
All costs are cumulative as the degree of treatment increases,
except that the cost determination of aerated and anaerobic
lagoons terminate as shown on the graphs. These unit processes
will not be used when tertiary treatment is desired.
67
-------
:: ::: * *.-! ₯>£
m CAPITAL
5 j ill vs
_| tg^i^j:::!
§'2| FLOW
u. SS 1
0 i: :::::::::::
CO
zio §ags=: ;; I 11
o |; i;;i ;;i :Mi;;;i;!;;;i;±;;;|;|
_i
-I ||r^_K:i=::::±::::::::|ES=:
5 [p
1 8
1-
co
o if ilii ;;!; [iiiiiiiii^ifipl
O ''[[
< 6 £ ACTIVA1
^^ ^ 1
Q- jtrt-rrr rrrr r T!! ... «U
t) n;|":: ::::j-:::: : ,rrt:±trtb
|s ^ ANAEROBIC
PRIMARY E;E«^^|
)D 1200 100
3D 500
5 100
!.-.;.. .: ^ i.. i .. i . .-: ....__
- ^...|..,..J : t I::::::::::::::::::
Figure 22
COST OF TREATMENT PLANT \
. SUBSTRATE REMOVED
10 MGD BOD 500 MG/L
00 MG/L COD 1200 MG/L
j I i ! ! ' - ! j I ! I - : t i ' 1 ' ' '
| SAND FILTER |
'ED SLUDGE INCLUDING =
JDGE TREATMENT p^gr^|s^g^g|
ERATED LAGOON g : ^ r^~ pa || |1 ^ =t=p= ~- -- ^-:ii::ggi:titt:g:l
LAGOON_pJS5aspS^355=E gll =Fft^^=f 535f^^^£gg;^
0 800 \ 600 400
700 100 25 15
50 100 20 1
1 ION EXCHANGE
iRBON ADSORPTION:
:::::::::::::::^:::t^.-_ _;:t:::^_:r:r:|^ir^l|^:|:_:- _
200 0
<\
<-\
-------
16
14 |
: : : :
to
«r 12 II
< : ::: ::::::::: : : ffiffi
O
O fflttff
LLlO :3
O ::::::::: ::::::::: :::
0
_l Q
_j ° ;
as
i
i-
(06
i_
4htTTr;:- -ii-f" 44.
O
;:::::::;:::::;:::!: tfcfetii**
olllllllHIIIIIIIHIIIIIIIIIIIIIIII
3D 1200
3D 500 450
B 500 175
ICAPITAL cc
-
vs.
FLOW 10
SS 500
::.: :: :i:r "T- ;:;! "-r,;~. :::!; "TIITTTT
Figure 23
)ST OF TREATMENT PL
SUBSTRATE REMOVAL
MGD BOD 500 MG/L
MG/L COD 1200 MG/L
§|||;g
rSAND
HH'f;ap
^ACTIVATED SLUDGE INCLUDING;
iij! SLUDGE TREATMENT
^AERATED LAGOON^
. - -- j j 1 .... 1 .....
rAEROBIC LAGOONgpP^K
1000 800
200
50
FILTER »p
-:.^; ;;-' :'
t
100
100
600
2!
2C
|
>
)
^:i^:;
Hrr~H
;:;:!;;;;
5
1
U
ANT±
II
- :
^CARBOf
i::::::::: ::::i:!:
"§i|
4
00
! :
jj
IONJ FY^^
1 A Kl ft C1 "'
-t-- - f- f''" ' * ' -- ---1
J ADSORPTION"! 1
"~f~ !--"-"*'-$r--t----l-"-:; ---
::.::;. ::::::::
::::::::::::§
:rg::::: :H
tSI r
III
i ; :;:! :
i 'iiin!
::::.:::::::;:::::
200 o
1
i
1C
-------
SJ
c
Figure 24
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
ION EXCHANGE
FLOW 10 MGD
SS 100 MG/L
BOD 200 MG/L
COD 550 MG/L
CARBON ADSORPTION
SAND FILTER
ACTIVATED SLUDGE INCLUDING
SLUDGE TREATMENT
AERAT ID LAGOON
COD 550
BOD 200
ss too
-------
Figure 25
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
ION EXCHANGE
BOD 200 MG/L
COD 550 MG/L
FLOW 10 MGD
SS 500 MG/L
I ! ' \ '. , ', '. ', '.', .'!'^J.lit"J"!'I!""'l--!ll-I ! '. i '. .Ttf
SAND FILTER
ACTIVATED SLUDGE INCLUDING
SLUDGE TREATMENT
AERATED LAGOON
COD 550 500
BOD 200 190
SS 500 175
-------
NJ
16 :::::::
its11
I4«c
c!l2 I
0
o pjmf
o !;; ;!j!
i
i 8 ;;;;;!;
0
CAPITAL
O)
4 :-m
- - rr-fr
^ - - ^-f H
::HH
8
oHPR
DD 5000
OD 2000
s i no
O
-AP1TAL COST OF TREATMENT PLANT ;
VS. SUBSTRATE REMOVAL 'j*:'1*0* *£
FLOW 5 MGD BOD 2000 MG/L
SS 100 MG/L
itiiiiiiiiiiiiiiiiiiiiiiiiiiiiiirnrnin
::::::ti^Timmf minimi mil 1'Hllt
[j ACTIVATED SLU
SLUDGE TF
: AERATED
;;;; :;.;; -n -:;
ANAEROBIC
JKiTttj. |i -^-Lit-Lt-lir
IMARYHUPmHIIIIIIIIIIIIItt
4000
COD 8000 MG/L
IB
4 liiilLilir-TtTtTTrn-iuiii::: Ttrr -rrrr rrrr Trrr rrrr 77 r rrrr rrrr rrrr rrrr rrrr rrrr rrrr ^~
.: :::p *:: ;::: ::::!:::: :r.: :::: ::::!:::. ::::!:: : ::::}:::: "-' "' ::f: t:.,*r jfi{ L
:|,:::|; ;j]j 4jjj j ;; :;;; :;:; jj: j:; :; ; :j y;; j ::::{:::: ;:;: ;,:: :rfi j| } JT ;
.j [iiiju i 11;: i;i; iiii ;; .] ;t .| ij-;| ;: lift tttt nil n F nuj:::; ::i: :r:i :;.": ft ::::::
- J -t-rtt m i
SAND FILTER ]
wjtiitiijj ::; ::lt :- :
HfflroUM^ntiltfftTm^::: ' - : ; ::::j:::: ::::::::::::[:::: ;::::::
DGE INCLUDING [
'EATMENT ^ | p
LAGOON-
:::::::::: * iii|ii iiiiii ii iiit iii: iii: ill: iiii : ii i iiiijiH
I ': r T jp ijj; ;:::::::!::::::: T:::::;::::::;;;:::;:::::::::;:.:::
^^^_^T^fl^^j-4i^4t--Hi-Jr4rif f- |ri ^llll ii': "'! i!': iil'p'l rHTTrf
LAGOON
3000 | \ /2000 10
200 100 25 15
5O 5O 2O 1
filtlllliilllMI^
Witt:--H- + mH:::MliimtH.tjt rff:::::::: :::: ::::::::
ir>M cvruA MAP E
!!K::K!!:H|!!:::;^^
i
i
: ::::::::i:::::::::::::::::::::::::::::::::::::i:i:i:i::i:::::::i::::i
!!!*"!!!
ssiiiSKssi:::::::::::::;:;::::::::;::: ::::::::::::::::::::::!::::::::;
I IB .* »*
i iiiii ii M pi ii H
!!!!:»!!:! !!!;!!!":!!!!!!!!!!!!!!!!!!!!!"!:!!!!!!!!:!!!
- I"'.'. --(--'"
.... ,.:- ..,; .--, ; j t^t; |-|,, -,-jj-f j, ]r|. ,.,» 4,., ,.,, |,t(
::::;:::: ;:*,;t:;;: ;::;;;;:; :;;: ;t ^ :tt:j:::i :::;;::;: +"|t| 'HIT
;;.;! ;;;; ;;;; ;;;; r::: :::: t;i: ii : j HJUJ; fjf| I;} I I4 :
1 1 iij1iinii!piH^i^^;!;^p:i^;;::
--f--- .».,»., p.., -.-__.._.
00 0
-Cl
-------
S
55
n
E
<
-J
-i
O
0
111
O
M
z
o
-1
_J
2
I
-
co
O
U
_,
<
ol
<
o
ro
o
.::
|
'
Figure 27
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
FLOW 5 MGD BOD 2000 MG/L
SS 500 MG/L COD 5000 MG/L
:~itr::: :::ii:i:: ::: :::; :::r::: ::r: : ~:pm
?.;!;;;:
n::j::::
lii!:!-i;
.j:-.::
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~
'
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:
Pr
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V
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::::;::::
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Figure 29
CAPITAL COST OF TREATME
VS. SUBSTRATE REMC
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CAPITAL COST OF TREATMENT PLANT
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Figure 31
CAPITAL COST OF TREATMENT PLANT
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CAPITAL COST OF TREATMENT PLANT
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78
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Figure 33
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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79
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Figure 34
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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Figure 35
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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Figure 36
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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Figure 37
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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COD 8000
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/4000 \ \
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83
-------
a
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
Figure 38
FLOW 0.5 MGD BOD 1000 mg / I
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ION EXCHANGE
CARBON ADSORPTION
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TREATMENT
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Figure 39
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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Figure 41
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
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Figure 40
CAPITAL COST OF TREATMENT PLANT
VS. SUBSTRATE REMOVAL
FLOW 0.5 MGD BOD 500 MG / L
SS 100 MG/L COD 1200 MG/L
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87
-------
XI. PROJECTED INDUSTRY COSTS
The available data indicate that in 1964 the average large plant
in the organic chemicals industries had a wastewater flow of
4,564,000 gpd and that about 211 plants produced 951 of the total
production of 71 billion pounds in that year. Approximately 238
plants will produce 117.2 billion pounds in 1968; 1968 data on
wastewater flows are not available for the industry as a whole.
The data indicate a growth rate in number of plants of about 3$
per year.
Total water discharged by plants in SIC industry categories 2815
(Cyclic Intermediates) and 2818 (Organic Chemicals n.e.c. was
1509 billion gallons in 1959 and 1760 billion gallons in 1964
according to the Census of Manufactures data. Water discharged
thus increased at the rate of about 3% per year during the 5-year
period, while production has maintained a growth rate of about
10% per year.
On the basis of these data and the projected production figures
given previously, Table XVIII presents actual and projected data
for various parameters of the organic chemicals industry through
1974 on the basis of current wastewater treatment practices.
The plant survey data indicate an average wastewater flow of 7.56
gpd per ton of annual production vs. an indicated average use
within the industry of 18.42 gpd per annual ton of production in
1968. The difference may be explained largely by the fact that
the plants surveyed had installed waste treatment facilities that
average 84.2% removal of the critical pollutant, usually referring
to BOD. The proper first step in implementing waste treatment in
a plant is to reduce wastewater volumes by conservation, segrega-
tion, or reuse; the data indicate that this has indeed been the
practice in plants that have installed waste treatment facilities.
In the absence of any other data, it may be assumed that the
average wastewater production would be the average of these two
figures if treatment facilities had been installed throughout the
industry, i.e., 13 gpd/annual ton in 1968.
On the basis of this assumption, the industry's wastewater produc-
tion if wastewater treatment facilities were to be installed would
be expected to be as shown in Table XIX:
TABLE XIX
WASTEWATER PRODUCTION FOR THE INDUSTRY THROUGH 1974
Year Wastewater, gpd/ton Wastewater 10 gpy
1968 13.0 278
1969 12.2 287
1970 11.3 295
1971 10.5 304
1972 9.85 313
1973 9.23 323
1974 8.65 333
88
-------
TABLE XVIII
ORGANIC CHEMICALS INDUSTRY - PROJECTIONS BASED ON CURRENT PRACTICE
Number of Large Plants
Wastewater (109 gpy)
Production Total (109 Ib)
1963
71.0
Production Large Plants (10y Ib)
Sales, Total (109 Ib)
Sales, Total (109 $)
Municipal Sewer Discharges (10 gpy) 49.8
Wastewater (gpd/annual ton)
1964
1965
1966
1967
1968
211
350
78.7
74.8
42.8
8.5
55.1
25.64
217
361
88.9
84.5
46.8
9.0
62.2
23.41
224
372
100.6
95.5
52.7
9.9
70.4
21.32
231
383
111.7
106.1
56.6
10.5
78.2
19.78
238
394
122.4
117.2
61.6
11.2
85.7
18.4
00
1_96£
Number of Large Plants 245
Wastewater (109 gpy) 406
Production Total (109 Ib) 135.6
Production Large Plants (109 Ib) 128.8
Sales, Total (109 Ib) 67.1
Sales, Total (109 $) 11.9
Municipal Sewer Discharges (109 gpy) 94.9
Wastewater (gpd/annual ton) 17.27
1970
1971
1972
1973
252
418
150.4
142.9
73.2
12.7
105.3
16.03
260
431
166.9
158.5
79.9
13.7
116.8
14.89
268
444
183.5
174.3
86.9
14.6
128.5
13.96
276
457
201.6
191.5
94.3
15.6
141.1
13.08
1974
284
471
221.8
210.7
155.2
12.25
-------
The capital costs for a typical plant discharging 4.56 mgd were
calculated using the unit cost method described in Sections X and
XI of this report, relating costs to various levels of removal of
BOD, COD, and suspended solids. The unit treatments and resulting
concentrations were as shown in Table XX.
These costs are plotted in Figure 42 versus percentage removals of
the various pollutants.
For the 24 plants in the survey for which sufficient information
was available, the following data were obtained:
Average production = 306,670 tons per year
Average wastewater flow = 2,318,692 gpd
Average capital cost = $1,036,522
Average operating cost = $193,125
Average removal of critical pollutants = 84.21
The following data were calculated from the above:
Average capital cost = $447/1000 gpd
Average operating cost = $83.2/1000 gpd
Average wastewater flow = 7.56 gpd/annual ton
Average capital cost = $3.38/annual ton
Average operating cost = $0.63/yr/annual ton
At 84.2% overall treatment efficiency, the average capital cost
per plant was $1,036,522. The industry cost at this level would
be $246,692,000 on the basis of 238 plants.
The figures in Table XIX indicate that wastewater disposed of by
the industry would be 762,000 x 103 gpd if treatment facilities
were installed throughout the industry. The capital costs in a
4.56 mgd plant would be $300 per 1000 gpd for 85% removal of BOD
according to Figure 69 and the industry total thus $228,600,000.
At $447/1000 gpd the total cost would be $340,614,000. Using the
calculated values for a 4.5 mgd plant, the capital cost at 831
removal of BOD would be $1,142,100 per plant or $271,819,000 for
the industry in 1968 on the basis of 238 plants.
Four methods of estimating 1968 industry costs in large plants to
achieve approximately 851 BOD reduction have thus yielded estimates
from $228,600,000 to $340,614,000 averaging $271,931,450; these
data are summarized in Table XXI.
90
-------
TABLE XX
CAPITAL COSTS FOR LEVELS OF TREATMENT IN A 4.56 mgd PLANT
L Treatment Processes Employed
(0) None
(1) Oil Separator, Equalization,
Neutralization
(2) (1) + Sedimentation
(3) (1) + Lagooning
(4) (2) + Activated Sludge and Final
Clarifier
(5) (4) + Filtration
(6) (1) + Filtration and Deep-Well
Disposal
BOD
1150
1150
1035
200
25
15
COD
3000
3000
2700
2600
2100
2000
SS
175
175
61
50
20
1
Installed Cost
0
669,600
804,600
1,142,100
3,194,100
3,423,600
7,514,100
Capital Costs/1000 gpd
0
147
176
250
700
751
1648
-------
1C
I >
Figure 42
CAPITAL COSTS IN
4.56 MOD PLANT
H; H Hit UH nit i:ti jiii ii
40 50
% REMOVAL
-------
TABLE XXI
ESTIMATED 1968 INDUSTRY COSTS IN LARGE PLANTS
Cost Basis
Cost per plant as per sample
Calculated cost per plant
Calculated cost per 1000 gpd
Cost per 1000 gpd as per
sample
Unit
No. of Plants
No. of Plants
Vol. of Wastewater
Capital Cost
$246,692,000
$271,819,800
$228,600,000
Vol. of Wastewater $340,614,000
The facts that the estimates based upon costs per unit of wastewater
show the greatest dispersion, that those based upon costs per plant
are both intermediate and that the estimate based upon calculated
costs per plant and number of plants equals the average, and that
the correlation analyses presented previously indicate that pro-
duction-related variables rather than wastewater-related variables
are of most importance, lead to the conclusion that industry esti-
mates are most reliably made on the basis of estimated costs per
plant and estimated number of plants.
In Table XXII production and wastewater figures are given for the
organic chemical industry through 1974 on the basis of widespread
installations of treatment facilities.
The data in Table XXII indicate that the average large plant would
be expected to treat 3.2 mgd of wastewater during the period
considered. The capital costs in such an average plant are given
in Table XXIII versus the level of treatment attained. Such costs
are projected for the industry in Table XXIV on the basis of the
projected numbers of plants.
Assuming that the capital costs of discharging to a municipal sewer
are those entailed in removing gross pollutants at $147/1000 gpd,
the figures in Table XXV estimate the total capital costs of
treatment facilities in the organic chemicals industry.
In terms of current dollars, using an average of 3.61 annual
increase in the price level as has been reflected in the Engineer-
ing News Record Construction Cost Index, total industry capital
costs are projected in Table XXVI.
93
-------
TABLE XXII
INDUSTRY PROJECTIONS BASED UPON WIDESPREAD TREATMENT
1968 1969 1970 1971 1972 1973 1974
Number of Large Plants 238 245 252 260 268 276 284
Production-Large Plants (1Q9 #) 117.2 128.8 142.9 158.6 174.3 191.5 210.7
Production-Total (109 #) 122.4 135.6 150.4 166.9 183.5 201.6 221.8
Wastewater-Large Plants (109 gpy) 278 287 295 304 313 323 333
Wastewater-Large Plants (gpd/T/yr) 13.0 12.2 11.3 10.5 9.85 9.23 8.65
Municipal Sewer Discharges (109 gpy) 85.7 94.9 105.3 116.8 128.5 141.1 155.2
Municipal Sewer Discharges ._ 0
(106 gpd) 234.8 260.0 288.5 320.0 352.0 386.3 425.2
-------
tn
TABLE XXIII
CAPITAL COSTS VS TREATMENT LEVELS IN AVERAGE LARGE PLANT
Level % Removal Critical Pollutants $/1000 gpd Cost (3.2 mgd)
BOD COD
1 Removal of Gross
2 10% 10%
3 83% 13%
4 98% 30%
5 99% 33%
6 100% 100%
SS
Pollutants
65%
71%
89%
99%
100%
147
176
250
700
751
1648
$
2,
2,
5,
470
563
800
240
403
273
,400
,200
,000
,000
,200
,600
TABLE XXIV
INDUSTRY CAPITAL COSTS OF IN-PLANT
Treatment Level 1968
1 112.0
2 134.0
3 190.4
4 533.1
5 572.0
6 1255.1
Cos
1969
115.2
138.0
196.0
548.8
588.8
1292.0
TREATMENT
ts in Mill
1970
118.5
141.9
201.6
564.5
605.6
1328.9
FACILITIES IN LARGE
ions of 1968 Dollars
1971 1972
122.3 126.1
146.4 150.9
208.0 214.4
582.4 600.3
624.8 644.1
1371.1 1413.3
PLANTS
1973
129.
155.
220.
618.
663.
1455.
8
4
8
2
3
5
1974
133.
160.
227 .
636.
682.
1497.
6
0
2
2
5
7
-------
Treatment Level
1
2
3
4
5
6
TABLE XXV
TOTAL INDUSTRY CAPITAL COSTS FOR WASTEWATER TREATMENT
1968
146.5
168.5
224.9
567.6
606.5
1289.5
1969
153.
176.
234.
587.
627.
1330.
iQ7fl 1971
4
2
2
0
0
2
160
184
244
606
648
1371
.9
.3
.0
.9
.0
.3
169.
193.
255.
629.
671.
1418.
3
4
0
4
8
1
19 7 Z
177.
202.
266.
652.
695.
1465.
8
6
1
0
8
0
T9T3
186.
212.
277 .
675.
720.
1512.
6
2
6
0
1
0
137T
196.1
222.5
289.7
698.7
745.0
1560.2
-------
TABLE XXVI
TOTAL INDUSTRY CAPITAL COSTS FOR WASTEWATER TREATMENT
Costs in Millions of Current Dollars
Treatment Level
1
2
3
4
5
6
' 1968
146.5
168.5
224.9
567.6
606.5
1289.5
1969
158.9
182.5
242.6
608.1
649.6
1378.1
1970
172.6
197.8
261.8
651.2
695.3
1471.4
1971
188.3
215.1
283.6
699.9
747.1
1576.9
1972
204.8
233.4
306.5
751.1
801.6
1687.7
1973
222.6
253.2
331.2
805.3
859.1
1804.2
1974
242.4
275.0
358.1
863.6
920.8
1928.4
-------
In Figure 43, capital and operating costs are given for various
levels of treatment efficiency based upon BOD and COD removals;
these curves are based upon data in the technical literature.
According to Equation (3) given previously, which was based upon
analysis of the industry survey data, operating costs of unit waste
treatment facilities are related to unit capital costs as shown by
the solid line in Figure 44. The indicated points in Figure 44 are
taken from the data of Figure 43 and show the extent of variation
between these data.
The survey data indicate that operating costs are essentially zero
for treatment facilities costing less than about $3000 per 1000 gpd,
while the plotted data based upon literature data assume that zero
capital costs = zero operating costs. Although a rational case can
be made for the fact that operating costs in primary facilities are
actually nil, the curves in Figure 45 combine estimates made from
the two data sources and assume that any facility will, in fact,
have an associated operating cost.
Based upon the data in Figure 45, operating costs in a 3.2 mgd
treatment plant would be those shown in Table XXVII for the various
levels of treatment. Operating costs for the industry would then
be those shown in Table XXVIII.
TABLE XXVII
OPERATING COSTS IN AVERAGE LARGE PLANT
Level % Removal Critical Pollutants $/yr/1000gpd $/yr (3.2 mgd)
BOD COD S.S.
1
2
3
4
5
6
Removal
10%
83%
98%
99%
100%
of Gross
10%
13%
30%
33%
100%
Pollutants
65%
71%
89%
99%
100%
7
8.5
13
105
120
350
22,400
27,200
41,600
336,000
384,000
1,120,000
TABLE XXVIII
INDUSTRY OPERATING COSTS OF FACILITIES IN LARGE PLANTS
Treatment Costs in Millions of 1968 Dollars
Level
2
3
4
5
6
1968
5.33
6.47
9.90
80.0
91.4
266.6
1969
5.49
6.66
10.2
82.3
94.1
274.4
1970
5.64
6.85
10.5
84.7
96.8
282.2
1971
5.82
7.07
10.8
87.4
99.8
291.2
1972
6.00
7.29
11.1
90.0
102.9
300.2
1973
6.18
7.51
11.5
92.7
106.0
309.1
1974
6.36
7.72
11.8
95.4
109.1
318.1
98
-------
100
Figure 43
ORGANIC REMOVAL VS. COST
;: :: j;H HH ffl: IHI ill! till ?»i nil iiilutLUi iUIl±u nil rtS HJt
0.4 0.6 0.6 1.0
CAPITAL COST - MILLION DOLLARS / MQ
99
-------
o
o
(O
o
o
o
01
Ul
Q-
O
440
4OO 4 -: ---
360
XOft -
""ill"
280
240
200
160
. . . i ......
120
80
.. in
40
:':-|!!!j lill M;i ;::'':
rJ
- |T IT r r ra
t^i rt'ii -t*& 4-4
OPERATING COST AS A
4 : FUNCTION OF CAPITAL COST
- i _ : - - :':":': -:::
. , ill
i 1 < i ! H ' ' ' ' i i ' ' ' i " 1 ' ' ' ' ' ' ' ' 1 t 1 1 III 1 Mil! Mill 1 1 1 1 1 1 1 1 1
i^t[i4-44!4i 1 1|
:.::;:::.,:|.,.:;- /
Hill
± iff 111
Jn
----.,?* '§ :
-
S ::::;:I U::::::::::::::::::::::
::y;!;;;:;;;;;;;;;;:^=^- ::
Htd i";:
i!::
, ; r :::::::::::::
_ . _ . (-J N-l
- - ' .1
1 - ' ' ; ]
, , :
i-||||||||||||||||||||||||i^
200
400
600 800 1000 1200
CAPITAL COST - $ / 1000 gpd
1400
1600
-------
560
520
480
440
400
40
80
CAPITAL COSTS-! / 1000 gpd
120 160 2OO 240
280
320
360
1
1
400
I
iii
I;
II
8$3»
i
i:i:
ti±t
1
1
i;
1
m
a
i
£
44-
il-J-t
\\
I-.
H
"'
48
44
40
Figure 45
f Hi
OPERATING COSTS VS CAPITAL COSTS £
SSI
i
11
I
.
i- -t
tTl
1 j i j
4fl
.rttt
-
"'t
;:
:;;
ta
t
ss
Jin
t
:
: ::
t.'tt
I
a
4 « « 4
E S
o
§
o
o
ttit
ffi
1
5K?
24
W
h
, o
g200
X
<
oe
80
40
::Hl-r fiH Hq rL ^i :H.r Hi igr HH. H ii ft: t trH HH i;H Si' tnr *H
t^r;^U-r-.^"q'T^ti^tr^r4"t-tTqH..:-HT4!<,.;it'rrtFmFrrrrR^trrTnfrtt-
MlH^ir"uniiln"riii'li!"ittt.t,Httt;^--^-.ti^:t:"-:ip
200 400 600 800 1000 1200
CAPITAL COSTS - % 1 1000 gpd
1400
1600
1800
2000
-------
Assuming that the operating costs associated with the discharge of
industrial wastes to municipal sewers are 10 cents per 1000 gpd, the
total operating costs for the industry in 1968 dollars are given in
Table XXIX in 1968 dollars and in Table XXX in current dollars.
TABLE XXIX
TOTAL INDUSTRY OPERATING COSTS FOR WASTEWATER TREATMENT
Treatment
Level
1
2
3
4
5
6
1968
13.9
15.0
18.5
88.6
100.0
275.2
Costs
1969
15.0
16.2
19.7
91.8
103.6
283.9
in Millions of 1968 Dollars
1970
16.1
17.4
21.0
95.2
107.3
292.7
1971
17.5
18.8
22.5
99.1
111.5
302.9
1972
18.9
-20.2
24.0
102.9
115.8
313.1
1973
20.3
21.6
25.6
106.8
120.1
323.2
1974
21.9
23.2
27.3
110.9
124.6
333.6
TABLE XXX
TOTAL INDUSTRY OPERATING COSTS FOR WASTEWATER TREATMENT
Treatment Costs in Millions of Current Dollars
Level
1
2
3
4
5
6 275.2 294.1 314.1 356.8 363.2 388.2 415.3
1968
13.9
15.0
15.5
88.6
100.0
1969
15.5
16.8
20.4
95.1
107.3
1970
17.3
18.7
22.5
102.1
115.1
1971
19.5
20.9
25.0
110.2
124.0
1972
21.9
23.4
27.8
119.4
134.3
1973
24.4
25.9
30.7
128.3
144.2
1974
27.3
28.9
34.0
138.1
155.1
102
-------
XII. METHODOLOGY FOR WASTEWATER TREATMENT
COSTS DETERMINATION
The methods which have been developed and used in this study
of the organic chemicals industry can be utilized to- determine
wastewater treatment costs for other industries. The method-
ology is intended to be used in establishing and projecting
costs for an industry or for groups of industries, rather than
for individual plants. Costs estimates for individual plants
are readily calculable by conventional engineering techniques
to almost any degree of precision desired, depending upon the
effort to be expended and the intended uses of the information.
Costs for an industry could, of course, be determined precisely
by calculating the costs of treatment facilities for each indi-
vidual plant in an industry and totalling these costs. Alter-
natives to this obviously impractical method are to estimate
the number of plants involved and multiply by the "average"
cost per plant or to estimate the volume of wastewater involved
and multiply by the "average" cost per unit volume of waste-
water; such alternative methods are practical and after a degree
of accuracy sufficient for purposes of industry-wide planning
and economic impact studies. The suggested methods for deter-
mining the total costs to an industry of attaining specified
degrees of wastewater effluent quality over a time period are
outlined below as a series of steps.
STEP 1: Characterization of the Industry
The industry to be studied must be defined and its general char-
acteristics understood as a first step. Although the SIC de-
finitions are not completely satisfactory, most data are given
in terms of these categories; as a practical matter; therefore,
the industry to be studied must be defined in terms of one or
more 4-digit SIC groups. The general nature of the industry's
production processes and operating philosophy should be under-
stood, since the former, of course, generate the wastewaters
and the latter influence to a large degree the methods by which
pollution control is implemented; such factors as rate of tech-
nological change, average process and/or equipment lives,
degree and types of competition, etc. in the industry should be
understood. Information on production processes are generally
found in the technical literature of the industry, in engineering
texts, in trade association publications and in some of the books
on industrial waste treatment. Information on other aspects of
the industry is to be found in Department of Commerce publications,
trade association publications, and business literature.
STEP 2: Projection of Industry Growth
The growth of the industry should be projected over the time
period set for purposes of the study. Projections should be
made in terms of physical production units for the industry
103
-------
as defined. Additional data such as growth in terms of values
of products, by industry segment, by geographical region, for
closely related or competitive industries, etc. may prove to
be of value for analytical purposes, but the primary data of
interest is that in terms of physical production units. Such
information can be obtained from Dept. of Commerce publica-
tions, trade association publications, technical societies,
trade magazines, and business literature.
STEP 3; Characterization of Wastewaters
Wastewaters of the industry should be characterized in terms
of typical volumes per unit of product and in terms of typical
concentrations at the most significant pollutants. The signi-
ficant pollutants will vary from one industry to another; many
industries produce wastewaters containing dozens or even hun-
dreds of different pollutants, but two or three specific ma-
terials or classes of materials are usually of controlling
significance. General parameters of wastewater contamination
such as biochemical oxygen demand, chemical oxygen demand,
suspended solids, oil and color are generally more useful than
are concentrations of specific compounds. The reason, of
course, lies in the fact that the general parameters relate to
both effluent quality and to the likely methods of waste treat-
ment. Such information is most likely to be found in the in-
dustrial wastewater technical literature, i.e., texts, study
reports, periodicals, and proceedings of technical meetings.
STEP 4: Wastewater Treatment Methods
The methods of wastewater treatment applicable to the waste-
waters of the particular industry should be determined and
generally classified in relation to the degree of treatment or
quality of effluent obtainable with the individual processes.
The methods to be considered will vary considerably from one
industry to another and will be primarily determined by the
volumes of wastewaters to be handled, the nature of the pollu-
tants, and the general experience within the industry with
various treatment methods. For purposes of such a study, new
or unique methods for which little operating or cost exper-
ience is available should not be considered. Two factors
of importance here are the degree to which wastewaters are
likely to be treated for reuse and the extent to which the
industry discharges to municipal sewers. Such information
is likely to be found again in the industrial wastewater
technical literature.
STEP 5: Plant Survey Data Acquisition
Data on specific plants in the industry operating wastewater
treatment facilities should be obtained in order to verify
the applicability of generalized data to the specific industry
studied and to determine the parameters of the industry oper-
104
-------
ations which best define wastewater treatment costs. The In-
dustrial Waste Treatment Practices Data Form provides a con-
venient format for obtaining data from specific plants and its
use is recommended for this purpose. This form will insure
that the needed data are obtained and that the data will be in
a readily usable form. The number of plants surveyed will de-
pend upon the nature and size of the industry and, of course,
the extent to which data can be obtained. As much of the data
indicated on the Form should be obtained as possible for each
plant; some data will be useful even when all that would be
desired cannot be obtained from each plant. Complete data on
production, wastewater volumes, effluent quality or treatment
efficiency, capital costs of facilities, and operating costs
of facilities on at least 15 to 20 plants should be obtained
as a minimum if statistical analyses of the data are to be of
use. Such data are best obtained through plant interviews,
but much of such data can be obtained from the industrial
wastewater technical literature.
STEP 6: Survey Data Analysis
The plant survey data should be analyzed to determine the ex-
tent to which it is representative of the industry as a whole
and to determine the nature of the relationships between costs
and such factors as production, wastewater volumes, and treat-
ment efficiencies. The variables Xi through Xg defined in
Section IX provide a basis for analyzing these relationships,
using multiple correlation techniques. Comparisons of geo-
graphical distributions, plant sizes, product mixes, etc. be-
tween the sample data and those for the industry as a whole pro-
vide basis for determining the adequacy of the s'ample; data for
the industry for such comparisons must generally be obtained
from trade sources, since the Department of Commerce data are
not sufficiently detailed for most industries.
STEP 7: Costs of Unit Wastewater Treatment Methods
The costs of unit wastewater treatment methods applicable to
the industry should be obtained in terms of daily wastewater
volumes in plants of sizes typical of the industry, or in
terms which can be translated into such units. The unit
costs given in Section X of this report cover many of the
generally applicable treatment methods. For some industries
such as metal finishing or steel mills the unit costs of
treating such wastewaters as plating solutions, spent pickle
liquors, etc. can be obtained from the industrial wastewater
literature.
STEP 8: Costs Related to Effluent Quality
The unit cost data must be related to effluent quality in a
manner similar to that outlined in Section XI of this report
for plants of typical size and effluent characteristics. The
105
-------
pollutants of importance and the extent to which degree of
removal can be defined and related to costs will vary with the
industry selected for study and little of a specific nature can
be said here beyond the fact that the figures of Section XI
illustrate the goal of such an effort.
STEP 9: Wastewater Projections for the Industry
The wastewater generation by the industry should be estimated
for the: period of interest, using all available data. It is
here that opinions and assumptions expect a very strong influ-
ence; wastewater generation will be a function not only of
production, but of the very methods installed to reduce pollu-
tion as well as the nature of the industry's projected growth.
All of the statistical data should be used in such projections,
but due regard should be taken of available expert opinion
within the industry of the nature of projected water utilization
practices.
STEP 10: Industry Cost Projections
Projection of the industry costs become a mechanical matter at
this stage; all of the necessary data have been accumulated.
Depending upon the relative reliabilities of the various data
and the indicated nature of the cost determining industry
parameters, the projections for the industry are made using
the most likely data set. In the present study production-
related parameters were shown to be of prime importance, a
reliable estimate of numbers of plants was available, and
the "average" plant costs were closely estimated by two
alternative techniques. In another industry the most likely
set of data might well be different; the only general guid-
ance that can be provided is to show the considerations
involved as outlined in Section XII of this report.
106
-------
APPENDIX A
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
107
-------
DOCUMENT TO DATA CENTER.
REVISION TO DATA CENTER
DATE
by.
NAME
sh. _
Rev.
DATE
NAME
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
| CARPI | GENERAL INFORMATION
PLANT NO. I I I I I I
12345
INITIAL FORM NO. II I I I I I
7 8 10 11
INITIAL ? I II I
YES NO
INDUSTRY
S.I.C. NO. I T I I 1
12 II 14 IB
FIRM
PLANT
YEAR PLANT CONSTRUCTED I I I I I STATE.
CITY AND/OR COUNTY
CODE
16 17 18 19
CD
2O 21
CODE I I I I I
22 23 24 25
STATISTICAL AREA
CODE i I I I
26 27 28
ECONOMIC AREA
WATER RESOURCE REGION
CODE I I I I
2* 30 31
m
CODE
32 33
MAJOR MINOR
RECEIVING STREAM
CODE
MO.
YR.
34 35 36 37
DATE OF DATA ACQUISITION | | | | | |
38 3» 40 41
SINGLE PLANTFIRM | |
46
SIZE OF FIRM: GROSS SALES ( S 1000 PER YEAR )
SUBSIDIARY OF
MULTIPLANT FIRM
BASE YEAR j 1 | | |
n
42 43 44 49
47
I I I I I I M
I 54
n
48 4* SO SI SZ S3 54
SB
SIZE OF FIRM IN THE INDUSTRY ( PERCENT OF THE MARKET )
SIZE OF FIRM IN THE INDUSTRY: LARGE | | MEDIUM
60
OWNERSHIP OF FIRM: PUBLICILY TRADED STOCK
PUBLICLY REGULATED FIRM | _ |
64
n
CLOSELY HELD
rm
88
n
n
S6 S7 88
SMALL
61
63
DEFENSE - ORIENTED
REVISION DATE
,. m
n
6S
REV. i I I END OF CARD JJJ
7* 79 80
108
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
I CARD 2 | BASES FOR TREATMENT DECISIONS
SAME AS CABD.l | Data Form No. iTl I I I I
12 13 14 IS 16 17
MO. YR.
m SOURCE MO. YR.
m DATE rn m
Data By
NAME 18 19 20 21 22 23 24 28
Basis Of Treatment Standards:
Common Law ' ' Statute Law ' ' Public Opinion l_l Within Firm ' I
26 27 28 29
Courts: Federal I I State I I Local I | Order I I Precedent I I
30 31 32 33 34
Agencies: Federal I | State I I Interstate I I Local I 1
35 36 37 38
I I Order I I Conference I I
Regulations I I Order I I Conference I I Hearsay
39 40 41
Action Initiation Within The Firm:
Cnrpornta CODE I I I I
43 44 4B
Plant CODE | I I |
46 47 48
Basis Of Action Decision*
| I Law I I Legal Action | 1
Public Opinion I I Law I I Legal Action | I Economic Incentive
49 SO SI 82
Other . CODE I I I |
S3 54 SS
Basis Of Treatment Decision
Least Cost: Total I ' Operating I 1 Capital I I Economic Return |__J
56 57 58 59
Water Conservation ' ' Minimum Compliance I 1 Ultimate Treatment l__l
6O 61 62
Other CODE LJ 1 1
63 64 68
Responsibility For Action Decision >
Corporate -CODE M I |
66 67 68
Plant . CODE LLLJ
Responsibility For Treatment Decision:
I I I 1
Corporate. CODE
72 73 74
«-- C°DE y^y
| SAME AS CARD 1 | END OF CARD I 2
79
109
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
| CARDS 3 1 PT ANT PRnnnr-TinN INFORMATION T
| SAME AS CARD 2
i
Product
CODE
1 1 1 II
16 19 20 21
CODE
1 1 1 II
26 27 28 29
CODE
1 1 1 II
34 35 36 37
CODE
1 1 1 II
42 43 44 45
CODE
1 1 1 1 1
80 SCOD? »
1 1 1 II
58 59 60 61
CODE
1 1 1 1 1
66 67 68 69
Production Schedule ___
Remarks :
m
17
Production Capacity
AMOUNT
MM
22 23 24
AMOUNT
1 1 II
30 31 32
AMOUNT
II II
38 39 40
AMOUNT
Mil
46 47 48
AMOUNT
MM
II II
AMOUNT
MM
70 71 72
Mrs. P*r. Uo. [.. ]
14
UNTT
a
25
UNIT
0
UNIT
a
41
UNIT
a
UNIT
a
5
UNIT
D
73
1 1
75 76
NO. OF CARDS 3 | J 1 SAME AS CARD
77 78
2 J END OF TABn |3,J
79 80
110
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
CARDS 4 j PLANT PRODUCTION INFORMATION II
L
SAME AS CARD 3
17
PRINCIPAL WASTE-PRODUCING PRODUCTION PROCESSES:
COPE
Mill
18 19 20 21
eopg
Mill
26 27 28 29
i i Ti i
MI i
22 23 24 28
CODE
Mill
30 31 32 33
cooe
III 1
34 35 36 37
SIZE OF PLANT:
Employment ( 10 )
Plant Area (.Acres )
Size In Industry :
MM
42 43 44
MM
49 80 51
Small
|
S2
D
Value Added
Production
Medium
D
(S104/YR.)
Large
MM
49 46 47
AMOUNT
MM
U 84 83
a
i
48
UNIT
a
M
57
AGE OF PLANT:
Age In Years
m
6O 61
Years Since Major Modification I I J
2 63
LEVEL OF TECHNOLOGY:
Old
a
Averagi
a
6B
Advanced | i
66
Typical
a
67
Unique
RAW MATERIALS USED:
6* 70
71 72
71 74
78 76
NO. OF CARDS 4 D I SAME AS CARD T[
77 78 7»
END Or CARD LU
80
111
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
I CARD 5 1 WATER USES
SAME AS CARD 4
17
WATER USE IN PLANT:
Primary
Purpose
Major
Source
Cost (t 11 000 gal. used)
Total Treatment
Principal
Treatment
Total
Total Process
Total Other
Use (104 qalj
rfh mn mn rfTi rm
30 31 32
It 19 2O 21 22 23 24 25 26 27 28
rTh mn mn rfti rrn
33 34 15 36 37 38 39 40 41 424144 45 4* 47
rTh mn mn rTTl rn~l
60 «1 62
48 4» 50 S152S3 S4SS56 57585*
Total Water Intake ___ (104 gal-) I M M
Total Water Use.
tlO
«aaU Mill
7 68 6» TO
PROCESS WATER QUALITY:
Completely Satisfactory
n
71
Marginal
n
Unsatisfactory
a
73
PROCESS WATER QUALITY REQUIREMENTS:
. COPES
DDDD
74 7S 76 77
| SAME AS CARD 4 | END 0F CARD
78
112
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
j CARD 6 I CHARACTERISTICS OF WASTE STREAMS.
SAME AS CARD 5
17
' ' ' Of I I I
WoBte Stream No. ' ' Of I Waste Streams In Plant
IS 19 20 21
Total Plant Effluent Calculated As Weighted Average
t nX
| I
i. nil
-, 1 1 1 1 1 1 1
23 24 tS 2« 27
-,,11111
21 2* 30 31
-.,,11111
32 33 34 35
_,, 1 1 1 1 1
3* 37 3« 39
-,,11111
4O 41 42 43
-,,11111
44 4S 46 47
Vl 1 1 1
- LL 11 1
SI S2 S3 S4
- LI 1 1 1
S3 M 87 U
- Mill
OK,/, Mill
_,,, 1 1 1 1 1
7 ea 69 TO
* IOX
U cooeD
71 72 73 74 78 7«
NO
.OFCARDS6 D I SAME AS CARD 5^ ENDOFCARD fe
*rt TA 79 ^^
113
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
j CARDS 7 I WASTE TREATMENT AND /OR REDUCTION PRACTICES
I SAME AS CARD 6 |
Practice No.
m of m
17
Practices In Use In Plant
18 19
20 21
Practice Instituted In Connection With Abatement Of Pollution From Waste Stream NosI
m m an en
22 23 24 25 26 27 28 29
1. Unit Treatment
2. Unit Treatment
3. Unit Treatment
4'. Unit Treatment
5. Unit Treatment
Installation Dates : Initial, 19 1 1 1
Size And / Or loadings :
Efficiency. % 1 1 1 On Basis Of
74 75
*n np r^n* ,11 1 SAME AS CARD 6 |
77 78 7»
SO
1 1 1 1
31 32 33
Mil
34 3S 3*
1 1 1 1
37 38 3*
MM
40 41 42
MM
43 44 43
Last Modified. 19 1 1 1
48 49
UNIT
1 II 1 M
BO 81 SZ S3
84 SS M 57
UNIT
I I M I I
58 59 60 61
62 63 64 65
66 67 68 6*
70 71 72 73
CODE l_l
76
END OF CARD LU
BO
114
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
I CAROS 8 I CHARACTERISTICS OF SLUDGES
SAME AS CARD 7
17
nn of nn
Sludge Source No. I I I Of < I I Sludge Sources In Plant
18 19 20 21
a
Total Of Sludges In Plant > I Calculated As An Average
22
Quantity
Description Of Sludge :
Lbs. Per Day
23 24 25 26 27
Treatment Of Sludge:
Disposal Of Sludge:
I I I I I
28 29 30 31
CODE
32 U M 35
Capital Cost.
Land Value
Operating Costs.
CODE LJ I II
36 37 38 3t
. sim a
40 41 42 43
,rm a
44 45 46 47
S/yrLXD D
^^^^^^^- 48 4* 50 81
Satisfactory I I Marginal | | Unsatisfactory I I
Ultimate Disposal LJ
52 S3 a*
NO. OF CARDS 8 CH I SAME AS CARD 7 | END 0F CARD L?
77 78
79
80
115
-------
INDUSTRIAL WASTE TREATMENT PRACTICES DATA FORM
I CARDS 9 I APERTURE CARDS
SAME AS CARD 8
17
jFIRST CARD 9 |
|T|R|E|A|T|M|E|NlT1 | P JR | A | C | T j 11 C \tfZ\ |D|AJT|A| |F|O|R|M|
18 4*
APERTURE CODE LI 1 J NO. OF CARDS 9 LJ
SO SI SZ 77
I ADD. CARDS 8|
n I M M M M M M M I I M M I M Ml
18 48
APERTURE CODE I I I J NO. OF CARDS 9 1 I
SO 51 SZ 77
i i 11 rm i i i 11 i rTi 11 TI m
18 48
APERTURE CODE i I I I NO. OF CARDS 9 LJ
SO SI 82
M I I I I M I I I I » I I I I I I I I I I I
APERTURE CODE I I I I NO. OF CARDS 9\ I
SO SI 82
rm i T rii r m i i M M i M i M i i i i i
4*
APERTURE CODE ill! NO. OF CARDS 9 LJ
18
SO SI SZ 77
» I »» I I M I I » I I I I I i I I I I I I I I I I I M
48
APERTURE CODE I I I I NO. OF CARDS 9 [j
18
SO SI 52 77
ULL CARDS 9 I
I SAME AS CARD 8 I END OF CARD \9\
78 79 80
116
-------
APPENDIX B
ORGANIC CHEMICALS INDUSTRY SURVEY DATA
117
-------
Plant Critical
Number Pollutant
Efficiency
1
1
1
1
1
1
* 2
2
2
3
3
* 4
4
4
* 5
* 6
7
* 8
8
8
8
9
*10
*11
11
11
11
11
*12
12
12
12
Oil
All
All
BOP
BOP
All
All
All
All
CN
CN
COP
COP
Oil
All
BOP
Oil
Oil
Acidity
Oil
Oil
Suspended
Solids
Suspended
Solids
BOP
Oil
Oil
Suspended
Solids
BOP
BOP
Oil
Color
Oil
.
100
100
85
85
100
98
100
100
95
95
95
95
95
100
91
-
75
99
75
-
90
98
85
98
-
75
85
90
-
50
-
Capital Cost Operating Cost Capital Cost Operating Cost Wastewater
Per 1000 GPP Per 1000 GPP Per Ton/Year Per Ton/Yr. GPP/Ton/Yr.
193.51
187.50
156.25
3,666.67
25,000.00
357.56
600.00
11.90
119.05
225.00
75.00
330.00
18.52
7.81
16.98
25,353.80
697.39
190.00
50.00
163.16
205.26
1,595.74
185.11
379.79
329.79
229.75
729.17
365.39
11.24
6.25
6.25
-
6,000.00
46.51
80.00
0.00
625.00
18.00
-
(42.97)
(275.00)
27.78
(109.38)
(1,048.22)
78.95
377.06
12.77
311.70
47.87
4.08
4.39
0.69
0.63
0.27
397.33
401.52
750.00
0.50
0.24
.57
0.00
3.62
0.05
(0.15)
(16.43)
45.45
177.50
2.18
21.08
12.28
5.79
2.81
3.55
15.67
575.76
470.00
-------
(Continued)
Plant
Number
12
*13
13
13
13
13
13
*14
14
14
14
14
14
14
14
*15
15
15
15
*16
*17
17
17
*18
18
18
18
*19
*20
20
20
*21
Critical
Pollutant
Oil
All
Oil
Oil
BOD
All
Color
BOD
All
BOD
Oil
Suspended
Solids
Oil
BOD
Oil
BOD
Oil
BOD
Oil
BOD
All
All
All
BOD
Oil
Oil
Oil
All
All
All
All
Oil
Efficiency
_
100
-
-
35
100
85
91
100
90
20
85
-
95
-
85
-
85
-
95
100
100
100
95
-
-
.
100
15
5
100
-
Capital Cost
Per 1000 GPD
85.11
1,160.00
65.00
81.00
48.00
860.00
296.00
736.98
7,700.00
677.97
22.88
34. -7 5
33.90
-
-
326.53
8.23
102.04
36.12
48.07
2,206.66
26,363.60
1,732.14
1,891.89
383.78
675.68
124.32
1,760.00
1,464.09
940.00
7,558.14
127.69
Operating Cost
Per 1000 GPD
5.32
48.00
2.00
34.00
4.00
4.00
94.00
64.87
520.00
61.02
-
-
-
-
-
32.31
-
-
-
15.17
399.30
8,000.00
250.00
421.62
-
-
-
200.00
101.29
20.00
1,046.51
13.85
Capital Cost
Per Ton/Year
644.44
Operating Cost
Per Ton/Yr.
26.67
3.93
2.67
1.42
8.40
33.85
39.75
1.66
0.34
0.26
0.45
1.52
3.85
2.75
0.18
Wastewater
GPD/Ton/Yr.
555.56
5.20
8.19
29.47
3.81
19.23
27.15
13.00
-------
(Continued)
Plant Critical Capital Cost Operating Cost Capital Cost Operating Cost Wastewater
Number Pollutant Efficiency Per 1000 GPP Per 1000 GPP Per Ton/Year Per Ton/Yr. GPP/Ton/Yr.
22 All 100 132.14 1,232.14 - - -
22 TOC 20 676.92 - - - '
*23 BOP 11 159.50 - 1.18 - 7.41
23 Oil - 48.21 -
23 Oil - 49.17 -
23 Oil - 40.00 - '
23 Oil - 50.00 -
23 BOP 11 56.00 - - - -
*24 BOP 50 290.27 - 4.19 - 14.43
24 BOP 98 440.00 26.67
24 Oil - 280.44 - "
25 BOP 95 3,672.43 335.71
25 Oil - 63.07 -
25 Oil - 178.03 - '
25 SS 95 289.93 - '
M 25 Oil - 467.96 - '
o 25 SS 98 335.71 - '
26 BOP 80 146.36 16.00
26 Oil - 60.00 -
26 Oil - 20.00 -
26 Oil - 212.50 -
26 Oil - 60.00 - - - -
*27 BOP 90 115.88 - 3.13 - 26.97
27 BOP 91 1,395.35 - '
27 Oil 95 -
28 BOP 87 296.56 56.25
28 BOP 20 151.56 - '
28 BOP 87 145.00 - "
29 BOP 85 84.03 - "
29 Oil - 31.02 4.63 -
29 BOP 85 26.16
29 Oil - 26.85 - '
30 BOP 80 250.00 26.19
-------
(Continued)
Plant Critical Capital Cost Operating Cost Capital Cost Operating Cost Wastewater
Number Pollutant Efficiency Per 1000 GPP Per 1000 GPP Per Ton/Year Per Ton/Yr. GPP/Ton/Yr.
30 Oil - -
30 Oil - - 19.04 -
30 BOP 80 226.19 7.14
31 Oil 90 84.22 - -
31 All 100 1,186.05 ....
31 Oil -
*32 BOP 91 850.00 265.00 3.40 1.06 4.00
*33 BOD 66 335.71 47.62 1.93 0.27 5.75
34 BOP 98 801.89 216.04
*35 BOP 98 1,207.48 - 2.09 - 1.73
35 All 100 30,000.00 - -
35 BOD 98 607.64 - - "
37 BOD 85 -
NOTES:
All plant numbers with an asterisk indicates information covering the entire plant.
All cost figures in parentheses indicate profit.
The following abbreviations are used.
BOP Biochemical Oxygen Pemand
COP Chemical Oxygen Demand
TOG Total Organic Carbon
SS Suspended Solids
-------
APPENDIX C
PETROCHEMICAL INDUSTRY PRODUCT PROFILES
Source of Data:
Chemical Profiles, Oil, Paint and Drug Reporter
Future Chemical Growth Patterns, R. N. Rickles
Chemical Growth, Vol. I, Aromatics, R. Strobaugh,
Gulf Publishing Company
122
-------
ACETALDEHYDE
Present Producers Capacity*
Celanese, Bay City, Texas 210
Celanese, Bishop, Texas 200
Celanese, Clear Lake, Texas 195
Celanese, Pampa, Texas 10
Eastman, Kingsport, Tennessee 200
Hercules, Parlin, New Jersey 250
Publicker, Philadelphia, Pa. 80
Union Carbide, various locations 650
Others 2_2
Total 1832
*million pounds
Production
1968: 1,600 million pounds
1973: 1,950 million pounds
Uses
Acetic acid and anhydride, n-butanol, 2-ethylhexanol
Process
Acetaldehyde is produced from the:
1) Hydration of acetylene
C2H2 + H20 » CH3CHO
2) Oxidation of Ethyl Alcohol
C2H5OH + hQ2 * CH3CHO + H20
3) Oxidation of lower paraffin (propane and butane)
4) Oxidation of ethylene via the Wacker process
CH2CH2 + PdCl2 + H20 * CH3CHO + Pd + 2HC1
Pd + 2HC1 = %02* PdCl2 + H20
123
-------
The Wacker process is the only major process being installed
today and it is anticipated that future expansions will be
based on this route.
Waste Problems
A typical Wacker process discharges about 1200 gallons per
ton of product. The composition of the waste stream is
primarily chlorinated aldehydes with a COD in the order of
10,000 mg/1. This is based on a yield of 95%. The waste is
difficult to treat biologically unless it is diluted with
other waters. In addition, it is quite acid and runs around
pH2. It is to be noted that several facilities handle these
wastes by means of a deep well rather than by biological
treatment.
Reduction in Waste Loading by Process Change
It is possible by means of a rather simple still design change
to concentrate the waste stream so as to reduce the discharge
to 150-200 gallons/ton of product. No reduction in organic
loading is produced and this approach is only practiced in those
cases where deep well disposal or incineration is planned. The
process change costs about $50,000 in a typical 200,000,000
pounds/year facility.
The only possible means of reducing the organic load center
around recovery and use of the chlorinated aldehydes, de-
chlorination of the aldehydes or improvements in yield. The
latter is where emphasis is placed. It is expected that the
average yeild will reach 97% in 5 years thereby reducing organic
loading by about 40%.
ACETIC ACID AND ANHYDRIDE
Acid Producers Capacity*
Borden, Geismer, La.
Celanese, Bishop, Texas
Celanese, Pampa, Texas
Eastman, Kingsport, Tennessee
Hercules, Parlin, New Jersey
Publicker, Philadelphia, Pa.
Union Carbide, Brownsville, Texas
Union Carbide, S. Charleston, W. Va.
Union Carbide, Texas City, Texas
Total 1985
*million pounds/year does not include by product and fermentation
acetic acid which amounts to 100,000,000 pounds.
124
-------
Production Property of
SOUTHEAST
1968: 1,700 million pounds WATFR LAft
1973: 2,500 million pounds I RRARY
Athens, Gau
Uses
Cellulose acetate, vinyl acetate, acetic esters, chloroacetric
acid
Process
Acetic acid is produced by:
1) oxidation of acetaldehyde
2) from ethanol
3) LPG oxidation (liquified petroleum gas)
4) from methanol and carbon monoxide
The most popular technique in use is the oxidation of acetal-
dehyde while production from ethanol is only of minor importance.
The Reppe method, from methanol and CO, is the newest method
(developed by BASF) and appears to be gaining favor in this
country. In the future it is expected that processes based on
acetaldehyde and methanol will predominate in the production of
acetic acid and anhydride.
Waste Problems
LPG oxidation results in the production of substantial amounts
of other acids such as formic and proponic which must be disposed
of incineration, resale or by biological oxidation. Unfortunately,
resale of these materials does not appear to be practical because
the markets for these chemicals are quite limited. Waste flow
for this system is in the order of 1000 gallons/ton of product
and the organic concentrations are in excess of 30,000 mg/1.
In some operations, the stream is neutralized (it usually runs
at pH4) with caustic and the sodium salts of the acid are re-
covered. Treatment by any number of means are quite routine.
Biological modes are quite adequate.
Oxidation of acetaldehyde also produces higher acids and other
oxidized species in quantities somewhat less than produced by
LPG oxidation. Water flows are of the same magnitude, but
organic load is about 50% of the load generated by the oxidation
of LPG.
125
-------
In the Reppe process, about 80 pounds of organics (50% propionic
acid and 50% higher organics) are produced in the liquid waste
stream per ton of product. The liquid stream amounts to about
50 gallons per ton of product including drains.
Reduction in Waste Loading by Process Change
The changes in process do not appear to change the nature of the
wastes generated by the production of acetic acid or the quantity
of the waste. Further the amounts and character of the waste
would not appear to create serious waste treatment problems or
expenditures.
There will be improvements in the yield picture which will cer-
tainly assist in reducing the waste management problems, but it
is not anticipated that any changes will radically change the
waste situation.
ACETONE
Producers Capacity*
Allied, Frankford, Pa. 150
Celanese, Bishop, Texas 35
Chevron, Richmond, Calif. 35
Clark, Blue Island, Illinois 30
Eastman, Kingsport, Tennessee 60
Enjay, Linden, New Jersey 110
Hercules, Gibbstown, New Jersey 30
Monsanto, Albin, Texas 75
Shell, Dominguez, Calif. 150
Shell, Houston, Texas 210
Shell, Norco, La. 100
Skelly, El Dorado, Kansas 30
Union Carbide Institute, W. Va. 120
Union Carbide, Bound Brook, N. J. 90
Union Carbide, Texas City, Texas 130
Union Carbide, Whiting, Indiana 120
Total 1475
*millions of pounds per year
Production
1968: 1.3 billion pounds
1973: 1.8 billion pounds
126
-------
Uses
Methyl isobutyl ketone and carbinol, Methyl acrylate, bisphenol A,
paint, lacquer and varnish solvent, cellulose acetate solvent.
Processes
Currently there are three major processes utilized for the
production of acetone.
These are:
a) Dehydration of isopropanol
(CH3)2 CHOH- - » (CH3)2 CO + H2
b) By product from the production of phenol from cumene
(C6H5) (C3H7) + 02 - * C6H5OH + C3H60
c) Direct oxidation of propylene
= CH2 + %02 - ^ CH3COCH3
It is expected that a major portion of the acetone will continue
to be produced from cumene as a phenol by product. It seems
likely that direct oxidation of propylene will gain acendency
relative to the production from isopropanol.
Waste Problems
The processes based on isopropanol dehydration produce about
200-250 pounds of organics per ton of product. These consist
of still bottoms (0.51 organics) principally. The nature of
the organics is somewhat complex but may include acetone, un-
reacted alcohol and higher polymeric species. The amount of
waste water depends in part upon the amount of cooling water
utilized as well as the frequency of equipment cleaning. It
is also important to note that the process utilizes either
metallic copper or zinc acetate as a catalyst and catalyst
cleanup could put significant amount of these materials into
the water course or to treatment.
The wastes produced during the production of phenol and acetone
from cumene will be discussed in the section on phenol.
Direct oxidation results in a yield of 931 which in turn produces
less than 80 pounds per ton of product as an organic load within
the system. Water load varies, but exclusive of cooling water
amounts to about 750 gal/ton. The regeneration of the cupric
chloride catalyst may also cause difficulty.
127
-------
Waste Reduction by Process Change
The utilization of direct oxidation will greatly reduce the amount
of organic discharge both when directly compared with isopropanol
based processes and when considering the additional wastes gen-
erated by the production of isopropanol. Therein lies another
key factor in the evaluation of trends in the chemical industry.
The desire to reduce the number of processing steps both to reduce
direct operating costs and to increase yield generally results in
greatly reduced waste loads.
It is possible through careful control and operation of the still
to greatly reduce the amount of acetone in the still bottoms.
These costs are generally minor relative to the value of the
recovered acetone but must be the result of a concious manage-
ment effort.
ACETYLENE
Producers Capacity*
Diamond, Deep Park, Texas 40
Dow, Freeport, Texas 15
Monochem, Geismer, La. 165
Monsanto, Texas City, Texas 100
Rohm and Haas, Deep Park, Texas 35
Tenneco, Houston, Texas 100
Union Carbide, various locations 150
Total 650
*millions of pounds per year
Production
1968: 610 million pounds
1973: 630 million pounds
Uses
Vinyl chloride, vinyl acetate, neoprene, acrylates and
acrylonitriles.
Processes
Acetylene is produced from two major sources in the U.S. About
501 of the acetylene is produced by the reaction of calcium
carbide and water.
CaC2 + 2H20 > C2H2 + Ca(OH)2
128
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The second process involves the partial oxidation of natural gas
CH4 + 02 - > C02 + H20
2CH4 - > C2H2 + H2
Other approaches involve the pyrolysis route as shown below is
typified by the Wulff process,
C4H10 - ^ C2H2 + C2H4 + CO
It is unlikely that many changes will occur with regard to the
production of acetylene in this country unless someone comes
up with a process with greatly reduced production costs which
would have the effect of bringing the cost of acetylene close
to the cost of ethylene. If this does not occur, it will not
be possible for acetylene to maintain many markets in face of
ethylene.
Waste Problems
The major waste associated with the production of acetylene from
calcium carbide is the lime slurry residue.
However, the hydrocarbon processes do generate large amounts of
water borne wastes. These quantities are quite variable and
depend upon the feedstock, the degree of pyrolysis, the ratio
of acetylene to olefins produced, etc.
The wastes arise from the gas cooler and the scrubbing of the
higher concentrations of tars and oils and are quite difficult
to treat in conventional treatment facilities.
Waste Reduction by Process Change
The key factor in waste management in the production of acetylene
from hydrocarbons centers around the control of the cracking
furnaces to maximize the production of valuable products.
Improvements in the dif ficult-to-optimize reaction system are a
key to the success of the process but quite difficult to improve.
Since efficiencies have been known to run as low as 40-50%, it
is not surprising that efficiency improvements is vital to the
process. This is the key process change which can be implemented
and returns from this operation are tremendous relative to pro-
duction of costs. Further, recoveries of waste products in
129
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burnable form is also vital to the effective operation of the
unit. In some operations, a solvent is used to recover the
acetylene. Solvent losses may be significant and add to the
dimensions of the waste treatment problem. Careful selection
of the solvent, and improved design of the vacuum stripper should
assist in reducing solvent losses.
ACRYLATES
Producers Capacity*
Celanese, Pampa, Texas 45
Dow, Freeport, Texas 40
Goodrich, Calvert City, Kentucky 5
Minnesota Mining, St. Paul, Minn. 3
Rohm and Haas, Deer Park, N. J. 200 (a)
Union Carbide, Taft, La. 200 (b)
Union Carbide, Institute, W. Va. 50 (b)
Total 543
*million of pounds/year
(a) 120 million pounds to be added by 1969
(b) Taft facility completed by October, 1968;
Institute may be retired
Production
1968: 240 million pounds
1973: 400 million pounds
Uses
Paint latices, textiles, acrylic acid specialties, acrylic fibers
Processes
The major process involved in the production of acrylates is the
oxidation of acetaldehyde.
Waste Problems
Waste streams associated with this operation are generally com-
posed of polymerization and degradation.
130
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The flow rate is about 1500 gallons per ton of product with
organic concentrations of about 10-20,000 mg/1. Yields in this
process could be improved thereby reducing waste problems. A
number of water waste streams and gas vents are often incinerated.
Extension of this practice would reduce the amount of waste waters
to be treated.
Waste Reduction by Process Change
Considerable efforts are underway to improve yields and this
should result in lower waste water discharges.
AMMONIA
Major Ammonia Producers (600 TPD and up)
Producer Capacity*
Air Products, Michoud, La. 600
Allied, Geismar, La. 1000
Allied, Hopewell, Va. 1000
Apple River, E. Dubuque, Illinois 700
American, Texas City, Texas 2100
American Cyanamid, Avondale, La. 1000
Arkla, Helena, Arkansas 600
Borden, Geismar, La. 900
Central Farmers, Donaldsonville, La. 1000
Chevron, Pascagoula, Miss. 1500
Coastal, Yazoo, Miss. 1000
Collier, Brea, California 750
Collier, Cook Inlet, Alaska 1500
Commercial Solvents, Sterlington, La. 1000
Consumers, Fort Dodge, Iowa 600
Continental, Blytheville, Arkansas 1000
duPont, Beaumont, Texas 1000
duPont, Belle, W. Va. 1000
Farmland, Dodge City, Kansas 600
First Mississippi, Donaldsonville, La. 1000
First Nitrogen, Donaldsonville, La. 1000
Gulf, Borger, Texas 1000
Mobil, Beaumont, Texas 750
Olin-Mathieson, Lake Charles, La. 1400
Phillips, Beatrice, Neb. 600
Sinclair, Ft. Madison, Iowa 1000
Terra, Port Neal, Iowa 600
U.S. Steel, Clairton, Pa. 1150
Valley Nitrogen, El Centre, Calif. 600
Total 29,550
*Tons/Day
131
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Production
1968: 14,200,000 tons/year
1973: 20,000,000 tons/year
Uses
Fertilizers, area, nitric acid
Processes
Ammonia is produced from synthesis gas (CO + H2) under conditions
of relatively high temperatures and high pressure. Synthesis gas
is produced primarily by the steam reformation of natural gas or
other hydrocarbon sources as shown below:
During the reformation, air is added to provide additional energy
for the endothermic reformation reaction. The air also provides
N2 for ammonia formation. The CO is converted to C02 and re-
moved. Conversion to ammonia then takes place:
The major change in processing technology which has taken place
recently has been the development of large single train ammonia
plants of capacities as high as 1500 tons/day. This trend is
expected to continue. These plants produce large point source
concentrations of ammonia and carbon dioxide. However, these
large streams have made the recovery of ammonia practical.
Waste Problems
The major streams arising from an ammonia plant are process
condensate and site drains. The flow and waste produce loads
are as listed below:
Flow (Gals/Ton of product) 300
NH3 (Lbs/Ton) 0.1
NH4HC03 (Lbs/Ton) 0.1
MEA (Monoethanolamine)
(Lbs/Ton) 0.2
C02 (Lbs/Ton) 0.7
132
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Normal practice in this county is to either strip the ammonia or
to release the discharge untreated although it is anticipated
that this practice cannot be continued in the future.
Waste Reduction by Process Change
It is possible to reduce the ammonia loss by some 60% by adjust-
ing pH and airs tripping. About 0.1 pounds of NaOH is added per
ton of product. This is normal practice. It is possible to
remove greater amounts of NH? (90-95%) by increasing the air
flow to perhaps 500-1000 scf/gal. Following the normal industry
practice a cost of the stripper and condenser is about $60,000
for a 1200 ton/day plant. The cost of removing additional
quantities of ammonia have not been calculated since no plants
practicing this extreme approach have ever been built.
BENZENE
Producers Capacity51
Allied, Winnie, Texas 4
Amoco, Texas City, Texas 15
Ashland, N. Tonawanda, N. Y. 10
Ashland, Catlettsburg, Ky. 20
Atlantic-Richfield, Wilmington, Calif. 18
Atlas, Shreveport, La. 10
Chevron, El Segundo, Calif. 25
Chevron, Richmond, Calif. 10
Continental, Lake Charles, La. 6
Continental, Ponca City, Okla. 6
Cosden, Big Spring, Texas 9
Crown Central, Houston, Texas 38
Dow, Bay City, Mich. 20
Dow, Freeport, Texas 30
Enjay, Baton Rouge, La. 24
Enjay, Baytown, Texas 55
Gulf, Philadelphia, Pa. 27
Gulf, Port Arthur, Texas 32
Hess, Corpus Christi, Texas 30
Leonard, Mt. Pleasant, Mich. 3
Marathon, Texas City, Texas 6
Mobil, Beaumont, Texas 30
Monsanto, Alvin, Texas 65
Phillips, Sweeny, Texas 22
Pontiac, Corpus Christi, Texas 9
Shell, Houston, Texas 31
Shell, Odessa, Texas 20
Shell, Wilmington, Calif. 15
Shell, Wood River, Illinois 30
133
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Producers
Capacity*
Signal, Houston, Texas 22
South Hampton, Silsbee, Texas 6
Sun, Marcus Hook, Pa. 15
Sunray DX, Tulsa, Oklahoma 22
Suntide, Corpus Christi, Texas 25
Tenneco, Chalmette, La. 15
Texaco, Port Arthur, Texas 30
Union Carbide, S. Charleston, W. Va. 10
Union Atlantic, Nederland, Texas 18
Union Oil, Lemont, Illinois 22
Vickers, Potwin, Kansas 3
Total from Petroleum Feedstocks 809
Total from 18 Cokeoven Producers and
3 Tar Distillers 142
Grand Total 951
Cities Service, Lake Charles, La. 55
Coastal States, Corpus Christi, Texas 6
Gulf, Port Arthur, Texas 25
Southwestern, Corpus Christi, Texas 6
Texaco, Port Arthur, Texas 15
Total announced new capacity 107
Grand Total, all U.S. Capacity 1058
*millions of gallons/year
Production
1968: 900 million gallons
1973: 1350 million gallons
Uses
Styrene, phenol, cyclohexane, detergent alkylate, aniline,
Maleic acid DDT
Processes
About 60% of U.S. benzene is produced by recovery (together
with toluene and xylenes) from refinery reformers while an
additional 201 is produced from the dealkylatron of toluene.
Coal tar, coke oven light oils and ethylene drip oils account
for the remainder. It is expected that refinery based
benzene will grow more rapidly than other sources. Naphtha-
lene is similar.
-------
Waste Sources
The major sources of waste water in the recovery of benzene,
xylenes and toluene from refinery reformate are two-fold.
First, cooling waters tend to pick up between 50-200 ppm of
COD in the form of aromatics because of heat exchanger leaks.
The quantity and quality of waste water arising from this
source will depend upon the cooling system and will in general
be associated with other cooling waters.
The aromatics are separated from the paraffins by extraction
with aqueous diethylene glycol. Discarding of this solvent
stream in order to control impurity buildup results in a
waste stream containing aromatics and diethylene glycol. Here
improvements in stripper design and careful control of blow-
down from the solvent cycle will assist in greatly reducing
waste water discharges. Aside from cooling waters, there are
no significant sources of waste waters in the Hydrodealkyla-
tion of toluene.
Waste Reduction by Process Change
This control is possible primarily by 1) close maintenance
of heat exchangers, 2) yield improvements, and 3) stripper
design.
BUTADIENE
Producers Capacity*
Chevron, El Segundo, Calif. 16,000
Copolymer, Baton Rouge, La. 60,000
Dow, Freeport, Texas 45,000
El Paso, Odessa, Texas 45,000
Enjay, Baton Rouge, La. 75,000
Enjay, Baytown, Texas 33,000
Firestone, Orange, Texas 110,000
Goodrich-Gulf, Port Neches, Texas 160,000
Mobil, Beaumont, Texas 25,000
Monsanto, Alvin, Texas 50,000
PCI (Cities Service), Lake Charles, La. 80,000
Petro-Tex, Houston, Texas 275,000
Phillips, Borger, Texas 112,000
Shell, Torrance, Calif. 70,000
Sinclair, Channelview, Texas 121,000
Texas-U.S., Port Neches, Texas 160,000
Tidewater, Delaware City, Del. 10,000
UCC, Seadrift, Texas; Ponce, P.R. 105,000
Total 1,577,000
*Tons per year
135
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Production
1968: 1.50 million tons
1973: 1.80 million tons
Uses
Styrene-butadiene rubber, polybutadiene rubber, adiponitrile,
nitrile rubber, S B and A-B-S plastics
Processes
Butadiene is produced from three major sources:
1. dehydrogenation of n butylenes
2. dehydrogenation of n butane
3. as a by-product of ethylene production
It is anticipated that by-product production will increase
rapidly because of the expected rapid increase in ethylene
production expected.
Waste Problems
Waste flows from butadiene production facilities amount to
some 100 gals/ton of product with waste compositions as
follows (taken from one source only):
pH 8-9
TOG 100-200 mg/1
filtered COD 250-375 mg/1
suspended solids 200-500 mg/1
total solids 3000-4000 mg/1 (sulfates and chlorides
principally)
Waste Reduction Through Process Modification
Little information is available regarding possible process
modifications.
136
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BUTANOL
Producers Capacity"
Celanese, Bishop, Texas 125
Continental Oil, Westlake, La. 5
Dow-Badische, Freeport, Texas 15
Eastman, Longview, Texas 60
Shell Chemical, Houston, Texas 50
Union Carbide, various locations 240
Total 495
*millions of pounds annually
Production
1968: 500 million pounds
1973: 620 million pounds
Uses
Glycolethers and amine resins, solvent, n butyl acetate,
plasticizers
Process
Butanol is produced by the oxidation of LPG or other petroleum
streams.
Waste Problems
Waste streams arise primarily from the still discharges follow-
ing the separation of various products together with wastes
resulting from catalyst and vessel cleanouts. Cooling waters
also contain considerable wastes. Waste waters discharged
amount to several hundred gallons per ton of product while
organic discharges amount to 100-300 pounds/ton of product.
Waste Reduction by Process Change
The waste problems of this process involve the low efficiency
and rather drastic conditions under which the reaction takes
place. Improvements in yields and improvement in still
efficiencies would improve the situation. Further provisions
can be made for the collection and direct incinerations of
still bottoms, vessel cleanout wastes, etc., without contam-
ination of the waste waters.
137
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A number of waste streams may be either sent to additional
strippers or vented to gas burners. The costs of such
controls amount to some $250,000-$500,000 for an 80 million
pound/year plant and will reduce the waste load by 25-50%.
CARBON MONOXIDE AND HYDROGEN (SYNTHESIS GAS)
See Ammonia
CARBON TETRACHLORIDE AND OTHER CHLORINATED HYDROCARBONS
Carbon Tetrachloride:
Producers
Allied, Moundsville, W. Va.
Diamond, Painesville, Ohio
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
Dow, Plaquemine, La.
FMC-Allied, S. Charleston, W. Va.
Stauffer, Le Moyne, Alabama
Stauffer, Louisville, Ky.
Stauffer, Niagara Falls, N. Y.
Vulcan, Wichita, Kansas
Total
*millions of pounds per year
Capacity*
8
35
130
30
20
200
85
70
125
25
728
Chloroform:
Producers
Allied, Moundsville, W. Va.
Diamond, Belle, W. Va.
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
DuPont, Niagara Falls, N. Y.
Stauffer, Louisville, Ky.
Vulcan, Newark, N. J.
Vulcan, Wichita, Kansas
Total
*millions of pounds per year
Capacity*
30
20
75
1
15
75
6
li
238
138
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Methylene Chloride:
Producers
Allied, Moundsville, W. Va.
Diamond, Belle, W. Va.
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
DuPont, Niagara Falls, N. Y.
Stauffer, Louisville, Ky.
Vulcan, Newark, N. J.
Vulcan, Wichita, Kansas
Total
*millions of pounds per year
Capacity*
50
30
85
20
60
70
20
355
Methyl Chloride:
Producers
Allied, Moundsville, W. Va.
Ancon, Lake Charles, La.
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
Dow Corning, Midland, Michigan
Dow Corning, Carrollton, Kentucky
DuPont, Niagara Falls, N. Y.
Ethyl, Baton Rouge, La.
General Electric, Waterford, N. Y,
Vulcan, Newark, N. J.
Total
^million of pounds per year
Capacity'
17
100
100
20
10
20
76
75
24
454
Production
1968:
1973:
700
900
CHC15
200
300
CH2C12
265
400
240
370
Use
Fluorocarbons, solvent
139
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Process
These chlorinated methanes are produced by the reaction of
chlorine with methane and then are separated by fractionation.
Carbon tetrachloride is also produced by the reaction of
hydrogen chloride with carbon bisulfide.
Waste Problems
The major waste stream results from the production of hydrogen
chloride as a by-product of the reaction.
Waste Reduction by Process Change
The main need is for routes to the economic recovery of chlorine
from hydrogen chloride or through the reuse of hydrogen chloride
A number of new oxychlorination processes have recently been
developed which enable the user to utilize hydrogen chloride
together with chlorine in a balanced facility. As an example,
for the production of carbon tetrachloride:
CH4 + 2HC12 ^CC14 + 4HC1
CH4 + 4HC1 + 02 ^CC14 + 2H20
This approach eliminates the problem of hydrogen chloride but
it does produce about 60 gallons of waste water per ton of
product which will contain minor amounts of chlorinated
methanes and HC1. Further, these reactions often have an
intermediate step involving copper chloride and small amounts
of this catalyst will be released to the waste water. Insuf-
ficient data is available to predict relative waste loads and
economics. This is anticipated that process changes will
substantially eliminate the HC1 being generated in these
operations.
CELLULOSE ACETATE
Producers Capacity*
Celanese, various locations 450
DuPont, Waynesboro, Va. 60
Eastman, Kingsport, Tenn. 215
FMC, Meadville, Pa. 25
Total 750
140
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Production
1968: 740 million pounds
1973: 850 million pounds
Uses
Fibers, cigarette filters, plastics
Processes
Reaction of wood, pulp with acetic acid and anhydride to
produce triacetate, hydrolysis to procude diacetate
Waste Problems
Major waste sources arise from the stills used to recover
acetic acid and acetone and other solvents. In addition,
considerable amounts of degraded celluloses as well as phos-
phates (used as catalyst) and sulfuric acid (from spills) .
About 3-3.5 gallons of waste waters are generated with a solid
loading of 200 mg/1 and a BOD of 1-3000 mg/1 depending upon
the relationship of flake to fiber production.
Waste Reduction Through Process Change
There are numerous opportunities for waste reduction in
cellulose acetate production. Among these are the following:
1. Recovery and reuse of CA fines
2. Careful pH control in acetone stills
3. Control of vessel cleanout and acid spills
4. Improved operation of acetone and acetic acid stills
Use of additional stills to improve recovery
5. Higher yields on cellulose (wood pulp)
CYCLOHEXANE
Producers Capacity*
Ashland, Catlettsburg, Ky. 30
Atlantic Richfield, Wilmington, Calif. 15
Commonwealth-Shell, Puerto Rico 30
Continental, Ponca City, Okla. 80
Continental, Lake Charles, La.
Cosden, Big Springs, Texas 8
DuPont, Belle, W. Va. 15
DuPont, Orange, Texas 15
*millions of gallons per year
141
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Producers Capacity*
Eastman, Longview, Texas 3
Enjay, Baytown, Texas 40
Gulf, Port Arthur, Texas 33
Phillips, Borger, Texas 47
Phillips, Sweeny, Texas 53
Phillips, Puerto Rico 40
Pontiac, Corpus Christi, Texas 12
Signal, Houston, Texas 17
South Hampton, Silsberg, Texas 3
Texaco, Port Arthur, Texas 40
Union Oil, Smith's Bluff, Texas 55
Total 514
*millions of gallons per year
Production
1968: 310 million gallons
1973: 570 million gallons
Uses
Nylon 66, Nylon 6
Processes
About 301 of the cyclohexane produced in this country is
produced from the fractionation of petroleum. The remainder
is produced by the catalytic hydrogenation of benzene. This
latter process will account for some 85% of the cyclohexane
produced in the U. S. after 1970.
Waste Problems
Outside of spills the only major source of water is the
cooling water which amounts to 200-2000 gallons/ton of
cyclohexane and which may contain 50-200 mg/1 of COD. In
aromatics extraction, there are two major sources of waste
water the extract water washing which contains aromatic
hydrocarbons and the wastes from solvent regeneration which
contains appropriate solvents. Both wastes may be minimized
by the use of stripping columns.
No discussion of cyclohexane recovery from petroleum fractions
is included because this more properly fits in a discussion of
petroleum refineries.
142
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Waste Reduction by Process Change
No foreseeable changes in process will have any significant
impact upon waste water discharges except for the replacement
of once-through cooling with cooling towers. However, once-
through cooling is generally not utilized in cyclohexane
facilities.
CUMENE
Producers Capacity*
Amoco, Texas City, Texas 50
Ashland, Catlettsburg, Ky. 300
Chevron, Richmond, Calif. 80
Clark, Blue Island, Illinois 100
Coastal States, Corpus Christi, Texas 100
Dow, Midland, Michigan 10
Gulf, Philadelphia, Pa. 400
Gulf, Port Arthur, Texas 300
Hercules, Gibbstown, New Jersey 60
Marathon Oil, Corpus Christi, Texas 125
Monsanto, Alvin, Texas 130
Shell, Houston, Texas 80
Skelly, El Dorado, Kansas 80
Sunray DX, Corpus Christi, Texas 125
Texaco, Westville, N. J. 140
Total 2220
*millions of pounds/year
Production
1968: 1.2 billion pounds
1973: 2.2 billion pounds
Uses
Phenol, acetone, a-methylstyrene
Process
The process for the production of cumene involves the reaction
of benzene with propylene in a phosphoric acid catalyzed
alkylation. No significant change in this technology is
anticipated in near future.
143
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Waste ^Problems
The principal waste streams from the manufacture of cumene
are the process slops and the "cumene" bottoms which are a
result of the recovery of cumene from the general process
stream. This stream contains some 1-4% of the product stream.
The quantity of water carrying the wastes depends largely
upon the use of propane to control bed temperature.
Waste Reduction Through Process Change
Careful temperature control through propane injection may
reduce the amount of byproducts and reduce the amount of
water required in the tower to control this highly exother-
mic reaction.
ETHANOL
Producer Capacity*
Synthetic (Ethylene)
Enjay, Baton Rouge, La. 60
Eastman, Longview, Texas 25
Publicker, Philadelphia, Pa. 25
Shell, Houston, Texas 40
Union Carbide, S. Charleston, W. Va. 60
Union Carbide, Texas City, Texas 100
USI, Tuscola, Illinois 53
*millions of wine gallons annually, 190 proof alcohol
Producer Capacity*
Other Industrial
Ga-Pacific, Bellingham, Wash.
Hercules, Hopewell, Va.
Publicker, Philadelphia, Pa., other 2Q_
Total 383
*millions of wine gallons annually, 190 proof alcohol
Production
1968: 299 million gallons
1973: 330 million gallons
144
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Uses
Ace t aldehyde, solvent, other chemicals
Process
Two processes are in use to produce ethanol from ethylene.
The first, called the ethyl hydrogen sulfate route follows
the following equation:
3C2H4 + 2H2S04
C2H5HS04 + (C2H5)2S04 - ^3C2H5OH + 2H2SC>4
Ethyl ether is a byproduct.
The second is the Shell or direct hydration process and
involves the temperature and pressure hydration over a
phosphoric acid catalyst:
C2H4 + H20 - > C2H5OH
Waste Sourges
The ethyl hydrogen sulfate has numerous waste sources. These
include slops from the recovery and reconcentration of sulfuric
acid (0.05 Ib/lb of product) and the discharge of a waste
caustic stream containing alcohol, ether and waste products
from the alcohol scrubber. This stream may amount to several
hundred gallons per ton of product and contain 1-3000 mg/1 of
COD at a high (11+) pH. An additional stream results from
the recycling column which removes the heavy ends, and is an
aqueous stream of perhaps 10-30 gals/ton of product and con-
tains about 5000 mg/1 of COD.
The direct hydration process involves considerably less waste.
The major stream would result from the separation of the product
ethanol from the process bottoms and may amount to 30-60 pounds
of COD/ton of product.
Waste Reduction Through Process Change
It is possible to minimize the waste products by careful control
of the use of sulfuric acid in the process and as is often the
case, in the use of acid and alkali, the avoidance of leaks and
spills. Additional stripping capacity and improved yields would
also reduce waste product loads.
145
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ETHYL BENZENE AND STYRENE
Producers (Styrene) Capacity*
Amoco, Texas City, Texas 300
Cosden, Big Spring, Texas 100
Cos-Mar, Carville, La. 500
Dow, Freeport, Texas 550
Dow, Midland, Michigan 350
El Paso, Odessa, Texas 120
Enjay, Baytown, Texas 150
Foster Grant, Baton Rouge, La. 200
Marbon, Baytown, Texas 125
Monsanto, Alvin, Texas 40
Monsanto, Texas City, Texas 750
Shell, Torrance, Calif. 240
Sinclair-Koppers, Houston, Texas 70
Sinclair-Koppers, Kobuta, Pa. 270
*millions of pounds annually
Producers (Styrene) Capacity*
Sinclair-Koppers, Port Arthur, Texas 150
Signal, Houston, Texas 35
Sunray DX, Corpus Christi, Texas 80
Suntide, Corpus Christi, Texas 75
Tenneco, Chalmette, La. 22
Union Carbide, Institute, W. Va. 130
Union Carbide, Seadrift, Texas 500
Total 3991
*millions of pounds annually
Production (Styrene)
1968: 3.5 billion pounds
1973: 5.0 billion pounds
Uses
Polystyrene, Rubber modified polystyrene, Styrene-butadiene
copolymer, ABS, SAN plastics, Styrene-butadrene elastomer
146
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Processes
About 10% of the ethyl benzene is obtained by fractionation of
petroleum streams. The dominant route is via alkylation of
benzene with ethylene. This is expected to continue in this
fashion in the future. There are two alternative routes to
ethyl benzene by alkylation. One involves the use of high
purity ethylene while the other involves the use of low con-
centration ethylene. It is expected that the latter will
become more prominent in the future.
Styrene is produced from ethyl benzene by the high temperature
dehydrogenation of the ethyl benzene.
Waste Problems
A number of waste streams arise from the alkylation of benzene
with high concentration ethylene. Among these are the caustic
and water washing streams used to wash the crude alkylate
which contain 5-10,000 mg/1 of tars and other polymers together
with significant amounts of ethyl benzene and benzene. The
overheads from the benzene drying column may contain minor
amounts of benzene. The residue from the PEB (polyethyl
benzenes) column contains tars and polymers formed during
the process. The total organic burden is in the order of
30-70 pounds/ton of product.
The process utilizing low concentration ethylene produces
primarily a waste stream containing polymers and tars and
amount to 50-100 pounds of organics per ton of product.
The styrene producing process condenses a water-styrene-ethyl
benzene mixture and the water leaving this step containing
oils as well as ethyl benzene and styrene.
Waste Reduction Through Process Change
Design of gas washers which improve contact conditions is one
key to the reduction of waste waters coming from this process
(high concentration). A larger benzene drying column will
reduce benzene losses from this system. The tars and polymers
produced from the final separator could be incinerated rather
than sent to a waste water system.
147
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ETHYLENE BICHLORIDE, VINYL CHLORIDE AND POLYVINYL CHLORIDE
Producers (Vinyl chloride) Capacity"
Allied, Moundsville, W. Va. 500
American Chemical, Watson, Calif. 170
Conoco-Stauffer, Lake Charles, La. 600
Cumberland Calvert, Calvert City, Ky. 100
Diamond, Deer Park, Texas 100
Dow, Freeport, Texas; Plaquemine, La. 1000
Ethyl, Baton Rouge, La.; Houston, Texas 300
General Tire, Ashtabula, Ohio 75
Goodrich, Calvert City, Ky. 800
Goodrich, Niagara Falls, N. Y. 40
Goodyear, Niagara Falls, N. Y. 70
Monochem, Geismer, La. 250
Monsanto, Texas City, Texas 150
Producers (Vinyl chloride) Capacity*
PPG, Lake Charles, La. 300
Tenneco, Houston, Texas 200
Union Carbide, S. Charleston, W. Va. 340
Union Carbide, Texas City, Texas
Wyandotte, Geismer, La. 150
Total 5150
*millions of pounds/year
Production
1968: 2.7 billion pounds
1973: 4.0 billion pounds
Uses
PVC
Processes
There are several major routes to vinylchloride. Acetylene
based processes employ the use of hydrogen chloride in a
direct addition in acetylene
+ HC1
148
-------
Ethylene processes involve direct chlorination plus dehydro-
chlorination
C2H4 + Cl * C2H4Cl2 (ethylene dichloride)
> C2H3C1 + HC1
A newer approach involves oxychlorination and permits the reuse
of the HC1 generated during dehydro chlorination (copper chloride
is the catalyst) .
C2H4 + hQ2 + 2HC1 - >C2H4C12 + H2°
It is expected that all vinyl chloride in the country will be
produced by a balanced chlorination-oxychlorination approach in
the future .
Polyvinyl chloride is polymerized directly from vinyl chloride
by a mode of different approaches.
Waste Problems
The vinyl chloride facility generates a waste stream containing
about 8 gallons/ton of product and containing minor amounts of
organics (0.01 Ibs/ton) with significant amounts of NaCl, FeCl3,
NaOH and NaC103.
The waste stream from the PVC operation is about 2000 gallons/ton
of product and has a COD of 1200-1500 mg/1.
Waste Reduction Through Process Change
The advent of oxychlorination has made a major reduction in waste
problems in the production of vinyl chloride. Waste problems are
quite minor and little promise of change exists. Only minor
pressure exists for the reduction in waste loadings from the PVC
operation although changes in polymerization techniques may ef-
fect changes.
ETHYLENE
Producers Capacity'
Allied-Wyandotte, Geismar, La. 500
American Can-Skelly, Clinton, Iowa 400
Atlantic, Watson, Calif. 100
Continental Oil, Lake Charles, La. 400
Dow, various locations 1920
DuPont, Orange, Texas 800
El Paso-Rexall, Odessa, Texas 290
149
-------
Producers Capacity*
Enjay, various locations 1265
Goodrich, Calvert City, Ky. 250
Gulf, various locations 825
Jefferson, Port Neches, Texas 450
Koppers, Kobuta, Pa. 35
Mobil, Beaumont, Texas 450
Monsanto, various locations 600
National Distillers, Tuscola, Illinois 320
Olin Mathieson, Brandenburg, Ky. 90
Petroleum Chemicals, Lake Charles, La. 360
Phillips, Sweeny, Texas 550
Phillips-Houston Natural Gas,
Sweeny, Texas 550
Shell, various locations 845
Sinclair-Koppers, Houston, Texas 500
Sun Olin, N. Claymont, Del. 125
Texas Eastman, Longview, Texas 450
Union Carbide, various locations 3975
Total 16000
*millions of pounds per year
Production
1968: 12,500,000,000 pounds per year
1973: 19,000,000,000 pounds per year
Uses
Polyethylene, ethylene oxide, ethanol, styrene, vinylchloride
Processes
Ethylene is produced from ethane and propane, refinery off gas
and other sources such as naphtha, gas oil, condensate. The
first step involves cracking, then compression followed by
purification. Ethylene production is an important source of
propylene butadiene and aromatics.
150
-------
Waste Problems
The major waste streams are:
a. blowdown from steam generation
b. coke and tar in the furnace
c. compressor water (oily)
d. spent caustic from acid gas scrubbing
e. water from dryers
f. green oil produced as a polymerization product during
acetylene hydrogenation
Typical Quantities are:
Spent caustic - 15 gallons/ton of product containing 2.5!
NaOH, 1.0% Na2S and 6.6% ppm of phenols and 100-500 mg/1
of COD.
Waste Reduction by Process Change
The process condensate stream may be reprocessed by being sent
to a stripper and stripped by live steam. This will strip most
of the non phenol contaminants and about 20-25% of phenol. If
fresh feed is contacted with the process condensate, it is
possible to strip out most of the phenol which is then sent
with the feed to the cracking furnace. The phenol free waste
water can then be steam stripped to remove residual volatile
hydrocarbons. The water stream, free of contaminants may be
reused in steam generation in the plant.
Studies are underway to recover the alkali values from the spent
caustic. For the moment, sulfide oxidation is generally prac-
ticed to reduce the immediate oxygen demand of this stream.
Green oil is piped to plant fuel systems and burnt along with
tar and other heavy polymer by-products.
ETHYLENE OXIDE
Producers (Ethylene Oxide) Capacity*
Allied, Orange, Texas 40
Calcasieu, Lake Charles, La. 150
Dow, various locations 900
DuPont 300
Eastman, Longview, Texas 60
GAP, Linden, N. J. 70
Houston Chemical 80
Jefferson, Port Neches, Texas 750
Olin Mathieson, Brandenburg, Ky. 120
Shell Chemical, Norco, La. 150
151
-------
Producers (Ethylene Oxide) Capacity*
Sun Olin, Marcus Hook, Pa. 100
Union Carbide, various locations 1700
Wyandotte, Geismer, La. 100
Total 4520
*millions of pounds per year
Production
1968: 3,000,000,000 pounds/year (Ethylene Oxide)
1973: 5,000,000,000 pounds/year
Use
Surfactants, ethanol amines, polyglycols, antifreeze, polyester
fibers
Processes
The chlorohydrin method involves the reaction of chlorine water
with ethylene to produce the chlorohydrin and HC1. This was
then treated with bicarbonate to produce the glycol:
+ C12 + H20 ^ CH2OH - CH2C1 + HC1
CH2OH - CH2C1 + NaHCl - > CH2OH - CH2OH + NaCl + C02
Ethylene oxide could be produced by adding caustic and rectifying
the vapors
Direct oxidation of ethylene:
is the process which is now widely practiced. Hydrolysis of
the oxide produces the glycol. The product of various glycol
ethers and glycols as by-products is quite common.
Waste Problems
The older chlorohydrin process produces great quantities of waste
HC1 which is usually lime neutralized as well as waste organic
streams. The major waste stream is a lime slurry (about 2000
gallons/ton) . It is not expected that any chlorohydrin plants
will be built in the future.
152
-------
Oxidation-hydration plants produce two major waste streams. One
is produced at the rate of 1500 gallons/ton of product and is
0.1% organic. The other is produced at the rate of 150 gallons/
ton of product and is 1% organic in one process. In a similar
system, the total water flow was about 1000 gallons/ton of product
with a concentration of 1-20,000 mg/1 COD. Both contain a mixture
of oxide, glycol, polyglycols, etc.
Waste Reduction Through Process Change
It is possible through the addition of stripping columns and the
addition of certain streams to cooling water systems to reduce
the waste water discharge to 10% of the numbers cited above.
The cost is in the order of $150-210,000 in a 50,000,000 pounds/
year plant.
Waste Reduction by Process Change
Water wastes can be largely eliminated by reusing the dimethyl
ether to produce additional formaldehyde and by reprocessing
the scrubber waters and truck washings to produce additional
formaldehyde.
ISOPROPANOL
Producers Capacity11
Enjay, Baton Rouge, La. 680
Shell, Dominguez, Calif. 225
Shell, Houston, Texas 380
Union Carbide, Texas City, Texas 400
Union Carbide, Whiting, Indiana 275
Total 1960
*millions of pounds per year
Production
1968: 1750 million pounds
1973: 2250 million pounds
Uses
Acetone, solvent
153
-------
Processes
Isopropanol is manufactured either by catalytic hydration of
propylene:
CH:
CH
CH
H20 ^ CH3CHOHCH3
or by the reaction or sulfuric acid propylene similar to the
ethanol reaction.
Waste Problems and Process Change
See Ethanol
FORMALDEHYDE
Producers
Allied
Borden
Celanese
Commercial Solvents
DuPont
GAP
Georgia Pacific
Gulf
Hercules
Hooker
Monsanto
Reichhold
Rohm and Haas
Tenneco
Trojan Powder
Union Carbide
Total
*millions of pounds per year
Capacity*
310
925
950
60
900
100
120
115
275
90
400
212
50
325
50
150
5042
Production
1968: 4.0 billion pounds
1973: 5.2 billion pounds
Uses
Phenolic resins, urea and melamine resins, ethylene glycol
154
-------
Process
Straight oxidation of methanol with air or oxygen. The major
by-products are dimethyl ether and formic acid which amount to
150 pounds/ton of product.
Waste Problems
The major sources of waste are the scrubber waters and the
dimethyl ether by-product. The total aqueous stream should
not exceed 100 gallons/ton containing 1-5000 mg/1 COD unless
truck washing is practiced at the site.
METHANOL
Producers Capacity*
Allied 26
Borden 160
Celanese 75
CSC 65
DuPont 380
Escambia 30
Gulf 9
Hercules 16
Monsanto-Tenneco 30
Rohm and Haas 22
Tenneco 76
Union Carbide £4_
Total 943
*millions of gallons per year
Production
1968: 600 million gallons
1973: 900 million gallons
Uses
Formaldehyde, methyl esters, amines, solvent
Processes
The major process for the production of methanol involves the high
pressure catalytic conversion of synthesis gas (CO + H£) to methanol
Recently ICI has developed a low pressure process.
155
-------
Waste Problems
Although little information is available on the lower pressure
process only minor differences between waste streams would
appear to exist. Major waste water streams are from slab and
vessel wash downs together with bottoms from the methanol
purification process. This amounts to 100-500 gallons/ton
of product and contains some oils, methanol and higher boiling
organics to the extent of several hundred mg/1.
Waste Reduction Through Process Change
More effective separations and better housekeeping can produce
greatly reduced water flows. The dimethyl ether produced from
this waste can be sent to a formaldehyde production facility
for conversion into formaldehyde.
PHENOL
Producers Capacity"
Allied 350
Chevron 50
Clark Oil 50
Dow 270
Hercules 50
Hooker 130
Monsanto 285
Reichhold 90
Shell 50
Skelly Oil 50
Union Carbide 575
Total 1950
*million pounds per year
Production
1968: 1500 million pounds
1973: 2200 million pounds
Uses
Phenolic resins, caprolactam, bisphenol-A, adipic acid
156
-------
Processes
Phenol is made from cumene, from benzene by the Raschig process
C6H6 + HC1 + %02 _ :> C6H5C1 + H20
C6H5C1 + H20 ^.C6H5OH + HC1
from benzene by the chlorobenzene route :
C6H6 + C12 - >C6H5C1 + HC1
C6H5C1 + ZNaOH > C6H5ONa + NaCl + H20
C6H5ONa + HC1 > C6H5OH + NaCl
and by the sulfonation process from benzene:
C6H6 + H2S04 - >C6H5S03H + H20
2C6H5S03H + Na2S03 ^ 2C6H5S03Na + S02 + H20(+Na2S04)
C6H5S03Na + 2NaOH > C6H5ONa + Na2S03 + H20
2C6H5ONa + S02 + H20 - > 2C6H5OH + Na2S03(+Na2S04)
Recently two new routes have been commercialized. One is Dow
Chemical process which involves direct oxidation of toluene to
benzoic acid and then oxidation of the benzoic acid to phenol
in a single step.
It is anticipated that cumene based phenol will continue to
hold a major share of the market. Furthermore, it is expected
that the direct oxidation routes will also gain importance.
Waste Problems
In addition to quantities of wastewaters discharged from the
separation of the phenol the less used processes all produce
major quantities of inorganic containing aqueous wastes which
create considerable difficulties relative to waste treatment.
A typical 100,000,000 pound/year phenol plant based on cumene
produces a stream of 200,000 gpd of waste water containing
13,200 mg/1 of COD and 180 mg/1 of phenol. Inorganics are
produced at the following rates:
Sodium carbonate (5000 Ibs/day) ; sodium formate (500 Ibs/day) ;
sodium bicarbonate (500 Ibs/day) and sodium sulfate (22,000
Ibs/day)
The waste production from the direct oxidation facility might
be considerably less than the older process.
157
-------
Waste Reduction Through Process Control
It is possible to reduce effluents by careful control of the
process involved, recovery of the inorganics by crystalliza-
tion, etc., and by solvent extraction of the phenol. It is
also likely that as the sulfonation and chlorination ap-
proaches are reduced in importance the amount of waste gen-
erated per pounds of phenol produced will be greatly reduced.
POLYETHYLENE - HD
Producers Capacity*
Allied, Baton Rouge, La. 150
Allied, Orange, Texas 25
Celanese, Pasadena, Texas 150
Chemplex, Clinton, la. 50
Dow, Freeport, Texas 50
Dow, Plaquemine, La. 50
DuPont, Orange, Texas 75
Gulf, Orange, Texas 100
Hercules, Parlin, N. J. 80
Monsanto, Texas City, Texas 50
National Petrochemicals, La Porte, Texas 125
Phillips, Pasadena, Texas 160
Sinclair-Koppers, Port Reading, N. J. 50
Union Carbide, Seadrift, Texas 125
Total 1230
*millions of pounds per year
Production
1968: 1200 million pounds
1973: 2000 million pounds
Uses
Blow molding, injection molding, film and sheet, wire and cable,
pipe and conduit
Processes
Polyethylene is produced by the catalyzed polymerization of
ethylene. High pressure processes use oxygen or peroxides
for a catalyst while the low pressure processes (which
produce high density products) use metal derived catalysts.
158
-------
Waste Problems
About 400 gallons/ton of product of waste water is produced
from these units and this flow has the following character-
istics:
Suspended Solids 100 ppm
COD 200 mg/1
Waste Reduction by Process Changes
It is possible to greatly reduce the discharge of solids by
improving the utilization of centrifuges and other separation
equipment.
POLYETHYLENE - LD
Producers Capacity*
Allied, Orange, Texas 25
Chemplex, Clinton, Iowa 100
Columbian Carbon, Lake Charles, La. 100
Dow, Freeport, Texas 170
Dow, Plaquemine, La. 130
DuPont, Orange, Texas 425
DuPont, Victoria, Texas 200
Eastman, Longview, Texas 175
Enjay, Baton Rouge, La. 200
Gulf, Cedar Bayou, Texas 200
Gulf, Orange, Texas 200
Monsanto, Texas City, Texas 130
National Distillers, Deer Park, Texas 300
National Distillers, Tuscola, Illinois 150
Rexall-El Paso, Odessa, Texas 250
Sinclair-Koppers, Port Arthur, Texas 125
Union Carbide, Seadrift, Texas 200
Union Carbide, S. Charleston, W. Va. 100
Union Carbide, Taft, La. 500
Union Carbide, Texas City, Texas 290
Union Carbide, Torrance, Calif. 80
Union Carbide, Whiting, Indiana 200
Total 4250
*millions of pounds per year
159
-------
Production
1968: 2900 million pounds
1973: 4700 million pounds
Itees
Film and sheet, injection molding, extension coating, wire
and cable
Processes
See Polytheylene-HD
Waste Problems
The waste stream which is primarily drains, amounts to 200
gpd/ton of product and contains 50-100 mg/1 COD and 100
mg/1 of oil.
Waste Reduction
See Polyethylene-HD
POLYSTYRENE
Producers Capacity*
Amoco, Leominster, Mass; Medina, 0;
Torrance, Calif; Willow Sp., 111. 120
Badische, Jamesburg, N. J. 25
Columbian, Hicksville, N. Y. 10
Cosden, Big Springs, Texas 120
Dow, Allyns Pt., Conn; Ironton, 0;
Midland, Mich; Torrance, Calif;
Riverside, Mo. 610
Foster Grant, Leominster, Mass; Peru, 111.
Hammond, Worcester, Mass. 50
Monsanto, Addyston, 0; Long Beach, Calif;
Springfield, Mass. 300
Rexall, Holyoke, Mass; Santa Clara, Calif. 70
Richardson, West Haven, Conn. 30
Shell, Wallingford, Conn. 25
Sinclair-Koppers, Kobuta, Pa. 190
160
-------
Producers
Solar, Leominster, Mass.
Union Carbide, Bound Brook, N. J.;
Marietta, 0.
Total
*million pounds per year
Capacity*
50
165
1865
Production
1968: 1.7 million tons
1973: 3.0 million tons
Uses
Molding, Blow extrusion
Processes
Polymerization with or without catalysts
Waste Problems
A typical plant produces a 600 gallons/ton of .product with the
following composition:
Styrene
Benzoyl Peroxide
Tricalcium Phosphate
Alkyl Aryl Sulfonate
Suspended Solids
3 ppm
1400 ppm
800 ppm Ca
2200 ppm P04
80 ppm
500 ppm
Waste Reduction by Process Change
It is possible by cleaning up this stream to recover Benzoyl
Peroxide for reuse. This scheme would cost less than $0.40/1000
gals, and would provide a completely closed system and eliminate
almost all reuse.
161
-------
PROPYLENE
Producers Capacity*
Ashland, Catlettsburg, Ky. 130
Atlantic-Richfield, Watson, Calif. 230
Amoco, various locations 510
Chevron, El Segundo, Calif. 160
Cities Services, Lake Charles, La. 320
Clark, Blue Island, 111. 70
Dow, various sites 440
DuPont, Orange, Texas 200
El Paso, Odessa, Texas 60
Enjay, various sites 1440
Goodrich, Calvert City, Ky. 90
Gulf, various sites 830
Jefferson, Port Neches, Texas 150
Marathon, Texas City, Texas 70
Mobil, Beaumont, Texas 520
Monsanto, various sites 360
Petroleum Chemicals, Lake Charles, La. 60
Phillips, Sweeney, Texas 180
Shell, various sites 630
Signal, Houston, Texas 90
Sinclair, Houston, Texas § Marcus Hook, Pa. 380
Sinclair-Koppers, Houston, Texas 100
Skelly, El Dorado, Kansas 90
Sohio, Lima, Ohio 110
Sun, Marcus Hook, Pa. 300
Suntide, Corpus Christi, Texas 70
Texaco, Westville, N. J. 140
Texas City Ref., Texas City, Texas 100
Texas Eastman, Longview, Texas 100
Tidewater-Air Products, Delaware City, Del. 250
Union Carbide, various sites 550
Union Oil, Los Angeles, Calif. 140
Total 8920
*millions of pounds per year
Production
1968: 7,000 million pounds per year
1973: 11,000 million pounds per year
Uses
Isopropanol, acrylonitrile, polypropylene, propylene oxide,
heptene, cumene, glycerine
162
-------
Processes
Propylene is produced together with ethylene and details may be
obtained from the section on ethylene. However, the major por-
tion of the propylene is produced as a by-product of gasoline
product (over 85%). It is expected that the amount of propylene
generated will increase as the demand for high octane low leaded
gasolines increase.
Waste Reduction
See ethylene section
PROPYLENE OXIDE
Producers Capacity*
Celanese, Bishop, Texas 10
Dow, Freeport, Texas 225
Dow, Midland, Mich. 25
Jefferson, Port Neches, Texas 120
Olin, Brandenburg, Ky. 80
Oxirane, Bayport, Texas 150
Union Carbide, S. Charleston, W. Va. 200
Wyandotte, Wyandotte, Mich. 160
Total 1020
*millions of pounds per year
Production
1968: 890 million pounds
1973: 1750 million pounds
Uses
Polypropoxyethers, propylene glycol, polypropylene glycol,
dipropylene glycol
Process
See Ethylene Oxide section. Oxirane has developed a process
based on the oxidation of acetaldehyde.
Waste
See Ethylene Oxide
163
-------
TOLUENE
Producers Capacity*
Amoco, Texas City, Texas 20
Ashland, North Tonawanda, N. Y.,
Catlettsburg, Ky. 20
Atlantic Richland, Wilmington, Calif. 24
Chevron, El Segundo, Calif;
Richmond, Calif. 32
Cities Services, Lake Charles, La. 36
Coastal States, Corpus Christi, Texas 10
Cosden, Big Spring, Texas 15
Crown Central, Houston, Texas 10
Dow, Bay City, Mich. 17
Enjay, Baton Rouge, La.; Baytown, Texas 65
Gulf, Philadelphia, Pa; Port Arthur, Texas 20
Hess, Corpus Christi, Texas 18
Leonard, Mount Pleasant, Mich. 3
Marathon, Texas City, Texas 12
Mobil, Beaumont, Texas 25
Monsanto, Alvin, Texas 32
Pontiac, Corpus Christi, Texas 13
Shell, Houston, Texas; Odessa, Texas 65
Wilmington, Calif; Wood River, 111.
Signal, Houston, Texas 16
Sinclair, Houston, Texas; Marcus Hook, Pa. 26
South Hampton, Silsbee, Texas 6
Southwestern, Corpus Christi, Texas 10
Sun, Marcus Hook, Pa. 25
Sunray DX, Tulsa, Okla. 4
Suntide, Corpus Christi, Texas 13
Tenneco, Chalmette, La. 8
Texaco, Port Arthur, Texas 31
Union Carbide, S. Charleston, W. Va. 10
Union Oil-Atlantic, Nederland, Texas 20
Union Oil, Lemont, 111. 10
Vickers, Potwin, Kansas 5
Total 620**
*millions of gallons per year
**also 65 million gallons from coke oven, tar distiller and
styrene monomer operations
Production
1968: 610 million gallons
1973: 800 million gallons
164
-------
Uses
Benzene, solvents, gasoline, TNT, Toluene diisocyanate, phenol
Process
Toluene is produced by extraction from refinery reformate as is
benzene. For details see benzene.
UREA
Producers Capacity*
Allied 320
American Cyanamid 150
Arkla 67
Armour 17
Best 20
Collier 50
Columbia Nitrogen 25
Cooperative Farmer 50
DuPont 205
Escambia 23
Farmers Chemical 30
Fel Tex 20
Grace 100
Gulf 90
Hawkeye 25
Hercules 60
Ke tman 7
Miss. Chem 80
Mobile 5
Monsanto 80
Nipack 260
Nitrin 23
Olin 150
Phillips 8
Phillips Pacific 20
Premier 70
Shell 185
Solar 140
Southern Nitrogen 60
Sun Olin 75
Valley Nitron 35
Wycon 50
Total 1500
*thousands of tons
165
-------
Production
1968: 2.3 million tons
1973: 3.7 million tons
Uses
Animal feed, fertilizer, plastics
Processes
All of the major processes involve the high pressure reaction
of C02 and ammonia. There are about 10 variations of this
scheme.
Waste Problems
Typical wastes amount to about 120 gallons/ton of product with
the following composition:
Ibs/ton
NH, 3.6
CC-2 0.6
Urea 0.8
Carbonate 0.1
Waste Reduction Through Process Change
It is normal practice to remove about 50% of the ammonia by
airstripping after adjusting pH with alkali. Recently two
new processes have been developed which strip the ammonia
and carbonate by contacting with either NH3 or C02 and
sending the overload directly to the reactor. This approach
is expected to reduce ammonia losses by 50% or more with a
more drastic effect on carbonate. These also involve operation
of the reaction at a lower temperature.
XYLENES
Ortho Para
Producers Capacity* Capacity*
Amoco 200
Chevron 130 536
Cities Service 120
Coastal 42 6
Commonwealth 70
Cosden 6
166
-------
Crown Central 19
Enjay 175 210
Hercor 100
Hess 45
Shell 100
Signal --- 15
Sinclair 80 215
Sunray DX 30 165
Tenneco 25 100
Total 736 1547
*millions of gallons per year
Production
Ortho Para
1968 500 750
1973 750 1800
Uses
Phthalic anhydride, polyesters
Process
Mixed xylenes are recovered primarily from refinery streams (see
benzene and ethyl benzene). It is separated out with ethyl
benzene and isomerization is carried out to increase the yield
of para xylene. A separation scheme involves crystallization
to separate out the various streams.
Waste Problems
Sludge from the crystallizer as well as bottoms, drains, etc.,
amount to perhaps 100-500 gallons/ton of product with an
organic content of 3-5,000 mg/1.
167
-------
APPENDIX D
COSTS OF UNIT WASTEWATER TREATMENT PRACTICES
168
-------
1000
CAPITAL COST RELATIONSHIP
EQUALIZATION
Figure 1-D
10
10 10
VOLUME OF EQUALIZATION TANK - GALLONS
169
-------
ih
$1
Figure Z-D
i CAPITAL COST RELATIONSHIP
NEUTRALIZATION
160
140
o
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o
120
,_ 100
O
40
20
- MOD
170
-------
CAPITAL COST RELATIONSHIP
OIL SEPARATION
Figure 3-D
10
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. 5
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171
-------
CAPITAL COST RELATIONSHIP
PRIMARY SEDIMENTATION
Figure 4-D
IOOO
10
10" 10'
SURFACE AREA OF PRIMARY CLARIFIER - FT*
172
-------
Figure 5-D
CAPITAL COST RELATIONSHIP
LAGOONS
SURFACE AREA - ACRES
-------
CAPITAL COST RELATIONSHIP
AERATED LAGOON
Figure 6-D
1C
0,1
VOLUME OF AERATION
10.0
BASIN-MILLION GALLONS
174
-------
CAPITAL COST RELATIONSHIP
AERATION BASIN
Figure 7-D
1.0 10.0
VOLUME OF AERATION BASIN-MILLION GALLONS
175
-------
CAPITAL COST RELATIONSHIP
FINAL CLARIFIERS
Figure 8-D
lOOO-o
SURFACE AREA OF FINAL CLARIFIER- FT*
176
-------
CAPITAL COST RELATIONSHIP
FILTRATION
Figure 9-D
10.0
0.01
100.0
FLOW-MOD
177
-------
CAPITAL COST RELATIONSHIP
CARBON ADSORPTION
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178
-------
CAPITAL COST RELATIONSHIP
ION EXCHANGE
Figure 11-D
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CAPACITY - MOD
179
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-------
XIV. BIBLIOGRAPHY
184
-------
BIBLIOGRAPHY
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191
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