WATER POLLUTION CONTROL RESEARCH SERIES
.'2020 --- 2/70
Petrochemical Effluents
Treatment Practices
SUMMARY
U.S. DEPARTMENT OF THE INTERIOR • FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Reports describe the
results and progress in the control and abatement of pollu-
tion of our Nation's waters. They provide a central source
of information on the research, development, and demonstra-
tion activities of the Federal Water Pollution Control
Administration, Department of the Interior, through in-house
research and grants and contracts with Federal, State, and
local agencies, research institutions, and industrial
organizations.
Water Pollution Control Research Reports will be distributed
to requesters as supplies permit. Requests should be sent
to the Planning and Resources Office, Office of Research and
Development, Federal Water Pollution Control Administration,
Department of the Interior, Washington, D. C. 20242, or
to the Robert S. Kerr Water Research Center, Federal Water
Pollution Control Administration, Department of the Interior,
P. 0. Box 1198, Ada, Oklahoma 74820.
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THE CHARACTERISTICS AND POLLUTIONAL PROBLEMS
ASSOCIATED WITH PETROCHEMICAL WASTES
Summary Report
Prepared by
ENGINEERING-SCIENCE, INC./TEXAS
Austin, Texas
Dr. Earnest F. Gloyna, Consultant
Dr. Davis L. Ford, Manager
for the
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
U. S. DEPARTMENT OF THE INTERIOR
Program No. 12020 Contract No. 14-12-461
February 1970
Copies of this report are available at the
Robert S. Kerr Water Research Center, P. 0.
Box 1198, Ada, Oklahoma 74820
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FWPCA Review Notice
This report has been reviewed by the Federal
Water Pollution Control Administration and
approved for publication. Approval does not
signify that the contents necessarily reflect
the views and policies of the Federal Water
Pollution Control Administration, nor does
mention of trade names or commercial products
constitute endorsement or recommendation for
use.
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ACKNOWLEDGMENTS
Appreciation is hereby expressed to the many contributors,
reviewers, and editors who helped compile this report and insure
its completeness and accuracy.
This profile was sponsored by the Federal Water Pollution
Control Administration, U. S. Department of the Interior. The
preliminary draft was reviewed on behalf of the Federal Water
Pollution Control Administration by Mr. J. A. Horn, Mr. L. D. Lively,
Mr. L. W. Muir, Mr. K. M. Mackenthun, Mr. Richard Duty, Mr. W. C.
Schilling, and Mr. George Rey. Their comments and suggestions are
duly acknowledged.
Members of the petrochemical industry also have been most
cooperative in the review and editing of the report. These
include Mr. R. D. Sadow of Monsanto Chemical Company, Mr. Sid 0.
Brady of Humble Oil and Refining Company, and Mr. R. D. Pruessner
of Petro-Tex Chemical Company.
Particular appreciation is expressed to Dr. Lial F. Tischler,
Dr. Carl E. Adams, and Dr. William Kwie who helped review the
literature and compile the original manuscript.
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TABLE OF CONTENTS
ACKNOWLEDGMENTS i
TABLE OF CONTENTS ii
LIST OF TABLES iv
LIST OF FIGURES v
RESEARCH NEEDS - CONCLUSIONS AND RECOMMENDATIONS 1
HISTORY OF PETROCHEMICAL INDUSTRY 1
DESCRIPTION OF THE PETROCHEMICAL INDUSTRY 1
PETROLEUM RAW MATERIALS 1
PETROCHEMICAL PROCESSES 2
CHEMICAL AND PROCESS RELATED CLASSIFICATION OF WASTES ... 2
WASTE POLLUTIONAL EFFECTS AND THEIR CHARACTERIZATION .... 3
TREATMENT AND CONTROL OF PETROCHEMICAL WASTES 3
ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT 5
INTRODUCTION 6
DESCRIPTION OF THE PETROCHEMICAL INDUSTRY 8
WATER USE AND PROJECTION 8
PRINCIPAL PRODUCTS AND INTERMEDIATES 10
PETROLEUM RAW MATERIALS 10
PROJECTED GROWTH OF THE PETROCHEMICAL INDUSTRY 16
PETROCHEMICAL PROCESSES 19
PRIMARY CONVERSION PROCESSES 20
SECONDARY CONVERSION PROCESSES 20
PETROCHEMICAL WASTES 25
PROCESSES AS WASTE SOURCES 26
WASTE CHARACTERISTICS 26
CHEMICAL CLASSIFICATION OF PETROCHEMICAL WASTES 29
POLLUTIONAL EFFECTS OF PETROCHEMICAL WASTES 40
CONVENTIONAL POLLUTIONAL PARAMETERS 40
EFFECTS OF POLLUTION ON RECEIVING WATER 42
EFFECTS OF POLLUTION ON WATER USE AND REUSE 43
PHYSIOLOGICAL EFFECTS 43
IDENTIFICATION AND MONITORING METHODS 48
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TREATMENT AND CONTROL OF PETROCHEMICAL WASTES 51
INTERNAL IMPROVEMENTS 51
PHYSICAL TREATMENT PROCESSES 55
CHEMICAL TREATMENT 60
BIOLOGICAL TREATMENT PROCESSES 62
OTHER METHODS OF DISPOSAL 75
ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT 82
GENERAL CONSIDERATIONS 82
PRIMARY TREATMENT 82
BIOLOGICAL TREATMENT PROCESSES 86
TERTIARY TREATMENT PROCESSES 86
SLUDGE HANDLING AND DISPOSAL 86
ULTIMATE DISPOSAL 89
REFERENCES 90
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LIST OF TABLES
Table Title Page
1 PROJECTION OF UNITED STATES PETROCHEMICAL
PRODUCTION CAPACITY FOR SELECTED CHEMICALS 17
2 COMPOSITION OF CLEAN WATER EFFLUENTS 27
3 PETROCHEMICAL PROCESSES AS WASTE SOURCES 30
4 WASTEWATER CHARACTERISTICS ASSOCIATED WITH SOME
CHEMICAL PRODUCTS 35
5 WATER QUALITY FOR SELECTED AGRICULTURAL USES 44
6 DETECTABLE CONCENTRATIONS OF SOME PETROCHEMICAL
COMPOUNDS CAUSING TASTE AND ODOR IN WATER 46
7 SOME ORGANIC CHEMICALS CAUSING ADVERSE TASTES IN
FISH 47
8 USABLE SIDE-PRODUCTS FROM SOME TYPICAL PETROCHEMICAL
PROCESSES 53
9 TYPICAL EFFICIENCIES OF OIL SEPARATION UNITS 57
10 RELATIVE BIODEGRADABILITY OF CERTAIN ORGANIC
COMPOUNDS 64
11 ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES .. 67
12 TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES . . 71
13 AERATED LAGOON TREATMENT OF PETROCHEMICAL WASTES ... 74
14 WASTE STABILIZATION POND TREATMENT OF PETROCHEMICAL
WASTES 76
15 PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL INJECTION -
TYPICAL INSTALLATIONS 79
16 SUGGESTED BASIS FOR COSTING UNIT PROCESSES 83
17 OPERATING COSTS - WASTE TREATMENT PLANTS 87
iv
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LIST OF FIGURES
Figure Title page
1 LOCATION OF HYDROCARBON PROCESSING PLANTS 7
2 TOTAL WATER INTAKE FOR CHEMICAL AND ALLIED PRODUCTS
INDUSTRY 9
3 FIRST-GENERATION PETROCHEMICALS 11
4 PRINCIPAL PRODUCT DERIVATIVES FROM THE OLEFINS .... 12
5 PRINCIPAL PRODUCT DERIVATIVES FROM THE AROMATICS ... 13
6 PRINCIPAL PRODUCT DERIVATIVES FROM THE PARAFFINS ... 14
7 PRINCIPAL PRODUCT DERIVATIVES FROM MISCELLANEOUS
SOURCES 15
8 PRIMARY CONVERSION PROCESSES 21
9 SECONDARY CONVERSION PROCESSES 22
10 PETROCHEMICAL WASTEWATER CHARACTERIZATION:
FLOW, BOD, COD 37
11 CLASSIFICATION OF INORGANIC COMPOUNDS WHICH
MAY OCCUR IN PETROCHEMICAL WASTESTREAMS 38
•
12 CLASSIFICATION OF ORGANIC COMPOUNDS WHICH MAY
OCCUR IN PETROCHEMICAL WASTESTREAMS 39
13 WASTEWATER TREATMENT SEQUENCE/PROCESS SUBSTITUTION
DIAGRAM 77
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RESEARCH NEEDS - CONCLUSIONS AND RECOMMENDATIONS
HISTORY OF THE PETROCHEMICAL INDUSTRY
It is concluded that the petrochemical industry will continue to
grow and diversify. The chemical and allied products industry is expec-
ted to increase from the present 5.5 billion gallons per year to 23
billion gallons per year by the year 2000. The production and sales of
organic chemicals are expected to increase from the present production
of 135 billion pounds per year to 200 billion pounds per year by the
year 1973. The petrochemical industry is projected to increase nine
percent per year through 1975. Water use patterns have changed: in
1954 and 1962, respectively, cooling water requirements were 82 percent
and 65 percent of the total water use. The industrial growth rates by
geographical areas through 1975 will be 25, 15, and 10 percent, respec-
tively, for the Pacific Coast and Alaska areas, Gulf Coast area, and
Southeast, Puerto Rico, and Virgin Islands areas.
It is recommended that an updated profile of this industry be made
every five years. Particular emphasis should be directed to the water
use and reuse patterns for the newer petrochemical processes, advanced
methods of waste handling, changes in water quality criteria for updated
processes, and changes in industrial growth patterns.
DESCRIPTION OF THE PETROCHEMICAL INDUSTRY
It is concluded that new products will be developed from existing
"intermediate" petrochemicals, but also new petroleum-based derivatives
will be developed to a greater extent. In 1955, the total petrochemical
production constituted 24 percent, by weight, of the total chemical pro-
duction. It is expected that the percentage will increase to 41 percent
by 1970. It is anticipated that ethylene, an important petrochemical
intermediate, will double (14 to 25 million metric tons annually) over the
1970-80 decade. Estimates indicate that about 500 new petroleum products
are introduced to the market every year.
It is recommended that each of the major processes developed by the
industry be studied with the objective of evaluating the trends in plant
locations, effects on area-wide water quality, and treatment requirements.
PETROLEUM RAW MATERIALS
It is concluded that there will be no significant changes in petro-
chemical feedstocks, although the increasing demand for ethylene and
butylene has required the petrochemical industry to look for additional
sources of base material. Heavy fractions such as fuel oils are finding
an increasing market as the source for these two olefins and other primary
petrochemicals.
It is recommended that the patterns of feedstock usage be monitored
and major changes be evaluated in terms of the water use and water reuse
requirements, potential pollution problems, and product development.
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PETROCHEMICAL PROCESSES
It is concluded that the main contribution to environmental pollution
from the petrochemical industry at present eminates from process waste
streams. However, the principal processes and characteristics of their
wastewaters are fairly well understood. The ranges of the waste volumes
and organic concentrations vary considerably. Within the same process
at different plant sites, the pollutant loads may range by more than one
order of magnitude. Typically, the reaction efficiency in the petro-
chemical industry has a wide variation. This efficiency may range from
60 percent to nearly 100 percent. Although the feedstock is recycled in
the case of low conversion efficiency, the practice is highly dependent
on market conditions. In addition to product losses, there are mechanical
losses and waste streams that contain side-products.
It is recommended that comparative cost analyses be made on several
typical recycle (feedstock) practices and on associated wastewater treat-
ment requirements, establishing a basis for optimizing the overall plant
operations. First, comparative studies need to be made on a computerized
model basis where operating variables can be generated and the results
studied in detail. Second, a series of field studies should be made t'o
test the model data and demonstrate the interrelationships of product
handling with wastewater treatment costs.
CHEMICAL AND PROCESS RELATED CLASSIFICATION OF WASTES
It is concluded that many of the conventional parameters, as compared
to those developed for characterizing domestic wastewaters, do not ade-
quately define the potential pollution characteristics of petrochemical
wastes. In many cases, the pertinent characteristics of a waste stream
were ignored, the analytical procedures were inadequate for such complex
wastes, and much of the reported data have been misinterpreted. Signifi-
cant inconsistencies have been found in the measurement of organic carbon,
including oil and oil-like substances; oxygen demand of compounds, as
measured both chemically and biochemically; toxicity as reflected in both
microbial and higher forms of plant and animal life, including man; inter-
ferences between petrochemical process waste constituents and reagents
used in conventionally-accepted organic and inorganic characterization
analyses; and availability of nutrients.
It is recommended that a comprehensive and coordinated evaluation
program be developed specifically for standardizing the characterization
techniques of wastewaters containing complex and undefinable petrochemical
and related wastewater constituents. Such a program should include a
correlation and interpretation of reported data and unpublished but
available industrial data. Currently, an evaluation must be made of
newly developed analytical techniques in comparison with conventional
procedures. Finally, a thorough study must be made on the adaptability
of newly developed parameters for governmental and industrial use. The
latter study would involve an evaluation of the adaptability of newly
developed parameters to (a) uniform nation-wide reporting practices;
(b) national monitoring networks; (c) pollution or stream assimilation
models (mathematical); and (d) on-stream and continuous monitoring systems,
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WASTE POLLUTIONAL EFFECTS AND THEIR CHARACTERIZATION
It is concluded that petrochemical wastes may provide potential
pollutants in the form of concentrated oxygen-demanding organic and
inorganic materials; organic compounds not amenable to biological degra-
dation; oil and oil-like substances; volatile and nonvolatile suspended
materials; color contributing solutions; toxic fractions; compounds
responsible for taste and odors; floatables and polymeric products; and
agents which interfere with conventional analytical techniques and
increasing problems associated with the treatment and/or discharge of
heated wastewaters.
Furthermore, it is concluded that much of these wastewaters could
be reused within the plants with varying degrees of treatment.
It is recommended that long-term tests be conducted to evaluate the
effects of intermediate and product waste streams on (a) aerobic and
anaerobic biological degradation rates; (b) toxicity of these wastes on
acclimated microbiological cultures, and both micro- and macro-plants
and animals; (c) speciation and diversity index evaluations below selected
plant sites.
It is further recommended that a serious evaluation be made on the
treatment required for in-plant reuse and cost analyses be established on
treatment for plant reuse and on treatment for discharge.
It is recommended that a series of studies be initiated to standar-
dize the evaluation of the potential pollutional characteristics of all
cooling tower and boiler water preparations, as well as their effects on
waste treatment systems.
A detailed evaluation should be made at an early date of all the
chemical interferences affecting the BOD and COD tests. Carefully con-
trolled tests should be conducted to establish the BOD5/BOD ratio.
It is additionally recommended that many of the more prevalent
petrochemical compounds be analyzed in terms of unit weight of BOD, COD,
TOC, and IOD per unit weight of the compound. A similar representation
per unit weight of suspended solids discharged from various related pro-
cesses would be of value.
Special properties of selected waste streams should be studied with
respect to fish "tainting" (taste and odors in both finfish and shellfish),
induced changes in the surface activity of receiving waters, interaction
of waste with chlorine and other water treatment disinfectants, and effects
of post polymerization on receiving waters.
Similarly, tests should be conducted to determine the effect of the
more common process wastes on benthic organisms, selected plankton, and
acclimated biological cultures.
TREATMENT AND CONTROL OF PETROCHEMICAL WASTES
It is concluded that most of the wastewaters produced by the
petrochemical industry require some form of primary product recovery and
treatment, oil removal, settleable solids removal, and reduction in the
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organic content. By-product recovery possibilities represent a significant
approach in reducing pollutants. There is much room for the use of in-plant
separation of product and feedstock for recovery purposes.
It is further concluded that physical separation and disposal schemes
have not been used as effectively as possible. For example, combustion
processes are often overlooked as a potential disposal process, particu-
larly when the wastes are too concentrated or too toxic for treatment
by lower-cost biological methods. Stripping processes can be used more
effectively throughout the petrochemical industry to remove volatile
fractions from the collection of contaminated stream water runoffs.
Most wastewater from petrochemical plants contain wastes which are
amenable to biological degradation. A significant group of these wastes
exhibit a low biodegradation rate. Consequently, an optimal balance
between physical, chemical, and biological treatment (with process modi-
fications) must be considered in the development of a pollution abatement
master plan.
For optimum wastewater management in the petrochemical industry, it
is necessary to develop the wastewater treatment as an integral process
of the overall plant. This necessitates the development of increased
product and feedstock recovery, improved housekeeping, separation of
noncontaminated wastes from waste streams, and separation of concentrated
nonsoluble or otherwise solid fractions near each source.
Additionally, it is concluded that the master plan for in-plant
wastewater collection should include facilities to segregate process
waste from less contaminated streams. The latter falls into two cate-
gories: (a) those wastes derived from dry weather flows such as leaks
from pumps, sample ports, packaging, container washings, kettle or batch
operations; and (b) those wastewaters derived from wet weather runoffs.
The containment and treatment of certain storm flows need evaluation.
It is recommended that the following treatment and control evaluations
be considered:
A. Physical Treatment Processes
1. The problem of oil-water and other emulsions should be
studied, both with respect to influences on secondary biological waste
treatment and the most efficient methods of breaking the emulsions,
thus enhancing separation.
2. As the process streams are reused or recycled, the effluents
will become increasingly wanner. Emphasis should be directed to evaluat-
ing methods of cooling various waste streams prior to subsequent treatment.
3. Many waste streams contain inorganic and organic solids which
are difficult to remove (i.e., lime sludges containing heavy tars, oils,
etc.). Physical separation processes in conjunction with coagulant aids,
therefore, should be more thoroughly investigated.
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B. Chemical Treatment
1. The development of better techniques for evaluating the
effects of various cooling tower and boiler water additives on secondary
biological treatment and such analyses as may be affected adversely by
these additives should be undertaken.
C- Biological Treatment
1. Evaluation of the effect of various wastes on bioflocculation,
settling, and all types of biological treatment systems is recommended.
Specific attention should be directed to the toxic characteristics of
these wastes.
2. The magnitude of biological reaction rates for major
process wastes within the petrochemical industry should be established.
3. Biological process modifications to maximize COD reduction
should be developed.
4. A determination of the effects of various wastewaters on
streams and brackish waters in terms of both biodegradation rates and
reaeration rates should be made.
5. A more satisfactory way of evaluating concentrations of
pollutants in brackish and salt waters should be developed.
6. The advantages (if any) of two-stage biological treatment
versus single-stage biological treatment should be determined. Similarly,
the advantages (if any) of tertiary treatment over other disposal means
should be investigated.
7. The availability of complexed forms of nitrogen and phos-
phorus as a nutrient source to microorganisms in biological waste treat-
ment plants should be evaluated.
D. Other Methods of Disposal
1. The technology by which persistent contaminants in benthic
deposits can be studied should be developed.
2. Guidelines for the development of dilution thresholds for
common petrochemical toxicants with respect to co-treatment with munici-
pal wastes should be established.
ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT
It is concluded that most waste streams from petrochemical plants
will require some form of solids or oil separation, waste stream separa-
tion and pretreatment, and secondary biological treatment. The cost of
this wastewater treatment can be reduced considerably by in-plant reuse
of product waste streams and wastewater in general. Trends toward the co-
treatment and joint treatment of industrial wastewaters necessitate the
establishment of a formula for equitably prorating pollution control costs.
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It is recommended that -a detailed and basic study be initiated to
evaluate the cost of treating wastes from single plants or process streams
with combined wastes from several plants. The economy of scale in treating
petrochemical wastes on an area-wide basis offers many advantages in
dampening the effect of peak releases from individual processes, possibly
neutralization, utilization and balance of nutrients, and more effective
treatment supervision.
However, the economy of scale is subject to geographical limitations.
Conveyance costs may override any economy of scale inherent with regional
type treatment concepts.
INTRODUCTION
A petroleum chemical industry based on hydrocarbons is relatively
new since synthetic chemicals were not produced in significant amounts
from petroleum until just prior to World War I. The petroleum industry
in the United States developed during 1919 to 1920 as a result of research
conducted during World War I. During World War II, the United States
produced vast quantities of synthetic rubber which gave the petroleum
industry great impetus. Thirty major synthetic rubber, butadiene, and
styrene plants were constructed from 1940 to 1950 at a cost of $900
million (16). Following the pattern of synthetic rubber production, the
petrochemical industry experienced an accelerated rate of growth, increas-
ing over fivefold from 1945 to 1960. This rapid growth continues today
with organic chemicals constituting a major product of the petrochemical
industry. Ammonia, sulfur, and carbon black are major inorganic products
which are being manufactured in large quantities within the petroleum
industry.
There are several reasons for the rapid growth of the petrochemical
industry, including the rise of industries which process petrochemicals
into final products such as plastics and synthetic fibers; the avail-
ability of cheap and abundant supplies of petroleum raw materials; the
ease and economics of producing petroleum-based chemicals as compared to
production using non-petroleum sources; and the increasing cost and
limited supply of non-petroleum raw materials.
The locations of the major petrochemical plants in the United States
are shown in Figure 1. The center of petrochemical activity in the United
States is situated along the Gulf Coast between New Orleans, Louisiana,
and Brownsville, Texas. This region contained approximately 80 percent of
the nation's petrochemical production capacity in I960 (16). The major
factors for location of the industry in this area include the availability
of sea transport, the fact that 75 percent of the United State's petroleum
reserves are located within easy reach of this area, the abundance of
fresh water, and the large quantities of cheap fuel (gas).
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REFINERY
NATURAL GAS
PROCESSING PLANT
PETROCHEMICAL PLANTS
(from Anon., Hydroc.
Proc. May I966~
FIGURE 1
LOCATION OF HYDROCARBON PROCESSING PLANTS
(Reference Anon., Hydroc. Proc., May 1966)
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DESCRIPTION OF TOE PETROCHEMICAL INDUSTRY
This description of the petrochemical industry includes raw
materials and water requirements, as well as principal products of the
industry. Based on this history and description, projections of future
petrochemical industrial growth patterns can be made and are included in
this section.
WATER USE AND PROJECTION
Although historical water usage data for the petrochemical industry
are not separately cited, the 1954 Census of Manufacturers showed that
the total chemical and allied products industry used 2,378 billion gallons
of water per year. This information was obtained from 1,164 plants which
used 20 million gallons or more water per year and comprised 95 percent
of the water intake by the industry. Water reuse was practiced by 67
percent of these plants; thus, the gross water usage was 4,032 billion
gallons annually. This water's major use was cooling (85 percent), with
9.5 percent employed as process water and the balance utilized for miscel-
laneous purposes. The water consumed by the chemical industry represented
23.4 percent of the total industrial water use in 1954 (94).
The 1958 Census of Manufacturers reported 933 chemical plants using
20 million gallons or more per year in 1959, resulting in a total water
intake of 3,240 billion gallons per year. About 74 percent of these
plants employed water reuse, and the gross industrial water use by the
chemical industry was 5,225 billion gallons per year. Approximately 66
percent of the total water intake was used for cooling water, a consider-
able drop from the 83 percent reported in 1954. Process water accounted
for 14 percent and water used for the generation of steam and electricity
comprised 15 percent of the industry's water intake in 1959. Organic
chemical production, which is predominantly petroleum-based, accounted for
44 percent of the annual water intake of the chemical industry.
The latest water use data for the chemical industry were collected
in 1962 (14) and included 875 plants in the United States. These data
should not be considered to represent the entire chemical industry
because some definitions of the industry include packaging, blending,
mixing, and distribution of chemical products, most of which use little
or no water. The total intake of these plants was 3,600 billion gallons
in 1962. The water used for cooling constituted 65 percent of the water
intake.
The water intake by the chemical and allied products industries is
projected to the year 2000 in Figure 2. Actual water intake for plants
which used 20 million or more gallons per year is depicted for 1954 and
1959. The projections indicate that the chemical industry will be the
major consumer of industrial water by the year 2000 (94).
8
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9
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PRINCIPAL PRODUCTS AND INTERMEDIATES
"A petrochemical is a chemical compound or element recovered from
petroleum or natural gas or derived in whole or in part from petroleum
or natural gas hydrocarbons and intended for chemical markets" (119).
Most petrochemicals are organic, but a few are inorganic, with the
exception of carbon black. Carbon black is a complex chemical which
cannot be classified as either completely organic or inorganic, but is
still considered as a petrochemical since petroleum is its principal
source (96).
The primary or first-generation petrochemicals derived directly
from petroleum raw materials are shown in Figure 3. All petrochemical
products come from these primary chemicals with the exception of carbon
black, which is not further processed. These primary petrochemicals
are followed through their intermediate phases to end-products as shown
in Figure 4 through Figure 7. Most end-products shown represent raw
materials used by subsequent industries in preparing consumer goods.
Examples of major petrochemicals range from ammonia, made from
natural gas, to synthetic rubber, which is a mixture of hydrocarbon
polymers. This list includes sulfur, carbon black, olefins, polyolefins,
olefin derivatives, aromatics and their derivatives, acetylene, phenol,
alcohols, ketones, acrylonitrile, acetic anhydride, phthalic anhydride,
maleic anhydride, and many others (119).
Relative to primary chemical definition, the olefins comprise the
commercial bases for a majority of the synthetic organic chemicals pro-
duced in the United States (103). The main chemical processes for the
conversion of olefins into chemical derivatives include polymerization,
hydration, halogenation, epoxidation, alkylation, and hydrocarboxylation
(100).
The aromatics rank second only to olefins in terms of quantities of
primary organic petrochemical production. Benzene is the most important
of the aromatics in terms of quantity produced.
The paraffins are the least reactive of the hydrocarbons, and all
the common processing steps for this family of compounds require elevated
temperatures and pressure. The principal paraffinic feedstocks used by
the chemical industry are the one-to-five carbon hydrocarbons (96).
Other petrochemicals not categorized herein are also important as
product sources. The principal uses of some of these miscellaneous
petrochemicals are shown in Figure 7.
PETROLEUM RAW MATERIALS
The first-generation petrochemicals are produced from a variety of
petroleum fractions. The four major fractions are natural gas, refinery
gas, natural gas condensate, light tops or naphtha, and heavy fractions
such as fuel oil.
10
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PETROLEUM
RAW MATERIALS
FIRST-GENERATION PETROCHEMICALS
Crude Petroleum-
Natural Gas-
i— Alkyne •
Natural Gas Liquids-
Coke Oven Processes-
—Olefins-
—Paraffins-
—Aromatics-
—Hydrogen
—Hydrogen Sulfide
•—Carbon Black
Acetylene
Ethylene
Propylene
Butylene
Higher Olefins
Methane
Ethane
Propane
Higher Paraffins
Benzene
Toluene
Xylene
Complex Aromatics
FIGURE 3
FIRST-GENERATION PETROCHEMICALS
11
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Rubber
Rubber s
C Bu F! R bb "^
^
rwioprene Rub et
Acetic Acid
ACT* lonilrile
r h i n
**"i ^ h d d
1 * C 'l C i
p p p c
* ^ AP' t y
'
'1C " Oflr "
jCtF
'
;J ' "
AUph«I
Alcohol
1
Non- ionic Determent*
ton ionic Detcricnti
Sulfato
Acetic Acid
Ithyl Alcohol
/icryioniiri ic
Tetncthvl Leid
Carbinol
Acetic Anhydride
Additivet
P Inc Clyeolt
Pol-iropv 1 rnc Tlyrnls
Jf J*1*7 '
i cr*yr^*In*
1 Trlchloroprop-c..
pi'i'r vlt-T
. Sulpholuc
t h 'l JLB l^K* " °"e
p-t«rt. Eutyl
Bcntolc AcllEO UtV • C
Additive*
— Alkyd r«ftnt
tL^Di " FC^ Chi
Propjn*
j AWrln
Endrln
12
-------
First-Generation Petrochemicals
Intermediate Chemicals
Products
BASES FOR
PLASTICS ,
SYNTHETIC
ROBBER
BASES
SYNTHETIC
FIBER
BASES
AROMATICS
BASIC
INDUSTRIAL
CHEMICALS
SYNTHETIC
DETERGENT
BASES
BASIC
AGRICULTURAL
CHEMICALS
Xylcnc - ... • —
Rubber
Complex °
Aromatics Aromatic E-tract-
, i_ Adipic Acid »,,!„„
Benzene Cycloncxanc Hexamethylene Diamine y
Naphthenic Naphthenir AfM
Acids
F Complex Aromatics
Pitch
1 Petroleum Resins
-------
First-Generation Chemicals
Intermediate Chemicals
Products
HAsns
PIASTICS
AND
KKSINS
SYNTHETIC
KIHIRF.R
HASKS
SYNTHETIC
I'lHfCR
KASKS
I'AKAFKINS
IIASIC
INDUSTRIAL
( IIKMICAL
HASKS
IIASIC
ACKICULTURAI.
CHEMICALS
SYtmiETic
and Hydrogen
Carbon Monoxide
and Hydrogen
Carbon Monoxide
Hydrogen
y
Formaldehyde, Acetaldehyde
Compounds
A
c^ty
Ethyl Chloride
Formaldehyde, Acetaldehyde
Compounds
I
p
j Hjdrogcn lu^ia
j », ri ,
y e |
C b D' -"d
Formaldehyde,
Other Oxygenated
Compounds
Reinforcing Agent
uutQdicnc KuDDor
Styrene-butadiene
Rubber
Acetaldehyde and
Other Oxygenated
Compounds
i Hydrogen Cyanide
' Nitric Acid
!Citrogeneous
Linearalkyl
Sulfonates
KKTKRCKNTS
FIGURE 6
PRINCIPAL PRODUCT DERIVATIVES FROM THE PARAFFINS
14
-------
FIRST-GENERATION CHEMICALS
INTERMEDIATE
CHEMICALS
PRODUCTS
Basic
Industrial
Chemicals
Synthetic
Detergent
Bases
Rubber
Bases
Synthetic
Fiber
Bases
Basic
Agricultural
Chemicals
Miscellaneous
Chemicals
L-
•Hydrocarbons
I-
Hydrogen
Sulfide"
jORGANIC
{INORGANIC]"
Hydrocarbons i
Hydrogen
Sulfide
Carbon
Black"
Hydrogen
Sulfide"
Hydrogen
Sulfide"
Petroleum
Sulfonates
•Sulfur•
•Sulfur-
•Sulfur-
Hydrocarbon
Solvents
Petroleum
Sulfonates
Sulfuric
Acid
Sulfonated
Detergents
•Vulcanization
Strengthening
Agent
Carbon
Disulfide
•Miscellaneous
FIGURE 7
PRINCIPAL PRODUCT DERIVATIVES FROM MISCELLANEOUS SOURCES
15
-------
Natural gas is probably the most desirable chemical feedstock in the
United States because it contains a relatively small number of hydrocarbons
and because of its availability. Methane is the major constituent of all
natural gases with smaller amounts of ethane, propane, butane, and pentane
commonly occurring. Small quantities of hydrogen sulfide, nitrogen, and
helium may be associated with certain natural gases. Enormous quantities
of natural gas are produced in the United States but only about three
percent are used for chemical production. The remainder are used for fuel.
In the future, larger quantities of natural gas will probably be used in
chemical production because of availability and low cost.
Crude petroleum contains a great number of hydrocarbons, most of which
are either paraffins, naphthenes, or aromatics. The crude oil is refined
by distillation, in order to obtain the fractions used for preparation of
the first-generation petrochemicals.
Refinery gases provide an important source of ethylene and propylene
used by the petrochemical industry. Once the crude oil has been distilled,
the resulting gasoline fractions are further processed by catalytic crack-
ing, which consists of splitting and rearranging hydrocarbon molecules
using heat, pressure, and catalysts. Considerable amounts of by-product
olefins are formed during cracking operations, and these olefins constitute
refinery gas.
Light naphtha contain the lower paraffinic gasoline fractions, which
are unsuitable for blending fuels or for conversion to fuel hydrocarbons
by catalytic reforming. The fractions generally are converted into ole-
fins and diolefins by cracking in the presence of steam (117).
The heavy fractions such as oils, waxes, and asphalts, which are
obtained during the primary distillation of crude petroleum, are finding
increasing value as the source of the olefins, ethylene, and butylene.
Synthesis gas also can be produced by partially oxidizing the heavy
fractions.
PROJECTED GROWTH OF THE PETROCHEMICAL INDUSTRY
The petrochemical industry has experienced tremendous growth and
expansion over the last two decades. Estimates of expected growth must
be constantly revised to reflect process changes, consumer demands, and
feedstocks. The projected data in Table 1 present current estimates of
consumption in 1975 for some of the more important petrochemicals.
The outlook for growth in the entire petrochemical industry is
favorable. In 1955, petrochemical production comprised about 24 percent
by weight of the total chemical production; by 1970, it should account
for 41 percent according to this projection (75). Petrochemical sales
for 1966 were estimated at $12 billion and, by 1970, are expected to
exceed $20 billion (15). The 1966 projection of petrochemical sales for
1970 was about $5 billion higher than a similar projection made in 1961.
Petrochemicals should account for 64 percent of the total dollar value of
all chemical products by 1970.
16
-------
TABLE 1
PROJECTION OF UNITED STATES PETROCHEMICAL PRODUCTION
CAPACITY FOR SELECTED CHEMICALS
(References 1, 7, 104)
Products and
Petrochemical
Intermediates
United States Production
billions of pounds/year
Recent Data
1954 year in parentheses 1975+
Synthetic Fibers
Acetate 0.34
Acetic Anhydride 0.696*
Nylon
Polyesters 0.035
Acrylic Fibers 0.097
Acrylonitrile 0.2*
Plastics and Resins 2.8
Phenolic Resins 0.434
Phenol 0.6*
Formaldehyde 1.03*
Phthalic Alkyd and
Nonbenzenoid 0.45
Alkyd Resins
Phthalic Anhydride
Synthetic Glycerol 0.115*
Styrene Resins 0.481
Styrene 0.500
Urea and Melamine Resins 0.265
Vinyl Resins 0.524
Polyolefins
Polyethylene 0.57
Polypropylene
Surface-Active Agents
(Not Detergents Them-
selves) 1.03
Ethanolamines 0.063
7.74 (1962)
0.66 (1962)
0.53 (1962)
1.25 (1962)
1.55 (1962)
2.16 (1962)
4 (1967)
0.66 (1967)
1.12
2.65*
0.8-1.0
1.0
1.5-1.6
1.5*
1.6*
2.25*
7.25*
1.66
0.915*
2.4
2.4
0.715
2.5
6.93
2.11
1.6
0.153
17
-------
TABLE 1 (Continued)
PROJECTION OF UNITED STATES PETROCHEMICAL PRODUCTION
CAPACITY FOR SELECTED CHEMICALS
Products and
Petrochemical
Intermediates
Synthetic Rubber
Copolymer
Butyl
Neoprene
Others
Ammonia (from petroleum
only)
Methanol
Methyl Chloride
Ethyl Chloride
Ethylene Bichloride
Ethanol (Synthetic)
Ethylene Glycol
Ethylene Oxide
Ethylene
United States Production -
billions of pounds/year
Recent Data
1954 year in parentheses
1.31
0.97
0.13
0.16
0.052
6.8
1.1
0.04
0.4
0.53
1.44
0.97
15.1 (1967)
1975+
5.6
4.35
0.4
0.58
0.27
11.2
3.6
0.15
1.46
2.1
4.9
1.6
21.0
17.3(1971)
+ Estimated Consumption
* Includes Other Uses for Intermediate
18
-------
Growth of the industry is also evidenced by the number of new
projects planned. In 1967, 81 new projects were in the planning or
construction stage in the United States, as compared to 41 in 1966 (1).
Global capital outlay for new petrochemical facilities was $2.4 billion
in 1965 (93). Estimates indicate that approximately 500 new petroleum
products are introduced to the market every year (97). In 1966, petro-
chemical production required the use of 650,000 barrels of petroleum
daily,and in 35 years the requirement will be 12 million barrles per
day (93).
jPlastics and resins, which are primarily used as construction and
packaging material, are the most important petrochemical products with
respect to volume and projected growth (104). In 1962, 7.7 billion
pounds of these materials were produced in the United States with a
corresponding domestic consumption exceeding 6.9 billion pounds (97).
Polyolefins constitute the most important category in the plastic indus-
try, and by 1975 the world demand for polyolefins is expected to approach
35.2 billion pounds, four times greater than the 1965 global output of
these materials (7). Miscellaneous plastics and resins are growing at
annual rates of three to four percent.
Synthetic Fibers - World nylon consumption should increase from two
billion pounds in 1964 to 3.3 billion pounds by 1975 (96). The United
States is expected to provide about 40 percent of the 1975 world nylon
capacity. Polyester resins are expected to double in production capacity,
and acrylonitrile should increase 165 percent between 1966 and 1975 (15).
Synthetic rubber accounted for 75 percent of total rubber produced
in 1966, and this fraction should increase to 82 percent by 1975 with
the average annual increase in consumption amounting to about four percent.
Other Petrochemical Products and Intermediates - Nitrogen production
on a global basis should rise from 26.5 million tons in 1965 to 50.3
million tons in 1970. In 1967, the United States capacity for ammonia
production was 17.3 million tons, an increase of• 33 percent over the
previous year. Current annual consumption of ethylene is about 14 million
metric tons, and this demand is expected to increase by more than 25
million metric tons during the 1970 to 1980 decade.
Effect of New Products on Growth - Based on present projections, the
petrochemical industry should continue to grow at least at its present
rate. The introduction of new products may even increase the growth rate.
PETROCHEMICAL PROCESSES
A working knowledge of the principal production processes which
comprise the major waste sources is necessary for proper evaluation of
the complexities associated with petrochemical waste treatment. The
petrochemical industry uses many variations of the chemical processes
discussed herein, but the details of most of these special processes are
proprietary.
19
-------
PRIMARY CONVERSION PROCESSES
The primary conversion processes constitute what is known as
petroleum refining. Four major methods are used to obtain the separation
of individual hydrocarbons from crude oil. The flow of the petroleum
raw materials through the primary conversion process is schematically
shown in Figure 8.
Three types of distillation are used, all involving separation of
hydrocarbons by differential boiling characteristics. Distillation at a
single pressure level separates compounds on the basis of molecular size,
while alternate use of two pressures will separate compounds of different
molecular configuration.
The extraction process purifies the mixtures by using solvents which
preferentially dissolve defined hydrocarbons. The various hydrocarbons
can be separated according to molecular orientation by using selective
solvents and different temperatures.
Adsorption and Absorption - Various materials which have selective
preference for individual hydrocarbons or impurities can be used in com-
bination or at different temperatures to isolate and purify hydrocarbon
mixtures. These materials operate by the mechanisms of adsorption and
absorption.
Crystallization - Certain constituents of a mixture can be crystal-
lized from solution by changing the pressure and temperature of the mix-
ture and using specific solvents. The constituent is removed in a
purified, solid form.
SECONDARY CONVERSION PROCESSES
Secondary conversion processes are used to convert the purified
hydrocarbon feedstocks into the final product exclusive of such final
finishing operations as the molding of plastics from polymers and the
manufacture of nylon fabrics. The secondary processes and the types of
petrochemicals derived from them are presented schematically in Figure 9.
Oxidation is one of the older petrochemical processes, and practically
every primary petrochemical feedstock can be involved in an oxidation
reaction to obtain usable products. Probably the single most important
petrochemical reaction in terms of chemical tonnage produced is the oxi-
dation of ethylene to ethylene oxide.
Chlorination, fluorination, and bromination are all commercially
important halogenation reactions. Processes which use the direct addition
of a halogen to an olefin are characterized by an absence of by-product
formation and a relatively rapid, complete reaction with no side-product
formation (112).
20
-------
CRUDE PETROLEUM
PRIMARY
DISTILLATION
CATALYTIC
CRACKING
I
MIXTURES OF
PARAFFINS, NAPHTHENES,
AND AROMATICS
SEPARATION
PROCESSES
I. DISTILLATION
2. EXTRACTION
3. ADSORPTION
4. CRYSTALLIZATION
I
PARAFFINS AROMATICS NAPHTHENES OLEFINS
FIGURE 8
PRIMARY CONVERSION PROCESSES
21
-------
OLEFINS
»Hydrogenation-
>Sulfation-
^Halogenation
^Hydrohalogenation
^Hypohalogenation—
>Oxidation-
^Polymerization-
^Alkylation
^Isomerization
-Addition-
•Substitution-
Hydrocarbolylation —j
ff\Vn Ron^M rtr>1 L
(0X0 Reaction)
Paraffin Hydrocarbons
Alcohols
Ethers
Alkyl Sulfates
Olefin Dihalides
Alkylic Halides
Vinyl Halides
-*• Alkyl Halides
•> Halohydrins—
r* Oxides
KEpoxides
^Glycols
-* Oxides
-»• Aldehydes and Acids
-> Glycols
-* Alkylates
-* Polyolefins
-> Alkylates
-> Alkyl Aromatics
-^ Isomeric Olefins
-» Aldehydes
FIGURE 9
SECONDARY CONVERSION PROCESSES
(Reference 52)
-* Alcohols
-------
|PARAFFINS|—»
NJ
LO
)NAPHTHENES[-»
^Catalytic Cracking
^Halogenation
^Nitration—•
»Dehydrogenation-
^-Isomerization—
*Oxidation-
^Catalytic Cracking-
(ALkyl Naphthenes)
Ufalogenation
^Dehydrogenation
••Isomerization-
>Oxidation-
-*Short-Chain Paraffins + lOLEFINS]
-^Alkyl Halides
-^Nitroparaffins
-»|OLEFINS]
-^Isomeric Paraffins
-^Alcohols
-^Aldehydes
-*Ketones
-^Naphthenes + |OLEFINS|
->Cycloalkyl Halides
-*Aromatics
-^•CycloalkyL Nitro Compounds
-^Methylcyclopentane to
Cyclohexane
-^Alcohols
->Ketones
-^Dicarboxylie Acids
FIGURE 9 (Continued)
SECONDARY CONVERSION PROCESSES
-------
IAROMATICS
-»Catalytic Cracking
(Alkyl Aromatics)
'Halogenation-
"Nitration-
••Sulfonation-
»Alkylation-
-*• Oxidation-
•Addition
Substitution-
•On Side Chain-
^Hydrodealkylation -
(Toluene, Xylenes)
-H AROMATICS
OLEFINS
-*• Hexahalocyclohexanes
-> Haloaromatics
•* Haloarylparaffins
•* Nitroaromatics
-^Aromatic Sulfonates
Ethyl Benzene
-*• Alkyl Aromatics Dodecyl Benzene
Etc.
•*• Phenol
-*Aromatic Monocarboxylic Acids
-> Aromatic Dicarboxylic Acids
•+• Unsaturated Dicarboxylic Acids
-> Benzene + Methane
FIGURE 9 (Continued)
SECONDARY CONVERSION PROCESSES
-------
Nitration and Sulfonation - Paraffins and aromatics can both be
nitrated; however, the nitrated aromatics have considerably more economic
importance than the nitrated paraffins. Nitroparaffins are used pri-
marily as solvents and chemical intermediates. Sulfonation is the
addition of the sulfonic acid group (-SOoH) to an organic compound and
should not be confused with sulfation, which involves the addition of a
sulfate (-0-803!!) group. Paraffins and aromatics are the hydrocarbons
which are most commonly sulfonated in petrochemical production.
The principal alkylation reaction used by the petrochemical industry
involves the addition of an olefln to an aromatic compound. The most
important of these reactions produce intermediate compounds from benzene,
namely, cumene, and dodecylbenzene.
The most significant commercial dehydrogenation process is the
formation of butadiene from n-butane and n-butylene. The butadiene
process requires the use of catalysts such as iron oxide and alumina-
chromium oxide, high reaction temperatures, and reduced pressure. An
additional important dehydrogenation use is the dehydrogenation of ethyl-
benzene to make styrene monomer.
Polymerization processes are best classified in terms of the two
mechanisms of polymer formation: step polymerization, a result of the
direct interaction of specific functional groups on the monomer; or chain
polymerization, which involves the reaction of active centers on the
monomers with growth occurring only by the addition of single monomers
to the chain. Some of the more common polymerization products include
plastics of all types, resins used in adhesives and paints, fibers such
as nylon and dacron, and elastomers known as synthetic rubbers.
Other Processes - Ammonia results from the catalytic combination of
nitrogen gas and hydrogen gas at high temperature and pressure. The most
common catalyst, iron, is used in combination with aluminum and potassium
oxides. Hydrocyanation is used to manufacture aerylonitrile, which is
used in acrylic fiber and plastics production. Hydrocarboxylation is a
process which combines an olefin with carbon monoxide and hydrogen in the
presence of a cobalt catalyst to produce aldehydes (52). Sulfation
reactions produce alcohols from olefins.
PETROCHEMICAL WASTES
This section presents a brief discussion into the various sources
of pollutants which may derive from petrochemical processes. These
pollutants are categorized with respect to origin. A chemical classifi-
cation of petrochemical wastes also is included.
25
-------
PROCESSES AS WASTE SOURCES
A review of major pollutants in the petrochemical industry reveals
that many can be traced to sources common to most petrochemical processes.
The characteristics of these sources are listed below (112).
By-products are compounds which result from chemical reaction
stoichiometry. In some cases, the by-products formed may have commercial
value but often are quite worthless and represent waste disposal problems.
Side-products are formed by reactions competing with primary reactions
during petrochemical processing. These side-products are often isomers of
the principal product, but they may be reaction products from impurities
present in the feedstock. Unlike by-products, side-product formation can
often be controlled.
Incomplete Reactions - The product stream from any petrochemical
process will contain quantities of unreacted feed. Often in cases of
low conversion efficiency the feed chemical is recycled through the
process; otherwise, these remaining raw materials are disposed of as
was tes.
Every mechanical or physical operation is subject to various losses
inherent within the individual operation being performed. Mechanical
losses include fluid losses from valves, defective seals in compressors
and pumps, leaks in various units, etc. Accidental losses may be attri-
buted to leaks, spills, explosions, as well as poor operation.
WASTE CHARACTERISTICS
Principal pollutional characteristics of petrochemical wastes will
be defined in accordance with the unit process from which these wastes
are discharged. This characterization will deal primarily with the type
of compound present in the process waste stream.
Cooling waters often contain organic contaminants because of pipe
leakages which may result in oil contamination and the addition of organic
corrosion inhibitors. Recirculated cooling water will tend to concen-
trate dissolved solids, and the blowdown from such a system may create
waste disposal problems. Potential pollutants and other characteristics
of typical cooling water operations are shown in Table 2.
Process Effluents - Most of the highly polluted waste streams from
a petrochemical plant originate from process areas. This category
includes condensed steam from stripping operations, wash waters from
process drum cleaning operations, water formed or eliminated during
various reactions, and other similar in-process sources. A variety of
pollutants are found in these wastewaters, including a portion or all of
the feedstock chemicals, products, by-products, side-products, and spent
catalytic materials.
26
-------
TABLE 2
COMPOSITION OF CLEAN WATER EFFLUENT
(Reference 88)
Water Sources
Total
Waste-
water
(%)
Flow Range
(gpm) Sources
Potential
Type
Pollutants
Concentration
Range
(mg/1)
Cooling Water
(excluding sea
water)
40-80 100-10,000
(500-200,000
gal. water ton
product)
Process Leaks:
Bearings, Exchangers,
•Etc.
Water Treatment
Scrubbed from Air
through Tower
Make-up Water
Extractables
Mercaptans
Sulfides
Phenols
Cyanide
Misc. N compounds
Acids
Chromate
Phosphate
Heavy metals
Fluoride
Sulfate
Biocides, algicides
Misc. organics
Hydrogen sulfide
Sulfur dioxide
Oxides of nitrogen
Ammonia
Particulates
Total dissolved solids
1-1,000
0-1,000,but
usually less
than 1 ppm
0-60
0-60
0-30
0-10
100-10,000
0-50
0-100
0-1,000
0-300
100-5,000
-------
TABLE 2 (Continued)
COMPOSITION OF CLEAN WATER EFFLUENT
NJ
00
Total
Waste-
water Flow Range
Water Sources (%) (gpm) Sources
Cooling Water
(cont.)
Steam 10 50-1,000 Boiler Slowdown
Equipment
Waste Condensate
Potential Pollutants
Type
Particulates
Phosphates
Fluoride
Total dissolved solids
Particulates
Extractables
Phosphate
Sulfite
Sulfide
Misc. Organic compounds
Misc. N compounds
Heavy metals
Alkalinity
Extractables
Ammonia
Concentration
Range
(mg/1)
0-100
0-5
0-2
500-10,000
5-300
0-10
1-50
0-50
. 0-5
0-200
1-100
0-10
50-400
0-100
0-10
-------
Solvent processes are used in petroleum processing to purify the
various chemical feedstock, intermediates, and products. In most
instances, the solvents used by the industry are expensive and are
recovered to a large extent. However, waste streams from the processes
using solvents commonly contain quantities of these materials.
Caustic washes utilizing aqueous sodium hydroxide solutions are
frequently used in petrochemical processes. Sodium hydroxide solutions
are used to extract from the process stream acidic contaminants such as
hydrogen sulfide, mercaptans, phenols, thiophenols, and organic acids
(20). Most spent caustic streams, therefore, can be expected to contain
quantities of these compounds in the form of sodium salts and unreacted
sodium hydroxide, as well as small amounts of the process products and
feed chemicals.
Acidic Washes - Petrochemical processing employs acidic washes to
remove basic materials from process streams. Acid washes are also used in
removing contaminants from phenolic product streams and other process
waters. Phenolic spent caustics are neutralized with acids or flue
gases to produce an acidic oily stream referred to as "spring acid."
Washing and Scrubbing Procedures - Caustic and acid washings are
often followed by clear water rinses to remove all traces of the washing
compounds. Water is used also to scrub off contaminant gases from various
units. The waste streams from these washing and scrubbing operations
contain pollutants which are similar in nature but lower in concentration
to those found in the spent caustic and acid washes.
Crude Petroleum Desalting - The desalting of crude oil is a petroleum
refinery process and, thus, found only in petrochemical plants which
include primary processing of crude oil feedstocks. Crude petroleum
desalting produces an effluent stream with a very high salt concentration,
considerable oils, a rather high oxygen demand, and other contaminants
such as abrasive sediments, and vanadium organometal compounds (20).
Typical processes and resulting pollutants are presented in Table 3.
Some selected materials along with their common wastewater characteristics
are shown in Table 4. Statistical plots of the more common parameters of
flow, BOD, and COD are presented in Figure 10.
CHEMICAL CLASSIFICATION OF PETROCHEMICAL WASTES
The vast number of products manufactured by the petrochemical
industry makes a complete listing of every compound which may be present
in a waste stream impractical. The two general classifications, inorganic
and organic, have been subdivided as required and are shown in Figures
11 and 12.
29
-------
TABLE 3
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
u>
o
Alkylation: Ethylbenxcne
Ammonia Production
Aromatics Recovery
Catalytic Cracking
Catalytic Reforming
Crude Processing
Uemineralization
Regeneration,Process
Condensates
Furnace Effluents
Extract Water
Solvent Purification
Catalyst Regeneration
Reactor Effluents and
Condensates
Condensates
Crude Washing
Primary Distillation
Tar, Hydrochloric Acid, Caustic Soda, Fuel Oil
Acids,Bases
Ammonia
Carbon Dioxide, Carbon Monoxide
Aromatic Hydrocarbons
Solvents - Sulfur Dioxide, Diethylene Glycol
Spent Catalyst, Catalyst Fines (Silica,Alumina
Hydrocarbons, Carbon Monoxide, Nitrogen Oxides )
Acids, Phenolic Compounds, Hydrogen Sulfide
Soluble Hydrocarbons, Sulfur Oxides, Cyanides
Catalyst (particularly Pt, Mo), Aromatic
Hydrocarbons, Hydrogen Sulfide, Ammonia
Inorganic Salts, Oils, Water Soluble Hydrocarbons
Hydrocarbons, Tars, Ammonia, Acids, Hydrogen
Sulfide
Cyanide Production
Water Slops
Hydrogen Cyanide, Unreacted Soluble Hydrocarbons
-------
TABLE 3 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Dehydrogenatton
Butadiene Prod, from
n-Butane and
Butylene
Ketone Production
Styrenc from Ethyl-
benzene
Desulfurization
Extraction and Purification
Isobutylene
Butylene
Styrene
Butadiene Absorption
Extractive Distilla-
tion
Halogenation (Principally
Chlorination)
Addition to Olefins
Substitution
Quench Waters
Distillation Slops
Catalyst
Condensates from Spray
Tower
Residue Gas, Tars, Oils, Soluble Hydrocarbons
Hydrocarbon Polymers, Chlorinated Hydrocarbons,
Glycerol, Sodium Chloride
Spent Catalyst (Fe, Mg, K, Cu, Cr, Zn)
Aromatic Hydrocarbons, including Styrene, Ethyl
Benzene, and Toluene, Tars
Hydrogen Sulfide, Mercaptans
Acid and Caustic Wastes Sulfuric Acid, C, Hydrocarbon,Caustic Soda
Solvent and Caustic Wash Acetone, Oils, C, Hydrocarbon, Caustic Soda, Sulfuric Acid
Still Bottoms Heavy Tars
Solvent Cuprous Ammonium Acetate, C. Hydrocarbons, Oils
Solvent Furfural, C, Hydrocarbons
Separator
HC1 Absorber, Scrubber
Spent Caustic
Chlorine, Hydrogen Chloride, Spent Caustic,
Hydrocarbon Isomers and Chlorinated Products, Oils
-------
TABLE 3 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Hypochlorination
Hydroch1orination
Hydrocarboxylation
(0X0 Process)
Hydrocyanation (for
Acrylonitrile, Adipic
w Acid, etc.)
Isomerization in General
Nitration
Paraffins
Aromatics
Oxidation
Ethylene Oxide and
Glycol Manufacture
Aldehydes, Alcohols,
and Acids from
Hydrocarbons
Dehydrohalogenation
Hydrolysis
Surge Tank
Still Slops
Process Effluents
Process Wastes
Process Slops
Process Slops
Dilute Salt Solution
Calcium Chloride, Soluble Organics, Tars
Tars, Spent Catalyst, Alkyl Halides
Soluble Hydrocarbons, Aldehydes
Cyanides, Organic and Inorganic
Hydrocarbons; Aliphatic, Aromatic, and Derivative
Tars
By-Product Aldehydes, Ketones, Acids, Alcohols,
Olefins, Carbon Dioxide
Sulfuric Acid, Nitric Acid, Aromatics
Calcium Chloride, Spent Lime, Hydrocarbon
Polymers, Ethylene Oxide, Glycols,
Dichloride
Acetone, Formaldehyde, Acetaldehyde, Methanol,
Higher Alcohols, Organic Acids
-------
TABLE 3 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Acids and Anhydrides
from Aromatic
Oxidation
Phenol and Acetone
from Aromatic
Oxidation
Carbon Black
Manufacture
Polymerization, Alkylation
Polymerization (Polyethy-
lene)
Butyl Rubber
Copolymer Rubber
Nylon 66
Sulfation of Olcfins
Sulfonation of Aromatics
Condensates
Still Slops
Decanter
Cooling, Quenching
Catalysts
Catalysts
Process Wastes
Process Wastes
Process Wastes
Caustic Wash
Anhydrides, Aromatics, Acids
Pitch
Formic Acid, Hydrocarbons
Carbon Black, Particulates, Dissolved Solids
Spent Acid Catalysts (Phosphoric Acid), Aluminum
Chloride
Chromium, Nickel, Cobalt, Molybdenum
Scrap Butyl, Oil, Light Hydrocarbons
Butadiene, Styrene Serum, Softener Sludge
Cyclohexane Oxidation Products, Succinic Acid,
Adipic Acid, Glutaric Acid, Hexamethylene, Diamine,
Adiponitrile, Acetone, Methyl Ethyl Ketone
Alcohols, Polymerized Hydrocarbons, Sodium
Sulfate, Ethers
Spent Caustic
-------
TABLE 3 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
•Thermal Cracking for
Olefin Production
(including Fractionation
and Purification)
Utilities
Furnace Effluent and
Caustic Treating
Boiler Blow-down
Cooling System Blow-
down
Water Treatment
Acids, Hydrogen Sulfide, Mercaptans, Soluble
Hydrocarbons, Polymerization Products, Spent
Caustic, Phenolic Compounds, Residue Gases,
Tars and Heavy Oils
Phosphates, Lignins, Heat, Total Dissolved Solids,
Tannins
Chromates, Phosphates, Algicides, Heat
Calcium and Magnesium Chlorides, Sulfates,
Carbonates
-------
Ui
TABLE 4
WASTEWATER CHARACTERISTICS ASSOCIATED WITH
SOME
CHEMICAL PRODUCTS
(Reference 88)
Chemical Product
Primary Petrochemicals :
Ethylene
Propylene
Primary Intermediates :
Toluene
Xylene
Ammonia
Methanol
Ethanol
Butanol
Ethyl Benzene
Chlorinated Hydrocarbons
Secondary Intermediates :
Phenol, Cumene
Acetone
Glycerin, Glycols
Urea
Flow
(gal/ton)
50-1,500
100-2,000
300-3,000
200-3,000
300-3,000
300-3,000
300-4,000
200-2,000
300-3,000
50-1,000
500-2,500
500-1,500
1,000-5,000
100-2,000
BOD
(mg/1)
100-1,000
100-1,000
300-2,500
500-4,000
25-100
300-1,000
300-3,000
500-4,000
500-3,000
50-150
1,200-10,000
1,000-5,000
500-3,500
50-300
COD
(mg/1)
500-3,000
500-3,000
1,000-5,000
1,000-8,000
50-250
500-2,000
1,000-4,000
1,000-8,000
1,000-7,000
100-500
2,000-15,000
2,000-10,000
1,000-7,000
100-500
Other Characteristics
phenol, pH, oil
phenol, pH
oil, nitrogen, pH
oil
oil, solids
heavy metals
heavy metals
pH, oil, solids
phenol, solids
-------
CO
Primary Polymers;
Polyethylene
Polypropylene
Polystyrene
Polyvinyl Chloride
Cellulose Acetate
Butyl Rubber
Dyes and Pigments;
Miscellaneous Organics;
Isocyanate
Phenyl Glycine
Parathion
Tributyl Phosphate
TABLE 4 (Continued)
WASTEWATER CHARACTERISTICS ASSOCIATED WITH
SOME CHEMICAL PRODUCTS
Chemical Product
Acetic Anhydride
Terephthalic Acid
Acrylates
Acrylonitrile
Butadiene
Styrene
Vinyl Chloride
Flow
(gal/ton)
1,000-8,000
1,000-3,000
1,000-3,000
1,000-10,000
100-2,000
1,000-10,000
10-200
BOD
-------
* 0
10.0
100,000
5.0
1.0
O.E
— Li— fi^
0.1
0.05
FLOW.
O
a
".•
G
O
O
O
•BOD
0°
3 • O
93 .
9 *
M» °
CP
1 o
O
• O
O
•COD
50,000
Q
O
O
10,000
5,000
1,000
500
0.01
0.1 0.2 0.5 I 2 5 10 20 30 40 50 60 70 80 90 95 98 99 99.8 99.9
% EQUAL TO OR LESS THAN
00
FIGURE 10
PETROCHEMICAL HASTEWATER CHARACTERIZATION: FLOW, BOD, COD
37
-------
Inorganic —
—Metals -
Metallic
catalysts
-Anti-corrosion-
-Algicidal
- Bactericidal
-Cuporous
-Ammonium
-Acetate sol'n-
1—Non-Metals-
Sodium
~ compounds*
Sulfur
compounds
-Miscellaneous
-Al, Ft, Mb, Fe-
Cr, N:, Co, Cu-
-Catalytic cracking
-Catalytic reforming
-Dehydrogenation, Alkylation
-Isomerization, Polymerization
-Cu, Cr, Zn •
-Cu-
-Sodium hydroxide-
-Sodium sulfate —
iium sulfite —
-Sodium sulfide—
-Cooler and boiler waters
-Extraction and purification
of butadiene
-Removal of carbon monoxide
from synthesis gas prior
to ammonia synthesis
.Spent caustic streams
-Sodium combined with
phenol, cresol, xylenol
-Sodium chloride
-Hydrogen sulfide-
mercaptans
-Sulfates
-Sulfuric acid-
-Sulfonates
-Thiophenols•
-Sulfur dioxide-
-CaCl-
-Cyanide•
-Chlorides-
hospKates and
polyphosphates
-Phosphoric acid —
-Magnesium and
calcium salts
-Potassium hydroxide-
-Ammonia (Ammonia
sulfide)
-Nitric acid
-Phenolic spent caustic
•Crude oil desalting
• Condensates and spent
caustics from primary
conversion and refining
processes
- Spent caustic from alkylation
solvent in extraction
- Spent caustic from aromatic
sulfonation
-Condensates from catalytic
cracking
-Gases from combustion colvent
in aromatic extraction
- Spent caustic from CaOH as
washing agent (Chlorination)
-Condensates from catalytic
cracking
- Hydrocyanation reactions
(Nylon manuf.)
-Crude desalter effluents
and spent caustic streams
-Corrosion control in
cooling and boiler water
-Catalyst in polymerization,
alkylation, and isomeriza-
tion
-Waste sludge from cooling
water treatment
-Caustic wash in refinery
operations
-Condensates from refinery
processes
-Aromatic nitration
FIGURE 11
CLASSIFICATION OF INORGANIC COMPOUNDS WHICH MAY OCCUR
IN PETROCHEMICAL MASTESTREAMS
38
-------
Organic
Compounds
1 Hydrocarbons
Substituted
compounds
Saturated «J.M»«*J-J.'-»
hydrocarbons
Unsaturated ,
hydrocarb ons ~
Organic acids and
salts
Aldehydes and
ke tones
Halogenated
n yd roc .
Nitrogenated
compounds
Organic sulfur
compound
' Cyclic aliphatics —
(Naphthanes)
aroma tics
Carboxylic
acids
alcohols
Alkyl
aldehydes
At ^
methyl ethyl ketone
Vinyl acetate
Ethylene diacetate
Isopropyl ether
1 Ethylene oxide
1 Propylene oxide
hydroc .
EC
Kylcnola
u y 5" cr
Ll U
—Comolex oils
1
J
y
-i Toluene
' Xylene •
Styrene
r— Formic 1
' Acetic 1
[ ** *nic
ethanol,
propanol,
isopro-
panol
j Formaldehyde— i
» Acetaldehyde -1
T
J
ethyl
chloride
chloro-
form,
carbon tet,
vinyl ,
chloride,
propylene
chloride
hexa-
chloride
EMonoethan
olamine
amine
lene
diamine
C Aliphatic — |
Aromatic 1
I
J
CLow solubility
High volatility
Not very biodegradable
Refinery processes
More soluble than sat.
hydroc. but very reactive
Dealkylation
" process
— Oxidation process
Oxidation and paraffin
nitration
1
of olefins
— Solvents
extraction
Spent caustics from primary
catalytic and thermal
cracking of petroleum
Detergent manufacture
Sulfonation processes
Spent caustic streams from
— primary converstion
petroleum cracking
— -Catalyst regeneration
High temp, treating processes
Solvent extraction, nylon
manufacture
FIGURE 12
CLASSIFICATION OF ORGANIC COMPOUNDS WHICH MAY OCCUR
IN PETROCHEMICAL WASIESTREAMS
39
-------
POLLUTIONAL EFFECTS OF PETROCHEMICAL WASTES
This section evaluates the effect of petrochemical pollution as it
applies to mankind, aquatic biota, downstream users, and water and land
use planning. Also included are explanations of the parameters most
commonly used to describe petrochemical pollution and analytical techniques
employed to evaluate the nature and amount of specific pollutants derived
from the petrochemical industry.
CONVENTIONAL POLLUTIONAL PARAMETERS
It is generally considered impossible to express waste characteristics
in terms of the quantities of pollutant produced per unit of product pro-
duced. This is true because the age of the plant, operational procedures,
etc., result in infinite variations. Therefore, the use of general pollu-
tional parameters is employed and provides a common yardstick for the
assessment of the pollutional characteristics of an effluent stream. The
more important parameters are discussed below.
Acidity in a petrochemical waste can be contributed by both organic
and inorganic compound dissociation. Most mineral acids found in petro-
chemical wastes (sulfuric, nitric, phosphoric) are typically strong acids
while the most common weaker acids include organic acids such as carboxylic
acid and the inorganic acid, carbonic acid.
Both inorganic and organic compounds can contribute to alkalinity,
but the most important alkaline wastes in the petrochemical industry are
the spent caustics containing sodium, calcium, and potassium salts.
Color and turbidity are physical properties related to the concen-
tration of certain solutes and suspended particles in wastewaters. Color
and turbidity diminish light penetration in natural water, thus, reducing
the number of photosynthetic organisms such as algae. Although this is
sometimes desirable, it is nonetheless considered as a pollutional effect
in this context.
The hydrogen ion concentration in an aqueous solution is represented
by the pfl of that solution. Most plants and animals function most effec-
tively at neutral or near-neutral pH levels. Values outside the neutral
range of pH five to pH nine will adversely affect most aquatic life;
therefore, pH is a valid indicator of the toxic potential of a waste due
to excessive acidity or alkalinity. The pH value also can serve as an
indicator of the corrosive potential of a process effluent.
Soluble and dissolved organic materials constitute the most signifi-
cant category of pollutants present in petrochemical wastewaters. In
order to predict the polluting potential of organic-laden wastewaters,
it is necessary to have some quantitative parameter. Because the oxygen
demand presents one of the major concerns in organic waste control, the
most commonly used parameters measure the chemical or biological oxygen
40
-------
demand potential of the wastes. Recently, a rapid and simple method of
determining total organic carbon has been introduced which measures the
polluting potential in terms of organic carbon present rather than
molecular oxygen required.
Biochemical oxygen demand (BOD) is a measure of the biologically
oxidizable organic material in a wastewater. Ideally, the BOD should
represent the oxygen demand which is exerted during the microbial oxi-
dation of organics in the waste, either in a biological treatment pro-
cess or in a receiving body of water. Because BOD is the oldest and
most common organic material, most effluent quality standards are based
on allowable BOD effluents concentrations. The BOD value is subject to
many variables and records only the biologically degradable fraction of
the organics.
The oxygen required to chemically oxidize the organic compounds in
a wastewater is termed the chemical oxygen demand (COD). This method
oxidizes many organic compounds present in a petrochemical wastewater.
Total organic carbon (TOG) is the measure of all organic carbon
present in a wastewater. Although there are still unresolved problems
associated with this test, it may well become one of the more important
methods of determining the organic content of wastewaters because it
measures completely all organic constituents. TOG, in combination with
COD and BOD, is probably ideal for determining the wastewater's true
organic nature.
The immediate oxygen demand (IOD) is exerted by compounds which react
immediately with the dissolved oxygen when they are introduced into solu-
tions containing oxygen. Such compounds include sulfides, thiosulfates,
sulfites, nitrites, ferrous iron, and aldehydes.
Solids material in waste streams can be either organic or inorganic
and may be dissolved or suspended. Dissolved organic solids are capable
of causing color, taste, odor, and oxygen demand at low as well as at
high concentrations. Certain forms of inorganic dissolved solids also
represent various forms of potential pollutants.
Surface active agents are compounds which tend to concentrate at an
interface, arranging their molecules in such a manner as to form a film
along the interface. This surface-active property enables them to
reduce the surface tension of liquids, emulsifying dirt and oily materials.
The major concern with this parameter has been the degree of foaming
caused in treatment units and the receiving waters.
Temperature - Thermal pollution has created serious problems in the
last few years. The primary effects are biologically related although
certain downstream users could also be affected economically because of
elevated water temperatures.
-------
Many compounds present in petrochemical wastes are toxic not only
to aquatic life but higher animals and plants as well. The bioassay
test is commonly used to assess wastewater toxicity. Various BOD and
Warburg tests can be used to establish the toxic effects against various
microorganisms.
Miscellaneous Pollutant Parameters - Other parameters necessary for
evaluating optimal treatment methods include analyses of oils, phenols,
inorganic ions, nitrogen in its various forms, volatility, and heavy
metals.
EFFECTS OF POLLUTION ON RECEIVING WATER
Many pollutional effects of wastes are interrelated. Gross
biological and physical changes in a body of water receiving wastes are
usually associated with physiological effects on the aquatic organisms
in the water.
Aesthetic Effects - The most aesthetically unappealing situation in
water receiving waste discharges is usually attributed to unsightly and
odoriferous conditions, the most obvious being the anaerobic decompo-
sition of organic materials (66). Other odors may eminate directly from
contaminants such as hydrogen sulfide and mercaptan in the waste stream.
Visible effects constitute another aesthetic effect of pollution. Rubber
particles from synthetic rubber manufacture are insoluble, relatively
non-biodegradable, and floatable. Small amounts of oil give an iridescent
sheen to a body of water. Surface active materials in petrochemical
wastes, principally from detergent manufacture, can cause foaming in a
receiving water. Many organic and inorganic compounds found in petro-
chemical effluents can impart undesirable color to these waters.
Biological Effects - The most prominent effect of biodegradable
organic matter is the biochemical oxygen demand which it exerts on the
receiving water. When large quantities of organic matter are involved,
the rate of oxygen demand by aerobic processes may exceed the rate of
oxygen replenishment from atmospheric or photosynthetic sources. This
oxygen deficit may cause anaerobic conditions to prevail, exerting a
deleterious effect on aerobic species present, including microorganisms
as well as fish and other higher animals. Thermal pollution may result
in higher temperatures which increase the rate of biological activity
and decrease the net transfer of oxygen to the water from the atmosphere.
High temperatures are also lethal to many species of microorganisms and
fish.
The net biological effect of petrochemical waste pollution is a
change in the environmental conditions of the receiving waters. Changes
in the microbial population (bacteria, algae, protozoa), which are
important members of the food chain may indirectly affect larger species.
Polluted water often favors the growth of one species of organism over
others. Pollution may not acutely affect the organisms present but may
alter their reproductive patterns affecting the progeny and living habits
of aquatic organisms and result in erratic patterns of behavior.
42
-------
Other effects which are closely related to the aforementioned
include recreational facilities and land development, which may be
impaired due to the aesthetic aspects. Navigation also can be hindered
because of sludge banks deposited in the waters and because of corrosive
conditions caused by acidic discharges into the receiving water.
EFFECTS OF POLLUTION ON WATER USE AND REUSE
Various petrochemical pollutants, both chemical and physical, may
affect the potential future uses of wastewaters or receiving water.
In-plant reuse of process water and recirculation of cooling water
is now common practice in many petrochemical plants. Such reuse often
requires demineralized water to the level that even trace quantities of
organics or inorganics may be considered as pollutional. The most
important consideration for cooling water use is preventing the deposition
of precipitates in water pipes and in the process coolers (20). The
principal precipitates include calcium carbonate, magnesium carbonate,
and calcium sulfate. Cooling water generally should not create excessive
biological growth and should be noncorrosive.
Domestic, Agriculture, and Industrial - The United States Public
Health Service has prepared a list of recommended drinking water stan-
dards which prescribe limits for many potential petrochemical pollutants.
Bases for the standards include both health and aesthetic considerations
(118).
Water used for livestock and crop irrigation must be free of toxic
materials. Heavy metals and high concentrations of inorganic dissolved
solids may be detrimental to plants and animals, and high salinities may
affect different crops adversely. Sodium, an important constituent of
spent caustic effluents, reacts with soil to reduce its permeability.
Control is therefore necessary. (The water quality requirements for
irrigation purposes are shown in Table 5.)
Groundwater - During the three-year period from 1957 through 1959,
twenty-two states reported groundwater pollution by oil or petroleum
products, and 15 states reported cases of pollution involving various
other chemical contaminants (6). Disposal wells, lagoons, and surface
dumping were the most important potential sources of petrochemical waste-
water pollution cited in the report.
PHYSIOLOGICAL EFFECTS
In a general sense, almost every effect of pollution can be consid-
ered as physiological. Even aesthetic effects can be considered physio-
logical in that they act on the senses of man to produce a reaction. The
physiological effects as discussed herein include those which are most
prevalent to the observer, namely, taste, odor, and toxicity.
43
-------
TABLE 5
WATER QUALITY FOR SELECTED AGRICULTURAL USES
(Reference 108)
Water
Class
Excellent
Good
Permissible
Doubtful
Unsuitable
Percent
Sodium of
Cationic
Content
<20
20-40
40-60
60-80
>80
EC X 106
at 25°C
<250
250-750
750-2,000
2,000-3,000
>3,000
Sensitive
Crops
<0.33
0.33-0.67
0.67-1.00
1.00-1.25
>1.25
Boron , ppm
Semi-
tolerant
Crops
<0.67
0.67-1.33
1.33-2.00
2.00-2.50
>2.50
Tolerant
Crops
<1.00
1.00-2.00
2.00-3.00
3.00-3.75
>3.75
Total
Solids
(mg/1)
<390
390-1,200
1,200-3,100
3,100-4,700
>4,700
-------
Taste and Odor - The senses of taste and odor are virtually inseparable
in most cases (17). Many compounds in petrochemical wastes cause tastes
and odors at very low concentrations with the synergistic effects of
complex mixtures magnifying these effects significantly. A study utilizing
the chemicals, m-cresol, n-butanol, pyridine, n-butyl-mercaptan, n-amyl
acetate, acrylonitrile, 2-4 dichlorophenol, and acetophenone showed marked
synergistic effects. Detectable concentrations of selected petrochemical
waste constituents are listed in Table 6. Probably the most common and
most objectionable odor-causing compound contained in this list is hydro-
gen sulfide. Compounds containing nitrogen, principally the amines, are
also malodorous and are found in various petrochemical wastes, particularly
those discharged from synthetic fiber manufacture (105).
Phenol probably has been the organic chemical most often associated
with taste and odor problems. These problems occur when water containing
phenols is disinfected by chlorination. Dichlorophenols are formed
which give water a characteristic medicinal taste at concentrations as
low as one part per billion. Recent investigations have shown that taste
and odor problems cannot always be correlated with phenol concentrations,
indicating that other organic compounds are often responsible for these
conditions (120). For example, chlorinated hydrocarbons have been identi-
fied as a major source of taste and odors. A study of a refinery waste-
water indicated that the non-polar organic compounds, consisting principally
of aliphatic and aromatic hydrocarbons, were the primary sources of odor
in the wastewater (90). Organic acids which are found in petrochemical
wastes also cause tastes and odors. Recently reported profile studies
for wastewaters from twelve different refineries indicated two types of
odor characteristics that generally appear to survive waste treatment.
These are described as a burnt rubber smell attributed to several series
of sulfides and disulfides such as diaryldisulfides and alkyl aryl sul-
fides, and burnt-oily odor identified with methylated polycylie hydro-
carbons such as dimethyl naphthalene and dimethyl anthracene (21).
Some organic chemicals can cause the flesh of fish to become "tainted,"
rendering the fish useless as a food source. A few chemicals which may be
found in petrochemical effluents and are able to cause these effects are
listed in Table 7.
Toxicity includes the effects of pH, lack of dissolved oxygen, high
temperature, and high dissolved solids as well as compounds which are
classified as poisons. It is the poison effect which will be considered
here. The classifications of toxic action are established on the basis
of the rate of action of the toxicant, the duration of the symptoms, and
the rate of intake of the compound (49). Acute toxicity is characterized
by the rapid onset of negative physiological effects after exposure to
the toxic concentration of a compound. Chronic toxicity is usually mani-
fested by the appearance of negative physiological effects after a pro-
longed dosage of a chemical at concentrations below the acute level.
While the toxic effect of petrochemicals on man is of great interest,
concentrations of these chemicals in water is usually so low that their
principal toxic effects on man are generally chronic. Carcinogenesis is
45
-------
TABLE 6
DETECTABLE CONCENTRATIONS OF SOME PETROCHEMICAL COMPOUNDS
CAUSING
Compound
Ammonia
Amyl Acetate (iso)
Benzaldehyde
Carbon Disulfide
Chlorophenolics
- Monochlorophenol
Dimethylamine
Ethyl Mercaptan
Formaldehyde
Furfural
Hydrogen Cyanide
Hydrogen Sulfide
Methyl Mercaptan
Nitrobenzene
Petrochemical Wastes
Phenol ics
Phenyl Ether
Picolines
Refinery Hydrocarbons
Sulfur Dioxide
Xylenes
TASTE AND ODOR IN WATER
Detectable
Concentration (mg/1)
0.037
0.0006
0.003
0.0026
0.001 - 0.1
0.00018
0.6
0.00019
50.0
4.0
0.001
0.001
0.0011
0.03
0.015 - 0.1
0.25 - 4.0
0.013
0.5 - 1.0
0.025 - 0.05
0.009
0.3 - 1.0
Reference
63
63
63
63
18
63
105
18
18
18
63
63
63
63
63
18
18
18
18
63
18
46
-------
TABLE 7
SOME ORGANIC CHEMICALS CAUSING ADVERSE TASTES IN FISH
Compound
Phenol
Cresols
1, 3, 4-Xylenol
1, 3, 5-Xylenol
1, 2, 4-Xylenol
Pyrocatechol
Resorcinol
p-Toluidine
Pyridine
Quinoline
Naphthalene
C( -Naphthylamine
o-sec butyl Phenol
p-tert butyl Phenol
o-Phenylphenol
o-Chlorophenol
p-Chlorophenol
2,4-Dichlorophenol
Diphenyloxide
Acetophenone
Styrene
c* -Methylstyrene
Isopropylbenzene
Ethyl Benzene
$ $ -Dichloroethylether
o-Dichlorobenzene
Toluene
Cresylic Acid (m,p)
Kerosene
Above Toxic Limit
Test Fish Not Reported
Type Fish
Tested
Trout, Carp
Trout, Carp
Carp
Rudd
Rudd
Carp
Carp
Rudd
Carp , Rudd
Carp
Rudd
Rudd
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Not Reported
Approx. Concen.
Causing Taste
(mg/1)
25*; 1.0
10
5
1
1
2.5
30.0
20.0
5.0
0.5-1.0
1.0
3.0
0.3
0.03
1.0
0.015
0.05
0.005
0.05
0.5
0.25
0.25
0.25
0.25
1.0
<0.25
<0.25
0.2
0.1
Ref
63, 107
63
63
63
63
63
63
63
63
63
63
63
107
107
107
107
107
107
107
107
107
107
107
107
107
107
107
107
107
47
-------
the chronic toxic effect which has probably received the most attention.
Certain polynuclear aromatic compounds, such as aromatic amines, and
aromatic nitro-compounds have been shown to cause cancer. The complex
hydrocarbons and tars have also been indicated as possible carcinogenic
agents (57). The use of carbon chloroform extract from water samples has
been proposed as a basis for limiting the exposure of man to these com-
pounds (40). Some research has considered the toxicity effects of
surface-active materials in water and indicated that these compounds do
not have chronic effects on higher animals at concentrations up to 1,000
mg/1 in drinking water (82).
The toxic effects of chemical compounds to aquatic microorganisms are
extremely important and a great deal of data is available concerning
these effects. The extinction of any of these organisms attributable
to toxic chemicals will have a profound adverse effect on the general
ecology of the aquatic system. Detailed investigations of the toxicity
of certain organic chemicals to algae have recently been reported (56; 107)
Data from studies considering structurally similar fatty acids, alcohols,
and aldehydes indicate that relative toxicity is somewhat dependent upon
molecular structure. For example, straight-chain organics seem to be
more toxic than those with branched-carbon chains (107). Certain phenolic
compounds and pesticides reduce the chlorophyll concentration and photo-
synthetic activity of Chlorella pyrenoidosa (56). Additionally, nitrated
and halogenated phenols are more toxic than alkylated and aminated
phenols, and the insecticide Lindane was found to be about 100 times as
toxic to Chlorella pyrenoidosa as was phenol.
Fish are the test animals most frequently used in determining the
toxicity of aqueous wastes. This is true for two reasons: (1) they are
relatively easy to use and control in the laboratory and (2) their res-
ponse to toxic materials is one of the more valid indicators of the true
toxicity in natural waters. The laboratory bioassay is the most popular
method for defining the acute toxicity of specific compounds to fish.
The most commonly accepted fish toxicity parameter is the median toler-
ance limit (TLM) which is the concentration of the test compound at
which 50 percent of the test fish survive for a selected time interval.
The avoidance of polluted water by fish has been suggested as a
toxicity parameter (61). However, several problems develop when avoidance
was used. In many cases, fish do not reliably avoid waters containing
lethal concentrations of particular toxicants (25). Carp, for example,
consistently entered an ammonia contaminated portion of a stream although
large numbers were killed (19).
IDENTIFICATION AND MONITORING METHODS
Standard analytical tools used for wastewater analysis (COD, BOD,
etc.) are inadequate for evaluating the effects of pollutants or for
predicting their occurrence. New analytical methods must be developed
so that low-level contaminants can be traced from the petrochemical
48
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processes through the waste system and into the aquatic environment. The
two general types of analytical categories include chamical techniques
and biological methods. Chemical techniques are used principally to
measure low-level contaminants causing color, taste, and odor while
biological methods are employed to observe toxic or inhibitory effects of
waste discharges to the aquatic biota.
Chemical Methods of Analysis - These can be broken down into two
categories, inorganic and organic.
Inorganic analyses often require two steps, a separation and/or
concentration step followed by the identification and quantification of
the desired compound. The separation processes most often used for
inorganic compounds are volatilization, precipitation, liquid-liquid
extraction, and adsorption (77). Chromatography and ion exchange are
the two most commonly used adsorptive methods of separation. Gravimetric
procedures are often used if the compound in question can be isolated
and maintained in a measurable form. Titrimetric methods are used for
several inorganic analyses, the most common of which measure alkalinity,
acidity, and calcium and magnesium ions using ethylene diaminetetraacetic
acid (EDTA).
Spectroscopic methods are also used to measure many inorganic
compounds. Flame photometry can be used to measure the alkali and
alkaline earth metals such as sodium and potassium (12). Emission
spectroscopes using high temperature arcs and rarefied gases can be
used to measure metals in the parts per billion concentration range (77).
Absorption spectrometers are available and can be used to identify and
measure inorganic compounds from trace concentrations to fairly large
quantities. In aqueous samples, interferences are common, and separation
procedures must often be employed. Infrared spectroscopy can be used to
measure inorganic compounds, but has not been used extensively in water
analyses. Gamma-ray and x-ray spectrometry also have been used to a
limited extent in water analyses.
Methods involving the measurements of the electrical properties of
systems are used for inorganic analyses of aqueous systems. Polarography
is not applicable for analyzing inorganics, but can be used for measuring
heavy metals more rapidly and avoiding many of the interferences asso-
ciated with the corresponding colorimetric methods.
Organic Analysis - Prior to analysis, most organic compounds in
natural waters must be concentrated and, for some analyses, separated.
Several methods are available for concentrating trace organic compounds,
including adsorption on carbon filters, liquid-liquid extraction, freeze
concentration, distillation, and various combinations of these techniques
(18). The two most commonly used organic analytical techniques are
spectroscopy and chromatography.
49
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Spectroscopic techniques are probably the most commonly used methods
of organic analyses, the principal ranges of the spectrum used being the
ultraviolet, the visible, and the infrared. Ultraviolet spectroscopy is
often used in water and wastewater analysis, but it is often difficult
to determine the molecular structure of unknown compounds due to inter-
ferences which prevent discrete adsorption bands (18). Differential
spectroscopy can be used to eliminate interferences by other compounds
in a wastewater sample. Spectroscopy in the visible range, known as
colorimetry, is widely used. Infrared spectroscopy is finding increasing
application in waste analysis and is often used in combination with other
techniques to identify the molecular structure of organic contaminants.
Differential absorption methods generally are utilized in infrared spec-
troscopy, and samples can be analyzed in the solid, liquid, or gaseous
form. Mass spectroscopy, in combination with other analytical techniques,
also has been used to elucidate the structure of organic contaminants.
Gas-liquid chromatography is another analytical tool used in water
analysis. Hie development of the sensitive flame-ionization, electron-
capture, and electron-affinity detectors has made gas-liquid chromatography
applicable for identifying most classes of organic compounds (18).
Electroncapture detectors have been used to identify the organic phosphate,
chlorinated hydrocarbon, and organic sulfur pesticides in the microgram-
per-liter concentration range. One of the most promising uses of gas-liquid
chromatography and the flame-ionization detector is the continuous
monitoring of process and treatment plant effluents. Gas-liquid pro-
cedures have been used extensively to separate organic compounds which
are subsequently analyzed by other techniques such as mass spectroscopy.
Both thin-layer and paper chromatography have been employed to some
extent for the determination of trace organic compounds in water. Some
compounds can be separated and identified in microgram-per-liter concen-
trations by paper chromatography. Paper chromatography is a slow pro-
cedure, and it is not extremely accurate for quantitative measurements.
Thin-layer chromatography, however, has the separation powers of paper
chromatography.
Combinations of the more important analytical techniques used in the
identification and measurement of trace organics in water samples are
often used. Infrared spectroscopy, nuclear magnetic resonance, and gas
chromatography-mass spectroscopy have been used to determine the struc-
tures of some compounds derived from petrochemicals (24). Carbon
absorption, liquid-liquid extraction, silica gel adsorption chromatography,
and gas chromatography were used to identify petroleum products in four
pollution incidents (70).
Biological Methods of Analysis - Procedures have been proposed to
measure the biological effects of a waste in the aquatic environment
in situ. Continuously operating biological monitoring systems have two
advantages over their chemical systems counterparts: namely, they
monitor the entire environment rather than sampled portions, and all the
environmental variables are considered rather than recording each
characteristic separately (26). Another environmental biological
50
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monitoring system assigns a "biotic index" to the natural waters
receiving pollutants (19). Based on the macro-invertebrate organisms
(insects, tubificial worms) in the receiving waters, the biotic index
can be calculated from samples taken by any method which gives an
accurate representation of population densities. Bioassay techniques
using organisms other than fish also have been proposed because it is
now realized that toxic effects of a compound on aquatic plants and
invertebrates are equally as important as the effects on fish. The use
of bacteria, protozoa, and algae present in the Winogradskey column has
also been suggested as a toxicity indicator (58). Protozoa are also
effective for toxicity determinations, and several bioassay techniques
have been used with protozoa as the indicators of toxicity.
TREATMENT AND CONTROL OF PETROCHEMICAL WASTES
The treatment and control processes discussed herein are categorized
as (a) reduction of waste strength by in-process and in-plant control
measures, (b) physical treatment processes, (c) chemical treatment pro-
cesses, (d) biological treatment processes, and (e) ultimate disposal
techniques.
INTERNAL IMPROVEMENTS
The ideal method of controlling petrochemical pollutants is to
eliminate them at the sources. This reduces the cost of waste treatment
and in many cases provides valuable economic gains in the form of reduced
losses of expensive petrochemicals and reduced intake of makeup water.
Reduction of Raw Material Losses - The losses of hydrocarbon raw
materials from storage, transport, and processing facilities are an
important source of water pollution in the petrochemical industry.
Several improvements can be made by the industry to reduce the magnitude
of these losses. The evaporation of light hydrocarbons from storage tanks
can be controlled by floating roof tanks and the use of tank vents with
vapor recovery lines. Purge lines used for process start-up and shut-
down can be connected to vapor recovery systems (78). The hydrocarbon
losses from vacuum jets can be reduced by installing refrigerated con-
densors ahead of the jets (60) or by connecting the jet exhaust to vapor
recovery systems (78). Pipeline systems should be used to transfer raw
materials whenever feasible in order to minimize transfer losses. Pro-
bably the most important source of hydrocarbon raw material loss is from
malfunctioning equipment, leakages, etc. These losses can be corrected
only by careful in-plant control.
Recovery of Usable Reaction Products - By-products represent a
significant pollutional fraction of petrochemical wastewaters. In many
cases, by-product recovery from the process wastes is justified, not only
in terms of producing a product, but also in reducing the pollutional
load to the waste treatment facility. The recovery of sulfur, for example,
51
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from petroleum hydrocarbons minimizes the sulfide and mercaptan pollution
The Glaus process (11) and a catalytic combustion process (10) are
currently used to convert hydrogen sulfide to elemental sulfur, thus,
obtaining a reusable product.
Other sources of usable materials found in petrochemical wastes
include catalyst complex metals and the tars from catalytic processes.
Usually, the recovery of materials from the tars does not result in a
direct profit to the petrochemical plant, but it may prove economically
justified by reducing the pollutional discharge. Alkaline wastes from
caustzc washes are most significant. Some spent caustic solutions con-
taining sulfides, phenolates, cresolates, and carbonates are marketable
(76). Spent caustics which contain large amounts of phenols and cresols
can be sold to processors who separate and purify the cresylic acid
fractions for commercial use (20). Sodium sulfide can be separated from
spent caustics high in sulfides and marketed. Spent caustics can also be
regenerated for reuse in washing processes by steam hydrolysis, electroly-
sis, air regeneration, and the use of slaked lime (76).
The recovery and recycling of process effluents containing unreacted
raw materials is common to most petrochemical processes in which the pro-
cess reaction is incomplete. Many of the secondary reaction by-products
are also valuable either for use within the petrochemical plant or as
marketable products. Some of the possible uses for by-products produced
in three common petrochemical processes are shown in Table 8. The recovery
and reuse of oils is very common in the petrochemical industry. Recover-
able oils are reprocessed while those which are uneconomical to purify are
used as fuels. Solvent recovery is practiced also, especially when the
high costs of solvents are redeemable.
Process modifications can be classed as (a) process selection,
(b) prevention of product and chemical losses, and (c) modified operating
conditions (9). If waste control is considered during process design, it
often can be an important factor in the economics of operation. The
substitution of continuous processes for batch processes tends to elimi-
nate peak discharges of wastes, thus reducing the cost of treatment
required for the waste. •The use of downgraded chemicals in processes
which do not require high-quality reactants facilitate both process and
waste control. This type of design often utilizes the waste effluents
from one process as reactants in another.
Water reuse is often one of the most effective and economical means
of decreasing the waste discharges from a petrochemical plant. In addi-
tion to reducing water costs and waste treatment costs, water reuse
increases the flexibility for plant expansion. Small quantities of con-
centrated wastes produced by reuse are easier to handle than larger
quantities of dilute wastes, and the plant benefits by more freedom from
upstream users (28).
Potential applications of water reuse include the utilization of
poorer quality cooling and boiler water and also the reuse of contaminated
steams in stripping operations (87). Water use systems are classified as
multiple recycle and cascade, but most frequently combinations of these
schemes are employed.
52
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TABLE 8
USABLE SIDE PRODUCTS FROM SOME
TYPICAL PETROCHEMICAL PROCESSES
(Reference 89)
Primary Product
Side-Products
Use
Butadiene:
Ethylene;
Residue Gas (Hydrogen,
methane, ethane ,carbon
dioxide)
Propane and Propylene
Butane and Butenes
Aromatic Oils
Residue Gas (Hydrogen,
Methane)
Acetylene
Ethane
Propane and Propylene
Butane and Butylene
Aromatic Concentrate
Heavy Oils and Tars
Fuel
Feedstock for Ethylene,
Alkylation
Recycle for Butadiene
Manufacture; Feedstock
for Alkylation
Resin or Plastic Manu-
facture
Fuel
Fuel for Welding Feed-
stock for Several
Petrochemical Processes
Recycle for Ethylene
Manufacture; Cracking
Feedstock; Fuel
Propane Recycle for
Ethylene Manufacture;
Feedstocks for Several
Petrochemical Processes
(Alcohol, Alkylation,
Polypropylene, etc.)
Feedstock for Synthetic
Rubber Aviation Gas;
Recycle to Cracking
Process
Resin and Plastic Manu-
facture
Refinery Charge Stock Fuel
53
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TABLE 8 (Continued)
USABLE SIDE-PRODUCTS FROM SOME
TYPICAL PETROCHEMICAL PROCESSES
Primary Product Side-Products Use
Ammonia; Carbon Dioxide Dry Ice, Bottled CO
Fuel
Methanol Manufacture
Helium Lifting Gas
Inert Gas
Argon Inert Gas
54
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Steam used for the stripping and quenching of process streams is an
important source of waste. Condensates with high sulfide contents can be
partially oxidized to sulfate and then used to generate low-quality
stripping steam, although oxygen-demanding thiosulfates may be present.
Another condensate reuse scheme has been described in which phenolic
condensate from an olefin unit is washed with the fresh hydrocarbon feed-
stream, thus removing.the phenol from the condensate (78). Other vola-
tile hydrocarbons are then steam-stripped from the condensate and reused
to generate additional steam. A potential source of water for reuse in
the petrochemical plant is for main boiler use. Boilers can often tolerate
high dissolved solids concentrations, depending on the type of dissolved
solids and the boiler design. Oils do not seem to deposit in boilers if
chelating agents prevent other depositions from forming; thus, the oils are
steam distilled or leave the boiler with the blowdown.
In-Plant Control - Operational control is one of the most important
facets of pollution abatement. In-plant operational control includes
(a) maintenance of pipes, valves, fittings, pump seals, etc., to prevent
leaks; (b) education of all plant personnel as to the effects of accidental
and careless losses of materials; (c) changes in selected operational
procedures; and (d) a highly developed monitoring system to detect the
sources and occurrences of pollutants within the plant. A continuous
monitoring program for important plant sewers can prove invaluable in
locating malfunctioning process units and leaks.
Waste Stream Segregation - Three main segregated collection systems
are normally used in petrochemical plants (9):
a) area drains which carry off unpolluted cooling
water and storm runoff from uncontaminated areas;
b) a contaminated water system which contains process
waters, polluted cooling waters, and storm water
runoff from contaminated areas; and
c) a sanitary sewerage system to collect plant
domestic wastes.
Segregation of many process streams may be necessary due to the
incompatability of certain waste components. Wastes with high solids
concentrations are usually segregated from oily streams since suspended
solids tend to decrease the efficiency of oil separation units. Sus-
pended solids also can interfere with oil recovery by increasing the
solids contents of separator skinmings (9).
PHYSICAL TREATMENT PROCESSES
The types of physical treatment processes most commonly used in the
treatment of petrochemical wastes include gravity separation, flotation,
stripping processes, adsorption, extraction, and combustion. The waste
from a petrochemical plant may require a combination of these processes
if proper treatment is to be provided.
55
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Gravity separation includes the removal of materials less dense than
water such as oils and air-entrained particulates by flotation and the
removal of suspended materials which are more dense than water by sedi-
mentation. Sedimentation and flotation techniques commonly employ chemical
conditioners to enhance the separation process. Many wastewaters from
petrochemical operations contain significant quantities of free and emul-
sified oil which must be removed prior to subsequent treatment. Free oils
are much easier to remove if their concentration is high. Slop oils which
are recovered by the separation process can be cleaned and reused in
various processing operations. Probably the most commonly employed
separator design is that presented by the American Petroleum Institute (8).
Reported efficiencies of some oil separators operated by the petroleum
industry are given in Table 9. Although some reduction in chemical oxy-
gen demand (COD) can be expected due to removal of oils and tars, little
or no biochemical oxygen demand (BOD) removal will be prevalent.
Oil emulsions present the biggest problem of oil-water separation
because they are not easily separated in gravity separators and other
conventional separation devices. Emulsifying agents prevent the oils
from coalescing and separating from the water phase. These emulsifying
agents are surface-active agents and include catalysts, the sulfonic acids,
naphthenic acids, and fatty acids, as well as their sodium and potassium
salts. In an alkaline medium, calcium and magnesium salts form finely
divided suspended solids which stabilize the emulsions (83). Sources of
oil emulsions within a petrochemical plant include (a) crude oil desalting
water, (b) condensates from distilling operations, (c) wash waters which
follow caustic or acid chemical treating operations, (d) cooling waters
from direct-contact condensers, (e) detergent manufacturing processes,
and (f) equipment cleaning operations (8).
In order to separate the emulsified oils from the wastewater, the
emulsion must be broken. The application of heat and pressure is pro-
bably one of the more effective methods used in de-emulsification of a
waste (8). Distillation methods, in lieu of the heat requirements, are
also effective in breaking emulsions as are filtration, acidification, and
electrical methods.
Sedimentation processes are utilized in the pre- or primary treatment
of petrochemical wastes with high suspended solids concentrations, in
secondary clarification, and for sludge thickening. Petrochemical waste-
waters high in colloidal material must be chemically treated before ade-
quate separation by sedimentation can be obtained. The removal of solids
and oils from petrochemical wastewaters and the concentration of sludges
can often be accomplished using the air flotation process. Air is
dissolved under pressures of 30 to 60 psig with the wastewater to be
treated. When the waste is then exposed to the atmosphere, minute air
bubbles are released from solution and carry the suspended materials to
the top of the tank. Gravity oil separators usually precede flotation
units in most industrial applications. One of the big advantages of
flotation over sedimentation is the shorter detention time required to
clarify a waste by flotation, resulting in a unit of considerably smaller
size.
56
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l/l
TABLE 9
TYPICAL EFFICIENCIES OF OIL SEPARATION UNITS
Oil Content
Influent
(mg/1)
7,000-8,000
3,200
400-200
220
108
108
90-98
50-100
42
Effluent
(mg/1)
125
10-50
10-40
49
20
50
40-44
20-40
20
Oil
Removed
(%)
98-99+
98-99+
90-95
78
81.5
54
55
60
52
COD BOD Phenol
Removed Removed Removed
Type (%) (%) (7.)
Circular - - -
Impounding 0
Parallel Plate ...
API* 45 - 55
Circular -
Circular 16 0 0
API -
API -
API -
Ref
115
83
59
20
111
20
20
20
20
API - American Petroleum Institute Standard Design
-------
Stripping processes are used to remove volatile materials from liquid
streams. These methods are employed generally to remove relatively small
quantities of volatile pollutants from large volumes of wastewater.
Stripping is essentially a low-temperature distillation process whereby
reduction of effective vapor pressure by the introduction of the stripping
medium replaces the high temperature requirement. The two types of
stripping agents commonly used are steam and inert gas.
The stripping of hydrogen sulfide and ammonia from sour water is
probably the most common use of stripping employed by the petrochemical
industry for waste treatment. The major stripping agents used to remove
these contaminants are steam, natural gas, and flue gas. Phenols also
can be removed from aqueous waste streams by steam stripping which is
applicable when a wastewater is subject to short variations in temperature,
specific gravity, phenol concentrations, and suspended solids (53).
Volatile organic compounds can be stripped from aqueous wastes by
using air as the stripping agent. The stripping rate of a volatile
organic compound is a function of temperature, the stripping gas flow
rate, and tank geometry (37; 46). Laboratory testing has indicated that
most of the BOD removal during the stripping of biodegradable volatile
organic compounds was the result of biological action rather than physi-
cal stripping (39). If an organic compound is non-biodegradable and vola-
tile, air stripping may be a feasible unit process.
Solvent extraction methods utilize the preferential solubility of
materials in a selected solvent as a separation technique. The criteria
for effective use of a solvent in wastewater treatment include (a) low
water solubility, (b) density differential greater than 0.02 between
solvent and wastewater, (c) high distribution coefficient for waste
component being extracted, (d) low volatility and resistance to degradation
by heat if distillation is used for regeneration or low solubility in
liquid regenerants, and (e) economical to use (49). Equipment used for
extraction of wastewater include counter current towers, mixer-settler
units, centrifugal extractors, and miscellaneous equipment of special
design.
Solvent extraction has been found to effectively remove phenols.
Tricresyl phosphates are excellent solvents for phenol due to their low
solubility in water and their high distribution coefficients for phenol.
However, they are expensive and deteriorate at high temperature. The
electrostatic extractor employed in one phenol recovery process also
recovers usable oil from wastewater which helps to make the process
economical (68).
Other solvent extraction processes which have been used by the
petrochemical industry include the extraction of thiazole-based chemicals
from a rubber processing effluent with benzene and the extraction of
salicylic and other hydroxy-aromatic acids from a wastewater using
methyl-isobutyl-ketone as the solvent (110).
58
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Adsorption is the process whereby substances are attached to the
surface of a solid by electrical, physical, or chemical phenomenon. A
carbon media has been the most successful adsorbent in removing certain
refractory chemicals from wastewaters. Phenols, nitriles, and substituted
organics are also adsorbed by carbon when present in low concentrations.
Additionally, benzene hexachloride and other chlorinated aromatics have
been removed from pesticide manufacturing effluents by carbon adsorption
(47). These chlorinated hydrocarbons can be recovered by regeneration
with steam or with benzene.
Combustion processes are often feasible for disposal of petrochemical
wastes which may be too concentrated, too toxic, or otherwise unsuitable
for other methods of disposal. Combustion may be either direct or catalytic,
depending on the waste to be oxidized. Incineration and submerged com-
bustion are both direct combustion methods used by the petrochemical
industry.
Submerged combustion has been used successfully in the total or
partial evaporation of waste streams as well as concentrating dissolved
solids. This method produces an effluent which either has reuse value
or which is easier to dispose of than large volumes of the liquid waste.
Incineration is the most commonly used combustion process for petrochemical
wastes. Recently, fluidized bed incinerators have been used for burning
oily sludges (50) . The fluidized bed incinerator is reported to provide
better controlled combustion with lower requirements for excess oxygen
than conventional incinerators for oily sludges. However, incineration
occasionally converts a water pollution problem into an air pollution pro-
blem. For example, the air pollutants, sulfur dioxide, and hydrogen sul-
fide (from incomplete combustion) may be released to the atmosphere when
petrochemical wastes are incinerated.
Filtration processes are used to remove and concentrate solids on
oily materials from a waste stream. A filter can be specifically designed
to remove small quantities of these materials as-a final step in waste
treatment, or it may be used to concentrate a waste so that further treat-
ability of wastewater will be enhanced. Sludges produced by chemical
coagulation and clarification of petrochemical wastes are often concentrated
using centrifugation or vacuum filtration for easier handling and disposal.
If effluent standards imposed on a plant are particularly stringent, a
polishing filter employing sand filtration can be used to remove additional
suspended material (110).
Miscellaneous Treatment Methods - Evaporation has been used as a
method for treating some petrochemical wastewaters. Solar evaporation is
feasible in areas with low annual rainfall and a relatively warm climate.
Spraying the wastewater into the air also will increase the evaporation
rate.
The separation of surface-active agents from wastewater by induced
foaming has been investigated in laboratory and pilot plant studies (22).
Most of these studies have considered the removal of synthetic detergents
59
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from domestic wastes (74). It has been demonstrated that the surface-
active agent, naphthylamine, which has little or no foaming ability,
could be removed from solution by adding a foaming agent and inducing
frothing (62). B
CHEMICAL TREATMENT
The use of chemical systems for treating specific petrochemical
wastes has been successfully employed. The most common methods for
chemically treating petrochemical wastes include neutralization, pre-
cipitation, coagulation, and oxidation.
Neutralization and pH Adjustment - Neutralization of petrochemical
wastes may be desired for several reasons, including:
a) preparation of a waste for biological treatment,
b) preparation of a waste for direct discharge,
c) pretreatment for efficient coagulation,
d) prevention of attack and corrosion of conveyance or
process equipment, and
e) prevention of unwanted precipitation of waste components.
Neutralization implies the adjustment of a wastewater pH to values
at or near neutral pH; i.e., pH seven. Types of wastes generally neutral-
ized are (a) dilute acid or alkaline wash waters; (b) spent caustics;
(c) acid sludges from alkylation, sulfonation, sulfation, and acid treat-
ing processes; and (d) spent acid catalysts (9).
Sulfuric acid is the most common neutralizing agent used to neutral-
ize spent caustic wastes (76). Acid sludges are normally hydrolyzed to
free acids prior to their use as neutralizing agents. Spent caustic
neutralization with an acid can be designed as a batch or a continuous
system. The carbon dioxide in flue gases can also be used to neutralize
spent caustic solutions. Flue gas neutralization is economically feasi-
ble provided that the gases are available at high enough pressures so
that no compressor is required to inject them into the spent caustic
solution. Spent acid catalyst and sludges have been spread in pits filled
with lime, limestone, or oyster shells for neutralization. It should be
noted that pH adjustment is commonly used to facilitate coagulation and
precipitation.
Coagulation - Precipitation - The addition of coagulants under proper
conditions causes the formation of a settleable precipitate containing
waste materials which can be removed by conventional sedimentation or
flotation processes. It should be noted that coagulation is always
followed by some type of solids-separation process. The most commonly
used coagulants are hydrated aluminum sulfate (alum), ferrous sulfate,
60
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and ferric salts. The conventional coagulation system utilizes a rapid
mix tank followed by slow agitation of the mixture to promote growth of
floe particles which settle. The sludge-blanket clarifier, which provides
mixing, flocculation, and settling in the same unit, has had many industrial
applications because of its compact dimensions.
Coagulant aids are sometimes necessary to promote bridging between
floe particles and render the floe more settleable. The most common
coagulant aids are activated silica, bentonite clays, the organic poly-
electrolytes, and water treatment clarifier sludge. The three types of
polyelectrolytes are categorized by their electrochemical nature, specifi-
cally, cationic, anionic, and nonionic.
A common application of coagulation in the petrochemical industry is
the removal of emulsified oils from waste streams. Suspended solids and
turbidity removals are often as high as 90 percent. However, most petro-
chemical wastes contain dissolved organic compounds which are not easily
removed using coagulation methods. Coagulation has been used also to
remove metals such as lead and zinc, water-soluble alkyl-aryl sulfonates
by lime coagulation enhanced with ferrous sulfate, and low concentrations
of sulfide which are precipitated with zinc chloride, ferric chloride, or
copper sulfate.
Provisions must be made for the disposal of the sludges formed by the
settled precipitates from coagulation-precipitation processes. Landfills
are the most common form of inorganic sludge disposal, while organic
sludges are usually dewatered by some filtration method and subsequently
incinerated or buried.
Oxidation processes are used to treat both organic and inorganic
contaminants using oxygen or other chemicals as the oxidizing agents.
The oxidation of sulfides to sulfates using steam and air is an effective
treatment method; however, wastes containing high concentrations of phenol
cannot be treated in this manner because phenols interfere with sulfide
oxidation. If large quantities of mercaptans or mercaptides are present
in the waste, a reoxidizer may be required to insure complete oxidation (20).
Catalytic oxidation is usually applied when the fuel value of a waste
is too low for conventional incineration. The process was originally
designed to operate in the vapor phase but has been successfully applied
to aqueous wastes. Laboratory studies have shown that dilute aqueous
organic wastes could be effectively oxidized at temperatures below 600 C
by using a copper-chromate catalyst (51). Investigations have demonstrated
that hydrocarbons also could be oxidized by using metal oxide catalysts (102).
The initial cost of catalytic oxidation units may be 20 to 30 percent greater
than that for conventional incinerators, but for dilute organic wastes the
operating costs may be 15 to 20 percent less (9).
Wastes containing sodium sulfite, which has a very high immediate
oxygen demand, can be oxidized by bubbling air through the system. Iron
catalysts have been employed occasionally to speed the oxidation reaction (110)
61
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The oxidation of sulfite to sulfate will increase the acidity of the waste
and require subsequent neutralization. Diffused air has also been used to
oxidize metal salts to insoluble hydroxides which were removed by sedimen-
tation (31).
Chlorine has been used successfully to oxidize phenol and cyanide in
petrochemical wastes. The oxidation of phenols must be carried to com-
pletion to prevent the release of chlorophenols which cause objectionable
tastes and odors in drinking water. Cyanides can be oxidized to carbon
dioxide and nitrogen by chlorination if the pH is maintained in excess of
8.5 and sufficient chlorine used, thus preventing the release of toxic
cyanogen chloride. Chlorine dioxide has been shown to overcome these and
other disadvantages of chlorine and hypochlorite oxidation, although this
treatment is very expensive.
Ozone has been proposed as an oxidizing agent for phenols, cyanides,
and other unsaturated organics because it is a considerably stronger
oxidizing agent than chlorine. The chief disadvantage is the high initial
cost of ozone generation equipment. Ozone has several advantages, one of
which is its ability to react rapidly with phenols and cyanide.
Oxidation of phenols using hydrogen peroxide and ferrous salts has
been investigated in the laboratory (38). Treatment of the industrial
wastes in this case produced colored effluents which required additional
treatment with alum.
Miscellaneous Methods - Ion exchange has been used to remove specific
petrochemical pollutants. Quaternary anmonium anion resins have success-
fully removed phenols in the laboratory (3). However, regeneration of the
resin was difficult and uneconomical. Salicylic acid recoveries of 80
percent were obtained from aspirin manufacturing effluents using a caustic-
soda regenerated resin (110). Chemical reduction has been used in isolated
cases to treat constituents of a waste stream.
BIOLOGICAL TREATMENT PROCESSES
Biological treatment of 'liquid petrochemical wastewaters is usually
the most economical method of reducing its toxicity, organic content,
and objectionable appearance. Extensive pretreatment is often required
before a petrochemical waste stream can be treated biologically.
The applicability of biologically treating a particular waste is a
function of the biological degradability of the dissolved organics present
in the wastewater. When considering the economics of a biological treat-
ment system, the time required to biologically degrade the dissolved
organics is of primary importance. This degradation rate of an organic
compound is a function of the molecular structure of the compound, the
genera and species of microorganisms utilizing it as a food source, and
the time required for the microorganism to develop the enzymes necessary
for substrate utilization.
62
-------
The biodegradability of an organic compound can be classified in
several ways (79) . The BOD parameter establishes a relative degree of
biodegradability provided that acclimated seed is used for the test.
There is much contradictory data relating the molecular structure of a
compound to its biodegradability. However, the amenability or resistance
of certain classifications of organic compounds to biological oxidation is
well documented as described below.
a) Aliphatic or cyclic aliphatics are usually more susceptible
to biological degradation than aromatics.
b) Unsaturated aliphatics, such as acrylics, vinyl, and carbonyl
compounds are generally biodegradable.
c) Molecular size is significant concerning the biodegradability
of an organic. Polymeric and complex molecular substances
have shown resistance to biological degradation, part of
which is attributed to the inability of the necessary enzymes
to approach and attack susceptible bonds within the compound
structure.
d) Structural isomerisms in organic compounds affect the relative
biodegradability of many compound classes. For example, pri-
mary and secondary alcohols are extremely degradable while
tertiary alcohols are resistant.
e) The addition or removal of a functional group affects the
biological oxidation. A hydroxyl or amino substitution to
a benzene ring renders the compound more degradable than the
parent benzene, while a halogen substitution causes it to be
less biodegradable.
f) Many organic compounds are extremely biodegradable at low
concentrations but are bio-static or bio-toxic at higher
concentrations.
The relative biodegradability of certain organic compounds is pre-
sented in Table 10.
Nutrients - Effective biological treatment of any organic contami-
nant requires the availability of essential nutrients for the organism.
The mineral nutrients required by bacteria are available in sufficient
amounts in most wastewaters, but nitrogen and phosphorus requirements
are more critical and many petrochemical wastes are deficient in one or
both of these elements. Nitrogen (N) and phosphorus (P) requirements
for biological treatment have been related to the magnitude of the
degradable organic content of wastewater as represented by BOD. Gen-
erally, a BOD:N:P ratio of 100:5:1 will provide sufficient amounts of
these nutrients. Nitrogen is most readily available in its reduced form
as ammonia, ammonium ion, or amino nitrogen. Organic nitrogen, nitrates,
63
-------
TABLE 10
RELATIVE BIODEGRADABILITY OF CERTAIN ORGANIC COMPOUNDS
(References 72, 73, 81)
Biodegradable Organic Compounds
Acrylic Acid
Aliphatic Acids
Aliphatic Alcohols
(normal, iso,
secondary)
Aliphatic Aldehydes
Aliphatic Esters
Alkyl Benzene Sulfonates
w/exception of
propylene-based
Benzaldehyde
Aromatic Amines
Dichlorophenols
E th ano1amine s
Glycols
Ketones
Methacrylic Acid
Methyl Methacrylate
Monochlorophenols
Nitriles
Phenols
Primary Aliphatic Amines
Styrene
Vinyl Acetate
Compounds Generally
Resistant to Biological
Degradation
Ethers
Ethylene Chlorohydrin
Isoprene
Methyl Vinyl Ketone
Morpholine
Oil
Polymeric Compounds
Polypropylene Benzene Sul-
fonates
Selected Hydrocarbons
Aliphatics
Aromatics
Alkyl-Aryl Groups
Tertiary Aliphatic Alcohols
Tertiary Benzene Sulfonates
Trichlorophenols
Some compounds can be degraded biologically only after
extended periods of seed acclimation.
64
-------
nitrites, and organic compounds containing these forms can also be used,
but a considerable expenditure of energy is required to reduce these
forms to ammonia nitrogen. Phosphorus is most readily available to the
microorganisms as a phosphate.
Neutralization - Most biological treatment systems operate efficiently
at pH values between five and nine, while optimum conditions usually fall
within the pH six to eight range. Therefore, neutralization or pH adjust-
ment is commonly required in many petrochemical wastewater treatment
systems.
Equalization - Petrochemical wastes are particularly subject to wide
variations in flow and composition; thus, some form of equalization may
be necessary to dampen these fluctuations and minimize transient effects
which may adversely affect the biological process.
Pre- and primary treatment may be required to remove certain materials
which would adversely affect the biological system. Oils are difficult
for the organisms to metabolize due to their low solubility. Inorganic
and non-biodegradable organic suspended solids will tend to build up in
a treatment system, decreasing the proportion of active biological solids,
and thus adversely affecting the treatment efficiency. Sulfides react
with dissolved oxygen and reduce the available oxygen to the organisms.
Heavy metals are toxic at defined concentrations and must be removed or
reduced to safe levels. Also, waste streams with potentially toxic
organic compounds should be separated and treated prior to discharge
into the biological treatment system.
Temperature - The optimum temperature for most aerobic biological
treatment systems is approximately 20 to 35°C (35). High temperatures
of waste cause a decrease in oxygen solubility as well as increased
oxygen utilization rates.
The activated sludge process is a continuous system where biological
growths are mixed with wastewater, aerated, and then undergo biological
sludge separation. A portion of the concentrated sludge is then recycled
and mixed with additional waste. Completely mixed aeration designs are
generally favored over plug flow systems for industrial waste treatment.
These effluents discharged from completely mixed activated sludge systems
generally are of better quality than those obtained from other biological
processes in terms of organic and solids concentrations, but construction
and operational costs are usually higher.
Parameters to be considered in the design of an activated sludge
system include the fundamental factors of temperature, pH, and nutrient
availability as well as the following:
a) the organic loading in terms of BOD applied per day per
unit weight of biological solids,
b) the BOD removal kinetics of the specific petrochemical
wastewater,
65
-------
c) the quantity of biological sludge produced including
accumulation of primary sludge,
d) the oxygen requirements of the system, and
e) the settleability of the biological sludge and the
ease of gravity solids-liquid separation.
A summary of activated sludge plants treating petrochemical wastes,
including information concerning the petrochemical products, applied
loadings, nutrient requirements, and effluent quality are tabulated in
Table 11. It should be recognized that many organic compounds can be
chemically oxidized while remaining resistant to biological degradation,
therefore being registered as COD but not BOD. The difference between
the measured COD and BOD values indicates the magnitude of the organic
fraction that is not readily amenable to biological degradation.
Trickling filters are commonly used in industrial waste treatment as
"roughing devices" designed to equalize and reduce organic loads to
activated sludge or aerated lagoon processes. Trickling filters employ
microbial films which are attached to rock or synthetic media to remove
organic materials from the wastewater solution. Most filter processes
employ recirculation to increase the overall filter efficiency and to
minimize shock loadings.
Although BOD removals obtained by trickling filters are usually
less than those found in the activated sludge process, toxic effects
are not as pronounced or perpetual. Additionally, filter design and
operation is relatively simple. The recorded treatment of various
chemical and petrochemical wastes using trickling filters is presented
in Table 12.
Aerated lagoons are basins six to twelve feet in depth where oxygen
is supplied mechanically. The two general types of aerated lagoons are
the aerobic lagoon and the facultative lagoon. In the aerobic lagoon,
all biological solids are kept in suspension, while sludge settling and
consequent anaerobic decomposition are characteristic of the facultative
aerated lagoon. In these lagoons, the solids concentration is allowed
to reach an equilibrium concentration which depends on the organic con-
centration of the waste, the synthesis sludge rate coefficients, and the
amount of power imparted to the basin liquid. Equilibrium suspended
solids normally range from 80 mg/1 to 250 mg/1.
High levels of treatment are generally not achieved in the aerated
lagoons because of the BOD and COD associated with the effluent sus-
pended solids and the relatively small number of active biological solids
in contact with the wastewater. Aerated lagoons are particularly sensi-
tive to transient organic loadings, toxic substances, and temperature
changes. A summary of reported data on treatment of petrochemical wastes
by aerated lagoons is given in Table 13.
66
-------
TABLE 11
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
BOD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
COD
Organic
Loading
Nutri-
In Out Rem lb BODg/day ents
(mg/1) (mg/1) (7.) ( lb MLSS ) Reqd.
Remarks
Ref
Refinery, Natural
Gas Liquids,
Chemical
Specialties,
Sanitary Sewage
Phthalic Anhydride,
Phenol, Salicylic
Acid, Rubber Chem.,
Aspirin, Phenacctin
Refinery,
Detergent
Alkylate
Butadiene
Maleic Acid
Butadiene
Alkylate
Butadiene,
Maleic Anhydride
Fumaric Acid,
Tetrahydrophthalic,
Anhydride, Butylene
feomers, Alkylate
4.87
2.54
90 20 78
45.7 6.1 86.7
200
2.45 345 50- 71- 855
100 85.5
2.0 2,000 25 98.8 2,990
1.5 1,960 24 98.8 2,980
1.5 1,960 24 98.8 2,980
90 55
150- 76.6-
200 82.5
480 84
477 98.3
51 84
0.1
0.031
0.08
0.24
0.24
(MLVSS)
None
None
PO,
NH,
NH,
Effl. phenol 0.05
Effl. oil 0.5 mg/1
Brush Aeration, treats
trickling filter
effluent, 55% sludge
return
Phenols in = 160 mg/1
Sulfide in = 150 mg/1
Lab scale
Surface aerators wastes
contain: alcohols,
maleic acid, fumaric
acid, cetic acid,
GI~C^ aldehydes, fur-
fural, water soluble
addition products
111
110
44
34
34
84
-------
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
BOD COD Organic
Ijuau4-llt> Nutri-
Flow In Out Rem In Out Rem ,lb BOD5/day ents
(MGD) (mg/1) (mg/1) (%) (rag/1) (mg/1) (%) ( Ib MLSS ; Reqd. Remarks
Ref
Ethylene
Propylene,
Benzene
Naphthalene,
Butadiene,
Phenol,
Acrylonitrile,
Soft Detergent
Bases, Resins,
gj Other Aromatics
Phenol, 2, 4-D
Aniline,Nitro-
Benzene, Rubber Chem.,
Polyester Resins,
Misc. Chem.
Ethylene, Propylene,
Butadiene, Benzene,
Polyethylene, Fuel
Oils
Refining Processes
Nylon
Petroleum Products
1.44
0.43
0.97
0.63
0 51-
0.63
600 90 85
500 60 85-
90
370
85
125
76 76.2
10 99
15- 80-
25 88
0.4 1,540 250 83.8
0.27 440 5 98.8
700 105 85
600 90 80-
85
200
500
75 62.5
65-
80
60 88
1.5
0.4
0.28-
0.4
None
PO;
NIL
PO,
PO,
Oily waters: C,-
C Q oils 90%
phenol removal
Sour waters: Oil
in = 500 mg/1
Phenol in = 65 mg/1
pH adjustment, pre-
ceeded by trickling
filter, phenol
removal = 99.9%
Accelator Pilot
Plant Sewage added
in ratio 1:600 once
a week
Quench waters, poly-
ethylene and benzene
wastes: proceeded
by trickling filter,
effl. phenol 0.01 ppm
Phenol removal 85-
94%; Oil removal 75-
85%; Effl. phenol 0.5
mg/1; Effl. oil 1-2
mg/1; Temp. - 30°C
Phenol in = 25 ppm
Phenol out - 1 ppm
92
92
80
95
59
34
34
-------
TABLE 1.1. CConeinuad)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
Aerv'Hc'. Flhprs
Flow In
(MGD) (mg/1)
0.252 2.260
BOD
Out Rem
(mg/1) (%)
118- 90-
COD
In Out
(mg/1) (mg/1)
• _ !_; _.lu,_™_m '"• " _"• — — ' ' _u "--.
Organic
lb BOD. /day
Rem , 5s
(%) ^ lb MLSS j
0.4
Nutri-
ents
Reqd. Remarks
Wastes contain acrylo-
Ref
105
vo
Acetone, Phenol
p-Cresol, Ditert.-
Butyl-p-Cresol,
Dicumyl Peroxide
Res ins-Formalin,
Aminoplasts,
Phenol-Formald.,
Epoxy Resins,
Textile Aux.
Ethylene and
Propylene Oxides,
Glycols, Mor-
pholines, Ethy-
lene-Diamines,
Ethers,
Piperazine
2, 4-D
2,4,5-T
(Acid Wash Wastes)
226 95
0.216 3,560- 1,030- 71-
4,400 750 83
0.2
890 444-
266
0.15 1,950 20 99
50-
70
7,970- 5,120- 25-
8,540 5,950 40
0.1 1,670 125 92.5 2,500 500 80
0.89-
1.1
0.8-
1.2
0.51
0.78
(MLVSS)
None
NH,
PO,
nitrile, dimethylamine
dimethylformamide,
formic acid temp. 35-
37°C return sludge 10-
50% mechanical aeration
Waste phenol 600 ppm 33
Waste BOD 7,500-8,000
Waste diluted w/ effl.
or water; pilot plant
Diffused-air; domestic 98
waste added; trickling
filter follows 100%
recycle sludge
Lab Scale; extended 43
aeration; high non-
biodegradable fraction
followed by stab, ponds
1:1 mixture of acid 42
wash streams diluted
9:1 prior to treatment
to reduced chlorides,
toxicity Lab Scale
-------
TABLE 11 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and/ or
Process
Cracking,
laomerization of
Butane and Naph-
thene, Alkylation,
Benzene, Toluene,
Alcohols, Ketones,
Cresyllc Acids
Ethylene,
««j Acetylene
Nylon Manuf.-
Adipic Acid
BOD COD
Flow In Out Rem In Out Rem lb BOD5/day
(MGD) (mg/1) (mg/1) (7,) (mg/1) (mg/1) (%) lb MLSS
1,100 55- 90- 0.5
110 95
20 0.23-
0.33
95 85 1.0-
3.0
Nutri-
ents
Reqd. Remarks
90-95% phenol re-
moved; Lab Scale
PO Effl. phenol 0.1
mg/1
Effl. oil 1 ppm
PO NH, OH used as nu-
.„. tnent and neutrali-
Ref
29
59
30
86
Aaidonitricz
Alk. Organics
zing agent waste
diluted 2:1
-------
TABLE 12
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/or Flow
Process (MGD)
Phenol, Salicylic 2.59
Acid, Rubber Chem.,
Aspirin, Phenacetin, 2.59
BOD COD
Organic
T.naH 1 no
In Out Rem In Out Rem lb BOD5/day ^utri-
(mg/1) (mg/1) (%) (mg/1) (mg/1) (%) ( 1>0QO ft3 ents Remarks
190 58 69.5
58 34 41.5
40.5 None Rock Media, recirc.
ratio 2.84:1
11.8 None Rock Media, treats
Ref
110
Phthalic Anhydride
Plastics, Amines,
Enzymes
Ethylene, Propy-
lene, Butadiene,
Benzene, Poly-
ethylene, Fuel Oil
Aliphatic Acids,
Esters, Alcohols,
Aromatics, Amines,
Inorganic Salts
Ethylene, Propy-
lene, Butadiene,
Benzene, Naph-
thalene, Phenol,
Acrylonitrile,
Soft. Detergent
Bases, Resins
1.06 1,960 37 98.1 2,660 230 91.5
0.63
170 85 50
400
200 50
0.57-
0.86
1,100-
2,300
23-
470
57-
99
0.43 1,300
1,500
450 60-
70
89
None
42.1- None
82
(Both filters
combined)
140 NH
PO,
effluent from above
filter, effluent
to act. sludge
2 filters, followed 34
Plastic filter media 95
followed by act.
sludge
phenol removal = 95%
influent diluted 2:1
w/cooling water
pH adjusted prior to 101
treatment; 2 filters in
series; Recycle on 1st
state is 14-21:1
Sour Waters, 92
Rock Media
-------
TABLE 12 (Continued)
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/ or
Process
Pentaerythritoc
Waste contains
Formaldehyde,
Sodium Formate,
Methanol, Pent-
aerthritol
Resins-Formaum,
Aminoplasts,
J^ Phenol -Formal,
Epoxy Resins,
Textile Aus.
BOD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
0.118 5,080- 225- 95-
5,800 232* 96*
0.17 82.6
0.03 89.3
COD Organic
Loading
In Out Rem ,lb BOD5/da* ,
(mg/1) (mg/1) (%) l 1,000 ft-»;
1st stage 65
11.7
14.6
cient
Nutri-
ents
NIL
J
T}/"\
P04
\t _
Yes
None
None
Remarks Ref
2 filters in series 3?
followed by act.
sludge; recycle
40-1 on prim, filter,
13-1 second
Both filters treat 98
act. sludge effluent,
Blast furnace slag
media
Waste contains
Acrylic Fibers
Synthetic Resins-
Phenol, Formalde-
hyde, Fatty Acids,
Phthalic Acid, Maleic
Acid, Glycerol,
Pentaerythritol,
H.C. Solvents
0.32
13 30-
70
95-
98
49 30- 50
70 84
1st stage 85
(as Phenol)
2nd stage 11.6-
18.2 gpd/ft3
phenol, formaldehyde,
methanol
NH,j Waste contains:
PQ, acrylonitrile and
zinc plastic filter
media
Plastic media, 2-
stage treatment;
Influent:
Phenol = 4,500 mg/1
Formaldehyde =
2,000 mg/1
Fatty acids = 800
mg/1
Phthalic and maleic
acids = 1,000 mg/1
Eff. phenol = 1.5 mg/1
91
27
-------
1.2
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/ or
Process
Waste contains
Acrylates,
Acetone,
Inhibitor oils,
Alcohols, Esters,
»2se>4
BOD COD Organic Defi_
, Loading
ron T lbBODc/day """"
Flow In Out Rem In Out Rem , 5 J. Nutri-
(MGD) (mg/1) (mg/1) (%) (mg/1) (mg/1) (%) ( 1,000 ft3; ents Remarks
51- None Original loading was
79 None lower value, loading
increased w/o any
adverse effects
15,000 Ib BOD5 re-
moval per day
Ref
23
Organic Acids
u>
Entire Treatment System
-------
TABLE 13
AERATED LAGOON TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
Refinery
Butadiene,
IJutyl Rubber
Refinery,
Detergent
Alkylate
BOD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
19.1 225 100 55
2.45 345 50- 71-
100 85
COD
In Out
(mg/1) (mg/1)
610 350
855 150-
200
Organic
Rem lb BOD5
(%) Acre • day
43 4,630
77- 6,300
83
Nutri-
ents
Reqd.
PO.
4
PO,
4
Remarks
Followed by stab.
pond
temp = 32°C
30% COD is non-bio-
degradable
Lab Scale
Influent phenols
160 mg/1
Influent sulfides
Ref
44
Cyclohexane, 0.51 100 25 75
p-Xylene,
benzene, Para-
ffin Ic Naphtha,
o-Xylene
Gasoline
Nylon Fibers
Chemicals for 0.2 465 180 61 1,050
Lubricating Oils
400
150 mg/1
Lab Scale
Surface aeration,
waste is extensively
pretreated.
Followed by pond
600
43
64
34
-------
Waste stabilization ponds, which depend on the natural aquatic
processes of bacterial and algal symbiosis, have been used successfully
to treat petrochemical wastes. These ponds are often designed to polish
the effluent from other biological waste treatment processes, but they
have been used in some instances to treat entire plant wastes.
Waste stabilization ponds are categorized as being "aerobic,"
"facultative," or "anaerobic." The BOD removal found in these oxidation
ponds is comparable to other biological unit processes, but the COD
reduction capacity is often higher. However, highly colored substances
reduce sunlight penetration and cause reduced photosynthesis, often
affecting COD removal capacities. There also are toxic effects of many
compounds on the pond algae which upset the symbiotic algal-bacterial
relationship. Operational data on these ponds in the petrochemical
industry are given in Table 14.
Miscellaneous Biological Treatment Processes - Cooling towers have
been used as biological treatment devices and provide a method for reuse
of water through the means of "free" biological treatment. Pilot plant
investigations using a percolating sand filter as a biological treatment
process have indicated some promise (33).
Multiple Biological Treatment Schemes - The complexity of most bio-
logical treatment systems and the associated effluent quality requirements
often circumvent single-stage biological treatment. Various combinations
of biological processes, therefore, may be employed to achieve the desired
effluent quality.
A general sequence of biological wastewater treatment processes is
demonstrated in Figure 13 (88).
OTHER METHODS OF DISPOSAL
Dilution - This form of disposal is becoming less and less popular
with regulatory authorities. However, certain petrochemical plants are
allowed to discharge their wastes to receiving waters without treatment
providing:
a) sufficient receiving water is available as a diluent,
b) there are no toxic or refractory compounds in the waste
stream, and
c) the assimilative and recovery capacity of the receiving
water is adequate.
Joint industrial-municipal treatment has been successful in certain
cases, especially where small petrochemical plants are located near large
metropolitan areas. Usually, some form of pretreatment is necessary
75
-------
TABLE 14
WASTE STABILIZATION POND TREATMENT OF PETROCHEMICAL WASTES
Product and/or Flow
Process (MGD)
Refinery, Butadiene 19.1
Hutyl Rubber
Kcflins, Alcohols, 5
Amines, Eaters,
Styrene, Ethylene 5
5
Butane, Propane, 3.25
Nat. Gas, Ethanol,
Ethyl Chloride,
Polyethylene,
Ammonia, H«SO,
Refinery, 2.45
Detergent Alkylate
Plastics 1.69
Ethylene and Pro- 0.15
pylene Oxides,
Glycols, Morpho-
lines, Ethylcne-
di amines, Ethers,
I'iperazine
Mixed Petrochemicals
In
(mg/1)
100
500-
1,000
400-
700
25-
50
150
50-
100
686
20
BOD
Out
(mg/1)
50
400-
700
25-
50
5-
30
7-
15
20-
50
186
COD Organic
Loadine
11 — . nnn Nutri-
Rem In Out Rem BOD5 ents
(%) radab]o Traction.
After activated
sludge
Facultative ponds
Ref
45
13
13
13
113
44
34
43
113
-------
Fig, 13. WASTEWATER TREATMENT SEQUENCE / PROCESS SUBSTITUTION DIAGRAM
-------
before the industry discharges into the municipal sewer. It generally
has been established, however, that individual treatment offers both
economic and political advantages, particularly where large volumes of
petrochemical wastewaters are involved.
Disposal wells used for the subsurface injection of wastewater are
listed in Table 15. Most of the petrochemical wastes noted in Table 15
must be pretreated prior to injection. The more common formations suit-
able for injection of wastes include unconsolidated sands, limestones,
and dolomites (109). The dangers of contaminating potable water-bearing
formations can be assessed by studying the overlying and underlying strata
and locating unplugged wells in the contiguous area.
Ocean Outfall - The direct discharge into the ocean is feasible when
locations permit. Most liquids flow through outfall pipelines, the dis-
tance of discharge from shore depending on the nature of the wastewater,
the ocean currents, and shoreline use. Barge disposal is another method
of conveying wastes to the ocean for disposal.
Submerged combustion is the burning of a gaseous fuel in a specially
designed burner with the burner chamber submerged in the wastewater.
This device has been used successfully in totally or partially evaporating
waste streams, concentrating any dissolved solids, either which have reuse
value or which are easier to dispose of than large volumes of the liquid
was te.
A submerged combustion unit reduced 75 percent of the volume of a
nylon waste stream, the remainder of which was mixed with other process
streams and treated biologically (86). A polymeric waste stream con-
taining suspended synthetic rubber particles, organic solvents, inorganic
salts, and synthetic detergents was not amenable to biological treatment
and consequently treated by submerged combustion (114). This waste stream
was evaporated to about 10 percent of its original waste volume with the
resulting slurry emptied to a drying bed. Volatile organic compounds in
the polymeric waste, such as alcohols and amines, were oxidized or burned
so that no odors were detected in the surrounding area.
Incineration of combustible and partially combustible liquid wastes
is often a feasible method of disposing of concentrated process streams.
The properly designed incineration system considers time, temperature,
and turbulence. Sufficient residence time should be provided to permit
complete oxidation of the organic material, the temperature should be
high enough for the reaction to proceed, and the system should be
sufficiently turbulent to insure that the oxygen in the air is contacted
with the dissolved organic material.
Although incineration is a practical means of handling a wide
variety of effluents, it should be evaluated only in the light of the
total pollution problem, particularly air pollution.
78
-------
TABLE IS
PETROCHEMICAL WASTE DISPOSAL BY UKEP WELL
INJECTION - TYPICAL INSTALLATIONS
Type Waste
Flow Depth
(ft)
Injection
Pressure
(psla)
Formation
Required
Pretreatment
Ref
Acrylonitrile and Deter-
gent Manuf. Wastes: COD
17,500 mg/1; Nitrites =
300 mg/1; pH = 5.4,
SO, =10,000 mg/1
10-15% NaCl; Diss.
Metal Salts; Trace
Organics; pH7.5-8.5
Refinery and Petrochem.
vo Cooling Water Blow-down
Hoiler Blow-down, Process
Waters
Petrochem. Waste
Organic Nitrogen
Nitrites
COD « 20,000 ppm
pll "12
Uranium 238
Phenolic Waste: COD =
12,000 ppm; 850 ppm
Phenol; 150 ppm Oil;
pH 10.8
Aromatics
Phenols 1,000-2,000 ppm
COD 10,000 ppm
pH 10.7
650 7,203
500 1,200
400 6,700
300 6,330
300 6,100
Up to
2,000
500- 4 wells: 200
600
75
400
1,000
1,000
Sat. Brine,
Miocene Sands
Unconsolida-
ted
Brine Sands
Sandstone
Sands
Sat. Brine,
Miocene Sands
Miocene Sands
Neutralization; Settling
and Equalization in Pond;
Coagulation pH Adjustment
and Clarification; Gravity
Sand Filters
Oil Separation; Settling;
Pressure Leaf Filtration;
Diatomite Filtration
92
Neutralization, Precipi-
tation - Sedimentation,
Filtration
Neutralization with H SO.;
Clarifier, Pressure
Sand Filter
54
31
48
92
48
-------
TABLE 15 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
oo
o
Type Waste
0.3% Acetic Acid and
Chlorinated Deriva-
tives
Flow
(gpm)
204
Depth
(ft)
3,700
Injection
Pressure
(psia)
2,000
Formation
Miocene Brine
Sand
Required
Pretreatment
Cool to 150°F. Adjust
pH to 4.0-5.0, Settling
Coal Filter; Cartridge
Filter for Solids >lQjk
Ref
115
65
Tcrephthallc Acid
Munuf.
Cooling and Boiler
Blow-down, Process Wastes
Containing Organic
Acids, H. C., inorganics
Nylon, Ammonia, Olefins,
Polyolefins, Refinery,
Butadiene, Styrene,
Synthetic Rubber 1
Cuprous Ammonium Acetate
from Butadiene Pond;
Caustic Waste from Ethy-
lene Prod., Caustic and
Phenols from Refinery
Refinery
Cooling and Boiler
Blowdown, Process Wastes,
Brines
150 5,600
Small- 5,802
96
85 >4,000
50 5,000
800-
1,100
1,500-
2,000
600
Sands
Limestone
Sandstone
Settling, Filtration
Conventional Waste Treat-
ment, 0.37, by Volume of
Acid, Added Before
Injection
Equalization, Settling
Settling and Storage
48
71
95
48
Ammonia Prod.
45 1,000
225
Sandstone
API Separator
48.
-------
TABLE 15 (Continued)
PETROCHEMICAL WASTE DISPOSAL aY DEE? WELL
INJECTION - TYPICAL INSTALLATIONS
00
Type Waste
Hydrochloric Acid
Detergent Product
Flow
(gpm)
40
35
Depth
(ft)
1,200
3,400
Injection
Pressure
(psia)
14.7
Formation
Sandstone
Miocene Sands
Required
Pretreatment
None
Dilution with Equal
Ref
48
48
32% HC1
Benzene
Chlorinated HC
Spent Alkylation Acid-
90% H2S04; 7% Oil;
3% HO
Filtrates and Distil-
lates from Chloromycetin
Manuf: BOD =45,000
ppin; pH 3.5, Dies. Solids
50,000 ppm
Saturated NaCl, Cone.
Ca-Mg, Liquors, Phenols,
Chloro-Phenols, Bis-
Phenols, Methocel, Weak
Caustic Washes
~ 1 5,100
1,400
3,000
Saturated
Brine,
Sand
Limestone
Volume Fresh Water
Suspended Solids
Removed
55
85
-------
ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT
The major economic factors considered in waste treatment include:
a) the capital cost of treatment process required to produce
a defined quality level of effluent and the operating costs
associated with the selected treatment process,
b) the returns to the petrochemical industry resulting from
the treatment of its wastewaters in terms of product
recovery and water reuse, and
c) the in-plant modifications required to render a treatment
process feasible or less costly.
GENERAL CONSIDERATIONS
Attempts to relate capital costs or production units, wastewater
flow, BOD, or their parameters have proved quite successful when certain
industrial wastewaters are considered. However, the diverse nature of
the petrochemical industry and its limited number of wastewater treat-
ment facilities has made it difficult to establish cost function relation-
ships which are applicable throughout the industry. An effective approach
for estimating the capital cost of a treatment facility is to calculate
the unit costs for each process within the treatment system and to increase
the total by a defined percentage to allow for piping, pumping, and
related appurtenances, engineering, and contingencies.
The bases for evaluating the capital and operating costs for many
of the unit processes used in the treatment of petrochemical wastewaters
are tabulated in Table 16. Other variables which affect these cost
relationships and are not considered herein include: (a) geographical
location, (b) climatic conditions, (c) area labor and materials cost
fluctuations, (d) land cost factors, and (e) over-design considerations.
Cognizant of these restraints, a series of capital cost-waste flow
relationships have been prepared (20; 36; 37; 88; 99). These graphs
have been developed based on 1968 construction costs (ENR 1,030) but are
given only in the Detailed Edition of this report. The relationships
were developed from reported costs of unit processes included in chemical,
refinery, petrochemical, and, in some cases, municipal waste treatment
systems. A generalized scheme can thereby be formulated, which sunmates
the individual process costs, including 35 to 45 percent of the subtotal,
to account for related appurtenances and engineering. Estimated costs
that would be incurred by the organic chemicals industry in attaining
various levels of pollution abatement over a five-year period have been
prepared (88).
PRIMARY TREATMENT
Capital cost relationships developed for equalization tanks,
neutralization, and primary clarification facilities have been reported
(36). Representations for gravity oil separators (20) indicate a
82
-------
TABLE 16
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
Type of Treatment
Design Basis
Construction
Cost Basis
Operational
Cost Basis
oo
Pre- or Primary Treatment;
Equalization
Neutralization
Oil Separation
Sedimentation
Biological Treatment:
Waste Stabilization Ponds
Aerated Lagoons
Activated Sludge
(Aeration tanks)
^Mechanical Surface
(Aeration equipment)
Secondary Clarifier
Trickling Filter
Volume
Waste Flow
Waste Flow-
Overflow Rate
Overflow Rate
Waste Flow-
Surface Loading
-Waste Flow-
Organic Loading
Waste Flow-
Organic Loading
Total HP
Overflow Rate
Waste Flow-
Organic Loading
Cost/Volume
Cost/Waste Flow
Cost/Waste Flow
Cost/Surface Area
Cost/Surface Area
Cost/Volume
Cost/Volume
Cost/Volume
Cost/Surface Area
Cost/Filter Volume
Acidity or
Alkalinity
-------
TABLE 16 (Continued)
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
Type of Treatment
Ultimate Disposal;
Deep Well Injection
Surface Treatment
Deep Well Injection
Incineration
Design Basis
Construction
Cost Basis
Waste Flow
Waste Flow-Depth
Waste Flow-
Heat Content
Cost/Waste Flow
Cost/Waste Flow
Cost/Waste Flow
Operational
Cost Basis
00
As Used in Aerated Lagoons and Activated Sludge
-------
TABLE 16 (Continued)
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
oo
Ln
Type of Treatment
Tertiary Treatment:
Ion Exchange
Carbon Adsorption
Miscellaneous Processes:
Gas Stripping
Coagulation
Sludge Handling and Disposal
Thickening
Flotation Thickening
Vacuum Filtration
Centrifugation
Design Basis
Waste Flow
Waste Flow
Waste Flow
Waste Flow
Mass Loading
Air/Solids Ratio-
Overflow Rate
Filter Loading
Waste Flow and
Solids Loading
Construction
Cost Basis
Cost/Waste Flow
Cost/Waste Flow
Cost/Waste Flow
Cost/Waste Flow
Cost/Thickener
Volume
Cost/Surface Area
Cost/Area of Filter
Cost/Waste Flow
Operational
Cost Basis
Air or Stream
Usage
Chemical Require-
ments
HP
-------
decrease in the unit capital cost for separators with increasing flow
volumes to a value of approximately 0.7 MGD, at which point the unit
cost remains virtually constant with flow.
BIOLOGICAL TREATMENT PROCESSES
Capital cost relationships for lagoons, aerated lagoons, and
activated sludge basins have been reported (36). The cost of the lagoon
or stabilization pond is highly dependent on the land cost; thus, the
correlation developed can only be considered as approximate. Large
mechanical surface aerators are more economical than small units based
on the same total power requirements. However, mixing considerations
often necessitate the use of smaller units. Secondary clarifier costs
parallel the cost required for primary clarifiers (36). The unit cost
of trickling filters related to waste flow has been graphically developed
from several sources (20; 34; 41; 110). The dispersion of reported values
is primarily attributable to differences in the organic loadings applied
to the various filters. A tabulation of reported daily operating costs
for biological treatment facilities in terms of volume treated and pounds
of pollutant is given in Table 17.
TERTIARY TREATMENT PROCESSES
At present, tertiary treatment of petrochemical wastes is not commonly
practiced. However, cost relationships for the treatment of municipal
effluents using ion exchange and carbon adsorption methods have been
reported (99) . A method has been suggested which uses these relationships
to estimate chemical and petrochemical flows (36). This approach considers
correcting the flow according to the following expressions:
Ion exchange -
[Corrected flowT , .. . 1 = [flow
Ind. Waste I Mun. Waste
___! 0>75
!J
COD
Mun.
Carbon adsorptions -
[Total Dissol. Solids ,
350 —\ °'75
The corresponding capital costs for the corrected flows can then be
determined.
SLUDGE HANDLING AND DISPOSAL PROCESSES
Capital cost relationships for sludge handling using flotation
thickening (20) and vacuum filtration (99) have been reported. A cost
relationship for total sludge disposal versus flow rate based on
86
-------
TABLE 17
OPERATING COSTS - WASTE TREATMENT PLANTS
oo
-vl
(Reference 34)
Industry
Refinery
Type of Treatment
Primary- includes oil sepa-
ration, coagulation,
flotation, and sedimen-
tation
Secondary-
Activated Sludge
Aerated Lagoon
Extended Aeration
Daily
$/MG
Operating Costs
$/l,000 lb
Pollutant
126-160 26-150 (COD)
161
22
28
292 (COD)
9 (COD)
14 (COD)
No.
Plants
Report-
ing
4
1
1
1
Solids
Disposal
Vacuum Filter
Landfill
Incineration
Landfill
Holding Ponds
Chemical Primary-all types including
oil separation, coagu-
lation, flotation
sedimentation, neutra-
lization, and equali-
zation
Secondary
Aerated Lagoon
11-1,540 3-40 (S.S.)
31-1,160 6-477 (BOD)
11
Landfill
Incineration
Vacuum Filter
Lagoons
Landfill
-------
TABLE 17 (Contlnurd)
OPERATING COSTS - WASTE TREATMENT PLANT'S
oo
oo
Daily Operating Costs
Industry
Chemical
(Cont.)
Type of Treatment
Secondary (Cont.)
Activated Sludge
Conventional
Extended Aeration
Contact Stabilization
Trickling Filter
Facultative Pond
Combination
Trickling filter and
activated sludge
$/MG
1,580
221-276
16-211
780-2,050
163
334-378
$/l,000 Ib
Pollutant
100 (BOD)
7-734 (BOD)
23-106 (BOD)
49-3,750 (BOD)
39 (BOD)
28-245 (BOD)
No.
Plants
Report-
ing
1
5
2
2
1
2
Solids
Disposal
-
Landfill, Lagoon
Landfill
Lagooning
Burning
Landfill
-------
questionnaire information reported by the chemical and petroleum industries
has been developed (36). "Total sludge disposal" included aerobic digestion,
sludge thickening, vacuum filtration or centrifugation, and final disposal.
ULTIMATE DISPOSAL
. The cost of incinerating waste liquids and slurries based on waste
flow has been reported (37). This relationship includes operational and
capital costs based on a 20-year amortization schedule.
The petroleum refineries reporting to a 1965 survey indicated that
the total replacement cost for their waste treatment facilities would be
$156,000,000 (14). This report also indicated that 134 refineries are
planning future treatment facilities and process modifications which will
cost $129,500,000. A similar report from the chemical industry showed a
present investment of $263,600,000 in waste treatment plants, with facili-
ties costing approximately $70,000,000 planned for the next five years (14),
It is possible for industry to experience a direct economic return
through water reuse and product recovery. In many instances, contaminants
can be removed less expensively in the plant than at the treatment facility,
These and other factors merit an engineering and economic review, the
implementation of which may produce a monetary return to the industry.
89
-------
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