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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         PROJECTION
     BY RESOURCES
    FOR THE
                                   PROJECTION BY
                                   BUSINESS AND
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                                   ADMINISTRATION
       1950
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   YEAR
1990
2000
                            FIGURE 2

                   TOTAL WATER INTAKE FOR CHEMICAL AND

                       ALLIED PRODUCTS INDUSTRY

                            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

-------
flrat-Gcncrattoa
                                                        Intermediate Chen it* I»
hASES
fLASTICS,



NAS£S
swncric
•ASH
	 1__
""• r~
snmnrric
nerucevr
uses
HAS 1C
imisniiAj.
IflTMinALS


— — £thylene—




__ ,





J
nijL*i Oleluif J




	 Butylen* — 1
'"*


	 Etbyleoc 	








	 fctyU- 	







' U J Oflt
f


	 ^^ 	
















	 Richer 01*f l«» 	 	

ti*yi«-i
— *^yl«« 	 1

raiKiFM.




Ethyl Ecnitne jtyrcnt
™1^^ 1 	 Ac«tone — I

.
py


of e yet o y
1


'
*" °"Tlu

r 7
tofiyicae UxLde Irlal

Aery Ion icri

Vinyl Acetylene Oiloroprcne
—Ethyl Alcohol 	 Acet. Aldehyde^— {






•opropj c o
1 Oiid ^r
opj ce c ropjc
JLlI^I Cl"l id "


* "
| DutJ tl c



f 	
T 	
*-^* "" fh rf nxtn°I


„ '
ertc y




y cue or e

,

J




J"""Ut"









1.. ClL I^nf| rflf^

FICUtE 4
DtOOUCT DEVIVATIVE5 FlttX T>C OLEFISS




•-0 h~tyrtnt
J

1 th n i
l! 1
»Ure 	 Alkyd Resins



Peroxide
Resins
Resins

Rubber
"
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

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                                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

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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

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             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

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     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

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                   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

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     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

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                          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

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                       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

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 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

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      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

-------
 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

-------
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

-------
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

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                              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

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                                                        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

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                                            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

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                                                  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

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                                                    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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                              REFERENCES
 1.   Aalund, L., "Petrochemical Activity Hits a New High Around the
        World," The Oil and Gas J.. v. 65, p. 108 (Sept. 4,  1967).

 2.   Adinoff, J., "Disposal of Organic Chemical Wastes to Under-
        ground Formations," Ind. Wastes, v. 1, n. 1, p. 4944
        (Sept.-Oct. 1955).

 3.   Anderson, R. D. and Hansen, R. D., "Phenol Sorption on Ion
        Exchange Resins," Ind. & Engr. Chem., v. 47, p. 71 (1955).

 4.   Anon., 1954 Census of Manufacturers:  Industrial Water Use
        Supplement, U. S. Dept. of Commerce, Bureau of the Census,
        Bull. MC-209 Supp., Washington, D. C. (1957).

 5.   Anon., 1958 Census of Manufacturers, Summary of Statistics,
        Vol. 1, U. S. Dept. of Commerce, Bureau of the Census,
        Washington, D. C. (1961).

 6.   Anon., Committee Report, Task Group 245, or "Survey of Ground
        Water Contamination and Waste Disposal Practices," J.  AWWA,
        v. 52, n. 9, p. 1211 (Sept. 1960).

 7.   Anon., "Huge Global Petroleum Gains Forecast," The Oil and
        Gas J.. v. 64, p. 180 (May 9, 1966).

 8.   Anon., Manual on Disposal of Refinery Wastes, Vol. I,  "Waste
        Water Containing Oil," American  Petrol.  Inst.,  New
        York, N. Y.  (1953).

 9.   Anon., Manual on Disposal of Refinery Wastes, Vol. Ill,  "Chemical
        Wastes," American Petrol- Inst., New York, N. Y.
        (1958).

10.   Anon., "Petrochemical Handbook 1967," Hydrocarbon Processing,
        v. 46, p. 11 (1967).

11.   Anon., "Selected Process Flow Sheets for Petrochemicals," The
        Oil and Gas J., v. 36, n. 36, p. 107 (1964).

12.   Anon., Standard Methods for the Examination of Water and
        Wastewater, American Public Health Assoc., New York, N. Y.,
        12th Edition (1965).
                                 90

-------
13.   Anon., Union Carbide Puts Corporate Muscle in Pollution Fight,"
        The Oil and Gas J., v. 64, n. 50, p. 132 (1966).

14.   Anon.. Water jln Industry. National Assoc. of Manufacturers and
        Chamber of Commerce of the U. S., New York and Washington,
        D. C.  (1965).

15.   Anon., "What Puts Zip in Petrochemicals," Business Week, p. 40
        (Dec.  17, 1966).

16.   Anon., "Why Petrochemicals Are Appealing," Business Week,
        Special Kept., p. 56  (Sept. 3, 1960).

17.   Baker, R. A., "Odor Effects of Aqueous Mixtures of Organic
        Chemicals," J. WPCF, v. 35, n. 6, p. 728 (June 1963).

18.   Baker, R. A. and Malo, B. A., "Water Quality Characteristics-
        Trace  Organics," ASCE-Proc. v. 93 (J.San. Engr. Div.) n. SA6,
        p. 41  (Dec. 1967).

19.   Beak, T. W., Discussion of "Behavior of Fish Exposed to Toxic
        Substances," Advances in Water Pollution Research, Vol. I,
        p. 38  (1965).

20.   Beychok, M. R. , Aqueous Wastes from Petroleum and Petrochemical
        Plants, John Wiley & Sons, London (1967).

21.   Brady, S. 0., "Taste and Odor Components in Refinery Effluents,"
        Air & Water Conservation Session, API, 33rd Mid-Year Meeting,
        Philadelphia, Pa. (1968).

22.   Brunner, C. A. and Stephan. D. G., "Foam Fractionation," Ind.
        & Engr. Chemistry, v. 57, n. 5, p. 40 (May 1965).

23.   Brush, A. E. and Wheeler, W. W., "Treatment of a Petrochemical
        Waste on a Trickling Filter," Proc.  2nd Ind. Water & Waste
        Conf., Texas Water Poll.  Control Assoc., Austin, Texas, p. 171
        (1962).

24.   Butler, P. E., et. al., "Modern Instrumental Techniques in
        Structure Elucidation of Products Derived from Petrochemicals,"
        Environ. Scl. & Tech., v.  1, n. 4, p. 315 (April 1967).

25.   Cairns, J., Jr., "Environment and Time in Fish Toxicity,"
        Ind. Wastes, v.  2, n. 1,  p. 1 (Jan., Feb. 1957).

26.   Cairns, J., Jr., "Biological Concepts  and Industrial Waste
        Disposal Problems," Proc. 20th Ind.  Wastes Conf., Purdue
        Univ., p. 49 (1965).
                                  91

-------
27.   Chipperfield, P. N. J., "Performance of Plastic Filter Media
        in Industrial and Domestic Waste Treatment," J.  WPCF. v.  39,
        n. 11, p. 1860 (Nov. 1967).

28.   Clark, F. E., "Industrial Re-Use of Wastewater," Ind.  & Engr.
        Chemistry, v. 54, n. 2, p. 18 (Feb. 1962).

29.   Coe, R. C., "Bench Scale Method for Treating  Waste by  Activated
        Sludge," Petrol  Proc.,   v. 7,  p. 1128 (Aug. 1952).

30.   Dean, B. T., "Nylon Waste Treatment," J. WPCF, v.  33,  n. 8,
        p. 864 (Aug. 1961).

31.   DeRopp, N. W., "Chemical Waste Disposal at Victoria, Texas,
        Plant of the DuPont Company," Sew, and Ind. Wastes,  v. 23,
        n. 2, p. 194 (1951).

32.   Dickerson, B. W. Campbell, C. J. and Stankard, M., "Further
        Operating Experiences on Biological Purification of  Formal-
        dehyde Wastes," Proc. 9th Ind. Waste  Conf., Purdue  Univ.,
        p. 331 (1954).

33.   Dickerson, B. W. and Laffey, W. T., "Pilot Plant Studies of
        Phenolic Wastes from Petrochemical Operarions,"  Proc.
        14th Ind. Waste Conf., Purdue Univ., p. 780 (1959).

34.   Eckenfelder, W. W., Jr., "Effluent Quality and Treatment
        Economics for Industrial Wastewater," Rept. to FWPCA,
        Washington, D. C. (1967).

35.   Eckenfelder, W. W., Jr., Industrial Water Pollution Control,
        McGraw-Hill Book Co., New York,  N. Y. (1966).

36.   Eckenfelder, W. W., Jr., et. al..  Unpublished Rept. (1968).

37.   Eckenfelder, W. W., Jr., Kleffman, R. and Walker J.,  "Some
        Theoretical Aspects of Solvent Stripping and Aeration of
        Industrial Wastes," Proc. llth Ind. Waste Conf., Purdue
        Univ., p. 14 (1956).

38.   Eisenhauer, H. R., "Oxidation of Phenolic Wastes," J.  WPCF,
        v. 36, n. 9, p. 1116 (Sept. 1964).

39.   Englebrecht, R. S. and Ewing, B. B., "Treatment of Petrochemical
        Wastes by Activated Sludge Process," Proc.  2nd Ind.  Water
        and Waste Conf., Texas Water Poll. Control  Assoc., Austin,
        Texas, p. 149 (1962).
                                 92

-------
40.   Ettinger, M. B., "Proposed Toxicity Screening Procedure for
        Use in Protecting Drinking Water Quality," J. AWWA. v. 52,
        n. 6, p. 689  (June 1960).

41.   Forbes, M. C. and Witt, P. A., "Estimate Cost of Waste Disposal,"
        Hydrocarbon Processing, v. 44, n. 8, p. 153 (1965).

42.   Ford, D. L. and Gloyna, E. F., Unpublished Kept. (Jan. 1967).

43.   Ford, D. L. and Gloyna, E. F., Unpublished Rept. (Feb. 1967).

44.   Ford, D. L. and Gloyna, E. F., Unpublished Rept. (May 1967).

45.   Ford, D. L. and Gloyna, E. F., Unpublished Rept. (July 1967).

46.   Gaudy, A. F., Jr., Englebrecht, R. S. and Turner, B. G.,
        "Stripping Kinetics of Volatile Components of Petrochemical
        Wastes, J. WPCF, v. 33, n. 4, p. 382  (April 1961).

47.   Giebler, G., "Treatment of Wastewaters  of the Pesticide Industry,"
        Von Wasser, v. 25, p. 197  (1958).

48.   Gloyna, E. F. and Ford, D. L., "Injection of Wastewaters into
        Disposal Wells," Unpublished Rept.  (1966).

49.   Gloyna, E. F. and Malina, J. F., Jr., "Petrochemical Wastes
        Effect on Water,"  Ind. Water & Wastes, pt. 1, Sept.-Oct.
        1962,pt. 2, Nov.-Dec. 1962, pt. 3,  Jan.-Feb.  1963, pt. 4,
        March-April 1963.

50.   Gossom, W. J. and Stevens, J. I., "The  Near Ultimate Disposal
        of Refinery Wastes," Tech. Paper 65-42. Rocky Mountain
        Regional Meeting.  Natl Petrol. Refiners Inst., Casper,
        Wyoming  (1965).

51.   Green,  R. V. and Moses, D. V., "Destructive Catalytic Oxidation
        of Aqueous Waste Materials," Sew, and Ind. Wastes, v. 24,
        n. 3, p.  288  (1952).

52.   Hatch,  L. F., The Chemistry  of Petrochemical Reactions, Gulf
        Pub.  Co., Houston, Texas  (1955).

53.   Heller, A. M.,  et. al.. "Some Factors in Selection  of a Phenol
        Recovery Process," Proc.  12th  Ind.  Waste Conf., Purdue Univ.,
        p. 103  (1957).

54.   Henkel, H.  0.,  "Deep Well Disposal of Chemical  Waste Water,"
        Proc. of  the  5th Annual Sanitary and  Water Resources Engr.
        Conf., Vanderbilt  Univ.,  Tech. Rept.  9, p. 26 (1966).
                                   93

-------
55.   Holland, H. R. and Clark, F. R.,  "A Disposal Well for Spent
        Sulphuric Acid from Alkylating Iso-Butane and Butylenes,"
        Proc. 19th Ind. Waste Conf., Purdue Univ., v. 49,  n.  1,
        p. 195 (1964).

56.   Huang, J. C. and Gloyna, E. F., "Effects of Toxic Organics on
        Photosynthetic Reoxygenation," Center for Research in.Water
        Resources Rept. No. 20, The Univ. of Texas, Austin,(1967).

57.   Hueper, W. C., "Cancer Hazards from Natural and Artificial
        Water Pollutants," Proc. Conf.  on PhysioL Aspects  of Water
        Quality.  U S  P H S , Washington, D. C., p. 181 (1960).

58.   Hutner, S. H., Baker, H., Arronson, A. and Zahalsky, A. C.,
        "Bacetria-Protozoa as Indicators in Purifying Water,"
        Biological Problems in Water Pollution - Third Seminar
        1962. R.  A.  Taft San.  Engr.  Center,  Cincinnati,  Ohio,
        p.  45 (1965).

59.   Huber, L., "Disposal of Effluents from Petroleum Refineries
        and Petrochemical Plants," Proc. 22nd Ind. Wastes  Conf.,
        Purdue Univ. (1967).

60.   Hyde, A. C., "Chemical Plant Waste Treatment by Ten Methods,"
        J. WPCF. v. 37, n. 11, p. 1486 (Nov. 1965).

61.   Ishio, S., "Behavior of Fish Exposed to Toxic Substances,"
         Advances in Water Pollution Research, 2nd Conf.,  Vol. I,
        p. 19 (1965).

62.   Karger, B. L. and Rogers, L. B.,  "Foam Fractionation of Organic
        Compounds," Anal. Chemistry, v. 33, n. 9, p. 1165  (Aug.   1961)

63.   Klein, L., River Pollution II. Causes and Effects, Butterworths
        & Co., Ltd., London (1962).

64.   Klippel, R. W.,  Rept. on Pollution Control Planning for the
        Guayama Petrochemical Complex,  Phillips Petroleum Co.,
        Bartlesville,  Oklahoma (1966).

65.   Klotzman, M. and Vier, B., "Celanese Pumps Wastes into Disposal
        Wells," The Oil and Gas J., v.  64, n. 15, p. 84 (1966).

66.   Kneese, A. V., Water Pollution - Economic Aspects and Research
        Needs. Resources for the Future, Inc., Washington, D. C.
        (1962).

67.   Koenig, L., "Ultimate Disposal of Advanced-Treatment Waste,"
        U S P H S,   Publication No. 999-WP-3, Cincinnati,  Ohio (1963).
                                  94

-------
68.   Lewis, W. L. and Martin, W. C., "Remove Phenols from Waste
        Waters," Hydrocarbon Processing, v. 46, n. 2, p. 131 (Feb.
        1967).

69.   Ling, J. T., "Pilot Study of Treating Chemical Wastes with
        Aerated Lagoon," J. WPCF, v. 35, n. 8, p. 963 (Aug. 1963).

70.   Lively, L., Rosen, A. A. and Mashni, C. I., "Identification
        of Petroleum Products in Water," Proc. 20th Ind. Waste Conf.,
        Purdue Univ.  (1965).

71.   Lockett, D. E., "Subsurface Disposal of Industrial Waste Waters,"
        Presented at Southwestern Petroleum Short Course, Dept. of
        Petro. Engr., Texas Tech. College, Lubbock, Texas (April
        1967).

72.   Ludzack, F. J. and Ettinger, M. B., "Chemical Structures
        Resistant to Aerobic Biochemical Stabilization," J. WPCF,
        v. 32, n. 11, p. 1173 (Nov. 1960).

73.   Ludzack, F. J., Scheffer, R. B. and Bloomhuff, R. N., "Experi-
        mental Treatment of Organic Cyanides by Conventional Processes,"
        J. WPCF. v. 33, n. 5, p. 492 (May 1961).

74.   McGauhey, P. H.  and Klein, S. A., "Removal of ABS from Sewage,"
        Public Works, v. 92, n. 5, p. 101  (May 1961).

75.   McGrath, H. G., "Petrochemicals to Star  '60's," The Oil and
        Gas J.. v. 59, p. 129 (Nov. 20, 1961).

76.   McRae, A. D., "Disposal of Alkaline Wastes in the Petrochemical
        Industry," Sew, and Ind. Wastes, v. 31, n. 6, p. 712 (July
        1959).

77.   Mellon, M. G., "Detection and Analysis of Chemicals in Water. I.
        Inorganic Constituents," Proc. Conf. on Physiol. Aspects of
        Water Quality. U S P H S ,  Washington, D. C., v. 27 (1960).

78.   Mencher, S. K., "Minimizing Waste in the Petrochemical Industry,"
        Chem. Engr. Progress, v. 63, n. 10, p. 80  (Oct. 1967).

79.   Mills, E. J. and Stack, V. T., "Biological Oxidation of
        Synthetic Organic Chemicals," Proc. 8th Ind. Waste Conf.,
        Purdue Univ. p. 492  (1953).

80.   Mills, R. E., "Development of Design Criteria for Biological
        Treatment of an Industrial Effluent Containing  2,4-D Waste
        Water," Proc. 14th Ind. Waste Conf., Purdue Univ., p. 340
        (1959).
                                 95

-------
81.   Pahren, H. R. and Bloodgood, D. E., "Biological Oxidation of
        Several Vinyl Compounds," J. WPCF, v. 33, n. 3, p. 233
        (May 1961).

82.   Paynter, 0. E., "Chronic Toxicity of Dodecylbenzene Sodium
        Sulfonate," Proc. Conf. on Physiol Aspects of Water Quality,
        U S P H S., Washington, D. C. p. 175 (1960).

83.   Phillips, C., Jr., "Treatment of Refinery Emulsions and Chemical
        Wastes," Ind. & Engr. Chemistry, v. 46, p. 300 (1954).

84.   Pruessner, R. D. and Mancini, J., "Extended Aeration Activated
        Sludge Treatment of Petrochemical Waste at the Houston Plant
        of Petro-Tex Chemical Corporation," Proc. 21st Ind. Waste
        Conf., Purdue Univ., v. 50, n. 2, p. 591 (1966).

85.   Querio, C. W.  and Power, T. J., "Deep Well Disposal of
        Industrial Wastewater," J. WPCF, v. 34, n. 2, p. 126 (1962).

86.   Remy, E. D. and Lauria, D. T., "Disposal of Nylon Wastes,"
        Proc. 13th Ind. Waste Conf.. Purdue Univ., v. 43, n. 3, p.
        596 (1958).

87.   Rice, J. K., "Eliminate Waste Water Discharge," Petro/Chem
        Engineer, p. 21 (Oct. 1966).

88.   Rice, C. W. and Company, Eckenfelder, W. W., Jr. and Associates
        and Weston, R. F., Inc., Projected Wastewater Treatment Costs
        in the Organic Chemicals Industry, Unpublished Rept. to the
        F W P C A  (January 1969).

89.   Ruggles, W. C., "Basic Petrochemical Processes as Waste
        Sources," Sew, and Ind. Wastes, v. 31, n. 3, p. 274 (March
        1959).

90.   Ruchhoft, C. C., et. al.. "Waste Disposal in Petroleum Industry,"
        Ind. & Engr. Chemistry, v. 46, n. 2, p. 283  (Feb. 1954).

91.   Sadow, R. D., "The Treatment of Zefran Fiber Wastes," Proc. 15th
        Ind. Waste Conf., Purdue Univ., p. 395 (1960).

92.   Sadow, R. D., "Waste Treatment at a Large Petrochemical Plant,"
        J. WPCF. v. 38, n. 3, p. 428 (March 1968).

93.   Sawyer, F. G., "Best Picks for '66:  Petrochemicals,"  Hydro-
        carbon Processing, v. 46, n. 1, p. 161 (Jan. 1966).

94.   Senate Reports, Future Water Requirements of Principal Water-
        Using Industries, Select Committee on Natl. Water Resources,
        86th Congress Committee Print No. 8 (1960).
                                  96

-------
 95.    Shannon,  E.  S.,  "Handling and  Treating Petrochemical Plant
         Wastes:  A Case History," Water & Sew. Works,  v.  Ill, n. 5
         p.  240  (1964).

 96.    Sherwood,  P.  W.,  "Firs-t-Generation Chemicals  Today," World
         Petrol.  Annual  Refinery Review,  v.  35, n. 8, p. 61 (1964).

 97.    Sherwood,  P.  W.,  "Whiter  Petrochemicals?"  The Oil  and Gas J.
         p.  73  (Dec.  16,  1963).                                  ~~

 98.    Singleton, K.  G.,  "Biological  Treatment of Waste Water from
         Synthetic  Resin Manufacture,"  Proc.  21st Ind.  Waste Conf.,
         p.  62,  Purdue Univ.  (1966).    "                     ~~~

 99.    Smith, R., "Cost  of  Conventional and  Advanced Treatment of
         Wastewater," J.  WPCF. v.  40, n.  9,  p. 1546  (Sept. 1968).

100.    Stanley,  H.  M., The  Petroleum-Chemicals Industry, Lecture
         Series  1963, n.  4, The  Royal Inst.  of Chemistry (1963).

101.    Steen, J.  H. ,  Majewski, F.  M.  and  lezzi, T.,  "Waste Treatment
         at  a Large Chemical Manufacturing Plant," Sew, and Ind.
         Wastes,  v.  28,  p.  866  (July  1956).

102.    Stein, K.  C.,  et.  al., "Oxidation  of  Hydrocarbons on Simple
         Oxide Catalysts," Air Poll.  Control Assoc.. v. 10, n. 4,
         p.  275  (Aug. 1960).

103.    Stephenson,  R. M., Introduction  to the Chemical  Process
         Industry.  Reinhold Pub.  Corp.,  New  York, N. Y. (1966).

104.    Stockton,  J.  R.,  Arbingast,  S. A.,  Henshaw, R. C.,  Jr. and
         Dale, A. G., Water for  the Future,  Vol. II, Bureau of
         Business Research, The  Univ. of  Texas, Austin, p. 30 (1959).

105.   Taylor, E. F., et. al.. "Orion Manufacturing Wastes Treatment,"
         J. WPCF, v. 33, n. 10, p.  1076  (Oct.  1961).

106.   Teal,  J. L., "The Control of Waste  Through Fish Taste,"
         American Chem. Society, Natl. Meeting (1959).

107.   Thirumurthi, D. and Gloyna, E. F.,  "Relative Toxicity of
         Organics to Chlorella pyrenoidosa,"  Center for Research in
         Water Resources Rept. No. 4, The  Univ. of Texas,  Austin
         (1965).

108.   Todd,  D. K., Ground Water Hydrology. John Wiley & Sons, Inc.,
         New York, N. Y., p. 85  (1959).

109.   Warner, D. L., "Deep Industrial Waste  Injection Wells in the
         United States, A Summary of Pertinent Data," Rept. to FWPCA,
         Cincinnati, Ohio (1966).

                                   97

-------
110.  Wilson,  I. S., "The Treatment of Chemical Wastes," Waste
        Treatment. Isaac, P. C. G., ed., Fergamon Press, London,
        p. 206 (1960).

111.  Word, J. C., Wright, M. V. and Klippel, R. W., "Treating
        Complex Petroleum Wastes at Borger, Texas," paper from
        Phillips Petroleum Co.

112.  Wright, E. R., "Secondary Petrochemical Process as Waste
        Sources," Sew, and Ind. Wastes, v. 31, n. 5, p. 575 (May
        1959).

113.  Wright, R. L,, "Treatment of Petro-Chemical Wastes at Port
        Lavaca, Texas," Sew, and Ind. Wastes, v. 29, p. 1033 (Sept.
        1957).

114.  Weyermuller, G. and Davidson, J. A., "Submerged Combustion
        Prevents Polymer-Waste Problem," Chem. Processing (Feb. 1958)

115.  Vier, B. B., "Celanese Deep Well Disposal Practice," Proc.
        7th Ind. Water and Waste Conf.. Texas WPCA  (1967).

116.  Vrablick, E. F., "An Evaluation of Circular Gravity Type
        Separation and Dissolved - Air Flotation for Treating Oil
        Refinery Waste Water," Proc. 12th  Ind. Waste Conf.. Purdue
        Univ., p. 72  (1957).

117.  Anon.,  The  Petroleum Handbook, Shell International Petroleum
        Co.,  Ltd., 5th Edition, Balding and  Manse11, Ltd., eds.,
        London  (1966).

118.  Anon.,  Drinking Water  Standards,  U.  S.  Public Health Service
        Publication No.  956  (1962).

119.  Bland,  W. F. and Davidson, R. L., eds., Petroleum Processing
        Handbook. McGraw-Hill, New York (1967).

120.  Kinney, J.  E.,  "Fusing the Phenol Frenzy," Proc.  15th Ind.
        Waste Conf.. Purdue  Univ., p.  29  (I960).
                                   98

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