WATER POLLUTION CONTROL RESEARCH SERIES • 12020 2/70
Petrochemical Effluents
Treatment Practices
DETAILED
U.S. DEPARTMENT OF THE INTERIOR • FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
-------
WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Reports describe
the results and progress in the control and abatement
of pollution of our Nation's waters. They provide a
central source of information on the research, develop-
ment, and demonstration 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.
-------
THE CHARACTERISTICS AND POLLUTIONAL PROBLEMS
ASSOCIATED WITH PETROCHEMICAL WASTES
Detailed 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
-------
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.
-------
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.
-------
TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS i
TABLE OF CONTENTS ii
LIST OF TABLES ix
LIST OF FIGURES xii
RESEARCH NEEDS - CONCLUSIONS AND RECOMMENDATIONS xiv
CHAPTER I xiv
CHAPTER II xiv
CHAPTER III xxiv
CHAPTER IV xv
CHAPTER V xv
CHAPTER VI xvi
CHAPTER VII xvii
CHAPTER VIII xix
Chapter
I HISTORY OF THE PETROCHEMICAL INDUSTRY 1-1
PRE-WORLD WAR II 1-1
WORLD WAR II 1-2
POST WORLD WAR II 1-2
Principal Products and Production Capacity 1-2
Comparison With Entire Chemical Industry 1-3
Geographical Location 1-3
Water Use 1-7
REFERENCES I-II
II DESCRIPTION OF THE PETROCHEMICAL INDUSTRY II-l
PRINCIPAL PETROCHEMICAL PRODUCTS AND INTER-
MEDIATES II-l
11
-------
Page
Categorization of Products II-3
Olefins II-3
Aromatics II-8
Paraffins 11-10
Miscellaneous Petrochemicals 11-10
PROJECTED GROWTH OF THE PETROCHEMICAL INDUSTRY 11-11
Plastics and Resins 11-14
Synthetic Fibers 11-15
Synthetic Rubbers 11-15
Other Petrochemical Products and Inter-
mediates 11-15
Effect of New Products on Growth 11-16
REFERENCES 11-17
III PETROLEUM RAW MATERIALS III-l
NATURAL GAS III-l
CRUDE PETROLEUM III-2
REFINERY GASES II1-3
LIGHT TOPS III-3
HEAVY FRACTIONS III-5
AROMATICS FROM PETROLEUM III-5
REFERENCES HE-7
IV PETROCHEMICAL PROCESSES IV-1
PRIMARY CONVERSION PROCESSES IV-1
Distillation IV-1
Extraction IV-2
Adsorption and Absorption IV-2
Crystallization IV-2
111
-------
Page
SECONDARY CONVERSION PROCESSES IV-3
Oxidation IV-5
Halogenation IV-9
Nitration and Sulfonation IV-10
Alkylation IV-11
Dehydrogenation IV-12
Polymerization IV-12
Other Processes IV-13
PROCESSES AS WASTE SOURCES IV-14
By-Product Formation IV-14
Side-Product Formation IV-14
Incomplete Reactions IV-14
Mechanical and Accidental Losses IV-14
REFERENCES IV-24
CHEMICAL AND PROCESS RELATED CLASSIFICATION OF WASTES V-l
COOLING WATER V-2
PROCESS EFFLUENTS V-2
Solvent Processes V-3
Caustic Washes V-3
Acidic Wastes V-3
Washing and Scrubbing Operations V-4
Crude Petroleum Desalting V-4
Other Sources V-4
CHEMICAL CLASSIFICATION OF PETROCHEMICAL WASTES V-4
Inorganic Compounds V-5
Metals V-5
Non-metals V-5
Organic Compounds V-7
Hydrocarbons V-7
Substituted Organic Compounds V-8
IV
-------
a. organic acids and their salts v"8
b. alcohols V-9
c. aldehydes and ketones ^"^
d. esters V-10
e. ethers V-10
f. halogenated hydrocarbons V-10
g. nitrogenated compounds V-ll
h. phenolic compounds V-12
i. organic sulfur compounds V-12
Miscellaneous Organics V-14
REFERENCES , V"15
VI WASTE POLLUTIONAL EFFECTS AND THEIR CHARACTERIZATION VI-1
EFFECTS OF POLLUTION ON RECEIVING WATER VI-1
Aesthetic Effects VI-1
Biological Effects VI-2
Miscellaneous Effects VI-9
EFFECTS OF POLLUTION ON WATER USE AND REUSE VI-10
Water Quality for In-Plant Reuse VI-10
Cooling Water VI-10
Process Waters VI-10
Water Quality Required for Other Users VI-12
Agriculture Uses VI-12
Industrial Uses VI-12
Effects on Water Treatment Processes VI-12
Effects on Groundwater VI-14
PHYSIOLOGICAL EFFECTS OF PETROCHEMICAL WASTES VI-14
Taste and Odor VI-16
Toxicity VI-19
Toxicity to Microorganisms VI-21
Fish Toxicity VI-22
-------
CONVENTIONAL POLLUTIONAL PARAMETERS VI-34
Acidity VI-35
Alkalinity VI-35
Color and Turbidity VI-44
pH VI-44
Organic Material VI-45
Biochemical Oxygen Demand VI-45
Chemical Oxygen Demand VI-50
Total Organic Carbon VI-51
Total Oxygen Demand VI-51
Immediate Oxygen Demand VI-52
Solids VI-52
Surface Activity VI-52
Taste and Odor VI-53
Temperature VI-53
Toxicity VI-54
Oils VI-54
Miscellaneous Pollutant Parameters VI-54
Phenols VI-54
Inorganic Ions VI-54
Volatility VI-55
Heavy Metals VI-55
Total Plant Effluent Analysis VI-55
IDENTIFICATION AND MONITORING METHODS VI-56
Chemical Methods of Analysis VI-56
Inorganic Chemicals VI-56
Organic Chemicals VI-58
Biological Methods VI-63
REFERENCES VI-68
•4-VII TREATMENT AND CONTROL OF PETROCHEMICAL WASTES VII-1
VI
-------
REDUCTION OF WASTE LOADS BY INTERNAL IMPROVE-
MENTS vii-i
Reduction of Raw Material Losses VII-1
Recovery of Usable Reaction Products VII-2
Process Modifications VII-7
Water Reuse VII-8
In-Plant Control VII-10
Waste Stream Segregation VII-10
PHYSICAL TREATMENT PROCESSES VII-11
Gravity Separation VII-H
Oil Separation VII-11
Sedimentation VII-16
Stripping Processes VII-20
Solvent Extraction VII-23
Adsorption VII-25
Combustion VII-26
Filtration VII-30
Miscellaneous Treatment Methods VII-30
CHEMICAL TREATMENT METHODS VII-33
Neutralization and pH Adjustment VII-33
Coagulation - Precipitation VII-39
Oxidation Processes VII-42
Miscellaneous Methods VII-51
BIOLOGICAL TREATMENT PROCESSES VII-51
General Considerations VII-51
Biodegradability VII-51
Nutrients VII-55
Neutralization Requirements VII-56
Equalization VII-57
Pre- and/or Primary Treatment VII-58
Temperature VII-58
vii
-------
Page
Activated Sludge Processes VII-61
Trickling Filter Processes VII-69
Aerated Lagoons VII-70
Waste Stabilization Ponds VII-74
Miscellaneous Biological Treatment Processes VII-78
Multiple Biological Treatment Schemes VII-78
OTHER METHODS OF DISPOSAL VII-81
Dilution VII-81
Discharge Into Municipal Sewerage Systems VII-85
Deep Well Disposal VII-85
Ocean Outfall VII-86
Submerged Combustion VII-91
Incineration of Liquid Wastes VII-91
REFERENCES VII-93
VIII ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT VIII-1
THE COST OF WASTE TREATMENT VIII-1
Primary Treatment VIII-2
Biological Treatment Processes VIII-2
Tertiary Treatment Processes VIII-10
Ion Exchange VIII-IO
Carbon Adsorption VIII-21
Sludge Handling and Disposal VIII-21
Ultimate Disposal VIII-21
RETURNS TO THE PETROCHEMICAL INDUSTRY VIII-21
REFERENCES VIII-27
APPENDIX I - PROCESS INFORMATION
A - Primary Petrochemicals
B - Common Intermediates
C - Third-Generation Petrochemicals
APPENDIX II - Major Petrochemical Products and
Wastes Profile
viii
-------
LIST OF TABLES
Table Title
II-1 PRINCIPAL ETHYLENE-BASED PRODUCTS I:L"9
II-2 PROJECTION OF UNITED STATES PETROCHEMICAL
PRODUCTION CAPACITY FOR SELECTED CHEMICALS 11-12
IV-1 PETROCHEMICAL PROCESSES AS WASTE SOURCES IV-15
IV-2 CALCULATION OF HYDROCARBON LOSSES FROM PROCESS
EQUIPMENT IN AN ETHYLENE PLANT IV-21
VI-1 FIVE-DAY BOD VALUES FOR SOME PURE ORGANIC
COMPOUNDS OFTEN FOUND IN PETROCHEMICAL
PLANTS VI-4
VI-2 LETHAL TEMPERATURES FOR SOME SELECTED FISH
SPECIES VI-8
VI-3 SOLUBILITY OF COMMON SALTS VI-11
VI-4 WATER QUALITY FOR SELECTED AGRICULTURE USES VI-13
VI-5 ORGANIC CHEMICAL POLLUTANTS IDENTIFIED IN
GROUNDWATER VI-15
VI-6 DETECTABLE CONCENTRATIONS OF SOME PETRO-
CHEMICAL COMPOUNDS CAUSING TASTE AND ODOR
IN WATER VI-17
VI-7 SOME ORGANIC CHEMICALS CAUSING ADVERSE TASTES
IN FISH VI-20
VI-8 TOXICITY OF SOME SELECTED PETROCHEMICALS TO
CHLORELLA PYRENOIDOSA VI-23
VI-9 TOXICITY BIOASSAY RESULTS VI-26
VI-10 TYPICAL WASTE CHARACTERISTICS OF PRIMARY CON-
VERSION AND REFINING PROCESSES VI-36
VI-11 TYPICAL SPENT CAUSTIC STREAM CHARACTERISTICS VI-37
VI-12 TYPICAL ACID WASTE CHARACTERISTICS VI-38
VI-13 TYPICAL PROCESS WASTE CHARACTERISTICS - MIS-
CELLANEOUS VI-40
VI-14 TYPICAL WASH WATER CHARACTERISTICS (SCRUBBING
PROCESSES) VI-43
ix
-------
Table Title
VI-15 TOTAL PLANT EFFLUENT ANALYSES VI-47
VII-1 USABLE SIDE-PRODUCTS FROM SOME TYPICAL PETRO-
CHEMICAL PROCESSES VII-5
VII-2 SPECIFIC APPLICATIONS OF OIL SEPARATORS IN THE
PETROCHEMICAL INDUSTRY VII-12
VII-3 TYPICAL EFFICIENCIES OF OIL SEPARATION UNITS VII-15
VII-4 SEDIMENTATION OF SOME PETROCHEMICAL WASTES VII-18
VII-5 PERFORMANCE AND OPERATING CHARACTERISTICS
OF FLOTATION UNITS TREATING PETROCHEMICAL
WASTES VII-19
VII-6 AVERAGE OPERATING CHARACTERISTICS OF SOUR
WATER STRIPPERS VII-21
VII-7 SOLVENTS USED TO EXTRACT PHENOLS FROM WASTE-
WATER VII-24
VII-8 DESTRUCTION OF PETROCHEMICAL WASTES BY COM-
BUSTION METHODS VII-27
VII-9 TYPICAL FILTRATION APPLICATIONS IN PETRO-
CHEMICAL WASTE TREATMENT VII-31
VII-10 TYPICAL APPLICATIONS OF NEUTRALIZATION OF pH
ADJUSTMENT TO PETROCHEMICAL WASTES VII-35
VII-11 COAGULATION AND SEDIMENTATION OF PETROCHEMICAL
WASTES VII-40
VII-12 OXIDATION PROCESSES USED IN PETROCHEMICAL
WASTE TREATMENT VII-43
VII-13 DESIGN AND EFFICIENCY OF SOME SULFIDE OXIDA-
TION UNITS VII-46
VII-14 OZONATION OF SYNTHETIC RUBBER PROCESS WASTES VII-50
VII-15 RELATIVE BIODEGRADABILITY OF CERTAIN ORGANIC
COMPOUNDS VII-53
VII-16 WASTEWATER CHARACTERISTICS REQUIRED FOR
OPTIMUM BIOLOGICAL TREATMENT VII-59
VII-17 ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL
WASTES VII-65
VII-18 TRICKLING FILTER TREATMENT OF PETROCHEMICAL
WASTES VII-71
x
-------
VII-20
VII-21
VII-22
VII-23
VII-24
VII-25
VIII-1
VIII-2
AERATED LAGOON TREATMENT OF PETROCHEMICAL
WASTES
WASTE STABILIZATION PONDS
MISCELLANEOUS BIOLOGICAL TREATMENT PROCESSES
FOR PETROCHEMICAL WASTES
MULTIPLE BIOLOGICAL TREATMENT SYSTEMS FOR
PETROCHEMICAL WASTES
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION
POLLUTANTS REQUIRING SURFACE TREATMENT PRIOR
TO DEEP WELL INJECTION
TYPES OF WASTE TREATMENT USED IN THE PETRO-
CHEMICAL AND CHEMICAL INDUSTRIES
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
OPERATING COSTS - WASTE TREATMENT PLANTS
VII-75
VII-77
VII-79
VII-82
VII-87
VII-90
VII-92
VIII-3
VIII-17
xi
-------
LIST OF FIGURES
Figure
Title
1-1 PETROCHEMICAL END-USES 1-4
1-2 PRODUCTION OF ORGANIC CHEMICALS IN THE UNITED
STATES 1-5
1-3 LOCATION OF HYDROCARBON PROCESSING PLANTS 1-6
1-4 TOTAL WATER INTAKE FOR CHEMICAL AND ALLIED
PRODUCTS INDUSTRY 1-9
1-5 CLASSIFICATION OF WATER USED BY THE PETRO-
CHEMICAL INDUSTRY 1-10
II-l FIRST-GENERATION PETROCHEMICALS II-2
II-2 PRINCIPAL PRODUCT DERIVATIVES FROM THE OLEFINS II-4
II-3 PRINCIPAL PRODUCT DERIVATIVES FROM THE ARO-
MATICS II-5
II-4 PRINCIPAL PRODUCT DERIVATIVES FROM THE PARAFFINS II-6
II-5 PRINCIPAL PRODUCT DERIVATIVES FROM VARIOUS
SOURCES II-7
III-l PRIMARY DISTILLATION OF CRUDE PETROLEUM III-4
IV-1 PRIMARY CONVERSION PROCESSES IV-4
IV-2 SECONDARY CONVERSION PROCESSES IV-6
V-l SOLUBILITY OF PHENOLS IN WATER V-13
VI-i SCHEME FOR IDENTIFICATION OF TRACE ORGANICS VI-64
VII-1 CAUSTIC REGENERATION PROCESSES VII-4
VII-2 SPENT CAUSTIC NEUTRALIZATION VII-38
VII-3 SULFIDE OXIDATION UNIT VII-47
VII-4 TEMPERATURE EFFECT ON COD REMOVAL VII-60
VII-5 PARAMETER RESPONSE TO ORGANIC LOADING VII-63
VII-6 BIOLOGICAL TREATMENT IN A COOLING TOWER VII-80
VIII-1 CAPITAL COST RELATIONSHIP - EQUALIZATION VIII-6
VIII-2 CAPITAL COST RELATIONSHIP - NEUTRALIZATION VIII-7
VIII-3 CAPITAL COST RELATIONSHIP - OIL SEPARATION VIII-8
VIII-4 CAPITAL COST RELATIONSHIP - PRIMARY SEDIMEN-
TATION VIII-9
XII
-------
Figure
Title
VIII-5
VIII-6
VIII-7
VIII-8
VIII-9
VIII-10
VIII-11
VIII-12
VIII-13
VIII-14
VIII-15
VIII-16
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
AERATORS
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
CAPITAL COST RELATIONSHIP
THICKENING
LAGOONS
AERATED LAGOON
ACTIVATED SLUDGE
MECHANICAL SURFACE
FINAL CLARIFIER
TRICKLING FILTERS
ION EXCHANGE
CARBON ADSORPTION
FLOTATION
CAPITAL COST RELATIONSHIP
TION
CAPITAL COST RELATIONSHIP
DISPOSAL
VACUUM FILTRA-
TOTAL SLUDGE
CAPITAL COST RELATIONSHIP - INCINERATION
VIII-11
VIII-12
VIII-13
VIII-14
VIII-15
VIII-16
VIII-19
VIII-20
VIII-23
VIII-24
VIII-25
VIII-26
Xlll
-------
RESEARCH NEEDS - CONCLUSIONS AND RECOMMENDATIONS
CHAPTER I:
It is concluded that the petrochemical industry will continue
to grow and diversify. The chemical and allied products industry is
expected to increase from the present 5.5 billion gallons per year
to 23 billion gallons per year by year 2000. The production and
sales of organic chemicals is expected to increase from the present
production of 135 billion pounds per year to 200 billion pounds per
year by 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 to 65 percent of the total water use. The industrial
growth rates by geographical areas through 1975 will be 25, 15, and
10 percent, respectively, for the Pacific Coast and Alaska areas, Gulf Coast
area, and Southeast, Puerto Rico and Virgin Islands area.
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 pro-
cesses; advanced methods of waste handling; changes in water quality
criteria for updated processes; and changes in industrial growth
patterns.
CHAPTER II:
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 production. It is expected that the percen-
tage 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 to 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.
CHAPTER III:
It is concluded that there will be no significant changes in
petrochemical feedstocks, although the increasing demand for ethylene
and butylene has required the petrochemical industry to look for
xiv
-------
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.
CHATTER IV:
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 charac-
teristics of their wastewaters are fairly well understood. The
ranges of the waste volumes and organic concentrations vary consid-
erably. Within the same process at different plant sites, the pol-
lutant loads may range by more than one order of magnitude. Typically
the reaction efficiency in the petrochemical 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 con-
version efficiency, the practice is highly dependent on market con-
ditions. In addition to produce 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 treatment 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 to test the model data and demonstrate
the interrelationships of product handling with wastewater treatment
costs.
CHAPTER V:
It is concluded that many of the conventional parameters, as
compared to those developed for characterizing domestic wastewaters,
do not adequately define the potential pollution characteristics
of petrochemical wastes. In many cases the pertinent characteristics
of a waste stream were ignored, the analytical procedures were inade-
quate for such complex wastes, and much of the reported data have been
misinterpreted. Significant 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 bio-
chemically; toxicity as reflected in both microbial and higher forms
of plant and animal life, including man; interferences between petro-
chemical process waste constituents and reagents used in conventionally-
accepted organic and inorganic characterization analyses; and avail-
ability of nutrients.
xv
-------
It is recommended that a comprehensive and coordinated evalua-
tion program be developed specifically for standardizing the charac-
terization 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 govern-
mental and industrial use. The latter study would involve an evalua-
tion 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.
CHAPTER VI:
It is concluded that petrochemical wastes may provide poten-
tial pollutants in the form of concentrated oxygen-demanding organic
and inorganic materials, organic compounds not amenable to bio-
logical degradation, oil and oil-like substances, volatile and non-
volatile suspended materials, color contributing solutions, toxic
fractions, compounds responsible for taste and odors, heat, floatables
and polymeric products, and agents which interfere with conventional
analytical techniques and increasing problems in the treatment of
heated waters.
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
standardize the evaluation of the potential pollutional characteris-
tics 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
controlled tests should be conducted to establish the BODr/BOD ratio.
xvi
-------
It is additionally recommended that many of the more prevalen>
petrochemical compounds be analyzed in terms of unit weight of BOD,
COD, TOC, and IOD per unit weight of the compound. A similar repre-
sentation per unit weight of suspended solids discharged from various
related processes would be of value.
Special properties of selected waste streams should be studied
with respect to fish "tainting M(taste and odors in both fin
fish and shell fish),induced changes in the surface activity of
receiving waters, interaction of waste with chlorine and other waste
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.
CHAPTER VII:
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 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 procesesses are often overlooked as a potential disposal
process, particularly 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 contami-
nated 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 modifications) 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 develop-
ment of increased product and feedstock recovery, improved house-
keeping, separation of non-contaminated wastes from waste streams, and
separation of concentrated nonsoluble or otherwise solid fractions
near each source.
xvii
-------
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 in
two categories: (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 needs 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 influence 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 warmer. Emphasis should be
directed to evaluating 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.
(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. An evaluation of the effect of various wastes on bio-
flocculation, 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
estimated.
3. Methods of biological process modifications to maxi-
mise COD reduction should be considered.
4. A determination of the effects of various waste-
waters on streams and brackish waters in terms of both biodegradation
rates and reaeration rates should be made.
5. A more satisfactory way of evaluating -
in brackish and salt waters should v
xviii
-------
6. The advantages (if any) of two-stage biological
treatment versus single-stage biological treatment should be deter-
mined. Similarly, the advantages (if any) of tertiary treatment
over other disposal means should be investigated.
7. The availability of complexed forms of nitrogen and
phosphorus as a nutrient source to microorganisms in biological
waste treatment 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
municipal wastes should be established.
CHAPTER VIII:
It is concluded that most waste streams from petrochemical
plants will require some form of solids or oil separation, waste
stream separation and pretreatment, and secondary biological treat-
ment. The cost of this wastewater treatment can be reduced consider-
ably by in-plant reuse of product waste streams and wastewater in
general. Trends toward the co-treatment and joint treatment of
industrial wastewaters necessitates the establishment of a formula
for equitably prorating pollution control costs.
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.
xix
-------
CHAPTER I
HISTORY OF THE PETROCHEMICAL INDUSTRY
The use of petroleum for the manufacture of chemical pro-
ducts is a relatively new addition to the chemical world. After
the industry gained momentum to meet the demands of the Second
World War, the growth rate continued to increase yearly. Modernized
techniques and methods have been developed to locate and secure new
sources of raw materials as the petroleum industry confronts the
challenge of dwindling supplies. The history of this complex of
industries is interesting and provides a foundation for understanding
the fundamentals of the various operations involved.
PRE-WORLD WAR II
It appears that the first proposal to extract useful chemical
derivatives from petroleum occurred in the late 19th century, but
no chemicals of significance were produced until just prior to World
War I. The first use of a petroleum fraction in a chemical process
occurred in 1908 when the Germans used a gasoline fraction to prepare
mononitrotoluene for dye production (Anon., Shell, 1966). This
process was modified during the First World War to produce TNT.
The United States petrochemical industry had its inception
in 1919 to 1920 as a result of research initiated during the war.
In 1917, petroleum-derived propylene was used to produce acetone
(Anon., Shell, 1966), but the first petrochemical produced in com-
mercially significant quantities was isopropanol, developed by New
Jersey Standard Oil Company in 1920 (Anon., Bus. Wk.,1960). The
principal source of petrochemicals following World War I was re-
finery off-gases. These gases had traditionally been burned, but
manufactures developed means for converting them to valuable chemical
products.
Probably the most predominant feature of the period between
the two world wars was the introduction of ethylene oxide derivatives
into the chemical industry. Propylene was also used extensively in
chemical manufacture, and butene was converted to ketones which were
used in various solvents (Goldstein, 1958). Most of the products
manufactured during this time were straight-chain aliphatic compounds.
The manufacture of ammonia and nitrogeneous fertilizers using natural
gas was also begun during this period (Anon., Shell, 1966). The
petrochemical industry steadily increased in size during these years.
1-1
-------
WORLD WAR II v
The petrochemical industry gained great impetus as a result
of the Second World War. When the war started the United State's
supply of imported rubber was significantly reduced. Since there
was an imperative need for synthetic rubber production the govern-
ment was forced to spend $900 million in the construction of 30
major synthetic rubber plants using butadiene and styrene from 1940
to 1950 (Anon., Bus. Wk., 1960). Many other uses for petroleum
hydrocarbons were developed during the war years; alcohols and
synthetic detergents were manufactured from petroleum materials,
and production of petroleum-based aromatics was initiated during this
period. Previously, aromatics had primarily been produced from
coal, and coke; aromatics obtained from petroleum rapidly replaced
these other sources. Improved separation methods for other hydro-
carbons added more petrochemicals to the list of products.
POST WORLD WAR II
Since World War II, the petrochemical industry has experi-
enced a tremendous growth; production increased more than five times
from 1945 to 1960. In 1960 the Department of Commerce listed more
than 3,000 different petrochemical products (Anon., Bus. Wk., 1960) with
organic chemicals constituting the major product of the industry.
Petrochemical production increased from 1.0 million tons of product
in 1945 to 11.5 million tons of product in 1963 (Anon., Shell, 1966).
This rapid expansion continued, and 81 new projects were planned or
are underway in the United States as of September, 1967 (Aalund, 1967).
Principal Products and Product Capacity
Organic chemicals are the chief product of the petrochemical
industry; however, there are several inorganic petrochemicals which
are manufactured in large quantities. Ammonia, sulfur, and carbon
black are all important products. For example, the domestic output
potential of ammonia as of September, 1967, was 17.3 million tons per
year, an increase of 33 percent from 1966 (Aalund, 1967). The
ammonia produced is used mainly in the manufacture of nitrogeneous
fertilizers. Organic petrochemicals are used in a wide variety of
products, including synthetic fibers, synthetic rubbers, plastics,
resins, synthetic detergents, a variety of automotive chemicals,
as well as numerous other products.
There has been a phenomenal growth of plastic production
during the last decade. Polyethylene production was 2.6 billion
pounds while polystyrene and vinyl production was much less than
two billion pounds each in 1966 (Sawyer, 1966). Polyethylene is
used in a variety of plastic products which include packaging mate-
rials for industrial and consumer goods; molded plastic products of
all types; and some extruded plastics such as floor tiles, cable
coverings, and hoses. Vinyls are used in surface coatings and many
1-2
-------
industrial plastic products, while polystyrenes are found in plastic
foams and adhesives (Lewis, 1966). The increasing use of plastic
both in industry and at home indicates that continued growth can be
expected.
The production of synthetic rubber is another rapidly growing
petrochemical industry. In 1966,synthetic rubber constituted 75
percent of the total rubber used in the United States (Sawyer, 1966).
Similar figures were available for almost every petrochemical product,
and growth predictions indicate that the industry will continue to
expand at this rapid rate. Distribution of the many end-uses of
petrochemicals is graphically illustrated in Figure 1-1. Miscel-
laneous uses, which include synthetic detergents and industrial
chemicals, are accounting for an increasing share of the total
production capacity, and can be expected to increase in number as
more chemicals are developed and new uses for existing chemicals are
discovered.
Comparison With Entire Chemical Industry
There are several reasons for the rapid growth of the petro-
chemical industry, some of which include the expansion of industries
which process petrochemicals into finished products, such as
plastics and synthetic fibers; availability of cheap and abundant
supplies of petroleum raw materials; low cost of producing petroleum-
based chemicals as compared to production using non-petroleum
sources; and increasing cost and limited supply of some non-petroleum
raw materials (Stanley, 1963). The increase of petroleum-based
stock in the production of organic chemicals is graphically depicted
in Figure 1-2. In 1963, more than 85 percent of the United States
organic chemical production was petroleum-based as compared to only
56 percent in 1950.
Graphical Location
The locations of the major petrochemical plants in the
United States are presented in Figure 1-3, the majority of which
are situated along the Gulf Coast between New Orleans, Louisiana,
and Brownsville, Texas. This area contained approximately 80 percent
of the nation's petrochemical production capacity in 1960. The two
largest complexes, located at Beaumont and Houston, Texas , contribute
30 percent of total United States petrochemical output (Anon., Bus.
Wk.,1960). Primary reasons for growth of the industry in this area
include the availability of sea transport, location of 75 percent of
United States petroleum reserves within easy reach, an abundance of
fresh water required to meet the industrial demand, and the low
cost of fuel available. Also, it is advisable for both economic and
technical considerations to locate plants in close proximity since
transferring chemicals from one plant site to another is common and
usually done by pipeline. The Gulf Coast is a relatively flat area
which makes pipeline construction economical. This region is now and
should continue to be the center of petrochemical activity in the
United States.
1-3
-------
AUTOMOTIVE
AND AVIATION
AGRICULTURE
RUBBER
SURFACE
COATINGS
PLASTICS
SYNTHETIC
FIBERS
EXPLOSIVES
MISCELLANEOUS
1952
1957
;^s^^^^
I I I I
05 10 15
PRODUCTION TONNAGE (%)
FIGURE 1-1
PETROCHEMICAL END -USES
(Reference 7)
1-4
20
-------
FROM PETROLEUM
ALL OTHER SOURCES
o
o
z>
o
o
14 -
12 —
10 -
0 8
CO
6
CO
4-
22
0
1945 1950 1955 I960 1961 1962 1963
YEAR
FIGURE 1-2
PRODUCTION OF ORGANIC CHEMICALS IN THE UNITED STATES
(Reference 4)
1-5
-------
• REFINERY
A NATURAL GAS
PROCESSING PLANT
• PETROCHEMICAL PLANTS
(from Anon., Hydroc.
Proc. May 1966
FIGURE 1-3
LOCATION OF HYDROCARBON PROCESSING PLANTS
(Reference Anon., Hydroc. Proc., May 1966)
-------
Water Use
Water use data for the petrochemical industry as distin-
guished from the total chemical industry is unaccomplished in the litera-
ture. However, historical data available from the chemical industry
indicate that water intake increased an average of 45 percent during
the decade from 1939 to 1949 (Anon., Water in Ind.,1950). These
figures came from 154 plants which reported to the survey and
represent increases in water use by each plant. This percentage
increase does not include the water use requirements of new
chemical plants constructed during this period. This represents a
considerable quantity, probably much greater than the increase
cited. The 1954 Census of Manufacturers showed that the chemical
and allied products industry used 2,378 billion gallons of water
per year. These data were obtained from the 1,164 plants which
used 20 million gallons or more of water per year and constituted
95 percent of the water intake by the industry. Water reuse was
practiced by 67 percent of these plants, and the gross water used
was 4,032 billion gallons. The chemical industry utilized 83
percent of the water intake for cooling purposes, 9.5 percent as
process water, and the balance for other miscellaneous purposes.
The water used by the chemical industry represented 23.4 percent of
the total industrial water use in 1954 (Senate Kept.No. 8.,1960).
The 1961 Census of Manufactureres indicated that in 1959
there were 933 chemical plants using 20 million gallons or more
per year and their total water intake comprised 3,240 billion
gallons per year. Some 74 percent of these plants reused their
water, and the gross industrial water use by the chemical industry
was 5,225 billion gallons per year. Approximately 66 percent of the
water intake was consumed for cooling, a considerable drop from the
83 percent reported in 1954. Process water accounted for 14 percent
and water used for generation of steam and electricity for 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.
Later water use data for the chemical industry was collected
in 1962 (Anon., Water in Ind., 1965). This survey included 875 plants
in the United States which employed approximately half of the total
number of persons who worked for the chemical and allied products
industries. These data should not be considered to represent the entire
chemical industry since the definition of the industry by some
includes packaging, blending, mixing, and distributing of chemical
products, most of which use little or no water (Anon., Water in Ind.,
1965). The total water withdrawal for these plants was 3,600 billion
gallons in 1962. These plants reported using a total of 7,875
separate processes, 19 percent of which had no water-borne wastes.
Water used for cooling constituted 65 percent of the water intake by
the chemical industry in 1962.
1-7
-------
The water intake by the chemical and allied products indus-
tries projected to the year 2000 is shown in Figure 1-4. Actual
water intakes for plants using 20 million gallons or more per year
are plotted for 1954 and 1959. The projected data were obtained
from a United States Senate Report, and those projections indicate
that the chemical industry will be the number one industrial water
consumer by the year 2000 (Senate Kept. No. 8 ., 1960) . One-fifth of
the industrial water demand in that year will have to be supplied
in the Gulf Coast region since it will be the center of the
chemical industry for reasons previously cited. The water use data
presented above are summarized in Figure 1-5.
1-8
-------
30
Is
» 5 25
- o
2 O
i | 20
r ~
D CD
ro
iJ O
* K
2 >-
Y ^
3 O
O
CM
15
10
0
PROJECTION
BY RESOURCES
FOR THE FUTURE
PROJECTION BY
BUSINESS AND
DEFENSE SERVICES
ADMINISTRATION
1950
1960
1970 I960
YEAR
FIGURE 1-4
1990
2000
TOTAL WATER INTAKE FOR CHEMICAL AND
ALLIED PRODUCTS INDUSTRY
1-9
-------
1962
INFORMATION NOTj
AVAILABLE !
5 1959
LU
954
0
20 40 60 80
TOTAL WATER USED (%)
100
COOLING
WATER
STEAM 8 POWER
GENERATION
PROCESS
WATER
MISCELLANEOUS
USES
FIGURE 1-5
CLASSIFICATION OF WATER USED BY THE PETROCHEMICAL INDUSTRY
1-10
-------
REFERENCES - CHAPTER I
1. Aalund, L., "Petrochemical Activity Hits a New High Around
the World," The Oil and Gas Journal, v. 65, p. 108 (Sept.
4, 1967).
2. 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).
3. Anon., 1958 Census of Manufacturers, Summary of Statistics,
v. 1, U. S. Dept. of Commerce, Bureau of the Census,
Washington, D. C. (1961).
4. Anon., The Petroleum Handbook, Shell International Petroleum
Co., Ltd., 5th Edition, Balding and Mansell, Ltd. eds.,
London (1966) .
5. Anon., Water in Industry, National Assoc. of Manufacturers and
The Conservation Foundation, New York, N. Y. (1950).
6. Anon., Water in Industry, National Assoc. of Manufacturers and
Chamber of Commerce of the United States, New York and
Washington, D. C. (1965).
7. Anon., "Why Petrochemicals Are Appealing," Business Week,
Special Rept. p. 56 (Sept. 3, 1960).
8. Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,
Spon, London (1958).
9. Lewis, N. J., "Natural Gas Liquids For Petrochemicals: How
Big?" Hydrocarbon Processing, v. 45, n. 6, p. 195 (June 1966).
10. Sawyer, F. G. , "Best Picks for '66: Petrochemicals," Hydro-
carbon Processing, v. 45, n. 1, p. 161 (Jan. 1966).
11. Senate Reports, Future Water Requirements of Principal Water-
Using Industries,Select Committee onNational Water Resources,
86th Congress Committee Print No. 8 (1960).
12. Stanley, H. M., The Petroleum-Chemicals Industry, Lecture
Series 1963, No. 4, The Royal Institute of Chemistry (1963).
1-11
-------
CHAPTER II
DESCRIPTION OF THE PETROCHEMICAL INDUSTRY
"Petrochemicals" can be defined as any chemicals which are
derived from petroleum or natural gas. The phrase "petroleum-chemicals"
is preferred by some authors who dislike the former expression; but,
in general, the term "petrochemical" is acceptable.
The variety of chemicals that are petroleum-based is enormous,
and it would be impossible to prepare a complete list of petrochemical
products. Profiles of major petrochemical products, however, are
presented in Appendix I.
Many of the petrochemicals as defined herein are difficult
to categorize according to the Standard Industrial Classification
(SIC) numbers, although the applicable categories based on 1967
revisions include: SIC 2813 (industrial gases), SIC 2815 (cyclic
intermediates, dyes, organic pigments, and crudes), SIC 2818 (organic
chemicals), SIC 2819 (inorganic chemicals derived from petroleum),
SIC 2821 (plastic materials and resins), SIC 2871 (agricultural
fertilizers), and SIC 2873 (insecticides).
Petroleum-chemicals can be divided into two principal cate-
gories, organics and inorganics. One exception to this division is
carbon black, a complex chemical which can be classified neither
completely organic nor completely inorganic but still is considered
a petrochemical since petroleum is its principal source (Sherwood,
1964). In 1953, approximately 70 percent of the carbon black produced
was used as a reinforcing agent in rubber for tires (Conklin, 1953) .
The furnace process and the contact process are used for the
production of carbon black. Both processes produce an extremely
fine powder which is normally pelletized using a small amount of
water to render the carbon black amenable to packaging and shipping.
The furnace method requires additional water for cooling the furnace
gases and for capture of entrained carbon black. The hydrocarbon
feedstocks used to produce carbon black are varied, ranging from
crude petroleum to pure methane.
PRINCIPAL PETROCHEMICAL PRODUCTS AND INTERMEDIATES
In order to better illustrate the processing of petroleum
chemicals from raw material to final product, schematic diagrams
have been prepared. The primary or first-generation petrochemicals
derived directly from the petroleum raw materials are shown in Figure
II-l. With the exception of carbon black, which is not further
II-l
-------
PETROLEUM
RAW MATERIALS
FIRST-GENERATION PETROCHEMICALS
Crude Petroleum-
Natural Gas-
j— 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 II-1
FIRST GENERATION PETROCHEMICALS
II-2
-------
processed, all petrochemical products come from these primary chemicals.
The processes used in the conversion of raw petroleum to these first-
generation chemicals will be subsequently described. These primary
petrochemicals are followed through their intermediate products to
their end-products by Figures II-2 through II-5. Actually, most of
the products shown in these figures are not the final products used
by the consumer, but instead represent the raw materials used by the
industries in preparing consumer goods. The final stages of manufac-
turing are not included in this report because they ordinarily are
considered to be outside the realm of the "petrochemical" industry.
Categorization of Products
Each of the groups of first-generation petrochemicals is
considered separately. For example, the principal products manufac-
tured from the olefins are illustrated in Figure II-2. The products
obtained by using olefins as the chemical base are divided into
six categories: bases for plastics and resins, synthetic rubber
bases, synthetic fiber bases, components of synthetic detergents,
basic industrial chemicals, and basic chemicals for agriculture.
Obviously, many more subdivisions would be possible, but to prevent
an excessively complicated categorization, these six were chosen
and are appropriate for an investigation of this scope.
The category of basic industrial chemicals includes the
miscellaneous olefin products. These chemicals have a broad appli-
cation in industry in solvents; paint, varnish, and other surface
coating ingredients; pharmaceuticals, food processing and auto-
motive chemicals; and a myriad of other products which could not be
placed in one of the other five categories.
This system of product classification was used for each of
the primary petrochemical groupings shown in Figure II-l. Inorganics
and some miscellaneous hydrocarbons are classified together in Figure
II-5. Carbon black, which can be obtained directly from raw petroleum
or from primary petrochemicals, also is included under the primary
petrochemicals from which it is formed.
There are several families of organic compounds which contain
only carbon and hydrogen in their molecules. These compounds are
termed "hydrocarbons" and almost every petrochemical product which
is organic based, and most of them are, is based on a hydrocarbon raw
material. The principal hydrocarbons used by the petrochemical industry
include the olefins, the aromatics, and the paraffins. These families
of compounds constitute the primary petrochemicals and must be separa-
ted from the raw petroleum before they can be used as feedstocks for
chemical processes. A brief discussion of each of these primary groups
of compounds will indicate how they are obtained and used.
Olefins - Olefins, principally ethylene and propylene, are the
commercial bases for the majority of synthetic organic chemicals
produced in the United States (Stephenson, 1966). The olefins, also
II-3
-------
it-Generation Petrochemicals
Intermediate Chemicals
BASES
FOR
SYNTHETIC
BASES
SYNTHETIC
FIBER
BASES
SYNTHETIC
CHEMICALS
AGRICULTURAL
Ethylene
Higher Olefln
Ethylene
— T
B 7 -^
Fropylene
D cr c i
7
Eutylcnc
Higher Olefi
Ethylene
Bu cylene
Ethylene
Propylene
y p
——— —polyethylene
-,.,,, -.< , , r-Ethylene GlycoU- , Polyethylene Glyeole
Plchlorof-thnnr-"-1""1 r-^^iAo ' pniyirinvl rhlorlHes
, i Ethyl Benzene —Styrene- Polystyrene
r-umcnc r J Acet:one^ : Kpnxv R^s-fns
1 Phenol- • J Polyamides
Prop-lcrtf 'HH" Pn1 viirpt-hanes
fnl wpT-nptrl BTl*"
Chloride— J Glycerol Dlchlorohydrin Epoxy Resins
-i-Butylene — Diisobutylene Ifenanol
Peroxide
J Resins
Resins
»n,yi a«T,»on*. .=:t-yT-onp Stvrene-butadlene
Rubber
Brmr,-, «n* r*,iA* Tr-< =1 = Polvuxetharua
, — SEyrene— Styrene -butadiene
Rubber
-i-butyleae ^^ ***«;..
-"la-1 Acetylene Chloroprene Efeoprene Rubber
EthvlAlcohol Acet. Aldehyde 1 ftrr-^- "*?*•* *-
F*Vl"i" A™-^ = Rtthvlene Glvcols
1 Ethanolamines
Tnt-prrp-1 A7""h"T A ^-rlc. Anhydride
_ Isopcopanolaniinea
__ Propylene Oxide-ipropylene Glycols Polypropyleae Glycols
n-hiitanol i -hiri-nniM- - «»*-*! tx-erxt*.
— ~- Allyl Chloride ^ irichloropropane
Alcohol
Alcohol
, Non-ionic Detergents
tumcnc co ^^ ^^ analaminc-
„ P3 cnc AH -1 " 1 ^ If r
1 nC l^.t-101. 1 M ^4 J I\ »•
, Oetergent Alkylate Alkyl Aryl Sulfonate
ns__J 1 _____ Secondary Alkyl
Sul fates
1 Acetic Acid
•F 1 Acetic Anhydride
Ethyl Alcohol
Zth-lcn'?^'1" cla""1"
1 Ethylene Chloride ~ Tetraethyl Lead
• Echylene Dibromide
~ Isopropyl Ether
• Acetone
Methyl Isobutyl
Carbinol
•ccto a6 i n i
Additives
• Prapylerie rtjf.ide — Propylene Glycols
1 , — Polypropylene Glycols
i • Epoxy Resins
1 , — . — Trichloropropane
pn-butyleae | —Butadiene— _ _ Sulpholase
Bentoic Acid
~" — ~~ — Lubricating Oil
Additives
Carboxylic Acido
" "~" — _— Glycldyl Esters
— — — — Ethylene Bromide
• • • — Allyl Chloride - — • 1,2 Dlbromo 3-Chloro
Propane
1,~ DI>.Lloropropcna 1,_ Dichloraproptim
pene
j- • — Aldrln
*- Endrin
FIGURE II-2
PRIHCIPAL PRODUCT DERIVATIVES FROM THE OLEFINS
-------
First-Generation Petrochemicals
Intermediate Chemicals
Products
BASES FOR
PLASTICS,
RESINS
SYNTHETIC
RUBBER
BASES
SWTHETIC
FIBER
BASES
AROMATTfiS
BASIC
INDUSTRIAL
CHEMICALS
SYNTHETIC
DETERGENT
BASES
BASIC
AGRICULTURAL
RHEMlnAT.S
vylcnc
Rubber
Aromatics
Bcn~cnc Cyclohcxanc Adipic Acid Nylon
J Hexamethylene Diamine
Naphthenic Nnrhrh-ni- ^H
Acids *
f Ccmiplex Aromatics
Complex pltch
Aromatics
' Petroleum Resins
(BHC)
DDT
T> Phenol 1 — — 7.4-T1
acetic Acid (MCPA)
FIGURE II-3
PRINCIPAL PRODUCT DERIVATIVES FROM THE AROMATICS
II-5
-------
First-Generation Chemicals
Intermediate Chemicals
Products
BASES
FOR
PIASTICS
AND
RESINS
SYNTHETIC
RUBBER
BASES
SYNTHETIC
FIBER
BASES
PARAFFINS
BASIC
INDUSTRIAL
CHEMICAL
BASES
BASIC
AGRICULTURAL
CHEMICALS
SYNTHETIC
DETERGENTS
1 Methane 1
and Hydrogen
-open anc
I ropane
Higher Paraffins
Carbon Monoxide
and Hydrogen
Carbon Monoxide
anj
Hydrogen
C, „ Hydrocarbons
12 '
^
Formaldehyde .Acetaldehyde
Compounds
Op C C
A
Formaldehyde, Acetaldehyde
Compounds
' Chloroparaffins
' Methanol
Formaldehyde,
Other Oxygenate,
Compounds
Reinforcing Agsi
* Styrene-butadiene
Rubber
1 Acetaldehyde
Acetaldehyde ani
Other Oxygenated
Compounds
T Hydrogen Cyanide
' Nitric Acid
-onna
Nitrogeneous
Linearalkyl
Sulfonates
FIGURE II-4
PRINCIPAL PRODUCT DERIVATIVES FROM THE PARAFFINS
-------
FIRST-GENERATION CHEMICALS
INTERMEDIATE
CHEMICALS
PRODUCTS
Basic
Industrial
Chemicals
•Hydrocarbons
I.
Hydrocarbon
Solvents
Petroleum
Sulfonates
•
Synthetic
Detergent •
Bases
Synthetic
Fiber
Bases
Basic
Chemicals
Miscellaneous
Chemicals
| ORGANIC !•_•§•!
Hydrogen
Sulfide
• Hydrocarbons •
Hydrogen
Sulfide
Carbon
Black
Hydrogen
Sulfide
Hydrogen
~~ Sulfide
Sulfuric
Acid
Petroleum Sulfonated
Sulfonates Detergents
Strengthening
Agent
"ill Cm Carbon
Bisulfide
FIGURE II-5
PRINCIPAL PRODUCT DERIVATIVES FROM MISCELLANEOUS SOURCES
II-7
-------
known as alkenes, are characterized by a highly reactive double bond
which renders them extremely useful in a variety of synthesis reactions.
Each double bond in a compound indicates that two fewer hydrogen atoms
will be present than the maximum which can exist in a hydrocarbon.
This is termed "unsaturation." Dienes, which contain two double bonds,
are not strictly olefins by definition but undergo similar reactions.
The most important diene, and one of the more important petrochemicals,
is 1,3 butadiene, a major component of many synthetic rubber's (Noller,
1958).
Some of the main chemical processes for the conversion of
olefins into chemical derivatives are polymerization, hydration,
halogenation, epoxidation, alkylation, and hydrocarboxylation
(Stanley, 1963). The most important products which originate from
olefins are illustrated in Figure II-2. Ethylene is by far the most
important petrochemical raw material. The distribution of the
principal uses for ethylene are given in Table II-1. Propylene,
although not produced in the same quantities as ethylene, is also an
extremely important petrochemical feedstock, and the chemical pro-
ducts derived from it are listed in Table II-l. With the exception
of the butylene used in the manufacture of butadiene, the four-carbon
and higher olefins are not widely used in chemical manufacture.
Aromatics - All aromatic compounds can be considered deriva-
tives of benzene, and thus a discussion of the characteristics and
reactions of benzene will apply to the rest of the aromatics. The
molecular formula of benzene is CgH5 which would seem to indicate
that this compound, like the olefins, would be highly unsaturated;
however, the aromatic ring has been found to be almost as stable as
completely saturated hydrocarbons. This stability indicates that
double bonds found in the olefins are not present in benzene or the
other aromatics. It is now believed that the six carbon atoms in
the benzene molecule are arranged in a ring, connected to each other
by a hybrid bond having properties intermediate between those of a
single bond and a double bond (Noller, 1958). These hybrid bonds
are all of equal strength and are relatively unreactive. However, the
hydrogen atoms of the aromatic nucleus are more readily substituted
than those on saturated hydrocarbons. The principal petrochemical
reactions of aromatics involve substitution of these hydrogens and
include halogenation, nitration, sulfonation, oxidation of side-chains,
alkylation, and the Friedel-Crafts reaction which results in ketone
formation when an aromatic is reacted with an acyl halide.
The aromatics rank second only to the olefins in terms of
quantities of primary organic petrochemicals produced annually. Sub-
stantial amounts of these aromatics are still produced from coal and
coke, but petroleum-based aromatics are satisfying the increased demand
for these chemicals. Benzene is the most important of the aromatics in
terms of quantity produced, and in 1964, approximately 84 percent of
the total benzene production came from petroleum-based raw materials
(Sawyer, 1966). With the exception of naphthalene, all of the common
aromatic chemicals are derived principally from petroleum hydrocarbons.
II-8
-------
TABLE II-1
PERCENTAGE OF ETHYLENE AND PROPYLENE REQUIRED
FOR VARIOUS PRODUCTS
(Reference 20)
% Total Ethylene Used
Product For Particular Product
Polyethylene 30
Ethylene Oxide 24
Ethanol 17
Ethylbenzene 8
Ethylene Dichloride 7
Other 14
% Total Propylene Used
Product For Particular Product
Isopropanol 37
Propylene Trimer, Tetramer 23
Polypropylene 13
Propylene Oxide 1-2
Cumene 6.5
Other 8.5
II-9
-------
Some of the chemical products and intermediates which are
manufactured from aromatics are illustrated in Figure II-3. Obviously,
the schematic is not complete, but it does give a representation of
the major aromatic-derived chemical products.
Paraffins - Paraffins, also known as alkanes, are the
simplest family of hydrocarbons. All members of the aliphatic or
acyclic series (straight-chain compounds) can be considered to be
derived from them (Noller, 1958). The simplest constituent of this
class of compounds is methane, 0114. All other members of this family
differ from methane by multiples of one carbon and two hydrogen
atoms, that is, by CH2- All of the paraffins with four carbon atoms
or less are gases at standard temperature and pressure, while those
with five or more carbons are liquids or solids. Paraffins with
four or more carbon atoms can exist in branched forms, the number of
possible isomers of each compound increasing with the number of car-
bons .
Paraffins are the least reactive of the hydrocarbons and all
of the common processing steps require elevated temperatures and
pressures. The most important paraffin reactions include dehydro-
genation and cracking, which produce olefins, the principal petro-
chemical feedstocks. Chlorination and isomerization are also
utilized to a lesser extent by the petrochemical industry.
Naphthenes, of which cyclopentane and cyclohexane are the
most important in the petrochemical industry, can be considered
special types of paraffins. These compounds have a ring structure,
but unlike aromatic compounds, the carbon-carbon bonds exhibit
exactly the same characteristics as the bonds in the paraffins.
The principal paraffinic feedstocks used by the chemical
industry are the one- to five-carbon hydrocarbons (Sherwood, 1§64).
Straight-chain paraffins in the twelve-carbon range are now becoming
important in the manufacture of the new biodegradable detergents
(Sherwood, 1964). Large quantities of ethane and propane are con-
verted to ethylene since the demand for this petrochemical far
exceeds its availability. Other manufactured products using paraffins
as the base-chemical such as synthesis gas, a mixture of carbon
monoxide and hydrogen, are shown in Figure II-4.
Miscellaneous Petrochemicals - Other petrochemicals not
categorized in the strictest sense in the previous headings are also
important. Hydrocarbon solvents, such as white gas, containing both
paraffins and aromatics are manufactured in the normal course of
refining operations (Anon., Shell, 1966). These solvents are clas-
sified according to their aromatic content.
Sulfur is also an important petrochemical which is obtained
primarily in the form of hydrogen sulfide during the refining of
crude oil. The principal uses for the miscellaneous petrochemicals
are shown in Figure II-5.
11-10
-------
PROJECTED GROWTH OF THE PETROCHEMICAL INDUSTRY
The petrochemical industry has grown tremendously during the
past two decades. In the eight-year period from 1955 to 1963,
production of organic petrochemicals more than doubled (Sherwood,
1963) . Estimates of projected production capacity of particular
petrochemicals or products are constantly revised to reflect changes
in processes, consumer demands, and feedstocks. The projected data
in Table II-2 presents current estimates of consumption in 1975 for
the more important petrochemicals and products. Some of these
estimates were made as early as 1955, however, and the accuracy of
these projections is subject to question.
Several factors have been important in the rapid development
of the petrochemical industry. These factors include the use of
petroleum rather than alternative sources as a raw material, the
expansion of markets for petrochemical products, and the development
of new commercial petrochemical products. Future demand for petro-
chemicals and their products will be controlled by developments in
the end-use markets and newly developed products (Sherwood, 1963).
Petroleum has already essentially displaced alternate raw materials
in the manufacture of products having multiple raw material sources.
The outlook for growth in the entire petrochemical industry
is favorable. In 1955, petrochemical production constituted about
24 percent by weight of total chemical production;by 1970, it should
account for 41 percent according to this projection (McGrath, 1961).
However, the rapid growth of the industry may prove this estimate
to be conservative. On the basis of sales, the growth of this
industry is equally impressive. Petrochemical sales for 1966 were
estimated to be $12 billion and projected sales for 1970 exceed
$20 billion (Anon., Bus . Wk.,1966). The 1966 projection of petro-
chemical 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.
Growth of the petrochemical industry is also reflected by
the number of projects planned or under construction. In 1967, 81
new petrochemical projects were in the planning or construction
stage in the United States, compared to 41 the previous year (Aalund,
1967) . Global capital outlay for new petrochemical facilities was
$2.4 billion in 1965 (Sawyer, 1966).
In order to continually grow and expand, the petroleum
industry must be assured of sufficient quantities of raw materials.
If raw materials continue to be used at the consumption rates
reported in 1967, the nation's proven reserves of crude oil and
natural gas liquids will be consumed in nine years, and the natural
gas reserves will be exhausted in sixteen years (Anon., Chem. &
Engr. News., April 15, 1968). It is interesting to note that while
11-11
-------
TABLE II-2
PROJECTION OF UNITED STATES PETROCHEMICAL PRODUCTION
CAPACITY FOR SELECTED CHEMICALS
(References 1, 5, 21)
Products and
Petrochemical
Intermediates
Synthetic Fibers
Acetate
Acetic Anhydride
Nylon
Polyesters
Acrylic Fibers
Acrylonitrile
Plastics and Resins
Phenolic Resins
Phenol
Formaldehyde
Phthalic Alkyd and
Nonbenzenoid
Alkyd Resins
Phthalic Anhydride
Synthetic Glycerol
Styrene Resins
Styrene
Urea and Melamine Resins
Vinyl Resins
Polyolef ins
Polyethylene
Polypropylene
Surface-Active Agents
(Not Detergents Them-
selves)
E thano 1 amine s
United States
billions of
Production -
pounds/year
Recent Data
1954 year in parentheses
0.34
0.696*
-
0.035
0.097
0.2*
2.8 7.74
0.434 0.66
0.6*
1.03*
0.45 0.53
-
0.115*
0.481 1.25
0.500
0.265
0.524 1.55
2.16
0.57 4
0.66
1.03
0.063
(1962)
(1962)
(1962)
(1962)
(1962)
(1962)
(1967)
(1967)
1975+
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
11-12
-------
TABLE II-2 (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 Dichloride
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
11-13
-------
thousands of different petrochemicals are manufactured, fewer than
100 chemically different products constitute over 90 percent of the
total sales of organic chemical intermediates (Sherwood, 1963).
The following discussion will briefly elaborate on the prospective
growth for the more important petrochemicals and products.
Plastics and Resins
Plastics and resins, which are primarily used as construction
and packaging materials, are the most important petrochemical
products in terms of volume and projected growth (Stockton, et. al.,
1959). In 1962, 7.7 billion pounds of these materials were produced
in the United States with a corresponding domestic consumption of
over 6.9 billion pounds (Sherwood, 1963).
Polyolefins constitute the most important petrochemical
category in the plastic industry. By 1975, the world demand for
polyolefins should approach 35.2 billion pounds, four times greater
than the 1965 global output of these materials (Anon., Oil & Gas
-J.,1966). United States polyethylene production is expected to
increase 160 percent by 1975 (Anon., Bus. Wk., 1966). The importance
of polypropylene is also coming into focus. The production of this
propylene derivative has risen from 643 million pounds in 1967 to
an expected 825 million pounds in 1968. The 1969 production of poly-
propylene is predicted to be one billion pounds. (Anon., Chem. &
Engr. News..August 5, 1968). The polypropylene plastics should
account for 7.5 percent of the world polyolefin market by 1975
(Anon., Oil & Gas J..1966). There are indications,that a 350 percent
increase can be expected in polypropylene production from 1966 to
1975 (Anon., Bus. Wk.,1966); however, the production of propylene
could influence the availability of polypropylene and other propylene
derivatives. Consumption of propylene is expected to exceed seven
billion pounds in 1968 and this should continue to increase 10
percent annually for the next five years. Producers of propylene-
based products, such as polypropylene and acrylonitrile, are con-
cerned that limited supplies of propylene will restrict future output of
these derivatives (Anon., Chem._& Engr. News.,Augus t 5, 1968).
Projections for 1970 indicate that propylene demand for
chemical use will exceed supply and the price will increase from
2.2c/lbs to 2.5c/lb. There appears to be a need to manufacture
propylene by a direct process, since propylene is presently produced
only as a by-product of ethylene manufacture. Propylene availability
is therefore a function of ethylene demand. Because of the low unit
price of propylene, it is not expected that presently available
processes, such as pyrolysis, catalytic dehydrogenation, or oxidative
dehydrogenation (using !„) of propane will be economically justified
in the next decade (Anon., Hydroc. Proc.,April 1968).
The production and consumption of other plastics and resins
are also expanding. United States consumption of vinyl compounds
11-14
-------
increased by 20 percent in 1962 while current annual growth of the
styrene resins is about 12 percent (Sherwood, 1963). Production
of propylene oxide could top 880 million pounds in 1968, a 10 percent
gain over 1967. The strong demand is based on two major products
from propylene oxide, urethane foam and unsaturated polyesters (Anon.,
Ghent. & Engr. News.,July 8, 1968). Other plastics and resins are
currently growing at annual rates of two to four percent.
Synthetic Fibers
Synthetic fibers constitute an important part of the total
petrochemical output. World nylon consumption is expected to
increase from two billion pounds in 1964 to 3.3 billion pounds in
1975 (Sherwood, 1966). It is estimated that the United States will provide
about 40 percent of the world nylon production capacity. Poly-
ester resins, used in textiles and tire cords, should double in
production capacity between 1966 and 1975, while the production of
acrylonitrile, used in the manufacture of acrylic fibers such as
dacron, should increase 165 percent during the same time period
(Anon., Bus. Wk.,1966). Polypropylene fiber producers are about to
contest for many of the textile markets now held by the big three
synthetic fibers: namely, nylon, polyester, and acrylic (Anon.,
Chem. & Engr. News.,May 27, 1968).
Synthetic Rubber
In 1966, synthetic rubber accounted for 75 percent of total
rubber produced, and this fraction should increase to 82 percent by
1975 (Sawyer, 1966). About 63 percent of the United States' syn-
thetic rubber production is used in tires and related products
(Sherwood, 1963). The average annual rate of increase of synthetic
rubber consumption is expected to be about four percent. Styrene-
butadiene rubber constituted 77.4 percent of United States produc-
tion in 1963, but this figure is expected to be reduced to approxi-
mately 59 percent by 1970 (Sherwood, 1963; Anon., Oil & Gas J.,,1966).
New types of synthetic rubbers are rapidly becoming important in the
general purpose rubber market. The demand for the stereo-specific
rubbers, such as cis-polybutadiene and cis-polyisoprene is expected
to triple in the next five years when they are expected to occupy
14 percent of the total synthetic rubber market (Anon., Oil & Gas
J.,1966). Production of ethylene-propylene rubbers should increase
by 90 percent between 1966 and 1975 (Anon., Bus. Wk.,1966).
Other Petrochemical Products and Intermediates
The data in Table II-2 also list selected important petro-
chemical products and intermediates which are not included in the
major categories previously discussed. Petrochemicals are the primary
raw materials used in the manufacture of synthetic detergents, pesti-
cides, solvents, automotive chemicals, and a myriad of other minor
products.
11-15
-------
Two additional important chemicals should be mentioned.
Ammonia is one of the most important petrochemicals in terms of
production capacity. By 1970 the global production capacity of
nitrogen should reach 50.3 million tons/year, compared with a 1965
capacity of 26.5 million tons/year (Aalund, 1967). In 1967, the
United State's capacity for ammonia production was 17.3 million
tons/year, an increase of 33 percent over the previous year. Another
three million tons/year of ammonia production capacity is scheduled
for operation by 1969.
The production of ethylene, the most important petrochemical
intermediate, has also grown rapidly. Currently annual consumption
of ethylene is about 14 million metric tons, and it is predicted
that the demand will rise by more than 25 million metric tons between
1970 and 1980. The petrochemical industry probably will add 10 to
15 new ethylene plants each year (Anon., Chem. & Engr. News.,
October 14, 1968). A firm in Houston, Texas predicts that the
operating ratio (output/capacity) for ethylene plants in the United
States will be 80 percent in 1971 to supply 17.3 billion pounds
(Anon., Chem. & Engr. News.,July 1, 1968).
Long-term projections of ethylene production are being re-
vised continuously because of the increasing demands of this petro-
chemical intermediate as a raw material. For example, ethylene has
replaced acetylene as a raw material choice in vinyl acetate monomer
production. All producers agree that the availability of much cheaper
ethylene on a large scale could bring about a 20 percent reduction in
raw material costs, thus leading to the switchover from acetylene-
based technology (Anon,, Chem. & Engr. News.,August 12, 1968).
Effect of New Products on Growth
The projected petrochemical capacities obviously can change
rapidly with the advent of new petrochemical products and new uses
for existing products. Estimates indicate that approximately 500 new
petroleum-based products are introduced to the market every year
(Sherwood, 1963). Although the majority of recent products have
limited consumption and short commerical life-span, many find an
important market and add considerably to the annual growth of the
petrochemical industry.
Based on projections which have been made to date, the petro-
chemical industry should continue to grow at least at its present
rate. The introduction of new uses and products may even increase
the industry's growth rate above its present level. In 1966, petro-
chemical production required the use of 650,000 barrels of petroleum
daily, and in 35 years this requirement will be 12 million barrels
per day (Sawyer, 1966). This expansion will present new and more
complex problems in the area of water pollution control. This
situation, coupled with more stringent pollution control regulations
expected in the future, will necessarily require the industry to
place more emphasis, attention, and capital investment toward solving
these problems.
11-16
-------
REFERENCES - CHAPTER II
1. Aalund, L,, "Petrochemical Activity Hits a New High Around
the World," The Oil and Gas Journal, v. 65, p. 108 (Sept. 4,
1967).
2. Anon., "Demand for Ethylene Worldwide Will Grow," Chem. &
Engr. News, v. 46, n. 44, p. 34 (Oct. 14, 1968).
3. Anon., "Ethylene or Acetylene Route to Vinyl Acetate?" Chem.
Engineering, v. 75, n. 17, p. 94 (Aug. 12, 1968).
4. Anon., "Ethylene Overcapacity Trend to Reverse in Next Three
Years," Chem. & Engr. News, v. 46, n. 28, p. 15 (July 1,
1968).
5. Anon., "Huge Global Petroleum Gains Forecast," The OiJ. and
Gas Journal, v. 64, p. 180 (May 9, 1966).
6. Anon., "Polypropylene Fiber Aims at Wider Market," Chem. &
Engr. News, v. 46, n. 23, p. 24 (May 27, 1968).
7. Anon., "Propylene Demand: Up 50 Percent by 1973," Chem. &
Engr. News, v. 46, n. 33, p. 26 (Aug. 5, 1968).
8. Anon., "Propylene Oxide Production May Grow 10 Percent This
Year," Chem. & Engr. News, v. 46, n. 29, p. 12 (July 8,
1968).
9. Anon., The Petroleum Handbook, Shell International Petroleum
Industry Co LTD. , 5th Edition, Balding and Mansell,
Ltd. eds., London (1966).
10. Anon., "Toray Signs Up UOP for Toluene-Based Benzene, Xylenes
Process," Chem. & Engr. News, v. 46, n. 16, p. 15 (April
15, 1968).
11. Anon., "What Puts Zip in Petrochemicals," Business Week, p. 40
(Dec. 17, 1966).
12. Conklin, H. L., "Water Requirements of the Carbon-Black
Industry,"U S G S, Water Supply Paper 1330-B, U. S.
Govn't. Printing Office, Washington, D. C. (1953).
13. McGrath, H. G., "Petrochemicals to Star '60's," The Oil and
Gas J., v. 59, p. 129 (Nov. 20, 1961).
11-17
-------
14. Noller, C. R., Textbook ofOrganic Chemistry, 2nd Edition, W. B.
Sanders Co., Philadelphia, pa. (1958).
15. Sawyer, F. G., "Best Picks for '66: Petrochemicals," Hydro-
carbon Processing, v. 45, n. 1, p. 161 (Jan. 1966).
16. Sherwood, P. W., "First-Generation Chemicals Today," World
Petroleum Annual Refinery Review, v. 35, n. 8, p. 61
(1964).
17. Sherwood, P. W., "Solvents and Plasticizers," Ind. and Engr.
Chemistry, v. 54, n. 9, p. 35 (Sept. 1962).
18. Sherwood, P. W., "Whither Petrochemicals?" The Oil and Gas
J., p. 73 (Dec. 16, 1963).
19. Stanley, H. M., The Petroleum-Chemicals Industry, Lecture
Series 1963,No. 4, The Royal Institute of Chemistry (1963).
20. Stephenson, R. M., Introduction to the Chemical Process
Industry, Reinhold Pub. Corp. New York (1966).
21. 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).
22. Weiss, A. H., "Which Propylene Process Is Best?" Hydrocarbon
Processing, v. 47, n. 4, p. 123 (April 1968).
11-18
-------
CHAPTER III
PETROLEUM RAW MATERIALS
The first-generation petrochemicals are the initial stock
in the synthesis of all petrochemical products and are produced
from a variety of petroleum fractions. Principal fractions
used for the preparation of primary petrochemical feedstocks include
natural gas, refinery gas, natural gas condensate, light tops or
naphtha, and heavy fractions such as fuel oil. The latter three
fractions are obtained from the distillation of crude petroleum or
crude oil. In some cases petrochemicals are produced directly from
crude oil, particularly in Europe where the demand for naphtha is
beginning to exceed the supply. The following section will briefly
discuss these raw materials and the primary processes used to convert
them to petrochemical feedstocks.
NATURAL GAS
Natural gas is probably the most desirable chemical feedstock
in the United States since it contains a relatively small number of
hydrocarbons and because it is readily available. Natural gas is
available in two forms: "wet" gas which is separated from crude
oil and "dry" gas which is unassociated with any other significant
petroleum fraction. The "wet" natural gas is dissolved in the crude
oil and is removed at the wellhead when the petroleum is brought to
the surface. "Dry" natural gas, which is liquid under normal tem-
peratures, comes to the surface under its own pressure and contains
no petroleum.
Methane is the primary constituent of all natural gases and
is usually combined with varying amounts of higher paraffins
(Goldstein, 1958). Small amounts of hydrogen sulfide, nitrogen, and
helium are also associated with some natural gases. Methane is
important in the production of carbon black, hydrogen, synthesis
gas, various chlorinated solvents, and acetylene. Acetylene is
the basic constituent in the synthesis of several important organic
compounds, but most of these can be produced from ethylene which is
considerably cheaper.
Ethane, propane, butane, and pentane also commonly occur in
natural gases. Propane, butane, and pentane can be separated in the
liquid form by scrubbing the gas with a heavy petroleum fraction
followed by distillation to obtain the absorbed liquids. Two other
methods are also used. One involves compression and cooling of the
natural gas and the other involves removal of the heavier hydrocarbons
III-l
-------
from the gas, then recycling it back into the ground where it picks
up additional amounts of the heavier hydrocarbons (Stephenson, 1966).
The natural gas liquids thus obtained are used for domestic heating
purposes and for feedstocks in the petrochemical industry. Propane
is used to prepare ethylene and propylene, the two principal olefins
used for chemical synthesis.
Ethane also is separated from natural gas, and virtually all
of this hydrocarbon produced is converted to ethylene. Natural gas
is produced in enormous quantities in the United States, but only
about three percent by volume is presently used in the preparation of
chemicals (Anon., Shell, 1966). The remainder of this gas is used
as fuel. In the future, liquified petroleum gases (LPG) obtained
from natural gas should occupy a larger percentage of the feedstocks
used for petrochemical production since large quantities are avail-
able at relatively low costs, particularly in the United States
(Lewis, 1966). Increased industrial requirements for ethylene, for
which ethane and propane are the most favored feedstocks, should
require the use of more natural gas as the raw material for the
petrochemical industry.
CRUDE PETROLEUM
Crude petroleum contains a great number of hydrocarbons,
most of which can be classified in three categories: paraffins,
naphthenes, and aromatics. The paraffins are straight-chain hydro-
carbons ranging from methane to heavy waxes containing thousands
of different isomers (Stephenson, 1966). Naphthenes are mostly
derivatives of cyclopentane and cyclohexane. The aromatics present
in crude petroleum are principally benzene related compounds.
Varying quantities of sulfur, nitrogen, and oxygen are also found
in crude oil. As expected, there are no olefins, diolefins, or
acetylene present in crude petroleum since these are all quite
reactive compounds.
In order to obtain useful products, the crude oil must be
refined. It is during the refining processes that the fractions
used for preparing the first-generation petrochemicals are obtained.
The particular refining operations vary from one refinery to another,
but the following general scheme will show how petrochemical raw
materials are obtained.
Crude petroleum is first separated into six broad fractions
by a primary distillation step. Most of the five-carbon and lighter
hydrocarbons are removed in the first step, called stabilization,
in which the crude is heated to about 300°F under a pressure of about
50 psig (Stephenson, 1966). After most of the gas is removed, the
crude is heated to 600-800°F and distilled at atmospheric pressure.
This distillation separates the crude, based on the boiling point,
into an overhead fraction containing methane, ethane, and other
gases; a bottom fraction of heavy residual oil; and 12 side streams
III-2
-------
which are removed from various heights of the column (Stephenson,
1966). The top gases, the light tops or naphtha, and the heavy
bottom fractions are those used for the preparation of petrochemical
feedstocks. The primary distillation of crude oil is schematically
illustrated in Figure III-l.
REFINERY GASES
Following the distillation process, the gasoline fractions
must be further refined prior to marketing. This refining consists
of converting the straight-chain paraffins to branched-chain
paraffins and thenapthenes to aromatics. The branched-chain par-
affins and aromatics are less prone to cause preignition in internal
combustion engines and thus are more desirable for fuels. The
processes used for this conversion vary somewhat, but all are based
on the catalytic cracking of the gasoline fractions, which basically
consists of splitting and rearranging hydrocarbon molecules using
heat and pressure. It is extremely complex, but the primary reactions
can be generally defined as follows (Stephenson, 1966).
Long-chain Paraffin >— Short-chain Paraffin + Olefin
Alkyl-Naphthene »— Naphthene + Olefin
Alkyl-Aromatic »— Aromatic + Olefin
These equations indicate that considerable amounts of by-
product olefins are formed during cracking operations. These olefins
constitute what is known as refinery gas and provide an important
source of ethylene and propylene. Some uncracked aliphatics,
principally ethane and propane, are also present in the refinery
gas. Ethylene/ethane, propylene/propane, and butylene/butane are
recovered from the gases by distillation and adsorption (Anon.,
Shell, 1966).
The propylene recovered from refinery gas is generally considered
adequate to meet the demands for petrochemical synthesis. However,
chemical demand for ethylene and butylene far exceeds the supply of
these compounds available from refinery cracking processes. Addi-
tional quantities of butylene and ethylene required by the industry
must be supplied by pyrolysis of aliphatic compounds, including the
ethane, propane, and butane from the refinery gases.
LIGHT TOPS
Another important source of petrochemical feedstock is
light tops or naphtha which contains the lower paraffinic gasoline
fractions. These fractions are unsuitable for blending fuels or
for conversion to fuel hydrocarbons by catalytic reforming. Con-
version of these fractions into olefins and diolefins is accomplished
by cracking in the presence of steam (Anon., Shell, 1966). Naphtha
is also important in the production of synthesis gas, particularly in
Europe.
III-3
-------
REFINERY
GASES,
C5 AND LIGHTER
HYDROCARBONS
CRUDE
OIL
LIGHT NAPTHA
HEAVY NAPTHA
HEATING OILS
GAS OILS
RESIDUAL
OILS
FIGURE III-l
PRIMARY DISTILLATION OF CRUDE PETROLEUM
III-4
-------
HEAVY FRACTIONS
The increasing demand for ethylene and butylene has required
the petrochemical industry to look for additional sources. The
heavy fractions such as fuel oils, which are obtained during the
primary distillation of crude petroleum, and condensate from light
gas and oils are finding an increasing market as the source for
these two olefins and for other primary petrochemicals. Cracking
these heavy fractions in the presence of steam results in the
formation of olefins and diolefins which are the basic petrochemical
feedstocks. Synthesis gas also can be produced by partially
oxidizing the heavy fractions.
Unrefined petroleum is also being used directly in the
production of petrochemical feedstocks, especially in Europe.
European petrochemistry has been based on the light tops or naphtha
produced during petroleum refining, but the increasing demand for
this feedstock is beginning to create deficits. Methods have now
been developed which can produce directly from crude oil many of the
basic petrochemicals such as synthesis gas, acetylene, and ethylene.
Crude oil, which is comparatively cheap, will probably be more
widely used in the future as the basic source of European petro-
chemical production. It is doubtful that this will occur in the
United States since other feedstocks which are more economical to
process are more readily available.
AROMATIGS FROM PETROLEUM
Certain petroleum fractions contain large, naturally
occurring quantities or aromatics, with substantial amounts of
these compounds also being formed during catalytic reforming opera-
tions. The increasing demand by the petrochemical industry for
benzene has created a market for aromatics derived from petroleum
and its fractions.
Several methods are used for extracting aromatics from these
fractions. These methods include extractive distillation, liquid/
liquid extraction, and adsorption on silica gel (Anon., Shell, 1966).
Increasing emphasis is also being placed on the hydrodealkylation
of branched chain aromatics, such as toluene, to produce benzene.
This hydrodealkylation process also produces a xylenes stream which
contains about 20 percent of ethylbenzene, an undesirable. An
alternative route to hydrodealkylation has been developed which
converts toluene to benzene plus a xylenes stream of only one percent
ethylbenzene.
In addition to benzene, the aromatics which are used in
significant amounts by the petrochemical industry include toluene
and the three isomeric xylenes: ortho, meta, and para. Petroleum
has now replaced coal and coke as the principal source of aromatic
III-5
-------
hydrocarbons. In 1962, petroleum accounted for 76.5 percent of all
benzene production, 91.5 percent of toluene production, and 97.5
percent of all xylene production in the United States (Sherwood,
1964).
Presently, aromatics are being isolated only from the
catalytic reformates and the petroleum fractions from the primary
distillation procedure. Naphthas from catalytic cracking contain
high percentages of aromatics, but the large amounts of olefins and
sulfur present in these fractions prevent easy separation of the
aromatics, thus making them undesirable as feedstocks for dealky-
lation (Stephenson, 1966) . Most of the aromatics present in petro-
leum are not currently used for chemical production but instead go
into gasolines to improve the octane rating. If the need arises,
the petroleum industry could easily supply several times the present
production of aromatics for the chemical industry.
III-6
-------
REFERENCES - CHAPTER III
1. Anon., The Petroleum Handbook, Shell International Petroleum
Co. Ltd., 5th Edition, Balding and Mansell, Ltd., eds.,
London,(1966).
2. Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,
Spon, London (1958) .
3. Lewis, N. J., "Natural Gas Liquids for Petrochemicals: How
Big?" Hydrocarbon Processing, v. 45, n. 6, p. 195 (June
1966).
4. Sherwood, P. W., "First-Generation Chemicals Today," World
Petroleum Annual Refinery Review, v. 35, n. 8, p. 61
(1964).
5. Stephenson, R. M., Introduction to the Chemical Process
Industry, Reinhold Pub. Corp., New York (1966).
III-7
-------
CHAPTER IV
PETROCHEMICAL PROCESSES
A working knowledge of the principal production processes
which constitute the major waste sources is required to understand
adequately the complexities involved in petrochemical waste treat-
ment. The petrochemical industry uses many variations of the chemical
processes discussed herein, but the details of most of these
special processes are proprietary. The principal wastewaters which
are associated with most of these processes are generally known
or can be deduced from the chemical operations which occur. The
processes for primary, intermediate, and third generation petro-
chemicals are tabulated in Appendix I.
PRIMARY CONVERSION PROCESSES
The majority of petrochemical feedstocks are produced from
crude petroleum. A heterogeneous mixture of many hydrocarbons,
crude petroleum must be subjected to various fractionation and
purification processes before it can be used in the production of
petrochemical products. These preliminary processes constitute what
is commonly known as petroleum refining. These refining processes
differ among various refineries, but a generalized description is
possible. Four methods are used to obtain the separation of individual
hydrocarbons from crude oil. Combinations of methods are often
used to produce the individual hydrocarbons of desired purity
(Hatch, 1955).
Distillation
Three types of distillation are used, all involving separa-
tion of hydrocarbons by differential boiling characterizations.
Distillation at a single pressure level separates compounds on the
basis of molecular size, while alternate use of two pressures will
separate molecular configuration.
The ease with which components of a mixture are separated
by distillation processes is a direct function of the relative
volatilities of the components. If two compounds boil at the same
or approximately the same temperature, they are inseparable by
ordinary distillation. However, artificial means may be used to
increase the difference between the volatilities of two components,
thus enabling them to be separated by distillation. Azeotropic and
extractive distillation are the most commonly used of these processes.
IV-1
-------
In azeotropic distillation, a third component is added to
a binary mixture of components having close boiling points. The
third component forms an azeotrope with one or both of the components
of the binary mixture, changing the relative volatility of each
component and resulting in an increase in boiling points differences
After distillation, the azeotrope-forming compound is removed from
the distilled fraction either by washing with water or by partial
immiscibility caused by lowering the temperature of the azeotrope.
Extraction
This process purifies the mixtures by using solvents which
preferentially dissolve defined hydrocarbons. The hydrocarbons can
be separated according to molecular orientation by using different
solvents and different temperatures (extractive distillation).
Adsorption and Absorption
Various materials having selective preference for individual
hydrocarbons or impurities can be used in combination or at different
temperatures to isolate and purify hydrocarbon mixtures.
These materials operate by the mechanisms of adsorption,
whereby a layer of solute molecules adheres onto a solid surface,
or absorption in which there is an actual transfer of the solute
molecules into the interstices of the absorbent.
Crystallization
By changing the pressure and temperature of a hydrocarbon
mixture or by using specific solvents, certain components of the
mixture can be crystallized and removed in a purified, solid form
since the crystallization-recrystallization characteristics are an
inherent property of a given compound.
The processes described are also used to isolate and purify
many of the final petrochemical products after they are manufactured.
In the early developmental stages of the petrochemical
industry, raw materials required were readily available as low-cost
by-products from oil refining operations. There is now a trend
toward so-called "vertical integration" in which manufacturers
utilize all processes from the refining of the crude oil to the
production of the final petrochemical product (Stephenson, 1966).
Thus, the processes which were formerly associated with refineries
are now being used at petrochemical complexes and contribute to the
wastewater emissions from the industry.
The first step in production of petrochemicals is the
separation of raw materials or feedstocks from crude petroleum. This
IV-2
-------
process is known as primary distillation, and it separates the crude
into six broad fractions or "cuts" which are still mixtures of various
hydrocarbons, Figure III-l.
The fractions obtained from the primary distillation procedure
are further refined by using one or more of the four separation
processes. These processes separate the simple hydrocarbons which
are used in petrochemical synthesis from the more complex hydro-
carbons which are used in fuels and lubricants.
Many of the hydrocarbons present in the heavier fractions
(gasoline, kerosene, residual oils) are made up of six or more
carbon chain molecules. Catalytic cracking is used to break these
long-chain hydrocarbons to six or less carbon chain compounds which
constitute the principal feedstock of the petrochemical industry.
The principal reaction in catalytic cracking is the rupture of a
paraffin molecule resulting in one olefin molecule and one paraffin
molecule each having fewer carbons than the original paraffin
(Goldstein, 1958) . Dehydrogenation occurs simultaneously with
the cracking process, producing an olefin with the same number of
carbons as the starting paraffin. These processes constitute the
primary source of olefins for the petrochemical industry.
The flow of the petrochemical raw materials through the
conversion processes is schematically described in Figure IV-1.
Only the most commonly used of the many possible combinations of
these processes are shown in the diagram.
Natural gas, also an important petrochemical feedstock, was
not included in Figure IV-1 because the primary processing is con-
siderably different from that of crude oil since the gas contains
relatively few types of hydrocarbons. Separation of these hydro-
carbons is normally carried out by using the same techniques as those
employed to obtain the fractions from the primary distillation of
crude petroleum.
Catalytic reforming processes are used to produce aromatics
fromnaphthenes and branched-chain paraffins from straight-chain
paraffins. The aromatics are removed from the product stream by
separation processes similar to those used on crude oil. This is an
important source of aromatics for use in the petrochemical industry.
SECONDARY CONVERSION PROCESSES
The primary conversion processes as defined herein consist
principally of those processes which provide for the separation of
the petroleum raw materials into the purified hydrocarbons used
in the manufacture of petrochemical products.
IV-3
-------
t
CRUDE PETROLEUM
PRIMARY
DISTILLATION
CATALYTIC
CRACKING
I
MIXTURES OF
PARAFFINS, NAPHTHENES,
AND AROMATICS
SEPARATION
PROCESSES
I. DISTILLATION
2. EXTRACTION
3. ADSORPTION
4. CRYSTALLIZATION
PARAFFINS AROMATICS NAPHTHENES OLEFINS
FIGURE IV-1
PRIMARY CONVERSION PROCESSES
XV-4
-------
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, the manufacture of nylon fabrics, and other similar opera-
tions. Many of the purification processes used to separate petro-
chemical products following secondary processing are identical to
the primary conversion processes previously discussed and need not
be reiterated.
Secondary conversion processes comprise a variety of chemical
reactions. These operations include oxidation, halogenation, hydro-
genation, alkylation, isomerization, polymerization, nitration,
sulfonation, hydrocyanation, and many combinations and variations of
these chemical reactions. The secondary processes and the types of
petrochemicals obtained from them are schematically shown in Figure
IV-2. A brief description of each of the processes will help to
identify the pollutants associated^jwith petrochemical production
and to locate the sources of these pollutants.
Before discussing secondary conversion processes, a brief
definition of the terms "side-product" and "by-product" should be
inserted. By-products are the inevitable result of the stoichiometry
of a particular reaction, while side-products are those products
formed by parallel reactions which compete with the primary reaction
taking place. A more detailed discussion of these products will be
given later.
Oxidation
Oxidation of propane and butane to various aldehydes, acids,
and alcohols is one of the older petrochemical processes (Wright,
1959) . Butane is the preferred raw material since it can be directly
oxidized to acetic acid and butyl alcohols which are "high profit"
chemicals (Hatch, 1955). The direct oxidation of paraffins is an
economically competitive process because these oxygenated chemicals
can be produced in one step, while the production of the same
chemicals from olefins usually requires a minimum of two separate
steps (Hatch, 1955). Another important direct oxidation product is
adipic acid, a nylon monomer obtained by oxidizing a naphthene
cyclohexane. A problem which must be coped with during the oxida-
tion of paraffins is the multiplicity of by-products and side-
products which are formed. These products must be separated from
the primary product and sold or used in subsequent reactions.
Another problem involves the loss of process carbon in the form of
carbon monoxide and carbon dioxide.
The oxidation of aromatic hydrocarbons is usually accomplished
by catalyzed reactions at temperatures considerably higher than
those required for paraffin and naphthene oxidation. One charac-
teristic inherent in aromatic oxidation is the usual formation of
one-product rather than the primary and many side-products which
are formed during paraffin oxidation. The most important industrial
IV-5
-------
[OLEFINS] >
^Hydrogenation-
"Sulfation-
^Halogenation-
^Hydrohalogenation•
^Hypohalogenation—
>0xidation-
>Polymerization-
>Alky1at ion
>Isomerization•
•Hydrocarbolylation•
(0X0 Reaction)
Addition-
Substitution-
FIGURE IV-2
SECONDARY CONVERSTION PROCESSES
(Reference 2)
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
•* Alcohols
-------
I—malogenation-
^Nitration
[PARAFFINS]—»|
|—*• Oxidation-
INAPHTHENESM
••Catalytic Cracking-
>Dehydrogenation-
>-Is omer i z at ion —
••Catalytic Cracking-
(Alkyl Naphthenes)
^Halogenation
••Dehydrogenation-
*Nitration
-Isomerization-
>0xidation-
•Short-Chain Paraffins + |OLEFINS|
•>Alkyl Halides
-*Nitroparaff ins
-HOLEFINSl
-*Isomeric Paraffins
•* Alcohols
-^Aldehydes
-*Ketones
-^ Acids
-*Naphthenes + |OLEFINS|
-*Cycloalkyl Halides
-^Cycloalkyl Nitro Compounds
-^•Methylcyclopentane to
Cyclohexane
-*Alcohols
-^Ketones
-»-Dicarboxylic Acids
FIGURE IV-2 (Continued)
SECONDARY CONVERSION PROCESSES
-------
IAROMATICS"
CO
-*-Sulfonation-
•Catalytic Cracking-
(Alkyl Aromatics)
'Halogenation-
"Nitration-
-^Alkylation-
—>• Oxidation-
•Addition
Substitution-
•On Side Chain-
^Hydrodealkylation -
(Toluene, Xylenes)
* AROMATICS
OLEFINS
-*• Hexahalocyclohexanes
-*• Haloaromatics
-* Haloarylparaffins
-*• Nitroaromatics
-> Aromatic Sulfonates
Ethyl Benzene
-fc-Alkyl Aromatics Dodecyl Benzene
Etc.
Phenol
-*• Aromatic Monocarboxylic Acids
-*• Aromatic Dicarboxylic Acids
-*• Unsaturated Dicarboxylic Acids
-+ Benzene + Methane
FIGURE IV-2 (Continued)
SECONDARY CONVERSION PROCESSES
-------
reactions include the oxidation of benzene to maleic acid and
anhydride, the manufacture of phenol and acetone from cumene and
the formation of phthalic anhydride from orthoxylene. Other impor-
tant aromatic oxidation products include benzoic acid, benzaldehyde,
and terephthalic acid.
Probably the single most important petrochemical reaction,
in terms of chemical tonnage produced, is the oxidation of ethylene
to ethylene oxide. This direct oxidation of ethylene, using a
selected catalyst, accounts for 85 percent of the ethylene oxide
production in the United States. Another important olefin oxidation
is the conversion of propylene to acrolein which can be further
oxidized to glycerine. Direct oxidation of propylene is not eco-
nomical due to the high yield of side-products.
Methane is oxidized to synthesis gas, a mixture of carbon
monoxide and hydrogen, which is used in the manufacture of ammonia
and methanol.
Hydration of olefins, which constitutes the addition of a
water molecule to an olefin molecule, can also be considered as an
oxidation process since oxygenated products are formed. The
principal petrochemical products available by olefin hydration
include ethanol from ethylene and acetaldehyde from acetylene.
Halogenation
Halogenation processes, principally chlorination, are also
important petrochemical reactions. Except in the case of the
olefins, chlorination is the only commercially important halogenation
reaction. This is partly because chlorinated products presently
have the largest economic market and partly because of the ease of
performing the chlorination reaction compared to the other halo-
genation reactions. Olefins, however, will react directly with
either bromine or chlorine at low temperatures, while under similar
conditions iodine is unreactive and fluorine is too reactive (Hatch,
1955). The saturated fluorine compounds which are now widely used
(Freon 12, Teflon) are obtained by reacting the appropriate chlorinated
hydrocarbons with various fluorine compounds, particularly hydro-
fluoric acid, rather than by direct fluoridation.
Additional reactions can be performed using chlorine, hydro-
chloric acid, and hypochlorous acid. Brominated derivatives of
olefins are also important commercially. These are the only types of
halogenated products other than the chlorine compounds which are
formed by direct halogen addition.
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
IV-9
-------
(Wright, 1959). Addition of chlorine to benzene is used in the
production of hexachlorocyclohexane, which does occur in several
isomeric forms. As a general rule, however, additional reactions
do not result in significant by- and side-product formation.
The addition of a hydrogen halide to an olefin is known as
hydrohalogenation. The only economically important process is
hydrochlorination, the principal products being vinyl chloride and
ethyl chloride. Ethyl chloride, obtained principally by the hydro-
halogenation of ethylene, is used in the manufacture of tetraethyl
lead.
Hypochlorination involves the addition of hypochlorous acid
to olefins. This process is an important intermediate step in the
production of epoxides and glycols. Ethylene chlorohydrin,
produced by a hypochlorous acid-ethylene reaction, is easily dehy-
drohalogenated to give ethylene oxide. This is one of the primary
sources of ethylene oxide. Hypochlorination .processes are charac-
terized also by low yields of side-products.
Nitration and Sulfonation
Paraffins and aromatics both can be nitrated; however, the
nitrated aromatics have considerably more economic importance
than the nitrated paraffins. Nitroparaffins are used primarily as
solvents and as chemical intermediates. The nitration of paraffins
results in the formation of many side-products with a simultaneous
oxidation of the paraffin and the production of acids, ketones,
aldehydes, alcohols, carbon dioxide, olefins, and water (Hatch, 1955)
The nitration of aromatic hydrocarbons is an extremely
important industrial reaction. Aromatics react easily with nitric
acid producing very little side-product formation and no ring oxi-
dation. For example, nitrobenzene formation is 95 to 98 percent
complete under the normal reaction conditions (Hatch, 1955). The
addition of more than one nitro group to an aromatic ring is con-
siderably more difficult because of the inactivation of the ring
by the first nitration. When more than one nitration is made on
the benzene ring, there will be a formation of the various product
isomers, requiring additional separation processing to obtain the
desired product.
Sulfonation is the addition of the sulfonic acid group
(-SO-jH) to an organic compound and should not be confused with
sulfation, which involves the addition of a sulfate (-O-SCLH) group.
In petrochemical production, paraffins and aromatics are the hydro-
carbon groups which are commonly sulfonated. The only important
commercial use of sulfonated paraffins is as surface active agents
present in detergent products. Rigorous reaction conditions are
IV-10
-------
required for the successful sulfonation of paraffins, resulting in
by-product formation. Typical by-products include hydrogen chloride
and sodium chloride.
Aromatics, particularly benzene, are easily sulfonated
using sulfuric acid, oleum, or free sulfur trioxide (Hatch, 1955).
Sulfonated aromatics are used in synthetic detergent manufacture,
in dye manufacture, and in the manufacture of many other chemical
products such as saccharin and phenol (Hatch, 1955).
Sulfonation of aromatics does not result in the formation
of by-products although substituted aromatic isomers are formed.
For example, all three sulfonated isomers of toluene are formed,
the distribution of each being determined by the reaction temperature.
Sulfonated alky aromatics provide the least expensive source of the
most important component of detergents, the surface-active material.
Alkylation
The principal type of alkylation, Friedal-Crafts reactions,
used by the petrochemical industry involves the addition of an
olefin to an aromatic compound. The addition of alcohols and alkyl
halides to aromatics, the dimerization of two olefins, and the
reaction between an olefin and a paraffin are also known as alkyla-
tion (Hatch, 1955).
The most important alkylation reactions are those used in
the production of various intermediate compounds from benzene,
notably ethylbenzene, which is used in styrene production; cumene,
which is used in the production of acetone and phenol; and dode-
cylbenzene, which is sulfonated and used in the production of surface-
active agents (Wright, 1959). Many catalysts are used in these
alkylation reactions, aluminum chloride being the most common.
Alkylation of aromatics results in the production of few side-products;
although in the manufacture of ethylbenzene, steps must be taken to
prevent the formation of polyethylbenzenes (Stephenson, 1966). The
production of cumene, resulting from the alkylation of benzene and
propylene, is carried out in the presence of a solid phosphoric
acid catalyst. However, formation of the by-product, diisopropyl-
benzene (DIPB), is unavoidable and undesirable. Originally this
reaction was carried out in the presence of excess benzene to
minimize this by-product formation, but this method was expensive
because of the extra process equipment and benzene recovery system
required. More recently, it has been determined that DIPB can be
transalkylated with benzene and other catalysts to yield 90 percent
cumene (Mita, and Kametaka, 1968). The alkylation of paraffins is
important in gasoline production but not particularly significant in
petrochemical production. A recent report claims that the modern
alkylation process can produce alkylate of acceptable quality from an
olefin feed of 100 percent propylene in the presence of a catalyst.
Thus, this alkylating technique may become increasingly attractive
as a propylene consumer (Vahlsing, 1968).
IV-11
-------
Dehydrogenation
Dehydrogenation is the removal of one or more hydrogen atoms
from an organic molecule. The most important commercial dehydro-
genation process is the formation of butadiene from n-butane and
n-butylene. Small amounts of butadiene are produced during catalytic
cracking, but the majority is formed by catalytic dehydrogenation.
The most common process used is the Houdry process, using n-butane
as the feedstock. Since the conversion process is incomplete,
conventional adsorption and distillation processes are required to
remove unreacted butane and butylene from the final product,
butadiene. These unreacted hydrocarbons are then recycled through
the process. This dehydrogenation process requires the use of
catalysts, high reaction temperatures, and reduced pressure. An
additional important dehydrogenation use is the dehydrogenation of
ethyl-benzene to make styrene monomers.
Polymerization
Polymerization processing is presently one of the most
active areas in petrochemistry. Some of the more common polymeriza-
tion products include plastics of all types, resins used in adhesives
and paints, fibers such as nylon and dacron, and elastomers known
commonly as synthetic rubbers.
High molecular weight polymers, or macromolecules, are
large molecules composed of two or more low molecular weight monomers.
The polymer configuration can be linear, chain, or branched. The
branched polymers may have their side chains joined by cross-links
which form a three-dimensional or network polymer (Stephenson, 1966).
The multiplicity of polymeric combinations possible make it impractical
to discuss polymerization processes specifically, but the principles
involved can be outlined in a general way.
Polymerization processes can be classified best in terms of
the two mechanisms of polymer formation: step polymerization, which
proceeds through the direct interaction of specific functional groups
on the monomers, usually with the elimination of a small molecule
such as water; 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.
The details of these polymerization processes depend on the
type of polymer being produced, but all require various catalysts and
other chemical additives in order to insure production of the desired
end-product. The polymers can be either liquid or solid with widely
varying chemical and physical properties.
IV-12
-------
Other Processes
Obviously, many other chemical reactions are important in
petrochemical production. A brief description of the more important
miscellaneous processes is desirable in order to fully explain the
sources and types of potential air and water pollutants.
Ammonia is an extremely important petrochemical product,
the largest single use for this compound being in the manufacture
of nitrogeneous fertilizers. Ammonia is produced from the catalytic
combination of nitrogen gas with hydrogen gas at high temperature
and pressure. The hydrogen gas used in the reaction is obtained
from synthesis gas, an important petrochemical intermediate. A
number of different processes for ammonia production are used,
their primary difference being the temperature, pressure, and
catalyst employed. The most common catalyst used is iron.
Hydrocyanation, using hydrogen cyanide as a reactant was
the process used to manufacture acrylonitrile, an important monomer
used in acrylic fiber and plastics production. Even older processes
used in acrylonitrile production involved the direct addition of
hydrogen cyanide to acetylene or the addition of hydrogen cyanide to
ethylene oxide, splitting off a molecule of water (Stephenson, 1966).
Replacing the older process is a newer method using propylene and
ammonia reactants instead of hydrogen cyanide. Hydrogen cyanide
is also used in the manufacture of organic acids.
Hydrocarboxylation, more commonly known as the 0X0 reaction,
can be used to produce aldehydes. This process combines an olefin
with carbon monoxide and hydrogen in the presence of a cobalt
catalyst to produce the desired aldehyde (Hatch, 1955). Hydro-
genation is used to convert the aldehydes produced by the 0X0 process
to alcohols and organic acids. The principal disadvantage of the
0X0 process is that the product stream usually contains a mixture
of many isomers, thereby handicapping its use as an intermediate for
other petrochemical products (Stephenson, 1966). The products from
the 0X0 reaction contain cobalt and iron carbonyls which must be
separated and, in the case of cobalt, reused. Hydrogenation reactions
use various catalysts including nickel and cobalt, and the product
streams will contain these catalysts as well as small amounts of
unreacted aldehydes.
Sulfation processes are also used to produce alcohols from
olefins. The olefin is absorbed in sulfuric acid using acid con-
centrations ranging from 50 percent to 98 percent and temperatures
in the range of 0° to 80°C. Ethers, polymers, and dialkyl sulfates
are three side products formed, but this formation can be adequately
controlled to reduce the total quantity produced (Hatch, 1965). The
alkyl hydrogen sulfates formed during sulfation are then hydrolized
to produce alcohols and dilute sulfuric acid which are separated by
distillation procedures. .... ---
IV-13.
-------
PROCESSES AS WASTE SOURCES
The multiplicity of processes used and products produced
by the petrochemical industry indicates the scope and complexity of
the petrochemical waste problem. If one considers all of the process
combinations used by the industry, it is obvious that many types of
air and water pollutants can result. The principal petrochemical
processes and the wastes which might be expected to emanate from
them are listed in Table IV-1.
A general review of major pollutants in the petrochemical
industry reveals that many of them can be traced to sources
common to most petrochemical processes. The characteristics of
these sources are listed below (Wright, 1959).
By-Product Formation
In some cases the by-products formed may have commercial
value, but usually this is not the case and more often these
products present waste disposal problems.
Side-Product Formation
Side-products are compounds which are formed by reactions
competing with primary reactions during petrochemical processing.
These side-products are often isomers of the principal product.
They may also be reaction products from impurities present in the
feedstock or other extraneous reactions which might occur during the
petrochemical process. These side-products range in composition
from pure chemical compounds which might have some commercial
value to unrecognizable tars and complexes. Unlike by-products,
side-product formation often can be controlled by modifying the
conditions of the chemical reaction (Wright, 1959).
Incomplete Reactions
In petrochemical practice, no reaction ever goes to comple-
tion. The many reactions used by the industry vary markedly in their
efficiency ranging from almost 100 percent completion to only
20 percent of completion. In other words, the product stream from
any petrochemical process will contain varying quantities of the feed
chemical which must be separated from the final product. Often,
especially in cases of low conversion efficiency, the feed chemical
is recycled through the process; but in some cases, it is not
economically justifiable and they are disposed of as wastes.
Mechanical and Accidental Losses
Every mechanical or physical operation is subject to various
losses, including accidental leaks, spills, and explosions, or
losses caused by human error (Wright, 1959). Mechanical losses
include fluid losses from valves, defective seals in compressors and
IV-14
-------
TABLE IV-1
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Alkylation: Ethylbenzene
Ammonia Production
Aromatics Recovery
Catalytic Cracking
Catalytic Reforming
Crude Processing
Cyanide Production
Demineralization
Regeneration,Process
Condensates
Furnace Effluents
Extract Water
Solvent Purification
Catalyst Regeneration
Reactor Effluents and
Condensates
Condensates
Crude Washing
Primary Distillation
Water Slops
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
Hydrogen Cyanide, Unreacted Soluble Hydrocarbons
-------
TABLE IV-1 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Dehydrogenation
Butadiene Prod, from
n-Butane and
Butylene
Ketone Production
Styrene from Ethyl-
benzene
^"1
,1, 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
Solvent
Solvent
Separator
HC1 Absorber, Scrubber
Heavy Tars
Cuprous Ammonium Acetate, C, Hydrocarbons, Oils
Furfural, C, Hydrocarbons
Spent Caustic
Chlorine, Hydrogen Chloride, Spent Caustic,
Hydrocarbon Isomers and Chlorinated Products, Oils
-------
TABLE IV-1 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
Hypochlorination
Hydrochlorination
Hydrocarboxylation
(0X0 Process)
Hydrocyanation (for
Acrylonitrile, Adipic
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 IV-1 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process
Source
Pollutants
oo
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 Olefins
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, Hexainethylene, Diamine,
Adiponitrile, Acetone, Methyl Ethyl Ketone
Alcohols, Polymerized Hydrocarbons, Sodium
Sulfate, Ethers
Spent Caustic
-------
TABLE IV-1 (Continued)
PETROCHEMICAL PROCESSES AS WASTE SOURCES
Process Source Pollutants
Thermal Cracking for Furnace Effluent and Acids, Hydrogen Sulfide, Mercaptans, Soluble
Olefin Production Caustic Treating Hydrocarbons, Polymerization Products, Spent
(including Fractionation Caustic, Phenolic Compounds, Residue Gases,
and Purification) Tars and Heavy Oils
Utilities Boiler Blow-down Phosphates, Lignins, Heat, Total Dissolved Solids,
Tannins
Cooling System Blow- Chromates, Phosphates, Algicides, Heat
down
Water Treatment Calcium and Magnesium Chlorides, Sulfates,
Carbonates
-------
pumps, leaks in various units, etc. Volatile hydrocarbons are often
lost to the atmosphere via relief valves and improperly sealed
storage facilities. Storm water runoff from the processing areas
often contains pollutants which have seeped from various process
units.
The losses of volatile hydrocarbons from valves, fittings,
etc., is significant in both quantity of hydrocarbon lost and in
air pollution created in the plant area. Calculations of the hydro-
carbon losses from an ethylene plant are shown in Table IV-2
(Mencher, 1967). This example shows that mechanical losses can be
quite significant, with the total being much higher if the leakage
of nonvolatile hydrocarbons was included. Obviously the degree of
maintenance practiced and condition of equipment at a particular
plant would be reflected in the mechanical and accidental losses
incurred by the plant.
No attempt was made to characterize the waste streams in
Table IV-1 with respect to individual chemical pollutants or to
wastewater management parameters such as chenical or biochemical
oxygen demand. The wastes associated with petrochemical processing
will be completely characterized in the following chapter.
The actual operations which are the principal contributors
of water pollutants in the petrochemical industry are listed below
(Mencher, 1967).
a) Steam distillation
b) Steam cracking
c) Steam stripping
d) Product washing with water, caustics, and acids
e) Barometric condensing of steam-driven prime movers
f) Catalyst regeneration
g) Boiling and cooling water blow-downs
h) Rainwater runoff from processing areas
i) Cleaning operations (Process)
j) Partial pressure reduction with dilution steam
k) Transfer and storage operations
1) Crude petroleum desalting
m) Solvent processes
n) Still tars from distillation processes
o) Product and feedstock drying
One or more of these operations are used in each of the primary and
secondary conversion processes and usually are the prime contributors
of water-borne pollutants.
All of the foregoing factors are involved in the waste
discharges from a large petrochemical complex. The actual quantities
IV-20
-------
TABLE IV-2
A CALCULATION OF HYDROCARBON LOSSES FROM PROCESS
EQUIPMENT IN A 500 MM LB/YR ETHYLENE PLANT
(Reference 3)
Emission Source
Loss Factor
(1)
Emission
Quantity
(Ib/day)
Valves
Pumps (mech. seal)
Compressors (centrif.,
mech. seal)
Compressors (recip.,
packed seal)
Cooling water
Process drains and
wastewater separators
Blow-down
Relief valves (opera-
ting vessels)
Relief valves (storage
tanks)
Storage tanks (floating
roof)
0.15 Ib/day/valve
3.2 Ib/day/seal
3.2 Ib/day/seal
5.4 Ib/day/seal
6.0 Ib/MM gal(circulated)
150 lb/1,000 bbl cap.
100 lb/1.,000 bbl cap.
2.9 Ib/day/valve
0.6 Ib/day/valve
4.8 lb/day/1,000 bbl cap.
4,500 valves x 0.15 =
150 pumps x 3.2 =
10 comp. x 2 x 3.2 =
1 c omp. x 5.4 =
50,000 gpm x 60 x 24 x 6
1,000,000
20,000 bbl x 150 _
1,000
20.000 bbl x 100
1,000
400 valves x 2.9 =
14 tanks x 2 x 0.6 =
500,000 bbl x 4.8
1,000
675
480
64
430
3,000
2,000
1,150
17
2,400
-------
TABLE IV-2 Continued)
A CALCULATION OF HYDROCARBON LOSSES FROM PROCESS
EQUIPMENT IN A 500 MM LB/YR ETHYLENE PLANT
i—i
<
i
N3
S3
Emission Source
Loss Factor
Quantity
Emission (Ib/day)
Storage tanks (floating 1.7 lb/day/1,000 bbl cap,
roof) (VP 1.5 Ib/sq in)
Miscellaneous losses
10 lb/day/1,000 bbl cap.
Total calculated hydrocarbon emission
(2)
Weight % loss on plant feed
5,000 bbl x 1.7 =
1,000
20.000 bbl x 10 =
1,000
10.430
20,000 x 250
9
200
10,430 Ib/day
(1) These loss factors are applicable to plants practicing extensive hydrocarbon control.
(2) The range of emissions from hydrocarbon processing plants may range from 0.1 to 0.6 percent
by weight of plant throughout. The lower value calculated here is applicable to an area as
Los Angeles County where stringent control is practiced.
-------
and types of pollutants discharged by a plant will depend on several
factors, including the type of raw petroleum feedstock used by the
plant, the products manufactured, the quantity of in-plant control,
and the maintenance, condition, and types of processing equipment
used. Marginally efficient processes may still be used in older
plants, resulting in the production of more side-products which are
evident in the plant wastewater. In general, however, the rapid
growth and active competition within the petrochemical industry
reduces the importance of this factor as a waste source.
IV-23
-------
REFERENCES - CHAPTER IV
1. Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,
Spon, London (1958).
2- Hatch, L. F., The Chemistry of Petrochemical Reactions, Gulf
Pub. Co., Houston, Texas (1955).
3. Mencher, S. K., "Change Your Process to Alleviate Your
Pollution Problem," Petro/Chem Engineer, p. 21 (May,1967).
4. Mita, Y. , and Kainetata, N., "Up Cumene Yield With Transalky-
lation," Hydrocarbon Processing, v. 47, n. 10, p. 122
(Oct. 1968).
5. Stephenson, R. M., Introduction to the Chemical Process Indus-
tries, Reinhold Pub. Corp., New York, (1966).
6. Wright, E. R., "Secondary Petrochemical Process as Waste
Sources," Sew, and Ind. Wastes, v. 31, n. 5, p. 575 (May
1959).
7. Vahlsing, D. H., "HF Alkylation Gets Propylene Feed," Hydro-
carbon Processing, v. 47, n. 9, p. 245 (Sept. 1968).
IV-24
-------
CHAPTER V
CHEMICAL AND PROCESS RELATED CLASSIFICATION OF WASTES
The petrochemical industry is extremely diversified in both
the processes used and the materials produced, and the widely fluc-
tuating characteristics of the wastewaters discharged from the
industry reflect this diversity. It can be expected that most of
the chemicals used in the manufacture of these products will be
present in the aqueous effluents from the industry, making it
extremely difficult to define or predict an average effluent from
the petrochemical industry. However, most of the unit processes
used in the industry are relatively similar, making it possible to
predict the general nature of the pollutants from any given unit
process.
Relating the general characteristics of a wastewater to the
individual unit processes, the effluent characteristics for any
given combination of petrochemical processes can be approximated.
These estimations provide a basis for designing effluent segregation
systems, in-plant pretreatment systems, and final treatment schemes
for petrochemical wastewaters (Beychok, 1967).
Principal pollutional characteristics of petrochemical
wastes will be defined in accordance with the unit process from
which these wastes are discharged. The volume and concentration
of these pollutants are as important as their inherent characteris-
tics, but much more difficult to predict. The concentration of
any given pollutant in a waste stream is dependent on the qualities
of waterused in the process. For example, a petrochemical plant
practicing extensive reuse of cooling water and minimum usage of
stripping steam would, for a given quantity of pollutant, have a
higher effluent concentration of the pollutant than a plant dis-
charging the same total quantity of the pollutant but in a greater
volume of water.
The one method of predicting the characteristics of a waste
stream discharged from a given unit process is to relate the quanti-
ties of pollutants produced to the unit quantity of feedstock utilized
or product manufactured by the process. A given unit process using
a particular feedstock should produce a fixed quantity of pollutant
per unit of feedstock utilized. These data can be statistically
correlated for a particular unit process, thereby providing a basis
for accurately predicting quantities of pollutants associated with
V-l
-------
the process. However, most of the published literature does not
include sufficient information to characterize the waste by feed-
stock quantities utilized or products processed. Often the effluent
flow rates are also excluded so that total pollutant quantities
from a process cannot be calculated.
Many of the unit processes used in the petrochemical industry
are also important in petroleum refining. The characteristics of
these refining wastes are well documented (Beychok, 1967), and a
detailed discussion will not be included in this report. The most
important unit processes used by the petrochemical industry and
their respective effluents are listed in Table IV-1. In some
cases, for example, nylon manufacture, a combination of several
unit processes, are listed. These processes normally will be com-
bined in the same order for production. It can be seen from Table
IV-1 that the effluent streams carrying the pollutants come from a
relatively small number of sources. A brief discussion of each of
these effluent streams will indicate the sources, nomenclature,
and type of wastes which might be expected.
COOLING WATER
Cooling water often contains organic contaminants because
of pipe leakage which may result in oil contamination. Also some
organic materials are frequently added along with the chemicals
used to control corrosion, scale formation, etc. Inorganic contami-
nation of the water may become a serious waste problem since
recirculated cooling water will tend to concentrate dissolved solids
with the blowdown from such a system containing high dissolved
solids concentration. Cooling water is often used to dilute toxic
organic wastes to biologically treatable levels of concentration.
Algicides and bacteriocides which may possibly restrict or inhibit
subsequent biological treatment of the combined wastewater are
sometimes added to cooling water.
PROCESS EFFLUENTS
Most of the highly polluted waste streams in a petrochemical
plant originate from process areas. This category includes con-
densed steam from stripping operations, wash waters from process
drum cleaning operations, water formed or eliminated during various
reactions, and other in-process sources. A variety of pollutants
are found in these wastewaters, including any or all of the chemicals
present in the feedstocks, products, by- and side-products, and
spent catalytic materials. Many of the compounds present in the
effluents from unit petrochemical processes are indicated in Table
IV-1. The pollutional characteristics of some typical process
effluents will be shown subsequently.
V-2
-------
The terminology used by the industry for the various process
waste streams gives an approximate indication of the source and comp-
osition of each effluent. Steam is used for stripping during
distillation operations and as a diluent in catalytic and thermal
cracking (Beychok, 1967). The condensed steam is known as "conden-
sate" which distinguishes it from other process wastes. Wastes
containing relatively large amounts of hydrogen sulfide are usually
referred to as "sour" water or sour condensates because of their
unpleasa'nt odor. Phenols or "phenolic wastes" are also common,
particularly in the effluents from cracking operations.
Solvent Processes
Numerous solvent processes are utilized in petrochemical
production to purify the chemical feedstocks, intermediates, and
products used and manufactured by the industry, and are commonly
found in aqueous waste streams discharged from processes using them.
Additional solvents may find their way into wastewater through
accidental leakage and solvent spills. Since the solvents used by
the petrochemical industry in most instances are expensive, it is
doubtful that large quantities of the commonly used solvents will
be found in waste streams, but even low concentrations of many
solvents used by the industry have deleterious biological effects.
In this case it may be necessary to remove the solvent completely
by pretreatment prior to biological treatment of the waste stream.
Many of the solvents used by the petrochemical industry are similar
to those used in petroleum refining.
Caustic Washes
Caustic washes utilizing aqueous sodium hydroxide solutions
are frequently used in petrochemical processes and are sources
of the various spent caustic streams cited in Table IV-1. Sodium
hydroxide solutions are used to extract from process streams various
acidic contaminants such as hydrogen sulfide, mercaptans, phenols,
thiophenols, and organic acids (Beychok, 1967). Most spent caustic
streams can therefore be expected to contain some or all of these
compounds in the forms of sodium salts and unreacted sodium hydroxide
as well as small quantities of the process product and feed chemicals.
Caustic washes are also used to recover unreacted acidic
chemicals in such processes as chlorination, sulfation, sulfonation,
polymerization, oxidation, and other processes utilizing or forming
acidic compounds not desired in the product stream. The caustic
washes from secondary petrochemical processes usually will not
contain large amounts of sulfur compounds since most of these are
removed by the preliminary refining processes.
Acidic Wastes
Petrochemical processing also involves the use of various
acid washes to remove basic materials from product streams. Acid
V-3
-------
washes are often used also in removing Contaminants from various
phenolic product streams such as those emanating from phenolic
resin manufacture. Acid process effluents also are present in
refining and petrochemical operations, notably alkylation processing.
Phenolic spent caustics are usually neutralized with
mineral acids (I^SO^, HC1) or flue gases containing SC>2 or C02,
releasing an acidic, oily effluent consisting predominantly of
phenolic compounds and referred to as "sprung acid" (Beychok, 1967) .
Acid sludges are also produced by various heavy oil treatment
processes.
Washing and Scrubbing Operations
Caustic and acid washings are often followed by clear water
rinses to remove all traces of the washing compounds. Off-gases
from various units also are scrubbed with water to remove contaminants.
Wash waters usually will contain pollutants similar in nature but
smaller in concentration to those found in the preceding spent
caustic or acid washes categories.
Crude Petroleum Desalting
The desalting of crude oil is primarily a petroleum refinery
process and is important only in petrochemical plants which include
primary processing of crude oil feedstocks. It is, however, a
significant source of pollutants. Water present in crude oil may
range in volume from 0.1 percent to 2.0 percent of the total. The
effluent water will contain a high salt concentration and considerable
oils and may exert a rather high oxygen demand. In a refinery the
desalter effluents often contribute a significant portion of the
total refinery biochemical oxygen demand (Beychok, 1967) . This
effect would probably occur less often in a petrochemical plant
but if such a stream were present, the high salt concentration could
raise the salinity of the plant effluent significantly. Desalter
wastes often contain other contaminants such as abrasive sediments,
arsenic, and vanadium organometal compounds (Beychok, 1967).
Other Sources
Other possible processing operations which may contribute
pollutants include spillage of petrochemicals during transport or
storage operations and runoff from processing areas. Spent catalytic
material may find its way into aqueous waste streams and often can
be a serious pollutant in terms of biological toxicity, even though
it may be present only in small quantities.
CHEMICAL CLASSIFICATION OF PETROCHEMICAL WASTES
The vast number of chemicals and products manufactured by
the petrochemical industry makes a complete listing of every compound
V-4
-------
which might be present in any petrochemical waste effluent impractical,
However, the principal classes of chemicals which might be expected
to emanate from various unit processes can be presented. The fol-
lowing discussion will separate the chemicals into two general
classifications, inorganic and organic, with each of these divisions
subdivided as required.
.Inorganic Compounds
Inorganic chemical pollutants may be conveniently classified
under two general subdivisions, metals and nonmetals.
Metals - Most of the metals associated with petrochemical
effluents are catalytic materials from various unit processes.
These metals often are associated with complex organic materials
found in tars and other residues. Some of the more commonly used
metallic catalysts are aluminum, platinum, molybdenum, iron, and
chromium. The processes from which spent metallic catalyst
pollutants might be expected are catalytic cracking, catalytic
reforming, dehydrogenation, alkylation, isomerization, and poly-
merization. Other metals which also might be used as catalysts
are nickel, cobalt, and copper.
Another source of copper in wastewater is the cuprous
ammonium acetate solution used in the extraction and purification
of butadiene. A similar cuprous solution is used to remove carbon
monoxide from synthesis gas in preparation for ammonia synthesis
(API, Vol. III.,1958). In both of these processes, a solution
containing a mixture of cuprous and cupric ions is formed. This
solution has an intense blue color, and the copper concentration
is sufficient to be toxic. These solutions are reused and
ordinarily are not allowed to escape from the process; however,
accidental spills and leakages may occur in small amounts. Although
most of the metals used as catalysts have a high economic value and
are recovered, others, for example aluminum chloride, used in
isomerization and treating processes, are usually discharged into
the waste stream.
Anti-corrosion, algicidal, and bactericidal chemicals
commonly composed of chromium and copper compounds, added to cooling
and boiler waters are additional sources of metal pollutants. Zinc
has been used also as a biocide to prevent undesirable growth of
microorganisms in cooling towers. These chemicals represent a
potential source of toxic materials and could have a deleterious
effect on the performance of a biological treatment system.
Non-metals - Non-metallic inorganic pollutants are present
in various petrochemical process effluents. In terms of total
quantity, the sodium salts present in spent caustic streams are
probably the most significant.
V-5
-------
The sodium is frequently combined with sulfates, sulfites,
and sulfides. Various quantities of unreacted sodium hydroxide
are present in the spent caustics. Much of the sodium in phenolic
spent caustics will be combined with phenols, cresols,and xylenols.
Crude oil desalter effluents contain large quantities of sodium
usually in the form of sodium chloride. Wash waters also contain
various sodium salts.
Calcium hydroxide is an important caustic washing agent,
particularly in chlorination processes. Spent caustic from
processes using this material consists principally of calcium
chloride, which is also present in desalter effluents in significant
concentrations.
Sulfur compounds are some of the most important inorganic
pollutants present in petrochemical effluents and many sulfur
compounds have undesirable odors. Hydrogen sulfide and mercaptans
contain the most reduced form of sulfur and have particularly
objectionable odors; they are usually present in condensates and
spent, caustics from primary conversion and refining processes.
Sulfates are present in the spent caustic from alkylation processes
as is sulfuric acid, the acid stream being comprised of 85 percent
to 90 percent sulfuric acid (Beychok, 1967) . Sulfuric acid is also
used as a solvent in various extraction processes and will appear
in the process effluents. Sulfonates are found in spent caustic
streams from aromatic sulfonation processes. Sulfur also can be
associated with phenolic compounds in the form of thiophenols, which
are often present in the condensates from catalytic cracking processes,
Sulfur dioxide is found in gases from combustion processes and it is
also found in waste from aromatic extraction processes where the
S02 is used as a solvent.
Cyanide, present as both hydrogen cyanide and organocyanides,
is found in some effluent streams and are particularly significant
because of their toxic nature. Condensates from catalytic cracking
units and process effluents from hydrocyanation reactions used in
the production of intermediate chemicals for nylon manufacture
contain cyanides.
Chlorides are present in crude desalter effluents and
certain spent caustic streams previously discussed. Hydrochloric
acid is found in the effluents from some chlorination processes and
appears as a spent catalyst in alkylation process wastes.
Phosphates and polyphosphates are used for corrosion control
in cooling and boiler waters. Phosphoric acid is used as a catalyst
in polymerization, alkylation, and isomerization processes, and the
spent acid catalyst may be found in process effluents if it is not
segregated for separate disposal.
V-6
-------
Potassium and magnesium also are found in effluents from
certain unit processes. Potassium hydroxide is used as a caustic
wash in some refinery operations. Magnesium and calcium salts are
present in the waste sludge from cooling water treatment processes.
Ammonia, usually present as ammonium sulfide, is an important
pollutant in condensates from refining processes. Nitric acid,
another nitrogen-containing compound, may be present in wastes
discharged from aromatic nitration processing.
Organic Compounds
The organic compounds present in petrochemical wastes are
probably the most important pollutants in terms of both quantity
and pollutional effects on biological environment. Organics in
petrochemical effluents are far more diverse in their characteristics
than inorganics. Only the classes of organic compounds commonly
found in petrochemical effluents will be included in this discussion.
The effluent from a specific unit process often is so complex that
it can be characterized only in a general sense.
Hydrocarbons - Wastewaters containing hydrocarbon contami-
nants can emanate from any process utilizing hydrocarbon feedstocks.
They are most common in condensates and caustic wastes from primary
conversion processes.
Three general classes of saturated hydrocarbons are found
in petrochemical wastes - aliphatics, aromatics, and cyclic aliphatics
or naphthenes. The chemical characteristics of these hydrocarbon
groups have been discussed. Saturated aliphatic hydrocarbons are
practically insoluble in water; therefore, relatively low concen-
trations of these compounds are normally present in process waste-
waters. The high volatility of the aliphatic hydrocarbons containing
chain lengths of five carbon atoms or less also tends to keep the
concentrations of these compounds in process effluents at low levels.
The cyclic aliphatic compounds have chemical and physical properties
similar to the aliphatic hydrocarbons. The aromatic hydrocarbons
although relatively insoluble are considerably more soluble and
less volatile than the other saturated hydrocarbons. Significant
quantities of aromatic hydrocarbons are therefore an important
constituent of process wastes from petrochemical processes in which
aromatics are utilized or formed. Complex aromatic compounds such as
naphthalene are also found in process effluents, particularly in
effluents from refining processes. It should be mentioned that
many saturated hydrocarbons are very difficult to degrade bio-
logically.
The principal unsaturated hydrocarbons used in the petro-
chemical industry are the olefins: ethylene, propylene, and
butylene; and the alkyne, acetylene. These compounds are considerably
V-7
-------
more soluble than the saturated hydrocarbons but will seldom be
found in process effluents in unreacted forms because of their high
reactivity. The double bond and triple bond compounds will enter
into additional reactions with many reagents, producing a variety
of chemical products which will be discussed under other classifica-
tions. Small amounts of butadiene are occasionally found in the
effluents from the polymerization of copolymer rubber (Dougan
and Bell, 1951) .
Other important types of hydrocarbons which can be found in
petrochemical effluents are the mixed aliphatic-aromatic hydro-
carbons. These compounds can be combinations of alkanes and
aromatics such as toluene and xylene or unsaturated hydrocarbons
and aromatics such as styrene. Ethyl benzene, which is used to
manufacture styrene, is produced by alkylating benzene. Toluenes
and xylenes are produced during the catalytic refoming and cracking
of crude petroleum and are usually dealkylated to benzene. The
effluents from dealkylation processes may contain these compounds.
Since the aliphatic-aromatic hydrocarbons also are relatively
insoluble in water, low concentrations of these compounds may be
expected in wastewater streams.
Substituted Organic Compounds - Most of the organic compounds
found in petrochemical effluents will be substituted organics or
hydrocarbons which have had one or more of the hydrogens substituted
by other functional groups. Most of the secondary petrochemical
processes involve the rearrangement of hydrocarbon molecules and
the addition of various reagents to them. These substituted
organics can find their way into the various process effluents by
any of the methods previously discussed. The following discussion
will describe the various classes and characteristies of these
substituted organics.
a. organic acids and their salts - Organic acids are
defined as those organic compounds which can serve as proton donors.
Although many organic compounds fit this description, the term
organic acid is usually reserved for those compounds containing a
carboxyl group consisting of two oxygen atoms, one carbon atom, and
one ionizable hydrogen atom. The sulfonic acid group will be dis-
cussed later. The polar nature of the carboxylic acids makes those
acids with four or less carbon atoms extremely water soluble so that
high concentrations of these compounds may be found in process waste-
waters coming in contact with them. The long-chain organic acids
are considerably less soluble in water. The effect of organic acids
on wastewater treatment systems is twofold. Their acidity tends to
lower the pH of the effluent; and most of them are quite biodegrad-
able, giving the waste a high potential oxygen demand. Organic
acids can be found in waste streams in the free form or combined
with various cations (Na, K, Ca) as a salt.
V-8
-------
The most common carboxylic organic acids found in petro-
chemical wastes are probably formic and acetic acids which occur
in the effluents from various oxidation processes. Nylon manu-
facture is the source of the following organic acids: succinic
acid, adipic acid, and glutaric acid. Other organic acid sources
are listed in Table IV-1.
The acid anhydrides are derivatives of organic acids which
contain two oxygen atoms connected by two double bonds to two carbon
atoms which, in turn, are connected to each other by another oxygen
atom. The remaining single bonds on each of the two carbons are
connected to an organic molecule, either aliphatic or aromatic.
The anhydrides are relatively insoluble in water, and only small
quantities should be expected in wastewater streams. The two most
important anhydrides are both aromatics, phthalic anhydride and
maleic anhydride, and are used in the manufacture of polymers.
Aliphatic acid anhydrides are used to synthesize certain esters.
k- alcohols - The alcohols are organic compounds
containing a hydroxyl group consisting of one hydrogen and one
oxygen atom. The hydroxyl group can be joined to any alkyl or
substituted alkyl group, giving the alcohol its prominent physical
characteristics. The hydroxyl group is highly polar, making alcohols
with chains of four or less carbon atoms highly water soluble.
Longer chain alcohols tend to exhibit the properties of the less
polar aliphatic portion of the molecule and are only slightly
soluble. Alcohols will be found in effluents discharged from oxi-
dation processes, in the form of by-products from nitration and
sulfation processes, and in the form of solvents in solvent applica-
tions .
The most common alcohols found in the petrochemical industry
include the simple alcohols such as methanol, ethanol, propanol,
isopropanol; the butanols and other longer chained alkylalcohols;
alkyl alcohol which contains a double bond; polyhydroxy alcohols,
which include the glycols; and the cyclic aliphatic alcohol, cyclo-
hexanol. The glycols are also used as solvents to extract aromatics
from hydrocarbon mixtures (Beychok, 1967). Processes which might
produce wastewaters containing alcohols are listed in Table IV-1.
c. aldehydes and ketones - Both aldehydes and ketones
are characterized by the presence of the carbonyl group consisting
of an oxygen atom attached to a carbon atom by a double bond.
Aldehydes and ketones have similar physical properties primarily
attributable to the carbonyl group, are relatively volatile, and
those with four or less carbon atoms are very soluble in water.
Aldehydes often are present in effluents discharged from
oxidation and paraffin nitration processing. Ketones are formed in
V-9
-------
the same processes and are often used as solvents in extraction and
purification processes. Formaldehyde and acetaldehyde are the most
common alkyl aldehydes, but many wastes will also contain the
higher aldehydes in complex mixtures. Acrolein is an unsaturated
aldehyde which occurs as a by-product in acrylonitrile manufacture
and as an intermediate in a new process for manufacturing glycerol
(Stephenson, 1966).
The most common ketones are acetone and methyl ethyl ketone.
Acetone is present as a by-product in oxidation processes, and
methyl ethyl ketone is a solvent used in a variety of extraction
and purification processes.
d. esters - Esters are organic compounds formed by
the reaction between an alcohol or phenol and a mineral or organic
acid. Esters with five or fewer carbon atoms are quite soluble in
water. Several common esters in petrochemical processing are vinyl
acetate, ethylene diacetate, and methyl formate (Gloyna and Malina,
1962). The primary pollutional effect of esters is the creation of
an oxygen demand due to their biodegradability- The lighter esters
are also quite volatile and can impart an odor to wastewater;
however, the odors of esters usually are considered pleasant.
e • ethers - Ethers are organic compounds which contain
an oxygen atom bound to two carbon atoms. Ethers can be aromatic,
aliphatic, or a combination of the two. They are nonpolar and
therefore relatively insoluble in water. These compounds are quite
volatile, their boiling points being comparable to those of alkanes
with the same number of carbon atoms. The most common ethers pro-
duced in petrochemical processes are diethyl ether and isopropyl
ether. Ethers occur as by-products during the sulfation of olefins
during alcohol production.
Epoxides are an important class of organics which are
closely related to ethers. Epoxides are highly reactive and will
rarely be found in significant quantities in wastewaters. The most
important epoxides are ethylene and propylene oxide, which are used
in many petrochemical syntheses.
f. halogenated hydrocarbons - Halogenation reactions
play an important role in petrochemical processing. Chlorine is the
most commonly used halogen. These processes result in the forma-
tion of many chlorinated by-products and side-products which are
discharged in the process effluents. Several classes of chlorinated
hydrocarbons can be identified by the processes from which they are
discharged.
Substitution reactions produce as side-products chlorinated
isomers or higher chlorinated hydrocarbons which are slightly soluble
in water and have an intermediate toxicity (Wright, 1959). Methyl
V-10
-------
and ethyl chlorides, chloroform, carbon tetrachloride, vinyl
chloride, and propylene chloride are examples of substitution
reaction products.
The addition of a halogen to an olefin is characterized by
an absence of by-product formation. Chlorinated hydrocarbons
from these processes are only slightly soluble and exhibit inter-
mediate toxicity (Wright, 1959). Another important addition product
is benzene hexachloride, which is used as an insecticide.
Hypochlorination reactions produce chlorohydrins which are
highly toxic but are normally hydrolyzed prior to discharge in the
process effluent. The hydrolyzed form is nontoxic and readily
biodegradable.
Chlorinated hydrocarbons are also used as solvents and as
cleaning fluids and may find their way into wastewaters from these
sources.
g. nitrogenated compounds - There are several different
types of nitrogenated organic compounds which may be found in petro-
chemical effluents.
The amines are alkyl or aryl compounds which contain a
nitrogen atom. They are characterized by the appreciable basicity.
The aliphatic amines are more basic than ammonia, while the aromatic
amines are considerably less basic. Amines with six or less carbon
atoms are water soluble, and the aromatic amines are usually
extremely toxic. Monoethanolamine and diethanalamine are important
solvents which are used to remove hydrogen sulfide and carbon
dioxide from gas or liquid petrochemical streams. These amine
treating units are sources of aqueous effluent containing amines.
Aliphatic and aromatic amines also can originate from processes
manufacturing or utilizing these compounds - hexamethylene diamine,
for example, appears in the effluent from nylon manufacture.
Nitriles, or organic cyanides, consist of a nitrogen atom
bound to a carbon atom by a triple bond constituting the cyanide
group. Nitriles can be either aliphatic or aromatic and yield the
corresponding alkyl or aryl acids when hydrolyzed. Acetonitrile is
used as a solvent to extract butadiene from mixed four-carbon
hydrocarbons (Beychok, 1967). Urea is a weakly basic compound which
forms salts with acids. It will hydrolyze to ammonia and carbon
dioxide in the presence of acids, bases, or through microbial action.
It is also used in the manufacture of urea-formaldehyde resins,
which are important in the manufacture of molded plastics.
Amides, derivatives of organic acids and ammonia, are
soluble in water and will hydrolyze in the presence of acids or bases
to produce ammonia and the corresponding acids.
V-ll
-------
h. phenolic compounds - Phenol consists of a benzene
molecule with one of the hydrogen atoms substituted by the hydroxyl
group. Cresols and xylenols, the other phenolic compounds which
are common in petrochemical wastes, differ from phenol in that
each has one or more alkyl groups connected to the benzene nucleus.
Phenol is relatively soluble in water, but some phenolic
compounds are considerably less soluble. The solubilities of
several phenolic-like compounds are presented in Figure V-l.
Phenols are more acidic in nature than the alcohols; they will form
salts with aqueous hydroxides, and aqueous mineral acids will
reconvert these salts to free phenols. These reactions are used
as the basis for treating petrochemical streams with caustic washes
to remove the phenolic contaminants. The majority of phenolic
pollutants in petrochemical effluents are found in spent caustics
used in the primary conversion processes, principally in the
catalytic and thermal cracking of petroleum.
i. organic sulfur compounds - There are several impor-
tant organic sulfur compounds which often appear in petrochemical
effluents, of which sulfonic acids, either aromatic or aliphatic,
are an important class. The sulfonic acid group consists of one
sulfur atom, three oxygen atoms,, and a hydrogen atom and is generally
indicated as -SOgH. Sulfonic acids are distinguished from the
esters of sulfuric acid by the direct bonding of the sulfur atom
to a carbon atom in the organic molecule rather than the bonding of
the oxygen atom to the carbon atom, as is the case with esters.
Sulfonic acids are highly polar and, therefore, more water soluble
than any other organic compound. Because of this high solubility,
sulfonic acid salts constitute the most common surface-active material
used in detergent manufacture. Sulfonic acids undergo all reactions
typical of organic acids, including salt formation, esterification,
and amide formation. Sulfonic acids and their salts will occur in
effluents from sulfonation processes and detergent manufacture.
Mercaptans are foul-smelling organic sulfur compounds which
contain a sulfhydryl group consisting of a sulfur atom and a hydrogen
atom bound to an organic molecule by a single carbon-sulfur bond.
These compounds are also known as thiols, and most of their chemical
and physical properties are similar to alcohols though considerably
more acidic in nature. Thiols are either aliphatic or aromatic, the
most common aromatic thiol being known as thiophenol. Considerable
quantities of thiols, particularly thiophenol, are present in some
crude petroleum stocks. Such crudes must be treated with caustic
washes to remove these compounds since they can poison catalysts
used in subsequent petrochemical processing. These sulfur compounds
will, therefore, be present in spent caustic streams from the primary
refining processes and in the effluents from catalytic and thermal
cracking of petroleum.
V-12
-------
460
420
380
340 +
IT 3004
UJ
DC
DC
UJ
OL
5
UJ
260
220 +
SOLUBILITY IN WATER (mg/l at 20°C)
200,000 400,000 600,000
2,6-XYLENOL,CST458°F
AT 45 WT %
2,5-XYLENOL.CST 426°F AT42 WT %
2,4-XYLENOL.CST 4I5°F AT 34 WT%
^- 2,3-XYLENOL,CST4IO°FAT 38 WT %
3,4 -XYLENOL, CST 372°F AT 35 WT%
3,5-XYLENOL,CST 388°F AT 35 WT%
0-,M-,P-CRESOL
0-CRESOL.CST 3308F AT 34 WT %
M-CRESOL.CST 300° F AT 36 WT %
P-CRESOL.CST 290°FAT 34 WT %
PHENOL,CST I54°F
AT 36 WT %
10 20 30 40 50
SOLUBILITY IN WATER (wt. %)
60
FIGURE V-l
SOLUBILITY OF PHENOLIC COMPOUNDS IN HATER
(Reference 4)
V-13
-------
Miscellaneous Organics - The classes of organic contaminants
previously listed include those which are common to several impor-
tant unit petrochemical processes and, as a rule, might be expected
in effluent streams. There are many compounds of miscellaneous
origin which cannot be simply categorized, but which are too impor-
tant to go unmentioned.
Wastes from many polymerization processes may contain small
amounts of the polymer or constituent being produced. For example,
butyl rubber scraps are present in process effluents from butyl
rubber polymerization and finishing processes. Polyethylene,
perchloroethylene, ABS, latex emulsions, and various vinyl polymers
might also be found in process wastewaters. Most of the polymers
are very insoluble in water and are essentially inert to biological
action.
Cokes and tars are complex organic wastes which are dis-
charged from the bottoms of distillation units. Cokes are formed
in high temperature treating processes and during catalyst regenera-
ation. These complex organics may contain significant quantities
of spent metallic catalysts, some having been previously discussed.
Tars and cokes are insoluble in water and normally are not amenable
to treatment by biological methods.
Furfural is a heterocyclic aldehyde which contains an oxygen
atom within the carbon ring. It is used as a solvent in several
extraction processes, including the extraction of butadiene from
four-carbon hydrocarbons and the removal of polycyclic aromatics
from oils (Beychok, 1967) .
Various complex oils are present in the effluents from many
unit processes. In aqueous process effluents, these oils may exist
in the free state or as emulsions. Some oils are forced as by-
products during polymerization and other processing. An example of
this type of oil is the "green oil" formed during acetylene hydro-
genation and butadiene manufacture from butylenes. Other oils are
simply mixtures of high molecular weight hydrocarbons.
V-14
-------
REFERENCES - CHAPTER V
1. Anon., Manual on Disposal of Refinery Wastes, Vol. Ill,
Chemical Wastes," American Petroleum Institute, New York
(1958).
2. Anon., "Petrochemicals Face New Challenge," Business Week,
no. 1618, p. 56 (Sept. 3, 1960).
3. Anon., Standard Methods for the Examination of Water and
Wastewater, American Public Health Assoc., New York, N. Y.,
12th ed. (1965).
4. Beychok, M. R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley & Sons, London (1967).
5. Chambers, C. W., Tabak, H. H. and Kabler, K. W., "Degradation
of Aromatic Compounds by Phenol-Adapted Bacteria," J. WPCF,
v. 35, n. 12, p. 1517 (Dec. 1963).
6. Cherry, A. B., Gabaccia, A. J. and Senn, H. W., "The Assimi-
lation Behavior of Certain Toxic Organic Compounds in
Natural Water," Sew. and Ind. Wastes, v. 28, n. 9, p. 1137
(Sept. 1956).
7. Dickerson, B. W., Campbell, C. J. and Stankard, M. , "Further
Operating Experiences on Biological Purification of Formal-
dehyde Wastes,1' Proc. 9th Ind. Waste Conf., Purdue Univ.,
p. 331 (1954).
8. Dougan, L. D. and Bell, J. C., "Waste Disposal Pit Synthetic
Rubber Plant," Sew, and Ind. Wastes, v. 23, n. 2, p. 181
(Feb. 1951).
9. Eckenfelder, W. W., Jr., Lecture Series Prepared for Manufac-
turing Chemists Assoc., The Univ. of Texas, Austin (1967).
10. Eckenfelder, W. W., Jr., Ford, D. L. and Burleson, N. K.,
Unpublished Report (July 1968).
11. Elkin, H. F., "Condensates, Quenches, Wash Waters as Petro-
chemical Waste Sources," Sew, and Ind. Wastes, v. 31, n. 7,
p. 838 (July 1959).
V-15
-------
12. Englebrecht, R. S., Gandy, A. F., Jr. and Cederstrand, J. R.,
"Diffused Air Stripping of Volatile Waste Components of
Petrochemical Wastes," J. WPCF, v. 33, p. 134 (Feb
1961).
13. Ford, D. L. and Eckenfelder, W. W., Jr., Unpublished Report
(March 1968).
14. Ford, D. L. and Gloyna, E. F., Unpublished Report (Jan. 1967).
15. Ford, D. L. and Gloyna, E. F., Unpublished Report (Feb. 1967).
16. Ford, D. L. and Gloyna, E. F., Unpublished Report (May 1967).
17. Ford, D. L. and Gloyna, E. F., Unpublished Report (July 1967).
18. Gandy, A. F., Jr. and Englebrecht, R. S., "The Stripping of
Volatile Compounds," Proc. 15th Ind. Waste Conf., Purdue
Univ., p. 224 (1960).
19. Gandy, A. F., Jr., Englebrecht, R. S. and Turner, B. G.,
"Stripping Kinetics of Volatile Components of Petrochemical
Wastes," J. WPCF, v. 33, p. 382 (1961).
20. Gloyna, E. F. and Burleson, N. K., Unpublished Report (March
1968).
21. Gloyna, E. F. and Malina, J. R., "Petrochemical Wastes Effect
on Water," Ind. Water & Wastes, pt. 1, Sept. - Oct. 1962,
p. 2, Nov. - Dec. 1962, pt. 3, Jan. - Feb. 1963, pt. 4,
March - April, 1963.
22. Heukelekian, H. and Rand, M. C,, "Biochemical Oxygen Demand of
Pure Organic Compounds," J. WPCF, v. 27, p. 1040
(1955).
23. Ludzack, F. J. and Ettinger, M. B., "Chemical Structures
Resistant to Aerobic Biological Stabilization," J. WPCF,
v. 32, p. 1173 (1960).
24. Martin, J. M., Kincannon, C. B. and Bishop, J. L., "Ultra-
violet Determination of Total Phenols," J. WPCF, v. 39,
n. 1, p. 21 (Jan. 1967).
25. Mencher, M. R., "Minimizing Waste in the Petrochemical Industry,"
Chemical Engineering Progress, v. 63, n. 10, p. 80 (1967).
26. Nemerow, N. L., Theories and Practices of Industrial Waste
Treatment, Addison-Wesley Pub. Co., Inc., Reading, Mass.
(1963).
V-16
-------
27. Noller, C. R., Textbook of Organic Chemistry, 2nd Edition.,
W. B. Sanders Co., Philadelphia, Pa. (1958).
28. Remy, E. D. and Lauria, D. T., "Disposal of Nylon Wastes,"
Proc. 13th Ind. Waste Conf., Purdue Univ., p. 596 (1958).
29. Senate Reports, Water Requirements for Pollution Abatement,
Select Committee on National Water Resources, 86th
Congress Committee Print No. 9 (1960).
30. Stephenson, R. M. , Introduction to the Chemical Process
Industry, Reinhold Pub. Corp., New York (1966).
31 Van Hall, R. E., Safranko, J. and Stenger, V. A., "Rapid
Combustion Method for the Determination of Organic
Substances in Aqueous Solutions," Analytical Chemistry,
v. 35, p. 315 (1963).
32. Willard, N. H. , Merritt, L. L. , and Dean, J. A., Instrumental
Methods of Analysis, Van Nostrand, Princeton, N. J. (1965).
33. Wilson, I. S., "The Treatment of Chemical Wastes," Waste
Treatment, Isaac, P. C. G., ed., Pergamon Press, London,
p. 206 (1960).
34. Wright, E. R. , "Secondary Petrochemical Processes as Waste
Sources," Sew, and Ind. Wastes J., v. 31, n. 5, p. 575
(May 1959).
V-17
-------
CHAPTER VI
WASTE POLLUTIONAL EFFECTS AND THEIR CHARACTERIZATION
The multitude of compounds present in petrochemical wastes
results in a variety of adverse effects that may be exerted on the
environment. A number of different methods have been used to
classify these pollutional effects, and they are categorized as
follows: (a) direct effects on the nature of the receiving waters,
(b) effects on the usability of the water, and (c) physiological
effects on the biological systems which either inhabit the receiving
waters or use them for purposes which might render them subject to
these effects. It should be recognized that groundwater as well
as surface water supplies can be subject to petrochemical pollution.
Although the effects of pollution on surface water are more readily
apparent, the less obvious pollution of groundwater is equally
important. The extent of some pollutional effects on surface
waters is documented (Klein, 1962; Hynes, 1965; Phelps, 1944).
Specific cases of pollution by petrochemicals in the Mississippi
River have been cited (Middleton, Licntenberg, 1960;Palange, 1960)
and in Europe (Krombach and Barthel, 1964).
EFFECTS OF POLLUTION ON RECEIVING WATERS
Many pollutional effects of wastes are interralated. For
example, biological and physical changes within a body of water
receiving wastes might affect the magnitude and diversity of the
aquatic organisms present. Additionally, water use might be affected
by the presence of an undesirable physical characteristic, such as
color.
Aesthetic Effects
The most graphic evidence of pollution is an unsightly and
odoriferous effluent caused by various types of pollutants. The
most obvious odors in receiving waters are those which result from
the anaerobic decomposition of organic materials (Kneese, 1962).
Visible effects of pollution, such as floating material, colored or
turbid water, and foaming are objectionable from an aesthetic stand-
point. The growth of large crops of algae caused by the addition of
plant nutrients in the form of nitrogen and phosphorus can cause
unsightly conditions (Kneese, 1962). Rubber particles from synthetic
rubber manufacture may be present in waste effluent from these
plants and are insoluble, relatively non-biodegradable, and floatable.
VI-1
-------
In a survey downstream from a plant producing butadiene and copolymer
rubbers, 650 pounds of rubber particles were found in a 25-mile
stretch of river (Dougan and Bell, 1951). Oil is a common petro-
chemical pollutant which is lighter than water and will float.
Oils can be present in wastewaters either as free oil or as emulsi-
fied oil. Generally, emulsified oils are dispersed throughout the
wastewater and will not physically separate from the aqueous phase.
Very small amounts of some oils can impart an iridescent sheen to
a body of water. It has been calculated that as little as 25
gallons of oil distributed over a water surface of one square mile
would be barely visible, but 200 gallons on the same area would cause
bright, iridescent colors on the water surface (Anon., API, Vol. I.,
1953).
Surface-active materials in petrochemical wastes, principally
from detergent manufacture, can cause foaming in receiving waters.
Some of these agents, particularly synthetic detergents such as
alkyl benzene sulfonate, are not readily degraded biologically, and
concentrations sufficient to cause foaming in receiving waters often
pass through waste treatment plants unaltered. As little as 0.5
mg/1 'of alkyl benzene sulfonate can result in foaming. New synthetic
detergents such as linear alkyl sulfonate and alpha olefin sulfonate
are biodegradable and have contributed towards alleviation of the
foaming problem. Most of the reported cases of foaming in surface
waters are caused by municipal wastes, but the possibility of surface-
active materials in wastes from petrochemical plants manufacturing
detergents also must be considered. Equipment washing operations
may also contribute surface-active agents to petrochemical waste
streams and must be recognized as another possible source of these
materials.
Many organic and inorganic compounds present in petrochemical
effluents can impart color to receiving waters. Anaerobic decompo-
sition can also cause a body of water to become black and unsightly.
Color has been discussed more thoroughly in the section on the
pollutional characteristics of petrochemical wastes.
Suspended solids can cause both color and turbidity.
Turbidity is a very objectionable quality not only as far as a
aesthetic aspects are concerned, but also because it decreases
light penetration, thus inhibiting photosynthetic organisms.
Biological Effects
Petrochemical wastes can exert a multiplicity of biological
effects in receiving waters. The most prominent effect of bio-
degradable organic matter is the biochemical oxygen demand which it
exerts on the receiving bodies of water. Aerobic microbial action
utilizes the dissolved oxygen in water to convert organic contami-
nants into new cellular products, partially oxidized intermediates,
carbon dioxide, and water. When large quantities of organic matter
are involved, the rate of oxygen demand by aerobic processes may
VI-2
-------
exceed the rate of oxygen replenishment from atmospheric or photo-
synthetic sources and this oxygen deficit can result in an anaerobic
environment which may cause deleterious effects. Anaerobic condi-
tions will also kill or drive off any aerobic organisms present in
the water, including fish and higher animals. Organic suspended
solids may settle out on stream bottoms where they undergo slow
anaerobic degradation. These settled organic solids can be re-
suspended during high stream flows and may exert an unexpected
oxygen demand on the stream. The biochemical oxygen demand (BOD)
values for many common petrochemicals are tabulated in Table VI-1.
Thermal pollution can have several biological effects on
receiving waters. Increasing temperatures increase the rate of
biological activity, enhance atmospheric oxygen transfer to the
liquid phase, and decrease oxygen solubility in water. The net
result of a temperature increase is the exertion of a higher oxygen
demand on the system, causing possible anaerobic conditions which
might not have occurred at normal temperatures. At temperatures
exceeding 35°C, many aquatic microorganisms will not survive (Anon.,
API, Vol. III.,1958). There are, however, some resistant species
of bacteria and algae which can tolerate temperatures as high as
55°C.
Most fish are adversely affected by elevated temperatures.
Some of these unfavorable effects are listed below (Klein, 1962):
a) death of the fish due to temperature above the
lethal limits;
b) death due to shock from a sudden temperature change;
c) death due to dissolved oxygen concentrations below
the lethal limit, resulting from the decrease in
oxygen solubility at increased temperatures;
d) decreased productivity at temperatures which are
nonlethal, but which exceed optimum spawning and
egg-hatching levels; and
e) increased toxicity of certain chemicals to fish at
elevated temperatures.
The lethal temperatures for some of the more important game fish
are listed in Table VI-2. Lethal effects of heated effluents are
discussed in detail in the paper by Alabaster (1964). The tempera-
tures given in Table VI-2 do not reflect the possibility that
temperatures below these lethal maximums may disrupt the reproduc-
tion of the species in question. The effects of water temperature
on the reproduction of various species of fish are still not fully
understood; however, these effects are of vital importance when the
disposal of a high temperature waste is considered.
VI-3
-------
TABLE VI-1
FIVE-DAY BOD VALUES FOR SOME PURE ORGANIC COMPOUNDS
Compound
Acid Anhydrides
Phthalic Anhydride
Maleic Anhydride
Alcohols
Methanol
Ethanol
n-Propanal
i-Propanal
n-Butanal
Cyclohexanol
Ethylene Glycol
Pentaerythritol
Aldehydes and Ketones
Formaldehyde
Acetaldehyde
Furfural
Acetone
Methyl Ethyl Ketone
Esters
Ethyl Acetate
Ethers Diethylether
OFTEN FOUND
BOD
(gm/gm)
0,72-1.26
0.4-0.6
0.76-1.12; 1.24
0.93-1.67; 1.46
0.47-1.5
1.29-1.59
1.1-1.65
0.08
0.16-0.68
-
0.33-1.06
1.27
0.77
0.31-1.63; 1.19
2.14
0.29-0.86
n:l
IN PETROCHEMICAL WASTES
Method
Std. dil.
Warburg
Warburg
Warburg
Warburg
Warburg
Warburg
Warburg
Warburg
-
Std. dil.
Std. dil.
Std. dil.
Std. dil.
Std. dil.
Std. dil.
Std. dil.
COD*
Seed (gm/gm)
Sewage
Sewage
Sewage 1.42
Sewage 2.0
Acclimated "
Sewage
Sewage
Sewage
Sewage
Sewage
1.23
Sewage 1.06
Sewage
Sewage
Sewage 1.63
Acclimated "
Sewage
Sewage
Sewage
Ref
51
28, 51 , 91
51 , 91
51
28
28, 51
51, 91
-------
TABLE VI-1 (Continued)
FIVE-DAY BOD VALUES FOR SOME PURE ORGANIC COMPOUNDS
<
M
I
OFTEN FOUND IN PETROCHEMICAL WASTES
Compound
Halogenated Hydrocarbons
Ethylene Dichloride
Ethylene Chlorohydrin
Chloroform
Monochlorobenzene
Hyd r oc arb on s
Benzene
Xylene
Toluene
Naphthalene
Nitrogen-containing Organics
Nitrobenzene
Pyridine
Ethanolamine
Diethanolamine
Aniline
p-Toluidine
o-Toluidine
Acrylonitrile
Acrylamide Monomer
Adiponitrile
Hexamethylene Imine
BOD
(gm/gm)
0.002
0.5
0-0.008
0.03
0
0
0; 1.23
0
0
0-1.47
0.78
0.10
1.49-2.26
1.44-1.63
0.24-1.43
0.72
0.97
-
1.31
Method
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
Std.
-
Std.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
dil.
*
COD
Seed (gm/gm) Ref
Sewage
Sewage
Sewage
Sewage
Sewage 51
Sewage
Sewage 1.88 51, 91
Acclimated "
Sewage "
Sewage
Sewage
Sewage
Sewage
Sewage 2.4
Sewage
Sewage
Acclimated 28
Acclimated
1.9 74
Acclimated 2.17 74
-------
TABLE VI-1 (Continued)
FIVE-DAY BOD VALUES FOR SOME PURE ORGANIC COMPOUNDS
i
ON
OFTEN FOUND IN PETROCHEMICAL WASTES
Compound
Organic Acids
Formic Acid
Acetic Acid
Propionic Acid
Butyric Acid
Maleic Acid
Benzoic Acid
Phthalic Acid
Methacrylic Acid
Salycylic Acid
Glutaric Acid
Succinic Acid
Valeric Acid
BOD
(gm/gm)
0.02-0.27
0.34-0.88; 0.62
0.36-0.84; 0.96
0.34-0.90; 1.16
0.38; 0.63
1.34-1.40; 1.36
0.85-1.44; 1.4
0.89
0.97
0.72
0.57
-
Method
Std.
Std.
Std.
Std.
Warburg;
Std.
Std.
Std.
Std.
Std.
Std.
dil.
dil.
dil.
dil..
Std. dil.
dil.
dil.
dil.
dil.
dil.
dil.
-
**
Seed
Sewage
Sewage
Acclimated
Sewage
Acclimated
Sewage
Acclimated
Sewage
Acclimated
Sewage
Acclimated
Sewage
Acclimated
Sewage
Acclimated
Acclimated
Acclimated
-
COD"
(gm/gm)
1.0
it
1.4
ii
1.65
ii
0.93
n
1.88
n
0.86
ii
1.58
1.21
1.85
1.85
Ref
51, 91
51, 91
51, 91
51
74
74
74
-------
TABLE VI-1 (Continued)
FIVE-DAY BOD VALUES FOR SOME PURE ORGANIC COMPOUNDS
OFTEN FOUND IN PETROCHEMICAL WASTES
Compound
Phenolic Compounds
Phenol
Phenol
o-Cresol
m-Cresol
p-Cresol
1, 3, 5-Xylenol
BOD
(gm/gm)
2.0
1.4-1.8; 1.66
1.69; 1.74
1.70; 1.88
1.4; 1.76
0.82
Method
Man ome trie
Std. dil.
Std. dil.
Std. dil.
Std. dil.
Std. dil.
**
Seed (gm/gm) Ref
Adapted 3.2 51
Sewage 2 . 28 51 , 91
Acclimated "
Sewage 2.39 91
Acclimated "
Sewage 2.4
Acclimated "
Sewage 2.4
Acclimated " 51
Sewage
* By Dichromate Method - Standard Methods, 1965
** BOD values obtained by the use of sewage seed (unacclimated waste seed) may not be representative
and most likely are low.
-------
TABLE VI-2
LETHAL TEMPERATURES FOR SOME SELECTED FISH SPECIES
(Reference 59)
Lethal Temperature*
Fish (°C)
Bluegill 30.7
Brown Trout 23-26
Carp 31-34
Catfish 31.8
Chinook Salmon (fry) 25
Coho Salmon 24.3
Fathead Minnow 28.2-33.2
Goldfish 30.8
Largemouth Bass 32.5-36.4
Perch 23-25
Rainbow Trout 28-24
Speckled Trout 25
*
The lethal temperature is a function of the acclimation
temperature of the test specimen. Higher acclimation
temperatures will result in higher lethal temperatures.
Vl-8
-------
The net biological effect of petrochemical waste pollution
is a change in the environmental conditions in the receiving waters.
Changes which are highly visible may occur, such as anaerobic
conditions. Other changes may be more subtle in nature, and although
not readily noticeable will possibly have far-reaching effects.
Some of these subtle effects follow.
a) There are changes in the flora, and fauna (bacteria, algae,
protozoa) which are important elements in the food
chain. Polluted water often favors the growth of
one species of organism over others, and the
degree of species diversity in natural waters has
been used as a pollution indicator. The bloom
of various algal species in water containing
excess nitrates and phosphates is a well-known
indicator. The change in predominance of one
member of the food chain affects all the other
members. For example, fish may have to leave an
area if a lower-chain food organism is eliminated.
b) Pollutional effects may not injure the organisms
present in the water but may alter their reproduc-
tive patterns so as to affect their progeny.
c) Various types of pollutants may affect the living
habits of aquatic organisms and may cause an erratic
pattern in their behavior.
Detailed accounts of the biological effects of pollution
are available elsewhere (Klein, 1962; Tarzwell, et. al.,1965;
Phelps, 1944; Anon., Oxygen Relationships in Streams, 1958).
Miscellaneous Effects
The effects of petrochemical wastes on the recreational
capacity of receiving waters are closely related to the aesthetic
and biological effects of wastes. Any pollution which causes
unsightly conditions and kills or drives off sport fish will decrease
the recreational aspects of the water.
Land use and transportation can also be affected directly by
pollution since chemical pollutants may make water unsuitable for
domestic, industrial, and agricultural uses. It is well known that
land used for public domain, such as parks and recreational areas,
depends upon the use of nearby bodies of water. Additionally, the
discharge of wastes carrying large quantities of suspended or
dissolved solids which precipitate under given conditions can result
in the formation of sludge banks in the receiving water, thus affecting
water-borne transportation (Anon., API, Vol. III.,1958). Waters of
low pH can also corrode the steel hulls of ships.
VI-9
-------
EFFECTS OF POLLUTION ON WATER USE AND REUSE
Various petrochemical pollutants, both chemical and physical,
may affect the potential future uses of wastewater or receiving
waters.
Water Quality for In-Plant Reuse
In-plant reuse of wastewater by the petrochemical industry
offers an economical approach for reducing wastewater discharges
to receiving waters. Water quality required for various in-plant
uses varies greatly with some processes requiring demineralized
water, while cooling water can often contain considerable quantities
of inorganic solids. The quality of water required for various
petrochemical processes is discussed below.
Cooling Water
Recirculation of cooling water is now common practice in
many petrochemical plants. The most important consideration in
cooling water use is preventing the deposition of precipitates in
water pipes and in the process coolers (Beychok, 1967) . The solu-
bilities of the most common salts found in cooling water are given
in Table VI-3. The principal problems are caused by calcium
carbonate, magnesium carbonate, and calcium sulfate as indicated
by their low solubility. Water can be used for cooling purposes
without pretreatment if the concentrations of these compounds,
particularly the carbonates, are below the values in Table VI-3.
It may be economically feasible to treat particular waste streams in
order to render them suitable for cooling water reuse. Water used
for cooling purposes should also be free of biological growth and
should be noncorrosive. The latter requirement eliminates the use
of acidic wastes as cooling water unless they are properly neutralized.
Cooling water should have a low organic content because these materials
serve as a substrate source and may create excessive biological
growth. Potentially toxic metal and organic compounds are often
added to prevent the growth of bacteria and algae and inhibit
corrosion in cooling water (chromates, phosphates and polyphosphates,
lignins and tannins, chlorinated phenols, copper compounds). The
concentrations of these additives are usually sufficiently low to
avoid toxicity problems.
Process Waters
Chemical processes used in the petrochemical industry require
many levels of water quality. All of these processes with their
respective quality requirements cannot be listed easily. Many
processes have stringent prerequisites for their water and the
required quality indicates the economic necessity for reusing some
waste streams as process waters.
VI-10
-------
TABLE VI-3
SOLUBILITY OF COMMON SALTS*
Chlorides
Carbonates Sulfates
Calcium 520,000
Magnesium 270,000
Sodium 270,000
17 2,200
125 330,000
290,000 310,000
At 120° F
Note: Solubilities are in mg/1.
VI-H
-------
Water Quality Required for Other Users
The effects of petrochemical wastes on the utility of water
for other users is important. These other users can be grouped
into three categories: domestic water supply, agricultural water
supply, and industrial water supply. It should be mentioned that
many "natural" waters, untouched by man-made pollution, do not meet
the quality standards required by potential users without pre-
treatment. The pollution of water by petrochemical wastes is only
an important factor when undesirable compounds which cannot be
removed at all or which can only be removed at a high cost to
the user are added to the water. Some of the petrochemical contami-
nants previously discussed fall into this category.
Agricultural Uses - Some of the compounds present in petro-
chemical wastes may be toxic to plants and livestock. High concen-
trations of inorganic dissolved solids are detrimental to both
plants and livestock. Water given to livestock is nearly always
untreated and must not contain toxic materials such as the catalytic
heavy metals discharged from petrochemical processing. The water
quality requirements for irrigation purposes are given in Table
VI-4.
Since crops vary greatly in their sensitivity to salinity,
the water qualities expressed in Table VI-4 are classified in terms
of their relative suitability for irrigation purposes. It should
be recognized that a few crops may be able to stand salinity
concentrations in excess of these concentrations. Sodium, an impor-
tant constituent of petrochemical spent caustic effluents, reacts
with soil to reduce its permeability and thus is an important
parameter for judging the utility of a water for irrigation (Todd,
1959).
Industrial Use - Industrial quality requirements are highly
variable. Some industries such as brewing and distilling industries
require high quality water. Others such as the chemical industry
and those which use large quantities of cooling water can tolerate
water relatively poor in quality. A recent nationwide survey of
industries showed that 58 percent of those reporting treated all or
part of their water intake (Anon., Water in Ind.,1965).
One industry which may be severely affected by petrochemical
pollution is the fishing industry. Besides the possibility of fish
mortality due to pollution, some petrochemicals have been blamed for
the tainting of fish flesh.
Effects on Water Treatment Processes
Some compounds present in petrochemical wastes have been
implicated in creating problems associated with conventional water
VI-12
-------
TABLE V1-4
WATER QUALITY FOR SELECTED AGRICULTURAL USES
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
(Reference
Sensitive
Crops
<0.33
0.33-0.67
0.67-1.00
1.00-1.25
>1.25
86)
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
-------
treatment. Oils will interfere with coagulation and filtration
processes (Gloyna and Malina, 1962) while organic acids have been
suspected of causing deterioration of anionic exchange resins used
for dimeralization (Skold and Wilkes, 1955)."" Suspended solids
may cause clogging and stoppage in the piping systems carrying them.
Surface-active chemicals, principally detergents, have
caused foaming problems in some water treatment plants and can also
impart tastes to drinking water.
Effects on Groundwater
During the three-year period from 1957 through 1959, 22
states reported groundwater pollution by oil or petroleum products
and 15 states reported cases of pollution involving various other
chemical contaminants (Anon., Comm. Kept., Task Grp. 245.,1960).
Petrochemicals were specifically indicated as a source of ground-
water pollution in one case, while high nitrate concentrations in
well water were attributed to the lagooning of wastes from nitro-
geneous fertilizer manufacture in another (Anon., Comm. Kept.
Task Grp. 245., 1960). Disposal wells, lagoons, and surface dumping
were the most important potential sources of pollution by petro-
chemical wastes listed in the report. Some of the organic compounds
which have been found in groundwater are listed in Table VI-5 (Gloyna
and Malina, 1962).
It is also possible for several innocuous compounds to
react, forming a product which is far more toxic or creates a con-
siderably more difficult taste and odor problem than the original
compounds.
PHYSIOLOGICAL EFFECTS OF PETROCHEMICAL WASTES
Almost every effect of pollution can be considered a physio-
logical effect in a general sense. The biological effects of
organic wastes in receiving waters are in reality physiological
effects on the inhabitants of the water. Even aesthetic effects
can be considered physiological in that they act on the senses of
man to produce a reaction. The physiological effects which will be
considered here are those which are most prevalent to the observer,
namely, taste, odor, and toxicity.
*
Organic matter can also interfere with ion exchange processes by
coating the resin or by reacting chemically with it (Bacon and
Lewis, 1960). The annual losses which can be caused by organic
interferences can be as high as 25 to 33 percent for anionic resins,
VI-14
-------
TABLE VI-5
ORGANIC CHEMICAL POLLUTANTS IDENTIFIED IN GROUNDWATER
(Reference 45)
Alkyl Benzene Sulfonates
2, 4-Dichlorophenoxyl Acetic Acid
Dichlorophenol
Gasoline
Hexachlorocyclohexane
Hydrocarbons
Nitrates
Oil
Pentachlorophenol
Phenol
Phosphates
Picoline
Picric Acid
Pyridine
Trichloroethylene
VI-15
-------
It is first important to understand the effects which mixtures
of compounds have on the toxicity or taste and odor of the individual
components. Antagonism occurs when the mixing of two or more
compounds causes the effects of each to be reduced. The combined
effects are therefore less than the sum of the individual effects.
Synergism is the cooperative action of each component in a mixture,
so that the effect produced by the mixture is equal to or greater
than the sum of the effects considered independently. Recently, a
new term - potentiation - has been used to describe the latter effect
while synergism has been used to describe the former. However, the
term synergism is commonly used to describe both effects.
Most investigations concerning taste and odor have not
included these effects due to the difficulty in assessing them.
More research is required to identify these synergistic and antago-
nistic interactions and until this is accomplished only general
statements about the effects can be made.
Taste and Odor
The senses of taste and odor are virtually inseparable in
most cases and most investigations emphasize or deal exclusively
with odor, since taste effects are biased by olfactory sensations.
(Baker, 1963). Probably the best discussion of these physiological
properties and all their implications is given in a review by
Baker prepared for the Manufacturing Chemist's Association (1961).
Detailed discussions of the various theories pertaining to taste
and odor are given in this review and in others (Raines, et. al. ,
1954; Anon., Soc. of Chem. Ind.,1957; Timmermans, 1954; Wright, et.
al., 1956).
Many compounds in petrochemical wastes cause tastes and
odors at very low concentrations with the synergistic effects of
complex mixtures significantly magnifying these effects. 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. A mixture containing
each compound at its threshold value produced a significant olfactory
response (Baker, 1963). Binary mixtures of selected pairs of these
compounds showed similar effects. Any or all of these chemicals
might be found in a petrochemical effluent, and the significance of
these results in taste and odor problems is apparent.
Detectable concentrations of some common petrochemical waste
constituents are listed in Table VI-6. Probably the most common and
most objectionable odor-causing compound contained in this list is
hydrogen sulfide. Hydrogen sulfide may be present in petrochemical
wastes or may be formed during the anaerobic decomposition of these
wastes.
VI-16
-------
TABLE VI-6
DETECTABLE CONCENTRATIONS OF SOME PETROCHEMICAL COMPOUNDS
CAUSING
Compound
Ammonia
Amyl Acetate (iso)
Benzaldehyde
Carbon Disulfide
Chlorophenoli.es
- Monochlorophenol
Dimethylamine
Ethyl Me re apt an
Formaldehyde
Furfural
Hydrogen Cyanide
Hydrogen Sulfide
Methyl Me re apt an
Nitrobenzene
Petrochemical Wastes
Phenolics
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
59
59
59
59
11
59
81
11
11
11
51
59
59
59
59
11
11
11
11
59
11
1 •
VI-17
-------
Compounds containing nitrogen, principally the amines, are
also malodorous and are found in various petrochemical wastes,
particularly in those discharged from synthetic fiber manufacture
(Taylor, et. al.,1961).
Phenol probably has been the organic chemical most often
associated with taste and odor problems. The United States
Public Health Service Standards establishing maximum allowable
phenol concentrations in drinking water are based solely upon taste
and odor considerations. Phenol itself is relatively odorless and
tasteless, the minimum detectable concentration being 0.25-4.0
mg/1 (Baker, 1963). The taste and odor problems caused by phenols
occur when water is disinfected by chlorination. Dichlorophenols
are formed and give water a characteristic medicinal taste at con-
centrations as low as one ppb. Various studies have shown the
mechanisms by which chlorophenols are formed and the conditions
required for their formation (Burttschell, et. al.,1959) . 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
(Kinney, 1960a; Kinney, 1960b) . For example, other chlorinated
hydrocarbons have been identified as a major source of tastes and
odors.
Petrochemical wastes contain many organic chemicals which
can interact to produce tastes and odors. A study of a refinery
wastewater indicated that the neutral organic compounds (nonpolar)
consisting principally of aliphatic and aromatic hydrocarbons were
the primary source of odor in the wastewater (Ruchhoft, et. al.,
1954). The oxygenated and aromatic fractions of the neutral organic
groups were also found to be the most odiferous in a similar investi-
gation. This was found to be a complex mixture of hydrocarbons,
alcohols, aldehydes, ketones, esters, and nitriles; and the odors
caused by this fraction could not be attributed to any single compound
(Middleton, et. al.,1956). Many neutral organic compounds are
commonly found in petrochemical wastes. Organic acids are also
found, and many of these acids can cause tastes and odors in water.
Alkyl benzene sulfonates can be detected by some people at concen-
trations below one mg/1 (Klein, 1962; Filicky and Hassler, 1950).
Many taste- and odor-producing compounds are therefore potentially
present in petrochemical wastewaters. Since tastes and odors in
water have such an anverse effect on many uses, each waste must be
carefully tested to determine if it causes such an effect and if so,
what treatment must be required.
One instance in which taste can be separated from odor is
in the causation of adverse tastes in fish flesh. 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
VI-18
-------
found in petrochemical effluents and are able to cause these effects
are listed in Table VI-7. Styrene and aldehydes from synthetic
rubber manufacture have also been demonstrated to taint fish flesh
(Klein, 1962).
Many natural compounds can also produce tastes and odors
in water. Decaying vegetation is often responsible for releasing
phenolic compounds to water (Hoak, 1956; Smith, 1961) and hydrogen
sulfide, mercaptans, and organic nitrogen compounds are formed
during the anaerobic decomposition of organic material. Algae and
their metabolic products are probably the most important cause of
taste and odor while other microorganisms such as actinomycetes have
also been implicated (Baker, 1961; Silvey, et. al.,1950).
Toxicity
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.
The toxicity of a chemical is directly related to the dosage
of the chemical ingested or otherwise taken into the body of the
aquatic organism. In water the toxic effects of a chemical can
best be described in terms of the concentration threshold, above
which some type of physiological damage to the organism will not
affect the subject during its normal life span, even if the com-
pound is administered throughout the life span. This later effect
has been demonstrated for every toxic compound which has been
studied, including the chemical carcinogens (Zapp, 1960).
It is desirable to distinguish between the classes of toxic
action. These classifications 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 (Gloyna and Malina, 1962).
Acute toxicity is characterized by the rapid onset of nega-
tive physiological effects after exposure. Chronic toxicity is
usually manifested by the appearance of negative physiological effects
after a prolonged dosage of a chemical at concentrations below the
acute level. These effects are often the result of the accumula-
tion of the toxic compound in the tissues or organs of the organism.
The mode of action of toxic compounds depends on their chemical
characteristics and is discussed in detail in many books on toxicology,
(i.e., Dubois and Ceiling, 1959).
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.
Garcinogenesis is the chronic effect which has probably received the
most attention. Many compounds which have been found to exhibit
carcinogenic effects are present in petrochemical wastes of which
VI-19
-------
TABLE VI-7
SOME ORGANICCHEMICALS 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
Ot -Methyl styrene
Isopropylbenzene
Ethyl Benzene
$ ^g -Dichloroethylether
o-Dichlorobenzene
Toluene
Cresylic Acid (m,p)
Kerosene
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
(tng/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
59, 82
59
59
59
59
59
59
59
59
59
59
59
82
82
82
82
82
82
82
82
82
82
82
82
82
82
82
82
82
Above Toxic Limit
Test Fish Not Reported
VI-20
-------
certain polynuclear aromatic compounds, aromatic amines, and aromatic
nitro-compounds are examples. The complex hydrocarbons and tars
have also been indicated as possible carcinogenic agents (Hueper
1960). These compounds can originate from any petrochemical
processes, and many of them are probably present in petrochemical
wastewaters. However, the concentrations of these compounds in
receiving waters are generally low. Little is known about the
physiological effects of chronic exposure to these compounds and
the possibility of synergistic action between a number of these
compounds. The use of carbon chloroform extract from water samples
has been proposed as a basis for limiting the exposure of man to
these compounds (Ettinger, 1960). The most recent United States
Public Health Service drinking water standards (1962) recommend
an arbitrary maximum carbon chloroform extract concentration of 0.2
mg/1. Much more data are needed before the actual chronic effects
of these compounds on man can be accurately determined.
The toxicity of other chemicals which have petrochemical
origins has also been investigated, but most of these studies deal
with gaseous contaminants such as nitrogen dioxide (Cooper and
Tabershaw, 1966) . Few studies have been made which show the effects
on higher animals by the ingestion of organic chemicals via the
water route. Some research has been directed toward determining the
toxicity effects of surface-active materials in water indicating
that these compounds do not have chronic effects on higher animals
at concentrations up to 1,000 mg/1 in drinking water (Paynter, 1960).
A great deal of data is available on the toxicity of chemical
compounds to aquatic organisms. The toxicity of many petrochemical
pollutants has been evaluated using both microorganisms and fish.
It must be noted that most of these investigations determine the
acute toxicity of a compound to a particular organism. Chronic
effects and any effects on the genetic reproduction characteristics
of the organism are difficult to determine and not usually listed.
Therefore, the toxicity data which are presented can only represent
the relative toxicity of a compound and do not consider the effects
of other toxic compounds which might be present.
Toxicity to Microorganisms - Toxic effects of chemicals on
aquatic microorganisms are extremely important. Bacteria in natural
waters decompose the organic material from petrochemical wastes and
subsequently serve as the food source for some higher microorganisms
such as protozoa. Protozoa and algae both serve as food sources
for macro-organisms (insects, fish) and algae are extremely important
in that they contribute an important source of oxygen to the
receiving waters via photosynthesis. The extinction of any of these
organisms due to toxic chemicals will have a profound adverse effect
on the general ecology of the aquatic system.
VI-21
-------
Two detailed investigations of the toxicity of certain
organic chemicals to algae have recently been reported. (Thirumurthi
and Gloyna, 1965; Huang and Gloyna, 1967). The results of these
studies are applicable to petrochemical wastes contaminants and
are shown in Table VI-8 . The algae used in these investigations was
Chlorella pyrenoidosa, a common inhabitant of ponds and streams.
Toxicity was determined by measuring the reduction in chlorophyll
content of a suspension of algae exposed to the compound under
rigidly controlled environmental conditions. Reduction in oxygen
production as measured manometrically was also used as an indication
of chemical toxicity (Huang and Gloyna, 1967). The effects of
environmental conditions on toxicity cannot be overemphasized. Slight
changes in temperature, incident light, and nutrients significantly
affect the nature of a compound as a toxicant.
Data obtained using structurally similar fatty acids,
alcohols, and aldehydes indicate that relative toxicity is somewhat
dependent upon the molecular structure. These data suggest that
(a) straight-chain fatty acids with an odd number of carbon atoms
are mo-re toxic than those with an even number of carbon atoms,
and (b) the straight-chain fatty acids with four- and five-carbon
atoms are more toxic than the corresponding branched-chain acids.
In general, straight-chain organics seem to be more toxic than those
with branched-carbon chains (Thirumurthi and Gloyna, 1965).
It has been observed that certain phenolic compounds and
pesticides reduce the chlorophyll concentration and photosynthetic
activity of Chlorella pyrendoisa (Huang and Gloyna, 1967). The
toxicity of phenolic compounds to this algae was found to be
dependent on the functional groups attached to the ring and their
position on the ring. Nitrated and halogenated phenols are more
toxic than alkylated and aminated phenols. The insecticide Lindane
was found to be about 100 times as toxic to Chlorella pyrenoidosa
as was phenol (Huang and Gloyna, 1967).
These investigations reveal that many compounds commonly
found in petrochemical effluents are highly toxic to algae. The
effects of this toxicity on the oxygen resources of a receiving
body of water or waste stabilization pond treatment system must be
considered when the toxic properties of a waste are being evaluated.
The use of microorganisms such as algae for indicators of
toxic pollutants will be discussed subsequently.
Fish Toxicity - Fish are the test animals most frequently
used in determining the toxicity of aqueous wastes. This is true
for two reasons: (a) they are relatively easy to use and control,and
(b) their response to toxic materials is one of the more valid
indicators of the true toxicity in natural waters. The toxicity
VI-22
-------
TABLE VI-8
COXICITY OF SOME SELECTED PETROCHEMICALS
TO CHLORELLA PYRENOIDOSA
Organic Chemical
Alcohols
Methanol
Ethanol
1 - propanal
2 - propanal
1 - butanal
2 - butanal
3 - butanal
Aldehydes
Propanal
1 - butanal
Glycols
1, 2 Ethanedial (Ethylene glycol)
1, 2 Propanediol
Pesticides
Lindane
2, 4 - D
t_ 5 -r
2, 4, 5 - T
*•" 5 ' 3
DDT in Xylene
Mai thane
Phenol ics
Phenol
Phenol
Cresol
Cresols (ortho,meta, para)
o-Bromophenol
m,p-Bromophenol
o-Chlorophenol
m,p-Chlorophenol
2, 4 - Dichlorophenol
2, 4, 5 - Trichlorophenol
Pentachlorophenol
Xylenols
Toxic Cone.
(mg/1)*
31,100
27,200
11,200
17,400
8,500
8,900
24,200
3,450
2,500
180,000
92,000
2.3
144
122
120.0
160.0
1,060
233
800
148 - 171
70
/ o
If*
JO
An
^•U
1 C
1 . 3
0 001
\J * \J \S -1-
49 - 81
!-(•_/ \J J~
. . —
Ref
84
84
84
84
84
84
84
84
o /
84
84
Ci /
84
50
50
50
84
84
84
cn
3U
QA
OH-
50
50
50
50
50
50
50
50
50
1 —
VI-23
-------
TABLE VI-8 (Continued)
TOXICITY OF SOME SELECTED PETROCHEMICALS
TO CHLORELLA PYRENOIDOSA
Toxic Cone.
Organic Chemical (mg/1)* Ref
Nitrophenols 9-14 50
o-Aminophenol 47 50
m,p-Aminophenols 140 50
Hydroquinone 178 50
Organic Acids and Salts
Methanoic acid 220 84
Ethanoic acid 350 84
Propanoic acid 250 84
Butanoic acid 340 84
2-Methyl Propanoic acid 345 84
Pentanoic acid 280 84
Propenoic acid 120 84
Butenoic acid 280 84
Ethanoic anhydride 360 84
Based on 50% Reduction in Chlorophyll Content
VI-24
-------
of a chemical is a function of the prevailing environmental condi-
tions. The most important environmental parameters in toxicity
tests include pH, temperature, dissolved oxygen concentration, and
the water hardness (Cairns, 1957). These environmental factors are
controlled in the laboratory bioassay which is the most commonly
used method for defining the acute toxicity of a specific compound
to fish. The bioassay basically consists of exposing acclimated
fish to various concentrations of the test compound. These procedures
are completely described in other sources (Jones, 1964; Standard
Methods. 1965).
The most commonly accepted fish toxicity parameter is the
median tolerance limit (TLjf) which is the concentration of the
test compound at which 50 percent of the test fish survive for a
selected test period. The TLM values obtained from the bioassay
are a measure of the acute toxicity of a specific chemical and
cannot be used to estimate possible chronic or cumulative effects.
In cases where it is necessary to measure the toxicity of a mixed
chemical waste, a bioassay using various concentrations of the
mixed waste is used to determine the toxic concentration. The TLM
values for an industrial waste of complex composition are reported
as a percent by volume dilution (Standard Methods, 1965). For
example, a 10 percent TL^ represents one part of wastewater diluted
with nine parts of receiving water.
A great deal of bioassay data are available for a variety
of chemicals and species of fish. The TLM values for many of the
compounds found in petrochemical wastes are given in Table VI-9.
Included with the TLj^ values for pure compounds are some TL^ values
for mixed wastes. By measuring the toxicity of a mixed waste, the
possibility of a reaction of nontoxic compounds in the waste to form
toxic compounds is considered. For example, a cholinesterase-
inhibiting compound was found naturally in the effluent formed in a
chemical plant by the oxidation of its precursor, which was manu-
factured in the plant (Teasley, 1967). Synergistic and antagonistic
effects can also be taken into account by using this procedure. It
can be seen from Table VI-9 that the toxic concentrations for a
given compound are dependent upon the species of fish tested and
the hardness of the test water. These factors must be considered
when the toxic effects of a pure compound are applied to a natural
stream. In general, game fish such as trout and bass are more
sensitive to the toxic effects of chemicals than are forage and
"rough" fish.
Median tolerance limits (TLM) determined in the laboratory
can be used only to estimate the toxicity of a compound to a given
species of fish under the environmental conditions imposed in the
laboratory. Since "no effect" or less than threshold concentrations
VI-25
-------
TOXICITY BIDASSAY RESULTS
<
M
TL (Median Tolerance Limit)
m
24 Hr 48 Hr
Compound (mg/1) (mg/1)
Acetamide 26,300 26,300
Acetic Acid 251 251
Acetone 13,500 13,000
Acetaldehyde 70
Acetonitrile
Acrylonitrile
Adiponitrile
Alkyl Aryl Sulfonate 4.2 3.7
4-Amino-m-Toluene
Sulfonic Acid 425 410
Ammonia
Ammonium Acetate 238 238
n-Amyl Acetate 65 65
96 Hr
(mg/1)
13,300
251
13,000
1,020
1,000
1,850
1,650
14.3
18.1
11.8
33.5
24.5
820
1,250
720
775
0.86
375
8.2
238
65
Test Animal
Mosquito fish
Mosquito fish
Mosquito fish
Pinperch
Fathead Minnows
Fathead Minnows
Bluegill
Guppies
Fathead Minnows
Fathead Minnows
Bluegill
Guppies
Pinperch
Fathead Minnows
Fathead Minnows
Bluegill
Guppies
Bluegill
Mosquito fish
Fathead Minnows
Mosquito fish
Mosquito fish
Remarks
Hard Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Hard Water
Ref
88
88
88
47
47
47
47
47
47
47
47
42
47
47
47
47
87
88
47
88
88
-------
TABLE VI-9 (Continued)
TOXICITY BIOASSAY RESULTS
TLm (Median Tolerance Limit)
Compound
Benzonitrile
Benzene
Benzoic Acid
< Butadiene
^ 2-Butanone
Carbon Disulfide
o - Ch 1 or opheno 1
Cresol
Cupric Chrome -
Gluconate
1-Cyano-l, 3 Butadiene
DDT (25% active in xylene)
Diethanolamine
24 Hr 48 Hr
(mg/1) (mg/1)
395 395
20 20
240 225
71.5
5,600 5,600
162 135
8.2 8.1
24 24
420 365
71.5
1,800 1,550
2,100 1,850
96 Hr
(mg/1)
78
135
78
400
386
6
180
5,600
135
24
13.6
10.9
10.0
83
0.180
0.100
0.010
0.001
0.100
1,400
430
Test Animal
Fathead Minnows
Fathead Minnows
Bluegill
Guppies
Mosquito fish
Bluegill
Mosquito fish
Pinperch
Mosquito fish
Mosquito fish
Bluegill
Mosquito fish
Bluegill
Bluegill
Bluegill
Bluegill
Pinperch
Acroneuria Pacifica
Pteronarcys California
Claassenia sabulosa
Daphnia magna
Arctopsyche grandis
Mosquito fish
Bluegill
Remarks Ref
Hard Water 47
Soft Water 47
Soft Water 47
Soft Water 47
88
87
88
42
88
88
62
88
Small (3.88 cm) 23
Medium (6.09cm) 23
Large (14.24cm) 23
87
42
43
43
43
43
88
88
87
-------
TABLE VI-9 (Continued)
TOXICITY BIOASSAY RESULTS
Compound
Diethylene Glycol
Furfural
Heptane
Hydrogen Cyanide
Lactonitrile
<
M
ro
°° Malathion (59% active
xylene)
Maleic Anhydride
Methyl Ethyl Ketone
Napthalene
Oxydipropionitrile
o-Nitrophenol
TL (Median
m
24 Hr
(mg/1)
32,000
44
32
4,924
0.069
0.215
240
5,640
220
66.9
Tolerance Limit)
48 Hr
(mg/1)
96 Hr
(mg/1)
32,000 32,000
44
16
4,924
4.009
0.0009
240
5,640
165
46.3-
51.6
24
1.2
4,924
0.90
0.90
0.90
1.37
0.0056
0.100
0.056
0.032
230
1,690
150
3,920
3,600
4,200
4,450
Test Animal Remarks
Mosquito fish
Mosquito fish
Bluegill
Mosquito fish
Pinperch
Pinperch
Fathead Minnows Hard Water
Fathead Minnows Soft Water
Bluegill Soft Water
Guppies Soft Water
Daphnia tnagna
Acroneuria Pacifica
Pteronarcys California
Claassenia sabulosa
Arctopsyche grandis
Mosquito fish
Bluegill
Mosquito fish
Fathead Minnows
Fathead Minnows
Bluegill
Guppies
Bluegill
Ref
88
88
87
88
42
42
47
47
47
47
43
43
43
43
88
87
88
47
47
47
47
62
-------
TABLE VI-9 (Continued)
TOXICITY BIOASSAY RESULTS
TL (Median Tolerance Limit)
m
Compound
Parathion (25% active
in xylene)
Phenol
Pyridine
Pyridyl Mercuric
Acetate
Sodium Butyl Mercaptide
Sodium Cyanide
Sodium Oxalate
Tetraethyl lead
Toluene
Benzene (reagent)
24 Hr
(mg/D
61
22.7
19
1,350
12.5
7.4
1,350
2.0
1,340
35.56
34.42
22.49
34.42
36.60
48 Hr
(mg/D
56
22.2
19
1,350
11.3
5.5
1,350
1.4
1,260
35.08
32.00
22.49
34.42
36.60
96 Hr
(mg/D
0.0001
0.0032
0.001
56
13.5
20.0
11.5
5.7
1,350
2.8
0.92
0.35
0.23
0.15
1,350
0.20
1,180
33.47
32.00
22.49
34.42
36.60
Test Animal
Acroneuria Pacifica
Pteronarcys Californica
Claassenia sabulosa
Arctopsyche grandis
Mosquito fish
Bluegill
Bluegill
Bluegill
Bluegill
Bluegill
Mosquito fish
Bluegill
Bluegill
Fathead Minnows
Fathead Minnows
Bluegills
Mosquito fish
Bluegill
Mosquito fish
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Remarks
Small (3.88cm)
Medium (6.09cm)
Large (14.24cm)
Hard Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Ref
43
43
43
43
88
62
23
23
23
87
88
87
87
47
47
47
88
87
88
73
73
73
73
73
-------
TABLE VI-9 (Continued)
TOXICITY BIDASSAY RESULTS
OJ
o
TL (Median Tolerance Limit)
Compound
Chlorobenzene
o-Chlorophenol
3-Chloro-propene
o-Cresol
Cyclohexane
24 Hr
(mg/D
29.12
33.93
39.19
24.00
73.03
45.53
21.96
21.52
11.31
14.48
22.17
24.00
25.86
59.30
26.56
57.68
Not found
18.00
22.17
Not found
49.13
35.08
42.33
42.33
42.33
57.68
48 Hr
(mg/1)
29.12
33.93
34.98
24.00
56.00
45.53
19.12
18.00
10.59
12.37
20.78
24.00
24.00
42.33
20.87
53.54
Not found
13.42
20.78
Not found
25.31
35.08
42.33
40.60
42.33
57.68
96 Hr
(mg/D
29.12
33.93
33.93
24.00
51.62
45.53
11.63
14.48
10.00
12.37
20.17
19.78
24.00
42.33
20.87
51.08
12.55
13.42
20.78
23.25
18.85
32.71
42.33
34.72
42.33
57.68
Test Animal
Fatheads
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Remarks
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Ref
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
-------
TABLE VI-9 (Continued)
TOXICITY BIOASSAY RESULTS
TL (Median Tolerance Limit)
24 Hr
Compound (mg/1)
Ethyl Benzene 48.51
42. 33
35.08
94.44
97.10
loprene 86.51
74.83
42.54
180.00
240.00
V Methyl Methacrylate 421.2
£ 455 .1
498.6
391.9
' 368.1
423.3
368.1
Phenol (U.S. P. 100%) 40.60
38.62
25.85
49.86
o-Phthalic anhydride Not found
Not found
Not found
Styrene (stabilized) 56.73
62.81
25.05
64.78
74.83
48 Hr
(fflg/D
48.51
42.33
32.00
94.44
97.10
86.51
74.83
42.54
180.00
240.00
338 . 2
455.1
338.2
368.1
357.5
423.3
368.1
40.60
38.62
23.88
49.13
Not found
Not found
Not found
53.58
62.81
25.05
64.74
74.83
96 Hr
(mg/1)
48.51
42.33
32.00
94.44
97.10
86.51
74.83
42.54
180.00
240.00
159.1
160.2
311.0
320.0
232.2
277.1
368.1
34.27
32.00
23.88
44.49
Not found
Not found
Not found
46.41
59.30
25.05
64.74
74.83
Test Animal
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Fatheads
Fatheads
Fatheads
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Remarks
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Ref
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
-------
TABLE VI-9 (Continued)
TOXICITY BIOASSAY RESULTS
TL (Median Tolerance Limit)
m
Compound
Toluene reagent
Vinyl acetate
Xylene
24 Hr
(mg/1)
46.31
56.00
24.00
57.68
62.81
24.00
22.17
39.19
36.81
18.53
42.33
31.08
28.77
28.77
24.00
36.81
34.73
48 Hr
(mg/1)
46.31
56.00
24.00
57.68
60.95
24.00
20.31
39.19
36.81
18.00
42.33
31.08
27.71
28.77
24.00
36.81
34.73
96 Hr
(mg/1)
34.27
42.33
24.00
57.68
59.30
24.00
19.73
39.19
35.75
18.00
42.33
31.08
26.70
28.77
20.87
36.81
34.73
Test Animal
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Fatheads
Fatheads
Bluegill
Goldfish
Guppies
Remarks
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Hard Water
Soft Water
Soft Water
Soft Water
Soft Water
Hard Water
Soft Water
Soft Water
Soft Water
Ref
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
73
-------
TABLE VI-9(Continued)
TOXICITY BIDASSAY RESULTS
TLjjj (Median Tolerance Limit)
Compound
Waste caustic
General refinery
Sulfuric acid
alkylation
Sodium sulfide
Sodium hydroxide
Sulfuric acid
24 Hr
(%)
0.039
21
0.4
25 mg/1
43 mg/1
49 mg/1
48 Hr
(%)
_
18
0.4
25 mg/1
42 mg/1
49 mg/1
96 Hr
(%)
_
4.0
0.1
7.5 mg/1
12 mg/1
15 mg/1
Test Animal
Bluegill
Bluegill
Bluegill
Bluegill
Bluegill
Bluegill
Remarks
20°C
20°C
20°C
20°C Hard Water
20°C Hard Water
20°C Hard Water
Ref
87
87
87
87
87
87
-------
of a compound or waste can never be demonstrated scientifically
(Pickering and Henderson, 1966), it is necessary to provide a
"safety factor" to the TLM values obtained in the laboratory. The
concentration of a waste discharged to a stream is usually one-
tenth to one-half its median tolerance limit (Gloyna and Malina,
1962). It was found that there was little significant difference
in the 24-hour and 96-hour TLM values for 10 of the 15 petro-
chemicals that were evaluated (Pickering and Henderson, 1966).
This appears to be true for many of the compounds listed in Table
VI-8. It appears from this data that many of the petrochemicals
affect fish within a short period of time. Since most fish kills
are usually the result of toxic material spills and because the
toxic conditions are manifested so rapidly in the fish, it has been
proposed that a much shorter time interval be used in the laboratory
bioassay (Burdick, 1965). However, very little data are available
when bioassays at time intervals shorter than 24 hours are consid-
ered.
The avoidance of polluted water by fish has been suggested
as a toxicity parameter (Ishio, 1965). In this investigation a
gradient tank was used to determine the discriminatory sensitivity
of fish exposed to toxic chemicals. The median avoidance concen-
trations of some pollutants tested were found to correspond to their
lowest lethal concentrations. However, several problems develop
when avoidance is used as a parameter. In many cases fish do not
reliable avoid lethal concentrations of some toxicants (Cairns,
1957). For example, most fish have been found to be attracted to
alkaline water. Ammonia and copper salts, both of which are poten-
tially toxic, were found to attract fish indirectly by chemical
reactions which reduced the alkalinity (Ishio, 1965). Carp have
been found to enter continuously an ammonia contaminated stream
even though large numbers were killed (Beak, 1965). The toxicity
bioassay is a valuable tool in the establishment of criteria for
wastewater discharge as long as its limitations are known and con-
sidered.
CONVENTIONAL POLLUTIONAL PARAMETERS
There is a multiplicity of constituent chemicals responsible
for the pollutional nature of petrochemical wastewater. Pollution
cannot be measured in terms of quantitative levels of specific con-
taminating components, but rather by general methods of characteriza-
tion. Many of the analytical techniques which are used to identify
the classes of chemicals in a waste stream are complicated and
expensive and, in the case of some compounds, quantitative methods
of analysis are extremely difficult to perform. Pollutants such
as tars, oils, and hydrocarbons are mixtures of many chemicals which
are sometimes impossible to separate, identify, and quantify. The
use of general pollutional parameters therefore provides a common
VI-34
-------
yardstick for the assessment of the pollutional characteristics of
an effluent stream. Total quantities of significant pollutants
can be determined and waste streams from different processes com-
pared with regard to their pollutional capacities by using these
parameters.
The one manner of expressing waste characteristics is in
terms of the ratio of quantity of pollutant produced to the quantity
of product manufactured. Such comparison provides an accurate way
of predicting effluent characteristics from any given petrochemical
process. Virtually no published data of this type are available from
the petrochemical industry, however, a limited amount of information
regarding pollutants in relation to the output of thirty major
products is presented in Appendix II. Information regarding major
producers, projected production, uses, petrochemical conversion
processes, and waste reduction by process change is also included.
It is normally necessary to select data from unit process waste-
waters which are typical of the industry. The characteristics of
effluents from typical unit processes are listed in Tables VI-10
through VI-14. In most cases, these values are taken from a single
plant and cannot be used as an absolute basis for predicting process
waste characteristics from every plant. However, these values can
be used to estimate the order of magnitude of the more important
pollutional characteristics of unit process effluents and, as such,
are useful in predicting effluent qualities.
Acidity
The acidity of a waste is a measure of the quantity of
compounds contained therein which will dissociate in an aqueous solu-
tion to produce hydrogen ions. Acidity in a petrochemical waste can
be contributed by both organic and inorganic compound dissociation.
Most mineral acids found in petrochemical wastes (sulfuric acid,
nitric acid, phosphoric acid) are typically strong acids. The most
common weaker acids found in petrochemical wastes include the
organic acids such as carboxylic acid and the inorganic acid, carbonic
acid (H2CO_). Typical acid wastes from petrochemical processing and
their acidity are listed in Table VI-12.
Alkalinity
Compounds which contribute to alkalinity in wastewaters are
those which dissociate in aqueous solutions to produce hydroxyl ions.
Alkalinity is often defined as the acid consuming ability of the
wastewater and is measured by titrating a given volume of waste with
standard acid until all of the alkaline material has reacted to form
salts. In effect, alkalinity is the exact opposite of acidity; high
alkalinities lower the hydrogen ion concentration of a solution and
raise its pH.
Both inorganic and organic compounds can contribute to alkalin-
ity, but the most important alkaline wastes in the petrochemical
industry are the spent caustics containing sodium, calcium, and
VI-35
-------
TABLE VI-10
TYPICAL PROCESS WASTE CHARACTERISTICS OF PRIMARY
CONVERSION AND REFINING PROCESSES
Sour Condensates
Crude Catalytic Naphtha from Distillation,
Characteristic Desalting Cracking Cracking Cracking, etc.
Ammonia (mg/1)
BOD (mg/1)
COD (mg/1)
Oil (mg/1)
pH (mg/1)
Phenols (mg/1)
80
60-610
124-470
20-516
7.2-9.1
10-25
-
230-440
500-2,800 53-180
200-2,600 160
-
20-26 6-10
135-6,550
500-1,000
500-2,000
100-1,000
4.5-9.5
100-1,000
Salt (as NaCl) 0.4-25 -
(wt.%)
Sulfides (mg/1) 0-13 - - 390-8,250 (H2S)
Reference (15) (33) (15) (15)
VI-36
-------
TABLE VI-11
TYPICAL SPENT CAUSTIC STREAM CHARACTERISTICS
Characteristics
Benzene Ortho-
Sulfona- phenyl-
tion phenol Alkylate
Scrubbing Washing Washing
Polymer
ization
Various
Refining
Processes
Alkalinity (mg/1) 33,800 18,400 46,250 209,330
BOD (mg/1) 53,600 18,400 256 8,440
COD (mg/1) 112,000 67,600 3,230 50,350
2,200-53,600
pH
Phenols (mg/1)
NaOH (wt % )
2 A-
Sul fates (mg/1)
Sulfides (mg/1)
Sulfites (mg/1)
Total Solids
Misc.
Reference
13.2
8.3
1
1.5-2.5
3,760
-
7,100
90,300
trace
(32)
9-12 12.8 12.7
5,500 50 22.2 2,000-25,300
0.2-0.5 - - 4.2-8.2
- -
2,440 - -
2 3,060
4,720 -
40,800 - -
trace
OP-
phenol
(32) (69) (69) (15)
VI-37
-------
TABLE VI-12
TYPICAL ACID WASTES CHARACTERISTICS
Characteristic
Acidity (mg/1)
BOD (mg/1)
COD (mg/1)
Dissolved
Solids (mg/1)
Oil (mg/1)
pH
Phenols (mg/1)
Sulfate (mg/1)
Sulfite (mg/1)
Total Solids
(mg/1)
Reference
Acid Wash-
Acid Wash- Phenol Still
Alkylation Bottoms
1,105-12,325
31 20,800
1,251 248,000
340,500
131.5
0.6-1.9 1.0
3,800
-
34,800
403 , 200
(69) (32)
Acid Wash-
Orthophenyl-
phenol
24,120
13,600
23,400
81,300
-
1.1
1,500
54,700
2,920
81,600
(32)
Sulfite Wash
Liq.OP-phenol
Distillation
675
105,000
689,000
176,800
-
3.8
16,400
-
74,000
176,900
(32)
VI-38
-------
TABLE VI-12 (continued)
TYPICAL ACID WASTES CHARACTERISTICS
2, 4 - D 2, 4, 5 - T
Characteristic Acid Wash Acid Wash
BOD (mg/1) 13,000-16,700 13,400-16,800
Chlorides (mg/1) 72,000-144,000 69,000-96,300
COD (mg/1) 22,700-27,500 19,600-25,700
Dissolved 166,770 171,770
Solids (mg/1)
pH 8.5-9.5 7.5-7.9
Total 45 40
Nitrogen (mg/1)
Total Solids (mg/1)
Total Volatile
Solids (mg/1)
Reference
167,220
22,100
(37)
172,470
18,150
(37)
VI-39
-------
TABLE VI-13
TYPICAL PROCESS WASTE CHARACTERISTICS-MISCELLANEOUS
Characteristic
Alkalinity (mg/1)
Chlorides (mg/1)
COD (mg/1)
Oil (mg/1)
PH
P04 (mg/1)
S04 (mg/1)
TOG (mg/1)
Total Kjeldahl
Nitrogen (mg/1)
Total Solids (mg/1)
Reference
Nylon
Manufacture
22,500-40,700
475-3,340
74,000-87,800
152-367
7.4-12.0
5-78
0-194
19,600-37,200
4,630-10,500
41,700-123,500
(32)
Synthetic
Rubber
37-40
2,670-2,800
173-192
-
6.4-6.7
19-22
1,425-1,470
97-110
74-89
7,420-12,000
(32)
Butadiene
(after API)
370
1,275-1,350
290-359
-
8.4-8.5
38
910
131-165
63
3,730
(32)
VI-40
-------
TABLE?I-13 (Continued)
TYPICAL PROCESS WASTES CHARACTERISTICS-MISCELLANEOUS
Hexarnethylene- Adipic Acid
Characteristic diamine Mfr. Manufacture
Alkalinity 40,000-82,000 1,500-6,000
(Total) (mg/1)
BOD (mg/1)
Chlorides (mg/1) 1,050-6,620 726-901
COD (mg/1) 23,400-65,800 112,600-169,800
Dissolved 1,613-6,618 54,000-74,000
Solids (mg/1)
pH 10.2-10.9 4.1-5.2
Phenols (mg/1)
P04 (mg/1) 89-125 1-4
S04 (mg/1) 104-128 142-160
Total N (mg/1) 18,000-33,000 98-280
Total Solids (mg/1) 1,685-7,030 55,000-76,500
Misc as TOC = 7,500 - TOG = 29,200 -
indicated 20,400 mg/1 80,000 mg/1
Reference
(32) (32)
VI-41
-------
TABLE VI-13 (Continued)
TYPICAL PROCESS WASTES CHARACTERISTICS-MISCELLANEOUS
Characteristic
Alkalinity (mg/1)
Chlorides (mg/1)
COD (mg/1)
PH
Oil (mg/1)
Phenol (mg/1)
P04 (mg/1)
S04 (mg/1)
Sulfide (mg/1)
TOG (mg/1)
Total Kjeldahl
Nitrogen (mg/1)
Total Dissolved
Solids (mg/1)
Total Solids (mg/1)
Reference
Olefin Production
(After Oil
Separator)
1,490
-
500-1,500
9.8-10.0
-
10-50
10
180
-
150-700
60
-
2,140
(32)
Chlorinated
Olefin Hydrocarbon Synthetic Rubber
Production Manuf.* Polymerization
-
116,000-123,000 550
500-2,000 3,340 3,072
4.0-8.5 12.6 7.8
10-300
10-50
-
- -
0-1
-
*• •" ""
5-100
_
(66) (36) (36)
-------
TABLE VI-14
TYPICAL WASH WATERS CHARACTERISTICS (SCRUBBING PROCESSES)
Process
Acidity (mg/1)
Alkalinity (mg/1)
COD (mg/1)
Dissolved
Solids (mg/1)
PH
Phenols (mg/1)
Total Solids (mg/1)
Misc. as
Indicated
Reference
Orthophenyl
phenol
Treating
296
9.1
830
608
Alkyd Scrubber
Solution
Resin Manufacture
(32)
6,120
30,000
37,100
19,400
2.1
8.3
19,500
traces of pentaery-
thritol,phthalic
anhydride, glycerine
(32)
VI-43
-------
potassium salts. These compounds present in such wastes tend to
raise the pH to extremely high levels. The alkalinities of typical
spent caustic streams are given in Table VI-11. Other process wastes
may also contain significant amounts of alkalinity. Nitrogen in the
ammonium form, for example, can contribute to the alkalinity of a
solution.
The principal adverse consequences of high alkalinities in
wastewater are biological, although caustic alkalinity, such as
sodium or potassium, can cause embrittlement in boiler tubing.
Color and Turbidity
Color and turbidity are physical properties related to the
concentration of certain solutes and suspended particles in waste-
waters. Many of the wastes produced by the petrochemical industry
contain color-producing compounds.
Color in wastewater, true and apparent, can be attributed to
two types of physical phenomena. Certain materials in solution or
suspension in water will absorb incident light and the wave lengths
of visible light absorbed will determine the color of the liquid.
The other color effect is caused by the scattering of incident light
by colloidal or suspended materials, and liquids which exhibit this
light-scattering effect are termed turbid. Both of these effects
are highly undesirable in waters receiving waste effluents. Color
and turbidity diminish light penetration in natural waters. This
effect was discussed previously. Color and turbidity also affect the
domestic use of water in that they must be removed prior to public
acceptance. This removal process often adds great expense to water
treatment costs.
Color in water is measured by comparing the sample with a
standard cobalt-platinum solution. Turbidity is measured by using
several different types of proprietary instruments which measure
either scattered or transmitted light. Color which is caused by
dissolved contaminants is often termed "true" color and color caused
by petrochemical wastes is predominantly of this type. Color caused
by suspended and colloidal material is referred to as "apparent"
color.
The hydrogen ion concentration in an aqueous solution is
represented by the pH of that solution. The pH is defined as the
negative logarithm of the hydrogen ion concentration in a solution.
The pH scale ranges from zero to fourteen with a pH of seven repre-
senting neutral conditions, that is, equal concentrations of hydrogen
and hydroxyl ions. Values of pH less than seven indicate increasing
hydrogen ion concentration or acidity; pH values greater than seven
indicate increasing basic conditions. The pH value is an effective
VI-44
-------
parameter for predicting chemical and biological properties of
aqueous solutions. It should be emphasized that pH is not a quanti-
tative measurement and cannot be used to predict the quantities of
alkaline or acidic materials in a water sample. However, most
effluent and stream standards are based on maximum and minumum allow-
able pH values rather than on alkalinity and acidity.
Most living aquatic organisms, either plant or animal, function
most effectively at neutral or near-neutral pH levels. Certain micro-
organisms, principally bacteria, can grow and proliferate at extremely
high or extremely low pH values. Most other aquatic organisms can
tolerate only brief exposures to high and low pH values before death
ensues. The pH range generally required by most aquatic organisms
is pH five to pH nine. Values outside this range will exert a toxic
influence on much of the aquatic life; therefore, pH is a valuable
indicator of the possible toxic effects due to excessive acidity or
alkalinity of a waste effluent. The pH value also can serve as an
indicator of the corrosive potential of a process effluent.
Most methods of measuring pH employ an instrument which
determines an electric potential developed between two electrodes
immersed in the solution to be tested. The most common of these
instruments utilizes the glass-calomel electrode system. In special
cases, special electrodes may have to be used to avoid interference
by certain chemicals.
Organic Material
In order to predict the polluting potential of organic-laden
wastewaters, it is necessary to employ some quantitative parameter.
Since the oxygen demand of organic wastes presents one of the primary
problems in organic waste control, the most commonly used parameters
measure the chemical or biochemical oxygen demand potential of the
wastes. These parameters are universally accepted although there
are many limitations in their use and application. 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. Such an evalua-
tion is a valuable supplement to oxygen demand tests when categorizing
a wastewater according to its organic polluting strength.
Biochemical Oxygen Demand - Biochemical oxygen demand (BOD)
is a measure of the biologically oxidizable organic material in a
waste. Ideally the Bod should represent the oxygen demand which is
exerted during the microbial oxidation of organics in the waste,
either in a biological treatment process or in a receiving body of
water. The ultimate BOD is the oxygen required to biochemically oxidize
all of the organic material to the less complex end-products. However,
the ultimate BOD may not include all the BOD expected by nitrogen com-
pounds. In practice, the BOD5 is usually used for laboratory determina-
tions of waste. This procedure is standardized and is described in
detail in Standard Methods (1965).
VI-45
-------
Petrochemical wastes present certain problems when BOD is
used as the pollution parameter. Certain compounds react chemically
with free oxygen and create an immediate oxygen demand (IOD). Comp-
ensation for this demand must be included when using the BOD test.
Certain organic compounds in petrochemical wastes are toxic at
higher concentrations to microorganisms but exert high oxygen
demands at nontoxic levels. Some inorganic compounds such as
sulfides, chlorides, ammonia, and heavy metal salts may cause a
toxic or deleterious effect in high concentrations and these effects
must be taken into account by employing a sufficient dilution
factor to prevent the toxic effects from occurring. Many of the
chemicals present in petrochemical effluents are not normally present
in nature; thus, it is necessary to use a microbial population
which is properly acclimated to the specific waste under investiga-
tion if accurate BOD values are to be obtained.
Since BOD is the oldest and most common of the parameters
used for estimating organic material, most effluent quality standards
are based on a maximum allowable BOD effluent concentration. One
disadvantage of BOD is that it measures only biologically degradable
organics.
The BOD concentrations in effluents from typical petro-
chemical process wastes are listed in Tables VI-10 through VI-14.
Typical effluent analyses from entire petrochemical plants are
shown in Table VI-15. Wastes discharged from the petrochemical
industry contain high concentrations of organic material, as
indicated in these tables. The biochemical oxygen demand values of
many important petrochemicals are given in Table VI-1.
Techniques .to measure the BOD values in Table VI-1 should
be mentioned. In nearly all cases sewage organisms were used as the
source of microbial seed for the BOD test. The importance of using
an acclimated seed for the measurement of the BOD values of complex
organic compounds has been stressed. For example, the 8005 val-ue
of acrylamide monomer was determined using an acclimated seed and
a sewage seed. The five-day BOD value obtained using the sewage
seed was only 17 percent of the value obtained when a seed acclimated
to the monomer was used (Cherry, et. al.,1956). Even a microbial
seed which is acclimated to a compound closely related in structure
to the test compound may not give the highest possible BOD value,
which is of utmost importance. The BODr values obtained from
acrylamide monomer using a microbial seed acclimated to acrylonitrile
were only 22 percent of the values obtained with a seed acclimated
to the monomer (Cherry, et. al.,1956). Thus, the BOD values in
Table VI-1 should be used only as a rough estimate of the ease of
biodegradability of the compounds since some of the compounds
probably will produce much higher BOD values if an acclimated seed
is used.
VI-46
-------
TABLE VI-15
TOTAL PLANT EFFLUENT ANALYSES
TYPICAL PETROCHEMICAL
PLANTS
(Process Waste Before Treatment)
Plant Products
Alkalinity (mg/1)
BOD (mg/1)
Chlorides (mg/1)
COD (mg/1)
Oils (mg/1)
pH
Phenols (mg/1)
Sulfates (mg/1)
Suspended
Solids (mg/1)
TOG (mg/1)
Total
Nitrogen (mg/1)
Total
Solids (mg/1)
Misc. as
Tnrl i r Ate>i\
Mixed Chemicals
incl. ethylene
oxide, propylene
oxide, glycols,
amines , and ethers
4,060
1,950
430-800
7,970-8,540
547
9.4-9.8
-
655
27-60
-
1,160-1,253
2,191-3,029
Refinery,
Detergent
Alkylate
365
345
1,980
855
73
9.2
160
280
121
-
89
3,770
Sulfide= ^
150 ppm "
Refinery,
Butadiene,
Butyl Rubber
164
225
825
610
-
7.5
17
-
110
160**
48
2,810
P0,=trace
4
Reference
(38)
(39)
(40)
Cooling Water Excluded
**
Filtered
VI-47
-------
TABLE VI-15 (Continued)
TOTAL PLANT EFFLUENT ANALYSES
TYPICAL PETROCHEMICAL PLANTS
Plant Products
BOD5 (mg/1)
Chlorides (mg/1)
COD (mg/1)
Oils (mg/1)
Phenols (mg/1)
Suspended
Solids (mg/1)
Total
Nitrogen (mg/1)
Total
Solids (mg/1)
Misc. as
Indicated
Reference
Mixed
Organics
1,950
800
1,972
547
10-50
60
1,253
3,029
SO. =
4
655 mg/1
(31)
2,4,5-Tri-
chloro- 2,4-Dichloro-
phenol phenol
16,800 16,700
96,300 144,000
21,700 27,500
-
-
700 348
40 45
172,467 167,221
7oVol. TS = 7oVol. TS =
10.5 13.2
(37) (37)
Nylon
170
800
2,000
45
400
neg.
100
3,000
12 mg/1
(31)
VI-48
-------
TABLE VI-15 (Continued)
TOTAL PLANT EFFLUENT ANALYSES
TYPICAL PETROCHEMICAL PLANTS
Plant Products
Phenols, Cresols
Alkalinity (mg/1)
Chlorides (mg/1)
COD (mg/1)
Color (Color Units)
Hardness (mg/1)
IOD (mg/1)
Kjeldahl-N (mg/1)
NH--N (mg/1)
Oil (mg/1)
pH
Phenols (mg/1)
PO, (mg/1)
Sulfides (mg/1)
Suspended
Solids (mg/1)
Temperature C
TOG (mg/1)
Total Solids (mg/1)
Reference
192
550-850
230
990-1,940
50
250
17
trace
trace
trace
4.6-7.2
280-550
3
trace-1
12-88
24.5
320-580
1,870-2,315
(44)
VI-49
-------
A thorough description of some chemical compounds which
are resistant to aerobic biological stabilization is given by
Ludzack and Ettinger (1960). The degradation of a number of different
aromatic compounds by bacteria acclimated to phenol is discussed
by Chambers, Tabak, and Kabler (1963). Many of the chemical
compounds characterized in these two papers are found in petro-
chemical wastes.
Chemical Oxygen Demand - The oxygen required to chemically
oxidize the organic compounds in a wastewater is termed the chemical
oxygen demand (COD). Several COD testing methods are used, the
most common one using potassium dichromate to oxidize the organic
matter under acid conditions at a temperature of 180°C. This method
completely oxidizes most organic compounds, which should represent
the majority of organic materials in an effluent; however, a few
of the more stable compounds in higher molecular weight materials
are not measured. Benzene, for example, is a significant petro-
chemical pollutant and is not oxidized by any of the COD oxidants.
The principal advantages of the COD test are the analytical time of
two hours instead of five days, accuracy, and independence from
temperature and acclimated seed considerations. COD is also
valuable in the determination of the non-biodegradable portion of a
waste, as indicated by the COD concentration when the corresponding
BOD is zero or negligible.
Several disadvantages are inherent in the COD approach. There
is no general correlation between the COD and BOD of petrochemical
effluents; however, a COD-BOD correlation often does exist for a
specific effluent, rendering COD a valuable parameters for a treat-
ment process operation once this correlation has been established.
The interference of high chloride concentrations common to
many petrochemical wastewaters may allude to erroneous COD deter-
minations. These chlorides are oxidized by dichromate to chlorine:
Cr20y + 6 Cl + 14 H —>- 3 C12 + 2Cr +7 H20
This interference can be minimized, however, by the addition
of HgSO^ to the mixture, as the Hg combine with Cl~ to form
essentially non-ionized HgCl2J
Hg4"* + 2 Cl" »_ HgCl2
If insufficient amounts of HgSO^ are added to the mixture to prevent
chloride oxidation, the excess Cl~ will precipitate the Ag"*" catalyst
necessary to oxidize straight chain acids and alcohols:
AgCl
VI-50
-------
From this discussion, it follows that the presence of excessive
chlorides do interfere with the COD test and can result in either
inordinately high or low readings, depending on the relative degrees
of chloride oxidation and silver catalyst precipitation.
The COD values for some typical chemical wastes are given
in Tables Vl-lOthrough VI-14.
Total Organic Carbon - Total organic carbon (TOC) is the
measure of all organic carbon present in a waste. It is measured
by completely oxidizing all of the organic material to carbon
dioxide and water with a subsequent quantitative determination of
the carbon dioxide released. The oldest procedure involved a wet
combustion process which was difficult and time consuming. A method
recently developed is rapid and accurate and insures complete organic
oxidation by providing a pure oxygen environment, heat, and a cobalt
catalyst followed by a quantitative analysis of the released carbon
dioxide on an infrared spectrophotometer (Van Hall, et. al.,1963).
This process may well become one of the more important methods of
determining the organic content of wastewaters because it completely
measures all organic compounds. However, like COD, there is no
general correlation with BOD. There may or may not be a correlation
between TOC and BOD for a specific waste stream; however, TOC can be
used to measure treatment plant efficiency and monitor effluent
streams whether or not this correlation exists.
Total organic carbon in combination with BOD and COD is
probably the ideal method for determining the non-biodegradable
fraction of an organic waste. The TOC parameter is particularly
valuable for assessing the organic content of petrochemical waste
since it is not affected by the interferences and variables prevalent
in the COD and BOD procedures.
Since TOC is a relatively new approach, effluent quality
data in terms of organic carbon is limited. Data presently available
for some petrochemical process wastes are listed in Tables VI-10
through VI-14.
Total Oxygen Demand
Total oxygen demand (TOD) has recently been proposed as a
waste strength parameter, primarily on the basis of the development
of an automated analyzer. The TOC of an aqueous sample using this
analyzer includes the total carbon, hydrogen, and nitrogen oxygen
demand, although only a partial oxidation of sulfur compounds occurs.
Total oxygen demand has been correlated in specific instances to
chemical oxygen demand, and is a promising parameter in this respect
(Clifford, 1967).
VI-51
-------
Immediate Oxygen Demand
Immediate oxygen demand (IOD) is exerted by compounds which
react immediately with the dissolved oxygen when they are introduced
into water containing oxygen. Such compounds include sulfides,
thiosulfates, sulfites, nitrites, and aldehydes. The procedure for
measuring IOD is standardized (Standard Methods for the Examination
of Water and Wastewater, 1965)
Solids
Solid materials in wastewater effluents can be either
organic or inorganic, dissolved or suspended. They consist of the
materials which were described earlier under the chemical classifi-
cations .
Dissolved organic solids may cause color, taste, odor, and
oxygen demand and are discussed under these headings. Inorganic
dissolved solids are not particularly harmful or undesirable at
lower concentrations. The main criteria for limiting dissolved
solids include: tastes that are often produced by dissolved solids
concentrations greater than 1,000 mg/1; high dissolved solids con-
centrations that may precipitate solids if the environmental con-
ditions change; and high dissolved solids concentrations that may
render water unfit for industrial uses such as boiler water (Beychok,
1967). The United States Public Health Service has set 1,000 mg/1
as the maximum desirable total dissolved solids concentration in
drinking water.
Some petrochemical process effluents, such as spent caustic
effluents and acid wash wastes, have extremely high dissolved
solids concentrations. Most of the solids in petrochemical wastes
are present in the dissolved form. Suspended solids constitute the
difference between total and dissolved solids and include colloidal
materials which will not settle, even under quiescent conditions.
Total and dissolved solids concentrations for typical process
effluents are included in Tables VI-10 through VI-14.
Surface Activity
Surface-active agents are compounds which tend to concentrate
at an interface, arranging their molecules so that they form a
film along the interface. This surface-active property enables them
to reduce the surface tension of liquids, emulsifying dirt and oily
material (Stephenson, 1966). The principal use of surface-active
agents is in synthetic detergents which have largely replaced soaps
as cleaning agents. Unlike soaps, synthetic detergents do not form
insoluble salts with calcium and magnesium ions, and they can there-
fore be used in hard water without the occurrence of undesirable
precipitates.
VI-52
-------
The chemical characteristics of synthetic detergents are
fully discussed elsewhere (Stephenson, 1966) and will be mentioned
only briefly here. Surface-active agents contain two important
functional groups, a water-soluble group and an oil-soluble group,
giving the molecule its surface-active properties. The oil-soluble
or hydrophobic group is usually a long-chain hydrocarbon containing
eight to twenty-two carbon atoms. The water-soluble or hydrophilic
group may be composed of one or four general types of polar groups:
(a) anionic groups consisting of sulfonates, sulfates, and carboxylic
acid groups; (b) cationic groups such as amine salts and ammonium
compounds; (c) amphoteric groups in which the molecule contains
both anionic and cationic groups; and (d) nonionic groups which do
not ionize but are water soluble, such as alcohols and glycols
(Stephenson, 1966).
Various laboratory procedures are available for the determi-
nation of synthetic detergents in water (Standard Methods, 1965).
Other surface-active chemicals (sulfonic acids, carboxylic acids,
etc.) must be determined by laboratory analyses which are not commonly
used as pollutional parameters.
Taste and^ Odor
Methods used to classify and measure taste and odor in
aquatic organisms are strictly arbitrary and most involve the use
of human testers who determine the dilution required to make
the taste and odor of a particular wastewater satisfactory. Since
taste and odor are human senses, this is probably the most suitable
method for their determination. Another possibility is the isola-
tion, identification, and measurement of substances which cause
taste and odor, but this procedure is currently impractical.
Temperature
Thermal pollution is a serious problem since elevated
temperatures in receiving waters can cause deleterious effects.
The primary effects are biological although downstream users may
also suffer.economically. Wastes from petrochemical industries
are often discharged at high temperatures and may require precooling
before treatment.
VI-53
-------
Toxicity
Many of the compounds and chemicals present in petrochemical
wastes are toxic to aquatic life. Petrochemicals can also exert
toxic effects on higher plants and animals and may render the
wastewater unfit for agricultural or livestock use.
The bioassay technique is commonly used for measuring
wastewater toxicity. The bioassay is used to determine the toxic
concentration of a taste by the use of a dilution technique. Results
obtained from a bioassay are usually reported in terms of the median
tolerance level. Fish are the most commonly used test organisms,
but new techniques are being developed which involve the use of
other aquatic organisms such as algae and protozoa.
Oils
Oils are significant petrochemical pollutants. Total oil
concentrations in the influents to biological treatment process
should be limited to approximately 50 mg/1. Measurements will
indicate which process streams will require oil separation prior to
additional treatment.
Miscellaneous Pollutant Parameters
The aforementioned waste characteristics include the more
commonly used methods for assessing pollutional effects of waste-
waters, both petrochemical and other methods. However, more
detailed descriptions of waste characteristics are often desired,
particularly when treatment methods are being prescribed. There are
several important parameters which are particularly important in
the assessment of a petrochemical waste.
Phenols - Several methods are available for the measurement
of phenols, the most common of them being the 4-aminoantipyrene
procedure described in Standard Methods (1965). One disadvantage
of this method is that certain phenolic compounds are not measured.
Total phenols in aqueous solutions also can be determined by utilizing
a differential ultraviolet absorption technique (Martin, et. al.,
1967). This technique can be used for continuous monitoring of
process effluents, and it measures all the phenolic compounds present
in solution. Data showing the concentrations of phenolic compounds
in some typical petrochemical process effluents are given in Tables
VI-10 through VI-14.
Inorganic Ions - In certain cases, it is desirable to know
the concentration of certain inorganic ions such as chlorides,
phosphates, nitrates, and sulfates. Phosphates and nitrates, for
example, are important biological nutrients, and the concentration
of these ions in wastewaters to be treated biologically is of
VI-54
-------
considerable importance in the design and operation of the treatment
unit. Standard analytical techniques are used to measure inorganic
ions in wastewater (Standard Methods., 1965).
Nitrogen must be present in its most reduced form, ammonia
or ammonium ion, to be available to most bacteria in an optimum
biological treatment system; however, many algae utilize nitrogen
as nitrate. The nitrogen required for an efficient biological
treatment process for nitrogen deficient petrochemical wastes can
be calculated if the nitrogen content of the waste stream is known.
The most common method is the Kjeldahl method described in Standard
Methods (1965). In this technique, the organic nitrogen is
converted to ammonia nitrogen which is then measured either by
titration or colorimetric procedures.
Volatility - Some of the organic and inorganic compounds in
petrochemical wastes are highly volatile and are subject to air-
stripping. The volatility of a compound is a function of both its
solubility and its vapor pressure. Volatile petrochemicals include
the aldehydes, ketones, alcohols, and ethers. Several studies have
shown the rate of air-stripping of some volatile organics which
may be found in petrochemical wastes (Gandy, et. al.,1961;
Englebrecht, et. al.,1961; and Gandy and Englebrecht, 1960).
Volatility tests on petrochemical wastes involve the aeration of a
waste sample at a given temperature, noting the removal of organic
material within a specified time and using a parameter such as COD.
Heavy Metals - Waste streams with potential heavy metal
contaminants are usually analyzed to determine the concentration of
these metals and thereby establish the potential toxicity. Several
techniques for heavy metal analysis are given in Standard Methods
(1965). Atomic absorption flame photometry can also be used
quantitatively to determine small quantities of metals. This method
is based on the measurement of light absorbed at a given wave
length by the unexcited atoms of the element being analyzed (Willard,
et. al. ,1965) . Quantities of some metals in concentrations lower than
one mg/1 can be detected by this procedure.
Total Plant Effluent Analysis
Petrochemical plants use some or all of the unit processes
which have been described. The many possible combinations of unit
processes which can be and are being used in petrochemical plants
make it impossible to correlate the effluent characteristics among
plants. Intra-plant differences in the effluent segreatation systems;
in-plant pretreatment systems; and process design, operation, and
maintenance also contribute to the variations. The ideal method for
predicting petrochemical wastewater characteristics would be to relate
the quantity of pollutant produced by a unit process to production
VI-55
-------
units, although enough data to develop these relationships is not
available at the present time. Instead, the effluent analyses
from several typical petrochemical plants are given in Table VI-15.
These data give a general idea of the variability of effluent
characteristics in the petrochemical industry, although basic simi-
larities are recognizable. In general, the pH values are greater
than pH seven and these high values suggest the influence of the
many caustic wastes employed in petrochemical processes. The effect
of spent caustics is also reflected in the high total solids and
low suspended solids concentrations of the wastewaters. This
indicates that most of the solids in petrochemical wastewaters are
in dissolved form. The data in Table VI-15 demonstrate that each
petrochemical waste must be analyzed separately to predict its
pollutional effects.
IDENTIFICATION AND MONITORING METHODS
There are many petrochemicals which cause marked adverse
effects on the environment, even in extremely small concentrations.
Standard analytical tools used for wastewater analysis (COD, BOD,
etc.) are inadequate for evaluating these effects and for predicting
their occurrence. New analytical methods must be developed so that
low-level contaminants can be traced from the petrochemical processes,
through the waste treatment system, and into the aquatic environment.
If compounds causing taste, odor, and toxicity can be identified
and traced to their source, methods for removing these persistent
compounds from the wastewater then can be developed. The two general
types of analytical procedures are chemical techniques and biological
methods. Chemical techniques are used principally to measure low-
level contaminants which cause color, taste, and odor while bio-
logical methods are used to observe toxic or* inhibitory effects of
waste discharges on the aquatic biota.
Chemical Methods of Analysis
This discussion considers the analyses of organic and
inorganic pollutants. The following techniques do not represent all
of the analytical methods which are used in water analysis, but
include those which are frequently utilized or may be particularly
applicable in the analysis of petrochemical wastes.
Inorganic Chemicals - A variety of analytical methods are
available for analyzing the inorganic ions in water. A good review
of these analytical techniques is available in the annual reviews of
Analytical Chemistry.
Inorganic analyses often require two steps; a separation
and/or concentration step followed by the identification and quan-
tification of the desired compound. When possible, it is simplest
to obtain a direct measure of a compound in the aqueous sample.
VI-56
-------
However, some type of separation procedure is usually required to
remove other interfering substances from other compounds to con-
centrate the desired compound to measurable quantities. The sepa-
ration processes most often used for inorganic compounds are
volatilization, precipitation, liquid-liquid extraction, and
adsorption (Mellon, 1960). 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
(Mellon, 1960). Several gravimetric procedures for determining
inorganic compounds, including methods of analysis for potassium,
sodium, calcium and silica are described in Standard Methods (1965).
Gravimetric procedures are time-consuming, difficult, and are
normally not used if other techniques are applicable.
Titrimetric methods are used for several inorganic analyses,
the most common of which measure alkalinity, acidity, and calcium
and magnesium ions using ethylene diaminetetracetic acid (EDTA).
New detectors have been developed to define more precisely the end-
point of the titration reaction. These detectors utilize poten-
tiometric, photometric, and conductometric methods in determining
the reaction end-point.
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 (Anon., Standard
Methods. 1965) . This method is simple and the equipment is relatively
inexpensive. Emission spectroscopes using high temperature arcs
and rarefied gases can be used to measure metals in the parts per
billion concentration range (Mellon, 1960). Atomic absorption
spectroscopy is another form of absorption spectroscopy which can be
used for trace metal analysis.
Absorption spectrometers are available for measuring absorption
in almost all regions of the electromagnetic spectrum. These methods
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 to eliminate these problems.
Most of the inorganic analyses employing the ultraviolet
and visible ranges of the spectrum involve the measurement of
chemical complexes of the inorganic compounds. Many colorimetric
methods used for determining the concentration of inorganic ions
are listed in Standard Methods (1965). The sensitivity of some of
the spectrometric techniques for inorganic compounds approaches one
part per billion (Mellon, 1960).
Infrared spectroscopy can also be used to measure inorganic
compounds, but has not been used extensively in water analyses (Mellon,I960)
VI-57
-------
One reason for this is that all water must be removed from a sample
prior to analysis, since water strongly absorbs across the entire
infrared spectrum. Gamma-ray and x-ray spectrometry have also
been used to a limited extent in water analysis.
Methods involving the measurement of the electrical
properties of systems are also used for inorganic analyses of
aqueous systems. Polarography, in which a potential is imposed
across two electrodes immersed in the test solution measuring
the resultant current, is probably the most commonly used
electrometric analysis for inorganics. Methods have been
standardized which can be used to determine simultaneously copper,
lead, cadmium, zinc, and nickel (Anon., Standard Methods, 1965).
Polarographic methods for measuring heavy metals are more rapid
than the corresponding colorimetric methods and avoid many of the
interferences; additionally, dissolved oxygen can be measured
using several polarographic techniques.
Potentiometry and coulometry have also been proposed as
tools, for water analysis, but have not been extensively used in
the identification of inorganic constituents of a wastewater. A
well-known use of potentiometry is in the pH measurement.
Other methods are also available for measuring inorganic
compounds of specific types and under specific conditions. For
example, radioactivity measurements can be used to detect the
presence of radioactive isotopes present in very low concentrations.
However, it is doubtful that this method would be applicable for
identifying most compounds present in a petrochemical waste. More
research into the analysis of wastewaters may demonstrate the utility
of these techniques.
None of the methods presented are universally applicable
since they are dependent on the compound to be determined and the
wastewater to be analyzed. The analyst will often find that he
will need to use two or more analytical techniques to complete
the analysis.
Organic Chemicals - Minute quantities of solubilized organic
compounds can cause toxic effects, tastes, odors, foaming, and
fouling of ion-exchange resins. Therefore, it is desirable to
identify and quantify these organics and this has been the objective
of much research.
Prior to analysis, most organic compounds in natural waters
must be concentrated, and for some analyses, separated. The concen-
trations of organic contaminants in receiving waters are usually
so low that they cannot be measured directly. Process effluents,
however, do not often require concentrating the organic pollutants
prior to analysis.
VI-58
-------
Several methods are available for concentrating trace organic
compounds, including adsorption on carbon filters, liquid-liquid
extraction, freeze concentration, distillation, and combinations of
the techniques (Baker and Malo, 1967). These procedures must not
alter the structure or relative distribution of the organic molecules
subject to analysis. The adsorption of organic compounds on
activated carbon filters is probably the best-known and most commonly
used method of organic concentration. The organic compounds are
removed from the carbon with a suitable solvent, usually chloroform.
The extract is separated into the four fractions of strong acids,
weak acids, basic, and neutral fractions using differential solu-
bility techniques. These fractions can then be subjected to the
various analytical methods for quantitative analysis. The carbon
absorption procedure is used by the United States Public Health
Service in its water quality surveillance network and is described
in detail in Standard Methods (1965). Several papers have described
the use of this technique for the determination of trace organics
in natural waters (Braus, et. al.,1951; Lively, et. al.,1965:
Middleton and Lichtenberg, 1960). The greatest disadvantage of
the carbon adsorption method is that not all of the organic compounds
are uniformly adsorbed and desorbed. Some chlorinated hydrocarbons
have been completely recovered, while phenol, for example, is
completely adsorbed but only 70 percent is desorbed from the
carbon (Baker and Malo, 1967). Oxidation and biodegradation of
organic compounds on the carbon surface has also been shown to
occur (Hoak, 1964), and volatile organic compounds may be lost
from the carbon prior to extraction. This volatilization of low
boiling point organic compounds can be prevented if the carbon is
kept wet and is extracted with the solvent without prior drying.
Because of the limitations of the carbon adsorption procedure,
particularly for quantitative analysis, other methods of organic
analysis have been investigated.
Liquid-liquid extraction can be used effectively to concen-
trate certain organic compounds. The quantitative recovery of
organic compounds from water is based on the affinity of the selected
solvent for the organics. This procedure is considerably more
rapid than the carbon adsorption technique and should eliminate
the problems of organic structure alteration which have been attribu-
ted to the carbon filter technique. Both batch and continuous
countercurrent extraction columns have been used, and ethyl ether is
the most commonly used solvent (Hoak, 1964; Baker and Malo, 1967).
Extremely small quantities of organics have been recovered using
extraction procedures employing diethyl ether solvent which was sub-
sequently vacuum evaporated to one milliliter (Caruso, et. al.,1966).
Solvent extraction has still not replaced carbon adsorption since
it is also subject to several problems. The principal problem
involves the selection of a solvent which has an affinity for most
organic compounds but which is readily separable from water. Separa-
tion of the solvent from water is the biggest limitation of the extrac-
tion process.
VI-59
-------
Freeze concentration methods have not yet found wide appli-
cation in water analysis. The biggest advantage of organic con-
centration by freezing is that organic compounds are completely
unaltered during the process. The effectiveness of freezing
techniques is dependent upon the rates of freezing, the ionic con-
centration of the sample, and the type of organic compounds in the
sample, The freezing technique is not yet fully developed but
offers an attractive method for concentrating trace organics when
it is perfected. Several examples of the application of freeze
concentration techniques to aqueous samples have been suggested
(Baker and Malo, 1967).
Distillation is the oldest concentration technique used in
trace organic analysis, but is difficult to apply if the organic
compounds being concentrated are volatile or heat labile. If the
organics are stable under heating and are not volatile, distillation
is probably the easiest method for concentrating them. The dis-
tillation procedure for concentrating phenols is a good example
(Anon., Standard Methods 1965). Often it is impossible to con-
centrate all of the desired organic compounds by a single technique.
Two or more concentration techniques often can be used in combina-
tion to produce measurable quantities of the contaminant in
question.
Many of the analytical methods used to determine trace
quantities of organic materials in water are the same as the techniques
employed in inorganic analysis. The two most commonly used organic
analytical techniques are spectroscopy and chromatography. For most
of these procedures, it is necessary first to concentrate the sample
using one of the methods previously described. In certain instances,
small quantities of organic compounds can be- determined directly
without any preparatory procedures. These direct methods are most
applicable for continuous monitoring of trace organics in waste
effluents and receiving waters.
Spectroscopic techniques are probably the most commonly
used methods of organic analysis, the principal ranges of the
spectrum used for these analyses being the ultraviolet range, the
visual range, and the infrared range.
Ultraviolet spectroscopy is often used in water and waste-
water analysis. Generally it is difficult to determine the molecular
structure of unknown compounds by ultraviolet analysis, since the
ultraviolet-absorbing groups in a compound are usually affected by
one another and discrete absorption bands do not often occur (Baker
and Malo, 1967). Differential spectroscopy can be used to eliminate
interferences by other compounds in a wastewater sample. A pro-
cedure has been developed which can be used to determine total
phenols in aqueous solution (Martin, et. al. ,1967) . This is a dif-
ferential absorption method based on the measurement of the phenolate
ion which is formed in alkaline solutions of phenols. A neutral
VI-60
-------
solution of sample Is used as the blank. This procedure is con-
siderably more rapid and less difficult than the standard colori-
metric procedures because it measures total phenols which the
colorimetric methods do not. No separation methods are required
prior to analysis since differential absorption eliminates most
interferences, and it is applicable to continuous monitoring of
effluent streams. This procedure for measuring total phenols is
presently being standardized by the ATSM Committee on Industrial
Water (Baker and Malo, 1967).
Spectroscopy in the visual range, also known as colorimetry,
is widely used in organic analyses. Most of these colorimetric
methods are based on measuring a colored complex formed when the
organic compound is chemically treated. The colored complexes pro-
duced are measured by differential absorption compared to reagent
blanks which contain all of the color-producing reagents but not
the organic compound. The phenol procedure (4-amino antipyrene
method, Standard Methods,1967) is sensitive to phenol concentrations
in the microgram per liter range, provided that the sample is properly
prepared. These colorimetric methods are nonspecific, and great
care must be taken to eliminate possible interfering compounds
(Baker and Malo, 1967).
Infrared spectroscopy is finding increased application in
water analysis. Infrared techniques are usually used in combination
with other analytical procedures to identify the molecular structure
of organic contaminants. Functional groups in organic molecules
absorb infrared light at various discrete wavelengths, providing a
means for identifying them. Differential absorption techniques are
usually used in infrared spectroscopy, and samples can be analyzed
in the solid, liquid, or gaseous form. The use of long-path infrared
sample cells for the analysis of gases makes infrared spectroscopy
an excellent method for the study of odors (Baker, 1961). Infrared
spectroscopy has been used extensively to analyze carbon adsorption
extracts obtained in the National Water Quality Monitoring Network
(Mlddleton and Lichtenberg, 1960).
Mass spectroscopy, in combination with other analytical
techniques, has also been used to elucidate the structure of organic
contaminants. The equipment required for mass spectroscopy is
expensive which has limited its use to a few research laboratories
(Baker and Malo, 1967). It offers several advantages in that it can
provide a rapid means of identifying extremely small amounts of
organics.
Gas-liquid chromatography is another analytical tool used in
water analysis. The development of the sensitive flame-ionization
electron-capture, and electron-affinity detectors has made gas-liquid
chromatography applicable for identifying most classes of organic
VI-61
-------
compounds (Baker and Malo, 1967). The flame ionization detector
has the added advantage of being insensitive to water, allowing
the direct injection of aqueous samples into the chromatograph.
This eliminates the time-consuming preparatory procedures required
to eliminate interference due to water and permits the use of con-
tinuous monitoring techniques.
Many applications of gas-liquid chromatography to water
analysis are mentioned in the literature. Baker and Malo (1967)
give an excellent discussion of some of these applications. Gas-
liquid chromatography techniques have been used extensively in
pesticide analyses. Electron-capture detectors are used to
identify the organic phosphate, chlorinated hydrocarbon, and organic
sulfur pesticides in the microgram per liter concentration range.
The flame-ionization detector has been used to measure many dif-
ferent organic compounds in aqueous samples. The sensitivity of
this detector encompasses the microgram per liter to milligram per
liter concentration range, depending upon the organic compound
being analyzed. One of the most promising uses of gas-liquid
chromatography and the flame-ionization detector is in the con-
tinuous monitoring of process and treatment plant effluents. A
system of this type has been developed and is presently used at a
chemical plant in West Virginia (Cochran and Bess, 1966). In one
instance this system was used to discover a malfunctioning distil-
lation unit by tracing an abnormal discharge of butanol to the unit.
It was determined, however, that interferences in this analytical
technique occurred in some process effluents, which precluded their
sampling by continuous monitoring procedures. New types of column
packings and changes in column temperature programming are being
investigated to eliminate problems such as these. Gas-liquid chroma-
tography probably offers the best possibility for continuous
monitoring of any of the present analytical techniques.
Gas-liquid chromatography has 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 used to
some extent for the determination of trace organic compounds in
water. Paper chromatography has been used to separate and identify
pesticides in polluted streams in quantities as small as 0.1 mg/1
(Baker and Malo, 1967). R. D. Hoak (1964) identified a number of
compounds, including phenol, guiacol, m-cresol, 3-5 xylenol, and a
number of aliphatic acids, in extracts from river water and oak leaf
fermentations. Some compounds can be separated and identified in
microgram per liter concentrations by paper chromatography. The
principal disadvantages of paper chromatography are that is is a slow
procedure and it is not extremely accurate for quantitative measure-
ments. Thin-layer chromatography, however, has the separation powers
of paper chromatography combined with the speed of gas chromatography.
VI-62
-------
A number of compounds have been separated by these techniques
including aldehydes, ketones, phenols, and a number of herbicides
(Baker and Malo, 1967). The two chromatographic procedures, paper
and thin-layer, are effective research tools for identifying trace
organic compounds in water; however, they must be used in conjunction
with other analytical and preparatory techniques and are not presently
applicable for continuous monitoring. Combinations of the more
important analytical techniques used in the identification and
measurement of trace organics in water samples are often used, as
a few brief examples will illustrate. Infrared spectroscopy, nuclear
magnetic resonance, and gas chromatography-mass spectrometry have
been used to quantify the structure of some products derived from
petrochemicals (Butler, et. al.,1967). Carbon absorption, liquid-
liquid extraction, silicagel adsorption chromatography, and
gas chromatography were used to identify petroleum products in four
water pollution incidents (Lively, et. al.,1965). The routine
analysis of carbon column extracts from the National Water Quality
Surveillance Network involves the use of solubility differentiation,
gas chromatography, and infrared spectroscopy to identify the
organic contaminants in surface xraters (Middleton,and Lichtenberg,
1960). Some of the compounds identified by the United States
Public Health Service in these surveys include DDT, 0-nitrochloro-
benzene, nitriles, substituted aromatics, phenols, detergents,
organic acids, ketones, aldehydes, alcohols, and amines. The iden-
tification of trace organics or even fairly large amounts of
organics in water samples is a difficult analytic problem. The
choice of the analytical technique must be based on the nature of
the compound to be measured, its concentration, and the presence
of possible interfering organics or inorganics. An investigation
was undertaken to develop laboratory techniques for efficiently
selecting gas-liquid chromatograph operating parameter which are
most suited to each type of petrochemical wastewater analysis
problem. A set of optimum conditions was developed for measuring
selected trace organics at levels at least down to one mg/1 using
direct aqueous injection. The practical means of applying these
techniques, as opposed to theoretical considerations, was emphasized.
Means of obtaining spectrometric confirmation of organic components
with and without preconcentration by freeze-out and carbon adsorption
also were studied. The resulting sequence of procedures for identi-
fication and measurement of the organics is illustrated in Figure
VI-1 (Sugar and Conway, 1968). Future research should develop more
and better techniques for estimating and evaluating the effects of
trace organic compounds in water.
Biological Methods
Problems involved in the toxicity bioassay and the use of
algae as toxicological indicators or any other laboratory method
arise when trying to translate and interpret results as they actually
apply to field conditions. Because of this uncertainty, safety
VI-63
-------
SAMPLE
DIRECT INJECTION
INTO CHROMATOGRAPH
E-B8
«CARBOWAX»2OM
PRECONCENTRATION
FREEZE OUT
6LC ANALYSIS
SPECTROMETRIC
II
IDENTIFICATION
DIRECT TRAP
OF ELUTED
FRACTIONS
f
FREEZE OUT
ACTIVATED
CARBON
GLC SEPARATION
GLC SEPARATION
TRAP ELUTED
FRACTIONS
TRAP ELUTED
FRACTIONS
INFRARED
(AND MASS SPEC.)
J
QUALITATIVE AND QUANTITATIVE ANALYSIS
FIGURE VI-1
SCHEME FOR IDENTIFICATION OF TRACE ORGANICS
(Reference 79)
VI - 64
-------
factors are used when laboratory results are transposed to field
conditions. In addition, long-term effects of nonlethal concen-
trations of chemicals on the biota cannot be predicted in the
laboratory. Effects on other members of the food chain cannot be
evaluated by measuring toxicity on only one organism, but then it
would obviously be impossible to measure the effects on each and
every organism. For these reasons, procedures have been proposed
which can be used to measure the biological effects of a waste
in the aquatic environment in situ. The continuously operating
biological systems have two advantages over their chemical monitoring
systems counterpart: namely, (a) the biological system monitors
the entire environment rather than preselected portions, and (b) the
biological system considers all of the environmental variables while
the chemical system records each characteristic separately (Cairns
1965).
Most of the proposed biological techniques for measuring
the effects of pollution in the environment are based on changes
in the dominant species which occur in the receiving waters when
pollutants are added. By studying the aquatic organisms upstream
and downstream from the source of pollution, the changes in the
ecosystem due to the pollution can be evaluated. One method for
evaluating these effects is by measuring the changes in the popu-
lation structure of the various aquatic communities. Severe pollu-
tion inevitably results in a reduction of the total number of
species, although this reduction may be accompanied by an increase
in the population of one particular species (Cairns, 1965). Normally
the change in population will only be measured for several species
of organisms.
For continuous monitoring purposes, it is desirable to
utilize indicator organisms with relatively short life cycles so
the response time will be relatively short. Diatoms, for example,
can be effectively used as an indicator organism since they reproduce
several times a day, will establish themselves on almost any type
of sampling surface, and 150 to 180 species are usually present in
unpolluted water (Cairns, 1965). It is desirable to have a large
population, both in number and species, to give statistical accuracy
to the monitoring system. Diatometers, which consist of suspended
glass slides, can be placed in the subject water and will indicate
any changes in the environment by the relative number of diatomites
present in each species.
Another environmental biological monitoring system assigns
a "biotic index" to the natural waters receiving pollutants (Beak,
1965). This biotic index is based on the macro-invertebrate organ-
isms (insects, tubificial worms) in the receiving waters and can be
calculated from samples taken by any method which gives an accurate
representation of population densities. Six distinct stages ot the
index are proposed ranging from natural conditions to situations ot
VI-65
-------
severe pollution. The study of macro-invertebrates can also be used
to observe the recovery of a stream from pollution, and there are
several examples of its use involving industrial effluents (Hynes,
1965).
Bioassay techniques using organisms other than fish have also
been proposed. These procedures are necessary since it is now
realized that toxic effects of a compound on aquatic plants and
invertebrates are equally as important as their effects on fish.
The use of bacteria and microcrustaceans in toxicity determinations
has been proposed (Willingham, and Andersen, 1966). Bacterial
toxicity could be evaluated by using the change in oxygen uptake of
aerobic bacteria or the change in luminescence in bioluminescient
bacteria. Microcrustaceans may prove useful for toxicity determina-
tions since they are easy to maintain in the laboratory and their
phototactic or heartbeat change is easily detected. The use of the
bacteria, protozoa, and algae present in the Winogradsky column
has also been suggested as a toxicity indicator (Hutner, et. al.,
1965). These organisms could be used to provide sensitive indicators
of the efficiency of biological treatment systems by employing
Winogradsky columns innoculated from the fauna of the biological
system.
Protozoa are also effective indicators of the toxic effects
of chemicals (Hutner, et. al.,1965) . Several bioassay techniques
have been used with protozoa as the indicators of toxicity. For
example, Paramecium can be used to identify polynuclear benzenoid
carcinogens (Hutner, et. al. .1965). This test is highly specific
and very sensitive and depends upon the carcinogen-sensitized
destruction of Paramecia by ultraviolet light. Conventional
growth inhibition studies similar to those used with bacteria and
algae are also common.
The conventional toxicity bioassay is undergoing changes.
Many bioassays are now being performed with time periods of several
months, in order to evaluate the chronic effects of chemical pol-
lutants (Cairns, 1965). Also, other indicators rather than death
are being used as the end-point of the bioassay, including changes
in respiration, cruising-speed abilities, and other behaviors (Cairns,
1965). These changes should help to make the results of the bioassay
more applicable and realistic.
Another type of biological measurement which should be men-
tioned is the panel test for taste and odor evaluation. These tests
are used to determine the threshold odor number of a waste which is
the dilution required to reduce the odor to barely detectable limits.
These methods are based on a subjective estimate of odors by a panel,
preferably trained in odor detection and are described in Standard
Methods (1965). Attempts have been made to develop qualitative tests
VI-66
-------
by preparing lists of terms describing odors and by using standard
odors as references (Rosen, 1966). In general, these methods have
been relatively unsuccessful since many variations and combinations
of odors are possible. However, developing a successful method of
odor characterization will be necessary if odor data from one source
is to be used elsewhere (Baker, 1963).
It would be desirable if some chemical or mechanical means
of measuring the intensity and character of odors was developed.
but as of now there is no device available which appraoches the sensi-
tivity of the natural sense of smell. Until these methods are
developed, panel testing will probably remain the principal method
of odor measurement.
These procedures represent only a few of the possible methods
of biologically analyzing the effects of pollution. More research
is needed to develop new methods and perfect the present ones so
that the optimum water quality criteria, which will satisfy the
needs of both the regulatory agencies and industry can be formulated
and made workable, resulting in a more pollution-free environment.
VI-67
-------
REFERENCES - CHAPTER VI
1. Alabaster, J. S., "The Effect of Heated Effluents on Fish,"
Advances in Water Pollution Research, Vol. I, Macmillan Co.,
p. 261, New York, N. Y. (1964).
2. Anon., Committee Report, Task Group 245, or "Survey of Ground
Water Contamination and Waste Disposal Practices," J. AWWA,
v. 52, p. 1211 (1960).
3. Anon., Drinking Water Standards, U.S.P.H.S. Publ. No. 956,
U. S. Department of Health, Education, and Welfare, Public
Health Service (1962).
4. Anon., Manual on Disposal of Refinery Wastes, Vol. I, "Waste
Water Containing Oil," American Petrol. Inst., New York, N. Y.
(1953).
5. Anon., Manual on Disposal of Refinery Wastes, Vol. I , "Chemical
Wastes," American Petrol. Inst., New York, N. Y. (1958).
6. Anon., Oxygen Relationships in Streams, Seminar Proceedings,
R. A. Taft, San. Engr. Center Tech. Rept. W58-2, Cincinnati,
Ohio (1958).
7. Anon., Society of Chemical Industry, Symposium, Geneva, May
2-3, 1957, "Molecular Structure and Organoleptic Quality,"
Monograph 1, Macmillan Co., New York, N. Y. (1957).
8. Anon., Standard Methods for the Examination of Water and
Wastewater, American Public Health Assoc., New York, N. Y.,
12th Edition (1965).
9. Anon., Water in Industry, Natl. Assoc. of Manufacturers and
the Chamber of Commerce of the U. S., New York, N. Y. (1965).
10. Bacon, H. E. and Lewis, W. J., "Interference of Organic Contami-
nants with Ion Exchange Processes - Occurrence, Prevention,
and Cost," Combustion, v. 32, p. 37 (July, 1960).
11. Baker, R. A., "Odor Effects of Aqueous Mixtures of Organic
Chemicals," J. WPCF, v. 35, n. 6, p. 728 (June 1963).
12. Baker, R. A., "Problems of Tastes and Odors," J.WPCF, v. 33,
n. 10, p. 1099 (Oct. 1961).
VI-68
-------
13. 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). -
14. Beak, T. W. , Discussion of "Behavior of Fish Exposed to Toxic
Substances," Advances in Water Pollution Research V I
p. 38 (1965). ' ' '
15. Beychok, M. R. , Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley & Sons, London (1967).
16. Braus, H. , et. al. , "A Study of the Concentration and Estimation
of Organic Chemical Compounds in Raw and Filtered Surface
Water," Anal. Chemistry, v. 23, p. 1160 (1951).
17. Burdick, G. E. , "Some Problems in the Determination of the
Cause of Fish Kills," Biological Problems in Water Pollution -
Third Seminar 1962, R. A. Taft Sanitary Engr. Center,
Cincinnati, Ohio p. 289 (1965).
18. Burttschell, R. H. , et. al., "Chlorine Derivatives of Phenol
Causing Taste and Odor," J . AWWA , v. 51, n. 2, p. 205
(Feb. 1959).
19. Butler, P. E., et. al . . "Modern Instrumental Techniques in
Structure Elucidation of Products Derived from Petrochemicals,"
Environ. Sci. & Tech., v. 1, n. 4, p. 315 (April 1967)'.
20. Cairns, J., Jr., "Environment and Time in Fish Toxicity,"
Ind. Wastes, v. 2, n. 1, p. 1 (Jan,, Feb. 1957).
21. Cairns, J. , Jr., "Biological Concepts and Industrial Waste
Disposal Problems," Proc . 20th Ind. Waste Conf., Purdue
Univ. , p. 49 (1965) .
22. Cairns, J., Jr. and Scheir, A., "The Relationship of Bluegill
Sunfish Body Size to Tolerance for Some Common Chemicals,"
Proc. 13th Ind. Waste Conf., Purdue Univ., p. 243 (1958).
23. Caruso, S. C., Bramer, H. C. and Hoak, R. D., "Tracing Organic
Compounds in Surface Streams," Air and Water Poll. Int. J . ,
v. 10, n. 1, p. 41 (Jan. 1966).
24. Cherry, A. B., Gabaccia, A. J. and Senn, H. W. , "The
lation Behavior of Certain Toxic Organic Compounds "Natural
Water," Sew, and Ind. Wastes,, v. 28, n. 9, p. 1137 (Sept- 1956)
25. Clifford, D. A., "Total Oxygen Demand - A New Instrumental
H~rh~* " •»-<- ^t-h Annual Scientificjjeetins, Midland Section,
Am. Ch'em. Soc., Midland, Michigan (1967).
VI-69
-------
26. Cochran, L. G. and Bess, F. D., "Waste Monitoring by Gas
Chromatography," J. WPCF, v. 38, n. 12, p. 2002 (Dec. 1966).
27. Cooper, W. C. and Tabershaw, I. R., "Biologic Effects of
Nitrogen Dixoide in Relation to Air Quality Standards,"
Arch. Environ. Health, v. 12, n. 3, p. 522 (1966).
28. 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).
29. Dougan, L. D. and Bell, J. D., "Waste Disposal at a Synthetic
Rubber Plant," Sew, and Ind. Wastes, v. 23, n. 2, p. 181
(1951).
30. DuBois, K. P. and Ceiling, E. M. K., Textbook on Toxicology.
Oxford University Press, New York, N. Y. (1959).
31. Eckenfelder, W. W., Jr., Lecture Series Prepared for Manufac-
turing Chemists Assoc., The Univ. of Texas, Austin (1967).
32. Eckenfelder, W. W., Jr., Ford, D. L. and Burleson, N. K.,
Unpublished Kept. (July 1968).
33. Elkin, H. F., "Condensates, Quenches, Wash Waters as Petro-
chemical Waste Sources," Sew, and Ind. Wastes, v. 31, n. 7,
p. 838 (July 1959).
34. Ettinger, M. B., "Proposed Toxicity Screening Procedure for
Use in Protecting Drinking Water Quality," J. AWWA, v. 52,
n. 6, p. 689 (June 1960).
35. Farrett, J. T., "Toxicity Considerations in Pollution Control,"
Ind. Wastes, v. 2, n. 1, p. 17 (Jan. 1957).
36. Ford, D. L. and Eckenfelder, W. W., Jr., Unpublished Rept.
(March 1968).
37. Ford, D. L. and Gloyna, E. F., Unpublished Rept. (Jan. 1967).
38. Ford, D. L. and Gloyna, E. F., Unpublished Rept. (Feb. 1967).
39. Ford, D. L. and Gloyna, E. F., Unpublished Rept. (May 1967).
40. Ford, D. L. and Gloyna, E. F., Unpublished Rept. (July 1967).
41. Filicky, J. G. and Hassler, J. W., "Effect of Synthetic
Detergent Pollution," J. AWWA. v. 42, n. 1, p. 17 (Jan. 1950),
VI-70
-------
42.
Garrett, J. T. , "Toxicity Considerations in Pollution Control "
Ind. Waste, v. 2, n. 1, p. 17 (jan. 1957).
43. Gaufin, A. R. , "Bioassays to Determine the Toxicity of
Pesticides to Aquatic Invertebrates," Proc. 15th Ind Waste
Conf., Purdue Univ., p. 94 (1960). ~~—~ —
44. Gloyna, E. F. and Burleson, N. K., Unpublished Kept. (March
1968).
45. 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-
46. Haines, R. M. , et^_al. , Annals of the New York Academy of
Sciences, v. 58, p. 158 (March 1954).
47. Henderson, C., Pickering, Q. H. and Lemke, A. E., "The Effect
of Some Organic Cyanides (Nitriles) on Fish," Proc. 14th
Ind. Waste Conf., Purdue Univ., p. 120 (1960),
48. Hoak, R. D. , "Recovery and Identification of Organics in Water,"
Advances in Water Pollution Research - v. 1, Macmillan, New
York, N. Y., p. 163 (1964).
49. Hoak, R. D., "The Causes of Tastes and Odors in Drinking
Water." Proc. llth Ind. Waste Conf.. Purdue Univ., P. 229
(1956).
50. 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).
51. Huekelekian, H. and Rand, M. C., "Biochemical Oxygen Demand of
Pure Organic Compounds," Sew. & Ind. Waste J., v. 27, p. 1040
(1955).
52. Hueper, W. C., "Cancer Hazards from Natural and Artificial Water
Pollutants," Proc. Conf. on Physiol Aspects of Water Quality,
USPHS, Washington, D. C,, p. 181 (1960).
53. Hutner, S. H., Baker, N. , Arronson, A. and Zahalsky, A^ C.,
"Bacteria-Protozoa as Indicators in Purifying Water,
Biological Problems in Water Pollution - Third Seminar 1962,
R. A. Taft San. Engr. Center, Cincinnate, Ohio, p. 45 (1965).
54. Hynes, H. B. N. , "A Survey of Water Pollution Problems,".Ecology.
and the Ind. Society, Goodman, G. T. , Edward, R. W. and
Lambert, J. M., eds. Blacfcwell Scientific Publications,
Oxford, p. 49 (1965).
VI-71
-------
55. Ishio, S., "Behavior of Fish Exposed to Toxic Substances,"
Advances in Water Pollution Research. 2nd Conference, Vol. I,
p. 19 (1965).
56. Jones, J. R. E., Fish and River Pollution., Butterworth and
Co. Ltd., Washington, D. C., 203 pp. (1964).
57. Kinney, J. E., "Evaluating the Taste and Odor Control Problem,"
J. AWWA, v. 52, n. 4, p. 505 (April 1960a).
58. Kinney, J. E., "Fusing the Phenol Frenzy," Proc. 15th Ind.
Waste Conf., Purdue Univ., p. 29 (1960b).
59. Klein, L., River Pollution II. Causes and Effects, Butterworth
and Co. Ltd., London (1962).
60. Kneese, A. V., Water Pollution - Economic Aspects and Research
Needs, Resources for the Future, Inc., Washington, D. C.
(1962).
61. Krombach, H. and Barthel, J., "Investigations of a Small Water-
course Accidently Polluted by Phenol Compounds," Advances in
Water Pollution Research, Vol. I, Macmillan Co., New York,
N. Y., p. 191 (1964).
62. Lammering, M. W. and Burbank, N. C., "The Toxicity of Phenol,
o-Chlorophenol, and o-Nitrophenol to Bluegill Sunfish,"
Proc. 15th Ind. Waste Conf.. Purdue Univ., p. 541 (1960).
63. Lively, L., Rosen, A. A., and Mashni, C. I., "Identification of
Petroleum Products in Water," Proc. 20th Ind. Waste Conf..
Purdue Univ., v. 49, n. 4, p. 657 (1965).
64. Martin, J. M., Orr, C. R., Kincannon, C. B., and Bishop, J. L.,
"Ultraviolet Determination of Phenols," J. WPCF, v. 39, n. 1,
p. 21 (Jan. 1967).
65. 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).
66. Mencher, M. R., "Minimizing Waste in the Petrochemical Industry,"
Chemical Engineering Progress, v. 63, n. 10, p. 80 (1967).
67. Middleton, F. M., Grant, W. and Rosen, A. A., "Drinking Water
Taste and Odor," Ind. & Engr. Chemistry, v. 48, n. 2, p. 268
(Feb. 1956).
VI-72
-------
68. Middleton, F. M. and Lichtenberg, J. J., "Measurements of
Organic Contaminants in the Nation's River," Ind. and Engr
Chemistry, v. 52, p. 99A (June 1960).
69. Nemerow, N. L., Theories and Practices of Industrial Waste
Treatment, Addison-Wesley Pub. Co., Inc., Reading, Mass
(1963).
70. Polange, R. C., "Mississippi River Water Quality," Southwest
Water Works J., v. 42, p. 23 (Aug. 1960).
71. 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).
72. Phelps, E.B., Stream Sanitation, John Wiley and Sons, Inc.,
New York, N. Y. (1944).
73. Pickering, Q. H. and Henderson, C., "Acute Toxicity of Some
Important Petrochemicals to Fish," J. WPCF, v. 38, n. 9,
p. 1419 (Sept. 1966).
74. Remy, E. D. andLauria, D. T,, "Disposal of Nylon Wastes," Proc.
13th Ind. Waste Conf., Purdue Univ., p. 596 (1958).
75. Rosen, A. A., "Recent Developments in Sensory Testing," J. AWWA,
v. 58, n. 6, p. 699 (June 1966).
76. Ruchhoft, C. C., et. al., "Waste Disposal in Petroleum Industry,"
Ind. & Engr. Chemistry, v- 46, n. 2, p. 283 (Feb. 1954).
77. Silvey, J. K. G-, et. al., "Actinomycetes and Common Tastes
and Odors," J. AWWA, v. 42, n. 11, p. 1018 (Nov. 1950).
78. Skold, R. V. and Wilkes, J. R., "Monobed Operation with a
Problem Water," Ind. & Engr. Chemistry, v. 47, p. 90 (1955).
79. Sugar, J. W. and Conway, R. A., "Gas-Liquid Chromatography
Techniques for Petrochemical Wastes," J. WPCF, v. 40, n. 9,
p. 1622 (Sept. 1968).
80. Tarzwell, C. M., et. al., Biological Problems in Water Pollution,
U S P H S Publication No. 999-WP-25, Cincinnati, Ohio (1965).
81. Taylor, E. F., et. al., "Orion Manufacturing Wastes Treatment,"
J. WPCF, v. 33, p- 1067 (Oct. 1961).
82. Teal, J. L, "The Control of Waste Through Fish Taste," American
Chem. Soc., Natl. Meeting (1959).
VI-73
-------
83. Teasley, J. I., "Identification of Cholinestrase-Inhibiting
Compound from Industrial Effluent," Environ.Sci. and Tech.,
v. 1, n. 5, p. 411 (May 1967).
84. Thirumurthi, D. and Gloyna, E. P., "Relative Toxicity of
Organics to Chlorella pyrenoidosa," Center for Research in
Water Resources Rept. No. 4, The Univ. of Texas, Austin
(1965).
85. Timmermans, J., "Odour and Chemical Constitution," Nature
(Brit.), v. 174, p. 235 (1954).
86. Todd, D. K., Ground Water Hydrology, John Wiley and Sons,
Inc., New York, N. Y., p. 185 (1959).
87. Turnbull, H. , Demann, J. G. and Weston, R. F., "Toxicity of
Various Refinery Materials to Fresh Water Fish," Ind. &
Chemistry, v. 46, p. 325 (1954).
88. Wallen, J. E., Greer, W. C. and Lasater, R., "Toxicity to
Gambusia affinis of Certain Pure Chemicals in Turbid Waters,"
Sew, and Ind. Wastes, v. 29, n. 6, p. 695 (June 1957).
89. Weintraub, R. L., Rocky Mountain Arsenal Waste Status Rept.
25 (May 1959).
90. Willingham, C. A. and Andersen, K. J., "Use of Microorganisms
for Detecting Toxic Materials in Water, Part I, Water and
Sew. Works, v. 113, n. 12, p. 464 (Dec. 1957).
91. Wilson, I. S., "The Treatment of Chemical Wastes," Waste
Treatment, Isaac, P.C.G., ed, Pergamon Press, London, p. 206
(1960) .
92. Wright, R. H., et. al., "Odour and Molecular Vibrations III.
A New Theory of Olfactory Stimulation," Chem. and Ind.
(Brit.) p. 973 (Sept. 1956).
93. Zapp, J. A., Jr., "Minimal Effects of Organic Water Contaminants,"
Proc. Conf. on Physiol. Aspects of Water Quality, U S P H S
Washington, D. C. (1960).
VI-74
-------
CHAPTER VII
TREATMENT AND CONTROL OF PETROCHEMICAL HASTES
This chapter deals with methods presently used for the
control, treatment, and ultimate disposal of petrochemical wastes.
The treatment and control processes discussed here are categorized
as follows: (a) reduction of waste strength by in-process and in-
plant control measures, (b) physical treatment processes, (c) chemical
treatment processes, (d) biological treatment processes, and (e) ulti-
mate disposal techniques.
REDUCTION OF WASTE LOADS BY INTERNAL IMPROVEMENTS
An ideal method for controlling petrochemical pollutants is
to minimize and control unavoidable losses near the source. Such
practice reduces the cost of waste treatment and in many cases provides
a valuable economic gain.
Reduction of Raw Material Losses
The losses of raw materials from storage, transport, and
processing facilities are an important source of water pollution
in the petrochemical industry. For example, Table IV-2 indicates
that 0.21 percent of hydrocarbon feedstock can be lost in a care-
fully controlled plant, but in plants where less extensive control
practices are employed, as much as 0.6 percent may be lost (Mencher,
1967). 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 through the use of floating
roof tanks and vapor recovery lines in tank vents and purge lines
used for process start-up and shut-down can be connected to vapor
recovery systems (Mencher, 1967). The hydrocarbon losses from vacuum
jets can be reduced by installing refrigerated condensers ahead
of the jets (Hyde, 1965) or by connecting the jet exhaust to vapor
recovery systems (Mencher, 1967).
Pipeline systems should be used to transfer raw materials
whenever feasible in order to minimize transfer losses. Many petro-
chemical industries minimize transport hydrocarbon losses by either
having subsidiary companies which supply raw materials or by producing
their own. Probably the most important source of hydrocarbon raw
material loss is from malfunctioning equipment lines, leakages, pump
gland leakage, etc. These losses can be corrected only by eareful
and persistent in-plant control.
VII-1
-------
Recovery of Usable Reaction Products
By-products represent a significant pollutional fraction of
petrochemical wastewaters and 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. The recovery
of sulfur from crude oils, for example, minimizes the sulfide and
mercaptan pollution. Many petroleum feedstocks contain large amounts
of these sulfur compounds which must be removed to prevent the
poisoning of process catalysts and products, and it is possible to
recover sulfur from these hydrocarbon feedstocks by removing hydrogen
sulfide in the form of acid gas using hydrodesulfurization. Hydro-
desulfurization consists of removing the hydrogen sulfide from a
process stream by stripping with steam or water. The hydrogen sulfide
then is stripped from the water or condensate as acid gas.
Two methods are currently used to convert hydrogen sulfide
to elemental sulfur. The Glaus Process and its modifications are the
most common methods or recovering sulfur from petroleum feedstocks.
Basically this process consists of forming sulfur dioxide by controlled
partial combustion of hydrogen sulfide with air, followed by a
reaction between sulfur dioxide and the remaining hydrogen sulfide
to yield elemental sulfur (Anon., Oil & Gas J., 1964) . The second
technique is a catalytic combustion process used for acid gases with
a hydrogen sulfide concentration too low to support non-catalytic
combustion (Anon., HydrocProc.,1967) . In 1963, the production of
sulfur in the United States from acid gases totaled nearly one million
tons. This procedure is usually an economical way of eliminating an
important source of pollutant. In another example, a refinery in
Germany hydrodesulfurizes the distillate from the crude-oil splitter
and converts the hydrogen sulfide to sulfur (Anon., Oil & Gas J.. 1960),
eliminating the need forsweetning, acid treatment, and caustic washing.
Other sources of usable materials found in petrochemical wastes
are the catalyst complex metals and the tars from catalytic processes.
For example, a chemical company has sold a copper-containing tar to
a smelter, which subsequently recovers the copper (Garrett, 1959).
Other metals such as nickel may also be present in evaluating
quantities in tars and metal complexes. Chemical recovery companies
also have reclaimed useful organic materials from tars. Usually the
recovery of materials from these tars does not result in a direct
profit to the petrochemical plant, but it may prove economically
justified in terms of a reduced pollutional discharge.
Alkaline wastes from caustic washes are most significant and
there are several methods available utilizing these caustic wastes
which may prove more feasible than attempting to treat and discharge
them. Some spent caustic solutions containing sulfides, phenolates,
cresolates, and carbonates are marketable (McRae, 1959). Spent
VII-2
-------
caustics containing large amounts of phenols and cresols can
be sold to processors who separate and purify the cresylic acid
fractions for commercial use (Beychok, 1967). Petroleum-based
cresylic acids have become an important marketable product and sodium
sulfide can be separated from spent caustics high in sulfides and can be
sold. The spent caustic is often enriched in sulfides by using it
to absorb hydrogen sulfide present in sour gas streams (Beychok,
1967). The recovery and marketing of spent caustics is probably the
most economical and desirable method for eliminating these wastes
is a favorable product demand is prevalent.
Spent caustics can also be regenerated by steam hydrolysis,
electrolysis, air regeneration, and the use of slaked lime (McRae, '
1959) for reuse in caustic washing processes. While this method
does not eliminate the problem of spent caustic disposal, it does
minimize the quantity of spent caustic wastes produced. Steam
hydrolysis is the most commonly used regeneration process (McRae,
1959) and as much as 90 percent of the caustic soda can be restored
by steam hydrolysis and air oxidation processes. Spent caustics
containing phenolic compounds cannot be recovered using these
processes, since phenolic compounds with sodium functional groups
cannot be renegerated by steam hydrolysis. Phenolics also interfere
with the oxidation process. Mercaptans but not sulfides can be
renovated; so a gradual buildup of sulfide occurs in the recovered
caustic, necessitating the eventual disposal of the caustic waste.
Electrical regeneration utilizes the oxygen formed from the electrol-
ysis of water to refresh the caustic and convert the sulfur to
marketable polysulfides. As with the other two processes, phenolic
compounds will interfere with the renewal process. The two methods
for caustic regeneration are steam and electrical (Figure VII-1).
The recovery and recycle of process effluents containing
unreacted raw materials allows substantial savings in raw material
purchases and is common to most petrochemical processes in which the
process reaction is incomplete. Many of the secondary reaction by-
products are also valuable 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
VII-1. An example of the in-plant use of a by-product is the use of
hydrogen chloride from hydrochlorination processes as one of the
reactants in the additional chlorination of olefins. Hydrogen
chloride can also be recovered and marketed as a salable product.
The removal of phenols from effluents containing recoverable quantities
of these compounds is often economical. For example, the Emscher
River Association in Germany recovers large quantities of phenol from
wastewater at a profit of about $300,000 per year (Clarke, 1962).
The recovery and reuse of oils is extremely common in the
petrochemical industry. Recoverable oils are reprocessed while those
which are uneconomical to purify are used as a fuel source. Solvent
recovery is also often practiced, especially when the high costs of
VII-3
-------
230°F
REGENERATOR
FEED DRUM
DISULFIDES
SPENT CAUSTIC
MERCAPTANS
(INCINERATION)
STRIPPER
WATER TO
'SEWER
REGENERATED
CAUSTIC
STEAM REGENERATION
ELECTROLYSIS TANK
HYDROGEN
WATER
SCRUBBER
NAPTHA
1
..._D
REGENERATED
CAUSTIC
DISULFIDES
ELECTRICAL REGENERATION
FIGURE VII-1
CAUSTIC REGENERATION PROCESSES
(Reference 81)
VII-4
-------
TABLE VII-1
USABLE SIDE-PRODUCTS FROM SOME
TYPICAL PETROCHEMICAL PROCESSES
(Reference 99)
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
VII-5
-------
TABLE VII-1 (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
VII-6
-------
solvents are considered. A comprehensive list of all of the pos-
sibilities of waste component reuse would be virtually limitless
Ingenuity often finds a use for a seemingly unusable waste or waste
component. For example, a styrene plant had an oily sludge which
was difficult to dispose of because of its physical and chemical
properties (Martin and Rostenbach, 1953). It was found that this
sludge could be separated into two fractions, an oil which could
be used for boiler fuel and an aqueous aluminum chloride solution
which was used effectively as a weed killer.
Process Modifications
Process modifications incorporated into the design and opera-
tion of petrochemical processing units can often lead to reductions
in the pollutional load from the plant. These modifications can be
classed as follows: (a) process selection, (b) prevention of product
and chemical losses, and (c) modified operating conditions (Anon.
API, Vol. III., 1958).
The problems of waste control 'should be initially considered
during the development and design of petrochemical processes, since
they can often be an important factor in the economics of operation.
Pilot plants used in the design of petrochemical processes can be
sampled to estimate the process losses and the type of pollutants
which will be discharged from the prototype unit (Anon., API, Vol.
III., 1958). Analyses of these samples will indicate possible process
modifications which can be implemented to reduce the pollutional load.
The incorporation of spent caustic regeneration schemes in
process and plant design is an example of process selection used to
reduce the waste load. The substitution of continuous processes for
batch processes also tends to eliminate peak discharges of wastes
and to reduce the cost of treatment required for the waste (Anon.,
API, Vol. III.,1958). Treatment facilities designed to absorb the
effects of shock discharges of wastes through equalization basins or
overdesigned tanks are considerably more expensive than those which
are designed to treat a waste of relatively constant consumption.
The use of downgraded chemicals in processes which do not
require high-quality reactants can facilitate both process and waste con-
trol (Anon., API, Vol. IV., 1958). This type of design utilizes the waste
effluents from one process as reactants in another. In the ideal
scheme, a chemical could be carried through several processes, each
using a slightly lower quality reactant. Caustic washes are often
so used in refining operations. For example, caustic washes used to
treat light hydrocarbons can later be used as make-up caustic for
gasoline treating (Anon., API, Vol. IV.,1958).
VII-7
-------
An example of how waste treatment costs can enter into both
process design and chemical loss control is shown in the example
below:
Redesign of Biological waste
extraction columns treatment plant
Capital Investment $300,000 $300,000
Yearly Operating Cost:
Labor, supplies, etc. 1,000 (addtl.) 73,000
Recovered organics -36,000 (savings) 0
Net cost -35,000 (savings) 73,000
Total difference $108,000
Such chemical recovery units are often designed so that
losses from the units are less than those which should be allowed
based solely on the economics of recovery (Anon., API, Vol. III., 1958).
The hydrocarbon losses associated with the use of barometric
condensors are an important source of pollution in petrochemical
processes (Gloyna and Malina, 1962). The use of shell and tube heat
exchangers rather than barometric condensors can significantly reduce
this source of pollution (Ruggles, 1959). Process sampling taps
connected directly to sewers are a source of pollution which can be
avoided by returning drainage to the process unit rather than the
sewer. Pollution caused by open-bottom steam stills can be controlled
by the installation of calandrias (Hyde, 1965). Distillation of
waste streams can also be used to eliminate the loss of volatile
materials (Martin, and Rostenbach, 1953). Furfural, for example,
is recovered by azeotropic distillation, eliminating this compound
from wastewaters while producing a valuable solvent for use in
extraction processes. One example of waste control by process
modification has been the elimination of oil emulsion losses from
barometric condensors on pipe still (Anon., API, Vol. III.,1958).
By rearranging the interior of the pipe still to reduce friction
losses through the trays and by lowering the temperature in the still,
losses were reduced to one-sixth of their original quantity.
Water Reuse
Water reuse is often one of the most effective and economical
means of reducing the waste discharges from a petrochemical plant.
In addition to reducing water costs and waste treatment costs, water
reuse increases the flexibility for plant expansion. Small quantities
VII-8
-------
of concentrated wastes produced by reuse are easier to handle than
large quantities of dilute wastes, and the plant enjoys more freedom
from upstream pollution (Clarke, 1962).
The recycle of cooling water is already common in the petro-
chemical industry, and the practice will become more popular in the
future. Potential applications of water reuse include the utiliza-
tion of poorer quality cooling water and boiler water and the reuse
of contaminated steams in stripping operations and in boilers (Rice,
1966). The advent of deposit control agents and the application
of corrosion resistant metal alloys in cooling coils and boilers
has greatly increased the concentrations allowed for cooling and
boiler waters.
Water use systems are classified .as multiple recycle and
cascade but most frequently combinations of these schemes are
utilized (Clarke, 1962). Multiple recycle involves the use of a
number of water systems carrying various qualities of cooling or
process waters. These systems are segregated and may have self-
contained treating systems, but usually operate with continuous
blow-down and make-up to keep the water at the desired quality. In
cascade systems which integrate process and cooling waters rather
than segregate them (Clarke, 1962), high quality water flows first
to the process requiring the cleanest water and subsequently to
successive processes where poorer water qualities can be tolerated.
Steam used for the stripping and quenching of process streams
is an important source of waste in the petrochemical industry.
Various treatment methods are available to reclaim these condensates
for reuse as will be discussed in detail later. One use for conden-
sates which requires little pretreatment is as a feedwater to waste
heat steam generators (Rice, 1966). Condensates with high sulfide
contents can be oxidized to convert the sulfides to sulfate and then
used to generate low-quality stripping steam. Another condensate
reuse scheme has been described (Mencher, 1967) in which phenolic
condensate from an olefin unit is washed with the fresh hydrocarbon
feed stream thus removing the phenol from the condensate. Other
volatile hydrocarbons are then steam stripped from the condensate and
reused to generate additional steam. Many additional schemes for
condensate reuse can be developed, depending on water quality require-
ments for a particular use.
A potential source of water for reuse in the petrochemical
plant is in the main boilers. These boilers usually operate with
superheated steam and can be damaged by solids deposition when poor
quality water is used (Rice, 1966). However, boilers can often
tolerate high dissolved solids concentrations, depending on the type
of dissolved matter and the boiler design. The use of sequestering
agents to prevent deposition has also contributed towards reducing
VII-9
-------
problems associated with oils in boiler waters (Rice, 1966). If
chelating agents are present, oils are distilled or leave the boiler
with the blow-down. If lower quality waters could be used in boilers,
the boilers could in effect aet as concentrating units for refractory
materials (Rice, 1966).
In-Plant Control
Operational control is one of the most important facets of
pollution abatement. The organic waste load (as BOD) at a West
Virginia chemical plant was reduced an estimated 40,000 Ib/day merely
by instituting proper control techniques. 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 some 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.
For example, butanol escaping from a distillation unit was discovered
in a wastewater which was continuously monitored using gas chromato-
graphy techniques (Cochran and Bess, 1966). The unit was subsequently
repaired, significantly reducing a source of pollution as well as
the loss of a valuable chemical product,
Waste Stream Segregation
Segregation systems used by the petrochemical industry vary
widely depending upon reuse requirements, effluent quality require-
ments, and possible undesirable effects which might occur if incom-
patible effluents are mixed. Three main segregated collection
systems are normally used (Anon., API, Vol. III.,1958):
a) area drains which carry unpolluted cooling water
and storm water 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 sewage system to collect plant domestic
wastes.
Many petrochemical plants segregate wastewaters to an even greater
extent. For example, oily process wastewaters are frequently segre-
gated from non-oily wastewaters to facilitate oil removal through
separators.
VII-10
-------
Segregation of many process streams may be necessary due to
the incompatability of certain waste components. Wastes containing
cyanides, for example, must be separated from acidic effluents to
prevent the release of gaseous hydrogen cyanide. Wastes with high
solids concentrations are usually segregated from oily streams since
suspended solids tend to increase the oil concentrations in oil
separation effluents. Suspended solids can also interfere with the
recovery of oils by increasing the solids contents of separator
skimmings (Anon., API, Vol. III., 1958).
Most water reuse schemes also require additional waste stream
segregation and the design of the segregation system will depend
upon the type of water reuse being employed at the individual plant.
If biological treatment is used to stabilize petrochemical wastes, the
sanitary sewage is usually added to it prior to treatment as a
source of biological nutrients; but many regulatory agencies require
effluent chlorination when sewage is added, making such a combination
unfeasible. The unpolluted cooling and storm waters which constitute
the largest volume of water discharged by the petrochemical industry
normally do not require treatment and are discharged directly to the
receiving body of water or effluent waterway.
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 combus-
tion.
Gravity Separation
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 sedimentation. Sedimentation and flotation techniques
commonly employ chemical conditioners to enhance the separation.
These separation aids will be discussed in a subsequent section.
Oil Separation - The separation of oil by gravity is a common
unit process in petrochemical plants. Many of the wastewaters from
petrochemical operations contain significant quantities of free and
emulsified oil-like materials which must be removed before subsequent
treatment can be obtained. Some of the petrochemical processes
which release sufficient amounts of oil are listed in Table VII-2.
In general free oils are easier to remove if their concentration is
high, indicating that treatment of oily water streams prior to dilution
with non-oily waste streams will provide for more efficient oil
separation. Slop oils recovered by the separation process can be
cleaned and reused in various processing operations and as fuel oils
for generating steam (Shannon, 1964; Martin and Rostenbach, 1953).
VII-11
-------
TABLE VII-2
SPECIFICAPPLICATIONS OF OIL SEPARATORS
IN THE PETROCHEMICAL INDUSTRY
Products
Waste Stream or Process
Effluent Requiring
Separation
Ref
Acrylonitrile and
Lineal Alkylate
Sulfonate Deter-
gents
Butadiene
Rubber
Copolymer
(GR-S)
Rubber
Cracking for
Ethylene, Propy-
lene and Butadiene
Hydrocarbons in
General (General
Refining Processes
Process Effluents
102
Process Area
Feed Preparation Area, Recovery
Area
Tank Farm
Polymerization
Process Area
Total Plant Effluent
Tank Farm
Excess Quench Water
Distillation
Thermal and Catalytic Cracking
Reforming
Alkylation
Isomerization
77
77
10.4
103
Hydrocarbons from
Cracking of Light
Crudes
Condensates
102
General
Petrochemicals
Acetaldehyde
Acetone
Acetylene Derivatives
CQ Aromatics
Benzene
Detergents
Diethyl Ether
Aromatic Distillates
Ethyl Benzene
Ethyl Ether
10
VII-12
-------
TABLEVII-2 (Continued)
SPECIFIC APPLICATIONS OF OIL SEPARATORS
IN THE PETROCHEMICAL TrcniTSTPv
Waste Stream or Process
Effluent Requiring
Products Separation
General Petro- Flux Oil
chemicals (Cont.) Gasolines
Kerosines
Naphtha
Polybutenes
Resins
Tars
Toluene
Urea
Xylene
Styrene Rubber Total Plant Effluent
VII-13
-------
For example, at a butadiene plant in California, 40 barrels of oil
per day were recovered and reused (Martin and Rostenbach, 1953).
Several basic designs of oil separators have been success-
fully implemented into the petroleum industry. Probably the most
commonly employed separator design is that presented in the American
Petroleum Institute's (API) Manual on the Disposal of Refinery
Wastes (1953). The API has performed extensive theoretical and experi-
mental research on separator design with the results summarized in
this manual (Anon., API, Vol. I., 1953). Other types of oil separators
used by the petrochemical industry are circular separators which
when properly designed can also be used as sedimentation tanks (Word,
et. al.); skim and surge tanks used to equalize the strength and
flow of wastewater are very effective oil removal facilities (Huber,
1967); and parallel-plate oil separators (Huber, 1967; Beychok, 1967;
Brunsmann, et. al., 1962). Such separators have given higher
oil removal efficiencies than conventional separators, probably because
of the shorter distance the oil must travel to the collecting surface
(Eckenfelder, 1966). Reported efficiencies of some oil-separators
operated by the petroleum industry are given in Table VII-3. High oil
concentrations are removed with greater efficiency than low oil con-
centrations since the lower limit of oil in the effluent from a separator
is usually 20 to 50 mg/1. Some reduction in chemical oxygen demand
(COD) can be anticipated because of the removal of oils and tars, but
little or no reduction in biochemical oxygen demand (BOD) can be
expected. One oil separator reported in Table VII-3 indicated a 55
percent removal of phenols, but it is doubtful that such a high phenol
removal can be maintained by physical separation. It is possible that
the oils in this separator acted as solvents, extracting the phenols
from the wastewater.
The principal factors which affect the design of oil-water
separators are
a) the specific gravity of the oil,
b) the specific gravity of the wastewater,
c) the temperature of the wastewater stream,
d) the presence or absence of emulsions, and
e) the suspended solids concentration.
The specific gravities of the oil and water determine the
separation rate while these specific gravities are in turn related to
temperature. These factors determine the allowable overflow rate from
the oil separator. Graphical solutions of oil-water separation rates
which can be used for separator design have been prepared (Reinbald, 1960)
VII-14
-------
1
I—>
Ln
TABLE VII-3
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 (%) (%) (%)
Circular - -
Impounding 0 -
Parallel Plate -
API* 45 - 55
Circular - - -
Circular 16 0 0
API -
API -
API -
Ref
112
90
6.6
13
117
13
13
13
13
API - American Petroleum Institute Standard Design
-------
Emulsions present the biggest problem of oil-water separa-
tion in the petroleum industry of which the most common type is the
oil-in-water emulsion where minute droplets of oil are dispersed
throughout the liquid medium (Anon., API, Vol. I, 1953). The usual
concentrations of oil found in wastewaters from the petrochemical
industry would cause these droplets to coalesce and separate from
the water phase, however the emulsions are stabilized by the presence
of a third compound, classified as an emulsifying agent. Some of
the compounds commonly found in petrochemical wastes which produce
this surface-active effect include the sulfonic acids, the naphthenic
acids and the 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 emulsions (Phillips,
1954). Also, other forms of suspended solids sometimes tend to
stabilize emulsions. Sources of oil emulsions within a petro-
chemical 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 barometric
or other direct-contact condensors, (e) detergent manufacturing
processes, and (f) equipment cleaning operations (Anon., API, Vol. I,
1953) .
In order to separate these oils from the wastewater, the
emulsion must first be broken by using both physical and chemical
methods. The appropriate procedures for effectively treating an
emulsified oil waste must be determined by a laboratory investigation,
The application of heat is probably one of the more effective methods
€sed for de-emulsification of a waste (Anon., API, Vol. I, 1953).
Heat decreases the viscosity of the oil phase, promotes the settling
of free water, and increases the vapor pressure of the water,
rupturing the film around the oil droplet (Anon., API, Vol. I, 1953).
Pressure and heat systems can be used, and distillation methods,
in lieu of the heat requirement, are also effective. Additionally
the surface active materials which act as emulsifying agents are
left in the still residue and can be disposed of separately.
Filtration and electrical methods have also been used to
treat emulsions. Filtration will be discussed separately in the
physical treatment section. Electrical methods involve the use of
a strong electrical field causing the water phase to coalesce and
separate from the oil by gravity (Anon., API, Vol. I, 1953).
Several of these emulsion-breaking methods are often combined to"
achieve the desired results. It should be noted that total oils in
excess of 50 mg/1 generally may have a deleterious effect on
secondary biological processes, and oil separation facilities in such
a system produce an effluent with less than this concentration.
Sedimentation - Sedimentation processes are employed in pre-
or primary treatment of petrochemical wastes with high suspended
solids concentrations, in secondary clarification, and as a sludge
thickening device. Petrochemical wastewaters high in colloidal
VII-16
-------
material must be chemically treated before adequate separation
by sedimentation can be obtained. Primary settling also has been
used to remove lead from wastes from tetraethyl lead manufacturP
(Gill, et. al.. 1960).
Operational data from the sedimentation of various petro-
chemical wastes are given in Table VII-4. These data indicate
that conventional removal efficiencies of suspended solids can be
obtained.
The removal of solids and oils from petrochemical waste-
waters and the concentration of sludges can often be accomplished
using a flotation process. When the mixture of suspended material
and air-saturated water is exposed to atmospheric pressure in the
flotation tank, minute air bubbles are released from solution and
carry the suspended materials to the top of the tank. In this
scheme air is dissolved under pressures of 30 to 60 psig in the raw
waste or in a portion of the clarified effluent. The efficiency
of this process is shown in Table VII-5.
The recycle system, where air is injected into a portion
of the effluent, has been successfully used for treating petroleum
and petrochemical wastes. In most cases, chemical aids must be
added to the waste to enhance the solids-liquid separation and
gravity oil separators precede the flotation unit. The high
efficiency of the flotation units in terms of COD removal for
petroleum waste is noted in Table VII-5 because many of the organics
are associated with the suspended material. However, flotation
unit efficiency is expected to be lower when considering petro-
chemical wastewaters in which more of the organic contaminants are
in soluble form.
The flotation design ranges for petrochemical wastes are
(a) pressure 30-60 psig, (b) detention time in the flotation tank 2
of 15-30 minutes, and (c) an overflow rate of two to three gal/min/ft .
A recycle system pressurizing clarified effluent is normally used
and the depth of the flotation tank will be six to eight feet,
depending upon the rise rate of the suspended material. Provisions
must be made for the disposal of the flotation tank skimmings, the
most common methods being incineration and landfill. One of the
big advantages of flotation over sedimentation is the shorter deten-
tion time required to clarify a waste by flotation, resulting in a
unit considerably smaller in size.
These separation processes will only partially treat a petro-
chemical waste; thus, the effluents from most plants may still be
objectionable from a pollutional point of view. If the waste stream
being treated is low in dissolved organic material, then it is pos-
sible that only filtration will be required as additional treatment
prior to discharge to the environment. This is an exception, how-
ever, and most petrochemical wastes have high concentrations of soluble
organic compounds requiring additional treatment prior to final discharge.
VII-17
-------
TABLE VII-4
SEDIMENTATION OF SOME PETROCHEMICAL WASTES
M
1
1 — i
CD
Waste
Amines ,
Amides
Drugs
PVC
Plastics
Refinery
Refinery,
Nat. 2
Gas Liquids,
Suspended
Influent
(mg/D
30
-
500
100
200
30-50
Solids
Effluent
(mg/D
3
200
20-40
25
30-50
5-20
BOD
Reduc. Influent
<%) (mg/D
90 150
-
92-96 150
75 125
75-85
33-90
Effluent Reduc.
(mg/1) (7«) Remarks
140 6.7 Neutral,
Follows
500
60 60 Neut . ,
Coagulation
90 28 Coagulation
Step (1) Neut.
Step (2)
Ref
26
26
26
117
90
Chem. Special-
ties
Coagulation
Resins
8,000
99+
130
125
3.8 pH Adjusted
26
-------
TABLE VII-5
PERFORMANCE AND OPERATING CHARACTERISTICS OF FLOTATION
UNITS TREATING PETROLEUM WASTES
Removal Efficiencies
Oil
S. S.
COD
Inf1. ppm Removal Infl. Removal Inf1. Removal
(mg/1) (%) (mg/1) (%) (mg/1)
Overflow
Pressure rate
o
(psig) (gpm/ftz)
Remarks
Ref
89-244 61-63
125 64-76
61-95
M 41-638
VO
Substantial
94
84
62
85-95
Substantial 100-
10,000
70-75
70-92
65-85
35-55
3.0
27
No Chemicals Added 112
7 ppm organic 13
polymer added
Phosphates Added, 92
+pH Adjustment
Recycle, 4 ppm 27
+ 4 ppm Activated
Silica
Recycle, 4ppm 27
Alum
Recycle 98
Recycle, 25 ppm 13
Alum Added
-------
Stripping Processes
Stripping methods are used to remove volatile materials from
liquid streams. Stripping is usually used to remove relatively
small quantities of volatile pollutants from large volumes of waste-
water (Anon., API, Vol. Ill, 1958). The two types of stripping
agents commonly used are steam and inert gas. When steam is used
to strip a volatile compound from an aqueous solution, the steam
serves both as a source of heat and a diluent to reduce the effective
pressure (Anon., API, Vol. Ill, 1958). The use of an inert gas,
such as natural gas, for a stripping agent precludes condensation of
volatile compounds stripped from solution. However, the indiscrimi-
nant use of inert gases for waste stripping may lead to air pollution
problems.
Stripping of hydrogen sulfide and occasionally ammonia from
sour waters is probably this method's most common use in the
petrochemical industry. The design criteria for sour water strippers
is well documented and is outlined comprehensively elsewhere (API,
Vol. Ill, 1958; Beychok, 1967). Most of the stripping methods
involve the continuous downward flow of the wastewater through a
packed or trayed tower while the stripping gas or steam flows upward
removing the desired constituent (Beychok, 1967). The operating
characteristics of steam, natural gas, and flue gas, the major
stripping agents used to remove hydrogen sulfide and ammonia, are
listed in Table VII-6. If the aqueous wastes are acidified with a
mineral acid prior to stripping, the ammonia is "fixed" in solution
as the ammonium salt of a strong acid and the hydrogen sulfide is
released to solution where it can easily be stripped. The tempera-
tures may be as low as 100°F. This method leaves ammonia in the
process wastewater, which may be desirable as a nutrient for bio-
logical waste treatment processes.
Steam is considered to be the preferred heating and stripping
agent for the removal of hydrogen sulfide and ammonia. One advantage
of steam is that hydrogen sulfide, which is concentrated in the steam
condensate, may be further treated. Flue gases are frequently used
because carbon dioxide produces a slightly stronger acid than
hydrogen sulffde thus releasing hydrogen sulfide from solution. In
this step the ammonia is not released. Additionally, the heat in
the flue gas is sufficient to raise the wastewater to stripping
temperature without a supplemental heat source. The principal dis-
advantages of flue gas are larger piping and equipment, corrosion,
and the release of hydrogen sulfide to the atmosphere.
Natural gas has also been used as an inert stripping gas
to remove hydrogen sulfide from sour wastewaters; however, steam
must be used to raise the temperature to at least 230°F (Beychok,
1967).
VII-20
-------
TABLE VII-6
AVERAGE OPERATING CHARACTERISTICS
OF SOUR WATER STRIPPERS
(Reference 12)
Removal
Type of Stripper
Steam
w/o acidifying
w/ acidifying """
Flue Gas
•A.
w/ steam'^,
w/o steam
Flow Rate of Stripping Medium
(SCF/gal)
8-32
4-6
12.7
11.9
H2S
(7.)
96-100
97-100
88-98
99
NH3
69-95
0
77-90
8
Tower
Temperature
Feed Tower Bottom
150-240 230-270
200 230-250
235
135
235
140
Natural Gas
w/ acidifying
7.5
98
70-100
70-100
Data from Eight Towers
Data from Only One Tower
Data from Two Towers
-------
Steam also has been used as a stripping agent in the
removal of other petrochemical waste components. Phenols can be
removed from aqueous waste streams by stripping them with steam.
Phenol removals of 24 percent and 36 percent were reported when
sour waters were stripped for hydrogen sulfide removal with steam and
flue gas (Anon., API, Vol. 111,1958). Steam stripping of phenolics
is applicable when a wastewater is subject to sharp variations in
temperature, specific gravity, phenol concentrations, and suspended
solids (Heller, et... al., 1957). The condensed phenolic steam is
reacted with caustic to remove the phenols. Superheated steam has
also been used to strip hydrocarbons from a spent acid catalyst
used in methylstyrene production (Federgreen and Weinberger, 1957).
This particular stripping process recovers 38 million pounds of
sulfuric acid, 9.3 million pounds of toluene, and 62 thousand pounds
of mercury per year of operation, which is sufficient to pay for the
entire operational cost. Steam has also been used to strip
aromatics from the condensate produced during the catalytic dehydro-
genation of ethylbenzene for styrene production.
Volatile organic compounds can be stripped from aqueous
wastes by using air as the stripping agent. Compressed air purged
through a container of wastewater will cause sufficient agitation
of the contents to remove large quantities of volatile organic
compounds. The stripping rate of a volatile organic compound is a
function of temperature, the stripping gas flow rate, and tank
geometry (Eckenfelder, et. al., 1956; Gaudy, Englebrecht and
Turner, 1961). Both exponential and linear equations have been
used to describe the removal of organic compounds from water by air
stripping. Laboratory investigations are required to determine how
many organic compounds in a particular wastewater can be stripped,
and which mathematical relationship defines the particular stripping
phenomenen.
Laboratory tests involving stripping of some biodegradable
volatile organic compounds indicated that most of the BOD removal
in an aeration tank was due to biological action rather than
physical stripping (Englebrecht and Ewing, 1962). This investigation
indicated that the stripping of biodegradable wastes is not usually
significant, even if the organics are quite volatile. If an organic
compound is non-biodegradable and volatile, however, air stripping
may be a significant mechanism for removing this pollutant from a
liquid system. For example, benzene and nitrobenzene,both of which
are relatively non-biodegradable, can be effectively air stripped
from wastewater. Air stripping systems are often not followed by
condensation units because of economic considerations, and the
practice of releasing volatile compounds to the atmosphere often
creates air pollution problems which limit this treatment technique's
efficiency.
VII-22
-------
Solvent Extraction
Solvent extraction methods utilize the preferential solu
bility of materials in a selected solvent. Solvent extraction
processes are common in petrochemical operations as a separation
technique. The criteria for an effective solvent for wastewater
treatment include (a) low water solubility, (b) density differen-
tial greater than 0.02 between solvent and wastewater, (c) high
distribution coefficient for waste component being extracted
(d) low volatility resistance to degradation of heat if distillation
is used for regeneration or low solubility in liquid regenerants
and (e) economical to use (Gloyna and Malina, 1962). The equipment
used for the extraction of wastewater includes countercurrent towers,
mixer-settler units, centrifugal extractors, and occasionally some
specially designed equipment (Anon., API, Vol. Ill, 1958).
Solvent extraction has been used very effectively by the
petroleum industry to remove phenols from various process streams.
Some of these solvents which have been used to extract phenols from
waste streams are tabulated in Table VII-7. Tri-cresyl phosphates
are excellent solvents due to their low solubility in water and their
high distribution coefficients for phenol, but they are expensive
and deteriorate at high distillation temperatures (Anon., API, Vol.
Ill, 1958). Tri-cresyl phosphates and the aliphatic esters might be
used when high phenol recoveries are desired for economic reasons,
justifying the use of expensive solvents. Most of the other phenol
solvents are available within the refinery-petrochemical complex and
are considerably cheaper to use in waste treatment operations. The
type of extraction equipment required for the use of a particular
solvent is also an important economic consideration. For example,
centrifugal extractors are much smaller than towers, but have higher
capital and operating costs. The electrostatic extractor used in
one phenol recovery process also recovers usable oil from wastewater,
which helps to make the process economical (Lewis and Martin, 1967).
The light cycle oil used as the solvent in this process is used in
certain refining processes not requiring phenol removal. This
results in much lower regeneration and disposal costs.
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 (Wilson, I960).
The applicability of solvent extraction methods to a particular
compound and waste stream must be investigated in the laboratory and
pilot plant. Extraction methods can often be used to significantly
reduce the pollutional load in a petrochemical effluent and at the
same time provide an economic method of product recovery.
VII-23
-------
TABLE VII-7
SOLVENTS USED TO EXTRACT PHENOLS FROM WASTEWATER
Phenol
Influent Effluent
Solvent (mg/1) (mg/1)
Aromatic s, 75% 200 0.2
Paraffins, 25%
< Aliphatic Esters 4,000 60
t— i
M
l-o
*" Benzene
Benzene 750 34
Light Cycle Oil >300 r^ 30
Light Oil *s 3,000 /x/ 35
Straw Oil Distillates
Tricresyl Phosphates 3,000 300-150
Phenol
Removal
(%)
99-9
98.5
90-95
95.5
90
98.2-99.5
95
90-95
Remarks
Solvent Regenerated with
Caustic-Lab Study
Regeneration by Distilla-
tion
Solvent Regenerated by
Distillation
Caustic Regeneration
Electrostatic Extraction
Also Removes Oil from
Water at Same Time
Centrifugal Extraction,
Caustic Regeneration
it it
Steam or Caustic Regen-
Ref
7
1
7
7
71
17
7
7
eration, Very High
Extraction Coefficient
-------
Adsorption
Adsorption is the process whereby substances are taken Up
and become attached to the surface of a solid, by either an
electrical, physical, or chemical phenomenon.
Carbon adsorption has been the most successful adsorbent in
removing special refractory chemicals from wastewater. Most of the
recent work in carbon adsorption has been concerned with the removal
of trace organics from treated wastewaters as one of the final
steps in complete water renovation. Activated carbon used as a
tertiary treatment method for a sewage effluent, for example, has
lowered effluent COD values from 40-70 mg/1 to 12-20 mg/1 (Eckenfelder
1966).
Examples of refractory materials which are difficult or
impossible to remove by conventional biological treatment processes
but are removable using adsorption techniques include benzene
sulfonates and heterocyclic organic compounds. The actual amount
of such a solute adsorbed per unit weight of adsorbent usually
increases with increasing concentration of solute. Specific adsorp-
tive capacities of different types of carbons vary for the same
solute and this is illustrated by the following data (Morris and
Weber, 1966).
Adsorptive Capacities of Activated Carbon:
(0.273 mm particle size @ 30°C)
Benzene Sulfonate 2-Dodecyl Benzene Sulfonate
Carbon (mol/g) (mol/g)
Columbia LC 131 400
Dareo S51 101 420
Fisher 120 344
Norit 92 338
Nuchar C-190 54 316
Phenols, nitriles, and substituted organics can also be
adsorbed from wastewaters when they are present in low concentrations.
Benzene hexachloride and other chlorinated aromatics have been
removed from pesticide manufacturing effluents by using carbon
adsorption (Geibler, 1958). These chlorinated hydrocarbons can be
recovered by regeneration with steam or with benzene.
Waste streams containing large concentrations of organics
cannot be economically treated by carbon adsorption which is limited
to the removal of small quantities of organic contaminants.
VII-25
-------
Combustion
Combustion processes are often feasible in disposing of
petrochemical wastes that are too concentrated or too toxic for
other treatment methods. Combustion may either be direct or
catalytic, depending on the waste being oxidized. Incineration and
submerged combustion are both direct combustion methods and both
have been used by the petrochemical industry. Submerged combustion
occurs in a specially-designed burner (Weisman, 1953) . This device
has been used successfully for total or partial evaporation of
waste streams and for concentrating dissolved solids. The products
produce an effluent which has reuse value or is more treatable.
For example, a nylon waste stream was reduced 75 percent,
the remainder of which was mixed with other process streams and
treated biologically (Remy and Lauria, 1958). Similarly, a polymeric
waste stream (containing suspended synthetic rubber particles,
organic solvents, inorganic salts, and synthetic detergents) which
was not amenable to biological treatment was reportedly treated by
submerged combustion (Weyermuller and Davidson, 1958). This waste
stream was evaporated to about 10 percent of its original waste
volume, with the resulting slurry dried on a drying bed. Also,
volatile organic compounds in the polymeric waste, such as alcohols
and amines, have been burned so that no odors were detected in the
surrounding areas. Submerged combustion also has been used to
remove toluene and cyclohexane from an effluent which was later
filtered and lagooned (Meinhold and Mandele, 1960).
The wide variety of wastes listed in Table VII-8 demonstrates
the extent to which incineration is used by the petrochemical
industry. The composition of both liquid and solid wastes dictates
the supplementary fuel requirements. Recently, fluidized bed incin-
erators have been used for burning refinery wastes (Gossom, and
Stevens, 1965) and are reported to provide better controlled combus-
tion. Additionally, excess biological solids from waste treatment
processes are often incinerated in conjunction with the petrochemical
wastes. The advantages of incineration include the ability to treat
concentrated and toxic waste streams as well as corresponding reduc-
tion of relatively large volumes of waste to small volumes of
innocuous ash. However, incineration often simply converts a water
pollution problem into an air pollution problem. Suitable equip-
ment must be installed on incinerators to control the discharge of
pollutants to the atmosphere. Sulfur compounds such as hydrogen
sulfide and sulfur dioxide are common air pollutants which may be
released when petrochemical wastes are incinerated. Fly ash also
can be released when tars containing inert materials are burned
(Garrett, 1959). These air pollutants should be removed from the
incinerator effluent gases. When an incinerator is designed, pro-
visions should also be made for the disposal of ash produced by the
combustion process. The properly designed incineration system
considers time, temperature, and turbulence. Sufficient residence
time should be provided to permit complete oxidation of the organic
VII-26
-------
TABLE VII-8
DESTRUCTION OF PETROCHEMICAL WASTES BY COMBUSTION METHODS
Combustion
Process
Waste
Remarks
Ref
I
K>
Incineration
Incineration
Incineration
Inc ine r at i on -
1600 OF
Incineration-
1500 °F
Incineration
Liquid wastes from manuf. of ammonia,
urea, nylon intermediates, ethylene
glycol, methylamines, methacrylates
Organic tars, catalyst complexes
Liquid Wastes containing hydrocarbons,
high-boiling degradation products,
tars from nylon intermediate manuf.
Liquid from acrylonitrile manuf. con-
taining acetonitrile and cyanides
+ slop oils 4- phenolic resin waste
(inorganic)
Two soot streams from acetylene manuf.;
still residues from acrylonitrile and
vinyl chloride processing; stripping
steam with acrylonitrile
Heavy sludge, acid, sulfonated tars
from benzene plant. General refuse,
scrap plastic
Wastes concentrated to 507, organ-
ic content-no auxiliary fuel re-
quired. Steam atomized burners
Metals must be collected when
catalysts are burned.
Nitrile wastes have high fuel
value. Provision for auxiliary
fuel gas was made.
67
47
23
101
Natural gas used as auxiliary fuel. 108
Flow and organic content of waste
fluctuates greatly.
Solid wastes fed first, then
liquid.
87
-------
TABLE VII-8 (Continued)
DESTRUCTION OF PETROCHEMICAL WASTES BY COMBUSTION METHODS
Combustion
Process
Waste
Remarks
Ref
i
K>
CO
Incineration Styrene sill residues
Incineration
Incineration
800-900 °C
Incineration
Incineration
Incineration
Incineration
Incineration
Submerged
combustion
Organic acids, salts, anhydrides,
Hydrocarbons and chlorinated hydro-
carbons from manufacture of chlorinated
organics
Sludges containing oil, solids from
separators, clarifiers, tank bottoms
Biological sludges
Vent gases - H^S, mercaptans
Spent caustic - 50% phenols
Spent sulfuric acid sludge
High- and low-boiling organics from
nylon manuf.
Organic acids and ketones from nylon
manufacture
Mixed with fuel oil and used in
heating furnaces
Natural gas fuel used in a vortex
burner. Wastes neutralized with
ammonia prior to incineration to
prevent corrosion
Fluidized-bed furnace
Fuel oil used as auxiliary fuel
87
76
66
7
7
7
113
96
-------
TABLE VII-8 (Continued)
DESTRUCTION OF PETROCHEMICAL WASTES BY C.OMBUSTION METHODS
Combustion
Process
Waste
Remarks
Ref
Submerged
Combustion
Submerged
Combustion
Cyclohexane and toluene from organo-
metallic processing
Hydrocarbons and polycyclic aromatics
from ethylene and acetylene produc-
tion
Cone, effluent is pressure- 82
filtered and lagooned
Stripped hydrocarbons are incin- 66
erated, stripped effluent goes
to biological treatment
-------
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 (Ross, 1967).
Filtration
Filtration processes are used to remove and concentrate
solid or oily materials from a waste stream. A filter can be speci-
fically 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 treatability of wastewater will be enhanced.
Some typical applications of vacuum and sand filtration processes
are listed in Table VII-9.
Filtration is a normal pre-treatment step in the preparation
of a petrochemical waste for deep well injection. Such filtration
facilities must be provided in order to prevent the clogging of
deep wells with suspended solids. Sludges produced by chemical
coagulation and clarification of petrochemical wastes are often
vacuum filtered to reduce their volume for easier handling and dis-
posal. Precoat vacuum filters have also been used to remove solids
from spent sulfuric acid catalysts which are subsequently sold for
use in fertilizer manufacture (Federgreen and Weinberger, 1957) , If
effluent standards imposed on a petrochemical plant are particularly
stringent, a polishing filter employing sand filtration can be used
to remove additional suspended material (Wilson, 1960). The prac-
ticality of filtering a wastewater should be based on laboratory or
pilot plant investigations. Such investigations establish the
criteria which will dictate the design of the filter.
Miscellaneous Treatment Methods
Certain other physical processes such as evaporation and
induced foaming have been used as methods of treating some petro-
chemical wastewaters. Dilute wastewaters containing small quantities
of salt and miscellaneous organic compounds are evaporated in a 64-
acre lagoon in Texas (DeRopp, 1951). Solar evaporation is feasible
if the petrochemical plant is located in an area with a low annual
rainfall and a relatively warm climate. Spraying the wastewater in
the air will expose a greater water surface to the atmosphere and
will increase the rate of evaporation (Gloyna and Malina, 1962).
Evaporation of wastewaters can also be accomplished in specially
designed evaporating units. A refinery in Germany has used evapora-
tion to reduce the volume of foul water condensates containing
sulfides and phenols by 10 percent (Huber, 1967). The mixture of
steam and volatile pollutants from the evaporator is used as
atomizing steam in the burners of a distillation unit. This evaporator
has effectively removed all of the sulfur compounds from the conden-
sates and requires very little maintenance. A similar type of
VII-30
-------
TABLE VII-9
TYPICAL FILTRATION APPLICATIONS IN PETROCHEMICAL WASTE TREATMENT
Waste
Vacuum
with
precoat
Filter
without
precoat
Sand Filter
with
pressure
without
pressure Others
Ref
M
M
Acids, aromatics from
detergent manuf.; nitriles;
pretreatment for injections
Biological sludges from
biological treatment processes
Neutralized effluent from
submerged combustion unit
treating organometallic
wastes
Oil-Ferric hydrate sludge
Oils from styrene and
butadiene production
Oils in separator effluents
X
X
X
X
X
X Chamber press
X
X Clay and coke
X
101
82
4
77
-------
TABLE VII-9 (Continued)
TYPICAL FILTRATION APPLICATIONS IN PETROCHEMICAL WASTE TREATMENT
Waste
Vacuum Filter
Sand Filter
with
precoat
without
precoat
with
pressure
without
pressure
Others
Ref
Stable oil-water emulsions X
from oil separator and
impounding basin
Sludge from coagulation of X
wash waters and spent caustics
from many petrochemical
processes
Secondary effluent from
activated sludge
Wastes from cumene phenol
and acetone production--
pretreatment for injections
Zinc-containing sludge from X
coagulating acrylic fiber wastes
Spent acid catalyst from X
Methylstyrene production
90
90
X
X
116
101
101
35
-------
evaporation process has been used to reduce the volume of a nylon
waste stream containing organic acids and metal salts prior to
incineration (Walker, 1958).
The separation of surface-active agents from wastewater by
induced foaming has been investigated in laboratory and pilot plant
studies (Brunner and Stephan, 1965). Most of these studies have
been concerned with the removal of synthetic detergents from domestic
wastes (McGauhey and Klein, 1961). There is little published data
available concerning foam separation, and no full-scale treatment
plants presently are operating in the United States. It has been
demonstrated that the surface-active agents naphthylamine and
naphthoic acid, which have little or no foaming ability, could be
removed from solution by adding a foaming agent and inducing
frothing (Karger and Rogers, 1961). It is possible that there may
be special applications in petrochemical waste treatment which might
require foaming techniques although laboratory and pilot plant
investigations are necessary to establish the applicability.
CHEMICAL TREATMENT METHODS
Many chemical methods are used in the partial treatment of
specific petrochemical waste streams. The most common include
neutralization, precipitation-coagulation, and oxidation. These
processes as well as some less frequently used methods will be
discussed herein.
Neutralization and pH Adjustment
Neutralization is often required in treating petrochemical
wastes since analysis of petrochemical waste characteristics
incidates that many process waste streams are highly acid or alkaline.
Neutralization 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 7. It should be noted that adju
ment to certain pH values is commonly used to facilitate coagulation
and precipitation.
VII-33
-------
Typical applications of neutralization and pH adjustment
requirements for treating petrochemical wastes are tabulated in
Table VII-10. In most of the cases cited, neutralization is used
as a primary treatment step, with coagulation and settling of the
waste often following. Types of wastes generally neutralized
include (a) dilute acid or alkaline wash waters from many petro-
chemical processes; (b) spent caustics from caustic treating opera-
tions; (c) acid sludges from alkylation, sulfonation, sulfation, and
acid treating processes; and (d) spent acid catalysts (Anon., API,
Vol. Ill, 1958).
Coagulation and sedimentation of wastes is more effective
if the pH of the waste is adjusted to the optimum value for the
coagulant used. Oil-in-water emulsions can sometimes be broken
by pH adjustment alone, and when coagulation is used to break
emulsions, prior pH adjustment of the wastewater is usually required.
Spent caustic wastes are often neutralized with acidic
waste streams, sulfuric acid being the most commonly used neutralizing
agents (McRae, 1959). Acid sludges are normally hydrolyzed to free
acids prior to their use as neutralizing agents. The neutralization
of a phenolic spent caustic solution separates it into two phases,
an aqueous phase containing the sodium salt of the neutralizing
acid and an oily phase containing phenolic compound, called "acid
oil" (Beychok, 1967), Sulfides in spent caustics are released as
hydrogen sulfide during the neutralization process and the "acid
oil" requires further treatment to remove the large quantities of
phenolic compounds. The salt solution from caustic neutralization
may be suitable for discharge without treatment, but since it still
contains some phenolic compounds, additional treatment is normally
required (Anon., API, Vol. Ill, 1958). Spent caustic neutralization
with an acid can be designed as a batch or a continuous system. A
typical installation for the neutralization of spent caustic solutions
with acid is schematically illustrated in Figure VII-2. In order to
liberate the acid oils and hydrogen sulfide most efficiently, the
system is operated at a value of pH five (Anon., API, Vol. Ill, 1958),
The carbon dioxide in flue gases can also be used to
neutralize spent caustic solutions in a manner similar to that des-
cribed for strong acids with sodium carbonate being the predominant
salt in the aqueous phase. Most of the phenols can be removed from
a caustic waste if flue gas stripping is continued for a sufficient
period (Anon., API, Vol. Ill, 1958). Flue gas neutralization is
feasible provided that the gases are available at high enough
pressures so that no blower is required to inject them into the spent
caustic solution (Anon., API, Vol. Ill, 1958). Some catalyst regen-
erators supply flue gas at high enough pressures to satisfy this
requirement. Spent caustic neutralization with flue gas is often
operated as a batch process. This type is shown in Figure VII-2. The
VII-34
-------
TABLE VII-10
TYPICAL APPLICATIONS OF NEUTRALIZATION OR
Process or Products
Manufactured
Acid treating processes
Adipic acid
Alkylation, sulfonation
M for detergents, etc.
i
m Amines , amides
Butadiene
Butadiene, olefins
Catalytic processes
Chemicals for lubrica-
ting oils
Freon
Herbicides
pH ADJUSTMENT TO PETROCHEMICAL WASTES
Waste Components Agent Remarks
Spent sulfuric acid Spent caustic
Organic acid Ammonium hydroxide
Sulfonic acids
Sulfonates Lime Coagulation follows
Cuprous ammonium Spent caustic
acetate
Follows coagulation
Aluminum chloride
phosphoric acid Lime
Coagulation follows
Inorganics
Chlorinated hydro- Lime
Ref
6
22
103
26
104
26
6
26
113
26
carbons
-------
TABLE VII-10 (Continued)
TYPICAL APPLICATIONS OF NEUTRALIZATION OR
pH ADJUSTMENT TO PETROCHEMICAL WASTES
Process or Products
Manufac tured
Waste Components
Agent
Remarks
Ref
Many Petrochemical
operations
Mixed Petrochemicals
Mixed Petrochemicals--
olefins, aromatics,
nitriles, resins,
detergents, etc.
Orion
Phenol, salycylic acid,
rubber chem., aspirin
Polyethylene
Polyvinylchloride
plastics
Emulsified oils
Aliphatic acids,
esters, alcohols;
aromatics; amines
Oily wastes
Mixed organics and
inorganics
Mixed organics
Hexane, catalyst
alcohols
Lime
Soda ash
Lime
For coagulation
61
Lime
For biological treatment 106
After biological treat- 102
ment as coagulant aid
Lime
Coagulation follows
pH adjustment, clarifi-
cation follows
Coagulation follows
113
146
104
26
-------
TABLE VII-10 (Continued)
TYPICAL APPLICATIONS OF NEUTRALIZATION OR
pH ADJUSTMENT TO PETROCHEMICAL WASTES
Process or Products
Manufactured
Waste Components
Agent
Remarks
Ref
Spent caustics from
caustic treating opera-
tions
Styrene
Tetraethyl lead
Spent caustic
Acid wastes
Lead; sodium
chlorides, sulfates;
Ethyl chloride
Waste alkaline
sodium alurninate
Sedimentation follows 77
For coagulation 51
-------
TREATING
UNIT
SPENT
CAUSTIC
ACID
HYDROGEN
WATER
I
SURGE TANK
OILS
PHASE
(a) ACID NEUTRALIZATION
SPENT
CAUSTIC
STRIPPING
TOWER
FLUE GAS
STEAM
SURGE TANK
VENT
GAS
•ACID OIL:
AQUEOU!
PHASE
(b) FLUE GAS NEUTRALIZATION
FIGURE VII-2
SPENT CAUSTIC NEUTRALIZATION
(Reference 81 )
VII-38
-------
spent caustic flows downward countercurrent to the flue gas and
the caustic solution is recycled until neutralization is complete
(Anon., API Vol. Ill, 1958). Normal neutralization period ranL
from 16 to 24 hours with a corresponding carbon dioxide utilization
of 25 to 50 percent. The effluent from flue gas neutralization will
require the same type of treatment as those from acid neutralization
The aqueous phase will usually contain carbonates, bicarbonates
sulfates, sulfites, thiosulfates and small quantities of phenolic^
(Anon., API, Vol. Ill, 1958).
Neutralization and pH adjustment of other aqueous waste
streams are usually carried out in simple neutralization tanks
which provide for mixing of the reactants, allowing sufficient time
for the neutralization reaction to approach completion. Spent acid
catalysts and sludges have been spread in pits filled with lime,
limestone, or oyster shells for neutralization (Anon, API, Vol! Ill,
1958). The most economical method of neutralization depends on the'
character and quantity of the waste being neutralized and the
source and supply of the neutralizing agent.
Coagulation-Precipitation
Coagulation and precipitation are used to remove suspended
and colloidal waste materials and their applications for various
petrochemical wastes are listed in Table VII-11. It should be
noted that coagulation is always followed by some type of solids-
separation process. Gravity separation in conventionally designed
clarifiers is the most common method, but flotation and filtration
are also used to remove agglomerated material. The most commonly
used coagulants are hydrated aluminum sulfate (alum), ferrous
sulfate, and ferric salts. Coagulant dosages and optimum coagula-
tion pH ranges are usually determined in laboratory investigations.
After the coagulants are added to a waste, sufficient time must be
provided to allow the buildup of settleable floe particles. The
conventional coagulation system utilizes a rapid-mix tank followed
first by slow agitation of the mixture in a flocculation tank to
promote the growth of floe particles, then by sedimentation. The
sludge-blanket clarifier, which provides mixing, flocculation, and
settling in the same unit, has had many industrial applications
because of its compact dimensions. This type of unit recycles
preformed floe which aids in the development of new floe particles
and enhances the entrapment of colloids. Occasionally, some form of
coagulant aid is required to help form a good-settling floe by
promoting bridging between floe particles and rendering the floe more
settleable. The most common coagulant aids are activated silica and
the organic polyelectrolytes. There are three types of these poly-
electrolytes: a cationic, which adsorbs on a negative colloid or
floe particle, an anionic which replaces the anionic groups on a
colloidal particle and permits hydrogen bonding between the colloid
and the polymer, and the non-ionic which adsorbs and flocculates by
hydrogen bonding between the solid surfaces and the polar groups in
VII-39
-------
Nylon monomers
Polyvinyl chloride
Plastics
TABLE VII-11
COAGULATION AND SEDIMENTATION .OF PETROCHEMICAL WASTES
Product or
Process
Acrylic Fiber
Alkylation,
< Sulfonation
}~H
M
1
g Butadiene;
Olefins
Copolymer
Rubber
Many petrochein
processes
Waste
Comp onen t s
(If known)
Zinc
Organic
sulfonates
Latex
Emulsified
oils
Coagulant (s) Remarks
Lime, ferrous pH 9.3
sulfate
Lime, ferrous
sulfate
Lime,
alum
Alum, ferrous sulfate, Effluent oil 5-10 ppm
ferric chloride - effluent turbidity
Ref
101
103
26
77
61
sodium silicate aid
Ferric chloride
Alum
10-20 ppm
High coagulant concen- 44
trations required opt.
pH = 4.5
>90%S.S. removed; 26
60% BOD. removed
-------
TABLE VII-11 (Continued)
COAGULATION ANDSEDIMENTATION OF PETROCHEMICAL WASTES
Product or
Process
Refinery and Natural
Gas Liquids
< Refining Process
M
4> Refining Process
Refining Process
Synthetic Rubber
Tetraethyl Lead
Waste
Components
(If known)
Coagulant(s)
Remarks
Oils
Oil emulsions,
sulfuric acids,
napthenic
acids, phenols,
fatty acids,
sodium salts
(Same as above)
Ferric sulfate
nontoxic poly-
electrolyte
Alum, activated silica
Lime (alum, iron
sulfate added if needed)
Aluminum and ferric
salts
Alum
Lead, ethyl Ferrous sulfate
chloride, sodium
chlorides, sul-
fates, sulfides
80% oil rem.
75% S.S. rem.
44% COD rem.
34% Sulfides rem.
flotation, 94% oil rem.
95% turbidity removed;
60-85% S.S. removed
Effluent oil <5ppm
90-95% oil rem.
35% COD rem.
82-5% S.S. rem.
82.5% BOD rem.
Ref
117
98
89
66
28
51
-------
the polymer. The most effective coagulant aid can be determined
only through a series of laboratory tests.
A common application of coagulation in the petrochemical
industry is the removal of emulsified oils from waste streams.
Almost every type of coagulant has been used to treat emulsions,
as illustrated in Table VII-11. Effluent oil concentrations from
coagulation processes have been reported as low as five mg/1 with
oil removal by coagulation usually in the range 75-85 percent
(Beychok, 1967). Suspended solids and turbidity removals are often
as high as 90 percent, depending upon the characteristics of the
wastes being treated. If large quantities of suspended and colloidal
organic materials are present in a wastewater, coagulation and
sedimentation can result in substantial COD and BOD removals. How-
ever, most petrochemical wastes contain primarily dissolved organic
compounds which are not removed to any extent by coagulation.
Coagulation is also effective in enhancing flotation of
emulsified oils and suspended material. The addition of alum and
activated silica to a refinery waste being treated by flotation
increased the oil removal from 62 percent to 94 percent (Rolich,
1954). The large floe particles formed by the coagulation process
provide more surface area for air bubble attachment, thus increasing
the flotation cell efficiency.
Coagulation has also been used to remove metals such as
lead and zinc from petrochemical wastes. Water-soluble alkyl-aryl
sulfonates can be removed from wastewater by coagulation with lime,
which forms insoluble precipitates. Settling of the precipitate
can be enhanced by adding ferrous sulfate (Schindler, 1949; 1951).
Low concentrations of sulfide can be precipitated with zinc chloride,
ferric chloride, or copper sulfate. This precipitate can then be
removed by flocculation of the precipitate (Anon., API, Vol. Ill, 1958).
Provisions must be made for the disposal of the sludges
formed by these settled precipitates. Landfills are the most common
form of inorganic sludge disposal. Some organic sludges are de-
watered and subsequently incinerated or buried. Anaerobic digestion
is rarely used by the petrochemical industry for organic solids treat-
ment .
Oxidation Processes
A variety of oxidation processes have been used in the treat-
ment of petrochemical wastes. Combustion processes were discussed
with the physical treatment methods, but catalytic oxidation, con-
sidered to be a combustion process, is discussed here. Oxidation
processes are used to treat both organic and inorganic contaminants
using oxygen or other chemicals as the oxidizing agents. Oxidation
processes as applied to various petrochemical wastes are tabulated in
Table VII-12. The following discussion briefly describes the most
commonly used oxidation methods.
VII-42
-------
TABLE VII-12
OXIDATION PROCESSES USED IN PETROCHEMICAL WASTE TREATMENT
Product or Process
Waste Components
(If known)
Type of Oxid. Process
Remarks
Ref
Acrylic fibers,
nitriles
Acrylic fibers
Acrylic fibers,
nitriles
Caustic treating
operations
Ethylene glycol
Mixed petrochemicals
Mixed petrochemicals
Cyanides
Dime thy lamine
Dimethylforma-
mide
Cyanides
Sulfidic Spent
Caustics
Hydrocarbons
0.5-1.0% Organic
from column heads
Ozone
Catalytic oxidation
Chlorination
Air and steam
Catalytic oxidation
Catalytic oxidation
Catalytic oxidation
Opt. pH 11-12 110
Pt. catalyst, 310 C, 109
combined with direct
combustion
1-2 hr treatment time 6
pH 8.5 required
Oxidizes sulfides to 80
thiosulfates and 13
sulfates
Copper-chroinite catalysts 59
977, organic destruction 33
Metal oxide catalysts 107
575°C Pt. catalyst' added 62
to control oxidation
Mixed petrochemicals 3-57= Organic acids Thermal cracking
800°C, natural gas
67
-------
TABLE VII-12 (Continued)
OXIDATION PROCESSES USED IN PETROCHEMICAL WASTE TREATMENT
Products or Process
i
4>
-P-
Synthetic Rubber
Nylon intermediates
Phenol, resins,
refining crude
Phenol
Phenol
Phenol
p-Cresol
^-Naphthol
Refinery
Waste Components
(If known)
Type of Oxid. Process
Remarks
Ref
Probably unsatura-
ted H.C. (some
chlorinated)
167= Nad, 0.5%
metal salts, 1%
misc. organics
Phenolics
Sulfite liquors
Sulfite liquors
Sulfite liquors
Sulfite liquors
Sulfite liquors
Ozonation
Air
Ferrous salts and
hydrogen peroxide
Chlorine
Ozone
Air-iron catalyst
in liq.
Air
Air
Petroleum products Ozonation
Opt. pH 12.6, 90.5%
COD reduction
Converts metals to
insoluble hydroxides
Expensive
Opt. pH 12
Aerations in venturi
units 99.9% S03
removed-11 hr
Mixco agitator w/ sparge
ring
Mixco agitator w/ sparge
ring
75-85% removal of petrol.
prod. 16 hr detention
23
32
32
88
116
26
91
-------
The oxidation of Bulfides to sulfates using steam and air
is an effective method of treating wastes containing such compound,
Sulfides cannot be effectively steam-stripped from spent caustics
since sodium sulfide does not hydrolyze appreciably under those
conditions. While wastes containing ammonium sulfides can be steam
stripped, the hydrogen sulfide stripped from such wastes can often
cause air pollution problems. Oxidation of sulfides to thiosulfates
and sulfates can be an economical method for the disposal of these
compounds; however, wastes containing high concentrations of phenol
cannot be treated by these methods because phenols interfere with
sulfide oxidation.
The chemistry and theory behind the oxidation of sulfides is
well documented (Beychok, 1967). Most sulfide oxidation units
presently used are patented designs. The design criteria and
operation conditions for several types of these units are listed in
Table VII-13. All of the units mentioned oxidize 100 percent of the
influent sulfides, but if large quantities of mercaptans or mer-
captides are present in the waste, a reoxidizer may be required to
insure complete oxidation (Beychok, 1967). The reoxidizer should
be operated at a temperature of 130-150°F with a pressure of 50
psi to prevent mercaptan stripping. The data in Table VII-13
indicates that sulfides can be oxidized to thiosulfates more easily
than to sulfates. It is possible that some sulfate was produced
in the towers, but to obtain maximum converstion, low sulfide
loadings are required. The oxidation of sulfides is a liquid phase
process with a typical unit shown in Figure VII-3. Temperatures
at the top of the oxidation tower are normally kept below 200 F for
ammonium sulfide feeds to prevent stripping of hydrogen sulfide,
since oxidation is not as effective in the vapor phase (Beychok,
1967) . Heavy oils should be eliminated from the waste prior to
oxidation since pilot plant studies indicated that five percent of
such oil could decrease the oxidation rate by 50 percent.
Catalytic oxidation has been used to treat petrochemical
wastes containing various toxic organic compounds not amenable
to biological degradation. It 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
it has been successfully applied to aqueous wastes. Laboratory
investigations have shown that dilute aqueous organic wastes could
be effectively oxidized at temperatures below 600°C by using a
copper-chromate catalyst (Green and Moses, 1952). These studies
indicated that sulfur compounds could seriously contaminate the
catalyst. Investigations have demonstrated that hydrocarbons could
be oxidized also by using metal oxide catalysts (Stein, et. aj..,
1960) . The following examples indicate the application ot this
treatment technique to petrochemical wastes.
VII-45
-------
TABLE VII-13
DESIGN AND EFFICIENCY OF SOME SULFIDE OXIDATION UNITS
Tower
Temp.
(Top)
Oxid. Products (°F)
Feed
Ib Sulfide,
v min '
(Reference
Air Flow
, Ib air ,
vlb S oxidized'
12)
Detention
Time
(hr)
Pressure
(Top)
(psia)
Sulfur
Oxidized
, Ib/hr ,
( 3 '
ft tower
Remarks
100% Thiosulf ite 185-250
547= Thiosulf ite
46% Sulf ate
230
1.4-11.7
0.68
7.3-12.2
6.8
1.1-7.9
3.87
50-79
75
0.29-0.39
0.03
Concurrent air-
water flow, no
catalyst
44% Thiosulf ite
56% Sulf ate
377o Thiosulf ite
637» Sulf ate
1007o Sulf ate
239
239
265
0.17
0.08
0.73
27.0
57.5
28.4
3.31 57
6.62 57
3.52 72
0.01
0.05
0.035
Countercurrent
air-water flow,
Copper chloride
catalyst 10
mg/1 as Cu*
*
The Sulfide Feed of 11.7 Ib/min corresponded to the tower with the 7.9 hr Detention Time. If this
tower were omitted, the range of Sulfide Feed would be 1.4-5.5 Ib/min and the Detention Time would
be 1.1-1.4 hr. All other design parameters for this tower were in close agreement with the others
oxidizing sulfides to thiosulfates
-------
SULFIDE-
CONTAINING
WASTES
HEAT
EXCHANGER
i
STEAM
AIR
OXIDIZING
TOWER
SEPARATOR
OIL
EFFLUENT
FIGURE VII-3
SULFIDE OXIDATION UNIT
(Reference 13)
VII-47
-------
Solvent recovery heads for acrylic fiber manufacture have
been successfully oxidized by using a combination of catalytic and
direct combustion techniques (Taylor and Bodurtha, et.. al., 1961).
The influent waste contained 3,000 mg/1 dimethylamine and 1,000
mg/1 dimethyIformamide. Oxidation at 310°C using a platinum catalyst
reduced the concentration of dimethylamine to five to 10 mg/1 in the
effluent and reduced the waste BOD5 by 1,000 pounds per day. Another
catalytic oxidation unit treats organic wastes in a concentration
range of 0.5 to 1.0 percent organics, using a platinum catalyst
at 575°C (Hyde, 1965). Steam is added as it is necessary to prevent
runaway reactions. The platinum catalyst is replaced once a year
at this installation.
Catalytic oxidation offers an economical means of treatment
for small volumes of organic wastes which are not susceptible to
other treatment processes. 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 (Anon., API, Vol. Ill, 1958).
Certain petrochemical wastes can be oxidized directly by
aeration techniques. Wastes containing sodium sulfite, which has
a very high immediate oxygen demand, can be oxidized by bubbling air
through the system. Various types of air diffusion devices can be
utilized to oxidize the sulfite liquors and iron catalysts have been
used in some installations to speed the oxidation reaction (Wilson,
1960). The oxidation of the sulfite to sulfate will cause an increase
in the acidity of the waste, requiring subsequent neutralization.
Diffused air has also been used to oxidize metal salts to insoluble
hydroxides in a nylon waste, the metal hydroxides then being removed
by sedimentation (DeRopp, 1951).
Chlorine and ozone have both been applied in oxidizing
phenol and cyanides in petrochemical wastes. The oxidation of
phenols must be carried to completion to prevent the release of
chlorophenols which are responsible for objectionable tastes and
odors in drinking water at very low concentrations. An excess of
chlorine is usually required because of the reaction with various
other chemical compounds such as ammonia, sulfides, and various
organics which can interfere with the chlorination process. An excess
of chlorine to phenol ratio up to 50:1 is often required for complete
phenol oxidation (Anon., API, Vol. Ill, 1958). To prevent the forma-
tion of chlorophenols, the pH of the waste is kept at seven or higher
and the usual reaction time required is one to two hours. Chlorine
can be used either as free chlorine or as hypochlorite.
Cyanides can be oxidized to carbon dioxide and nitrogen by
chlorination. The wastewater must be kept at a pH value greater
than 8.5 during treatment to prevent the release of toxic cyanogen
VII-48
-------
chloride (Anon API, Vol. Ill, 1958). The reaction time usually is one to
two hours and the process is subject to the same interferences as
in phenol chlorination. Batch treatment with hypochlorite is used
for small volumes of waste while continuous systems normally use
chlorine gas.
Chlorine dioxide which has been investigated as an oxidant
for phenols and cyanides (Anon., API, Vol. Ill, 1958), seems to
have several advantages over chlorine or hypochlorite which
include (a) no chlorophenols produced by undertreatment of phenols
(b) less rigorous process control required, (c) no requirement for'
pH adjustment, (d) shorter reaction times are needed, and (e) less
trouble with formation of cyanogen chloride during cyanide oxida-
tion. The chief disadvantage of chlorine dioxide is its high cost
(Anon., API, Vol. Ill, 1958).
Ozone has also been proposed as an oxidizing agent for
phenols, cyanides, and unsaturated organics, since it is a consid-
erably stronger oxidizing agent than chlorine. The chief dis-
advantage is the high initial cost of the equipment required for
ozone generation (Anon., API, Vol. Ill, 1958). Ozone has several
advantages, the most important being its ability to rapidly react
with phenol and cyanide. The optimum pH for phenol destruction is
pH 11.4 and ozone is added as a one to two percent gaseous solution
(Anon., API, Vol. Ill, 1958). Thiocyanates and cyanides can also
be effectively oxidized in a waste containing phenols (Niegowski,
1953) . Cyanides are also ozonated at an influent pH of 11 to 12
which drops to approximately pH eight, (Tyler, et. al., 1951). Thio-
cyanates, sulfates, sulfides, and unsaturated organic compounds will
also exert an ozone demand which must be satisfied. This demand
serves as the basis of design for an ozonation unit treating a waste-
water containing these compounds (Anon., API, Vol. Ill, 1958).
Sulfides also can be removed from a wastewater which is to be
ozonated by air stripping them at low pH values, thus economically
reducing the ozone demand (Niegowski, 1953). The pH of the waste-
water can then be raised to the appropriate level required for
optimum ozonation. Recent investigations at The University of Texas
at Austin have indicated the applicability of ozonating wastes from
the manufacture of chlorinated hydrocarbons. The data obtained from
laboratory ozonation studies are shown in Table VII-14. The optimum
pH for ozonation of this wastewater was found to be 12.6, and as
much as 90 percent of the waste COD was removed. This waste contains
large quantities of unsaturated hydrocarbons, which are readily
amenable to ozonation. Ozonation of a wastewater can be either a
batch or continuous operation, depending on the characteristics of
the waste and the waste flow rate.
VII-49
-------
TABLE VII-14
OZONATION OF CHLORINATED HYDROCARBONS
(Reference 38)
COD COD COD
Ozone Dosage pH Raw Waste Treated Waste Reduction
(mg/1) Initial (mg/1) (mg/1) (%)
994 12.2 3,340 1,410 57.8
2,530 12.6 " 900 73
2,700 7.0 " 1,460 56.5
3,920 12.6 " 745 77.5
4-,640 12.6 " 450 86.5
5,400 12.6 " 314 90.5
VII-50
-------
Oxidation of phenols using hydrogen peroxide and ferrous
salts has been investigated in the laboratory (Eisenhauer 196M
Treatment of the industrial wastes studied produced colored effluents
which required additional treatment with alum for color removal
This method is probably not economical for most phenolic petro-'
chemical wastes but may be useful in removing phenols from inter-
mittently discharged low-volume wastes.
Miscellaneous Methods
Ion exchange has been used to remove certain petrochemical
pollutants. Quatenary ammonium anion resins were successfully used
to remove phenols in laboratory investigations (Anderson and
Hansen, 1955). However, regeneration of the resin was difficult,
making this method of phenol removal uneconomical for most industrial
applications, Ion-exchange, however, has been used successfully to
recover salicylic acid from aspirin manufacture effluents (Wilson,
1960). Salicylic acid recoveries of 80 percent were obtained using
a caustic-soda regenerated resin and the recovered acid was then
reused in the manufacture of aspirin. The only problem associated
with this process was a partial physical breakdown of the resin.
Chemical reduction can also be used to treat certain
chemical compounds found in petrochemical wastes. The manufacture
of phenetole produces an effluent containing p-nitrophenol, an
aromatic compound which is toxic, relatively non-biodegradable, and
imparts a yellow color to water (Wilson, 1960). The p-nitrophenol
is reduced at the source of the process effluent by using iron
turnings and sulfuric acid. The reduced organic compounds are bio-
degradable and colorless.
BIOLOGICAL TREATMENT PROCESSES
Biological treatment of liquid petrochemical wastewaters
is usually the most economical method of reducing organic content,
toxicity, and objectionable appearance. The treatment of petro-
chemical wastes using biological methods is considerably more
complex than the treatment of domestic wastes and many of the indus-
trial wastes. For example, extensive pretreatment is of ten required
before a petrochemical waste stream can be treated biologically.
The following discussion will elaborate on those aspects of petro-
chemical wastewater characteristics which require special considera-
tion for successful biological treatment. Where available, design
and operating parameters from existing petrochemical treatment
facilities will be cited.
General Considerations
Biodegradability - The applicability of ^logically treating
a particular Saste is a function of the biodegradability £ the
dissolved organics present in the wastewater. Almost every organic
VII-51
-------
compound can be degraded biologically under defined environmental
conditions provided that sufficient time is available. When con-
sidering the economics of a biological treatment system, however,
the required degradation time for the organic compounds in the
waste is of primary importance. The rate at which an organic
compound can be degraded is a function of its availability to
microorganisms as an energy supply and as a source for cellular
carbon. The molecular structure of an organic compound, the
genera and species of microorganism utilizing it as a food source,
and the time required for the microorganism to develop the enzymes
necessary for successful substrate utilization determine the
degradation rate of the compound. Certain molecular structures,
especially those not occurring in nature, are difficult to degrade
biologically. The amenability of a particular compound to biological
degradation is highly dependent on such environmental and growth
factors as the nutrient requirements necessary for biological growth,
and proper pH and temperature conditions for the microorganisms.
The organic compounds must also be in a form suitable for easy bio-
logical attack. One of the factors involved in the relative non-
biodegradability of oils is their insolubility in water. Oil
globules in a wastewater, for example, are not readily accessible to
the microorganisms. Proper acclimation is very important since
organic compounds which are completely biodegraded by acclimated
organisms may be completely resistant to unacclimated microorganisms
(Mills and Stack, 1953). To have meaning, a classification system
must indicate the biodegradability of a compound by a properly-
acclimated microbial system.
The biodegradability classification used in Table VII-15 is
strictly an arbitrary system based on the relative biodegradability
of selected organic compounds by an acclimated microbial population.
These data were obtained from both laboratory and field-scale inves-
tigations. The biodegradable class of compounds in Table VII-15
includes substances which are rapidly degraded with little or no
biological acclimation required as well as those compounds which
require extensive periods for adaptation of the microbial system to
the organic substrate. The important consideration is that all of
these organic constituents have been shown to be significantly
degraded by biological treatment systems or subject to conditions
similar to those found in such systems.
The time factor is most significant when considering an
adaptive biological system. An organic compound which can be
stabilized biologically but which requires time intervals for degra-
dation considerably longer than those available in normal biological
treatment systems may be non-biodegradable for all practical purposes.
Some of those compounds indicated in Table VII-15 as being resistant
to biological degradation may be categorized as such. It is also
possible that some of these resistant chemicals might be more readily
degraded by specific species of microorganisms.
VII-52
-------
TABLE VII-15
RELATIVE BIODEGRADABILITY OF CERTAIN ORGANIC COMPOUNDS
(References 74, 75, 89)
Biodegradable Organic Compounds
Compounds Generally
Resistant to Biological
Degradation
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
Ethanolamines
Glycols
Ketones
Methacrylic Acid
Methyl Methacrylate
Monochlorophenols
Nitriles
Phenols
Primary Aliphatic Amines
Styrene
Vinyl Acetate
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.
VII-53
-------
While there is contradictory data relating the molecular
structure of a compound to its biodegradability, the amenability of
resistance of certain classifications of organic compounds to bio-
logical degradation is well documented.
a) Aliphatic or cyclic aliphatics are usually more
susceptible to biological degradation than are aromatics.
b) Unsaturated aliphatics, such as acrylic, vinyl,
and carbonyl compounds are generally biodegradable (Pahren and
Bloodgood, 1961). Styrene, when in solution, is readily degradable>
but the degree of breakdown may be adversely affected by its rela-
tive insolubility (Harkness and Jenkins, 1958). Organic compounds
which contain elements other than carbon in the primary molecular
chain, such as ethers, are often resistant to biological attack.
Morpholine and tertiary amines are included in this grouping.
c) Molecular size is an important factor concerning
the biodegradability of an organic compound. Part of the resistance
demonstrated by polymeric and complex molecular substances is attrib-
uted to the inability of necessary microbial enzymes to approach
and attack susceptible bonds within the compound structure. Insoluble
or partially soluble compounds in wastewater are also resistant
because of the limited contact surface which is subject to microbial
contact.
d) The many possibilities for structural isomerism in
substituted organic compounds affect the relative biodegradability
of many compound classes. For example, primary and secondary
alcohols are extremely biodegradable, while tertiary alcohols are
resistant. Alkyl benzene sulfonates using propylene as a base
contain a tertiary carbon atom and are consequently resistant while
alkyl-aryl sulfonates without tertiary carbon atoms can be completely
biodegraded (Ryckman and Sawyer, 1957). The stable bonds of the
tertiary carbon atom therefore appear to be just as resistant to
biochemical reaction as they are to chemical reaction.
e) The addition or removal of a functional group
affects the relative biodegradability of an organic compound. Electro-
philic substitution of certain functional groups to aromatics
significantly affects the biological amenability of a compound. A
hydroxyl or amino substitution to a benzene ring renders the compound
more biodegradable than the parent benzene, while a halogen sub-
stitution causes it to be less biodegradable.
f) Many organic compounds are completely biodegradable
at low concentrations, and bio-static or bio-toxic at higher con-
centrations, of which phenol is a good example. Slug concentrations
of 50 mg/1 phenol have been known to exert a toxic effect on bio-
logical waste treatment systems (McKinney, 1967); but by providing
a completely mixed system and dampening inflow fluctuations, higher
VII-54
-------
concentrations have been successfully treated biologically (Reid and
Libby, 1957). A similar response of biological treatment systems
to nitriles has been observed.
It should be noted that the biodegradability of individual
organic compounds in petrochemical wastewaters may be altered
when mixed with other constituents. Organic compounds which tend
to polymerize upon contact, such as many of the unsaturated compounds
will probably have an adverse affect on the wastewater biodegradability.
Two or more compounds occasionally form a complex which would have
a similar effect. It may therefore be necessary to conduct extensive
laboratory studies to determine which compounds possibly affect a
biological system in this manner, giving a basis for possible
stream segregation within the waste collection system.
Finally, the proper acclimation of the microorganisms to a
particular wastewater containing one or many compounds should be
emphasized relative to accurate biodegradability determination.
The lack of "true acclimation" of a biological seed to the waste-
water has probably been the main source of contradictory data, mis-
interpretation and misunderstanding.
Nutrients - Effective biological treatment of any organic
wastes requires the availability of essential nutrients for the micro-
organisms. The predominant organisms in biological treatment
systems are bacteria which normally require only trace amounts of
nutrients for growth. The mineral nutrients required by bacteria
are available in sufficient amounts in most wastewaters. However,
nitrogen and phosphorus requirements are considerably more critical,
and many petrochemical wastes are deficient in one or both of these
elements. If this is the case, these compounds must be added to the
wastewater prior to biological treatment.
Nitrogen and phosphorus requirements for biological treat-
ment have been related to the magnitude of the degradable organic
content of wastewaters, as represented by BOD. Insufficient nitrogen
and phosphorus restrict the rate of organic removal and also may
favor the growth of filamentous organisms which cannot be separated
by gravity from the wastewater after biological treatment. Generally
a BOD:N:P ratio of 100:5:1 will be sufficient to satisfy nutrient
requirements for an industrial wastewater. These nutrients must also
be in a form which is readily available to the microorganisms.
Nitrogen is most readily available in its reduced form, as ammonia,
ammonium ion, or amino nitrogen. The reduced form of nitrogen_is
the form used in building cell protein and oxidized forms of nitrogen
and must be reduced by bacterial action prior to assimilation into
the cell structure. Organic nitrogen, nitrates, nitrites and organic
compounds containing these nitrogen forms can also be used as a
VII-55
-------
nutrient source by most microorganisms, but a considerable expendi-
ture of energy is required to reduce these forms to ammonia nitrogen.
Phosphorus is most readily available to the microorganisms as a
phosphate, which is the predominant form of phosphorus in most
wastewaters.
Refinery wastes usually contain large quantities of ammonia
nitrogen, and may contain sufficient nitrogen to meet the nutrient
requirements when mixed with petrochemical wastewaters. Sanitary
sewage can often be used as a source of nitrogen and phosphorus for
petrochemical wastes. Phosphorus requirements of a petrochemical
waste can generally be satisfied by including cooling or boiler
blow-down waters within the waste stream.
It is necessary to establish the nutrient requirements for
each wastewater considered by measuring the total BOD, analyzing the
wastewater for available nitrogen and phosphorus, and providing
additional nutrients are required, either by chemical addition or by
adding nutrient-rich streams to the system.
Neutralization Requirements - Neutralization or pH
adjustment is commonly required in petrochemical wastewater treatment
systems. This step is often necessary to provide optimum chemical
or biological treatment.
Existing acid or alkaline streams should first be considered
as possible pH adjustment sources. Flue gases, normally containing
14 percent carbon dioxide, can often be used to neutralize alkaline
wastes. If waste streams are not available, any strong acid can be
used to effectively neutralize basic wastes; but cost limitations
usually limit the choice to sulfuric or hydrochloric acid. Acid
wastes are commonly neutralized in mixing tanks using strongly
basic compounds, although downflow or upflow limestone beds are often
used. Dual purpose chemicals can often be used as a neutralizing
agent and as a nutrient source, such as ammonium hydroxide added
to a nitrogen deficient acid waste or phosphoric acid added to a
phosphorus deficient alkaline waste. Such practice, when practical,
can result in a substantial savings in operating costs. Since
neutralization reactions are rapid and sensitive, the neutralization
system design must include the following factors:
a) provisions for adequate mixing and holding to
allow the reaction to approach completion,
b) provisions for separating and removing any sludge
produced, and
c) provisions for adequate neutralization during
fluctuating flow-under automatic control.
VII-56
-------
Some problems have been encountered with automatic PH control
systems particularly when small additions of reagents caused marked
changes in pH around a value of 7.0. "»j.<^eu
Most biological treatment systems cannot operate efficiently
at pH values greater than nine or less than five, while optimum
process efficiency is usually obtained in the six to eight pH
range (Eckenfelder, 1966). Biological systems employing completely
mixed aeration basins have a certain degree of buffering capacity
Carbon dioxide produced during biological oxidation, for example
can neutralize as much as 0.7 pounds of caustic alkalinity per '
pound of COD removed (Eckenfelder, 1966). Consideration of these
factors can often reduce pre-neutralization requirements. The
buffering capacity of a biological treatment system, its effect on
a particular petrochemical waste, and the precise neutralization
requirements can only be determined through laboratory or pilot
plant studies.
Equalization - Biological and even chemical and physical
treatment processes operate most effectively if the composition and
volume of the wastewater remains relatively constant. For example,
rapid fluctuations in the organic content or flow rate of a waste
stream can cause biological treatment plant upsets due to the shock
effects on the microorganisms in the system. Equalization is used
to dampen these fluctuations in flow and waste composition and
minimize the transient effects which adversely affect the process.
The holding basin is designed to contain and provide mixing for a
selected volume of the wastewater which is pumped from the equaliza-
tion basin at a constant rate to the treatment facility. The
required size of the equalization tank depends on the waste charac-
teristics, the plant operating schedule, and consequent cyclic
fluctuations. For example, the maximum to minimum BOD ratio of a
wastewater bed to an aerobic biological treatment process should
not exceed 3:1 on a 24-hour basis and equalization basins should
be designed to limit the BOD fluctuations to this range.
Petrochemical wastes are particularly subject to wide varia-
tions in flow and composition and an equalization step is often
required. Many smaller and specialized petrochemical processes are
batch operations from which sudden releases of wastes can be
expected. Often, equalization can also permit the neutralization of
wastewaters by premixing acidic and alkaline waste streams which
would normally enter the plant waste streams at different times.
Various types of construction have been used for equalization
basins, including steel tanks and concrete tanks, earth-lined
lagoons, and vinyl or butyl-rubber lined lagoons. The type ot tank
required will depend on the wastewater characteristics and its _
affect on the construction material. Mixing equipment or battling
is also required to insure adequate tank equalization.
VII-57
-------
Pre- and/or Primary Treatment - Pre- and primary treatment
may be required to remove certain materials from petrochemical
wastewaters to prevent adverse effects on a biological treatment
system. Maximum limits for selected wastewater characteristics
are given in Table VII-16 and biological treatment processes will
usually operate at decreased efficiencies if these limits are
exceeded.
Oils in wastewater are difficult for the microorganisms to
metabolize due to their low solubility (McKinney, 1967) . Non-
biodegradable oily materials tend to accumulate in biological treat-
ment processes and cause sludge settling difficulties due to their
low specific gravity. Suspended solids in wastewater will be incorp-
orated into the biological solids in a waste treatment system
(McKinney, 1967). Inorganic and non-biodegradable organic suspended
solids will tend to build up in the treatment system, decreasing
the proportion of active biological solids and adversely affecting
the treatment efficiency. Sulfides react with dissolved oxygen and
thus reduce the oxygen available for microbial oxidation of the
organics in a biological treatment process, the permissible sulfide
concentration normally being a function of the amount of oxygen
available. Sulfides at high concentrations can also exert toxic
effects in addition to depleting available oxygen, this toxic
threshold normally considered to be approximately 250 mg/1 as
sulfide.
In addition to the characteristics discussed, certain other
waste materials may have to be removed prior to biological treat-
ment. Some heavy metals, for example, are toxic to microorganisms
at certain concentrations and must be removed or reduced if these
thresholds are exceeded. Waste streams containing potentially toxic
organic compounds should be separated and treated before discharge
into a biological treatment system. A careful laboratory charac-
terization should reveal the type and extent of pretreatment
required before a particular petrochemical wastewater can be treated
biologically.
Temperature - Temperature effects on biological treatment
systems are extremely important and sometimes critical relative to
the ability of the system to function properly. High temperature
loadings to an activated sludge plant cause a decrease in oxygen
solubility as well as an increased oxygen utilization. Summer temp-
atures therefore represent the most critical stage as far as oxygen
supply is concerned, and aeration systems should be designed on
this basis. Winter temperatures usually control detention time
requirements, however, because of the slower biochemical removal
rates of dissolved organic materials. This temperature effect on
relative COD removals for a petrochemical waste is shown in Figure
VII-4 (Ford, Gloyna and Eckenfelder, 1968).
VII-58
-------
TABLE VII-16
WASTEWATER CHARACTERISTICS REQUIRED FOR OPTIMUM
BIOLOGICAL TREATMENT (MAXIMUMS)
(Reference 25)
Characteristic
Value
Oils, Grease
Suspended Solids
pH
*
Sulfides
Temperature
Heavy Metals
<75mg/l
<125mg/l
5-9
<200mg/l
<36°C
Below Toxic Levels
Depends Upon Oxygen Available
VII-59
-------
<
M
M
o
o
9*
1-
*»
Q.
E
o
E
-------
The optimum temperature is approximately 30°C for most
aerobic biological treatment systems (Eckenfelder, 1966), while a
decrease in plant efficiency has been observed when temperatures
exceed 38°C. Some attempts have been made to develop and perfect
aerobic systems operating in the 40°C to 65°C range using thermo-
philic bacteria, but with only moderate success (Ford, 1964).
The system operation at these temperatures is extremely sensitive,
solids-liquid separation is difficult, and a cloudy effluent is
normally produced.
High-temperature petrochemical wastes may require pre-
cooling before they are discharged to a biological facility, but
cool dilution streams and temperature dissipation in equalization
or aeration basins normally preclude this.
Activated Sludge Processes
The activated sludge process is a continuous system where
biological growths are mixed with wastewater, aerated, and followed
by a biological sludge separation step. A portion of the concen-
trated sludge is then recycled and mixed with additional waste.
This process has been applied very effectively in the treatment of
refinery and petrochemical wastewaters.
Although the conventional plug flow system has been used
successfully in the treatment of domestic wastes, it has several
disadvantages in this design when petrochemical wastes are to be
treated. These include
a) erratic effluent quality because of the uneven
distribution of effluent solids in the aeration tank and wastewater
short-circuiting;
b) localization of certain contaminants, such as
phenol, which may exert a toxic effect on the biological solids;
and
c) the inability of the plug-flow aeration basin to
dampen load variations caused by in-plant dumps or spills, making
operation and control difficult.
Completely mixed aeration designs are therefore generally
considered for industrial wastewater treatment. In a completely
mixed system the aeration tank serves as an equalization basin to
dampen load variations and evenly distribute the wastewater an
biologically active solids throughout the basin. Since all porti
of the tank are mixed, the oxygen utilization rate willbe
throughout the basin, and aeration equipment can be equally
The effluents discuarged from completely mixed acciva
systems are generally better than those obtained from other
logical processes in terms of organic and solids conce
although construction and operational costs are usually higher.
VII-61
-------
Many of the organic compounds present in petrochemical
wastes are volatile and consequently stripped from solution in the
aeration basin. Laboratory investigations have studied air stripping
of volatile organics during the activated sludge process (Englebrecht
and Ewing, 1962). These studies indicated that approximately 30
percent of the highly volatile compounds were stripped from solution
during the six-hour aeration period normally employed in the
activated sludge process. Similar studies indicated that significant
concentrations of benzene and nitrobenzene present in a petrochemical
waste were air stripped from solution (Eckenfelder and Ford, 1968).
The exact removal of volatile organics by this mechanism will be
dependent on the type of aeration system as well as the power level
in the aeration basins.
The basis for the design of an activated sludge system is
predicated on producing and maintaining an environment for micro-
organisms so that their growth and activity are as near optimal as
possible. These parameters include fundamental factors such as
temperature, hydrogen ion concentration-, and nutrient availability,
as well as the following considerations:
a) the organic loading in terms of BOD applied per
day per unit wt. of biological solids,
b) the BOD removal kinetics of the specific petro-
chemical wastewater,
c) the oxygen requirements of the system,
d) the quantity of biological sludge produced
including the accumulation of primary sludge, and
e) the settleability of the biological sludge and
the ease of gravity liquids-solids separation.
Previous studies concerning petrochemical waste treatment
have indicated the following ranges with respect to the parameters
(Eckenfelder, et. al., 1968):
a) organic loading (IbsBOD/day/lb MLVSS 0.10 - 3.0
b) BOD removal as a function of the K range
effluent concentration, .00028-.0006
BOD removed (mg/1) = K (BOD of the
MLVSS cone(mg/1) xdetention time (hrs) effluent)
VII-62
-------
c) oxygen requirements, fraction of .40 - .70
BOD removed
d) biological sludge production, .22 - .60
fraction per day of MLVSS (aeration
basin)
It is apparent that the magnitude of these range of values
requires an exact determination for each wastewater considered,
especially due to the diverse nature of petrochemical wastes.
Laboratory or pilot plant studies should therefore preceed actual
design and construction.
It is important to recognize the response of treatment
plant efficiency in terms of BOD and COD removal, and biological
sludge settleability in terms of zone settling velocity and sludge
volume index, to the applied organic loading. These responses
are graphically illustrated in Figure VII-5.
-7lOOr
o"
o
•z.
UJ
o
O
2
90
80
70
60
o
o
0 50
500 r Z 25
§400
- s 300
- >200
o
o
00
0
Lf'
Lf
0
Removal
Zone settling
velocity
% COD Removal
1.0 2.0 3.0 4.0
LOADING FACTOR
( Ibs COD/day/lb solids)
. . I L_
"40 1*0L20 1.60
(Ibs BOD5/day/lbsolids)
100
90
80
70
60
a
o
2.0
UJ
FIGURE VII-5
PARAMETER RESPONSE TO ORGANIC LOADING - PETROCHEMICAL WASTES
(Reference 38)
VII-63
-------
A wide range of applied organic loadings to activated sludge
plants have been reported for petrochemical waste treatment.
Extended aeration, a process where long detention periods allow oxida-
tion of biological solids thus minimizing sludge disposal requirements,
is characterized by organic loading values of 0.1 to 0.3 Ibs BOD/day/
Ib MLSS. Conversely, loadings in excess of 1.0 Ibs BOD/day/lb MLVSS
are not uncommon for some high-rate activated sludge processes,
although loading ranges of 0.2 to 0.7 are usually considered as
optimal in the treatment of industrial wastes.
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 VII-17. It is noted that the treatment efficiency
in terms of COD removal is highly variable while maximum BOD
removals are generally the same. It should be recognized that many
organic compounds can be chemically oxidized while remaining resis-
tant to biochemical degradation, therefore being registered as COD
but not BOD. The difference between the measured COD and BOD values
therefore indicates the magnitude of the non-biodegradable organic
fraction in the wastewater. For example, 99 percent of the BOD
was removed from a petrochemical wastewater containing morpholine
and ethers, while the COD removal only ranged from 25 to 40 percent
(Gloyna and Ford, 1966).
There are two categories of aeration systems utilized in
activated sludge systems. One system uses compressed air which is
sparged or diffused directly into the mixed liquor, while the other
moves the mixed liquor, bringing it into contact with the air.
These categories are known respectively as diffused air and mech-
anical aeration systems. The requirements of both systems can be
summarized as follows:
a) to transfer oxygen from the gas phase to the
liquid phase, insuring liquid dissolved oxygen;
b) to mix and disperse the dissolved oxygen through-
out the aeration basin;
c) to mix and uniformly disperse the wastewater; and
d) to maintain the biological solids in suspension,
allowing sufficient bacteria-wastewater contact and thus promote
full utilization of the microbes,
Mechanical aeration systems are normally used in
aeration basins treating industrial wastes because of lower instal-
lation and maintenance costs. These surface aerators are either
pier-mounted or float-mounted. The impeller, shaft, and bearing
design differ with the manufacturer, although the transfer mechanism
VII-64
-------
TABLE VII-17
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and /or
Process
Refinery, Natural
Gas Liquids,
Chemical
Specialties,
Sanitary Sewage
Phthalic Anhydride,
Phenol, Salicylic
Acid, Rubber Chem.,
Aspirin, Phenacetin
Refinery,
Detergent
Alky late
Butadiene
Maleic Acid
Butadiene
Alky late
Butadiene,
Maleic Anhydride
BOD
Flow In Out
(MGD) (mg/1) (mg/1)
4.87 90 20
2.54 45.7 6.1
2.45 345 50-
100
2.0 2,000 25
1.5 1,960 24
1.5 1,960 24
Rem
(%)
78
86.7
71-
85.5
98.8
98.8
98.8
COD
In Out
(mg/1) (mg/1)
200 90
855 150-
200
2,990 480
2,980 477
2,980 51
Organic
Loading
Rem lbBOD5/day
(%) ^ lb MLSS ^
55 0.1
0.031
76.6- 0.08
82.5
84 0 . 24
98.3
84 0.24
(MLVSS)
Nutri-
ents
Reqd . Remarks
None Effl. phenol 0.05
Effl. oil 0.5 mg/1
None Brush Aeration, treats
trickling filter
effluent, 55% sludge
return
PO, Phenols in - 160 mg/1
Sulfide in = 150 mg/1
Lab scale
NH3
NH Surface aerators wastes
contain: alcohols,
Ref
117
116
42
26
26
93
Fumaric Acid,
Tetrahydrophthalic ,
Anhydride, Butylene
Isomers, Alkylate
maleic acid, fumaric
acid, acetic acid,
Ci'C^ aldehydes, fur-
fural, water soluble
addition products
-------
TABLE VII-17 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD
Product and/or Flow In Out Rem
Process (MGD) (mg/1) (mg/1) (%)
Ethylene 1.44 600 90 85
Propylene,
Benzene
Naphthalene, 0.43 500 60 85-
Butadiehe, 90
Phenol ,
Acrylonitrile,
Soft Detergent
< Bases, Resins,
£ Other Aromatics
<£ Phenol, 2, 4-D 0.97 370 76 76.2
Aniline, Nitro-
Benzene, Rubber Chem. ,
Polyester Resins,
Misc. Chem.
Ethylene, Propylene, 0.63 85 10 99
Butadiene, Benzene,
Polyethylene, Fuel
Oils
Refining Processes 0 51- 125 15- 80-
0.63 25 88
Nylon 0.4 1,540 250 83.8
Petroleum Products 0.27 440 5 98.8
COD Organic
T f\oA -i •*-» r>
L,oaaing Ntitri-
lb BOD _ /day 1N
In Out Rem . 5 i ents
(mg/1) (mg/1) (%) <• lb MLSS ; Reqd. Remarks
700 105 85 None Oily waters: C,-
C 0 oils 90%
pnenol removal
600 90 80- 1.5 NH Sour waters: Oil
85 PO^ in = 500 mg/1
Phenol in = 65 mg/1
pH adjustment, pre-
ceeded by trickling
filter, phenol
removal =99.9%
0.4 NH Accelator Pilot
Plant Sewage added
PO, in ratio 1:600 once
a week
200 75 62.5 Quench waters, poly-
ethylene and benzene
wastes: preceeded
by trickling filter,
effl. phenol 0.01 ppm
65- 0.28- PO. Phenol removal 85-
/i
80 0.4 94%; Oil removal 75-
85%; Effl. phenol 0.5
mg/1; Effl. oil 1-2
mg/1; Temp. - 30°C
500 60 88 Phenol in = 25 ppm
Ref
102
102
85
104
66
26
26
-------
TABLE VII-17 (.Continued.)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
BOD
COD
Product and/or
Process
Flow In Out Rem
(MGD) (mg/1) (tag/1) (%)
In Out
(mg/1) (mg/1)
Rem
Organic
Loading
Ib BOD /day
*• Ib MLSS ^
Nutri-
ents
Reqd.
Remarks
Ref
Acrylic Fibers
Ac e t one, Pheno1
p-Cresol, Ditert.-
Butyl-p-Cresol,
Dicumyl Peroxide
Resins-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)
0.252 2,260 118- 90-
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
0.4
0.89-
1.1
0.8-
1.2
0.51
0.78
(MLVSS)
None
NIL
PO,
Wastes contain acrylo- 109
nitrile, dimethylamine,
dimethylformamide,
formic acid temp. 35-
37°C return sludge 10-
50% mechanical aeration
Waste phenol 600 ppm 25
Waste BOD 7,500-8,000
Waste diluted w/ effl.
or water; pilot plant
Diffused-air; domestic 105
waste added; trickling
filter follows 100%
recycle sludge
Lab Scale; extended 41
aeration; high non-
biodegradable fraction
followed by stab, ponds
1:1 mixture of acid 40
wash streams diluted
9:1 prior to treatment
to reduced chlorides,
toxicity Lab Scale
-------
TABLE VII-17 (Continued)
ACTIVATED SLUDGE TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
BOD
COD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
In Out
(mg/1) (mg/1) (%)
Ib MLSS
„ Ib BOD /day
Rem 5 ents
Reqd.
Remarks
Ref
Cracking,
Isomerization of
Butane and Naph-
thene, Alkylation,
Benzene, Toluene,
Alcohols, Ketones,
Cresylic Acids
Ethylene,
<. Acetylene
M
M
oo Nylon Manuf.-
Adipic Acid
Aaidonitricz
Alk. Organics
1,100 55- 90-
110 95
20
95
85
0.5
0.23-
0.33
1.0-
3.0
PO
'4
NH.
90-95% phenol re-
moved; Lab Scale
Effl. phenol 0.1
mg/1
Effl. oil 1 ppm
NH, OH used as nu-
A
trient and neutrali-
zing agent waste
diluted 2:1
21
66
22
96
-------
is
conditions (20°C, pure ___
a power level of about 0.1 horsepower "per MOO gallons of
basin required to keep solids in suspension, 'although this
a function of tank geometry and aerator spacing.
Horizontal shaft aerators have also been used in the treat-
ment of industrial wastes. These steel cage rotors can be adjusted
by varying the speed of rotation and the paddle immersion depth.
Turbine aeration systems are commonly used when complete
mixing is required and a deep basin is necessary. Compressed air
is released through a sparge ring beneath an impeller close to the
bottom of the aeration tank. An additional surface impeller is
attached to the same shaft. Although the oxygen transfer effic-
iency is slightly lower than surface mechanical systems, these
units have a better mixing ability.
Trickling Filter Processes
Trickling filters are commonly used in industrial waste
treatment systems, primarily as "roughing devices" designed to level
out and reduce organic loads to activated sludge or aerated lagoon
processes. They have been used quite successfully in this manner
although stringent effluent quality standards are rarely met when
filters are used singularly.
Trickling filters employ microbial films attached to rock
or synthetic media to remove organic materials from the wastewater
solution. Most filter processes incorporate recirculation of the
treated effluent in order to increase the filter efficiency. The
recirculated effluent dilutes the raw wastewater, thereby reducing
the organic concentration of the waste applied to the microbial
slime. Recycle ratios as high as 40:1 have been required in the
treatment of some petrochemical wastes because of their high initial
concentration of dissolved organics.
Although the organic loading plays an important role in
their performance, a trickling filter with a definite depth and
media size can undergo loading changes with very little effect on
the effluent quality until the optimum loading is reached (Anon.,
API, Biological Treatment of Petroleum Refinery Wastes) . Once this
loading is surpassed, the excess organics merely pass through the
filter, causing a rapid deterioration in effluent quality.
Although BOD removals obtained in trickling filters are
usually less than that removed in the activated sludge Pr°cess>
toxic effects are not as pronounced or perpetual. When the ac
biological slime in contact with the toxic substances dies «ul
sloughs away, it is simply replaced by the underlying growth
VII-69
-------
attached to the media. Additionally, filter design and operation
is relatively simple.
Rock and synthetic media are used to provide the necessary •
surface area for the growth and proliferation of microorganisms.
Media specifications consider both maximum surface area for bacterial
growth, and maximum voids area for optimum wastewater passage and
ventilation. It has been determined that two-inch to four-inch
diameter rocks offer the best stone media for filters which are
usually six to 12 feet in depth. Plastic media are used primarily
in filters which have higher hydraulic and organic loadings than
rock filters. The original plastic filter media, polystyrene, was
subject to chemical attack by solvent spills, etc., although the
advent of polyethylene filter media has eliminated this problem.
Because of the controlled void space, no plugging or ventilation
problems have been encountered in synthetic media type filters
employing depths up to 40 feet.
The recorded treatment of various chemical and petrochemical
wastes using trickling filters is tabulated in Table VII-18.
Although BOD removals as high as 98 percent were observed, the usual
treatment efficiency ranged from 75 percent to 90 percent removal
of five-day BOD.
A variety of wastes have been successfully treated, as shown
in Table VII-18. Excellent phenol reductions ranging from 73 to
96 percent have been obtained at phenol loadings of 0.17 to 18.0
Ibs phenol/day/I,000 ft3 (Anon., API, Biological Treatment of
Petroleum Refinery Wastes). The phenol content of synthetic resin
wastes was reduced from 4,500 mg/1 to 1.5 mg/1 by treatment using
two filters in series containing plastic media (Chipperfield, 1967).
In addition to phenol, this waste also contained large quantities of
formaldehyde, fatty acids, phthalic acid, and maleic acid and an
overall reduction in BOD of 95 percent was observed. Another
plastic media filter was used to treat acrylic fiber wastes con-
taining both acrylonitrile and large quantities of zinc (Sadow,
1960). Effective treatment was obtained at the reported zinc levels,
the metal being extracellularly adsorbed by the microorganisms in
the filter slime. Other data, as indicated in Table VII-18, indicate
that trickling filters can be used effectively to completely or
partially remove many compounds commonly found in petrochemical
wastewaters.
Aerated Lagoons
Aerated lagoons are basins six to 12 feet in depth where
oxygen is supplied by mechanical or diffused aeration units. There
are two general types of aerated lagoons, 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
VII-70
-------
TABLE VII-18
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
BOD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
COD
In
Out
Organic Defi_
Loading
Ib BOD,/day cient
Rem . 5' * . Nutri-
v I ^. ^ )
(mg/1) (mg/1) (%) V 1,000 ft3 ; ents
Remarks
Ref
Phenol, Salicylic 2.59
Acid, Rubber Chem.,
Aspirin, Phenacetin, 2.59
Phthalic Anhydride
190 58 69.5
58 34 41.5
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
0.63 170
37 98.1 2,660 230 91.5
85 50
0.57- 1,100- 23-
0.86 2,300 470
0.43 1,300
57-
99
400
200 50
1,500
450 60-
70
40.5
11.8
89
None Rock Media, r.ecirc. 116
ratio 2.84:1
None Rock Media, treats
effluent from above
filter, effluent
to act. sludge
2 filters, followed 26
None Plastic filter media 104
followed by act.
sludge
phenol removal = 95%
influent diluted 2:1
w/cooling water
42.1-
82
(Both filters
combined)
140
None pH adjusted prior to 106
treatment; 2 filters in
series; Recycle on 1st
state is 14-21:1
NH Sour Waters,
Rock Media
PO,
102
-------
TABLE VII-18 (Continued)
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/ or
Process
BOD
Flow In Out Rem
(MGD) (mg/1) (mg/1) (%)
i
COD
In Out
(mg/1) (mg/1)
Rem
(%)
Organic
Loading
Ib BOD /day
^ 1,000 ft3 ^
Defi-
cient
Nutri-
ents Remarks
Ref
Pentaerythritoc
Waste contains
Formaldehyde,
Sodium Formate,
Methanol, Pent-
aerthritol
Resins-Formaum,
Aminoplasts,
Phenol-Formal,
Epoxy Resins,
Textile Aus.
Acrylic Fibers
Synthetic Resins-
Phenol, Formalde-
hyde, Fatty Acids,
Phthalic Acid, Maleic
Acid, Glycerol,
Pentaerythritol,
H.C. Solvents
0.118 5,080- 225- 95-
5,800 232* 96*
0.17
0.03
0.32
82.6
89.3
13 30-
70
95-
98
49
30-
70
1st stage 65 NH,
Yes
11.7
14.6
50
84
1st stage 85
(as Phenol)
2nd stage 11.6-
18.2 gpd/ft3
P0
2 filters in series
followed by act.
sludge; recycle
40-1 on prim, filter,
13-1 second
24
None Both filters treat
act. sludge effluent,
None Blast furnace slag
media
Waste contains
phenol, formaldehyde,
methanol
Waste contains:
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 andmaleic
acids = 1,000 mg/1
Eff. phenol = 1.5 mg/1
105
101
18
-------
TABLE VII-18 (Continued)
TRICKLING FILTER TREATMENT OF PETROCHEMICAL WASTES
Product and/ or
Process
Waste contains
Acrylates,
Acetone ,
Inhibitor oils,
Alcohols, Esters,
BOD COD Organic
Loading
Flow In Out Rem In Out Rem , 5 ay,.
(MGD) (mg/1) (mg/1) (%) (mg/1) (mg/1) (%) ( L,000ft3;
51-
79
Def i-
Nutri-
ents
None
None
Remarks
Original loading was
lower value, loading
increased w/o any
adverse effects
15,000 Ib BOD,. re-
Re f
16
mov.al per day
Organic Acids
M
M
I
Entire Treatment System
-------
aerated lagoon. Since there are no secondary sedimentation and
sludge recycle provisions associated with aerated lagoons, the
suspended solids concentration (MLSS) in the basin is quite low.
The exact solids concentration will reach an equilibrium level which
depends upon the organic concentration of the waste, the synthesis
sludge rate coefficients, and the amount of power imparted to the
basin liquid. Equilibrium MLSS levels in aerated lagoons normally
range from 80 mg/1 to 250 mg/1.
Aerated lagoon basins normally involve excavation - earthern
embankment type construction - although concrete structures are
sometimes used. Earthern tank bottoms and side-slopes should be
lined with materials such as vinyl, granite, lean concrete, or
rip-rap to insure erosion protection.
High levels of treatment are not normally obtained in the
aerated lagoons because of the BOD and COD associated with the
effluent suspended solids and the relatively small number of active
biological solids in contact with the wastewater. Aerated lagoons
are .particularly sensitive to transient organic loadings, toxic
substances, and temperature changes. In one instance, a pilot plant
aerated lagoon treating a mixed chemical waste reduced 87 percent
of the BOD in the summer while only a 23 percent removal was
obtained during winter operating conditions (Ling, 1963),
Aerated lagoons are being used successfully as economical
treatment devices, either as a process preceeding waste stabiliza-
tion ponds or as an interim treatment process which can later be
converted to an activated sludge unit by adding secondary clarifi-
cation and recycle facilities.
A recently completed aerated lagoon - waste stabilization
pond facility, for example, has proven to be quite successful in
treating a refinery-petrochemical wastewater (Gloyna, Brady and
Lyles, 1968). If the organic load increases, it is envisioned to
convert the aerated lagoon to activated sludge.
A summary of reported data from the aerated lagoon treatment
of petrochemical wastewater is given in Table VII-19.
Waste Stabilization Ponds
Waste stabilization ponds are wastewater treatment devices
which depend on the natural aquatic processes of bacterial and
algal symbiosis and have been used in the successful treatment of
petrochemical wastes. Although ponds are often used to polish the
effluent from other biological waste treatment processes, they have
been used in some instances to treat entire plant wastes (Anon.,
API, Vol. Ill, 1958).
VII-74
-------
o-Xylene
Gasoline
Nylon Fibers
Chemicals for
Lubricating Oils
TABLE VII-19
AERATED LAGOON TREATMENT OF PETROCHEMICAL WASTES
Product and/or
Process
Refinery
Butadiene,
Butyl Rubber
Refinery,
< Detergent
£ Alky late
i
-~j
Ul
Cyclohexane ,
p-Xylene,
Benzene, Para-
ffinic Naphtha,
BOD COD Organic
Ib BOD Nutri-
Flow In Out Rem In Out Rem 5 ents
(MGD) (mg/1) (mg/1) (%) (mg/1) (mg/1) (%) Acre • day Reqd. Remarks
19.1 225 100 55 610 350 43 4,630 PO, Followed by stab.
pond
temp = 32°C
30% COD is non-bio-
degradable
Lab Scale
2.45 345 50- 71- 855 150- 77- 6,300 PO Influent phenols
100 85 200 83 160 mg/1
Influent sulfides
150 mg/1
Lab Scale
0.51 100 25 75 400 Surface aeration,
waste is extensively
pretreated.
Followed by pond
Ref
43
42
69
0.2
465
180
61 1,050
600
43
26
-------
Functional waste stabilization ponds are normally categorized
as "facultative," that is the upper layers of the pond are kept
aerobic while anaerobic decomposition is prevalent in the lower
layers.
Empirical equations which consider the BOD loading, tempera-
ture, and toxic substance effect on microorganisms have been
developed and successfully used to design facultative waste
stabilization ponds (Gloyna, 1966).
Anaerobic ponds are devoid of oxygen because of the high
organic loads, normally above 200 to 500 Ibs/day/acre. These units
function best when there is a large biodegradable solid load.
Although odors are a problem, it is an effective device in partially
reducing the organic concentration of the wastewater prior to being
discharged to subsequent biological treatment processes. Pre-
treatment by anaerobic ponds, for example, minimizes floating sludge
problems which occur in facultative ponds during the summer months
(Gloyna, 1966). Anaerobic ponds, however, are more pH and tempera-
ture sensitive than are facultative ponds.
The performance of pilot plant and prototype waste stabiliza-
tion ponds in treating petrochemical wastes is shown in Table VII-20.
The effluent BOD is a function of the surface loading, detention
time, and environmental factors as well as the quantity of BOD
associated with the suspended solid fraction (dead algal cells,
debris, etc.). Although the effluent quality of waste stabilization
ponds in terms of BOD is comparable to other unit processes, the
COD reduction capability is often higher. This is attributable to
the extended detention time which provides the microorganisms
sufficient time to degrade the more refractory compounds, or those
substances which exert a COD but little or no 6005. As a rule,
oxidation ponds are more efficient in reducing oils and sulfide con-
centrations than they are in reducing phenols. One heavily loaded
waste stabilization pond with a detention time of 1.25 days reduced
oil from 68 to 43 mg/1, sulfide from 42 to five mg/1, while phenols
decreased only from 42 to 40 mg/1 (Anon., API, Biological Treatment
of Petroleum Refinery Wastes). Another pond, with a detention
time of 30 days, reduced oil from 150 to 0 mg/1, sulfides from 15
to 0 mg/1, while reducing phenols from 20 to seven mg/1.
The salient problems associated with waste stabilization
ponds treating petrochemical wastes are twofold: (a) the adverse
effect of emulsions and highly colored substances which prevent
sunlight penetration and cause reduced photosynthesis and (b) the
toxic effects of many compounds on the pond algae, upsetting the
symbiotic algal-bacterial relationship. Dumps of waste containing
hydrogen sulfide, sulfates, phenols, etc., can cause severe reduc-
tions in BOD removals. Excessive releases of sulfur-containing
VII-76
-------
TABLE VII-20
WASTE STABILIZATION POND TREATMENT OF PETROCHEMICAL WASTES
M
M
I
Product and/or Flow
Process (MGD)
Refinery, Butadiene 19.1
Butyl Rubber
Resins, Alcohols, 5
Amines, Esters,
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, Ethylene-
diamines, Ethers,
Piperazine
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
Rem In Out
(%) (mg/1) (mg/1)
50 350 200
20-
60
88
96
40-
90
90- 260
95
50- 150- 120
80 200
1,681 590
5,120- 4,610-
5,950 4,450
95-
99
Organic
Loading „ ..
Ib BODr Nutri
Rem , 5 v ents
(%) Acre • day' Reqd. Remarks
43 Primary pond None Ponds in series after
91; Total aerated lagoon
ponds 46 Lab Scale
96 None Anaerobic
164 None Anaerobic
5 None Aerobic
75 None Facultative pond,
18 days detention
Infl. SO, = 650 mg/1
H-
20- 95 None After Aerated Lagoon
40 Or Act. Sludge
Lab Scale
65 Facultative Ponds
10- 25 None Lab Scale
25 Facultative Ponds
to remove some res id.
COD. High non-bio-
degradable fraction.
After activated
sludge
Ref
41
12
12
12
118
42
26
41
75~ 10° Facultative ponds 119
-------
compounds enhance the growth of colored bacteria and there is a
concurrent reduction of green algae. Laboratory tests have indicated
that when hydrogen sulfide content of the pond reaches five to 10
mg/1, the pond will cease to function (Gloyna, Brady and Lyles,
1968) . The concentrations of selected petrochemical inhibitors
toxic to algae were noted in the previous chapter, Table VI-8
Miscellaneous Biological Treatment Processes
Two more promising treatment processes, Table VII-21, are
cooling towers and sand filters. The use of cooling towers is
schematically illustrated in Figure VII-6. In addition to reducing
the temperature of the cooling water by evaporation, cooling towers
also provide for the introduction of dissolved oxygen to the
wastewater, enhancing aerobic bio-oxidation of organics within the
tower. A cooling tower system treating one refinery waste removes
3,800 Ibs of BOD per day and reduces the phenol concentration from
12 mg/1 to 0.09 mg/1. A similar system reduces the phenolic
concentration from three mg/1 to 0.06 mg/1. In both cases, low-
solids process wastes are used as make-up water.
Periodicblowdowns are necessary to keep the dissolved and
suspended solids in the cooling water at required levels. The
BOD of this blowdown will still be high because of the pressure
of suspended biological sloughing, so that subsequent treatment of
blow-down is required. Backwashing of the process coolers is often
employed to prevent clogging or fouling by biological materials.
Generally, only a few problems associated with additional equipment
corrosion have been observed while using this system.
Although cooling water treatment has been used exclusively
in refinery complexes, such systems undoubtedly have application
for reuse of specific petrochemical wastewaters.
Similar to the spray irrigation practices which have been
used in treating industrial wastewaters, is the percolating sand
filter which has been used in pilot plant investigations using a
percolating sand filter as a biological treatment device and has
shown some promise (Dickerson and Laffey, 1959). Microorganisms
which are capable of degrading the particular wastes are developed
in the sand-soil medium. Intermittent dosing then provides the
contact time necessary for adequate biodegradation.
Multiple Biological Treatment Schemes
Many petrochemical wastes are treated by multiple component
biological treatment systems (Gloyna and Malina, 1963) . The
complexity of most petrochemical wastes and the associated effluent
qualities requirements often circumvent single-stage biological
VII-78
-------
TABLE VII-21
MISCELLANEOUS BIOLOGICAL TREATMENT PROCESSES FOR
FOR PETROCHEMICAL WASTES
Treatment Process
Product and/or
Process
Waste Characteristics
Remarks
Ref
Cooling Towers
i
•-a
vo
Refining Process
Low Solids Process
Wastes
BOD removal = 80% weight
basis
30-50% concentration
basis
Phenol removal = 98-99%
concentration basis
77
Sand Filter
(w/Biol. Growth)
Acetone, Phenol,
p-Cresol,
di-tert-butyl-p-
cresol,
Dicumyl Peroxide
BOD 3,200 mg/1
Volatile acids 860-
2,150 mg/1
Phenol 50 mg/1
50 gpm flow
Pilot plant - 6' deep
92-97% BOD removed
100% volatile acids removed
load= 70,000 gal/
acre • day
24
-------
PROCESS
WASTEWATERS
1
OIL
SEPARATOR
T
HOLDING
POND
EVAPORATION
MAKE-UP
WATER
I
PROCES
COOLEF
COOLING
TOWER
SLOWDOWN
FIGURE VII-6
BIOLOGICAL TREATMENT IN A COOLING TOWER - SCHEMATIC DIAGRAM
VII-80
-------
treatment. Various combinations of biological processes are there-
fore used to treat petrochemical wastes, depending on wastewater
characteristics, treatability, economic considerations, and effluent
quality requirements. Applications of multiple biological treatment
systems are tabulated in Table VII-22. The organic removal data
indicated include that BOD and COD chemically or physically removed
in pretreatment processes. The data as presented in this table show
that activated sludge, trickling filters, and waste stabilization
ponds are the most common processes used in multiple treatment
systems.
OTHER METHODS OF DISPOSAL
There are several methods which are of ten employed for the
disposal of petrochemical solid and liquid wastes. The following
methods are discussed herein:
a) dilution,
b) discharge into municipal sewerage systems,
c) deep well disposal,
d) ocean disposal,
e) submerged combustion, and
f) incineration.
The process selected from those mentioned above will depend
on the volume and nature of the wastewater, capital and operating
cost considerations, and plant location.
Dilution
This form of waste disposal is becoming less and less
popular with regulatory authorities and the trend is toward the
mandatory primary and secondary treatment of all wastewaters.
However, certain petrochemical plants are allowed to discharge
their wastewaters to receiving bodies of water 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 based on the pollutional input
is adequate.
VII-81
-------
I
00
TABLE VII-22
MULTIPLE BIOLOGICAL TREATMENT SYSTEMS
FOR PETROCHEMICAL WASTES'
Products and/or
Process
Butadiene, Butyl
Rubber, Refinery
Cyclohexane, p-
Xylene , Benzene ,
Paraffinic Naphtha,
o-Xylene, Gasoline,
Nylon
Detergent Alkylate,
Refinery
Refinery-Chemical
Ethylene and Propy-
lene Oxides, Glycols,
Morpholines, Ethyl-
enediamines, Ethers,
Piperazine
Polyester Fibers
Biological
1st Stage
Aerated
Lagoon
Aerated
Lagoon
Aerated
Lagoon
Aerated
Activated
Sludge
Activated
Sludge
Treatment
3rH Stage
2nd Stage (If Applicable)
Facultative
Pond
Facultative
Pond
Facultative
Pond
Stabilization
Facultative
Pond
Stabilization
Pond
Removal
BOD COD
(%) (%) Ref
>78 >67 44
>75 69
95 86 42
95 88 54
>99 35-65 41
97.5 26
-------
I
00
TABLE VII-22 (Continued)
MULTIPLE BIOLOGICAL TREATMENT SYSTEMS
FOR PETROCHEMICAL WASTES
Product and /or
Process
Refinery, Natural Gas
Liquids, Chemical
Specialties
Synthetic Resins
Resins, Alcohols,
Amines, Esters,
Styrene, Ethylene
Ethylene , Propylene ,
Butadiene, Benzene,
Gasoline, Poly-
ethylene, Fuel Oils
Phenol, Salicylic
Acid, Aspirin, Phen-
acetin, Phthalic
Anhydride, Rubber
Chemicals
Refinery
Biological
1st Stage
Activated
Sludge
Activated
Sludge
Anaerobic
Lagoon
Trickling
Filters
Trickling
Filters
Trickling
Filter
Treatment
2nd Stage (If Applicable)
Stabilization
Pond
Trickling
Filters
Anaerobic Aerobic Lagoon
Lagoon
Activated
Sludge
Activated
Sludge
Activated Stabilization
Sludge Pond
Removal
BOD COD
(%) (%) Ref
86 70 117
>99 105
97-99 11
>98 >93 104
98 116
52
-------
TABLE VI-22 (Continued)
MULTIPLE BIOLOGICAL TREATMENT SYSTEMS
Products and/ or
Process
Plastics, Amines
Pentaerythritol
Synthetic Resins
Aliphatic Acids,
Alcohols, Esters,
FOR PETROCHEMICAL
Biological Treatment
1st Stage
Trickling
Filter
Trickling
Filter
Trickling
Filter
Trickling
Filter
2nd Stage
Stabilization
Pond
Trickling
Filter
Trickling
Filter
Trickling
Filter
WASTES
3rd Stage
(If Applicable)
Activated
Sludge
Stabilization
Pond
Removal
BOD COD
(%) (%) Ref
>98 91.5 26
95-96 24
95-98 18
106
Aromatics, Amines
-------
Rapid wastewater-diluent mixing is required, and this often is
accomplished by the use of jets or diffusers.
The quality and use of the receiving water often dictates
direct discharge practices. For example, regulatory authorities
often permit the discharge of spent caustic wastes directly into
salt lakes, brackish streams, and estuaries (McRae, 1959).
Discharge Into Municipal Sewerage Systems
Joint industrial-municipal treatment has proved to be
workable in treating petrochemical wastewaters, especially where
small plants are located near large metropolitan areas (Elkin, 1959).
The ability to successfully co-treat, however, has certain con-
straints. Discharges of petrochemical wastes containing high con-
centrations of toxic materials to municipal sewerage systems may
upset the treatment facility. Therefore, pre- treatment may be
required before many industries are allowed to connect with the
municipal system. For example, the wastewaters from two Los Angeles,
California synthetic rubber plants must be pre-treated to remove
oil, rubber particulates, and other suspended and floating matter
prior to discharge (Martin and Rostenbach, 1953).
Although joint industrial-municipal wastewater collection
and treatment is feasible in certain cases, it has generally been
found that individual treatment has both economic and political
advantages, particularly where large volumes of petrochemical
wastewater are involved. It is for this reason that less than three
percent of the chemical-petrochemical plants in the United States
discharged their wastes to municipal sewers in 1963 (U. S. Bureau
of Census, 1963) with no future increases expected in this percentage.
Deep Well Disposal
Subsurface disposal of liquid wastes is not a new concept
as the oil and gas producers have been using this method for dis-
posing of oil field brines for half a century. However, only
recently have the process industries realized the applicability of
deep well injection for disposing of concentrated and relatively
untreatable waste streams. Since much of the land surface is underlain
by great aquifers containing salt water or brines, these formations
offer convenient and safe repositories for these wastes, preventing
pollution of usable surface and subsurface water supplies.
In 1967 30 permits for industrial disposal wells had been
issued in Texas, 26 of which were for industries producing petroleum-
based products (Fink, 1967). The national total number of industrial
waste disposal wells in 1966 was estimated at 71 (Warner, 1966).
This does not include those wells in which oil field brines are
injected, either for the purpose of disposal or to increase formation
pressures in oil-bearing strata.
VII-85
-------
Disposal wells used for the subsurface injection of petro-
chemical wastewaters are listed in Table VII-23. Injection rates
range from a few gallons per minute to over 600 gallons per minute.
The depth at which these wastes are discharged vary from a few
hundred feet to as deep as 12,000 feet, with most systems injecting
a wellhead pressure of 2,000 pounds per square inch or less
(Gloyna and Ford, 1967). The more common formations into which
wastes are injected include unconsolidated sands, sandstone, lime-
stones, and dolomites (Warner, 1966). It is necessary to determine
the permeability of the formation by drilling test wells. Addi-
tionally, the compatability of the wastewater with the formation
water must be established. 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.
Most of the petrochemical wastewaters noted in Table VII-23
must be pretreated prior to injection. The characteristics of
the wastewater and the nature of the receiving formation dictate
the exact pre-treatment requirements. Conditions that require surface
treatment and those facilities commonly employed are summarized in
Table VII-24.
The pH adjustment of wastewaters is often of primary impor-
tance when considering the performance of the injection well.
Neutralization is often required, but adjustments to the acid or
base range are sometime advantageous. For example, the acidifica-
tion of a petrochemical wastewater prior to injection in a limestone
formation resulted in higher "injection" rates at lower wellhead
pressures (Lockett, 1967). In another case, rigid pH control was
required, as a wastewater containing acetic acid and its chlorinated
derivatives formed polymeric tars at pH values greater than five,
while precipitates were formed at a pH of less than four (Vier,
1967).
Ocean Outfall
The direct discharge of petrochemical wastes into the ocean
is feasible when locations permit. Most liquid wastes flow through
outfall pipelines, the distance of discharge from shore depending
on the nature of the wastewater, the ocean currents, and shoreline
use. Barge disposal is another method of conveying wastewaters
to the ocean for disposal, but this practice has been abused and
requires strict control. Chlorinated hydrocarbons have been barged
to a point 100 miles from the Gulf Coast and discharged over a 30-
mile wide area (Hood, et. al., 1958).
A review of the literature indicates that many different unit
processes are applicable in treating the diverse wastewaters dis-
charged from the petrochemical industy. The number of process
installations reported in 1965 by the Petroleum and Chemical indus-
tries, each interrelated with petrochemical production, is listed
VII-86
-------
TABLE VII-23
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
Type Waste
Flow Depth
(ft)
Injection
Pressure
(psia)
Formation
Required
Pretreatment
Ref
00
—i
Acrylonitrile and Deter-
gent Manuf. Wastes: COD=
17,500 mg/1; Nitrites=
300 mg/1; pH=5.4,
S04 = 10,000 mg/1
10-15% NaCl; Diss.
Metal Salts; Trace
Organics; pH7.5-8.5
Refinery and Petrochem.
Cooling Water Blow-down
Boiler Blow-down, Process
Waters
Petrochem. Waste
Organic Nitrogen
Nitrites
COD = 20,000 ppm
pH = 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
102
Neutralization, Precipi-
tation - Sedimentation,
Filtration
Neutralization with H-SO,;
Clarifier, Pressure
Sand Filter
63
23
55
55
102
55
-------
TABLE VII-23 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY DEEP WELL
INJECTION - TYPICAL INSTALLATIONS
i
oo
oo
Type Waste
0.3% Acetic Acid and
Chlorinated Deriva-
tives
Injection
Flow Depth Pressure
(gpm) (ft) (psia) Formation
204 3,700 2,000 Miocene Brine
Sand
Required
Pretreatment
Cool to 150°F. Adjust
pH to 4.0-5.0, Settling
Coal Filter; Cartridge
Filter for Solids >lQjb
Ref
111
70
Terephthalic Acid 150 5,600
Manuf.
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 50 5,000
Cooling and Boiler
Slowdown, Process Wastes,
Brines
Ammonia Prod. 45 1,000
Small- 5,802
96
85 >4,000
800-
1,100
1,500-
2,000
600
225
Sands
Limestone
Sandstone
Sandstone
Settling, Filtration
Conventional Waste Treat-
ment, 0.3% by Volume of
Acid, Added Before
Injection
Equalization, Settling
Settling and Storage
API Separator
55
73
104
55
55
-------
TABLE VII-23 (Continued)
PETROCHEMICAL WASTE DISPOSAL BY.DEEP WELL
i
oo
VO
INJECTION - TYPICAL INSTALLATIONS
Type Waste
Hydrochloric Acid
Detergent Product
32% HC1
Benzene
Chlorinated HC
Spent Alkylation Acid-
90% H2S04; 7% Oil;
O^/ TJ f\
3/0 H20
Filtrates and Distil-
lates from Chloromycetin
Manuf : BOD = 45 ,000
Flow Depth
(gpm) (ft)
40 1 , 200
35 3,400
~ 1 5,100
1,400
Injection
Pressure Required
(psia) Formation Pretreatment
14.7 Sandstone None
Miocene Sands Dilution with Equal
Volume Fresh Water
Saturated
Brine,
Sand
Ref
55
55
64
1
ppm; pH 3.5, Diss. Solids
50,000 ppm
Saturated NaCl, Cone.
Ca-Mg, Liquors, Phenols,
Chloro-Phenols, Bis-
Phenols, Methocel, Weak
Caustic Washes
3,000
Limestone
Suspended Solids
Removed
93
-------
TABLE VII-24
POLLUTANTS REQUIRING SURFACE TREATMENT
PRIOR TO DEEP WELL INJECTION
Wastewater Characteristics
Surface Treatment
1. Suspended solids
2. Dissolved gases
3. Colloidal matter,
turbidity
4. Ions which precipitate
on contact with formation
waters
5. Oils and oil-like polymers
6. Corrosive character
7. Biological activity and
growth
settling, centrifugation,
or filtration *
degasification by purging,
air stripping, etc.
coagulation and precipita-
tion, followed by sedimen-
tation and/or filtration
possible pH adjustment,
coagulation and precipita-
tion followed by sedimenta-
tion and/or filtration
skimming devices, oil
separators
neutralization or instal-
lation of corrosion-resis-
tant piping and appurten-
ances
chlorination, filtration
Filter aids may be required.
VII-90
-------
in Table VII-25. The data indicate that lagoons or stabilization
basins are the most commonly used processes, probably based on
the economics as related to current effluent quality requirements.
Submerged Combustion
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 waste.
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 (Remy, E. D. and Lauria,
D. T., 1958). A polymeric waste stream containing suspended
synthetic rubber particles, organic solvents, inorganic salts, and
synthetic detergents was not amenable to biological treatment and
consequently treated by submerged combustion (Weyermuller, G. and
Davidson, J., 1958). 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 Liquid Wastes
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
(Ross, R. D., August 1967).
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.
VII-91
-------
TABLE VII-25
TYPES OF WASTE TREATMENT USED IN THE PETROLEUM
AND CHEMICAL INDUSTRIES
Secondary Treatment Process*
Number of Installations
Reported
Activated sludge
Anaerobic digestion
Biological filtration
Centrifuging
Chemical coagulation
Chemical oxidation or reduction
Distillation and stripping
Extraction
Fermenta t ion
Filtration
Flotation (air)
Incineration
Stabilization ponds
Wet oxidation
12
9
6
4
13
12
43
4
1
15
26
2
59
5
Waste Treatment Method*
Number of
Mentions
Percent
Biological oxidation
Chemical oxidation or reduction
Flotation
Incineration
Lagooning or settling
Neutralization
Other
TOTAL
1,211
6
39
25
10
100
More than one treatment process may be in use at each plant.
VII-92
-------
REFERENCES - CHAPTER VII
1. Adinoff, J., "Disposal of Organic Chemical Wastes to Under-
ground Formations," Ind. Wastes, v. 1, n. 1, p. 4944 (Sept.-
WC (••- i. j* J J y •
2. Anderson, R. E. and Hansen, R. D., "Phenol Sorption on Ion
Exchange Resins," Ind. & Engr. Chemistry, v. 47, p. 71
3. Anon., Biological Treatment of Petroleum Refinery Wastes,
American Petrol. Inst., New York, N. Y.
4. Anon., "How Shell Cut Pollution in Rhinelands," The Oil and
Gas J., v. 58, p. 93 (Oct. 31, 1960).
5. Anon., Manual on Disposal of Refinery Wastes. Vol. I, "Waste
Water Containing Oil," American Petrol. Inst., New York,
N. Y. (1953).
6. Anon., Manual on Disposal of Refinery Wastes, Vol. Ill,
"Chemical Wastes," American Petrol. Inst., New York, N. Y.
(1958).
7. Anon., Manual on Disposal of Refinery Wastes, Vol. IV, "Sampling
and Analysis of Waste Water," American Petrol. Inst., New
York, N. Y. (1958).
8. Anon., "Petrochemical Handbook 1967," Hydrocarbon Processing,
v. 46, p. 11 (1967).
9. Anon., "Selected Process Flow Sheets for Petrochemicals,"
The Oil and Gas J., v. 36, n. 36, p. 107 (1964).
10. Anon., "Tables Show How to Treat Petrochemical Wastes," Petro/
Chem. Engineer, p. 25 (May 1967).
11. Anon.,"Union Carbide Puts Corporate Muscle in Pollution Fight,"
The Oil and Gas J., v. 64, n. 50, p. 132 (1966).
12. Anon., Water in Industry, National Assoc. of Manufacturers and
Chamber of Commerce of the U. S., New York and Washington,
D. C. (1965).
13. Beychok, M. R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley & Sons, London (1967).
VII-93
-------
14. Brunner, C. A. and Stephan, D. G., "Foam Fractionation,"
Ind. & Engr. Chemistry, v. 57, n. 5, p. 40 (May 1965).
15. Brunsmann, J. J., .et... al., "Improved Oil Separation in Gravity
Separators," J. WPCF, v. 34, n. 1, p. 44 (Jan. 1962).
16. 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).
17. Carbone, W. E., et. al.., "Commercial Dephenolization of
Ammoniadal Liquors with Centrifugal Extractors," Proc. 13th
Ind. Waste Conf., Purdue Univ., p. 87 (1958).
18, 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).
19. Clark, F. E., "Industrial Re-Use of Wastewater," Ind. & Engr.
Chemistry, v. 54, n. 2, p. 18 (Feb. 1962).
20. Cochran, L. G. and Bess, F. D., "Waste Monitoring by Gas
Chromatography," J. WPCF, v. 38, n. 12, p. 2002 (Dec. 1966).
21 Coe, R. C., "Bench Scale Method for Treating Waste by Activated
Sludge," Petrol. Proc., v. 7, p. 1128 (Aug. 1952).
22. Dean, B. T., "Nylon Waste Treatment," J. WPCF, v. 33, n. 8,
p. 864 (Aug. 1961).
23. DeRopp, H. W., "Chemical Waste Disposal at Victoria, Texas,
Plan of the DuPont Co.," Sew, and Ind. Wastes, v. 23, n. 2,
p. 194 (1951).
24. 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).
25. Dickerson, B. W. and Laffey, W. T., "Pilot Plant Studies of
Phenolic Wastes from Petrochemical Operations," Proc. 14th
Ind. Waste Conf., Purdue Univ., p. 780 (1959).
26. Eckenfelder, W. W., Jr., "Effluent Quality and Treatment
Economics for Industrial Wastewater," Rept. to the F.W.P.C.A.,
Washington, D. C. (1967).
VII-94
-------
27. Eckenfelder, W. W., Jr., Industrial Water Pollution Control
McGraw-Hill Book Co., New York, N. Y. (1966). "—'
28. Eckenf elder, W. W., Jr., et. al_.. Unpublished Kept. (1968).
29. Eckenfelder, W. W., Jr. and Ford, D. L., Unpublished Kept.
(1968) .
30. Eckenfelder, W. W., Jr., Ford, D. L. and Burleson, N. K.
Unpublished Kept. (July 1968). '
31. 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)!. ~"
32. Eisenhauer, H. R., "Oxidation of Phenolic Wastes," j. WPCF,
v. 36, n. 9, p. 1116 (Sept. 1964). '
33. Elkin, H. G., "Condensates, Quenches, and Wash Waters as
Petrochemical Waste Sources," Petrochemical Wastes, v. 31,
n. 7, p. 836 (July 1959).
34. 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).
35. Federgreen, N. and Weinberger, A. J., "Methyl Styrene-A Case
Study in Spent Acid Catalyst Treatment," Ind. & Engr.
Chemistry, v. 49, p. 46 (1957).
36. Fink, B. E., "State Regulation of Subsurface Waste Disposal in
Texas," Proc. 7th Ind. Water and Waste Conf., Texas WPCA
(1967).
37. Ford, D. L., "Kinetics of Aerobic Oxidation in the Thermo-
phyllic Range," Master's Thesis, The Univ. of Texas, Austin
(1964).
38. Ford, D. L., "The Effect of Process Variables on Sludge Floe
Formation and Settling Characteristics," Doctoral Disserta-
tion, The Univ. of Texas, Austin (1960).
39. Ford, D. L. and Eckenfelder, W. W., Jr., Unpublished Kept.
(March 1968).
40.
Ford, D. L. and Gloyna, E. F., Unpublished Kept. (Jan. 1967).
VH-95
-------
41. Ford, D. L. and Gloyna, E. F., Unpublished Kept. (Feb. 1967).
42. Ford, D. L. and Gloyna, E. F., Unpublished Kept. (May 1967).
43. Ford, D. L. and Gloyna, E. F., Unpublished Kept. (July 1967).
44. Ford, D. L. and Gloyna, E. F., Unpublished Kept. (June 1968).
45. Ford, D. L., Gloyna, E. F. and Eckenfelder, W. W., Jr.,
Unpublished Kept. (June 1968).
46. Garrett, J. T., "Multipurpose Incineration," Ind. Wastes, v. 2
n. 5, p. Ill (1957).
47, Garrett, J. T., "Tars, Spent Catalysts, and Complexes as Petro-
chemical Waste," Sew, and Ind. Wastes, v. 31, n. 7, p. 841
(July 1959).
48. 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).
49. Giebler, G., "Treatment of Wastewaters of the Pesticide Industry,1
Vonn Wasser, v. 25, p. 197 (1958).
50, Gill, J. M., et. al., "Submarine Disposal System for Treated
Chemical Wastes," J. WPCF, v. 32, p. 858 (August 1960).
51. Gill, J. M., Huguet, J. H. and Pearson, E. A., "Submarine
Disposal System of Treated Chemical Wastes," J. WPCF,
v. 32, n, 8, p. 858 (Sept. 1960),
52, Gilliam, A. S., "Biological Disposal of Refinery Wastes,"
Proc. 14th Ind. Waste Conf., Purdue Univ., p. 145 (1959).
53. Gloyna, E. F., Waste Stabilization Pond Design, Seminar "Water
Pollution Control in the Chemical Industry," Sponsored by the
Manufacturing Chemists Assoc., Austin, Texas (1966).
54. Gloyna, E. F., Brady, S, 0. and Lyles, H., "Use of Aerated
Lagoons and Ponds in Refinery and Chemical Waste Treatment,"
Presented at 41st Annual WPCF Conf., Chicago, 111. (Sept. 22,
1968).
55. Gloyna, E. F. and Ford, D. L,, "Injection of Wastewaters into
Disposal Wells," Unpublished Rept. (1966).
56, Gloyna, E. F., Ford, D. L. and Burleson, N. K., Unpublished
Rept. (March 1968).
VII-96
-------
57. Gloyna, E. F. and Malina, J. R., "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.
58. 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). '
59. 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). ~~ ' ' '
60. Harkness, N. and Jenkins, S. H., "Chemical and Biological
Oxidation of Styrene and Koprene,: J. Inst. of Sew. Purif.
pt. 2, p. 216 (1958). ~~"
61. Hart, W. B., "Flocculation as a Treatment for Petroleum Refinery
Wastes," Ind. & Engr. Chemistry, v. 49, n. 5, p. 77A (1957).
62, Heller, A. M., et. al., "Some Factors in Selection of a Phenol
Recovery Process," Proc. 12th Ind. Waste Conf., Purdue
Univ., p. 103 (1957).
63. Henkel, H. 0., "Deep Well Disposal of Chemical Waste Water,"
Proc. of the 5th Annual Sanitary and Water Resources Engr.
Conf., Vanderbilt Univ., Tech. Kept. 9, p. 26 (1966).
64. 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).
65. Hood, D. W., Stevenson, B. and Jeffrey, L. M., "Deep Sea Disposal
of Industrial Wastes," Ind. & Engr. Chemistry, v. 50, n. 6,
p. 885 (1958).
66. Huber, L., "Disposal of Effluents from Petroleum Refineries and
Petrochemical Plants," Proc. 22nd Ind. Waste Conf., Purdue
Univ. (1967).
67. Hyde, A. C., "Chemical Plant Waste Treatment by Ten Methods,"
J. WPCF. v. 37, n. 11, p. I486 (Nov. 1965).
68. Karger, B. L. and Rogers, L. B., "Foam Fractionation of Organic
Compounds," Anal. Chemistry, v. 33, n. 9, p. 1165 (August 1961).
VII-97
-------
69. Klippel, R. W., Report on Pollution Control Planning for the
Guayama Petrochemical Complex, Phillips Petrol. Co.,
Bartlesville, Oklahoma (1966).
70. Klotzman, M. and Vier, B., "Celanese Pumps Wastes into Disposal
Wells," The Oil and Gas J., v. 64, n. 15, p. 84 (1966).
71. Lewis, W. L. and Martin, W. C., "Remove Phenols from Waste
Waters," Hydrocarbon Processing, v. 46, n. 2, p. 131
(Feb. 1967).
72. Ling, J. T., "Pilot Study of Treating Chemical Wastes with
Aerated Lagoon," J. WPCF, V. 35, n. 8, p. 963 (August 1963).
73. Lockett, D. E., "Subsurface Disposal of Industrial Waste Waters,"
Presented at Southwestern Petrol. Short Course, Dept. of
Petrol. Engr., Texas Tech College, Lubbock, Texas (April 1967).
74. Ludzack, F. J. and Ettinger, M. B., "Chemical Structures Resistant
to Aerobic Biochemical Stabilization," J. WPCF, v. 32, n. 11,
p. 1173 (Nov. 1960).
75. Ludzack, F. J., Scheffer, R. B. and Bloomhuff, R. N., "Experimental
Treatment of Organic Cyanides by Conventional Processes,"
J. WPCF, v. 33, n. 5, p. 492 (May 1961).
76. Marks, D. R., "Operation and Problems of a Chemical Waste
Incinerator," Proc. of the 5th Annual Sanitary and Water
Resources Engr. Conf., Vanderbilt Univ., Tech. Rept. 9, p.
99 (1966).
77. Martin, A. E. and Rostenbach, R. E., "Industrial Waste Treatment
and Disposal," Ind. & Engr. Chemistry, v. 45, n. 12, p. 2680
(Dec. 1953).
78. McKinney, R. E., American Petrol. Inst., Division of Refining,
Biological Treatment of Petrol. Refinery Wastes, Chapter 2,
New York, N. Y. (1963).
79. McKinney, R. E., "Biological Treatment Systems for Refinery
Wastes," J. WPCF, v. 39, n. 3, p. 345 (1967).
80. McGauhey, P. H. and Klein, S. A., "Removal of ABS from Sewage,"
Public Works, v. 92, n. 5, p. 101 (May 1961).
81. McRae, A. D., "Disposal of Alkaline Wastes in the Petrochemical
Industry," Sew, and Ind. Wastes, v. 31, n. 6, p. 712 (July
1959).
VII-98
-------
82. Meinhold, T. and Mandele, A., "Organo-metallic Plant Waste
Purer Than River Waste," Chem. Processing, v. 23 p 41
(1960).
83. Mencher, S. K., "Minimizing Waste in the Petrochemical Industry,"
Chem. Engr. Progress^ v. 63, n. 10, p. 80 (Oct. 1967).
84. Mills, E. J. and Stack, V. T., "Biological Oxidation of Synthetic
Organic Chemicals," Proc. 8th Ind. Waste Conf. Purdue
Univ. p. 492 (1953).~~
85. 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).
86. Morris, J. C. and Weber, W., Jr., Adsorption of Biochemically
Resistant Materials From Solution. 2., AWTR-16, F.W.P.C.A.,
Cincinnati, Ohio (March 1966).
87, Nagy, C. K., "The Construction and Operation of an Incinerator
for Chemical Plant Wastes," Proc. 12th Ind. Waste Conf.,
Purdue Univ., v. 42, n. 3, p. 177 (1958).
88. Niegowski, S. J., "Destruction of Phenols by Oxidation with
Ozone," Ind. & Engr. Chemistry, v. 45, p. 632 (1953).
89. Pahren, H. R. and Bloodgood, D. E., "Biological Oxidation of
Several Vinyl Compounds," J. WPCF, v. 33, n. 3, p. 233
(May 1961).
90. Phillips, C., Jr., "Treatment of Refinery Emulsions and Chemical
Wastes," Ind. & Engr. Chemistry, v. 46, p. 300 (1954).
91. Popov, M. A., "Use of Ozone for the Final Treatment of Effluents
from an Oil Refinery," Gigiena i Sanit., v. 25, n. 5, p. 92
(1960).
92. Prather, B. V., "Will Air Flotation Remove the Chemical Oxygen
Demand of Refinery Waste Water?" Petroleum Refiner, v. 40,
p. 177 (May 1961).
93. 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).
94. Reid, G. W., and Libby, R. W., "Phenolic Waste Treatment Studies,"
Proc. i->Hn TnH, Waste Con£^. Purdue Univ., p. 250 (1957).
VII-99
-------
95. Reinbald, H., "Graphical Solutions Given to Oil-Water Separa-
tion Rates," Petroleum Refiner, v. 39, n. 12, p. 180 (1960).
96. 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).
97. Rice, J. K., "Eliminate Waste Water Discharge," Petro/Chem
Engineer, p. 21 (Oct. 1966).
98. Rolich, G. A., "Applications of Air Flotation to Refinery Waste
Waters," Ind. & Engr. Chemistry, v. 46, p. 304 (1954).
99. Ruggles, W. C., "Basic Petrochemical Processes as Wastes Sources,"
Sew, and Ind. Wastes, v. 31, n. 3, p. 274 (March 1959).
100. Ryckmann, D. W. and Sawyer, C. N., "Anionic Synthetic Detergents
and Water Supply Problems," J. AWWA, v. 49, n. 4, p. 480
(April 1957).
101. Sadow, R. D-, "The Treatment of Zefran Fiber Wastes," Proc. 15th
Ind. Waste Conf., Purdue Univ., p. 395 (1960).
102. Sadow, R. D., "Waste Treatment at a Large Petrochemical Plant,"
J. WPCF, v. 38, n. 3, p. 428 (March 1968).
103. Schindler, H., "Disposal of Refinery Waste Water Containing Water-
Soluble Sulfonates," Petroleum Refiner, v. 28, n. 10, p. 152
(Oct. 1949).
104. Shannon, E. S., "Handling and Treating Petrochemical Plant Wastes:
A Case History," Water & Sew. Works, v. Ill, n. 5, p. 240
(1964).
105. Singleton, K. G., "Biological Treatment of Waste Water from
Synthetic Resin Manufacture," Proc. 21st Ind. Waste Conf.,
Purdue Univ., p. 62 (1966).
106. 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).
107. Stein, K. C., et. al., "Oxidation of Hydrocarbons on Simple Oxide
Catalysts," Air Poll. Control Assoc., v. 10, n. 4, p. 275
(August 1960).
108. Talbot, J. S. and Beardon, J., "The Deep Well Method of Indus-
trial Waste Disposal," Chem. Engr. Progress, v. 60 (1964).
VII-100
-------
109. Taylor, E. F., et. al., "Orion Manufacturing Wastes Treatment,"
J. WPCF, v. 33, p. 1076 (Oct. 1961).
110. Tyler, R. G., et. al., "The Ozonation of Cyanide Wastes," Sew.
and Ind. Wastes, v. 23, n. 9, p. 1150 (Sept. 1951).
111. Vier, B. B., "Celanese Deep Well Disposal Practices," Proc.
7th Ind. Water and Waste Conf., Texas WPCA (1967).
112. Vrablick, E. R., "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).
13. Walker, R. F.,, "Disposal of Industrial Wastes at Maitland,
Ontario, Works of DuPont of Canada," Proc. 13th Ind. Waste
Conf., Purdue Univ., p. 720 (1958).
114. Warner, D. L., "Deep Industrial Waste Injection Wells in the
United States, A Summary of Pertinent Data," Report to the
F.W.P.C.A., Cincinnati, Ohio (1966).
115. Weisman, W. I., "Applications of Submerged Combustion in Indus-
trial Waste Treatment," Proc. 8th Ind. Waste Conf., Purdue
Univ., p. 363 (1953).
116. Wilson, I. S., "The Treatment of Chemical Wastes," Waste
Treatment, Isaac, P.C.G., ed., Pergamon Press, London,
p. 206 (1960).
117, Word, J. C., Wright, M. V. and Klippel, R. W., paper entitled
"Treating Complex Petroleum Wastes at Borger, Texas," all
are of Phillips Petrol. Co.
118. Weyermuller, G. and Davidson, J. A., "Submerged Combustion
Prevents Polymer-Waste Problem," Chemical Processing
(Feb. 1958).
vii-ioi
-------
CHAPTER VIII
ECONOMIC ASPECTS OF PETROCHEMICAL WASTE TREATMENT
Economics play an important and sometimes critical role in
dictating the level of treatment petrochemical wastewaters receive.
The major economic factors include
a) the capital cost of a 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.
A discussion of these and related factors as well as treat-
ment cost data obtained from public and private sources are included
herein.
THE COST OF WASTE TREATMENT
There are many approaches in predicting the treatment costs
required to reduce petrochemical pollutants to the acceptable
level. Attempts to relate capital costs to production units, waste-
water flow, BOD, or other parameters have proved quite successful
when certain industrial wastewaters are considered. However, the
diverse nature of the petrochemical industry and the limited
number of wastewater treatment facilities specifically designed for
treating its wastewaters has made it difficult to establish cost
function relationships which can be applied throughout the industry.
Most cost information available in the literature includes
the entire waste treatment facility containing an infinite number of
physical, chemical, and biological treatment process combinations.
The statistical correlation of these costs with the aforementioned
process parameters is poor, and there is consequently no basis for
translating this information from one plant to another within the
industry. A more effective approach for estimating the capital cost
VIII-1
-------
of a treatment facility is to calculate the unit costs of each
process within the treatment system and add a given percentage of
the total to include 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 VIII-1.
It is recognized that there are many variables that affect
these cost relationships which are not considered herein. Some of
these factors .include
a) geographical location,
b) climatic conditions,
c) fluctuations in area labor and material costs,
d) land cost factors, and
e) overdesign considerations.
Cognizant of these constraints, a series of capital cost-
waste flow relationships are presented. These graphs, Figures
VIII-1 to VIII-16 represent costs based on 1968 construction costs
(ENR 1,030). These relationships were developed from reported costs
of unit processes included in chemical, refinery, petrochemical,
and in some cases, municipal waste treatment systems. A generalized
estimate thereby can be formulated which summarizes individual
process costs and adds 35 to 45 percent of the sub-total to include
related appurtenances and engineering. It is apparent that this
approach is a general one, but based on the information available,
it provides a means of estimating capital costs of plants treating
petrochemical wastewaters.
Primary Treatment
The capital cost relationships developed for equalization
tanks and neutralization facilities are shown in Figures VIII-1 and
VIII-2. Similar information derived from published literature for
gravity oil separators is described in Figure VIII-3. It is recognized
that many factors, including the plant layout and nature of the
wastewater, dictate the number and size of separators. The capital
cost relationships for primary clarification facilities are shown
in Figure VIII-4. Considering overflow rate and detention time as
the bases for design, this cost function can be applied to both
industrial and municipal waste.
Biological Treatment Processes
Attempts to correlate the capital cost of complete treatment
systems to hydraulic and organic loadings have generally been unsuc-
cessful due to the diverse nature of the industry.
VIII-2
-------
TABLE VIII-1
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
Type of Treatment
Design Basis
Construction
Cost Basis
Operational
Cost Basis
M
I
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 VIII-1 (Continued)
SUGGESTED BASIS FOR COSTING UNIT PROCESSES
M
I—I
*>
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
-------
TABLE VIII-1 (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
i
Ul
As Used in Aerated Lagoons and Activated Sludge
-------
I03
x
XO:
CO
o
o
b: 10 —
g
Q_
O
IOZ :
I01
!0D I06
VOLUME OF EQUALIZATION TANK (gal)
FIGURE VIII-1
CAPITAL COST RELATION - EQUALIZATION
(Reference 4)
VIII-6
10'
-------
160 h
140 h
~ 120 h
X
a*
z: 100 h-
fe
o
o
80 H
60 h
40
20
3 4
FLOW (MGD)
FIGURE VIII-2
CAPITAL COST RELATIONSHIP - NEUTRALIZATION
(Reference 4)
VIII-7
-------
I0f
O
O
a.
<
o
10s
I04
AJL
I I I I
I I I I I
O.I
1.0
WASTE FLOW (MGD)
FIGURE VIII-3
CAPITAL COST RELATIONSHIP - OIL SEPARATION
(Reference 2 )
VIII-8
lO.f)
-------
o
x
2 ioz
CO
O
O
9? I0
<
o
II LA
I I I
10 io3 10*
SURFACE AREA OF PRIMARY CLARIFIER (ft2)
10
FIGURE VIII-4
CAPITAL COST RELATIONSHIP - PRIMARY SEDIMENTATION
(Reference 4 )
VIII-9
-------
The capital cost relationships for waste stabilization ponds,
aerated lagoons, and activated sludge basins are shown in Figures
VIII-5 through VIlI-7. The cdst of the waste stabilization ponds is
dependetit on the land cost, which was1 not considered in the prepara-
tion. Total capital costs of aerated lagoons and activated sludge
basins, including aeration equipment, depend on the type of basin
construction, subsoil conditions, and aeration system.
The equipment cost of mechanical surface aerators is illus-
trated in Figure VIII-8. Large aeration units are more economical
than small units; however, mixing considerations often necessitate
the use of the smaller units and this may take precedence over the
economical aspects. Secondary clarifier costs, Figure VIII-9,
parallel the costs required for primary clarifiers and are governed
by the same considerations.
The unit cost of trickling filters related to waste flow
is given in Figure VIII-10. The dispersion of reported values which
is observed from this relationship is primarily attributable to
differences in the organic loadings applied to the various filters.
There are not enough trickling filter units presently treating
petrochemical wastes to statistically establish the organic loading
effect, but a generalized trend is indicated in Figure VIII-10.
It is difficult to tabulate and compare operating costs of
various treatment facilities because of the many different accounting
methods, amortization procedures and depreciation schedules used by
the industry. However, a tabulation of reported daily operating
costs in terms of volume and organic load treated is given in Table
VIII-2.
Tertiary Treatment Processes
Tertiary treatment of petrochemical wastewaters is not
common. However, cost relationships for the treatment of municipal
effluents using ion exchange and carbon adsorption methods have been
reported (Smith, 1968; Eckenfelder, et. al., 1968). These correla-
tions have been graphically represented in Figures VIII-11 and VIII-
12. This approach considers correcting the flow according to the
following expressions.
Ion Exchange -
"COD
Corrected flow
Ind. Waste j
flow
Mun. Waste!
Ind.
COD
Mun.
0.75
VIII-10
-------
"b
* 500
Q 400
o
1
O
O
300
200
CO
O
o
100
10
20
SURFACE AREA (acres)
30
40
FIGURE VIII-5
CAPITAL COST RELATIONSHIP - LAGOONS
(Reference 4 )
VIII-11
-------
I04
"
2 I03
X
O
o
is
s:
<
o
10s
10
*
O.I
1.0 10.0
VOLUME OF AERATION BASIN (MG)
FIGURE VIII-6
CAPITAL COST RELATIONSHIP - AERATED LAGOON
(INCL. AERATION EQUIP.)
(Reference 4)
VIII-12
o
o
E
<
o
100.0
-------
I04
2 in3
x I0
O
O
g
Q.
<
O
IOZ
10
O.I
LO 10.0
VOLUME OF AERATION BASIN (MG)
FIGURE VIII-7
CAPITAL COST RELATIONSHIP - ACTIVATED SLUDGE
(INCL. AERATION EQUIP.)
(Reference 4 )
VIII-1.3
100.0
-------
I0e
o
0
m
o
u_
I05
CO
o
o
g
Q.
O
id4
10'
Using fewer large HP
units in lieu of more
small HP units de-
creases cost for
same HP reqmt.
from manufacturers of
surface aerator equipment
(5 sources)
10 10
TOTAL HP REQUIREMENT
10
FIGURE VIII-8
MECHANICAL SURFACE AERATORS
(EQUIPMENT COST)
VIII-14
-------
I0a
"o
I02
O
O
a:
u.
O
CO
o
o
10
I02
I0
I04
I05
SURFACE AREA OF FINAL CLARIFIER ( ft2 )
FIGURE VIII-9
CAPITAL COST RELATIONSHIP - FINAL CLARIFIERS
(Reference 4^
VIII-15
-------
I04
Q
O
2
•6
x
P
CO
O
o
Q.
<
O
!03
SOURCES
Eckenfelder, W.W., Jr., 1967
Wilson, I.S., I960
Beychok,M.R., 1967
Forbes, M.C. a Witt, PA, 1965
•Influent BOD5
I960 mg/l
Influent BOD
150-700 mg/l
O.I
1.0
10.0
WASTE FLOW (MGD)
FIGURE VIII-10
CAPITAL COST RELATIONSHIP - TRICKLING FILTERS
VIII-1'6
-------
TABLE VIII-2
OPERATING COSTS - WASTE TREATMENT PLANTS
(Reference 3)
Industry
Refinery
Type of Treatment
Primary-includes oil sepa-
ration, coagulation,
flotation, and sedimen-
tation
Secondary-
Activated Sludge
Aerated Lagoon
Extended Aeration
Daily Operating Costs
$/l,000 Ib
$/MG Pollutant
126-160 26-150 (COD)
161 292 (COD)
22 9 (COD)
28 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 VIII-2 (Continued)
OPERATING COSTS - WASTE TREATMENT PLANTS
M
M
00
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
Daily Operating Costs
$/MG
1,580
221-276
16-211
780-2,050
163
334-378
$/ 1,000 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
-------
I07
p
<0
O
O
o
I05
I04
O.I
1.0
10.0
100.0
CAPACITY (MGD)
FIGURE VIII-11
CAPITAL COST RELATIONSHIP - ION EXCHANGE
(Reference 9)
VIII-19
-------
I07
10*
Itf
1.0
I I
10.0
100.0
DESIGN CAPACITY (MGD)
FIGURE VIII-12
CAPITAL COST RELATIONSHIP - CARBON ADSORPTION
(Reference 9)
VIII-20
-------
ICorrected flow
Carbon Adsorption -
1 TotalDissol. Solids
Ind. Waste
flow
Mun. Waste
Ind.
350
0.75
The corresponding capital costs for the corrected flows can
then be determined.
Sludge Handling and Disposal Processes
Capital cost relationships for sludge handling using flota-
tion thickening and vacuum filtration are developed in Figures VIII-
13 and VIII-14. The flotation thickening correlaton is based on
data made available primarily from the petroleum refining industry
(Beychok, 1967), while the vacuum filter description is predicated
on municipal waste treatment experience (Smith, 1968).
A total sludge disposal-cost relationship based on question-
naire information reported by chemical and petrochemical industries
is shown in Figure VIII-15. The costs indicated for a given waste
flow include aerobic digestion, sludge thickening, vacuum filtration
or centrifugation, and disposal. The obvious significance of waste-
water suspended solids concentration and the nature of the resultant
sludge is not considered here, but again, a generalized estimate
based solely on wastewater flow can be formulated.
Ultimate Disposal
The petroleum refineries reporting to a 1965 survey indicated
that the total replacement cost for their waste treatment facilities
would be $156,000,000 (Anon., Water in Ind.. 1965). 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 invest-
ment of $263,600,000 in waste treatment plants, with facilities
costing approximately $70,000,000 planned for the next five years
(Anon., Water in Ind., 1965). The cost of incinerating liquid wastes
and slurries is shown in Figure VIII-16. Operating and capital
costs, based on a 20-year amortization schedule, are included.
The annual operating budget for a waste treatment facility
which includes two disposal wells, a trickling filter, an activated
sludge plant and an incinerator, including amortization is $750,000
(Sadow, 1966).
RETURNS TO THE PETROCHEMICAL INDUSTRY
The petrochemical industry can appreciate a direct economic
return through water reuse. Generally, industry pays from $.02 to
$.35 per 1,000 gallons for treated water while recycled cooling water
VIII- 21
-------
can be purchased for as little as $.01 to $.05 per 1,000 gallons
(Clarke, 1962). Therefore, it can be stated that
a) certain costs are associated with obtaining a
supply of water, conditioning or treating it for
use, and properly disposing of the waste;
b) certain costs are associated with the alternative
of treating wastewater for direct reuse, thus
minimizing the purchase and disposal costs; and
c) when the costs of (b) are less than those of (a),
an economic return in the form of water reuse can
be appreciated.
The second mechanism of realizing an economic return to the
industry is in the form of product recovery. This determination
must be predicated on the recovery cost-market value economics,
recognizing that a reduction in waste treatment costs is normally
associated with product recovery.
All of the aforementioned factors merit an engineering and
economic review, the implementation of which may produce a monetary
return to the industry.
VIII-22
-------
o
o
2
o
o
CL
<
O
O.I
1.0
WASTE FLOW (MGD)
10.0
FIGURE VIII-13
CAPITAL COST RELATIONSHIP - FLOTATION THICKENING
(Reference 2)
VIII- 23
-------
"o
CO
o
o
0.
<
o
300
280
260
240
220
200
180
160
140
120
100
80
60
40
20
0
FILTER AREA (ft'xIO2)
FIGURE VIII-14
CAPITAL COST RELATIONSHIP - VACUUM FILTRATION
(Reference 9)
VIII-24
-------
to
O
o
g
Q_
<
O
COST INCLUDES:
a. Aerobic Digestion
b. Sludge Thickening
c. Vacuum Filtration
or Centrifugation
d. Disposal
8
10
12
14
16
18
20
FLOW (MGD)
FIGURE VIII-15
CAPITAL COST RELATIONSHIP - TOTAL SLUDGE DISPOSAL
(Reference 4)
VIII-25
-------
100.0
10.0
o
o>
o
o
CO
o
Q.
CO
o
1.0
O.I
Incineration: >I05 mg /1 COD
Does not include ash disposal
Operating 8 capital costs based
on 20 year amortization
11
10
I02 I03
WASTE FLOW (galxloVday)
I04
FIGURE VIII-16
CAPITAL COST RELATIONSHIP* - INCINERATION
(Reference 6)
VIII-26
-------
REFERENCES - CHAPTER VIII
1. Anon., Water in Industry, National Assoc. of Manufacturers
and the Chamber of Commerce of the U. S., New York and
Washington, D. C. (1965).
2. Beychok, M. R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley & Sons, London (1967).
3. Eckenfelder, W. W., Jr., "Effluent Quality and Treatment
Economics for Industrial Wastewater," Rept. to FWPCA,
Washington, D. C. (1967).
4. Eckenfelder, W. W., Jr., et. al., Unpublished Rept. (1968).
5. Forbes, M. C. and Witt, P. A., "Estimate Cost of Waste
Disposal," Hydrocarbon Processing, v. 44, n. 8, p. 153
(1965).
6. Koenig, L., "Ultimate Disposal of Advanced Treatment Waste,"
USPHS, Publ. No. 999-WP-3, Cincinnati, Ohio (1963).
7. 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
FWPCA (January 1969).
8. Sadow, R. D., "Waste Treatment at a Large Petrochemical Plant,"
J. WPCF, v. 38, n. 3, p. 428 (March 1966).
9. Smith, R., "Cost of Conventional and Advanced Treatment of
Wastewater, J. WPCF, v. 40, n. 0, p. 1546 (Sept. 1968).
10. Wilson, I. S., "The Treatment of Chemical Wastes," Waste
Treatment. Isaac, P. C. G., ed., Pergamon Press, London,
p. 206 (1960).
VIH-27
-------
APPENDIX I
Process Information
A - Primary Petrochemicals
B - Common Intermediate Petrochemicals
C - Third-Generation Petrochemicals
-------
I-A PROCESSES FOR PRIMARY PETROCHEMICALS
PRODUCT
Acetylene
Aromatics (Benzene
Toluene, Xylene
Benzene .-
Butenes
Cyclohexane-
Ethylene and
Propylene
Hydrogen
FEEDSTOCK
.. ligfyt paraffins,
steam
. Natural gas , 0.
.'.- Aromatic frac-
tion from
reformer
.. See Aromatics
2. Toluene/Xylene,
.. Refinery streams
2. Butanes
1. Natural gas liq.
2. Benzene, H-
1. Various refinery
. streams
2. Refinery gas,
ethane, propane
butane, nat. gas
light refinery
fractions , heavy
distillates
1. Refinery off-
gases
2. Synthesis gas
3. Any hydrocarbon
REACTION SEQUENCE
v.p. thermal cracking
v.p. purification
v.p". partial oxidation
v.p. purification
l.p. solvent extraction
v.p. -stripping
l.p. fractionation
direct recovery
l.p. hydrodealkylation
(thermal) or
hydrodealkylation
(catalytic)
direct recovery
v.p. dehydrogenation
direct recovery
l.p. • hydrogen'ation
direct recovery
v.p. pyrolysis (thermal)
direct recovery
v.p. water gas conver-
sion of CO & steam
(catalytic)
decomposition
(catalytic)
TEMP.
"""
™
594~760 .
-
750-900
PRESSURE
(psig)
-7.3
-
500-1,000
••
--
-
CATALYSTS
' -
Or oxide on
alumina
precious metals
REMARKS
Heat supplied by fuel
gas ethylene co-prod.
C~HC by-products.
Note: direct recovery
CH, by-product
CH, by-product
Butane feed determines
.butene formed
Small amounts
Major source" •
Ethylene, propylene,
butene formed by-
products: acetylene,
methane, aromatics
CO- by-product
Carbon by-product
-------
I-A PROCESSES FOR PRIMARY PETROCHEMICALS (Continued)
PRODUCT
Synthesis Gas
Naphthalene
l.p. liquid phase
v.p. vapor phase
(-) indicates da
FEEDSTOCK
1. Naphthas /refin-
ery gas/H.C.,
steam, air
2. Hydrocarbons,
air or
0.
. 2
2. Alkynaphthalenes
:a not available
REACTION SEQUENCE
v.p. reforming (cataly-
tic)
v.p. partial oxidation
hydrodealkylation
(catalytic)
TEMP.
<°C)
700-850
*
-
_
-
PRESSURE
(psig)
350-550
-
_
CATALYSTS
Ni
None
REMARKS
CH,, CO , by-product
, (two stages)
Thermal; CH,, CO
by-product
CH. by-product
^t
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS
PRODUCT
Acetaldehyde
Acetic Acid
Acetic Anhydride
FEEDSTOCK
1 . Ethanol
2 . Ethanol , air
3. Butane/Propane,
oxygen
4 . Ethylene , oxygen
or air
5. Acetylene, water
1. Acetaldehyde,
air or oxygen
2. Acetaldehyde,
oxygen, olefins
3 . Butane , air
or hexane,air
4. Methanol,
carbon monoxide
1. Acetaldehyde,
air or oxygen
2. Acetic acid
3. Acetone, acetic
acid
REACTION SEQUENCE
v.p. dehydrogenation
v.p. oxidation, dehydro-
genation
v.p. oxidation
..p. oxidation
..p. hydration
..p. oxidation
L.p. or v.p. oxidation
to acetaldehyde
peracetate
1 .p. 'oxidation or
l.p. oxidation
l.p. reaction
l.p. oxidation
v.p. cracking to ketone
l.p. reaction of ketene &
autic acid
v.p. cracking of acetone
to ketene
quench ketene with
acetic acid to
produce anhydride
TEMP.
275-280
550
430-530
20-100
80-95
50-70
-5-0
165-170
170
250
_
740
750-800
PRESSURE
(psig)
-
.
100-300
120
-
-
-
815
1,170
9,580
_
-
(-12.5)-
(-11.6)
CATALYSTS
Cu & Co; Cr on
abestos
Ag
Noncatalytic
CuCl2, PdCl2
HgO
MnC2H302
-
CrC2H 0
Noncatalyti c
Cobaltous Iodide
Cobalt acetate-
copper acetate
Triethyl phosphate
REMARKS
-
-
Formaldehyde, methanol,
acetone by-products
Polladium chloride sol.
is oxygen carrier
Minor process in U.S.
Exothermic
Acetic acid solvent
By-products: formic &
propionic acids, esters
ketones
Propionic acid by-
product
_
Fractionation req'd to
separate anhydride
from acid .
CS2 added to suppress
carbon formation
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Acetone
Acrolein
Acrylates
Acrylonitrile
FEEDSTOCK
1 , Isopfropanol
2.- Propylene, air
3 . Cumene , air
4. Acrolein
5. Isopropanol,
oxygen
1. Propylene, air
1. Acetylene,
carbon monoxide,
alcohols
2. Ketene, formal-
dehyde, alcohol
3. Ethylene oxide
hydrogen,
cyanide,
alcohol
1. Acetylene, HCN
2. Propylene,
ammonia, air
REACTION SEQUENCE
l.p. dehydrogenation
v.p. dehydrogenation
l.p'. oxidation
l.p. autooxidation
l.p. clearage
v.p. reduction
l.p. oxidation
v.p. oxidation
l.p. formylation of
acetylene
l.p. esterification with
alcohol
v.p. formylation of
ketene alcohol
quench
l.p. condensation to
ethylene cyanohy-
drian
l.p. reaction with
alcohol
l.p. condensation
v.p. oxidation to
acrolein
v.p. conversion to
acrylonitrile
or
TEMP.
<°C)
150
380
100
110-130
45-65
350-450
90-140
400
225
45-50
250-260
55-60
150
80-90
400
3.80
PRESSURE
(psig)
0
-
-
-
-
..
200-300
"
1,455
.. 0
-
•-
-
15
--
-
CATALYSTS
Ni
Zn 0
Pd Cl , Cu C13
copper porphyrins
sulfuric acid
Mg 0 - Zn 0
H?0 (autocatal-
yEic)
Cu 0 or Bismuth
.phosphomolybdate
Ni (CO.), HC1
. BF3
NaOH, diethylamine
Sulfuric acid or
ion exchange resin
Cu C12
CuO or Bismuth
phosphomolybdate
MoOj on alumina
Uranium based
REMARKS
Diisopropylethen and
propylene by-products
-
pH 8.5-10
Phenol is co -product
Allyl alcohol is
primary product,
acetone is co-product
Hydrogen peroxide
co-product
-
Tetrahydrofuran
Solvent
Acetaldehyde by-
product
diluted with N. prior
to quench
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS
PRODUCT
Acrylonitrile
(Cont.)
/
Adipic A_cid
Adiponitrile
FEEDSTOCK
3. Propylene, NO
4; Ethylene -oxide,
HCN
5 . Acetaldehyde ,
HCN
1. Cyclohexanol,
cyclohexanone,
HNO,-,
O
2 . Cyclohexanol ,
cyclohexanone ,
air
1. Butadiene, HCN,
' C12' H2
2. Adipic acid,
NH,
O
3 . Acrylonitrile
.
REACTION SEQUENCE
v.p. ammoxidation
v.p. reaction
l.p. condensation to
ethylene cyanhydride
l.p. dehydration
l.p. Lactonitrile f orm-
'ation
v.p. dehydrogenation
l.p. oxidation
l.p. oxidation
v.p. chlorination (also
lip.)
l.p. reaction with HCN
l.p.' hydrogenation
OR
v.p. hydrogenation
v.p.- condensation -
dehydration
• el ectrolytic reduc -
tion
TEMP.
380-510
460-500
55- 60
200
10- 20
600-700
60- 80
180- 85
65- 75
as
250-300
75-150
360
. PRESSURE
(psig)
5-30
-
-
-
-
-
—
.-
-
.
-i
CATALYSTS
Bismuth phospho-
molybdate or Bis
muth vanadotung
state
Ca promoted Ag
NaOH, diethyla-
mine
Mg CO.,
None
H3P°4
Cu, V
Mn & Cu aceta-
tes
CuCl HCI
Pd
Pd
Boron phosphate
or
• silico phosphoric
acid
REMARKS '
Acetonitrile & HCN
by-products
fluid or fixed bed
process
Acetic acid s-blvent
-}
•> Alternate routes
J
Not yet commercial
-------
I-B. PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Cont.)
PRODUCT
Aldehydes
Alcohols, long
chain primary
Alpha Olefins,
linear
Aniline
Bisphenol-A
1 , 3 Butadiene
FEEDSTOCK
1 . Olefins, CO, H2
1 . Ethylene, tri-r-
ethyl aluminum ,
H S04> air
1 . Ethylene, tri-
ethyl aluminum
2. Linear paraffins
1. Nitrobenzene,
H2
2. Chlorobenzene,
NH3
3. Nitrobenzene,
iron filings
1 . Phenol , acetone
1 . n-Butene
2 . n-Butane
REACTION SEQUENCE
l.p. hydrocarboxylation
(0X0)
l.p. buildup reaction
l.p. oxidation
l.p. fission (w/H2SO4)
l.p. buildup reaction
l.p. displacement
v.p. cracking
v.p. hydrogenation
v.p. hydrogenation
l.p. ammonolysis
hydrogenation
l.p. condensation
v.p. dehydrogenation
v.p. dehydrogenation
.
TEMP.
140-175
160
95
40
160
285
550-575
200-350
270
200-210
—
.50- 70
620-675
500-675
595-675
650
600-650
PRESSURE
(psig)
1,500-4,000
2,185
0
0
2,185
1,455
""
> 0
20
850-950
-
—
~ 0
— 0
~ 0
— 0
-11.7
CATALYSTS
Cobalt hydrocar-
boxylation
Cu
Cu
None
—
CuCO, or Nickel
sulfide
Cu or silicon
CuO
iron filings
HC1 or HBr .
promoted by methyl -
mercaptan
Fe203+Cr203
Mg-Fe oxide
Ca-Ni phosphate
Chromia-alumina
Chromia-alumina
i
REMARKS
• Mixed olefins in
products stream
Phenol & diphenyl-
amine by-products
Used only is small
plants
~1
y Alternate s
— .
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Butanol
Butyric Acid
n-Butyraldehyde
Caprolactam
FEEDSTOCK
Ace£aldehyde
Propylene, CO,
H20
. n-Buteneori-bu-
tene, H-SO, , H 0
. n-butene, ore-
butene, HO
.. n-Butyraldehyde
air or oxygen
.. See aldehydes
.. Cyclohexanone,
hydroxylamine
sulfate, H_SO,,
NH3
2. Cyclohexane,
HN03, H2,
H_SO. , NH,
24 3
3. Toluene, air,
H2, NH3, oleum
REACTION SEQUENCE
l.p. aldol condensation
l.p. dehydration
v.p. hydrogenation
l.p. reaction
l.p. sulfation
l.p. hydrolysis
v.p. -hydration
l.p. oxidation
l.p. formation of cyclo-
hexanone oxime
l.p. Beckmann rearrange-
ment
l.p. nitration
l.p. reduction to cyclo-
hexanone oxime
1 .p . Beckman rearrange-
ment
v.p. oxidation to benzoic
acid
l.p. hydrogenation
l.p. reaction with
nitrosylsufuric
acid
TEMP".
(° c)
5-25
95
200
100
60-70
b.p.
300
50-70
20
140
80-85
140
•
160
170
55-65
PRESSURE .
(psig)
~ 0
2,200
225-350
— 0
1,000
-
-
-
500
132
132
-
CATALYSTS
Caustic
Sodium acid
Phosphate
Cu or Ni
Iron pentacarbony!
butylpyrrolidine
H PO, or tungsten
oxide
Mn acetate
-
-
Pd, Pb oxide or
carbonate
Pd
HSO
£, *-r
REMARKS
n-Butanol)
.n-Butanol, i-butanol
Sec-butanol,
teirt-butanol
Sec-butanol
tert-butanol
Exothermic
1st reaction can be
skipped if benzoic
acid is used
(NH,) SO by-product
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Caprolactam
. (Continued)
Carbon Bisulfide
Carbon Tetra-
chloride
Chlorinated
Methanes
(Chloroform, etc)
Chloroprene
Cresol (para)
Cresylic Acids
FEEDSTOCK
4. Benzene, H ,
NH,, oleumf
S°2
5. Cyclohexane,
NH,, Naci,
H SO
24
1. Methane, sulfur
1. Methane, chlorine
2. Carbon disul-
fide, chlorine
3. Methane, HC1.0
See Processes 1 & 3
for CC1,
4
1. Acetylene, HC1
1. p-cymene
1. Cracked naphtha,
CO or H SO,
REACTION SEQUENCE
v.p. hydrogenation to
'i cyclohexane
v.p. oxidation to cyclo-
hexane
See process #1 above
l.p. photochemical re-
action to cyclo-
hexanone oxime HC1
l.p. Beckmann rearrange-
ment
v.p. catalytic conver-
sion or
v.p. catalytic conver-
sion
v.p. chlorination (2
steps)
v.p. chlorination (2
steps)
v.p. hydrochlorination
l.p. dimerization
l.p. hydrochlorination
l.p. caustic extraction
l.p. acid neutralization
TEMP.
(° c)
150-160
15
140
600
680-700
370-520
30
60
-
•
65-75
25-50
PRESSURE
(psig)
112-117
15-2-5
15-25
-
-
-
-
2-5
-
-
CATALYSTS
Co
Various incl. Si,
Al, Mg, Zr, Ni,
Co oxides
Activated bauxite
None
Iron oxide
Copper chloride
CuCl2, Nh^tl,
CuCl2
/
-
REMARKS
(NH, ) SO, by-product
(NH, ) SO, by-product
By-products HC1,
chlorinated methanes
Step 1
.Step 2 4
Mixed chlorinated
methanes
Direct recovery
-------
I-B. PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS CCont.')
PRODUCT
Cumene
Cyclohexanol
Cyclohexanone
Dodecene
Dodecylbenzene
Epichlorohydrin
FEEDSTOCK
. . Propylene,
benzene
. .• Cyclohexane,
air
2. Phenol, H2
. . Cyclohexanol
2. Phenol, U
3. Cyclohexane,
air
1 . Propylene
1 . Dodecene,
benzene
1 . Propylene, Cl,,,
lime
REACTION SEQUENCE
v.p. alkylation
OR
. . p . alkylation
. p . oxidation
OR
..p. oxidation
. p . hydrogenation
v.p. or l.p. dehydrogena-
tion
l.p. hydrogenation
tetramerization
OR
tetramerization
OR
tetramerization
l.p. alkylation
OR
l.p. alkylation
v.p. chlorination to allyl
chloride
l.p..;chlorination to gly-
cerol chlorohydrin
l.p. conversion w/lime
TEMP.
250
90-100
180
155-160
150
-
120-128
95-140
90-110
95-100
45- 55
0- 10
500-530
25 - 35
80- 90
PRESSURE
(psig)
250-400
500
50 •
-
~ 0
~250
500
900
-
-
10- 15
-
-
CATALYSTS
H3P04
A1C13
none
Co
Pd
v.p. - Zn, Fe
l.p. - N'i
Pd
H3P04
H3P04
H3P04
A1C13
HF
-
-
REMARKS
Cyclohexanone co-
product
Cyclohexanone co-
product
See processes # l &3
under Cyclohexanol-
. Adiabatic
Adiabatic
Isothermal
pH 0.5. - 2.0
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Esters (all types)
Ethanol
Ethyl Acetate
-
Ethyl Benzene'1
Ethanolamines
Ethyl Chloride
FEEDSTOCK
1 . Acid, alcohols
1 . Ethylene,
' H2S°4
2. Ethylene, steam
1 . Acid, alcohols
2 . Acetaldehyde
1 . C0 reformate
o
2.- Ethylene,
benzene
1 . Ethylene oxide ,
NH,
O
1. Ethylene, HC1
2. Ethane,, Cl 2
REACTION SEQUENCE
l.p. esterification
l.p. sulfation
l.p. hydrolysis
v.p. hydration
See Esters
l.p. conversion
Super fractionatiori
l.p. alkylation
OR
v.p. alkylation
l.p. ammonolysis
v.p. addition
OR
l.p. addition
v.p. chlorination
OR
v.p. chlorination.
TEMP.
b.p.'
60- 70
b.p.
300-570
0
-
90-100
310
35- 40
175
52
390
420
PRESSURE
-
225-350
1,000
"""
-
r-0
900
-
250
125
110
80
CATALYSTS
-
H.PO or Tungsten
oxide
Aluminum ethoxide,
A1C13, ZnO
A1C13
Silica-Al
-
CuCl , ZnCl2 on
alumina
Al C13 or BF3
"T" ti_ ir U . . OTC A 1.0 J. rt
j A * "3
+ FeCl3
Act. charcoal-
photo chemical
.Thermal
REMARKS
Direct recovery
Polyethyl benzene .
.by-product
Butyl-benzene
polyethyl benzene by-
product
All 3 ethanolamines
formed as co-products
HC1 by-product
HC1 by-product
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Ethyl Chloride
(Continued)
Ethyl ene Dicho-
ride
Ethylene Glycol
Ethylene Oxide.
2 -Ethyl Hexanol
FEEDSTOCK
3. Ethanol, HC1- -
. Ethylene, Cl.
2. Ethylene, HC1,
- 0.
2
.. Ethylene oxide,
HO
Z.
2 . Formaldehyde ,
CO, Methanol,
H2 •
1. Ethylene, C12>
lime
2. Ethylene, air or
°2
1. n-Butyraldehyde,
H2
REACTION SEQUENCE
V.p. esterification
OR
l.p. esterification
l.p. chlorination
v.p. oxychlorination
l.p. hydration
OR
l.p. hydration (Thermal)
l.p. reaction of CO
and HCHO
l.p. esterification
v.p. hydrogenation
l.p. chlorohydronation
l.p. saponification with
lime
v.p. oxidation
l.p. aldolization
l.p. dehydration
l.p. hydrogenation
'•-
TEMP.
<°C)
145
46
285
50-70
195
150-225-
210-220
210-215
225
20-35
96-102
240-290
5-25
95
200
PRESSURE
(psig)
30
75
0
-
200
7,300-
14,700
11,700-
13,200
427
.565
variable
0-10
_
.
-
CATALYSTS
zncr
2
ZnCI2
FeCl
J
CuCl^ on alumina
HSO
tL *~t
None
HC1 orH0SO.
L 4-
V°4
£t *-r
CuO,ZnO, chromia
MgO, CuO
Ag
Aqueous caustic
Sodium acid phos-
phate
Ni
i
REMARKS
Di & triethylene
glycol by-products
Di & triethylene
glycol by-products
/"" '
• Alternate steps
V
pH 8-9
Feed purity require-
ments vary
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Conttnued)
PRODUCT
Formaldehyde
Fumaric Acid
Glycerbl
Hexainethylene
Diamine
FEEDSTOCK
1. Methanol,air
2 . Propane or bu-
' tane, O2
3. Dimethyl ether,
air
1 . Maleic acid
1 . Epichlorohydrin,
..caustic
2. Acrolein,isopro-
panol, H2O2
3. Propylene oxide,
-.Cl2or.H202
1 . Adiponitrile , HZ
REACTION SEQUENCE
v.p, oxidation-dehydro-
genation
OR
v.p. oxidation
see Acetaldehyde Process
#3
v.p. oxidation
l.p. isomerization
l.p. hydrolysis
v.p. reduction to allyl
alcohol
l.p. reaction w/H2O2
v.p. isomerization to
Allyl alcohol
AND
l.p. chlorination to gly-
cerol chlorohydrin
l.p.. conversion to epi-
chlorohydrin
See process #1 above
OR
See process #2
l.p. hydrogenation
TEMP.
600-660
300-400
450-500
-
150
350-450
90- 98-
280
-
100-135
PRESSURE
(psig)
-
0
-"
-
- -
-
CATALYSTS
Ag
MoO3/ Iron
Metallic oxides
MgO + ZnO
Sulfonic acids
Li3 P04
-
Co sometimes + Cu
REMARKS
Thermal conversion
NaOH,Na2CO3 used
Acetone by-prod.
."^
Fixed bed process
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
• 'PRODUCT ' ••'
Hydrogen Cyanide
i
Hydrogen Peroxide
Isophthalic Acid
Isoprene
\
Isopropanol
FEEDSTOCK- -•• -:
1. Methane, NHV
0- J
2
2. Methane, NH_
.-. Isopropanol,
':°2
.. -m-Xylene, -air
2. ,m-Xylene, NH ,
sulfur
. . Isopentene
2. Isopentane
,3, Propylene
1 . Propylene ,
2. Propylene, water
OR
Propyl ene , s team
-
RE-ACTION SEQUENCE '
:v.p. ammoxidation
v,p. non-oxidative
reaction
l.p, oxidation
l.p. oxidation
l.p. oxidation
v.p. dehydrogenation
(alternates)
v.p. dehydrogenation
(one step)
. l.p. dimerization
V.p. isomerization
v.p. pyrolysis (demath-
anization)
l.p. sulfation
l.p. hydrolysis
v.p. hydration
OR
v.p. hydration
TEMP.
(°C)
950-1,000
1,200-
1,300
90-140
190-200
315-360
620-675
500-675
595-675
650
600-650
150-250
150-300
650-800
60-70
b.p.
180-260
300
.PRESSURE .
(psig)
'-
-
200-300
to maintain
l.p.
2,500-
6,000
~ 0
~ 0
~ 0
-~ 0
-11.7
300
-
-
300-400
0
352-940
1,000
CATALYSTS
Pt, Rhodium
Pt
H 0? (autocataly-
tic)
. Mn acetate, NH.Br
"None
Fe203-K:r203+K2C03
Mg-Fe oxide
Ca-Ni phosphate
Chromia -alumina
Chromia-alumina
Tripropyl aluminum
acid
HBr
_
-
-
H PO, or tungsten
oxide
i
REMARKS
Acetone co-product
High mole ratio H "0:
xylene required
All procedures produce
Complex Cs mixture
as by-product
H
ii
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Maleic Anhydride
Melamine
Methacrylates
''<
Methanol
Methyl Chloride
FEEDSTOCK
1. Benz'ene, air
2 . Butenes , air
1. Urea
1. Acetone, HCN,
alcohol, H SO,
2. Isobutene,
alcohol
1. CO, H
£.
2 . Natural gas ,
steam, CO, or
3. Butanal Propane,
air
1. Methanol, HC1
See Processes 1&3
for carbontetra-
chloride
REACTION SEQUENCE
v.p. oxidation
v.p. oxidation
v.p. decomposition
v.p. conversion (cataly-
tic)
OR
V.p. conversion (cataly-
tic one step)
l.p. cyanhydr in forma -
tion
l.p. sulfation
l.p. rearrangement
l.p. esterification
L.p. oxidation
l.p. dehydration
l.p, esterification
v.p. hydrogenation
v.p. reforming
v.p. conversion
v.p. oxidation
v.p. hydrochlorination
or
l.p'.
TEMP.
(° C)
400-450
350
350
400-450
-
<25
80
125
90
5
-
350-375
-
-
430-530
_
PRESSURE
(psig)
_
-
-
-
103-132
_
•
-
-
-
-
3,665-
14,685
4,300
100-300
_
CATALYSTS
V 0 , MoO
M°°3' V2°5
None
•
-
-
Alkaline
-
-
-
N oxides , HN03
ammonium vanactate
CuO or ZnO
None
-
None
i
„.
-
REMARKS
Recovery by water
scrubbing and dehy-
' dration
By-products: dimethyl-
ether, higher alcohols
Co-products acetalde-
hyde, formaldehyde,
acetone, misc.
oxygenated HC
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Methyl Ethyl
Ketone
Methyl Isobutyl
Carbinol
.
Methyl Isobutyl
Ketone
Nitrobenzene
Nitroparaffins
Nonene
Oxo Alcohols
Pentaerythritol
FEEDSTOCK
*
1 . Sec-Butanol,H
2 . n-Butylene , Air
' or °2
3. By product in
acetic acid
process #3
1 . Acetone, H,
1. Acetone, H0
1 . Benzene, HNO-
1. Propane, HNO,
1 . Propylene
1 . Olefins, CO,H2
1 . Formaldehyde ,
Acetaldehyde
REACTION SEQUENCE
v.p. dehydrogenation
OR
.p. dehydrogenation
.p. oxidation
*
..p. adol condensation
.p. dehydration
v.p. hydrogenation
Same as process for
methyl isobutyl carbinol
. .p. nitration
v.p. nitration
Trimerization - same as
process for Dodecene
l.p. hydrocarboxylation
l.p. or v.p. hydrogenation
l.p. condensation-reduc-
tion 2 stages
TEMP-.
(° C)
380
150
20-100
5-25
95.
-
200
.
.35- 70
400-425
130-175
100-150
30-45
55
PRESSURE
(psig)
— 0
-
-
-
~ 0
-
^- 0
_
~o
-
1,500-4,000
575-1,160
r
"
CATALYSTS
ZnO or Cu,Ni
•
Ni
PdCl3,CuCl2
Caustic
Sodium acid phos-
phate
Cu or Ni on pumic
H2S04
Thermal
Cobalt
hydrocarboxyl
Ca(OH) or NaOH,
sometimes Cu
REMARKS
*
By-product Methyl
isobutyl ketone
By-product methyl
isobutyl carbinol
Continuous or batch
process
Mixed nitroparaffins
formed
pH 9.0-9.5
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PROD.DCT
Phenol
Phthalic Anhy-
dride
FEEDSTOCK
1 . Benzene, Cl,,
' NaOH
2. Benzene, H SO, ,
NaOH,
Lime, Na9SO,
z o
3. Benzene, air,
HC1
4. Cumene, 'air
5 . Toluene, air,
steam
6. Benzene, air
7. Cyclohexane,
air, H
1. Naphthalene, air
2 . o-Xylene , air
.
REACTION SEQUENCE
l.p. chlorination
l.p. hydrolysis
l.p. acidification
l.p. sulfonation
l.p. neutralization w/
Na SO and lime
l.p fusion w/NaOH
l.p. acidification
v.p . oxychlorination
v.p. hydration
l.p. oxidation
l.p. fission
••
l.p. oxidation to benzoic
acid
l.p. oxidation-hydrolysis
v.p oxidation
l.p. oxidation
l.p. dehydrogenation
v.p. oxidation
OR
v.p. oxidation
Same as; #1 but w/catalyst
variations
OR
TEMP.
(° C)
60- 70
370-400
-
-
-
335-340
_
250-270
480-500
110-130
45- 65
121-176
221-243
500
400-500
350-385
PRESSURE
(psig)
-
4000
-
-
-
-'
-
_
-
"-0
~0
30
~o
-
-
-
.
CATALYSTS
FeCl3 .
-
-
oxides of Al , Cu, Fe
Ca3(P04)2
Cu porphyrins
H2S04
Co
Cu •+ Mn or Mg
Co or AgNO, or
V2°5
Pt
V2°5
V205+K '
REMARKS
By-products: dichloro-
benzene, diphenyl,
diphenyl oxide
*
By-product: sodium
sulfite
Polychlorinated
benzene by-products
Main by-product:
acetone minor:
methyl styrene,
acetophenone
Benzene can be
hydrogenated to
.cyclohexane as
alternate scheme
Fixed bed
Fixed or fluidized bed
-------
I-B. PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Phthalic Anhydride
(Cont.)
Propylene Glycol.
Propylene Oxide •
Styrene
Terephthalic Acid
FEEDSTOCK
•
. . Propylene oxide,
. Propylene, C17,
H2O, lime
2. Butane/ Propane,
air
.'. Ethylbenzene
1 . p-Xylene, HNO
2. p-Xylene, air
3 . p-Xylene , sulfur
4. -p-Xylene,air,
Methanol
5. Potassium
phthalate, CO,
6. Toluene, Formal-
dehyde ,
lime, HNO,
vJ
REACTION SEQUENCE
.p. oxidation
l.p. hydration
l.p. chlorohydrination
.p. dehydrochlorination
See Acetaldehyde process
#3 '
v.p. dehydrogenation
l.p. oxidation
. . p . oxidation
..p. oxidation
L.p. oxidation
l.p. esterification w/
methanol
l.p. oxidation
l.p.. isomerization
l.p. chloromethylation w/
l.p. saponificationw/lime
l.p. oxidation w/HNO.,
o
l.p. esterification
TEMP.
C°c)
190-200
50- 70
35
90-b.p.
-
520
200
190-200
315-360
140-160
b.p.
200-215
380-420 .
70
125
160-180
PRESSURE
(psig)
to maintain
l.p.
0
0
- -
400
to maintain
l.p.
2,500-6,000
200
-
-
720-1,455
— -
280
CATALYSTS
Br, Mn salts
H2S04
-
-
ZnO or Mg & Fe
oxides
Mn acetate, NH Jr
None
Co toluate
HCl
Co toluate
Cd salts
-
-
REMARKS
Dipropylene & mono-
propylene glycols as
by-products
By-prod: propylene di-
chloride, chloroiso-
propyl ethe'r
Occurs as by-product
"Aqueous NH, solvent
o-Phthalic acid
by-product
-------
I-B PRODUCTION OF COMMON INTERMEDIATE PETROCHEMICALS (Continued,
PRODUCT
Terephthalic
Acid (Continued)
Tetrachloroethy-
lene
Toluene Diiso-
cyanate
Urea .
Vinyl Acetate
Vinyl Chloride
FEEDSTOCK
7. Potassium
benzoate
8. Potassium ortho
or isophthalate
1 . Propylene,Cl2
2. Ethylene, CU
3 . Ethylene dich-
loride, C12
4. P.entachloroeth-
ane
5 . Carbon tetra-
chloride
1 . Toluene,
chlorine, H
HNS03'
1. C02, NH3
1 . Acetic acid,
acetylene
2 . Acetic anhydride
Acetaldehyde
1 . Ethylene
dichloride
2. Acetylene, HC1
REACTION SEQUENCE
v.p. conversion
v.p. conversion
v.p. chlorinolysis
v.p. chlorination
v.p. chlorination - de-
hydrochlorination -
dehydrochlorination
decomposition
Nitration of toluene
hydrogenation to dicimino-
toluene
phosgenation -
v.p. carbonate formation
dehydration
v.p. esterification
l.p. formation of ethyli-
dene diacetate
l.p. decomposition
v.p. dehydrochlorination
v.p, hydrochlorination
,
TEMP.
410-430
410-430
400-500
600-650
-
-
140
140-150
160-200
170-200
110-120
-
500
100-180
PRESSURE
(psig) .
132-205
29-103
-
-
-
-
2,780-4,000
1,900-2,180
-
-
—
7-15
-
\
CATALYSTS
Cd
Cd
Thermal
Thermal
• -
Thermal
-
Thermal
Zn Acetate
H2SQ4
Benzene sulfonic
acid /
-
HgCl2
REMARKS
Benzene by-prod .
-
CC14, HC1 by-products
HC1 by-product
HC1 by-product
"
HC1 , 2 , 6-diisocyanate
by-products
Exothermic reaction
Acetic anhydride •
solvent
HC1 by-product
-------
I-B PRODUCTION OF COMMON IHTEKMEDIATE PETROCHEMICALS (Continued)
PRODUCT
Vinylidene
Chloride
v.p. vapor ph
l.p. liquid p
(-) indicate
b.p. boiling
FEEDSTOCK
. . Vinyl chloride or
dichloroethane ,
lime or NaOH
se
ase
data not available
oint
REACTION SEQUENCE
chlorination to
1, 1, 2-trichloroethane
. p . dehydrochlorination
w/lime or NaOH
TEMP.
(° C)
98- 99,
PRESSURE
(psig)
_
CATALYSTS
_
'
REMARKS
By products: NaCl
w/NaOH,HCl w/lime
-------
I-C
SOME PROCESSES FOR THIRD-GENERATION PETROCHEMICALS
(Polymers, final products, etc.)
PRODUCT'
Ammonia
Butyl Rubber
Carbon Black.
Melamine
Nitrile Rubber
Neoprene
Cis-Polybutadi-
ene
Polybutenes (ISO
FEEDSTOCK
1 . Synthesis gas
1 . Isobutylene ,
isoprene, methyl
chloride
1 . Aromatic oils ,
air, fuel gas
1. Urea
1 . Butadiene ,
acrylonitrile
1 . Chloroprene
1. 1 ,3 -Butadiene
Benzene , antioxi-
dant, modifier,
short-stop agent
1 . i-Butylene
REACTION' SEQUENCE
v.p. shift conversion
(catalytic) (2 -stages)
v.p. gas purification.
v.p. synthesis (cataly-
tic)
l.p. polymerization
(catalytic)
l.p. purification
v.p. cracking (thermal)
v.p. decomposition
v.p. conversion (catal-
ytic)
l.p. polymerization
(catalytic)
l.p. emulsification
l.p. polymerization
(catalytic)
l.p. polymerization
OR
l.p. polymerization
l.p. polymerization
TEMP.
<°c>
340-455
205-260
-95
1,320-
1,600
350
400-450
<27
38
38
20-50
5-40
-
PRESSURE
(psig)
2,000-9,000
0
0
0
0-130
0
0
0
0
0
0
CATALYSTS
-
none
—
.
none
Al -organic, Co
Aluminum chloro-
. hydrile etherate ,
A1I3, TiCl4
A1C13
' REMARKS
1st stage
2nd stage -
CO_ removed
Hydrocarbons recycled
CH , acetylene ,
CO, , CO , water by-
products
NH_ is used as
carrier gas
Reaction takes place
in soapy water sol.
Regulating chemicals
added
Light polymers , €4
hydro-carbon by--
product
-------
I-C SOME PROCESSES FOR THIRD GENERATION PETROCHEMICALS (Continued)
(Polymers, final products, etc.)
- - PRODUCT
Polycarbonates
Polyethylene
(low density)
Polyethylene
Polypropylene
Polyisoprene
Polyolef in Copoly-
mers; Ethylene -
Propylene
Styrene-Butadiene
Sulfur
v.p. vapor
l.p. liquic
(-) indie*
FEEDSTOCK
1. Bisphenol-A,
phosgene,
• pyridine, sol-
vent
1. Ethylene
1. Ethylene
1 . Propylene
1. Isoprene, ali-
phatic hydro-
carbon
1. Propylene, ethy-
lene
1. Styrene, buta-
diene" (oil/car-
bon black)
1. Acid gas (H S)
phase
phase
tes data not availa
REACTION SEQUENCE
l.p. polymerization
l.p. polymerization
(catalytic)
l.p. polymerization OR
.l.p. polymerization OR
l.p. polymerization
l.p. polymerization
l.p. polymerization
l.p. polymerization
l.p. polymerization -
cold
hot
v.p, partial oxidation
v.p. reaction of SO.
with H2S
OR
v.p. oxidation
TEMP.
38
150-250
50-75
150-180
200-260
80-95
5-40
5
27
-
-
PRESSURE
(psig)
0
14,600-
32,500
25-150
500
500-1,000
25-50
0
500-1,000
0
0
-
-
CATALYSTS
-
peroxides
Al-alkyl,TiCl,
Cr2 3 on Si02-Al203
MoO- on A120,
Al-alkyl, TiCl3
TiCl^, Al -organic
metal oxides
(Al, V)
•
None
None
Bauxite
REMARKS
Pyridine hydrochlorine
by-product
Oxygen is Initiator
HC suspension medium
HC suspension medium
HC suspension medium
HC suspension medium
Soap 'solution used
as solvent
-
SO^ by-product
-------
APPENDIX II
Major Petrochemical Products and Wastes Profile
(Reference VIII - 7)
-------
ACETALDEHYDE
Present Producers Capacity*
Celanese, Bay City, Texas
Celanese, Bishop, Texas
Celanese, Clear Lake, Texas
Celanese, Parapa, Texas
Eastman,'Kingsport, Tennessee
Hercules, Parlin, New Jersey
Publicker, Philadelphia, Pa.
Union Carbide, various locations
Others
Total Ij832
*million pounds
Production
1968: 1,600 million pounds
1973: 1,950 million pounds
Uses
Acetic acid and anhydride, n-butanol, 2-ethylhexanol
Process
Acetaldehyde is produced from
1) Hydration of acetylene
C2H2 + H20 CH3CHO
2) Oxidation of Ethyl Alcohol
C H OH + 1/2 0 — CH CHO + HO
3) Oxidation of lower paraffin (propane and butane)
4) Oxidation of ethylene via the Wacker process
CH CH + PdCl + H20 »• CH3CHO + Pd + 2HC1
Pd + 2HC1 = 1/202 —- PdCl2 + H20
The Wacker process is the only major process being installed today
and it is anticipated that future expansions will be based on this
route.
Waste Problems
A typical Wacker process discharges about 1,200 gallons per ton of
product. The composition of the waste stream is primarily chlorinated
aldehydes with a COD in the order of 10,000 mg/1. This is based on
-------
a yield of 95 percent. The waste is difficult to treat biologically
unless it is diluted with others waters. In addition, it is quite
acid and runs around pHtwo. It is to be noted that several facilities
handle these wastes by means of a deep well rather than by biological
treatment.
Reduction in Waste Loading by Process Change
It is possible by means of a rather simple still design change to
concentrate the waste stream so as to reduce the discharge to 150-
200 gallons/ton of product. No reduction in organic loading is
produced and this approach is only practiced in those cases where
deep well disposal or incineration is planned. The process change
costs about $50,000 in a typical 200,000,000 pounds/year facility.
The only possible means of reducing the organic load center around
recovery and use of the chlorinated aldehydes, dechlorination of the
aldehydes or improvements in yield. The latter is where emphasis
is placed. It is expected that the average yield will reach 97
percent in five years thereby reducing organic loading by about 40
percent.
ACETIC ACID AND ANHYDRIDE
Acid Producers Capacity*
Borden, Geismer, La. 100
Celanese, Bishop, Texas 200
Celanese, Pampa, Texas 500
Eastman, Kingsport, Tennessee 325
Hercules, Par1in, New Jersey 40
Publicker, Philadelphia, Pa. 80
Union Carbide, Brownsville, Texas 500
Union Carbide, S. Charleston, W. Va. 140
Union Carbide, Texas City, Texas 100
Total 1,985
^million pounds/year does not include by-product and fermentation
acetic acid which amounts to 100,000,000 pounds.
Production
1968: 1,700 million pounds
1973: 2,500 million pounds
Uses
Cellulose acetate, vinyl acetate, acetic esters, chloroacetic acid
-------
Process
Acetic acid is produced:
1) by oxidation of acetaldehyde,
2) from ethanol,
3) by LPG oxidation (liquified petroleum gas), and
4) from methanol and carbon monoxide.
The most popular technique in use is the oxidation of acetaldehyde
while production from ethanol is only of minor importance. The
Reppe method, from methanol and CO, is the newest method (developed
by BASF) and appears to be gaining favor in this country. In the
future it is expected that processes based on acetaldehyde and
methanol will predominate in the production of acetic acid and
anhydride.
Waste Problems
LPG oxidation results in the production of substantial amounts of
other acids such as formic and propionic which must be disposed of
by incineration, resale or biological oxidation. Unfortunately,
resale of these materials does not appear to be practical because the
markets for these chemicals are quite limited. Waste flow for this
system is in the order of 1,000 gal Ions/ton of product and the
organic concentrations are in excess of 30,000 mg/1. In some opera-
tions, the stream is neutralized (it usually runs at pH 4) with
caustic and the sodium salts of the acid are recovered. Treatment
by a number of means is routine. Biological modes are quite adequate.
Oxidation of acetaldehyde also produces higher acids and other
oxidized species in quantities somewhat less than produced by LPG
oxidation. Water flows are of the same magnitude, but organic load
is about 50 percent of the load generated by the oxidation of LPG.
In the Reppe process, about 80 pounds of organics (50 percent propionic
acid and 50 percent higher organics) are produced in the liquid waste
stream per ton of product. The liquid stream amounts to about 50
gallons per ton of product including drains.
Reduction in Waste Loading by Process Change
The changes in process do not appear to change the nature of the
wastes generated by the production of acetic acid or the quantity of
the waste. Further,the amounts and character of the waste would not
appear to create serious waste treatment problems or expenditures.
There will be improvements in the yield picture which will certainly
assist in reducing the waste management problems, but it is not antici-
ated that any changes will radically change the waste situation.
-------
ACETONE
Producers Capacity*
Allied, Frankford, Pa. 150
Celanese, Bishop, Texas 35
Chevron, Richmond, Calif. 35
Clark, Blue Island, Illinois 30
Eastman, Kingsport, Tennessee 60
Enjay, Linden, New Jersey 110
Hercules, Gibbstown, New Jersey 30
Monsanto, Alvin, Texas 75
Shell, Dominquez, Calif. 150
Shell, Houston, Texas 210
Shell, Norco, La. 100
Skelly, El Dorado, Kansas 30
Union Carbide, Institute, W. Va. 120
Union Carbide, Bound Brook, N. J. 90
Union Carbide, Texas City, Texas 130
Union Carbide, Whiting, Indiana i/U
Total 1,475
*mil lions of pounds per year
Production
1968: 1.3 billion pounds
1973: 1.8 billion pounds
Uses
Methyl isobutyl ketone and carbinol, Methyl acrylate, bisphenol A,
paint, lacquer and varnish solvent, cellulose acetate solvent.
Processes
Currently there are three major processes utilized for the production
of acetone.
There are
a) dehydrogenation of isopropyl alcohol,
CHOH - - (CH) CO + H
b) by-product from the production of phenol fromcumene, and
C6H5OH + C3H6°
c) direct oxidation of propylene.
CHCH = CH + 1/20
-------
It is expected that a major portion of the acetone will continue
to be produced from cumene as a phenol by-product. It seems likely
that direct oxidation of propylene will gain asendency relative to
the production from isopropyl alcohol.
Waste Problems
The processes based on isopropyl alcohol dehydration produce about
200-250 pounds of organics per ton of product. These consist of
still bottoms (0.5 percent organics) principally. The nature of the
organics is somewhat complex but may include acetone, unreacted
alcohol and higher polymeric species. The amount of wastewater
depends in part upon the amount of cooling water utilized as well
as the frequency of equipment cleaning. It is also important to
note that the process utilizes either metallic copper or zinc
acetate as a catalyst and catalyst cleanup could put significant
amounts of these materials into the water course or to treatment.
Direct oxidation results in a yield of 93 percent which in turn
produces less than 80 pounds per ton of product as an organic load
within the system. Water load varies, but exclusive of cooling water,
amounts to about 750 gal/ton. The regeneration of the cupric
chloride catalyst may cause difficulty.
Waste Reduction by Process Change
The utilization of direct oxidation will greatly reduce the amount
of organic discharge both when directly compared with isopropyl
alcohol based processes and when considering the additional waste
generated by the production of isopropyl alcohol. Therein lies
another key factor in the evaluation of trends in the chemical
industry. The desire to reduce the number of processing steps
both to reduce direct operating costs and to increase yield generally
results in greatly reduced waste loads.
It is possible through careful control and operation of the still
to greatly reduce the amount of acetone in the still bottoms. These
costs are generally minor relative to the value of the recovered
acetone but must be the result of a conscious management effort.
ACETYLENE
Producers Capacity*
Diamond, Deep Park, Texas 4-0
Dow, Freeport, Texas ^
Monochem, Geismer, La.
Monsanto, Texas City, Texas 10°
Rohm and Haas, Deep Park, Texas 35
-------
Producers Capacity*
Tenneco, Houston, Texas 100
Union Carbide, various locations 150
Total 650
^millions of pounds per year
Production
1968: 610 million pounds
1973: 630 million pounds
Uses
Vinyl chloride, vinyl acetate, neoprene, acrylates and acrylonitriles
Processes
Acetylene is produced from two major sources in the United States.
About 50 percent of the acetylene is produced by the reaction of
calcium carbide and water.
CaC2 + 2H20 - *-G2H2 + Ca(OH)2
The second process involves the partial oxidation of natural gas.
Other approaches involve the pyrolysis route as shown below as
typified by the Wulff process,
CO
2CH, ~~~ C_HL 4" 3H«
It is unlikely that many changes will occur with regard to the
production of acetylene in this country unless someone comes up with
a process with greatly reduced production costs which would have the
effect of bringing the cost of acetylene close to the cost of
ethylene. It this does not occur, it will not be possible for
acetylene to maintain many markets in the face of ethylene.
Waste Problems
The major waste associated with the production of acetylene from
calcium carbide is the lime slurry residue.
However, the hydrocarbon processes do generate large amounts of
water borne wastes. These quantities are quite variable and depend
upon the feedstock, the degree of pyrolysis, the ratio of acetylene
to olefins produced, etc.
-------
The wastes arise from the gas cooler and the scrubbing of the higher
concentrations of tars and oils and are quite difficult to treat in
conventional biological treatment facilities. Incineration is
usually used to burn soot oil, soot water, and organic tars.
Waste Reduction by Process Change
The key factor in waste management in the production of acetylene
from hydrocarbons centers around the control of the cracking
furnaces to maximize the production of valuable products. Improve-
ments in the difficult-to-optimize reaction system are keys to the
success of the process but quite difficult to improve. Since
efficiencies have been known to run as low as 40-50 percent, it is
not surprising that efficiency improvement is vital to the process.
This is the key process change which can be implemented and returns
from this operation are tremendous relative to production of costs.
Further, recoveries of waste products in burnable form is also
vital to the effective operation of the unit. In some operations, a
solvent is used to recover the acetylene. Solvent losses may be
significant and add to the dimensions of the waste treatment problem.
Careful selection of the solvent, and improved design of the vacuum
stripper should assist in reducing solvent losses.
ACRYLATES
Producers Capacity*
Celanese, Pampa, Texas
Dow, Freeport, Texas
Goodrich, Calvert City, Kentucky
Minnesota Mining, St. Paul, Minn.
Rohm and Haas, Deer Park, N. J.
Union Carbide, Taft, La.
Union Carbide, Institute, ¥. Va.
Total 543
^million of pounds/year
(a) 120 million pounds to be added by 1969
(b) Taft facility completed by October, 1968;
Institute may be retired
Production
1968: 240 million pounds
1973: 400 million pounds
Uses
Paint latices, textiles, acrylic specialities, acrylic fibers
-------
Processes
The major process involved in the production of acrylates is the
oxidation of acetaldehyde.
Waste Problems
Waste streams associated with this operation are generally composed
of polymerization and degradation.
The flow rate is about 1,500 gallons per ton of product with organic
concentrations about 10-20,000 mg/1. Yields in this process
could be improved thereby reducing waste problems. A number of
waste streams and gas vents are often incinerated. Extension of this
practice would reduce the amount of wastewaters to be treated.
Waste Reduction by Process Change
Considerable efforts are underway to improve yields and this should
result in lower wastewater discharge.
AMMONIA
Major Ammonia Producers (600 TPD and up)
Producer Capacity'
Air Products, Michoud, La. 600
Allied, Geismar, La. 1,000
Allied, Hopewell, Va. 1,000
Apple River, E. Dubuque, Illinois 700
American, Texas City, Texas 2,100
American Cyanamid, Avondale, La. 1,000
Arkla, Helena, Arkansas 600
Borden, Geismar, La. 900
Central Farmers, Donaldsonville, La. 1,000
Chevron, Pascagoula, Miss. 1,500
Coastal, Yazoo, Miss, 1,000
Collier, Brea, California 750
Collier, Cook Inlet, Alaska 1,500
Commercial Solvents, Sterlington, La. 1,000
Consumers, Fort Dodge, Iowa 600
Continental, Blytheville, Arkansas 1,000
duPont, Beaumont, Texas 1,000
duPont, Belle, W. Va. 1,000
Farmland, Dodge City, Kansas 600
First Mississippi, Donaldsonville, La. 1,000
First Nitrogen, Donaldsonville, La. 1,000
Gulf, Borger, Texas 1,000
Mobil, Beaumont, Texas 750
Monsanto, Luling, La. 1,000
-------
Producer Capacity*
Olin-Mathieson, Lake Charles, La.
Phillips, Beatrice, Neb.
Sinclair, Ft. Madison, Iowa
Terra, Port Neal, Iowa
U. S. Steel, Clairton, Pa.
Valley Nitrogen, El Centre, Calif.
Total 29,550
*Tons/Day
Production
1968: 14,200,000 tons/year
1973: 20,000,000 tons/year
Uses
Fertilizers, urea, nitric acid
Processes
Ammonia is produced from syhthesis gas (CO + KL) under conditions
of relatively high temperatures and high pressure. Synthesis gas
is produced primarily by the steam reformation of natural gas or
other hydrocarbon sources as shown below:
CH4 + H20 »- CO + 3H
During the reformation, air is added to provide additional energy
for the endothermic reformation reaction. The air also provides
N2 f°r ammonia formation. The CO is converted to C02 and removed.
Conversion to ammonia then takes place:
The major change in processing technology which has taken place
recently has been the development of large single train ammonia
plants of capacities as high as 1,500 tons/day. This trend is
expected to continue. These plants produce large point source
concentrations of ammonia and carbon dioxide. However, these large
streams have made the recovery of ammonia practical.
Waste Problems
The major streams arising from an ammonia plant are process condensate
and site drains. The flow and waste produce loads are as listed
below:
Flow (Gals/Ton of product) 30°
NH3 (Lbs/Ton) O-1
-------
NH,HCCL (Lbs/Ton) 0.1
4 3
MEA (Monoethanolamine)
(Lbs/Ton) 0.2
CO (Lbs/Ton) 0.7
Normal practice in this country is to either strip the ammonia or
to release the discharge untreated although it is anticipated that
this practice cannot be continued in the future.
Waste Reduction by Process Change
It is possible to reduce the ammonia loss by some 60 percent by
adjusting pH and airstripping. About 0.1 pounds of NaOH is added
per ton of product. This is normal practice. It is possible to
remove greater amounts of NH3 (90-95 percent) by increasing the air
flow to perhaps 500-1,000 scf/gal. Following the normal industry
practice cost of the stripper and condenser is about $60,000 for
a 1,200 ton/day plant. The cost of removing additional quantities
of ammonia have not been calculated since no plants practicing this
extreme approach have ever been built.
BENZENE
Producers Capacity*
Allied, Winnie, Texas 4
Amoco, Texas City, Texas 15
Ashland, N. Tonawanda, N. Y. 10
Ashland, Catlettsburg, Ky. 20
Atlantic-Richfield, Wilmington, Calif. 18
Atlas, Shreveport, La. 10
Chevron, El Segundo, Calif. 25
Chevron, Richmond, Calif. 10
Continental, Lake Charles, La. 6
Continental, Ponca City, Okla. 6
Cosden, Big Spring, Texas 9
Crown Central, Houston, Texas 38
Dow, Bay City, Mich. 20
Dow, Freeport, Texas 30
Enjay, Baton Rouge, La. 24
Enjay, Baytown, Texas 55
Gulf, Philadelphia, Pa. 27
Gulf, Port Arthur, Texas 32
Hess, Corpus Christi, Texas 30
Leonard, Mt. Pleasant, Mich. 3
Marathon, Texas City, Texas 6
Mobil, Beaumont, Texas 30
Monsanto, Alvin, Texas 65
Phillips, Sweeny, Texas 22
-------
Producers Capacity*
Pontiac, Corpus Christ!, Texas 9
Shell, Houston, Texas 3^
Shell, Odessa, Texas 20
Shell, Wilmington, Calif. ^5
Shell, Wood River, Illinois 30
Signal, Houston, Texas 22
South Hampton, Silsbee, Texas 6
Sun, Marcus Hook, Pa. 15
Sunray DX, Tulsa, Oklahoma 22
Suntide, Corpus Christi, Texas 25
Tenneco, Chalmette, La. 15
Texaco, Port Arthur, Texas 30
Union Carbide, S. Charleston, W. Va. 10
Union Atlantic, Nederland, Texas 18
Union Oil, Lemont, Illinois 22
Vickers, Potwin, Kansas 3
Total from Petroleum Feedstocks 809
Total from 18 Cokeoven Producers and
3 Tar Distillers 142
Grand Total 951
Cities Service, Lake Charles, La. 55
Coastal States, Corpus Christi, Texas 6
Gulf, Port Arthur, Texas 25
Southwestern, Corpus Christi, Texas 6
Texaco, Port Arthur, Texas 15
Total announced new capacity 107
Grand Total, all United States Capacity 1,058
-'millions of gallons/year
Production
1968: 900 million gallons
1973: 1,350 million gallons
Uses
Styrene, phenol, cyclohexane, detergent, aniline, Maleic acid, DDT
Processes
About 60 percent of United States benzene is produced by recovery
(together with toluene and xylenes) from refinery reformers while an
additional 20 percent is produced from the dealkylation of toluene.
Coal, tar, coke oven light oils, and ethylene drip oils account for
-------
the remainder. It is expected that refinery based benzene will grow
more rapidly than other sources. Naphthalene is similar.
Waste Sources
The major sources of wastewater in the recovery of benzene, xylenes,
and toluene from refinery reformate are two-fold. First, cooling
waters tend to pick up between 50-200 ppm of COD in the form of
aromatics because of heat exchanger leaks. The quantity and
quality of wastewater arising from this source will depend upon the
cooling system and will in general be associated with other cooling
waters.
The aromatics are separated from the paraffins by extraction with
aqueous diethylene glycol. Discarding of this solvent stream in
order to control impurity buildup results in a waste stream containing
aromatics and diethylene glycol. Here improvements in stripper
design and careful control of blowdown from the solvent cycle will
assist in greatly reducing wastewater discharges.
Waste Reduction by Process Change
This control is possible primarily by (1) close maintenance of heat
exchangers, (2) yield improvements, and (3) stripper design.
BUTADIENE
Producers Capacity*
Chevron, El Segundo, Calif. 16,000
Copolymer, Baton Rouge, La. 60,000
Dow, Freeport, Texas 45,000
El Paso, Odessa, Texas 45,000
Enjay, Baton Rouge, La. 75,000
Enjay, Baytown, Texas 33,000
Firestone, Orange, Texas 110,000
Goodrich-Gulf, Port Neches, Texas 160,000
Mobil, Beaumont, Texas 25,000
Monsanto, Alvin, Texas 50,000
PCI (Cities Service), Lake Charles, La. 80,000
Petro-Tex, Houston, Texas 275,000
Phillips, Borger, Texas 112,000
Shell, Torrance, Calif. 70,000
Sinclair, Channelview, Texas 121,000
Texas-U.S., Port Neches, Texas 160,000
Tidewater, Delaware City, Del. 10,000
UCC, Seadrift, Texas; Ponce, P.R. 105,000
Total 1,577,000
*Tons per year
-------
Production
1968: 1.50 million tons
1973: 1.80 million tons
Uses
Styrene-butadiene rubber, polybutadiene rubber, adiponitrile,
nitrile rubber, S-B and A-B-S plastics
Processes
Butadiene is produced from three major sources:
1) dehydrogenation of n-butylenes,
2) dehydrogenation of n-butane,and
3) as a by-product of ethylene production
It is anticipated that by-product production will increase rapidly
because of the expected rapid increase in ethylene production .
Waste Problems
Waste flows from butadiene production facilities amount to some
100 gals/ton of product with waste compositions as follows (taken
from one source only):
pH 8-9
TOG 100-200 mg/1
filtered COD 250-375 mg/1
suspended solids 200-500 mg/1
total solids 3,000-4,000 mg/1
(sulfates and chlorides
principally)
Waste Reduction Through Process Modification
Little information is available regarding possible process
modifications.
BUTANOL
Producers Capacity*
Celanese, Bishop, Texas 125
Continental Oil, Westlake, La. 5
Dow-Badische, Freeport, Texas 15
Eastman, Longview, Texas 60
-------
Producers Capacity*
Shell Chemical, Houston, Texas 50
Union Carbide, various locations 240
Total 495
^millions of pounds annually
Production
1968: 500 million pounds
1973: 620 million pounds
Uses
Glycolethers and amine resins, solvent, n-butyl acetate, plasticizers
Process
Butanol is produced by the oxidation of LPG or other petroleum
streams.
Waste Problems
Waste streams arise primarily from the still discharges following the
separation of various products together with wastes resulting from
catalyst and vessel cleanouts. Cooling waters also contain consid-
erable wastes. Wastewaters discharged amount to several hundred
gallons per ton of product while organic discharges amount to 100-
300 pounds/ton of product.
Waste Reduction by Process Change
The waste problems of this process involve the low efficiency and
rather drastic conditions under which the reaction takes place.
Improvements in yields and improvements in still efficiencies would
improve the situation. Further provisions can be made for the
collection and direct incinerations of still bottoms, vessel cleanout
wastes, etc., without contamination of the wastewaters.
A number of waste streams may be either sent to additional strippers
or vented to gas burners. The costs of such controls amount to
some $250,000-$500,000 for an 80 million pound/year plant and will
reduce the waste load by 25-50 percent.
CARBON MONOXIDE AND HYDROGEN (SYNTHESIS GAS)
See Ammonia
-------
CARBON TETRACHLORIDE AND OTHER CHLORINATED HYDROCARBONS
Carbon Tetrachloride:
Producers
Allied, Moundsville, W. Va.
Diamond, Painesville, Ohio
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
Dow, Plaquemine, La.
FMC-Allied, S. Charleston, W. Va.
Stauf fer, Le Moyne, Alabama
Stauffer, Louisville, Ky.
Stauffer, Niagara Falls, N. Y.
Volcan, Wichita, Kansas
Total
""millions of pounds per year
Chloroform:
Producers
Allied, Moundsville, W. Va.
Diamond, Belle, W. Va.
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
DuPont, Niagara Falls, N. Y.
Stauffer, Louisville, Ky.
Vulcan, Newark, N. J.
Vulcan, Wichita, Kansas
Total
^millions of pounds per year
Methylene Chloride:
Producers
Allied, Moundsville, W. Va.
Diamond, Belle, W. Va.
Dow, Freeport, Texas
Dow, Pittsburg, Calif.
DuPont, Niagara, Falls, N. Y.
Stauffer, Louisville, Ky.
Vulcan, Newark, N. J.
Vulcan, Wichita, Kansas
Total
%iil lions of pounds per year
Capacity'"
8
35
130
30
20
200
85
70
125
25
728
Capacity*
30
20
75
1
1.5
75
6
16
238
Capacity*
50
30
85
20
60
70
20
20
355
-------
Methyl Chloride:
Producers Capacity"
Allied, Moundsville, W. Va. 17
Ancon, Lake Charles, La. 100
Dow, Freeport, Texas 100
Dow, Pittsburg, Calif. 20
Dow Corning, Midland,, Michigan 10
Dow Corning, Carrollton, Kentucky 20
DuPont, Niagara Falls, N. Y. 76
Ethyl, Baton Rouge, La. 75
General Electric, Waterford, N, Y. 24
Vulcan, Newark, N. J. 2
Total 454
^millions of pounds per year
Production
CC14 CHC13 CH2C12 CH3C1
1968: 700 200 265 240
1973: 900 300 400 370
Use
Fluorocarbons, solvents
Process
These chlorinated methanes are produced by the reaction of chlorine
with methane and then are separated by fractionation. Carbon
tetrachloride is also produced by the reaction of hydrogen chloride
with carbon disulfide.
Waste Problems
The major waste stream results from the production of hydrogen chloride
as a by-product of the reaction.
Waste Reduction by Process Change
The main need is for routes to the economic recovery of chlorine
from hydrogen chloride or through the reuse of hydrogen chloride.
A number of new oxychlorination processes have recently been
developed which enable the user to utilize hydrogen chloride together
with chlorine in a balanced facility. As an example, for the produc-
tion of carbon tetrachloride:
-------
4HC1
CH4 + 4HC1
This approach eliminates the problem of hydrogen chloride but it
does produce about 60 gallons of wastewater per ton of product
which will contain minor amounts of chlorinated methanes and HC1.
Further, these reactions often have an intermediate step involving
copper chloride and small amounts of this catalyst will be released
to the wastewater. Insufficient data is available to predict rela-
tive waste loads and economics. It is anticipated that process
changes will substantially eliminate the HC1 being generated in these
operations.
CELLULOSE ACETATE
Producers Capacity*
Celanese, various locations 450
DuPont, Waynesb&ro, Va. 60
Eastman, Kingsport, Tenn. 215
FMC, Meadville, Pa. 25
Total 750
Production
1968: 740 million pounds
1973: 850 million pounds
Uses
Fibers, cigarette filters, plastics
Processes
Reaction of wood pulp with acetic acid and anhydride to produce
triacetate, hydrolysis to produce diacetate.
Waste Problems
Major waste sources arise from the stills used to recover acetic
acid and acetone and other solvents. In addition, the wastes contain
considerable amounts of degraded celluloses as well as phosphates
(used as catalyst) and sulfuric acid (from spills). About 3-3.5
gallons of wastewaters are generated with a solid loading of 200 mg/1
and a BOD of 1-3,000 mg/1 depending upon the relationship of flake
to fiber production.
-------
Waste Reduction Through Process Change
There are numerous opportunities for waste reduction in cellulose
acetate production. Among these are the following:
1) recovery and reuse of CA fines,
2) careful pH control in acetone stills,
control of vessel cleanout and acid spills,
3)
4)
improved operation of acetone and acetic acid stills,
use of additional stills to improve recovery, and
5) higher yields on cellulose (wood pulp)
CYCLOHEXANE
Producers
Ashland, Catlettsburg, Ky.
Atlantic Richfield, Wilmington, Calif.
Commonwealth-Shell, Puerto Rico
Continental, Ponca City, Okla.
Continental, Lake Charles, La.
Cosden, Big Springs, Texas
DuPont, Belle, W. Va.
DuPont, Orange, Texas
*millions of gallons per year
Producers
Eastman, Longview, Texas
Enjay, Baytown, Texas
Gulf, Port Arthur, Texas
Phillips, Borger, Texas
Phillips, Sweeny, Texas
Phillips, Puerto Rico
Pontiac, Corpus Christi, Texas
Signal, Houston, Texas
South Hampton, Silsberg, Texas
Texaco, Port Arthur, Texas
Union Oil, Smith's Bluff, Texas
Total
"millions of gallons per year
Production
1968: 310 million gallons
1973: 570 million gallons
Capacity*
30
15
30
80
8
15
15
Capacity"
3
40
33
47
53
40
12
17
3
40
33
514
-------
Uses
Nylon 66, Nylon 6
Processes
About 30 percent of the cyclohexane produced in this country is
produced from the fractionation of petroleum. The remainder is
produced by the catalytic hydrogenation of benzene. This latter
process will account for some 85 percent of the cyclohexane produced
in the United States after 1970.
Waste Problems
Outside of spills, the only major source of water is the cooling
water which amounts to 200-2,000 gallons/ton of cyclohexane and
which may contain 50-200 mg/1 of COD. In aromatics extraction,
there are two major sources of wastewater, the extract water washing
which contains aromatic hydrocarbons and the wastes from solvent
degeneration which contain appropriate solvents. Both wastes may
be minimized by the use of stripping columns.
Waste Reduction by Process Change
No forseeable changes in process will have any significant impact
upon wastewater discharges except for the replacement of once-
through cooling with cooling towers. However, once-through cooling
is generally not utilized in cyclohexane facilities.
CUMENE
Producers Capacity'"
Amoco, Texas City, Texas 50
Ashland, Catlettsburg, Ky. 300
Chevron, Richmond, Calif. 80
Clark, Blue Island, Illinois 100
Coastal States, Corpus Christi, Texas 100
Dow, Midland, Michigan 10
Gulf, Philadelphia, Pa. 400
Gulf, Port Arthur, Texas 300
Hercules, Gibbstown, New Jersey 60
Marathon Oil, Corpus Christi, Texas 125
Monsanto, Alvin, Texas 130
Shell, Houston, Texas 80
Skelly, El Dorado, Kansas 80
Sunray DX, Corpus Christi, Texas 125
Texaco, Westville, N. J. 140
Total 2,220
^millions of pounds/year
-------
Production
L968: 1.2 billion pounds
1973: 2.2 billion pounds
Uses
Phenol, acetone, oC-methylstyrene
Process
The process for the production of cumene involves a phosphoric
acid catalyzed alkylation of benzene with propylene. No significant
change in this technology is anticipated in the near future.
Waste Problems
The principal waste streams from the manufacture of cumene are the
process slops and the "cumene" bottoms which are a result of the
recovery of cumene from the general process stream. This stream
contains some 1-4 percent of the product stream. The quantity of
water carrying the wastes depends largely upon the use of propane
to control bed temperature.
Waste Reduction Through Process Change
Careful temperature control through propane injection may reduce
the amount of by-products and reduce the amount of water required
in the tower to control this highly exothermic reaction.
ETHANOL
Producer Capacity*
Synthetic (Ethylene)
Enjay, Baton Rouge, La. 60
Eastman, Longview, Texas 25
Publicker, Philadelphia, Pa. 25
Shell, Houston, Texas 40
Union Carbide, S. Charleston, W. Va. 60
Union Carbide, Texas City, Texas 100
USI, Tuscola, Illinois 53
'^millions of wine gallons annually, 190 proof alcohol
Producer Capacity*
Other Industrial
Ga-Pacific, Bellingham, Wash.
Hercules, Hopewell, Va.
-------
Producer Capacity*
Publicker, Philadelphia, Pa., other 20
Total 383
^millions of wine gallons annually, 190 proof alcohol
Production
1968: 299 million gallons
1973: 330 million gallons
Uses
Acetaldehyde, solvent, other chemicals
Process
Two processes are in use to produce ethanol from ethylene. The
first, called the ethyl hydrogen sulfate route follows the following
equation:
Ethyl ether is a by-product.
The second is the Shell or direct hydration process and involves
the temperature and pressure hydration over a phosphoric acid
catalyst:
Waste Sources
The ethyl hydrogen sulfate has numerous waste sources. These include
slops from the recovery and reconcentration of sulfuric acid
(0.05 Ib/lb of product) and the discharge of a caustic waste stream
containing alcohol, ether and waste products from the alcohol
scrubber. This stream may amount to several hundred gallons per
ton of product and contain 1-3,000 mg/1 of COD at a high pH (11).
An additional stream results from the recycling column which removes
the heavy ends, and is an aqueous stream of perhaps 10-30 gals/ton
of product and contains about 5,000 mg/1 of COD.
The direct hydration process involves considerably less waste. The
major stream would result from the separation of the product
ethanol from the process bottoms and may amount to 30-60 pounds
of COD/ ton of product.
-------
Waste Reduction Through Process Change
It is possible to minimize the waste products by careful control
of the use of sulfuric acid in the process and as is often the case,
in the use of acid and alkali, the avoidance of leaks and spills.
Additional stripping capacity and improved yields would also reduce
waste product loads.
ETHYL BENZENE AND STYRENE
Producers (Styrene) Capacity*
Amoco, Texas City, Texas 300
Cosden, Big Spring, Texas 100
Cos-Mar, Carville, La. 500
Dow, Freeport, Texas 550
Dow, Midland, Michigan 350
El Paso, Odessa, Texas 120
Enjay, Baytown, Texas 150
Foster Grant, Baton Rouge, La. 200
Marbon, Baytown, Texas 125
Monsanto, Alvin, Texas 40
Monsanto, Texas City, Texas 750
Shell, Torrance, Calif. 240
Sinclair-Koppers, Houston, Texas 70
Sinclair-Koppers, Kobuta, Pa. 270
*millions of pounds annually
Producers (Styrene) Capacity*
Sinclair-Koppers, Port Arthur, Texas 150
Signal, Houston, Texas 35
Sunray DX, Corpus Christi, Texas 80
Suntide, Corpus Christi, Texas 75
Tenneco, Chalmette, La. 22
Union Carbide, Institute, W- Va. 130
Union Carbide, Seadrift, Texas 3QQ
Total 3,991
*millions of pounds annually
Producers (Styrene) Capacity*
Sinclair-Koppers, Port Arthur, Texas 150
Signal, Houston, Texas 35
Sunray DX, Corpus Christi, Texas 80
Suntide, Corpus Christi, Texas 75
Tenneco, Chalmette, La. 22
-------
Producers (Styrene) Capacity*
Union Carbide, Institute, W. Va. 139
Union Carbide, Seadrift, Texas 390
Total 3j991
^millions of pounds annually
Production (Styrene)
1968: 3.5 billion pounds
1973: 5.0 billion pounds
Uses
Polystyrene, Rubber modified polystyrene, Styrene-butadiene
copolymer, ABS, SAN plastics, Styrene-butadiene elastomer
Processes
About 10 percent of the ethyl benzene is obtained by fractionation
of petroleum streams. The dominant route is via alkylation of
benzene with ethylene. It is expected to continue in this fashion
in the future. There are two alternative routes to ethyl benzene
by alkylation. One involves the use of high purity ethylene while
the other involves the use of low concentration ethylene. It is
expected that the latter will become more prominent in the future.
Styrene is produced from ethyl benzene by the high temperature
dehydrogenation of the ethyl benzene.
Waste Problems
A number of waste streams arise from the alkylation of benzene with
high concentration ethylene. Among these are the caustic and water
washing streams used to wash the crude alkylate which contain 5-
10,000 mg/1 of tars and other polymers together with significant
amounts of ethyl benzene and benzene. The overheads from the benzene
drying column may contain minor amounts of benzene. The residue
from the PEB (polyethyl benzenes) column contain tars and polymers
formed during the process. The total organic burden is in the
order of 30-70 pounds/ton of product.
The process utilizing low concentration ethylene produces primarily
a waste stream containing polymers and tars and amounts to 50-100
pounds of organics per ton of product.
The Styrene producing process condenses a water-styrene-ethyl
benzene mixture and the water leaving this step contains oils as
well as ethyl benzene and styrene.
-------
Waste Reduction Through Process Change
Design of gas washers which improve contact conditions is one key
to the reduction of wastewaters coming from this process (high
concentration). A larger benzene drying column will reduce benzene
losses from this system. The tars and polymers produced from the
final separator could be incinerated rather than sent to a wastewater
system.
ETHYLENE BICHLORIDE. VINYL CHLORIDE AND POLYVINYL CHLORIDE
Producers (Vinyl chloride) Capacity*
Allied, Moundsville, W. Va. 500
American Chemical, Watson, Calif. 170
Conoco-Stauffer, Lake Charles, La. 600
Cumberland Calvert, Calvert City, Ky. 100
Diamond, Deer Park, Texas 100
Dow, Freeport, Texas; Plaquemine, La. 1,000
Ethyl, Baton Rouge, La.; Houston, Texas 300
General' Tire, Ashtabula, Ohio 75
Goodrich, Calvert City, Ky. 800
Goodrich, Niagara Falls, N. Y. 40
Goodyear, Niagara Falls, N. Y. 70
Monochem, Geismer, La. 250
PPG, Lake Charles, La. 300
Tenneco, Houston, Texas 200
Union Carbide, S. Charleston, W. Va. 340
Union Carbide, Texas City, Texas
Wyandotte, Geismer, La. 150
Total 5,150
^millions of pounds per year
Production
1968: 2.7 billion pounds
1973: 4.0 billion pounds
Uses
PVC
Processes
There are several major routes to vinylchloride. Acetylene based
processes employ the use of hydrogen chloride in a direct addition
in acetylene.
CH + HC1
-------
Ethylene processes involve direct chlorination plus dehydro
chlorination
^2^4^2 (ethyle1e dichloride)
HC1
A newer approach involves oxychlorination and permits the reuse of
the HC1 generated during dehydro chlorination (Copper chloride is
the catalyst.)..
C2H4 + 1/2 02 + 2HC1 — C2H4C12 + 1^0
It is expected that all vinyl chloride in the country will be pro-
duced by a balanced chlorination-oxychlorination approach in the
future.
Polyvinyl chloride is polymerized directly from vinyl chloride
using different approaches.
Waste Problems
The vinyl chloride facility generates a waste stream containing
about eight gallons/ton of product and containing minor amounts of
organics (0.01 Ibs/ton) with significant amounts of NaCl, FeCl ,
NaOH , and NaCIO .
The waste stream from the PVC operation is about 2,000 gallons/ton
of product and has a COD of 1,200-1,400 mg/1.
Waste Reduction Through Process Change
The advent of oxychlorination has made a major reduction in waste
problems in the production of vinyl chloride. Waste problems are
quite minor and little promise of change exists. Only minor
pressure exists for the reduction in waste loadings from the PVC
operation although changes in polymerization techniques may effect
changes.
ETHYLENE
Producers Capacity*
Allied-Wyandotte, Geismar, La. 500
American Can-Skelly, Clinton, Iowa 400
Atlantic, Watson, Calif.
Continental Oil, Lake Charles, La.
Dow, various locations snn
DuPont, Orange, Texas °
El Paso-Rexall, Odessa,, Texas 2yu
-------
Producers Capacity*
Enjay, various locations 1,265
Goodrich, Calvert City, Ky. 250
Gulf, various locations 825
Jefferson, Port Neches, Texas 450
Koppers, Kobuta, Pa. 35
Mobil, Beaumont, Texas 450
Monsanto, various locations 750
National Distillers, Tuscola, Illinois 320
Olin-Mathieson, Brandenburg, Ky. 90
Petroleum Chemicals, Lake Charles, La. 360
Phillips, Sweeny, Texas 550
Phillips-Houston Natural Gas, Sweeney,
Texas 550
Shell, various locations 845
Sinclair-Koppers, Houston, Texas 500
Sun Olin, N. Claymount, Del. 125
Texas Eastman, Longview, Texas 450
Union Carbide, various locations 3,975
Total 16,000
*millions of pounds per year
Production
1968: 12,500,000,000 pounds per year
1973: 19,000,000,000 pounds per year
Uses
Polyethylene, ethylene oxide, ethanol, styrene, vinylchloride
Processes
Ethylene is produced from ethane and propane, refinery off-gas and
other sources such as naphtha, gas oil, condensate. The first step
involves cracking, then compression followed by purification.
Ethylene production is an important source of propylene, butadiene,
and aromatics.
Waste Problems
The major waste streams are
1) blowdown from steam cracking,
2) coke and tar in the furnace,
3) compressor water (oily),
4) spent caustic from acid gas scrubbing,
5) water from dryers,
6) green oil produced as a polymerization product during
acetylene hydrogenation, and
-------
g) acidic pH from thermal cracking step.
Typical quantities are:
Spent caustic - 15 gallons/ton of product containing 2.5 percent
NaOH, 1.0 percent Na2S and 6.6 percent ppm of phenols and 1,000 to
2,000 mg/1 of COD.
Waste Reduction by Process Change
The process condensate stream may be reprocessed by being sent to a
stripper and stripped by live steam. This will strip most of the
non-phenol contaminants and about 20-25 percent of phenol. If
fresh feed is contacted with the process condensate, it is possible
to strip out most of the phenol which is then sent with the feed
to the cracking furnace. The phenol free wastewater can then be
steam stripped to remove residual volatile hydrocarbons. The water
stream, free of contaminants may be reused in steam generation in
the plant.
Studies are underway to recover the alkali from the spent caustic.
For the moment, sulfide oxidation is generally practiced to reduce
the immediate oxygen demand of this stream.
Green oil is piped to plant fuel systems or incinerators and burnt
along with tar and other heavy polymer by-products.
ETHYLENE OXIDE
Producers (Ethylene Oxide) Capacity*
Allied, Orange, Texas 40
Calcasieu, Lake Charles, La. 150
Dow, various locations 900
DuPont 30°
Eastman, Longview, Texas 60
GAP, Linden, N. J. 70
Houston Chemical 80
Jefferson, Port Neches, Texas 50
Olin-1-lathieson, Brandenburg, Ky. 120
Shell Chemical, Norco, La. !50
Sun Olin, Marcus Hook, Pa. 1°°
Union Carbide, various locations QQ
Wyandotte, Geismer, La. —±—
Total 4>52°
Millions of pounds per year
Production
1968: 3,000,000,000 pounds/year (Ethylene Oxide)
1973: 5,000,000,000 pounds/year
-------
Use
Surfactants, ethanol amines, polyglycols, anti-freeze, polyester
fibers
Processes
The chlorohydrin method involves the reaction of chlorine water with
ethylene to produce the chlorohydrin and HC1. This was then treated
with bicarbonate to produce the glycol:
C0H. 4- Cl- 4- H00 - —CH.OH - CH0C1 + HC1
2422 2 2
CH OH - CH2C1 + H20 NaHC03 - — CH^H - CH2OH + NaCl + H2C03
Ethylene oxide could be produced by adding caustic and rectifying
the vapors .
Direct oxidation of ethylene:
• C2H4 + 1/2 °2 ~~ C2H4°
is the process which is now widely practiced. Hydrolysis of the
oxide produces the glycol. The product of various glycol ethers
and glycols as by-products is quite common.
Waste Problems
The older chlorohydrin process produces great quantites of waste
HC1 (which is usually lime neutralized) as well as waste organic
streams. The major waste stream is a lime slurry (about 2,000
gallons/ton) . It is not expected that any chlorohydrin plants will
be built in the future.
Oxidation -hydrat ion plants produce two major waste streams. One
is produced at the rate of 1,500 gallons/ton of product and contains
0.1 percent organic. The other is produced at the rate of 150
gallons/ton of product and contains one percent organics in the
process. In a similar system, the total water flow was about 1,000
gallons/ton of product with a concentration of 1-20,000 mg/1 COD.
Both contain a mixture of oxide, glycol, polyglycols, etc.
Waste Reduction Through Process Change
It is possible through the addition of stripping columns and the
addition of certain streams to cooling water systems to reduce the
wastewater discharge to 10 percent of the numbers cited above. The
cost is in the order of $150-210,000 in a 50,000,000 pounds/year
plant.
-------
ISOPROPYL ALCOHOL
Producers Capacity"
Enjay, Baton Rouge, La. 680
Shell, Dominguez, Calif. 225
Shell, Houston, Texas 380
Union Carbide, Texas City, Texas 400
Union Carbide, Whiting, Indiana 275
Total 1,960
^millions of pounds per year
Production
1968: 1,750 million pounds
1973: 2,250 million pounds
Uses
Acetone, solvent
Processes
Isopropyl alcohol is manufactured either by catalytic hydration of
propylene:
CH - CH = CH + HO — CH CHOHCH
or by the reaction of sulfuric acid-propylene similar to the
ethanol reaction.
Waste Problems and Process Change
See Ethanol
FORMALDEHYDE
Producers Capacity*
Allied 31°
Borden 925
950
60
900
Commercial Solvents 60
DuPont
IS
Georgia Pacific
Gulf ll5
Hercules
Hooker
Monsanto
-------
Producers Capacity*
Reichhold 212
Rohm and Haas 50
Tenneco 325
Trojan Powder 50
Union Carbide 150
Total 5,042
•^millions of pounds per year
Production
1968: 4.0 billion pounds
1973: 5.2 billion pounds
Uses
Phenolic resins, urea and melamine resins, ethylene glycol.
Process
Straight oxidation of methanol with air or oxygen. The major by-
products are dimethyl ether and formic acid which amount to 150
pounds/ton of product.
Waste Problems
The major sources of waste are the scrubber waters and the dimethyl
ether by-product. The total aqueous stream should not exceed 100
gallons/ton containing 1-5,000 mg/1 COD unless truck washing is
practiced at the site.
METHANOL
Producers Capacity*
Allied 26
Borden 160
Celanese 75
CSC 65
DuPont 380
Escambia 30
Gulf 9
Hercules 16
Monsanto-Tenneco 30
Rohm and Haas 22
Tenneco 76
Union Carbide 64
Total 943
*millions of gallons per year
-------
Production
1968: 600 million gallons
1973: 900 million gallons
Uses
Formaldehyde, methyl esters, amines, solvent
Processes
The major process for the production of methanol involves the high
pressure catalytic conversion of synthesis gas (CO + H2) to
methanol. Recently ICI has developed a low pressure process.
Waste Problems
Although little information is available on the lower pressure
process, only minor differences between waste streams would appear
to exist. Major wastewater streams are from slab and vessel wash
downs together with bottoms from the methanol purification process.
This amounts to 100-500 gallons/ton of product and contains some
oils, methanol and higher boiling organics to the extent of
several hundred mg/1.
Waste Reduction Through Process Change
More effective separations and better housekeeping can produce
greatly reduced water flows. The dimethyl ether produced from this
waste can be sent to a formaldehyde production facility for conver-
sion into formaldehyde.
PHENOL
Producers Capacity-
Allied 350
Chevron 50
Clark Oil 50
Dow 270
Hercules 50
Hooker 13°
Monsanto 285
Reichhold 90
Shell 50
Skelly Oil 50
Union Carbide —5-Z5_
Total M50
""million pounds per year
-------
Production
1968: 1,500 million pounds
1973: 2,200 million pounds
Uses
Phenolic resins, caprolactam, bisphenol-A, adipic acid
Processes
Phenol is made from benzene by the Raschig process
C,H, + HC1 + 1/2 0. - — C,H_C1 + H.O
DO 2 D _> Z
C,H.C1 + H.O - »- C,HCOH 4- HC1
o 5 2. fa 5
from benzene by the chlorobenzene route:
C,H, + C10 - — C,HrCl + HC1
DO 2. O J
CrHcCl + 2NaOH - »- C,HrONa + NaCl + H_0
65 D 5 2
C H ONa + HC1 - "~ C&E OH + NaCl
and by the sulfonation process from benzene:
2C,HCS00H + Na0S00 - — 2C,HcSO_Na + S00 + H_0(+Na0SO,)
ojj 2j ojj 2 2 24
C,H So'Na + 2NaOH - ^ C H ONa + Na SO + HO
2C,HcONa + SO^ + H00 — — 2C,H..OH + Na S00 0.
55 22 DJ 23 24
Recently two new routes have been commercialized. One is the Dow
Chemical process which involves direct oxidation of toluene to benzoic
acid and then oxidation of the benzoic acid to phenol in a single
step .
It is anticipated that cumene based phenol will continue to hold a
major share of the market. Furthermore, it is expected that the
direct oxidation routes will also gain importance.
Waste Problems
In addition to quantities of wastewaters discharged from the separa-
tion of the phenol the less used processes all produce major quanti-
ties of inorganic containing aqueous wastes which create considerable
difficulties relative to waste treatment. A typical 100,000,000
pound/year phenol plant based on cumene produces a stream of 200,000
-------
gpd of wastewater containing 13,200 mg/1 of COD and 180 mg/1 of
phenol. Inorganics are produced at the following rates:
Sodium carbonate (5,000 Ibs/day); sodium formate (500 Ibs/day);
sodium bicarbonate (500 Ibs/day) and sodium sulfate (22,000 Ibs/day)
The waste production from the direct oxidation facility might be
considerably less than the older process.
Waste Reduction Through Process Control
It is possible to reduce effluents by careful control of the process
involved, recovery of the inorganics by crystallization, etc., and
by solvent extraction of the phenol. It is also likely that as the
sulfonation and chlorination approaches are reduced in importance,
the amount of waste generated per pound of phenol produced will be
greatly reduced.
POLYETHYLENE - HP
Producers Capacity"
Allied, Baton Rouge, La. 150
Allied, Orange, Texas 25
Celanese, Pasadena, Texas 150
Chemplex, Clinton, La. 50
Dow, Freeport, Texas 50
Dow, Plaquemine, La. 50
DuPont, Orange, Texas 75
Gulf, Orange, Texas 100
Hercules, Parlin, N. J. 80
Monsanto, Texas City, Texas 100
National Petrochemicals, La Porte, Texas 125
Phillips, Pasadena, Texas 160
Sinclair-Koppers, Port Reading, N. J. 50
Union Carbide, Seadrift, Texas , 125
Total 1>280
^millions of pounds per year
Production
1968: 1,200 million pounds
1973: 2,000 million pounds
Uses
Blow molding, injection molding, film and sheet, wire and cable,
pipe and conduit
-------
Processes
Polyethylene is produced by the catalyzed polymerization of ethylene.
High pressure processes use oxygen or peroxides as a catalyst
while the low pressure processes (which produce high density pro-
ducts) use metal derived catalysts.
Waj3te Problems
About 400 gallons/ton of product of wastewater is produced from
these units and this flow has the following characteristics:
Suspended Solids 100 ppm
COD 500-800 mg/1
Waste Reduction by Process Changes
It is possible to greatly reduce the discharge of solids by improving
the utilization of centrifuges and other separation equipment.
POLYETHYLENE - LD
Producers Capacity*
Allied, Orange, Texas 25
Chemplex, Clinton, Iowa 100
Columbian Carbon, Lake Charles, La. 100
Dow, Freeport, Texas 170
Dow, Plaquemine, La. 130
DuPont, Orange, Texas 425
DuPont, Victoria, Texas 200
Eastman, Longview, Texas 175
Enjay, Baton Rouge, La. 200
Gulf, Cedar Bayou, Texas 200
Gulf, Orange, Texas 200
Monsanto, Texas City, Texas 130
National Distillers, Deer Park, Texas 300
National Distillers, Tuscola, Illinois 150
Rexall-El Paso, Odessa, Texas 250
Sinclair-Koppers, Port Arthur, Texas 125
Union Carbide, Seadrift, Texas 200
Union Carbide, S. Charleston, W. Va. 100
Union Carbide, Taft, La. 500
Union Carbide, Texas City, Texas 290
Union Carbide, Torrance, Calif. 80
Union Carbide, Whiting, Indiana 200
Total 4,250
*millions of pounds per year
-------
Production
1968: 2,900 million pounds
1973: 4,700 million pounds
Uses
Film and sheet, injection molding, extension coating, wire and cable
Processes
See Polyethylene-HD
Waste Problems
The waste stream which is primarily drains, amounts to 200 gpd/ton
of product and contains 50-100 mg/1 COD and 100 mg/1 of oil.
Waste Reduction
See Polyethylene-HD
POLYSTYRENE
Producers Capacity*
Amoco, Leominster, Mass; Medina, 0;
Torrance, Calif; Willow Sp., 111. 120
Badische, Jamesburg, N. J. 25
Columbian, Hicksville, N. Y. 10
Cosden, Big Springs, Texas 120
Dow, Allyns Pt., Conn; Ironton, 0;
Midland, Mich; Torrance, Calif;
Riverside, Mo. 610
Foster Grant, Leominster, Mass; Peru, 111.
Hammond, Worcester, Mass. 50
Monsanto, Addyston, 0; Long Beach, Calif;
Springfield, Mass. 300
Rexall, Holyoke, Mass; Santa Clara, Calif. 70
Richardson, West Haven, Conn. 30
Shell, Wallingford, Conn. 25
Sinclair-Koppers, Kobuta, Pa. 190
Solar, Leominster, Mass. 50
Union Carbide, Bound Brook, N. J.;
Marietta, 0. 165
Total 1,865
-^millions pounds per year
Production
1968: 1.7 million tons
1973: 3.0 million tons
-------
Uses
Molding, Blow extrusion
Processes^
Polymerization with or without catalysts
Waste Problems
A typical plant produces a waste of 600 gallons/ton of product with
the following composition:
Styrene 3 ppm
Benzoyl Peroxide 1,400 ppm
Tricalcium Phosphate 800 ppm Ca
2,200 ppm P04
Alkyl Aryl Sulfonate 80 ppm
Suspended Solids 500 ppm
PROPYLENE
Producers Capacity*
Ashland, Catlettsburg, Ky. 130
Atlantic-Richfield, Watson, Calif. 230
Amoco, various locations 510
Chevron, El Segundo, Calif. 160
Cities Services, Lake Charles, La. 320
Clark, Blue Island, 111. 70
Dow, various sites 440
DuPont, Orange, Texas 200
El Paso, Odessa, Texas 60
Enjay, various sites 1,440
Goodrich, Calvert City, Ky. 90
Gulf, various sites 830
Jefferson, Port Neches, Texas 150
Marathon, Texas City, Texas 70
Mobil, Beaumont, Texas 520
Monsanto, various sites 360
Petroleum Chemicals, Lake Charles, La. 60
Phillips, Sweeney, Texas 180
Shell, various sites 630
Signal, Houston, Texas 90
Sinclair, Houston, Texas & Marcus Hook,
Pa. 380
Sinclair-Koppers, Houston, Texas 100
Skelly, El Dorado, Kansas 90
Sohio, Lima, Ohio 110
Sun, Marcus Hook, Pa. 300
Suntide, Corpus Christi, Texas 70
Texaco, Westville, N. J. 140
-------
Producers Capacity*
Texas City Ref., Texas City, Texas 100
Texas Eastman, Longview, Texas 100
Tidewater-Air Products, Delaware
City, Del.
Union Carbide, various sites
Union Oil, Los Angeles, Calif.
Total 8,920
^millions of pounds per year
Production
1968: 7,000 million pounds per year
1973: 11,000 million pounds per year
Uses
Isopropanol, acrylonitrile, polypropylene, propylene oxide,
heptene, cumene, glycerine
Processes
Propylene is produced together with ethylene and details may be
obtained from the section on ethylene. However, the major portion
of the propylene is produced as a by-product of gasoline product
(over 85 percent) . It is expected that the amount of propylene
generated will increase as the demand for high octane low leaded
gasolines increase.
Waste Reduction
See ethylene section
PROPYLENE_OXIDE .
Producers
Celanese, Bishop, Texas
Dow, Freeport, Texas
Dow, Midland, Mich.
Jefferson, Port Neches, Texas
01in, Brandenburg, Ky.
Oxirane, Bayport, Texas
Union Carbide, S. Charleston, W. Va.
Wyandotte, Wyandotte, Mich.
Total i'020
^millions of pounds per year
-------
Production
1968: 890 million pounds
1973: 1,750 million pounds
Uses
Polypropoxyethers, propylene glycol, polypropylene glycol, dipropylene
glycol
Process
See Ethylene Oxide section. Oxirane has developed a process based
on the oxidation of acetaldehyde.
Waste
See Ethylene Oxide
TOLUENE
Producers Capacity*
Amoco, Texas City, Texas 20
Ashland, North Tonawanda, N. Y.,
Catlettsburg, Ky. 20
Atlantic-Richland, Wilmington, Calif. 24
Chevron, El Segundo, Calif;
Richmond, Calif. 32
Cities Services, Lake Charles, La. 36
Coastal States, Corpus Christi, Texas 10
Cosden, Big Spring, Texas 15
Crown Central, Houston, Texas 10
Dow, Bay City, Mich. 17
Enjay, Baton Rouge, La; Baytown, Texas 65
Gulf, Philadelphia, Pa; Port Arthur, Texas 20
Hess, Corpus Christi, Texas 18
Leonard, Mount Pleasant, Mich. 3
Marathon, Texas City, Texas 12
Mobil, Beaumont, Texas 25
Monsanto, Alvin, Texas 32
Pontiac, Corpus Christi, Texas 13
Shell, Houston, Texas; Odessa, Texas;
Wilmington, Calif; Wood River, 111. 65
Signal, Houston, Texas 16
Sinclair, Houston, Texas; Marcus Hook, Pa. 26
South Hampton, Silsbee, Texas 6
Southwester, Corpus Christi, Texas 10
Sun, Marcus Hook, Pa. 25
Sunray DX, Tulsa, Okla 4
Suntide, Corpus Christi, Texas 13
Tenneco, Chalmette, La. 8
-------
Producers Capacity*
Texaco, Port Arthur, Texas 31
Union Carbide, S. Charleston W. Va. 10
Union Oil-Atlantic, Nederland, Texas 20
Union Oil, Lemont, 111. 10
Vickers, Potwin, Kansas 5
Total 620**
*millions of gallons per year
**also 65 million gallons from coke oven, tar distiller and
styrene monomer operations
Production
1968: 610 million gallons
1973: 800 million gallons
Uses
Benzene, solvents, gasoline, TNT, Toluene diisocyanate, phenol
Process
Toluene is produced by extraction from refinery reformate as is
benzene. For details see benzene.
UREA
*
Producers Capacity
Allied 320
American Cyanamid 150
Arkla 67
Armour 11
Best 20
Collier 50
Columbia Nitrogen 25
Cooperative Farmer 50
DuPont 205
Escambia 23
*yr\
Farmers Chemical JU
Fel Tex 20
lll
Gulf f
Hawkeye
Hercules
Ketman
Miss. Chem. °^
Mobile
-------
Producers Capacity*
Monsanto 80
Nipack 260
Nitrin 23
01 in 150
Phillips 8
Phillips Pacific 20
Premier 70
Shell 185
Solar 140
Southern Nitrogen 60
Sun 01 in 75
Valley Nitron 35
Wyeon 50
Total 1,500
-'-thousands of tons
Production
1968: 2.3 million tons
1973: 3.7 million tons
Uses
Animal feed, fertilizer, plastics
Processes
All of the major processes involve the high pressure reaction of
C02 and ammonia. There are about 10 variations of this scheme.
Waste Probiems
Typical wastes amount to about 120 gallons/ton of product with the
following composition:
Ibs/ton
NH,, 3.6
C02 0.6
Urea 0.8
Carbonate 0.1
Waste Reduction Through Process Change
It is normal practice to remove about 50 percent of the ammonia by
airstripping after adjusting pH with alkali. Recently two new
processes have been developed which strip the ammonia and carbonate
by contacting with either NH~ or C02 and sending the overload
directly to the reactor. This approach is expected to reduce
ammonia losses by 50 percent or more with a more drastic effect on
carbonate. These also involve operation of the reaction at a lower
temperature.
-------
XYLENES
Producers
Amoco
Chevron
Cities Service
Coastal
Commonwealth
Cosden
Crown Central
En jay
Hercor
Hess
Monsanto
Shell
Signal
Sinclair
Sunray DX
Tenneco
Total
-^millions of gallons per year
Production
Ortho
Capacity''
130
120
42
70
19
175
45
75
80
30
25
736
Para
Capacity"
200
536
6
6
210
100
100
15
215
165
100
1,547
Ortho
500
750
Para
750
1,800
1968
1973
Uses
Phthalic anhydride, polyesters
Process
Mixed xylenes are recovered primarily from refinery streams (see
benzene and ethyl benzene). It is separated with ethyl benzene and
isomerization is carried out to increase the yield of para xylene.
A separation scheme involves crystallization to separate the various
streams.
Waste Problems
Sludge from the crystallizer as well as bottoms, drains, etc.,
amount to perhaps 100-500 galIons/ton of product with an organic
content of 3-5,000 mg/1.
-------
As-the Nation's principal conservation agency, the Department of the
Interior has basic responsibilities for water, fish, wildlife, mineral, land,
park, and recreational resources. Indian and Territorial affairs are other
major concerns of America's "Department of Natural Resources."
The Department works to assure the wisest choice in managing all our
resources so each will make its full contribution to a better United
States-now and in the future.
12020 —2/70
------- |