DEVELOPMENT DOCUMENT
for
PROPOSED EFFLUENT LIMITATIONS GUIDELINES
AND
NEW SOURCE PERFORMANCE STANDARDS
FOR THE
ORGANIC CHEMICALS AND PLASTICS AND SYNTHETIC FIBERS INDUSTRY
VOLUME II (BAT)
Anne M. Burford
Administrator
Frederic A. Eidsness, Jr.
Assistant Administrator for Water
Steven Schatzow, Director
Office of Water Regulations and Standards
Jeffery D. Denit, Director
Effluent Guidelines Division
Devereaux Barnes, Acting Branch Chief
Organic Chemicals Branch
Elwood H. Forsht
Project Officer
FEBRUARY 1933
EFFLUENT GUIDELINES DIVISION
OFFICE OF WATER REGULATIONS AND STANDARDS
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, DC 20460
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NOTICE MAR 311983
On February 28, 19R3, EPA proposed effluent limitations guidelines and
standards for the organic chemicals and plastics and synthetic fibers (OCPSF)
point source category. TTie Federal Register notice of this proposal was printed
on March 21, 19R3 (48 _FR 11R2R to 11^67).
Information received hy the Agency after proposal indicates that the total
OCPSF industry estimated annual discharges of toxic pollutants are too high.
The Agency will be reevaluating these estimates when additional information
becomes available prior to promulgation of a final regulation. In the interim,
the Agency advises that there should be no reliance on the annual total toxic
pollutant discharge estimates presented in the Federal Register notice, the
February 19R3 OCPSF Development Document., and February 10, 19R3 OCPSF Regulatory
Impact Analysis.
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VOLUME It (BAT)
TABLE OF CONTENTS
PAGE
SECTION I: EXECUTIVE SUMMARY
SUMMARY 1-1
CONCLUSIONS 1-5
SECTION II: INTRODUCTION
LEGAL AUTHORITY 11-1
Background il-1
Federal Water Pollution Control Act Amendments of 1972 11-2
Initial EPA Efforts to Develop Regulations for the
Organic Chemicals and Plastics/Synthetic Fibers Industries 11-2
Initial EPA Efforts to Develop Effluent Standards for
Individual Toxic Pollutants 11-3
Clean Water Act of 1977 11-5
Subsequent EPA Developments and Regulations 11-5
Recent Developments and Current Deadlines 11-6
GUIDELINES DEVELOPMENT METHODOLOGY 11-7
General 11-7
Definition and Surveys of the Industry 11-8
308 BPT Questionnaires 11-8
308 BAT Questionnaire 11-12
Screening and Verification Sampling and Analysis Program 11-12
CMA Five-Plant Sampling Program 11-14
Other EPA Studies 11-14
SECTION III: INDUSTRY DESCRIPTION
INTRODUCTION III-1
DEFINITION OF THE INDUSTRY 111-2
Settlement Agreement Definition 111-2
Primary, Secondary, and Tertiary SIC Codes 111-3
Il-i b
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TABLE OF CONTENTS
(continued)
PRODUCT LINE
Products of Various SIC Categories
Industry Structure by Product and Process
Plant Variations
PRODUCTION AND SALES
GEOGRAPHIC DISTRIBUTION
PLANT SIZE
PLANT AGE
REFERENCES
SECTION IV: SUBCATEGORIZATION OF THE ORGANIC CHEMICALS
AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES
INTRODUCTION
METHODOLOGY
ENGINEERING ASPECTS OF CONTROL TECHNOLOGIES
(TREATABILITY)
Biological Treatment of Wastewaters
Physical-Chemical Technologies
Treatment System Performance
FACILITY SIZE
GEOGRAPHICAL LOCATION
AGE OF EQUIPMENT AND FACILITY
COST OF ACHIEVING EFFLUENT REDUCTION
NONWATER QUALITY ENVIRONMENTAL IMPACTS
PROCESSES EMPLOYED AND PROCESS CHANGES
Raw Materials and Products
Process Chemistry
Product/Processes
ll-ii
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TABLE OF CONTENTS
(continued)
PAGE
SUMMARY IV-27
REFERENCES IV-29
SECTION V: WASTEWATER GENERATION AND CHARACTERIZATION
WATER USAGE V-1
General V-1
Water Use by Purpose V-1
Water Use by Subcategory V-6
Water Reuse and Recycle V-8
Current Levels of Reuse and Recycling V-8
Water Conservation and Reuse Technologies V-12
OCCURRENCE AND PREDICTION OF PRIORITY POLLUTANTS V-15
General V-1G
Product/Process Chemistry Overview V-24
Product/Process Sources of Priority Pollutants V-39
Implications of the Verification Data for Monitoring
Priority Pollutants in Wastewater V-59
RAW WASTEWATER CHARACTERIZATION DATA V-61
General V-61
Raw Wastewater Data Collection Studies V-61
Screening Phase I V-61
Screening Phase II V-63
Verification Program V-64
CMA Five-Plant Sampling Program V-69
Wastewater Data Summary V-71
General V-71
Waste Loadings from Verification and CMA Five-Plant Studies V-71
Waste Loadings for the Entire OCPSF Industrial Category V-77
REFERENCES V-78
SECTION VI: SELECTION OF POLLUTANT PARAMETERS
INTRODUCTION VI-1
SELECTION RATIONALE FOR BAT AND NSPS POLLUTANTS VI-1
General VI-1
ll-iii
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TABLE OF CONTENTS
(continued)
PAGE
Selection Criteria VI-2
Nonconventional and Toxic Non-Priority Pollutants VI-2
Priority Pollutants VI-2
Pollutant Parameters Selected VI-4
SELECTION CRITERIA FOR PSES AND PSNS POLLUTANTS VI-4
General Vl-4
Pass-Through Analysis VI-8
General VI-8
Database and Methodology VI-8
Pollutant Parameters Selected VI-9
REFERENCES VI-15
SECTION VII: POLLUTANT CONTROL AND TREATMENT
TECHNOLOGY
INTRODUCTION VIM
IN-PLANT SOURCE CONTROLS VI1-1
Process Modification VII-1
Instrumentation VI1-2
Solvent Recovery VI1-2
Water Reuse, Recovery, and Recycle VI1-2
IN-PLANT TREATMENT VII-3
END-OF-PIPE TREATMENT AND DISCHARGE VII-4
General VII-4
Physical Treatment Processes VII-4
Settling (Clarification, Sedimentation) VII-4
Oil Separation VII-10
Filtration VII-10
Gas Stripping (Air and Steam) VII-10
Distillation VII-11
Gas Flotation (Dissolved Air, Air, Vacuum) VII-11
Biological Treatment Processes VII-11
Activated Sludge VI1-13
Aerated Lagoon VI1-14
Stabilization Ponds VI1-14
Anaerobic Denitrification VI1-15
Trickling Filters VII-15
Rotating Biological Contactors VII-16
ll-iv
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TABLE OF CONTENTS
(continued)
PAGE
Physical-Chemical Treatment Processes VI1-16
Neutralization VII-16
Chemical Precipitation (Coagulation and Flocculation) VII-16
Chemical Oxidation V11 -17
Activated Carbon Adsorption VI1-17
Ion Exchange VII-17
Resin Adsorption V11 -18
Solvent (Liquid-Liquid) Extraction VII-18
Other ("Zero") Wastewater Discharge or Disposal Methods VII-19
Incineration VII-19
Evaporation VII-19
Surface Impoundment VII-19
Land Application VII-19
Deep Well Injection V11-21
Offsite Treatment VII-21
Contract Hauling Vll-21
SLUDGE TREATMENT AND DISPOSAL VI1-22
General VII- 22
Treatment and Disposal Processes VI1-22
WASTEWATER AND SLUDGE TREATMENT TECHNOLOGIES
USED TO DEVELOP EFFLUENT LIMITATIONS COSTS V11-24
REFERENCES VI1-27
SECTION VIII: EVALUATION OF TREATMENT TECHNOLOGY
PERFORMANCE AND COST
INTRODUCTION VI11-1
DESCRIPTION AND USE OF MODEL VIII-2
Development of the Model VIII-2
Model Components and Use VIII-3
ESTIMATION OF BAT AND PSES COSTS USING THE MODEL VIII-3
General VIII-3
Description of GPCs VIII-3
Use of GPCs to Estimate OCPSF Regulatory Costs VIII-4
Overview VIII-4
1980 GPC Runs VIII-4
Revisions to 1980 GPC Runs VIII-5
Estimating Compliance Costs for Each Establishment VIII-7
Estimating Compliance Costs for the Whole OCPSF Industry VIII-7
11 - v
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TABLE OF CONTENTS
(continued)
PAGE
EVALUATION OF NON-WATER QUALITY CONSIDERATIONS VI11-14
General V111 -14
Energy Consumption VI11-14
Air Pollution V111 -14
Solid and Hazardous Waste Generation VI11-16
Solid Waste VI11-16
Hazardous Waste V111 -18
Noise Generation VI11-18
REFERENCES VI11-19
SECTION IX: EFFLUENT QUALITY ATTAINABLE THROUGH
THE APPLICATION OF THE BEST AVAILABLE
TECHNOLOGY ECONOMICALLY ACHIEVABLE
INTRODUCTION IX-1
LIMITATION TYPE IX-2
General IX-2
Mass Limitations IX-2
Concentration Limitations IX-3
BAT SELECTION IX-3
General IX-3
Alternative Approaches to Developing BAT Limitations IX-4
General IX-4
Computer Model Evaluation of GPCs IX-5
Performance of Existing Plants IX-5
Derivation of Limitations IX-5
Overview IX-5
Revised and Final BAT Databases IX-5
Pollutants Addressed IX-8
Limitation Calculations IX-8
Treatment Technologies Reflected in the Limitations IX-27
IMPACTS OF BAT IMPLEMENTATION IX-27
General IX-27
Present Compliance IX-30
Benefits and Costs of BAT Implementation IX-30
Wasteload Reduction Benefits IX-30
Capital and Annual Costs Incurred IX-30
ll-vi
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TABLE OF CONTENTS
(concluded)
PAGE
Non-Water Quality Environmental Impacts IX-30
Energy Consumption IX-31
Air Pollution Emissions IX-31
Solid Waste Generation IX-31
Noise Generation IX-31
Conclusion IX-32
REFERENCES IX-33
SECTION X: EFFLUENT QUALITY ATTAINABLE THROUGH THE
APPLICATION OF NEW SOURCE PERFORMANCE STANDARDS
INTRODUCTION X-1
LIMITATION TYPE X-2
NSPS LIMITATION SELECTION X-2
SECTION XI: EFFLUENT QUALITY ATTAINABLE THROUGH THE
APPLICATION OF PRETREATMENT STANDARDS FOR
EXISTING SOURCES AND PRETREATMENT STANDARDS
FOR NEW SOURCES
INTRODUCTION XI-1
POLLUTANTS SELECTED FOR REGULATION UNDER PSES AND PSNS XI-2
DEVELOPMENT OF PSES AND PSNS EFFLUENT LIMITATIONS XI-2
General XI-2
Methodology XI-2
Proposed PSES and PSNS Effluent Limitations XI-3
EFFECTS OF PSES AND PSNS IMPLEMENTATION XI-3
Cost of Application and Effluent Reduction Benefits XI-3
Non-Water Quality Environmental Impacts XI-3
SECTION XII: ACKNOWLEDGEMENTS XII-1
SECTION XIII: GLOSSARY Xlll-l
I l-vii
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LIST OF TABLES
TABLE TITLE PAGE
1-1 BAT Effluent Limitations: Plastics-Only Plants 1-6
1-2 BAT Effluent Limitations: Not Plastics-Only Plants 1-7
I-3 Pretreatment Standards for Existing and New Sources 1-10
II-l EPA Technical Databases Used in Effluent Guidelines
Development 11-9
III-1 Major Products by Process of the Organic Chemicals
Industry 111-10)
111-2 Major Products by Process of the Plastics/Synthetic
Fibers Industry 111-23
111-3 Number of Plants and Sales in the OCPSF Industries
by SIC Code, 1980 111-27
111-4 1980 Production Volume of Organic Chemicals in
1980 "Top 50" List 111-23
111-5 Production Volume of Plastics and Synthetic
Fibers - 1980 111-29
111-6 Value of Shipments for the Organic Chemicals
Industry By Product Class - 1977 111-30
111-7 Value of Shipments for the Plastics/Synthetic
Fibers Industry By Product Class - 1977 111-33
111-8 The Organic Chemicals and Plastics/Synthetic
Fibers Industries by Primary Product
Specialization 111-37
III-9 Plant Distribution by State 111-38
IV-1 Mean Concentrations of Priority Pollutant Groups
by Plant Type IV-3
IV-2 Influence of Structure on Degradability IV-9
IV-3 Major Processes of the Organic Chemicals and
Plastics/Synthetic Fibers Industries IV-25
V-1 Summary Water Use Statistics for the OCPSF
Industries --1978 Census Data V-2
I l-viii
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LIST OF TABLES
(continued)
TABLE TITLE PAGE
V-2 Water Intake by Source for the OCPSF
Industries --1978 Census Data V-3
V-3 Water Intake by Purpose for the OCPSF
Industries --1978 Census Data V-4
V-4 Water Usage Data for Organic Chemicals and
Plastics/Synthetic Fibers Industry Plants
in the 308 Survey V-5
V-5 Summary of Total Water Usage for Plastics-Only and
Not Plastics-Only Plants in the 308 Survey V-7
V-6 Summary of Noncontact Cooling Water Usage for
Plastics-Only and Not Plastics-Only Plants in the
308 Survey V-9
V-7 Summary of Direct Process Contact Water Usage for
Plastics-Only and Not Plastics-Only Plants in
the 308 Survey V-10
V-8 Water Recirculated and Reused by Use for the
OCPSF Industries -- 1978 Census Data V-11
V-9 Plants Reporting Recycling of All Process Contact
Wastewaters V-13
V-10 Water Conservation and Reuse Technologies V-14
V-11 Generic Processes Used to Manufacture Organic
Chemical Products V-19
V-12 Major Plastics and Synthetic Fibers Products
by Generic Process V-23
V-13 Critical Precursor/Generic Process Combinations
that Generate Priority Pollutants V-40
V-14 Organic Chemicals Effluents with Significant
Concentrations of Priority Pollutants V-44
V-15 Plastics/Synthetic Fibers Effluents with Significant
Concentrations of Priority Pollutants V^g
V-16 Priority Pollutants in Effluents of Precursor-
Generic Process Combinations V- 49
ll-ix
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LIST OF TABLES
(continued)
TABLE TITLE PAGE
V-17 Number of Priority Pollutants Reported vs.
Concentration V-60
V-18 Overview of Wastewater Studies Included in BAT
Raw Waste Stream Database V-62
V-19 Phase II Screening -- Product/Process and Other
Waste Streams Sampled at Each Plant V-65
V-20 Selection Criteria for Testing Priority Pollutants
in Verification Samples V-68
V-21 Influent Wastewater Concentration Summary
Statistics for Twenty-Eight Not Plastics-Only
Direct Discharging Plants V-72
V-22 Influent Wastewater Concentration Summary
Statistics for Three Not Plastics-Only
Indirect Discharging Plants V-75
V-23 Influent Wastewater Concentration Summary
Statistics for Three Plastics-Only Direct
Discharging Plants V-76
VI -1 Eighteen Toxic Pollutants Proposed for Exclusion VI-3
VI-2 Frequency of Occurrence and Concentration
Ranges for Selected Priority Pollutants
in Influent Wastewaters VI-5
VI-3 Results of Pretreatment Pass-Through Analysis:
Plastics-Only Plants VI-10
VI-4 Results of Pretreatment Pass-Through Analysis:
Not Plastics-Only Plants VI-11
VI-5 Pollutants Selected for Regulation Under PSES
and PSNS V1-13
VI-6 Pollutants Excluded as Candidates from
Regulation Under PSES and PSNS VI-14
VII-1A Wastewater and Sludge Treatment and Disposal
Technologies Reported By Plastics-Only Plants VII-5
VII-1B Wastewater and Sludge Treatment and Disposal
Technologies Reported By Not Plastics-Only
Plants VI1-7
ll-x
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LIST OF TABLES
(concluded)
TABLE TITLE PAGE
VII-2 Candidate Wastewater Treatment Technologies Vli-y
VII-3 Other ("Zero") Discharge and Disposal Methods V11-20
VI1-4 Candidate Sludge Treatment and Disposal
Technologies VII-23
VII-5 Wastewater and Sludge Treatment Technologies
Used in Computer Model VII-25
VIII-1 Revised BAT and PSES Treatment Costs for
Each GPC VIII-8
VIII-2 1980 Energy Consumption in the Organic Chemicals
and Plastics/Synthetic Fibers Industries VII1-15
VIII-3 1980 Solid Waste Generation and Disposal in the
Organic Chemicals and Plastics/Synthetic Fibers
Industries VIII-17
IX-1 Final BAT Database -- Summary Statistics for
Not Plastics-Only Plants IX-9
IX-2 Final BAT Database -- Summary Statistics for
Plastics-Only Plants IX-13
IX-3 Priority Pollutant Classes IX-16
IX-4 Variability Factors by Priority Pollutant Class IX-20
IX-5 BAT Effluent Limitations (yg/i) --
Plastics-Only Plants IX-23
IX-G BAT Effluent Limitations (yg/1) --
Not Plastics-Only Plants IX-24
IX-7 Treatment Systems at Plants Used to Calculate
BAT Limitations IX-28
Xl-l Pretreatment Standard Effluent Limitations for
Existing and New Sources XI-4
XI-2 Pollutants for which PSES and PSNS Effluent
Limitations Could Not Be Established XI-5
11 - x i
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LIST OF FIGURES
FIGURE TITLE PAGE
111-1 Relationships Among the SIC Codes Related to the
Production of Organic Chemicals, Plastics, and
Synthetic Fibers 111-4
111-2 Major Synthetic Pathways of The Organic Chemicals
Industry 111-7
111-3 Plant Distribution by Geographic Location III-4C
111-4 Number of Product/Processes by Plant 111-41
111 -5 Plant Distribution by Number of Employees 111-43
111-6 Plant Distribution by Sales Volume 111-44
III-7 Plant Age of the Organic Chemicals and
Plastics/Synthetic Fibers Industries 111-45
IV-1 Average Influent Concentration by Pollutant IV-4
IV-2 Some Products Derived from Methane IV-19
IV-3 Some Products Derived from Ethene IV-20
IV-4 Some Products Derived from Propene IV-21
IV-5 Some Products Derived from C. and Higher Aliphatic
IV-22
Compounds
IV-6 Some Products Derived from Aromatic Compounds IV-23
V-1 Primary Feedstock Sources V-25i
V-2 Coal Tar Refining V-26
V-3 Methane y_?7
V-4 Ethylene y_2g
V-5 Propylene V-29
V-6 Butanes/Butenes V-30
V-7 Aromatics y_31
V-8 Plastics and Synthetic Fibers V-3?
I l-xii
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LIST OF FIGURES
(continued)
TITLE
Plastics and Synthetic Fibers
Nitroaromatics, Nitrophenols, Benzidines, Phenols,
Nitrosamines
Chlorophenols, Chloroaromatics, Chloropolyaromatics
Haloaryl Ethers, PCBs
Chlorinated C2s, C4-Chloroalkyl Ethers
Chlorinated C3s, Chloroalkyl Ethers, Acrolein,
Acrylonitrile, Isophorone
Halogenated Methanes
Priority Pollutant Profile of the Organic
Chemicals Industry
Generic Chemical Processes
Development of Final BAT Database
11- xiii
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SECTION I
EXECUTIVE SUMMARY
This document describes the technical development of EPA's proposed BAT, NSPS,
PSES and PSNS effluent limitations guidelines. This Section summarizes the
document and presents the proposal limitations.
SUMMARY
The major underlying legislative authority for water pollution control
programs is the Federal Water Pollution Control Act Amendments of 1972 (33
U.S.C. §§1251 et seq.). Substantial revisions were made in 1977 with
passage of the Clean Water Act (P.L. 95-217), which resulted in the
incorporation into the Act of major provisions of the 1976 Consent Decree, an
agreement reached by the Agency and environmental groups. The provisions of
the Clean Water Act and the Consent Decree (as modified in 1979), require EPA
to develop and issue best available technology (BAT), best conventional
technology (BCT), and best practicable technology (BPT) effluent limitations
guidelines, pretreatment standards for existing sources (PSES) and for new
sources (PSNS), and new source performance standards (NSPS) for 34 major
industries, including the Organic Chemicals and Plastics/Synthetic Fibers
(OCPSF) Industries, covering 126 toxic pollutants. Under a court order filed
on October 26., 1982, EPA must promulgate the final regulations by March 1984.
Section II of this document summarizes the methodology used by the Agency in
developing effluent limitations guidelines and standards for the Organic
Chemicals and Plastics/Synthetic Fibers (OCPSF) Industries. To ensure sound
technical development of effluent guidelines, the Agency has had to collect
and evaluate substantial amounts of data on these industries. The surveys
used to gather data on the industry have included:
• Collection of historical data on production and
treatment of wastewaters from specific plants within
the industries under the authority of Section 308 of
the FWPCA.
• Sampling and analysis programs at selected industry
plants to characterize specific waste streams which
are discharged into both aquatic environments and
POTWs.
• Treatability studies on the industries' wastewaters
using specific physical and biological treatment
processes.
The specific data collection efforts that EPA completed in developing the
proposed regulations for the OCPSF Industries are summarized in Table II-1 of
Section II.
1-1
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The OCPSF Industries are large, diverse and complex industries. The
industries include approximately 1,200 facilities which are primary producers
of products under the OCPSF SIC groups; the total number of plants may be as
high as 2,100 if secondary producers are included. Over 25,000 different
organic chemicals, plastics, and synthetic fibers are manufactured by plants
in the industries, although only 1,200 products are produced in excess of
1,000 pounds per year. Within the industries, substantial variation is
observed in the selection of chemical processes used to synthesize products,
in the product mix, and in the method of manufacture (i.e., batch or
continuous operations). Sales for 1980 OCPSF primary producers were reported
to be 80 billion dollars.
The majority of OCPSF plants are located in coastal regions or on waterways
near sources of raw materials or transportation centers. The greatest number
of plants in the industries are 10 to 15 years old, and over 70 percent of the
plants are less than 25 years old. A detailed description of the OCPSF
Industries is presented in Section III, which includes industry profiles based
on product line, product sales, geographic distribution, facility size,
facility age, and process chemistry.
The Agency considered subcategorization of the OCPSF Industries based on:
engineering aspects of control technologies (treatability); facility size (as
measured by plant production and/or sales); geographical location; age of
equipment and facilities; cost of achieving effluent reduction; non-water
quality environmental impacts; and processes employed and process changes.
However, these factors failed to distinquish meaningfully among industry
plants.
The Agency is proposing that the plants in the OCPSF industry category be
divided into two subcategories: plants that manufacture plastics and
synthetic fibers only (Plastics-Only plants); and plants that manufacture
organic chemicals only or both plastics materials and organic chemicals (Not
Plastics-Only plants). This subcategorization scheme is derived primarily
from an engineering analysis of priority pollutants detected or likely to be
present in the OCPSF Industries wastewaters. This subcategorization scheme is
also supported by a statistical analysis of raw wastewater data from the Phase
I and Phase II Screening Studies.
The Agency further sought to develop a BAT subcategorization scheme similar to
the BPT proposed subcategorization. The Agency believes that two
substantially different subcategorization schemes for BPT and BAT would
complicate the process of implementing and applying both sets of effluent
regulations at a specific plant. Although four subcategories are proposed
under the BPT effluent limitatons (see Volume I), the scheme is compatible
with the two subcategories proposed under the BAT limitations. Both BAT and
BPT have a Plastics-Only subcategory. While BPT has an Oxidation subcategory,
Type I subcategory, and Other Discharge subcategory, these three subcategories
are incorporated into the Not Plastics-Only subcategory of BAT.
The OCPSF Industries use large amounts of water in process operations.
Noncontact cooling water comprises over 80 percent of the total water used in
the OCPSF Industries. Direct process contact water, the primary source of
1-2
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water pollution, accounts for only about ten percent of total industry water
consumption.
Typically, Not Plastics-Only plants use more water than do Plastics-Only
plants. In both subcategories, direct discharge plants tend to use more water
than do indirect discharge plants or plants that discharge by other methods
(sometimes referred to as "zero" dischargers). About 80 percent of OCPSF
plants report some recirculation or reuse of water. However, less than ten
percent of the plants in the OCPSF Industries eliminate discharge of process
contact wastewaters to surface water bodies or POTWs through recycling.
Various practices and technologies available for water conservation and
recycling are discussed in Section V.
A major task for the Agency was to develop data characterizing the presence
(or absence) of 129 priority pollutants in raw and treated wastewaters of the
OCPSF Industries. EPA has collected wastewater data generated by individual
plants within these industries and has performed extensive sampling and
analysis of individual process wastewaters. An adjunct to these data
collection efforts was the qualitative evaluation of which priority pollutants
would be expected in wastewaters, from consideration of the starting materials
and the chemical reactions employed. A systematic method for applying
product/process considerations to the prediction of priority pollutants is
presented in Section V.
To decide which pollutants merit regulation and to evaluate which technologies
effectively reduce discharge of these pollutants, data characterizing the raw_-
wastewaters were collected and evaluated. The studies which produced
significant data on raw wastewater characteristics include the 308 Surveys,
the Screening Study Phases I and II, the Verification Study, and the CMA
Five-Plant Study (see Sections II and V and Appendix C).
The Agency's wastewater data collection efforts yielded data of mixed quality
on the concentrations of priority pollutants in product/process effluents and
wastewater treatment influents and effluents at over 170 OCPSF manufacturing
plants. EPA reviewed these data and concluded that the edited data from the
Verification Phase and CMA Five-Plant studies were of sufficient quality to
use to develop numerical effluent limits, while data from Phases I and II of
the Screening Study were appropriate for deciding which pollutants discharged
by OCPSF Industries are of national concern and for performing the
subcategorization principal component analysis. Analytical and QA/QC methods
used to generate and to review the study data are discussed in detail in
Appendix C to this report.
The waste loading data from the Verification and CMA Five-Plant studies for
Plastics-Only plants and Not Plastics-Only plants are summarized in Section V,
Tables V-9 and V-10.
In the development of BAT and New Source Performance Standards (NSPS)
regulations, EPA considered for regulation specific nonconventional pollutants
and all of the 129 priority pollutants. The Agency has chosen to defer
regulation of nonconventional pollutants and to exclude from regulation the 18
pesticides which are priority pollutants. The remaining 108 priority
pollutants, each detected in at least 42 percent of the plants sampled in the
1-3
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Screening (Phases I and II), Verification and CMA studies, were candidates for
BAT and NSPS regulation.
Pretreatment Standards for Existing Sources (PSES) and Pretreatment Standards
for New Sources (PSNS) for indirect dischargers need only address those
pollutants which upset, inhibit, pass-through, or contaminate sludges at
POTWs. In selecting pollutants to regulate for pretreatment standards, the
Agency has only addressed those 108 priority pollutants .that the Agency
considered as candidates for BAT regulation. A pollutant is deemed to pass
through a POTW if the average percent removal achieved by well-operated POTWs
nationwide (as reflected in the 50 POTW Study) is less than the percent
removal achieved by direct dischargers complying with the proposed BAT
effluent limitations guidelines for that pollutant. Pollutants shown not to
pass through were eliminated from consideration for regulation under PSES and
PSNS. Where adequate removal data were not available for a particular
pollutant, the pollutant was included for regulation under PSES and PSNS.
Using these pass-through criteria, the Agency selected six pollutants in the
Plastics-Only subcategory and 29 pollutants in the Not Plastics-Only
subcategory for potential regulation under PSES and PSNS. These pollutants
are listed in Table VI-5.
A variety of physical, chemical, and biological treatment processes are in use
or available for OCPSF manufacturing plants to control and treat both
wastewater pollutants and the solid residues (sludges) produced by treating
the wastewaters. These control and treatment technologies include: in-plant
source controls (e.g., process modification, solvent recovery, and water
reuse); in-plant treatment technologies; end-of-pipe treatment and disposal
technologies; and sludge treatment and disposal technologies. The predominant
end-of-pipe wastewater treatment technologies employed by the industry are
equalization, neutralization, sedimentation, and biological treatment,
preceded by a variety of in-plant controls and physical/chemical treatment
(e.g., steam stripping and carbon adsorption) of specific product/process
waste streams. -The specific technologies and their application to the
industry in general are discussed in Section VII.
EPA sponsored several treatability studies to develop data on the removal of
individual priority pollutants by candidate BAT technologies. These studies
are described in Section VII and Appendix E to this report.
Faced with the task of evaluating alternative sets of priority pollutant
effluent limitations for a highly complex and diverse industry, the Agency
developed a computer model capable of estimating the performance, non-water
quality environmental impacts, and the construction and operating costs of
various combinations of available treatment technologies adequate to meet each
candidate set of effluent limitations. A description of the computer model is
presented in Section VIII and Appendix K.
The Agency estimated the costs to the OCPSF Industries of complying with the
proposed BAT and PSES regulations from estimated costs generated by the model
for treating wastewaters from 55 Generalized Plant Configurations (GPCs).
Each GPC is a group of organic and plastic product/processes that represents
an entire manufacturing plant or major portions of plants contained in the 308
Database. A discussion of the methods used to estimate costs from the Model
GPCs is presented in Section VIII.
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Sections 304(b) and 306 of the Clean Water Act require the Agency to consider
the non-water quality impacts of these proposed regulations. Section VIII
presents the factors considered by the Agency in evaluating the impacts of
compliance with this regulation on energy consumption, air pollution, solid
waste generation, and noise generation.
CONCLUSIONS
EPA considered alternative approaches in developing BAT effluent limitations.
Since significantly different combinations and concentrations of priority
pollutants are found at different OCPSF plants, no single pollutant control
and treatment technology is adequate to address the entire industry or each
subcategory; the BAT technologies are plant-specific. EPA is proposing BAT
effluent concentration limitations for this industry that reflect the
performance of existing well-designed and well-operated OCPSF treatment plants
in the Agency's Verification and CMA study database. Derivation of the
limitations is (detailed in Section IX and Appendix F. Maximum daily and
four-day average limitations have been calculated for each regulated
pollutant. Effluent limitations have been proposed for 10 pollutants for the
Plastics-Only subcategory and 44 pollutants for the Not Plastics-Only
subcategory; these limitations are listed in Tables 1-1 and 1-2.
Limitations are not proposed for pollutants for which sampling data were
insufficient. Limitations are not proposed for pollutants in classes where no
variability factor could be estimated from the CMA data or for pollutants
where no long-term median could be estimated from the CMA and Verification
data. The Agency has been unable to develop limitations for 60 of the other
pollutants listed in Table VI-2 because of inadequate data. EPA plans to
assess the need for effluent limitations for these pollutants during the
additional data gathering and field sampling studies planned between proposal
and promulgation.
EPA is proposing NSPS limitations that are identical to those proposed for BPT
for conventional pollutants (contained in Volume I) and BAT for priority toxic
pollutants. The Agency did not estimate the future cost to the OCPSF
Industries of these NSPS limitations, since they will not generate incremental
costs or economic impacts.
The Agency is proposing for PSES and PSNS effluent limitations that have been
derived from performance data for end-of-pipe technologies, since the Agency
does not currently have sufficient performance data on in-plant controls
alone. The proposed PSES and PSNS effluent limitations address 21 of the 35
priority pollutants selected as candidates for PSES and PSNS regulation. The
pollutants and the proposed effluent limitations are listed in Table 1-3.
1-5
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TABLE 1-1
BAT EFFLUENT LIMITATIONS (ug/1)
PLASTICS-ONLY PLANTS
POLLUTANT
FOUR-DAY
LIMITATION*
DALLY
LIMITATION
(65)
Phenol
--
50
(66)
Bis(2-ethylhexyl)phthalate
50
100
(118)
Cadmium
20
30
(119)
Chromium
60
110
(120)
Copper
60
120
(121)
Cyanide
20
50
(122)
Lead
20
40
(2)
Acrolein
--
50
(38)
Ethylbenzene
--
50
(88)
Vinyl chloride
50
* No four-day average limitation was given if the daily
limitation was 50 ug/liter.
1-6
-------
TABLE 1-2
BAT EFFLUENT LIMITATIONS (ug/1)
NOT PLASTICS-ONLY PLANTS
FOUR-DAY DAILY
POLLUTANT LIMITATION" LIMITATION
(21)
2,4,6-trichlorophenol
100
175
(24)
2-chlorophenol
50
75
(31)
2,4-dichlorophenol
100
200
(34)
2,4-dimethylphenol
--
50
(57)
2-nitrophenol
75
100
(58)
4-nitrophenol
325
500
(59)
2,4-dinitrophenol
100
150
(64)
Pent achloropheno1
• 50
100
(65)
Phenol
--
50
(1)
Acenaphthene
--
50.
(8)
1,2,4-trichlorobenzene
125
225
(25)
1,2-dichlorobenzene
125
' 250
(54)
Isophorone
--
50
(66)
Bis(2-ethylhexyl)phthalate
150
350
(68)
Di-n-butyl phthalate
150
300
1-7
-------
TABLE 1-2 (continued)
FOUR-DAY DAILY
POLLUTANT LIMITATION* LIMITATION
(70) Diethyl Phthalate
125
275
(71) Dimethyl phthalate
175
375
(77) Acenaphthylene
--
50
(80) Fluorene
--
50
(81) Phenanthrene
--
50
(114) Antimony
370
780
(118) Cadmium
40
70
(119) Chromium
90
190
(120) Copp.er
70
150
(121) Cyanide
180
410
(122) Lead
40
70
(123) Mercury
50
90
(128) Zinc
100
210
(4) Benzene
75
125
(6) Carbon tetrachloride
--
50
(10) 1,2-dichloroethane
100
150
1-8
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TABLE 1-2 (concluded)
FOUR-DAY DAILY
POLLUTANT LIMITATION* LIMITATION
(11)
1,1,1-trichloroethane
50
(13)
1,1-dichloroethane
125
225
(14)
1,1,2-trichloroethane
50 '
75
(16)
Chloroethane
..
50
(23)
Chloroform
50
75
(29)
1,1-dichloroethylene
75
125
(38)
Ethylbenzene
150
275
(44)
Methylene chloride
--
50
(45)
Methyl chloride
--
50
(46)
Methyl bromide
--
50
(48)
Dichlorobromomethane
--
50
(86)
Toluene
125
225
(87)
Trichloroethylene
50
75
No four-day average limitation was given if the daily
limitation was 50 ug/liter.
1-9
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TABLE 1-3
PRETREATMENT STANDARDS FOR
EXISTING AND NEW SOURCES
• DAILY
FOUR-Di
POLLUTANT NAME
MAXIMUM (ppb)
AVERAGE
Plastics-Only Subcategory
Acrolein
50
--
Cyanide
50
20
Lead
40
20
Vinyl Chloride
50
--
Not Plastics-Only Subcategory
2,4-D imethylpheno1
50
2,4-Dichlorophenol
200
100
2,4,6-Trichlorophenol
175
100
2-Chlorophenol
75
50
2-Nitrophenol
100
75
2,4-Dinitrophenol
150
100
4-Nitrophenol
500
325
Diraethyl Phthalate
375
175
Phenanthrene
50
--
Fluorene
50
__
Acenaphthylene
50
--
Isophorone
50
--
Methyl Bromide
50
Chloroethane
50
1,2-Dichloroethane
150
100
Total Chromium
190
90
Total Mercury
90
50
1-10
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SECTION II
INTRODUCTION
LEGAL AUTHORITY
Background
The major underlying legislative authority for water pollution control
programs is the Federal Water Pollution Control Act (FWPCA), originally
enacted in 1948. Current federal efforts to control water pollution emanate
from the Federal Water Pollution Control Act Amendments of 1972 (33 U.S.C.
§§1251 et scq.), which represents a comprehensive re-write of the original
Act. Further and substantial revisions were made in 1977 with passage of the
Clean Water Act (P.L. 95-217), although the structure established in 1972 was
not changed.
Prior to 1948, there were limited federal efforts to address problems
associated with water pollution (e.g., the Public Health Service Act of 1912
and the Oil Pollution Control Act of 1924). However, it was not until passage
of the FWPCA that there was any comprehensive legislation directed
specifically at water pollution control. This Act had the following major
purposes:
• Encouraged state efforts to control water pollution.
• Supported water pollution related research.
• Authorized the Department of Justice to bring suits
to require entities to cease pollution of interstate
waters after notice and hearing and State consent.
• Established a federal advisory board for water
pollution.
• Authorized low-interest loans for construction of
sewer and waste facilities.
From 1948 until passage of the 1972 Amendments, the FWPCA was amended on
numerous occasions. (See: Public Law No. 660, 84th Congress, 2d Session
(1956); Public Law No. 88, 87th Congress, 1st Session (1961), Public Law No.
234, 89th Congress, 1st Session (1965), Public Law No. 753, 89th Congress, 2d
Session (1966), Public Law No. 224, 91st Congress, 2d Session (1970)).
Significant amendments occurred with the passage of the Water Quality Act of
1965. This Act required States to adopt water quality standards for
interstate waters by June 30, 1967 and submit them for approval to the
Secretary of the Interior (whose duties under the Act were later transferrred
to the Administrator of the Environmental Protection Agency). If no standards
were submitted by a State, or the standards submitted were not approve-d, or
the Secretary or an affected State requested a revision in standards, a
11 -1
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complex procedure was established to resolve the dispute. Water quality
standards were to include water quality criteria applicable to interstate
waters and a plan for the implementation and enforcement of such criteria. By
19 72, with few exceptions all.States had adopted water quality standards.
Federal Water Pollution Control Act Amendments of 1972
The Federal Water Pollution Control Act Amendments of 1972 (P.L. 92-500)
required the Environmental Protection Agency, in cooperation with other
Federal agencies, State agencies, interstate agencies, municipalities, and
industries, to "prepare or develop comprehensive programs for preventing,
reducing, or eliminating the pollution of the navigable waters and ground
waters and improving the sanitary condition of surface and underground waters"
(Section 102(a)). The purposes of the law were to be achieved largely through
the control of industrial and municipal discharges. These Amendments required
EPA to develop technology-based effluent limitations for conventional
pollutants (Section 301), and, in certain cases, water quality related
effluent limitations (Section 302). By July 1, 1977, existing industrial
dischargers were required to achieve effluent limitations using the best
practicable control technology currently available (BPT) (Section
301(b)(1)(A)). By July 1, 1983, these dischargers were required to achieve
effluent limitations using the best available technology economically
achievable (BAT) (Section 301(b)(2)(A)). Industrial direct dischargers
operating new plants were required to comply with new source performance
standards (NSPS) (Section 306); both new and existing dischargers to publicly
owned treatment works (POTWs) were subject to pretreatment standards (Section
307). The Amendments also created a National Pollutant Discharge Elimination
System (NPDES) whereby EPA was authorized to issue permits for the discharge
of pollutants by individual dischargers (Section 402).
While the NPDES permit process envisioned the issuance of permits on a
case-by-case basis, control requirements were to be primarily based upon
promulgated regulations. The Amendments required EPA to promulgate
regulations setting forth effluent limitation guidelines. The law further
provided regulation of categories of point sources that discharge specific
toxic pollutants (Section 307).
The Amendments specified 27 industrial point source categories for which EPA
was to develop new source performance standards for effluents (Section 306).
EPA began its regulatory activities by establishing effluent limitations
guidelines as well as new source performance and pretreatment standards for
the industrial categories identified in this legislation, which included the
Organic Chemicals Manufacturing Industry and the Plastics and Synthetic Fibers
Materials Manufacturing Industry.
Initial EPA Efforts to Develop Regulations for the Organic Chemicals
and Plastics/Synthetic Fibers Industries
Initial efforts to develop regulations for the Organic Chemicals Industry and
the Plastics and Synthetic Fibers Industry began in 1973. Under a two-phase
program, conventional pollutant parameters of the Organic Chemicals
Manufacturing Industry were regulated separately from those of the Plastics
and Synthetic Fibers Industry. Selected nonconventional toxic pollutant
II-2
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parameters such as chemical oxygen demand, zinc, copper, chromium, cyanide,
phenolic compounds, and fluorides were regulated for at least one or more
subcategories.
Phase I regulations for the Organic Chemicals Manufacturing Industry were
promulgated under court order on April 25, 1974 (39 FR 14676). These
regulations established effluent limitations guidelines for existing sources
and pretreatment and performance standards for new sources for 40 of 260
identified product/process segments. Phase II regulations, promulgated under
court order on January 5, 1976 (41 FR 902), established effluent limitations
guidelines and pretreatment and performance standards for an additional 27
product/process segments.
Phase I regulations for the Plastics and Synthetic Fibers Industry were
promulgated under court order on April 5, 1974 (39 FR 12502). They
established effluent limitations guidelines and pretreatment and performance
standards for 13 of the 21 identified plastic/synthetic fibers subcategories.
The Phase II regulations, promulgated on January 23, 1975 (40 FR 3730),
established guidelines and standards for the remaining eight subcategories.
When the Phase II regulations for the Organic Chemicals Manufacturing Industry
were published, litigation challenging the Phase I regulations was pending.
On February 10, 1976 (a month after publication of the Phase II regulations),
the Court ordered EPA to withdraw, reconsider, and repromulgate both the Phase
I and Phase II regulations, Union Carbide v. Train, 541 F.2d 1171 (4th Cir.
1976). In accordance with this ruling, on April 1, 1976, EPA published a
notice revoking all of the Phase I and II regulations except those relating to
the manufacture of. butadiene (41 FR 13936).
During the same time period, existing regulations (except those concerning pH
limitations) for the Plastics and Synthetic Fibers Industry were also being
challenged in court. On March 10, 1976, the Phase I plastics and synthetics
fibers guidelines and standards were remanded to EPA for reconsideration. On
August 4, 1976, EPA published a notice (41 FR 32587) revoking all Phase I
guidelines and standards except the unchallenged pH limitations. Since the
Phase II guidelines and standards were based on data similar to the Phase I
regulations which the court found to be defective, the Agency also revoked
these Phase II regulations.
Initial EPA Efforts to Develop Effluent Standards for Individual
Toxic Pollutants
Section 307(a) of the FWPCA, as amended, required that EPA develop effluent
standards for individual toxic pollutants within ninety days. Because of the
lack of available data, EPA failed to list any toxic pollutants by the initial
deadline; as a result, the Natural Resources Defense Council (NRDC) filed a
lawsuit to force the Agency to fulfill its statutory obligations. This
lawsuit resulted in a June 1973 Consent Decree that set a deadline for EPA to
publish a list of the toxic pollutants which would be regulated. On September
7, 1973, EPA published a list of nine toxic pollutants for which it intended
to establish effluent guidelines: aldrin/dieldrin, benzidine, cadmium,
cyanide, DDT (DDE, DDD), endrin, polychlorinated biphenyls (PCBs), mercury,
and toxaphene.
II -3
-------
The NRDC filed a new action against EPA, alleging that the toxic pollutant
list was illegally narrow and- that EPA used unpublished criteria in selecting
the nine compounds. This lawsuit was dismissed by the U.S. District Court on
May 23, 1974. The Court ruled that the Administrator had acted within his
discretion in listing only nine compounds and that the selection criteria used
were not unreasonable. The Court further asserted that Congress did not
expect the Administrator to regulate all toxic pollutants at one time and that
narrowing the list to a feasible number of compounds was reasonable.
This dismissal was appealed by NRDC. The D.C. Court of Appeals reversed the
lower court's decision on September 15, 1975 (NRDC v. Train, 519 F.2d 287)
finding that NRDC had substantially shown in District Court that EPA had not
filed the entire administrative record with the Court and the Court was in
error when it ruled on the basis of a partial administrative record. The case
was remanded to the District Court for a decision on the entire record, which
it instructed the Administrator to provide.
While the length of the list was being challenged, on December 27, 1973, EPA
did propose effluent standards for the nine toxic pollutants identified on the
original list (38 FR 35388). EPA then held hearings on the proposal in April
and May of 1974. The Agency interpreted the FWPCA to require a formal hearing
and findings based on the hearing record, which placed the burden of proof on
EPA to justify the proposed regulations. The proposed standards were
vigorously attacked by both industry and environmental groups; at the close of
the hearing, EPA concluded that the record would not support the standards as
proposed and withdrew them. Subsequently, the Environmental Defense Fund
(EDF) in conjunction with NRDC filed a suit alleging that EPA had failed to
perform a nondiscretionary duty by not promulgating final standards.
Recognizing that these lawsuits needed to be settled so that the Agency could
devote its efforts to developing its regulatory program, EPA entered into a
Settlement Agreement with both EDF and NRDC which was approved in a Consent
Decree issued by the U. S. District Court for the District of Columbia on June
9, 1976, Natural Resources Defense Counci1, et al. v. Train, 8 E.R.C.
2120 (D.D.C. 1976). In the Agreement, EPA proposed a new regulatory strategy
for toxic pollutants -- an industry-by-industry approach rather than a
pollutant-by-pollutant approach. EPA was to develop and issue BAT effluent
limitation guidelines, pretreatment standards, and new source performance
standards for 21 major industries (including the Organic Chemicals and
Plastics/Synthetic Fibers - OCPSF - Industry) covering 65 toxic pollutants or
group of pollutants by December 31, 1979. Under this strategy, section 307(a)
was used to issue standards for six of the nine toxic pollutants originally
listed but never regulated. Thereafter, the use of section 307(a) was limited
to cases where control beyond BAT was needed.
By early 1976, the Agency had uniform national standards that controlled the
discharge of conventional and toxic pollutants for only one portion of the
OCPSF Industries -- butadiene manufacturing. Pursuant to the Consent Decree
for toxic pollutants, effluent standards were proposed under Section 307(a)
for six of the nine originally listed toxic pollutants (aldrin/dieldrin, DDT,
endrin, toxaphene, benzidine, and PCBs) on a staggered schedule through July
23, 1976; the formal rulemaking hearings with public comments were held during
the summer and fall of that year. Subsequently, standards were promulgated
II-4
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for the four pesticides and benzidine on January 12, 1977 and for PCBs on
February 2, 1977. Pretreatment standards for eight of the 21 industrial
categories were also developed and published by July 1977.
Clean Water Act of 1977
On December 27, 1977, the President signed into law amendments to the FWPCA,
known as the Clean Water Act of 1977 (P.L. 95-217). Major provisions of the
1976 Consent Decree were incorporated into the FWPCA. BAT levels of control
were required for all toxic pollutants referred to in Table 1 of Committee
Print No. 95-30 of the House Committee on Public Works and Transportation
(identical to the list of 65 classes of toxic pollutants listed in the Consent
Decree). For toxic pollutants subsequently added to this list, BAT
regulations were to be promulgated within three years of listing. Section
307(a) was also amended to reflect the Consent Decree. The 65 classes of
pollutants in the Committee Print were listed as toxic pollutants. BAT was
established as the minimum level of control for all toxic pollutants listed
under Section 307. (More stringent effluent standards are still available for
use at the discretion of the Administrator in cases of extreme hazard.) To
strengthen the toxics control program, Congress added a new section 304(e) to
the Act, authorizing the Administrator to prescribe what have been termed
"best management practices" (BMPs) to prevent the release of toxic pollutants
through plant site runoff, spillage or leaks, sludge or waste disposal, and
drainage from raw material storage associated with, or ancillary to, the
manufacturing or treatment process.
The Clean Water Act also significantly revised the framework of the Agency's
technology-based pollution abatement efforts. Distinctions among pollutants
were made and regulations requiring different technical and economic bases
were incorporated into the Act. The original BPT and BAT regulations were
modified by a new regulatory concept, Best Conventional Technology (BCT), and
the universe of pollutants previously considered was subdivided into three
categories: conventional, toxic, and nonconventional. Conventional
pollutants were defined as biochemical oxygen demand (BOD), total suspended
solids (TSS), fecal coliform, pH, and oil and grease (O&G). Toxic pollutants
were defined as those substances (compounds) included in the Section 307(a)
list. Nonconventional pollutants were defined as all other pollutants. Toxic
and conventional pollutants were to be subject to BAT and BCT effluent
limitations, respectively, no later than July 1, 1984. The factors to be
considered in assessing BCT include: (1) the reasonableness of the
relationship between the costs and the benefits of reducing the effluent
wasteload; and (2) the comparison of the cost and level of reduction for an
industrial discharge with the cost and level of reduction of similar
pollutants for a typical POTW (Section 304(b)(4)(B)).
Subsequent EPA Developments and Regulations
After entering into the Consent Decree (major provisions of which were
subsequently incorporated into the Clean Water Act), EPA faced the major task
of establishing comprehensive technology-based standards for the 21 industries
and 65 classes of priority pollutants. Shortly after the publication of the
Consent Decree, EPA began to collect the technical and economic information
necessary to establish toxic pollutant effluent standards. EPA used its
11-5
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authority under Section 306 of the Clean Water Act to gather information
directly from manufacturing facilities (see Guidelines Development
Methodology, the second part of this chapter). Recognizing that some of the
listed substances represented classes of compounds, EPA refined the list by
specifically listing some members of the classes and excluding others,
producing-a list of 129 priority pollutants. EPA has since eliminated three
pollutants from the original list: bis(chloromethyl) ether,
dichlorodifluoromethane, and trichlorofluoremethane. EPA is developing
effluent limitation guidelines for the 126 priority pollutants currently on
its list.
This effort did not meet its original deadlines, and the NRDC and others filed
a motion with the District Court on September 26, 1978 requesting that EPA
show cause why it should not be held in contempt of court for failing to
comply with the timetable of the Consent Decree. This action resulted in a
modification of the Consent Decree which was approved by the Court on March 9,
1979 (NRDC et al¦, vs. Costle, 12 ERC 1833). The modifications outlined
by the Court included:
• Expansion and refinement of the original 21 Point
Source Categories into 34 Point Source Categories.
• Extension of deadlines to reflect the Clean Water
Act amendments requiring the proposal and promulgation
of technology-based effluent limitations, standards of
performance, pretreatment standards, and water
quality standards.
• Extension of deadlines for compliance with BAT until
July 1, 1984.
• Broadening of EPA discretion in excluding certain
pollutants from regulation.
• Granting EPA additional time to develop pretreatment
standards for pollutants that are "incompatible" with
the operation of POTWs. These pollutants may be in
addition to the 65 classes specifically mentioned in
the Consent Decree and referred to in the Clean Water
Act.
" Detailed specification of the steps EPA must take to
determine when effluent limitations more stringent
than the technology-based limitations are necessary to
protect aquatic life and human health.
Recent Developments and Current Deadlines
In 1981, NRDC sued EPA in the D. C. District Court for not meeting the second
set of deadlines for technology-based regulations which had been set in the
1979 modification of the Consent Decree. On April 7, 1982, District Court
Judge Flannery ordered EPA to propose all regulations within six months and
promulgate all regulations within six additional months. EPA asked that the
11-6
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deadlines for the regulations for the Organic Chemicals and Plastics and
Synthetic Fibers Industries be extended. After considering the Agency's
request, the Judge filed an order on October 26, 1982, requiring EPA to
propose the regulations on this industry by February 1983 and promulgate the
final regulation by March 1984.
GUIDELINES DEVELOPMENT METHODOLOGY
General
Developing effluent limitations guidelines and standards for the Organic
Chemicals and Plastics/Synthetic Fibers (OCPSF) Industries has required that
the Agency collect and evaluate substantial amounts of data on these
industries. Major tasks undertaken to ensure sound technical development of
effluent guidelines have included:
• Definition of these industries in terms of product
coverage.
• Collection and evaluation of industry data
regarding product/processes used, water usage,
quantity and quality of wastewater generated, and the
performance and cost of the pollutant control
technologies (both in-plant and end-of-pipe)
currently in place.
• Collection and assessment of information concerning
innovative pollutant control technologies which might
be used in these industries.
• Measurement of pollutant concentrations present in
industry wastewaters (including selection and
refinement of appropriate analytical techniques).
• Examination of the industry to determine whether
differences in raw materials, product/processes,
final products, equipment, age and size of plants,
water usage, wastewater constituents, or other
factors justify developing separate effluent
limitations and standards for different segments
(subcategories) of the industry.
• Selection of pollutants to be addressed by BAT
regulations by considering raw wastewater data in
light of the process chemistry/engineering practiced
by these industries together with pollutant
detectability, frequency of occurrence, environmental
significance, treatability limits, and (for indirect
dischargers) removal and impacts of individual
pollutants at POTWs.
II-7
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• Evaluation of the performance and costs of the
pollutant control technologies available to the
industry for meeting each of several candidate
effluent limitations.
• Evaluation of the non-water quality environmental
impacts of the pollutant control technologies,
including air quality impacts, solid waste
generation, water consumption and energy consumption.
• Selection of specific control and treatment
technologies as the bases for BAT, NSPS, PSES and
PSNS effluent limitation regulations by comparing
pollutant reduction, other environmental impacts,
cost effectiveness, and the economic impact on the
industry of each alternative technology.
Descriptions of the details and results of these tasks make up the bulk of the
remaining chapters of this Development Document. The surveys used to gather
the data on the industry are described below.
Definition and Surveys of the Industry
The Consent Decree (discussed under Legal Authority, above) requires that
effluent.limitations and guidelines, including pretreatment standards, extend
to 95% of the point sources within the Organic Chemicals and
Plastics/Synthetic Fibers Industries. EPA's first tasks were to determine
what manufacturing facilities (and SIC codes) are included in the industry,
and then to collect sufficient technical and economic information to establish
technically sound toxic pollutant effluent standards. After determining what
plants must be covered by the regulations (see Section III), EPA collected
historical data from specific plants within these industries on their
production and treatment of wastewater as authorized by Section 308 of the
FWPCA. EPA then funded and directed several sampling and analysis programs at
selected industry plants, characterizing specific waste streams that
introduced priority pollutants into both aquatic environments and Publically
Owned Treatment Works (POTV).
The Agency also executed several studies on the treatment of industry
wastewaters using specific treatment processes. The various data collection
studies EPA completed in developing regulations for this industry are listed
in TABLE 11 — 1, along with brief statements on the focus and scope of each
study, and a reference to a detailed discussion of each study. The various
studies are summarized individually below.
308 BPT Questionnaires. In 1976, EPA contracted Rychman, Edgerley,
Tomlinson, and Associates (RETA - now known as Envirodyne Engineers) of St.
Louis, Missouri to survey the Organic Chemicals and Plastics/Synthetic Fibers
Industries concerning their current wastewater control procedures. To aid in
developing the BPT regulations, RETA and the Agency developed a "BPT
Questionnaire" (see Appendix A) requesting basic information about wastewater
II-8
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TABLE 11-1
EPA TECHNICAL DATABASES USED IN EFFLUENT GUIDELINES DEVELOPMENT
i
UD
STUDY DATE
308 BPT 1976-
Questionnaire 1977
Catalytic 1976-
Biological 1978
Stud ies
308 BAT 1977-
Questionnaire 1978
Screening 1977-
Phase I 1978
PURPOSE
Indicatory Fate
Study
Veri f i cat ion
Study
Sc reen i ng
Phase I I
Phys icaI-ChemicaI
Samp Iing
Program
OSU
Bio log icaI
T rea tment
Production and treatment of conven-
tional and' nonconventionaI pollutants
Determination of kinetic constants
and treatability factors for
activated sludge treatment models
of specific organic chemicals.
Production and treatment of priority
pollutants.
EPA-executed sampling study of
pollutant occurrence and removal
at plants manufacturing high volume
chemicaIs.
SCOPE
1978 Determination of the fate of
1978 specific priority pollutants
in biological treatment.
1978- EPA-executed sampling study of
1980 influents and effluents at
major product/processes within
the industry.
1979 EPA-executed sampling study
of pollutant occurrence and removal
at plants manufacturing
specialty chemicals.
1979- Performance of treatment techno-
1981 logics: steam stripping, activated
carbon, Iiquid-liquid extraction.
1979- Determination of kinetic constants
1982 for activated sludge treatment;
models; toxicity of priority
pollutants to the activated sludge
process.
Deta iled
Di s-
cuss ion
I I
VI I I 1
Responses from 566 plants in the
Organic Chemicals and Plastics/
Synthetic Fibers Industries
Bench scale studies of 22
individual organic chemicals in
synthetic wastewaters.
Same as above. I I
103 plants; one day of V
sampling at each plant.
Three plants. A<>P E
Thirty-seven plants; three days
sampling at each plant.
UO plants; one day of
sampling at each plant.
Four plants, one to two months VII
at each plant.
Pilot studies of 2U organic com- APP E
pounds - toxicity work completed in
two years; kinetic work continues.
I I -9
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TABLE 11-1 (concluded)
STUDY
Organic Adsorption
Re s i n s
CMA 5-PI ant
Sampling Program
Carbon Adsorption
and Steam Strip-
ping Question-
na i res
Two-Plant Pollutant
Pred i ctab iI Ity
Study
DATE PURPOSE
1979- Removal of priority pollutants
1982 in pure solutions using activated
carbon and resins.
1980- Study on removals of priority
1981 pollutants at we I I-designed
and we I I-operated biological
treatment systems.
1980 Design and operating experience,
and predictability of priority
pollutant removals.
1981 Confirm predictions of priority
pollutants from feedstock and
generic process chemistry.
SCOPE
Bench scale batch studies of
5 organic compounds.
Five plants; four to six weeks
of dally sampling at each plant.
Responses from 93 plants using
carbon adsorption, 20 using steam
stripping.
Two plants, 50 to 75 product/
processes at each, "long term"
samp Ii ng.
Deta iIed
D i s-
cussI on
APP E .
APP E
i
o
-------
generation and treatment at each plant. This was sent to plants that EPA
determined manufactured products found in Lists 1, 2, and 3 in the
questionnaire.
The mailing list was developed from a number of sources. The original list of
organic chemicals producers was developed by Radian Corporation under EPA
contract. This list was corrected and expanded by an examination of other
sources, including the SRI Directory of Chemical Manufacturers, the Dun and
Bradstreet Middle Market Directory, Moody's Industrial Manual, Standard and
Poor's Index, the Thomas Register, and the Red Book of Plastics
Manufacturers. From this work, 1,500 manufacturing sites were selected for
the original mailing.
Of the approximately 1,500 questionnaires mailed, approximately 900 were
returned with information appropriate to development of effluent limitations
for the Organic Chemicals and Plastics/Synthetic Fibers Industries;
apparently, the remaining questionnaires had been sent to sales offices,
warehouses, and companies that did riot manufacture either organic chemicals or
plastics/synthetic fibers. The list of 900 plants was reduced by
approximately 300 by deleting those plants that were believed to either belong
to the Inorganics, Pharmaceuticals, Pesticides, or Gum and Wood categories;
largely formulate adhesives and sealants, paints and inks; or manufacture
plastic products. Manufacturers of such products (including latexes,
polyvinyl acetates, phenol-urea resins, and phenol-formaldehyde resins) are to
be regulated under either the Adhesives and Sealants, Paint and Ink
Formulation, or Plastics Processing industrial categories. As a result, the
1,500 questionnaires produced a 308 database of 566 plants.
The Agency then re-evaluated the Criteria for listing plants as manufacturers
of plastics or synthetic fibers in the 308 database. EPA determined that a
plant must manufacture a product or products fitting the descriptions listed
in Standard Industrial Classification 2821, 2823, or 2824 (see Section III) to
be included in the database for these regulations. EPA wished to supplement
its information on the modes of discharge used at plastics/synthetic fibers
plants. The Agency phoned each plastics/synthetic fibers plant listed in the
SRI Directory of Chemical Producers that was not one of the 566 plants and
asked:
(1) Whether the plant did not merely process finished resins but actually
converted monomers to polymers;
(2) Whether the plant generated wastewaters from that conversion process;
(3) How such wastewaters were discharged (e.g., direct discharge to a
river, discharge to a P01V, deepwell injection); and
(4) Whether and how these wastewaters were treated on site.
From this survey, EPA added approximately 240 plastics/synthetics plants to
the 308 list. Since the Agency did not send out questionnaires to these 300
plants, no data from them was added to the 308 database.
11-11
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308 BAT Questionnaire. The Agency received and analyzed approximately 900
completed BP^ questionnaires by the summer of 1977 and concluded that the
development of Best Available Technology Economically Achievable (BAT)
regulations required more data on priority pollutants. The 1976 BPT
questionnaire had asked each plant for information on products and production
levels, in-plant and end-of-pipe wastewater treatment systems, water use and
disposition, end-of-pipe treatment plant influent and effluent
characteristics, raw water intake characteristics, discharge stream
characteristics, and product/process waste stream characteristics. Individual
priority pollution data reported on these questionnaires was limited. To
supplement these data, in late 1977 EPA developed a second questionnaire, the
BAT Questionnaire (see Appendix A) requesting data from industry on the
occurrence and treatability of priority pollutants. The BAT questionnaire
requested updated information from each plant about product/process
configurations, production levels, wastewater treatment technology, chemical
methods for priority pollutant analysis, and priority pollutant waste loads.
This information was requested in a mailing to those plants in the database
that had been determined to manufacture one or more products of concern (see
Lists 1, 2, and 3 in the original questionnaire) or had reported production of
priority pollutants in the BPT Questionnaire. Upon receipt, these data were
entered into a computer file.
Screening and Verification Sampling and Analysis Program. The responses to
the Agency's 1976 BPT and 1977 BAT 308 questionnaires were useful as an
initial survey of what priority pollutants occurred at what concentrations in
OCPSF wastewaters, but did not provide sufficient priority pollutant data to
permit statistical derivation of effluent limitation concentrations. To
gather the needed data, in 1977 EPA initiated a sampling and analysis
program. This program, implemented in three parts -- Phase I Screening, Phase
II Screening, and Verification -- was managed by EPA and performed by EPA
contractors and EPA Regional Surveillance and Analysis staff. The analytical
work was performed by several EPA Regional and contract laboratories listed in
Section V. The major goal of the Screening Program was to gather qualitative
data on the presence or absence of priority pollutants in OCPSF waste
streams. The major goals of the Verification Program were to:
• Obtain priority pollutant raw waste load information
on specific product/processes.
• Obtain information regarding the effectiveness of
current wastewater treatment systems in reducing
priority pollutant loadings, both at "end-of-pipe" and
"in-process" treatment systems.
• Develop analytical methods for organic compounds
based upon gas chromatography using conventional
detectors rather than mass spectrometric detection.
Because the Agency did not have the massive funds and manpower necessary to
gather data on the production, wastewater flow, and priority pollutant
concentrations for all the individual product/processes in the Organic
Chemicals and Plastics/Synthetic Fibers Industries, for its Verification
11-12
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Program the Agency developed a ranking list of the categories of products
manufactured by these industries. The priorities for regulation were as
follows:
Priority 1 Chemicals manufactured in excess of 5 million pounds per year
(top 100 production items) that are priority pollutants. This
list contains 25 products.
Priority 2 Chemicals derived from priority pollutants and are manufactured
in excess of 5 million pounds per year. This list contains 19
products.
Priority 3 Chemicals on the list of priority pollutants, not including
Priority 1 above and not including pesticides. This list
contains 67 products.
Priority 4 Chemicals derived from priority pollutants but that are
manufactured at less than 5 million pounds per year. This list
contains 146 products.
Priority 5 All other organic chemicals manufactured in excess of 5 million
pounds per year. This list contains 81 products.
Priority 6 Organic, non-pesticide entries on the Toxic Substances Control
Act (TSCA) "Candidate List of Chemical Substances," Volumes I to
IV, USEPA, Office of Toxic Substances, April 1977, that are not
in Priorities 1 through 5 above. This list contains 325
products.
Priority 7 The remainder of the 25,000 commercial industrial chemicals.
Appendix B lists the products in each of the first five priorities. EPA
designed its product/process sampling program to produce data adequate for
developing regulations for as many of the priority categories as possible,
starting at Priority 1. The responses to both 308 Surveys were used to choose
plants for sampling that utilized the maximum number of desired
product/processes. Product/processes other than those targeted for sampling
were also in operation at most of these facilities. Because it was
convenient, some of these product/processes were sampled and added to the
original list of product/processes to be sampled. The sampling studies
completed through 1982 covered all of Priorities 1 through 4 and some of
Priorities 5 and 6.
Time, staff, and money constraints forced EPA to study the industry in
phases. Those product/processes considered essential in determining the
economic and environmental impact of regulation on the industry were sampled
in the Phase I Verification Study. The remainder of the industry was to be
addressed in the Phase II Verification Study, which was never performed. The
Phase II Screening Study was designed to show that specialty and small volume
chemicals could be represented by the Phase I Verification results.
The Screening Study initially included 171 plants. However, because of
various infractions of sampling protocols, 28 plants were deleted.
11-13
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Thirty-seven plants were included in the Verification Study. Six plants,
however, were eventually dropped from the database. Among the plants dropped
from the Verification database were: zero discharge plants, plants where
influents were not sampled, and plants where both blind spike samples were
taken for organic analyses (see Appendix C) and where no metal sampling took
place. Details and discussion of each study can be found in Section V.
EPA's other priority pollutant data collection efforts are each briefly
described in the rest of this chapter. More details on each appear in the
chapter of this report cited in Table II-l.
CMA Five-Plant Sampling Program. The Screening and Verification studies were
one to three-day samplings at a large number of plants. In 1980 and 1981, the
Chemical Manufacturers Association (CMA) and EPA cooperated on a series of 4-
to 6-week studies at five chemical manufacturing plants that appeared to have
well-designed and well-operated biological (activated sludge) treatment
facilities. The five-plant study was structured to develop a long-term
database on the removal of toxic organics by biological treatment systems. An
extensive quality assurance/quality control program was executed to assure
that the reliability of the analytical results could be defined so the
database could be properly interpreted. More details of this study are in
Section V.
Other EPA Studies.
(1) Physical-Chemical Sampling Program. EPA conducted a series of one
to two-month sampling studies at four plants during 1979 through 1981 to
determine the effectiveness of physical-chemical treatment technologies for
removing toxic pollutants. Effluent streams from the following treatment
technologies were monitored: steam stripping, activated carbon, and
liquid-liquid extraction. The data were intended to be used to evaluate the
priority pollutant influent concentration fluctuations and achievable effluent
concentrations.
(2) Carbon Adsorption and Steam Stripping Questionnaires. The 308
questionnaires of 1976 and 1977 had gathered general information on in-plant
treatment systems in use by the industry. In 1980 EPA conducted two
additional surveys to assess the status of industrial usage of carbon
adsorption and steam stripping for the removal of priority pollutants from
process wastewaters, requesting specific information on system design,
operating parameters, and efficiency of removal of priority pollutants for
carbon adsorption and steam stripping treatments (see Appendix D for the
questionnaires). The survey forms were prepared with the assistance of a task
force from the American Institute of Chemical Engineers (AIChE). Survey
response, although voluntary, was better than 80 percent for carbon adsorption
(116 surveys distributed, 93 respondents) and approximately 50 percent for
steam stripping (41 distributed, 20 respondents). More details of these
questionnaires are given in Section VII.
(3) Two-Plant Pollutant Predictability Study. In 1981, EPA conducted
long-term sampling programs at two plants to evaluate the concept of
predicting priority pollutants in the product/process waste streams from
knowledge of the process feedstock and of generic process chemistry. The
11-14
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objective of these studies was to try to correlate daily loadings of priority
pollutant levels with the product/processes being operated. The study was
confined to a specific production area within each plant where 50 to 75
product/processes were being operated concurrently. Most of these
product/processes were batch steps in multi-step syntheses and represented the
wide variety of product/processes associated with the production of low-volume
organic chemicals not investigated in previous sampling programs. More
details of this study are given in Section V.
(4) Miscellaneous Studies. In developing these guidelines and in
related work, EPA and its contractors have performed many other studies on
priority pollutant occurrence, fate, predictability, removal kinetics, removal
equilibria, some of which are listed in Table 11 — 1. The results of these
studies have facilitated evaluation of the occurrence and treatment of the
priority pollutants discharged by the Organic Chemicals and Plastics/Synthetic
Fibers Industries. The details of these studies are presented later in this
report, where appropriate.
11-15
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SECTION III
INDUSTRY DESCRIPTION
INTRODUCTION
The organic chemicals industry began modestly in the middle of the 19th
century. The production of coke, used both as a fuel and reductant in blast
furnaces for steel production, generated coal tar as a by-product. These tars
were initially regarded as wastes. However, with the synthesis of the first
coal tar dye (mauve) by Perkin in 1856, chemists and engineers began to
recover and use them. The organic chemicals industry began with the isolation
and commercial production of aromatic hydrocarbons such as benzene and toluene
from coal tar.
As more organic compounds possessing valuable properties were identified,
commercial production methods for these compounds became desirable. Not
surprisingly, the early products of the chemical industry were those most
desired by society: dyes, explosives, and pharmaceuticals. The economic
incentive to recover and use industrial wastes and by-products continued to be
a driving force behind the burgeoning chemical industry. For example, the
chlorinated aromatic chemicals segment of the industry developed mainly
because of: (1)- the availability of large quantities of chlorine formed as a
by-product from caustic soda production (already a commodity chemical); (2)
the availability of benzene derived from coal tar; and (3) the discovery that
such compounds could serve as useful intermediates for production of more
valuable materials, such as phenol and picric acid. Specialty products such
as surfactants, pesticides, and aerosol propellants were developed later to
satisfy particular commercial needs.
The Plastics/Synthetic Fibers Industry began somewhat later as an outgrowth of
the Organic Chemicals Industry. The first commercial polymers, rayon and
bakelite, were produced in the early 1900s from feedstocks manufactured by the
organic chemicals industry. In the last several decades, the variety of
plastic and synthetic fiber products developed and the diversity of markets
and applications of these products have made the Plastic/Synthetic Fibers
Industry the largest (measured by volume) consumer of organic chemicals.
Chemicals derived from coal were the principal feedstocks of the early
industry, although ethanol, derived from fermentation, was a source of some
aliphatic compounds. Changing the source of industry feedstocks to less
expensive petroleum derivatives lowered prices and opened new markets for
organic chemicals and plastics/synthetic fibers during the 1920s and 1930s.
By World War II, the modern Organic Chemicals and Plastics/Synthetic Fiber
Industries based on petro-chemicals were firmly established in the United
States. Future development of a synthetic fuel industry may again make coal a
significant source of feedstocks to the organic chemicals industry.
Today the Organic Chemicals and Plastics/Synthetic Fibers Industries include
production facilities of two distinct types: those whose primary function is
III-l
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chemical synthesis, and those that recover organic chemicals as by-products
from unrelated manufacturing operations such as coke plants (steel production)
and pulp mills (paper production). The bulk of the plants in these industries
are of the former type: plants that process chemical precursors (raw
materials) into a wide variety of products for virtually every industrial and
consumer market. Approximately ninety percent of the precursors, the primary
feedstocks for all of the industry's thousands of products, are derived from
petroleum and natural gas. The remaining ten percent is supplied by plants
that recover organic chemicals from coal tar condensates generated by coke
production.
There are numerous ways to describe the Organic Chemicals and
Plastics/Synthetic Fibers Industries; however, traditional profiles such as
number of product lines or volume of product sales mask the industry's
complexity and diversity. Even more difficult is to describe these industries
in terms that distinguish among plants according to wastewater
characteristics. Subsequent sections of this chapter discuss the Organic
Chemicals and Plastics/Synthetic Fibers Industries from several different
perspectives, including product line, product sales, geographic distribution,
facility size, facility age, and wastewater treatment practiced by these
industries. The subcategorization of plants within the Organic Chemicals and
Plastics/Synthetic Fibers Industries by process chemistry, raw and treated
wastewater characteristics, and other plant-specific factors is discussed in
Section IV.
DEFINITION OF THE INDUSTRY
Settlement Agreement Definition
Standard Industrial Classification (SIC) codes, established by the U.S.
Department of Commerce, are classifications of commercial and industrial
establishments by type of activity in which they are engaged. The Settlement
Agreement (see Section II) defines the Organic Chemicals and
Plastics/Synthetic Fibers Industries, addressed by this Development Document,
to comprise the following SIC codes:
2865 Cyclic (Coal Tar) Crudes, and Cyclic Intermediates, Dyes, and Organic
Pigments (Lakes and Toners).
2869 Industrial Organic Chemicals, Not Elsewhere Classified.
2821 Plastics Materials, Synthetic Resins, and Nonvulcanizable Elastomers.
2823 Cellulosic Mau-Made Fibers.
2824 Synthetic Organic Fibers, Except Cellulosic.
The Settlement Agreement defines the Organic Chemicals Manufacturing and
Plastics/Synthetic Materials Manufacturing Industries (since combined into the
industry category addressed by this development document) to include all
facilities within specific SIC codes. The Organic Chemicals Manufacturing
industry includes two of these SIC codes: SIC 2865, Cyclic (Coal Tar) Crudes,
III-2
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and Cylic Intermediates, Dyes, and Organic Pigments (Lakes and Toners); and
SIC 2869, Industrial Organic Chemicals, Not Elsewhere Classified.
The products that the SIC Manual includes in the industrial organic chemical
industry (SIC 286) are natural products such as gum and wood chemicals (SIC
2861), aromatic and other cyclic organic chemicals from the processing of coal
tar and petroleum (SIC 2865), and aliphatic or acyclic organic chemicals (SIC
2869). These chemicals are the raw materials for deriving products such as
plastics, rubbers, fibers, protective coatings, and detergents, but have few
direct consumer uses. Gum and Wood Chemicals (SIC 2861) are regulated under a
separate Consent Degree industrial category, Gum and Wood Chemicals
Manufacturing.
The Plastics/Synthetic Materials Manufacturing category as defined by the
Consent Decree, comprises SIC 282, Plastic Materials and Synthetic Resins,
Synthetic and Other Manmade Fibers, except Glass. SIC 282, in turn, includes
the following four-digit SIC codes:
2821 Plastics Materials, Synthetic Resins, and Nonvulcanizable Elastomers;
2822 Synthetic Rubber (Vulcanizable Elastomers)
2823 Cellulosic Man-Made Fibers
2824 Synthetic Organic Fibers, Except Cellulosic.
Of these codes, SIC 2822 is covered specifically by another Consent Decree
industrial category, Rubber Processing. Similarly, another SIC code which
might be considered as part of the Plastics industry, SIC 3079, the
miscellaneous plastics products industry, is covered by the Consent Decree
industriaL category Plastics Molding and Forming.
The relationship of all the industries listed in the SIC Manual as being
related to production of organic chemicals or plastics and synthetic fibers is
shown in FIGURE III-1.
Primary, Secondary, and Tertiary SIC Codes
Standard Industrial Classification (SIC) codes, established by the U.S.
Department of Commerce, are classifications of commerical and industrial
establishments by type of activity in which they are engaged. The SIC code
system is commonly employed for collection and organization of data (e.g.,
gross production, sales, number of employees, and geographic location) for U.
S. industries. An establishment is an economic unit which produces goods or
services — for example, a chemical plant, a mine, a factory, or a store. The
establishment is at a single physical location and is typically engaged in a
single or dominant type of economic activity for which an industry code is
applicable.
Where a single physical location encompasses two or more distinct and separate
economic activities for which different industrial classification codes seem
applicable (for example, a steel plant that produces organic chemicals as a
result of its coking operations), such activities are treated as separate
III-3
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FIGURE 111-1
RELATIONSHIPS AMONG THE SIC CODES RELATED TO THE PRODUCTION
OF ORGANIC CHEMICALS, PLASTICS, AND SYNTHETIC FIBERS
Petrochemical Inter-Industry Relationship
Feedstock Industries
?«itroc»«m'Cai innusmes
Petrochemtcal-Deoenoent
Chemical industries
2321
F'astic
Materials
. 1322
Svruh«f»c
"uQOef s
. 2324
Synxhetic
r oers
mi _
Crude
Petroleum
i Natural Gas
m* *321 ^
Natural \
Gat Liquids
p. 2911 _
Petroleum
Refining
» 2365 _i
CvC' CS and
Arorr atics
» 2269 ,
Acvcmcs b
Aliphntics
„ 2373
N-troqencus
f erutijers
. 2395
CutDon
Slack
2543
'iur»ac:ants
- 2823 Callulosic Fiber*
2831 Biological*
» 2833 Medtcinals & Botanicals
_ 2834 Pharmaceuticals
« 2841 Detergents
p. 2842 Polishes
2844 Toiletries
|_2851 Paints
I
2879 Pesticides
2891 Adhesive®
2874
2875
2892
Phosphatic Fertilizer*
Mixed Fertilizer*
Explosives
2893 Printing Inks
SOURCE: U.S. Department of Commerce, 1981b.
111 -4
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establishments under separate SIC codes, provided that: (1) no one industry
description in the Standard Industrial Classification includes such combined
activities; (2) the employment in each such economic activity is significant;
(3) such activities are not ordinarily associated with one another at common
physical locations; and (4) reports can be prepared on the number of
employees, their wages and salaries, and other establishment type data. A
single plant may include more than one establishment and more than one SIC
code.
A plant is assigned a primary SIC code corresponding to its primary activity,
which is the activity producing its primary product or group of products. The
primary product is the product having the highest total annual shipment
value. The secondary products of a plant are all products other than the
primary products. Frequently in the chemical industry a plant may produce
large amounts of a low-cost chemical but be assigned another SIC code because
of lower-volume production of a high-priced specialty chemical. Many plants
are also assigned secondary, tertiary, or lower order SIC codes corresponding
to plant activities beyond their primary activities. The inclusion of plants
with a secondary or lower order SIC code produces a list of plants
manufacturing a given class of industrial products but also includes plants
that produced only minor (or in some cases insignificant) amounts of those
products. While the latter plants are part of an industry economically, their
inclusion may distort seriously the description of the industry's wastewater
production and treatment, unless the wastewaters can be segregated by SIC
codes.
PRODUCT LINE
Products of Various SIC Categories
Important products of the Organic Chemicals Industry within SIC 2865 include:
(1) derivatives of benzene, toluene, naphthalene, anthracene, pyridine,
carbazole, and other cyclic chemical products; (2) synthetic organic dyes; (3)
synthetic organic pigments; and (4) cyclic (coal tar) crudes, such as light
oils and light oil products; coal tar acids; and products of medium and heavy
oil such as creosote oil, naphthalene, anthracene, and their high homologues,
and tar. Important products of the Organic Chemicals Industry within SIC 2869
include: (1) non-cyclic organic chemicals such as acetic, chloroacetic,
adipic, formic, oxalic and tartaric acids and their metallic salts; chloral,
formaldehyde and methy1amine; (2) solvents such as amyl, butyl, and ethyl
alcohols; methanol; amyl, butyl and ethyl acetates; ethyl ether, ethylene
glycol ether and diethylene glycol ether; acetone, carbon disulfide and
chlorinated solvents such as carbon tetrachloride, tetrachloroethene and
trichloroethene; (3) polyhydric alcohols such as ethylene glycol, sorbitol,
pentaerythritol, synthetic glycerin; (4) synthetic perfume and flavoring
materials such as coumarin, methyl salicylate, saccharin, citral, citronellal,
synthetic geraniol, ionone, terpineol, and synthetic vanillin; (5) rubber
processing chemicals such as accelerators and antioxidants, both cyclic and
acyclic; (6) plasticizers, both cyclic and acyclic, such as esters of
phosphoric acid, phthalic anhydride, adipic acid, lauric acid, oleic acid,
sebacic acid, and stearic acid; (7) synthetic tanning agents such as
III-5
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naphthalene sulfonic acid condensates; (6) chemical warfare gases; and (9)
esters, amines, etc. of polyhydric alcohols and fatty and other acids.
Products produced by the Plastics/Synthetic Fibers Industry are considerably
more difficult to define. Within SIC 2621 important products include:
cellulose plastic materials; phenolic and other tar acid resins; urea and
melamine resins; vinyl resins; styrene resins; alkyd resins; acrylic resins;
polyethylene resins; polypropylene resins; rosin modified resins;
coumarone-indene and petroleum polymer resins; and miscellaneous resins
including polyamide resins, silicones, polyisobutylenes, polyesters,
polycarbonate resins, acetal resins, fluorohydrocarbon resins; and casein
plastics. Important cellulosic man-made fibers (SIC 2823) include: acetate
fibers, cellulose acetate, cellulose rayon, triacetate fibers, and viscose
fibers. Important non-cellulosic synthetic organic fibers (SIC 2824)
include: acrylic, acrylonitrile, casein, fluorocarbon, linear ester,
modacrylic, nylon, olefin, polyester, polyvinyl, and polyvinylidene fibers.
Industry Structure by Product and Process
The branched product structure of the Organic Chemicals and Plastics/Synthetic
Fibers Industries is illustrated in FIGURE III-2, which includes all the
compounds that are currently produced in excess of 100 million pounds/year.
The total product line of the industry is considerably more complex, but
Figure III-2 illustrates the ability of the Organic Chemicals Industry to
produce a product by different synthesis pathways. For each of the
approximately 1,200 products that are produced in excess of one thousand
pounds per year, there is an average of two synthetic routes. The more than
20,000 compounds that are produced in smaller quantities by the industry tend
to be more complex molecules that can be synthesized by multiple routes.
Because all products are generally produced by one or more manufacturers by
different synthetic routes, few plants have exactly the same products and
process combinations as other plants.
The apparently complex and diverse Organic Chemicals and Plastics/Synthetic
Fibers Industries can be simplified by recognizing that approximately 2,500
distinct chemical products are synthesized from only seven parent
compounds--methane, ethene, propene, butane/butenes, benzene, toluene, and
o,p-xylenes. These seven compounds are processed into derivatives which in
turn are sold or used as feedstocks for the synthesis of other derivatives.
All chemical plants share another trait: the transformation of one chemical
to another is accomplished by chemical reactions and physical processes in the
stepwise fashion implied in Figure III-2. Although each transformation
represents at least one chemical reaction, virtually all transformations can
be classified by generalized chemical reactions/processes. Imposition of
these processes upon the seven basic feedstocks leads to commercially produced
organic chemicals. The numerous permutations of feedstocks and processes
permit the industries to produce a wide variety of products.
These industries can also produce a given product by more than one process.
Since different processes require different raw materials and reaction
conditions, the wastewater generated in producing one chemical can vary
greatly depending on the process used. For example, 1,2-dichloroethane may be
III-6
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QO
FIGURE 111-2 MAJOR SYNTHETIC PATHWAYS OF THE ORGANIC
CHEMICALS INDUSTRY
TS- - ^
-------
manufactured by direct chlorination or oxychlorination of ethene; the toxic
pollutant load from the former product/process is negligible while that from
oxychlorination is significant. TABLES III-l ANT) III-2 list the major
product/processes of the Organic Chemicals and Plastics/Synthetic Fibers
Industries.
Additionally, processes are not product-specific and allow plants a degree of
flexibility not found in most industries. Using the same equipment, a plant
may vary its'product mix relatively easily to respond to market fluctuations.
Plants are often modified to produce other products, increase capacity, or
produce the same product by a different synthetic route. Overall production
of a product, however, is of course limited by the unit operation with the
smallest capacity within a series of unit operations. Plant capacities are
highly variable, even between plants that use the same unit process to produce
the same product.
Plant Variations
The Organic Chemicals and Plastics/Synthetic Fibers Industries' manufacturing
plants consist of a small number of very large plants and a large number of
very small plants (see "Plant Size"). Most of the small plants are batch
process plants that make only low-volume chemicals. Such a plant may produce
a total of 1,000 different products with 70 to 100 of these being produced on
any given operating day. Manufacturing plants that produce large quantities
of specific chemicals often incorporate fewer unit processes than smaller
plants that generate a large number of products. A representative high-volume
plant may produce a total of 45 high volume products with an additional 300
lower volume products.
The production level at which it becomes economical to convert a batch to a
continuous process is typically 500,000 to 1,000,000 kg of product per year.
While most high volume chemicals are produced by continuous or semi-continuous
processes and most low-volume chemicals are produced by batch processes, many
products, including some high-volume products, can only be produced by batch
processes, because of the chemical reactions invoLved. For polyvinylchloride
(PVC), for example, one of the largest volume synthetic polymers produced in
the United States, most PVC processing steps are batch reactions.
Because production efficiencies are greater for the high-volume products, the
waste production per ton of product for the sraal1-volume products is often
higher than for the large volume products. Moreover, the wastewater volume
and strength generated by plants using batch processes is inherently more
variable than plants using continuous processes. Regardless of the process
type, wastewater treatment facilities typically serve the entire process
complex, rather than individual process units.
Many plants or companies exhibit a pronounced degree of vertical integration
while others produce only a limited number of products from one level of the
chemical product tree (Figure III-2). Vertical integration is typified by
petroleum refiners (SIC 2911), which use their hydrocarbons to produce primary
and intermediate chemical materials (SIC 2865 and SIC 2869) and subsequently
convert them to such products as plastics (SIC 2821 and SIC Table 3079),
synthetic fibers (2824), and synthetic rubber (SIC 2822). Horizontal
111-9
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TABLE I I 1-1
MAJOR PRODUCTS BY PROCESS OF THE ORGANIC CHEMICALS INDUSTRY
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
ACENAPHTHENE
ACETALDEHYDE
ACETIC ACID
ACETIC ACID SALTS
ACETIC ANHYDRIDE
ACETONE
ACETONE CYANOHYDRIN
ACETONITRILE
ACETOPHENONE
ACETYL SALICYLIC ACID
ACETYLENE
ACROLEIN
ACRYLAMIDE
ACRYLIC ACID
ACRYLIC ACID ESTERS
ACRYLIC ACID,
ACRYLIC ACID,
ACRYLIC ACID,
ACRYLIC ACID,
ALLYL 2-CYANO
ETHYL
ETHYL 2-CYANO
ETHYLHEXYL
BY-PRODUCT (PROPANE PYROLYSIS)
BY-PRODUCT (ACROLEIN/PROPENE/OXI DAT I ON)
DEHYDROGENATI ON (ETHANOL)
OXIDATION (ETHENE)
BY-PRODUCT (DIATRIZOIC ACID)
BY-PRODUCT (POLYVINYL ACETAL)
BY-PRODUCT (POLYVINYL ALCOHOL)
BY-PRODUCT (p-AMINOPHENOL)
CARBONYLATI ON (METHANOL)
CO-PRODUCT (TEREPHTHALIC ACID)
OXIDATION (ACETALDEHYDE)
OXIDATION (BUTANE)
RECOVERY (POLYOL PROCESS)
RECOVERY (SULFITE PULP WASTEWATER)
TRANSESTERIFlCATION (METHYL ACETATE/FORM IC ACID)
NEUTRALIZATION
ADDITION (ACETIC AC ID/KETENE)
PYROLYSIS (ACETIC ACID)
DEHYDROGENATI ON (ISOPROPANOL)
OXIDATION (BUTANE/PROPANE)
OX I DAT I ON (IS0PR0PAN0L/H202)
PEROXI DAT I ON/AC ID CLEAVAGE (CUMENE)
HYDROCYANATI ON (ACETONE)
AM I NAT I ON/DEHYDRATION (ACETAMIDE ACID)
BY-PRODUCT (ACRYLONITRILE/AMMOXI DAT I ON/PROPENE)
BY-PRODUCT (PHENOL/PEROXI DAT I ON/AC ID CLEAVAGE)
ACETYLATI ON (SALICYLIC AC ID/ACETYL CHLORIDE)
ACETYLATI ON (SALICYLIC AC ID/ACETIC ANHYDRIDE)
BY-PRODUCT (PROPANE PYROLYSIS)
HYDROLYSIS (CALCIUM CARBIDE)
OXIDATION (METHANE)
OXIDATION (PROPENE)
HYDRATION (ACRYLONITRILE)
FORMLYATION/HYDRATI ON (ACETYLENE/CARBON
MONOXIDE/WATER)
OXIDATION (ACROLEIN)
OXIDATION (PROPENE)
ESTER IFI CAT I ON (MISCELLANEOUS ALCOHOLS)
MODIFIED REPPE PROCESS
CONDENSATION (ACRYLONITRILE/FORMALDEHYDE/ALLYLIC ALCOHOL)
ESTER IFI CAT I ON (ACRYLIC ACID)
CONDENSATI ON (ACRYLONITRILE/FORMALDEHYDE/ETHANOL)
ESTER IFI CAT ION (ACRYLIC ACID)
1,339,547
12,998
189,971
7HH,129
122,068
11,349
1,901
34,585
275,027
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
ACRYLIC ACID,
ACRYLIC ACID,
ACRYLIC ACID,
ACRYLONITRILE
AD I PIC ACID
ISOBUTYL
METHYL 2-CYANO
N-BUTYL
ADI
PIC
AC 1
1 D, D
ADI
PIC
AC 1
1 D, D
ADI
PIC
AC 1
1D, D
ADI
PON
1 TR 1
1 LE
AC ID,DI(2-ETHYLHEXYL)ESTER
SODECYL ESTER
RIDECYL ESTER
ALKOXY ALKANOLS
ALKYL
AMINES
ALKYL
BENZENES
ALKYL
PHENOLS
ALLYL
ALCOHOL
ALLYL
ALCOHOL
ALLYL
CHLORIDE
AMANTADINE HYDROCHLORI
AMINO ALCOHOLS
DE
AM INOETHYLETHANOLAMINE
BIS-PARA-AM INOCYCLOHEXYLMETHANE
AMYL ACETATES
ANILINE
ANISIDINE
ANTHRACENE
ANTHRAQUI NONE
BENZALDEHYDE
BENZENE
ESTER IFI CAT ION (ACRYLIC ACID)
CONDENSATI ON (ACRYLONITRILE/FORMALDEHYDE/METHANOL)
ESTER IFI CAT I ON (ACRYLIC ACID)
AMMOXI DAT I ON (PROPENE)
DEPOLYMERIZATI ON (NYLON 6)
OXIDATION (CYCLOHEXANE)
OXIDATION (CYCLOHEXANOL)
OXIDATION (CYCLOHEXANONE)
ESTER IFI CAT I ON (AD I PIC ACID)
ESTER IFI CAT I ON (AD I PIC ACID)
ESTERIFICATION (ADIPIC ACID)
AMMONOLYSIS (ADIPIC AC ID)/DEHYDRATI ON)
CHLORI NAT ION/CYANATI ON (BUTADIENE)
ELECTROHYDRODIMERIZATI ON (ACRYLONITRILE)
HYDROCYANATI ON (BUTADIENE)
HYDROLYSIS (ALKYL OXIDES)
AM I NAT I ON (ALCOHOLS)
HYDROGENATI ON (FATTY NITRILES)
ALKYLATI ON (BENZENE/ALPHA-OLEFINS)
ALKYLATI ON (PHENOL)
ALKYLATI ON (PHENOL)
HYDROLYSIS (ALLYL CHLORIDE)
REDUCTION (ACROLEIN/ALUMINUM BUTOXIDE)
CHLORI NAT I ON (PROPENE)
AM I NAT I ON (ADAMANTYL CHLORIDE)
CONDENSATI ON (NITROPARAFFINS/FORMALDEHYDE)
REDUCTION
CONDENSATION ( ETHYLENEDI AM INE/ETHYLENE OXIDE)
CONDENSATI ON (AN ILINE/FORMALDEHYDE)
HYDROGENATI ON
ESTER IFICATION (ACETIC AC ID/AMYL ALCOHOLS)
BY-PRODUCT (P-AMINOPHENOL)
HYDROGENATI ON (NITROBENZENE)
METHYLATION/HYDROGENATI ON (NITROPHENOL)
DISTILLATION (COAL TAR)
OXIDATION (ANTHRACENE)
OXIDATION (TOLUENE)
BY-PRODUCT (ACRYLIC ACID/REPPE PROCESS)
BY-PRODUCT (SILICONE MANUFACTURE)
BY-PRODUCT (STYRENE/ETHYLBENZENE
DEHYDROGENATI ON)
DISTILLATION (BTX EXTRACT CAT REFORMATE)
DISTILLATION (BTX EXTRACT-COAL TAR LIGHT OIL)
DISTILLATION (BTX EXTRACT-PYROLYSIS GASOLINE)
823, *452
14,424
493
402,984
296,739
7,597,998*
6,4*45,09*4
-------
TABLE I I 1-1 (continued)
PRODUCT ION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
BENZENE (contd)
BENZO-A-PVRENE
BENZOIC ACID
BENZOYL PEROXIDE
BENZYL CHLORIDE
BlPHENYL
BlSPHENOL-A
BROMOFORM
BTX
1.3-BUTADIENE
BUTANE
BUTANE (ALL FORMS)
1.4-BUTANEDIOL
BUTENES
2-BUTENE-1,4-DIOL
n-BUTYL ALCOHOL
tert-BUTYL ALCOHOL
BUTYL LACTATE
n-BUTYLACETATE
1,3-BUTYLENE GLYCOL
tert-BUTYLPHENOL
n-BUTYRALDEHYDE
n-BUTYRIC ACID
3-BUTYROLACTONE
n-BUTYRONITRILE
C-13 TO C19 ALKYL AMINES
CAPROLACTAM
CARBON TETRACHLORIDE
CHLORINATED PARAFFIN
CHLOROACETIC ACID
CHLOROBENZENE
HYDRODEALKYLIZATI ON (TOLUENE/XYLENE)
STEAM PYROLYSIS (LPG)
STEAM PYROLYSIS (COAL TARS)
OXIDATION (TOLUENE)
OXIDATION (BENZOYL CHLORIDE/SODIUM PEROXIDE)
CHLORI NAT I ON (TOLUENE)
PYROLYSIS (BENZENE)
CONDENSATION (ACETONE/PHENOL)
BROMI NAT I ON (ACETONE/SODIUM HYPOBROMITE)
PYROLYSIS (GASOLINE)
DEHYDRATION (n-BUTANE)
EXTRACTIVE DISTILLATION (C-4 PYROLYZATES)
BY-PRODUCT (BUTADIENE)
NATURAL GAS BY-PRODUCT
CATALYTIC REFORMING (NAPHTHA)
REFINERY BY-PRODUCT
FORMYLATION/HYDROGENATI ON (ACETYLENE)
EXTRACTIVE DISTILLATION (C4 PYROLYZATES)
HYDROGENATI ON (BUTYNEDIOL)
BY PRODUCT (1,3-BUTYLENE GLYCOL)
DISTILLATION (DILUTE AqUEOUS BUTANOL)
HYDROGENATI ON (n-BUTYRALDEHYDE/OXO PROCESS)
HYDRATION (ISOBUTENE)
ESTER IFI CAT I ON (LACTIC ACID)
ESTERIFICATION (BUTANOL/ACETIC ANHYDRIDE)
HYDROGENATION (ACETALDOL)
ALKYLATION (PHENOL/ISOBUTENE)
HYDROFORMYLATI ON (PROPENE/OXO PROCESS)
CO-PRODUCT (BUTANE OXIDATION)
OXIDATION (BUTYRALDEHYDE)
OXIDATION (1,4-BUTANEDIOL)
AM I NAT ION/DEHYDRATI ON (BUTANOL/NH3)
HYDROCYANATION/HYDROGENATI ON (C-12 TO
C-18 OLEFINS)
AM I NAT I ON (CYCLOHEXANONE OX I ME)
DEPOLYMER IZATI ON (NYLON 6)
BY-PRODUCT (PHOSGENE)
CHLORI NAT I ON (CARBON DISULFIDE)
CHLORI NAT I ON (METHANE)
CHLORI NAT I ON (METHYL CHLORIDE)
CO-PRODUCT (TETRACHLOROETHENE)
CHLORI NAT I ON (PARAFFINS)
CHLORI NAT I ON (ACETIC ACID)
CHLORI NAT I ON (BENZENE)
33,036
3,086
21,407
238,359
1,259,528
677,907
48,424
302,645
355,722
56,748
412,065
319,316
44,955
7,072
127,275
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
CHLOROBUTADIENE
CHLORODIFLUOROMETHANE
CHLOROFORM
BIS-(2-CHLOROISOPROPVL) ETHER
3-CHLORONITROBENZENE
2-CHLORONITROBENZENE
4-CHLORON I TROBENZENE
2-CHLOROPHENOL
4-CHLOROPHENYL PHENYL ETHER
CHLOROPRENE
CHOLINE CHLORIDE
COAL TAR
COAL TAR PRODUCTS (MISC.)
CREOSOTE
CRESOLS, MIXED
CROTYL ALCOHOL
CUMENE
CYANOACETIC ACID
CYANURIC ACID
CYCLOHEXANE
CYCLOHEXANE DI METHANOL
CYCLOHEXANOL
CYCLOHEXANOL/ONE(MIXED)
CYCLOHEXANONE
CYCLOHEXYL MERCAPTAN
CYCLOOCTADIENE
CYCLOPENTADIENE DIMER
DI ACETONE ALCOHOL
DI ACETONE ALCOHOL PEROXIDE
DIAMINO DIPHENYL METHANE
DIBUTYLPHENYL PHOSPHATE
1.2-DICHLOROBENZENE
1.3-D ICHLOROBENZENE
1.4-DICHLOROBENZENE
DICHLORODIFLUOROMETHANE
CHLORI NAT ION/DEHYDROCHLORI NAT I ON (BUTADIENE)
CHLORI NAT ION/DEHYDROCHLORI NAT I ON (BUTADIENE)
HYDROFLUORI NAT I ON (CHLOROFORM)
BY-PRODUCT (ACETALDEHYDE PRODUCTION)
CHLORI NAT I ON (METHANE)
CHLORI NAT I ON (METHYL CHLORIDE)
BY-PRODUCT (PROPENE OX IDE/CHLOROHYDRI NAT I ON)
CHLORI NAT I ON (NITROBENZENE)
NITRATION (CHLOROBENZENE)
NITRATION (CHLOROBENZENE)
CHLORI NAT I ON (PHENOL)
CHLORI NAT I ON (PHENYL PHENYL ETHER)
DEHYDROCHLORI NAT I ON (3,4-DICHL0R0-2-BUTENE)
CONDENSATION (ETHYLENE CHLOROHYDRIN/TRI METHYL
AMINE)
CONDENSATION (ETHYLENE OXIDE/
TRIMETHYLAMINE/HCL)
COKING (COAL)
DISTILLATION (COAL TAR)
DISTILLATION (COAL TAR LIGHT OIL)
REFINING (TAR ACID)
HYDROGENATI ON (CROTONALDEHYDE)
ALKYLATI ON (BENZENE/PROPENE)
CYANATI ON (CHLOROACETIC ACID)
TRIMERIZATI ON (UREA)
HYDROGENATION (BENZENE)
HYDROGENATI ON (DIMETHYL TERAPHTHALATE)
HYDROGENATI ON (PHENOL)
OXIDATION (CYCLOHEXANE)
DEHYDROGENATION (CYCLOHEXANOL)
HYDROGENATI ON (PHENOL)
OXIDATION (CYCLOHEXANE)
HYDROSULFURATION (CYCLOHEXENE)
DIMERIZATI ON (BUTADIENE)
EXTRACTIVE DISTILLATION (C5 PYROLYZATES)
CONDENSATION (ACETONE)
PEROXIDATION (DI ACETONE ALCOHOL)
CONDENSATI ON (AN ILINE/FORMALDEHYDE)
ESTER IFI CAT I ON (BUTANOL/PHENOL/POCL3)
CHLORI NAT I ON (BENZENE)
PHOSGENATI ON SOLVENT RECOVERY (MDI/TDI MANUFACTURE)
CHLORI NAT I ON (BENZENE)
CHLORI NAT I ON (BENZENE)
HYDROFLUORI NAT I ON (CARBON TETRACHLORIDE)
102,408
158,894
2,055,512*
229,553*
35,181
1,556,672
883,684
345,067
30,846
21,954
132,741
-------
TABLE I 11-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
DICHLORODIPHENYL SULFONE
1.1-DICHLOROETHANE
1.2-DICHLOROETHANE
DICHLORONITROBENZENE
2,U-DICHLOROPHENOL
DICHLOROPROPANE
1,2-DICHLOROPROPENE
DIETHANOL AMMONIUM LAURYL SULFATE
N, N-DI ETHYL ANILINE
DIETHYL MALONATE
DIETHYL SULFIDE
DI ETHYLENE GLYCOL
DIETHYLENE TRIAMINE
DI ISOPROPYL BENZENE
N,N,DI ISOPROPYL-2 BENZOTHIAZOLE
DIKETENE
DIMERCAPTAN D-LIMONENE
2-DIMETHYLAMINOETHANOL
DIMETHYL ETHER
DIMETHYL MALONATE
2,4-DI METHYL PHENOL
DIMETHYL SULFATE
DIMETHYL TEREPHTHALATE
DIMETHYLACETAMIDE
N,N-DIMETHYLANILINE
DIMETHYLBENZYL ALCOHOL
N,N-DIMETHYLFORMAMIDE
DINITROBENZENE (MIXED)
DINITROTOLUENE (MIXED)
2, iJ-D I N I TROTOLUENE
2,6-DINITROTOLUENE
DINONENE
DlPHENYL ETHER
DIPHENYLAMINE
DI PROPYLENE GLYCOL
2,2-DITHI OB ISBENZOTHIAZOLE
SULFONATI ON (S03/THIONYL CHLORIDE/CHLOROBENZENE)
HYDROCHLORI NAT I ON (VINYL CHLORIDE)
DIRECT CHLORI NAT I ON (ETHENE)
OXYCHLORI NAT I ON (ETHENE)
CHLORI NAT I ON (NITROBENZENE)
CHLORI NAT I ON (PHENOL)
BY-PRODUCT (CHLOROHYDRI NAT I ON PROPENE)
BY-PRODUCT (ALLYL CHLORIDE)
ALKYLATI ON (LAURYLAMINE/ETHLENE OXIDE)
ALKYLATI ON (AN ILINE/ETHANOL)
ESTER IFI CAT I ON (MALONIC ACID)
ALKYLATI ON (K ETHYLSULFATE/K2S)
CO-PRODUCT (ETHENE GLYCOL)
CO-PRODUCT (HYDROLYSIS OF ETHYLENE OXIDE)
ETHERIFICATION/HYDROLYSIS (ETHYLENE OXIDE)
AM I NAT I ON (ETHLENE DIAMINE/
1,2-DICHLOROETHANE/NH3)
ALKYLATI ON OF BENZENE (CUMENE)
AM I NAT I ON (DllSOPROPYL AMINE/2-
MERCAPTOBENZOTHIAZOLE)
DIMERIZATI ON (KETENE/ACETIC ACID)
HYDROSULFURATI ON (D-LIMONENE)
AM I NAT I ON (ETHANOL)
DEHYDRATION (METHANOL)
ESTER IFI CAT ION (MALONIC ACID)
EXTRACTION DISTILLATION (REFINERY CRESYLATES)
ESTER IFI CAT I ON (METHANOL/SULFURIC ACID)
ESTER IFI CAT I ON (TERPHTHALLIC ACID)
OX I DAT I ON/ESTER IFI CAT I ON (P-XYLENE)
AM I NAT I ON (DIMETHYLAMINE/ACETIC ACID)
CONDENSATION (AN ILINE/METHANOL)
HYDROLYSIS (CUMENE HYDROPEROXIDE)
CONDENSATI ON (DIMETHYLAMINE/FORMALDEHYDE)
CONDENSATION (DIMETHYLAMINE/FORM IC ACID)
NITRATION (BENZENE)
NITRATION (TOLUENE)
NITRATION (TOLUENE)
NITRAT TON (TOLUENE)
DEALKYLATI ON (TERPINENE)
ETHER IFI CAT I ON (CHLOROBENZENE/SODIUM PHENOLATE)
CONDENSATION (AN I LINE)
CO-PRODUCT (HYDROLYSIS/PROPENE OXIDE)
CONDENSATION (PROPYLENE GLYCOL)
OX I DAT I ON (2-MERCAPTOBENZOTRIAZOLE)
U.998.52U
172,085
U.U91
12,215
-------
TABLE I I 1-1 (continued)
PRODUCT ION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
DODECYLBENZENE SULFONIC ACID SALTS
DODECYLGUANIDINE ACETATE
DODECYLMERCAPTAN
EPICHLOROHYDRIN
ETHANE
ETHANOL
ETHANOLAMINES
ETHYLENEDI AM INETETRAACETIC ACID
ETHOXYLATES, ALKYL
ETHOXYLATES, ALKYLPHENOL
ETHOXYLATES, C11, C12
ETHYL ACETATE
ETHYL ACETOACETATE
N-ETHYL ANILINE
ETHYL CHLORIDE
ETHYL ORTHOFORMATE
ETHYLAMINE
ETHYLBENZENE
ETHYLCYANOACETATE
ETHLENE
ETHYLENE CYANOHYDRIN
ETHYLENE DIAMINE
ETHYLENE DI BROMIDE
ETHYLENE GLYCOL
ETHYLENE GLYCOL MONOETHYL ETHER
ETHYLENE GLYCOL MONOMETHYL ETHER
ETHYLENE OXIDE
2-ETHYLHEXANOIC ACID
2-ETHYLHEXANOL
FORMALDEHYDE
SULFONATI ON (DODECYLBENZENE)
ADD ITI ON (DODECYLAMINE/CYANAMIDE)
HYDROSULFURATI ON (DODECENE)
EPOX I DAT I ON (ALLYL CHLORIDE/CHLOROHYDRI NAT I ON)
BY-PRODUCT (NATURAL GAS)
CRACKING (NAPTHA)
REFINERY BY-PRODUCT
CO-PRODUCT (BUTANE OXIDATION)
HYDRATION (ETHENE)
AMMONOLYSIS (ETHYLENE OXIDE)
ACYLATI ON (ETHYLENEDI AM INE/FORMALDEHYDE/NACN)
ETHER IFI CAT I ON (ALKYLENE OX IDE/ALKANOL)
ETHOXYLATI ON (PHENOL/ETHYlENE OXIDE)
ETHOXYLATI ON (LINEAR ALCOHOLS/ETHLENE OXIDE)
CO-PRODUCT (BUTANE OXIDATION)
ESTER IFI CAT I ON (ACETIC AC ID/ETHANOL)
TRANSESTERIFI CAT I ON (POLYVINYL ACETATE/ETHANOL)
CONDENSATION (ACETIC ACID)
ALKYLATI ON (ETHANOL/AN ILINE)
HYDROCHLORI NAT I ON (ETHENE)
ESTHER IFICATION (CHLOROFORM/SODIUM ETHOXIDE)
AMMONOLYSIS (ETHANOL)
ALKYLATI ON (BENZENE)
DISTILLATION (BTX EXTRACT)
DISTILLATION (COAL TAR)
ESTER IFICATI ON (CYANOACETIC ACID)
FRACTIONATION (REFINERY LIGHT ENDS)
PYROLYSIS (ETHANE)
PYROLYSIS (ETHANE/PROPANE/BUTANE/LPG)
PYROLYSIS (NAPHTHA/GAS OIL)
CYANATI ON (ETHYLENE CHLOROHYDRIN/NACN)
HYDROCYANATI ON (ACETALDEHYDE)
AM I NAT I ON (1,2-DICHLOROETHANE)
BROMI NAT I ON (ETHENE)
HYDROLYSIS (ETHYLENE OXIDE)
ALKYLATI ON (ETHANOL/ETHYLENE OXIDE/ACETIC
ANHYDRIDE)
ALKYLATI ON (METHANOL/ETHYLENE OXIDE)
EPOXIDAT ION (ETHYLENE CHLOROHYDRIN)
OXIDATION (ETHENE)
OXIDATION (2-ETHYLHEXANAL)
CONDENSATION/HYDROGENATI ON (n-BUTALDEHYDE)
OXIDATION (METHANOL-METAL OXIDE PROCESS)
OXIDATION (METHANOL-SILVER CATALYST)
3,149,938
18,692
169,242
105,141
178,370
3,438,956
12,899,938
1,973,579
43,768
2,349,180
6,633
2,499,907
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
FORMAMIDE
FORMIC ACID
FUMARIC ACID
GLUTAMIC ACID, MONOSODIUM SALT
GLYCERINE (SYNTHETIC)
GLYCOLS, MIXED
GLYOXAL
HEPTANE
HEXACHLOROBENZENE
HEXACHLOROETHANE
HEXAMETHYLENED I AM INE
HEXAMETHYLENETETRAMINE
HEXANE
HEXYLENE GLYCOL
HEXYLENE GLYCOL (1,6-HEXANEDIOL)
HYDROQUI NONE
HYDROXYACETIC ACID
2 — IMIDAZOLI DONE
IMINODIACETIC ACID
ISOAMYLENE
ISOBUTANOL
ISOBUTYL ACETATE
ISOBUTYLENE
ISOBUTYRALDEHYDE
ISOBUTYRIC ACID
ISOBUTYRONITRILE
ISODECANOL
ISOOCTYL ALCOHOL
ISOPENTANE
ISOPHORONE
ISOPHTHALIC ACID
ISOPRENE
ISOPROPANOL
AM I NAT I ON (FORMIC ACID)
BY-PRODUCT (BUTANE OXIDATION)
RECOVERY (SULFITE PULP WASTEWATER)
ISOMERIZATI ON (MALE IC ACID)
NEUTRALIZATION
HYDRATION (ALLYL ALCOHOL)
HYDROLYSIS (EPICHLOROHYDRIN)
OXO PROCESS
OZONATION (BENZENE)
EXTRACTION/ADSORPTION (BTX SOLVENT)
BY-PRODUCT (CHLOROSI LANES)
BY-PRODUCT (TETRACHLOROETHENE)
CHLORI NAT I ON (BENZENE)
CHLORI NAT I ON (ETHANE)
AMMONOLYSIS (1,6-HEXANEDIOL)
DEPOLYMERIZATI ON (NYLON 66)
HYDROGENATI ON (AD I PON ITRILE)
CONDENSATION (F0RMALDEHYDE/NH3)
EXTRACTION/ADSORPTION (BTX SOLVENT)
REFINERY BY-PRODUCT
HYDROGENATI ON (01 ACETONE ALCOHOL)
CONDENSATION (ACETONE)
OXIDATION (ANILINE)
HYDROLYSIS (CHLOROACETIC ACID)
CARBONYLATI ON (ETHYLENE DIAMINE/C02)
CONDENSATI ON (NH3/F0RMALDEHYDE/NACN)
EXTRACTIVE DISTILLATION (BTX RAFF I NATE)
CONDENSATION (ACETALDEHYDE)
HYDROGENATION (IS0BUTYRALDEHYDE-0*0 PROCESS)
ESTER IFI CAT I ON ( ISOBUTANOL/ACETIC ANHYDRIDE)
DEHYDRATION (tert-BUTANOL)
EXTRACTION (CU PYROLYZATE)
HYDROFORMYLATI ON (PROPENE/OXO PROCESS)
OXIDATION (ISOBUTYRALDEHYDE)
AM I NAT ION/DEHYDRATI ON (ISOBUTANOL)
HYDROGENATI ON (ALPHA-METHACRYLONITRILE)
CARBONYLATION/HYDROGENATI ON (OLEFIN OLIGOMERS)
CARBONYLATION/HYDROGENATI ON (OLEFIN OLIGOMERS)
DISTILLATION (C4/C5 HYDROCARBON MIX)
CONDENSATION (ACETONE)
OXIDATION (XYLENE)
EXTRACTIVE DISTILLATION (C5 PYROLYZATE)
HYDRATION (PROPENE)
HYDROGENATI ON (ACETONE)
17,923
147,736
40,916
176,802
30,340
116,655
92,390
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
ISOPROPYL ACETATE
M-XYLENE (IMPURE)
MALE IC ANHYDRIDE
MALIC ACID
MELAMINE
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MERCAPTAN,
MESITYL OXIDE
METANILIC ACID
METHACRYLIC ACID
METHACRYLIC ACID
METHANOL
ETHYL
METHYL
i-PROPYL
n-BUTYL
n-DECYL
n-HEXADECYL
n-HEXYL
n-OCTYL
n-PROPYL
n-TETRADECYL
n-TRIDECYL
sec-BUTYL
t-BUTYL
ESTERS
METHYL AMYL ALCOHOL
METHYL BROMIDE
METHYL CHLORIDE
METHYL CYANOACETATE
METHYL ETHYL KETONE
METHYL FORMATE
N-METHYL CLYCINE (SARCOSINE)
METHYL ISOBUTYL CARBINOL
METHYL ISOBUTYL KETONE
METHYL KETONE
HYDROSULFURATI ON
HYDROSULFURATION
HYDROSULFURATION
HYDROSULFURATI ON
HYDROSULFURATI ON
HYDROSULFURATI ON
HYDROSULFURATI ON
HYDROSULFURATI ON
HYDROSULFURATI ON
HYDROSULFURATI ON
ESTER IFI CAT I ON ( ISOPROPANOL/ACETIC ANHYDRIDE)
FRACTIONATION (MIXED XYLENES)
BY-PRODUCT (PHTHALIC ANHYDRIDE/OXIDATION)
OXIDATION (BENZENE)
HYDRATION (MALE IC ACID)
CONDENSATION (UREA)
HYDROSULFURATI ON (ETHENE)
ALKYLATI ON (METHYL CHLORIDE/SODIUM HYDROSULFIDE)
HYDROSULFURATI ON (ISOPROPENE)
(N-BUTENE)
(n-DECENE)
(N-HEXADECENE)
(N-HEXENE)
(N-OCTENE)
(n-PROPENE)
(n-TETRADELENE)
(n-TRIDECENE)
(ISOBUTENE)
(ISOBUTENE)
DEHYDRATION (0 I ACETONE ALCOHOL)
HYDROCENATI ON (3 — NITR0BEN2ENE SULFONIC ACID)
HYDROLYSIS (ACETONE CYANOHYDRIN)
ESTER IFI CAT I ON (METHACRYLIC ACID)
BY-PRODUCT (ALKYLOLAMIDES MANUFACTURE)
BY-PRODUCT (POLYESTER MANUFACTURE)
HYDROCENATI ON (CARBON MONOXIDE)
HYDROCENATION (FORMALDEHYDE)
OXIDATION (BUTANE)
OXIDATION (H.P. SYNTHESIS NATURAL GAS/SYNTHETIC GAS)
OXIDATION (L.P. SYNTHESIS NATURAL GAS/
SYNTHETIC CAS)
CONDENSATION (ACETONE)
HYDROHALOCENATI ON (METHANOL)
BY-PRODUCT (ETHYLENE OXIDE)
CHLORI NAT I ON (METHANE)
HYDROCHLORI NAT I ON (METHANOL)
ESTER IFI CAT I ON (CYANOACETIC ACID)
BY-PRODUCT (BUTANE OXIDATION)
REDUCTION (ACROLEIN/ALUMINUM BUTOXIDE)
OXIDATION/REDUCTION (FORMALDEHYDE)
CONDENSATI ON (METHYLAMINE/FORMALDEHYDE/NACN)
CONDENSATION (ACETONE)
HYDROCENATION (MESITYL OXIDE)
DEHYDROCENATI ON (sec-BUTANOL)
136,590
14,293
3,218,838
163,045
264,067
75,726
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
METHYL METHACRYLATE
METHYL ORTHOFORMATE
METHYL SALICYLATE
METHYL SULFIDE
METHYLAMINES
2,2'-METHYLENEBIS(6-t-BUTYL-4-ETHYLPHENOL)
METHYLENE CHLORIDE
4,4'-METHYLENE DIANILINE
METHYLENE DIPHENYL DI ISOCYANATE
METHYLETHYL KETOXIME
N-METHYL-2-PYRROL I DONE
METHYLSTYRENE
METHYLSTYRENE
2-(MORPHOLINO-TH10) -BENZOTHIAZOLE
NAPHTHALENE
NEOPENTANOIC ACID
4-NITROANILINE
NITROBENZENE
1-NITRO-3,4-DICHLOROBENZENE
2-NITROPHENOL
4-NITROPHENOL & SODIUM SALT
N-NITROSODIPHENYLAMINE
NITROTOLUENE
5-NITRO-o-TOLUENE SULFONIC ACID
O-CRESOL
0-PHENYL PHENOL
O-XYLENE
OCTANE
0X0 ALDEHYDES/ALCOHOLS
p-OCTYL PHENOL
P-AMINOPHENOL
P-HYDROXYACETANILIDE
P-XYLENE
PENTACHLOROBENZENE
PENTACHLOROPHENOL
PENTAERYTHRITOL
PENTANE
ESTER IFI CAT I ON (METHACRYLIC ACID)
METHANOLYSIS (ACETONE CYANOHYDRIN)
POLYMER CRACKING
ETHER IFI CAT I ON (CHLOROFORM/SODIUM METHOXIDE)
ESTER IFI CAT I ON (SALICYLIC ACID)
ALKYLATI ON (POTASSIUM METHYL SULFATE/K2S)
AMMI NAT I ON (METHANOL/AMMONIA)
CONDENSATION (4-ETHYL-6-t-BUTYLPHENOL/FORMALDEHYDE)
(METHANE)
(METHYL CHLORIDE)
(FORMALDEHYDE/AN ILINE)
(METHYLENEDIANILINE)
ION (METHYLETHYL KETONE/
350,924
CHLORI NAT I ON
CHLORINATION
CONDENSATION
PHOSGENATI ON
HYDROXYAMI NAT I
HYDROXYLAM INE)
CONDENSATI ON (3-BUTYROLACTONE/METHYLAMINE)
BY-PRODUCT (ACETONE/PHENOL BY CUMENE OXIDATION)
DEHYDROGENATI ON (CUMENE)
AM I NAT I ON (MORPHOLINE/2-MERCAPT0BENZ0THIAZOLE)
DISTILLATION (PYROLYSIS GAS)
SEPARATION (COAL TAR DISTILLATE)
OXIDATION (ISOBUTYLENE VIA 0X0 PROCESS)
AMMONOLYSIS (4-NITROCHLOROBENZEtyE)
NITRATION (BENZENE)
NITRATION (o-DICHLOROBENZENE)
NITRATION (PHENOL)
NITRATION (PHENOL)
NITROSATI ON (DIPHENYLAMINE/NITROUS OXIDE)
NITRATION (TOLUENE)
SULFONATI ON/NITRATION (TOLUENE)
REFINING (MIXED CRESOLS)
HYDROGENOLYSIS (DIBENZOFURAN)
DISTILLATION (MIXED XYLENE)
EXTRACTION/ADSORPTION (BTX SOLVENT)
OXIDATION (HYDROCARBONS-OXO PROCESS)
ALKYLATI ON (PHENOL)
REDUCTION (NITROPHENOL)
NITRATION, HYDROGENATION, ACETYLATI ON
(BENZENE)
CRYSTAL IZATION (MIXED XYLENES)
ISOMERIZATION-CRYSTALLIZATION (MIXED XYLENES)
CHLORINATION OF BENZENE
CHLORINATION (PHENOL)
CONDENSATI ON (ACETALDEHYDE/FORMALDEHYDE)
REFINERY BY-PRODUCT
253,774
17,436
46,511
6,493
275,232
12,267
447,717
1,906,912
52,434
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
PERACETIC ACID
PHENOL
PHENYL GLYCINE
PHOSGENE
PHOSPHATE ESTERS
PHTHALATE ESTER
PEROXIDATION (ACETALDEHYDE)
BY-PRODUCT (DlPHENYL OXIDE)
BY-PRODUCT (ISOCYANATES PRODUCT I ON.)
OXIDATION (BENZOIC ACID)
OXIDATION (TOLUENE)
PEROXI DAT I ON/AC ID CLEAVAGE (CUMENE)
RECOVERY (PYROLYSIS GASOLINE)
RECOVERY (TAR ACID)
SULFONATI ON/HYDROLYSIS (BENZENE)
ACYLATI ON (AN ILINE/CHLOROACETIC ACID)
CHLORI NAT ION (CARBON MONOXIDE)
PHTHALIC ANH>
PITCH TAR RESIDUE
PROPANE
PROPENE
OXIDATION (O-XYLENE)
SEPARATION (COAL TAR LIGHT OIL DISTILLATE)
BY-PRODUCT (NATURAL GAS)
PYROLYSIS (BUTANE)
REFINERY BY-PRODUCT
FRACTIONATION (REFINERY LIGHT ENDS)
PYROLYSIS (ETHANE/PROPANE/BUTANE/LPG)
PYROLYSIS (NAPHTHA AND OR GAS OIL)
PYROLYSIS (NAPHTHA,PROPANE,ETHANE,BUTANE)
60,68U
U69,0U9
PHOSGENAT1 ON
BIS 2-ETHYLHEXYL
ESTER
F
CAT 1 ON
(ALCOHOL)
BUTYLBENZYL
ESTER
F
CATION
(BUTANOL/BENZYL CHLORIDE)
BUTYLOCTYL
ESTER
F
CATION
(ALCOHOL)
C11-C1U
ESTER
F
CATION
(ALCOHOL)
C7-C10
ESTER
F
CAT 1 ON
(ALCOHOL)
DIDECYL
ESTER
F
CATION
(ALCOHOL)
DIETHYL
ESTER
F
CAT 1 ON
(ALCOHOL)
9,^23
Dl1SODECYL
ESTER
F
CATION
(ALCOHOL)
5U.828
DlISOOCTYL
ESTER
F
CAT 1 ON
(ALCOHOL)
115,733
D1-N-HEXYL
ESTER
F
CAT 1 ON
(ALCOHOL)
Dl-N-OCTYL
ESTER
F
CATION
(ALCOHOL)
7, 157
DI-TRIDECYL
ESTER
F
CATION
(ALCOHOL)
11, U96
DlBUTYL
ESTER
F
CATION
(ALCOHOL)
8,1UU
DIMETHYL
ESTER
F
CATION
(ALCOHOL)
3,169
DlPHENYL
ESTER
F
CATION
(PHENOL/PHTHALYL CHLORIDE)
MIXED ALCOHOL
ESTER
F
CATION
(ALCOHOL)
OCTYLDECYL
ESTER
F
CAT 1 ON
(ALCOHOL)
n-HEPTYLNONYLUNDECYL
ESTER
F
CAT 1 ON
(ALCOHOL)
n-HEXYL-2-ETHYLHEXYL1SODECYL
ESTER
F
CATION
(ALCOHOL)
n-HEXYL-2-ETHYLHEXYL
ESTER
F
CATION
(ALCOHOL)
n-HEXYLHEPTYLNONYLUNDECYL
ESTER
F
CAT 1 ON
(ALCOHOL)
n-HEXYLOCTYLDECYL
ESTER
F
CATION
(ALCOHOL)
DE
OXIDATION (NAPHTHALENE)
368,211
3,920,500
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
PROP IONALDEHYDE
PROPIONIC ACID
n-PROPYL ACETATE
n-PROPYL ALCOHOL
PROPYLENE CHLOROHYDRIN
PROPYLENE DI CHLORIDE
PROPYLENE GLYCOL
PROPYLENE OXIDE
PYROLYSIS GASOLINE
2-PYRROLI DONE
SALICYLIC ACID
SEC-BUTYL ALCOHOL
SODIUM BENZOATE
SODIUM FORMATE
SODIUM LAURYL SULFATE
SODIUM LINEAR ALKYL BENZENE SULFONATE
SODIUM NITROBENZENESULFONIC ACID
SODIUM STYRENE SULFONATE
STYRENE
SULFANILIC ACID
SULFOLANE
TEREPHTHALIC ACID
1.2.3.4-TETRACHLOROBENZENE
1.2.3.5-TETRACHLOROBENZENE
1,2,U,5-TETRACHLOROBENZENE
1,1,2,2-TETRACHLOROETHANE
TETRACHLOROETHENE
TETRACHLOROPHTHALIC ANHYDRIDE
TETRAETHLENE GLYCOL
TETRAETHLENE PENTAMINE
TETRAETHYL LEAD
TETRAFLUORODICHLOROETHANE
TETRAHYDROFURAN
TETRAHYDROTHIOPHENE
HYDROFORMYLATI ON (ETHENE-OXO PROCESS)
BY-PRODUCT (NITROPARAFFINS PRODUCTION)
CO-PRODUCT (BUTANE OXIDATION)
OXIDATION (PROP IONALDEHYDE)
ESTER IFI CAT I ON (ACETIC AC ID/PROPANOL)
HYDROGENATI ON (PROP IONALDEHYDE)
HYDROCYANATI ON (PROPENE)
BY-PRODUCT (PROPENE OXIDE PRODUCTION)
CHLOROHYDRI NAT I ON (ALLYL CHLORIDE)
HYDROLYSIS (PROPENE OXIDE)
EPOXI DAT I ON (PROPENE VIA CHLOROHYDRIN)
CRACKING (ETHANE/PROPANE/BUTANE/LPG)
CRACKING (ETHANE/PROPANE/BUTANE AND NAPTHA)
CONDENSATI ON (3-BUTYROLACTONE/NH3)
CARBOXYLATI ON (SODIUM PHENOLATE)
HYDRATION (BUTENES)
NEUTRALIZATION
NEUTRALIZATION
SULFONATI ON (LAURYL ALCOHOL)
SULFONATI ON (ALKYLBENZENE)
NEUTRALIZATION
SULFONATI ON (STYRENE)
DEHYDROGENATI ON (ETHYLBENZENE)
DISTILLATION (PYROLSIS GASOLINE)
SULFONATI ON (ANILINE)
SULFONATION/HYDROGENATION (1,4-BUTADIENE)
CATALYTIC OXIDATION (P-XYLENE)
HYDROLYSIS (DIMETHYL TEREPHTHALATE)
CHLORI NAT I ON (BENZENE)
CHLORI NAT I ON (BENZENE)
CHLORI NAT I ON (BENZENE)
CHLORI NAT I ON (ETHLENE)
CHLORI NAT I ON (1,2-DICHLOROETHANE/OTHER
CHLORINATED HYDROCARBONS)
CHLORI NAT I ON (HYDROCARBONS)
OXYCHLORI NAT I ON (HYDROCARBONS)
CHLORI NAT I ON (PHTHALIC ANHYDRIDE)
CO-PRODUCT (ETHYLENE GLYCOL)
CONDENSATION (ETHYLENE DIAMINE/
1,2-DICHLOROETHANE/NH3)
ALKYLATI ON (ETHYL CHLORIDE/SODIUM-LEAD ALLOY)
HYDROFLUORI NAT I ON (TETRACHLOROETHENE)
HYDROGENATI ON (MALE IC ANHYDRIDE)
HYDROGENATI ON (THIOPHENE)
112,257
46,339
22,630
80,212
31,629
219,387
795,22U
17,572
3,085,358
2,348,384
3UU,381
9,320
-------
TABLE I I 1-1 (continued)
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
TETRAMETHYL LEAD
THIOPHENE
TOLUENE
TOLUENE DIAMINE (MIXTURE)
2, Ij-TOLUENE DIAMINE
TOLUENE DlISOCYANATES(MIXTURE)
2,4-TOLUENE DI ISOCYANATE
TOLUENESULFONAM I DE
TOLUENESULFONYL CHLORIDE
TOLUIDINE
1 ,2-TRANS-DICHLOROETHLENE
TRI-OCTYL TRIMELLI TATE
1,2,3 — TRICHLOROBENZENE
1,2,4-TRICHLOROBENZENE
1 ,3,5-TRICHLOROBENZENE
1,1, 1 - TRICHLOROETHANE
1 , 1 ,2-TRICHLOROETHANE
TR ICHLOROETHENE
TRICHLOROFLUOROMETHANE
2,U,6-TRICHLOROPHENOL
TRICHLOROPROPENE
1,1,2-TRICHL0R0-1,2,2-TRIFLUOROETHANE
TRIETHANOL AMMONIUM LAURYL SULFATE
TRIETHANOLAMINE LINEAR ALKYLBENZENE SULFONATE
TRIETHYLENE GLYCOL
TRIETHYLENETETRAMINE
TRIFLUORODICHLOROETHANE
TRIMELLITIC ANHYDRIDE
TRIMETHYLOLETHANE
TRIMETHYLOLPROPANE
ALKYLATI ON (METHYL CHLORIDE/SODIUM-LEAD ALLOY)
DEHYDROGENATI ON (BUTANE/SULFUR)
BY-PRODUCT (STYRENE MANUFACTURE)
DISTILLATION (BTX EXTRACT-CAT REFORMATE)
DISTILLATION (BTX EXTRACT-COAL TAR LIGHT OIL) 3,850,560»
DISTILLATION (BTX EXTRACT-PYROLYSIS GASOLINE) 3,275,355
STEAM PYROLYSIS (LPG)
HYDROGENATI ON (DINITROTOLUENES)
HYDROGEflATION (,D I N I TROTOLUENE ) 109,689
PHOSGENATI ON (TOLUENEDI AM INES)
PHOSGENATI ON (2, 1<-T0LUENE DIAMINE) 26U.398
AM I NAT I ON (TOLUENE SULFONYL CHLORIDE)
CHLORI NAT I ON (TOLUENE SULFONIC AC ID/CHLOROSULFONIC ACID)
CATALYTIC REDUCTION (0-NITROTOLUENE)
CHLORI NAT I ON (ETHENE)
ESTER IFI CAT I ON (TRIMELLITIC ANHYDRIDE) 5,69U
BY-PRODUCT (BENZENE CHLORI NAT I ON)
BY-PRODUCT (BENZENE CHLORI NAT I ON)
CHLORI NAT I ON (1,U-DICHLOROBENZENE)
BY-PRODUCT (BENZENE CHLORI NAT I ON)
CHLORI NAT I ON (1,2-DICHLOROETHANE) 311,521
CHLORI NAT I ON (ETHANE)
HYDROCHLORI NAT I ON (VINYL CHLORIDE)
BY-PRODUCT (VINYL CHLORIDE MANUFACTURE)
CHLORI NAT I ON (1,2-DICHLOROETHANE)
CHLORI NAT I ON (VINYL CHLORIDE)
CHLORI NAT I ON (1,2-DICHLOROETHANE/OTHER 119,918
HYDROCARBONS)
OXYCHLORI NAT I ON (HYDROCARBONS)
HYDROFLUORI NAT I ON (CARBON TETRACHLORIDE) 71,136
CHLORI NAT I ON (PHENOL)
CHLORI NAT ION/DEHYDROCHLORI NAT I ON (PROPENE)
HYDROFLUORI NAT I ON (CO-PRODUCT TETRAFLUORODICHLOROETHANE)
ALKYLATI ON (LAURYL AMINE/ETHYLENE OXIDE)
ETHOXYLATI ON
CO-PRODUCT (ETHYLENE GLYCOL/ETHYLENE OXIDE) 55,227
CO-PRODUCT/HYDROLYSIS (ETHLENE OXIDE)
CONDENSATION (ETHYLENE GLYCOL/ETHYLENE OXIDE)
RECOVERY FROM ETHYLENE GLYCOL STILL BOTTOMS
AM I NAT I ON (1,2-DICHLOROETHANE)
HYDROFLUORI NAT I ON (TETRACHLOROETHENE)
OXIDATION (1,2,4-TRI METHYL BENZENE)
CONDENSATION (PROP IONALDEHYDE/FORMALDEHYDE)
CONDENSATI ON (n-BUTYRALDEHYDE/FORMALDEHYDE)
-------
TABLE 111-1 (concluded)
PRODUCT ION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
2,2,4-TRI METHYL-1, 3 - PENTANEDIOL
TRI PROPYLENE GLYCOL
UREA
VINYL ACETATE
VINYL CHLORIDE
VINYL I DENE CHLORIDE
N-VINYL-2-PYRROLIDONE
XYLENES, MIXED
XYLENESULFONIC ACID, SODIUM SALT
XYLENOL, MIXED
CONDENSATION (ISOBUTYRALDEHYDE)
CONDENSATION (PROPYLENE GLYCOL/PROPYLENE OXIDE)
CONDENSATION (NH3/C02)
ESTER IFI CAT ION (ACETYLENE/ACETIC ACID)
ESTER IFI CAT I ON (ETHENE/ACETIC ACID)
DEHYDROCHLORI NAT I ON (1,2-DICHLOROETHANE)
DEHYDROCHLORI NAT I ON (TRICHLOROETHANE)
CONDENSATI ON (3-BUTYROLACTONE/ETHANOLAMINE)
EXTRACTION (CAT REFORMATE)
EXTRACTION (COAL TAR LIGHT OIL)
EXTRACTION (PYROLYSIS GASOLINE)
ISOMERIZATI ON (CRUDE P-XYLENE)
SEPARATION (XYLENE BOTTOMS)
SULFONATI ON (XYLENE)
TAR ACID RECOVERY AND REFINING
8611,680
2,909,646
3, 438,847*
3,102,564
15,091
* measured in 1,000 liter units
-------
TABLE I I 1-2
MAJOR PRODUCTS BY PROCESS OF THE PLASTICS/SYNTHETIC FIBERS INDUSTRY
PRODUCTION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
ABS RESIN
ACRYLIC FIBER (85% POLYACRYLONITRILE)
ACRYLIC LATEX
ACRYLIC RESINS
ALKYD RESINS
CARBOXMETHYL CELL'ULOSE
CELLOPHANE
CELLULOSE ACETATES FIBERS
CELLULOSE ACETATES RESIN
CELLULOSE ACETATES/PROP IONATES
CELLULOSE NITRATE
CELLULOSE SPONGE
CHLOROSILANES
COPOLYMERS (POLYVINYL ACETATE
EPOXIDIZED ESTERS,TOTAL
EPOXY RESINS
ETHYL CELLULOSE
FLUOROCARBON RESINS
HYDROXYETHYL CELLULOSE
HYDROXYPROPYL CELLULOSE
ISOBUTYLENE POLYMERS
MELAMINE RESINS
METHYL CELLULOSE
MODACRYLIC RESIN
NYLON
NYLON 6
NYLON 6 & 66 COPOLYMER
NYLON 612
NYLON 66
EMULSION POLYMERIZATION
MASS POLYMERIZATION
SUSPENSION POLYMERIZATION
SUSPENSION POLYMERIZATION-WET SPINNING
SUSPENSION POLYMERIZATION-WET SPINNING
EMULSION POLYMERIZATION
BULK POLYMERIZATION
EMULSION POLYMERIZATION
POLYACRYLAMIDE BY SOLUTION POLYMERIZATION
SOLUTION POLYMERIZATION
SUSPENSION POLYMERIZATION
CONDENSATI ON/POLYMER IZATI ON
ETHER IFI CAT I ON (CELLULOSE)
VISCOSE PROCESS
SPINNING FROM ACETYLATED CELLULOSE
ACETYLATI ON (CELLULOSE)
ESTER IFI CAT I ON (CELLULOSE)
NITRATION (CELLULOSE)
VISCOSE PROCESS
CHLORI NAT I ON (SILICON DI OX IDE/SILI CONE MONOMERS)
EMULSION POLYMERIZATION
EPOXI DAT I ON (UNSATURATED ESTERS)
CONDENSATION (EPICHLOROHYDRIN/NOVOLAK RESINS)
CONDENSATION (EPICHLOROHYDRIN/BISPHENOL A)
CONDENSATI ON (POLYOLS/EPICHLOROHYDRIN)
EPOXI DAT I ON (POLYMERS)
ALKYLATI ON (CELLULOSE/ETHYL CHLORIDE)
POLYMERIZATION (FLUOR INATED OLEFINS)
ETHOXYLATI ON (ALKALI CELLULOSE)
ETHER IFI CAT I ON (CELLULOSE)
POLYMER IZATI ON (ISOBUTENE)
POLYCONDENSATI ON (MELAMINE/FORMAL)
METHYLATI ON (CELLULOSE/METHYL CHLORIDE)
FIBER-POLYACRYLONITRILE & COMONOMER
RES IN-POLYACRYLONITRILE & COMONOMER
MISCELLANEOUS NYLON PRODUCTS-RESINS
NYLON FORMALDEHYDE RES I N.
FIBER - POLYCONDENSATI ON (CAPROLACTAM)
RESIN - POLYCONDENSATI ON (CAPROLACTAM)
POLYCONDENSATI ON (NYLON SALT/CAPROLACTAM)
RESIN-POLYCONDENSATI ON (HMDA/CISDI AC IDS)
FIBER - POLYCONDENSATI ON (NYLON SALT)
RESIN - POLYCONDENSATI ON (NYLON SALT)
UU1.U81
U62.669
316,260
U8.U82
199,558
83,71U
121,073
-------
TABLE I I 1-2 (continued)
PRODUCT ION
PRODUCT PROCESS FEEDSTOCK VOLUME
(METRIC TON)
NYLON SALT
NYLONS
PETROLEUM HYDROCARBON RESINS
PHENOLIC RESINS
POLYAM IDES
POLYBUTENES
POLYESTER
POLYETHYLENE GYCOL
POLYETHYLENE POLYAM INES
POLYETHYLENE RESINS
POLYMERIC METHYLENE DIANILINE
POLYMERIC METHYLENE DI PHENYL
POLYOXYETHYLENE GLYCOL
POLYOXYPROPYLENE GLYCOL
POLYPROPYLENE
POLYSTYRENE AND COPOLYMERS
POLYSTYRENE, EXPANDED
POLYSULFONE RESINS
POLYURETHANE RESINS
DIISOCYANATE
CONDENSATION (ADIPIC AC ID/HMDA-AQUEOU.S SOLUTION)
CONDENSATION (ADIPIC AC ID/HMDA-METHANOL SOLUTION)
CONDENSATION (ADIPIC AC ID/DIETHYLENETRI AM INE/
EPICHLOROHYDRIN)
CONDENSATION (C5-C8 UNSATURATES)
CONDENSATION (PHENOL/FORMALDEHYDE)
AM I NAT I ON (ETHYLENE AMINES/FATTY ACIDS)
CONDENSATION (DICARBOXYLIC AC ID/DI AM INE)
SOLUTION POLYMERIZATION (BUTENES)
FIBER BY MELT SPINNING (DMT/1,4-CYCLOHEXANE
DIMETHANOL)
FIBER BY MELT
BY MELT
BY MELT
(DMT/1,4
BY
BY
BY
BY
BY
BY
BY
FIBER
FIBER
F I LM
RESIN
RESIN
RESIN
RESIN
RESIN
RESIN
RESIN
SPINNING
SPINNING
SPINNING
CYCLOHEXANE
POLYCONDENSATI ON
POLYCONDENSATI ON
POLYCONDENSATI ON
POLYCONDENSATI ON
POLYCONDENSATI ON
POLYCONDENSATI ON
POLYCONDENSATION
POLYMERIZATION (ETHYLENE OXIDE)
AM I NAT I ON (ETHYLENE DIAMINE/
1,2-DICHLOROETHANE/NH3)
GAS PHASE POLYMERIZATION (HDPE)
HIGH PRESSURE POLYMERIZATION (LDPE)
SOLUTION POLYMERIZATION (HDPE)
SUSPENSION POLYMERIZATION (PARTICLE
CONDENSATI ON (AN ILINE/FORMALDEHYDE)
PHOSGENATI ON (POLYMETHYLENE DIANILINE)
ETHOXYLATI ON (ETHYLENE GLYCOL)
CONDENSATION (PROPYLENE GYCOL/PROPYLENE
PROPOXYLATI ON (GLYCERINE)
GAS PHASE ' POLYMER IZATI ON
POLYMER EXTRUSION
RESIN BY SOLUTION POLYMERIZATION
RESIN BY SUSPENSION POLYMERIZATION
BULK POLYMERIZATION W/O RUBBER
BULK POLYMERIZATION WITH RUBBER
SUSPENSION POLYMERIZATION W/O RUBBER
POLYMERIZATION (POLYSTYRENE)
CONDENSATION (BISPHENOL A/DICHLOROPHENYL
SULFONE)
CONDENSATION (POLYOLS/DIISOCYANATES)
(DMT/ETHYL GLYCOL)
(TPA/ETHYL GLYCOL)
(TPA/DMT/ETHYL GLYCOL)
DIMETHANOL)
(DMT/1,4-CYCL0HEXAN0L)
(TPA/ETHYLENE GLYCOL)
(PHTHALIC ANHYDRIDE)
(DMT/ETHYLENE GLYCOL)
(TPA/DMT/ETHYLGLYCOL)
(DMT/BUTANEDIOL)
(VARIOUS ACID/ALCOHOLS)
FORM HDPE)
OXIDE)
329,432
119,019
785,218
233,629
39,838
49,332
5,273,952
1,664,544
114,095
-------
TABLE I I 1-2 (concluded)
PRODUCT
PROCESS FEEDSTOCK
PRODUCT ION
VOLUME
(METRIC TON)
POLYVINYL ACETATE & PVC COPOLYMERS
POLYVINYL ACETATE COPOLYMERS
POLYVINYL ACETATE RESINS
POLYVINYL ACETATE+ACRYLIC COPOLYMERS
POLYVINYL ALCOHOL
POLYVINYL BUTYRAL
POLYVINYL CHLORIDE
POLYVINYL CHLORIDE COPOLYMERS
POLYVINYL PYRROL I DONE
POLYVINYL I DENE CHLORIDE
RAYON
SAN RESINS
SI LI CONES
STYRENE MALEIC ANHYDRIDE RESINS
STYRENE-BUTADIENE RESIN
STYRENE-METHYL METHACRYLATE COPOLYMERS
UNSATURATED POLYESTER RESIN
UREA RESINS
EMULSION POLYMERIZATION
SOLUTION POLYMERIZATION
STAPLE FIBER FROM RESIN
SUSPENSION POLYMERIZATION
COPOLYMER IZATI ON WITH ETHENE
SOLUTION POLYMERIZATION (VINYL PYRROL IDI NONE)
EMULSION POLYMERIZATION
SOLUTION POLYMERIZATION
EMULSION POLYMERIZATION
HYDROLYSIS (POLYVINYL ACETATE)
RESIN-SOLUTION POLYMERIZATION (VINYL
ACETATE/HYDROLYSIS OF POLYMER)
CONDENSATION (POLYVINYL ACETATE/BUTYRALDEHYDE)
BULK POLYMERIZATION
EMULSION POLYMERIZATION
SUSPENSION POLYMERIZATION
SUSPENSION POLYMERIZATION
POLYMERIZATION (VINYL PYRROL IDI NONE)
EMULSION POLYMERIZATION
VISCOSE PROCESS
MASS POLYMERIZATION
SUSPENSION POLYMERIZATION
ELASTOMER PRODUCTION
HYDROLYSIS (CHLOROSI LANES)
SILICONE FLUIDS (HYDROLYSIS AND CYCLIZATION)
SILICONE RESINS
SILICONE RUBBERS
COPOLYMER IZATI ON (STYRENE/MALEIC ANHYDRIDE)
EMULSION POLYMERIZATION
SUSPENSION POLYMERIZATION
CONDENSATION (MALEIC AND PHTHALIC
ANHYDRIDES/GLYCOLS)
CONDENSATION (UREA/FORMALDEHYDE)
300,754
70,241
2,468,417**
103,617
5,571
428,611
589,896
** figure for sum of PVC + copolymers.
-------
integration is apparent in firms that manufacture a family of related
chemicals of similar type or for related markets. Plastic products (SIC
3079), pharmaceuticals (SIC 2834), and pesticides (SIC 2879) are examples of
groups of related products.
PRODUCTION AND SALES
The Organic Chemicals and Plastics/Synthetic Fibers (OCPSF) Industries
comprise some 1236 plants within the continental United States and Puerto Rico
(U.S. Department of Commerce 1980, EIS 1981). These are primary plants, as
previously defined. The number of plants increases to 1481 if other producers
(secondary producers of scope chemicals represented by the 176 priority OCPSF
product/processes) are included (USEPA 1983). Using EPA lists of wastewater
discharge permit holders throughout the United States and other surveys, as
many as 2,100 Organic Chemicals and Plastics/Synthetic Fibers Industries
plants may be obtained. This variance is attributed to the difficulties
inherent in segregating the Organic Chemicals and Plastic Synthetic Fibers
industries from other chemical producing industries such as petroleum refining
and industrial inorganic chemicals, as described in this Section.
Estimates of 1980 sales by subindustry are shown in TABLE III-3. The numbers
include secondary as well as captive production (products which are not sold
but are used at the plant where produced), and reflect some double counting
since certain products are derived from intermediate products that are also
included in the total (e.g., 1,2-dichloroethane is included as well as the
ethene from which it is produced). Furthermore,"the Department of Commerce
presents statistics on products or groups of products within a specific use
category; often these use categories contain products from more than one SIC
Code.
The 1980 production volumes of the 29 organic chemicals included in the
Chemical and Engineering News' 1980 Top 50 List of Chemicals are listed in
TABLE III-4. TABLE. Ill-5 gives the production volumes of the highest volume
products in the plastics and synthetic fibers categories.
It is difficult to define the extent to which establishments belonging to the
Organic Chemicals and Plastics/Synthetic Fibers Industries account for the
total primary production of the industry, produce secondary products and use
similar materials or processes. TABLES 111-6 AND 111 — 7 subdivide industry
shipments into primary and secondary products and "miscellaneous receipts" and
show the amount of a given product class that each industry produced. Table
III-6 indicates where the products of the Organic Chemicals Industry are made
and what products are made by establishments classified within this industry.
Only product groups that have at least $2 million in shipments from
establishments classified in this industry are shown. Where some of the
primary products are made in industries other than the Organic Chemicals
Industry, the value of such shipments is shown in the Other Industries
column. Table 111-7 similarly indicates where the products of the
Plastics/Synthetic Fibers Industries are made and in what proportion products
are made by establishments within this industry. Again only product groups
with at least S2 million in shipments are shown.
111-26
-------
TABLE III-3
NUMBER OF PLANTS AND SALES
IN THE OCPSF INDUSTRIES BY SIC CODE, 1980.
PRIMARY PRODUCERS
Number of Sales
SIC Code Establishments (billion dollars)
Organic
2865
198
11.0
chemicals
2869
466
43.2
Plastics/
2821
488
16.1
synthetic
2823
19
1.2
fibers
2824
65
8.7
Total
1236
80.2
Notes: Some plants have operations under more than one SIC
code.
SOURCE: Number of establishments: EIS 1981 (Continental United
States); U.S. Department of Commerce 1980--1977 Census
of Outlying Areas (Puerto Rico).
Sales: U.S. Department of Commerce 1981b.
111-27
-------
TABLE III-4
1980 PRODUCTION VOLUME OF
ORGANIC CHEMICALS IN 1980 "TOP 50" LIST
Rank
Chemical
Production
(million metric
tons)
6
Ethylene
12.50
13
Urea
6.51
14
Propylene
6.22
15
Toluene
5. 12
16
Benzene
4.98
17
Ethylene dichloride
4.53
18
Ethylbenzene
3.45
20
Methanol
3.18
21
Styrene
3.13
22
Vinyl chloride
2.93
23
Xylene
2.91
24
Terephthalic acid
2.69
25
Formaldehyde
2.62
27
Ethylene oxide
2.25
28
Ethylene glycol
1.92
30
p-Xylene
1. 74
31
Cumene
1.43
32
Butadiene (1,3-)
1.31
33
Acetic acid
1.28
36
Phenol
1.12
38
Acetone
0.96
39
Cyclohexame
0.89
41
Vinyl acetate
0.87
42
Acrylonitrile
0.83
43
Isopropyl alcohol
0.81
44
Propylene oxide
0. 80
46
Acetic anhydride
0.67
49
Ethanol
0.55
50
Adipic acid
0.55
Total
r-»
r-»
00
SOURCE: Chemical and Engineering News, June 1981.
111-28
-------
TABLE III-5
PRODUCTION VOLUME OF PLASTICS AND SYNTHETIC FIBERS
1980
Production
(million
Resin/Fiber
(metric tons)
Thermosetting resins
1.86
Phenolic and other tar acid resins
0.68
Polyesters (unsaturated)
0.41
Urea resins
0.53
Epoxies (unmodified)
0. 15
Melamine resins
0.08
Thermoplastic resins
11.52
Low-density polyethylene
3.31
Polyvinyl chloride and copolymers
2.48
Polystyrene and copolymers
2.06
High-density polyethylene
2.00
Polypropylene and copolymers
1.66
TOTAL
13.37
Cellulosics
0.37
Rayon
0.22
Acetate
0. 15
Noncellulosics
3.97
Polyester
1.81
Nylon
1 .07
Glass fiber
0.39
Acrylic
0.35
Olefin
0.34
TOTAL
4.34
SOURCE: Chemical and Engineering News, June 1981.
II1-29
-------
TABLE I I 1-6
VALUE OF SHIPMENTS FOR THE ORGANIC CHEMICALS INDUSTRY
BY PRODUCT CLASS: 1977 (a)
SIC
CODE
PRODUCT GROUP
A I I
I ndustries
VALUE OF SHIPMENTS. S Million
CycIic Crudes
and Intermediates
(SIC 2865)
I ndustriaI
Organ i c ChemicaIs,
(SIC 2869)
Other
Industries
i
CO
o
TOTAL
Primary Products
Secondary Products
Miscellaneous Receipts
2865- CYCLIC CRUDES AND INTERMEDIATES 5,514.3
28651 Cyclic intermediates 4,048.4
28652 Synthetic organic dyes 722.1
28653 Synthetic organic pigments, lakes, and
toners 414.5
28655 Cyclic (coal tar) crudes 250.9
28650 Cyclic crudes and intermediates, n.s.k 42.4
2869- INDUSTRIAL ORGANIC CHEMICALS, n.e.c. 19,377.6
28693 Synthetic organic chemicals, n.e.c. 1,600.5
28694 Pesticides and other organic
agricultural chemicals 1,474.0
28695 Ethyl alcohol and other industrial
organic chemicals, n.e.c. 645.9
28696 Miscellaneous end-use chemicals and chemical
products, excluding urea 2,070.5
28697 Miscellaneous cyclic and acyclic chemicals
and chemical products 13,424.7
28690 Industrial organic chemicals, n.e.c., n.s.k. 162.1
OTHER SHIPMENTS BY 4-DIGIT PRODUCT GROUP:.
1321- Natural gas liquids
2022- Cheese, natural and processed
2035- Pickles sauces, and salad dressings
2048- Prepared feeds, n.e.c.
2085- Distilled liquor, except brandy
2611- Pulp mi I Is
2812- Alkalies and chlorine
2813- Industrial gases
2816- Inorganic pigments
5,637.0
3,699.9
1.769.8
167.3
3.699.9
2,438.4
595.5
373.7
(D)
(D)
(D)
121.4
(D)
(D)
21.4
(D)
(D)
(D)
66.6
24.232.8
16.238.9
7.327.8
666. 1
1.166.9
1,124. 1
(D)
(D)
16,238.9
1.247.4
1,194.0
541.4
1.900.5
11,197.8
157.7
(D)
(D)
(D)
(D)
(D)
(D)
(D)
(D)
(D)
647.5(b)
521.9
(D)
( D)
(D)
(D)
2,400.2(c)
231.7
181.9
(D)
148.5
1,733.9
(D)
-------
SI c
CODE PRODUCT GROUP
2819- Industrial inorganic chemicals, n.e.c.
2821- Plastics materials and resins
2822- Synthetic rubber
2824- Organic fibers, noncellulosic
2831- Biological products
2833- Medicinals and botanicals
2834- Pharmaceutical preparations
2842- Polishes and sanitation goods
2843- Surface active agents
2844- Toilet preparations
2851- Paints and allied products
2861- Other gum and wood chemicals
2873- Nitrogenous fertilizers
2874- Phosphatic fertilizers
2879- Agricultural chemicals, n.e.c.
2891- Adhesives and sealants
2892- Explosives
2893- Printing ink
2899- Chemical preparations, n.e.c.
2911- Petroleum refining
2952- Asphalt felts and coatings
2992- Lubricating oils and greases
3079- Miscellaneous plastics products
3291- Abrasive products
551- Food products machinery
3679- Electronic components, n.e.c.
3693- X-ray, electromedical and electrotherauputic
appa ratus
3832- Optical instruments and lenses
I I 1-6 (continued)
VALUE OF SHIPMENTS. S Million
Cyclic Crudes Industrial
All and intermediates Organic Chemicals, Other
Industries (SIC 2865) (SIC 2869) Industries
( D)
384.4
( D)
(D)
(D)
(D)
(D)
16.7
(D)
(D)
(D)
(D)
(D)
(D>
(D)
(D)
(P)
(D)
(D)
1,820.4
404.7
(D)
(D)
(D)
(D)
(D)
251 .2
(D)
(D)
(D)
(D)
(D)
(D)
(D)
(D)
198.8
1,329.1
(D)
(D)
(D)
(D)
(D)
-------
TABLE I It-6 (concluded)
VALUE OF SHIPMENTS. S Million
Cyc1ic Crudes
IndustriaI
SIC
A1 1
and Intermediates
Organic Chemicals,
Other
CODE
PRODUCT GROUP
Industries
(SIC 2865)
(SIC 2869)
Industries
MISCELLANEOUS RECEIPTS:
93000
00
Contract work
34.0
156.1
99980
13
Sales of scrap and refuse
(D)
7.3
99980
41
Receipts for research and developmental work
(D)
99980
98
Other miscellaneous receipts
(D)
(D)
99989
00
Resa1es
127.2
U96.1
a. - Represents zero. All other entries represent shipment values of at least two million dollars annually.
n. e.c.
Not elsewhere classified.
(D)
Withheld to avoid disclosing operations of individual companies.
Other
industries and their respective
va 1 ue
of shipments
in mi
I I ions of dollars for this industry include:
2812
Alkalies and chlorine
(0)
2834
Pharmaceutical preparations
(D)
2816
Inorganic Pigments
(D)
2843
Surface active agents
(D)
2819
Industrial inorganic chemicals.
n.e.c.
53.8
2873
Nitrogenous fertilizers
(D)
2821
Plastics materials and resins
110.2
2879
Agricultural chemicals, n.e.c.
(D)
2824
Organic fibers, nonce I IuIosic
(D)
2911
Petroleum refining
110.2
Other
industries and their respective
va I ue
of shipment
in mil
lions of dollars for this industry include:
2046
Wet corn miI 1ing
(D)
2843
Surface active agents
(0)
2812
Alkalies and chlorine
( D)
2844
Toilet preparations
(D)
2816
Inorganic pigments
(D)
2873
Nitrogenous fertilizers
165.4
2819
Industrial inorganic chemicals.
n.e.c.
163. 1
2879
Agricultural chemicals, n.e.c.
(D)
2821
Plastics materials and resins
(D)
2891
Adhesives and sealants
27.8
2822
Synthetic rubber
108.8
2899
Chemical preparations, n.e.c.
(D)
2823
Cellulosic manmade fibers
( D)
2911
Petroleum refining
241 .8
2824
Organic fibers, nonce 11u1osic
(D)
3011
Tires and inner tubes
(D)
2833
Medicinals and botanicals
(D)
3079
Miscellaneous plastics products
(D)
2834
Pharmaceutical preparations
(0)
3861
Photographic equipment and supplies
(D)
2841
Soap and other detergents
(D)
3999
Manufacturing industries, n.e.c.
(D)
2842
Polishes and sanitation goods
(D)
SOURCE:
U. S. Department of Commerce 1981a.
-------
TABLE I I 1-7
VALUE OF SHIPMENTS FOR THE PLASTICS/SYNTHETIC FIBERS
INDUSTRY BY PRODUCT CLASS: 1977(a)
SIC
CODE
PRODUCT CROUP
AI I
I industries
VALUE OF SHIPMENTS. S Million
Plastics
Materia Is
and Resins
(SIC 2821)
Cellulosic
Manmade
Fibers
(SIC 2823)
Organic Fibers,
Nonce Ilulosic
(SIC 2824)
Othe r
Industries
i
oo
oo
TOTAL
Primary Products
Secondary Products
Miscellaneous Receipts
2821- PLASTICS MATERIALS AND RESINS
28213 Thermoplastic resins and plastics materials
28214 Thermosetting resins and plastics materials
28210 Plastics materials and resins, n.s.k.
28233 Rayon and acetate fiber
2824- ORCANIC FIBERS, NONCELLULOSIC
28241 Nylon fibers, except producer textured
28243 Acrylic and modacrylic fibers, except
textured
28244 Polyester fibers, except producer textured
28245 Other nonce I IuIosic manmade fibers, except
producer textured
28246 Producer textured manmade fibers, group
f iIament
28240 Organic fibers, nonce I IuIosic, n.s.k.
OTHER SHIPMENTS BY 4-DICIT PRODUCT CROUP:
2281- Yarns, except wool
2295- Coated fabrics, not rubberized
2297- Nonwoven fabrics
2298- Cordage and twine
2299- Textile goods, n.e.c.
2621- Paper mill products, except building paper
2649- Converted paper products, n.e.c.
2812- Alkalies and chlorine
2813- Industrial gases
12,181.1
9,897.7
2,226.7
56.7
851.1
5.471.5
1,962.9
495.8
1.938.6
178.2
890.6
5.4
10,818.2
8,967.8
1,588.5
261 .9
8,967.8
7,367.0
(0)
(D)
(0)
(D)
(0)
(D)
(0)
( D)
(D)
(0)
998.9
(D)
(D)
(D)
(D)
(D)
(D)
( D)
(D)
6,379.8
5,308.7
1,002.4
68.7
(D)
(D)
(D)
5,308.7
(D)
(D)
1,809.9
168.0
890.6
(D)
(D)
(D)
(D)
2,879.5(b)
2,223.6
(D)
(D)
(D)(C)
(D)
(D)
(D)
(D)
-------
TABLE I I 1-7 (continued)
VALUE OF SHIPMENTS. S Million
Plastics
Cellulosic
Materia 1s
Manmade
Organic Fibers,
SIC
Al 1
and Resins
Fibers
Nonce 1lulosic
Other
CODE
PRODUCT GROUP
Industries
(SIC 2821)
(SIC 2823)
(SIC 2824)
Industries
2819-
Industrial inorganic chemicals, n.e.c.
(D)
(D)
(D)
2822
Synthetic rubber (vulcanizable elastomers)
85.9
1,670.3
-
-
2833-
Medicinals and botanicals
(D)
-
-
2841-
Soap and other detergents
(D)
-
-
2843-
Surface active agents
(D)
(D)
2851-
Pains and allied products
28.2
_
-
2861-
Gum and wood chemicals
(D)
-
-
2865-
Cyclic crudes and intermediates
110.2
-
(D)
2869-
Industrial organic chemicals, n.e.c.
ID)
(D)
(D)
2873-
Nitrogenous fertilizers
(D)
-
-
2879-
Agricultural chemicals, n.e.c.
(D)
-
-
2891-
Adhesives and sealants
67.5
-
(D)
2899-
Chemical preparations, n.e.c.
67.5
-
-
2911 -
Petroleum refining products
(D)
-
(D)
3079-
Miscellaneous plastics products
406.2
(D)
3231-
Products of purchased glass
(D)
-
-
3861-
Photographic equipment and supplies
-
(D)
-
MISCELLANEOUS RECEIPTS:
93000
00
Contract work
48.2
(D)
(D)
99980
13
Sales of scrap
(D)
(D)
(D)
99980
41
Receipts for research and development work
(D)
-
-
99980
98
Other miscellaneous receipts
40.5
(Z)
(D)
99989
00
Resa1es
168.8
(D)
62.7
a. - Represents zero. All other entries represent shipment values of at least two million dollars annually.
n.e.c. Not elsewhere classified. (0) Withheld to avoid disclosing operations of individual companies.
(Z) Less than 50 thousand dollars or hours; under 50 employees.
-------
TABLE I I 1-7 (concluded)
Other
industries and their respective value
of shipments
in mi
II ions of dollars for this industry include:
2812
Alkalies and chlorine
108.6
2879
Pesticides and agricultural
2819
Industrial inorganic chemicals, n.e.c.
(D)
chemicals, n.e.c.
(D)
2843
Surface active agents
17.8
2891
Adhesives and sealants
38.7
2851
Paints, varnishes, lacquers, enamels.
2892
Explosives
(D)
and allied products
137.7
2899
Chemical preparations, n.e.c.
41.0
2861
Gum and wood chemicals
24.1
2911
Petroleum refining
(D)
2865
Cyclic crudes and intermediates
384.4
3079
Miscellaneous plastics products
92.0
2869
Industrial organic chemicals, n.e.c.
1,820.4
3229
Pressed and blown glass, n.e.c.
(D)
c. Other industries with over $5 million shipment of primary products include: Thread mills (2284); and
Industrial organic chemicals, N.E.C. Production data are unavailable to avoid disclosing operations of
individual companies.
SOURCE: U. S. Department of Commerce 1981a
i
CO
cn
-------
TABLE III-8, calculated from data shown in Tables III-6 and III-7, summarizes
the distribution among the subindustries of the Organic Chemicals and
Plastics/Synthetic Fibers Industries. Although the degree of specialization
varies widely among individual subindustries, the two industries each receive
relatively little revenue from products other than those defined as primary.
GEOGRAPHIC DISTRIBUTION
TABLE 111 — 9 presents'plant distribution by state while FIGURE III-3 shows the
distribution of plants within the states. Most organic chemical plants are
located in coastal regions or on waterways near either sources of raw
materials (especially petrochemicals) or transportation centers.
Plastics/synthetic fibers industry plants are generally located near organic
chemicals plants to minimize costs of monomer feedstock transportation.
However, a significant number of plastic plants are situated near product
markets (i.e., large population centers) to minimize costs of transporting the
products to market.
PLANT SIZE
Although plant size may be defined in many ways, including number of
employees, number of product/processes, plant capacity, production volume, and
sales volume, none of these factors alone is sufficient to define plant size;
each is discussed in this section. Perhaps the most obvious definition of
plant size would be the number of workers employed. However, continuous
process plants producing high volume commodity chemicals typically employ
fewer workers per unit of production than do plants producing specialty
(relatively low volume) chemicals. For example, the total employment of the
Organic Chemicals Industry and the total employment of the Plastics/Synthetics
Industry are about the same (148,000 v. 147,000), but the production of the
Organics industry is about five times that of the Plastics/Synthetics
Industry.
Plant size may also be expressed in terms of the number of product/processes
which are operated at a plant. Analysis of the number of product/processes
for 551 plants in the edited 308 database is presented in FIGURE III-4. This
database consists of the 291 direct and indirect discharge plants in the 308
Summary database and an additional 260 indirect discharge plants included in
the 30B Survey. Most plants.(90%) in the Organic Chemicals Industry have 10
or fewer product/processes, with a fairly even distribution among plants with
one to ten product/processes. In contrast, the majority of plastics plants
(76%) within the Plastics/Synthetic Fibers Industry have only one or two
product/processes; no plastics plant has more than 10 product/processes.
Integrated plants (plants which produce both organic chemicals and plastic
products) typically have far more product/processes. Over 50% of the plants
have five to ten product/processes; five percent of integrated plants have as
many as 30 product/processes.
Plant capacity is defined as the maximum production of a given product/process
per unit time. Neither production volume nor plant capacity clearly defines
plant size. Plants continuously producing high-volume chemicals (generally
111-36
-------
TABLE I I 1-8
THE ORGANIC CHEMICALS AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES
BY PRIMARY PRODUCT SPECIALIZATION (a, b)
SIC
CODE
PRODUCT GROUP
OCPSF
I indus-
tries
CycIi c
Crudes and
Intermediates
(SIC 2865)
PERCENT OF TOTAL VALUE OF SHIPMENTS
IndustriaI
Organ ic
ChemicaIs,
(SIC 2869)
Plastics
Materia Is
and Resins
(SIC 2821)
Cellulosic
Manmade
Fibers
(SIC 2823)
Organ ic
Fibers,
Nonce Ilulosic
(SIC 2824)
ORGANIC CHEMICALS
2865- CYCLIC CRUDES AND INTERMEDIATES 90
2869- INDUSTRIAL ORGANIC CHEMICALS, n.e.c.(c) 84
67
(0)
21
84
2
(D)
(D)
(D)
(D)
PLASTICS AND SYNTHETIC FIBERS
2821- PLASTICS MATERIALS AND RESINS
2823- CELLULOSIC MANMADE FIBERS
2824- ORGANIC FIBERS, NONCELLULOSIC
92
100
97
15
(D)
74
100
97
(D)
(D)
a. Primary products are those products which define the industry (see text and Figure I I 1-1).
b. - = Represents zero. All other entries represent shipment values of at least two million dollars annually.
(D) = Withheld to avoid disclosing operations of individual companies.
c. n.e.c. Not elsewhere classified.
SOURCE: U.S. Department of Commerce 1981a.
-------
TABLE III-9
PLANT DISTRIBUTION BY STATE
PRIMARY PRODUCERS
Organic Chemicals Plastics and Synthetic
Industry Fibers Industry
SIC Code SIC Code
STATE 2865 2869 Total 2821 2823 2824 Total
Alabama
4
5
9
7
1
2
10
Alaska
0
1
1
0
0
0
0
Arizona
0
1
1
1
0
0
1
Arkansas
1
3
4
5
0
1
6
California
6
30
36
45
0
1
46
Colorado
1
4
5
3
0
0
3
Connecticut
0
8
8
11
0
3 .
14
Delaware
1
5
6
12
0
1
13
Florida
3
6
9
7
0
2
9
Georgia
1
6
7
7
1
5
13
Hawaii
0
0
0
0
0
0
0
Idaho
0
0
0
0
0
0
0
I1linois
12
32
44
28
1
1
30
Indiana
4
4
8
7
1
1
9
Iowa
0
2
2
4
0
0
4
Kansas
2
3
5
1
0
0
1
Kentucky
2
8
10
5
0
0
5
Louisiana
3
33
36
10
0
0
10
Maine
0
0
0
1
0
0
1
Maryland
0
4
4
3
1
1
5
Massachusetts
7
14
21
32
0
2
34
Michigan
3
16
19
16
1
0
17
Minnesota
1
3
4
3
0
0
3
Missouri
1
7
8
8
0
0
8
Mississippi
3
1
4
6
0
1
7
Montana
0
1
1
1
0
0
1
North Carolina
12
11
23
12
0
11
23
North Dakota
0
0
0
0
1
0
1
Nebraska
0
2
2
0
0
0
0
New Hampshire
1
2
3
4
0
0
4
New Jersey
48
67
115
60
1
1
62
New Mexico
0
1
1
0
0
0
0
Nevada
0
2
2
1
0
0
1
New York
10
27
37
24
1
1
26
Ohio
18
19
37
43
2
1
46
Oklahoma
0
2
2
5
0
0
5
I11-38
-------
TABLE 111-9 (concluded)
PRIMARY PRODUCERS
Organic Chemicals Plastics and Synthetic
Industry Fibers Indnstry
SIC Code SIC Code
STATE 2865 2869 Total 2821 2823 2824 Total
Oregon
0
4
4
4
0
0
4
Pennsylvania
12
21
33
31
2
0
33
Puerto Rico
3
9
12
4
0
3
7
Rhode Is1and
5
6
11
1
0
0
1
South Carolina
10
9
19
5
1
15
21
South Dakota
0
0
0
0
0
0
0
Tennessee
1
5
6
7
2
4
13
Texas
17
57
74
35
0
0
35
Utah
1
0
1
2
0
0
2
Virginia
1
4
5
5
2
7,
14
Vermont
0
0
0
1
0
0
1
Washington
2
4
6
5
1
0
6
Wisconsin
0
6
6
9
0
0
9
West Virginia
1
11
12
7
0
1
8
Wyoming
1
0
1
0
0
0
0
TOTAL
198.
466
664
488
19
65
572
SOURCE: EIS 1981 (Continental United States); U.S. Department of
Commerce 1980 (Puerto Rico).
II1-39
-------
r"\
FIGURE 111-3
PLANT DISTRIBUTION BY
GEOGRAPHIC LOCATION
-------
FIGURE II1-4 NUMBER OF PRODUCT/PROCESSES BY PLANT
SOURCE:
308 EDITED DATA
BASE ; DIRECT,
T.HDTYaECT, AND
ZI^O fgCHARQERS
5 6-10 11-20 21-40 41+
NO, OF PROD/PROC
100>
80.
60.
40.
20.
j Organi
/ Both
/ P L asi i c<
-------
employing relatively few workers), may be physically smaller than plants
producing specialty chemicals by batch processes. High volume commodity
chemicals are typically less expensive than specialty chemicals. Sales volume
therefore does not correlate directly with plant employment or production
volume. FIGURES III-5 and III-6 illustrate the plant distribution of the
Organic Chemicals and Plastics/Synthetic Fibers Industries by number of
employees and sales volume, respectively.
PLANT AGE
The ages of plants within the Organic Chemicals and Plastics/Synthetic Fibers
Industries are difficult to define since the plants are generally made up of
more than one process unit, each designed to produce different products. As
the industry introduces new products and product demand grows, process units
are added to a plant. It is not clear which process should be chosen to
define plant age. Typically, the oldest process in current operation is used
to define plant age. Information concerning plant age is not available in the
general trade literature and has been compiled from the 308 Summary Database
for direct and zero discharge plants. Two-hundred eighty-two of the 291
plants in the 308 Summary Database provided information on plant age. FIGURE
III-7 illustrates the age (as defined above) of manufacturing facilities
within these industries.
111-42
-------
FIGURE III-5
PLANT DISTRIBUTION BY NUMBER OF EMPLOYEES
i
CO
7BB-
Z3B-
-e ZBB —
IT!
Q_
15B —
u
-------
FIGURE III-6
PLANT DISTRIBUTION BY SALES VOLUME
lOOO-i
\
A
: V
\
• \
\
\
A
'••N
\.
N
Plastics/Synthetic Fibers Plants
Organic Chemicals Plants
N
—i r 1
1, 600 1, 800 2, 000
200 400 600 800 1. 000 1, 200 1, 400
Sales Volume (millions of dollars)
SOURCE: EIS 1981
-------
FIGURE 111-7
PLANT AGE OF THE ORGANIC CHEMICALS
AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES
70—,
60 —
PI ant Age
SOURCE:
308 Summary Database;
Direct and Zero discharge plants only.
-------
REFERENCES
CHEMICAL AND ENGINEERING NEWS. 1981. 59:37
ECONOMIC INFORMATION SYSTEMS, INC. (EIS). 1981. EIS Industrial Plants
Database, Dialog Information Retrieval Service, Lockheed Information
Services. March 1981.
SHREVE, R.N., and BRINK, J.A. 1977. Chemical Process Industries. 4th ed.
McGraw-Hill, New York.
U.S. DEPARTMENT OF COMMERCE. 1980. 19 77 Economic Census of Outlying Areas:
Puerto Rico and U.S. Virgin Islands. Bureau of the Census. OAC-77-4 and 5
U.S. DEPARTMENT OF COMMERCE. 1981a. 1977 Census of Manufacturers. Volume II
Industry Statistics. Part 2. SIC Major Groups 27-34. Washington, D.C.
U.S. DEPARTMENT OF COMMERCE. 1981b. 1981 U.S. Industrial Outlook. Bureau of
Industrial Economics. Washington, D.C.
U.S. ENVIRONMENTAL PROTECTION AGENCY (USEPA). 1983. Economic Analysis of
Proposed Effluent Standards and Limitations for the Organic Chemicals and
Plastics, Synthetics, and Fibers Industries. EPA 440/2-83-004
II1-46
-------
SECTION IV
SUBCATEGORY ATI ON OF THE ORGANIC CHEMICALS AND
PLASTICS/SYNTHETIC FIBERS INDUSTRIES
INTRODUCTION
Section 304(b)(2)(B) of the Clean Water Act requires EPA to consider certain
factors in determining best available technology limitations. Factors to be
considered include: the age of equipment and facilities involved; the process
employed; the engineering aspects of the application of various types of
control techniques; process changes; the cost of achieving such effluent
reduction; non-water quality environmental impact (including energy
requirements); and such other factors as the Administrator deems appropriate.
The purpose of such consideration is to determine whether these industries (or
segments of these industries) exhibit unique wastewater characteristics which
support the development of separate national effluent limitations guidelines.
Thus major industry groups may require division into smaller homogeneous
groups that account for the individual characteristics of different
facilities.
In order to consider subcategorization an the basis of the factors listed
above, it is necessary to demonstrate that significant differences among the
plant wastewater quality or that differences in the treatability of plant
wastewaters exist. The Organic Chemicals and Plastics/Synthetic Fibers
Industries (OCPSF) might be subcategorized into groups with significant
differences in terras of influent and effluent quality based on the following
factors:
• Engineering aspects of control technologies;
• Facility size (as measured by plant production
and/or sales);
• Geographical location;
• Age of equipment and facilities;
• Cost of achieving effluent reduction;
• Nonwater quality environmental impacts;
¦ Processes employed and process changes.
The Organic Chemicals and Plastics/Synthetic Fibers Industries are recognized
as separate industries within the U. S. economy; however, vertical integration
of plants within these industries is common, blurring distinctions between
organic chemical plants and plastics/synthetic fibers plants. As a practical
matter, the OCPSF is divided among three types of plants:
" Plants manufacturing only organic chemicals.
• Plants manufacturing only plastics and synthetic
materials.
IV-1
-------
Integrated plants manufacturing both organic
chemicals and plastics and synthetic materials at the
same facility.
Most importantly, this distinction is also reasonable from the viewpoint of
wastewater generation. Chemical plants manufacturing only organic chemicals
are predicted to have higher raw waste concentrations (i.e., influents to
wastewater treatment systems) of organic priority pollutants than facilities
manufacturing plastics/synthetics fibers only, with combined plants lying
between these two groups. This is empirically substantiated by the data
collected by EPA. TABLE IV-1 shows the mean concentrations of priority
pollutant groups (organics vs. metals) in raw wastewaters for facilities
manufacturing organic chemicals only, plastics/synthetic fibers only, and
integrated organic and plastics plants. As can be seen, the mean influent
concentrations of- the organic priority pollutant fractions are considerably
less for plastics/synthetic fibers plants (i.e., have a cleaner influent) than
the other two groups. Only the metal fraction is of higher concentration for
plastics/synthetic fibers plants. Similarly, FIGURE IV-1 illustrates the
average influent concentrations of Plastics-Only and Not Plastics-Only plants
by pollutant. The'differences in types of pollutants regulated, effluent
levels achievable, and/or costs to reach that level result in a proposal that
plants within these industries be placed in one of two categories: plants
which manufacture plastics and synthetic fibers only (Plastics-Only Plants);
and plants that manufacture both plastic materials and organic chemicals (Not
Plastics-Only Plants).
METHODOLOGY
In the interest of consistency and simplicity, the Agency sought a BAT
subcategorization scheme which was similar to the proposed BPT
subcategorization. The Agency's approach presumes that radically different
subcategories for BPT and BAT would not be useful to either industry or the
permit authorities. Two substantially different subcategorization schemes for
BPT and BAT would complicate the process of implementing and applying both
sets of effluent guidelines at a specific plant. Therefore, the Agency chose
as a basis for its BAT subcategories the two major categories of plants in the
BPT subcategories: Plastics-Only and Not Plastics-Only.
The subcategorization proposed for these industries is based primarily upon
the priority pollutants detected or likely to be present in their
wastewaters. The engineering analysis therefore considered the relative
treatability of the waste streams generated by the Plastics-Only and Not
Plastics-Only subcategories. This analysis considered the applicability of
the following major treatment units: equalization, sedimentation, steam
stripping, precipitation and coagulation, carbon adsorption, biochemical
oxidation, and filtration. The data upon which this analysis is made includes
Phase I and II Screening data, Verification data, and CMA/EPA Five-Plant data
within the Organic Chemicals and PIastics/Synthetic Fibers Industries.
Statistical analyses were performed to determine whether priority pollutant
data supported the conclusions of engineering analyses. As in BPT, a
nonparametric test procedure (the Terry-Hoeffding test) was used to compare
IV-2
-------
TABLE IV-1
MEAN CONCENTRATIONS OF PRIORITY POLLUTANT
GROUPS BY PLANT TYPE
PLANT TYPE
MEAN INFLUENT CONCENTRATION, yg/1
NUMBER All Organic Priority
OF Priority Pollutant
PLANTS Pollutants Metals
Organic Chemical Plants 12 11,400
Plastic and Synthetic
Fibers Plants 8 260
Organic and Plastics Plants 31 1,900
230
12,000
.5,500
IV-3
-------
FIGURE IV-1
AVERAGE INFLUENT CONCENTRATION OF ORGANIC POLLUTANTS
PPB
100000-
5 10000"
0
1
CO
(J
H
ID
<
hJ
Ph
J
S3
o
I
VJ
U
1000-
100"
10H
0"
10"
100-
1000"
3 10000-
H 100000-1
o
z
ct %
.4>?
<~
~
9,
9
rr^yr
10
I | I 1 I 1 I t I I I j I I I Ml I * ' | I
Ipll » TTTfTyi TTIlTTTT|y»M'l'l|lt|
20 20 40 56 60 70 30 90
Pollutant Number
NOTE: Screening data used.
Influent concentrations less than or equal to 10 ppb deleted.
Excludes pesticides (pollutant numbers 89 through 113) and
dioxin.
IV-4
-------
median pollutant levels of different types of plants (e.g., Plastics-Only vs.
Not Plastics-Only plants). A statistically significant test result implied
that there were differences in influent quality between groups of plants that
suggested aneed for subcategories.
Unlike the BPT analysis, the Terry-Hoeffding test was not applied directly to
pollutant concentrations of different plants one pollutant at a time. Such
analyses would have been inefficient and difficult to interpret because there
were measurements on over 100 pollutants, the measurements on some groups of
pollutants were highly correlated, and measurements of some pollutants showed
little plant-to-plant variation. Therefore the Agency decided to focus on
pollutants or pollutant groups exhibiting the most plant-to-plant variation.
This was accomplished through a preliminary data "reduction step that grouped
pollutants by defining weighted averages of pollutant levels through a
raulti-variate statistical procedure called principal component analysis (this
analysis is described briefly below). The comparisons of groups of plants via
the Terry-Hoeffding test were based on these new weighted average or aggregate
pollutant variables.
To perform the BAT subcategorization analyses, the Agency utilized the
influent data available from the Phase I and Phase II Screening studies.
These data were used because they provided a broad assessment of the presence
of priority pollutants at OCPSF plants. In the data reduction step, these
data covered 143 plants. Fewer plaints were included in some of the
plant-group comparisons, however, because of inability to identify the group
to which some plants belonged. Data for organic priority pollutants in the
acid, base/neutral, and volatile fractions and for metals and cyanide were
included in the analyses.
The principal component analysis effectively reduced the large set of original
pollutant-specific variables to a smaller number of aggregated new variables
which were uncorrelated and accounted for a large portion of the variability
in the original pollutant data. This data reduction procedure was'performed
separately on the 88 organic priority pollutants and on metals/cyanide because
of differences in analytical methods for the two groups of pollutants. Each
principal component or aggregate pollutant variable, Y, had the form
Y = I a.X.,
i i
where a^ was a numeric weight determined by the correlation structure of the
original data, and represented the level of pollutant i. The a^
weights assigned to a given pollutant differed for each principal component.)
Typically, the utility of principal component analysis is evaluated by
comparing the sum of the variances of the aggregate variables to the sum of
the variances of the original variables. In the BAT analysis, five principal
components accounted in this sense for 74 and 78 percent, respectively, of the
variation in the original organics and metals/cyanide data. Morrison (1976)
suggests that up to five principal components be retained for subsequent
analysis if they account for 75 percent of the variation. Therefore, the
Agency believes that statistical comparisons of subcategories based on the
more manageable set of five aggregated pollutant variables is a reasonable
practical alternative to one pollutant at a time analyses. Further details on
the principal component analysis are provided in Appendix F.
IV-5
-------
Subsequently, each of the five principal components was evaluated for each
plant by substituting measured pollutant concentrations for that plant into
the appropriate weighted average formulas. Then statistical subcategorization
analyses were performed by using the Terry-Hoeffding test (or a generalization
of it) to compare median principal component scores of plants in different
groups. The first step in the analysis compared Plastics-Only and Not
Plastics-Only plants. The tests showed statistical differences (probability
less than 0.001) between these plant groups for the first and fifth principal
components for organics, i.e., they showed that Plastics-Only plants had lower •
aggregate organic pollutant levels than other plants. No significant
differences were found for the five metals/cyanide principal components.
Further tests were performed to investigate whether differences existed
between Not Plastics-Only plants if they were further subcategorized into
Organics Only and Integrated (mixed organics/plastics) plants, or into the
three process-related BPT subcategories (Type I with oxidation, Type I without
oxidation, and Not Type I). No significant differences were found for either
the organics or the metals/cyanide principal components. Thus these
statistical analyses provided no evidence that further subcategorization of
Not Plastics-Only plants was necessary.
Based on the results of the engineering and statistical analyses, the Agency
concluded that Plastics-Only and Not Plastics-Only subcategories are needed.
Details of the statistical subcategorization analysis are provided in Appendix
F. Details of the engineering analyses are discussed in the remainder of this
section.
ENGINEERING ASPECTS OF CONTROL TECHNOLOGIES (TREATABILITY)
The selection of a treatment train for OCPSF Industries wastewaters is done on
a plant-by-plant basis. The selection is based on the desired effluent
quality and thermodynamic properties of the waste stream contaminants. While
the different product/process mixes which exist at individual plants are
unique and result in process waste streams of widely varying quality, priority
pollutant wasteloads are treatable by commonly employed physical-chemical and
biological unit operations (see Sections VII and IX).
Typically, the treatability of a waste stream is described in terms of its
biodegradability, as biological treatment usually provides the most
cost-effective means of treating a high volume, high (organic) strength
industrial waste (i.e., minimum capital and operating costs). Furthermore,
biodegradability serves as an important indicator of the toxic nature of the
waste load upon discharge to the environment. Aerobic (oxygen-rich)
biological treatment processes achieve accelerated versions of the same type
of biodegradation that would occur much more slowly in the receiving water.
These treatment processes accelerate biodegradation by aerating the wastewater
to keep the dissolved oxygen concentration high and recycling microorganisms
to maintain extremely high concentrations of bacteria, algae, fungi and
protozoa in the treatment system. Certain compounds which resist biological
degradation in natural waters may be readily oxidized by a microbial
population adapted to the waste. As would occur in the natural environment,
IV-6
-------
organic compounds may be removed by volatization (e.g., aeration) and
adsorption on solid materials (e.g., sludge) during biological treatment.
One of the primary limitations of biological treatment of wastewaters from the
Organic Chemicals and Plastics/Synthetic Fibers Industries is the presence of
both refractory (difficult to treat) compounds as well as compounds which are
toxic or inhibitory to biological processes. Compounds oxidized slowly by
microorganisms can generally be treated by subjecting the wastewater to
biological treatment for a longer time; thereby increasing the overall
conventional and toxic pollutant removals. Lengthening the duration of
treatment however requires larger treatment tanks and more aeration, both of
which add to the expense of the treatment. Alternatively, pollutants that are
refractory, toxic, or inhibitory to biological process can be removed prior to
biological treatment of wastewaters. Removal of pollutants prior to
biological treatment is known as pretreatment.
The successful treatment of wastewaters of the OCPSF industries primarily
depends on effective physical-chemical pretreatment of wastewaters, the
ability to acclimate biological organisms to the remaining pollutants in the
waste stream (as in activated sludge processes), the year-round operation of
the treatment system at an efficient removal rate, the resistance of the
treatment system to toxic or inhibitory concentrations and the stability of
the treatment system during variations in the waste loading (i.e., changes in
product mixes). The following sections discuss briefly both biological and
physical-chemical treatment technologies.
Biological Treatment of Wastewaters
In general aerobic bacteria are responsible for the biodegradation of
synthetic organic chemicals, employing most of the sequences and cycles which
occupy a central position in metabolic pathways and which are found in other
living organisms. Their unique biochemical asset is an ability to catalyze
early steps in degradation that other organisms cannot, thereby forming
metabolites that can enter the common pathways of metabolism (e.g., the Krebs
cycle or the fatty acid "spiral"; Dagley 1975).
Microorganisms able to utilize organic compounds for growth do so by
degradation into simpler compounds which are central to the processes of
intermediary metabolism before synthesis of cell constituents can occur.
Sufficient energy for synthesis is derived by complete oxidation of the
remainder to carbon dioxide and water. As many of the chemical products
produced by the Organic Chemicals and Plastics/Synthetic Fibers Industries do
not bear close structural similarity to intermediary metabolites found within
common pathways of metabolism, such compounds often require extensive
structural modification before they can enter central metabolic schemes.
However, microorganisms capable of producing the necessary enzymes for such
structural modifications are numerous and widespread.
IV-7
-------
Thus, whether a man-made chemical will be biodegradable is largely dependent
on two factors:
(1) The ability of microbial enzymes to accept substrate compounds, with
structures similar to, but not identical with, chemicals found in
nature (i.e., the lack of substrate specificity).
(2) The ability of novel substrates to induce or derepress the synthesis
of the necessary degradative enzyme in the microorganisms.
These two factors are mechanisms for acclimation - the process by which
microorganisms learn to degrade new chemicals. While there are a great number
of factors affecting the degradation or lack of degradation in a given system,
these factors may be aggregated under three broad parameters:
• The structure of the compound. Presence or
absence of certain moieties and substituents; steric
factors, molecular size or other structural features.
• Available microorganisms. Types and number of
microorganisms; presence of available or inducible
enzymes.
• The environment. Temperature, pH, presence or
absence of oxygen, nutrients, light.
Chemical structure may effect the biodegradation of a compound in two
principal ways. First, the molecule may possess groups or substituents which
cannot react with available or inducible enzymes (e.g., carbon-fluorine bonds
are difficult to break). Secondly, the structure may determine the Compound
to be in a physical state, (e.g., absorbed onto particulate matter, or in the
gas phase) where microbial degradation does not easily occur. For example,
oils and fats typically have very low solubilities in water and strongly
adsorb to carbon-containing particulate matter. For this reason, such
pollutants are removed in pretreatment trains. When present in a biological
system, such pollutants are more likely to be removed via adsorption onto
sludge than biodegraded.
Few known correlations of structure to biodegradation are valid for a variety
of chemical compound types although a number of biodegradability relationships
for compounds have been established within narrowly defined structural
groups. Since biodegradation of organic compounds occurs by biochemical
oxidation, compounds containing carbon-oxygen bonds are more amenable to
degradation then those compounds that do not. This and other relationships
between structure and biodegradability which seem generally established are
outlined in TABLE IV-2. In general, those compounds less amenable to
biodegradation as shown in Table IV-2 require physical-chemical pretreatment.
Basic environmental conditions (i.e., proper microbial conditions) should be
optimized to enhance biodegradation in well operated biological treatment
trains. Biological treatment units are operated to provide oxygen and
nutrients and contro 1 pH to provide optimum growth conditions. Furthermore
biological processes (e.g., activated sludge, aerated lagoon systems,
IV-8
-------
TABLE IV-2
INFLUENCE OF STRUCTURE ON DEGRADABILITY
Type of Compounds
or Substituents
More Degradable
Less Degradable
Hydrocarbons
Higher alkanes (~ 12)
Alkanes
Straight-chain paraf-
f inic
Paraffinic
Mono- and bicyclic
aromatic
Lower alkanes
High molecular weight
alkanes
Branched-chain paraf-
f inic
Aromatic
Polycyclic aromatic
Aromatic
substituent
—OH
—COOH
—NH
2
—p
—CI
—NO
2
—OCH
3
—SO H
3
Aliphatic chlorine
—CI more than six
carbon atoms from
terminal C
—CI six or less carbon
atoms from terminal C
Source: Hutzinger and Veerkamp (1981).
IV-9
-------
trickling filters, oxidation stabilization ponds (see Section VII)) can be
designed to operate optimally by properly controlling the rate-controlling
variables: (1) microorganism concentration, (2) bacterial acclimation, (3)
temperature level, (4) contact duration and mode, and (5) organic feed
concentration. The theoretical approach used in the design of biological
treatment systems is to develop mathematical models which depict relationships
between parameters that control efficiency of microbial growth and substrate
removal. The purpose of these design models is to provide predictive
equations consistent with the underlying metabolic principles governing the
waste treatment process. In commonly used models (see Appendix E), effluent
quality is related to residence time and is independent of influent
concentration. More sophisticated multi-media models have been developed (see
Hwang 1980a, Freeman, 1979 and Freeman et al., 1980) to reflect the
recognition that biological treatment not only involves oxidation of organic
compounds, but removal through air stripping and waste sludge as well.
A primary limitation of biological treatment of OCPSF process wastewaters is
the great variability of toxic pollutant loadings. While microbial
populations within a biological treatment system gradually acclimate to
specific compounds in the waste streams from a given organic chemicals plant,
the composition of a waste stream may rapidly vary as different production
processes are operated. The microbial population treating a complex waste
stream of widely varying composition will not be as well acclimated as a
microbial population treating a relatively constant waste stream. Thus, in
order to maintain desired removal rates, physical-chemical pretreatment may be
required prior to the biological treatment train.
The kinetics of pollutant removal by biological systems are, in general, more
sensitive to pollutant concentration than pollutant loading. When biochemical
inhibition can be attributed solely to the concentration of pollutants in raw
wastewater, rather than to inherent non-biodegradability, dilution of such
wastewaters is an appropriate and effective pretreatment step to improve the
overall performance of a biological system. Typical diluent streams include
utility plant blowdown, once through cooling water, or fresh water from wells
or surface supplies.
Physical-Chemical Treatment
Physical-chemical technologies are commonly used by industrial manufacturers
as in-process recovery and treatment steps, as a means of rendering
wastewaters more amenable to treatment by biological processes, and in certain
cases, as the sole end-of-pipe treatment of wastewaters where such streams are
ineffectively treated by biological processes (e.g., low in BOD and COD or low
in BOD and high in COD). Such operations include: equalization,
sedimentation, filtration, phase separation, solvent extraction, stripping,
aeration, absorption on a synthetic resin or activated carbon, azeotropic or
extractive distillation, chemical precipitation, chemical coagulation, and
polishing ponds. These techniques may be combined or repeated in sequence, as
required, to achieve the desired level of treatment of the waste effluent.
The following discussion briefly summarizes important physical-chemical
treatment concepts.
IV-10
-------
Wastewaters from individual product lines are generally fed to a common tank
or basin of sufficient volume to allow mixing of different wastewaters and
thereby minimize influent variations. Wastewaters containing inordinately
high concentrations of organic pollutants can also be diverted to auxiliary
basins; off-specification wastewaters are then fed to the biological system at
a suitable rate. Both equalization and auxiliary basins reduce hydraulic and
pollutant concentration variation to the biological system and result in
significantly higher overall efficiency.
Solids present in wastewaters can be removed by a wide variety of processes
including sedimentation, dissolved air flotation, mixed media filtration,
chemical coagulation with gravity sedimentation, and polishing ponds. Oily
wastewaters can be treated in a similar manner.
Steam, air, or solvent stripping of certain waste streams can also reduce high
loadings of organic pollutants, minimize organic loading variations, and
remove potentially toxic or inhibitory contaminants. Examples of waste
streams successfully treated by stripping include process wastewaters from
chlorinated hydrocarbon and complex aldehyde manufacture. A more detailed
discussion of the amenability of specific toxic pollutants to removal by steam
stripping may be found in Section VII and Appendix E.
Adsorption is among the most conation of pretreatment processes used to remove
organic pollutants from aqueous waste streams. Activated carbon is the most
common adsorption medium, although advances in macroreticular polymerization
techniques (allowing for the manufacture of microporous molecular sieves with
a predetermined (average) pore size, pore size distribution, and surface area)
enable the selection of a synthetic resin with specific adsorption
selectivity. In either system, the adsorbent becomes saturated with the
adsorbate and requires regeneration. For carbon this is generally
accomplished in multihearth or rotary tube furnaces. Synthetic resins may be
regenerated by a basic or acidic solution, or an organic solvent such as
methanol, water, or steam, depending on the adsorption characteristics of the
solute; in many cases, recovery of the solute is also practiced (Simpson,
1972; Kim et a_l. 1976; Breck, 1977; and Lyman, 1976). For additional detail
on adsorption processes and their use in treating priority
pollutant-containing wastewaters, see Section VII and Appendix E.
Treatment System Performance
Selection of the appropriate treatment train for a waste stream is almost
solely dependent on the desired performance characteristics. Biological
systems are based on the required residence time to achieve the desired
effluent quality. Where extended residence times are infeasible (e.g. space
limitations on reactor size), pretreatment upstream of the biological unit may
be employed to remove toxic pollutants which slow, prevent, or interfere with
the biological process.
In selecting a physical-chemical treatment unit, the thermodynamics of the
operation dictate effluent quality. Steam stripping, for example, is a mass
transfer operation that is used to remove volatile organic contaminants from
dilute solutions. The practicality of using steam stripping to treat a
particular waste stream is dependent on the solubility, vapor pressure, and
IV-11
-------
the activity coefficients of pollutants to be treated. These thermodynamic
properties dictate tray and steam requirements, and ultimately, column
efficiencies. Excessive tray requirements to obtain the desired outlet
(effluent) concentration organic pollutants would rule out steam stripping as
a desirable treatment operation.
In summary, though the design of a treatment train can be unique to each
plant, by selection and proper operation of appropriate treatment
technologies, it is possible for individual plants to meet common effluent
limitations regardless of raw wastewater quality. From this discussion of
treatability and available treatment technologies, EPA found no basis for
subcategorization on the basis of engineering controls.
FACILITY SIZE
Although sales volume, number of employees, area of a plant site, plant
capacity, and production rate might logically be considered to define facility
size, none of these factors alone describes facility size in a satisfactory
manner as discussed in Section III of this report. Recognizing these
limitations, for the purpose of this report, size is best defined as the sum
of process line production rates present at individual plants production rates
are those reported in the 308 Questionnaire. Although the production sizes of
the waste streams within the Organic Chemicals and Plastics/Synthetic Fibers
Industries vary widely, ranging from less than 10,000 lbs/day to more than
5,000,000 lbs/day (a range of over five hundredfold), this definition fails to
embody fundamental characteristics such as continuous or batch manufacturing
processes. While equivalent production rates may be accomplished by either
production method, characteristics of the wastewater streams may vary
substantially because of different yield losses inherent in each process.
Therefore, there is no adequate method to define facility size, and it cannot
be used as a technical basis for subcategorization. In addition, statistical
analysis of production rate as a factor for subcategorization was
inappropriate for the same reason.
GEOGRAPHICAL LOCATION
Companies in the OCPSF Industries usually locate their plants based on a
number of factors. These include:
• Sources of raw materials
• Proximity of markets for products
• Availability of an adequate water supply
• Cheap sources of energy
• Proximity to proper modes of transportation
• Reasonably priced labor markets.
The availability and proximity of raw materials determine both the location
and nature of a facility; the petrochemical industry for example is located
largely in the gulf states where supplies of natural gas and other petroleum
based materials are readily available. Companies also locate their facilities
based on the type of production involved. For example, specialty producers
IV-12
-------
may be located closer to their major markets, whereas producers of commodity
chemicals may be centrally located to service a wide variety of markets. The
availability of water may also be an influencing factor on the plant location
and may moreover influence the product/processes employed by a plant. A
limited water .supply will, for example, encourage water conservation.
Availability of energy, transportation, and labor also affect the economic
viability of plant and are related to a plant's location.
Most importantly, plant location may affect the design of biological treatment
systems (and thus the effectiveness of such systems) because of the influence
of temperature on biodegradation rates. It is generally accepted that
wastewater temperature affects the performance of the biological treatment
process since the biodegradation rate is temperature dependent. The
relationship between biodegradation rate and reaction temperature is generally
written as:
(T-20)
*r = K20°c * 0
kinetic rate at temperature T (°C)
kinetic rate at 20(°C)
temperature coefficient
= reaction temperature
Reaction temperature is a complex function of ambient air temperature,
wastewater temperature, and system design. The sensitivity of the reaction
rate to temperature is defined by 0, an empirically determined dimensionless
coefficient. A value of 0 equal to 1.00 would imply that the reaction
kinetics are unaffected by changes in temperature. As the value of 0
increases above 1.0 the reaction becomes increasingly sensitive to changes in
operating temperature. The value of 0 for several organic-chemical
wastewaters has been reported to vary from 1.055 to 1.10. Although not
reported for individual priority pollutants, the effect of temperature on BOD
removal in an organic chemicals plant shows that although treatment efficiency
decreases with decreasing temperature, a high degree of BOD removal can be
achieved even at very low temperatures if suitable food to microorganism
ratios are maintained. Other references show conflicting results in
evaluating the effect of temperature on wastewater treatment plant
performance. Berthouex, et al. (1976) developed linear and time series
models relating effluent BOD 5 to influent BOD 5, mixed liquor suspended
solids (MLSS), temperature and hydraulic retention time based on three years
of data compiled at the Madison Sewage Treatment Plant (Wisconsin). They
found no significant effect of temperature on performance when gradual changes
in temperature (4-24°C) occurred.
B.A. Sayigh (19 77) conducted activated-sludge laboratory studies with
continuous stirred-tank reactors and concluded that the effects of temperature
using domestic sewage, organic-chemicals wastewaters and petro-chemical
wastewaters depend on the specific type of wastewater being treated. The
author also found that the higher the sludge age, the less the susceptibility
of the process to variations in temperature. Work done by Del Pino (1982)
using wastewaters from three organic chemical plants showed that low
where:
K20°
0
T
IV-13
-------
temperature operation did reduce treatment efficiency, but this could
generally be compensated for by operation at higher MLSS concentrations.
The principal difficulty encountered when evaluating the impact of ambient
temperature on treatment system performance is that temperature is only one of
several characteristics which affect the operation of the system. Changes in
ambient temperature (both seasonal and short term), raw waste load, product
mix, flow, food to microorganism ratio, dissolved solids and suspended solids
will all have some impact on treatment. In reviewing full scale plant
operating data, it is difficult to isolate ambient temperature effects from
changes caused by variables other than temperature. This problem can be
overcome in laboratory scale studies where ambient and wastewater temperature
can be controlled and other variables held constant, but the usefulness of
applying temperature data collected in this manner to the operation of a full
scale system is questionable. This is particularly true in the OCPSF Industry
where raw waste load variability is significant due to batch operations,
frequent product mix changes, and raw materials variations.
While ambient temperature can have an impact on the treatment efficiency in
some cases, temperature is only one of several factors which impact
treatment. Waste load variations, biomass acclimation, flow variations, waste
treatability and temperature of the wastewater during treatment must all be
taken into consideration when developing a treatment sequence for a specific
industrial site. With proper treatment system design (e.g., extended
aeration), seasonal temperature variations can be accommodated. Thus,
temperature considerations must be viewed as specific to a given site design,
rather than as specific to any given region or geographic area and is
therefore inappropriate as a basis for subcat-egorization.
AGE OF EQUIPMENT AND FACILITY
Facility age can affect raw waste pollutant concentrations in several ways.
Older plants may use open sewers and drainage ditches to collect process
wastewater. These ditches may run inside the process buildings as well as
between manufacturing centers. Because of their convenience and lack of other
collection alternatives, cooling waters, steam condensates, wash waters, and
tank drainage waters as well as contact wastewaters are generally collected in
these drains. Older facilities, therefore, are likely to exhibit higher
wastewater discharge flow rates than newer facilities which typically
segregate process contact wastewaters from non-contact process wastewaters.
In addition, the inclusion of relatively clean waters (e.g., noncontact
cooling waters, steam condensates) dilutes raw wastewaters. Older plants are
also less amenable to recycle techniques and wastewater segregation efforts;
both methods require the installation of new collection lines as well as the
isolation of the existing collection ditches and are difficult to accomplished
with existing piping systems.
Facility age, for the purposes of this report and as reported in the 308
Questionnaire, is defined as the oldest process in operation at the site.
Because most plants within the Organic Chemicals and Plastics/Synthetic Fibers
Industries consist of more than one process however, this definition fails to
reflect the true age of an OCPSF plant. Moreover production facilities are
IV-14
-------
continually modified to meet current production goals and to accommodate new
product lines. Actual process equipment is generally modern (i.e., 0-15 years
old) while major building structures and plant sewers are not generally
upgraded unless the plant expands significantly by new construction. Because
the age of plants within the Organic Chemicals and Plastics/Synthetic Fibers
Industries cannot be accurately defined, plant age is inappropriate for
subcategorization.
Process equipment common the the OCPSF Industries can be divided into the
following general categories: vessels in which the chemical reaction takes
place; equipment used to separate products from unwanted materials; equipment
used to control emissions from the process train; and vessels used to store
raw materials and products. Process wastewaters may be generated in this
equipment as a reaction product, reaction solvent, working fluid, heat
transfer medium, and maintenance/cleaning operations. Emission control
equipment such as scrubbers may also generate wastewaters.
The extent to which process wastewaters are contaminated with priority
pollutants depends mainly upon the degree of contact that process water has
with reactants/products, the effectiveness of the separation train, and the
physico-chemical properties of those priority pollutants formed in the
reaction. Raw wastewater quality is determined by the specific process design
and chemistry. For example, water formed during a reaction, used to quench a
reaction mixture, or used to wash reaction products will contain greater
amounts of pollutants than does water that does not come into direct contact
with reactants or products. The effectiveness of a separation train is
determined by the process design and the physico-chemical properties of those
pollutants present (see Engineering Aspects of Pollution Control). While
improvements are continually made in the design and construction of process
equipment, the basic design of such equipment may be quite old. Process
equipment does however deteriorate during use and requires maintenance to
ensure optimal performance. When process losses can no longer be effectively
controlled by maintenance, process equipment is replaced. The maintenance
schedule and useful life associated with each piece of equipment are in part
determined by equipment age and process conditions. Equipment age however
does not directly affect either pollutant concentrations in influent or
effluent wastewaters and is therefore inappropriate as a basis for
subcategorization.
COST OF ACHIEVING EFFLUENT REDUCTION
The waste treatment investment and operating costs for a specific chemical
plant depend on several factors:
• The ability to recycle process wastewaters.
• The ability to recover products from process
wastewaters.
• The composition and quantity flow of waste
streams.
IV-15
-------
• The geographical area within which the wastes are
generated and disposed of.
• The existence of POTWs to accept waste streams.
• The generation of solid waste.
• The nature of the chemical process.
• The kind and purity of the raw materials.
The technology for pollution abatement consists mainly of the same physical
and chemical separations and reaction technologies used in chemical
manufacture. Wastewater streams such as process water, boiler blow-down, and
runoff water may be treated separately or collectively by appropriate
operations in one or more treatment stages. Streams requiring different
treatment methods are segregated and subsequently combined at the point where
treatment becomes similar. For example, runoff waters might be settled in a
thickener; certain process waters might be separated by dissolved air
flotation, steam stripped, and treated biologically; other process wastewaters
might be neutralized and filtered; and the sanitary sewer flow might either be
treated biologically. All streams might then be combined for a water quality
check, flow equalization, and discharge to an adjacent water body.
Each of these factors is considered in this section. The composition of raw
wastewaters is largely a function of the products and processes by which these
products are made. The treatability of these wastewaters (as discussed
earlier) is largely independent of the raw waste load; that is, by selection
and proper operation of appropriate treatment technologies, it is possible for
individual plants to meet common effluent limitation. Accordingly, treatment
costs are dependent upon effluent quality and inappropriate as a basis for
subcategorization. Industry wide costs of compliance with proposed effluent
limitations are analyzed in the separate companion study, Economic Analysis of
Proposed Effluent Standards and Limitations for the Organic Chemicals and
Plastics/Synthetic Fibers Industry, EPA 440/2-83-004, which accompanies the
proposed OCPSF regulations.
NONWATER QUALITY ENVIRONMENTAL IMPACTS
Plants within the Organic Chemicals and Plastics/Synthetic Fibers Industries,
in addition to producing process wastewaters requiring treatment, may generate
significant amounts of airborne pollutants and solid wastes. Air emissions
are controlled by a wide variety of technologies including absorption,
adsorption, filtration, condensation, and incineration. Absorption
technologies in controlling atmospheric emissions generate both solid and
liquid waste streams. Solid wastes generated by OCPSF plants are treated by
technologies including: filtration, coagulation, stripping, extraction,
distillation, carbon adsorption, chemical reaction, chemical fixation, and
incineration. Many of these technologies used to treat solid wastes also
generate wastewater streams.
IV-16
-------
Generation of both airborne waste streams and solid waste streams is subject
to the same considerations that are process wastewaters: chemical
manufacturing processes do not convert raw materials to products at 100
percent efficiency; that is, a portion of the raw materials used in a
manufacturing process are inevitably converted into unwanted products. These
products may potentially be discharged to the atmosphere, the aquatic
environment, and the terrestrial environment depending upon the specific
manufacturing configuration (e.g., use of an aqueous reaction medium, use of
gaseous reactants). Both the impacts of air and solid waste emissions
parallel those of wastewater and do not provide an alternate subcategorization
system.
Similarly the energy consumption of wastewater treatment technologies fails to
provide meaningful subcategorization. The high energy content of raw
materials and products of the OCPSF Industries results in only a small
fraction of the total energy used for pollution control. Specific energy
requirements are determined by the nature of the processes and by such unit
operations as thermal cracking, distillation, heating or reactors, and similar
processing steps. In contrast, practically all wastewater treatment
technologies require a modest energy input that is a small fraction of the
total plant energy requirements. The energy requirements of the wastewater
treatment facility is small in comparison to the plant total.
PROCESSES EMPLOYED AND PROCESS CHANGES
The product/processes alone employed at individual plants -- that is the raw
materials used, the products manufactured, and the chemistry of production --
provide a logical basis for subcategorization of the Organic Chemicals and
Plastics/Synthetic Fibers Industry. Statistical analyses of priority
pollutant data within these industries as discussed in Appendix C moreover
indicate that individual plants can be grouped by ranges of priority
pollutants present in untreated wastewater, i.e., the wastewaters of some
plants have a higher loadings of certain toxic pollutant than others. The
various chemical processes yield wastewaters containing individual chemical
species which differ in molecular structure and consequently in susceptability
to various types of treatment. These considerations are discussed more fully
below.
An important characteristic of the Organic Chemicals and Plastics/Synthetic
Fibers Industries is the degree of vertical and horizontal integration between
manufacturing units at individual plants. Since the bulk of the basic raw
materials is derived from petroleum or natural gas, many of the commodity
organic chemical manufacturing plants are either part of or contiguous to
petroleum refineries; most of these plants have the flexibility to produce a
wide variety of products. Relatively few organic manufacturing facilities are
single product/process plants unless the final product is near the fabrication
or consumer product stage. Additionally, many process units are integrated in
such a fashion that amounts of related products can be varied as desired over
wide ranges. There can be a wide variation in the size (production capacity)
of the manufacturing complex as well as diversity of products and processes.
In addition to the variations based on the design capacity and design product
mix, economic and market conditions of both the products and raw materials can
IV-17
-------
greatly influence the production rate and processes employed even on a
relatively short-term basis.
Raw Haterials and Products
Synthetic organic chemicals are derivatives of naturally-occurring materials
(petroleum, natural gas, and coal) which have undergone at least one chemical
reaction. Given the large number of potential starting materials and chemical
reactions available to the industry, many thousands of organic chemicals are
produced by a potentially large number of basic processes having many
variations. Similar considerations also apply to the Plastics/Synthetic
Fibers Industry although both the number of starting materials and processes
are more limited. Both organic chemicals and plastics are commercially
produced from six major raw material classifications: methane, ethene,
propene, butanes/butenes, and higher aliphatic and aromatic compounds. This
list can be expanded to eight by further defining the aromatic compounds to
include benzene, toluene, and xylene. These raw materials are derived from
natural gas and petroleum, although a small portion of the aromatic compounds
are derived from coal.
Using these eight basic raw materials (feedstocks) derived from the petroleum
refining industry, process technologies used by the Organic Chemicals and
Plastics/Synthetic Fibers Industries lead to the formation of a wide variety
of products and intermediates, many of which are produced from more than one
basic raw material either as a primary reaction product or as a co-product.
Furthermore, the reaction product of one process is frequently used as the raw
material for a subsequent process. The primary products of the Organic
Chemicals Industry, for example, are the raw materials of the
Plastics/Synthetics Industry. As the chemical complexity of a raw material
increases, the variety and number of potential products and chemical
intermediates also tend to increase (see FIGURES IV-2 THROUGH IV-6). This
lack of distinction is more pronounced as products become further removed from
basic feedstocks. Many products/intermediates can be made from more than one
raw material. Acetone, for example, is produced by three separate processes
using propene, C 4 hydrocarbons, and cumene as raw materials. Frequently,
there are alternate processes by which a product can be made from the same
basic raw material.
Neither raw materials nor products provide meaningful subcategorization of the
OCPSF Industries. The raw materials of these industries comprise thousands of
compounds. These industries also produce as many as 25,000 products.
Aggregation of industry plants according to basic feedstocks fails to provide
meaningful differences in plant wastewaters because of the wide variations in
process chemistry employed by plants. Similarly, the large number of products
manufactured by typical industry plants makes subcategorization by products
impractical.
Process Chemistry
Chemical and plastics manufacturing plants share an important characteristic:
chemical processes never convert 100 percent of the feed stocks to the desired
products, since the chemical reactions/processes never proceed to total
completion. Moreover, because there are generally a variety of reaction
IV-18
-------
SYNTHESIS CAS
CHLORINATEO
METHANES
HCN
ACETYlENf
AMMONIA OXO METHANOL
CHEMICALS
AOIPONITRILE
AMMONIUM
SALTS
UREA
ACRVLONITRIIE
ACETONE
CYANOHYORIN
METHYL
AMINES
OMT
\o
FORMAIOEHYOE
RESINS
METHYL
CHLORIOE
SILICONES VINYL
CHLORIDE
METHYL
METHACRYLATES
«1
cli
CELLULOSE
kooucts
ElUOROCARiONS
VINYL
ACETATE
MEOPMENE
CHIORINATEO
ETHYLENE
ACRYLIC
ACIOt ESTERS
Riegel's Handbook of Industrial Chemistry, Seventh Edition, by James A. Kent;
Copyright (c) 1974 by Van Nostrand Reinhold Company. Reprinted by permission of the
publisher.
FIGURE IV-2~ SOME PRODUCTS DERIVED FROM METHANE
-------
ethylene
ETHANOL
ACETALOEHYOE
ETHYl
AMINES
ETHYl
(ROMIOE
CHLORAL
1
ETIUl
ETHER.
ETHYL BLN2ENE
I
EIIIYL TOLUENE
I
SEE AROMATIC*
ACETALOOl
2ETHYl
HEXANOL
ACETIC ACID
• ANHYOHIOE
HUTYUNE
GLYCOL
CROTON-
ALDEHYOE
ACETATE
ESTERS
ACETYL
CHLORIOE
ACETANILIOE
ASPIRIN
PENT AERY-
THRITOL
~t~
OOT
I
VINYL
ACETATE
CELLULOSE
ACETATE
MISCELLANEOUS
DERIVATIVES
PERACETIC ACIO
PARALOEHYOE
PYRIOINE
TRIMETIIYLOL
PROPANE
TETRAETHYL
* LEAD
I
ETHYL
CHLORIDE
ETHYL
CELLULOSE
ETHYLENE
OIBROMlOE
ETHYLENE
OICHLORIOE
ETHYLENE
AMINES
1
VINYL
CHLORIDE
I.U TRICHLORO
ETHANE
ETHANf
METHYL
CHLOROFORM
I
PENTACHLORO
ETHANE
I
PERCHLORO
ETHYLENE
1
TETRACHLORO
ETHANE
I
TRICHLORO
ETHYLENE
VINYLIOENE
CHLORIDE
METHYL
CHLOROFORM
<
I
N>
O
POLYVINYL
ALCOHOL
CHLOROACETIC*
ACIDS
I
POLYETHYLENE
LOW
DENSITY
I
HIGH
OENSITY
COPOLYMERS
PROPYLENE
ETHYL
ACETATE
1
VINYL
ACEIATi
1
PROPIONALOEHYOE
I
PROPIONIC ACIO
1
ETHYLENE OXIOE
ETHYLENE
GLYCOL
POLYETHYLENE
GLYCOLS
ETHOXYLATEO
SURFACTANTS
GLYCOL
ITHERS
ethanolamines
HYOROXYETHYl
CELLULOSE
POLYESTERS
OIOXANE
ETHYLENE
CARBONATE
GLYOXAl
OlOXOLANES
FROM: Riegel's Handbook of Industrial Chemistry, Seventh Edition, by James A. Kent;
Copyright (c) 1974 by Van Nostrand Reinhold Company. Reprinted by permission of the
publisher.
FIGURE IV-3-SOME PRODUCTS FROM ETHENE
-------
polypropylene
I—
NONYl-
PMCNOl
NONENE
i
IJOPROPANOl CUMENE
IrH
ACEIONE PHENOL
I
ISOOECYl
AlCOHOl
propylene
ACROLEIN All VI
CHIORIOE
OOOECENE
AllVI PROPYLENE
AlCOHOl OXIOE
HEPIENi
IUTVRAIOEHVOES
GIVCERINE
OOOECVl RlilANOt |
IEN2ENE
• 1
HANOI I
tSO OCTYL
AlCOHOl
ACRYIONIIRIIE
CIVCOl 1 POIYGIYCOIS
ElllEHS
EIHYl
HEXAhOl
POLYMERS
FR0M: Riegel's Handbook of Industrial Chemistry, Seventh Edition, by James A. Kent}
Copyright (c) 1974 by Van Nostrand Reinhold Company. Reprinted by permission of the
publisher.
FIGURE IV-4-SOME PRODUCTS DERIVED FROM PROPENE
-------
PETROIEUH
-I/O-
IUTANES
IUTVLENES
I
n-BUTANE
| |
AClfAlOfHYOt
•-BUTANOL
PENTAERYTHRITOL
ETHYLHEXANOL
I
SEC.RUTANOL
ACETIC ACIO
MEK
ACETIC
ANHYORIOi
FORMAIOEHVOE
MiTHANOl
fROfRONlC ACID
IUTYRIC ACIO
ACf TONE. ETC.
CEUIHOSE
ACETATE
I
VINYL
ACETATE
OTHER'
ACETATE
ESIERS
heptenes
ISOOCTYl
ALCOHOL
MALEIC
ANIIYURIOE
¦-IUIVIENES
I
1
a-IUTANE
lUTADIENE
MR
I
CHLORO-
PRENE
I
NEOPRENi
NIR
AOIPONITRILE
ISO IUTANE
TERT IUTVL
HYDROPEROXIDE
I
"I
HICHER
ALIPHATIC
HVOROCARIONS
ISO-IUIVLENI
PROPYLENE
OXIOE
l-IUTYl
ALCOHOL
ISOIUIYLENE
PLASTICS
STYRENE
COPOLYMER
LATEX
fOLYIUTAOIENE
AlS
AMVl
ALCOHOLS
IUTYL
RUBBER
~T~
•HT
I IUTYL
PHENOLS
MEIHACRYLO-
NITRILE
(UTYLENE
OXIOE
POLY-
ISOIUTYLENES
rOLYRUTENES
OIISO-
¦UTYLENE
IIUTYL
ALCOHOL
I
• PENTANE
I
AMYL
CHLORIOE
POLY CIILORO
CVCLOPENTANES
I
AMYL
MERCAPTANS
AUYL
ALCOHOLS
PENTENES
HEXACIILORO
CYCLO fENTAOIENE
IMSECTICIOES
I
ISO PENTANE
I
ISOPRENE
PARAFFIN WAXES
OEHYOROGfNATE
I
LINEAR OLEFINS
I
LINEAR PRIMARY
HICHER ALCOHOLS
OXIOATION
LINEAR SECONDARY
HIGHER ALCOHOLS
FROM: Riegel's Handbook of Industrial Chemistry, Seventh Edition, by James A. Kent;
Copyright (c) 1974 by Von Nostrond Reinhold Company. Reprinted by permission of the
publisher.
FIGURE IV-5-SOME PRODUCTS DERIVED FROM C, AND HIGHER ALIPHATIC COMPOUNDS
4
-------
AROMA!ICS
uliu
UWH
WHJIHl
_l_
tflUNf
HAUIC
AMMMIOC
I
CUMCHt
1
(IN/fhf
SUirONAK
r~
ACdottr
NITBO
IfHIEHE
adoti3u£»HM
J
DOHWM
AllCHAH
ncicnifi**t
I
Nil ON
ANIlINt
rn
NUL
IISPIKHOl
SAIICHIC
ACIO
IM MNC
-r
tlN/OIC
ACIO
NAfMII
HUMS
I
ISOPIIIIIAIIC
ACIO
LIMC
rUIIMLIC J-WMTMl
AMIfMIOr
KRinnitALic
ACIO
INI
LOMII
rtAsiicuiu
At Hi
USIM
OICMLOMIOlUCNf
I
101
AlHl FlltNOU
ciaatfiAwn
FROM: Riegel's Handbook of Industrial Chemistry, Seventh Edition, by James A. Kent;
Copyright (c) 1974 by Van Nostrand Reinhold Company. Reprinted by permission of the
publisher.
FIGURE IV-6-SOME PRODUCTS DERIVED FROM AROMATIC COMPOUNDS
-------
pathways available to reactants, undesirable by-products are often generated.
This produces a mixture of unreacted raw materials, products, and by-products
that must be separated and recovered by operations that generate residues with
little or no commercial value. These losses appear in process wastewater, in
air emissions, or directly as chemical wastes. The specific chemicals that
appear as losses are determined by the feedstock and the process chemistry
imposed upon it. The different combinations of products and production
processes distinguish the wastewater characteristics of one plant from that of
another.
Manufacture of a chemical product necessarily consists of three steps: (1)
combination of reactants under suitable conditions to yield the desired
product; (2) separation of the product from the reaction matrix (e.g.,
by-products, co-products, reaction solvents); and (3) final purification of
the product. Each step may lead to the introduction of pollutants to process
wastewaters: pollutants arise from the first step as a result of alternate
reaction pathways; separation of reactants and products from a reaction
mixture is imperfect and both raw materials and products are typically found
in process wastewaters.
Though there is strong economic incentive to recover both raw materials and
products, there is little incentive to recover the myriad of by-products
formed as the result of alternate reaction pathways. An extremely wide
variety of compounds can form within a given process. Typically, chemical
species do not react via a single reaction pathway; depending on the nature of
the reactive intermediate, there is a variety of pathways which lead to a
series of reaction products. Often, and certainly the case for reactions of
industrial significance, one pathway may be greatly favored over all others,
but never to total exclusion. The direction of reactions in a process
sequence is controlled through careful adjustment and maintenance of
conditions in the reaction vessel. The physical condition of species present
(liquid, solid, or gaseous phase), conditions of temperature and pressure, the
presence of solvents and catalysts, and the configuration of process equipment
dictate the kinetic pathway by which a particular reaction will proceed.
Therefore, despite the differences between individual chemical production
plants, all transform one chemical to another by chemical reactions and
physical processes. Though each transformation represents at least one
chemical reaction, production of virtually all the industry's products can be
described by one or more of 41 generalized chemical reactions/processes shown
in TABLE IV-3. Subjecting the basic feedstocks to sequences of these 41
generic processes produces most commercial organic chemicals and plastics.
Pollutant formation is dependent upon both the raw material and process
chemistry and broad generalizations regarding raw wastewater loads based
solely on process chemistry are difficult at best. Additionally OCPSF
typically employ unique combinations of the processes shown in Table IV-3 to
produce organic chemicals and plastics/synthetic fibers that tend to blur any
distinctions possible. For the purposes of studying the priority pollutants
(as opposed to BOD 5), process chemistry fails to provide meaningful
subcategorization of the OCPSF Industries. The following section examines the
combination of raw material and process chemistry by considering
product/processes found within the OCPSF.
IV-24
-------
TABLE IV-3
MAJOR PROCESSES OF THE ORGANIC CHEMICALS
AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES
Acid Cleavage
Alkoxylation
AIky1at ion
Am iiiation
Ammonolysis
Amrooxidation
Carbonylation
Chlorohydrination
Condensation
Cracking
Crystallization/Distillation
Cyanat ion/Hydrocyanat ion
Dehydration
Dehydrogenat ion
Dehydrohalogenat ion
Distillation
E1ect rohydrod imer ization
Epoxidation
Esterification
Etherification
Extractive distillation
Extraction
Fiber Production
Halogenation
Hydration
Hydroacetylat ion
HydrodeaIkylation
Hydrogenation
Hydrohalogenat ion
Hydrolysis
Isomerization
Neutralization
Nitration
Oxidation
Oxyhalogenation
Oxymation
Peroxidation
Phosgenation
Polymerization
Pyrolysis
Sulfonation
IV-25
-------
Product/Processes
Each chemical product may be made by one or more combinations of raw feedstock
and generic process sequences. Specification of the sequence of product
synthesis by identification of the product and the generic process by which it
is produced is called a "product/process." There are, however, thousands of
product/processes within the OCPSF Industries. Data gathered on the nature
and quantity of pollutants associated with the manufacture of specific
products within the Organic Chemicals and Plastics/Synthetic Fibers Industries
hdve been indexed for 176 product/process.
Organic chemical plants vary greatly as to the number of products manufactured
and processes employed and may be either vertically or horizontally
integrated. One representative complex which is both vertically and
horizontally integrated may produce a total of 45 high volume products with an
additional 300 lower volume products. In contrast, a specialties chemicals
plant may produce a total of 1000 different products with 70 to 100 of these
being produced on any given day. Organic chemical plants typically utilize
many feedstocks and may employ many of the processes shown in Table IV-3 at
individual plants.
Specialty chemicals on the other hand may involve several chemical reactions
and require a fuller description. For example, preparation of toluene
diisocyanate from commodity chemicals involves four synthetic steps and three
generic processes as shown below.
CH
CH
.NO
NH
Nitration
Hydrogenation
NO
NH,
CH
NCO
Phosgenation
N
C
0
This example in fact is relatively simple and manufacture of other specialty
chemicals is more complex. Thus as individual chemicals become further
IV-26
-------
removed from the basic feedstocks of the industry, more processes are required
to produce them.
In contrast to organic chemicals, plastics and synthetic fibers are polymeric
products, their manufacture directly utilizes only a small subset of either
the chemicals manufactured or processes used within the Organic Chemical
Industry- Such products are manufactured by polymerization processes in which
organic chemicals (monomers) react to form macromolecules or polymers,
composed of thousands of monomers units. Reaction conditions are designed to
drive the polymerization as far to completion as practical and to recover
unreacted monomer. Unless a solvent is used in the polymerization,
by-products of polymeric product manufactures are usually restricted to the
monomer(s) or to oligomers (a polymer consisting of only a few monomer
units). Because the mild reaction conditions generate few by-products, there
is economic incentive to recover the monomer(s) and oligomers for recycle; the
principal yield loss is typically scrap polymer. Thus, smaller amounts of
fewer organic chemical co-products (pollutants) are generated by the
production of polymeric plastics and synthetic fibers than are generated by
the manufacture of the monomers and other organic chemicals.
There are several ways by which the Organic Chemicals and Plastics/Synthetic
Fibers Industries might be potentially subcategorized on the basis of process
chemistry. For example, subcategorization could be based upon the particular
combination of product/processes in use at individual plants. Individual
plants within these industries however are unique in terras of the numbers and
types of product/processes employed and raw wastewater quality. As plants are
made subject to effluent limitations or standards, pretreatment and treatment
trains are uniquely designed and operated to meet pollutant removal criteria;
and although raw wastewater quality may differ greatly among plants, similar
removal efficiencies may be obtained (see Engineering Aspects of Pollution
Control). Thus, a scheme that would subcategorize plants based on raw
wastewater quality alone would unnecessarily separate plants that are
appropriately covered by a single set of uniform requirements.
Product/process is inappropriate as a basis for subcategorization.
SUMMARY
Plants within the Organic Chemicals and Plastics/Synthetic Fibers Industries
share the following characteristics:
• Products are usually made in multiproduct plants.
• One or more unit processes may be applied during
the product manufacture.
• Production rates of the individual products can
vary widely during short periods of time.
• There can be fairly rapid changes in technology
within a manufacturing complex in the industry.
IV-27
-------
• Relatively minor changes in process conditions can
lead to significant changes in wastewater.
• Effluent quality is independent of the size of a
facility or its geographical location.
• Treatment trains which achieve equivalent removal
efficiencies are designed on a plant-by-plant basis.
As a result of this analysis, the Organic Chemicals and Plastics/Synthetic
Fibers Industries may be divided into two subcategories: plants which produce
plastic and synthetic fiber products only (Plastics-Only plants); and plants
which produce both organic chemicals and plastics/synthetic fiber products
(Not Plastics-Only). Two subcategories are proposed under the BAT effluent
limitations. Although four subcategories are proposed for the BPT limitations
(see Volume I), the two subcategorization schemes are inherently compatible.
Both BAT and BPT have a Plastics-Only subcategory. While BPT has an oxidation
subcategory, Type 1 subcategory, and Other Discharge subcategory, these three
subcategories are incorporated in the Not Plastics-Only subcategory of BAT.
IV-2B
-------
REFERENCES
BERTHOUEX, P.M., HUNTER, W.G., PALLESEN, L. and SHIH, C.Y. 1976. The use
stochastic models in the interpretation of historical data from sewage
treatment plants. Water Research 10: 689-698.
del PINO, M.P. and ZIRK, W.E. 1982. Temperature effects on biological
treatment of petrochemical wastewaters. Environmental Progress 1(2): 104.
MORRISON, D.F. 1976. Multivariate Statistical Methods. McGraw-Hill Book
Company, New York.
SAYIGH, B.A. 1977. Temperature Effects on the Activated Sludge Process.
Ph.D. thesis presented in May 1977, University of Texas at Austin.
IV-29
-------
SECTION V
WASTEWATER GENERATION AND CHARACTERIZATION
WATER USAGE
General
The Organic Chemicals and Plastics/Synthetic Fibers Industries use large
volumes of water in the manufacture of products. According to 1978 Census
Bureau statistics on industrial water use, manufacturers of industrial organic
chemicals used about 17 percent of the total water consumed by manufacturing
establishments in 1978 (Bureau of the Census 1981). Census Bureau water use
statistics for the QCPSF Industries for 1973 are presented in TABLE V-l.
The major sources of intake water for the OCPSF Industries are provided in
TABLE V-2. The majority of water used by the industries (about 55 percent) is
supplied by surface water. Only about 12 to 16 percent of intake water comes
from public water systems. Ground water and tide water are additional sources
of water for OCPSF plants.
Water Use by Purpose
Organic Chemicals and Plastics/Synthetic Fibers Industry plants use water for
many different purposes: noncontact cooling; direct process contact uses;
indirect process contact uses (e.g., in pumps, seals, and vacuum jet and steam
ejector systems); noncontact ancillary uses (e.g., boilers and utilities);
maintenance, equipment cleaning, and work area washdown; air pollution control
(b.g., Venturi scrubbers); for drinking water; and to transport wastes.
Water usage data by categories of use for OCPSF plants included in a 19 78
Census Bureau survey are presented in TABLE V-3. Similar water usage data for
OCPSF plants responding to EPA's 308 Questionnaire are presented in TABLE
V-4. The 308 data reflect information on water use provided by 406 of the
original 566 plants in the 308 database. Forty-four of the 566 plants were
deleted from the 308 database because a review of updated plant information
revealed plants that had since been shut down, that were no longer producing
products within the scope of this regulation, or whose wastewater flows came
predominantly from inorganic product/processes (see Section III of the BPT
document, Volume I of this publication). Twenty-five plants provided no water
usage data, and the data reported by an additional 91 plants were incomplete.
Most water used in the Organic Chemicals and Plastics/Synthetic Fibers
Industries is cooling water. Cooling water is either contaminated, such as
contact cooling water from barometric condensors, or uncontaminated, such as
noncontact cooling waters. According to Census Bureau data, over 80 percent
of intake water used in the industry is for cooling and condensing purposes
(see Table V-3). This is consistent with water usage data from the 308 Survey
V-l
-------
TABLE V-1
SUMMARY WATER
USE STATISTICS FOR
1978 CENSUS DATA
THE OCPSF
(a)
INDUSTRIES
TOTAL
WATER
GROSS
USED (b)
WATER INTAKE
-------
TABLE V-2
WATER INTAKE BY SOURCE FOR THE OCPSF INDUSTRIES
1978 CENSUS DATA (a)
INDUSTRY
NUMBER
WATER INTAKE BY
SOURCE (Billion Gallons)
GROUP
OF
Public
Company System
(by SIC Code)
ESTABLISHMENTS
Total
Water System
Surface
Ground Tidewater
Organic Chemicals
2865
2869
76
197
(b)
1,910
124
165
32
1,555
9
57
(b)
(b)
Total
273
289
1,187
66
--
PIastics/Synthetic
Fibers'
2821
2823
2824
132
7
41
151
109
189
22
Cb)
6
44
(b)
151
33
(b)
13
(b)
(b)
Total
180
449
--
--
--
__
TOTAL
453
--
--
--
--
SOURCE: Bureau of the Census 1981
(a) Represents data collected in a special 1978 Survey of Water Use for establishments
using 20 million gallons or more of water/year in 1977; smaller volume users were
excluded in this survey.
(b) Data withheld to avoid disclosing operations of individual companies.
V-3
-------
TABLE V-3
WATER INTAKE BY PURPOSE FOR THE OCPSF INDUSTRIES
1978 CENSUS DATA (a)
(BiI I ion GaI Ions)
INDUSTRY TOTAL PROCESS COOL I NG AND CONDENS I NG SANITARY BOILER OTHER
GROUP Steam SERVICE FEED
(by SIC Code) Electric Power Air
Generation Conditioning Other
Organ i c Chemi caIs
i
-Pi
2865
1910
136
2869
241
148
Tota 1
2151
284
P1 a st i cs/Synthet ic
F ibers
2821
151
15
2823
109
33
2824
189
20
Tota 1
449
68
TOTAL
2600
352
318
(b)
(b)
(b)
27.1
7.7
(b)
(b)
(b)
34.3
88
1373
1461
171
58
90
319
1780
1.7
6.6
2.5
6.8
39.6
19.5
8.5
46.2
22.0
1.6
7.3
(b)
0.3
3.5
(b)
1.4
5.3
11.0
3.3
16. 1
-
11.8
62.3
.
SOURCE: Bureau of the Census 1981
(a) Represents data collected in a special 1978 Survey of Water Use for establishments using 20
million gallons or more of water/year in 1977; smaller volume users were excluded in this
survey.
(b) Data withheld to avoid disclosing operations of individual companies.
-------
TABLE V-4
WATER USAGE DATA FOR ORGANIC CHEMICALS AND
PLASTICS/SYNTHETIC FIBERS INDUSTRY PLANTS
IN THE 308 SURVEY (a)
WATER USAGE
FLOW
% OF TOTAL
(MGD)
WATER USAGE
Total
5677
100.0
Noncontact Cooling
4765
83.9
Direct Process Contact
523
9.2
Other (b)
389
6.9
(a) Derived from water usage data for 406 direct, indirect, and other
discharge plants of the 566 plants in the 308 database.
Forty-four of the 566 plants were deleted from the 308 database
because the plants had been shut down or were considered outside
the scope of this regulation. An additional 116 plants reported
data which was inadequate to estimate total, noncontact cooling,
and direct process contact water usage (see text).
(b) Other uses of water include indirect process contact uses (e.g.,
in pumps, seals, vacuum jets, and steam ejector systems);
noncontact ancillary uses (e.g., boilers and utilities);
maintenance, equipment cleaning, and work area washdown; air
pollution control (e.g., Venturi scrubbers); for drinking
purposes; and to transport sanitary wastes.
V-5
-------
which indicate that noncontact cooling water comprises about 84 percent of the
total water used in the OCPSF Industries (see Table V-4).
At many plants, large volumes of cooling water are used once and discharged
with process wastewaters. Many of the effluent concentrations and loadings
reported by plants in the 308 Survey were calculated from flow rates which
included cooling water. To calculate the effluent characteristics and actual
performance of treatment systems for these plants, the reported flows needed
adjustments. The uncontaminated cooling water flows were subtracted from the
reported total flow rates to yield the adjusted wastewater flow rates. These
adjustments assumed that the uncontaminated cooling water contained no
pollutants. However, some cooling waters may contain a relatively high BOD
and TSS loading as well as chromium and other algaecides commonly added to
noncontact cooling waters to suppress biological growth.
Direct process contact water includes water used for a variety of purposes,
such as solvent, reactant, reaction medium, and coolant. Water used as a
reaction medium for certain chemical processes may become a major
high-strength wastewater as a result of incomplete recovery from the water
medium of the final product or unwanted by-products formed during secondary
reactions in solution.
While the major source of pollutant loading, the quantity of process water
used by the OCPSF Industries is relatively small. For the 406 plants covered
in Table V-4, direct process contact water comprises only 9.2 percent of the
total water used. Similarly, Census statistics reveal that about 14 percent
of intake water is used in process operations.
Water Use by Subcategory
TABLE V-5 summarizes total water usage data for 497 plants in the 308 database
classified by Plastics-Oqly and Not Plastics-Only plants, and by direct,
indirect, or other discharge-type. (See the preceding section for an
explanation of the database used to estimate industry water usage for plants
in the 308 Survey.) "Other" discharge methods (also referred to as zero
discharge) include no discharge, land application, deep well injection,
incineration, contractor removal, evaporation, and discharge to septic and
leachate fields.
Some of the plants in the 308 database discharge waste streams by more than
one method. However, for purposes of tabulating water usage data, each plant
was assigned to a single discharge category (i.e., no double counting appears
in the direct, indirect, and other discharge data columns in Tables V-5 to
V-7). A plant was classified as an other or zero discharger only if all of
its waste streams were zero discharge streams. Plants were classified as
direct dischargers if at least one process contact waste stream was direct.
Plants whose process contact waste streams were discharged to POTWs were
classified as indirect dischargers. Many of the indirect discharge plants
discharge noncontact cooling water directly to surface waters.
Table V-5 shows that aver 60% of these 497 plants use between 0.1 and 10
million gallons of water per day (MGD). Not Plastics-Only plants typically
use a greater average amount of water than do Plastics-Only plants; sixty-one
V-6
-------
TABLE V-5
SUMMARY OF TOTAL WATER USAGE FOR
PLASTICS-ONLY AND NOT PLASTICS-ONLY PLANTS IN THE 308 SURVEY (1)
Total PLASTICS-ONLY PLANTS NOT PLASTICS-ONLY PLANTS
TotaI Number All All
Water of Direct Indirect Other (2) Plastics Direct Indirect Other (2) Not Plastics
Usage (MGD) Plants Dischargers Dischargers Dischargers Plants Dischargers Dischargers Dischargers Plants
<0.01
28
4
15
7
26
0
2
0
2
0.01-0.1
96
4
52
8
64
12
12
8
32
0.1-1.0
157
28
54
11
93
29
25
10
64
1.0-10.0
144
25
18
2
45
58
34
7
99
10.0-100.0
55
13
4
2
19
26
7
3
36
>100.0
17
1
0
0
1
11
3
2
16
TOTAL
497
75
143
30
248
136
83
30
249
(1) Water usage data was derived from the 308 database. See text for further description of the database used to
estimate industry water usage.
(2) Other discharge methods include zero discharge, land application, deep well injection, incineration, contractor
removal, evaporation, and discharge to septic and leachate fields.
-------
percent of the Not Plastics-Only plants (151 plants) use more than 1.0 MGD
while only 26 percent of the Plastics-Only plants (65 plants) use more than
1.0 MGD. Only one of 248 Plastics-Only plants reported using greater than 100
MGD, while 6.4 percent of the Not Plastics-Only plants (16 plants) reported
using greater-than 100 MGD. In both the Plastics-Only and Not Plastics-Only
subcategories, direct dischargers typically reported greater water use.
Sixty-one percent of the direct dischargers, as compared to only 34 percent of
the indirect dischargers, use more than 1.0 MGD.
As noted previously, noncontact cooling water represents the single largest
use of water in the OCPSF Industries. Noncontact cooling water usage data
provided by plants in the 308 Survey are presented by subcategory in TABLE
V-6. Not Plastics-Only plants generally use greater volumes of noncontact
cooling water than do Plastics-Only plants. About half (49 percent) of the
Not Plastics-Only plants use greater than 1.0 MGD noncontact cooling water, in
comparison to 20 percent of Plastics-Only plants that use greater than 1.0
MGD. Direct dischargers in both the Plastics-Only and Not Plastics-Only
categories tend to use more noncontact cooling water than do indirect
dischargers, with almost half (48 percent) of the direct dischargers using
greater than 1.0 MGD and only 25 percent of the indirect dischargers using
more than this volume.
TABLE V-7 summarizes data from the 308 Survey on use of direct process contact
water. Typically, the Not Plastics-Only plants use more direct process
contact water than do Plastics-Only plants. Of the plants that supplied data,
57 percent of the Not Plastics-Only plants (125 plants) use greater than 0.1
MGD direct process contact water, while only 39 percent of the Plastics-Only
plants (81 plants) use greater than 0.1 MGD. Direct discharge plants
typically use more direct process contact water than do indirect dischargers.
Sixty-eight percent of the direct dischargers use more than 0.1 MGD of process
contact water, as compared with 36 percent of indirect discharge plants which
use greater than this volume.
Water Reuse and Recycle
Current Levels of Reuse and Recycling. Data on the amount of water
recirculated and reused by plants in the OCPSF Industries as reported in a
1978 Census Bureau survey are presented in Table V-l and TABLE V-8. The
Census Bureau defines "recirculated or reused water" as the volume of water
recirculated multiplied by the number of times the water was recirculated.
Seventy-nine percent of the OCPSF plants surveyed reported some recirculation
or reuse of water (see Table V-8). At least 60% of the total gross water used
by OCPSF plants consists of recirculated and reused water (see Table V-l).
Census Bureau statistics show that the bulk of recirculated water is used for
cooling and condensing operations (see Table V-8), such as closed-loop cooling
systems for heat transport. Chemical algaecides and fungicides are routinely
added to these cooling waters to prevent organism growth and suppress
corrosion, both of which can cause exchanger fouling and a reduction of heat
transfer coefficients. As water evaporates and leaks from such closed
systems, the concentration of minerals in these waters increases, which may
lead to scale formation, reducing heat transfer efficiency. To reduce such
V-8
-------
TABLE V-6
SUMMARY OF NONCONTACT COOLING WATER USAGE FOR
PLASTICS-ONLY AND NOT PLASTICS-ONLY PLANTS IN THE 308 SURVEY (1)
Tota l
PLASTICS-ONLY PLANTS
NOT PLASTICS-ONLY PLANTS
Noncontact
Number
At I
Al I
Coo 1ing Wa te r
of
Oi rect
Ind i rect
Other (2)
Plastics
Di rect
1nd i rect Other (2)
Not Plastics
Usage (MGO)
Plants
Discha rgers
0 i scha rgers
Di scha rgers
Plants
Di schargers
Dischargers Dischargers
Plants
<0.001
9
0
2
4
6
0
3 0
3
0.001-0.01
42
1
27
5
33
3
5 1
9
0.01-0.1
107
11
46
7
64
18
17 8
43
0. 1-1.0
136
33
32
7
72
31
23 10
64
1.0-10.0
101
16
11
2
29
45
21 6
72
10.0-100.0
39
9
3
2
14
15
7 3
25
>100.0
17
1
0
0
1
13
2 1
16
No data
reported
46
4
22
3
29
11
5 1
17
TOTAL
497
75
143
30
248
136
83 30
249
(1) Water usage data was derived from the 308 database. See text for further description of the database used to
estimate industry water usage.
(2) Other discharge methods include zero discharge, land application, deep well injection, incineration, contractor
removal, evaporation, and discharge to septic and leachate fields.
-------
TABLE V-7
SUMMARY OF DIRECT PROCESS CONTACT WATER USAGE FOR
PLASTICS-ONLY AND NOT PLASTICS-ONLY PLANTS IN THE 308 SURVEY (1)
Tota I
PLASTICS-ONLY PLANTS
NOT PLASTICS-
•ONLY PLANTS
Direct Process
Number
AI I
AI I
Contact Water
of
D i rect
Ind i rect
Other (2)
Plastics
D i rect
Ind i rect
Other (2)
Not Plastics
Usage (MGD)
PI ants
D i scha rgers
Di schargers
Di schargers
Plants
Di scha rgers
Di scha rgers
Di scha rgers
Plants
<0.001
25
1
15
5
21
1
2
1
4
0.001-0.01
92
5
41
10
56
15
10
11
36
0.01-0.1
105
11
34
5
50
27
20
8
55
0.1-1.0
125
33
21
1
55
44
22
4
70
1.0-10.0
73
18
7
0
25
31
15
2
48
>10.0
8
1
0
0
1
3
4
0
7
No data
reported
69
6
25
9
40
15
10
4
29
TOTAL
i+97
75
143
30
248
136
83
30
249
(1) Water usage data was derived from the 308 database. See text further description of the database used to
estimate industry water usage.
(2)
Other discharge methods include zero discharge, land application, deep well
removal, evaporation, and discharge to septic and leachate fields.
injection, incineration, contractor
-------
TABLE V-8
WATER RECIRCULATED AND REUSED BY USE FOR THE OCPSF INDUSTRIES
1978 CENSUS DATA (a)
WATER RECIRCULATED BY USE (Billions of Gallons) (b)
INDUSTRY NO. OF ESTABLISH- Cooling and Condensing
CROUP
(by SIC Code)
MENTS REPORTING
RECIRC/REUSE (AS
% OF EST. SURVEYED)
Tota 1
Process
Steam
Electric Power
Gene rat ion
Ai r
Cond i t i on i ng
Other
San i ta ry
Serv i ce
Boiler
Feed
Organic Chemicals
2865
51
(67%)
279
1.3
(c)
0.2
274
-
3.4
2869
165
(84%)
3,583
76
(c)
33
3,380
(c)
51
Tota 1
216
(79%)
3,862
78
-
34
3,654
-
54
P1astics/Synthet ic
F i be rs
2821
102
(77%)
653
62
(c)
(c)
575
(C)
8.8
2823
6
(86%)
89
(c)
(c)
6
45
(c)
26214
32
(78%)
458
44
36
163
205
(C)
2.8
Tota 1
140
(78%)
1,200
-
-
-
825
-
TOTAL
356
(79%)
5,062
-
-
-
4,479
-
-
SOURCE: Bureau of the Census 1981
(a) Represents data collected in a special 1978 Survey of Water Use for establishments using 20 million gallons
or more of water/year in 1977; smaller volume users were excluded in this survey.
(b) Water Recirculated and Reused was defined as the volume of water recirculated multiplied by the number of
times recirculated; e.g., if 100 million gallons of intake water were recirculated twice, the manufacturer
reported recircuI at ion/reuse of 200 million gallons.
(c) Data withheld to avoid disclosing operations of individual companies.
-------
scaling, a portion of such closed system waters is periodically discharged as
blowdown and replaced by clean water.
The recycling of treated process contact wastewaters is limited because
existing wastewater treatment facilities, primarily biological systems, rarely
produce effluents which meet the water quality required of even the least
stringent manufacturing plant uses, such as make-up water for most heat
exchange systems. According to Census Bureau statistics, recirculated process
water constitutes less than 4 percent of all water recirculated.
TABLE V-9 presents data from the 308 Survey on plants that practice total
recycling of process contact wastewater streams and consequently do not
discharge their effluents to surface waters or to POTWs. Of the 291 direct
and zero discharge plants in the 308 database, 32 percent (94 plants) use
alternate methods of wastewater disposal (i.e., do not discharge to surface
waters or to POTWs); of these 94 plants, only 24 report recycling all of their
process contact wastewaters. Thus, although about 80 percent of plants in the
OCPSF Industries practice some reuse of industrial water, less than 10 percent
eliminate discharge of process contact wastewaters through recycling.
Water Conservation and Reuse Technologies. A variety of water conservation
practices and technologies are available to OCPSF plants. Because of the
diversity within the OCPSF Industries, no one set of conservation practices
and/or technologies is appropriate for all plants. Decisions regarding water
reuse and conservation depend on plant-specific characteristics as well as
site-specific water-supply and environmental factors (e.g., water
availability, cost and quality). Therefore, this section will describe the
range of practices and technologies available for water conservation.
Conventional water conservation practices include (McGovern 1973, and Holiday
1982):
• Recovery and reuse of steam condensates, and
process condensates where possible.
• Process modifications to recover more product and
solvents.
• Effective control of cooling-tower treatment and
blowdown to optimize cycles of concentration.
• Elimination of contact cooling for off vapors.
• Careful monitoring of water users; maintenance of
raw-water treatment systems; and prompt attention to
faulty equipment, leaks and other problems.
• Installation of automatic monitoring and alarm
systems on in-plant discharges.
TABLE V-10 summarizes water conservation technologies, and their applications,
limitations, and relative costs to industry plants. Some of these
technologies, such as steam stripping, are also considered effluent pollution
V-12
-------
TABLE V-9
PLANTS REPORTING RECYCLING OF ALL PROCESS
CONTACT WASTEWATERS (a)
PLANTS STREAMS
Number Number
in Number Percent in Number Percent
PLANT TYPE Database Recycling Recycling Database Recycling Recycling
Plastics-Only 118 9 7.6 146 10 6.8
Not Plastics-Only 173 15 8.7 231 15 6.5
Total 291 24 8.2 377 25 6.6
(a) From 291 plants responding to the 1976 BPT and the 1977 BAT 308
Questionnaires; direct and zero discharge plants only. See also Table
VII-1 of the BPT document, Volume I of this Development Document.
V-13
-------
TABLE V-10
WATER CONSERVATION AND REUSE TECHNOLOGIES
TECHNIQUE
APPLICATIONS
LIMITATIONS
RELATIVE COSTS
Cap ItaI Ope ratinq
COMMENTS
Vapor-compress ion
evaporat ion
Waste heat
evaporation
Reverse osmosis,
u 11 raf i 11rat ion
EIectrodialys i s
Steam stripping
Combination wet/dry
cooling towers
Air-fin cooling
Sidestream
softening
Concentration of Not for organics that
wastewater or cooling form azeotropes or
-tower blowdown steam-distill
Concurrent production Fouling must be
of high-purity water controllable
High
High
Concentration of
wastewater
Condensate recovery
Removal of ionized
sa I ts, pI us many
organ i cs
Recovery of heavy
metaIs, colloidaI
materia I
Production of
ultrapure water
Potable water from
saIine or brackish
source
Recovery of process
condensates and
other contaminated
waters
Recovery of H2S, NH3
pI us some Iight
organ i cs
Puts part of tower
Ioad on air fins
Can cut fogging
Numerous process
appIicat ions
Reduce cooling-
tower blowdown
Not for organics
that form azeotropes
or steam-d i st iI I
FouIi ng-sens i t ive
Stream must not
degrade membranes
Reject stream may
be high-volume
L i m i ted
salts
to ionizable
Med i um Med i urn
Med i um Med i um
Med i um-
high
Med i um
Med i um
Med i um-
h igh
Stripped condensates
may need further
process i ng
Costly compared with
wet cooling tower
For higher-I eve I
heat transfer
Can be prone to
freeze-up, waxing
Dissolved solids must Low- Low-
be removable medium medium
Control can be difficult
Medium Medium
Med i um Med i um
Rapid growth
High-quality distillate
handles broad range of
contaminants in water
Not widely used now
Future potential good
Future potential strong
Intense application
development underway
Modest future potential
Well-established as part
of some processes
Growth expected
areas
in arid
We I I -estabIi shed
Good for higher-tempera-
ature heat rejection
Not widely used
Future potential good
SOURCE: Holiday 1982
V-14
-------
control technologies. Water conservation, in fact, can often be a benefit of
mandated pollution control.
OCCURRENCE AND PREDICTION OF PRIORITY POLLUTANTS
The Clean Water Act required the Agency to develop data characterizing the
presence (or absence) of 129 priority pollutants in raw and treated
wastewaters of the Organic Chemicals and Plastics/Synthetic Fibers
Industries. These data have been gathered by EPA from two sources: existing
wastewater data previously gathered by individual plants within these
industries; and extensive sampling and analysis of individual process
wastewaters in these industries. An adjunct to these data collection efforts
was the evaluation of which priority pollutants would be likely to occur from
consideration of the reactants and reaction pathway. This process has the
advantage of being able to predict qualitatively pollutants likely to be
present in plant wastewaters from knowledge of starting materials and chemical
reaction. A systematic means of anticipating the occurrence of priority
pollutants is beneficial to both the development and implementation of
regulatory guidelines:
1. Industry-wide qualitative product/process coverage becomes feasible
without the necessity of sampling and analyzing hundreds of effluents
beyond major product/processes. By focusing resources on any
additional product/processes that are probable sources of priority
pollutants, the data required for regulation development can be
accrued more cost-effectively.
2. Guidance is provided for discharge permit writers, permit applicants,
or anyone trying to anticipate priority pollutants that are likely to
be found in the combined wastewaters of a chemical plant when the
product/processes operating at the facility are known.
Qualitative prediction of priority pollutants for these industries is possible
because, claims of uniqueness not withstanding, all plants within the -OCPSF
Industries are alike in one important sense: all transform feedstocks to
products by chemical reactions and physical processes in a stepwise fashion.
Though each transformation represents at least one chemical reaction,
virtually all can be classified by one or more generalized chemical
reactions/processes. Imposition of these processes upon the eight basic
feedstocks lead to commercially produced organic chemicals and plastics. It
is the permutation of the feedstock/process combinations that permit the
industries to produce such a wide variety of products.
Chemical manufacturing plants share a second important similarity: chemical
processes never convert 100% of the feedstocks to the desired products; that
is, the chemical reactions/processes never proceed to total completion.
Moreover, because there are generally a variety of reaction pathways available
to reactants, undesirable by-products are often unavoidably generated. This
results in a mixture of unreacted raw materials and products that must be
separated and recovered by unit operations that often generate residues with
little or no commercial value. These yield losses appear in process contact
wastewater, in air emissions, or directly as chemical wastes. The specific
V-15
-------
chemicals that appear as yield losses are determined by the feedstock and the
process chemistry imposed upon it, i.e., the. feedstock/generic process
combination.
General
Potentially, an extremely wide variety of compounds could form within a given
process. The formation of products from reactants depends upon the
relationship of the free enthalpies of products and reactants; more important
however is the existence of suitable reaction pathways. The rate at which
such transformations occur cannot (in general) be calculated from first
principles and must be empirically derived. Detailed thermodynamic
calculations therefore are of limited value in predicting the entire spectrum
of products produced in a process since both the identity of true reacting
species and the assumption of equilibrium between reacting species are often
speculative. Although kinetic models can in principle predict the entire
spectrum of products formed in a process, kinetic data concerning minor side
reactions are generally unavailable. Thus, neither thermodynamic nor kinetic
analyses alone can be used for prediction of specie formation.1 What these
analyses do provide, however, is a framework within which pollutant formation
may be considered and generalized.
The reaction chemistry of a process sequence is controlled through careful
adjustment and maintenance of conditions in the reaction vessel. The physical
condition of species present (liquid, solid, or gaseous phase), conditions of
temperature and pressure, the presence of solvents and catalysts, and the
configuration of process equipment are designed to favor a reaction pathway by
which a particular product is produced. From this knowledge, it is possible
to identify reactive intermediates and thus anticipate species (potential
pollutants) formed.
The bulk of chemical transformations performed by the industry have long been
reduced to a small number of basic steps or unit processes (Shreve 1977).
Each step or process represents a chemical modification labeled a "generic
process." For example, the generic process "nitration" may represent either
the substitution or addition of an "-NO^" functional group to an organic
substrate. Generic processes may be quite complex from a chemical standpoint
however; any reaction in which a large number of bonds are broken
necessarily requires passage through a number of distinct (if transitory)
intermediates. Simple stoichiometic equations, therefore, are inadequate
Prediction of pollutant formation is necessarily of a qualitative
rather than quantitative nature; though reactive intermediates may be
identified without extensive kinetic measurements, their rate of formation
(and thus quantities produced) are difficult to predict without kinetic
measurements. Other quantitative approaches, for example, detailed
calculation of an equilibrium composition by minimization of the free energy
of a system, require complete specification of all species to be considered.
Because such methods necessarily assume equilibrium, the concentrations
generated by such methods represent only trends or, perhaps at best,
concentration ratios.
V-16
-------
descriptions of chemical reactions and only rarely account for observed
by-products.
TABLE V-ll lists the major organic chemicals produced by industry
(approximately 250) by process, and TABLE V-12 gives the same information for
the plastics/synthetic fibers industry. Certain products shown in Table V-ll
are not derived from primary feedstocks but rather from secondary or higher
order materials (e.g., aniline is produced by hydrogenation of nitrobenzene
that is produced by nitration of benzene). For such raultistep syntheses,
generic processes appropriate to each step must be evaluated separately. For
commodity chemicals generally it is sufficient to specify a feedstock and a
single generic process. Nitration of benzene to produce nitrobenzene for
example is sufficient description to predict composition of process
wastewaters: nitrophenols will be the principal process wastewater
constituents. Similarly oxidation of butane to produce acetic acid results in
wastewaters containing a wide variety of oxidized species including
formaldehydej methanol, acetaldehyde, n-propanol, acetone, methyl ethyl
ketone, etc.
Specialty chemicals on the other hand may involve several chemical reactions
and require a fuller description. For example, preparation of toluene
diisocyanate from commodity chemicals involves four synthetic steps and three
generic processes as shown below.
CH
CH,
NO
NH
Nitration
Hydrogenation
NO
NH
CH
NCO
Phosgenation
N
C
0
This example in fact is relatively simple and manufacture of other specialty
chemicals is more complex. Thus as individual chemicals become further
removed from the basic feedstocks of the industry, fuller description is
required for unique specification of process wastewaters. A mechanistic
analysis of individual generic processes, permits a spectrum of product
classes to be associated with every generic process. Each product class
V-17
-------
TABU V II
GENERIC PROCESSES USED TO MANUFACTURE ORGANIC CHEMICAL PRODUCTS
Mm
AMINES
ALDEHYDES
AMIDES
ALCOHOLS
ESTERS
o#oo o
• •• #o
• ••o •
DO
09
•totoo«ototo« ootootoott
• •
000 a•
00
• •••o
O OOOO
otoo o
Preceding page blank
-------
GENERI
ACIDS
GENERIC
PROCESS
*mdM- mi
iiiilllMillllfiilll! }!!l
5,
alkoxtlahon
CONDENSATION
HALOGENATION
OXIDATION
POLYMERIZATION
HYDROLYSIS
HYDROGENATION
ESTERIFICATION
PYROLYSIS
ALKYLATION
DEHYDROGENATK3N
AMINATK3N (AMMONOLYHS)
NITRATION
SULFONATION
AUMOXIDATION
CARftONYLATlON
HYOROHALOGENATK3N
DEHYDRATION
OEHYDROHALOGENATION
OXYHALOGENATION
CATALYTIC CRACKING
HYOROOEALKYLATION
PHOSGENATION
EXTRACTION
DISTILLATION
OTHER
HYDRATION
O O
O O
••••o o oo •• #o o» •
oo •
o o
• o • •
o
o •
••oo o o#oo
• «
• Preduct/Ptece* Elflumt bf OCB
I'"I O ^jct/Ptoc«M Elllum N«t
-------
TABIC V-II (Continued)
GENERIC PROCESSES USED TO MANUFACTURE ORGANIC CHEMICAL PRODUCTS
RBONS
HYDROCARBONS
KETONES NTTR1LES PHENOLS SALTS MISCELLANEOUS
ilil illihli
Slllllil IfllliJiilnlfsillillliJ!!!]!
I *
lilSiilfi I
s
- i - ¦
llili u< Ht|j| ill
•J.- ihi ij||;|
llfl Ulll iflllHHHl jil jjjii dlillljlifl
oo
o o «o
•••oo*o*«o« OOl
o.
• •
> ••
• •
oo
o
o o
oo o
• oo o
Oi
o
a o•o •o• • • too •o• iooo ••
o • «o •
o o o
o«o o
o • mo o o
o o 0
\ if (
Preceding page blank
V-21-W
-------
GENERIC
PROCESS
ALKOXYIATON
CONDENSATION
HALOGENATION
OXIDATION
POLYMERIZATION
HYDROLYSIS
HYDROGENATION
ESTERIFICATION
PYROLYSIS
ALK YLATION
OEHYDROCENATION
AMINAHON (AMMONOLYSIS)
NTT RATION
SULFONATION
AMMOXIDATION
CAR BON YLATION
HYDRONALOCENATION
DEHYDRATION
DEHYDROHALOG£NATK)N
OXYHALOGENATION
CATALYTIC CRACKING
HYDROOEALK YLATION
PHOSGENATION
EXTRACTION
DISTILLATION
OTHER
hydration
ETHERS
HALOCARBONS
..I.
in.
'ftst .{}till tifHIiii
l^lllluMl if ill
ills!*
*
!piu
ffiilt
•••••O tototoott OO • ••OO'
• o o
o OO
o •
O O OO
• ProAict/Piocfu Elllutni StmpM by OCK
I O Produrt/Pvocc-M Elflumt Not Sampled
-------
TABLE V-12
MAJOR PI.AST ICS AND SYNTHETIC FIBERS PRODUCTS BY GENERIC PROCESS
tn
GENERIC
PROCESS
c
in *
st o
sc a: x _
ui w re i/> >.
VI to H
r-o
oo
ADDITION POLYMERIZATION
Mass
Emulsion
SuspensIon
Solvent
Solvent-nonsolvent
Other8
CONDENSATION POLYMERIZATION
• •
• •
•••• ••
• •
*Rlng opening and other "addition* polymerization processes In which the polywec growa In a Banner other than
hy a chain reaction.
Preceding page blank
-------
represents compounds that are .structurally related to a feedstock through the
chemical modification 'afforded by the generic process.2
Product/Process Chemistry Overview
The primary feedstocks of the Organic Chemicals Industry include: benzene,
toluene, o,p-xylene, ethene, propene, butane/butene and methane; secondary
feedstocks include the principal intermediates of the synthetic routes to high
volume organic chemicals and plastics/synthetic fibers. Other products that
are extraneous to these routes, but are priority pollutants, are also
considered because of their obvious importance to guideline development.
Flow charts used to illustrate a profile of the key products of the two
categories were constructed by compositing the synthetic routes from crude oil
fractions, natural gas, and coal tar distillates (three sources of primary
feedstocks) to the major plastics and synthetic fibers. FIGURES V-l THROUGH
V-7 depict the routes through the eight primary feedstocks and various
intermediates to commercially produced organic chemicals; FIGURES V-8 and V-9
show the combinations of monomers that are polymerized in the manufacture of
major plastics and synthetic fiber products. Also shown in Figures V-l
through V-7 are processes in current use within these industries.
These charts illustrate the dendritic structure of this industry's product
profile (i.e., several products derive from the same precursor). By changing
the specific conditions of a process, or use of a different process, several
different groups of products can be manufactured from the same feedstock.
There is an obvious advantage in having to purchase and maintain a supply of
as few precursors (feedstocks) and solvents as possible. It is also important
to integrate the product mix at a plant so that one product provides feedstock
for another. A typical chemical plant is a community of production areas,
each of which may produce a different product group. While the product mix at
a given plant is self-consistently interrelated, a different mix of products
may be manufactured from plant-to-plant. Thus, a plant's product mix may be
independent of, or may complement the product mix at other plants within a
corporate system.
The synthetic routes to priority pollutants are illustrated in FIGURES V-10
THROUGH V-14; these flow charts provide a separate scheme for each of
the following five classes of generic groups of priority pollutants.
1. Nitroaromatic compounds, nitrophenols, phenols, benzidines and
nitrosamines.
2. Chlorophenols, chloroaromatic compounds, chloropolyaromatic
compounds, haloaryl ethers and PCB's.
- 1 M ¦ ¦ 1 " 1 " ¦¦¦•¦
Limited plant data however were available by which to assign generic
processes to a product and in many cases the product was specified while the
feedstock was not. In such cases a generic process assignment was made on the
basis of process chemistry and engineering; i.e., judgment was made as to the
feedstock and chemistry employed at the plant. This analysis has been
previously discussed in Volume 1 of this document.
V- 24
-------
riGUHK v-l
REFINERY OPERATIONS
Crude-
1
•Refinery Gas-
LP Gas
Naphtha
1
J-t
I
I i
-Gas oil—4 L
•Kerosine-
Waxy j
'Disti1lates"
Heavy
Fuel oil
.Vacuum
Bottoms
PROCESS CODE
1. Distillation
2. Steam Cracking (pyrolysis)
3. Steam Reforming
4. Catalytic Reforming
5. Ilydrocrack ing
6. Ilydrodealkyl at ion
PRIMARY FEEDSTOCK SOURCES
PETROCHEMICAL PLANT OPERATIONS
3
¦METHANE
1_
•Pyrolysis Gasoline-
Reformate
7. Liqtiid-1 iquid extraction
8. Extractive distillation
9. Dtihydrogenation
10. Alkylalion
11. Ilydroijenat ion
-•-Synthesis Gas (C0.H2)
Hydrogen -
-^ETHYLENE
-^-PROPYLENE
-•-Cyclohexane:
TT
-Ethylbenzene*
-~•Naphthalene*
+.BUTYLENES
-ISOBUTYLENE
-BUTADIENE
•Cyclopentadiene
-Isoprene
'BENZENE-*————
¦TOLUENE*-
. XYLENES-
Polyaromatics *
* Priority pollutant
-------
FIGURE V-2
Coal Tar Refining
Coal
Gas
•Condensate'1"
-Light oils-
-Tars
•Naphtha•
.-METHANE
•-Pyridines
•.Pico!ines
• BENZENE*
~TOLUENE*
-^XYLEN'ES
¦m Coumarone-Indene
r^-Phenol *
•Carbolic oil'
¦Light cresote oil
•Heavy cresote oil
¦Refined tar
•Pi tch
-Cresols
~Naohtnalene *
¦Anthracene *
¦ Phenanthrene *
¦Other Polyaromatics
.Coke
Process Code
1. Pyrolysis
2. Distillation
2. Liquid-liquid extraction (pH adjust}
* Priority pollutant
V-26
-------
FIGURE V-3
METHANE
METHANE•
2
Synthesis
Gas CO.Hj
•Methanol
Methyl* -
¦ chloride
Acrylic
ac i d '
Methacrylic-
acid
~ Methylene chloride*
'Chloroform*
'Carbon tetrachloride*
-Formaldehyde
•Acetic acid
•Methylacrylate
¦Methylmethacrylate
Generic Processes:
1. Chlorination
2. Oxidation
3. Oxo carbonylation
~Priority pollutant
4. Esterification
5. Hydrochlorination
V-27
-------
FIGURE V-4
ETHYLENE
-^-•-Ethylene
oxide
ETHYLENE-
BENZENE*
-JjU-Ethylbenzene*
-!*¦ Acetyl dehyde -
-1&- Ethylene*"
12
-14-Ethanol-
Acetic acid
6
Ketene
4
Acrylic-
acid
-^¦Styrene
H
>Acetic
anhydride
-•-Vinyl acetate
-S-^Ethylene glycol
e 10
13
Ethoxylates
Vinyl chloride*
•Perchloroethylene*
•Carbon tetrachloride*
Methyl chloroform*
¦Ethyl acrylate
Generic Processes:
1.
Alkylation
6.
Esterification
11.
Oxychlorination
2.
Dehydrogenation
7.
Epoxidation
12.
Dehydroch1 orination
3.
Oxidation
8.
Hydrolysi s
13.
Hydrochlorination
4.
Dehydration
9.
Ethoxylat ion
14.
Direct Hydration
5.
Condensation
10.
ChTori nation
~Priority pollutant
V-28
-------
FIGURE V-5
PROPYL ENE
PROPYLENE
iT
BENZENE*
CumeneZZ
Propylene
oxide
n-Butanol
Acrylic acid-
8 —n-Butyraldehyde-11.12.5 »-2-Ethylhexanol-
-1-3—•_ A1 lyl chloride.
¦Acrolein*-
1S-
-»-Al lyl alcohol.
16
""Phenol*
•Acetone li^Methacryl ic acld/MMA
^ .-Propylene glycol
polyethers
-Isopropanol
•n-Butylacrylate
10
-12—»-2-Ethylhexyl
acrylate
2,14
-^•Epichlorohydrin
in-« h!
~-Glycerii
•Acrylonitrlle*
Generic Processes:
1. Alkylation
6.
Propoxylation
11.
Aldol condensation
2. Peroxidation
7.
Direct hydration
12.
Dehydration
3. Epoxidation
8.
Oxo
13.
Chlorination
4. Chlorohydrination
9.
Ox idat ion
14.
Hydrolysis
5. Hydroyenation
10.
Esterification
15.
Reduction
16.
Ammoxidation
17.
Cyanation
~Priority pollutant
-------
FIGURE V-6
BUTANES/BUTENES
8utene-l!
Butene-2
n-Butane.
iso-Butane—S_
'sec-Butanol.
rButadiene*
4
-PROPYLENE
5
¦t-Butanol•
MEK
Hexamethylene diamine
r~
7 ^Polybutadiene
fi a
Maleic anhydride
Acetic acid
Propylene oxide
Methylmethacrylate
Generic Processes:
1. Hydration
2. Dehydrogenatlon
3. CMorination/cyanation
4. Oxidation
5. Epoxidation
6. Dehydration
7. Polymerization
8. Peroxidation
V-30
-------
TOLUENE*.
FIGURE V-7
AROHATICS
. Dinitro-* 2 Toluene 2 —TDI
toluene diamine
XYLENES.
.p-xylene
¦m-xylene
o-xylene
r
•Terephthal ic acid
OMT
Isophthalic acid
BENZENE*
»Phthal ic
anhydride
Naphthalene*
-l—» Nitrobenzene*—216.
Ani1ine
Formaldehyde.
—^ Polymervc 3 .-Polymeric
MDA MO I
•Maleic anhydride
.Cyclohexane
-Cyclohexanone —8—»» Caprol actam
-Cvclohexanol~—!—»Adipic acid
~.»Cjmene
14
Acrylonitrile'
10
Pi. 12 L
•Adiponi trile £-»Hexamethy1ene
diamine
9.8
•Propylene
I
'7 *.5i sphenol A
-Acetone
15
^Ethyl benzene*-
Ethylene
u
Propylene oxide
!£.
16
•Methyl styrene
-2 -Styrene
— Chlorophenols*
» Chlcrobenzenes1
Generic Processes:
1.
Nitration
5.
Reduction
11.
Amid ification
2.
Hydrogenation
7.
Condensation
12.
Dehydration
3.
Phosgenation
8.
Oximation/
13.
Alkylation
4.
Oxidation
Rearrangement
14.
Peroxidation
5.
Ester ification
9.
Dehydrogenation
15.
Epoxidation
10.
Hydrodimerization
16.
Chlorination
~Priority pollutant
V-31
-------
FIGURE V-8
Monomers(s )
Styrene"
Polybutadiene
Acrylonitrile"
+Vinylacetate:
~L
+Vinylchloride:
+Methylmethacrylate-
~Methylaery!ate
+Acrylamide
Acrylic acid esters'
Methylmethacryl atei:
Phenol*-
1
Formaldehyde-
r
Lir e a ¦
Mel amine'
la
2r
2d
2a, b
Plastics
(Resins )
Synthetic
Fibers
Polystyrene Resins
—2&_Styrene-Butadiene Resins
(Latex)
2c.d ^ $an Resins
2d
•ABS Resins
Polyvinyl Alcohol Resins-
"Polyvinyl Acetate Resins-
(Latex)
Hydrolysis
•Copolymer Resin
(85% Acrylonitrile)
JlA.
•Acrylic Resins (Latex)
.Acrylic Resins
•Phenolic Resins
¦Melamine Resins
-Urea Resins
Acrylic
Fibers
Epichlorohydrin-
Bisphenol a
Phosgene
•Epoxy Resins
•Polycarbonate Resins
+ Variable comonomer
* Priority Pollutant
Resin
Polymerization Process
1. Condensation
2. Addition
a. Mass c. Suspension
b. Solution d. Emulsion
Fiber
Spinning Process
3. Wet
4. Dry
5. Melt
V-32
-------
FIGURE V-9
Monomers(s)
Terephthalic acid/DMT-
Ethylene Wycol
Plastics
(Resins )
•Polyester
Resins
Synthetic
Fibers
Polyester
Fibers
Glycerin
Isophthalic acid'
Phthallc anhydride:
Maleic anhydride—
Propylene glycol —
Styrene
Cellulose
CS2
Acetic anhydride
Diketene
Coumarone-Indene -
Oicyclopentadiene
ethylene
2a
PROPYLENE
2b
-2c.
Vinyl chloride-
^ p'Alkyd Resins
•Unsaturated
Polyester Resins
.Cellulose Xanthate
2b
Hexamethylene
diamine
Adipic acid-
Caprolactam-
•Nylon
Salt
TDI
Polymeric MDI
Propylene glycol
polyethers
.Cellulose acetate
Resins
¦Petroleum
•Hydrocarbon Resins
*LD Polyethylene Resins
.HD Polyethylene Resins
¦Polypropylene Resins-
-Polyvinyl chloride
Resins
•Nylon 66
Resins
•Rayon
Fiber
¦Cellulose
Acetate
Fiber
•Polypropylene
Fibers
• Nylon 6
Resins
•Polyurethanes
Foams
Resin
Polymerization Process
1. Condensation
2. Add i t i on
a. Mass c. Suspension
b. Solution d. Emulsion
¦Nylon 66
Fiber
•Nylon 6
Fiber
Fiber
Spinning Process
3. Wet
4. Dry
5. Melt
* Priority pollutant
V-33
-------
BENZENE*
i
OJ
-c*
TOLUENE
•-Xylene •
FIGURE V-10
Hiiroaromatics, Hitrophenols, Benzidines, Phenols, Nitrosamines
m-ChloronilroLienzene
-Za.
• 3,3'-Oichlorodiphenylhydraz ine ¦
-1,2-Oiphenylhydrazine*
Jl.
r
-Diphenylaratne-
5b
Phenyl Esters
¦^Nitrobenzene* ¦
JiiA
i
Phenol*;
3
• AnlI inef**Beniene diazoniun chloride-
2-Nitrophenol*;~
-2-Nttroanl)inel
Li
i-;
« ' ^ | * 2',4-Pini
I »2,6-0ini
I—*¦ o-Cresol
u.
Nitroani1ine
JL
5a
trotoluene*
-Dinitrotoluene*
¦#.4,6-0initro-o-cresol
2,4-Dimethylphenol*
4-Nitrophenol
Jl
Generic Processes
1. Chlor(nation (FeClj cat.)
2. Olazotization
3. Hydrolysis
4. Nitration
-3,3'-Dtchlorobeniidine*
-Benzidine*
-N-Nitrosodiphenylaraine*
N-Nitrosodi-n-Propy1anine• ¦
N-Nitrosodimethylanine* «•—
-Plienylhydrazine
-2,4-Oinitrophenol*
-2,4-Oinitroaniline
m-Oinitrobenzene -•
_5il_
5b
-Oi-n-Propylanine
-Dimethylauine
5. Oxidation (a. oxygen b. NO*)
6. Rearrangement (acid cat.)
7. Reduction (a. Zinc/caustic b. iron/acid)
0. liydrogenat ion
(totes
— Hajor synthetic route
— Principal coproducl
Minor coproduct
•Priority pollutant
-------
m-Cresol-
2b
Phenol
Aniline
"if"
oiii—
BENZENE* :
FIGURE V-ll
Chlorophenols, Chloroaroinat les, CMoropolyarouiat ics, llaloaryl Ethers. PCB's
•4-Chloro-m-cresol*
•2-Chloronhenol* —-
-2-Chloroaniline
±
2b
4 -Chloropheno l^Lir -
Chloroani1ine
"3.
w
2L.
*
"Chlorobemene*¦
Jk.
-Sodium phenolate-
-Broinobeniene
Naphthalene*—2t!—«. 2-Chloronaphthalene*
r
2h
•2,4-Dichlornphenol" —.
"•2,4-Dichloroani I ine!-"*
c
p-Dlchlorobenzene*
Dichlorobenzene*
*
_Ljto-Dichluiobeniene* Tl'.
• p-Dibromobemene •
r
»
'2,4,6-Trichlorophenol*
-2,4,6-Tr ichloroani 1 ine-2-.
2b I
1,3,5-Tr Ichlorobenzene-*—
2b ! .
1 •• 1»1j
I i
Trithlorobeniene*'
Trichlorobenzene*:
2b
7B"
-4-BromophenyI phenyl Ether*
-~.4-Clilorophenyl phenyl Ether*
'Pentachlorophenol*
Hexjchlorobenzene*
PCB's*-*-
iPentachlorobenzene* ¦ ¦
.1,2,3,5-Tetrachlorobeniene*-^-
Generic Processes
1. Brominatton
2. Cti lor mat ion (a. Thermal b. F eC 13 cat.)
3. Diazot izat ion
4. Hydrolysis (alkaline)
b. Rearrangement (AICI3 cat.)
Niites
— Major synthetic route
— Principal coproduct
— Hinur coproduct
'Priority pollutant
-------
FIGURE V-12
Chlorinated C?'s. C4- Chloroaltyl Ethers
[thine
Propane
la
ETHYLENE"
i
to
-------
BtNZEtf*
PROPYL Eft4
i
oo
•Cumene4
FIGURE V-13
Chlorinated C3's. Chloroalkyl Ethers. Acrolein, Acrylonttrile, Isophorone
^ i fiu»pnp ^ ¦
-bis(2-chloroisopropyl)* —i
Ether
..Propylene .
chlorohydrin
9a
11,2-Dichloropropane*-
•Allyl chloride
1,3-Oichlorrpropene*
-ID
Acrolein*.
zr
IT
sec-Butanol
(Butadiene)
Mcrylonitrile*
—v-Acetonitri le
—^Cyanide *
-Cunene —
hydroperoxide
Acetic acid
ul |8
c
Phenol*
Pcetone-
t l1
Ketune-
¦Isophorone*
Acetic anhydride
^.Propylene oxide
9a
"~"P ylene ~
d.chlorohydrin
Acrylic acid
Allyl alcoho1i1¦2i
• - •
-*ȣpichlorohydrin
9a 9a
'Glycerin
1
J Benzene* Phenol*
i
i—>. Naphthalene*
Generic Processes
(Oiels-Alder
adducts)
Notes
1. Addition
5.
Chlorohydrinat ion
10. Oxidation
(1.4-Diels Alder)
2. Alkylation
6.
Condensalion
II. Peroxidation
3. Ammoxidation
Dehydrogenat ion
12. Deduction
4. Chlorination
B.
(khydrat ion
(isoalkox ide)
9.
Hydrolys is
(a. alkaline b. acid)
— Major synthetic route
—Principal coproduct
— Minor coproduct
'Priority pollutant
-------
Dibromochloromethane*
FIGURE V-14
Halogenated Methanes
METHANE •
1'
Methanol-
'Kethyl chloride*
-^Methyl bromide*-
Methylene chloride*
bis(chloromethyl )*
Ether
Generic Processes
1. Bromination
2. Chlorination (thermal)
3. Ilydrobromi nation
4. Ilydrochlorination (ZnC 12)
6. Ilydrofluor inat ion
6. Hydrolysis (acid)
7. via synthesis gas (CO.II?)
Carbon tetrachloride*
Is
Tr ichlorofluoromethane*
Is
Dichlorodifluoromethane*
Notes
— Major synthetic routes
— Minor coproduct
'Priority po)lutant
Chloroform* "
Bromodichloromethane*
Broffloform*
-------
3.
Chlorinated C^, C^ and hydrocarbons; chloroalkyl ethers.
4. Chlorinated C^, hydrocarbons, acrolein, acrylonitrile,
isophorone and chloroalkyl ethers.
5. Halogenated methanes.
The generic processes associated with these synthesis routes are denoted by
numbers individually keyed to each chart.
The precursor(s) for each of these classes is reasonably obvious from the
generic group name. Classes 1 and 2 are, for the most part, substituted
aromatic compounds, while Classes 3, 4 and 5 are derivatives of ethene,
propene and methane, respectively. The common response of these precursors to
the chemistry of a process has important implications, not only for the
prediction of priority pollutants but for their regulation as well: that is,
group members generally occur together.
It is significant to note that among the many product/processes of the
industry, the collection of products and generic processes shown in Figures
V-10 through V-14 are primarily responsible for the generation of priority
pollutants. The critical precursor-generic process combinations associated
with these products are summarized in TABLE V-13. While there may be critical
combinations other than those considered here, Table V-13 contains certainly
the most obvious and probably the most likely combinations to be encountered
in the Organic Chemicals and Plastics/Synthetic Fibers industrial categories.
Product/Process Sources of Priority Pollutants
The product/processes that generate priority pollutants become obvious if the
synthesis routes to the priority pollutants are, in effect, superimposed upon
the synthesis routes employed by the industry in the manufacture of its major
products. FIGURE V-15 represents a priority pollutant profile of the OCPSF
Industries by superimposing Figures V-l through V-9 and V-10 through V-14 upon
on another so as to relate priority pollutants to feedstocks and products.
In any product/process, as typified by FIGURE V-16, if the feedstock
(reactant), solvent, catalyst system, or product is a priority pollutant, then
it is quite likely to be found in that product/process's wastewater effluent.
Equally obvious are metallic priority pollutants, which are certainly not
transformed to another metal (transmutation) by exposure to process
conditions. Since side reactions are inevitable and characteristic of all
chemical processes, priority pollutants may appear among the several
co-products of the main reaction. Subtler sources of priority pollutants are
the impurities in feedstocks and solvents.
Priority pollutant impurities may remain unaffected, or be transformed to
other priority pollutants, by process conditions. Commercial grades of
primary feedstocks and solvents commonly contain 0.5% or more of impurities.
While 99.5% purity approaches laboratory reagent quality, 0.5% is nevertheless
equal to 5000 ppm. Thus, it is not surprising that water coming into direct
contact with these process streams will acquire up to 1 ppm (or more) of the
impurities. It is not unusual to find priority pollutants representing raw
material impurities or their derivatives reported in the 0.1-1 ppm
V-39
-------
TABLE V-13
CRITICAL PRECURSOR/GENERIC PROCESS COMBINATIONS THAT GENERATE PRIORITY POLLUTANTS
FEEDSTOCK
Oxidation
GENERIC PROCESS
Chlorination
Nitration
Diazotization
Reduction
I
O
Benzene
Toluene
Xylene
Naphthalene
Phenol
Cresols
Chloroanilines
Nitroanilines
Nitrobenzene
m-Chloronitrobenzene
Ethene
Propene
Methane
Phenol
o,m-Cresol
2,4-Dimethylphenol
Acrolein
Chloroaromat ics
Chlorophenols
2-Chloronaphthalene
Chlorophenols
4-Chloro-m-cresol
Chlorinated C2's
Chlorinated C4
Chloroaromatics
Chlorinated C3's
Chlorinated Methanes
Nitroaromatics
Nitrophenols
Nitroaromatics
2,4-Diaethylphenol
Nitrophenols
4,6-Dinitro-o-cresol
Chlorophenols
Chloroaromatics
Aromatics
Nitrophenols
Nitroaromatics
Aromatics
N-Nitrosodiphenyl-
anine*
Benzidines**
Aniline*
(Diphenylamine)
1,2-Diphenylhydrazines**
* Derived directly from aniline, or indirectly via phenylhydrazine, diphenylamine is one of three secondary amines that are
precursors for Nitrosamines, when exposed to nitrites (as in diazotization) or N0X.
** Diphenylhydrazines rearrange to Benzidines under acid conditions (as in diazotization).
-------
FIGURE V-15
Priority Pollutant Profile of the Organic Chemical Industry
Phthalate.
Esters*
Alcohols -
_Phthalic
Anhydride
~ 14
o-Xylene
I
Nitrophenols*!
13
Nitroaromatics*
m
Acetic acid-
Isophorone*-
-Ketene
¦Acetone
Coal tar _
Distillates
Cumene-
Chloroalkyl*..
Ethers
Propylene.
1 Oxide
-Chlorinated C3's*
5J2
Epichlorohydrin , Allyl chloride-
I
Glycerin-. 6.12 ,1
16( . 17 ^ 14.
Ally! alcohol — Acrolein*.*
Acrylic acid—- I
4a
L.
Cyanide*
1PR0PYLENE-
'Phenols*"
M.
:AR0MAT1CS*
4b
18
.Acrylonitrile*
¦Cyanide*
>olyaromatics*
4b
19
-Crude oil
L
ETHYLENE
Methane
Methanol.
Ta~
10
—Natural gas
-Ethane/Propane
15 4b
LChlorophenols*
;Chloroaromatics*
¦Chlorinated*
polyaromatic
Chlorinated C4*
Chlorinated C2's*—i
+ 4a I
1 .. ».Halogenated
I Methanes
11
-Cyclopentadiene—^-^Chlorinated C5*
Generic Processes
1.
Alkylation
8.
Dehydrogenation
14.
Oxidation
2.
Ammoxidation
9.
Esterification
15.
Oxychlorination
3.
Bromination (thermal)
10.
Hydrobromination (ZnBr2)
16.
Peroxidation
4.
Chlorination
11.
Hydrochlorination
17.
Reduction (alkoxide)
a. Thermal b. FeCl3, AICI3)
a. FeCl3 b. ZnCl2 )
18.
Solvent extraction
5.
Chlorohydrination
12.
Hydrolysis
19.
Steam pyrolysis
6.
Dehydration
13.
Nitration
20.
Via synthesis gas
7.
Distillation
*Priority Pollutants
-------
FIGURE V-16
Generic Chemical Process
¦Catalyst-
¦Spent Catalyst-
|Reactant(s )1«
Impurities •
CHEMICAL
PROCESS
Solvent}"
-^Product (s
Equipment
Cleaning
Derivatives
"of Impurities'
¦Coproducts-
•Byproducts
*Misc. Resinous
" Materials
•Material Losses"
~Still bottoms, reactor coke, etc.
V-42
-------
concentration range in analyses of product/process effluents. Sensitive
instrumental methods currently employed in wastewater analysis have the
capability of measuring priority pollutants at concentrations below 0.1 ppm.
Specifications or assays of commercial chemicals at these trace levels are
seldom available, or were not previously (before BAT) of any interest, since
even 0.5% impurity in the feedstock and/or solvent would typically have
negligible effect on process efficiency or product quality. Only in cases
where impurities affect a process (e.g., poisoning of a catalyst) are
contaminants specifically limited.
Priority Pollutants in Product/Process Effluents
During the verification stage of the BAT review, representative samples were
taken from the effluents of 150 product/processes manufacturing organic
chemicals and 26 product/processes manufacturing plastics/synthetic fibers.
These 176 product/processes included virtually all of those shown on Figures
V-l through V-9. Analyses of these samples, averaged and summarized by
individual product/process, showed the priority pollutants observed in these
effluents to be preponderantly consistent with those that would have been
predicted, based on the precursor (with impurities)-generic process
combinations involved in each case.
Consistency between observation and prediction was most evident at
concentrations >0.5 ppm. Below that level, an increasing number of
extraneous priority pollutants were reported. Unrelated to the chemistry or
feedstock of the process, and typically reported at concentrations <0.1 ppm,
these anomalies could usually be attributed to one or more of the following
sources:
1. Extraction solvent (methylene chloride), or its associated
impurities.
2. Plasticizers (usually phthalates) from auto-sampler tubing, process
water supply, pump seals, gaskets, etc.
3. Sample contamination during sampling or during sample preparation at
the laboratory.
4. Jji situ generation in the wastewater collection system (sewer).
In the reconciliation of product/process effluent analytical data, it was
expedient to initially sort out the extraneous from the legitimate priority
pollutants. In most cases, only the latter can be related to the
product/process. Less than half of the effluents of key product/processes
manufacturing organic chemicals contained priority pollutants at
concentrations >0.5 ppm. The generic groups of priority pollutants associated
with these product/processes are summarized in TABLE V-14 and are consistent
with those predicted in Table V-ll. Many product/process effluents have
little potential to contain >0.5 ppm of priority pollutants, because they do
not involve critical precursor-generic process combinations.
Generic classes of priority pollutants reported at >0.5 ppm in the effluent of
product/processes manufacturing plastics/synthetic fibers are summarized in
TABLE V-15. Of the resins and fibers shown in Figures V-8 and V-9, only 18
V-43
-------
TABLE V-14
ORGANIC CHEMICALS EFFLUENTS WITH SIGNIFICANT CONCENTRATIONS
(>0.5 PPM) OF PRIORITY POLLUTANTS
PRODUCT
GENERIC PROCESS
FEEDSTOCK(S)
ASSOCIATED PRIORITY POLLUTANTS
Acetone
Acetylene
Acrolein
Acrylic acid
Adiponitrile
Alkyl (CI3, C19) amines
Alky! (C8, C9) phenols
Allyl alcohol
Aniline
Benzene
Benzyl chloride
Bisphenol A
Butadiene
Butenes
Butylbenzyl phthalate
Caprolactam
Carbon tetrachloride
Chlorobenzenes
Chloroform
m-Chloron i trobenzene
Creosote
Cumene
Cyclohexanol/-one
1,2-D ichloroethane
Dicyclopentadiene
Diethylphthalate
Diketene
Dimethyl terephthalate
Dinitrotoluenes
Diphenylisodecy1
phosphate ester
Epichlorohydrin
Ethoxylates-Alkylphenol
Ethylbenzene
Ethylene
Ethylene amines
Ethylene diamine
Ethylene oxide
Alkylation, Peroxidation
Dehyd rogena t ion
Oxidation
Oxidation
Anunonolysis, Dehydration
Hydrodimerization
Cyanation, Uydrogenation
Alkylation
Reduction (by alkoxide)
Hydrogenation
Hydrodealkylation
BTX Extraction
BTX Extraction
BTX Extraction
Chlorination
Condensation
Extractive distillation
Bsterification
Oxidation, Oximation
Dehydrogenation, Oximation
Chlorination
Chlorination
Chlorination
Chlorination
Chlorination
Distillation
Alkylation
Oxidation
Oxychlorination
Extraction, Diaerization
Esterification
Dehydration
Esterification
Nitration
Esterification
Chlorohyd r inat ion
Ethoxylation
Alkylation
Extraction from BTX
Steaa pyrolysis
AmiDonation
Amnonation
Oxidation
Chlorohydrination
Benzene, Propylene
Methane
Propylene
Propylene
Adipic acid
Acrylonitrile, Hydrogen
C12-C18 alpha olefin, HCN
Phenol, C8-C9 Olefins
Acrolein, sec-Butinol
Nitrobenzene
Toluene
Catalytic Reformate
Coal tar light oil
Pyrolysis Gasoline
Toluene
Phenol, Acetone
C4 Pyrolysates
n-Butanol, Benzyl chloride
Phthalic anhydride
Cyclohexane
Phenol
Me thane
Ethylene dichloride
Benzene
Methane, Methyl chloride
Nitrobenzene
Coal tar light oil
Benzene
Cyclohexane
Bthylene, HC1
C5 Pyrolysate
Ethanol, Phthalic anhydride
Acetic acid
Methanol, TPA
Toluene
Phenol, Isodecanol
POCI3
Allyl chloride
Alkylphejiol, Ethylene oxide
Benzene, Ethylene
BTX Extract
LPG, Naphtha, or Gas oil
1,2-Dichloroethane, NH3
1,2-Dichloroethane, NH3
Ethylene
Ethylene
Aroaatics
Aromatica, Polyaroaatics
Acrolein, Aromatics, Phenol
Acrolein
Acrylonitrile
Acrylonitrile
Cyanide
Phenol, Aromatics
Acrolein, Phenol, .Aromatics, Polyaroaatics
Aromatics
Aroaatics, Polyaromatics
Aromatics
Aromatics, Polyaroaatics, Phenols, Cyanide
Aromatics, Polyaromatics
Aromatics
Phenol, Aroaatics
Acrylonitrile (acetonitrile solvent),
Aromatics, Polyaromatics
Phthalates
Aromatics
Aromatics, Phenol
Chloroaethanes, Chlorinated C2's
Chloronethanes, Chlorinated C2's
Chloroaromatlcs, Aromatics
Chloromethanes, Chlorinated C2's
Aromatics, Nitroaromatics, Chloroaromatics
Phenols, Aroaatics, Polyaromatics
Aromatics
Phenol, Aromatics
Chlorinated C2's
Aromatics, Polyaromatics
Phthalates
Isophorone
Phthalates, Phenol
Nitroaromatics, Aromatics, Nitrophenols
Phenol, Chlorophenols
Aromatics
Chlorinated C3's
Phenol, Aromatics
Aromatics, Polyaroaatics, Phenol
Aromatics, Polyaromatics
Acrylonitrile (acetonitrile solvent)
Aromatics, Polyaromatics, Phenol
Chlorinated C2's
Chlorinated C2's
1,2-Dichloroethane (CO2 inhibitor)
Chlorinated C2's, Chloroalkyl ethers
-------
TABLE V-14 (concluded)
PRODUCT
GENERIC PROCESS
FEEDSTOCK(S)
ASSOCIATED PRIORITY POLLUTANTS
2-Ethylhexyl phthalate
Ester ification
2-Ethylhexanol
Phthalates
Phthalic anhydride
Glycerine
Hydrolysis
Ep ichlorohyd r i n
Chlorinated C3's
Hexaoethylene diamine
Hydrogenation
Adiponitrile
Acrylonitrile
Isobutylene
Extraction
C4 Pyrolysate
Aromatics
Isoprene
Extractive distillation
C5 Pyrolysate
Aroaatics, Polyaromatics
Acrylonitrile (Acetonitrile solvent)
Maleic anhydride
Oxidation
Benzene
Aroaatics
Methacrylic acid
Cyanohydr ination
Acetone
Cyanide
Methyl chloride
Chlorination
Methane
Chloromethane8, Chlorinated C2's
Hydrochlorination
Methanol
Chloromethanes
Methylene chloride
Chlorination
Methane
Cloromethanes, Chlorinated C2's
Methyl chloride
Methylethyl Ketone
Reduction (alkoxide)
Acrolein, sec-Butanol
Acrolein, Aromatics, Polyaromatics, Phenol
a-Methyl styrene
Peroxidation
Cumene '
Aroaatics, Phenol
Naphthalene
Distillation
Coal tar distillates
Aromatics, Polyaromatics, Phenols, Cyanide
Distillation
Pyrolysis Gasoline
Aroaatics, Polyaromatics
Nitrobenzene
Nitration
Benzene
Aroaatics, Nitroaromatics
Nitrophenols
Phenol
Peroxidation
Cuaene
Aromatics, Phenols
Phthalic anhydride
Oxidation
Napththalene
Polyaromatics
Oxidation
o-Xylene
Aromatics
Polymeric methylene
Condensation
Aniline, Formaldehyde
Nitroaromatics
dianiline
Polymeric methylene
Phosgenation
Polymeric methylene
Chloroaronatics
diphenyl diisocyanate
dianiline. Phosgene
(phosgenation solvent)
Propylene
Steam Pyrolysis
LPG, Naphtha, Gas oil
Aromatics, Polyaromatics, Phenols
Propylene oxide
Chlorohydrination
Propylene
Chlorinated C3's, Chloroalkyl ethers
Styrene
Dehydrogenation
Ethylbenzene
Aromatics, Phenol
Tetrachloroethylene
Chlorination
1,2-Dichloroethane
Chloromethanes, Chlorinated C2's
RC1 heavies
Chlorinated C3's
Tetrachlorophthalic
Chlorination
Phthalic anhydride
Chloroaronatics
anhydride
Toluene
BTX Extraction
Catalytic reforaate
Aromatics
BTX Extraction
Coal tar light oil
Aromatics, Polyaromatics, Phenols, Cyanide
BTX Extraction
Pyrolysis gasoline
Aromatics
Tolylenedi isocyanate
Phosgenation
Tolylenediamine
Chloroaromatics
1,2,4-Trichlorobenzene
Chlorination
1,4-Dichlorobenzene
Chloroaromatics
Tr ichloroethylene
Chlorination
1,2-Dichloroethane
Chlorinated C2's, Chloromethanes
RC1 heavies
Vinyl acetate
Acetylation
Ethylene, Acetic acid
Acrolein
Vinyl chloride
Dehydrochlorination
1,2-Dichloroethane
Chlorinated C2's, Chloromethanes
Vinylidene chloride
Dehyd rochlor inat ion
1,1,2-Trichloroethane
Chlorinated C2's, Cloronethanes
Xylenes (mixed)
BTX Extraction
Pyrolysis gasoline
Aromatics
BTX Extraction
Catalytic reformate
Aromatics
BTX Extraction
Coal tar distillates
Phenols, Aromatics, Polyaromatics, Cyanide
m,p-Xylenes
Distillation
BTX extract
Aromatics, Polyaromatics
o-Xylene
Distillation
BTX extract
Aromatics, Polyaromatics
-------
TABLE V-15
PLASTICS/SYNTHETIC FIBERS EFFLUENTS WITH
SIGNIFICANT CONCENTRATIONS (>0:5 ppm)
OF PRIORITY POLLUTANTS
ASSOCIATED
PRODUCT MONOMER(S) PRIORITY POLLUTANTS
ABS resins
Acrylic fibers
Acrylic resins (Latex)
Acrylic resins
Alkyd resins
Cellulose acetate
Epoxy resins
Petroleum hydrocarbon
res ins
Phenolic resins
Polycarbonates
Polyester
Acrylonitrile
Styrene
Polybutadiene
Acrylonitrile
Comonomer (variable):
Vinyl chloride
Acrylonitrile
Acrylate Ester
Methylmethacrylate
Methylmethacrylate
Glycerin
Isophthalic acid
Phthalic anhydride
Diketene (acetylating
agent)
Bisphenol A
Epichlorohydrin
Dicyclopentadiene
Phenol
Formaldehyde
Bisphenol A
Phosgene
Terephthalic acid/
Dimethylterephalate
Ethylene glycol
Acrylonitrile
Aromatics
Acrylonitrile
Chlorinated C2's
Acrylonitrile
Acrolein
Cyanide
Acrolein
Aromatics
Polyaromat ics
Isophorone
Phenol
Chlorinated C3*s
Aromatics
Aromatics
Phenol
Aromatics
(Not investigated)
Predicted: Phenol
Chloroaromatics
Halomethanes
Phenol
Aromatics
V-46
-------
TABLE V-15 (concluded)
PRODUCT
MONOMER(S)
ASSOCIATED
PRIORITY POLLUTANTS
HD Polyethylene resin
Ethylene
Aromatics
Polypropylene resin
Propylene
Aromatics
Polystyrene
Stryrene
Aromatics
Polyvinyl chloride resin
Vinyl chloride
Chlorinated C2's
SAN resin
Styrene
Acrylonitrile
Aromatics
Acrylonitrile
Styrene - Butadiene resin
(Latex)
Styrene (>50%)
Polybutadiene
Aromatics
Unsaturated polyester
Maleic anhydride
Phthalic anhydride
Propylene glycol
(Styrene-added later)
Phenol
Aromatics
V-47
-------
appear in Table V-15. This is attributable to the fact that plastics and
synthetic fibers are polymeric products manufactured from monomeric
precursors. The priojity pollutants found in polymeric product/process
effluents are usually restricted to the monomer(s) and its impurities or
derivatives. Since all monomers or accompanying impurities are not priority
pollutants, some plastics/synthetic fibers effluents are essentially free of
priority pollutants.
In comparison with effluents from product/processes manufacturing organic
chemicals, effluents from polymeric product/processes generally contained
fewer priority pollutants at lower concentrations. The polymeric plastics and
synthetic fibers considered here have virtually no water solubility.
Furthermore, the process is designed to drive the polymerization as far to
completion as is practical and to recover unreacted monomer (often with its
impurities) for recycle to the process. Thus, the use of only a few priority
pollutant-related monomers, the limited solubility of polymeric products, and
monomer recovery results in the reduction of the number of priority
pollutants and their relative loading in plastics/synthetic fibers
effluents.
TABLE V-16 lists priority pollutants detected in OCPSF process wastewaters by
generic process. Priority pollutants are generically grouped and the groups
are arrayed horizontally. Priority pollutants reported from verification
analyses of product/process effluents are noted in four concentration ranges,
reading across from each precursor. This arrangement makes it more apparent,
particularly at higher concentration ranges, that reported priority pollutants
tend to aggregate within those groups that would be expected from the
corresponding precursor-generic process combination.
In contrast with organic priority pollutants that are co-produced from other
organic chemicals, metallic priority pollutants cannot be formed from other
metals. Except for a possible change of oxidation state, metals remain
immutable throughout the generic process. Thus, to anticipate metallic
priority pollutants, the metals that were introduced into a generic process
must be known.
Metallic priority pollutants, individually and in combinations, are most often
related to a generic process via the catalyst system. The metals composing
catalyst systems that are commonly employed with particular precursor-generic
process combinations to manufacture important petrochemical products have been
generally characterized in the technical literature (especially in patents).
An obvious way to offer clues for predicting metallic priority pollutants was
to expand the generic process descriptors in the listing of Table V-16 to
include this information.
Copper, chromium and zinc were the metallic priority pollutants most
frequently reported in the higher concentration ranges for all product/process
effluents. Copper and chromium are used in many catalyst systems. Another
significant source of chromium, as well as zinc, is the "blowdown" that is
periodically wasted from an in-plant production area's recycled non-contact
cooling water. These metals find application in non-contract cooling waters
as corrosion inhibitors. In some wastewater collection systems, it is
possible for the blowdown to become mixed with product/process effluent before
V-48
-------
TABLE V-16
RIORITY POLLUTANTS IN EFFLUENTS OF PRECURSOR GENERIC PROCESS COMBINATIONS
NHROAHOWAllCS
CHI OROPHt NOl S NI1MOPMCNOIS Ct N2lC>INlS
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CHLORINATED C3*» MISCELLANEOUS
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$ $ 0
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*
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CHLOROHYDRIN ATION
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0
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Ethylene 7
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1,1,2-Trichloroe thane
HYDROFLUORIN ATION
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PHOSGEN ATION
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-------
TABLE V-L6(Contiru*ed)
RIORITY POLLUTANTS IN EFFLUENTS OF PRECURSOR-GENERIC PROCESS COMBINATIONS
N11ROAROMATICS
CMLOROFHENOLS NITROPNENOLS BENZIDINES
CHLUROAROMATICS MAIOARVI ETMfcRS NIT ROS AMINES PHTHM..AKS HALOGfcNAIED METHANES
I
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-------
PRIORITY
NOTES:
\i ¦ '1I
phenols
AROMATlCS
POL Y AROMA TICS
PRIORITY
POLLUTANT
GROUPS
PRECURSOR
(FEEDSTOCK)
CRACKING
LPG 2
Naphtha/Gas oil3
Naphtha/LPG 4
Naphtha/LPG
CTR ACTION/DISTILLATION
Catalytic reformate*5
Coal tar light oil 6
Pyrolysis gasoline7
C4 Pyrolyzates
C5 Pyrolyzates
Pyrolysis gasoline
C4 Pyrolyzates
BTX Extract
C5 Pyrolyzates
C4 Pyrolyzates*
ALKYLATION
Benzene/Etbylene
Benzene/Propylene9
Phenol/Octene/Nonene
HYDRODEALKYLATION
Toluene/Xylene
OXIMATION
Phenol/Cyclohexanone
Cyclohexane/Cyclohexanont
DEMERIZATION
Cyclopentadiene
Ketene
C ARBOX YLATION
Phenol
NITRATION
Toluene
Benzene
DIAZOTI2ATION
2,4,6-Trjchloroaniline
Aniline
4-Nitroaniline
2-Nitroaniline
I
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-------
lABl.t V-10 (Cominued)
PRIORITY POLLUTANTS IN FFFl UENTS OF PRF CURSOR-GFNliRIC PROCLSS COMBINATIONS
NIlROAftOMMICS
CHLOROPHrNOLS NIT ROPHt NOL S 01K*IDIHLS
c:m DNO*«OWAT»CS HAIOaRVI MHtRS NITROSAMINES PHThmMES MM OGt ma fLl> ml 1 HANE.E
CHiOR'NA If.O Cd'ft MISCELLANEOUS
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-------
7 ABl E V-1 fi (Continued)
NORITY POUIJTANTS IN EIFFl UENTS OF PRECURSOR-GENERIC PROCESS COMBINATIONS
NITROAHOMATICS
rHlONOPMLNUtS NifHUPHIMOLS BENZIDINES
CMIOHOAHOMaTICS HMOaRYI ETHERS NITROSAMINFS fHlHAlATfS HM OGLNA ItO MElMANtS
chlorinmed ca'i miscellaneous
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PRIORITY
PHfcNOlS
AROMATlCS
POL Y AROMA 11CS
PRIORITY
POLLUTANT
GROUPS
PRECURSOR
(FEEDSTOCK)
AI DITION POLYMERIZATION
ACN/Polybutadiene/Styrene
ACN/Styrene
Styrene/Butadiene
Styrene (suspension)
Styrene (bulk)
ACN/AA esters/MMA
Methylmethacrylate
Dicyclopentadiene
Ethylene (HDPE)
Ethylene (LDPE)
Propylene
Vinyl acetate
Vinyl chloride (susp.)
Vinyl chloride (emul.)
Vinyl chloride (bulk)
FIBER SPINNING
Acrylic resin
Cellulose
CONDENSATION/POLYMERIZATION
Acetone/Phenol
n-Butyr aldehyde
Epichlorohydrin/Bisphenol A
Mel a mine/Form aldehyde
Phenol/Formaldehyde
Urea/Formaldehyde
CaprolactaiD
Nylon salt
Aniline/Formaldehyde
ETHOX YLATION
Ethylene oxide/water
Ethylene glycol2
Ethylene glycol still btm's3
Cll, CI2 Linear alcohols*
Alkylphenol
PR OPOX YLATION
Propylene glycol
Glycerin
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4 {pair • »»•!» •lotsici piaiiaat to 101 piccais
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-------
TABLE V-1 b(Continued)
PRIORITY POLLUI ANTS IN LFFLUEN7 S OF PRF CURSOR-GENERIC PROCESS COMBINATIONS
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PA/Butanol/Benzyl chloride
PA Glyceric
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POClj/Phenol/lsodecanol
Salicylic acid/Methanol
HYDR ATION/HYDROLYSIS
Allyl alcohol
Epic hlorohy drin
Acetone cyanohydrin
Polyvinyl acetate 3
Ethylene
Propylene
Butene
HYDROCY ANATION
Acetone
A cet one/Me thanol
C13-C19 Olefins
HYDRODIMERIZ ATION
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the combined flaw leaves the production area to join the main body of
wastewater within the plant. A minor source of metallic priority pollutants
is the normal deterioration of production equipment that comes into contact
with process water.
Extraneous priority pollutants were also reported in product/process
effluents. Priority pollutants may be considered extraneous when they cannot
be reconciled with the precursor (or its impurities) and the process
chemistry. In Table V-16, extraneous priority pollutants were flagged only
when they were reported at >.5 ppm. Thus, the failure to flag a priority
pollutant at <.5 ppm does not necessarily preclude it from being extraneous.
As a general rule, one extraneous generic group member indicates that the
entire group is probably anomalous. The phthalate esters are an example of
such a group that persists throughout the verification data.
Given the several sources of extraneous priority pollutants reported in
product/process effluents, these anomalies may simply reflect the practical
sampling difficulty of completely isolating an individual effluent from the
effluents of surrounding production areas. Wastewater collection systems were
not, in most cases, designed with that objective in mind. Another possible
explanation for extraneous priority pollutants is the sensitivity of the GC
detector, which responds to a number of compounds that may be present at low
levels. Without extra analytical effort, it becomes increasingly difficult to
unequivocally identify priority pollutants at lower concentrations.
Implications of the Verification Data for Monitoring Priority
Pollutants in Wastewater
A review of the verification data summarized in TABLE V-17 shows an increasing
number of both predictable and extraneous priority pollutants being reported
at progressively lower concentration ranges for virtually all of the
product/process effluents. This trend has been tabulated in Table V-16.
Current analytical techniques have the capacity to measure priority pollutants
to very low levels. As detection limits are extended to ever lower
concentrations ranges, the number of priority pollutants reported would be
expected to increase sharply. The number of compounds detected in a sample of
water is related to the sensitivity of the measurement technique: as the
detection level decreases an order of magnitude, the number of compounds
detected increases accordingly. Based on the number of compounds detected by
current methods, one would expect to find every known compound at a
-12
concentration 10 g/1 (1 ppt) or higher in a sample of treated drinking
water (Donaldson, 1977). Though not the same for all priority pollutants,
there is a concentration level below which their reliable identification and
measurement becomes routinely impractical.
In Table V-17, it is important to note the average number of pollutants
reported in the three higher concentration ranges (i.e., >.01 ppm) for
individual product/process effluents. These typically total around 9 to 10
pollutants per effluent. Within a plant, the wastewater collection system
combines the product/process effluents of a production area and merges with
the combined effluents of other production areas, ultimately routing the
overall combination to the main treatment facility. Because of the limited
V-59
-------
TABLE V-17
NUMBER OF PRIORITY POLLUTANTS REPORTED VS. CONCENTRATION
Concentration Range, ppm
<.01
.01 - .1 •
.1 - .5
>.5
Pollutants Reported in Range
1256
564
303
454
% Total Pollutants in Range
48.7
21.8
11.7
17.6
Average* Number of Pollutants
8.8
4.0
2.1
3.2
in Each Product/Process
Effluent
*142 product/process effluents with unique analyses were used to tabulate the
number of pollutants falling into each concentration range. Approximately 30
product/process effluents in Table V-16 could not be isolated for individual
sampling, but were assigned an analysis duplicating that of a product/process
effluent with which they were closely associated.
V-60
-------
number of critical precursor-generic process combinations and duplication
among product/processes contributing to these various in-plant effluents,
there are usually no more than 10 to 20 priority pollutants in the combined
wastewater of an entire plant. These may be condensed into only a few generic
groups of organic priority pollutants that are generally predictable from the
precursor-generic process combinations represented by the mix of
product/processes at a plant.
RAW WASTEWATER CHARACTERIZATION DATA
General
As described under Water Usage earlier in this chapter, the Organic Chemicals
and Plastics/Synthetic Fibers industries generate significant volumes of
wastewater containing a variety of pollutants. Most of this raw wastewater
receives some treatment either as an individual process waste stream or at a
wastewater treatment plant serving waste streams from the whole manufacturing
facility (see Section VII). To decide what pollutants merit regulation and
evaluate what technologies effectively reduce discharge of these pollutants,
data characterizing the raw wastewaters were collected and evaluated. This
section describes the Agency's approach to this important task and summarizes
the results.
Raw Wastewater Data Collection Studies
The Guidelines Development Methodology in Section II introduced the many
wastewater data collection efforts undertaken for development of these
regulations (see especially Table 11 — 1). Studies'which produced significant
data on faw wastewater characteristics include the 308 Surveys, the Screening
Study Phases I and II, the Verification Study, and the CMA Five-Plant Study.
The 308 Surveys have been described in Section II; the remaining studies are
summarized in TABLE V-18 and discussed below. The analytical and QA/QC
methods used in each of the studies are discussed in Appendix C to this
report. The results of the studies are presented in "Wastewater Data Summary"
at the end of this Section.
Screening Phase I. The wastewater quality data reported in the 308
Questionnaires were the result of monitoring and analyses by each of the
individual plants and their contract laboratories. To expand its priority
pollutant database and improve data quality by minimizing the discrepancies
among sampling and analysis procedures, EPA in 1977 and 1978 performed its
Phase I Screening Study. The Agency and its contractors sampled at 131
plants. As discussed under Guidelines Development Methodology, the plants
were chosen because they operated product/processes that produce the highest
volume organic chemicals and plastics/synthetic fibers.
Samples were taken of the raw plant water, some product/processes influents
and effluents, and influents and effluents at the plant wastewater treatment
facilities. Samples were analyzed for all priority pollutants except
asbestos, and for several conventional and nonconventional pollutants.
Screening samples were collected in accordance with procedures described in an
EPA Screening Procedures Manual (EPA 1977). Samples for liquid-liquid
V-61
-------
TABLE V-18
OVERVIEW OF WASTEWATER STUDIES INCLUDED IN
BAT RAW WASTE STREAM DATA BASE
STUDY
ELEMENT
SCREENING
VERIFICATION
CMA 5-PLANT
Phase 1
Phase I I
Dates
August 1977 to
March 1978
December 1979
1978 to 1980
June 1980 to
May 1981
Number of Plants
Direct Dischargers
Indirect Dischargers
Other Dischargers
131
40
14
24
2
37
30
5
2
5
5
Plant Selection
object ive
High volume
chemicaIs
Specialty chemicals
Verify specific pol-
lutants from product/
processes
Chemical plants with
we 1 1 -des igned and
we 11-operated acti-
vated sludge treat-
ment systems
Sampling Locations
Raw water. Treat-
ment influent and
effluent. Some
product/process
effluents.
Same as
Phase I.
Product/process
influents and
effluents in 29
plastic, 147 organic.
Raw water.
Treatment influent
and effluent.
"Treatment" included
neutralization and
c1 a ri f icat ion.
Sampling duration (a)
1 day
1 day
3 days
4 to 6 weeks
Po11utants tested:
All priority
poI Iutants but
a sbestos.
/
Same as Phase 1
Spec i f i c poI Iutants
from specific
p roduct/processes
Conventiona1s and
T0C, COD;
no heavy metals;
seiected organic
pollutants, no PCB's
or pesticides
Analytical methods
for organic
po1 Iutants
GC/MS, 1977 qA/qc
protocol; 4-AAP
for phenols
GC/MS, 1979 qA/qc
protocol.
GC/CD with confirma-
tory GC/MS on 10% of
samples.
Mostly GC/MS or
GC
Labs Participating
EPA Regions VII, V,
IV; Envirodyne,
Carborundum, Midwest
Research Institute
(MRI )
Environmental Science
& Engineering.
Labs: Envirodyne,
MR I, Southwest
Research Institute,
Gulf South Research
Institute, Jacobs (PJB
Labs), Acurex.
3 EPA contract labs,
1 CMA contract lab, &
4 chemical plant labs
(a) Generally, samples were 24-hour composites; cyanide, phenols, and volatile organics were generally grab samples or
a series or grab samples.
-------
extraction (all organic pollutants except the volatile fraction) and for
metals analyses were collected in glass compositing bottles over a 24-hour
period, using an automatic sampler generally set for a constant aliquot volume
and constant time, although flow- or time-proportional sampling was allowed.
For metals analysis, an aliquot of the final composite sample was poured into
a clean bottle. Some samples were preserved by acid addition in the field, in
accordance with the 1977 manual; acid was added to the remaining samples when
they arrived at the laboratory.
For purge and trap (volatile organic) analysis, wastewater samples were
collected in 40- or 125-ml vials, filled to overflowing, and sealed with
Teflon-faced rubber septa. Where dechlorination of the samples was required,
sodium thiosulfate or sodium bisulfite was used.
Cyanide samples were collected in 1-liter plastic bottles as separate grab
samples. These samples were checked for chlorine by using potassium-iodide
starch test-paper strips, treated with ascorbic acid to eliminate the
chlorine, then preserved with 2 ml of ION sodium hydroxide/liter of sample (pH
12).
Samples for total (4AAP) phenol colorimetric analysis were collected in glass
bottles as separate grab samples. These samples were acidified with
phosphoric or sulfuric acid to pH 4, then sealed.
All samples were maintained at 4°C for transport and storage during
analysis. Where sufficient data were available, other sample preservation
requirements (e.g., those for cyanide, phenol and VOA's by purge and trap as
described above) were deleted as appropriate (e.g., if chlorine was known to
be absent). No analysis was performed for asbestos during the screening and
verification efforts. A separate program was subsequently undertaken for
determination of asbestos (See Section VI).
Screening Phase II. In December 1979, samples were collected from an
additional 40 plants (known as Phase II facilities) manufacturing products
such as dyes, flame retardants, coal tar distillates, photographic chemicals,
flavors, surface active agents, aerosols, petroleum additives, chelating
agents, microcrystal1ine waxes, and other low volume specialty chemicals. As
in the Phase I Screening study, samples were analyzed for the all priority
pollutants except asbestos. The 1977 EPA Screening Procedures Manual was
followed in analyzing priority pollutants. As in Screening Phase I, some
samples for metals analysis were preserved by addition of acid in the field
(in accordance with the 1977 Manual) and acid was added to the remaining
samples when they arrived at the laboratory. In addition, the organic
compounds producing peaks not attributable to priority pollutants with a
magnitude of at least one percent of the total ion current were identified by
computer matching.
Intake, raw influent, and effluent samples were collected for nearly every
facility sampled. In addition, product/process wastewaters which could be
isolated at a facility were also sampled, as were influents and effluents from
some treatment technologies in place. Fourteen direct dischargers, 24
indirect dischargers and 2 plants discharging to deep wells were sampled.
V-63
-------
TABLE V-19 lists the product/process and other waste streams sampled at each
plant.
Verification Program. The Verification Program was designed to verify the
occurrence of specific priority pollutants in waste streams from individual
product/processes. Product/processes to be sampled were chosen to maximize
coverage of the product/processes used to manufacture chemicals selected
according to the priorities discussed in Section II, Guidelines Development
Methodology. The priority pollutants selected for analysis in the waste
stream from each product/process were chosen to meet either of two criteria:
(1) They were believed to be raw materials, precursors, or products in
the product/process, according to the process chemistry (see Section
IV); or
(2) They had been detected in the grab samples taken several weeks before
the three-day Verification exercise (see below) at concentrations
exceeding the threshold concentrations listed in TABLE V-20.
The threshold concentrations listed in Table V-20 were selected as follows.
The concentrations for pesticides, PCBs, and other organics are approximate
quantitative detection limits. The concentrations for arsenic, cadmium,
chromium, lead, and mercury are one half the national Drinking Water Standard
(Federal Register, Vol. 40, No. 248, December 24, 1975, pp. 59566-74).
The Agency sampled at six integrated manufacturing facilities for the pilot
program to develop the "Verification Protocol". Thirty-seven plants were
eventually involved in the Verification effort. Samples were taken from the
effluents of 147 product/processes manufacturing organic chemicals and 29
product/processes manufacturing plastics/synthetic fibers, as well as from
treatment system influents and effluents at each facility.
Each plant was visited about four weeks before the three-day verification
sampling to discuss the sampling program with plant personnel, to determine
in-plant sampling locations and to take a grab sample at each designated
sampling site. These samples were analyzed to develop the analytical methods
used at each plant for the three-day verification exercise and to develop the
target list of pollutants described above for analyses at each site during the
three-day sampling. Some pollutants that had been put on the list for
verification since they were believed to be raw materials, precursors, or
coproducts were not detected in the verification progrmn grab samples. If
such a pollutant was also not detected in the sample from the first day of the
three-day verification sampling, it was dropped from the analysis list for
that sample location. Other compounds were added to the analysis list since
they were found in the Verification grab sample at a concentration exceeding
the threshold criteria in Table V-20. Priority pollutants known by plant
personnel to be present in the plant's wastewater were also added to the
Verification list.
At each plant, Verification samples generally included: process water supply;
product/process effluents; and treatment facility influent and effluent.
Water being supplied to the process was sampled to establish the background
concentration of priority pollutants. The product/process effluent waste
V-64
-------
TABLE V-19
PHASE II SCREENING - PRODUCT/PROCESS AND OTHER
WASTE STREAMS SAMPLED AT EACH PLANT
Plant
Number Waste Streams Sampled
1 Combined raw waste (fluorocarbon)
2 Anthracene
Coal tar pitch
3 Combined raw wastes- (dyes)
4 Combined raw wastes (coal tar)
5 Combined raw wastes (dyes)
6 Oxide
Polymer
7 Freon
6 Freon
9 Ethoxylation
10 Nonlube oil Additives
Lube oil Additives
11 Combined raw wastes (dyes)
12 Combined raw wastes (flavors)
13 Combined raw wastes (specialty chemicals)
14 Combined raw wastes (flavors)
15 Hydroquinone
16 Esters
Polyethylene
Sorbitan raonosterate
17 Dyes
18 Combined raw wastes (surface active agents)
19 Fatty acids
V-65
-------
TABLE V-19 (continued)
Plant
Number Waste Streams Sampled
20 Organic pigments
Salicylic acid
Fluorescent brightening agent
21 Surfactants
22 Dyes
23 Combined raw wastes (flavors)
24 Chlorination of paraffin
25 Phthalic anhydride
26 Combined raw waste (unspecified)
27 Dicyclohexyl phthalate
28 Plasticizers
Resins
29 Combined raw waste (unspecified)
30 Polybutyl phenol
Zinc Dialkyldithiophosphate
Calcium phenate
Dithiothiadiazole
Calcium sulphonate
Mannich condensation product
Oxidized co-polymers
31 Tris (U-chloroethyl) phosphate
32 Ether sulfate sodium salt
Lauryl sulfate sodium salt
Xylene distillation
33 Dyes
34 Maleic anhydride
Formox formaldehyde
Phosphate ester
Hexamethylenetetramine
V-66
-------
TABLE V-19 (concluded)
Plant
Number Waste Streams Sampled
35 Acetic acid
36 Combined raw waste (coal tar)
37 "680" Brominated fire retardants
Tetrabromophthalic anhydride
Hexabromocyclododecane
38 Hexabromocyclododecane
39 Fatty acid amine ester
Calcium sulfonate in solvent (alcohol)
Oil field deemulsifier blend
(aromatic solvent)
Oxylakylated phenol — formaldehyde resin
Ethoxylated monyl phenol
Ethoxylated phenol--formaldehyde resin
40 Combined raw waste (surface active agents)
V- 67
-------
TABLE V-20
SELECTION CRITERIA FOR TESTING
PRIORITY POLLUTANTS IN VERIFICATION SAMPLES
Parameter Criterion (yg/1)
Pesticides and PCBs 0.1 .
Other Organics
10
Total Metals:
Antimony
100
Arsenic
25
Beryllium
50
Cadmium
5
Chromium
25
Copper
20
Lead
25
Mercury
1
Nickel
500
Selenium
10
Silver
5
Thallium
50
Zinc
1,000
Total Cyanides
20
V-68
-------
loads were later corrected for these influent waste loadings. Product/process
samples were taken at locations that would best provide representative
samples. At various plants, samples were taken at the influent to and
effluent from both "in-process" and "end-of-pipe" wastewater treatment
systems.
Samples were taken on each of three days during the Verification exercise. As
in Phase I and II Screening studies, 24-hour composite samples for extractable
organic compounds and metals were taken with automatic samplers. Where
automatic sampling equipment would violate plant safety codes requiring
explosion-proof motors, equal volumes of sample were collected every two hours
over an 8-hour day and manually composited in a glass (2.5-gal) container.
Raw water supply samples were typically collected as daily grab samples
because of the low variability of these waters.
Samples for cyanides analysis were collected in plastic bottles (either as a
single grab sample each day or as an equal-volume, 8-hour composite) and were
preserved as in the screening program. Samples for analysis of volatile
organic compounds were also collected and preserved as 411 t^ie screening
program, in headspace-free sealed vials; where headspace analysis of volatile
organic compounds was planned, sample bottles were filled half way. No 4-AAP
phenol analyses were run during Verification. Sample collection and
preservation procedures for each analytical method are documented in Appendix
C.
The temperature and pH of the sample, the measured or estimated wastewater
flow at the time of sampling, and the process production levels were all
recorded. Weather and plant operating conditions during the sampling period
were also recorded, particularly in connection with operational upsets (in the
production units or wastewater treatment facilities) that could yield a sample
not representative of typical operation.
Analytical methods for cyanides were the same as those used in Phases I and II
of Screening. Analytical methods for heavy metals conformed to the 1977
Manual; all samples were preserved by addition of acid in the field. For
organic compounds, however, gas chromatography with conventional detectors was
used instead of the GC/MS that was used in the Screening program. GC/MS
analysis was used on about ten percent of the samples to confirm the presence
or absence of pollutants whose GC peaks overlapped other peaks. The
analytical methods finally developed were usually applicable (with minor
modifications) to all sampling sites at any given plant.
GMA Five-Plant Sampling Program. From June 1980 to May 1981, the Chemical
Manufacturers Association (CMA), with cooperation from EPA and five
participating chemical plants, performed the CMA Five-Plant Study to gather
longer-term data on biological treatment of toxic pollutants at organic
chemicals plants. The three primary objectives of the program were to:
Assess the effectiveness of biological wastewater
treatment for the removal of toxic organic pollutants;
V - 69
-------
• Investigate the accuracy, precision, and
reproducibility of the analytical methods used for
measuring toxic organic pollutants in organic
chemicals industry wastewaters; and
• Evaluate potential correlations between biological
removal of toxic organic pollutants and biological
removal of conventional and nonconventional
pollutants.
Since the biological wastewater treatment system influent samples were taken
upstream not only of the biological treatment but also of any preliminary
neutralization and settling of each chemical plant's combined waste stream,
the biological treatment influent samples reflect each facility's raw waste
load following any in-plant treatment of waste streams from individual
product/processes.
EPA nominated the five participants because of the specific toxic organic
pollutants expected to be found. The five participating organic, chemicals
manufacturing plants were characterized as having well-designed and
well-operated activated sludge treatment systems. Typically, seven to thirty
sets of influent and effluent samples (generally 24-hour composites) were
collected at each plant over a four- to six-week sampling period.
Only selected toxic organic pollutants were included in this study;
pesticides, polychlorinated biphenyls, metals, and cyanides were not
measured. Samples were analyzed for a selected group of toxic organic
pollutants specific to each location.and for specified conventional and
nonconventional pollutants. Not all toxic organic pollutants included in this
study were analyzed at all locations.
EPA's contract laboratories analyzed all influent and effluent samples for
toxic organic pollutants using gas chromatography/mass spectrometry (GC/MS) or
gas chromatography (GC) procedures (44 FR 69464 et. seq., December 3, 1979,
or variations acceptable to the EPA Effluent Guidelines Division). One EPA
laboratory used GC coupled with flame ionization detection (GC/FID).
Approximately 25 percent of the influent and effluent samples collected at
each participating plant were analyzed by the CMA contractor using GC/MS
procedures (44 FR 69464 et. seq., December 3, 1979, or equivalent). Some
variation occurred in the analytical procedures for the toxic organic
pollutants used by both the EPA contract laboratories and the CMA laboratory
during this study. An extensive quality control/quality assurance program was
included to define the precision and accuracy of the analytical results.
Each participant analyzed conventional and nonconventional pollutants in their
influent and effluent wastewaters using the methods found in "Methods of
Chemical Analysis of Water and Wastes," EPA 600/4-79-020, March 1979.
Additionally, four of the participants analyzed from 25 to 100 percent of the
samples collected by EPA for some of the toxic organic pollutants being
discharged by the Plant. Those analyses at least duplicated the CMA
contractor's analyses.
V-70
-------
The influent loadings measured in this study prior to end-of-pipe treatment
are discussed later in this chapter. The biological treatment effluent
results are discussed and used in Section IX. The report by CMA's contractor
(Engineering-Science, Inc., "CMA/EPA Five-Plant Study", April, 1982) includes
details of the sampling, analysis, data and evaluation of results.
Wastewater Data Summary
General. The Agency's wastewater data collection studies discussed above
yielded data of varying quality on the concentrations of priority pollutants
in product/process effluents and wastewater treatment influents and effluents
at over 170 OCPSF manufacturing plants. Before being used for developing
regulations as described in the rest of this document, these data were
reviewed as explained in Appendix C to eliminate questionable numbers
resulting from improper sampling, faulty sample preservation, and
inappropriate analytical or quality assurance/quality control procedures. The
Agency concluded that the reviewed and edited data from the Verification Phase
and CMA Five-Plant studies were good enough to use quantitatively (e.g., to
develop numerical effluent limits), while data from Phases I and II of the
Screening Study were only good enough to use qualitatively -- to decide which
pollutants discharged by the OCPSF Industries are of national concern (Section
VI) and for the multi-variate subcategorization analysis (Section IV).
This section summarizes estimated priority pollutant waste loadings for two
sets of OCPSF industry plants -- first, the small number of plants sampled in
the Verification and CMA Five-Plant studies; and second, all the plants
addressed by this regulation. The two sets of waste loadings are presented
and described below.
Waste Loadings from Verification and CMA Five-Plant Studies. The
Verification and CMA Five-Plant studies were both described earlier in this
section. In these wastewater data collection studies, the waste water
concentrations at each plant were measured upstream of the end-of-pipe
treatment plants, but often downstream of treatment of individual
product/process waste streams. TABLES V-21 THROUGH V-23 present the summary
statistics on the influent wastewater concentrations measured at 34 plants. .
These are the same 34 Verification and CMA plants for which summary statistics
from a slightly different analysis are presented in Section VI. The data
incorporated into this summary from the CMA study includes only the GC/MS
data, not the GC/CD data. Table V-21 presents the statistics for 28
direct-discharging plants in the Not Plastics-Only subcategory; Table V-22
presents the statistics for three indirect-discharging plants in the Not
Plastics-Only subcategory; and Table V-23 presents the statistics for three
direct-discharging plants in the Plastics-Only subcategory. The Verification
and CMA sampling programs did not include any indirect-discharging plants in
the Plastics-Only subcategory.
As noted previously in this section (Raw Wastewater Data Collection Studies),
each sample was analyzed for specific priority pollutants. No tests were run
for the priority pollutants not listed in Tables V-21 through V-23, including
asbestos and most of the pesticides (pollutants number 89 to 105). N-DET is
the number of readings above 10 ppb; N-NOTDET is the number of readings at or
below 10 ppb. Values below 10 ppb were excluded from the descriptive
V-71
-------
TABLE V-21
INFLUENT WASTEWATER CONCENTRATION
SUMMARY STATISTICS FOR TWENTY-EIGHT NOT PLASTICS-ONLY DIRECT DISCHARGING PLANTS*
HEMNUM NAME
FRACTI ON
N NOTDET
N DET
N PLANTS
MINIMUM
MEAN
MEDIAN
MAXIMUM
1
ACENAPHTHENE
BASE/NEUTRAL
26
26
5
12.00
1466.64
103.00
9600.00
2
ACROLEIN
VOLATILES
6
0
0
10.00
10.00
10.00
10.00
3
ACRYLONITRILE
VOLATILES
22
76
4
48.00
58290.11
17200.00
890000.00
4
BENZENE
VOLATILES
31
212
16
11 .00
19485.66
1440.00
390000.00
5
BENZIDINE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
6
CARBON TETRACHLORIDE
VOLATILES
193
23
6
18.00
5087.61
313.00
45000.00
7
CHLOROBENZENE
VOLATILES
115
40
6
11 .00
737.38
33.50
7200.00
8
1,2,4-TRICHLOROBENZENE
BASE/NEUTRAL
11
29
1
98.00
221.21
160.00
550.00
9
HEXACHLOROBENZENE
BASE/NEUTRAL
1
6
1
13.00
35.50
41.00
52.00
10
1,2 — D1CHLOROETHANE
VOLATILES
84
121
7
35.00
9103.04
530.00
100000.00
11
1,1,1-TR1CHLOROETHANE
VOLATILES
108
34
5
12.00
1646.56
215.00
20000.00
12
HEXACHLOROETHANE
BASE/NEUTRAL
1
6
1
52.00
2308.67
2600.00
3400.00
13
1,1-DICHLOROETHANE
VOLATILES
83
15
3
11.00
505.00
382.00
1200.00
14
1,1,2-TRICHLOROETHANE
VOLATILES
94
21
4
11 .00
526.24
64.00
1700.00
15
1,1,2,2-TETRACHLOROETHANE
VOLAT1LES
78
5
2
47.00
454.40
352.00
1100.00
16
CHLOROETHANE
VOLAT1LES
95
12
2
14.00
402.08
91.00
1563.00
17
BIS (CHLOROMETHYL) ETHER
VOLAT1LES
1
0
0
10.00
10.00
10.00
10.00
18
BIS (2-CHL0R0ETHYL) ETHER
BASE/NEUTRAL
0
1
1
2800.00
2800.00
2800.00
2800.00
19
2-CHLOROETHYLV1NYL ETHER
VOLAT1LES
2
0
0
10.00
10.00
10.00
10.00
20
2-CHLORONAPHTHALENE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
21
2,4,6-TR1CHLOROPHENOL
ACIDS
37
115
7
10.81
110.37
61.00
1449.00
22
4-CHLORO-M-CRESOL
AC 1 DS
24
0
0
10.00
10.00
10.00
10.00
23
CHLOROFORM
VOLAT1LES
144
129
15
10.30
1065.31
520.00
6600.00
24
2-CHLOROPHENOL
ACIDS
107
40
5
11 .00
800.38
74.50
15540.00
25
1,2-DICHL0R0BENZENE
BASE/NEUTRAL
19
44
5
11.00
659.64
425.00
4350.00
26
1,3-D ICHLOROBENZENE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
27
1,4-DICHLOROBENZENE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
28
3,3-D 1CHLOROBENZ1D1NE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
29
1,1-DICHLOROETHYLENE
VOLAT1LES
115
63
7
11.00
843.67
350.00
9100.00
30
1,2-TRANSDICHLOROETHYLENE
VOLATILES
178
24
5
12.00
5417.04
410.00
38000.00
31
2,4-D1CHLOROPHENOL
ACIDS
90
33
4
24.00
556.06
600.00
890.00
32
1,2—D1CHLOROPROPANE
VOLATILES
7
83
4
14.00
794.92
127.00
14000.00
33
1,3-D ICHLOROPROPYLENE
VOLATILES
21
70
2
13.00
513.66
184.50
8700.00
34
2,4-DI METHYLPHENOL
ACIDS
44
33
5
17.00
3447.38
634.15
19000.00
35
2,4-DINITROTOLUENE
BASE/NEUTRAL
1
5
1
120.00
12924.00
16000.00
18000.00
36
2,6-DINITROTOLUENE
BASE/NEUTRAL
1
5
1
34.00
3436.80
4400.00
4750.00
37
1,2-DIPHENYLHYDRAZINE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
38
ETHYLBENZENE
VOLATILES
30
209
13
20.00
2678.87
223.00
120000.00
39
FLUORANTHENE
BASE/NEUTRAL
63
33
5
19.51
1294.03
91.00
7900.00
40
4-CHLOROPHENYLPHENYL ETHER
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
41
4-BROMOPHENYLPHENYL ETHER
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
42
BIS-(2-CHLOROISOPROPYL) ETHER
BASE/NEUTRAL
3
6
2
520.00
4736.67
4950.00
9300.00
43
BIS-(2-CHL0R0ETH0XY) METHANE
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
-------
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-------
TABLE V-21 (concluded)
CHEMNUM
NAME
FRACT1 ON
N NOTDET
N DET N
PLANTS
MINIMUM
MEAN
MEDIAN
MAXIMUM
104
BHC-GAMMA
PESTICIDES
3
0
0
10.00
10.00
10.00
10.00
106
PCB-1242 (AROCHLOR
1242).
PESTICIDES
8
0
0
10.00
10.00
10.00
10.00
107
PCB-1254 (AROCHLOR
1254).
PESTICIDES
3
0
0
10.00
10.00
10.00
10.00
108
PCB-1221 (AROCHLOR
1221).
PESTICIDES
3
0
0
10.00
10.00
10.00
10.00
110
PCB-1248 (AROCHLOR
1248).
PESTICIDES
2
1
1
12.00
12.00
12.00
12.00
114
ANTIMONY (TOTAL)
METALS
3
20
4
30.00
163.00
80.00
630.00
115
ARSENIC (TOTAL)
METALS
17
25
9
11.00
108.96
25.00
1300.00
117
BERYLLIUM (TOTAL)
METALS
0
2
1
20.00
35.00
35.00
50.00
118
CADMIUM (TOTAL)
METALS
48
7
4
12.00
20.57
20.00
40.00
119
CHROMIUM (TOTAL)
METALS
8
115
23
11.00
584.15
300.00
6400.00
120
COPPER (TOTAL)
METALS
22
102
24
13.00
308.40
80.50
9710.00
121
CYANIDE (TOTAL)
METALS
12
80
12
16.00
7761.62
121.59
200000.00
122
LEAD (TOTAL)
METALS
15
54
11
11.00
175.02
58.50
1100.00
123
MERCURY (TOTAL)
METALS
57
5
2
12.00
37.80
37.00
60.00
124
NICKEL (TOTAL)
METALS
4
28
8
15.00
528.71
230.00
2080.00
125
SELENIUM (TOTAL)
METALS
10
25
6
13.00
274.28
50.00
2000.00
126
SILVER (TOTAL)
METALS
17
9
4
15.00
62.67
40.00
170.00
127
THALLIUM (TOTAL)
METALS
4
7
3
15.00
47.86
50.00
70.00
128
ZINC (TOTAL)
METALS
2
50
12
50.00
580.68
325.00
2800.00
129
TETRACHLORODIBENZO-
P-DIOXIN
BASE/NEUTRAL
1
0
0
10.00
10.00
10.00
10.00
999
TOTAL UNIQUE PLANTS
•
•
28
•
•
•
•
*N DET: Number of readings above 10 ppb.
N NOTDET: Number of readings at or below 10 ppb.
N PLANTS: Number of plants at which pollutant was detected above 10 ppb.
-------
TABLE V-22
INFLUENT WASTEWATER CONCENTRATION SUMMARY STATISTICS
FOR THREE NOT PLASTICS-ONLY INDIRECT DISCHARGING PLANTS*
CHEMNUM
NAME
FRACTION
N NOTDET
N DET N
PLANTS
MINIMUM
MEAN
MEDIAN
MAX I MUM
2
ACROLEIN
VOLATILES
0
4
1
2500.00
18850.00
18450.00
36000.00
4
BENZENE
VOLATILES
4
3
1
14.00
44.33
59.00
60.00
23
CHLOROFORM
VOLATILES
3
0
0
10.00
10.00
10.00
10.00
38
ETHYLBENZENE
VOLATILES
3
4
1
28.00
45.75
45.00
65.00
55
NAPHTHALENE
BASE/NEUTRAL
0
4
1
40.00
988.75
157.50
3600.00
56
NITROBENZENE
BASE/NEUTRAL
2
0
0
10.00
10.00
10.00
10.00
57
2-NITROPHENOL
ACIDS
0
4
1
21.00
43.75
42.00
70.00
62
N-NITROSODIPHENYLAMINE
BASE/NEUTRAL
3
0
0
10.00
10.00
10.00
10.00
65
PHENOL
ACIDS
0
8
2
430.00
1353.75
1275.00
2700.00
66
BIS-(2-ETHYLHEXYL) PHTHALATE
BASE/NEUTRAL
3
0
0
10.00
10.00
10.00
10.00
68
DI-N-BUTYL PHTHALATE
BASE/NEUTRAL
4
0
0
10.00
10.00
10.00
10.00
70
DIETHYL PHTHALATE
BASE/NEUTRAL
2
2
1
490.00
715.00
715.00
940.00
86
TOLUENE
VOLATILES
0
8
2
55.00
2743.00
295.00
12000.00
107
PCB-1254 (AROCHLOR 1254).
PESTICIDES
2
0
0
10.00
10.00
10.00
10.00
114
ANTIMONY (TOTAL)
METALS
8
0
0
10.00
10.00
10.00
10.00
115
ARSENIC (TOTAL)
METALS
8
0
0
10.00
10.00
10.00
10.00
118
CADMIUM (TOTAL)
METALS
8
0
0
10.00
10.00
10.00
10.00
119
CHROMIUM (TOTAL)
METALS
0
16
3
21.00
906.69
240.00
2800.00
120
COPPER (TOTAL)
METALS
0
16
3
22.00
195.56
90.00
730.00
122
LEAD (TOTAL)
METALS
2
6
1
15.00
95.83
75.00
250.00
123
MERCURY (TOTAL)
METALS
11
4
1
22.00
270.50
80.00
900.00
124
NICKEL (TOTAL)
METALS
2
6
1
20.00
63.33
60.00
120.00
125
SELENIUM (TOTAL)
METALS
8
0
0
10.00
10.00
10.00
10.00
127
THALLIUM (TOTAL)
METALS
8
0
0
10.00
10.00
10.00
10.00
128
ZINC (TOTAL)
METALS
0
12
2
80.00
549.17
595.00
1100.00
999
TOTAL UNIQUE PLANTS
•
3
•
•
•
•
*N DET: Number of readings above 10 ppb.
N NOTDET: Number of readings at or below 10 ppb.
N PLANTS: Number of plants at which pollutant was detected above 10 ppb.
-------
TABLE V-23
INFLUENT WASTEWATER CONCENTRATI ON-SUMMARY STATISTICS
FOR THREE PLASTICS-ONLY DIRECT DISCHARGING PLANTS*
CHEMNUM NAME
FRACTION
N NOTDET
N DET N
PLANTS
MINI MUM
MEAN
MEDIAN
MAX I MUM
2
ACROLEIN
VOLATILES
2
2
1
82.00
1841.00
1841.00
3600.00
3
ACRYLONITR1LE
VOLATILES
0
9
2
1200.00
19608.89
21310.00
36990.00
4
BENZENE
VOLATILES
4
0
0
10.00
10.00
10.00
10.00
6
CARBON TETRACHLORIDE
VOLATILES
2
0
0
10.00
10.00
10.00
10.00
7
CHLOROBENZENE
VOLATILES
4
0
0
10.00
10.00
10.00
10.00
13
1,1-D1CHLOROETHANE
VOLATILES
2
0
0
10.00
10.00
10.00
10.00
22
4-CHLORO-M-CRESOL
ACIDS
4
0
0
10.00
10.00
10.00
10.00
23
CHLOROFORM
VOLATILES
4
0
0
10.00
10.00
10.00
10.00
38
ETHYLBENZENE
VOLATILES
14
14
1
2158.00
2893.75
2794.00
3829.00
44
METHYLENE CHLORIDE
VOLATILES
3
0
0
10.00
10.00
10.00
10.00
148
DICHLOROBROMOMETHANE
VOLATILES
2
0
0
10.00
10.00
10.00
10.00
49
TRICHLOROFLUOROMETHANE
VOLATILES
2
0
0
10.00
10.00
10.00
10.00
65
PHENOL
ACIDS
5
6
2
11.00
48.17
62.50
70.00
66
B1S-(2-ETHYLHEXYL) PHTHALATE
BASE/NEUTRAL
3
6
2
30.00
75.33
42.00
161.00
85
TETRACHLOROETHYLENE
VOLATILES
3
0
0
10.00
10.00
10.00
10.00
86
TOLUENE
VOLATILES
4
0
0
10.00
10.00
10.00
10.00
88
VINYL CHLORIDE
VOLATILES
0
7
1
97.00
924.14
460.00
2500.00
115
ARSENIC (TOTAL)
METALS
3
0
0
10.00
10.00
10.00
10.00
118
CADMIUM (TOTAL)
METALS
1
2
1
28.00
34.00
34.00
40.00
119
CHROMIUM (TOTAL)
METALS
0
9
3
11 .00
130.78
120.00
290.00
120
COPPER (TOTAL)
METALS
0
6
2
41.00
88.33
83.00
163.00
121
CYANIDE (TOTAL)
METALS
0
6
2
20.00
51.33
41.00
130.00
122
LEAD (TOTAL)
METALS
0
9
3
20.00
122.67
38.00
540.00
123
MERCURY (TOTAL)
METALS
3
0
0
10.00
10.00
10.00
10.00
125
SELENIUM (TOTAL)
METALS
6
0
0
10.00
10.00
10.00
10.00
128
ZINC (TOTAL)
METALS
0
3
1
162000.00
325666.67
365000.00
O
o
o
o
o
o
&
999
TOTAL UNIQUE PLANTS
•
•
3
•
•
•
•
*N DET: Number of readings above 10 ppb.
N NOTDET: Number of readings at or below 10 ppb.
N PLANTS: Number of plants at which pollutant was detected above 10 ppb.
-------
statistics (minimum, mean, median, maximum) presented in Tables V-21 through
V-23, except where all values were below 10 ppb.
Even when split- or multiple samples were taken during one day, each daily
value (a single reading or an average of several single readings) counted as
one observation for this summary. Not averaging the results from split
samples would have improperly biased the data by weighting split samples more
than samples that had not been split. The maxima and minima shown are the
highest and lowest (respectively) daily values observed at any plant.
Waste Loadings for the Entire OCPSF Industrial Category. The Agency
estimated raw, current, projected BPT effluent, and projected PSES effluent
and projected BAT effluent priority pollutant waste loadings for the entire
OCPSF industrial category using data developed as part of the Regulatory
Impact Analysis of these proposed regulations. These data are presented in
the February 18, 1983, draft report from EPA's Office of Water Regulations and
Standards, Monitoring and Data Support Division (MDSD), entitled "Summary of
Priority Pollutant Loadings for the Organic Chemicals, Plastics, and
Synthetics Industry." The methodology used for developing the estimated waste
loads from the data in the MDSD draft report is described below.
The MDSD draft report estimated the total industry-wide raw, current,
projected BPTV projected PSES, and projected BAT effluent waste loadings and
flow for the 176 product/processes discussed in Section IV and Appendix G of"
this BAT Development Document. The Agency extrapolated these loadings
according to flow to cover all the product/processes comprising OCPSF
production, as follows: the MDSD flow estimates for the 176 product/processes
were 222.4 MGD for direct dischargers and 96.6 MGD for indirect dischargers.
Assuming 520 direct dischargers at 2.31 MGD each, total industry direct
discharge flow is 1,201.2 MGD. Assuming 468 indirect dischargers at 0.80 MGD
each, total industry indirect discharge flow is 374.4 MGD. The direct waste
loads for the total industry were estimated by multiplying the MDSD waste
loads for the 176 product/processes by 1201.2/222.4 = 5.40. The indirect
waste loads for the total industry were estimated by multiplying the MDSD
waste loads for the 176 product/processes by 374.4/96.6 = 3.88.
The results of these calculations are presented in Section IX (BAT) for direct
dischargers and Section XI (PSES) for indirect dischargers.
V-77
-------
REFERENCES
DONALDSON, W.T. 1977. Identification and measurement of trace organics in
water: an overview. Env. Sci. and Tech. 11:348. April 1977
HOLIDAY, A.D. 1982. Conserving and reusing water. Chemical Engineering
89:118-737.
McGOVERN, J.G. 1973. Inplant wastewater control. Chemical Engineering
80:137-139.
U.S. BUREAU OF THE CENSUS. 1981. 1977 Census of Manufacturers. Volume I:
Subject Statistics. U.S. Department of Commerce, Washington, D.C.
U.S. ENVIRONMENTAL PROTECTION AGENCY. 1979. Toxic Pollutant Identification:
Catalog of Organic Chemical Industries Unit Processes. EPA-IMPQCE Series
01/79-06
WISE, H.E. and FAHRENTHOLD, P.D. 1981a. Symposium on Treatability of
Industrial Aqueous Effluents. Presented in part at the 181st National meeting
of the Anjerican Chemical Society, Division of Industrial Engineering
Chemistry. Atlanta, Ga., March 29-April 3, 1981
WISE, H.E. and FAHRENTHOLD, P.D. 1981b. Predicting priority pollutants from
petrochemical processes. Env. Sci. and Tech. 15:1292-1304. November 1981
V-78
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
INTRODUCTION
The Agency has addressed two classes of pollutants for the BAT, NSPS, PSES,
and PSNS regulations in this document: the 126 priority pollutants and those
nonconventional pollutants which are found in the wastewaters of the Organic
Chemicals and Plastics/Synthetic Fibers (OCPSF) Industries. As the list of 65
toxic pollutants and classes of pollutants designated in the Clean Water Act
includes potentially thousands of specific pollutants, EPA limited its data
collection efforts to the 126 specific compounds referred to as "priority"
pollutants. The criteria that were used in the late 1970's to classify these
pollutants as "priority" pollutants included the frequency of their occurrence
in water, their chemical stability and structure, the amount of the chemical
produced, and the availability of chemical standards for measurement.
While sampling wastewaters to develop regulations on the OCPSF Industries, EPA
collected data at some facilities on specific nonconventional parameters such
as COD and TOC. Conventional pollutants (five-day biochemical oxygen demand
(BOD), total suspended solids (TSS), pH, and oil and grease) have been
considered in the development of the proposed BPT and BCT effluent limitations
for the OCPSF industries, and accordingly, are not addressed in this section.
In order to determine the presence and significance of nonconventional and
toxic pollutants in the wastewaters of the Organic Chemicals and
Plastics/Synthetic Fibers Industries, data have been compiled and reviewed
from (1) industry 308 questionnaires, (2) the screening, verification,, and the
CMA Five-Plant Study sampling efforts, (3) literature studies, and (4)
product/process chemistry considerations. This chapter discusses how these
data were used to determine which pollutant parameters are found in the
wastewaters of direct and indirect dischargers and describes the selection
criteria used to select pollutants for regulation under BAT, NSPS, PSNS, and
PSES. Each pollutant has been evaluated to: (1) consider the pollutant for
proposed regulation, (2) exclude the pollutant under Paragraph 8(a) of the
Revised Settlement Agreement, or (3) defer regulation because of inadequate
data.
SELECTION RATIONALE FOR BAT AND NSPS POLLUTANTS
General
Specific nonconventional and toxic wastewater parameters determined to be
significant in the Organic Chemicals and Plastics/Synthetic Fibers Industries
have been considered for regulation. Nonconventional pollutant parameters
commonly found in significant quantities in OCPSF wastewaters include chemical
oxygen demand (COD), total organic carbon (TOC), and ammonia nitrogen. In
VI-1
-------
addition to these pollutants, certain other nonconventional pollutants known
to have toxic properties, such as formaldehyde or methylene dianiline, have
been found in some OCPSF industries wastewaters. While EPA has not run
analyses for most of these nonconventional compounds in OCPSF wastewaters,
product/process chemistry implies that they are present in OCPSF wastewaters.
All of the 126 priority pollutants have been considered for potential
regulation -- including 28 volatile organic compounds, 47 base/neutral
extractable organic compounds, 11 acid extractable organic compounds, 18.
pesticides, 7 PCB's, and 15 metals.
Selection Criteria
Nonconventional and Toxic Non-Priority Pollutants. While the Agency had
considered proposing regulations for specific nonconventional pollutants, EPA
has determined that additional technical data is required to complete its
analysis. Therefore, BAT regulation of nonconventional pollutants has been
deferred.
The proposed regulations do not address toxic pollutants other than those
listed as priority pollutants. The enormity of the task of developing
analytical methods and treatment data for the priority pollutants alone
precluded study of other toxic pollutants. The installation and proper
operation of treatment equipment to meet BPT and BAT limitations will result,
however, in significant reductions of non-priority and nonconventional
pollutants.
Priority Pollutants. Paragraph 8 of the Settlement Agreement contains
provisions authorizing EPA to exclude toxic pollutants and industry
subcategories from regulation under certain circumstances. Paragraph
8(a)(iii) authorizes the Administrator to exclude from regulation: toxic
pollutants not detectable by Section 304(h) analytical methods or other
state-of-the-art methods; toxic pollutants present in amounts too small to be
effectively reduced by available technologies; toxic pollutants present only
in trace amounts and neither causing nor likely to cause toxic effects; toxic
pollutants detected in the effluent from only a small number of sources within
a subcategory and uniquely related to only those sources; toxic pollutants
that will be effectively controlled by the technologies upon which are based
other effluent limitations and standards; or toxic pollutants for which more
stringent protection is already provided under Section 307(a) of the Act.
Pursuant to these criteria, the Agency has chosen to eliminate from further
consideration the 18 pesticides which are priority pollutants (see TABLE
VI-1). The priority pollutants proposed for exclusion are pesticides which
are not produced as products or co-product>s and are unlikely to appear as raw
material contaminants in OCPSF product/processes. At manufacturing facilities
consisting predominantly of OCPSF product/processes, but where these pesticide
pollutants are intentionally synthesized by product/processes in SIC codes
corresponding to the pesticides category, pesticide discharges will be
regulated under effluent limitations for the separate pesticides category. On
occasion, pesticides may appear in discharges that contain OCPSF effluents
only. This results from the application of pesticide formulations around the
plant grounds.
VI-2
-------
TABLE VI-1
EIGHTEEN TOXIC POLLUTANTS
PROPOSED FOR EXCLUSION
Aldrin
Dieldrin
Chlordane
4,4'-DDT
4,4'-DDE
4,4'-DDD
alpha-Endosulfan
beta-Endosulfan
Endosulfansulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Toxaphene
VI -3
-------
The data on the remaining 108 priority pollutants considered for regulation
have been evaluated using the following two criteria:
(1) Was the pollutant ever detected in influent OCPSF wastewaters during
industry-wide sampling?
(2) What is the frequency of occurrence of each pollutant? Was it
detected at enough plants to merit national regulation?
All of the 108 pollutants currently under consideration for regulation were
detected in influent OCPSF wastewaters during the EPA's Effluent Guidelines
Division Organic Chemicals Branch Screening, Verification, and CMA studies.
These programs are described in Section V. As shown in TABLE VI-2, each of
these pollutants was detected in the wastewaters influent to end-of-pipe
treatment systems from at least 42 percent of the plants sampled. Therefore,
all of the pollutants under consideration satisfied both selection criteria.
The database used for Table VI-2 includes 149 plants, including 85 Screen
Phase I plants, 36 Screening Phase II plants, 31 Verification plants, and five
CMA plants. Overlaps were as follows: six plants were part of the Screening
and Verification studies; one plant was part of the Screening and CMA studies;
two plants were part of the Verification and CMA studies; and one plant was
part of all three studies. Of these data points, 76 plants are direct
dischargers, 42 plants are indirect dischargers, and the discharge mode for
the remaining 30 plants is unknown.
Pollutant Parameters Selected
Also presented in Table VI-2 is the range of concentrations (minimum and
maximum values) at which these pollutants were detected in the influent
wastewaters sampled during the Verification and CMA studies. While EPA
considered eliminating from regulation those pollutants that had been found
during the Verification and CMA studies in the raw wastewater at low
concentrations (e.g., maximum influent value detected was less than the lowest
reported concentration for chronic toxicity in freshwater species), the Agency
has chosen to defer the use of any such criteria. The Agency, therefore,
considers all the 108 priority pollutants in Table VI-2 to be candidates for
BAT regulation. The fate of these priority pollutants in aquatic environments
is discussed in USEPA (1979). Appendix H to this report presents a
description of the toxic human health and environmental effects associated
with each of the 108 priority pollutants. Section IX describes the derivation
of numerical BAT limitations for direct dischargers.
SELECTION RATIONALE FOR PSES AND PSNS POLLUTANTS
General
As discussed in Section XI, Pretreatmerit Standards of Existing Sources (PSES)
and Pretreatment Standards for New Sources (PSNS) for direct dischargers need
only address those pollutants which upset, inhibit, pass-through, or
contaminate sludges at POTWs. The Agency has assumed for purposes of this
analysis and based upon the available data, that within each subcategory, the
raw wastewaters at indirect discharging OCPSF plants are not significantly
VI-4
-------
TABLE VI-2
FREQUENCY OF OCCURRENCE AND CONCENTRATION RANGES
FOR SELECTED PRIORITY POLLUTANTS
IN INFLUENT WASTEWATERS
PERCENT
MINIMUM
MAXIMUM
PRIORITY POLLUTANT
FRACTION
PLANTS
(b)
(b)
DETECTED(a)
(Vg/1)
(Hg/1)
ACENAPHTHENE
BASE/NEUTRAL
61.1650
4.6150
9600.0000
ACROLEIN
VOLATILES
50.0000
82.0000
36000.0000
ACRYLONITRILE
VOLATILES
57.6923
S.0000
890000.0000
BENZENE
VOLATILES
86.6667
3.4800
390000.0000
BENZIDINE
BASE/NEUTRAL
45.4545
<10.0000
<10.0000
CARBON TETRACHLORIDE
VOLATILES
66.6667
1.0000
45000.0000
CHLOROBENZENE
VOLATILES
66.6667
1.0000
7200.0000
1,2,4-TRICHLOROBENZENE
BASE/NEUTRAL
44.5545
<10.0000
550.0000
HEXACHLOROBENZENE
BASE/NEUTRAL
47.4747
<10.0000
52.0000
1,2-DICHLOROETHANE
VOLATILES
59 .6154
1.0000
100000.0000
1,1,1-TRICHLOROETHANE
VOLATILES
70.1923
1.0000
20000.0000
HEXACHLOROETHANE
BASE/NEUTRAL
47.9592
<10.0000
3400.0000
1,1-DICHLOROETHANE
VOLATILES
55.0000
1.0000
1200.0000
1,1,2-TRICHLOROETHANE
VOLATILES
55.6701
4.0000
1700.0000
1,1,2,2-TETRACHLOROETHANE
VOLATILES
52.9412
7.0000
1100.0000
CHLOROETHANE
VOLATILES
51.5464
• 2.0000
1563.0000
BIS (2-CHLOROETHYL) ETHER
BASE/NEUTRAL
46.5347
2800.0000
2800.0000
2-CHLOROETHYLVINYL ETHER
VOLATILES
45.6522
<10.0000
<10.0000
2-CHLORONAPHTHALENE
BASE/NEUTRAL
44.8980
<10.0000
<10.0000
2,4,6-TRICHLOROPHENOL
ACIDS
59.4340
2.0000
1449.0000
4-CHL0R0-M-CRES0L
ACIDS
46.0000
2.0000
<10.0000
CHLOROFORM
VOLATILES
87.8049
1.0000
6600.0000
2-CHLOROPHENOL
ACIDS
57.5472
1.0000
15540.0000
1,2-DICHLOROBENZENE
BASE/NEUTRAL
50.9615
2.1000
4350.0000
1,3-DICHLOROBENZENE
BASE/NEUTRAL
47.0000
<10.0000
<10.0000
1,4-DICHLOROBENZENE
BASE/NEUTRAL
51.0000
<10.0000
<10.0000
3,3-DICHLOROBENZIDINE
BASE/NEUTRAL
43.8776
<10.0000
<10.0000
1,1-DICHLOROETHYLENE
VOLATILES
62.2449
2.0000
9100.0000
1,2-TRANSDICHLOROETHYLENE
VOLATILES
58.5859
5.0000
38000.0000
2,4-DICHL0R0PHEN0L
ACIDS
59.8131
1.5000
890.0000
1,2-DICHLOROPROPANE
VOLATILES
51.0204
8.0000
14000.0000
1,3-DICHLOROPROPYLENE
VOLATILES
51.0000
<10.0000
8700.0000
2,4-DIMETHYLPHENOL
ACIDS
63.4615
1.9000
19000.0000
2,4-DINITR0T0LUENE
BASE/NEUTRAL
47.4747
<10.0000
18000.0000
2,6-DINITROTOLUENE
BASE/NEUTRAL
50.0000
<10.0000
4750.0000
1,2-DIPHENYLHYDRAZINE
BASE/NEUTRAL
50.0000
<10.0000
<10.0000
ETHYLBENZENE
VOLATILES
79.6610
<10.0000
120000.0000
FLUORANTHENE
BASE/NEUTRAL
57.5472
1.0000
7900.0000
4-CHLOROPHENYLPHENYL ETHER
BASE/NEUTRAL
42.8571
<10.0000
<10.0000
4-BR0M0PHENYLPHENYL ETHER
BASE/NEUTRAL
43.4343
<10.0000
<10.0000
BIS-(2-CHLOROISOPROPYL) ETHER
BASE/NEUTRAL
47.5248
520.0000
9300.0000
BIS-(2-CHLOROETHOXY) METHANE
BASE/NEUTRAL
44.3299
<10.0000
<10.0000
VI-5
-------
TABLE VI-2 (continued)
PERCENT
MINIMUM
MAXIMUM
PRIORITY POLLUTANT
FRACTION
PLANTS
(b)
(b)
DETECTED(a)
(yg/D
(yg/i)
METHYLENE CHLORIDE
VOLATILES
86.6667
1.0000
29000.0000
METHYL CHLORIDE
VOLATILES
52.1277
<10.0000
30.0000
METHYL BROMIDE
VOLATILES
48.3516
<10.0000
1000.0000
BROMOFORM
VOLATILES .
50.0000
<10.0000
120.0000
DICHLOROBROMOMETHANE
VOLATILES
58.6538
0.2000
250.0000
CHLORODIBROMOMETHANE
VOLATILES
49.4949
1.0000
21.0000
HEXACHLOROBUTADIENE
BASE/NEUTRAL
43.4343
<10.0000
170.0000
HEXACHLOROCYCLOPENTADIENE
BASE/NEUTRAL
43.0000
<10.0000
<10.0000
ISOPHORONE
BASE/NEUTRAL
47.4747
<10.0000
650.0000
NAPHTHALENE
BASE/NEUTRAL
64.5455
7.0000
7849.0000
NITROBENZENE
BASE/NEUTRAL
51.4851
5.0000
98000.0000
2-NITROPHENOL
ACIDS
51.9231
2.2000
3B000.0000
4-NITR0PHEN0L
ACIDS
51.4B50
<10.0000
1900.0000
2,4-DINITROPHENOL
ACIDS
46.0784
<10.0000
3900.0000
4,6-DINITR0-0-CRES0L
ACIDS
44.0000
<10.0000
<10.0000
N-NITROSODIMETHYLAMINE
BASE/NEUTRAL
42.3913
<10.0000
<10.0000
N-NITROSODIPHENYLAMINE
BASE/NEUTRAL
50.0000
5.0000
<10.0000
N-NITROSODI-N-PROPYLAMINE
BASE/NEUTRAL
45.360B
<10.0000
<10.0000
PENTACHLOROPHENOL
ACIDS
57.6923
1.0000
6800.0000
PHENOL
ACIDS
94.0299
0.5000
250000.0000
BIS-(2-ETHYLHEXYL) PHTHALATE
BASE/NEUTRAL
86.7769
0.6500
33000.0000
BUTYLBENZYL PHTHALATE
BASE/NEUTRAL
59.2233
<10.0000
<10.0000
DI-N-BUTYL PHTHALATE
. BASE/NEUTRAL
81.1321
3.0000
6300.0000
DI-N-OCTYL PHTHALATE
BASE/NEUTRAL
55.0000
4.3000
94.0000
DIETHYL PHTHALATE
BASE/NEUTRAL
70.2970
1.0000
15000.0000
DIMETHYL PHTHALATE
BASE/NEUTRAL
60.5769
2.0000
1470.0000
BENZO(A)ANTHRACENE
BASE/NEUTRAL
53.5354
0.6100
2400.0000
BENZO(A)PYRENE
BASE/NEUTRAL
51.0204
4.0000
44.0000
3,4-BEN ZOFLUORANTHENE
BASE/NEUTRAL
45.9184
3.0000
34.0000
BENZO(K)FLUORANTHENE
BASE/NEUTRAL
47.4227
6.0000
12.0000
CHRYSENE
BASE/NEUTRAL
55.0000
1.3000
1900.0000
ACENAPHTHYLENE
BASE/NEUTRAL
54.7170
4.6150
22000.0000
ANTHRACENE
BASE/NEUTRAL
64.7059
0.5100
3300.0000
BENZO(GHI)PERYLENE
BASE/NEUTRAL
47.5248
1.0000
12.2000
FLUORENE
BASE/NEUTRAL
60.0000
3.4000
973.0000
PHENANTHRENE
BASE/NEUTRAL
60.5769
2.4000
13000.0000
DIBENZO(A,H)ANTHRACENE
BASE/NEUTRAL
46.4646
<10.0000
16.5714
INDENO(1,2,3-C,D)PYRENE
BASE/NEUTRAL
46.5347
1.0000
12.2000
PYRENE
BASE/NEUTRAL
59.8131
1.0000
6100.0000
TETRACHLOROETHYLENE
VOLATILES
75.7282
1.0000
32000.0000
TOLUENE
VOLATILES
91.0569
<10.0000
160000.0000
TRICHLOROETHYLENE
VOLATILES
71.9626
1.0000
9000.0000
VINYL CHLORIDE
VOLATILES
50.0000
5.0000
31900.0000
PCB-1242 (AROCHLOR 1242)
PESTICIDES
46.465
1.2000
4.0000
VI-6
-------
TABLE VI-2 (concluded)
•
PERCENT
MINIMUM
MAXIMUM
PRIORITY POLLUTANT
FRACTION
PLANTS
(b)
(b)
DETECTED(a)
(vg/i)
(Vg/1)
PCB-1254 (AROCHLOR
1254)
PESTICIDES
48.980
-------
different from those at direct discharging OCPSF plants. In selecting
pollutants to regulate for pretreatment standards, therefore, only those 108
priority pollutants that the Agency considers as candidates for BAT regulation
are addressed. For each OCPSF subcategory (See Section IV), the Agency
evaluated data on removal of these pollutants at POTWs and at Industrial
treatment plants meetlug BAT, to establish which pollutants pass through
POTWs. Pollutants found not to pass through were eliminated from
consideration for regulation under PSES and PSNS. The remaining pollutants
were then selected as candidates for regulation. The procedure used for the
pass-through analysis Is described below.
Pass-Through Analysis
General. . In developing categorical pretreatment standards, EPA evaluated the
percentage of a pollutant removed by POTWs with the percentage removed by
direct dischargers applying BAT. A pollutant Is deemed to pass through the
POTW where tie average percentage removed nationwide by well-operated POTWs
Is less than the percentage removed by direct dischargers with well operated
treatment systems.
For POTW removals, the Agency used the median POTW removal efficiencies from
the 50 POTW Study (see Appendix I). For each pollutant, the median POTW
removal efficiencies were compared to median plant removal efficiencies
derived from Verification and (MA Study plants that achieve either 95" percent
BOD removal or an effluent BOD less than or equal to 50 mg/1. In soma
Instances, the removal of organic pollutants may be understated because of
¦ the location of the Influent sampling point prior to end-of-plpe treatment.
The data excludes, In such cases, reductions due to removals across ln-plant
treatment systems.
In light of the analytical variability associated with organic pollutants at
low concentrations In OCPSF and POTW wastewaters however, and the fact that
EPA had less data In the POTWs studies on organic priority pollutants than
It has for the metals, EPA believes that differences of five percent or less
between the OCPSF and POTW data for organic priority pollutant reduction may
not reflect real differences In treatment efficiency. Therefore, EPA has
determined that pass-through of organic priority pollutants occurs when the
removal Is at least five percentage points greater than the removal at a
POTW. Where adequate 50 POTW Study removal data were not available for a
particular pollutant (see TABLE Vl-4), the pollutant was Included for
regulation under PSES and PSNS.
Database and Methodology. The final BAT database Included 21 direct
dischargers; four of the plants were In the CMA Study and 19 were In the
Verification Study (two plants were In both). Nineteen of the plants employ
biological treatment, while two Verification plants use only physical—chemical
treatment. This OCPSF BAT database Includes removal data for 70 priority
pollutants from Not Plastics-Only plants and for 12 priority pollutants from
Plastics-Only plants.
VI-8
-------
In calculating median removals for the OCPSF plants, influent-effluent data
pairs were deleted if the influent value was less than or equal to 10 ppb.
All remaining effluent values less than 10 ppb were changed to 10 ppb (to
minimize analytical concerns) and only pairs showing positive removals were
used. A level of 10 ppb was considered the level of analytical
detectability. For each plant, mean influent and effluent values were
calculated and the plant removal efficiency was calculated from these two
means. For each pollutant, the plant removals were ordered and the removal
efficiency of the median plant was then determined.
In calculating median removals for the 50 P0TW Study plants, influent-effluent
data pairs were deleted if the influent value was less than or equal to 20
ppb, and only pairs showing positive removals were used. Effluent values less
than 10 ppb or not detected were reported as 10 ppb in the POTW study. The
removals for all daily influent-effluent pairs from all POTWs were ordered and
the median percent removal was determined and compared to the BAT removals.
It should be recognized that the 50 POTW Study database and the OCPSF database
were analyzed in separate efforts which utilized different editing rules for
determining the median percent removals. TABLES VI-3 and VI-4 list the median
percent removals for each pollutant parameter derived in this fashion from the
OCPSF and 50 POTV Study databases for the Plastics-Only and Not Plastics-Only
subcategories, respectively.
Pollutant Parameters Selected
TABLE VI-5 lists the six pollutants in the Plastics-Only subcategory and the
29 pollutants in the Not Plastics-Only subcategory selected as candidates for
regulation under PSES and PSNS on the basis of pass-through. The derivation
of numerical PSES and PSNS limitations for these pollutants is described in
Section XI.
TABLE VI-6 lists by subcategory those pollutants which are not proposed for
regulation on the basis of pass-through, since the preceding analysis
documents that they do riot pass-through POTWS (see Section XI for discussion
of interference). Consideration of the remaining priority pollutants in Table
VI-2 for PSES and PSNS regulation is deferred pending the collection of
additional data.
VI -9
-------
TABLE VI-3
RESULTS OF PRETREATMENT PASS-THROUGH ANALYSIS
PLASTICS-ONLY PLANTS
PERCENT REMOVAL
FRACTION POLLUTANT NAME BAT POTW DIFFERENCE(a)
ACID
Phenol
84.04
97.81
-14
BASE/NEUTRAL
Bis(2-Ethylhexyl) Phthalate
77.88
76.19
+ 2
VOLATILE
Vinyl Chloride
96.48
88.97
+ 8
Ethylbenzene
99.64
95.00
+ 5
Acrolein
99.45
ir
-
Acrylonitrile
99.53
*
-
METALS
Zinc (Total)
98.99
76.04
+25
Cyanide (Total)
81.07
68.61
+ 12
Lead (Total)
67.47
58.59
+ 9
Cadmium (Total)
69.64
90.91
-21
Chromium (Total)
56.24
77.83
-22
Copper (Total)
54.69
85.00
-30
(a) Difference = (BAT Removal) - (POTW Removal)
* Sampling data not available.
VI-10
-------
TABLE VI-4
RESULTS OF PRETREATMENT PASS-THROUGH ANALYSIS
NOT PLASTICS-ONLY PLANTS
FRACTION
POLLUTANT NAME
PERCENT REMOVAL
BAT
POTW DIFFERENCE(a)
ACID
BASE NEUTRAL
2,4-Dichlorophenol
97.
.51
60.
.67
+37
2,4-Dimethylphenol
80,
.32
53.
.27
+27
Phenol
97
.56
97.
,81
-.3
Pentachlorophenol
33
.26
44.
.98
-12
2-Chlorophenol
86
.56
> *
-
2,4-Dinitrophenol
76,
.51
*
-
2-Nitrophenol
98,
.22
it
-
4-Nitrophenol
41,
.68
it
-
2,4,6-Trichlorophenol
55,
.14
it
-
Isophorone
96,
.97
56.
,52
+40
Dimethyl Phthalate
67,
.22
55.
.88
+ 11
Fluoranthene
78,
.53
73.
.02
+ 6
Naphthalene
90,
.49
89.
.66
+ 1
Diethyl Phthalate
87,
.50
88.
.70
- 1
Pyrene
77,
,78
80.
.00
- 2
Anthracene
87,
.52
90.
.43
- 3
Di-n-Butyl Phthalate
84,
.66
89.
.93
- 5
Bis(2-Ethylhexyl) Phthalate
64,
.88
76.
. 19
-11
Acenaphthene
82,
.30
95.
.00
-13
Di-n-Octyl Phthalate
51.
.54
67.
,19
-16
1,2-Dichlorobenzene
74,
.77
93.
.06
-18
1,2,4-Trichlorobenzene
75,
.48
93.
.00
-18
Acenaphthylene
87,
.70
•h
-
B enzo(a)Anthracene
16,
.87
*
-
Bis(2-Chloroisopropy1) Ether
42,
.84
it
-
Benzo(a)Pyrene
43,
.87
it
-
2,4-Dinitrotoluene
88.
.40
*
-
2,6-Dinitrotoluene
93.
.15
*
-
Fluorene
46.
.49
it
-
Nitrobenzene
99,
.84
it
-
Phenanthrene
70,
.09
it
-
VI-11
-------
TABLE VI-4 (concluded)
FRACTION
POLLUTANT NAME
PERCENT REMOVAL
BAT
POTW DIFFERENCE(a)
METAL
VOLATILE
Chromium (Total)
83.
.48
77.
.83
+ 6
Mercury (Total)
66.
.04
60.
.00
+ 6
Cyanide (Total)
67.
,21
68.
,61
- 1
Zinc (Total)
74,
,96
76.
.04
- 1
Arsenic (Total)
31,
,45
38.
.89
- 7
Lead (Total)
48.
,64
58.
.59
-10
Nickel (Total)
24.
,70
45.
,51
-21
Copper (Total)
54.
,95
85.
,00
-30
Antimony (Total)
30.
, 19
66.
.18
-36
Silver (Total)
39.
,58
90.
.00
-50
Cadmium (Total)
16.
,67
90.
.91
-74
Beryllium (Total)
25.
.00
*
-
Selenium (Total)
26.
.31
*
-
Thallium (Total)
12.
,50
*
Methyl Bromide
99.
.00
81.
.82
+17
1,2-Dichloroethane¦
95.
.19
87.
,81
+ 7
1,1-Dichloroethane
91.
,55
86.
.90
+ 5
Ethylbenzene
97.
.58
95.
.00
+ 3
1,1,2,2-Tetrachloroethane
94,
,69
91.
,67
+ 3
Toluene
99.
.68
96.
.55
+ 3
Benzene
99.
,27
97,
.65
+ 2
1,1-Dichloroethylene
86.
66
84.
,41
+ 2
Methylene Chloride
66.
,72
70.
.90
- 4
Dichlorobromomethane
62.
,17
71.
.36
- 9
1,3-Dichloropropylene
84.
,93
99.
.00
-14
1,1,1-Trichloroethane
74.
,47
90,
.91
-16
Chloroform
63.
,95
82.
.73
-19
1,2-Dichloropropane
74.
.59
94.
.30
-20
Methyl Chloride
66.
.67
89
.58
-23
Carbon Tetrachloride
64.
.81
91.
.38
-27
1,2-Trans-Dichloroethylene
53.
,72
94,
.87
-41
Trichloroethylene
49,
,77
95,
.00
-45
Chlorobenzene
50,
.82
98,
.36
-48
Tetrachloroethylene
40.
.78
89,
.80
-49
1,1,2-Trichloroethane
35.
.32
88.
.89
-54
Vinyl Chloride
16.
.67
88.
.97
-72
Acrylonitrile
99,
.81
*
-
Chlorodibromomethane
31.
.70
*
-
Chloroethane
65,
.98
*
-
* Sampling data not available.
(a) Difference = (BAT Removal) - (POTV Removal)-
VI-12
-------
TABLE VI-5
POLLUTANTS SELECTED AS CANDIDATES FOR REGULATION
UNDER PSES AND PSNS
PLASTICS-ONLY
Acrolein
Acrylonitrile
Cyanide
Lead
Vinyl Chloride
Zinc
NOT PLASTICS-ONLY
Acenaphthylene
Acrylonitrile
Benzo(a)Anthracene
Benzo(a)Pyrene
Beryllium
Bis(2-Chloroisopropyl) Ether
Chlorodibromomethane
Chloroethane
2-Chlorophenol
Chromium
1,2-Dichloroethane
2,4-Dichlorophenol
Dimethyl Phthalate
2,4-Dimethylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluoranthene
Fluorene
Isophorone
Mercury
Methyl Bromide
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
Phenanthrene
Selenium
Thallium
2,4,6-Trichlorophenol
VI-13
-------
TABLE VI-6
POLLUTANTS EXCLUDED FROM REGULATION
UNP™ PSES AND PSNS
PLASTICS-ONLY
Bis(2-Ethylhexyl) Phthalate
Cadmium
Chromium
Copper
Ethylbenzene
Phenol
Acenaphthene
Anthracene
Antimony
Arsenic
Benzene
Bis(2-Ethylhexyl) Phthalate
Cadmium
Carbon Tetrachloride
Chlorobenzene
Chloroform
Copper
Cyanide
Di-n-Butyl Phthalate
Di-n-Octyl Phthalate
NOT PLASTICS-ONLY
1,2-Dichlorobenzene
Dichlorobromomethane
1.1-Dichloroethylene
1.2-Trans-Dichloroethylene
1.2-Dichloropropane
1.3-Dichloropropylene
Diethyl Phthalate
Ethylbenzene
Lead
Methyl Chloride
Methylene Chloride
Naphthalene
Nickel
Pentachlorophenol
Phenol
Pyrene
Silver
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
Toluene
1,2,4-Trichlorobenzene
1,1,2-Trichloroethane
1,1,1-Trichloroethane
Trichloroethylene
Vinyl Chloride
Zinc
VI-14
-------
REFERENCES
U.S. ENVIRONMENTAL PROTECTION AGENCY (USEPA). 1979. Water Related
Environmental Fate of 129 Priority Pollutants. Vol. II. Monitoring and Data
Support Division, Office of Water Planning and Standards, Report No.
EPA-440/4-79-0296
VI-15
-------
SECTION VII
POLLUTANT CONTROL AND TREATMENT TECHNOLOGY
INTRODUCTION
A variety of physical, chemical and biological treatment processes are in use
or available for manufacturing plants in the Organic Chemicals and
Plastics/Synthetic Fibers (OCPSF) category to control and treat both the
pollutants of concern in the wastewaters (identified in Section VI) and the
solid residues (sludges) produced by treating the wastewaters. This chapter
identifies and describes in-plant and end-of-pipe control and treatment
technologies that may be applied to OCPSF wastewaters to remove pollutants,
especially the priority toxic pollutants listed in Section VI.
This chapter first discusses in-plant source controls, in-plant treatment
technologies, end-of-pipe treatment and disposal technologies, and sludge
treatment and disposal technologies. The final section summarizes the
applicability and performance of the treatment technologies.
The specific technologies discussed in this chapter have been considered for
application to the industry in general. For a particular manufacturing
facility, however, wastewater monitoring and treatability data are necessary
to select and design the most efficient and cost-effective treatment system.
IN-PLANT SOURCE CONTROLS
In-plant source controls are processes or operations which reduce pollutant
discharges within a plant. Some in-plant controls (e.g., recycle) reduce or
eliminate waste streams, while otherp recover valuable manufacturing
by-products. In-plant controls provide several advantages: income from the
sale of recovered material, reduction of end-of-pipe treatment costs, and
removal of pollutants that upset or inhibit end-of-pipe treatment processes.
While many chemical manufacturing plants were designed to reduce water use and
pollutant generation, improvements can be made in other existing plants to
control pollution from their manufacturing activities (Campbell, 1981 and
Royston, 1980). The major in-plant source controls that are effective in
reducing pollution loads in the OCPSF industries are described in the
following paragraphs.
Process Modification
Some older plants were designed with little regard for conservation of raw
materials or water. As costs have increased and environmental regulations
have become more stringent, some plants have modified their manufacturing
processes. For example, some plants which once used batch processes have gone
to continuous operation, eliminating the wastewaters generated by cleanup with
VII-1
-------
solvents or caustic between batches. Such modifications increase production
yields and reduce wastewater generation.
Instrumentation
Occasional process upsets that discharge products, raw materials, or
by-products are important sources of pollution in the OCPSF industries.
Reaction kettles, for example, occasionally become overpressurized, bursting
the rupture-discs and discharging chemical pollutants. More sophisticated
instrumentation and added operator training can reduce these process upsets.
Alarms connected to pH and flow sensors can detect process upsets early.
Solvent Recovery
The recovery of waste solvents has become a common practice among plants using
solvents in their manufacturing processes. Several plants have instituted
measures to further reduce the amount of waste solvent discharged, including
better solvent recovery columns, incineration of solvents that cannot be
recovered economically, and incineration of bottoms from solvent recovery
units. Recovery is no longer economical when the cost of recovering
additional solvent (less the value of the recovered solvent) is greater than
the cost of treating or disposing of the solvent.
Water Reuse, Recovery, and Recycle
Replacing barometric condensers with surface condensers can reduce hydraulic
or organic loads from condensation. Water-sealed vacuum pumps can be replaced
if they create water pollution problems. Recirculation systems can greatly
reduce the amount' of contaminated water discharged from the pump seals.
In the past, plants often used cooling water once, then discharged it.
Recycling through cooling towers is now a common industrial practice that
dramatically decreases total discharge volume. Stormwater runoff from
manufacturing areas can contain significant quantities of pollutants.
Separation of stormwater from process wastewater has been practiced throughout
the industry and often facilitates the isolation and treatment of contaminated
runoff.
Another source of pollutant generation is contamination of the raw materials
for production. Specific pollutants that are impurities in plant raw
materials can be reduced by ordering purer raw materials from suppliers. Some
highly toxic solvents can be replaced by less toxic substitute solvents.
Prompt repair and replacement of faulty equipment can reduce waste losses. A
good housekeeping and wastewater monitoring program can minimize wastewater
generation. Spills can be cleaned up using dry methods instead of by washing
into floor drains.
Process modifications to enhance wastewater recycle are also used within the
OCPSF industry. Twenty-four facilities in the Summary Database indicated
that, through wastewater recycle, they achieved zero discharge (See Table
V-5).
VII-2
-------
IN-PLANT TREATMENT
In-plant treatment is directed toward removing certain pollutants from
segregated product/process waste streams before these waste streams are
combined with the plant's remaining wastewaters. In-plant technologies,
usually designed to treat toxic or priority pollutants, are often technologies
which could be used for end-of-pipe treatment of the plant's combined waste.
Using these technologies on segregated internal wastestreams is usually more
cost-effective, since treatment of low volume, concentrated and homogenous
waste streams generated by specific product/processes is more efficient.
In-plant treatment, which is frequently employed to protect the plant's
end-of-pipe treatment, may be designed to remove the following types of
pollutants:
• Pollutants toxic or inhibitory to biological
treatment systems.
• Biologically refractive pollutants.
• High concentrations of specific pollutants.
• Pollutants that may offer an economic recovery
potential (e.g., solvent recovery).
• Pollutants that are hazardous if combined with
other chemicals downstream.
• Pollutants generated in"small volumes in remote
areas of the plant.
• Corrosive pollutants that are difficult to
transport.
• Pollutants that would contaminate the waste sludge
from end-of-pipe treatment systems, thereby limiting
disposal options.
Many technologies have proven effective in removing specific pollutants from
the wastewaters produced by manufacturers of organic chemicals and plastics.
The selection of a specific in-plant treatment scheme depends on the nature of
the pollutant to be removed and on engineering and cost considerations.
The most frequently-used or promising in-plant treatment technologies include
activated carbon adsorption, adsorption with ion-exchange resins,
liquid-liquid extraction, steam stripping and various metals removal
processes. Since all of these technologies are also end-of-pipe technologies,
they are discussed under the next section, "End of Pipe Treatment and
Discharge".
VII -3
-------
END-OF PIPE TREATMENT AND DISCHARGE
General
End-of-pipe treatment processes remove pollutants from the manufacturing
plant's combined waste stream before discharge or disposal of the waste
stream. TABLES VII-1A AND VII-1B list the wastewater treatment and disposal
technologies that 561 plants reported using. The 561 plants consist of 326
Summary Database plants (direct dischargers and other or "zero" dischargers)
and 235 indirect dischargers. Table VII-1A lists the technologies used by the
Plastics-Only plants; Table VII-1B lists the technologies used by the
remaining plants, the Not Plastics-Only plants.
In each table, the plants are subdivided into three types of dischargers:
direct dischargers, indirect dischargers, and all other dischargers. Direct
discharge is the release of treated or untreated wastewater to a receiving
water (e.g., stream, river, lake). Indirect discharge is discharge to a
municipal wastewater collection system, which transports the wastewater to a
municipal sewage treatment plant (POTW -- publicly owned treatment works).
The wastewater discharge and disposal methods other than direct or indirect
discharge that are used by the OCPSF plants (sometimes called zero discharge)
are described in section D.6 of this chapter. Processes not shown in one or
both tables were never reported used in one or both categories, respectively.
Since many plants treat more than one separate waste stream, the tables give
both the number of plants and number of separate waste streams reported
treated by each technology.
The treatment technologies considered for application to OCPSF plants are
listed in TABLE VII-2, grouped by physical processes, biological processes,
and physical-chemical processes. The choice of which individual treatment
process or combination of processes to apply to a particular waste stream
depends on the required effluent quality, the treatability of the wastestream,
the space available for treatment facilities, details of the site, and cost
considerations. The next three sections of this chapter include descriptions
of each of the technologies listed in Table VII-2. Design removals of
specific priority pollutants by the individual treatment processes have been
incorporated into the Computer Model (Section VIII).
Physical Treatment Processes
Settling (Clarification, Sedimentation). Settling tanks, clarifiers, and
sedimentation basins are designed to let wastewater flow slowly and
quiescently, permitting solids more dense than water to settle to the bottom
and materials less dense than water (including oil and grease) to float to the
surface. The settling solids form a sludge at the bottom of the tank or
basin; this sludge is usually pumped out continuously or intermittently from
settling tanks and clarifiers or scraped out periodically from drained
sedimentation ponds or basins. Oil and grease and other floating materials
may be skimmed off the surface.
Settling may be used alone or as part of a more complex treatment process. It
is usually the first process applied to wastewaters containing high
concentrations of settleable suspended solids. Sedimentation is the second
VII-4
-------
TABLE VII-1A
WASTEWATER AND SLUDGE TREATMENT AND DISPOSAL TECHNOLOGIES
REPORTED BY PLASTICS-ONLY PLANTS
TECHNOLOGY NUMBER OF USES REPORTED
Direct Indirect
D i scha rqers Oi scharoers AlI Others Total
p* w# p« w* p« w# P* W*~
I. Wastewater Treatment
A. Physical Processes
Sett Iing or CI a r i f i -
cation
31
32
31
34
0
0
62
66
Oi I Separation
15
15
12
12
. 0
0
27
27
Screen i ng
11
12
0
0
0
0
11
12
F i I trat ion( a)
U
14
U
4
0
0
8
8
Ai r Stripping
3
3
3
3
1
1
7
7
Stripping (b)
0
0
3
3
0
0
3
3
D i st iI I at ion
-
-
1
1
-
-
1
1
Flotation (DAF)
2
2
0
0
0
0
2
2
EquaIizat ion
no
140
22
23
1
1
63
64
Grit Removal
-
-
1
1
-
-
1
1
Skimming
5
5
1
1
0
0
6
6
PoIi sh i ng Ponds
17
17
0
0
0
0
17
17
I nc i nera t i on
-
-
6
6
-
-
6
6
Evaporation Tank
0
0
1
1
0
0
1
1
Scrubber
-
-
1
1
-
-
1
1
Decant Water
-
-
1
1
-
-
1
1
Biological Processes
Activated Sludge-
Air
39
39
U
4
0
0
43
43
Activated Sludge-
Oxygen
1
1
-
-
0
0
1
1
Aerated Lagoon
7
7
3
3
0
0
10
10
Stabilization Pond(d)
-
-
1
1
-
-
1
1
Aerobic Lagoon
8
9
-
-
0
0
8
9
Facultative Lagoon
1
1
-
-
0
0
1
1
Trickli ng F iIter
3
3
0
0
0
0
3
3
Rotating Biological
Contactor
U
U
0
0
0
0
4
4
Imhoff Tank
1
1
0
0
0
0
1
1
Secondary Clarifier
48
48
(e)
(e)
0
0
48
48
Nutrient Addition
-
-
1
1
-
-
1
1
*P = Number of Plants; W = Number of Wastestreams; 0 = None reported; - = Not tabulated
VI I -5
-------
TABLE VI I-1A (concluded)
TECHNOLOGY NUMBER OF USES REPORTED
Direct Indirect
Pi scha rqers D i scha raers AlI Others TotaI
P» W» P» W* P* W* P* W»
C. Chemical Processes
Neutra1ization
33
3U
2U
26
-
-
57
60
pH Adjustment
0
0
1
1
0
0
1
1
Prec i p i tat ion(g)
12
12
3
3
2
2
15
15
Chlorination
15
15
1
2
0
0
16
17
Activated Carbon
2
2
0
0
0
0
2
2
Ion Exchange
0
0
1
1
0
0
1
1
Chemical Treatment(n)
-
3
3
~~
3
3
II. Sludge Treatment and
D i sposa1
A. Physical Processes
Thickening (k)
11
11
1
1
0
0
12
12
Thickening (DAF)
3
3
U
U
0
0
7
7
Centri fugat ion
6
6
1
1
0
0
7
7
F i1trat ion (1 )
12
12
-
-
-
-
12
12
Pressure Filtration
-
-
1
1
0
0
1
1
Vacuum F i1trat ion
-
-
2
2
0
0
2
2
B. Biological Processes
Digestion (m)
23
23
-
-
0
0
23
23
C. Disposal
Storage (n)
-
-
1
1
-
-
1
1
Sludge Ponds
1U
1U
0
0
0
0
1U
1U
D. Sludge Handling (n)
-
-
7
7
-
-
7
7
No Treatment
-
-
82
-
-
-
82
-
Total Number of Plants
72
1U8
55
275
Total Number of Wastestreams
77
161
67
305
*P = Number of Plants; W = Number of Wastestreams; 0 = None reported; - = Not tabulated
(a) Specific type (sand, dual media, diatomaceous
(earth) unknown
(b) Specific type (steam or air) unknown.
(c) Apparently to treat incinerator off gas.
(d) Includes oxidation ponds.
(e) Probably included in "Settling or Clarification"
(g) Includes coagulation and flocculation.
(h) Not specified whether ammonia, phosphorus, or both
a re removed.
(j) Method of removal not specified.
(k) Specific method unknown-probably gravity
thickening.
(I) Specific method (pressure, vacuum, belt) unknown.
(m) Type (aerobic, anaerobic) unknown.
(n) Deta iIs unknown.
-------
TABLE VI I-1B
WASTEWATER AND SLUDGE TREATMENT AND DISPOSAL TECHNOLOGIES
REPORTED BY NOT PLASTICS-ONLY PLANTS
TECHNOLOGY NUMBER OF USES REPORTED
Direct Indirect
Pi scharaers Pi scharoers AlI Others TotaI
P* W* P* W* P* W5 P* W*
I. Wastewater Treatment
A. Physical Processes
Settling or Clarifi-
cat ion
66
68
38
39
5
6
109
113
Oil Separation
33
33
15
18
0
0
U8
51
Screening
6
6
0
0
0
0
6
6
F i1trat ion(a)
11
11
-
-
U
U
15
15
Sand F i1trat ion
-
-
1
1
-
-
1
1
Dua 1 Med i a F i 11 ra t i on
-
-
1
1
-
-
1
1
Air Stripping
5
5
U
U
1
1
10
10
Stripping (b)
-
-
u
U
-
-
U
U
D i st i1lat ion
-
-
1
1
-
-
1
1
Flotation (DAF)
6
6
0
0
1
1
7
7
Equa1ization
79
80
23
28
u
6
106
11U
Grit Removal
-
-
3
3
-
-
3
3
Skimming
U
U
0
0
0
0
U
U
Po1Ishing Ponds
27
28
0
0
0
0
27
28
Incineration
-
-
U
U
-
-
U
U
Coo 1i ng Pond
0
0
2
2
0
0
2
2
Scrubber (c)
-
-
1
2
1
2
Decant Water
-
-
1
1
1
1
Biological Processes
Activated Sludge-
Ai r
65
65
10
10
1
1
76
76
Activated Sludge-
Oxygen
7
7
-
-
0
0
7
7
Nutri ficat ion
1
1
-
-
0
0
1
1
Aerated tagoon
20
20
5
5
2
2
27
27
Stabilization Pond(d)
-
-
3
3
-
-
3
3
Aerobic Lagoon
7
7
-
-
2
2
9
9
Anaerobic Lagoon
6
6
0
0
2
2
8
8
Facultative Lagoon
U
U
-
-
1
1
5
5
Trick1i ng Fi1ter
6
6
0
0
0
0
6
6
Rotating Biological
Contactor
0
0
1
1
0
0
1
1
Imhoff Tank
2
2
0
0
0
0
2
2
Secondary Clarifier
87
88
(e)
(e)
2
2
89
90
Nutrient Addition
-
-
2
2
-
-
2
2
*P = Number or Plants; W = Number of Wastestreams; 0 = None reported; - = Not tabulated
-------
TABLE VII-1B (concluded)
TECHNOLOGY
Direct
IndIrect
NUMBER OF USES REPORTED
Discharaers
Oi scharaers
Al I
Others
Tota I
P*
W*
P*
W*
P*
W*
P*
W*
C. Chemical Processes
NeutraIization
78
79
35
37
2
2
115
118
Prec i p i tat ion(g)
10
10
4
4
1
1
15
15
Chlorination
9
9
2
2
1
1
12
12
Activated Carbon
8
8
5
5
-
-
13
13
Chemical Treatment(n)
-
-
1
1
-
-
1
1
Ammon i a/Phosphorus
Removal(h)
-
-
1
1
-
-
1
1
Heavy MetaI
Removal (j)
-
-
2
2
-
-
2
2
Dephenolization
-
-
1
1
-
-
1
1
Hydrolysis
-
-
1
2
-
-
1
2
Organic Extraction
-
-
2
3
-
-
2
3
II. Sludge Treatment and
Di sposaI
A. Physical Processes
Thickening (k)
24
24
1
1
0
0
25
25
Thickening (DAF)
4
4
3
3
0
0
7
7
Centri fugat i on
11
11
1 '
1
0
0
12
12
Fi11ration (I)
19
19
0
0
0
0
19
19
B. Biological Processes
Digestion (m)
28
28
-
-
0
0
28
28
C. Disposal to Ponds
19
19
0
0
1
1
20
20
D. Sludge Handling (n)
-
-
8
8
-
-
8
8
No Treatment
0
26
0
26
Total Number of Plants
125
87
74
286
Total Number of Wastestreams
136
114
95
345
*P = Number of Plants; W = Number of Wastestreams; 0 = None reported; - = Not tabulated
(a) Specific type (sand, dual media, diatomaceous
(earth) unknown
(b) Specific type (steam or air) unknown.
(c) Apparently to treat incinerator off gas.
(d) Includes oxidation ponds.
(e) Probably included in "Settling or Clarification"
(gj Includes coagulation and flocculation.
(h) Not specified whether ammonia, phosphorus, or both
are removed.
(j) Method of removal not specified.
(k) Specific method unknown-probably gravity
thickening.
(I) Specific method (pressure, vacuum, belt) unknown,
(m) Type (aerobic, anaerobic) unknown.
(nj Details unknown.
VI I-8
-------
TABLE VII-2
CANDIDATE WASTEWATER TREATMENT TECHNOLOGIES
A. Physical Processes
Settling (Clarification, Sedimentation)
Oil separation
Filtration
Sand
Mixed media
Gas stripping
Air stripping
Steam stripping
Distillation
Flotation
B. Biological Processes
Suspended growth
Activated sludge
Air
Pure oxygen
Aerated lagoon
Stabilization Ponds
Anaerobic Denitrification
Fixed-film
Trickling filter
Rotating biological contactor
C. Physical-Chemical Processes
Neutralization
Chemical Precipitation (Coagulation and Flocculation)
Chemical oxidation
Adsorption
Activated carbon
Powdered
Granular
Resin
Ion exchange
Solvent (liquid-liquid) extraction
VII-9
-------
stage of most biological treatment processes: it removes the settleable
materials, including microorganisms, from the wastewater; the microorganisms
can then be either recycled to the biological reactor or discharged to the
plant's sludge handling facilities. Clarification is used after most chemical
coagulation-flocculation and pH adjustment processes to remove the inorganic
particles from the wastewater. Polishing ponds, often the final step after
biological treatment, are primarily quiescent settling ponds. The performance
of settling facilities can often be improved by adding polymers to the
wastewater.
Settling (or clarification, or sedimentation) is the end-of pipe treatment
most frequently used by OCPSF industry plants. As shown in Tables VII-1A and
VII-1B, over 300 of the 523 OCPSF plants listing their treatment technologies
reported using it either alone or as part of a biological treatment system.
Oil Separation. Many toxic organic chemicals (typically large non-polar
molecules) tend to concentrate in oils and greases. This oily phase can be
removed from wastewaters through skimming, filtration, or flotation.
Filtration and flotation are described in subsequent sections of this
chapter. Skimming may be applied to settling, clarification and sedimentation
tanks as noted above, or may be performed in separate quiescent basins if the
wastestream contains no settleable material. According to Tables VII-1A and
VII-IB, 75 of the 523 plants reported using skimming.
Filtration. Wastewater is filtered by passing it through a wire mesh screen
(e.g., microstraining) or more commonly through a filter bed composed of
granular materials such as sand and gravel. Suspended solids are removed
through a combination of mechanisms including straining, interception,
impaction, sedimentation, and adsorption. Oil and grease from the wastewater
adhere to the filter media; high influent oil and grease concentrations may
rapidly clog the filter. Filtration is usually the final treatment step when
consistently low effluent suspended solids concentrations are desired.
Mixed media filters hdve multiple layers, typically sand, garnet, and coal.
Membrane filters (used in ultrafiltration and reverse osmosis) have pores
small enough to filter out large and medium-sized organic molecules. Membrane
filters can remove not only suspended particles but also substantial fractions
of dissolved impurities, including organic and inorganic materials. Membrane
systems generally require extensive pretreatment of the wastewater (pH
adjustment, filtration, chemical precipitation, activated carbon adsorption)
to prevent rapid fouling or chemical damage to the membrane.
According to Tables VII-1A and VII-1B, 25 of the 523 plants reported using
some type of filter.
Gas Stripping (Air and Steam). Gas stripping is the removal of volatile
pollutants from wastewater by passing a gas through the wastewater. The
volatile pollutant moves from the water phase into the gas phase to achieve an
equilibrium, and is carried off by the gas. Air may be added to the
wastewater through diffusers on the bottom of the tank, by mechanically
aerating the top layer of the wastewater in a pond, or by cascading the
wastewater down a tower.
VII-10
-------
A frequent municipal wastewater application of gas stripping is stripping
ammonia with air. Many industrial plants use steam rather than air to strip
solvents and other volatile organics from wastewaters, since higher
temperatures shift the water phase-gas phase equilibrium for volatile
compounds towards the gas phase. Before stripping ammonia with air or steam,
the wastewater pH is raised by adding a base (often lime) to shift the water
phase-gas phase ammonia equilibrium towards the gas phase. Although most
commonly employed as an in-plant technology for solvent recovery, steam
stripping is also used for end-of-pipe wastewater treatment. According to
Tables VII-1A and VII-1B, 24 of the 523 plants reported using either air or
steam stripping.
Distillation. Distillation is the separation of the components of a liquid
solution by boiling the liquid and condensing the more volatile components
which predominate in the vapor. It can be used in-plant to recover solvents
from concentrated product/process wastestreams. According to Tables VII-1A
and VII-1B, two of the 523 plants reported using distillation for end-of-pipe
wastewater treatment.
Gas Flotation (Dissolved Air, Air, Vacuum). Particles approximately as dense
as water neither float nor sink quickly enough to be removed in a simple
settling tank equipped with surface skimmers. Gas flotation can be used to
carry such particles to the surface for skimming.
Gas flotation introduces fine gas (usually air) bubbles into the wastewater;
the bubbles attach to particles and carry them to the surface. Since oils and
emulsions tend to concentrate at surfaces, the rising bubbles often carry
oils, greases and emulsions to the surface for removal. Flotation is used in
wastewater treatment primarily to remove suspended matter and to thicken
biological sludges. Bubbles are added to or produced in the wastewater or
sludge using one of the following methods:
(1) Dissolved-air floatation: Injection of air while the liquid is under
pressure, followed by release of the pressure.
(2) Air flotation: Aeration at atmospheric pressure.
(3) Vacuum flotation: Saturation with air at atmospheric pressure,
followed by application of a vacuum to the liquid.
In all of these systems, removal can be enhanced through addition of various
chemicals that facilitate absorption or entrapment of the air bubbles.
According to Tables VII-1A and VII-1B, nine of the 523 plants reported using
dissolved air flotation as part of their treatment systems.
Biological Treatment Processes
Biological treatment systems contact wastewater containing biologically
degradable organic compounds with a mixture of microorganisms, in an
environment containing the nutrients required for the microorganisms to
utilize organic carbon as a food source. The microorganisms are classified as
aerobic, anaerobic, or facultative. Aerobic microorganisms require free
VII-11
-------
dissolved oxygen to biologically oxidize the waste. Anaerobic microorganisms
break down the organic material in the absence of oxygen and are usually
inhibited by free dissolved oxygen. Facultative organisms can function under
aerobic or anaerobic conditions as the oxygen availability dictates. In
practice both aerobic and anaerobic conditions may exist in the same treatment
unit, depending" on degree of aeration, degree of mixing, effects of
photosynthesis, thickness of the biological growth on fixed surfaces, and
other factors which contribute to the supply and distribution of oxygen to the
treatment system.
The BPT Development Document for the OCPSF industries contains detailed
information on the biological treatment of conventional pollutants, especially
biochemical oxygen demand (BOD) and total suspended solids (TSS), at OCPSF
treatment plants. That information is not reproduced in this document.
Although the primary purpose of biological treatment is usually to reduce the
overall oxygen demand of a wastewater, biological treatment can also remove
some specific toxic compounds from wastewater. The major mechanisms for
removal of toxic chemicals are:
• Biodegradation of the chemical into simpler
compounds. Sometimes, however, the chemicals
produced may be more toxic than the chemicals
degraded. Chlorinated compounds are often difficult
to degrade.
• Adsorption of the chemical onto biological solids.
Heavy metals and large hydrophobic organic compounds
are most readily adsorbed. The sludge containing
these toxic solids must be properly treated prior to
disposal.
• Air stripping to the atmosphere of volatile
compounds in those processes, such as activated
sludge, which include aeration. High concentrations
of toxic volatile compounds in the wastewater may
thereby produce air pollution hazards near the
treatment facility.
The toxic compounds frequently present in industrial wastes can inhibit or
upset biological processes. Acclimation can produce strains of organisms
which are tolerant to normally toxic substances. However, once the
specialized strain is established, major changes in wastewater composition or
concentration can kill the acclimated organisms and cause failure of the
treatment process. Reestablishment of a suitable microbial population can
require months.
Biological wastewater treatment processes may be loosely grouped into two
operational categories: "suspended growth," where the microoganisms are
suspended in a mixture with the wastewater, and "fixed film", where the
microorganisms grow on a fixed surface such as the rocks in a trickling
filter. The biological treatment processes considered for application to
OCPSF plants are listed in Table VII-2 and are described individually below.
VII-12
-------
Activated Sludge. Activated sludge is an aerobic suspended growth process
typically requiring two tanks or ponds; it can be run as a batch process in
one vessel. Wastewater flows into the first tank (the biological reactor or
aeration tank) where it mixes with microorganisms and other suspended solids
while being aerated, forming the activated sludge, also called the mixed
liquor. After several hours to several days of aeration, the mixed liquor
flows into the quiescent second tank (the secondary clarifier or settling
tank) where the solids have several hours to settle to the bottom. The
supernatant (relatively solids-free liquid at the top) leaves the tank as the
treated effluent. The concentrated solids (sludge) at the tank bottom thicken
and are drawn out by a sludge pump, which either returns them to the first
tank (as return activated sludge) or discharges them to the plant's sludge
treatment facilities (as waste activated sludge). Major configurations of the
activated sludge process include the following:
(1) Conventional -- The aeration tanks are long and narrow, with plug
flow (i.e., little forward or backwards mixing).
(2) Complete mix -- The aeration tanks are shorter and wider and the
aerators, diffusers, and entry points of the influent and return
sludge are arranged so that the wastewater mixes completely.
(3) Tapered aeration -- A modification of the conventional process in
which the diffusers are arranged to supply more air to the influent
end. of the tank, where the oxygen demand is highest.
(4) Step aeration -- A modification of the conventional process in which
the wastewater is introduced to the aeration tank at several points,
lowering the peak oxygen demand.
(5) Modified aeration -- A modification of conventional or tapered
aeration in which the aeration times are shorter, the pollutants
loadings are higher per unit mass of microorganisms in the tank and
the BOD removals are only 60 to 75 percent.
(6) Pure oxygen -- An activated sludge variation in which pure oxygen
instead of air is added to the aeration tanks, the tanks are covered
and the oxygen-containing off-gas is recycled. Compared to normal
air aeration, pure oxygen aeration requires a smaller aeration tank
volume and treats high-strength wastewaters and widely-fluctuating
organic loadings more effectively. One of the most widely-used
pure-oxygen processes is Union Carbide's UNOX.
(7) Extended aeration -- A variation of complete mix in which low organic
loadings and long aeration times permit more complete wastewater
degradation and partial aerobic digestion of the microorganisms.
(8) Contact stabilization -- An activated sludge modification using two
aeration stages. In the first, wastewater is aerated with the return
sludge in the contact tank for 30 to 90 minutes, allowing finely
suspended colloidal and dissolved organics to absorb to the activated
sludge. The solids are settled out in a clarifier and then aerated
VII-13
-------
in the sludge aeration (stabilization) tank for three to six hours
before flowing into the first aeration tank.
Activated sludge is the most common end-of-pipe biological treatment employed
in the OCPSF industry Summary Database. According to Tables VII-1A and
VII-1B, of the 523 plants, 121 reported using activated sludge, including two
plants which used pure oxygen activated sludge.
Aerated Lagoon. An aerated lagoon is a pond which is kept aerobic and
completely-mixed using either mechanical surface aerators or diffused air
units. After treatment in the aerated lagoon, the wastewater flows into a
settling tank or basin for solids separation. For those systems where the
solids are returned to the aerated lagoon, the biological treatment is
identical to activated sludge. Where the solids are not recycled, the aerated
lagoon is a type of stabilization pond (see below). Where inexpensive land is
available, aerated lagoons are easier and cheaper to construct than activated
sludge aeration tanks.
According to Tables VII-1A and VII-1B, 37 of. the 523 plants reported using
aerated lagoon treatment.
Stabilization Ponds. Stabilization ponds (or stabilization lagoons or
oxidation ponds) are relatively shallow earthen basins where wastewater is
treated without recycle of biological solids (in contrast to activated
sludge). Because they are inexpensive to build and operate, ponds are very
popular in treating domestic wastewater from small communities and are used
extensively for the treatment of industrial wastewater and mixtures of
industrial and domestic wastewater that are amenable to biological treatment.
Ponds can be built and operated in many configurations: with continuous or
intermittent discharge; with mechanical aeration, natural surface reaeration,
or algae photosynthesis; as suspended-, attached- or combination-growth
processes. The two types most often used by OCPSF plants, aerobic lagoons and
anaerobic lagoons, are described below.
(1) Aerobic Lagoons. Aerobic lagoons are ponds usually less than 18
inches deep which are mixed periodically. Oxygen is supplied to the lagoon by
natural surface reaeration and algae photosynthesis. Bacteria breaks down the
wastes and generates carbon dioxide and nutrients (primarily nitrogen and
phosphorus). Algae reproduce in the presence of sunlight using the nutrients
and inorganic carbon to yield the oxygen needed by the aerobic bacteria.
Algae do not settle well using conventional clarification. To achieve
reasonably low effluent suspended solids (algae) concentrations, coagulation,
filtration, and multiple cell settling lagoons are often used.
According to Tables VII-1A and VII-1B, nine OCPSF industry plants reported
using aerobic lagoons.
(2) Anaerobic Lagoons. Anaerobic lagoons are up to 20 feet deep and may
be constructed with steep side walls to minimize wall area and thereby
minimize loss of the heat generated by the anaerobic biological degradation of
the wastewater. A natural organism cover (pellicle) usually forms on the
surface and helps retain heat, suppress odor, and maintain anaerobic
VII-14
-------
conditions. Typically, wastewater enters near the lagoon bottom and is
discharged on the opposite side of the lagoon below the pellicle.
According to Tables VII-1A and VII-1B, eight OCPSF plants reported using
anaerobic lagoons.
Anaerobic Denitrification. Denitrification is the biological conversion of
nitrates to nitrogen, which returns to the atmosphere as a gas. The
biological process requires anaerobic conditions. Denitrification is used
most frequently as a suspended growth process following an activated sludge
system that has converted most forms of nitrogen to nitrates. In this
application, the denitrification treatment system has three major components:
• A complete-mix reaction tank without aeration. A
carbon source such as methanol is usually added to
this tank to support the biological reaction.
• A sedimentation tank where the anaerobic
microorganisms settle out and are either recycled to
the reaction tank or wasted as sludge.
• A flash stripper between the two tanks which strips
the nitrogen gas to the atmosphere.
Anaerobic denitrification can also be performed in a submerged fixed film
reactor.
Trickling Filters. Trickling filters are the traditional fixed-film or
attached-growth wastewater treatment process. Older trickling filters are
circular beds of rock one to three meters deep, over which the wastewater is
intermittently or continuously sprayed through fixed or rotating distribution
arms. Microorganisms (mostly bacteria, fungi, and protozoa) growing on the
rocks degrade organic compounds in the wastewater, producing more
microorganisms and thickening the biomass film on the rock. When this
biological slime become too heavy, it falls (sloughs) off the rocks into the
treated wastewater collecting underneath the trickling filter J The wastewater
is clarified in a sedimentation tank; some plants recycle part of the
clarified effluent or even part of the sludge back into the wastewater applied
to the trickling filter. Trickling filters may be used in series (stages)
with or without settling tanks between them.
Trickling filters may be grouped as low-, intermediate-, high-, and super-rate
filters with increasing organic and hydraulic loading rates. The first three
classes are one to three meters deep. Super-rate (also called roughing)
filters are five to twelve meters deep and made of redwood slats or plastic
media, either of which have much higher surface to volume ratios than rock.
High-rate filters may be either rock or synthetic media; low- and intermediate
rate filters are always rock, slag, or a similar material. Super- and
high-rate installations have high ratios of recycling effluent onto the
filters; low-rate filters have no such recirculation; intermediate-rate
filters have zero or low recirculation ratios.
VII-15
-------
According to Tables VII-1A and VII-1B, nine of the 523 plants reported using
trickling filters.
Rotating Biological Contactors. A rotating biological contactor (RBC)
treatment system consists of multiple parallel rows of horizontal shafts each
of which is an axis for a large number of parallel corrugated plastic disks.
The shafts are mounted on a contour-bottomed tank containing wastewater such
that about forty percent of each disk is submerged. Microorganisms growing on
the disks degrade the organic materials in the wastewater. As wastewater
flows through the tank, the disks rotate slowly, exposing the microorganisms
on the disks alternately to the wastewater and to oxygen in the air. As with
the trickling filter, biomass sloughs off the disks and is separated from the
effluent in a clarifier.
According to Tables VII-1A and VII-1B, five of the 523 OCPSF plants reported
using rotating biological contactors. Four of these plants are
"Plastics-Only" facilities.
Physical-Chemical Treatment Processes
Wastewater treatment processes which rely on chemical reactions are classified
as chemical treatment processes. The chemical treatment processes considered
for application to OCPSF plants are listed in Table VII-2 and described
individually below.
Neutralization. Before discharge to a receiving water and often before
biological or chemical treatment, the pH of a wastewater should be fairly
neutral (pH 6 to pH 9). Neutralization is the addition of chemicals to bring
the wastewater closer to a neutral pH. Alkaline (high pH or basic)
wastewaters may be neutralized with hydrochloric acid, carbon dioxide, sulfur
dioxide, and, most commonly, sulfuric acid. Acidic (low pH) wastewaters may
be neutralized with limestone or lime slurries, soda ash, caustic soda, or
anhydrous ammonia. Acidic and alkaline process wastewaters are used in some
plants for neutralization. The selection of neutralizing agents incorporates
cost, availability, ease of use, reaction by-products, reaction rates, and
quantities of sludge formed.
According to Tables VII-1A and VII-1B, over 170 of the 523 plants reported
using neutralization.
Chemical Precipitation (Coagulation and Flocculation). Chemical coagulants
such as lime, aluminum sulfate (alum), ferrous sulfate (copperas), ferric
sulfate, and ferric chloride are often added to wastewater to alter the
chemical and physical states of suspended solids and dissolved solids such as
heavy metals and thereby facilitate their removal by sedimentation. Many
metals ions form insoluble compounds when hydroxides or sulfides are added to
wastewater at high pH. In some cases the removal is effected by entrapment
within a voluminous precipitate (sweep floe) consisting primarily of the added
coagulant. Chemical addition also increases the concentration of dissolved
constituents in the wastewater.
To achieve maximum pollutant removals, chemical precipitation should be
carried out in four phases: addition of the chemical to the wastewater; rapid
VII-16
-------
(flash) mixing to distribute the chemical homogeneously into the wastewater;
slow stirring (flocculation) to promote particle growth by various coagulation
mechanisms; and clarification (or settling or sedimentation) to remove the
flocculated solid particles. Polymers are sometimes added to promote
flocculation.
According to Tables VII-1A and VII-IB, about 30 of the 523 plants reported
using precipitation.
Chemical Oxidation. Chemical oxidation is the addition of oxidizing agents
such as chlorine, hypochlorite, hydrogen peroxide, potassium permanganate,
ozone, and chlorine dioxide to industrial wastestreams containing cyanides,
sulfides, ammonia, phenols, and other harmful substances. The pollutants may
be completely destroyed (as in the oxidation of cyanide to carbon dioxide and
elemental nitrogen) or chemically changed to less harmful forms (as in the
oxidation of sulfides to sulfates). According to Tables VII-1A and VII-1B,
about 28 of the 523 plants reported using chlorination. In many of these
plants, chlorine was apparently used for disinfection rather than for
oxidation of chemical pollutants.
Activated Carbon Adsorption. As applied to wastewater treatment, adsorption
is the process of concentrating substances dissolved in the wastewater at a
solid surface. The dominant application of adsorption in wastewater treatment
is the use of activated carbon to adsorb dissolved organic materials.
Activated carbon is also often used in water treatment to remove organic
compounds which impart taste, color, and odor. The organic priority
pollutants removed best by activated carbon are large hydrophobic molecules
such as PCBs and pesticides. Granular activated carbon in a fixed bed can
also remove low concentrations of particulate matter; high influent
particulate concentrations will clog the bed rapidly.
Activated carbon is a carbonaceous material, typically wood or charcoal, that
has been chemically and thermally treated to produce a very porous structure
having a large surface area dotted with chemically active sites. Chemicals in
the wastewater migrate into the pores and adsorb (attach) to the surface
through physical and chemical bonds, both weak and strong . When the surface
sites are all occupied by pollutants, the activated carbon must be either
replaced or regenerated. The carbon is regenerated by heating it in a furnace
to oxidize the organic pollutants, making the surface sites available for
adsorption once again.
Activated carbon may be used in two physical forms: granular activated carbon
(GAC) or powdered activated carbon (PAC). GAC is usually placed in a
fixed-bed, expanded-bed, or moving-bed column through which the wastewater is
passed. PAC is usually mixed into the wastewater (often in the activated
sludge aeration tank) and later removed from the wastewater by settling or
filtration.
According to Tables VII-1A and VII-1B, fifteen of the 523 plants reported
using activated carbon.
Ion Exchange. Ion exchange is a unit process by which ions of a given
species are displaced from an insoluble exchange material (resin) by ions of a
VII-17
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different species in solution. It may be operated in either a batch or a
continuous mode. In a batch process, the resin is simply stirred with the
water to be treated in a reactor until the reaction is complete. The spent
resin is removed by settling and subsequently is regenerated and reused. In a
continuous process, the exchange material is placed in a bed or a packed
column, and the water to be treated is passed through it.
Ion exchange is occasionally used to lower drinking water hardness by removing
calcium and magnesium ions. In domestic and industrial wastewaters, ion
exchange resins may be used to remove ammonia, chromium, and heavy metals such
as arsenic and nickel. Ion exchange is frequently used in the metals and
electronics industries to recover precious metals such as gold and silver from
concentrated process wastestreams. According to Tables VII-1A and VII-1B,
only one of the 523 plants reported using ion exchange for end-of-pipe
treatment.
Resin Adsorption. Resin adsorption is analogous to activated carbon
adsorption. The major difference is that the resins are chemically
regenerated (with solvents or acidic or basic solutions), so the compounds
adsorbed are not destroyed as happens in thermal regeneration of activated
carbon. Resin adsorption is often used to recover chemicals from concentrated
process wastestreams. None of the 523 plants reported using resin adsorption
of end-of-pipe treatment.
Solvent (Liquid-Liquid) Extraction. Solvent extraction or liquid-liquid
extraction is the removal of specific components (e.g., organic pollutants)
from a solution (e.g., a product/process effluent) by mixing the solution with
an immiscible liquid (e.g., solvent) in which the specific components are more
soluble than in the original solution. The process requires the following
steps:
• Contact of the solvent with the solution.
• Separation of the solvent from the solution.
• Removal of the solute (the specific components)
from the solvent, usually by distillation or by a
second extraction.
• Further recovery of solvent from the solution,
usually by stripping, distillation, or adsorption.
" Disposal of the solute.
• Discharge of the treated solution.
" Recycle of the solvent.
In OCPSF wastewater treatment, solvent extraction is most often used as an
in-plant treatment to remove hydrophobic organic pollutants from the
segregated wastewaters produced by individual product/processes. Removal of
phenols and related compounds from wastewaters using solvents such as crude
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oil, benzene, and toluene, is a principal application. According to Tables
VII-1A and VII-1B, two of the 523 plants reported using extraction with
organic solvents as an end-of-pipe treatment.
Other ("Zero") Wastewater Discharge or Disposal Methods
Wastewater discharge or disposal methods other than direct and indirect
discharge used by OCPSF plants, frequently called "zero discharge" methods,
are tabulated numerically in TABLE VII-3 for 94 plants and are described in
the following paragraphs.
Incineration. Incineration is the burning of the waste stream in an
incinerator, with or without auxiliary fuel, as dictated by the heat value of
the material being incinerated. Incineration is typically used for the
disposal of flammable liquids, tars, solids, or low volume hazardous waste.
The gaseous combustion products may require scrubbing, particulate removal, or
other treatment to capture materials that cannot be discharged to the
atmosphere. Incineration of an aqueous waste stream greatly reduces the water
content by evaporation, and may produce either a concentrated waste stream
requiring further treatment or simply a solid residue (ash) requiring
disposal.
Evaporation. The purpose of evaporation is to remove water from.wastewater
and thereby concentrate the pollutants, rendering the waste stream more
amenable to disposal or further treatment. Evaporation is normally applied to
wastewaters prior to incineration or landfilling.
Evaporation can be performed in equipment ranging from open solar ponds or
tanks without heating equipment to large, sophisticated, multi-effect
evaporators capable of handling large volumes of liquid. Typically, steam or
some other external heat source is used. The major design concern in
evaporation is supplying the energy required.
Surface Impoundment. Surface impoundments, into which wastewaters are placed
so the volume can decrease by evaporation and percolation, require relatively
large land areas. The liquid discharged to surface impoundments (large
storage ponds or lagoons) eventually evaporates into the atmosphere or
percolates into the soil (becoming groundwater). A net reduction of liquid
requires that temperature, wind, and humidity enable evaporation to outweigh
precipitation. Evaporation may be enhanced by mechanical aeration, spraying
or heating of the liquid.
The rate of percolation depends on the soil composition and structure. Where
infiltration to groundwater is undesirable, impoundment ponds are often lined
with synthetic liners or clay, making the impoundments evaporation ponds.
Wastewater solids accumulate in the impoundments, usually reducing
percolation, and must be removed periodically.
Land Application. Land application of wastewater, such as spray irrigation,
both treats and disposes of the wastewater. The plants, soil, and soil
microorganisms treat the wastewater by physical filtration, biological uptake
and degradation, and physical-chemical surface adsorption and exchange. Since
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TABLE VII-3
OTHER
("ZERO") DISCHARGE
AND DISPOSAL METHODS
NUMBER OF PLACES
TECHNOLOGY
USED
PLASTICS-
-ONLY PLANTS
NOT PLASTICS-ONLY PLANTS
METHOD
Number of
Plants
Number of(a)
Wastestreams
Number of
Plants
Number of(a'
Wastestreams
No Wastewater Reported
12
15
8
20
All Wastewater Recycled
9
10
15
15
Incineration
3
10
4
14
Evaporation
2
2
0
0
Surface Impoundment
3
7
9
11
Land Application
3
3
0
0
Deep Well Injection
2
3
• 5
24
Offsite Treatment
1
1
3
5
Contract Hauling
11
16
_4
_6
TOTAL
46
67
48
95
(a) Includes other ("zero") discharge waste streams at direct discharge plants.
VII-20
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the liquid either evaporates, percolates to groundwater, or runs off to
surface waters, the site should be chosen and maintained to protect ground and
surface waters. Wastewaters containing pollutants that may persist in the
soil for months or years and later be assimilated by the crops should not be
applied to existing or potential farm land.
Deep Well Injection. Deep well injection is wastewater disposal by pumping
under pressure into a well, usually 3,000 to 15,000 feet deep. The wells
should be drilled through impervious caprock layers into underlying porous
strata which have no present or future value such as domestic or agricultural
water supply; brine (high salt concentration) aquifers are often used.
Pretreatment of the waste is normally required to reduce pump and pipe
corrosion and to remove suspended solids which can plug the receiving strata.
Chemical conditioning may be required to prevent reactions between the waste
and the receiving environment.
Because relatively high pressures are required for injection and dispersion of
the waste, pumping costs for deep well disposal may be high.
Because deep well injection may contaminate usable aquifers, some states
prohibit deep well disposal. Contamination of aquifers can occur either from
improperly sealed well casings which allow the waste to flow up the bore hole
or from unknown faults and fissures in the caprock which allow the waste to
escape into the usable strata. This problem could be aggravated by the
increased subterranean pressure created by the injection well, especially if
substantial withdrawals of water from the usable aquifer are made nearby.
Offsite Treatment. Offsite treatment is an arrangement where a plant's
wastewaters are transported by pipe or tank truck to a central treatment
facility owned by and serving several production plants. Typically the plants
involved have developed such an arrangement because it is .more economical than
for each plant to treat its own wastewaters. The capital and operating costs
are usually allocated among the individual plants according to waste flow and
pollutant loading. Depending on the nature of the individual plant's
wastewater and restrictions established by the central treatment plant, wastes
sent offsite for treatment may require pretreatment at the generating plant.
Contract Hauling. Contract hauling is a wastewater disposal method in which
the wastewater generator pays a contract hauler to pick up the wastes at the
generation site and haul them to another site for treatment or disposal. The
hauling may be by truck, rail or barge.
Contract hauling is frequently used on toxic small volume wastes that may
require highly specialized treatment before proper disposal. The
environmental impact is not eliminated but only shifted from the generating
site to another treatment and disposal site.
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SLUDGE TREATMENT AND DISPOSAL
General
The solid residues (sludges) resulting from wastewater treatment are usually
liquids or semisolids, containing 0.25 to 12 percent solids, depending on the
operations and processes used (Metcalf & Eddy, 1979). The cost of treating
and disposing of these sludges is typically about equal to the plant's
wastewater treatment and disposal cost.
Handling sludges from industrial wastewater treatment may be complex, because
(1) the sludge is mostly water, not solid matter, (2) sludge from biological
treatment will decompose and become offensive if not properly treated, and (3)
many toxic pollutants, such as heavy metals and large hydrophobic organic
compounds, tend to concentrate in the biological or physical-chemical solids
in the sludge.
Treatment and Disposal Processes
TABLE VII-4 lists the treatment and disposal technologies most applicable to
industrial wastewater sludges. The typical sludge handling sequence is
thickening using gravity, flotation, or centrifugation; stabilization using
biological, chemical or heat treatment; conditioning to improve dewatering;
dewatering using filtration, centrifugation, bed drying or heat treatment; and
disposal of the concentrated, stabilized sludge cake. Numerous combinations
of the processes listed in Table VII-3 are possible in this sequence.
Frequently, sludges from biological wastewater treatment are thickened through
air flotation, biologically digested, dewatered on drying beds and disposed to
landfills. Sludges from chemical wastewater treatment are often thickened by
gravity or centrifugation, chemically stabilized and conditioned, and
dewatered on centrifuges or belt filters before disposal.
The choice of which treatment and disposal processes to use at a particular
industrial wastewater treatment plant depends on the physical, chemical, and
biological characteristics of the plant sludges, the space available for
sludge handling facilities, and other site-specific engineering considerations
developed in this document. The regulations developed in this document focus
on wastewater treatment Cnot sludge handling) technologies for the OCPSF
industries. Specific sludge handling technologies are closely linked to
specific wastewater treatment processes. The individual sludge treatment and
disposal technologies are not described in detail in this report. A brief
description of each appears with performance assumptions and application
limitations in Appendix J, The Treatment Catalogue.
The physical, chemical, and biological principals underlying sludge handling
are the same as those underlying wastewater treatment. Thorough descriptions
of the sludge treatment and disposal technologies may be found in standard
textbooks such as Metcalf and Eddy (1979).
VII-22
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TABLE VII-4
CANDIDATE SLUDGE TREATMENT
AND DISPOSAL TECHNOLOGIES
FUNCTION
Thicken Stabilize Condition
Dewater
I. TREATMENT PROCESS
A. Physical Processes
Thickening
Gravity x
Flotation x
Centrifugation x x
Filtration
Vacuum x
Pressure x
Belt x
Drying Bed x
B. Biological Processes
Anaerobic Digestion
Aerobic Digestion
Composting
C. Physical-Chemical Processes
Chemical Oxidation
Chemical Conditioning
Elutriation
Heat Treatment (Wet Air Oxidation)
Pyrolysis
Incineration
II. DISPOSAL
Incineration
Ocean Dumping
Landfilling
Land Application
Reuse
x
x
X
X
X
X
X
X
X
VII-23
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WASTEWATER AND SLUDGE TREATMENT TECHNOLOGIES USED TO DEVELOP EFFLUENT
LIMITATIONS COSTS
As explained iir Section VIII, EPA has developed a computer model of OCPSF
wastewater treatment train performance and costs to facilitate selection of
effluent limitations for this industry. The wastewater and sludge treatment
technologies for OCPSF Industries used in the computer model are listed in
TABLE VII-5; these technologies are a subset of the candidate technologies
listed in Tables VII-2 and VII-4. The detailed priority pollutant removal
assumptions, application limitations, and cost estimating algorithms for each
technology listed in Table VII-5 were derived from the technical literature,
engineering experience, and the Agency's OCPSF data-gathering efforts. These
details are presented in Appendix J (Treatment Catalogue) and the Computer
Model Documentation (Appendix K).
The Agency's data-gathering efforts included a major research program
initiated by EPA's Organic Chemicals Branch (OCB) to develop priority
pollutant-specific data necessary to verify, modify, and apply treatment
technology models for the wastewater treatment technologies used in the
computer Model. The research program included: the derivation and
compilation of biological and physical constants data for specific priority
pollutants, an evaluation of methods for predicting the removal of priority
pollutants in single and multi-component waste streams, and an assessment of
the effects of priority pollutants on certain treatment processes.
OCB-sponsored treatability studies were conducted for activated sludge,
activated carbon adsorption, steam stripping, and organic resin adsorption
processes, A discussion of the development of mathematical models for these
technologies and a summary of the OCB-sponsored treatability studies and other
relevant treatability data are presented in Appendix E.
VII-24
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TABLE VII-5
WASTEWATER AND SLUDGE TREATMENT TECHNOLOGIES
USED IN COMPUTER MODEL
I. WASTEWATER TREATMENT
A. Physical Treatment Processes
Settling (Clarification, Sedimentation)
Oil Separation
Dual Media Filtration
Steam Stripping
Conventional
Alkaline Stripping of Ammonia
Dissolved Air Flotation
B. Biological Treatment Processes
Air Activated Sludge
Standard (Oxidation of Carbonaceous Pollutants)
Nitrification
Anaerobic Denitrification
C. Chemical Processes
Neutralization
Chemical Precipitation (Coagulation and Flocculation)
Chemical Oxidation
Ozonation of Cyanide and Phenol
Alkaline Chlorination
Granular Activated Carbon Adsorption
Ion Exchange
Solvent (Liquid-Liquid) Extraction
D. Ancillary Processes
Deep Well Disposal
Equalization
Aeration for Aerobic Biological Treatment
Nutrient Addition for Biological Treatment
Activated Carbon Regeneration
Lime Handling
Cooling Towers
Heat Exchangers
Steam.Injectors
VII-25
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TABLE VII-5 (concluded)
II. SLUDGE TREATMENT AND DISPOSAL
Gravity Thickening
Vacuum Filtration
Pressure Filtration
Aerobic Digestion
Incineration
Landfilling
VII-26
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REFERENCES
CAMPBELL, MONICA E. and GLENN, W.M. Profit from Pollution Prevention - A
Guide to Industrial Waste Reduction and Recycling. Pollution Probe
Foundation, Ontario, Canada. 1981.
ARTHUR D. LITTLE, INC. Physical, Chemical, and Biological Treatment
Techniques for Industrial Wastes, U.S. Environmental Protection Agency
(USEPA) Office of Solid Waste C-78950, November 1976.
METCALF AND EDDY, INC., Wastewater Engineering: Treatment, Disposal Reuse,
McGraw-Hill, New York. 1979.
ROYSTON, MICHAEL G., "Making Pollution Prevention Pay," Harvard Business
Review, November-December 1980, p. 6-27.
VI1-27
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SECTION VIII
EVALUATION OF TREATMENT TECHNOLOGY PERFORMANCE AND COST
INTRODUCTION
Earlier chapters of this report have described EPA's collection of data on
wastewaters discharged by Organic Chemicals and Plastics/Synthetic Fibers
(OCPSF) Industry plants, EPA's selection of which toxic pollutants to regulate
by setting technology-based BAT, NSPS, and Pretreatment effluent limitations,
and the pollutant control and treatment technologies that can be applied to
these wastewaters. To select BAT, NSPS, and Pretreatment limitations for the
OCPSF industries, the Agency evaluated the following:
• The priority pollutant concentrations in
representative OCPSF wastestreams that meet the
proposed BPT limitations on conventional pollutants
(see the BPT Development Document);
• The priority pollutant effluent quality attainable
by applying various treatment trains to the BPT
effluents;
• The construction and operating costs of each such
treatment train; and
• The energy consumption, solid waste generation, air
pollutant emissions, and other non-water quality
environmental impacts of each treatment train.
The numerous product/process combinations employed in OCPSF manufacturing
plants, the diversity of the toxic pollutants found in the industry's
wastewater, and che variety of treatment technologies meriting consideration
convinced the Agency that the most effective approach to evaluating
alternative sets of numerical limitations would be to develop and use a
computer model that could estimate the construction and operating costs of
various combinations of available treatment technologies, and non-water
quality environmental impacts of each set of numerical limitations.
This chapter describes the history and structure of the computer model
developed by EPA to evaluate cost estimations associated with candidate sets
of numerical effluent limitations, explains the use of the computer model
evaluations, and discusses non-water quality environmental considerations.
The Agency's model was used to estimate the costs to the OCPSF industry of the
BAT, NSPS, find Pretreatment limitations proposed in Sections IX, X and XI,
respectively, but not to actually select the numerical limitations. The
procedure for selecting the numerical limitations is explained in each of the
respective chapters.
VIII-1
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DESCRIPTION AND USE OF MODEL
Development of the Model
Catalytic, Inc. had previously developed and used a manual cost estimating
technique in a study prepared for the National Commission on Water Quality
(NCWQ 1975). Under EPA Contract No. 68-01-5011, Catalytic expanded its manual
technique into a computer-assisted wastewater and sludge treatment design and
cost estimation model (the Model) applicable to evaluating the economic
impacts of effluent limitations on the OCPSF industry. The Model incorporated
the following features to facilitate accurate evaluation of costs associated
with alternative OCPSF limitations:
• Data on mean and peak pollutant loadings and flows
for 176 high-priority product/processes.
• Flexible treatment train design procedures for
in-process pollutant controls, pretreatment of
segregated and combined wastestreams, and end-of-pipe
treatment of combined wastestreams.
• Design and cost estimating procedures incorporating
all significant factors associated with OCPSF
treatment unit processes and disposal methods.
• Procedures for estimating cost-effluent
relationships for treatment trains and their
component unit processes.
• Procedures for varying the pollutant effluent
concentration targets which the Model designs
treatment trains to meet.
• Segregation of data and design and cost algorithms
into discrete computer program modules to facilitate
updating, as needed, of the cost and treatability
assumptions in the Model.
During the Model's design and use, the Agency took the following steps to
validate the Model and improve its estimates of treatment cost and effluent
quality: (1) comments from the Chemical Manufacturer's Association (formerly
the Manufacturing Chemists' Association) were periodically solicited and
incorporated into the Model, as appropriate, to ensure that the Model reflects
current industry practice; (2) Agency contractors and staff performed
bench-scale studies to supplement and improve the treatability data in the
Model; (3) the Agency's Science Advisory Board reviewed the Model's
engineering design assumptions and methodology; and (4) costs estimated by the
Model were compared with costs from actual plants.
The comparison of costs generated by the Model with real plant costs revealed
discrepancies in both capital and operating costs. Some of these
discrepancies resulted from differences in accounting practices used by the
participating plants; others resulted from differences between the treatment
VIII-2
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technologies used at the plants and the technologies available in the Model.
For example, one plant operated a UNOX system but the Model can only design an
air activated sludge system. Not surprisingly, the costs reported by the
plant for constructing and operating the UNOX system were higher than those
estimated by the Model for an activated sludge system. The details of this
benchmarking effort are described in the November, 1981, USEPA Contractors
Engineering Report - Analysis of Organic Chemicals and Plastics/Synthetic
Fibers Industry - Toxic Pollutants, Volume I, Section 3.3.2.6 and Appendix
0.) The Agency intends to perform a new benchmarking study to more accurately
assess the validity of the Model's cost estimating abilities.
Model Components and Use
The Model has three distinct components: (1) the permanent files which
contain default values for product/process-specific pollutant loadings,
pollutant-specific treatability factors, and technology-specific cost data;
(2) the 28 treatment technology program modules which model the specific
treatment unit process design, performance, and significant factors affecting
cost; and (3) the control programs that sequence the treatment units, track
changes in wasteload characteristics following treatment or merging of
streams, and estimate the overall cost. Details of each of these three basic
components are discussed in Appendix K. The design assumptions incorporated
into each treatment technology module are stated in Appendix J, the Treatment
Catalogue.
ESTIMATION OF BAT AND PSES COSTS USING THE MODEL
General
The Agency estimated the costs to the entire Organic Chemicals and
Plastics/Synthetic Fibers Industry (OCPSF) of complying with the proposed BAT
and PSES regulations from estimated cos~ts generated by the Model for treating
wastewaters from OCPSF plant configurations. This section describes the model
plant configurations used (Generalized Plant Configurations, or GPCs) and
summarizes how costs were estimated both for treating the wastewater from each
GPC and for compliance by the entire OCPSF industry. The results of these
cost estimates are presented in Section IX for BAT and in Section XI for
PSES.
Description of GPCs
The previous section described the computer model which EPA used to estimate
BAT and PSES compliance costs in the OCPSF industry. The Model's Master
Process File contains wasteload information for 176 priority OCPSF
product/processes. Using these product/processes, EPA created a set of 55
Generalized Plant Configurations (GPCs). Each GPC represents a typical
combination of product/processes found in the OCPSF industry.
The product/processes used in GPCs were those 147 organic chemicals
product/processes and 29 plastic/synthetic fibers product/processes whose
process wastewaters had been analyzed for the presence of priority pollutants
in the Agency's Verification program discussed in Section V. Each GPC is a
VIII-3
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group of organic and plastic product/processes that represents an entire
manufacturing plant or major portions of plants contained in the database
which had been developed from responses to the §308 Questionnaires (see
Section II). The GPCs reflect combinations of product/processes reported by
plants in the database. Each plant's product mix was evaluated to determine
similarities with other plants. The configurations were developed in the
following steps:
1. Development of chemical trees that included all product/processes to
be modeled.
2. Selection of portions of the chemical trees and development of
matrices of plants and products for preliminary evaluation of
similarity.
3. Re-examination of those plants with initial similarity, by comparison
of all product/processes and production levels, and development of a
preliminary GPC.
4. Selection of final configurations after all products and plants were
evaluated and assigned to a configuration.
5. Performance of a mass balance on the average production reported by
plants used in the configuration.
These procedures are discussed in greater detail in the November, 1981 U.S.
EPA Contractors Engineering Report - Analysis of Organic Chemicals and
Plastics/Synthetic Fibers Industries - Toxic Pollutants, pp. 3-280ff.
Descriptions of the individual GPCs are given in Appendix G of this BAT
Development Document.
Use of GPCs to Estimate OCPSF Regulatory Costs
Overview. Appendix K discusses the cost estimating assumptions and unit
costs programmed into the Model. In 1980, the Agency performed Model runs for
the product/process mixes and average daily production levels constituting
each GPC, using stringent sets of effluent target limits for BAT and PSES.
The BAT and PSES limitations proposed in this document (see Sections IX and
XI, respectively) are less stringent than the 1980 targets. To reflect these
less stringent limits, EPA revised the costs that had been calculated in 1980
for each GPC and used these revised GPC costs to first estimate the costs at
individual OCPSF plants and then to estimate compliance costs for the OCPSF
industrial category. This section discusses each of those steps.
1980 GPC Runs. In the summer of 1980, the Agency estimated the costs for
compliance by each of the 55 GPCs with the BPT, BCT, BAT, and NSPS limitations
then being considered. The Model was run using an option which allows the
user to specify the major treatment processes to be included in the treatment
train. The Model then designs the complete treatment train (including
ancillary wastewater treatment processes and sludge handling), estimates
treatment costs and calculates the effluent quality produced by the train and
any ancillary unit processes needed.
VIII-4
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The first step in evaluating BAT technology for each GPC was to generate BPT
priority pollutant effluent concentrations produced by a biological treatment
train adequate to meet effluent target levels of 30 mg/1 each of BOD and TSS.
Additional in-process control requirements and treatment of individual
product/process waste streams were then added for those GPCs where BPT
effluent priority pollutant concentrations exceeded ten times the
concentration listed in the Multi-Media Environmental Goals (USEPA, 1977).
The multiplier of ten reflected an assumed effluent dilution of ten to one,
since the multi-media goals are receiving water, not effluent,
concentrations. Where these target concentrations did not appear achievable
using the Model, they were raised to 50 ug/1. The costs associated with
these BAT treatment and control requirements were then estimated. The
treatment unit processes specified by the Agency's contractor in these BAT
runs depended on the GPC product/processes, and generally included some
combination of chemical precipitation, steam stripping, ion exchange, solvent
extraction, and activated carbon adsorption. Necessary ancillary units were
inserted by the Model.
Revisions to 1980 GPC Runs. In many cases, the target concentrations used in
1980 were more stringent than the BAT and PSES effluent limitations and
standards now being proposed. The 1980 treatment systems, therefore, were
designed for greater removal of toxic pollutants and cost more than necessary
to meet the present proposed limitations. The 1980 treatment systems were
revised to reflect the new proposed BAT limitations and adapted to the
proposed PSES limitations, as described in this section.
The final proposed limitations were not yet available when these cost
revisions were made. The revised effluent targets used are slightly more
stringent than the 30-day limitations now being proposed. The revised targets
were 25 ppb for acid-extractable organics, 60 ppb for base/neutral-extractable
organics, 50 ppb for volatile organics, and 75 ppb for heavy metals. These
targets apply to each individual pollutant in a group, not to the sum of the
concentrations of each pollutant in the group.
Each GPC was examined to see what, if any, treatment would be required to meet
the targets proposed for both BAT and PSES. For the BAT regulation, the
concentration of each pollutant proposed for BAT regulation that was found in
the 1980 run BPT system effluent was compared to the new target concentration
to determine if further treatment would be required. The effluent heavy metal
concentrations from biological treatment systems calculated in the 1980 runs
were reduced by 18 to 69 percent for individual metals to reflect removals
which the 1980 runs had not calculated. For the PSES regulation, the
concentration of each priority pollutant proposed for PSES regulation that was
found in the 1980 run raw waste stream of each GPC was compared with the new
target concentration. Treatment was required whenever the GPC pollutant
concentrations exceeded one or more of the new targets.
If additional treatment was found necessary, the 1980 treatment systems were
modified until the revised targets were met. Since the pollutants proposed
for regulation under BAT and PSES differ (see Sections IX and XI), the systems
VIII-5
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selected for some individual GPCs differ for the two regulations. The
following guidelines were followed in adjusting the 1980 treatment trains:
• No unit sizes were changed and no units were
added. The time available did not suffice for
performing the necessary engineering evaluations.
• Treatment units treating only pollutants no longer
exceeding the revised targets after BPT were
removed.
• Vhenever pollutants met the target concentrations
through the dilution that occurred when multiple
waste streams were combined before discharge,
treatment units that only treated segregated streams
were deleted.
• Since the metals target concentrations were
normally met by coagulation/flocculation, ion
exchange units following coagulation/flocculation
units were removed except where several metals were
present in excessive concentrations.
• Final filters, second stage activated sludge, and
other "polishing" units were removed if the Agency
judged that the remaining units alone would meet the
targets.
• Downstream units were removed when upstream
concentrations met the new targets.
• In some cases, units had been included erroneously
or were shown by influent and effluent concentrations
of the unit to be ineffective in removing pollutants
that exceeded the new targets. Those units were
removed.
• Many of the units in the treatment trains, such as
clarifiers and dual media filters, had only protected
subsequent units. Such units were removed whenever
the units they had protected were removed.
The total capital cost for each GPC was the sum of two components: the capital
costs directly associated with each treatment unit and the miscellaneous
capital costs. These miscellaneous capital costs reflected the number of and
sizing of total treatment units in the train and the power requirements of
each unit. From a regression of miscellaneous capital costs on those total
capital costs that are directly associated with all the treatment units for
the 1980 BAT treatment systems, miscellaneous capital costs were estimated as
0.237 times the total directly associated capital cost, plus $85,000 (Third
Quarter, 1977) .
VII1-6
-------
TABLE VIII-1 lists the BAT and PSES treatment costs that were produced by
modifying 4s described above the treatment costs for each GPC that had been
generated in the 1980 runs. For each GPC, Table VIII-1 lists the production,
wastewater flow, capital and annual costs for both the BAT and PSES treatment
systems, and the technologies used by the Model for BAT and PSES treatment.
The annual cost is the sum of 0&M costs and the amortized capital cost. The
treatment technology abbreviations are explained in the footnotes to the
Table.
Estimating Compliance Costs for Each Establishment. As noted above, the 55
GPCs for which compliance costs had been estimated incorporated 176 major
OCPSF manufacturing product/processes. The manufacturing plants
(establishments) in OCPSF fall into three groups: plants having only
product/processes that are included in the 176, plants having some
product/processes included in the 176 and some not included, and plants with
no product/processes included in the 176. For both BAT and PSES, the total
compliance cost for all product/processes was estimated at each plant
(establishment) by aggregating and, where necessary, extrapolating the
compliance costs estimated for the individual GPCs, as described next.
For most establishments, total product/process wastewater flow was known from
either 308 Questionnaires or NPDES discharge permits. Where the flow for the
whole establishment or some of its product/processes was not known, flow was
estimated from the Agency's equations relating wastewater flow to sales
volume. These equations that had been developed from sales data and 308
Questionnaire flow data for 261 establishments.
For each establishment With known total wastewater flow and some or all
manufacturing product/processes outside the 176 product/processes covered by
the GPCs, the portion of the total wastewater flow attributable to
product/processes outside the 176 was calculated using:
(Total Flow) = (Flow Covered by GPCs) + (Flow Not Covered by GPCs),
where the first and second terms are known.
The compliance costs at each establishment for the flow not covered by the 176
product/processes in the GPCs were then estimated from the Agency's equations
relating compliance cost to wastewater flow. These equations had been
developed from cost and flow estimates calculated for the 55 GPCs. The total
compliance cost at each establishment was then:
(Total Cost) = (Cost for Flow Covered by GPCs) +
(Cost for Flow Not Covered by GPCs)
Estimating Compliance Costs for the Whole OCPSF Industry. The estimated
costs for the whole OCPSF industry to comply with the proposed regulations
were then calculated by summing the individual establishment costs estimated
above for all direct dischargers for BAT and for all indirect dischargers for
PSES. The total number of establishments for this estimate was 1479; 566 were
directs, 913 were indirects. About 19 percent of the wastewater flow at these
indirect dischargers was disposed as an "other" discharge (neither direct nor
VIII-7
-------
TABLE VI I 1-1
REVISED BAT AND PSES TREATMENT COSTS FOR EACH GPC
1
I BAT TREATMENT
PSES TREATMENT
I
TECHNOLOGY BASIS
1
1
1 GPC
1 1?
1
1 Model GPC
I Product ion
1(1000 Lbs/
I Day)
ICapftal Cost
I ($1000;
1 1977 $)
I
1 Annual Cost
1 ($1000/yr;
1 1977 $)
1
Capital Cost
($1000;
1977 $)
|0 8c M Cost
1 ($1000;
I 1977 $)
I
I Mode I
I Flow
I (MGD)
I
BAT
1
1
(Direct) 1
1
PSES ( Indi rect)
1
1 500
1
1
I 3700
1 947
1
1 315
I
I
4721
I 908
i
I 0.400
I
CNF,
CNF
1
CLR, STR, |
1
1
NEU,
ASL,
GRS,
AER,
DAF,
CLR,
EQU,
DMF.,
NUT
SHS
1
1 501
1
1
I 7700
1 1291
I
I 2095
I
I
6422
I 1261
I 1.412
I
I
CNF,
1
STR 1
1
1
NEU,
ASL,
GRS,
AER,
DAF,
CLR,
EQU,
SHS
NUT,
1
1 502
1
1
1
I 13140
I 1368
I
I 810
1
1
1
16958
I 4009
I
I 2.404
I
I
I
CNF
1
1
1
1
DMF,
NUT,
CNF
DPW,
ASL,
EQU.
aer;
NUT,
CLR,
OSP,
SHS,
1
1 503
1
1
1 7785
1 1854
1
1 3674
1
1
23900
I 4166
I
I 12.040
I
STR,
SPS I
1
1
GRS,
NUT,
DAF,
ASL,
DMF,
AER,
EQU,
CLR,
NEU,
SHS
1
1 504
1
1
I
1 4315
1 1296
1
1 421
1
1
1
2849
1 890
I 0.154
I
I
I
OSP,
CLR,
1
DMF, CNF, 1
STR 1
1
1
NEU,
ASL,
SHS
GRS,
AER,
DAF,
CLR,
EQU,
DMF,
NUT,
CON
1
1 505
1
1
1 4125
1 389
1
1 115
I
I
5134
1 1198
I
I 0.909
I
I
CNF
1
1
1
1
NEU,
CLR,
EQU,
SHS
NUT,
ASL,
AER,
1
1 506
1
1
1 14365
1 656
I
I 130
1
1
I
18888
I 5222
I
I 6.183
1
1
CNF
1
1
1
1
DMF,
NUT,
CNF
DPW,
ASL,
STR,
AER,
EQU,
CLR,
NEU,
SHS,
1 507
1
1
1
1 815
1 4487
1
1 1060
1
1
3505
I 823
1 0.289
1
1
I
EQU,
ASL,
DMF,
NEU, NUT, |
AER, CLR, I
SHS, 1 EX |
EQU,
CLR,
NEU,
DMF,
NUT,
SHS
ASL,
AER,
1
1 508
1
I 3140
1 12001
1 4557
1
10540
I 4318
1
1 5.099
ACR,
1 EX I
1
AGR
1
1 509
1
I 4050
1 689
1
1 161
I
674
I 202
1 0.071
1
STR,
1
1 EX |
1
GRS,
DAF,
STR
-------
TABLE VI I 1-1 (continued)
i
vo
I BAT TREATMENT
PSES TREATMENT
I
I
TECHNOLOGY BASIS
GPC
ft
I Model GPC
I Product ion
I (1000 Lbs/
1 Day)
iCapita I Cost
I ($1000;
I 1977 $)
I
1 Annual Cost
1 ($1000/yr;
1 1977 $)
I
Capital Cost
($1000;
1977 $)
I
|0 & M Cost
I ($1000;
1 1977 $)
I
I Model
I FI ow
I (MGD)
I
I
l
I
I BAT
I
I
I
I
(Direct) I
I
PSES (Ind i rect)
510
1 3850
1 1599
i
1 315
603
1 148
1
I
I 0.934
I
I
I I EX,
!
I
DMF |
CLR,
DMF,
STR*
511
1 150
1 1456
I 963
I
I
I
I
2940
1
1 1545
I
I
I
I
I
I 0.051
1
1
1
1
I
I CNF,
I SPS,
I
I
I
CLR, STR, I
DMF I
I
I
I
EQU,
CLR,
SHS,
DMF
NEU,
ASL,
CNF,
NUT,
AER,
CLR,
ASL,
CLR,
STR,
AER,
DMF,
SPS,
512
1 5150
I 2487
I
I 3103
5501
I
I 3796
I
1
1 1.748
I
I CNF,
I
I
CLR, STR |
CNF,
CLR,
STR,
I EX,
SHS
513
I 1925
I 637
I 233
I
I
3347
I
I 945
I
I
1 0.597
1
1
I
I STR
I
I
I
I
STR,
NUT,
EQU,
CLR,
NEU,
SHS
ASL,
AER,
514
I 375
I 0
I
I 0
I
1121
I
I 294
I
I
1
1 0.050
1
1
I
I
I
I
I
I
I
Equ,
DMF
NEU,
ASL,
AER,
CLR,
515
I 1000
I 0
I 0
I
431
I
I 120
I
1
1 0.077
1
I
I
I
I
I
STR
516
1 375
I 588
I
I 191
1
1
3477
I
I 971
1
1
1
1
I 0.144
I
I
I
I I EX,
I
I
I
I
DMF, I EX |
I
I
I
OSP,
ASL,
CLR,
DMF,
AER,
SHS
NEU,
CLR,
EQU,
ASL,
NUT,
AER,
517
1 900
I 4534
1 4565
1
4534
1
1 4565
I
I 1.881
I
I STR,
I
I
ACR, SHS |
I
STR,
ACR,
SHS
518
1 1985
I 1054
1
1 215
I
I
I
26982
1 13259
I
I
I
1 9.401
I
I
I -
I CNF,
I
I
I
CNF |
I
I
I
CNF,
ASL,
CLR,
CNF,
AER,
SHS
EQU,
CLR,
NEU,
ASL,
NUT,
AER,
519
I 225
1 0
I
I 0
I
0
I
I 0
I
I 0.051
I
I
I
I
I
520
I 95
1 300
I
I 92
I
I
3659
I
I 951
I
I
I
I 0.427
I
I
I CNF
I
I
I
I
I
I
EQU,
CLR,
NEU,
SHS
NUT,
ASL,
AER,
-------
TABLE VI I 1-1 (continued)
1
1 BAT TREATMENT
1 PSES TREATMENT
1
TECHNOLOGY BASIS
1 GPC
1 *
I Model GPC
| Product ion
I(1000 Lbs/
1 Day)
1
jcapital Cost
1 ($1000;
1 1977 $)
I
jAnnua I Cost
I ($1000/yr;
1 1977 $)
1 Capital Cost
1 ($1000;
1 1977 $)
1
|0 & M Cost
1 ($1000;
1 1977 $)
1
I Mode 1
1 Flow
1 (MGO)
1 BAT
1
1
1
(Direct) 1
1
PSES (Indirect)
1 521
1
1 975
1
1
I
I 2774
I
I
1 456
1
1 2774
1
1 457
1 2.471
1
1
1 STR,
1 1 EX
1
CNF, CLR, I
1
STR,
CNF,
CLR,
1 EX,
1 EX |
I 522
1
1 175
1
1
I
I 1067
1
1 211
1
1 3003
1
1
1 808
1
1 0.239
1
1
1 DMF,
1 EX |
1
1
EQU,
CLR,
NEU,
SHS
NUT,
ASL,
AER, |
I 523
1
1 1375
I
I
1 26
1
1
1 80
1
1 2728
1
1 806
1
1 0.193
1
1
1 CNF
1
1
1
1
EQU,
CLR,
NEU,
SHS,
NUT,
CNF
ASL,
AER, |
I 524
I
I 1800
I
I
1
1 984
1
1
1 775
1 6094
1
1 1587
1 0.819
1
1 STR
1
1
1
1
EQU,
CLR,
NEU,
SHS
NUT,
ASL,
AER, |
I 525
I
I 2880
I
I
1
1 62
1
1 51
1 3443
1
1 889
1 0.671
1
1
1 CNF
1
1
1
1
EQU,
CLR,
NEU,
SHS
NUT,
ASL,
AER, I
I 526
I
I 3690
I
I
I
1 0
1
1
1
1 0
1 26424
1
1
1
1 7490
1
1 3.923
1
1
1
1
1
1
1
1
EQU,
ASL,
CLR,
NEU,
AER,
SHS
CNF,
CLR,
DMF,
ASL,
NUT, |
AER, |
I 527
I
I 4750
I
I
1
1 326
1
I
I 94
1
1 11491
1
1 2630
1
1 4.068
1
1
1 CNF
1
1
1
1
EQU,
CLR,
NEU,
DMF,
NUT,
SHS
ASL,
AER, |
I 528
I
I 975
I
1
1 0
1 0
1 0
1
1 0
1
1 4.281
1
1
1
I 529
I
I 3550
I
I
1 1576
I
I
I
1 171
1
1 14333
1
1
1 4505
1 1.926
1
1
1
I 1 EX
1
1
1
1
1
OZO,
NUT,
AER,
OZO,
ASL,
CLR,
CNF,
AER,
SHS
EQU,
CLR,
NEU, |
ASL, |
I 530
I 50
I
I 957
I
1 265
1 957
I
1 265
1
1 0.090
1
1 CLR,
1
OMF, STR I
1
CLR,
OMF,
STR
I 531
I 100
1
1
I
I 405
I
I
1 168
1
1 845
1
1
1 233
1
1 0.162
1
1
1 asl,
I CLR
1
AER, NUT I
1
1
CLR,
DMF,
STR
-------
TABLE VI I 1-1 (continued)
1
1
1 BAT TREATMENT
PSES TREATMENT
1
1 TECHNOLOGY
BAS1S 1
1
1
1 GPC
1 K
1 Model GPC
I Product ion
1 (1000 Lbs/
1 Day)
jcapital Cost
1 ($1000;
I 1977 $)
1
I Annual Cost
1 ($1000/yr;
1 1977 $)
I
Capital Cost
($1000;
1977 $)
I
|0 & M Cost
I ($1000;
1 1977 $)
1
1
I Model
I Flow
I (MGD)
1
1 1
1 1
1 1
I BAT (Direct) I
PSES ( Indirect) I
1 532
1
1 190
1
1 958
1
1
1 320
1
1049
1
1 338
1
1 0.550
I CLR, DMF, STR |
I I
CLR, DMF, STR I
1
1 533
1
1
1 210
1
1
1 0
1
1
1 0
1
0
1 0
1 0.315
I
1 1
1 1
I 1
1
1 534
1
1
1
1
1
1 300
1
1
1
1
1
1 5660
1
1
1
1
1
1 1201
I
I
I
1061
1 219
1
1
1
1
1
1 0.664
1
1
1
1
i 1
I NTR, DNT, STR, |
I SHS, DMF, CLR, |
I AER, SHS, CLR, I
1 CLR I
CLR, DMF, STR I
1
1 535
1
1
1 15
1
1
1 0
I 0
1349
1
1 562
1
1
1 0.003
1
1 1
1 1
CLR, ASL, CNF |
1
1 536
1
1
1
1 150
1
1
1 524
1
I 195
1
3888
1
1 1079
1
1
1
1 0.102
I
I
1 1
1 CNF |
1 1
EQU, NEU, CLR, NUT, ASL,|
AER, CLR, DMF, SHS |
1
1 537
I
1
1 60
1 329
1
1 138
I
0
1
1 0
j
I
I 0.054
I
1 CNF |
1 1
1
1 538
1
1 350
1
1
1 0
1
I
I 0
I
0
1
1 0
1
I
I 1.286
1 1
1 1
1
1 539
1
1
1 440
1
1
1
1 3342
1
1
I
I 1020
1
I
I
5773
1
1 1761
1
1
1 0.151
1
1
I ACR I
1 1
1 1
EQU, NEU, CLR, DMF, NUT,I
ASL, AER, CLR, ACR, SHS I
1 540
1
1 350
1
1
1 0
1
1 0
I
I 0
1
1 0
1
1
1 0.059
I
1 1
1 1
1 541
1
1
1
1 520
1
1
1 577
1
1
1 185
I
I 0
I
I
1
1 0
1
1
1
1 0.054
1
1
I CNF, CLR, DMF, |
1 STR |
1
1 542
1
1
1
1
1 480
1
1
1
1
1 0
1
1
1
I 0
I
I
I
I
I 14777
I
I
I
1
1 3655
1 •
1
1
1
1 2.214
1
1
1
1 1
1 1
1 1
1 1
EQU, NEU, CLR, NUT, ASL,I
AER, CLR, ASL, AER, CLR,I
DMF, SHS |
-------
TABLE VI I 1-1 (concluded)
1 BAT TREATMENT
PSES TREATMENT
1
TECHNOLOGY BASIS
I GPC
1 H
I Model GPC
| Product ion
|(1000 Lbs/
1 Day)
jCapital Cost
1 ($1000;
1 1977 $)
1
IAnnual Cost
1 ( $1000/y r;
1 1977 $)
1
Capital Cost
($1000;
1977 $)
1
10 & M Cost
1 ($1000;
I 1977 $)
1
1
1 Model
1 Flow
1 (MOD)
1
1 BAT
1
1
1
(Direct) 1
PSES (Indirect)
1 543
1 85
1 527
1
1 131
1
0
1
1 0
1
1
1 0.112
I
1 STR,
DMF I
1
1 544
1 1320
1 2009
1
1 6317
1
1
14292
1
1 9868
1
1
i
I 3.264
I
1 STR,
1
SPS I
1
EQU, NEU,
CLR, SHS,
NUT, ASL,
STR
AER, |
1 545
1 955
1 2970
1
1 325
1
1
17739
1
1 5475
1
1
I 4.642
I
I
1 dmf.
1 EX |
1
1
NEU, EQU,
AER, NUT,
CNF, CLR,
CLR, SHS
ASL, I
1 546
1 950
1 156
1
1 82
I
0
1
1 0
1
I
I 0.106
1 CNF
1
1
1
1 547
I 240
1 0
i
1 0
1
0
1
1 0
1
1 0.153
1
1
1 548
1 320
1 414
1
1 159
1
0
1
1 0
1
I 0.458
I
1 1 EX
1
1
1 549
1 150
1 379
1
1 80
1
0
1 •
1 0
1
I
I 0.073
I
1 STR
1
1
1
1 550
1 450
1 1026
1
1 524
1712
1
1 465
I
I 1.500
1
1 STR,
1
CNF |
CNF, DMF,
SHS
1 551
1 70
1 0
1 0
1
1
1
2861
1 1769
1
1
1
1
1 0.052
1
1
1
1
1
1
1
DMF, SPS,
NUT, ASL,
SHS
CHX, EQU,
AER, CLR,
NEU, I
CON, 1
1 552
1 330
1 447
1
1 169
1
608
1
1 144
1
1
1
1 0.276
1
1 asl,
1 NUT
1
AER, CLR, I
1
1
DMF, STR
1 553
1 320
1 0
1 0
1
0
1
1 0
1
1 0.876
1
1
1
1
1 554
1 210
1 0
1
1 0
1
0
1
1 0
1
1
1 1.442
1
1
1
1
-------
FOOTNOTES FOR TABLE VIII-1
TREATMENT PROCESS ABBREVIATIONS
EQU Equalization
NEU Neutralization
OSP Oil Separation
DAF Dissolved Air Flotation
CNF Coagulation and Flocculation
CLR Clarification
DMF Dual Media Filtration
ASL Activated Sludge
AER Aeration
NUT Nutrient Addition
NTR Nitrification
DNT Denitrification
0Z0 Ozonation
ACA Activated Carbon Adsorption
ACR Activated Carbon Regeneration
IEX Ion Exchange
SHS Sludge Handling Systems
Thickening
Aerobic Digestion
Vacuum Filtration
Landfill
Incineration
SPS Special Systems
Ammonia Stripping
Distillation or Evaporation
Incineration
Solvent Extraction
Cooling/Heat Exchange
STR Steam Stripping
GRS Gravity Separation
DPW Deep Well
CON Contract Haul
CHX Chemical Oxidation
VIII-13
-------
indirect). The estimated costs for treating this portion of the flow were
deleted from the PSES compliance costs.
The resulting estimated costs are presented in Section IX for BAT and Section
XI for PSES. A capital recovery factor of 0.22 was used to amortize capital
costs to annual costs. The total annual costs are the sum of the annual
operating and maintenance cost and the amortized capital cost. The costs
given are in first quarter 1982 dollars. The details of the entire cost
estimating procedure are presented in EPA's Economic Analysis of Proposed
Effluent Standards and Limitations for the Organic Chemicals and Plastics,
Synthetics, and Fibers Industry, EPA 440/2-83-004, which accompanies the
proposed OCPSF regulations.
EVALUATION OF NON-WATER QUALITY CONSIDERATIONS
General
The elimination or reduction of water pollution may aggravate other
environmental problems. Sections 504(b) and 306 of the Clean Water Act
require the Agency to consider the non-water quality environmental impacts of
these proposed regulations. In compliance with these provisions, the Agency
has considered the effect of this regulation on energy consumption, air
pollution, solid waste generation, and noise generation. There is no precise
methodology for balancing changes in water pollution, air pollution, energy
consumption, and noise and solid waste generation. The methods used to
evaluate the non-water quality impacts of the proposed regulations are
discussed below. Conclusions from the evaluations of the non-water quality
impacts of the proposed BAT, NSPS, and Pretreatment limitations are presented
in Sections IX, X, and XI, respectively.
Energy Consumption
The Organic Chemicals and Plastics/Synthetic Fibers (OCPSF) Industries use
large amounts of energy in manufacturing processes. Industrial organic
chemicals, SIC 2869, was the third largest energy-consuming industry by SIC
code in 1980, using 1,005.9 trillion BTUs. For 1980, OCPSF energy consumption
data are presented in TABLE VIII-2. The OCPSF Industries consumed a total of
1,529.3 trillion BTUs in 1980.
The Agency has not completed a formal analysis of the impacts on energy
consumption resulting from implementation of the proposed effluent
limitations, but will before promulgating the final regulations. The Agency's
preliminary assessment of the impact of each of the proposed limitations on
energy consumption is presented in Sections IX, X, and XI.
Air Pollution
Some treatment processes that OCPSF plants may use to meet the proposed BAT
limitations can release air pollutants to the atmosphere as discussed below.
Certain treatment processes in which vapor condensation and collection is
difficult or impractical may release volatile materials. If improperly
VIII-14
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TABLE VI I 1-2
1980 ENERGY CONSUMPTION IN THE ORGANIC CHEMICALS '
AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES
INDUSTRY ELECTRIC ENERGY PURCHASED TOTAL PURCHASED FUELS
Purchased
Net (b)
FUELS
(a)
AND ELECTRIC
ENERGY
BY
SIC CODE
Quant i ty
(mi 11 ion
kWh)
Cost
(mi 11 ion
do 11 a rs)
Generated
Quant i ty
(tr111 ion
BTUs)
Cost
(mill ion
dollars)
Quant i ty
(trill ion
BTUs)
Cost
(mi 11 ion
dolla rs)
Organic Chemicals
2865
2869
Tota 1
5,391.7
25,581.9
30,973.6
161.0
773.2
934.2
78.4
5,263.0
5,341.4
133.7
918.6
1,052.3
394.0
1,765.5
2,159.5
152.1
.1,005.9
1,158.0
555.0
2,538.7
3,093.7
Plast ics/Synthet ic
F ibers
2821
2823
2824
Tota 1
11,885.3
492.9
7,141.5
19,519.7
378.8
14. 1
210.0
602.9
272.5
1,008.4
524.4
1,805.3
146.8
54.9
103.0
304.7
389.0
84.8
247. 5
721.3
187.3
56.6
127.4
371.3
767.9
98.9
457.5
1,324.3
TOTAL
50,193.3
1,537.1
7,146.7
1,357.0
2,880.8
1,529.3
4,418.0
SOURCE: Bureau of the Census 1982
(a) Purchased fuels include fuel oil (distillate and residual); bituminous
coai. lignite, and anthracite; natural gas; and liquified petroleum
gases.
(b) Electric energy generated by the establishment minus the quantity sold or
transferred to other establishments.
One Kwh = 3413 BTU
-------
designed and maintained, landfills used for the disposal of solids, and of
skimnable material can also emit volatile compounds. Because air emissions
depend on the nature and concentration of the volatile components, weather
conditions at the treatment or disposal site, and the specific treatment
technologies, air pollution emissions for the entire industry can only be
estimated qualitatively.
Incineration of concentrated organic waste streams and sludges may release
particulates, hydrocarbons, and other noxious gases to the atmosphere. Air
emissions from incineration can be minimized by accurately controlling
combustion time and temperature and by the installation of scrubbers.
Scrubbers reduce the release of air pollutants by capturing gaseous combustion
products. Incineration of sludges containing heavy metals often emits
volatilized heavy metals.
The Agency recently evaluated the potential for generation of air pollution
from water pollution control practices for the chlorinated organic solvents
industry, a segment of the Organic Chemicals Industry (USEPA 1981). This
evaluation was part of the Toxics Integration Project's attempt to develop
cost-effective strategies for multi-media toxic pollutant control. One of the
conclusions was that air emissions from water pollution control equipment and
from surface waters can be a major source of toxic air pollution and can
create a health risk because many of the pollutants generated by this industry
segment are highly volatile. The analysis also revealed that in some cases
the addition of certain water pollution control equipment may increase
emissions of volatile pollutants and increase slightly the health risk
generated near these production plants. However, the installation and proper
operation of other technologies, such as steam stripping, can eliminate this
source of air pollution and cost-effectively reduce risk. The report cautions
that the results for the chlorinated organic solvents industry should not be
generalized to the entire Organic Chemicals Industry, since solvents plants
typically produce and handle greater amounts of volatile chemicals than other
segments of the Organic Chemicals Industry.
Solid and Hazardous Waste Generation
Solid Waste. TABLE VIII-3 presents Bureau of the Census data on 1980 solid
waste generation and disposal in the OCPSF Industries. OCPSF plants disposed
of approximately 5.75 million short tons of solid waste in 1980. Included in
this figure is the solid waste generated by water pollution abatement
facilities. Water pollution abatement solid wastes include sludges and
residues from both biological treatment (e.g., waste activated sludge) and
physical-chemical treatment ^e.g., lime precipitate). The Census survey did
not differentiate between dry and wet weight when the data was gathered.
The Agency has considered the effect of the proposed regulations on the
generation of solid waste, including hazardous waste as defined under Section
3001 of the Resource Conserration and Recovery Act (RCRA). A formal analysis
of solid waste generation his not yet been completed. The Agency's
preliminary assessment of the impact of each proposed limitation on solid
waste generation is presented in Sections IX, X, and XI.
VIII-16
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TABLE VIII-3
1980 SOLID WASTE GENERATION AND DISPOSAL IN THE
ORGANIC CHEMICALS AND PLASTICS/SYNTHETIC FIBERS INDUSTRIES (a)
INDUSTRY
QUANTITY
CAPITAL
OPERATING
COST
BY
REMOVED(b)
COST
COST
RECOVERED (c)
SIC CODE
(Thousands of
(Millions of
(Millions of
(Millions of
short tons)
dollars
dollars)
dollars)
Organic Chemicals
2865
596.1
NR(d)
24.0
0.8
2869
3,148.6
46.6
118.6
10.1
Total
3,744.7
-
142.6
10.9
Plastics/Synthetic
Fibers
2821
1,040.3
7.1
32.2
4.7
2823
199.7
NR
NR
-
2824
763.0
NR
NR
-
Total
2,003.0
NR
NR
-
TOTAL
5,747.7
-
-
-
SOURCE: Bureau of the Census 1981
(a) Solid waste includes garbage, trash, sewage sludge, dredged spoil,
incinerator residue, wrecked or discarded equipment, biological and
chemical wastes, radioactive and other toxic materials, and solid waste
produced as a result of air and water pollution abatement.
(b) Defined as waste properly disposed of in 1980.
(c) Estimate of (1) the value of materials or energy reclaimed through
abatement activities that were reused in production, and (2) revenue that
was obtained from the sale of materials or energy reclaimed through
abatement activities.
(d) NR: Data withheld to avoid disclosing operations of individual companies.
One short ton = 2000 pounds.
VI11-17
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Hazardous Wastes. Many of the materials identified in the waste streams of
OCPSF plants are "hazardous wastes" as defined by EPA regulations (40 CFR Part
261) promulgated under the authority of the Resource Conservation and Recovery
Act (RCRA) of 1976 (42 USC Section 6901 et seq.). The storage, transport,
treatment, and disposal of hazardous wastes are regulated under RCRA standards
(40 CFR Parts 122 and 262 to 267), Since many heavy metals and high molecular
weight organic compounds tend to adsorb to biological and chemical solids,
wastewater treatment sludges would be expected to contain many of the
hazardous wastes found in the untreated OCPSF wastewaters. RCRA regulations,
therefore, may effect the disposal of solid wastes generated as a result of
BAT limitations.
OCPSF hazardous waste generators that transport hazardous wastes for offsite
treatment, storage, or disposal, or that contract for removal and disposal of
hazardous wastes, are subject to the provisions of 40 CFR 262. Transportation
regulations include standards for preparation of a manifest before
transporting the waste offsite, packaging and labeling, and record-keeping and
reporting. The receiver of the wastes is responsible for meeting treatment,
storage, and disposal requirements.
OCPSF plant operators that transport their hazardous wastes are subject to
compliance with the manifest system and record-keeping provisions of the
regulation (40 CFR Part 263).
OCPSF generators that treat, store, or dispose of hazardous wastes onsite
(including end-of-pipe systems, deepwells, incineration followed by scrubbing,
evaporation ponds, and land disposal) must comply with the standards for
owners and operators of hazardous waste treatment, storage, and disposal
facilities set forth in 40 CFR 264, 265, and 266, and must obtain a permit as
required in 40 CFR 122.
Noise Generation
The Organic Chemicals and Plastics/Synthetic Fibers Industries have not been
identified by EPA as being significant sources of noise pollution.
VIII-18
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REFERENCES
BUREAU OF THE CENSUS. 1981, Pollution Abatement Costs and Expenditures,
1980, MA-200(80)-1. U.S. Department of Commerce. U.S. Government Printing
Office, Washington, D.C.
BUREAU OF THE CENSUS. 1982. 1980 Annual Survey of Manufacturers, Fuels and
Electric Energy Consumed, Industry Groups and Industries, M80(AS)-4.1. U.S.
Department of Commerce. U.S. Government Printing Office, Washington, D.C.
CATALYTIC, INC. 1980. Computerized Wastewater Treatment Model. Technical
Documentation. Prepared for the U.S. Environmental Protection Agency.
NATIONAL COMMISSION ON WATER QUALITY (NCWQ). 1975. Staff Draft
Report—National Commission on Water Quality Report to Congress, Washington,
D.C.
U.S. ENVIRONMENTAL PROTECTION AGENCY (USEPA). 1981. An Industry Approach for
the Regulation of Toxic Pollutants. Prepared for Toxics Integration Project.
Prepared by Putnam, Hayes, and Bartlett, Inc., Cambridge, Massachusetts.
U.S. ENVIRONMENTAL PROTECTION AGENCY (USEPA). Multi-Media Environmental Goals
for Environmental Assessment, Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina, 1977.
VIII-19
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SECTION IX
EFFLUENT QUALITY ATTAINABLE THROUGH THE
APPLICATION OF THE BEST AVAILABLE TECHNOLOGY
ECONOMICALLY ACHIEVABLE
INTRODUCTION
Under Section 301(b)(2)(A) of the Clean Water Act, EPA must develop, and
existing dischargers in the Organic Chemicals and Plastics/Synthetic Fibers
Industries subsequently must comply with, effluent limitations which require
application of the best available technology economically achievable (BAT).
According to Section 304(b)(2)(B) of the Clean Water Act, all of the following
factors must be considered in developing BAT:
¦ The age of equipment and facilities involved.
¦ The production processes employed.
• The engineering aspects of the application of
various types of pollution control techniques.
• Process changes.
• The cost of achieving effluent waste load reductions.
• Non-water quality environmental impacts (including
energy requirements).
In regulations addressing the development of BAT, the following legal
principles apply:
• In contrast to BPT, BAT does not reflect an average
of the best performances within an industrial
category, but reflects the best control and treatment
technology within the industrial subcategory.
• BAT limitations may reflect product/process changes
and plant management and operation practices that
help reduce pollutant discharges.
• Where existing treatment practices in an industry
are inadequate, if a technology has been shown
effective on similar wastewaters in another industry,
such technology may be "transferred" to and
identified as BAT technology for the industry being
addressed.
• Best available technology may be the highest degree
of control technology that has been achieved or has
IX-1
-------
been demonstrated for plant scale operation up to and
including "no discharge" of pollutants.
This section discusses the Agency's development of BAT effluent limitations
for the Organic Chemicals and Plastics/Synthetic Fibers Industries. After
explaining the type of effluent limitations chosen, this section describes the
BAT limitation development procedure, presents the proposed limitations, and
summarizes the estimated wasteload reduction benefits and the costs of these
limitations.
LIMITATION TYPE
General
Effluent limitations may be specified as mass limitations, separate
concentration and flow limitations, or simple concentration limitations. BAT
limitations may be set not only for the priority pollutants, but also for
toxic non-priority pollutants and nonconventional pollutants. As noted in
Section VI, the Agency is not proposing limitations on'toxic non-priority
pollutants and nonconventional pollutants. This section discusses the
Agency's rationale for choosing to set concentration-based limitations.
Mass Limitations
EPA prefers setting mass limitations, where feasible, since mass limitations
encourage flow reduction and prevent the substitution of dilution for
treatment. Mass can be limited directly by mass limitations (e.g., pounds per
day) or indirectly by simultaneous limitations on the discharge flow rat&
(e.g., millions of gallons per day, mgd) and concentration (e.g., milligrams
per liter, mg/£), since flow rate times concentration equals mass discharge
rate.
In industries such as the iron and steel industry, where the processes used to
manufacture a specific product at a specific plant do not change significantly
from one day of production to the next and where most plants use the same or
similar processes for manufacturing a specific product, setting national
limitations on the mass of pollutants discharged per unit (e.g., pound) of
product manufactured is an efficient way to regulate the discharge of
pollutants by the industry. As explained in earlier sections of this report,
however, the processes used in the Organic Chemicals and Plastics/Synthetic
Fibers Industries to manufacture a specific product may differ significantly
both between different plants on the same day and at the same plant on
different days. To set a discharge limit on the mass of pollutant discharged
per unit of product manufactured in each OCPSF plant's discharge permit, the
Agency would need information on the types and quantities of pollutants
created by each of the processes used to manufacture each product, and the
permit writer would need to know not only what days the plant manufactures
each product, but also how long the plant uses each of the several processes
available for manufacturing that product. From its experience in gathering
product/process wasteload information and in writing and enforcing permits,
the Agency recognizes that gathering all the necessary information would be a
monumental task. For this reason, the Agency has concluded that setting
IX-2
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limitations on the mass of pollutant discharged per unit of product
manufactured for the OCPSF industries is infeasible.
Concentration Limitations
The OCPSF raw wastewater data collection studies described in Section V
yielded much information on the ranges of each pollutant generally found in
product/process effluents and in combined waste streams before end-of-pipe
treatment. Most of the end-of-pipe control technologies described in Section
VII do not reduce the influent concentration by a fixed percentage, but are
controlled by pollutant concentration gradients and therefore yield a similar
effluent concentration over a wide range of influent concentrations under
standard, cost-effective design criteria. For example, a good activated
sludge plant will usually discharge 20 to 40 mg/fc of BOD whether the
influent BOD concentration is 100 mg/fc or 500 mg/l, if the plant is well
designed and the design loadings are not exceeded. Similarly, activated
carbon adsorption of an organic pollutant will usually produce a fairly
constant effluent concentration over a wide range of influent concentrations
as long as the contact time is adequate and the carbon capacity has not been
exhausted.
From its OCPSF data collection studies, EPA knows the typical product/process
raw waste stream concentration range for each pollutant to be regulated.
Since the treated wastewater concentration produced by the sequence of first
treating the individual product/process waste streams and then treating the
combined waste streams at an end-of-pipe treatment facility is relatively
uniform over most of these ranges, the Agency can specify an achievable
effluent concentration reflecting the performance of the treatment technology
over this range of product/process waste stream concentrations. Limitations
for all the pollutants that have been regulated in a subcategory will be
written into the permit of each plant in that subcategory. Knowing the
plant's total process wastewater flow, the writer of the NPDES permit for the
plant can impose on the plant both the Agency's effluent concentration
limitation for each pollutant and a total process wastewater flow limitation.
Even without knowing either the specific product/process wasteload
characteristics or the temporal variations in the plant's product/process mix,
the writer can thereby set a plant mass discharge limitation (e.g., pounds per
day) for each regulated pollutant. Monitoring requirements at each specific
OCPSF plant will only address those pollutants that are likely to be detected
at the individual plant.
BAT SELECTION
General
As discussed in Section III, each plant in the Organic Chemicals and
Plastics/Synthetic Fibers industrial categories uses a variable array of
product/processes to produce not only a unique and varying mix of products but
also a unique raw wastewater containing varying concentrations of different
toxic pollutants. Water use varies among product/processes at each plant and
among plants for each product/process. Two manufacturers producing the same
product via the same process sometimes discharge equal flows per unit of
IX-3
-------
production, but often one plant will have as much as 30 times the flow per
unit of.production as another plant (R. Roegner, 1982). Similar variations
between plants have been found in the masses and concentrations of individual
toxic pollutants discharged from the same product/processes, since different
plants practice different degrees of water conservation and recycling.
As noted in Section VII, the predominant end-of-pipe wastewater treatment
technologies employed by the industry are equalization, neutralization,
sedimentation, and biological treatment, preceded by a variety of in-plant
controls (e.g., reuse of individual product/process waste streams) and
physical/chemical treatment (e.g., steam stripping, carbon adsorption, and
chemical precipitation) of specific product/process wastestreams. The extent
of waste stream reuse or waste product recovery ahead of biological treatment
depends on plant operating economics, including the specific product/processes
used at the plant and their raw waste loads. At many OCPSF plants, prior to
waste stream coiningling and final treatment at the end-of-pipe biological
system, specific waste streams or groups of waste streams are treated to
protect the biological system from toxic pollutants which could inhibit or
upset the biological treatment processes. Many plants practice in-plant
treatment simply to reduce environmental discharges of toxic pollutants. Over
one-third of the plants also have treatment after the biological system (e.g.,
polishing ponds and filtration) to further reduce discharges of solids.
As noted in Section VI, virtually all of the priority pollutants are detected
consistently in Che untreated combined wastewaters of the OCPSF industries.
Even after well-operated biological treatment (as defined by 95% BOD removal
or greater or BOD effluent concentration of less than or equal to 50 mg/£),
the waste stream concentrations of many priority pollutants are significant
and treatable at many OCPSF plants.
The subsections below describe the Agency's approach to developing BAT
limitations for this industry and present the limitations selected.
Alternative Approaches to Developing BAT Limitations
General. Since significantly different combinations and concentrations of
priority pollutants are found at different OCPSF manufacturing plants,, no
single BAT pollutant control and treatment technology is adequate to address
this entire industry; BAT is plant-specific. As noted above, some of the
controls or technologies used at OCPSF plants to reduce waste stream
concentrations of priority pollutants are installed specifically to reduce
priority pollutant discharges; others are installed to protect biological
treatment systems from toxic chemical interference and thereby facilitate
compliance with discharge limitations on conventional pollutants (e.g., BPT
limitations). For this industry, therefore, it is inappropriate to classify
any particular technology as a "priority pollutant control" technology for
protecting biological systems or as a "BAT technology" for reducing priority
pollutant discharges, since the reason for using the particular technology may
differ at different OCPSF plants.
Each plant controlling priority pollutant discharges may employ different
combinations of controls and treatment technologies (and, in some instances,
dilution) to achieve the desired reduction of pollutant mass or
IX-4
-------
concentration. The development of BAT limitations on a given pollutant,
therefore, must reflect effluent qualities attainable using reasonable
combinations of appropriate controls and technologies at different plants,
rather than all the applications of a particular control technology at all
plants.
Computer Modal Evaluation of GPCs. One method for developing
technology-based BAT effluent limitations is to set several alternate sets of
target effluent concentrations, identify plant-specific technologies (for
either all existing plants, a representative sample of existing plants, or a
representative group of hypothetical plants) that can achieve these effluent
concentrations, and estimate the costs and economic impacts to the entire
industry of achieving each set of levels. The Agency has used a computer
model (described in Section VIII) to perform this comparison for 55
hypothetical plants, known as "generalized plant configurations" or GPCs. The
model uses information collected on 176 product/processes in the 37 plant
Verification program to simulate pollutant loadings and to calculate
investment and operating costs for the GPCs. EPA conservatively estimated
compliance costs for real plants from these results. The Model's generalized
design parameters do not always allow specification of the lowest-cost system
capable of achieving a given set of effluent concentrations. The Model has
not yet been adequately validated for use in developing effluent limitations.
EPA is further evaluating this Model for use in determining the performance of
treatment technologies.
Performance of Existing Plants. The Agency has decided that the best way to
develop the proposed BAT effluent limitations for this industry with the
available data is to specify effluent concentrations that reflect the
performance of the existing well-designed and well-operated OCPSF treatment
plants in the Agency's database. The details of this development are
presented in the next section.
Derivation of Limitations
Overview. The Agency calculated numerical effluent concentration limitations
by statistically analyzing the priority pollutant concentrations in the
effluents from the treatment plants that it had classified as well-designed
and well-operated in its OCPSF database. EPA reviewed the wastewater analysis
procedures used for each data point and deleted all questionable effluent data
(see Appendix C). For each of the priority pollutants, the valid effluent
data from each of the well-designed and well-operated plants were then
tabulated and the in-plant and end-of-pipe treatment systems used at each
plant were noted. The Agency then dropped the data from those plants where,
in EPA's judgment, the treatment train did not represent best available
treatment for the priority pollutant being addressed. The data from the
remaining plants were evaluated statistically to yield daily maximum and
four-day average effluent concentration limitations. Each of these steps are
described below. The details of the review of analytical data are given in
Appendix C; the details of the statistical development of the limitations are
given in Appendix F.
Revised and Final BAT Databases. The development of the final BAT database
is displayed in FIGURE IX-1 and explained below.
IX-5
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FIGURE IX-1
DEVELOPMENT OF FINAL BAT DATABASE
Final BAT Database
(Twenty-one Plants)
Revised BAT Database
(Thirty-one Plants)
Effluent Data from
Verification and CMA
Sampling Programs
Review of Analytical
Methods - Questionable
Data Here Deleted
Only Plants Having Both
Influent and Effluent
End-of-Pipe Treatment System
Data Were Retained
Only Plants That Removed
at Least 95 Percent
of BOD or Achieved
Effluent BOD of 50 ppm or
Less Were Retained
IX-6
-------
As described in Section V, the complete OCPSF database consists of the data
gathered in the Screening Phase I, Screening Phase II, Verification, and CMA
Five-Plant studies described in Section V. As described in Appendix C,
because of the analytical methodologies used and the protocols followed, the
precision and accuracy of the data from the two Screening phases are
appropriate only for qualitative application. These data were used in Section
IV for the subcategorization analysis and in Section VI to indicate the
frequency of occurrence of individual priority pollutants in OCPSF
wastestreams. Because more stringent analytical methods and quality
assurance/quality control (QA/QC) procedures had been employed in the
Verification and CMA studies, data from these studies were used to develop
numerical BAT effluent limitations. The Verification and CMA study methods
and data were reviewed as explained in Appendix C; organic priority pollutant
data from plants and samples where improper methods had been employed were
deleted. This editing deleted all of the organic priority pollutant data for
six of the Verification plants; heavy metals data from these plants was not
deleted.
After the data editing had been performed, Verification plants that did not
have data for both influent to and effluent from the end-of-pipe treatment
system were deleted. This removed a total of nine plants from the BAT
Verification database for the following reasons: three indirect dischargers
had no effluent data; one indirect discharger had no influent data; one direct
discharger had no end-of-pipe treatment plant influent data; one indirect
discharger had no end-of-pipe treatment plant influent data; and three plants
were neither direct nor indirect dischargers. The product of this step was
the Agency's revised BAT database.
EPA's revised BAT database consists of three days of data from each of 26
Verification plants and six to 25 days of data from each of five plants
sampled in the CMA Five-Plant Sampling Program. Two plants were sampled in
both studies, so the revised database included 31 plants. These plants differ
in product/process, mix, pollutants discharged, and the combination of process
controls and wastewater technologies used to control priority pollutants.
EPA used the data from only the well-designed and well-operated plants in this
revised database in calculating the proposed BAT limitations. As explained in
the OCPSF BPT Development Document accompanying this BAT document, the Agency
defined well-designed and well-operated OCPSF treatment plants as those that
removed an average of at least 95 percent of the influent BOD or achieved an
average effluent BOD concentration of 50 mg/fc. This final BAT database
included 21 plants, all direct dischargers. Nineteen of the plants employ
biological treatment, while two (both Verification, Not Plastics-Only plants)
employ only physical-chemical treatment. Four of the plants are in the CMA
study -- CMA Plant Number 2 was deleted because none of the effluent values
exceeded 10 ppb, making the estimation of variability impossible. Nineteen
plants are in the Verification study and two are in both. All four of the CMA
plants are in the proposed Not Plastics-Only category; the only plants in the
Plastics-Only category are three of the Verification plants. Only heavy
metals data (no organic priority pollutant data) was used from two of the
plants sampled only during Verification -- one Plastics-Only plant with
biological treatment and one Not Plastics-Only plant with only
physical-chemical treatment.
IX-7
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For each pollutant, the limitations were calculated using only the data from
those final BAT database plants that use technologies appropriate to BAT for
the pollutant.
As explained subsequently, long-term median effluent concentrations for
individual pollutants were calculated from data from all 21 plants in this
final BAT database. For organic priority pollutants, data from only the four
CMA study plants were used to analyze effluent variability and calculate
variability factors which were then used to calculate the four-day average and
daily maximum limitations. Data for calculating variability factors for
cyanide came from one CMA plant. Since the CMA study only addressed organic
priority pollutants, data for calculating variability factors for heavy metals
were taken from six well-operated plants in the BPT Daily Data file. (See the
BPT Development Document for details on the BPT Daily Data file.)
The Verification study employed primarily GC analysis, with GC-MS
confirmation. In accordance with EPA's finding discussed in Appendix C, all
6C/CD data were deleted from the CMA database because of the disparities with
GC/MS results, the impossibility of determining which GC/CD data points were
valid, and the failure to use the interference elimination options which had
been employed in Verification Phase GC/CD methods; only GC/MS results were
used. Data for pentachlorophenol and 2,4,6-trichlorophenol at CMA plant 4
were excluded from the BAT limitation calculations, since this plant did not
employ an appropriate treatment technology (such as solvent extraction) to
remove these pollutants; the treatment of these pollutants at this plant was
therefore judged inadequate for BAT. Data for the following pollutants at CMA
plant 5 were deleted because the overall average percent removals were
negative: chloroform, methylene chloride, and dibenzo(a,h)anthracene.
Pollutants Addressed. The priority pollutants for which the Agency attempted
to develop BAT effluent limitations are listed in Table VI-2. As explained
below, EPA was unable to develop limitations for some of these pollutants
because of data deficiencies.
Limitation Calculations. TABLES IX-1 and IX-2 present the influent and
effluent long-term concentration values for Not Plastics-Only and
Plastics-Only plants, respectively, for those pollutants analyzed for and
detected at the 21 final BAT database plants. Limitations are proposed for
all the pollutants listed in Tables IX-1 and IX-2, except for the following:
• Pollutants for which a pollutant class variability
factor (explained below) was not available--e.g.,
nitrobenzene, bis(2-chloroisopropyl)ether,
anthracene, and acrylonitrile.
• Pollutants for which adequate performance data for
technologies known to be effective were not
available--e.g., nickel, selenium, chlorobenzene,
thallium, and silver.
• Zinc, which was not regulated in the Plastics-Only
subcategory because the Agency obtained zinc
concentration data only from rayon manufacturers.
IX-8
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TABLE IX-1
FINAL BAT DATABASE —
SUMMARY STATISTICS
X
i
o
FOR NOT
PLASTICS-ONLY
PLANTS
POLLUTANT CODE
NUMBER
CONCENTRATION
ACID
OF
Influent
Effluent
Influent
Effluent
EXTRACTABLES
Name
PLANTS
Mean
Mean
Median
Median
65
Phenol
5
999.556
14.051
299.000
13.500
34
2,4-Dimethylphenol
4
234.343
18.847
105.700
16.000
31
2 ,4-Dicholorophenol
I
560.000
34.250
560.000
34.250
21
2 ,4,6-Tricholorophenol
1
59.315
31.389
59.315
31.389
64
Pentachlorophenol
I
17.125
15.938
17.125
15.938
24
2-Chlorophenol
1
78.000
10.375
78.000
10.375
57
2-Nitrophenol
1
114.500
28.500
114.500
28.500
58
4-Nitrophenol
I
772.200
141.600
772.200
141.600
59
2,4-Dinitrophenol
I
126.571
41.500
126.571
41.500
BASE/NEUTRAL
EXTRACTABLES
66
Bis-(2-Ethylhexyl) Phthalate
2
3239.0
56.97
3239.0
56.97
68
Di-N-Butyl Phthalate
3
905.5
94.31
245.1
50.00
70
Diethyl Phthalate
2
1008.3
44.96
1008.3
44.96
78
Anthracene
I
206.7
12.00
206.7
12.00
55
Naphthalene
4
1562.5
22.04
335.5
17.33
71
Dimethyl Phthalate
I
193.3
63.67
193.3
63.67
84
Pyrene
2
332.4
26.75
332.4
26.75
39
Fluoranthrene
2
207.4
16.88
207.4
16.88
56
Nitrobenzene
1
68764,3
163.25
68764.3
163.25
25
1,2-Dichlorobenzene
2
1539.5
46.41
1539.5
46.41
36
2,6-DinLtrotoluene
I
3436.8
264.00
3436.8
264.00
42
Bis-(2-Chloroisopropyl) Ether
I
5583.3
2250.00
5583.3
2250.00
35
2 ,4-Dinitrotoluene
I
12924.0
109.20
12924.0
109.20
-------
TABLE IX-
POLLUTANT CODE NUMBER
BASE/NEUTRAL op
EXTRACTABLES (contd) NanUl PLANTS
8 1,2,4-Trichlorobenzene 1
1* Acenaphthene 3
81* Phenanthrene 6
80* Fluorene 6
i-h 69* Di-N-Octyl Phthalate 1
i 77* Acenaphthylene 4
o 72* Benzo(A)Anthracene 1
73 Benzo(A)Pyrene 2
54* Isophorone 1
PESTICIDES
110* PCB-1248 (Arochlor 1248) 1
METALS
114
Antimony (Total)
2
115
Arsenic (Total)
1
119
Chromium (Total)
14
120
Copper (Total)
9
123
Mercury (Total)
1
124
Nickel (Total)
2
125
Selenium (Total)
I
128
Zinc (Total)
5
122
Lead (Total)
6
118
Cadmium (Total)
1
\
(continued)
CONCENTRATION, ug/1
Influent
Effluent
Influent
Effluent
Mean
Mean
Median
Median
233.3
42.7b
233.3
42.76
45.5
10.00
18.0
10.00
449.7
10.00
23.6
10.00
48.4
10.00
14.4
10.00
23.0
10.00
23.0
10.00
194.7
10.00
63.1
10.00
10.7
10.00
10.7
10.00
14.6
13.93
14.6
13.93
55.7
10.00
55.7
10.00
10.6667
10
10.6667
10
290.000
225.000
290.000
225.000
19.140
13.000
19.140
13.000
673.397
95.400
428.433
51.250
440.877
61.827
100.000
40.000
48.780
25.000
48.780
25.000
844.250
456.250
844.250
455.250
216.667
143.333
216.667
143.333
695.583
226.033
438.333
60.000
234.491
136.366
56.867
22.555
23.000
20.000
2 3.000
20.000
-------
POLLUTANT CODE
METALS (contd) Name
127
Thallium (Total)
121
Cyanide
126*
SiLver (Total)
VOLATILES
86
Toluene
23
Chlproform
4
Benzene
44
Methylene Chloride
38
Ethylbenzene
87
Trichloroethylene
7
Chlorobenzene
29
1,1-Dichloroethylene
10
1,2-Dichloroethane
3
Acrylonitrile
14
I,1,2-Trichloroethane
13
1, l-Dichloroethane
33
I,3-Dichloropropylene
32
1,2-Dichloropropane
85*
Tetrachloroethylene
11*
1,1,l-Trichloroethane
6*
Carbon Tetrachloride
18*
Dichlorobromomethane
45*
Methyl Chloride
16*
Chloroethane
(continued)
CONCENTRATION, ug/1
Influent
Effluent
Influent
Effluent
Mean
Mean
Median
Median
40.000
36.500
40.000
36.500
500.479
110.593
357.384
95.111
22.667
10.00
22.667
10.000
11330.2
57.591
7779.3
46.925
1146.8
18.782
865.0
19.125
5918.9
48.125
6267.0
21.875
49.0
18.505
42.8
16.250
970.0
55.000
970.0
55.000
483.7
16.250
483.7
16.250
3523.3
287.050
3523.3
287.050
1200.0
32.750
1200.0
32.750
2263.5
280.497
1429.9
44.744
20252.5
27.500
20252.5
27.500
313.8
19.625
313.8
19.625
775.0
65.500
775.0
65.500
2699.8
39.737
2699.8
39.737
3283.1
335.565
2258.0
59.417
10.6
10.000
10.6
10.000
270.7
10.000
64.8
10.000
31.8
10.000
19.4
10.000
25.6
10.000
27.1
10.000
30.0
10.000
30.0
10.000
91.2
10.000
91.2
10.000
-------
TABLE IX-1 (concluded)
POLLUTANT CODE
VOLATILES (contd) Name
88*
51*
46*
Vinyl Chloride
Chlorodibromomethane
Methyl Bromide
NUMBER
OF
PLANTS
1
1
1
Influent
Mean
10.08
10.58
40.94
CONCENTRATION, ug/1
Effluent
Mean
10.000
10.000
10.000
Influent
Median
10.08
10.58
40.94
Effluent
Median
10.000
10.000
10.000
NOTE: Effluent mean and median values were calculated using only effluent data greater than 10 ppb except
for the asterisked (*) pollutants, which had all effluent values less than or equal to 10 ppb.
-------
TABLE IX-2
FINAL BAT DATABASE — SUMMARY STATISTICS
FOR PLASTICS-ONLY PLANTS
POLLUTANT CODE
ACID
EXTRACTABLES
NAME
65
Phenol
NUMBER
OF
PLANTS
1
Influent
Mean
66.5
CONCENTRATIONS, ug/1
Effluent
Mean
10.5
Influent
Median
66.5
Effluent
Median
10.5
BASE/NEUTRAL EXTRATABLES
66
Bis-(2-Ethylhexyl) Phthalate
23.25
13.75
23.25
13.75
METALS
119
120
128
122
118*
121*
Chromium (Total)
Copper (Total)
Zinc (Total)
Lead (Total)
Cadmium (Total)
Cyanide (Total)
77.0
88.0
325667.0
25.0
26.0
73.0
39.00
40.83
3133.33
13.00
10.00
10.00
77.0
88.0
325667.0
25.0
26.0
73.0
39.00
40.83
3133.33
13.00
10.00
10.00
VOLATILES
3
38*
2*
88*
Acrylonitrile
Ethylbenzene
Acrolein
Vinyl Chloride
30630.0
2926.0
907.5
993.2
122.667
10.000
10.000
10.000
30630.0
2926.0
907.5
993.2
122.667
10.000
10.000
10.000
NOTE: Effluent mean and median values were calculated using only effluent data greater than 10 ppb except
for the asterisked (*) pollutants, which had all effluent values less than or equal to 10 ppb.
-------
Zinc concentrations in rayon manufacturing
wastewaters are typically several orders of magnitude
higher than in wastewaters from other Plastics-Only
manufacturers. The Agency is evaluating the data to
decide whether a separate subcategory for rayon
manufacturers is warranted.
• Pollutants for which all effluent values were less
than or equal to 10 ppb and influent means were less
than 25 ppb. The Agency felt that these data might
not be characteristic of the OCPSF Industry.
The Agency typically calculated daily maximum and four-day average effluent
limitations for each pollutant by multiplying the long-term median
concentration by daily maximum and four-day average variability factors,
respectively. The variability factors reflect the product/process, treatment,
and analytical variability that occur at well-designed and well-operated OCPSF
treatment facilities. The four-day average limitations apply to the average
of the daily values for four consecutive monitoring days, whether the values
are from four consecutive days, one day weekly for four*weeks, or one day
monthly for four months. The required monitoring frequency will vary from
plant to plant. EPA feels that four times a month is a reasonable monitoring
frequency for some plants. For others, once a month may be more appropriate.
The calculations are explained below; the statistical details are given in
Appendix F.
(1) Calculation of Long-Term Medians. For each pollutant, the long-term
median, of all the daily effluent values in the final BAT database was
calculated as follows: Organic priority pollutants results reported as "below
detection limit" were assigned the value of 10 ppb (the detection limit).
Single daily samples had often been analyzed in replicate and at more than one
laboratory. Where multiple aliquots of a single sample had been analyzed at
one laboratory, all the results at that laboratory were averaged, giving an
intra-laboratory average. The intra-laboratory averages for all the
laboratories were then averaged, giving a plant single-day mean. For each
plant, all the single-day means above 10 ppb were averaged, giving a plant
multi-day mean. The median of the plant multi-day means from all the plants
in the database for that pollutant was determined and called the long-term
median.
(2) Variability Factors. Variability factors are pollutant-specific
peaking factors that relate the numerical limitations for the maximum day and
the four-day average to the long-term median. The Agency derived the two
variability factors for each pollutant by fitting an appropriate mathematical
model to the statistical distribution of the daily data. This model was used
to calculate the daily maximum and four-day average variability factors, VF1
and VF4, for each pollutant at each plant. For each pollutant, each of the
two variability factors were averaged over all plants, giving an overall VF1
and VF4 for each pollutant.
For some pollutants, variability information was limited. For such
pollutants, variability factors were extrapolated from the variability factors
for groups of pollutants with related chemical structure and thus comparable
IX-14
-------
treatment variability. The priority pollutants have been grouped by chemical
characteristics into groups of chemicals possessing similar structure and
properties, as shown in TABLE IX-3. The derivation of these groupings is
explained in the document referenced in Table IX-3. Each pollutant in each
chemical group was assigned a VFl and a VF4 equal to the average of the VFls
and VF4s possessed by any pollutants in the same group. Daily and four-day
average limitations were then calculated for each pollutant by multiplying its
long-term median value by each of the two variability factors.
Variability factors were applied differently to the Group 7 (heavy metals)
pollutants than to the other groups. The plants were segregated into the two
subcategories, Plastics-Only and Not Plastics-Only, and the variability
factors for each metal from each plant were separately averaged within each
subcategory, giving a variability factor in each of the two subcategories for
each metal. For metals where no variability factor could be calculated
directly, a variability factor was estimated by averaging the variability
factors for each of the other metals at each plant. For example, since no
variability factor for antimony was available in the Not Plastics-Only
subcategory but factors for copper, chromium, lead, and zinc were, the average
of the four variability factors was assigned to antimony.
The variability factors for each priority pollutant class are listed in
TABLE IX-4. The statistical model used and the variability factor
calculations are described in more detail below.
(a) Selection of a Statistical Model. The Agency chose a
statistical probability model appropriate .to the concentration data reported
for organic priority pollutants. Typically, effluent wastewater analyses are
modeled with the lognormal distribution, because measurements of treated
wastewater concentrations usually yield many data points at the lower end of
the concentration scale (which is limited by zero) and fewer data points at
the higher (unlimited) end of the concentration scale. For such results, the
mean of the concentration values exceeds the median concentration value,
statistical skewness is positive (i.e., the distribution exhibits a long tail
of values over higher concentrations), and the variation below the median is
less than the variation above the median. OCPSF effluent data exhibit the
characteristics cited above and typically have a portion of their data at the
lower end of the concentration scale reported as not detected, trace, less
than detection limit, detection limit, or less than some small specified
concentration values (e.g., less than W ppb).
Because such reported values are not quantitative, the Agency
selected the delta distribution (sometimes referred to as the delta-lognormal
distribution) as practical and defensible for analyzing data that exhibit the
characteristics cited above. The delta distribution incorporates both the
positive probability that reported values will fall below some chosen
analytical method detection limit and the positively skewed distribution of
reported concentration values above the chosen detection limit. To ensure
that the model was appropriate, goodness-of-fit tests were run on each
plant-specific and pollutant-specific data set; the results support the model
selection. Further details on the model and the goodness-of-fit tests are
presented in Appendix F.
IX-15
-------
TABLE IX-3
PRIORITY POLLUTANT CLASSES
1. Halogenated Methanes (Cl's)
46 Methyl bromide
45 Methyl chloride
44 Methylene chloride (dichlorotnethane)
47 Bromoform (tribromoraethane)
23 Chloroform (trichloromethane)
48 Broroodichlororaethane
51 Dibromochloromethane
50 Dichlorodifluoromethane
49 Trichlorofluoromethane
6 Carbon tetrachloride (tetrachloromethane)
Chlorinated C2's
16 Chloroethane (ethyl chloride)
88 Chloroethylene (vinyl chloride)
10 1,2-Dichloroethane (ethylene dichloride)
13 1,1-Dichloroethane
30 1,2-trans-Dichloroethylene
29 1,1-Dichloroethylene (vinylidene chloride)
14 1,1,2-Trichloroethane
11 1,1,1-Trichloroethane (methyl chloroform)
87 Trichloroethylene
85 Tetrachloroethylene
15 1,1,2,2-Tetrachloroethane
12 Hexachloroethane
Chlorinated C3*s
32 1,2-Dichloropropane
33 1,3-Dichloropropylene
4. Chlorinated C4
a 52 Hexachlorobutadiene
5. Chlorinated C5
* 53 Hexachlorocylopentadiene
NOTES: (1) Numbers refer to a published alphabetical listing of the priority
pollutants.
(2) • Priority pollutants found in verification.
REFERENCE: Wise, H.E., and P. 0. Fahrenthold (1981). Occurrence and
Predictability of Priority Pollutants in Wastewaters of the Organic
Chemicals and Plastics/Synthetic Fibers Industrial Categories,
USEPA, 1981.
IX-16
-------
TABLE IX-3 (continued)
6. Chloroalkyl Ethers
17
bis(chloromethyl)ether
• 18
bis(2-chloroethyl)ether
• 42
bis(2-chloroisopropyl)ether
19
2-chloroethylvinyl ether
• 43
bis(2-chloroethoxy) methane
Metals
•114
Antimony
•115
Arsenic
•117
Beryllium
•118
Cadmium
•119
Chromium
•120
Copper
•122
Lead
•123
Mercury
•124
Nickel
•125
Selenium
•126
Silver •
127
Thallium
•128
Zinc
8. Pesticides
89
Aldrin
90
Dieldrin
91
Chlordane
95
alpha-Endosulfan
98
Endrin
99
Endrin aldehyde
100
Heptachlor
101
Heptachlor epoxide
102
alpha-BHC
103
beta-BHC
104
gamma-BHC (Lindane)
105
delta-BHC
92
4,4'-DDT
93
4,4'-DDE (p.p'-DDx)
94
4,4'-DDD (p,p'-TDE)
113
Toxaphene
9. Nitrosamines
61 N-Nitrosodimethyl amine
• 62 N-Nitrosodiphenyl amine
63 N-Nitrosodi-n-propyl amine
10. Miscellaneous
• 2 Acrolein
• 3 Acrylonitrile
• 54 Isophorone
•121 Cyanide
IX-17
-------
TABLE IX-3 (continued)
11. Aromatics
4 Benzene
86 Toluene
38 Ethylbenzene
12. Polyaromatics
55
Naphthalene
1
Acenaphthene
77
Acenaphthylene
78
Anthracene
72
Benzo(a)anthracene (1,2-benzanthracene)
73
Benzo(a)pyrene (e,4-benzopyrene)
74
3 ,4-Benzofluoranthene
75
Benzo(k)fluoranthene (11,12-benzofluoranthene)
79
Benzo(ghi)perylene (1,12-benzoperylene)
76
Chrysene
82
Dibenzo(a,h)anthracene (1,2,5,6-dibenzanthraoene)
80
Fluorene
39
Fluoranthene
83
Indeno(l,2,3-cd)pyrene (2,3-o-Phenylene pyrene)
81
Phenanthrene
84
Pyrene
13. Chloroaromatics
• 7 Chlorobenzene
• 25 o-Dichlorobenzene
• 27 p-Dichlorobenzene
• 26 m-Dichlorobenzene
• 8 1,2,4-Trichlorobenzene
• 9 Hexachlorobenzene
14. Chlorinated Polyaromatic
20 2-Chloronaphthalene
15. Polychlorinated Biphenyls
106-112 Seven listed
16. Phthalate Esters
• 66 bis(2-Ethylhexyl)
• 67 Butylbenzyl
• 68 Di-n-butyl
• 69 Di-n-octyl
" 70 Diethyl
• 71 Dimethyl
17. Nitroaromatics
• 56 Nitrobenzene
• 35 2,4-Dinitrotoluene
• 36 2,6-Dinitrotoluene
IX-18
-------
TABLE IX-3 (concluded)
18. Benzidines
5 Benzidine
28 3,3'-Dichlorobenzidine
37 1,2-Diphenylhydrazine
19. Phenols
• 65 Phenol
• 34 2,4-Dimethylphenol
20. Nitrophenols
• 57 2-Nitrophenol
• 58 4-Nitrophenol
• 59 2,4-Dinitrophenol
• 60 4,6-Dinitro-o-cresol
21. Chlorophenols
• 24 2-Chlorophenol
22 4-Chloro-m-cresol
• 31 2,4-Dichlorophenol
• 21 2,4,6-Trichlorophenol
• 64 Pentachlorophenol
22. 144 TCDD (2,3,7,8-Tetrachloro-dibenzo-p-dioxin)
23. Haloaryl Ethers
40 4-Chlorophenylphenyl ether
41 4-Bromophenylphenyl ether
IX-19
-------
TABLE IX-4
VARIABILITY FACTORS BY PRIORITY POLLUTANT CLASS
POLLUTANT
NUMBER
NUMBER
CLASS*
FRACTION
POLLUTANT
PLANT
DAYS
DETECTS
MA
P99
P95
VF(1)**
VF(4)»«
1
V
Chloroform (23)
PI
24
14
25
81
48
3.18
1.90
V
Methylene Chloride (44)
PI
24
13
16
42
27
1,69
2.90
1.80
2
V
1,2-dichloroethane (10)
PI
24
7
309
1224
578
3.96
1.87
P3
33
7
21
52
38
2,50
1,35
3.23
1.86
11
V
Toluene (86)
P3
32
10
59
282
154
4.74
2.60
13
B
1,2,4-trichlorobenzene (8)
P4
11
11
46
198
83
4.32
1.80
1,2-dich1orobenzene (25)
P4
11
6
36
206
102
5,76
2.87
5.04
2.34
16
B
Bis(2-ethylhexyl)phthalate (66)
P3
33
26
67
537
207
8.02
3.08
B
Di-n-butyl phthalate (68)
P3
33
10
21
59
42
2.80
1.99
B
Diethyl Phthalate (70)
P3
33
24
28
190
79
6,67
2.76
5.83
2.61
19
A
Phenol (65)
P3
33
3
12
15
14
1.20
1.11
P5
7
4
1$
24
21
1,29
Ldi
1.24
1.13
20
A
2,4-dinitrophenol (59)
P3
33
7
57
200
127
3.49
2.23
"Priority pollutant classes are defined in Table IX—1.
••The arithmetic average is given Tor pollutant classes with more than one value.
-------
TABLE IX-4 (concluded)
POLLUTANT
CLASS*
FRACTION
POLLUTANT
PLANT
NUMBER
DAYS
NUMBER
DETECTS
MA
P99
P95
VF(1)««
VF(4)««
21
A
2,4,6-trichlorophenoi (21)
2,4-d ichlorophenol (31)
Pentachlorophenol (6U)
P3
P4
P3
33
11
7
18
5
4
42
52
18
255
325
71
125
148
38
6.08
6.29
3.94
5.44
2.99
2.87
141
7
M
Chromium (11'9)
Plast ics
3
110
16
26
46
26
19
57
65
110
30
72
3.50
1.94
2,72
1.64
1.M
1.46
Not Plastics
113
126
8
90
8
90
77
21
325
59
138
31
4.24
?.86
3.55
1.80
1.50
1.65
Copper (120)
Not Plastics
113
118
145
27
145
27
32
152
88
692
47
284
2.76
4.55
3.66
1.47
1.87
1.67
Lead (122)
Not Plastics
113
13
13
11
31
16
2.87
1.50
Zinc (128)
Elastics
Not Plastics
27
110
113
158
8
150
158
8
150
2896
137
124
7902
531
365
4242
236
188
2.73
3.87
2.94
3.41
1.46
1.72
hH
TOTAL METALS
Plastics
Not Plastics
2.73
3.37
1.45
1.61
10
-
Cyanide (121)
P5 .
29
27
97
410
180
4.23
1.86
-------
(b) Calculation of Daily Maximum Variability Factors (VF1) and
Four-Day Average Variability Factors (VF4).' For each pollutant, VF1 and VF4
for each plant were calculated for those of the four CMA plants that have at
least three single-day averages (see Calculation of Long-Term Medians) above
10 ppb. To develop VF1 (the daily maximum variability factor), at each plant
the Agency applied the delta distribution to the plant single-day means to
calculate two terms -- the estimated 99th percentile value and the estimated
arithmetic mean value. VF1 for that plant was then calculated as the 99th
percentile value divided by the estimated arithmetic mean value. The VFls
from all the plants were then averaged, giving an overall VF1 for each
pollutant.
To develop VF4 (the four-day average variability factor), at each
plant the Agency assumed that the distribution of the four-day averages of the
four samples followed a modified delta distribution. The 95th percentile
value and the estimated arithmetic mean value were then calculated from this
distribution. The four-day model's estimated arithmetic mean value was
identical to the individual-day model's estimated arithmetic mean value. VF4
for that plant was then calculated as the estimated 95th percentile value
divided by the estimated arithmetic mean value. The VF4s from all the plants
were then averaged, giving an overall VF4 for each pollutant.
The details of the statistical development of the variability factors
are described in Appendix F. Results of the effluent variability analysis are
summarized in Table IX-4, which includes the following information: number of
days of data used, number of plant single-day means above 10 ppb, estimated
long-term mean (MA) for days above 10 ppb, estimated 99th percentile value for
the plant single-day means .(P99), estimated 95th percentile value for plant
four-day means (P95), daily maximum variability factor (VF1), and four-day
average variability factor (VF4). The table also notes the analytical
fraction and priority pollutant class of each pollutant and the overall VF1
and VF4 for each pollutant class. Variability factors could not be calculated
separately for the Plastics-Only subcategory because there were no
Plastics-Only plants in the CMA study.
(3) Proposed Limitations. TABLES IX-5 AND IX-6 give daily and four-day
effluent limitations for the Plastics-Only and Not Plastics-Only plants,
respectively. The pollutants in Tables IX-5 and IX-6 are listed by pollutant
number and analytical fraction, where V=volatile fraction, A=acid extractable
fraction, and B=the base/neutral extractable fraction. The four-day average
limitations apply to the arithmetic average of any four consecutive daily
monitoring samples, whether the daily samples are taken every day, weekly, or
monthly.
All organic priority pollutant limitations that had been calculated as
less than 50 yg/l were rounded up to 50 vg/i. Limitations on organic
pollutants were rounded up to the next number divisible by 25; limitations on
heavy metals were rounded up to the next number divisible by 10. For example,
the daily maximum limitation in the Plastics-Only subcategory for phenol is 50
(1.24 x 10.5 = 13.0, which was rounded up to 50); the daily maximum limitation
for chromium is 110 (2.72 x 39.0 — 106.1, which was rounded up to 110).
Pollutants for which the influent mean values in the CMA or Verification
IX-22
-------
TABLE IX-5
BAT EFFLUENT LIMITATIONS (ug/l)
PLASTICS-ONLY
POLLUTANT
FRACT1 ON
POLLUTANT
CLASS
LONG-TERM
MEDIAN*
NUMBER
OF PLANTS
FOUR-DAY
LIMITATION**
DAILY
LIMITATION
(65)
Pheno1
A
19
10.5
1
--
50
(66)
Bis(2-ethyIhexyl)phthalate
B
16
13.8
1
50
100
(118)
Cadmium
M
7
10.0
1
20
30
(119)
Chromium
M
7
39.0
1
60
110
(120)
Copper
H
7
tO. 8
60
120
(121)
Cyanide
10
10.0
1
20
50
(122)
Lead
M
7
13.0
1
20
to
(2)
Ac ro1e i n
V
10
10.0
1
—
50
(38)
Ethyl benzene
V
11
10.0
1
--
50
(88)
Vinyl chloride
V
2
10.0
—
50
* A long-term median of 10 ug/l for organic toxic pollutants indicates that all effluent values were less
than the detection limit and influent was greater than 25 ug/liter; the daily limitation was set at 50
ug/liter in such cases.
** No four-day average limitation was given if the dally I imitation was 50 ug/liter.
-------
TABLE IX-6
BAT EFFLUENT LIMITATIONS (ug/l)
NOT PLASTICS-ONLY PLANTS
POLLUTANT
FRACTION
POLLUTANT
CLASS
LONG-TERM
MEDIAN*
NUMBER
OF PLANTS
FOUR-DAY
MAXIMUM**
DAILY
MAXIMUM
(21 )
2,4,6-trichlo ropheno1
A
21
31.4
1
100
175
(24)
2-chlorophenol
A
21
10.4
1
50
75
(31 )
2,4-dichloropheno1
A
21
34.3
1
100
200
(34)
2,4-dimethyIphenoI
A
19
16.0
4
—
50
(57)
2-n i tropheno1
A
20
28.5
1
75
100
(58)
4-n1tropheno1
A
20
141.6
1
325
500
(59)
2,4-d i n i tropheno1
A
20
41.5
1
100
150
(64)
Pentachloropheno1
A
21
15.9
1
50
100
(65)
Pheno1
A
19
13.5
5
—
50
(1)
Acenaphthene
B
12
10.0
3
—
50
(8)
1^ 2,4-trich1orobenzene
B
13
42.8
1
125
225
(25)
1,2-d i ch1o robenzene
B
13
46.4
2
125
250
(54)
1 sophorone
B
10
10.0
1
—
50
(66)
Bi s(2-ethy1hexy1)phthalate
B
16
57.0
2
150
350
(68)
Di-n-butyl phthalate
B
16
50.0
3
150
300
-------
TABLE IX-6 (continued)
POLLUTANT
FRACTION
POLLUTANT
CLASS
LONG-TERM
MEDIAN*
NUMBER
OF PLANTS
FOUR-DAY
MAXIMUM**
DAILY
MAXIMUM
(70)
Diethyl Phthalate
B
16
45.0
2
125
275
(71)
Dimethyl phthalate
B
16
63.7
1
175
375
(77)
Acenaphthylene
B
12
10.0
4
—
50
(80)
F1uorene
B
12
10.0
6
—
50
(81)
Phenanthrene
B
12
10.0
6
—
50
( 11U)
Antimony
M
7
225.0
2
370
780
(118)
Cadmi um
M
7
20.0
1
40
70
(119)
Chromi um
M
7
51.3
14
90
190
( 120)
Copper
M
7
40.0
9
70
150
(121)
Cyanide
10
95.1
3
180
410
(122)
Lead
M
7
22.6
6
40
70
( 123)
Me rcury
M
7
25.0
1
50
90
(128)
Z i nc
M
7
60.0
5
100
210
CO
Benzene
V
11
21.9
4
75
125
(6)
Carbon tetrachloride
V
1
10.0
4
—
50
(10)
1,2-d ichloroethane
V
2
44.7
4
100
150
-------
TABLE IX-6 (concluded)
POLLUTANT
FRACTION
POLLUTANT
CLASS
LONG-TERM
MEDIAN*
NUMBER
OF PLANTS
FOUR-DAY
MAXIMUM**
DAI LY
MAX1 MUM
(11)
1,1,1-trichloroethane
V
2
10.0
4
--
50
(13)
1,1-d ich1oroethane
V
2
65.5
1
125
225
(HO
1,1,2-trichloroethane
V
2
19.6
2
50
75
(16)
Ch1oroethane
V
2
10.0
2
—
50
(23)
Chloroform
V
1
19.1
3
50
75
(29)
1,1-d ichIoroethy 1ene
V
2
32.8
1
75
125
(38)
Ethylbenzene
V
11
55.0
1
150
275
C4U)
Methylene chloride
V
1
16.3
3
—
50
(45)
Methyl chloride
V
1
10.0
1
—
50
(46)
Methyl bromide
V
1
10.0
1
—
50
(48)
Dichto robromomethane
V
1
10.0
3
--
50
(86)
Toluene
V
11
46.9
6
125
225
(87)
T ri chloroethylene
V
2
16.3
1
50
75
* A long-term median of 10 ug/liter for organics indicates that all effluent values were less than the
detection limit and influent was greater than 25 ug/liter; the daily limitation was set at 50 ug/liter in
such cases.
** No four-day average limitation was given if the daily limitation was 50 ug/liter.
-------
databases were above 25 yg/l and all effluent values were less than 10
yg/fc were assigned a daily limitation of 50 yg/fc (e.g., acenaphthene
in Table IX-4). Pollutants that were assigned daily limitations of 50
Vg/l were not assigned four-day average limitations.
EPA believes that setting effluent limitations at 10 yg/fc, even where
warranted by appropriate statistical techniques applied to the data, will
frequently produce apparent violations that actually only result from
analytical variability at this low concentration. In such cases, the
discharger and the pretreatment control or permitting authority would have to
review the analytical procedures used to determine whether a violation had
actually occurred. The associated disputes over incidental analytical methods
issues would divert attention from the central issue of whether the
appropriate set of BAT controls and treatments have been installed and are
being properly operated. EPA believes that sound regulatory policy requires
limitations high enough to reduce the probability of serious analytical
disputes without being so high that inadequate treatment is allowed.
To avoid analytical methods disputes, a concentration of 50 yg/fc has
been set as the daily maximum limitation for organic priority pollutants
whenever the statistical methodology yields concentrations below 50 yg/t.
Although the four-day average limitations should be lower than the daily
maximum limitations, the daily maximum limitations of 50 yg/% will suffice
for regulation and enforcement. The 50 yg/l limitation may be higher than
necessary to avoid non-trivial analytical methods disputes, since lower
concentrations are both technically achievable and measurable.
Limitations were not developed for pollutants in classes where no
variability factor could be estimated from the CMA data or for pollutants
where no long-term median could be estimated from the CMA and Verification
data. The Agency has been unable to develop limitations for 60 of the other
pollutants listed in Table VI-2 because of inadequate data. EPA intends to
assess the need for effluent limitations for these pollutants during the
additional data gathering and field sampling studies that the Agency plans to
perform before promulgation.
Treatment Technologies Reflected in the Limitations
TABLE IX-7 tabulates the technologies used for in-plant and end-of-pipe
treatment at the 21 final BAT database plants from which the proposed BAT
limitations were derived.
IMPACTS OF BAT IMPLEMENTATION
General
This section summarizes EPA's evaluation of the impacts of implementation of
the proposed BAT limitations for the 0CPSF Industry. The subsections address
the number of 0CPSF plants in and out of compliance with the proposed
limitations, the reduction in priority pollutants discharged, the capital and
annual costs of compliance, and non-water quality environmental impacts.
IX-27
-------
TABLE IX-7
TREATMENT SYSTEMS AT PLANTS
USED TO CALCULATE BAT LIMITATIONS
TECHNOLOGY
VERIFICAT
ON PLANTS
CMA
PLANTS
TOTAL
PLANTS
E-O-P
l-P
E-O-P
lr£
E-O-P
Steam Stripping
6
1
1
0
7
1
Solvent Recovery
2
0
0
0
2
0
Chemica1ly-Assisted Clarification
0
8
0
1
0
9
Equa1ization
0
15
0
2
0
17
Neutra1izat ion
0
14
0
1
0
15
Aerated Lagoons -First Stage
0
4
0
0
0
4
Aerated Lagoons - Second Stage
0
1
0
0
0
1
Polishing Pond
0
3
0
1
0
4
Toluene Recovery Decant Tank
1
0
0
0
1
0
Cla ri f icat i on
0
' 6
0
2
0
8
Activated Sludge
0
8
0
3
0
11
Xylene Recovery Column
0
0
1
0
1
0
Methanol Recovery Column
0
0
1
0
1
0
Anaerobic Lagoon - First Stage
0
1
0
0
0
1
Anaerobic Lagoon - Second Stage
0
1.
0
0
0
1
API Oil Separator
0
4
0
1
0
5
Trickli ng F i1ter
0
2
0
1
0
3
Pure Oxygen Activated Sludge
0
3
0
0
0
3
Flocculation
0
1
0
0
0
1
Carbon Adsorption
0
2
0
0
0
2
Multi-media Filtration
0
1
0
0
0
1
Solvent Extraction
0
0
0
1
0
1
Post Aeration
0
0
1
0
1
0
Alcohol Recovery Stripper
2
0
0
0
2
0
Triethanol Amine (TEA) Recovery
1
0
0
0
1
0
Benzene Stripper
1
0
0
0
1
0
Low Temperature Hydrolysis
0
0
1
0
1
0
Olefin Condensate Stripper
1
0
0
0
1
0
Recovery Column
1
0
0
0
1
0
Ai r Stripping
0
1
0
0
0
1
-------
TABLE IX-7 (concluded)
TECHNOLOGY
VERIFICATION PLANTS
E-O-P
CMA PLANTS
l-P E-O-P
TOTAL PLANTS
l-P E-O-P
Dissolved Air Flotation
0
2
0
1
0
3
Powdered Activated Carbon
0
1
0
0
0
1
OiI Separation
0
4
0
0
0
4
Solvent Recovery Stripper
3
0
0
0
3
0
Se 111i ng
0
1
0
0
0
1
Aerobic Lagoon - First Stage
0
2
0
0
0
2
- Second and Third
Stage
0
1
0
0
0
1
Alcohol Recovery
0
0
1
0
1
0
Solvent Recovery Flash Column
0
0
1
0
1
0
TOTALS
18
88
14
25
102
Total Number of Plants
17
21
NOTE:
l-P
E-O-P
= in-plant
= end-of-pipe
-------
Present Compliance
The Agency evaluated present compliance for two groups of plants: 33 plants
in the BAT database and 566 direct discharge plants evaluated in the Economic
Impact Analysis. The evaluation and results are discussed below.
Data from the Verification and CMA Sampling programs for 33 of the BAT
database plants were tabulated. At each plant, all the daily values (three
for each Verification plant, six to twenty-five for each CMA plant) were
averaged. For each plant, this multi-day average and the maximum daily value
for each pollutant were compared to the proposed four-day average and maximum
day effluent limitations, respectively. Any plant that exceeded at least one
of the proposed limitations for any pollutant was judged to be out of
compliance; thirteen of the thirty-three were. Each of the plants lacked data
for many of the pollutants for which limitations are being proposed, since
only selected pollutants were analyzed during the Verification and CMA
Studies.
Of the 566 direct dischargers addressed in the BAT cost analysis, 453 were
found to incur compliance costs. Details of this cost analysis are presented
in the next section.
Benefits and Costs of BAT Implementation
This section presents the Agency's estimates for the industry-wide direct
benefits and costs of implementing these proposed BAT regulations: the
reduction in discharge of priority pollutants and the capital and annual costs
incurred.
Wasteload Reduction Benefits. The methodology for estimating reduction of •
the priority pollutant wasteload for direct dischargers is described in
Section V. The proposed BAT regulation is expected to remove about 648
million pounds of priority pollutants annually from BPT effluents.
Capital and Annual Costs Incurred. As described in Section VIII, the Agency
estimated BAT compliance costs for the whole OCPSF industrial category by
summing the estimated costs incurred for the 566 direct dischargers covered by
the BAT 308 Questionnaire. The estimated capital cost for compliance with the
proposed BAT regulation is 520 million dollars. Capital costs were amortized
using a capital recovery factor of 0.22. The estimated annual cost (including
amortization of the capital cost) is 243 million dollars a year. Costs are in
1982 dollars.
In addition, BAT monitoring costs for these 566 plants were estimated to be
5.4 million dollars a year, assuming one $800 sample a month at each plant.
The projected impacts of these costs on the industry are described in EPA's
Economic Impact Analysis referenced in Section VIII.
Non-Water Quality Environmental Impacts
This section summarizes the Agency's evaluation of the changes in energy
consumption, air pollutant emissions, solid and hazardous waste generation,
and noise generation which may result from OCPSF industry compliance with the
IX-30
-------
proposed BAT limitations. The background material for these evaluations is
presented in Section VIII.
Energy Consumption. Implementation of the proposed BAT regulation will
result in the installation of certain energy-consuming-technologies, such as
activated carbon regeneration, increasing OCPSF energy consumption. However,
the Agency anticipates that the BAT will not significantly increase total
energy consumption by the industry. The Agency plans to generate and evaluate
revised energy consumption estimates before promulgating the final BAT
regulation.
Air Pollutant Emissions. The Agency anticipates that many plants will comply
with the BAT limitations by installing in-process controls that effectively
remove volatile organic compounds before they reach the end-of-pipe treatment
systems installed to meet BPT regulations.. This removal will reduce air
pollutant emissions presently resulting from evaporation and gas stripping
from the end-of-pipe systems. The Agency concludes that compliance with the
proposed BAT regulations by OCPSF plants may reduce emissions of air
pollutants.
Solid Waste Generation. The Agency's preliminary analysis of the solid waste
generation projections from the early GPC runs (see Section VIII) indicates
that the proposed BAT regulation will not significantly increase the total
amount of solid waste produced by the OCPSF industries. The Agency plans to
generate and evaluate revised solid waste generation estimates before
promulgating the final BAT regulation.
EPA has also considered the effect these proposed regulations would have on
the generation of hazardous waste. EPA's Office of Solid Waste has- analyzed
the hazardous waste management and disposal costs imposed by the RCRA
requirements and has published some results in 45 FR 33066 (May 19, 1980).
Additional cost estimates for land disposal of hazardous wastes were published
in 47 FR 32274 (July 26, 1982). Thirty solid waste streams currently
generated at OCPSF plants have been listed as hazardous under Section 3001 of
RCRA (See 40 (FR Part 261.32)). Other waste streams not listed may be
hazardous by virtue of possessing characteristics of ignitability,
corrosivity, reactivity or toxicity (see 40 CFR 261.21-.24, 45 FR 33066, May
19, 1980). It is currently estimated that total solid waste, including
hazardous wastes, generated as a result of the proposed regulations will
increase insignificantly compared to current loadings. The annual increase in
RCRA costs due to these proposed regulations is estimated to be §9 million, or
approximately one percent of the total current estimated annual cost for the
industry.
Noise Generation. The mechanical equipment required by the BAT technologies
is not substantially noisier than the equipment currently in use in the OCPSF
production plants. Implementation of BAT, therefore, is not expected to
significantly increase noise production by the OCPSF industries.
Occupational Safety and Health Administration (OSHA) standards indirectly
affect the level of noise to which the public might be exposed. New
IX-31
-------
wastewater treatment equipment must comply with prescribed OSHA workplace
standards. Reduction of workplace noise levels also reduces community noise
levels.
Conclusion. After evaluating the anticipated non-water quality environmental
impacts o£ the proposed BAT regulations, the Agency concludes that the
proposed regulation adequately serves the nation's environmental goals.
IX-32
-------
REFERENCES
Memo from Russ Roegner, Statistician, Program Integration and Evaluation Staff
and Maria Irizarry, Project Officer, Effluent Guidelines Division, to
Devereaux Barnes, Acting Deputy Director, EGD, "Examination of Product/Process
- Specific Approach for Determining Mass-Based Limitations for the Organic
Chemicals Industry," August 2, 1982;
Memo from Russ Roegner to Devereaux Barnes, "Product/Process Flow to
Production Ratios for Verification Plants with Ttoo or Three of the 176
Product/ProcessesAugust 10, 1982.
U.S. Environmental Protection Agency (USEPA). 1983. Economic Analysis of
Proposed Effluent Standards and Limitations for the Organic Chemicals and
Plastics, Synthetics, and Fibers Industries. EPA 440/2-83-004
IX-33
-------
SECTION X
EFFLUENT QUALITY ATTAINABLE THROUGH THE
APPLICATION OF NEW SOURCE PERFORMANCE STANDARDS
INTRODUCTION
Under the Consent Decree and Section 306 of the Clean Water Act, EPA must
develop, and new direct discharge sources in the OCPSF industries must
subsequently comply with, "national standards of performance" or New Source
Performance Standards (NSPS) for the control of discharge of pollutants.
These standards ..reflect[s] the greatest degree of effluent
reduction...achievable through application of the best available demonstrated
control technology, processes, operating methods, or other alternatives,
including, where practicable, standard[s] permitting no discharge of
pollutants." (Section 306(a)(1)).
A "new source" is defined as "...any source, the construation of which is
commenced after the publication of proposed regulations prescribing a standard
of performance...which will be applicable to such source, if such standard is
thereafter promulgated..." (Section 306(a)(2). Any direct discharge source
which does not meet this new source definition is an existing source and must
instead comply with BPT, BCT, and BAT standards.
According to Section 306(b) of the Act., in setting the standard, EPA must
consider all of the following factors:
• The cost of achieving effluent reductions.
• Non-water quality environmental impacts and energy
requirements.
• Classes, types, and sizes of new source plants.
• The type of production process employed (e.g.,
batch or continuous).
Because new plants can be designed with pollution control as a goal,
innovations in plant design, product/process technology, and wastewater
treatment technology can cost-effectively minimize wastewater production and
discharge. This section discusses the Agency's selection of NSPS effluent
limitations for the Organic Chemicals and Plastics/Synthetic Fibers
Industries.
X-l
-------
LIMITATION TYPE
This discussion is the same as the discussion presented In Section IX.
NSPS LIMITATION SELECTION
The technologies used to control conventional and priority pollutants at
existing plants are fully applicable to new plants. EPA has not identified
any technologies or combination of technologies for new sources that differ
from those used to establish BPT and BAT limitations for existing sources.
EPA is proposing NSPS limitations that are identical to those proposed for BPT
and BAT, which are contained in the BPT Development Document and Section IX of
this BAT Development Document, respectively. The Agency did not estimate the
future cost to the OCPSF industries of these NSPS limitations, since they will
not generate incremental costs or economic impacts.
X-2
-------
SECTION XI
EFFLUENT QUALITY ATTAINABLE THROUGH THE APPLICATION OF
PRETREATMENT STANDARDS FOR EXISTING SOURCES AND
PRETREATMENT STANDARDS FOR NEW SOURCES
INTRODUCTION
Under the Consent Decree and Section 307 of the Clean Water Act, EPA must
develop, and indirect dischargers in the Organic Chemicals and
Plastics/Synthetic Fibers Industries (OCPSF) must comply with, pretreatment
standards for existing sources (PSES) and for new sources (PSNS),
respectively. The definitions of new source and existing source are given in
the Introduction to Section X. The pollutants covered by PSES and PSNS are
those pollutants which "...may interfere with, pass through, or otherwise be
incompatible with..." the POTWs (publicly-owned treatment works, commonly
known as municipal sewage treatment plants) to which the pollutants are
discharged (Sections 307(b) and (c)). In addition, many of the pollutants in
OCPSF wastewaters, at sufficiently high concentrations, can inhibit
biodegradation in POTW operations. In some cases, as documented in the
regulatory impact analysis which was performed in support of the general
pretreatment regulations, OCPSF discharges to POTWs have caused upsets at
POTWs resulting not only in pass-through of OCPSF discharges, but also in the
partial or complete inability of the POTW to treat other wastewaters.
Pollutants which "pass through" POTWs are also termed "not susceptible to.
treatment by" POTWs. "incompatible" pollutants include pollutants that
contaminate POTW sludges and thereby restrict POTW sludge reclamation and
disposal options, including the beneficial use of sludges on agricultural
lands.
The legislative history of the 1977 Act indicates that pretreatment standards
are to be technology-based and analogous to the best available technology
(BAT) standards for direct dischargers. PSNS may be more -stringent than PSES,
since new indirect dischargers, like new direct dischargers, have the
opportunity to construct a production facility incorporating the best
available technologies for pollution control, including production process
design improvements, in-plant controls, end-of-pipe treatment, and optimal
plant site selection. The categorical pretreatment standards developed for
the OCPSF industry category in this section will be applied to OCPSF indirect
dischargers through the federal, state, local, and municipal pretreatment
programs being established under the general pretreatment regulations (40 CFR,
Part 403).
This section lists the pollutants selected for regulation under PSES and PSNS;
describes the development of PSES and PSNS effluent limitations; presents the
numerical limitations, their costs and water quality benefits; and addresses
non-water quality environmental benefits.
XI-1
-------
POLLUTANTS SELECTED FOR REGULATION UNDER PSES AND PSNS
The toxic pollutants selected as candidates for regulation are listed in Table
VI-5 of Section VI. Table XI-1 gives the pretreatment standard effluent
limitations for existing and new sources. The toxic pollutants proposed for
regulation under PSES and PSNS in the Plastics-Only subcategory are acrolein,
cyanide, lead, and vinyl chloride. The toxic pollutants proposed for similar
regulation in the Not Plastics-Only subcategory are 2,4-dimethylphenol,
2,4-dichlorophenol, 2,4,6-trichlorophenol, 2-chlorophenol, 2-nitrophenol,
4-nitrophenol, 2,4-dinitrophenol, dimethyl phthalate, phenanthrene, fluorene,
acenaphthylene, isophorone, chloroethane, 1,2-dichloroethane, methyl bromide,
chromium, and mercury. All of the above toxic pollutants have been determined
to pass through PQTW treatment systems.
DEVELOPMENT OF PSES AND PSNS EFFLUENT LIMITATIONS
General
The Agency's performance data for in-plant controls (such as steam stripping,
solvent extraction and chemical (precipitation) that remove specific toxic
pollutants prior to end-of-pipe treatment is not sufficient for development of
pretreatment standards. Therefore, performance data from the same CMA and
Verification plants from which BAT and NSPS effluent limitations were
developed were utilized in establishing PSES and PSNS (see Sections IX and
X). As explained in Section V, the effluent data in the Verification and CMA
databases reflect either the complete (in-plant and end-of-pipe) treatment
systems at some production plants but just the end-of-pipe (predominantly
biological) treatment systems at other production plants. Since the Agency
cannot segregate the data on the actual performance of the in-plant controls
preceding the BPT (mostly biological) end-of-pipe systems, the Agency has
developed these proposed PSES and PSNS effluent limitations from performance
data for the complete treatment systems.
Methodology
The BAT and NSPS effluent limitations were adopted for PSES and PSNS. The
limitations reflect the performance of plants in the Verification and CMA
databases whose average BOD removal is at least 95% or whose average effluent
BOD concentration is less than or equal to 50 mg/1. End-of-pipe treatment
technologies at plants which meet this BOD performance criteria include
activated sludge, aerated lagoons, chemical precipitation and carbon
adsorption; in-plant controls used to control specific toxic pollutants from
segregated product/process waste stream include steam stripping, solvent
extraction and chemical precipitation.
As outlined in Section VI, a pass-through analysis was performed to select
pollutant parameters to be regulated under PSES and PSNS. A list of the
selected pollutants is presented in Table VI-5. As discussed in the previous
subsection, due to the absence of performance data for certain in-plant
controls, the BAT and NSPS effluent limitations were adopted for PSES and
PSNS. However, BAT and NSPS effluent limitations have not been proposed for
all pollutants which require regulation under PSES and PSNS based on the
XI -2
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results of the pass-through analysis because insufficient data were available
to calculate variability factors to apply to pollutant long-term medians for
BAT and NSPS.
Proposed PSES.and PSNS Effluent Limitations
The proposed PSES and PSNS effluent limitations are presented in TABLE XI-1.
TABLE XI-2 presents a list of the pollutants for which PSES and PSNS effluent
limitations cannot be proposed at this time due to the absence of proposed BAT
and NSPS effluent limitations.
EFFECTS OF PSES AND PSNS IMPLEMENTATION
Cost of Application and Effluent Reduction Benefits
The cost (1982 dollars) of implementation of PSES based on the installation of
a complete treatment system, which includes end-of-pipe controls, is estimated
to be 880 million dollars in capital costs with annual costs (including
amortization of the capital costs) of 404 million dollars' per year. The total
mass of toxic pollutants removed from discharges to POTWs is estimated to be
165 million lbs/yr.
Non-Water Quality Environmental Impacts
The non-water quality environmental impacts of PSES and PSNS will be similar
to those impacts from compliance with BAT and NSPS effluent limitations. For
more detailed information, refer to Sections IX and X.
XI -3
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TABLE XI-1
PRETREATMENT STANDARD EFFLUENT LIMITATIONS FOR
EXISTING AND NEW SOURCES
DAILY FOUR-DAY
POLLUTANT NAME MAXIMUM (ppb) AVERAGE (ppb)
Plastics-Only Subcategory
Acrolein 50
Cyanide 50 20
Lead 40 20
Vinyl Chloride 50
Not Plastics-Only Subcategory
2,4-Dimethylphenol 50
2,4-Dichlorophenol 200 100
2,4,6-Trichlorophenol 175 100
2-Chlorophenol 75 50
2-Nitrophenol 100 75
2,4-Dinitrophenol 150 100
4-Nitrophenol 500 325
Dimethyl Phthalate 375 175
Phenanthrene 50
Fluorene 50
Acenaphthylene 50
Isophorone 50
Methyl Bromide 50
Chloroethane 50
1,2-Dichloroethane 150 100
Total Chromium 190 90
Total Mercury 90 50
XI-4
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TABLE XI-2
POLLUTANTS FOR WHICH PSES AND PSNS EFFLUENT
LIMITATIONS COULD NOT BE ESTABLISHED
Plastics-Only Subcategory
Acrylonitrile
Zinc
Not Plastics-Only Subcategory
Benzo(a)Anthracene
Nitrobenzene
Benzo(a)Pyrene
2,6-Dinitrotoluene
Bis(2-Chloroisopropyl) Ether
2,4-Dinitrotoluene
Beryllium
Selenium
Thailium
Acrylonitrile
Chlorodibromomethane
Fluoranthene
XI-5
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SECTION XIII
GLOSSARY
ABSORPTION. A process in which one material (the absorbent) takes up and
retains another (the absorbate) with the formation of a homogeneous mixture
having the attributes of a solution. Chemical reaction may accompany or
follow absorption.
ACCLIMATION. The ability of an organism to adapt to changes in its immediate
environment.
ACID. A substance which dissolves in water forming hydrogen ions.
ACTIVATED CARBON. Carbon which is treated by high temperature heating with
steam or carbon dioxide to produce an internal porous particle structure. It
is used for adsorbing gases, vapojrs, and colloidal particles.
ACTIVATED CARBON ADSORPTION. A method of wastewater treatment used to remove
dissolved and colloidal organic material. Treatment systems can involve the
application of wastewater to a fixed-bed column containing granular carbon, or
the addition of powdered activated carbon to wastewater in a contacting
basin.
ACTIVATED CARBON REGENERATION. Regeneration of carbon after its adsorptive
capacity has been reached, involving oxidation and removal of organic matter
from the carbon surface.
ACTIVATED SLUDGE. Floe produced from raw or settled wastewater by the growth
of aerobic microorganisms during activated sludge treatment.
ACTIVATED SLUDGE PROCESS. A biological wastewater treatment process in which
a mixture of wastewater and activated sludge is agitated and aerated. The
activated sludge is subsequently separated from the treated wastewater (mixed
liquor) by sedimentation and wasted or returned to the process as needed.
ADDITION POLYMERIZATION. The combination of monomers by the direct addition
or combination of the monomer molecules with one another to form polymers.
ADSORPTION. A phenomenon whereby molecules in a fluid phase are attracted to
and held on a solid surface by a physical or weak chemical bond.
ADSORPTION" ISOTHERM. A plot used in evaluating the effectiveness of
activated carbon treatment by showing the amount of impurity adsorbed versus
the amount remaining. They are determined at a constant temperature by
varying the amount of carbon used or the concentration of the impurity in
contact with the carbon.
ADVANCED WASTE TREATMENT. Any treatment method or process employed following
biological treatment to increase the removal of pollutants, to remove
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substances that may be deleterious to receiving waters or the environment, or
to produce a high-quality effluent suitable for reuse in any specific manner
or for discharge under critical conditions. The term tertiary treatment is
commonly used to denote advanced waste treatment methods.
AERATED LAGOON. Bacterial stabilization of wastewater in a natural or
artificial wastewater treatment pond in which mechanical or diffused-air
aeration is used to supplement the oxygen supply.
AERATION. Contact between oxygen and a liquid by one of the following
methods: spraying the liquid in the air, bubbling air through the liquid, or
agitation of the liquid to promote surface absorption of air.
AERATION PERIOD. (1) The theoretical time, usually expressed in hours, that
the mixed liquor is subjected to aeration in an aeration tank undergoing
activated-sludge treatment. It is equal to the volume of the tank divided by
the volumetric rate of flow of wastes and return sludge. (2) The theoretical
time that liquids are subjected to aeration.
AERATION TANK. A vessel for injecting air into the water.
AEROBIC. Taking place in the presence of free molecular oxygen.
AEROBIC BIOLOGICAL OXIDATION. Any waste treatment or process utilizing
aerobic organisms, in the presence of air or oxygen, as agents for stabilizing
the organic load in a wastewater.
AEROBIC DIGESTION. A process in which microorganisms obtain energy by
endogenous or auto-oxidation of their cellular protoplasm. The biologically
degradable constituents of cellular material are slowly oxidized to carbon
dioxide, water and ammonia, with the ammonia being further converted into
nitrates during the process.
ALKALI. A water-soluble metallic hydroxide that ionizes strongly.
ALKYLATION- A process wherein an alkyl group (-R) is added to a molecule.
ALUM. A hydrated aluminum sulfate or potassium aluminum sulfate or anmioniuni
aluminum sulfate which is used as a settling agent. A coagulant.
AMMONIA NITROGEN. A gas released by the microbiological decay of plant and
animal proteins. When ammonia nitrogen is found in waters, it is indicative
of incomplete treatment.
AMMONIA STRIPPING. A modification of the aeration process for removing gases
in water. Ammonium ions in wastewater exist in equilibrium with ammonia and
hydrogen ions. As pH increases, the equilibrium shifts to the right and above
pH 9 ammonia may be liberated as a gas by agitating the wastewater in the
presence of air. This is usually done in a packed tower with an air blower.
AMMONIFICATION. The process in which ammonium is liberated from organic
compounds by microorganisms.
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AMMONOLYSIS. The formation of an amino compound using aqueous ammonia.
AMMOXIDATION^ The introduction of a cyanide group into an organic compound
via interaction with ammonia and oxygen to form nitriles.
ANAEROBIC. Taking place only in the absence of free molecular oxygen.
ANAEROBIC BIOLOGICAL TREATMENT. Any treatment method or process utilizing
anaerobic of facultative organisms, in the absence of air, for the purpose of
reducing the organic matter in wastes or organic solids settled out from
wastes.
ANAEROBIC DIGESTION. Stabilization of biodegradable materials in primary and
excess activated sludge by oxidation to carbon dioxide, methane and other
inert products. The primary digester serves mainly to reduce volatile
suspended solids (VSS), while the secondary digester is mainly for
solids-liquid separation, sludge thickening, and storage.
ANION. Ail ion with a negative charge.
API SEPARATOR. A primary physical wastewater treatment process capable of
removing free oil and sectleable solids from water.
AQUEOUS SOLUTION. A solution in which water is the solvent.
AUXILIARY FACILITIES. The non-productive facilities which provide utilities
and other services used by the manufacturing plant; also known as "offsite" or
"off-battery-limits" facilities: Includes "non-process equipment" and other
service facilities and buildings, change houses, etc.
AVERAGE. See "Mean."
AZEOTROPE. A liquid mixture that is characterized by a constant minimum or
maximum boiling point which is lower or higher than that of any of the
components and that distills without change in composition.
BACKWASHING. The process of cleaning a rapid sand or mechanical filter by
reversing the flow of water.
BADCT (NSPS) EFFLUENT LIMITATIONS. Limitations for new sources which are
based on the application of the Best Available Demonstrated Control
Technology.
BASE. A substance which dissolves in water forming hydroxy 1 ions.
BASIN. See "Lagoon."
BAT EFFLUENT LIMITATIONS. Limitations for point sources, other than publicly
owned treatment works, which are based on the application of the Best
Available Technology Economically Achievable. These limitations must be
achieved by July 1, 1964.
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BATCH PROCESS. A process which has'an intermittent flow of raw materials
into the process and, consequently, an intermittent flow of product and
process waste from the process.
BCT EFFLUENT LIMITATIONS. Limitations for conventional pollutants from point
sources, other than publicly owned treatment works, which are based on the
application of the Best Conventional Pollutant Control Technology; these
limitations must be achieved by July 1, 1984.
BIOCHEMICAL OXYGEN DEMAND (BOD). A measure of organic pollution in a water
or wastewater sample. It is determined by measuring the oxygen used by
microorganisms to oxidize the organic contaminants of a sample under standard
laboratory conditions.
BIOLOGICAL WASTEWATER TREATMENT. Forms of wastewater treatment in which
aerobic or anaerobic microorganisms are used to stabilize, oxidize, and
nitrify the unstable organic matter present.
BIOLOGICALLY REFRACTIVE. A substance which is partially or totally
nonbiodegradable in biological waste treatment processes.
BIOTA. The plant and animal life of a stream or other water body.
BLOWDOWN. The removal of a portion of any process flow to maintain the
constituents of the flow at desired levels.
B0D5. The standard test for biochemical oxygen demand (BOD) involving
incubation of the water or wastewater sample at -20°C for 5 days.
BPT EFFLUENT LIMITATIONS. Limitations for point sources, other than publicly
owned treatment works, which are based on the application of the Best
Practicable Control Technology Currently Available. These limitations must be
achieved by July 1, 1977.
BREAK POINT. The point at which impurities first appear in the effluent of a
granular activated carbon adsorption bed.
BREAK POINT CHLORINATION. The addition of sufficient chlorine to destroy or
oxidize all substances that create a chlorine demand with an excess amount
remaining in the free residual state.
BUFFER. A solution containing either a weak acid and its salt or a weak base
and its salt which thereby resists changes in acidity or basicity, i.e.,
resists changes in pH.
BULK ADDITION. See "Addition Polymerization."
CARBON ADSORPTION. A process used to remove pollutants from wastewaters by
contacting the water with activated carbon.
CARCINOGEN. A substance that causes cancer in animal tissue.
XIII-4
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CATALYST. A substance which changes the rate of a chemical reaction but
undergoes no permanent chemical change itself.
CATION. An ion with a positive charge.
CENTRAL LIMIT THEOREM. A statistical result which states that for a
sufficiently large sample size n, the distribution of means of random samples
from a population with finite variance will be approximately normal in form,
regardless of the form of the underlying population distribution.
CENTRATE. The liquid fraction that is separated from the solids fraction of
a slurry through centrifugation.
CENTRIFUGE. (a) The treatment process whereby solids such as sludge can be
separated from a liquid by the use of centrifugal force, (b) The machine used
to separate solids by centrifugal force.
CHELATING. Forming a compound containing a metal ion in a ring-like
molecular configuration.
CHEMICAL OXYGEN DEMAND (COD). A measure of the oxygen demand equivalent to
that portion of organic matter in a sample which can be oxidized by a strong
chemical oxidant.
CHLORINATION. The application of chlorine to water, sewage or industrial
wastes, generally for the purpose of disinfection but frequently for
accomplishing other biological or chemical results.
CLARIFICATION. Process of removing turbidity and suspended solids by
settling.
CLARIFIER. -A mechanical unit in which clarification is performed.
CLAYS. Aluminum silicates less than 0.002 mm (2.0 ym) in size. Because of
their size, most clay types can go into colloidal suspension.
CLEAN WATER ACT OF 197 7. P.L. 95-217; the 1977 Amendments to the Federal
Water Pollution Control Act of 1972.
COAGULANTS¦ Chemicals, such as alum, iron salts, or lime, added in
relatively large concentrations to reduce the forces tending to keep suspended
particles apart.
COAGULATION. The process whereby chemicals are added to a wastewater
resulting in a reduction of the forces tending to keep suspended particles
apart. The process occurs in a rapid or flash mix basin.
COLLOID. Tiny solid, semi-solid, or liquid particulates in a solvent that
are not removable by sedimentation.
COMBINED SEWER. A sewer which carries both sewage and storm water run-off.
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COMPLEXING. Forming a compound containing a number of parts, often used to
describe a metal atom associated with a set of organic ligands.
COMPOSITE SAMPLE. A combination of individual samples of wastes taken at
selected intervals to minimize the effect of the variations in individual
samples. Individual samples making up the composite may be of equal volume or
be roughly proportioned to the volume of flow of liquid at the time of
sampling.
CONCENTRATION. The total mass of the suspended or dissolved particles
contained in a unit volume at a given temperature and pressure.
CONDENSATION. (a) The change of state of a substance from the vapor to the
liquid form. (b) A chemical reaction in which two or more molecules combine,
with the separation of water or some other simple substance.
CONDUCTIVITY. A measurement of electrolyte concentration by determining
electrical conductance in a water sample.
CONSENT DECREE. The Settlement Agreement entered into by EPA with the
Natural Resources Defense Council and other environmental groups and approved
by the U.S. District Court for the District of Columbia on June 7, 1976 (8 ERC
2120, D.D.C. 1976), modified on March 9, 1979 (12 ERC 1833, D.D.C. 1979) and
again by Order of the Court dated October 26, 1982. One of the principal
provisions of the Settlement Agreement was to direct EPA to consider an
extended list of 65 classes of toxic pollutants in 21 industrial categories in
the development of effluent limitations guidelines and new source performance
standards. This list has since been, limited to 129 specific toxic pollutants
and expanded to 34 industrial' categories.
CONTACT PROCESS WASTEWATERS. Process-generated wastewaters which have come
in direct or indirect contact with the reactants used in the process. These
include such streams as contact cooling water, filtrates, centrates, wash
waters, etc.
CONTACT STABILIZATION. Aerobic digestion.
CONTINUOUS PROCESS. A process which has a constant flow of raw materials
into the process and consequently a constant flow of product from the
process.
CONTRACT DISPOSAL. Disposal of waste products through an outside party for a
fee.
CONVENTIONAL POLLUTANTS. Constituents of wastewater as determined under
Section 304(a)(4) of the Clean Water Act of 1977, including pollutants
classified as biochemical oxygen demand, suspended solids, fecal coliform, pH,
and oil and grease.
COOLING WATER - CONTAMINATED. Water used for cooling purposes only which may
become contaminated either through the use of water treatment chemicals such
as corrosion inhibitors or biocides, or by direct contact with process
materials and/or wastewater.
XIII-6
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COOLING WATER - UNCONTAMINATED. Water used for cooling purposes only which
has no direct contact with any raw material, intermediate, or final product
and which does not contain a level of contaminants detectably higher than that
of the intake water.
CRACKING. A process wherein heat and pressure are used for the rearrangement
of the molecular structure of hydrocarbons or low-octane petroleum fractions.
CRYSTALLIZATION. The formation of solid particles within a homogeneous
phase. Formation of crystals separates a solute from a solution and generally
leaves impurities, behind in the mother liquid.
CYANIDE A. Cyanides amendable to chlorination as described in "1972 Annual
Book of ASTM Standards" 1972: Standard D 2036-72, Method B, p. 553.
CYANIDE, TOTAL¦ Total cyanide as determined by the test procedure specified
in 40 CFR Part 136 (Federal Register, Vol. 38, no. 199, October 16, 1973).
CYCLONE. A conical shaped vessel for separating either entrained solids or
liquid materials from the carrying air or vapor. The vessel has a tangential
entry nozzle at or near the largest diameter, with an overhead exit for air or
vapor and a lower exit for the more dense materials.
DAILY DATA. Flow and pollutant measurements (BOD, COD, TOC, pH, etc.) taken
by certain plants on a daily basis for extended periods of time.
DAILY MAXIMUM LIMITATIONS. Effluent limitations for particular priority
pollutants determined by multiplying long-term median effluent concentrations
by appropriate variability factors.
DEALKYLATION¦ The removal of an alkyl group (-R) from a molecule.
DEEP WELL INJECTION. Disposal gf wastewater .into a deep well such that a
porous, permeable formation of a larger area and thickness is available at
sufficient depth to ensure continued, permanent storage.
DEGREASING. The process of removing greases and oils from sewage, waste and
sludge.
DEHYDRATION. The removal of water from a material.
DEHYDROGENATION¦ The removal of one or more hydrogen atoms from an organic
molecule.
DEMINERALIZATICN. The removal of ions from wastewater. Demineralization
processes include reverse osmosis, electrodialysis, and ion exchange.
DENITRIFICATION• Bacterial mediated reduction of nitrate to nitrite. Other
bacteria may further reduce the nitrite to ammonia and finally nitrogen gas.
This reduction of nitrate occurs under anaerobic conditions. The nitrate
replaces oxygen as an electron acceptor during the metabolism of carbon
XI11 - 7
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compounds under anaerobic conditions. The heterotrophic microorganisms which
participate in this process include pseudomonades, achromobacters and
bacilli.
DESORPTION. The reverse of adsorption. A phenomenon whereby an adsorbed
molecule leaves the surface of the adsorbent.
DIAZOTIZATION. The conversion of an amine (-NH2) to a diazonium salt by
reaction with nitrous acid.
DIGESTER. A tank, in which biological decomposition (digestion) of the
organic matter in sludge takes place.
DIGESTION, (a) The biological decomposition of organic matter in sludge. (b)
The process carried out in a digester.
DIRECT DISCHARGE. Discharge of wastewater into navigable water.
DISCHARGE. (a) To dispose of wastewater before or aftBr treatment to a water
source (stream, river, etc.) or to an additional treatment facility (e.g.,
POTW). (b) The wastewater being disposed.
DISSOLVED AIR FLOTATION. A flotation process that adds air to wastewater in
thB form of fine bubbles which become attached to suspended sludge particles,
increasing the buoyancy of the particles and producing more positive
flotation.
DISSOLVED OXYGEN (DO). The oxygen dissolved in sewage, water or other
liquids, usually expressed either in milligrams per liter or percent of
saturation. It is the test used in BOD determination.
DISTILLATION. A separation or purification process that involves
vaporization of a portion of a liquid feed by heating and subsequent
condensation of the vapor.
DOUBLE-EFFECT EVAPORATORS. Double effect evaporators are two evaporators in
series where the vapors from one are used to boil liquid in the other.
DRYING BED. A wastewater treatment unit usually consisting of a bed of sand
on which sludge is placed to dry by evaporation and drainage.
DUAL MEDIA FILTRATION. A deep-bed filtration system utilizing two separate
and discrete layers of dissimilar media (e.g., anthracite and sand) placed one
on top of the other to perform the filtration function.
EFFLUENT. (a) A liquid which leaves a unit operation or process.
(b) Sewage, water or other liquids which flow out of a reservoir basin,
treatment plant or any other unit operation.
EFFLUENT LIMITATION. A maximum permissible concentration or mass of
pollutant per unit of production (or time or other unit) of selected
constituents of effluent that is subject to regulation under the National
Pollutant Discharge Elimination System (NPDES).
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ELECTRODIALYSIS. The separation of a substance from solution through a
membrane accomplished by the application of an electric potential across to
the membrane.
ELECTROLYTIC. Relating to a chemical change produced by passage of a current
through a conducting substance (such as water).
ELUTION. (1) The process of washing out or removing a substance through the
use of a solvent. (2) In an ion exchange process, the stripping of adsorbed
ions from an ion exchange resin by passing solutions containing other ions in
relatively high concentrations through the resin.
ELUTRIATION. A process of sludge conditioning whereby the sludge is washed,
either with fresh water or plant effluent, to reduce the sludge alkalinity and
fine particles, thus decreasing the amount of required coagulant in further
treatment steps or in sludge dewatering.
EMULSION. A suspension of fine droplets of one liquid in another.
EMULSION ADDITION. See "Addition Polymerization."
END-OF-PIPE (EOP) TECHNOLOGIES. Final treatment processes used to remove or
alter selected constituents of the wastewater from manufacturing operations.
ENTRAINMENT SEPARATOR. A device to remove liquid and/or solids from a gas
stream. Energy source is usually derived from pressure drop to create
centrifugal force.
EQUALIZATION. A process by which variations in flow and composition of a
waste stream are averaged in an impoundment or basin.
EQUALIZATION BASIN. A holding basin in which variations in flow and
composition of a liquid are averaged.
ESTERIFICATION. The production of esters from carboxylic acids by the
replacement of the hydrogen of the hydroxy 1 group with a hydrocarbon group.
EVAPORATION POND. An open holding facility which depends primarily on
climatic conditions such as evaporation, precipitation, temperature, humidity,
and wind velocity to effect dissipation (evaporation) of wastewater. External
means such as spray recirculation or heating can be used to increase the rate
of evaporation.
EXISTING SOURCE. Any facility from which there is or may be a discharge of
pollutants, the construction of which is commenced before the publication of
proposed regulations prescribing a standard of performance under Section 306
of the Act.
FACULTATIVE. Having the ability to live under both aerobic or anaerobic
conditions.
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FACULTATIVE LAGOON. A treatment method combining both aerobic and anaerobic
lagoons. It is divided by loading and thermal stratifications into an aerobic
surface and an anaerobic bottom.
FEDERAL WATER POLLUTION CONTROL ACT AMENDMENTS OF 1972. Public Law 92-500
which provides the legal authority for current EPA water pollution abatement
projects, regulations, and policies. The Federal Water Pollution Control Act
was amended further on December 27, 1977, in legislation referred to as The
Clean Water Act (P.L. 95-217).
FEEDSTOCK. The material initially supplied to a process and used in the
production of a final product.
FERMENTATION. Oxidative decomposition of complex substances through the
action of enzymes or ferments produced by microorganisms.
FERRITE. A chemical compound containing iron.
FID. Flame ionization detection.
FILTER CAKES. Wet solids generated by the filtration of solids from a
liquid. This filter cake may be a pure material (product) or a waste material
containing additional fine solids (i.e., diatomaceous earth) that has been
added to aid in the filtration.
FILTRATION. A process whereby a liquid is passed through a porous medium in
order to capture and remove particles from the liquid.
FLOCCULANTS. Water-soluble organic polyelectrolytes that are used alone or
in conjunction with inorganic coagulants, such as lime, alum or ferric
chloride, or with coagulant aids to agglomerate solids suspended in aqueous
systems.
FLOCCULATION. The agglomeration of colloidal and finely divided suspended
matter that will settle by gravity.
FLOTATION. The raising of suspended matter as scum to the surface of the
liquid in a tank by aeration, the evolution of gas, chemicals, electrolysis,
heat, bacterial decomposition or natural density difference, and the
subsequent removal of the scum by skimming.
FLOW RATES. The amount of water or wastewater going into or out of a plant
during a certain time period (GPM, MGD, etc).
FRACTIONATION (OR FRACTIONAL DISTILLATION). The separation of constituents,
or group of constituents, of a liquid mixture of miscible and volatile
substances by vaporization and recondensing at specific boiling point ranges.
GC. Gas chromatography.
GC/CD. Gas chromatography/conventional detectors.
XIII-10
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«•
GC/MS. Gas chromatography/mass spectrometry.
GENERALIZED PLANT CONFIGURATION (GPC). Groups of organic and/or plastic
product/processes that represent entire manufacturing facilities or major
portions of plants, developed from responses to the 308 questionnaires. GPCs
have been used as part of EPA's investigation and computer analysis of
treatment unit process effectiveness and costs for the Organic Chemicals and
Plastics/Synthetic Fibers Industries.
GENERIC PROCESS CHEMISTRY. As defined in this document, classes of chemical
reactions which share a common mechanism or yield related products (e.g.,
chlorination, oxidation, aounoxidation, cracking and reforming, and
hydrolysis). Forty-one major generic processes have been identified in the
Organic Chemicals and Plastics/Synthetic Fibers Industries.
GRAB SAMPLE. (a) Instantaneous sampling; (b) a sample taken at a random
location and at a random time.
GRAVITY SEPARATOR. A treatment unit that uses density differences and
gravitational pull to separate two immiscible substances.
GRIT CHAMBER. A small detention chamber or an enlargement of a sewer
designed to reduce the velocity of flow of the liquid and permit the
separation of mineral from organic solids by differential sedimentation.
GROUND WATER. The body of water that is retained in the saturated zone which
tends to move by hydraulic gradient to lower levels.
HALOGENATION. The incorporation tsf one of the halogen elements (bromine,
chlorine, or fluorine) into a chemical compound.
HARDNESS. A measure of the capacity of water for precipitating soap. It is
reported as the hardness that would be produced if a certain amount of CaC03
were dissolved in water.
HEAVY METALS. A general name given for the ions of metallic elements, such
as copper, zinc, iron, chromium and aluminum. Heavy metals are normally
removed from a wastewater by the formation of an insoluble precipitate
(usually a metallic hydroxide).
HYDROCARBON. A compound containing only carbon and hydrogen.
HYDROFQRMYLATION. Addition of a formyl molecule (H-CHO) across a double bond
to form an aldehyde.
HYDROGENATION¦ A reaction of hydrogen with an organic compound.
HYDROLYSIS. A chemical reaction in which water reacts with another substance
to form two or more new substances.
HYDROXIDE. A chemical compound containing the radical group OH .
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IMHOFF TANK. A combination wastewater treatment tank which allows
sedimentation to take place in its upper compartment and digestion to take
place in its lower compartment.
IN-PLANT CONTROL TECHNOLOGIES. Controls or measures applied within the
manufacturing process to reduce or eliminate pollutant and hydraulic loadings
of raw wastewater.
IN-PLANT SOURCE CONTROL. Controls or measures applied at the source of a
waste to eliminate or reduce the necessity for further excessive treatment.
INCINERATION. The combustion (by burning) of organic matter in wastewater
sludge.
INDIRECT DISCHARGE. The discharge of wastewaters to publicly owned treatment
works (POTW).
INFLUENT. Any sewage, water or other liquid, either raw or partly treated,
flowing into a reservoir, basin, treatment plant, or any part thereof. The
influent is the stream entering a unit operation.
ION EXCHANGE. A treatment process in which metal ions and other contaminants
may be removed from waters by exchanging them with ions on a solid (resin)
matrix.
LAGOON. A pond containing raw or partially treated wastewater in which
aerobic or anaerobic stabilization occurs.
LANDFILL. A controlled dump for solid wastes in which garbage, trash, etc.,
is buried in layers separated and covered by dirt.
LC50. Lethal concentration 50; the concentration of a toxic material at
which 50 percent of the exposed test organisms die.
LD50. Lethal dose 50; the dose of a toxic material at which 50 percent of
the exposed test organisms die.
LEACH. To dissolve out by the action of a percolating liquid, such as water,
seeping through a sanitary landfill.
LIME. A substance formed from limestone, which is an accumulation of organic
remains consisting mostly of calcium carbonate. When burned, limestone yields
lime (a solid). The hydrated form of chemical lime is calcium hydroxide.
LIQUID-LIQUID EXTRACTION. The removal of a solute from another liquid by
mixing that combination with a solvent preferential to the substance to be
removed.
MASS FLOW. A measure of the transfer of mass in units of mass per time-area
mass (time x area).
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MEAN. Average; the sum of the items in a set divided by the number of
items.
MEDIAN. The number lying in the middle of an increasing or decreasing series
of number-s such that the same number of values appears above the median as do
below it.
METAL CATALYZED ADDITION. See "addition polymerization."
MICROBIAL. Of or pertaining to microbes, single-celled organisms (e.g.,
bacteria).
MIXED LIQUOR. A mixture of activated sludge and organic matter undergoing
activated sludge treatment in an aeration tank.
MIXED LIQUOR SUSPENDED SOLIDS (MLSS). A measure of the concentration of
matter in a biological treatment process.
MODE. The number which occurs with the greatest frequency in a set of
values.
MOLECULAR WEIGHT. The relative weight of a molecule compared to the weight
of an atom of carbon taken as exactly 12.00; the sum of the atomic weights of
the atoms in a molecule.
MONTHLY (4-DAY) AVERAGE LIMITATIONS. Effluent limitations for particular
priority pollutants determined by multiplying long-term median effluent
concentrations by appropriate variability factors.
MUTAGEN. Substance causing mutations or changes in the genetic material of
an organisms.
NATIONAL POLLUTION DISCHARGE ELIMINATION SYSTEM (NPDES). A federal program
requiring industry to obtain permits to discharge plant effluents to the
nation's water courses.
NAVIGABLE WATERS. Includes all navigable waters of the United States;
tributaries of navigable waters; interstate waters; intrastate lakes, rivers
and streams which are utilized by interstate travellers for recreational or
other purposes; intrastate lakes, rivers and streams from which fish or
shellfish are taken and sold in interstate commerce; and intrastate lakes,
rivers and streams which are utilized for industrial purposes by industries in
interstate commerce.
NEUTRALIZATION. The restoration of the hydrogen or hydroxyl ion balance in a
solution so that the ionic concentrations of each are equal.
NEW SOURCE. Any facility from which there is or may be a discharge of
pollutants, the construction of which is commenced after the promulgation of
proposed regulations prescribing a standard of performance under section 306
of the Act.
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NITRATE NITROGEN. The final decomposition product of the organic nitrogen
compounds. Determination of this parameter indicates the degree of waste
treatment.
NITRATION. The replacement of a hydrogen on a carbon atom with a nitro group
(-NO^) through the use of nitric acid or mixed acid.
NITRIFICATION. The conversion of nitrogenous matter into nitrates by
bacteria.
NITRITE NITROGEN. An intermediate stage in the decomposition of organic
nitrogen to the nitrate form. Tests for nitrite nitrogen can determine
whether the applied treatment is sufficient.
NON-CONTACT COOLING WATER. Water used for cooling that does not come into
direct contact with any raw material, intermediate product, waste product or
finished product.
NON-CONTACT PROCESS WASTEWATERS. Wastewaters generated by a manufacturing
process which have not come in direct contact with the products, wastes, or
reactants used in the process. These include such streams as noncontact
cooling water, cooling tower blowdown, boiler blowdown, etc.
NON-CONVENTIONAL POLLUTANTS. Pollutant parameters which have not been
designated as either conventional pollutants or toxic pollutants.
NON-WATER QUALITY ENVIRONMENTAL IMPACT. Effects of wastewater control and
treatment technologies upon aspects of the environment other than water,
including, but not limited to, air pollution, noise, radiation, sludge and
solid waste generation, and energy usage. Consideration of non-water quality
environmental impacts during the development of effluent limitations
regulations is required in sections 304(b) and 306 of the Clean Water Act.
NORMAL SOLUTION. A solution that contains 1 gm molecular weight of the
dissolved substance divided by the hydrogen equivalent of the substance (that
is, one gram equivalent) per liter of solution. Thus, a one normal solution
of sulfuric acid (H^SO^, mol. wt. 98) contains 98/2 or 49 gms of H S0^
per liter.
NSPS. New Source Performance Standards for new sources.
NUTRIENT. Any substance assimilated by an organisms which promotes growth
and replacement of cellular constituents.
NUTRIENT ADDITION. The process of adding nitrogen or phosphorous in a
chemically combined form to a waste stream.
OIL AND GREASE. (a) Oligenous liquids or gels that form scums and slicks on
water. (b) Those substances soluble in freon which are present in water and
wastes. Oil and grease are conventional pollutants as defined under EPA
regulations.
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OIL-RECOVERY SYSTEM. Equipment used to reclaim oil from wastewater.
ORGANIC LOADING. In the activated sludge process, the food to microorganisms
(F/M) ratio defined as the amount of biodegradable material available to a
given amount of microorganisms per unit of time.
OXIDATION, (a) A process in which an atom or group of atoms loses electrons,
(b) The introduction of one or more oxygen atoms into a molecule, accompanied
by the release of energy.
OXIDATION POND. A man-made lake or body of water in which wastes are
consumed by bacteria. An oxidation pond receives an influent which has gone
through primary treatment in contrast to a lagoon which receives raw untreated
sewage.
OXIDATION/REDUCTION (OR). A class of chemical reactions in which one of the
reacting species gives up electrons (oxidation) while another species in the
reaction accepts electrons (reduction).
0X0 PROCESS. A process wherein olefinic hydrocarbon vapors are passed over
cobalt catalysts in the presence of carbon monoxide and hydrogen to produce
alcohols, aldehydes, and other oxygenated organic compounds. Also known as
Tiydrocarbonylation and hydroformylation.
OXYACETYLATION. A process using ethylene, acetic acid, and oxygen commonly
used, to produce vinyl acetate.
OXYGEN ACTIVATED SLUDGE. An activated sludge process using pure oxygen as an
aeration gas (rather than air). This is a patented process marketed by Union
Carbide under the trade name "Unox".
OXYGEN, AVAILABLE. The quantity of atmospheric oxygen dissolved in the water
of a stream; the quantity of dissolved oxygen available for the oxidation of
organic matter in sewage.
OXYGEN, DISSOLVED. The oxygen (usually designated as DO) dissolved in
sewage, water, or another liquid and usually expressed in parts per million or
percent of saturation.
OZONATION. A water or wastewater treatment process involving the use of
ozone as an oxidizing agent.
OZONE. That molecular oxygen with three atoms of oxygen forming each
molecule. The third atom of oxygen in each molecule of ozone is loosely bound
and easily released. Ozone is used sometimes for the disinfection of water
but more frequently for the oxidation of taste-producing substances, such as
phenol, in water and for the neutralization of odors in gases or air.
PARAMETER. A representative variable which describes some sort of pollution
(BOD, TOC, etc.).
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PARTS PER MILLION (PPM). Parts by weight in sewage analysis, equal to
milligrams per liter divided by the specific gravity. Parts per million (ppm)
is always understood to imply a weight/weight ratio, although in practice
volume may be measured instead of weight.
PERCOLATION. The movement of water beneath the ground surface both
vertically and horizontally, but above the groundwater table.
PHOSPHATE. Phosphate ions exist as an ester or salt of phosphoric acid, such
as calcium phosphate rock. In municipal wastewater, it is most frequently
present as orthophosphate.
PHOSPHORUS PRECIPITATION. The addition of the multivalent metallic ions of
calcium, iron and aluminum to wastewater to form insoluble precipitates with
phosphorus.
PHYSICAL-CHEMICAL WASTEWATER TREATMENT. Processes that utilize physical and
chemical means to treat wastewaters.
POINT SOURCE. Any discernible, confined, and discrete conveyance from which
pollutants are or may be discharged.
POINT SOURCE CATEGORY. A collection of industrial sources with similar
function or product, established for the purpose of establishing federal
standards for the disposal of wastewater.
POLISHING. A final water treatment step used to remove any remaining
organics from the water.
POLISHING PONDS. Stabilization lagoons used as a final treatment step to
remove any remaining organics.
POLLUTANT LOADING. The ratio of the total daily mass discharge of a
particular pollutant to the total daily production expressed in terms of (g
pollutant)/(kg wet production).
POLYELECTROLYTES. Linear or branched synthetic chemicals (polymers) used to
speed up the removal of solids from sewage. These chemicals cause solids to
coagulate or clump together more rapidly than do chemicals such as alum or
lime. They can be anionic (negative charge), nonionic (positive and negative
charges) or cationic (positive charge—the most common). They have high
molecular weights and are water-soluble. Compounds similar to the
polyelectrolyte flocculants include surface-active agents and ion exchange
resins. The former are low molecular weight, water soluble compounds used to
disperse solids in aqueous systems. The latter are high molecular weight,
water-insoluble compounds used to selectively replace certain ions already
present in water with more desirable or less noxious ions.
POLYMER. A large molecule consisting of S or more identical connecting
units.
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PRECIPITATION. The phenomenon which occurs when a substance held in solution
passes out of that solution into solid form.
PRETREATMENT. Any wastewater treatment process used to reduce the pollution
load before the wastewater is discharged to a publicly owned treatment works
(POTW).
PRIMARY TREATMENT. The first major treatment in a wastewater treatment works
normally consisting of clarification, neutralization, and related
physical/chemical treatment.
PRIORITY POLLUTANTS. One hundred twenty-six compounds that are a subset of
the toxic pollutants specified in the 1976 Consent Decree and that were the
focus of study in the development of BAT regulations for the Organic Chemicals
and Plastics/Synthetic Fibers Industry.
PROCESS EQUIPMENT. All equipment and appurtenances employed in the actual
manufacturing process.
PROCESS WASTEWATER. Any water which, during manufacturing or processing,
comes into direct contact with or results from the production or use of any
raw material, intermediate product, finished product, by-product, or waste
product.
PROCESS WATER. Any water (solid, liquid or vapor) which, during the
manufacturing process, comes into direct contact with any raw materials,
intermediate product, by-product, waste product, or finished product.
PRODUCT/PROCESS. That chemical process used for producing a certain chemical
product; one process may be used for producing many products and, similarly,
one product may be made using different chemical processes.
PUBLICLY OWNED TREATMENT WORKS (POTW). Facilities that collect, treat, or
otherwise dispose of wastewaters, and are owned and operated by a village,
town, county, authority or other public agency.
PYROLYSIS. The transformation of a compound into one or more substances by
heat alone (i.e., without oxidation).
pH. A measure of the acidity or alkalinity of a water sample; equal to the
negative common logarithm of the hydrogen ion concentration.
QA/QC. Quality assurance/quality control.
RAW WASTE LOAD. The quantity of pollutant in wastewater prior to treatment.
RECEIVING WATERS. Rivers, lakes, oceans or other courses that receive
treated or untreated wastewaters.
RECYCLING. The reuse of materials by returning them to the process from
which they came or by using them in another process.
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REDUCTION. A process in which an atom (or group of atoms) gains electrons.
REFORMING. A process wherein heat and pressure are used for the
rearrangement of the molecular structure of hydrocarbons or low-octane
petroleum fractions.
REGENERATION. The renewing for reuse of materials such as activated carbon,
single ion exchange resins, and filter beds by appropriate means to remove
organics, metals, solids, etc.
RESIN. The solid substrate used in ion exchange process.
RETENTION TIME. Volume of the vessel divided by the flow rate through the
vessel.
REVERSE OSMOSIS. The separation of a solvent and a solute by the application
of pressure in excess of natural osmotic pressure to the solution side of the
membrane forcing the solvent to the other side.
ROTATING BIOLOGICAL CONTACTOR. See "rotating biological disc."
ROTATING BIOLOGICAL DISC. A treatment unit used to remove pollutants from
wastewaters whereby rotating discs containing sludge are partially submerged
into the wastewater allowing the sludge microorganisms to degrade the wastes.
SANITARY LANDFILL. A sanitary landfill is a land disposal site employing an
engineered method of disposing of solid wastes on land in a manner that
minimizes environmental hazards by spreading the wastes in thin layers,
compacting the solid waste to the smallest practical volume, and applying
cover material at the end of each operating day. The two basic sanitary
landfill methods are trench fill and area or ramp fill. The method chosen is
dependent on many factors such as drainage and type of soil at the proposed
landfill site.
SCREENING. The removal of relatively coarse, floating, and suspended solids
by straining through racks or screens.
SECONDARY TREATMENT. The second major step in a waste treatment system,
generally considered to be biological treatment.
SEDIMENTATION. The separation of suspended solids from wastewater by
gravity.
SEED. To introduce microorganisms into a culture medium.
SETTLEABLE SOLIDS. Suspended solids which will settle out of a liquid waste
in a given period of time.
SETTLEMENT AGREEMENT. See "Consent Agreement."
SETILING PONDS. An impoundment for the settling out of solids.
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SIC CODES. Standard Industrial Classification Codes used by the U.S.
Department of Commerce to denote segments of industry.
SKIMMING. The process of removing floating grease or scum from the surface
of wastewater in a tank.
SLUDGE. The accumulated solids separated from liquids, such as water or
wastewater, during processing.
SLUDGE POND. A basin used for the storage, digestion, or dewatering of
sludge.
SOLUBILITY. The ability of a substance to dissolve or become soluble in
another substance, usually water.
SOLUTE. The substance dissolved in a solvent.
SOLVENT. A liquid commonly used to dissolve or disperse another substance.
SOLVENT EXTRACTION. The extraction of selected components from a mixture of
two or more components by treating with a substance that preferentially
dissolves one or more of the components in.the mixture (liquid-liquid
extraction).
SPENT. Used material that will no longer accomplish that purpose for which
it is designed (e.g., spent activated carbon which will no longer adsorb
pollutants to an acceptable degree).
SPRAY EVAPORATION. A method of wastewater disposal in which the water in a
holding lagoon equipped with spray nozzles is sprayed into the air to expedite
evaporation.
SPRAY IRRIGATION. A method of disposing of some wastewaters by spraying them
on land, usually from pipes equipped with spray nozzles.
STABILIZATION POND. Large, shallow', earthen basins used for the treatment of
wastewater by natural processes involving the use of both algae and bacteria.
STANDARD OF PERFORMANCE. A maximum concentration or mass of pollutant per
unit of production (or time or other unit) for selected constituents of an
effluent that are subject to regulation.
STEAM DISTILLATION. Fractionation in which steam is introduced as one of the
vapors or in which steam is injected to provide the heat of the system.
STEAM STRIPPING. A treatment process used to remove relatively volatile
components by passing steam through a solution which transfers the components
from a liquid mixture to the gas phase.
STILL BOTTOM. The residue remaining after distillation of a material. The
residue can vary from a watery slurry to a thick tar which may turn hard when
cool.
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STOICHIOMETRIC. Characteristic of a chemical reaction in which reactants are
present in proportions such that there is no excess of any reactant following
completion of the reaction.
SUBCATEGORY. A segment of a point source category where most
characteristics of that segment are related but are distinct from other
segments of the category and are therefore subject to uniform national
standards.
SUBSTRATE. (1) Reactant portion of any biochemical reaction; the material
transformed into a product. (2) Any substance used as a nutrient by a
microorganisms. (3) The liquor in which activated sludge or other material is
kept in suspension.
SUPERNATANT. A substance floating above or on the surface of another
substance.
SURGE TANK. A tank for absorbing and dampening the wavelike motion of a
volume of liquid; an in-process storage tank that acts as a flow buffer
between process tanks.
SUSPENDED SOLIDS. Solids that either float on the surface of, or are in
suspension in, water, wastewater, or other liquids.
SUSPENSION ADDITION. See "Addition Polymerization."
TERATOGEN. Substance causing birth defects in the offspring following
exposure of one or both of the parents.
TERTIARY TREATMENT. The third major step in a waste treatment facility,
generally referring to treatment processes following biological treatment.
THICKENING. A process by which sludge is concentrated, usually by
sedimentation or centrifugation.
308 DATA. Information gathered from plants under authority of Section 308 of
the Clean Water Act.
TOTAL ORGANIC CARBON (TOC). A measure of the organic contamination of a water
sample.
TOTAL SUSPENDED SOLIDS (TSS). The entire amount of suspended solids in a
sample of water.
TOXIC POLLUTANTS. Pollutants declared "toxic" under Section 307(a)(1) of the
Clean Water Act.
TREATMENT TECHNOLOGY. Any pretreatment or end-of-line treatment unit which
is used in conjunction with process wastewater. The unit may be used at any
point from the process wastewater source to final discharge from plant
property.
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TRICKLING FILTER. A treatment unit consisting of broken stone or other
coarse material over which wastewater is applied and is allowed to trickle
through. Attached to the media are microorganisms'(sludge) which degrade
wastes in the wastewater.
ULTRAFILTRATION. A treatment similar to reverse osmosis except that
ultrafiltration treats solutions with larger solute particles so that the
solvents can more easily filter through the membrane.
UPSET. An unintentional noncompliance occurring for reasons beyond control
of the permittee.
VACUUM FILTRATION. A process used to reduce the water content of sludge. A
filter consisting of a cylindrical drum mounted on a horizontal axis and
covered with a filter cloth revolves partially submergenced in the liquid, and
a vacuum is maintained under the cloth for the larger part of each revolution
to extract moisture. The cake which forms on the filter is continuously
scraped off.
VARIABILITY FACTORS. Pollutant-specific peaking factors that relate the
numerical limitations for the maximum day and the monthly average to the
long-term median value.
VOLATILE SUSPENDED SOLIDS (VSS). The quantity of suspended solids lost after
the ignition of total suspended solids.
VOLATILITY. The ability of a substance to volatilize or evaporate.
WASTE STREAM. A separated or combined polluted water flow resulting from a
plant's processCes).
WASTE TREATMENT PLANT. A series of tanks, screens, filters, pumps and other
equipment by which pollutants are removed from water.
WASTEWATER. Process water contaminated to such an extent that it cannot be
reused in the process without repurification.
WATER USAGE. Ratio of the spent water from a manufacturing operation to the
total production, expressed in terms of (liters of wastewater/day)/(kilogram
of production/day).
WET AIR POLLUTION CONTROL. The technique of air pollution abatement
utilizing water as an absorptive media.
WET SCRUBBER¦ An air pollution control device which involves the wetting of
particles in an air stream and the impingement of wet or dry particles on
collecting surfaces, followed by flushing.
ZERO DISCHARGE. Methods of wastewater discharge from point sources which do
not involve discharge to navigable waters either directly or indirectly
through publicly owned treatment works. Zero discharge methods include
evaporation ponds, deep well injection, and land application.
XIII-21
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technical report data
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA 440/1-83/00%
3. RECIPIENT'S ACCESSION NO.
?<& 3 2 0 5 6 4 1
4. TITLE AND SUBTITLE
Development Document for Effluent Limitations Guide-
lines and Standards for the Organic Chemicals and
Plastics and Synthetic Fibers Point Source Category
5. REPORT DATE
February 1983 prpparat.inn
6. PERFORMING ORGANIZATION CODE
7. author(s) ¦ V0! i i» (bat)
E. H. Forsht
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADORESS 1
Effluent Guidelines Division WH-552
U.S. Environmental Protection Agency
401 M.St. S.W.
Washington, D.C. 20460
10. PROGRAM ELEMENT NO.
B4FB2B
11. CONTRACT/GRANT NO.
68-01-6701
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
401 M St. S.W.
Washington, P.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Proposed Develooment Pocumpnt
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This document presents the findings of studies of the organic chemicals and plastics
and synthetic fibers manufacturing point source category for the purpose of developine
effluent limitations guidelines for existing point sources. Effluent limitations
guidelines proposed herein are for "best practicable technology", "best conventional
technology", and "best available technoloay", new source performance standards and
pretreatment standards as recuired under Sections 301, 304, 306, 307, and 501 of the
Clean Water Act (the Federal Water Pollution Control Act Amendments of 1972, 33 U.S.C.
1251 et sea., as amended by the Clean Water Act of 1977, P.L. 0C-217 (the "Act")),
and as required under the Settlement Aareement in Natural Resources Defense Council,
Inc. v. Train, .8. ERC 2120 (D.D.C. 1976), modified 12 EP.C 1833 (D.D.C. 1979), and
modified again by*order of the court dated October 26, 1982.
This document contains the supporting data and rationale for development of the
effluent limitations and guidelines includinq subcategorization schemes, wastewater
characteristics* treatment technologies and costs.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS -
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Wastewater, Treatment, EPA, ReiUlations,
BPT, BAT, NSPS, PSES, PSNS, Organic
Chemicals, Plastics, Synthetic Fibers
18. DISTRIBUTION STATEMENT
Release Unlimited
IS. SECURITY CLASS /This Report)
21. NO. OF PAGES
<3.3 H
20. SECURITY CLASS (This page)
22. PRICE
EPA Form 2220-1 (9-73)
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