EPA
Addendum To
Development Document for
Proposed Effluent Limitations Guidelines
and New Source Performance Standards
for the
SYNTHETIC RESINS
Segment of the
PLASTICS AND SYNTHETIC
MATERIALS MANUFACTURING
Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
SI:PTI:MBI:K i<>74
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ADDENDUM
to the
DEVELOPMENT DOCUMENT
for
PROPOSED EFFLUENT LIMITATION GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
SYNTHETIC RESINS SEGMENT
of the
PLASTICS AND SYNTHETICS MANUFACTURING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
James L. Agee
Acting Assistant Administrator for
Water and Hazardous Materials
Allen Cyvvin
Director, Effluent Guidelines Division
David L. Becker
Project Officer
September, 1974
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, B.C. 20U60
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ABSTRACT
This document is an addendum to the Development Document for
Effluent Limitations Guidelines and Standards of Performance for
the Resins Segment of the Plastics and Synthetics Industry which
was prepared for the purpose of developing effluent limitations
guidelines for the industry to implement Sections 304, 306 and
307 of the Federal Water Pollution Control Act of 1972 (PL 92-
500). This addendum is a result of a substantial amount of
additional information made available by industrial sources
following publication of the original document. The guidelines
and standards developed herein are for the following products:
Epoxy Resins, Melamine Resins, Phenolic Resins, Urea Resins
The effluent limitations guidelines in this report set forth the
degree of reduction of pollutants in effluents that is attainable
through the application of best practicable control technology
currently available (BPCTCA) and the degree of reduction
attainable through the application of best available technology
economically achievable (BATEA) by existing point sources for
July 1, 1977, and July 1, 1983, respectively. Standards of
performance for new sources are based on the application of best
available demonstrated technology (BADT).
Annual costs for this segment of the plastics and synthetics
industry for achieving BPCTCA control by 1977 are estimated at
$2.0 million, and costs for attaining BATEA control by 1983 are
estimated at $6.4 million. The annual costs of BADT for new
sources in 1977 is estimated at $1.9 nrillion.
Supporting data and rationale for the development of proposed
effluent limitations guidelines and standards of performance are
contained in this development document.
iii
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TABLE OF CONTENTS
Section
I
II
III
IV
V
VI
VII
VIII
IX
Page No.
CONCLUSIONS 1
RECOMMENDATIONS 3
INTRODUCTION 11
Purpose and Authority 11
Methodology 12
General Description of the Industry 13
Product and Process Technology 17
Epoxy Resins 17
Phenolic Resins 24
Amino Resins 32
INDUSTRY CATEGORIZATION 39
WASTE CHARACTERIZATION 45
Raw Waste Loads 45
SELECTION OF POLLUTANT PARAMETERS 49
CONTROL AND TREATMENT TECHNOLOGY 51
Presently Used Waste Water Treat- 51
ment Technology
Potentially Usable Waste Water 54
Treatment Technology
COST, ENERGY, AND NONWATER QUALITY 55
ASPECTS
Cost Models of Treatment Tech- 55
nolcgies
Annual Cost Perspectives 55
Cost Per Unit Perspectives 56
Waste Water Treatment Cost Estimates 56
Industrial Waste Treatment Model 57
Data
Energy Cost Perspectives 57
Nonwater Quality Effects 57
Alternative Treatment Technologies 58
BEST PRACTICABLE CONTROL TECHNOLOGY 73
CURRENTLY AVAILABLE GUIDELINES AND
LIMITATIONS
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TAuLL OF CONTENTS (CCNT'D)
S-ction Paqe No.
Detinition of Best Fracticacle 73
Control Technoloqy Currently
Available (BPCTCA)
The Guidelines 74
Attainable Ettluent concentrations 7u
Cerrcnstrated Waste Water Flow 77
Statistical Variability of a 77
Properly Designed and Operated
Waste Treatment Plant
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY ^5
ACHIEVABLE
XI NEW SOURCE PERFORMANCE STANDARDS - BEST Q1
AVAILABLE DEMONSTRATED TiiCLNGLCGY
XII ACKNOWLEDGMENTS 9 "7
XIII REFERENCES ^y
XIV GLCSSARY 10?
VI
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LIST OF TABLES
Table No. Page
II-l Best Practicable Control Technology 5
Currently Available Effluent Limita-
tions Guidelines
II-2 Best Practicable Control Technology 6
Currently Available Effluent Limita-
tions Guidelines (Phenolic Compounds)
II-3 Best Available Technology Economically 7
Achievable Effluent Limitations
Guidelines
II-4 Best Available Technology Economically 8
Achievable Effluent Limitations
Guidelines (Phenolic Compounds)
II-5 Best Available Demonstrated Technology 9
for New Source Performance Standards
II-6 Best Available Demonstrated Technology 10
for New Source Performance Standards
(Phenolic Compounds)
III-l 1972 Consumption of Plastics and 15
Synthetics
III-2 Representative Plant Production 16
Capacities
III-3 Markets for Amino Resins 35
IV-1 Performance of Observed Waste Water 40
Treatment Plants
IV-2 Industry Subcategorization 42
V-l fcaste Water Loading for the Plastics and 46
Synthetics Industry
V-2 Plastics and Synthetics Industry - Raw 47
Waste Loads
V-3 Other Elements, Compounds and Parameters 48
VI-1 Other Eleirents and Compounds Specific 49
to Epoxy, Phenolic, Urea and Melamine
Resins
VII
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LIST OF TABLES (CONT'D)
Table No.
VII-1
VII-2
VIII-1
VII.I-2
VIII-3
viu-a
vin-a/i
vm-a/2
vin-a/3
VIII-4/U
vm-a/5
VIII-4/6
vm-a/7
vin-a/8
VIII-4/9
VIII-5
Operational Parameters of Waste Water
Treatment Plants (Metric Units)
Operational Parameters of Waste Water
Treatment Plants (English Units)
Perspectives on the Plastics and Syn-
thetics Industry - Water Usage
Perspectives on the Plastics and Syn-
thetics Industry - Treatment Costs
Perspectives on the Plastics and Syn-
thetics Industry - Cost Impact
Summary of Water Effluent Treatment
Costs - Cost Per Unit Volume Basis
Page
52
53
53
63
61
62
Water Effluent Treatment Costs - Epoxies 63
Water Effluent Treatment Costs - Epoxies 6U
Water Effluent Treatment Costs - Epoxies 65
Water Effluent Treatment Costs - Phenolics 65
water Effluent Treatment Costs - Phenolics 67
Water Effluent Treatment Costs - Phenolics 63
Water Effluent Treatment Costs - Phenolics 69
70
Water Effluent Treatment Costs - Urea
and Melamine
Water Effluent Treatment Costs - Urea
and Melamine
Industrial Waste Treatment Model Data
Plastics and Synthetics Industry
71
72
Vlll
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LIST OF TAELES (CONT'D)
Table No. Page
IX-1 COD/BOD Ratios in Effluent Streams 75
IX-2 CCD/BOD Guideline Bases 76
IX-3 Demonstrated toaste Water Flows 78
IX-U Demonstrated Variability 80
IX-5 Variability Factor 81
IX-6 Variables Projected for Suspended Solids 82
Removal
IX-7 Eest Practicable Control Technology 83
Currently Available - Effluent Limitations
Guidelines
IX-8 Eest Practicable Control Technology 84
Currently Available - Effluent Limitations
Guidelines (Phenolic Compounds)
X-l Key Parameters for Best Available Tech- 86
nology Economically Achievable
X-2 Best Available Technology Economically 87
Achievable - Effluent Limitations
Guidelines
X-3 Best Available Technology Economically 88
Achievable - Effluent Limitations
Guidelines (Phenolic Compounds)
X-4 Eest Available Technology Economically 89
Achievable - Flow Rate Basis
XI-1 Key Parameters for New Source Performance 92
Standards - Best Available Demonstrated
Technology
XI-2 Lowest Demonstrated Waste Water Flows 93
XI-3 Eest Available Demonstrated Technology for 9U
New Source Performance Standards
XI-4 Eest Available Demonstrated Technology for 95
New Source Performance Standards (Phenolic
Compounds)
XIII-1 Conversion Factors 110
IX
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LIST OF FIGURES
Figure No. Page
III-l Reactions Between Epichlorohydrin and 18
Bisphenol A
III-2 Liquid Epoxy Resin Production 20
III-3 Eatch Epoxy Resin Production 22
III-U Batch Fusion Solid Epoxy Resin Production 23
III-5 Typical Reaction to Form One-Step Resins 25
or Resols
III-6 Typical Reaction to Form Novolak Resin 27
III-7 Phenolic Resin Production 29
III-8 Phenolic Resin Processing 30
III-9 Typical Polymerization for Urea and 33
Formaldehyde
111-10 Typical Polymerization Reactions for 34
Melamine and Formaldehyde
III-ll Amino Formaldehyde Resin Production 37
XI
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SECTION I
CONCLUSIONS
In this reassessment of a part of the plastics and synthetics
industry, approximately 100 company operations are involved in
the production of the four products: epoxies, melamines, ureas,
and phenolics. The 1972 production for these four products was
estimated to be l.C million kkg (2.3 billion pounds) per year.
This is about 9 percent of the total (26 billion) pounds per year
production of eighteen larger-volume synthetic resins which were
studied earlier (including these four products).
The 1972 water usage was estimated to be 20 thousand cubic meters
per day (5.3 MGD). Water usage (at current hydraulic loads) was
projected to increase at 7.2 percent per year through 1977, while
production was projected to increase at 8 percent per year in the
same period.
For the purpose of setting effluent limitations guidelines and
standards of performance, the industry parameters giving the most
effective categorization were found to be those waste water
characteristics established earlier,(16) i.e..
Raw waste load, with a BODj> value of more than or less
than 10 kg/kkg of product separating high and low
waste load sufccategories and attainable BOD5> concen-
trations as demonstrated by plastics and synthetics
plants using technologies which are defined herein
as the basis for EPCTCA. Three groupings were
defined with average effluent concentrations under
2C mg/liter (low attainable BCD5> concentration) ,
from 30 to 75 mg/liter (medium attainable BODJ5
concentration), and over 75 mg/liter (high attainable
BOD5_ concentration) .
Based on these two dimensions of categorization, the four
products were placed in Major Sufccategories III and IV as given
below.
Major Subcategory I - low waste load, low attainable BOD^
concentration (0 products).
Major Subcategory II - high waste load, low attainable
EOD5 concentration (0 products) .
Major Subcategory III - high waste load, medium attainable
BOD5 concentration treatability (1 product: epoxy resins).
Major Subcategory IV - high waste load, low treatability
(3 products: phenolics, urea and melamines).
Additional subcategorization within the above four major
subcategories was necessary to account for the waste water
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generation wxiich is specific to the individual products and their
various processing irethcds. The separation of each individual
product into separate subcategories simplifies the application of
the effluent limitations guidelines and standards of performance
by providing clear and unambiguous direction for the proper
standard applicable to that product. The substantial advantage
of clarity appears to outweigh any technical advantages of
product grouping. Hence, for these reasons the individual
product subcategories are used for the application of effluent
limitations guidelines and standards of performance in this
category.
Further subdivisions was found desirable for these four resins.
For epoxy resins these were (1) batch and continuous manufacture
of liquid resins and the manufacture of solids and solution
resins and (2) manufacture by batch fusion. Fhenolics were
treated as a single category, cased on data from a plant that
produces a maximum of waste loading for this category. As more
information is developed, further subcategorization may be
desirable. Melamines and urea were combined into one category
since they are often produced in the same location, and are
processed in a similar fashion. Guidelines were developed for
all subdivisions except solids or solution manufacture of
melamines, phenolics and urea.
Annual costs of treatment in 1977 under EPCTCA guidelines for
tnese four products were estimated at $2.0 million cut of a total
of $62.5 million for the eighteen synthetic resins. By 1983,
under BATEA guidelines, existing plants would be expected to have
annual costs of $6.4 rrillicn (4 products) out of a total of
$177.1 million (18 synthetic resins). Ey 1977, under BADT-NSPS,
the annual costs for new plants are estimated at $1.9 million (4
products) out of a total of $34.9 million (18 products). The
estimated average costs over the four products for BPCTCA, BATEA,
and BADT-NSPS technologies respectively were: $0.34 ($1.29),
$1.06 ($4.00), and $0.75 ($2.85) per cubic meter (per thousand
gallons) .
The average range of water pollution control costs under BPCTCA
for the four products was estimated at 0.4 tc 1.0 percent of
current sales price. On average, the range of costs for applying
EATEA to existing plants was 1.4 to 3.5 percent of sales price.
The average cost of BADT-NSPS was estimated at 1.4 percent of
sales price.
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SECTION II
RECOMMENDATIONS
BODj>, COD and suspended solids are the critical constituents
requiring guidelines and standards. Other constituents are even
more specific to the product sutcategory and are summarized below
for this addendum group:
Sufccategory Other Element or Compound
Epoxy Resins Phenolic Compounds
Phenolic Resins Phenolic Corrpounds
Urea Resins Organic Nitrogen
Melamine Organic Nitrogen
Effluent limitations guidelines and standards of performance are
proposed for phenolic compounds for the specified product. The
additional pollutant parameter, organic nitrogen, was selected
because nitrogen chemicals are used in the processes and appear
in the waste waters of specific product subcategories. However,
insufficient data was available on raw waste loads or treated
waste waters to permit proposing guidelines and standards at this
time. Receiving water quality standards should determine if
limitations are necessary fcr organic nitrogen.
Best practicable control technology currently available (BPCTCA)
for existing point sources is based on the use of municipal
sewage treatment systems or the application of end-of-pipe
technology such as biological treatment for BOD.5 reduction as
typified by activated sludge, aerated lagoons, trickling filters,
aerobic-anaerobic lagoons, etc., with appropriate preliminary
treatment typified by equalization to dampen shock loadings,
settling, clarification, and chemical treatment for removal of
suspended solids, oils, other elements, and pH control, and
subsequent treatment typified by clarification and polishing
processes for additional BOD and suspended solids removal and
dephenolizing units for phenolic compound removal when needed.
Application of in-plant technology and changes which may be
helpful in meeting EPCTCA include segregation of contact process
waste from noncontact waste waters, elimination of once-through
barometric condensers, control of leaks, and good housekeeping
practices.
Best available technology economically achievable (EATEA) for
existing point sources is based en the best in-plant practices of
the industry which minimize the volume of waste-generating water
as typified by segregation of contact process waters from
noncontact waste water, maximum waste water recycle and reuse,
elimination of once-through barometric condensers, control of
leaks, good housekeeping practices, and end-of-pipe technology,
for the further removal of suspended solids and other elements
typified by media filtration, chemical treatment, etc., and
further COD removal as typified by the application of adsorption
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processes such as activated carbon and adsorptive floes, and
incineration for the treatment of highly concentrated small
volume wastes and additional biological treatment for further
BODJ3 removal when needed.
Best available demonstrated technology (EADT) for new source
performance standards (NSPS) are based on BPCTCA and the maximum
possible reduction cf process waste water generation as defined
in BATEA, the application of media filtration and chemical
treatment for additional suspended solids and other element
removal, and additional biological treatment for further BOD5
removal as needed.
The levels of technology defined above as EPCTCA, EATEA, and
3ADT-NSPS are correlated to effluent limitations guidelines and
standards of performance in the following tables. The tables are
based on attainable effluent concentration by the application of
EPCTCA, EATEA and EACT as defined above, demonstrated process
waste water flow rates, and consideration for the normal
variations which occur in properly designed and operated
treatment facilities.
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TABLE II-l
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
(kg/kkg (lb/1000 Ib) of Production)
Subcategory
BOD5
Maximum average
of daily values
for any period
of thirty
consecutive days
COD SS
Maximum for Maximum average Maximum for Maximum average Maximum for
any one day of daily values any one day of daily values any one day
for any period
of thirty
consecutive days
for any period
of thirty
consecutive days
Epoxy Resins
Batch & Continuous
(liquid, solid 6. solution)
Batch, Fusion (solid
& solution)
Phenolic Resins
0,25
3.7
3.9
0.45
6.7
32
3.9
19
58
6.7
34
1.4
0.17
1.5
2.6
0.30
2.7
Urea & Melanine Resins
Batch (liquid)
Q. 20
0.38
3.2
5.5
0.13
0.25
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TABLE II-2
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
(PHENOLIC COMPOUNDS)
kg/kkg (lb/1000 Ib) of production
Product Parameter Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
Epoxy Resins
Batch & Continuous
(liquid, solid &
solution) Phenolic Cmpds 0.011 0.022
Batch Fusion (solid
& solution) Phenolic Cmpds 0.0013 0.0025
Phenolic Resins Phenolic Cmpds 0.011 0.023
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TABLE II-3
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
kg/kkg (lb/1000 Ib of production)
Subcategory
BOD5
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
COD
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
SS
Maximum average Maximum for
of daily value's any one day
for any period
of thirty
consecutive days
Epoxy Resins
Batch & Continuous
(liquid, solid
& solution)
Batch, Fusion
(solid & solution)
0.95
0.12
1.3
0.17
4.8
0.65
6.5
0.8f
0.28
0.04
0.33
0.05
Phenolic Resins
0.96
1.3
6.8
0.30
0. 3.
Urea & Melamine Resins
Batch (liquid)
0.06
0.08
0.09
0.13
0.017
0.021
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TABLE 11-4
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
(PHENOLIC COMPOUNDS)
Product
Parameter
kg/kkg (lb/1000 Ib) of production
Maximum average
of daily values
for any period
of thirty
consecutive davs
Maximum for
any one day
co
Epoxy Resins
Batch & Continuous
(liquid, solid &
solution)
Batch, Fusion (solid
& solution)
Phenolic Cmpds
Phenolic Cmpds
0.0017
0.00022
0.0033
0.00044
Phenolic Resins
Phenolic Cmpds
C.0035
0.0035
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TABLE H-5
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
Subcategory
Epoxy Resins
Batch & Continuous
(liquid, solid &
solution)
kg/kkg (lb/1000 Ib of production)
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
0.67
1.2
COD
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
9.2
12.9
SS
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
0.20
0.30
Batch Fusion (solid
& solution)
0.11
0.19
1.5
2.1
0.03
0.05
Phenolic Resins
Batch (liquid)
0.69
1.3
19
34
0.21
0.31
Urea & Melamine Resins
Batch (liquid)
0.06
0.11
0.10
0.18
0.02
c.o.
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TABLE II-6
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
(PHENOLIC COMPOUNDS)
Parameter
kg/kkg (lb/1000 Ib of production)
Maximum average Maximum for
of 4aily values any one day
for any period
of thirty
consecutive davs
Epoxy Resins
Batch & Continuous
(liquid, solid &
solution)
Batch, Fusion
(solid & solution)
Phenolic Cmpds
Phenolic Cmpds
0.0012
0.00019
0.0024
0.00038
Phenolic Resins
Phenolic Cmpds
0.0013
0.0025
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SECTION III
INTRODUCTION
Purpose and Authority
Section 301 (b) of the Act requires the achievement by not later
than July 1, 1977, of effluent limitations for point sources,
other than publicly owned treatment works, which are based on the
application of the best practicable control technology currently
available as defined by the Administrator pursuant to Section 304
(b) of the Act. Section 301 (b) also requires the achievement by
not later than July 1, 1983, of effluent limitations for point
sources, other than publicly owned treatment works, which are
based on the application of the best available technology
economically achievable and which will result in reasonable
further progress toward the national goal of eliminating the
discharge of all pollutants, as determined in accordance with
regulations issued by the Administrator pursuant to Section 305
(b) of the Act. Section 306 of the Act requires achievement by
new sources of a Federal standard of performance providing for
the control of the discharge of pollutants which reflects the
greatest degree of effluent reduction which the Administrator
determines to be achievable through the application of the best
available demonstrated control technology, processes, operating
methods, or other alternatives, including, where practicable, a
standard permitting no discharge of pollutants.
Section 304 (b) of the Act requires the Administrator to publish,
within one year of enactment of the Act, regulations providing
guidelines for effluent limitations setting forth the degree of
effluent reduction attainable through the application of the best
practicable control technology currently available and the degree
of effluent reduction attainable through the application of the
best control measures and procedure innovations, operation
methods and other alternatives. The regulations proposed herein
set forth effluent limitations guidelines pursuant to Section 304
(b) of the Act for the epoxy, melamine, phenolic, and urea resins
of the plastic and synthetic materials manufacturing source
category.
Section 306 of the Act requires the Administrator, within one
year after a category of sources is included in a list published
pursuant to Section 306 (b) (1) (A) of the Act, to propose
regulations establishing Federal standards of performances for
new sources within such categories. The Administrator published
in the Federal Register of January 16, 1973 (38 F.R. 1624), a
list of 27 source categories. Publication of the list
constituted announcement of the Administrator's intention of
establishing, under Section 306, standards of performance
applicable to new sources within the plastic and synthetic
materials manufacturing source category, which was included
within the list published January 16, 1973.
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The effluent limitations guidelines and standards of performance
proposed in EPA U40/1-73/010, "Development for Proposed Effluent
Limitations Guidelines and New Source Performance Standards for
the Synthetic Resins Segment of the Plastics and Synthetic
Materials Manufacturing Point Source Category," were developed in
the following manner. The plastics and synthetics industry was
first categorized for the purpose of determining whether separate
limitations and standards are appropriate for its different
segments. Considerations in the industry subcategorization
process included raw materials, products, manufacturing
processes, raw waste characteristics and raw waste treatability
and attainable effluent concentrations.
The raw waste characteristics for each subcategory were
identified througn analyses of (1) the sources and volumes of
water and waste waters and (2) the constituents (including
thermal) of all waste waters including toxic or hazardous
constituents and ether constituents which result in taste, odor,
color, or are toxic to aquatic organisms. The constituents of
waste waters which should be subject to effluent limitations
auidelines and standards of performance were identified.
The full range of control and treatment technologies existing
within the industry was identified. This included an identi-
fication of each distinct control and treatment technology,
including both in-plant and end-of-process technologies, which
are existent or capable of being designed for each subcategory.
It also included an identification, in terms of the amount of
constituents (including thermal) and the chemical, physical, and
biological characteristics of pollutants, of the effluent level
resulting from the application of each of the treatment and
control technologies. The problems, limitations, and reliability
of each treatment and control technology and the required
implementation time were also identified. In addition, the
nonwater quality environmental impact, such as the effects of the
application of such technologies upon other pollution problems,
including air, solid waste, noise, and radiation, were
identified. The energy requirements of each of the control and
treatment technologies were identified as well as the cost of the
application of such technologies.
The information, as outlined above, was then evaluated in order
to determine what levels of technology constituted the "best
practicable control technology currently available," "best
available technology economically achievable," and the "best
available demonstrated control technology, processes, operating
methods, or other alternatives." In identifying such
technologies, various factors were considered. These included
the total cost of application of technology in relation to the
effluent reduction benefits to be achieved from such application,
the age of equipment and facilities involved, the process
employed, the engineering aspects of the application of various
types of control techniques process changes, nonwater quality
12
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environmental impact (including energy requirements), the
treatability of the wastes, water use practices, and other
factors.
The data for identification and analyses were derived from a
number of sources. These sources included EPA research informa-
tion, EPA permit applications, records of selected state
agencies, published literature, previous EPA technical guidance
for plastics and synthetics manufacture, a survey of waste water
treatment practice by the Manufacturing Chemists Association,
qualified technical consultation, and on-site visits and
interviews at plastics and synthetics manufacturing facilities
practicing exemplary waste water treatment in plants within the
United States. Samples for analyses were obtained from selected
plants in order to establish the reliability of the data
obtained. All references used in developing the guidelines for
effluent limitations and standards of performance for new sources
reported in EPA 440/1-73/010 are listed in Section XIII of that
document.
For these resins, the effluent limitations guidelines recommended
in the development document for Synthetic Resins (EPA 440/1-73/
010) were based on engineering judgment since no plant with an
exemplary waste water treatment facility was found. Subsequent
to publication of those guidelines, various manufacturers of
these resins preferred data and opinions on raw waste loads and
treatability to assist in the development of guidelines on a more
realistic basis. These data are the bases for the guidelines
developed in this document. Because these resins are usually
produced in multi-product manufacturing plants, the data have
been in the form of raw waste loads, hydraulic flows and the
performance characteristics of waste water treatment facilities
receiving effluents from more than one manufacturing process.
General Description of the industry
The plastics and synthetics industry in general is described in
EPA 440/1-73/010. Items relating directly to the resins covered
in this addendum, along with additional specific information, are
discussed in the following paragraph.
Epoxy resins are more frequently produced at different locations
than the phenolics, urea, and melamine resins. The latter three
are usually produced at the same location and often in the same
basic equipment. Therefore, the waste water from their
manufacture will often be combined.
Much of the liquid resin production of phenolics, ureas and
melamines are located near their principal end users, such as the
forest products industry where large quantities are used in
manufacturing chip beard and exterior plywood.
Except for the continuous processes for producing liquid epoxies,
these resins are made in batch kettles and reactors; the larger
13
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producers obtain their high rates by multiple vessels. Table
III-l shows an estimate of the 1972 consumption of these resins.
The principal producers of epoxy resins are Celanese, Ciba, Dow
Chemical, Reichhold, Resyn, Shell and Union Carbide. There are,
however, many other companies that buy resin from the major
producers for modification into special formulations.
Some of the larger producers of phenolic resins are Ashland,
Borden, Celanese, Ciba, Dow Chemical, General Electric, Georgia
Pacific, Hooker, Monsanto, OCF, PPG Industries, Pioneer, Rohm &
Haas, Schenectady Chemical and Union Carbide.
The major manufacturers of urea and melamine resins are Allied
Chemical, American Cyanamid, Ashland Chemical, Borden, Cargil,
Monsanto, Reichhold, Rohm & Haas and Scott Paper.
Plant sizes vary considerably within the subcategories discussed
in this addendum. There are many small plants making special
formulations from purchased resins; however, some also begin with
the monomers. Many of these are individual plants which may vary
production between several or all of the resin product
subcategories described. The larger plants are often part of a
petrochemical complex, often including production of one or more
of the monomers. Representative plant production capacities for
these subcategories are shown in Table III-2.
Because of their dependence on petroleum and gas feedstocks, many
of the large resin manufacturing plants are located on the Gulf
Coast. The Gulf Coast is a fortuitous location since a large
market exists in the lumber industry of the Southeast. However,
a significant number of resin manufacturing plants are located in
the Northwest and Central United States as well as a few in the
Northeast because the limited shelf life of the formulations
makes it more desirable to ship the raw materials over great
distances than the final product. Thus, a manufacturer of phenol
formaldehyde resin for grinding wheels may locate a plant in
upper New York State and buy his raw materials from petrochemical
plants located elsewhere in the country. Such products are
produced in relatively small quantities and often discharge their
waste water to municipal systems.
14
-------
TABLE III-l
1972 CONSUMPTION OF PLASTICS AND SYNTHETICS
Products
Urea and Melamine Resins
Phenolic Resins
Epoxy Resins
Consumption
1000 kkg
411
652
95
Number of
Companies
11
81
>29*
*Includes both unmodified and modified resins.
15
-------
TABLE III-2
REPRESENTATIVE PLANT PRODUCTION CAPACITIES
Product
Epoxy Resins
Batch & continuous (liquid, solid
& solution)
Batch, fusion (solid & solution)
Phenolic Resins
Batch (liquid)
Urea & Melamine Resins
Batch (liquid)
Plant Capacities
Small Large
Mil Ibs/yr 1QQQ kkg/yr Mil Ibs/yr 1QQQ kkg/yr
11.3
11.3
11.3
6.8
25
25
25
15
45.4
45.4
45.4
27.2
ICO
100
100
60
-------
Product, and Process Technology
Brief descriptions of the chemical nature of the products and the
manufacturing process technology are presented in this section
with special emphasis on indicating those process operations
which generate waste waters.
Epoxy Resins
Epoxy resins are characterized by the presence of the epoxy group
within their structure. Rather than an end resin in itself, the
epoxy family should be regarded as intermediates. They all
require further reaction with a second component, or curing agent
as the second material is often termed, in order to yield the
final thermoset material.
Almost all of the ccirmercially produced epoxy resins are made by
the reaction between epichlorohydrin and bisphenol A. Small
volumes, however, are produced from polyols other than bisphenol
A, such as aliphatic glycols and novolak resins formed from
phenol and formaldehyde. It is also possible to produce epoxy
resins by introducing the epoxy group after the polymer has been
formed. An example of this is the epoxidation of a polybutadiene
material. The double bond present in these materials forms the
site for the epoxy linkage. The following discussion, however,
is limited to the materials produced from epichlorohydrin and
bisphenol A.
Epichlorohydrin is a liquid with a boiling point of 117°C
(242°F). Bisphenol A is a solid which melts at 152°C (305°F).
Bisphenol A is insoluble in water, dissolving to the extent of
0.3 percent at 85°C (185°F) whereas epichlorohydrin is somewhat
more soluble (approximately 5 percent). The reaction between the
two raw materials takes place under alkaline conditions as shown
by the equations in Figure III-l. The first step, shown by
Equation 1, is the condensation of the epichlorohydrin with the
bisphenol A to form the chlorohydrin compound. This compound is
dehydrohalogenated with caustic soda to form epoxy linkages
yielding diglycidyl ether of bisphenol A, as shown by Equation 2.
Sodium chloride and water of reaction are also formed as by-
products with the ether. Further reaction between the ether and
additional bisphenol A results in growth in the chain length, as
shown by Equation 3.
Operating conditions and type of catalyst are selected to
minimize the formation of side chains and to prevent phenolic
termination of the principal chain. The final resin properties
are enhanced when the chain is terminated with epoxy groups, as
shown in Equation 3, and when the chain is linear with minimum
branching. The possibility of branching exists since
epichlorohydrin could react with the hydroxyl group to start a
side chain.
The product epoxy resins fall into two broad categories, the low
molecular weight liquids and the high molecular weight solids.
17
-------
(1) 2CH,-CHCHjCI
0
Epichlorohydrin
CH,
HO-V '~~c~^ y~°H
pH > 7
CH, Bfephenol A
CHi // \
CHjCHCHjO — \\ ,/— C —(' 7—OCH,CHCH,
\\ // I \ / I I
Cl OH ""' HO Cl
(2)
CHjCHCH,0
Cl OH
OCHjCHCH,
I I
OH Cl
2N«OH
2NaCI
(3)
—• + 1 CHjCHCH,0
' ' \\
Diglycidyl Ether of Bisphenol A
CH3
, + (-S-) HO-
—
• CH,CHCH2
\l
0
CH
. 0 (\ /V-C
\A // I
CH
CH3
OH
CH,
CH,
FIGURE 111-1 REACTIONS BETWEEN EPICHLOROHYDRIN AND BISPHENOL A
18
-------
In the liquids, n, the number of repeating units in the final
chain as designated in Equation 3, is low, ranging in commercial
materials from 0.1 to 0.6 as the average value. For solid
materials, n ranges from 1.8 to 16. Control over chain length is
exercised primarily by the ratio of the two reactants charged to
the system. To produce the low molecular weight liquids, a large
excess of epichlorohydrin is used so that n is close to 0 in the
final product. In order to produce the high molecular weight
solid resins, the ratio of epichlorohydrin per mole of bisphenol
A is usually less than 2.
There are two general approaches to carrying out the synthesis of
epoxy resins. In the one-step process all of the reactions shown
earlier proceed at the same time. These are usually carried out
in the presence of sodium or potassium hydroxide. In the two-
step process, reaction 1 is carried out by itself in the presence
of a catalyst. Sodium or potassium hydroxide is then added to
carry out the dehydrohalogenation and further condensation or
polymerization as a second stage.
Regardless of which of these two approaches is used, the overall
chemistry remains the same.
The product resins are utilized by the customer in conjunction
with a curing agent tc provide the crosslinking necessary to form
a thermo-set material. The curing agents used cover a broad
variety of materials such as amines, polyamides, acids, acid
anhydrides, resins such as phenolic, urea or rrelamine
formaldehyde combinations, any of which are capable of reacting
with either the epoxy groups or the hydroxyl groups present in
the resin. The specific material picked depends upon the
properties desired in the end resin.
There is substantial production of the so-called modified
epoxies. Most of these are manufactured by reacting some
material such as a fatty acid, tall oil or the like to form an
ester with some of the epoxy groups present in the resin. The
degree of esterification carried out depends upon the properties
desired in the final material. Most of these modified epoxies
find their way into coatings markets.
Manufacture and Waste Water Generation
Continuous Process, Liquid Resins and Liquid Resin Solutions
The low molecular weight liquid resins can be manufactured by
either batch or continuous processes. Most of the larger
producers utilize a continuous process for this material as well
as batch processes for the lower volume products. Figure III-2
shows a schematic flowsheet cf a typical continuous process.
Bisphenol A, with a large mole excess of epichlorohydrin, is
introduced into the polymerizer where, under the influence of the
catalyst and caustic conditions, the reaccion takes place. The
excess epichlorohydrin is vaporized from the material and
recycled.
19
-------
CATALYST
BISPHENOL A
SOLVENT
EPICHLOROHYDRIN
DILUTION WATER
50% NoOH
WATER
METHYL ISOBUTYL
KETONE
I
POLYMERIZATION
EPICHLOROHYDRIN
REMOVAL
EXTRACTION
SOLVENT
RECOVERY
LIQUID RESIN
PRODUCT
WASH
WATER
REACTIVE
SOLVENT
SOLVENT
BLENDING
1
LIQUID RESIN
SOLUTION
PRODUCT
FIGURE 111-2 LIQUID EPOXY RESIN PRODUCTION
20
-------
A solvent, usually a ketone such as methylisobutyl ketone, is
then added together with additional caustic and water. The
epoxidation of the resin takes place with the formation of salt.
A solution of resin in the ketone solvent is water-washed to
remove the final traces of salt, the decanted water is sent to
waste, and the solvent is removed by vaporization. The liquid
epcxy resin product is then sent to storage. Some resins are
redissolved in solvent to produce a liquid resin solution
product. Liquid resins are also produced in batch reactors, with
reactant ratios similar to the above description of the
continuous process, but in the equipment and processing steps as
described below.
Batch ProcesSj_Li.guid_and_Solid_Re_sins - The solid resins, which
have a high molecular weight, are produced by batch techniques in
resin kettles. In producing these marerials where the repeating
part of the epoxy chain is a high number ranging from 1.8 to 16,
the mole ratio of epichlorohydrin to bisphenol A charged to the
kettle is less than 2. No excess epichlorohydrin is used in this
case. The process is shown schematically in Figure III-3.
Aqueous sodium or potassium hydroxide is added to serve both as a
catalytic agent and as one of the reactants to form the epoxy
links during the polymerization reaction. Upon completion of the
polymerization reaction, the water-containing salt and a very
small amount of excess caustic are decanted to the process waste
water system.
A solvent such as methylisobutyl ketone is then added to dissolve
the resin, and the solution is washed with water to remove the
remaining amounts of sodium chloride and other salts which may be
present. This water is decanted to the process waste system, and
then the methylisobutyl ketone is vaporized and recovered from
the resin. The resins have melting points ranging from about 70-
150°C (158-302°F), if a solid resin is being made, and the final
temperature is such that the resin is molten. It is then drained
and cooled to form a solid mass which is crushed to provide the
final granular solid product, or blended with a solvent to make a
solid resin solution product.
If a liquid resin is being made, after recovery of the solvent,
the resin is either packaged directly as a liquid resin or a
solvent is introduced tc provide a liquid resin solution.
Batch Fus ion and_SoJ.id_Resin - A third process used by both the
basic epoxy resin producer and by those customers tailoring the
resin to various end uses is a nonaqueous fusion reaction
involving the thermoplastic epoxy resin, a reactive diluent and a
catalyst as shown in Figure III-4. Additional water of reaction
is produced, and the waste water load is primarily due to the
barometric condenser water (used to develop the vacuum in the
reactor), vent scrubbers (when not reacting under vacuum), and
housekeeping and maintenance water. The result is a low waste
water volume that contains a significant quantity of pollutants.
21
-------
BISPHENOL A
EPICHLOROHYDRIN
50% No OH
CAUSTIC DILUTION
WATER
WATER
METHYL ISOBUTYL
KETONE
SOLVENT
RECOVERY
SOLVENT
BLENDING
RESIN
SOLIDIFICATION
SOLID OR LIQUID
RESIN SOLUTION
PRODUCTS
RESIN
GRINDING
SOLID RESIN
PRODUCT
WASTE
WATER
FIGURE 111-3 BATCH EPOXY RESIN PRODUCTION
22
-------
LIQUID OR SOLID
EPOXY RESIN '
BISPHENOL A.
CATALYSTS-
REACTION
SOLVENT
1
REDISSOLVING
1
SOLID RESIN
PRODUCT
SOLID RESIN
SOLUTIONS
FIGURE 111-4 BATCH FUSION SOLID EPOXY RESIN PRODUCTION
23
-------
Phenolic Resins
The family of phenolic resins includes the oldest synthetic
polymers. The term is used to describe a broad variety of
materials, all of which are based upon the reaction between
phenol, or a substituted phenol such as creosol or resorcinol,
and an aldehyde such as formaldehyde or acetaldehyde. Nearly all
industrially significant resins, however, are based upon the
reaction of phenol with formaldehyde.
Phenol, commonly known as carbolic acid, is a solid at room
temperature but melts at between 42 and U3°C (107-109°F). It is
usually shipped and handled as a liquid by keeping it above its
melting pcint. Formaldehyde is normally a gas. Its most common
commercial form is foriralin, a 37 percent by weight solution of
formaldehyde and water.
There are two broad types of resins produced by this industry:
resols and novolaks.
Resols are formed frorr a mixture of phenol and formaldehyde which
contains an excess of formaldehyde. Often the mole ratio is about
1.5 to 1. An alkali such as sodium hydroxide is used to catalyze
the polymerization which takes place at a pH of between 8 and 11.
The reaction is shown in Figure III-5.
The reacting mixture contains sufficient formaldehyde so that, if
allowed to proceed to completion, a cross-linked thermo-set resin
would be formed. The reaction, however, is stopped short of
completion at an average molecular weight of the polymer
appropriate for the end use of the material. Three classes of
products are produced under the general grouping of "resols":
1. The least degree of reaction produces a
water soluble bonding resin which is either
sold "as is" or neutralized and partially
dehydrated.
2. Further reaction produces a water-"insoluble
resin which is vacuum dehydrated and dissolved
in solvents to produce laminating resins and
varnishes, using much less basic catalyst than
in making bonding resins. Some resols, such as
varnishes that are used in rubber cement, require
washing of the resin to remove salts; most other
resins do not require washing.
3. The third class of product is similar to 2, but
the water is removed and the reaction carried
even further to make a "one-stage" solid resin
that is then vacuum dehydrated and dropped from
the reactor for cooling and solidification.
These "one-stage" resins are then compounded into
a. bonding compounds and surface coatings,
24
-------
OH
Alkaline
Catalyst
HO-CH2
HO-CH2
4- 3H2O
CH2OH
FIGURE 111-5 TYPICAL REACTION TO FORM ONE-STEP RESINS OR RESOLS
25
-------
by adding catalysts and lubricants;
b. thermosetting molding powders by adding
catalysts, lubricants, pigments and fillers.
The compounding is sorretimes performed in the
same facilities where the resin is produced,
but more often the resin is shipped to custom
ccmpounders. Compounding is a dry operation
and adds negligible wastes to the resin manu-
facturing waste generation.
The material already contains sufficient formaldehyde to
completely cross-link the ultimate product so that it can be
thermally set into an infusable material by the application of
heat at the customer's facilities. Since cooling the mixture in
its partially polymerized form does not completely stop further
polymerization but merely retards it, these materials have a
somewhat limited shelf life (in the order of 60 days for many
types).
Novo_lakj5 are the second category of phenolic resins. These are
formed from a reacting mixture which contains a deficiency of
formaldehyde. The normal commercial range for this mole ratio is
between 0.75 and 0.90. To produce this material, polymerization
is carried out in an acid medium using a catalyst such as
sulfuric acid. The pH of the reaction usually ranges from 0.5 to
1.5. For special uses where high ortho linkage is desired, the
polymerization may be carried out at a pH of from 4 to 7, but
this is not typical. The reaction is shown in Figure III-6.
Since the reacting mixture contains a deficiency of formaldehyde,
essentially all of the formaldehyde is consumed during
polymerization. Since no further polymerization can take place,
the product is a low molecular weight, thermoplastic, stable
material. The water which enters with the formaldehyde plus the
water of reaction is removed under vacuum at the end of the
reaction, and a solid, meltable material results.
In order to complete the polymerization, the user must add
additional formaldehyde. Sometimes this is done by using
paraformaldehyde, a solid polymer of formaldehyde, but the
extremely irritating nature of this material has limited its use.
Most users complete the reaction by using hexamethylenetetramine.
With this material ammonia is evolved from the reacting mass,
leaving the same types of methylene linkages as can be obtained
by using additional formaldehyde.
The basic resins described above are sometiires modified by the
use of materials such as drying oils or epoxy compounds in the
final stages of polymerization. These modified phenolics find
many specialty uses but do not affect the basic manufacturing
processes to any significant degree.
26
-------
OH
Acid Catalyst
FIGURE 111-6 TYPICAL REACTION TO FORM NOVOLAK RESIN
27
-------
Manufacture and Waste Water Generation for Typical Phenolic
Resins
Although continuous processes for the production of phenolic
resins have been developed, they are seldom used. The production
of these continuous units must be high, and the industry calls
for such a wide variety of materials that it is seldom possible
to have a large enough run en a single grade of polymer to
justify their use.
The standard producing unit of the industry is typically a batch
resin kettle arrangement, such as is shown in Figure III-7. The
heart of the process, the resin kettle, varies in size from 7.6
to 38 cu m (2,000 to 10,000 gal.). These are jacketed, and in
the larger sizes internal cooling coils are used in order to
provide sufficient surface-to-volume ratio to remove the
considerable amount of heat generated during polymerization. The
kettles are agitated and can operate under either pressure or
vacuum conditions.
The feed system generally consists of two weigh tanks which weigh
in the required amounts of phenol and formaldehyde solution.
Commercial formaldehyde solution is available at 37 percent by
weight formaldehyde, but other concentrations are used, such as
44 or 50 percent. This solution often contains about 5 percent
methanol (from incomplete conversion or separation in
formaldehyde manufacture) which acts as a stabilizer. Other
stabilizers are now sorretimes used.
The kettle is equipped with a water-cooled condenser, which is
also joined to a vacuum system.
Figure III-8 shows the basic manufacturing steps and the
resulting products for resol and novclak production.
Resol Manufacture - In a typical production cycle for a resol
resin, the phenol is charged in a molten form to the kettle
followed by formaldehyde, which washes any residual phenol out of
the lines leading to the kettle. A sodium hydroxide catalyst
solution is then added, and the kettle is heated to bring the
mixture to a temperature of about 60°C (140°F). During this
period the condensation reaction starts and the reaction becomes
highly exothermic so that a change is made from supplying steam
to the coils to supplying cooling water. The mixture is held at
a temperature ranging from 60°C tc about 80°C (140-176°F) for a
period of three to five hours. During this period temperature is
controlled by circulating cooling water through the coils as well
as by using total reflux returning from the water-cooled
condenser mounted above the kettle. When the polymerization has
reached the desired degree, as shown by laboratory tests, the
mixture is cooled to about 35°C (95°F) to essentially stop
further reaction. At this point the caustic may be neutralized
by the addition of sulfuric acid, which brings the mixture to a
pH of about 7.
28
-------
CATALYST
/50% NaOH\
\66° H2S04/
PHENOL
VACUUM JET
WATER OR STEAM
4.
to
VD
FORMALDEHYDE
37%SOLN
WASH
WATER
(ONE STEP)
COOLING
WATER
(OR CONDENSATE)
COOLING
WATER
(OR STEAM)
SEWER
PRODUCT RESIN
MOLTEN SOLID TO COOLING & GRINDING
SYRUPS OR SOLUTIONS TO STORAGE
FIGURE 111-7 PHENOLIC RESIN PRODUCTION
-------
RESOLS
NOVOLAKS
MOLTON PHENOL CHGD TO REACTOR
U)
O
EXCESS FORMALDEHYDE CHGD
MOLTON PHENOL CHGD TO REACTOR
nzzzrz:
DEFICIENCY OF FORMALDEHYDE SOLN
CAUSTIC CATALYST CHGD
COOK 3-5 HRS ® 60-80°C UNDER
TOTAL REFLUX
[ SULFURIC ACID CATALYST CHGD
I
,'N CHGD I
COOL TO 35°C, NEUTRALIZE WITH SULFURIC
ACID TO STOP REACTION (OPTIONAL)
BONDING RESINS
(WATER SOLUBLE)
COOK 3-6HRS© 85-90°C UNDER
VACUUM REFLUX
VARNISHES AND LAMINATING
RESINS
UN ORGANIC SOLVENTS)
BONDING, SURFACE COATING
AND THERMOSETTING
MOLDING COMPOUNDS
(SOLID RESINS)
FIGURE 1118 PHENOLIC RESIN PROCESSING
-------
The mixture is then heated by admitting steam to the coil, and
the resin is purified by distillation. The water from this
distillation is a concentrated waste which contains unreacted
formaldehyde and phenol and low molecular weight resin, and may
be segregated for disposal by incineration.
The batch is then dumped. A few resins, such as varnish type
resols used as tackifiers for rubber cement, are washed two or
three times, thereby resulting in a considerable increase in
waste water and contaminants.
If a resin is required which contains a very small amount of
water such that it cannot be dehydrated at a temperature low
enough to prevent further polymerization, a vacuum is applied
during the latter part of the dehydration cycle. This technique
can be used to produce an essentially anhydrous melt of a single-
step resin.
The molten resin must be quickly discharged from the bottom of
the kettle through cooling plates for a quick quench in order to
prevent the mass from setting up into an insoluble, infusible
material. The cast material, when solidified, can be broken up
and crushed for shipment as a powder.
Noyolak Resin Manufacture - The manufacture of novolak resins is
entirely analogous except that an acid catalyst, such as sulfuric
acid, is added at the start of the batch. With strongly acid
catalysts it is necessary to utilize a vacuum reflux in order to
maintain temperatures at 85 to 90°C (185°F-194°F), a slightly
higher temperature range than that used for the one-step
reaction. Under milder reaction conditions, atmospheric reflux
is adequate to control the temperature.
At the end of the reflux period, three to six hours after
initiating the reaction, the condensate is switched to the
receiver and water is removed from the batch. When the
temperature reaches the order of 120 to 150°C (248-302°F) the
vacuum is applied to aid in removing the final traces of water
and part of any unreacted phenol. Final temperatures may rise to
about 160°C (320°F) under a vacuum of 63.5 to 68.5 cm (25 to 27
in.) of mercury. These higher temperatures are possible since
the reaction has proceeded to completion and, therefore, no
further polymerization can be carried out until additional
formaldehyde is added. The completed batch is dumped in the
molten form onto cooling pans where it solidifies, or onto a
flaker. If the product is needed in solution form, solvent is
added at the end of the batch as it cools in the kettle and the
solution discharged from the kettle to storage tanks for
drumming.
The finished products may be shipped to customers as such or may
be compounded with additives at the resin-producing point. The
solid resins may be ground, and wood fillers, pigmenting
materials and hexamethylenetetramine added to form a finished
31
-------
-------
molding compound. These processes all involve solids-handling
and do not normally give rise to waste water generation.
-------
Amino Resins - Urea and iMelamine
The term "amino resins" is used to describe a broad group of
polymers formed from formaldehyde and various nitrogen containing
organic chemicals. The nitrogen group is in the form of the NH£
radical. Although called amino resins most of the compounds used
are more of the nature of amides than true amines. The resins
are characterized as being thermo-setting, amorphous materials
which are insoluble in most solvents. Although many amino
compounds are used in the formation of amino resins, the two of
primary commercial significance are urea and melamine. Specialty
materials are formed from other aminc compounds such as thiourea,
acrylomide or aniline. These, however, are produced only in
small volumes and have little significance in the total amino
resin market.
Formaldehyde, the common raw material in all types of amino
resins, is normally a gas but is handled industrially as an
aqueous solution. It is infinitely miscible with water. Urea, a
solid under normal conditions, is highly soluble in water.
Melamine could be described as sparingly soluble and is also a
solid under the usual conditions, melting at the high temperature
of 355°C (671°F).
Another characteristic of the group of amino resins is that the
polymerization reaction proceeds in two distinct stages. In the
first of these, as indicated in Figure III-9, Equations 1 and 2
urea (depending upon the mole ratio of the reactants) forms
materials such as monomethylol urea and dimethylol urea which are
the reactive monomers involved in the final polymer. As
indicated in Equation 3, these materials may react among them-
selves to form dimers. Although the structure of just one dimer
is shown, a consideration of the active hydrogen groups involved
shows that many other dimers containing both methylene and ether
linkages are possible. The initial reaction is an addition
reaction with no water formed as a result of the combination.
The condensation reaction, as indicated by Equation 3, involves
the formation of one mole of water for each linkage formed.
As shown in Figure 111-10, the reactions in the case of rrelamine
and formaldehyde are entirely analagous to those shown for urea-
formaldehyde. It should be noted, however, that since melamine
contains three NH2 groups, permutations are much greater than is
the case for urea. Again, the first two reactions indicate the
initial step of the polymerization. This consists of the
formation of reactive monomers between melamine and formaldehyde.
The further reactions, as indicated schematically by Equation 3.
can involve the reaction of an additional mole of melamine with
one of the ironomers, shown in this case as trimethylol melamine,
to form condensation compounds which involve the elimination of
water of reaction. Although not shown, it can be readily
visualized that a mole of trimethylolamine could react with an
additional mole of triirethylolamine to eliminate water and form
an ether linkage as contrasted to the methylene linkage formed
between the trimethylolamine and another molecule of melamine.
32
-------
° o
II II
(1) H,N -C-NH2 + CH:O »• H2N-C-NH-CH2OH
Urea Formaldehyde Monomethylolurea
0 O
II II
(21 H2N-C-IMH2 + 2CH20 »• HOCH2 -NH-C-NH-CH2OH
Dimethylolurea
0 0
(3) H:N-C-NH-CH2OH + HOCH2-NH-C-NH-CH;OH
HOCH,
\u
II
0 N-C-NH-CH2OH +H20
H2N-C-NH-CH
FIGURE 111-9 TYPICAL POLYMERIZATION FOR UREA AND FORMALDEHYDE
33
-------
NH,
NHCH,OH
N N
(II
3 CH;0
NH,
N N
12)
NH.
N N
(3)
NH,
6 CH]0
NHCHjOH
N "N
II I
NOHjCHN—C C — NHCH-OH
\N<^
Trimethylol Melamine
HOCHj CH,OH
N N
HOH!C
CH,OH
HOH2C CHjOH
Hexamethylol Melamine
NH
NHCHjOH
CHjOH
NH,
NHCH.OH
N N
NH CH, NH
H,O
C C
\N^ \
NH,
NHCH.OH
FIGURE 111-10 TYPICAL POLYMERIZATION REACTIONS FOR
MELAMINE AND FORMALDEHYDE
34
-------
These reactions are catalyzed by hydrogen ions and, in general,
are moderated or slowed down by hydroxyl ions. Thus, the proper
pH selection is an important consideration in determining the
structure of the ultiirate polymer formed.
The basic amino resin manufacturing process is generally stopped
with the formation of a predetermined amount of monomers, dimers
and trimers depending upon the specifications desired for the
ultimate resin. This mixture of materials is then utilized by
the custorrer to form the final thermoset resin which is an
insoluble, heat resistant material. This is contrasted with the
mixture of very low rrolecular weignt materials produced by the
basic manufacturer which are usually water soluble, very heat
sensitive materials.
Consideration of the equations presented above will show there
are numerous possibilities for cross-linking the various
monomers, dimers and trimers which would be involved in the
initial stages of the reaction. The ultimate customer forms
these cross-links between the molecules by the application of
heat and pressure, sometimes with the aid of a catalyst depending
upon the nature of the application.
The ultimate markets for the amino resins are approximately as
shown in Table III-3.
TABLE III-3
MARKETS FOR AMINC RESINS
Percentage of Total Consumption
Application Amino Resins
Adhesives 36
Textile and Paper Treating and Coating 22
Laminating and Protective Coatings 18
Moulding Compounds and All Other Applications 2U
100
For most of these applications the resin is used in the form of
either an aqueous solution or a mixture of an aqueous and alcohol
solution, ethanol being the usual alcohol. For moulding
compounds and some of the others, a solid material is utilized.
In nearly all of these applications, the melamine part of the
amino resin family has superior properties. Because of its
higher cost, however, it is utilized principally where these
superior properties are necessary. The urea formaldehyde resins,
which are lower cost, are equally applicable in other instances.
Since, as mentioned above, the reactive monomers, polymers,
trimers and low molecular weight material formed by the basic
resin manufacturer contain all of the reactive groups necessary
to further crosslink, the solution materials have a limited shelf
35
-------
life, in the order of 60 days. Thus tne users who have a large
volume requirement for solution forms, such as paper mills,
textile mills, and the like, may purchase material made in
solution form by the manufacturer since they will utilize it
quickly and not have a residual inventory. Other users, where
the shelf life of the product is of considerable importance, will
purchase the material in an anhydrous solid form which has a
relatively indefinite shelf life. Often, before the final use,
the solid may be re-dissolved in either water or alcohcl or
mixtures thereof if a solution form is utilized in the
application.
Manufacture and Waste Water Generation
Since amino resins are produced in many specialty grades with
each run being a relatively modest volume, continuous processes
are not in general use in the industry. The typical process is a
standard tatch polymer kettle arrangement. As shown in Figure
111-11, the normal arrangement consists of a jacketed polymer
kettle ranged in size frcm about 7.6 to 38 cu m (2,000 to 10,000
gal.). The larger sizes contain internal coils for additional
heating and cooling surface in order tc provide a reasonable
surface-to-volume ratio. The kettles are agitated and can
operate under either pressure or vacuum conditions.
The kettle is equipped with a water-cooled condenser and tied
into a vacuum system so that the operating temperature can be
controlled through the use of both reflux and cooling or heating
in the jacket and coils of the kettle. The feed system consists
generally of weigh tanks for the batch operation of the kettle.
The techniques used are very similar for both melamine or urea
types of formaldehyde amino resins. As a typical example, the
production of a plywood adhesive grade urea formaldehyde resin is
as follows. Formaldehyde as a 30 percent solution is added to
the kettle and the pH adjusted to about 7 to 7.8. Boric acid,
the catalyst, is then added, and then urea in the form of a solid
is fed into the reaction vessel. The pH of the mixture is again
brought back to approximately neutral and the mixture heated to
100°C (212°F) under atmospheric reflux conditions. During this
initial heating period the pH drops to about 4 as the reaction
between urea and formaldehyde takes place to form di- and
trimethylol urea. Atmospheric reflux is maintained for a period
of about two hours. Then the vacuum is applied, and the system
temperature drops to approximately 40°C (104°F). It is
maintained at this level for approximately five hours. During
this period of time there is a small amount of condensation
reactions taking place between the various monomers formed
earlier. Simultaneously with this further reaction, water is
removed from the system so that the final water content, in the
case of this particular adhesive formulation, is about 50
percent. The water in the system comes from two sources - that
introduced with the 30 percent formaldehyde solution used as a
raw material, and that produced by the reaction between the
36
-------
FORMALDEHYDE
30% SOLN
BURIt, AUU
SODIUM
HYDROXIDE
I
\
UREA
(OR MELAMINE)
I
I
WEIGH
TANKS
COOLING
WATER
COOLING
WATER
(OR STEAM)
SEWER
RESIN SYRUP
TO STORAGE
OR DRYING
FIGURE 111-11 AMINO FORMALDEHYDE RESIN PRODUCTION
-------
monomers, which eliminates a mole cf water for each pair of
monomers cr trimers reacting.
At the end of the vacuum reflux period, the system is put on
total reflux and the pH adjusted to slightly alkaline conditions.
The reactor is then returned to atmospheric pressure, and the
product is ready to be removed. The total cycle time is about 10
hours.
The mixture, at this point in the form of a thick syrup, is
drained to storage where quality checks are made to determine the
exact condition of the polymers. The material may be shipped in
this form for further polymerization by the customer or it may be
dried to be shipped as a solid which, as mentioned earlier, has a
much longer shelf life. If the material is to be dried, it is
fed to either a belt drier or a spray drier where the remaining
water is removed at low temperature in order to prevent further
polymerization. As mentioned earlier, the final adjustment of
the pH also helps prevent further condensation reaction and
polymerization of the monomers. The water removed during these
final drying operations is vented to the atmosphere.
Depending upon the end-use requirements, the final solid product
may be milled with pigments, dyes and fillers to provide a
moulding compound suitable for the particular end use desired.
The equipment used for the production of the first-step amino
resins is often used for other materials, such as phenolics.
Between these different uses, and indeed between production
batches of melamine and urea resins or between batches of
significantly different resins, it is customary to clean the
equipment by utilizing a hot dilute caustic solution. This
material is drained as process waste.
38
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SECTION IV
INDUSTRY CATEGORIZATION
The most effective means of categorizing the plastics industry
for setting effluent guidelines is based on the characteristics
of the waste water. In particular, the two most relevant
characteristice are (1) raw waste load, expressed in kg of
pollutant/kkg of product, and (2) attainable BOD5_ concentrations
as demonstrated by plastics and synthetics plants using
technologies which are defined as the basis for EPCTCA. The data
on treated waste water characteristics obtained from
manufacturers of epoxy, melamine, phenolic and urea resins are
summarized in Table IV-1 along with data obtained on other
synthetic resins. They are grouped in four major subcategories
representing combinations of the waste characteristics discussed
above.
Major Subcategory I - A low raw waste load; raw waste
load less than 10 units/1000 units of product; attain-
able low BOD5 concentrations - less than 20 mg/liter.
Major Subcategory II - High raw waste load; raw waste
load greater than 1C units/1000 units of product;
attainable low BOD5 concentrations.
Major Subcategory III - High raw waste load;
attainable medium BOD5 concentrations - in the
30-75 mg/liter range.
Major Subcategory IV- High raw waste load; attain-
able high BOD5 concentrations over 75 mg/liter.
The attainable BOD5 concentration in the effluent is influenced
by the treatability and, for a specific plant, by the variations
in the influent concentrations. In major Subcategory I, where
raw waste loads are less than 10 units/1000 units and where
hydraulic flows ranged from 8.3 to 29.3 cu/m/kkg (1000 to 3500
gal/1000 Ib), the influent concentrations ranged from 33 to 530
mg/liter. Disregarding the low influent concentration of the
high density polyethylene plant, the influent concentrations
varied over nearly a five-fold range while the effluents varied
over a two-fold range. This indicates that practicable waste
water treatment plants should be capable of attaining effluent
BOD5 average concentrations in the vicinity of 15 mg/liter when
using properly designed and well operated biological systems.
The major Subcategory II plants are characterized by high raw
waste loads, but the waste waters can be treated to low
attainable BOD5 concentrations. Raw and effluent loads are a
factor of 10 higher than for the rrajor subcategory I plants,
largely because of the high water usage for rayon and cellophane
and the high BOD.5 influent concentration for ABS/SAN resins.
Major subcategory III plants are characterized by high raw waste
loads and moderate observed flows, which lead to high influent
concentrations. The waste treatment plants achieve BOD5_ removals
39
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TABLE IV-1
PERFORMANCE OF OBSERVED WASTEWATER TREATMENT PLANTS
BOD
COD
SS
Inlet Outlet Inlet Outlet Inlet Outlet
(mg/liter) (mg/liter) (rig/liter) (mg/llter) (ng/liter) (mg/liter)
Category III
*Epoxy, Batch & Cont. (liquid, solid
and solution)
*Epoxy, Batch Fusion (solid & solu.)
793
793
36
36
2063
2063
363
363
84
84
Category IV
**Urea & Melamine (liquid)
**Phenolic Resin
1310
1466
28
450
6460
5139
406
677
298
50
8
* These values were derived from raw waste data from the individual process combined with treatability
efficiencies observediimrmulti-product chemical complex treatment plants where the epoxy wastes were
a. significant portion of the total load.
** These values were calculated from expected wastes in a multi-product plant and using the treatability
demonstrated for the total wastes shown in Table VII-1 and VII-2.
-------
ranging from 96.5 to 99.3 percent, which are high efficiencies by
general standards of industrial waste treatment. Even with these
high removal efficiencies, effluent concentrations are moderate
due to the high concentration of the raw wastes. Major
subcategory IV plants have relatively high raw waste loads and
the observed attainable BOD_5 concentrations were found to be
high.
The design bases and operational modes of these plants are such
as to indicate that practicable waste water treatment technology
(e.g., two-stage biological treatment) might reduce the effluent
concentrations by a factor of nearly two which would make them
comparable to the plants appearing in major subcategory III.
However, attainable BOD5 concentrations below these levels has
not been documented.
Additional subcategorization within the above four major
subcategories was necessary to account for the waste water
generation which is specific to the individual products and their
various processing methods. The separation of each individual
product into separate subcategories simplifies the application of
the effluent limitations guidelines and standards of performance
by providing clear and unambiguous direction as to the proper
standard application to that product. The substantial advantage
of clarity appears to outweigh any technical advantage of product
grouping.
Further subdivisions were found desirable for these resins. For
epcxy resins these were (1) batch and continuous manufacture of
liquid resins and the manufacture of solids and solution resins
and (2) manufacture by batch fusion. Phenolics were not
subdivided: the guidelines were developed for a process employing
what we believe is maximum water and probably close to maximum
pollutant generation, due to product washings and product
changes. Some plants that do not wash the resin after reaction
will have considerably lower waste water generation as well as
pollutant discharge. Melamines and urea were combined and
treated similarly to phenclics. Guidelines were developed for
all subdivisions except solids or solution manufacture of
melamines, phenolics and urea; data were not made available for
these latter subdivisions.
The performance of observed waste water treatment plants in the
group of resins reported upon in this addendum report is shown in
Table IV-1. The resulting major industry subcategories and
product and process subdivisions for the groups of plastics and
synthetic material are reported in EPA U40/1-73/010 plus those
reported in this addendum. (See Table IV-2)
The exemplary treatment plant for phenolics manufacture employs
neutralization, settling and activated carbon treatment; this
system should be capable of achieving major subcategory IV
guideline limitations with the addition of biological oxidation.
41
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TABLE IV-2
INDUSTRY SUBCATEGORIZATION
Major Major
Subcategory III Subcategory IV
Epoxy Resin (batch, & cont., Phenolic Resin
liquid solid & solution)
Urea & Melamine Resin
Epoxy Resin (batch, fusion, solid (liquid)
& solution)
42
-------
Several other methods of subcategorization of the industry were
considered. These included plent size, plant age, raw materials
and products, and air pollution and solid waste generation. The
rate of higher unit treatment costs on smaller plants or their
potential for utilizing municipal systems was examined in the
economic analysis but was not sufficient to warrant
categorization. The age of the plants in this industry are
determined by obsolescence due to size or process changes and not
physical age. Siirilar raw materials are often used to make
dissimilar products. The impact of air pollution control and
solid waste disposal is not sufficient to warrant segmentation.
For those reasons, none of the above-mentioned factors had
sufficient impact on categorization of the industry to be
considered further.
43
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-------
SECTION V
WASTE CHARACTERIZATION
The general process flow diagrams in Section III indicate the
major waste water generation points for individual processes as
furnished by the manufacturers. Flow rates and compositions of
process waste water streams were limited in number and are
usually based on either estimates established in conjunction with
operating personnel or limited measurements. In the manufacture
of epoxy, melamine, phenolic and urea resins, there is a
significant volume of waste water from housekeeping and ether
nonprocess sources such as the cleaning of reactors.
Raw Waste Loads
The waste water loadings for these resins are shown in Table V-l,
and the ranges of raw waste loads are recorded in Table V-2.
Other pollutants which may occur from the manufacture of resins
are listed in Table V-3.
45
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TABLE V-l
WASTEWATER LOADING FOR THE PLASTICS AND SYNTHETICS INDUSTRY
Product
Wastewater Loading
(cu m/kkg)
Observed Reported
Flow Range
Wastewater Loading
(gal./lOOO Ibs)
Observed Reported
Flow Range
Epoxy Resins
Batch & Continuous (liquid, solid
& solution)
Batch Fusion (solids & solution)
24.2
7.1
2)9oo 2,200-4,200
850 600-1,100
Phenolic Resins
Urea & Melamine Resins
Batch (liquid)
6.9
1.0
0.5-20
830
150
60-2400
-------
TABLE V-2
PLASTICS AND SYNTHETICS INDUSTRY
RAW WASTE LOADS
All units expressed as kg/kkg (lb/1000 Ib) of production
, COD SS
Product *Reported Observed *Reported Observed *Reported Observed
Range Value Range Value Range Value
Epoxy Resins
Batch & Continuous
(liquid, solid &
solution) 57-82 15-150 30-127 65-618 5-24
Batch Fusion (solids and
solution) 57-82 0-25 30-127 0-100 5-24
Phenolic Resins **15-51 ***20-72 **90-64 ***52-188 **0.5-7 1.2-21
Urea & Melamine Resins
Batch (liquid) - 13 - 60 -
* From survey by the Manufacturing Chemist Association and Celanese Corporation studies.
** Presumed to include all raw waste load.
Assumes concentrated wastes from reactor does not appear in wastewaters.
-------
TABLE V-3
OTHER ELEMENTS, COMPOUNDS AND PARAMETERS
PH
Color
Turbidity
Alkalinity
Temperature
Nitrogenous Compounds(organic, ammonias and nitrates)
Oils and Greases
Dissolved Solids - principally inorganic chemicals
Phosphates
Phenolic Compounds
Sulfides
Cyanides
Fluorides
Mercury
Chromium
Copper
Lead
Zinc
Iron
Cobalt
Cadmium
Manganese
Aluminum
Magnesium
Molybdenum
Nickel
Vanadium
Antimony
Numerous Organic Chemicals
48
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SECTION VI
SELECTION OF POLLUTANT PARAMETERS
The rationale for the selection of pollutant parameters has been
discussed in EPA Document 440/1-73/010 and remains the same for
these resins. Other elements and compounds specific to epoxy,
melamine, phenolic and urea resins are given in Table VI-1.
TABLE VI-1
OTHER ELEMENTS AND CONFOUNDS SPECIFIC TO
EPOXY, PHENOLIC, UREA AND MELAMINE RESINS
Other Element or Compound
Epoxy Resins Phenolic Compounds
Phenolic Resins Phenolic Compounds
Urea & Melamine
Resins Organic Nitrogen
49
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-------
SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
The control and treatment technology applicable to the waste
waters frcm epoxy, melamine, phenolic and urea resin manufacture
is similar to that discussed in the EPA Document UUO/1-73/010.
The operational parameters of waste water treatment facilities
for these resins are given in Tables VII-1 and VII-2.
Pollutional parameters of special significance to this group of
resins are (1) phenolic compounds from the epo^cy and phenolic
resins and (2) nitrogenous compounds from melamine and urea resin
manufacture. Otherwise, the waste water treatment parameters are
the same as for other resin manufacturing operations.
Presently Used Waste Water Treatment Technology
Since the bulk of these resins are produced in batch processes
where the probability of spills or tad batches tend to be higher
than with continuous processes, shock loads on treatment
facilities are of particular concern; hence, good current
practice includes not only equalization basins but also holding
capacity to absorb the surges of the concentrated wastes which
are subsequently slowly bled into the treatment plant.
Neutralization is also generally practiced since acids or bases
are common catalysts used in the polymerization reactions.
Initial treatment frequently consists of removal of solid
polymeric materials which are not significantly affected by
biological systems.
The concentrated wastes obtained from decanting the reactor
products from liquid phenolics manufacture are usually segregated
and dc not appear in waste water streams.
The phenolics compounds in waste water from epoxy and phenolic
resin manufacture are treated by both biological and activated
carbon systems. The biological treatment plants observed handle
mixed wastes from chemical complexes; consequently insufficient
data was obtained to establish the effectiveness of biological
treatment on wastes from a plant producing only one of these
resins. The phenolics plant where activated carbon is used for
waste water treatment was essentially manufacturing a single
product.
The urea and melamine compounds contained in the waste streams
from those processes present a particularly difficult problem in
biological treatment plants since they oxidize slowly and,
therefore, need long retention times to be adequately degraded.
In addition, the excess of nitrogenous compounds requires the
controlled additior of phosphorous to maintain the proper balance
of nutrients. Control of this balance is difficult due to the
51
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TAF.LE VU-1
OPERATIONAL PARAMETERS 01' WASTKWATT.K TKIIAIVII.NT PLANTS
(Metric Units)
Type of Plant
1. Type of Treatment
Epoxy Resins
„<*>
Phenolic Kt.-.-.In
(4)
OJ1 Sep., Neut.
Chcm. Coag.,
Flotation, Bio-ox.,
Clarlfier
Settling, Knit.,
Chera. Cd.i|;. , Kqual . ,
Clarlf., At I. Carbon
Mr.-;i Resins
(4)
I'.io-i.x., Cl.-uif.
Pol f';h
2. Hydraulic Load 27,252
(cu m/day)
3. Residence Time (hrs) 30
4. SOU. (kg removed/ 0.65
day/cu m)
5. COD (kg removed/ 1.56
day/cu m)
6. Power (hp/cu m) 0.079
7. BOU, (kg removed/ 0.36
hp-fir)
8. Suspended Solids 84
(mg/liter)
9. Clarifler Overflow 10.6
(m/day)
10. Blomass (mg/liter) 3,500
11. BOD (kg removed/day/ 0.23
kg HLSS)
12. Typical Values NH.-N out (1)
(mg/liter)
13. Typical Values TKN out (1)
(mg/liter)
14. BOD, in (mg/liter) 837
15. BODj out (mg/liter) 36
16. COD/BOD in 2.7
17. COD in (mg/llter) 2,255
18. COD out (mg/liter) 363
19. COD/BOD out 10.1
20. Efficiency, BOD (%) 95
21. Efficiency, COD (*) 82
22. Phenolics in (mg/llter) 200
23. Phenolics out (mg/liter) 1.4
24. Efficiency, Phenolics (2) 99
1,041
246
43
0.54
3.15
10
1,466
450
3.5
5,139
677
1.5
70(2)
87
159
39
76
354(3)
0.088
0.41
0.029
0.11
50
21.1
4,000
0.03
1.8
16.6
131
2.8
4.9
646
41
14.7
98
94
0.018
(1) Nutrients added.
(2) No bio-oxidation, primary and tertiary treatment only.
(3) Residence time is 40 days (9&0 hours) if total volume of system is included:
urea compounds are slow-release chemicals.
(4) Data arc from wastewater treatment facilities handling effluents from multi-product plants.
52
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TAlil.K VI1-2
DPI.RATIONAL PARAMKTERS 01' WASTEWATER TRLATMENT PLANTS
(English Units)
1.
2.
3 _
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
Ty;.r (.f I'KUlt
Type i,l' 'i'lv.Hi'vut
llydr.iuiK- U-.id (MGD)
BOD (/•'!, i.,,-v,'d/day/
1000 it-1)
COD (II ri-iuovcd/d.iy/
1000 ft )
Power (Hl'/iOOO It3)
BODt (i: n-vovu d/dav/
5 1000 UJ) '
Suspended Solids
(Eg/liter)
Clarifier Overflow
(GPD/ft )
Bioraass (lag/liter)
HOD, (II reaoved/day/ff
MLSS)
Typical Values Nil
N-out (eg/liter)
Typical Values TKN out
(mg/liter)
BOD, In (mg/liter)
BOD out (icg/liter)
COD/BOD^ in
COD in (mg/liter)
COD out (mg/liter)
COD/BODjOut
Efficiency, EODj (%)
Efficiency, COD (%)
Phenolics in (mg/liter)
Phenolics out (mg/litar)
Efficiency, Phenolics (X)
(4)
l.poxy Resins
Oil Sup. , Ncut .
Chen. Coag.,
KloLntion, Blo-ox.,
Clavifier
7.2
30
40
96
2.2
0.8
84
260
3,500
0.23
(1)
(1)
837
36
2.7
2,255
363
10.1
95
82
200
1.4
99
Phenolic Rosins ' Urea Resins^ '
Settling, Neut., Equal., 2-stage
Chem Coag., Equal., Bio-ox., Clarif.
Clarif., Act. Carbon Polish
0.275 0.065
(Vl
43 354
33 5.4
194 25.5
0.8
0.24
10 50
517
4,000
0.03
18.4
166
1,466 1,310
450 28
3.5 4.9
5,139 6,460
677 406
1.5 14.5
70<2) 98
87 94
159
39 0.018
76
(1) Nutrients added.
(2) No bio-oxidation, primary and tertiary treatment only.
(3) Residence time is 40 days (9bO hours) if total volume of system is included:
urea compounds arc slow-release chemicals.
(A) Data ate from wastewater treatment facilities handling effuents from
multi-product, plants.
53
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lack of a good on-line measurement. Further discussion of this
problem is found in Section VII of EPA 440/1-73/010.
During the course of the survey on this group of resins, four
plant visits were made and three companies were contacted by
telephone to obtain information relative to waste loads and
treatability. The visits were made to companies who had
expressed dissatisfaction with the original guidelines and who
offered assistance to obtain a better data base. Even with this
new base, considerable judgment was required to develop
guidelines since most plants were part of chemical plant
complexes.
It was found that the principal differences between this new data
base and that used in developing the original guidelines were due
to a greater hydraulic and pollutant load that arises from
housekeeping, equipment cleaning and once-through barometric
condensers and coolers. In addition, further subcategorization
appeared reasonable. Although no completely independent
exemplary waste water treatment plants were found for this
section of the industry, the data provided were presumed to be
the best available and guidelines were developed accordingly.
Potentially Usable Waste Water Treatment Technology
The discussion in EPA 440/1-73/010 of potentially usable waste
water treatment technology applies to the subgroups considered in
this addendum. The use of activated carbon for removal of
phenolic compounds from the waste waters of phenolic resin plants
was found to be in practical operation as well as the use of
extended aeration for the degradation of the slowly oxidizable
wastes frcm urea resin manufacture.
54
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SECTION VIII
COST, ENERGY, AND NONWATER QUALITY ASPECTS
Approximately 100 company operations participate in the
manufacture of the four products for which guidelines and
standards are recommended. Seme of the 100 company operations
include multi-plant divisions; seme represent multi-product
plants.
Total production in 1972 for these products was estimated at 1.0
million kkg or 2.2 billion pounds per year. Overall, production
of these products is expected to grow at 8 percent per year.
Current water usage (1972) is estimated at 20 thousand cubic
meters per day (5.3 MGD). Assuming that hydraulic loads (unit of
flow/unit cf production) remain constant, water usage is expected
to grow to 29 thousand cubic meters per day (7.5 MGD) or at 7.2
percent per year through 1977. Approximately 10 percent of
current discharge from the production of these products was
estimated to be treated in municipal systems.
The first part of this section (Tables VIII-1 to VIII-4)
summarizes the costs (necessarily generalized) of end-of-pipe
treatment systems either currently in use or recommended for
future use in synthetic polymers production facilities. In order
to reflect the different treatment economics of existing versus
new plants, large versus small plants, free-standing versus joint
treatment facilities, or municipal versus industrial facilities,
costs have been developed typically for more than one plant
situation in each product subcategory. These product-specific
analyses are presented in Tables VIII-4/1 to VIII-4/9.
Cost Models of^Treatment Technologies
Information on treatment cost experience for these products was
scarce. In large part this was due to the small number of free-
standing plants in this industry. Much of the wastes resulting
from these products are treated in the central facilities of the
large chemical complexes in which they are located.
Consequently, the basic data for estimating the costs of treating
the wastes was that developed in the first study. These cost
models were developed around standard waste water treatment
practice and compared to actual data from a dozen resin plants.
That comparison resulted in deviations within * 20 percent of
model values. For details on the basis of the cost models and
their assumptions, see the cost section of the earlier
development document for the resins industry.
Annual Cost Perspectives
The expected annual costs for existing plants in 1977 consistent
with best practicable technology was estimated at $2.0 million.
55
-------
This estimate (Table VIII-2) was the result of the following
considerations: the production volumes and waste loads for each
of the product groups; the average costs of treatment for
different plant sizes; or the costs to be expected from handling
these wastes as part of a larger municipal or industrial system.
Similarly, by 1983, the estimated costs (Table VIII-2) for
existing plants using best available technology were $6.4
million. It is noted that these costs were associated with end-
of-pipe treatment only. Costs for in-plant additions or
modifications were not included.
The above annual cost estimates for existing plants for 1977 and
1983 indicate average increases of 21 percent per year between
1977 and 1983. To the costs for existing plants must be added
the costs associated with new plants - governed by BADT-NSPS.
Assuming the production volume of new plants to be equal to the
expected growth in production, the potential annual cost
associated with new plants in 1977 was estimated at $1.9 trillion
(Table VIII-2).
Cost_Per_Unit_Persp_ectives
Another measure by which to gauge the importance of the costs in
Table VIII-2 is to relate them to the sales price of the products
as is done in Table VIII-3. The average range of water pollution
control costs under BPCTCA was estimated at 0.4 percent to 1.0
percent of current sales prices. On average, the range of costs
for applying EATEA to existing plants was 1.4 to 3.5 percent of
sales price. The cost of BADT-NSPS was estimated at 1.4 percent
of sales price.
Wa_s t e_ Wa te r_Tre at m en t _ Co s t_ Es t i m a t es
The average range of water pollution control costs (Table VIII-4)
under BPCTCA, BATEA, and BADT-NSPS technologies respectively was:
$0.34 ($1.29), $1.06 ($4.00), and $0.75 ($2.85) per cubic meter
(per thousand gallons) .
Table VIII-4 and its 9 associated tables portray the costs of
major treatment steps required to achieve the recommended
technologies. Where municipal user charges are not considered
directly, the appropriate charge would be $0.39 or $0.63 per
thousand gallons depending on the size economies of the
representative municipal system.
In each of the representative plant cost analyses, typical plant
situations were identified in terms of production capacity,
hydraulic load, and treatment plant size. Capital costs have
been assumed to be a constant percentage (8 percent of fixed
investment. Depreciation costs have been calculated consistent
with the faster write-off (financial life) allowed for these
facilities (10 percent per year) over 10 years even though the
physical life is longer. cost-effectiveness relationships are
implicit in the calculation of these costs together with the
effluent levels achieved by each treatment step in each major
56
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relevant pollutant dimension. These effluent levels are
indicated at the bottom of each representative plant sheet.
Industrial_Waste_Treatn;,ent_Model_Data
In Table VIII-5 the total discharges for each product subcategory
are estimated for 1972 and 1977. The quality of effluents
remaining untreated in 1977 is indicated as that consistent with
the application of EPCTCA technology. Finally, the current
status of treatment in the product group is estimated in terms of
the proportion utilizing primary treatment and that utilizing a
form of biological treatment - whether industrial or municipal.
Energy Cost Perspectives
Each of the representative plant analyses in the 9 tables
summarized by Table VTII-4 includes an estimate of energy costs
(of control). The basis for these energy cost estimates was
explained in the earlier development document for resins
production. The ir.cst important assumption therein was one of
1972 energy prices. That assumption has been retained, for
purposes cf comparison, in this analysis.
Generally, the biological treatment systems employed by
industries and municipalities are not large consumers of energy.
By the cost models employed in this report, the energy costs of
BPCTCA and BADT-NSPS technologies in this industry were estimated
at about 2 percent of the total annual waste water treatment
costs in Table VIII-2. The add-on technologies for BATEA
compliance, however, were estimated to raise that proportion to 6
percent (physical-chemical) cr 24 percent (incineration) by 1983.
No nw a t er _O_uaJ. it y_ E ffects
The nonwater quality aspects of the treatment and control
technology found in the synthetics and plastics industry are
related to (1) the disposal of solids or slurries resulting from
waste water treatment and in-process plant control methods, (2)
the generation of a by-product cf commercial value, (3) disposal
of off-specification and scrap products, and (H) the creation of
problems of air pollution and land utilization. These effects
were discussed in the development document for resins production.
Other nonwater quality aspects of treatment and pollution control
are minimal in this industry and largely depend upon the type of
waste water treatment technology employed. In general, noise
levels from typical waste water treatment plants are not
excessive. If incineration of waste sludges is employed, there
is potential for air pollution, principally particulates and
possibly nitrogen oxides, although the latter should be minimal
because incineration of sludges does not normally take place at
temperature levels where the greatest amounts of nitrogen oxide
are generated. There are no radioactive nuclides used within the
industry, ether than in instrumentation, so that no radiation
problems will be encountered. Odors from the waste water
57
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treatment plants may cause occasional problems since waste waters
are sometimes such that heavy, stable foams occur on aerated
basins and septicity is present. But, in general, odors are not
expected to be a significant problem when compared with odor
emissions possible from other plant sources.
Alternative TTreatment Technologies
The range cf components used or needed to effect best practicable
control technology current available (BPCTCA), best available
technology economically achievable (BA1EA), and best available
demonstrated technology for new source performance standards
(BADT-NSPS) in this portion of the plastics and synthetics
industry have been combined into eight alternative end-of-pipe
treatment steps. These are as follows:
A. In it i.al_Tr eatment: For removal of suspended
solids and heavy metals. Includes equalization,
neutralization, chemical coagulation or preci-
pitation, API separators, and primary clarification.
B- Bi^logical_Treatment: Primarily for removal of
BOC. Includes activated sludge (or aerated
stabilization basins), sludge disposal, and final
clarification.
C. Multi-StageJBiological; For further removal of
BOD loadings. Either another biological treat-
ment system in series cr a Icng-residence-time
polishing lagoon.
D. Granular Media Filtration: For further removal
of suspended solids (and heavy metals) from
biological treatment effluents. Includes some
chemical coagulation as well as granular media
filtration.
E. Phisical-Chem_ica.l_Tr_eatment: For further removal
of COD, primarily that attributable to refrac-
tory organics, e.g., with activated carbon
adsorption.
F« ki3uid_Waste_Incineration: for complete treat-
ment of sirall volume wastes.
H. £henol_Extraction. p-or removal of phenol compounds,
e.g., from epoxy, acrylics, and phenolics wastes.
M. Municipal Treatment; Conventional municipal
treatment of industrial discharge into sewer
collection systems. Primary settling and
secondary biological stages assumed.
58
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TABLE VIII-1
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- WATER USAGE -
Product
Number of
Company
Operations(1)
Percent
Of Total 18
Product
Production(2)
Percent of
Water Used by
18 Products
Percent of Growth
in Water Usage
of 18 Products(3)
8
11
81
100
280
0.7
3.5
4.7
8.9
100.0
0.6
0.2
1.1
1.9
100.0
0.7
0.4
1.0
2.1
100.0
(1) Number of companies producing each of the products; the number
of plants is greater because of multiple sites for any one
company.
(2) Estimated 18-product production in 1972: 12 million kkg
(26 billion Ibs).
(3) Result of projected product growth at current hydraulic
loads.
59
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TABLE VIII-2
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- TREATMENT COSTS -
Product
Total Annual Costs, $ Million
Existing Plants
1977 1983
New Plants
1973 - 1977
Epoxies
Melamines/Ureas
Phenolics
Subtotal
Total - 18 Resins
0.3
0.6
1.1
2.0
62.5
1.0
1.5
3.9
6.4
177.1
0.1
0.5
1.3
1.9
34.9
60
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TABLE VIII-3
PERSPECTIVES ON THE PLASTICS AND SYNTHETICS INDUSTRY
- COST IMPACT -
Product
Price Level
C/lb
Control Cost Range as % of Sales Price
BPCTCA BATEA BADT-NSPS
Epoxies 60
Melamine/Urea 20
Phenolics 22
0.2-0.8
0.3-0.4
0.6-1.9
0.7-2.3
0.7-0.8
2.7-7.3
0.7
0.7
2.7
Unweighted Average
- 14 other Resins 35
0.7-3.1
1.7-8.7
1.0
61
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Product
TABLE VIII-4
SUMMARY OF WATER EFFLUENT TREATMENT COSTS
COST PER UNIT VOLUME BASIS
BPCTCA
BATEA
BADT
$/cu m $/1000 gal $/cu m $/1000 gal $ cu m $/1000 gal
Epoxies 0.12-0.41 0.45-1.55 0.44-1.28 1.51-4.83 0.14 0.52
Melamines/
Ureas 0.96-1.06 3.63-4.00 2.32-2.43 8.78-9.21 1.03 3.88
Phenolics 0.25-0.46 0.94-1.74 1.05-1.78 3.97-6.73 1.05 3.97
62
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TABLE VIII-4/1
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Epoxies
Plant Description: Small Plant - in industrial complex
Batch and/or continuous (liquid, solid, & solution)
Representative Plant Capacity
million kilograms (pounds) per year: 11.3 (25)
Hydraulic Load
cubic meters/metric ton of product: 24 (2.9)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 8.3 (2.2)*
Costs - $1000 Alternative Treatment Steps
A 1 P. E.
Initial Investment 57 147 29 167
Annual Costs:
Capital Costs (8%) 5 12 2 13
Depreciation (10%) 6 15 3 17
Operation and Maintenance 0.8 13 0.3 15
Energy and Power 0.2 2 — 2
Total Annual Costs 12 42 8.3 47
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A J5 P_ JL
B.O.D. 34 - 1.1 - 0.6
C.O.D. 141 - 16 - 9
Suspended Solids N/A 0.8 - 0.2
Phenolics N/A - 0.012 - 0.0023
* The epoxy contribution is 0.83 thousand cubic meters per day (0.22 mgd),
this is approximately 10% of the total flow to be treated.
63
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TABLE VIII-4/2
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Epoxies
Plant Description: Small Plant in industrial complex
Batch Fusion (solid and solution)
Representative Plant Capacity
million kilograms (pounds) per year: 11.3 (25)
Hydraulic Load
cubic meters/metric ton of product: 2.5 (0.3)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.76 (0.2)'
Costs - $1000 Alternative Treatment Steps
Initial Investment 11 28 8 56
Annual Costs:
Capital Costs (8%) 0.9 2 0.6 4
Depreciation (10%) l.l 3 0.8 6
Operation and Maintenance 0.2 4 0.2 12
Energy and Power 0.1 0.3 - 1
Total Annual Costs 2.3 9.3 1.6 23
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A J3 H !
B.O.D. 12.5 - 0.3 - 0.1
C.O.D. 50 - 5 - 2
Suspended Solids N/A 0.2 - 0.05
Phenolics N/A - 0.0035 - 0.00048
* The epoxy contribution is 0.08 thousand cubic meters per day (0.02 mgd),
this is approximately 10% of the total flow to be treated.
64
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TABLE VIII-4/3
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Epoxies
Plant Description: Large Plant in industrial complex
Batch and/or Continuous (liquid, solid & solution)
Representative Plant Capacity
million kilograms (pounds) per year: 45.4 (100)
Hydraulic Load
cubic meters/metric ton of product: 24 (2.9)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 16.7 (4.4)*
Costs - $1000 Alternative Treatment Steps
Initial Investment igQ 440 96 716
Annual Costs:
Capital Costs (8%) 14 35 8 57
Depreciation (10%) 18 44 10 72
Operation and Maintenance 1.6 26 0.8 152
Energy and Power 0.4 2 - 47
Total Annual Costs 34 107 18.8 328
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
A 1 P. 1
B.O.D. 34 - 1.1 - 0.6
C.O.D. 141 16 - 9
Suspended Solids N/A 0.8 - 0.2
Phenolics N/A - 0.012 - 0.0023
* The epoxy contribution is 3.3 thousand cubic meters per day (0.88 mgd)
this is approximately 20% of the total flow to be treated.
65
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TABLE VIII-4/4
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Phenolics
Plant Description: Small plant in industrial complex
Batch (liquid)
Representative Plant Capacity
million kilograms (pounds) per year: 11.3 (25)
Hydraulic Load
cubic meters/metric ton of product: 7.1 (0.85)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.49 (0.13)*
Costs - $1000 Alternative Treatment Steps
A _B F**
Initial Investment 22 116 500
Annual Costs:
Capital Costs (8%) 1.8 9 40
Depreciation (10%) 2.2 12 50
Operation and Maintenance 1 10 19
Energy and Power - 1 34
Total Annual Costs 5 32 143
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
All
B.O.D. 0.045 - 0.1 0
C.O.D. 0.091 - 0.5 0
Suspended Solids N/A 0.3 - 0
Phenolics N/A - 0.0035 0
* The phenalic contribution is 0.24 thousand cubic meters per day (0.064 mgd),
this is approximately 50% of the total flow to be treated.
** Based upon assumption that flow will be reduced to 10% and incinerated.
66
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TABLE VII1-4/5
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Phenolics
Plant Description: Small Plant in industrial complex
Batch (solid and solution)
Representative Plant Capacity
million kilograms (pounds) per year: 11.3 (25)
Hydraulic Load
cubic meters/metric ton of product: 12.5 (1.5)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.83 (0.22)*
Costs - $1000 Alternative Treatment Steps
Initial Investment 54 136 700
Annual Costs:
Capital Costs (8%) 4 11 56
Depreciation (10%) ' 5 14 70
Operation and Maintenance 1 17 19
Energy and Power - 2 57
Total Annual Costs 10 44 202
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D. N/A
c-°-D- ^ No Specific Guidelines
Suspended Solids N/A
Phenolics N/A
* The phenolic contribution is 0.42 thousand cubic meters per day (0.11 mgd),
this is approximately 50% of the total flow to be treated.
** Based upon the assumption that the flow will be reduced to 10% and incinerated.
67
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TABLE VII1-4/6
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Phenolics
Plant Description: Large plant in industrial complex
Batch (liquid)
Representative Plant Capacity
million kilograms (pounds) per year: 45.4 (100)
Hydraulic Load
cubic meters/metrie ton of product: 7.1 (0.85)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 1.97 (0.52)*
Costs - $1000 Alternative Treatment Steps
A B
Initial Investment 133 350 1300
Annual Costs:
Capital Costs (8%) 11 28 104
Depreciation (10%) 13 35 130
Operation and Maintenance 2 33 36
Energy and Power 1 4 113
Total Annual Costs 27 100 383
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
All
B.O.D. 0.045 - 0.1 0
C.O.D. 0.091 - 0.5 0
Suspended Solids N/A 0.3 - 0
Phenolics N/A - 0.0035 0
* The phenolic contribution is 0.98 thousand cubic meters per day (0.26 mgd) ,
this is approximately 50% of the total flow to be treated.
** Based upon the assumption that flow will be reduced to 10% and incinerated.
68
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TABLE VIII-4/7
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Phenolics
Plant Description: Large plant in industrial complex
Batch (solid and solution)
Representative Plant Capacity
million kilograms (pounds) per year: 45.4 (100)
Hydraulic Load
cubic meters/metric ton of product: 12.5 (1.5)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 3.4 (0.9)'
Costs - $1000 Alternative Treatment Steps
Initial Investment 153 392 1800
Annual Costs:
Capital Costs (8%) 12 31 144
Depreciation (10%) 15 39 180
Operation and Maintenance 2.5 35 56
Energy and Power 0-5 6 215
Total Annual Costs 30 111 595
Effluent Quality (expressed in terms of yearly averages)
Raw Waste Load Resulting Effluent Levels
(units per 1000 units of product)
B.O.D.
No Specific Guidelines
Suspended Solids
Phenolics N/A
* The phenolic contribution is 1.7 thousand cubic meters per day (0.45 mgd) ,
this is approximately 50% of the total flow to be treated.
** Based upon the assumption that the flow will be reduced to 10% and incinerated.
69
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TABLE VIII-4/8
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory: Urea and Melamine
Plant Description: Small plant in industrial complex
Batch (liquid)
Representative Plant Capacity
million kilograms (pounds) per year: 6.8 (15)
Hydraulic Load
cubic meters/metric ton of product: 1.25 (0.15)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.53 (0.14)*
Costs - $1000
Alternative Treatment Steps
Initial Investment
13
13
24
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
0.4
0.5
0.1
-
1.0
1.3
1.6
0.1
1.0
1.3
1.6
0.1
0.2 '
0.3
0.1
-
1.9
2.4
5.9
0.8
0.6 11
Effluent Quality (expressed in terms of yearly averages)
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
13
60
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A E £ ID E
0.05 - 0.03
- - 0.8 - 0.4
0.04 - - 0.01
* The urea and/or melamine contribution is 0.03 thousand cubic meters
per day (0.07 mgd), this is approximately 5% of the total flow to be
treated.
70
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TABLE VIII-4/9
WATER EFFLUENT TREATMENT COSTS
PLASTICS AND SYNTHETICS INDUSTRY
Industry Subcategory:
Plant Description:
Urea and Melamine
Large plant in industrial complex
Batch (liquid)
Representative Plant Capacity
million kilograms (pounds) per year: 27.2 (60)
Hydraulic Load
cubic meters/metric ton of product: 1.25 (0.15)
(gal/lb)
Treatment Plant Size
thousand cubic meters per day (MGD): 0.42 (0.11)*
Costs - $1000
Alternative Treatment Steps
A B C D E
Initial Investment
23
53
53
10
101
Annual Costs:
Capital Costs (8%)
Depreciation (10%)
Operation and Maintenance
Energy and Power
Total Annual Costs
1.8
2.3
0.5
0.1
4.2
5.3
4.2
0.3
4.2
5.3
4.2
0.3
0.8
1.0
0.5
-
8.1
10.1
25
0.8
4.7 14
14
Effluent Quality (expressed in terms of yearly averages)
2.3 44
B.O.D.
C.O.D.
Suspended Solids
Raw Waste Load
13
60
N/A
Resulting Effluent Levels
(units per 1000 units of product)
A _B £ I) JL
0.05 - 0.03
0.8 - 0.4
0.04 - - 0.01
* The urea and/or melamine contribution is 0.1 thousand cubic meters per day
(0.027 mgd), this is approximately 25% of the total flow to be treated.
71
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TABLE VIII-5
INDUSTRIAL WASTE TREATMENT MODEL DATA
PLASTICS AND SYNTHETICS INDUSTRY
Product Subcategory
Epoxies Melamine/Urea Phenolics
Total Industry Discharge
1000 cubic meters/day or
(million gallons/day)
1972 6.0(1.6) 2.3(0.6) 11.8(3.1)
1977 8.9(2.3) 3.8(1.0) 15.8(4.2)
Flow through Components Employed
One hundred percent of total flow in each industry subcategory is
assumed to pass through each treatment step or component.
Quality of Untreated Wastewater in 1977
(Expressed in terms of monthly average limits)
Parameters:
(in units/1000 units of product)
B.O.D. 1.1 0.05 0.1
C.O.D. 16 0.8 0.5
S.S. 0.8 0.04 0.3
Number of Companies in Subcategory
8 11 81
Percent of Treatment in 1972
Treatment Steps:
(in percent now treated) Estimate
A. Primary Treatment 55
B. Secondary Treatment 30
72
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
GUIDELINES AND LIMITATIONS
Definition of Best Practicable Control Technology Currently
Available (EPCTCA)
Based on the analysis of the information presented in Sections
IV-VIII the basis for BPCTCA is defined herein as it was in EPA
440/1-73/010.
Best practicable control technology currently available (BPCTCA)
for existing point sources is based on the application of end-of-
pipe technology such as biological treatment for BOD.5 reduction
as typified by equalization, to dampen shock loadings, settling,
clarification, and chemical treatment, for removal of suspended
solids, oils, other elements, and pH control, and subsequent
treatment typified by clarification and polishing processes for
additional BOD5 and suspended solids removal, and dephenolizing
units for the removal of phenolic compounds. Application of in-
plant technology and changes which may be helpful in meeting
BPCTCA include segregation of contact process waste from
noncontact waste waters, elimination of once through barometric
condensers, control of leaks, and good housekeeping practices.
The best practicable control technology currently available has
been found to be capable of achieving ef*"nent concentrations of
BOCj> comparable to the secondary treatment of municipal sewage.
For phenolic resins manufacture, activated carbon was found to be
required as a pretreatment for phenol extraction; subsequent
biological treatment should be capable of treating the residual
formaldehyde and phenolics to achieve the guideline limitations.
The design and operational conditions of these biological systems
are, of course, significantly different than for municipal
sewage. The capabilities of biolcgic-ii roatment for industrial
wastes are specific to a particular plant's waste waters.
However, as discussed in Section VII, end-of-pipe treatment for
the removal of biologically active substances from waste waters
has been demonstrated successfully in different sections of the
plastics and synthetics industry. This technology has proven
applicable regardless of the age or size of the manufacturing
plant. Depending upon the treatability of the waste waters, it
has been demonstrated to be practical in maintaining
concentrations of biologically active substances in the effluent
stream within reasonable limits. However, variations due to the
vagaries of micro-organisms as well as process and climatic
conditions are normal for any biologic<1 waste water treatment
plant. The guidelines for best practicable control technology
take these factors into consideration and recognize that certain
unique properties such as measured by COD exists in the waste
waters from the industry. Besides BOD5, COD, and SS, certain
metals, phenolic compounds, and nitrogen compounds are among the
parameters of major concern to the industry.
73
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Table 21, Section VII of EFA 4UC/1-73/010 describes effluent
loadings which are currently being attained by the product
subcategories of the industry for EOD5_, COD, and suspended
solids. The results of this work show that exemplary, practical
waste water treatment plants are presently in operation and that
their operational procedures are comparable with those of
biological systeir.s in ether industries. Consequently, the most
significant factors in establishing effluent limitation
guidelines on a basis of units cf pollutants per unit of
production are (1) the waste water generation rates per unit of
production capacity and (2) the practicable treatment levels of
the waste waters from the particular manufacturing process.
The_Guidelines
The guidelines in terms of kg of pollutant per kkg of production
(lb/1000 Ib) are based on attainable effluent concentrations and
demonstrated waste water flows for each product and process
Subcategory.
Attainable Effluent Concentrations
Based on the definition of EFCTCA the following long-term average
5CD_5 and S3 concentrations were used as a basis for the
Guidelines.
mg/liter
EOD5 SS
Major Subcategory I 15 3C
Major Subcategory II 20 30
Major Subcategory III 45 30
Major Subcategory IV 75 3C
The BOD_5 and SS concentrations are based on exemplary plant
data presented in Tacle 18, Section VII, of ZPA 440/1-73/010.
The COD characteristics of process wastes in the plastics
industry vary significantly frcm product to product, and within a
plant over time. The ratio of CCD to £CD^ in plant effluents is
shown in Table IX-1 to rar.ge from a lew of 1.5 for phenolic
resins to a high of 15 for epcxy resins. The CCD limits for
EFCTCA are based en levels achieved in the exemplary plants for
whicn data were available. They are expressed as a ratio to the
5CC5_ limits in Table IX-2.
Considering the variability of the CCD/ECD ratio between plants,
the upper limits of COD/SOD of 5, 1C, and 15 were used.
There is a real need for mere data in most segments of the
industry tc provide a basis for better understanding of how the
COD load can be reduced. In the interim, the purpose of the
EPCTCA guidelines is simply to reflect the removal of COD tc be
expected along with best practicable SOD.5 removal.
74
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TABLE IX-1
COD/BOD RATIOS IN EFFLUENT STREAMS
Product COD/BOD
Epoxy resins 1C.1
Phenolic resins 1>5
Urea & melamine resins 14-3
75
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TABLE IX-2
COD/BOD GUIDELINE BASES
Phenolics
Epoxy, Urea and Melamine Resins 15
76
-------
The removal of phenolic compounds is based on an attainable
concentration level of 0.5 mg/liter monthly limit as demonstrated
by dephenolizing units, activated carbon or biological
degradation as referenced in EPA 440/1-73/010.
Demonstrated Waste Water Flow
The waste water flow basis for BPCTCA is based on demonstrated
waste water flows found within the industry for each product and
process sutcategory. Waste Water flows observed at exemplary
plants were used as the basis when they fell at the approximate
middle of the waste water flew ranges reported by previous
industry and EPA surveys. When the observed flows fell outside
of the middle range, a waste water flow within this range was
used as the basis.
The waste water flow basis includes process water, and excludes
utility blowdowns and auxiliary facilities such as laboratories,
etc., where definable. The waste water flow basis is summarized
in Table IX-3. It is essential to note that the waste water flow
is often an integral part of the basic design and operation of
the plant or the process and may therefore be subject to
significant reduction only at large expense. In general, the
hydraulic load is larger for older plants. However, the
availability of water also influences design as does the
philosophy of the company constructing the plant. No simple
formula for relating hydraulic load to plant age, size or
location can be established. Demonstrated waste water flows
which fall in the rriddle of the reported range of waste water
flow is the best available basis for use in determining
guidelines.
Statistical Variability of a Properly Designed and Operated Waste
Treatment Plant
The effluent from a properly designed and operated treatment
plant changes continually due to a variety of factors. Changes
in production mix, production rate and reaction chemistry
influence the composition of raw wasteload and, therefore, its
treatability. Changes in biological factors influence the
efficiency of the treatment process. A common indicator of the
pollution characteristics of the discharge from a plant is the
long-term average of the effluent load. The long-term (e.g.,
design or yearly) average is not a suitable parameter on which to
base an enforcement standard. However, using data which show the
variability in the effluent load, statistical analyses can be
used to compute short-term limits (monthly or daily) which should
never be exceeded, provided that the plant is designed and run in
the proper way to achieve the desired long-term average load. It
is these short-term limits on which the effluent guidelines are
based.
In order to reflect the variabilities associated with properly
designed and operated treatment plants for each of the major
sufccategories as discussed above, a statistical analysis was made
77
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TABLE IX-3
DEMONSTRATED WASTEWATER FLOWS
Wastewater Flow Basis
Epoxy Resins
Batch & Continuous (liquid, solid
& solution) 24.2 2';CC
Batch Fusion (solid & solution) 7.1 300
Phenolic Resins
6.9 2700
Urea & Melamine Resins
Batch (liquid) ]-25 15°
-j
oo
-------
of plants where sufficient data was available to determine these
variances for day-to-day and month-to-month operations. The
standard deviations for day-to-day and month-to-month operations
were calculated. For the purpose of determining effluent
limitation a variability factor was defined as follows:
Standard deviation = Q monthly, Q daily
Long-term average (yearly or design) = x
Variability factor = y monthly, y daily
y monthly = x_+_22_B3Onthly_
x
y daily = x_+_3Q_daily
x
The variability factor is multiplied by the long-term yearly
average to determine the effluent limitations guideline for each
product subcategory. The monthly effluent limitations guideline
is calculated by use of a variability factor based on two
standard deviations and is only exceeded 2-3 percent of the time
for a plant that is attaining the long-term average. The daily
effluent limitations guideline is calculated by the use of a
variability factor based on three standard deviations and is
exceeded only 0.0-0.5 percent of the time for a plant that is
attaining the long term average. Any plant designed to meet the
monthly limits should never exceed the daily limits. The data
used for the variability analysis came from plants under
voluntary operation. By the application of mandatory
requirements, the effluent limitations guidelines as discussed in
this paragraph should never be exceeded by a properly designed
and operated waste treatment facility.
The variability factors in Table IX-5 are based on the data
obtained in the synthetic resin segment (16) of the plastics and
synthetics industry.
The variability factors for suspended solids removal are the same
as used in the resins segment of the industry, i.e., a monthly
variability of 2.2 and a daily variability of 4.0.
The variability factors recommended for phenolic compounds are
based on the monthly limits and a variability factor of 2.0 for
the daily iraximum.
Based on the factors discussed in this section, the effluent
limitations guidelines for BPCTCA are presented in Tables IX-7
and IX-8.
79
-------
The following table summarizes the basis for the variability
factors.
TABLE IX-4
DEMONSTRATED VARIABILITY
Long Term
Influent Effluent
Concentration Concentration Variability Factor
Major Sub-
category
I
II
II
III
IV
mg/liter
33
380
380
1206
91
1267
793
1503
_
mg/liter
6
9
17
11
20
44
36
182
_
Monthly
1.50
1.33
1.80
1.76
1.77
2.2
4.3
2.2*
Daily
2.00
1.71
2.60
2.50
2.84
3.0*
3.85
3.0*
* Estimated values
80
NOTIf'E
.'';;o.-v a*v? tentative ivtuMni^i'^ti•-,•?-„•; b;:vd upon
:1I'o:";Ki'.i^n in :hL- ;r;i(.:i' .'~tt •"•. • :!•'.•>••; \\j ciinr'.gt1
cL-:A"i ur»or. con'in i-i-jts i-eceived and further internal
-------
Based on the table of demonstrated variability the following
variability factors were applied to determine the effluent
limitation guidelines for BOD^.
TABLE IX-5
VARIABILITY FACTOR
Major
Subcategory Monthly Daily
I 1.6 3.1
II 1.8 3.7
III 2.2 4.0
IV 2.2 4.0
NOTICE
These are tentative recommendations based upon
81
Jformation in this report and arc subject to change
based upon oommenits received and iurihar internal
review by EPA.
-------
The variability factors for suspended solids removal are
based on the variables projected in Table IX-6 for S. S.
removal. The monthly variability was calculated at 2.2
and the daily estimated at 4.0.
The variability for phenolic compounds are based on the
monthly limits and a variability factor of 2.0 for the
daily maximum
TABLE IX-6
VARIABILITIES PROJECTED FOR SUSPENDED SOLIDS REMOVAL
Demo. Monthly
S. S. Removal Variability
Cellulose Acetate 2.2
Nylon 6 1.7
Polyester 2.2
Nylon 66 2.2
Acrylics 2.6
Polyvinyl Chloride 1.9
Phenolic Resin 3.6*-4.3
Epoxy Resin 2.8
*Daily Variability
82
-------
TABLE IX-7
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
(kg/kkg (lb/1000 Ib) of Production)
Subcategory
BOD5
Maximum average
of daily values
for any period
of thirty
consecutive days
COD SS
Maximum for Maximum average Maximum for Maximum average Maximum for
any one day of daily values any one day of daily values any one dav
for any period
of thirty
consecutive days
for any period
of thirty
consecutive days
Epoxy Resins
Batch & Continuous
(liquid, solid & solution)
Batch, Fusion (solid
& solution)
Phenolic Resins
ro
00
2.1
0.25
3.7
3.9
0.45
6.7
32
3.9
19
58
6.7
34
1.4
0.17
1.5
2.6
0.30
2.7
Urea & Melanine Resins
Batch (liquid)
0.20
0.38
1.5
2.7
0.13
0.25
-------
TABLE IX-8
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
EFFLUENT LIMITATIONS GUIDELINES
(PHENOLIC COMPOUNDS)
Product
Parameter
kg/kkg (lb/1000 Ib) of production
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
oo
Epoxy Resins
Batch & Continuous
(liquid, solid & solution)
Batch Fusion (solid & solution)
Phenolic Cmpds
Phenolic Cmpds
O.C11
0.0013
0.022
0.0025
Phenolic Resins
Phenolic Cmpds
0.011
0.023
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
The definition of Best Available Technology Economically
Achievable given in EPA 440/1-73/010 is directly applicable to
the epoxy, phenolic, urea and melamine resins. Key parameters
are summarized in Table X-1. The flow basis is summarized in
Table X-2. The BATEA guidelines are presented in Tables X-3 and
X-4.
85
-------
TABLE X-l
KEY PARAMETERS FOR BEST AVAILABLE TECHNOLOGY
ECONOMICALLY ACHIEVABLE
JOD
Suspended Solids
Phenolics
Group
I
00
III
IV
Monthly
mg/liter Variability
15 1.6
15 1.8
25 2.2
25 2.2
Daily
Variability mg/liter
2.4 10
2.8 10
3.0 10
3.0 10
Monthly Daily
Variability Variability mg/liter
1.7 2.0 0.1
1.7 2.0 0.1
1.7 2.0 0.1
1.7 2.0 0.1
Monthly Daily
Variability Variability
1.0 2.0
1.0 2.0
1.0 2.0
1.0 2.0
-------
TABLE X-2
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
Subcategory
kg/kkg (lb/1000 Ib of production)
BOD5
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
COD
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
SS
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
arv one day
Epoxy Resins
Batch & Continuous
(liquid, solid
& solution)
Batch, Fusion
(solid & solution)
0.95
0.12
1.3
0.17
4.8
0.65
6.5
U.88
0.28
0.04
0.33
0.05
Phenolic Resins
0.96
1.3
6.8
0.30
0.35
Urea & Melamine Resina
Batch (liquid)
0.06
0.08
0.09
0.13
0..017
0.021
-------
TABLE
X-3
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
EFFLUENT LIMITATIONS GUIDELINES
(PHENOLIC COMPOUNDS)
Product
Parameter
kg/kkg (lb/1000 Ib of production)
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
oo
oo
Epoxy Resins
Batch & Continuous (liquid
solid & solution)
Phenolic Cmpds
0.0017
0.0033
Batch, Fusion (solid &
solution)
Phenolic Cmpds
0.00022
0.00044
Phenolic Resins
Phenolic Cmpds
0.0018
0.0035
-------
TAKLE X-4
Best Available Technology Economically
Achievable - Flow Rate Basis
Subcategory Flov basis
gal/1000 Ibs curr\/kkg
Epoxy Resins
Batch 2000 16,68
Batch-Fusion 265 2.21
Phenolic Resins 2100 17.51
Urea and Melamine Resins 138 1.15
89
-------
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEiMONSTRAlED TECHNOLOGY
The definitions, standards and waste load reduction basis
described in EPA 4UO/1-73/010 are applicable to the epoxy,
phenolic, urea and rcelamine resins.
Key parameters are summarized in Table XI-1. The lowest
demonstrated waste water flows are shown in Table XI-2. Effluent
Limitation Guidelines for Best Available Demonstrated Technology
for New Source Performance Standards (BADT-NSPS) are presented in
Tables XI-3 and XI-U.
91
-------
TABLE XI-1
KEY PARAMETERS FOR NEW SOURCE PERFORMANCE STANDARDS
BEST AVAILABLE DEMONSTRATED TECHNOLOGY
BODr
Suspended Solids
Phenolics
Group
I
II
III
IV
rag/liter
15
15
25
25
Monthly
Variability
1.6
1.8
2.2
2.2
Daily
Variability
3.1
3.7
4.0
4.0
mg/liter
10
10
10
10
Monthly
Variability
1.7
1.7
1.7
1.7
Daily
Variability
2.5
2.5
2.5
2.5
mg / 1 i t e r
0.1
0
0
0
.1
.1
.1
Monthly
Variability
1.0
1.0
1.0
1.0
Daily
Variability
2.0
2.0
2.0
2.0
-------
TABLE XI-2
LOWEST DEMONSTRATED WASTEWATER FLOWS
Product
Lowest Demonstrated Wastewater Flow
cu m/kkg gal/1000 Ibs
Epoxy Resins
Batch & Continuous
(liquid, solid and
solution)
21.7
1400
Batch Fusion
2.5
230
Phenolics Resins
12.5
1500
Urea & Melamine Resins
1.0
125
93
-------
TABU: XI-3
BEST AVAILABLE DEMONSTFATED TECHNOLOGY FOR
NEW SOURCE PERFOR1-ANCE STANDARDS
Subcategory
Epoxy Resins
Batch & Continuous
(liquid, solid 4
solution)
kg/kkg (Ib/lOCO Ib of production)
BODr
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
0.67
1.2
COD
Maximum average Maximum for
of daily values any one day
for any period
of thirty
consecutive days
9.2
12.9
SS
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
0.20
0.30
Batch Fusion (solid
& solution)
0.11
0.19
1.5
2.1
0.03
0.05
Phenolic Resins
Batch (liquid)
0.69
1.3
19
0.21
0.31
Urea & Melamir.e Resins
Batch (liquid)
0.06
0.11
0.10
0.18
0.02
0.04
-------
TABLE XI-4
BEST AVAILABLE DEMONSTRATED TECHNOLOGY FOR
NEW SOURCE PERFORMANCE STANDARDS
(PHENOLIC COMPOUNDS)
Product
Parameter
kg/kkg (lb/1000 Ib of production)
Maximum average
of daily values
for any period
of thirty
consecutive days
Maximum for
any one day
t_n
Epoxy Resins
Batch & Continuous
(liquid, solid & solution
Phenolic Cmpds
0.0012
0.0024
Batch Fusion (solid &
solution)
Phenolic Cmpds
0. 00019
0.00038
Phenolic Resins
Phenolic Cmpds
0.0012
0.0025
-------
-------
SECTION XII
ACKNOWLEDGMENTS
The preparation of the initial draft report was accomplished
through a contract with Arthur D. Little, Inc., and the efforts
of their staff under the direction of Henry Haley, with James I.
Stevens and Terry Rothermel as the principal investigators.
Industry subcategory leaders were Robert Green and Harry Lambe,
and Anne Witkos was administrative assistant.
David L. Becker, Project Officer, Effluent Guidelines Division,
through his assistance, leadership, advice, and reviews has made
an invaluable contribution to the overall supervision of this
study and the preparation of this report.
Allen Cywin, Director, Effluent Guidelines Division, Ernst Hall,
Assistant Director, Effluent Guidelines Division, and Walter J.
Hunt, Chief, Effluent Guidelines Development Branch, offered many
helpful suggestions during the program.
The members of the working group/steering committee who
coordinated the internal EPA review are:
Walter J. Hunt - Effluent Guidelines Division (Chairman)
Allen Cywin - Effluent Guidelines Division
David Becker - Effluent Guidelines Division (Project Officer)
William Frick - Office of General Counsel
Judy Nelson - Office of Planning and Evaluation
Robert Wooten - Region IV
Walter Lee - Region III
Frank Mayhue - Office cf Research and Monitoring (Ada)
Wayne Smith - National Field Investigation Center (Denver)
David Garrett - Office of Categorical Programs
Paul Des Rosiers - Office of Research and Monitoring
Herbert Skovronek - Office of Research and Monitoring
Acknowledgment and appreciation is also given to the secretarial
staffs of both the Effluent Guidelines Division and Arthur D.
Little, Inc., for the administrative coordination, typing of
drafts, necessary revisions, and final preparation of the
effluent guidelines document. The following individuals are
acknowledged for their contributions. Brenda Holmone, Kay Starr,
and Nancy Zrubek - Effluent Guidelines Division. Mary Jane
Demarco and Martha Hananian - Arthur D. Little, Inc.
Appreciation is also extended to both the Manufacturing Chemists
Association and the Synthetic Organic Chemical Manufacturers
Association for the valuable assistance and cooperation given to
this program. Appreciation is also extended to those companies
which participated in this study:
Borden, Inc.
Pioneer Plastics Corporation
97
-------
Reichhold Chemicals, Inc.
Schenectady Chemicals, Inc.
Shell Chemical Company
98
-------
SECTION XIII
REFERENCES
1 . "Advanced Waste Water Treatment as Practiced at South
Tahoe," EPA Water Pollution Control Research
Series Report No. 17010 ELP, Washington, D.C.
(August 1971) .
2. "An Act to Amend the Federal Water Pollution Control
Act," Public Law 92-500, Ninety-Second Congress,
S.2770 (October 18, 1972).
3. Arthur D. Little, Inc., "Technical Proposal: Effluent
Limitations Guidelines for the Plastics and
Synthetics Industry to the Environmental Protec-
tion Agency," Cambridge, Massachusetts
(November 16, 1972).
4. Black and Veatch, "Process Design Manual for Phosphorus
Removal," Environmental Protection Agency,
Contract 14-12-936, October 1971.
5. Boardman, Harold, "Penton (Chloroethers) ," from
M£Du^a_cture_of_Plasticsx_VoJL.._IA edited by
W. Mayo Smith, Reinhold Publishing Corporation,
New York, 535-7, 550 (1964).
6. Chemic al_Economic s_Handbook , Stanford Research Institute,
Menlo Park, California (1971).
7. Chemical Engineering Flowsheets, Prepared by the editors
of Chemical and Metallurgical Engineering, McGraw-
Hill, New York (1940) .
8. Chemic al_Horizgns_F ile , Predicasts, Cleveland,
Ohio.
9. Chemical Marketing Reporter, "Chemical Profile" Section,
from~June 2&7~1972 through July 23, 1973.
10. Chopey, N. P., ed. , "Chlorinated Polyether," Chemical
Engj-neerina 68 (2) , 112-115 (January 23, 1961) .
11. Connelly, F. J., "Case History of a Polymer Process
De ve lo pment , " Chemical Engineering Progresg
Syjnp_osium_Series 60 (49) , 49-57 (1964) .
12. Contract for Development of Data and Recommendations
for Industrial Effluent Limitations Guidelines
and Standards of Performance for the Plastics
and Synthetics Industry, No. 68-01-1500, Issued
to Arthur D. Little, Inc., Cambridge, Massachusetts
(December 1972) .
99
-------
13. Conway, R. A., et al. , "Conclusions from Analyzing
Report. • Treatability of Waste Water from Organic
Chemical and Plastics Manufacturing - Experience
and Concepts'," Unpublished document (January
1973) .
14. Conway, R. A., J. C. Hovious, D.C. Macauley, R. E.
Riemer, A. H. Cheely, K. S. Price, C. T. Lawson,
"Treatability of Waste water from Organic
Chemical and Plastics Manufacturing - Experience
and Concepts," Prepared by Union Carbide
Corporation, Scuth Charleston, W. Virginia
(February 1973) .
15. Gulp, Gordon L. and Robert W. Gulp, Advanced Waste-
Water Treatment, Van Nostrand Reinhold Company,
New York, New York (1971).
1 6 . Development Document for Proposed Ef flugnt Limitations
Guidelines and New Source Performance Standards
for the Synthetic Resins Segment of -the Plastics
and Synthetic Materials Manufacturing Point
gource Category , Report No.~EPA 440/1-73/010,
Effluent Guidelines Division, Office of Air and
Water Programs, U.S. EPA, Washington, D.C.
(September 1973) .
17. Directory of Chemical Producers, Chemical Information
Services, Stanford Research Institute, Menlo
Park, California (1973) .
18. "Directory of the Plastics Industry, 1972-1973,"
special edition of Plastics World 30 (11)
(August 1972) .
1 9 . Federal Water^ggllutign Control Act
House of Representatives, Report No. 92-1465,
U.S. Government Printing Office, Washington, D.C.
(September 28, 1972).
20. Forbath, T. P., ed., "For Host of Silicones: One
Versatile Process , " Chemi c a 1_ Engineer ing 64
(12), 228-231 (1957).
21. Galanti, A. V. and Mantell, C. L. , Proprogylene Fibers
and_Films, Plenum Press, New York, New York (1965) .
22. "Integration of Chemical Plant Facilities, " Chemical and
Metallurgical Engineering 52 (9), 129-141
(September 1945) .
23. Johnson, R. N. , A. G. Farnham, R. A. Clendinning, W. F.
Hale, C. N. Merriam, "Poly (aryl Ethers) by
Nucleophilic Aromatic Substitution. I. Synthesis and
100
-------
Properties," Journal cf Polymer Science -
Part_A-l (5), 2375-2398 (1967).
2U. Jones, R. Vernon, "Newest Thermoplastic - PPS,"
HY^£0£^£bon_Processin2 51 (11), 89-91 (November
1972).
25. Kirk-Othmer, eds., Encyclopedia of^Chemical^TechnQlogy,
2nd Ed., Interscience Division of John Wiley and
Sons, New York, New York (1963-1971).
26. Labine, R. A., ed., "Flexible Process Makes Silicone
Rubber," Chemical_Engineerin3 67 (14), 102-105
(1960) .
27. Lee, H., D. Stoffey, K. Neville, New Linear Polymers,
New York, McGraw-Hill (1967).
28. "Making Polycarbonates: A First Look," Chemical
Engineering &2 (23), 174-177 (1960).
29. Mark, H., ed., Encyclopedia of Polymer Science and
Technology, Interscience Division of John Wiley
and Sons, New York, New York (1964-1972).
30. Modern Plastics Encyclopedia, McGraw-Hill, New York,
New York (1973-1974).
31. Monsanto Flow Sheet, Chemical_Engineering, 346-349
(February 1954) .
32. Mudrack, Klaus, "Nitro-Cellulose Industrial Waste,"
Proc.^Qf_the 21st Industriaj. Waste Conference
May__3_t_4:x_and_5_t_196_6_, Engineering Extension
Series No. 121, Purdue University, Lafayette,
Indiana.
33. "National Pollutant Discharge Elimination System, Proposed
Forms and Guidelines for Acquisition of Information
From Owners and Operators of Point Sources,"
E§deral_Register 37 (234), 25898-25906 (December
5, 1972) .
34. "Parylene Conformal Coatings," brochure prepared by
Union Carbide Corporation, New York, New York.
35. Paterson, James W. and Roger A. Minear, Waste_Water Treat-
ment, Technology, 2nd Ed., January 1973, for the
State of Illinois Institute for Environmental
Quality.
36. "Polycarbonates - General Electric Company," Hydro-
carbon Processing, p. 262 (November 1965) .
37. "Procedures, Actions and Rationale for Establishing
101
-------
Effluent Levels and Compiling Effluent Limitation
Guidance for the Plastic Materials and Synthetics
Industries," Unpublished report of the Environmental
Protection Agency and the Manufacturing Chemists
Association, Washington, D.C. (November 1972).
38. "Proposed Environmental Protection Agency Regulations
on Toxic Pollutant Standards," 38 FR 35388,
Federa l_Recjij3 ter , December 27, 1973.
39. Shumaker, T. P., "Granular Carbon Process Removes 99.0
to 99.2% Phenols," Chemical_Processincj (May 1973).
40. Sittig, M. , Organic Chemical Process Encyclopedia,
2nd Edition, Noyes Development Corp., Park
Ridge, New Jersey (1969) .
41. Supplement to this report, Detailed Record of Data Base.
42. "Supplement B - Detailed Record of Data Base," DevelOE-
H!§Qt_Document_f gr_Proppsed_E^f luent_Limitations
Guidelines and New Source Performance Standards
For the Synthetic Resins Segment of the Plastics
and Synthet ic _Materia Is Manufacturing Point
Sour ce_Cat egory. , Report No. EPA 440/1-73/010,
Effluent Guidelines Division, Office of Air and
Water Programs, U.S. EPA, Washington, D.C.
(September 1973) .
43. Text ile_Orc[an , Textile Economics Bureau, Inc., New
York, New York.
44. U.S. Patent 2,964,509 (December 13, 1960), D. M. Hurt
(to DuPont) .
45. U.S. Patent 2,994,668 (August 1, 1961), Eugene D. Klug
(to Hercules Powder Company) .
46. U.S. Patent 3,144,432 (August 11, 1964), Daniel W.
Fox (to General Electric Company) .
47. U.S. Patent 3,354,129 (November 21, 1967), James T.
Edmonds, Jr., and Harold Wayne Hill, Jr. (to
Phillips Petroleum Company) .
48. U.S. Patent 3,426,102 (February 4, 1969), T. A. Solak
and J. T. Duke (to Standard Oil Company) .
49. Weaver, D. Gray, ed., and O'Connors, Ralph J., "Manu-
facture of Basic Silicone Products," Modern
£hemical_Proc esses, 6, 7-11 (1961) .
102
-------
SECTION XIV
GLOSSARY
Acety.1
Refers to that portion of a molecular structure which is derived
frcnn acetic acid.
Pol y_mer_i z at ion
Polymerization without formation of a by-product (in contrast to
condensaticn polymerization) .
Aerobic
A living or active biological system in the presence of free,
dissolved oxygen.
A general term for monovalent aliphatic hydrocarbons.
Allopjianate
A derivative of an acid, NH2CCKHCOOH, which is only known in
derivative forms such as esters.
Amorphous
Without apparent crystalline form.
Alumina
The oxide of aluminum.
Anaerobic
Living or active in the absence of free oxygen.
Annealing
A process to reduce strains in a plastic by heating and
subsequent cooling.
A general term denoting the presence of unsaturated ring
structures in the molecular structure of hydrocarbons.
Atactic Polymer
* _
A polymer in which the side chain groups are randomly distributed
on one side or the other of the polymer chain. (An atactic
polymer can be molded at much lower temperatures and is more
103
-------
soluble in most solvents than the corresponding isotactic
polymer, g.q. ) .
Autoclave
An enclosed vessel where various conditions of temperature and
pressure can be controlled.
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.
Bacteriostat
An agent which inhibits the growth of bacteria.
Slowdown
Removal of a portion of a circulating stream to prevent buildup
of dissolved solids, e.g., boiler and cooling tower blowdown.
BCD5
Biochemical Oxygen Demand - 5 days as determined by procedures in
s£andard_ Methods_, 19th Edition, Water Pollution Control
Federation, or EPA's Manual 16020-07/71, Methods for Chemical
of Water and Wastes
Catalyst
A substance which initiates primary polymerization or increases
the rate of cure or crosslinking when added in quantities which
are minor as compared with the aircunt of primary reactants.
Caustic Soda
A name for sodium hydroxide.
Chain Terminator
An agent which, when added to the components of a polymerization
reaction, will stop the growth of a polymer chain, thereby
preventing the addition of MER units.
COD
Chemical Oxygen Demand - Determined by methods explained in the
references given under BOD5.
104
-------
The polymer obtained when two or more monomers are involved in
the polymerization reaction.
Cross-link
A comparatively short connecting unit (such as a chemical bond or
a chemically bonded atom or group) between neighboring polymer
chains.
CrYSt.all.ine
Having regular arrangement of the atoms in a space lattice --
opposed to amorphous.
D e jUas t er an t
A compound (usually an inorganic mineral) added to reduce gloss
or surface reflectivity of plastic resins or fibers.
Dialysis
The separation of substances in solution by means of their
unequal diffusion through semipermeatle membranes.
Diatomaceous, Earth
A naturally-occurring material containing the skeletal structures
of diatoms - often used as an aid to filtration.
Effluent
The flow of waste waters from a plant or waste water treatment
plant.
Emulsifier
An agent which promotes formation and stabilization of an
emulsion, usually a surface-active agent.
Emulsion
A suspension of fine droplets of cne liquid in another.
Facultative Lagcon cr Pond
A combination of aerobic surface and anaerobic bottom existing in
a basin holding biologically active waste waters.
Fatty, Acids
An organic acid obtained by the hydrolysis (saponification) of
natural fats and oils, e.g., stearic and palmitic acids. These
acids are monobasic and may or may not contain some double bonds.
They usually contain sixteen or more carbon atoms.
105
-------
Filtration
The removal of particulates from liquids by membranes on in-depth
media.
Formalin
A solution of formaldehyde in water.
Free_Radical
An atom or a group of atoms, such as triphenyl methyl (C6H5) 3C» ,
characterized by the presence of at least one unpaired electron.
Free radicals are effective in initiating many polymerizations.
Godgt^goll
Glass or plastic rollers around which synthetic filaments are
passed under tension for stretching.
Gallons per day.
GPM
Gallons per minute.
Halocjen
The chemical group containing chlorine, fluorine, bromine,
iodine.
Isptactic Polymer
A polymer in which the side chain groups are all located on one
side of the polymer chain. See also "Atactic Polymer."
Lev>js_ Acid
A substance capable of accepting frcm a base an unshared pair of
electrons which then form a covalent bond. Examples are boron
fluoride, aluminuir chlcride.
Hcmogol^mer
A polymer containing only units cf one single monomer.
Humect ant
An agent which absorbs water. It is often added to resin
formulations in order to increase water absorption and thereby
minimize problems associated with electrostatic charge.
106
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Influent
The flow of waste waters into a treatment plant.
M
Thousands (e.g. , thousands metric tons) .
MM
Millions (e.g., million pounds).
Monomer
A relatively simple compound which can react to form a polymer.
A measure of the relative acidity or alkalinity of water on a
scale of 0-14. A pH of 7 indicates a neutral condition, less
than 7 an acid condition, greater than 7 an alkaline condition.
Phenol
Class of cyclic organic derivatives with the basic chemical
formula C6H5OH.
A chemical added to polymers to impart flexibility, workability
or distensibility.
Polymer
A high molecular weight organic ccrrpound, natural or synthetic,
whose structure can be represented by a repeated small unit, the
(MER) .
Polymerization
A chemical reaction in which the molecules of a monomer are
linked together tc forrr large molecules whose molecular weight is
a multiple of that of the original substance. When twc or more
monomers are involved, the process is called copolymerization.
Pr etr eatment
Treatment of waste waters prior to discharge to a publicly owned
waste water treatment plant.
Primary Treatment
First stage in sequential treatment of waste waters - essentially
limited to removal of readily settlatle solids.
107
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Quenching
Sudden cooling of a warm plastic, usually by air or water.
Reflux
Condensation of a vapor and return of the liquid to the zone from
which it was removed.
Resin
Any of a class of solid or semi solid organic products of natural
or synthetic origin, generally of high molecular weight with no
definite melting point. Most resins are polymers.
Scrubber
Equipment for removing condensable vapors and particulates from
gas streams by contacting with water cr other liquid.
Secondary Treatment
Removal of biologically active soluble substances by the growth
of micro-organisms.
Slurry
Solid particles dispersed in a liquid medium.
A type of extrusion die consisting of a metal plate with many
small holes through which a molten plastic resin is forced to
make fibers and filaments.
.e
Textile fibers of short length, usually one-half to three inches.
StQichigmetric
Characterized by being a proportion of substances exactly right
for a specific chemical reaction with no excess of any reactant
or product.
TDS
Total dissolved solids - soluble substances as determined by
procedures given in reference under EOD5.
Thermoplastic
Having property of softening or fusing when heated and of
hardening to a rigid form again when cooled.
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Thermosetting
Having the property cf becoming permanently hard and rigid when
heated or cured.
TOC
Total organic carbon - a method fcr determining the organic
carbon content of waste waters.
Tow
A large number of continuous filaments of long length. Tow is
the usual form of fibers after spinning and stretching and prior
to being chopped into- short lengths of staple.
Transester ification
A reaction in which one ester is converted into another.
Vacuum
A condition where the pressure is less than atmospheric.
Ziegler-Natta Catalyst
A catalyst (such as a transition metal halide or an
organometallic compound) that promotes an ionic type of
polymerization of ethylene or other olefins at atmospheric
pressure with the resultant formation of a relatively high-
melting polyethylene or similar product.
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TABLE XIII-1
METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS)
ENGLISH UNIT ABBREVIATION
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
* Actual conversion, not a multiplier
by TO OBTAIN (METRIC UNITS)
CONVERSION ABBREVIATION METRIC UNIT
hectares
cubic meters
«
kilogram - calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric ton (1000 kilograms
meter
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
m
110
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