PRETREATMENT OF POLLUTANTS
INTRODUCED INTO
PUBLICLY OWNED
TREATMENT WORKS
OCTOBER 1973
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAM OPERATIONS
WASHINGTON,D.C. 20460
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833R73003
FEDERAL GUIDELINES
PRETREATMENT OF POLLUTANTS
INTRODUCED INTO
PUBLICLY OWNED
TREATMENT WORKS
OCTOBER 1973
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAM OPERATIONS
WASHINGTON, D.C. 20460
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FOREWORD
In response to the Federal Water Pollution Control Act Amendments
of 1972 (P.L. 92-500), this country has undertaken an unprecedented
program of cleaning up our Nation's waters. There will be a sub-
stantial investment by Federal, State, and local government as well as
by private industry in treatment works to achieve the goals of the Act.
It is i mpo rtant that the i nves tment in pub 1 i cly owned t reat:-nent
works be protected from damage and interference wi th proper opera ti on.
These guidelines were developed by the Environmental Protection
Agency in accordance with Section 304(f) of the Act. It is important
to note the clear requirements in the Act that there be both national
pretreatment standards, Federally enforceable, and pretreatment
guidelines to assist States and municipalities in developing local
pretreatment requirements. Some factors in pretreatment are not
amenable to a national standard. The Environmental Protection Agency
therefore encourages the establishment of local pretreatment require-
ments, tailored to the conditions at a specific publ icly owned treat-
ment works. Such requirements are considered essential to ensure
compl i ance with permits issued under the National Poll utant Discharge
Elimination System.
The guidelines were the subject of numerous extensive reviews,
both within the Government and by affected segments of the public.
A 11 of the many comments were carefully cons i dered in arri vi ng at
this publication. It is the intention of the Environmental Protection
Agency to revise these guidelines from time to time as additional
technical information becomes available and as industrial effluent
guidelines are issued pursuant to Section 304(b) of the Act. The
most valuable source of information for revisions, however, will be
actual experiences of those using the guidelines. All users are
encouraged to submit such information to the Director of the r'~unicipal
Waste Water Systems Division, Office of Air and Water Programs,
Environmental Protection Agency, Washington, D.C. 20460.
r!~'--~
Acting Administrator
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SECTION I
SECTION II
SECTION I I I
SECTION IV
APPENDIX A
APPENDIX B
APPENDIX C
TABLE OF CONTENTS
INTRODUCTION
1 .
2.
3.
4.
Purpose
Author i ty
Definitions
The Federal Water Pollution
Amendments of 1972
Contro1
EFFLUENT LIMITATIONS AND NPDES PERMITS
5.
6.
NPDES Municipal Permits
Effluent Limitations for Pub I icly
Owned Treatment Works
JOINT TREATMENT AND PRETREATMENT
7.
8.
9.
Joint Treatment
Pretreatment Policy
Federa1 Pretreatment Standards
STATE AND LOCAL PRETREATMENT
REQUIREMENTS
10.
11 .
12.
13.
14.
Objectives
Pretreatment Information
Pretreatment Ordinance
Example Calculations
Other Considerations
Pretreatment Standards (40 CFR 128)
Secondary Treatment Information
(40 CFR 133)
Information on Materials Which Inhibit
Biologica1 Treatment Systems
PaCJe No.
1
1
2
3
4
4
5
6
6
7
7
10
10
10
13
14
15
A-1
B-1
C-1
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APPENDIX D
TABLE OF CONTENTS
(continued)
Information on Pretreatment Unit
Operations
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
Annex
l-Paper and All ied Products
2-Dairy Products
3 - T ex t i 1 e s
4-Seafoods
5-Pharmaceuticals
6-Leather Tanning and
Finishing
7-Sugar
8-Petroleum Refining
9-Meat Products
1 O-G r a i n Mill i ng
l1-Fruit and Vegetable
12-Beverages
13-Plastic and Synthetic
Materials
14-Blast Furnaces, Steel Works,
and Rol I ing and Finishing
15-0rganic Chemicals
16-Metal Finishing
17-0ther Industries
Inorganic Ferti 1 izer
Electric and Steam
Generation
Aluminum
Flat Glass, Cement,
Lime, Concrete
Products. Gypsum,
and Asbestos
Inorganic Chemicals
Industrial Gas Products
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Federal Guidel ines
Pretreatment of Po11utants Introduced
Into Publ icly Owned Treatment Works
SECTION I
I NTRODUCT ION
1.
Pu rpose
These guidel ines are establ ished to assist municipal ities,
States, and Federal agencies in developing requirements for
the pretreatment of wastewaters which are discharged to pub-
1 icly owned treatment works. The Guidel ines also explain
the relationship between pretreatment and the effluent
1 imitations for a publ icly owned treatment works.
The U.S. Environmental Protection Agency (EPA) has publ ished
Pretreatment Standards in 40 CFR 128 (Appendix A). The stan-
dards will be enforceable by the EPA. These guidel ines
provide technical information useful to States and municipal-
ities in establishing pretreatment requirements to supplement
the Federal pretreatment standards.
2.
Authority
Authority for these guidelines is contained in Section 304(f)
(1) of the Federal Water Pollution Control Act Amendments of
1972 (the Act), which states:
"For the purpose of assisting States in carrying out
programs under Section 402 of this Act, the Adminis-
trator shall publ ish. . . guidel ines for pretreatment
of pollutants which he determines are not susceptible to
treatment by publ icly owned treatment works. Guidel ines
under this subsection shall be establ ished to control
and prevent the discharge. . . of any pollutant which
interferes with, passes through, or otherwise is in-
compatible with such works".
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3.
Definitions
Compatible Pollutant:
Biochemical oxygen demand, suspended sol ids, pH, and fecal
coliform bacteria, plus additional pollutants identified in
the NPDES permit if the publ icly owned treatment works was
designed to treat such pollutants, and in fact does remove such
pollutants to a substantial degree. The term substantial
degree is not subject to precise definition, but generally
contemplates removals in the order of 80 percent or greater.
Minor incidental removals in the order of 10 to 30 percent are
not considered substantial. Examples of the additional pollutants
which may be considered compatible include:
Chemical oxygen demand
Total organic carbon
Phosphorus and phosphorus compounds
Nitrogen and nitrogen compounds
Fats, oils, and greases of animal or vegetable
origin (except as prohibited where these materials
would interfere with the operation of the publ icly
owned treatment works) .
Incompatible pollutant:
Any pollutant which is not defined as a compatible pollutant.
Joint Treatment Works:
Treatment works for both non-industrial and industrial waste-
wa te r.
Major Contributing Industry:
A major contributing industry is one that: 1) has a flow of
50,000 gallons or more per average work day; 2) has a flow
greater than five percent of the flow carried by the municipal
system receiving the waste; 3) has in its waste a toxic pol-
lutant in toxic amounts as defined in standards issued under
Section 307 (a) of the Act; or 4) has a significant impact,
either singly or in combination with other contributing
industries, on a publ icly owned treatment works or on the
quality of effluent from that treatment works.
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Pretreatment:
Treatment of wastewaters from sources before introduction
into the joint treatment works.
4.
The Federal Water Pollution Control Act Amendments of 197~
The Act established a national system for preventing, reducing,
and eventually eliminating water pollution. The ultimate goal
is to eliminate the discharge of pollutants into the navigable
waters of the United States.
Under the National Pollutant Discharge EI imination System
(NPDES), all point sources (including publicly owned treatment
works) must obtain a permit for the discharge of wastewaters
to the navigable waters of the United States.
The Act further requires that, as a minimum intermediate ob-
jective, all point sources other than publicly,owned treatment
works treat their wastewaters by the application of the best
practicable control technology. Subsequently, the minimum
requirement for industrial wastewaters would be the application
of best avai lab1e treatment technology. For publicly owned
treatment works, the initial objective is secondary treatment,
followed by best practicable treatment technology.
Monitoring for comp1 iance with effluent limitations and pre-
treatment requirements will be in accordance with EPA guide-
lines establ ished under Section 304 and implemented under
Section 308 of the Act.
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SECTION I I
EFFLUENT LIMITATIONS NPDES PERMITS
5.
NPDES Municipal Permits
Procedures developed under Section 402 of the Act will provide
the detai 1s for implementation of permit programs. The purpose
of the following discussion is to highlight the relation be-
tween the permit programs and the pretreatment standards and
guidelines.
Under the National Pollutant Discharge Elimination System
(NPDES), all point sources (including pub1 ic1y owned treat-
ment works) must obtain a permit for the discharge of waste-
waters to the navigable waters of the United States. Permits
wi 11 not be required for industrial sources discharging into
publ icly owned treatment works.
The pretreatment standards (Appendix A) will be directly en-
forceable by EPA on industry.
The effluent 1 imitations for a pollutant in the discharge from
a publicly owned treatment works will be individually deter-
mined by the permitting agency, based on information supplied
by the municipal ity. These effluent 1 imitations will be in-
cluded in the discharge permit issued to the municipal ity for
the publ icly owned treatment works.
Additionally the permit for a publicly owned treatment works
wi I I require provisions for adequate notice to the permitting
agency of:
a.
New introductions into such works of pollutants from
any source which would be a new source as defined
in Section jJo of the Act if such source were dis-
charging pollutants.
b.
New introductions of pollutants into such works from a
source which would be subject to Section 301 of the
Act if it were discharging such pollutants.
c.
A substantial change in volume or character of pol-
lutants being introduced into such works by a source
already discharging pollutants into such works at the
time the permit is issued.
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This notice wil 1 include information on the quantity and quality
of the wastewater introduced by the new source into the publ icly
owned treatment works, and on any anticipated impact on the
effluent discharged from such works.
The permit programs developed under Section 402 of the Act
should be consulted for details regarding permit appl ication.
6.
Effluent Limitations for Publicly Owned Treatment Works
There are various sources of effluent I imitations. including:
a.
Effluent I imitations for publ icly owned treatment
works (Section 301(b) of the Act). Secondary treatment
information is contained in 40 CFR Part 133 (Appendix B).
b.
Toxic Effluent Standards or Prohibitions (Section 307
(a) of the Act).
c.
Water Qual ity Standards (Section 303 of the Act).
The most stringent limitation for each pollutant will govern.
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SECTION III
JOINT TREATMENT AND PRETREATMENT
7.
Joint Treatment
Joint treatment of industrial and municipal wastewaters in the
same treatment works is generally a desirable practice. Treat-
ment of the combined wastewaters can benefit the environment,
the municipal ity, and industry if properly designed and oper-
ated.
Some of the advantages of joint treatment are:
a.
Increased flow which can result in reduced ratios of
peak to average flows.
b.
Savings in capital and operating expenses due to the
economics of large-scale treatment faci I ities.
c.
Better use of manpower and land.
d.
Improved operation (larger plants are potentially
better operated than smaller plants).
e.
Increased number of treatment modules with resultant
gains in reliability and flexibil ity.
f.
More efficient disposal of sludges resulting from
treatment of wastewaters containing compatible
pollutants.
In some cases, the characteristics of the industrial wastewaters
may be beneficial in the publicly owned treatment works proc-
esses. For example, some industrial wastewaters contain organic
material but are devoid of the nutrients required for biological
treatment. In joint biological treatment the nutrients are
present in the domestic wastewater and consequently do not have
to be added (as they would in separate industrial treatment).
For a plant required to remove nutrients, the joint biological
treatment of nutrient-free organic industrial wastes would re-
sult in lower amounts of nutrients to be removed in a subsequent
process.
There may be characteristics present, however, which make a
wastewater not susceptible to joint treatment if introduced
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directly into the municipal system. In such cases, it wi 11 be
necessary to pretreat the wastewater.
8.
Pretreatment Policy
The fol lowing are basic pretreatment policy considerations used
in developing these guidelines:
a.
Joint treatment of domestic wastewaters and adequately
pretreated industrial wastewaters is encouraged where
it is the economical choice.
b.
In-plant measures to reduce the quantity and strength
of industrial wastewater flows can be beneficial to
joint treatment, and should be encouraged.
c.
Pretreatment for removal of compatible pollutants is
not required by the Federal pretreatment standards.
d.
In recognition of the broad spectrum of industries,
waste constituents, and treatment plants, State and
municipal pretreatment requirements should be based
on an individual analysis of the permitted effluent
I imitations placed on a publicly owned treatment
works and on the potential for adverse effects on
such works.
9.
Federal Pretreatment Standards
EPA has issued standards in 40 CFR Part 128 for pretreatment
of pollutants introduced into publicly owned treatment works
(Appendix A). These standards are designed to protect the
operation of a publicly owned treatment works and to prevent
the introduction of pollutants into publicly owned treatment
works which would pass through such works inadequately
treated.
The pretreatment standards are intended to be national in
scope, i.e. generally applicable to all situations. In many
cases, it will be necessary for a State or a municipality to
supplement the Federal Standards with additional pretreatment
requirements which take into account local conditions. The
purpose of these guid~lines is to provide information to States
and municipalities to assist in the development of these
supplemental pretreatment requirements. The following para-
graphs describe the basis and extent of the Federal pretreat-
ment standards.
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Section 128.131 of the Standards (Appendix A) is designed to
protect the operation of publicly owned treatment works.
Wastes which are prohibited from introduction into publ icly
owned treatment works are 1 isted. This Section is appl icable
to non-domestic users only.
Section 128.133 is designed to prevent the introduction of
incompatible pollutants to publ icly owned treatment works
which would pass through such works inadequately treated.
Any pollutant that is not a compatible pollutant as defined in
Section 128.121 is by definition incompatible. Section 128.133
is applicable only to "major contributing industries" as
defined. Pretreatment is required for incompatible pollutants
to the levels of best practicable control technology currently
avai lable as defined for industry categories in guidel ines
issued pursuant to Section 304(b) of the Act. Provision is
made for the Administrator to segment the industrial users of
municipal systems as a special category for the purposes of
defining best practicable control technology currently avai 1-
able. Provision is also made to permit a less stringent pre-
treatment standard for an incompatible pollutant if the munic-
ipal ity is committed in its NP~ES permit to remove a specified
percentage of the incompatible pollutant. These requirements
are based on the premise that incompatible pollutants introduced
into a publ icly owned treatment works generally should not
pass th~ough such works in amounts greater than would be permitted
for direct discharge.
Biochemical oxygen demand, suspended sol ids, pH, and fecal
col iform bacteria, which are defined as compatible, are the
pollutants used to describe the effluent quality attainable
by secondary treatment in 40 CFR Part 133 (Appendix B). Not
later than July 1,1977, secondary treatment effluent limita-
tions must be met by all publicly owned treatment works which
discharge into navigable waters unless more stringent effluent
1 imitations are necessary to ensure compliance with water qual ity
standards or toxic effluent standards.
The terms compatible and incompatible pollutant should not be
misinterpreted. For incompatible pollutants, it wi 11 be
necessary for the municipal ity to assess the capabi Ii ties of
its treatment works in order to determine whether it can make
a commitment in its NPDES permit to remove some percentage
of the incompatible pollutants in the treatment works. Such
a commitment might be made if there is some removal of in-
compatible pollutants in the treatment works which occurs as
an incident to the removal of compatible pollutants. In this
case it must be determined that the incidental removal can be
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relied upon and wi I I not cause harm to the treatment works or
interfere with its operation (including sludge hand] ing and
disposal processes).
There wi I I also be situations when the Federal pretreatment
standards (without credit for removal in the publ icly owned
treatment works) will not be sufficient to protect the opea-
tion of the publ icly owned treatment works. This might be
the case when the quantity of an incompatible pollutant intro-
duced by al I major contributing industries would result in a
concentration of the pollutant in the influent to the treat-
ment works which would inhibit the performance of the treat-
ment process. In such a case, the municipal ity would have to
supplement the Federal standards.
Pretreatment for removal of compatible pollutants is not re-
qui red by the Federal pretreatment standards. This is based
on the premise that pretreatment facil ities should not be
required for removal of compatible pollutants as a substitute
for adequate municipal waste treatment works. This, however,
does not preclude State or local pretreatment requirements
for compatible pollutants. Pretreatment of wastewaters con-
taining compatible pollutants may be necessary in the form of
spill protection or flow equal ization in order to ensure
compliance with the Federal pretreatment standards and per-
mitted effluent limitations.
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SECTION IV
STATE AND LOCAL
PRETREATMENT REQUIREMENTS
10.
Objectives
The Act specifically provides for pretreatment requi rements
established by State or local law not in confl ict with the
Federal standards in Appendix A. The Federal standards were
established on the basis that each publ icly owned treatment
works may requi re pretreatment by users, consistent with
applicable State or municipal law. The State or local pre-
treatment requirements can recognize specific factors (such
as treatment processes and plant capacities) which would not
be national in scope.
11.
Pretreatment Information
Pretreatment information has been compiled, in appendices to
these guidelines, as a data source to assist municipal ities
and others in arriving at effective pretreatment requi rements
to supplement the Federal pretreatment standards for a specific
publ icly owned treatment works. This subsection describes
the information available, how it was developed, and its appl ica-
tion.
a.
Information on Materials which Inhibit Biological
Treatment Processes
The information in Appendix C identifies concentrations of
various materials which can inhibit four types of biological
treatment processes: activated sludge, trickl ing filter,
anaerobic digestion, and nitrification. This information was
derived from data reported in the technical I iterature. Docu-
mented information on this subject is I imited, especially for
the synergistic effects of many pollutants present in the
wastewaters. Caution must be exercised In applying the data
to a specific situation. Appendix C should be used as a
guide to evaluate when more detailed study is necessary.
In practice, the concentrations of the materials in the influent
to the publ icly owned treatment works should be determined.
Comparison with the concentrations in Appendix C will indicate
whether or not there may be problems. If the influent wa:te-
water concentration is close to the inhibitory concentration
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in Appendix C, then further study may be necessary. The
wastewaters must be analyzed to determine the presence of
inhibitory materials and their potential impact on treatment
plant performance. This includes consideration of intermittent
batch discharges, variations in concentration, and back-
ground levels al ready present in the wastewater. When inhibi-
tory material is present, testing the public water supply will
provide an indication of a domestic source of the inhibitory
material. However, it must be real ized that materials of
this type can also be added during domestic water usage.
If information is not given in Appendix C concerning a suspected
inhibitory material, it may be necessary to obtain additional
data. Potential sources of such data include works treating
similar wastes or the results of treatability studies.
b.
l~formatio~~~_l~~ustrial Wastewater Characteristics
and Pretreatment Unit Operations
The information in Appendix D identifies wastewater characteris-
tics and pretreatment unit operations for twenty-two industrial
groups. Characteristics which may require pretreatment or are
significant to the joint treatment design are indicated. Also,
the unit operations which may be necessary to meet the pre-
treatment requirements are 1 isted. It is emphasized that the
1 isted unit operations are not mandatory. It is anticipated
there will be cases when not all unit operations shown will
be needed and other cases where additional unit operations
will be needed.
For each of sixteen industries in Appendix D a brief summary
is provided concerning the nature of the industry, industrial
practices, and pretreatment information.
Appendix D groups the industries in terms of Standard Industrial
Classification Codes. These codes are as contained in the 1972
edition of the Standard Industrial Classification Manual pre-
pared by the Executive Office of Management and Budget. The
Manua 1 is ava i 1 ab 1 e f rom the Super i ntendent of Documents,
Government Printing Office, Washington, D. C. 20402. For some
industry groups, subgroups with common pretreatment characteristics
have been identified.
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The following industry groups are included in Appendix D:
Paper and All ied Products
Dairy Products
Texti 1es
Seafoods
Pha rmaceut i ca 1 s
Leather Tanning and Finishing
Sugar
Petroleum Refining
Meat Products
Grain Mi 11 ing
Fruit and Vegetables
Beve rages
Plastic and Synthetic Materials
Blast Furnaces, Steel Works, and Roll ing and Finishing
Organic Chemicals
Metal Finishing
Inorganic Fertil izers
Electric and Steam Generation
Aluminum
Flat Glass, Cement, Lime, Concrete Products, Gypsum, and
Asbestos
Inorganic Chemicals
Industrial Gas Products
The major data sources used to characterize the wastewater
include:
(1)
Industrial effluent guidance documents developed by
EPA.
(2)
EPA research reports.
(3)
Information in the technical
1 iterature.
Most of the data were derived from EPA publ ications; other
sou rces we re used to fill in data gaps. Ranges of d i ffe rent
waste constituents present in industrial wastewaters were
designated on the basis of a review of the data avai lable.
The following classification system was used to describe the
characteristics of industrial wastewaters in relation to domestic
wastewaters:
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Classification
Waste
Constituents
Extremely
High
> 1,000
> 1,500
> 1,000
Low
Ave rage
200-300
300-450
200-300
15-25
6-9
High
300-1,000
450-1,500
300-1,000
> 25
> 9 (alkaline)
BOD5' mg/L
COD, mg/L
SS. mg6L
Temp., C
pH
< 200
< 300
< 200
< 15
< 6
(acid)
The wastewater characteristics information can be used to
identify conditions which should be carefully evaluated when
establishing pretreatment requirements for a specific industry
and in the design of the joint treatment works. The list of
wastewater characteristics can be used as a guidel ine for
developing a wastewater testing program for a particular industry.
For industrial wastewaters from each industry group or pre-
treatment sub-group, pretreatment unit operations generally
considered necessary for three types of municipal secondary
treatment processes are identified. These processes are:
1.
Suspended biological systems (activated sludge process
including modifications, aerated lagoon process).
2.
Fixed biological systems (trickl ing filter and modi-
fications, rotary disc).
3.
Independent physical/chemical
sedimentation, pH adjustment,
adsorption) .
system (chemical addition,
filtration, carbon
Before appl ication of the pretreatment unit operations infor-
mation, full consideration must be given to Federal pretreat-
ment standards, permit effluent I imitations, relative flow
ratios, and pollutants which could inhibit biological processes.
12.
Pretreatment Ordinance
National requirements for major contributing industries
will be controlled under the pretreatment standards (Appendix A).
However, it is important that no discharge, from any source,
to the publ icly owned treatment works cause physical damage,
interfere with treatment processes, or result in a violation
of effluent limitations. There must, therefore, be a legal
basis for regulating and controll ing all discharges to the
publ icly owned treatment works. A municipal ordinance or
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statute, embodying the pretreatment principles in these guide-
1ines, would meet this requirement. It may be necessary to
establish a local system which will allocate waste loads to
industrial users so that biological treatment processes are
not inhibited and to ensure that effluent limitations are met.
Detai led information and suggested formats are readily available
regarding ordinances to regulate the use of sewers and the waste-
waters discharged to them. Many States and regional authori-
ties have publ ished instructions or model ordinances. These
sources should be consulted for comprehensive information on
ordinance preparation. The ordinance should then be adapted
to local conditions and to the pretreatment principles in
these guidelines.
13.
Example Calculations
When the Federal pretreatment standards (Appendix A) govern,
industrial users wil I be able to determine their pretreatment
requirements with other information which is publicly avail-
able. However, when effluent limitations (such as water qual ity
standards or toxic effluent standards) govern for a particular
pol~utant, then the pretreatment requirements may have to be
made more stringent than the Federal standards, so that effluent
limitations are met. In this case, it will be necessary for
the municipal ity to allocate loads of these pollutants which
the industry or industries will be permitted to introduce
into the municipal system.
There are numerous ways to accomplish waste load allocation.
Some large municipal ities, where there are many industries of
the same type and similar size, specify an allowable pollutant
concentration to be met by all users.
Another method would be to al locate waste loads in proportion
to the waste load which would be allowable if the Federal
pretreatment standards governed. This procedure is illustrated
in the following example:
Wastewater flow
8 MGD
Major Contributing Industries:
Industry X
Production
Wastewater
Wastewater
flow
contains incompatible
10J tons/day
1 MGD
pollutant I
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Industry Y
Production
Wastewater
Wastewater
flow
contai I1S incompatihle
200 tons/day
1 MGD
pollutant I
The guidel ines for best practicable control technology
currently available for pollutant I are:
Industry X
Industry Y
1.0 pounds/ton
1.5 pounds/ton
The Federal pretreatment standards for the major contributing
industries would be as follows (the municipality is not
committed in its NPDES permit to remove any percentage of the
incompatible pollutant I):
Industry X:
100 tons/day x 1.0 pound/ton = 100 pounds/day
Industry Y:
200 tons/day x 1.5 pound/ton = 300 pounds/day
Total
400 pound s / da y
However, the municipal ity makes a determination, based on an
evaluation of the permitted effluent limitations for the treat-
ment works, that it can accept a total of only 280 pounds per
day of incompatible pollutant I. If the allocation is in propor-
tion to the quantity of pollutant each could have introduced
under the Federal pretreatment standards, then:
Pollutant I Allocation to Industry X =
100
400
(280) = 70 pounds/day
Pollutant I Al location to Industry Y =
t~6 (280) = 210 pounds/day
14.
Other Considerations
The sample calculations presented in the immediately preceding
Subsection show Jne method for determining waste load al loca-
tions. However, in addition to ensuring that the effluent limi-
tations are met, it is necessary to evaluate the industria]
wastewaters to ensure that there is no interference with the
publ icly owned treatment works operation.
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Some of the factors to be evaluated are:
a.
Conformance with Federal pretreatment standards
(Append i x A).
b.
Compatibility with the entire treatment works,
including sewers, pumping stations, and sludge handling
and disposal. Potential for the following types of
interference should be considered:
( 1 )
(2)
Severe corrosion damage.
Significant deposits or abrasion which would
substantially reduce the design capacity of sewers
and wet wells or which would cause structural
collapse.
(3)
Pollutant concentration in sludges such that
sludge handling, stabilization, or disposal
is adversely affected.
c.
Cost-effectiveness of treatment in the publ icly
owned treatment works compared with pretreatment.
d.
Possible presence of materials, in significant con-
centrations, which could inhibit the treatment process
(see Appendix C).
e.
Need for pretreatment unit operations discussed in
Section IV-Subsection 11 and in Appendix D.
f.
Appl icability of more stringent State or local pretreat-
ment requi rements which govern.
g.
Need to conduct treatability studies or test programs
to verify findings.
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No 2 Jfi-Pt. llI-1
APPENDIX A
THURSDAY, NOVEMBER 8, 1973
WASHINGTON. D.C.
Volume 38 . Number 215
PART III
ENVIRONMENTAL
PROTECTION
AGENCY
.
WATER PROGRAMS
Pretreatment Standards
A-I
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:}09S:2
Title 40-Protection of the Environment
CHAPTER I-ENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER D-WATER PROGRAMS
PART 128-PRETREATMENT STANDARDS
On July 19, 1971, notIce was pub-
li.,;hed In the FEDERAL REGISTER that the
Environmental Protection Agency was
proposing standards for pretrea tment of
pollutants intl'Oduced mto pUblldy
owned treatment works pur,uant. to sec-
tIOn :3071 b' of t.he Feder~d Water Pollu-
t.lOn Control Act Amendments of 1972
1 the Act.) . Wntten comments on t.he pro-
posed rulemakm~ \\'ere InVlt.ed and re-
ceived from mt.erested parl1es and t.he
public, In adcl1t.IOn, a publrc hearmg was
held in Washmgton, D,C" on September
26, 1973, The EnVIronmental Protection'
Agency has carefully considered all com-
ments received and the record of the
public hearing, All wntten comments
and a transcript of the publrc hearing
are on file wit.h the Agency. As rndlcated
below, the regulation has been modified
in response to some of the comments.
The following discussion also outlines
the reasons why other suggested changes
were not made,
Under sectIOn 307 (b' of the Act, Fed-
eral pretreatment st.andards are designed
to achie\'e two purposes: 11. To protect
the operation of pUbhclv owned treat-
ment works, and 12 " t.o I"revent. the dis-
charge of pollutants which pass t.hrough
such works rnadequately treat.ed,
Sect.ion 128.131 sets forth a number of
prohibItIOns desIgned to protect the op-
eration of publIcly owned treatment
works. The prohibitions are self-ex-
planatory. One commenter suggested
that * 128131 is deficIent in that it falls
to Impose specIfic numerical limitations
on the dIscharge of pollut.ants that in-
terfere wIth the operation of publicly
owned treatment \\'orks Ho'.\'ever, the
Agency has been unable to formulate
such specific numerical linutations. In
the first place, t.he data that are
presently available are not. consIdered
sufficient to support unIform natIOnal
standards prescnbing permIssible con-
centrations of particular pOllutants in
pubhcly owncd treat.ment works. More-
over, the degree that any pollutant in-
terferes with the ojJPratlOn of a publicly
owned treatment works depends on
the concentratIOn of pollutant in
the treatment works Ibelf, rather
than the concentratIOn in each user's
effiuent. But for a natIOnal pretreat-
ment standaard to be w'ort:able alld
enforceable, It must prc.scnbe the qual-
Ity of the us('r'~ effiucnL: otllel'l'.'l:.e, the
uspr \\'Ill not know what steps he must
take to comply wIth the standard. It IS
impossIble ill a ul1l!orm ILltlUnal pre-
treatment standard to relatt. tlJe qualIty
of the user'~ effluent to the concentratIOn
of various pollutant:-. in the publicly
owned treatmenL \\'od:s, S!llce tll1s reLi-
tion,hlp \\'1]] valY in c;lch sc\\'er s,"otem
dppendmg on the quantity of the user's
effiuent as compared with the quantity of
other effluents in the system.
RULES AND REGULATIONS
Section 128 133 is based on the premise
that pollutants which pass through pub-
hcly owned treatment works 111 amounts
gn'ater than would be pel'miLted as a
111lmmum treatment requirement for
SIlI1llar industrial sources dlschargll1g di-
rectly to na\'lgable waters should be con-
sIdered adequately treated. The fact that
a discharger chooses to use a mUl\lclpal
sewer system. rather tlWIl dischar~ing
hIs wastes directly to the navIgable
waters, .should not as " ma tter of general
pnnciple lll\'olve a pellalty to the en-
nronmpnt
On the ba,c:is of thIs premIse, ~ 128.133
requrres lL,er, in Inuustrwl cate:,;ories
subJect Lo effluent Rllidelmes issued under
sectIOn 3041 b. of the Act. whIch are
dbcha rging 1I1compa tlble pollutan ts to
publicly owned treatment works to
adopt best practicable control technol-
ogy currently avaIlable, as defined by the
Administrator pursuant to section 304
(b) of the Act.
Dunng the public commellt period.
questions were raised as t.o whether the
effluent limitations guidelines would be
appropriate in all cases for application to
users of pUblicly owned treatment
works. The Agency recognizes that for
some industrial categories it may be
necessary to further refine the effluent
limitatIOns guidelines to deal with prob-
lems that may arise in the application of
such guidelines to users of publicly
owned treatment works. However, the
Agency believes that any adjustments re-
quired for particular industrial catego-
nes should be considered in connection
with the promulgation of the indlvldual
effluent guidelmes, rather t.han 111 the na-
tional pretleatment standard. Accord-
ingly, when emuent limItations guidelines
are promulgated for individual mdustrial
categories, the Agency will also propose
a separate provIsion for theIr applicltron
to users of pnblicly owned trea tmen t
works Additional language has been
added to ~ 128.133 to clarify thIs mlent.
It was unclear whether ~ 128.133 as
proposed co\'ered sources that would be
new sources if they were dischargll1g di-
rectly mto the navigable waters. SectIOn
3071c) of the Act requires promulgatIOn
of ~eparate pretrpatment standards for
such sourCles. Pur.;uant to section 3071 c',
the Agencv has proposed pretreatment.
standards for ,such sourccs in COlU1ectwn
\\'lth its proposal of new source perform-
anee ~t;mdards under Sect.lOn 306 of tJ1e
Act. A('cordmgly, ) 1~8.133 has bcen mod-
lfif'd to make It dear t.lJat It COH:rs olily
sources t.h:it are not :,ub,lect to sectlOll
30"i I c 1 of the Act
SectIon I ~8 U3 allO\\ s a nedit for the
percent.age removal of an incompatIble
pollutant to whIch tlle publicly owned.
treat.ment works is COl1lIllJUcd ll1 Itl.. per-
mIt. To 111S11re the ba.'ls for allowll1g such
crecllt, a cummltment. wJlh re.,p"ct to a
percentagc removal of an incomp[1 t.ible
pollutant wl11 be m(')uded in t.hc lJe'rmlt
at the request of a mUl1lclpallty where
a basIs for such comnlltmpnt can be
demonstrated.
Some com mentel's suggesLcd that the
credit in ) 128.133 for removal at the
jomt treatment. works. where there is a
commitment to 'llch ITmo\'al in the
NPDES permIt, is unrea11stlc, since mu-
nicipalities wIll be ul1\\'llling t.o enter int.o
such commitments. However, 111 order to
achIeve the goal of pre\'enting the dIs-
charge of incompatible pollutants
through municipal systems in amounts
greater than the I1lin1111U1I1 J'('qUlrunents
If t.he discharge were dIrectly mto the
navIgable waters, it. is necessary that. the
required reduction be con tamed rn an
enforceable conlml tment eitller on the
part of the industrial user or t.he joint
treatment works. The industnal user
should not be relieved vf the commit.-
ment t.o achIeve the required degree of
reduction except to the extpnt that the
joint treatment works is able to assume
a commitment to remove the pollutant.
One commenter suggested that users
should be required to comply with toxic
effluent standards under section 3071 a)
of the Act, as well as the requirement of
best practicable control technology cur-
rently avaIlable under section 3011 b) and
3041 b) of the Act. However. toxic effluent
standards \\'111 be desIgned to protect
aquatic life in the receiving body of
water from both acut.e and chronic ef-
fect.s. Acute effects will be covered bv
concentrat.ion standards while chroni~
effects wiJl be covered by weight limita-
tIOns. Both t.ypes of st.andards will be
applicable to the disclurge f!'Om the pub-
licly owned treatment works. Toxic efflu-
ent st.andards \\'111 not be designed to
protect sewer systems, and thus It would
not be appropnate to apply them to dis-
charges into the system. To the extent
that toxic matenals in the users' dis-
charges interfere with the operation of
pubhcly owned treat.ment. works the
problem can be otherwise add1:essed
under these st.andards I) 128.131) or
under local standards using the pretreat-
ment guidelrne.s issued under section
:304 ( f) of the Act WhIle tOXIC materials
In t.he users' dIscharge may appear in
the sludge generated by the publIcly
owned treatment \\'orks, the Agency has
no basis for l1Jakmg a national deter-
mlllation that the resultant sludge dis-
po,al problem IS any worse than the
problem tha t wou Id be nea ted if the
mdlVldual users J't'mo\'ed the t.oxics from
their effluent aJ)(1 disposed of thp resu1t-
:ll1t matE'rials indindua11y. This is a
factor which must be determined bv
State and local autIlOl'lt1P', taking into
['CCoUllt the c1jXtbllItles of t.heir sJudge
chsposal ;,\,....tem anr! tl1(' )',,]]utants prps-
enr. In the wa,tes f]'um mdustri[11 w;prs.
The prespnce of toxic pollutants in
to..uc amounts is utihzpd in the regula-
tIOn III orctpr to identIfy "maJOr con-
tI lbutmg 1ll(;1i;;t1'lC~;" fo]' purposes of the
prdreatmc']\c lequlrements for incom-
patIble pollutants. The purpose here is to
Identify industnal u,ers w'hose emuent
IS sIgnIficant enough to W'[lITant the 1111-
posItion of contrc.b bused on best prac-
tll,,,ble control t.echnology currently
[i\'allable without undue :ldlllimst.rative
burden, rat.her th,u1 to indicate that it
IS appropriatE' to impose toxic eftjuent
standards on mdustrial users.
FEDERAL REGISTER, VOL. 38, NO. 21S-THURSDAY, NOVEMBER 8. 1973
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The definition of "compatible pollut-
ant" has been broadened to recognize
the fact that some joint treatment works
are designed to achieve substantial re-
moval of pollutants other than the four
pollutants listed in the definition in the
proposed regulation (BOD, suspended
solids, pH, and fecal coliform bacteria I.
Where the joint treatment works was
designed to and does achieve substantial
removal of a pollutant. it is not appropri-
ate to require the industrial user to
achieve best practicable control tech-
nology currently a\'ailable, since this
would lead to an uneconomical dupl1ca-
tion of treatment facilIties. \Vlule the
term "substantial removal" IS not sub-
ject to precise defillltion. it generally con-
templates removals in the order of 80
percent or greater. Minor incidental re-
1110\'als in the order of 10 to 30 percent
are not considered "substantial".
There \\'as a diversIty of comments on
the length of the time for compliance
and its relation to the promulgation of
the definition of best pra~ticable control
technology currently available. The Act
requires that pretreatment must specify
a time for compliance not to exceed three
years from the date of promulgation. The
Agency has concluded that a period not
greater than three years from the date
of promulgation is appropriate for com-
pliance for ~ 128.131. For Section 128.133
the same period is also considered an ap-
propriate tIme for compliance. However,
the standard set forth in ~ 128.133 will
not be complete untIl promulgatIOn of
the separate provision, as required by
Section 128.133, setting forth the applica-
tion to pretreatment of the effluent
Irnlltations guideline for a gi\'en in-
d ustrial category.
Accordingly, ~ 128.140 provides that
the period of compliance with ~ 128.133
\\'il! not commence for any particular
category of user until promulgation of
that separate provision. SectIOn 128.140
has been further modified to establish an
interim requirement for commencement
of construction. and a requirement for
compliance reports. It was concluded that
\\ithout such requirements, timely com-
pliance with the pretreatment standard
might be unenforceable as a practIcal
matter.
Some commenters questioned the need
for these pretreatment standards or the
relationshIP between these standards and
local pretreatment programs. It is im-
portant to note the clear requirements in
the Act that there be both national pre-
treatment standard:;, Federally enforce-
able, and EP A pretl ea tmen t gUIdelines to
as"lst States and mUl1lcipahties in
de\'eloping local pretreatment programs
The Agency recognizes that in some cases,
these pretreatment ~tandards may not be
sUfficIent to protect the operation of a
pUblicly o\\'ned treatment works or to
enable the treatment works to comply
with the terms of its NPDES permit. ThIs
may be the case, for example, when the
terms of the permit for the pUblicly
owned treatment works are dictated by
water quality standards or toxic stand-
ards. In such cases, the State or munici-
pality may have to impose more stringent
RULES AND REGULATIONS
pretreatment standards under State or
local laws than are specified in these
regulations to enable compliance with
NPDES permits issued to publicly owned
treatment works. The agency considers it
essential that such local pretreatment
requirements be established for each Sys-
tem where necessary to ensure compl1-
ance with the NPDES permit.
Pretreatment gUldelll1es will be pub-
lished, pursuant to sectJOn 3041fl of the
Act, to assist the States and municipal1-
tIes in establishing their own pretreat-
ment requIrements.
Ellectil'e date. This regulation will be-
come effectn'e December 10, 1973.
.JOHN QUARLES,
Acting Administrator.
NOVEMBER 1, 1973.
NOTE -The EPA pamphlet, Pretreatment of
DIscharges to Publicly Owned Treatment
Work, IS filed as part of the original docu-
n1ent.
Sec
128.100
128.101
128.110
128120
128121
128122
128.12:3
12812-1
128121)
128130
128.131
128132
Pll rpose
Apphcabllity.
State or local law.
Defin ItlOTIS.
Compatible pollutant.
Incompatl ble poilu tan t.
JOInt treatn1ent works.
J\lajor contnbutlng Industry.
Pretreatlnent.
Pretreatment standards.
ProhIbIted wastes.
Pretreatment for compatible pol-
lutants.
Pretreatn1cnt for inconlpatlble pol-
lutants.
Tlllle for COtnpllance.
:W9~:3
pH and fecal col1foJ'ln bacleria. plus ad-
ditional pollutants identIfied in the
NPDES permIt If the publicly owned
treatment works was desIgned to treat
such pollutunts, and in fact does remove
such pollutants to a substantial degree.
Examples of such additIOnal pollutants
may include:
C'henlical oxygen dernand
Total nqi,anlc carbon
Pho~,ph(.Jru:. and pll()':,ph(Jfu.::. compuunds.
Nlt[f)~ell and 111trogel1 cr,nlpounds.
Fat'-., oIls. .tnd gn:asc'-,; of anirnal vI' vegeta-
ble (Jrlgll1 except .1:-) prohibIted UJldr>r
: 128 J:,IIC')
S 123,122 1 ,,,'of1lpali"'" pollulanl.
The term "ll1compatlble pollutant"
means any pollutant whIch is not a com-
patIble pollutant as defined in ~ 128.121.
(; 128.123 Joillllr('alllwnl work,.
Publicly owned treatment works for
both non-industnal and industnal
wastewa tel'.
(; 128.12 ~ Major {,olll,.;hulin~ indu'lrr.
A major contributing industry is an
industrial user of the publicly o\\l1ed
treatment works that: (a I Has a flow
of 50,000 gallons or more per average
work day; I b' has a flow greater than
five percent of the flow carried bv the
mWlicipal system recei\'ing the \\:aste;
IC) has 111 its waste, a toxic pollutant m
toxic amounts as defined 111 standards
I,sued under section 307 (a) of the Act;
or I d' is found by the pernllt issuance
authonty, in connection wIth the issu-
ance of an NPDES permit to the pub-
I1cTy owned treatment works l'ece1\'ing
the waste, to have siglllficant impact,
eIther sll1gly or in combination with
other contributmg industries, on that
treatment works or upon the quahty of
effluent from that treatment 1\'orks.
S 128.12:; Prt'lreatmclIl.
Treatment of wastewaters from
sources bpfore mtroduction 1I1to the joint
treatment works.
S 128.130
Prf'lreahnf>nt ...tandards.
128133
128 HO
.~F1'HORITY: Sec. 3071b) PUI). L. 92-500: 86
8tol 857133 USC.1317,
S 128.100 I'urpo,...
The provisions of this part implement
5ection 3071 b) of the Federal Water Pol-
lution Control Act Amendments of 1972
(Public La w 92-500' hereinafter referred
to as "the Act"
S 128.101 .\ppli,'ahili1r.
The standards set forth in ~ 128.131
apply to all non-domestIc users of pub-
licly o\\'ned treatment works. The stand-
ard set forth in ~ 128.133 applies only to
major contributing industnes.
S 128.110 Stal.. or local law.
Nothing in this part shall affect. any
pretreatment requirement established by
any State or local law not in conflict with
any standard established pursuant to this
Part. In particular cases. a State or
municIpality, in order to meet the effluent
lImitations in a NPDES permit for a pub-
licly owned treatment works may find it
necessary to impose pretreatment re-
quirements stricter than those contained
herein.
(; 128.120 Ddinilio'h.
Definitions of terms used in this part
are as follows:
(; 128,121 Compalihle polllltant
For purposes of establishing Federal
reqUIrements for pretreatment, the term
"compatible pollutant" means biochem-
ical oxygen demand. suspended solids,
The following sections set forth pre-
treatment standards for pollutants intro-
duced into publicly owned treatn1<'nt
\\'orks.
(; 123.131
P,'()hihited wa:-.lcIi;.
No waste mtroduced into a publicly
o\\'ned treatment works shall interfere
\nth the operation or performance of the
works. Specifically, the following wastes
shall not be mtlOduced mto the publicly
o\\"lled treatment works:
1 ~ I \V[lstes which crea te a fire or ex-
plosion hazard in the pUbhcly owncd
treatment works
1 b 1 Wastes which wIll cause corrosi\'e
structur[ll damage to treatment works,
but in no case wastes \\'ith a pH lo\wr
th[ln 5.0. unless the works is designed to
accommodate such wastes.
1 c I Sol1d or viscous wastes in amounts
which would cause obstruction to the
flow m sewers, or other interference wIth
the proper operation of the publicly
o\\l1ed treatment works.
FEDERAL REGISTER, VOL. 38, NO. 215-THURSDAY, NOVEM8ER 8, 1973
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fd) \'astcs at a flow rate 3nd 'or P01-
Jutant dIscharge rate WI1I( h IS excessive
over rE'latlvely short tIme pE'nods so that
then' b ':1, treatment process upset and
~ubsequent loss of treatment efficiency
t;. J28.132 Pr~'~rt~.itnH'nt rur "oIHpa'ihl~
. poll..lanh.
Exccpt a" requJ!cd by ,1:211131. plC-
1 rei, lment for I emo\',,1 of compatIble poJ-
Jutants IS not reqmred by these regu]a-
110n.'3. However, 8t,) IR" and mUlllC'JpaIJ\.Jes
may reqUIre such pretreatment. pursu:Jnt,
to sectJOn 307'1)' '4' of tile Ad
~. I ~3. i 3.3 Prf'lrt';QnH'''' t or ~nl OltipOlII.
hi., ""lIlIlalll-,
In addItion to tl1(' proI1JI}ltIon" 'el.
forth 111 ~ 128131. the pretreatment
~tandard for ineomp3 tible pollutants 111-
troduced mto a publIcly owned treat-
ment works by a m3jOr eontnbutmg 111-
dustry not subject. to section 307' CI of
the Act shall be for sources \\'ithin the
corresponding IndustnaJ or commerCIal
category. that eS(.'.bll"}1ed by a promul-
gated effluent Imut.aUons gUJdehne de-
fining best practicable control technology
currently a\31lable pursuant to sections
301rb) and 304 \\ 1t!11JJ the sI10rIR,:t reasonable time
but not later than tlHee years flom the
da te of the1l. promulgatIOn; except that
for ~ 128.133 the three year complIance
penod for any user shall commence wIth
the date of promulgatIOn of a provIsion,
as required by ~ 128.133. sett1l1g forth the
applIcation to pretreatment of the efflu-
ent lImItatIOn,; gUldelll1es for the applI-
cable industrial category.
'b) In order to ensure such complI-
ance' each such owner or operator shall
commence construction of any required
pretreatment facilities within 18 months
from the date of final promulgation of
the provIsion rE'Quired by ~ 128.133, set-
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No. I59-Pt. II-I
APPENDIX B
FRIDAY, AUGUST 17, 1973
WASHINGTON, D.C.
Volume 38 . Number 159
PART II
ENVIRONMENTAL
PROTECTION
AGENCY
.
WATER PROGRAMS
Secondary Treatment
Information
B-1
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22298
Title 4O--Protectlon of Environment
CHAPTER I-ENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER D-WATER PROGRAMS
PART 133-SECONDARY TREATMENT
INFORMATION
On Aprll 30, 1973, notice wa.s published
in the FEDERAL REGISTER that the En-
vironmental Protection Agency wa.s pro-
posing information on secondary treat-
ment pursuant to section 304 (d) (1) of
the Federal Water Pollution Control
Act Amendments of 1972 (the Act).
Reference should be made to the pre-
amble of the proposed rulemaking for a
description of the purposes and Intended
use of the regulation.
Written comments on the proposed
rulemaking were invited and received
from interested parties. The Environ-
mental Protection Agency ha.s care-
fully considered all comments received.
All \Hitten comments are on file with the
Agency.
The regulation has been reorganized
and rewritten to 1mprove clarity.
Major changes that were made a.s a re-
sult of comments received are sum-
marized below:
(a) Tbe terms "I-week" and "1-
month" as used in ~ 133.102 (a) and
(b) of the proposed rulemaking have
been changed to 7 consecutive days and
30 consecutive days respectively (See
~ 133.102 (a), (b), and (CI ).
(b) Some comments indicated that the
proposed rulemaking appeared to re-
Quire 85 percent removal of biochemical
oxygen demand and suspended solids
only In cases when a treatment works
would treat a substantial portion of ex-
tremely high strength industrial waste
(See ~ 133.102ig) of the proposed rule-
making). The intent was that in no case
should the percentage removal of bio-
ch"mical oxygen demand and suspended
solids in a 30 day period be less than 85
percent. This has been clarified in the
regula tion. In addition, it has been ex-
pressed a.s percent remaining rather than
percent removal calculated using the
arithmetic means of the Iialues for in-
fluent and effluent samples collected in
a 30 day period (See ~ l33.l02(a) and
(bl) .
ic) Comments were made as to the
difficulty of achieving 85 percent removal
of biochemical oxygen demand and sus-
pended solids during wet weather for
treatment works receiving flows from
combined sewer systems. Recognizing
this, a paragraph was added which
w1ll allow waiver or adjustment of that
requirement on a case-by-case ba.sis
(See ~ 133.103(a».
idi The definition of a 24-hour com-
posite sample (See ~ 133.102icl of the
proposed rulemaking I was deleted from
the regulation. The sampling require-
ments for publicly owned treatment
works will be established in guldellnes
Issued pursuant to sections 3011 g I and
402 of the Act.
'e) In ~ 133103 of the proposed ruJe-
IT'hlring, It was recognized that secondary
RULES AND REGULATIONS
treatment processes J.re subject to upsets
over which little or no control may be
exercised. This provision has been de-
leted. It Is no longer considered necessary
1n this regulation since procedures for
notice and review of up8et incidents will
be Included In discharge permits issued
pursuant to section 402 of the Act.
(f) Paragraph (f) of A 133.102 of the
proposed rulemaklng, which relates to
treatment work8 which receive substan-
tial portions of high strength Industrial
wastes, has been rewritten for clarity. In
addition, a provision has been added
which limits the use of the upwards ad-
justment provislon to only those cases in
which the flow or loading from an indus-
try category !'xceeds 10 percent of the
design flow or lo~'\ding of the treatment
works. This intended to reduce or elimi-
nate the administrative burden which
would be involved In making insignift-
cant adjustments In the biochemical
'oxygen demand and suspended solids
criteria (See ~ 133.103(b».
The major comments for which
changes were not made are discussed
below:
(a) Comments were received which
recommended that the regulation be
written to allow effluent limitations to be
based on the treatment necessary to meet
water quality standards. No change has
been made in the regulations because the'
Act and its legislative history clearly
show that the regulation is to be based
on the capabilities of secondary treat-
ment technology and not ambient water
Quality effects.
(b) A number of comments were re-
ceived which pointed out that waste sta-
bilization ponds alone are not generally
capable of achieving the proposed efflu-
ent quality in terms of suspended solids
and fecal coliform bacteria. A few com-
mentel's expressed the opposite view. The
Agency is of the opinion that wIth proper
design (including solids separation proc-
esses and disinfection in some cases) and
operation, the level of effluent quality
speclfted can be achieved with waste
stabiLzation ponds. A technical bulletin
will be published in the near future wWch
will provIde guidance on the design and
operation of waste stabilization ponds.
(c) Disinfection must be employed in
order t'J achieve the fecal coliform bac-
teria levels specified. A few commenters
argued that dlsinfect8.nt is not a second-
ary treatment process ~mct therefore the
fecal collfonn bacteria requirements
should be deleted, No changes were made
because disinfection is considered by the
Agency to be an 1mport.gnt element of
secondary treatment which Is necessary
for prot.ection of r'Jblic health (See
~133102(c).
Etfectil'e dat,-' TilCo'O r2~1.Llations shall
be-<::ome eff0CU';e c':, Au;,ust 17, 1973.
JOH:1 QVARLE!I,
Aclili[l ArI"linistratoT
At:G1..'ST 14, Il1,~.
Cha.pter I of tJtle 40 of the Code of
Federal Regula.tions 18 amended by add-
tng a new Part, 133 as follows:
Sec.
133.100 Purpose.
133.101 Authority.
133.102 Secondary treatment.
133.103 Specle.l considerations.
133.104 Sampling e.nd test procedures.
AUTHORITY: Bees. 304() (1). S01(b) (1) (B).
Federal Water Pollution Control Act Amend-
ments, 1!J72, PL. 92-600.
S 133.100 Purpose.
This part provides information on the
level of effluent Quality attainable
through the application of secondary
treatment.
S 133.101 Authorit}".
The information contained In this
Part Is provided pursuant to sections
304(d) (1) and 301
-------
(2) The geometric mean of the values
for effluent samples collected In a period
of seven consecutive days shall not ex-
ceed 400 per 100 milliliters.
(d) pH. The effiuent values for pH shall
remain within the I1mlts of 6.0 to 9.0.
~ 133.103 Spedal con-iderl1liofl"
(a) Combined sewers. Secondary
treatment may not be capable of meet-
Ing the percentage removal requirements
of paragraphs (11.)(3) and (h) (3) of
~ 133.102 during wet weather In trea.t-
ment works which receive ftov,"s f~om
combined sewers 1 sewers which are de-
signed to transport both stann water
and sanitary sewage). For such treat-
ment works. the decision must be made
on a case-by-case basis as to whether
any attainable peruntage removal level
can be defined, and if so what that level
should be.
RULES AND REGULATIONS
(b) Industrial wastes, For certain In-
dustrhil categories, the discharge to nav-
Igable waters of biochemical oxygen de-
mand and suspended solids permitted
under sections 301(b) (1) (A) (j) or 306 of
the Act may be less stringent than the
values giv2n In parnluaphs (a) (1) and
(b) (1) of ~ 133.102. In cases when wastes
would be Introdwed from such an Indus-
trial category Into a publ1clY owned
treatment works, the values for biochemi-
cal oxygen demand and suspended solids
In paragraphs (a) (1) and (b) 0) of
!\ 133.102 may be adjusted upwards pro-
vided that: 111 the permitted discharge
of such pollutants, attributable to the
industrial category, would not be greater
than that which would be permitted
under sections 3011bl 0) (a) (iI or 306
of the Act If such Industrial category
were to discharge directly Into the navi-
gable waters, and (2) the ftow or loading
~229!)
of such pollutants Introduced by the In-
du.strlal category exceeds 10 percent of
the design flow or loading of the publ1cly
owned treatment works. When such an
adjustment Is made, the values for bio-
chemical oxygen demand or suspended
sol1ds in paragraphs (al (2) and (b1121
of ~ 133.102 should be adjusted propor-
tionally.
~ 133.10l Sumpl;n!; and 1£'..1 proc('(]ur£'.,
(a) Sampl1ng and test procedures for
pollutants listed in !\ 133.102 shall be in
accordance with guidelines promulgated
by the Administrator pursuant to sec-
tions 3041 g I and 402 of the Act
(bl Chemical oxygen demand ICODI
or total organic carbon (TOC) may be
substituted for biochemical oxygen 'de-
mand (BOD) when a long-term BOD:
COD or BOD:TOC correlation has been
demonstra ted.
[FR Doc.7.3-\'719~ Filed 8-16-73:8:45 am)
FEDERAL REGISTER, VOL 38, NO. i S9---FKIDAY, AUGUSr 17, 1973
B-3
-------
Appendix C
Information on Materials which Inhibit
Biological Treatment Processes
The fol Jowing paragraphs comprise a discussion of the sources
of information on various materials. which inhibit biological
treatment systems. presented in this Appendix.
Coppe r
Rudolfs (1) has indicated that copper in raw sewage at 1 mg/L
either inhibited or retarded the aerobic metabolism. Barth,
et al (2), and ticDermott, et al (3) have shown, from pi lot-
plant studies, that continuous addi tion of 1.0 mg/L of copper
is the threshold value for activated sludge. The maximum
concentration of copper that can be received continuously with-
out having a detectable effect on common parameters for
effluent quality is 1.0 mg/L (3). Where there is concern
about turbidity, a concentration of 0.8 mg/L of copper
appears to be the upper limit beyond which an effluent on
pi lot-plant studies conducted with copper sulfate and copper-
cyanide complex additions.
When four-hour slug d0ses of copper were added to the activated
sludge system, the performance was affected when the copper
concentration in the feed approached 75 mg/L (2,3,4). The
same studies have indicated that heavy metals present in
sewage (whether alone or in combination) affected the nitri-
fication process and that no acclimation was possible.
Kalabina, et al (5) have indicated that copper fed as copper
sulfate inhibited nitrification when the concentration of
copper exceeded 0.5 mg/L. They also recommended a copper
concentration of less than 0.1 mg/L in raw sewage for bio-
logical treatment.
Wi th respect to anaerobic digestion, a copper concentration of
10 mg/L in raw sewage affected gas production in the digestion
of primary sludge (2) When anaerobic digestion of combined
primary and secondary sludges was involved, a copper concentra-
tion of 5 mg/L in rdW sewage affected the digestion process (2).
Huwever, other reports indicated that copper concentrations in
the range of 0.2 mg/L to 2.5 mg/L in raw sewage were deleterious
to the anaerobic digestion process (1,5).
Zinc
McDermott, et al (6) And Barth, et al (2), have shown from
pilot-plant studies that zinc (either in the form of ZnS04 or
in the form found in a typical alkal ine cyanide plating bath)
added to raw sewage produced similar effects on bioiogical
C -1
-------
s y stem s . The max i mum
significant effect on
being between 2.5 and
biological system.
level of zinc that wi 1 1 not produce a
treatment efficiency was indicated as
10 mg/L when continuously added to the
When zinc at a concentration of 160 mg/L was added as a slug
dose over a four-hour period, a serious reduction in treatment
efficiency was observed. The same authors have shown that
the anaerobic digestion process was retarded when the zinc
concentration in ra~ sewage reached 20 mg/L. This concentra-
tion is in agreement ''lith those reported by Rudolfs (1). Other
investigators have indicated a maximum concentration of 5
mg/L Zn in raw sewage to prevent decrease in gas production
in the anaerobic digestion process (7,8).
Zinc concentrations of approximately 0.5 mg/L in raw sewage
have been reported to inhibit nitrification process (9).
Lead
Rudolfs (1) has indicated that lead in raw sewage at concentrations
of about 0.1 mg/L 1:Ji 11 inhibit or retard the aerobic biological
metabolism. This is in agreement with the values reported by
Kalabina from studies conducted using lead sulfate (5).
K~labina also studied the effects of lead on nitrification
process and showed that 0.5 mg/L of lead in raw sewage
inhibited the nitrificai:ion process (5).
Cadmium
110'o2Y (10, i 1) reported that cadmium ions, added to experimental
digesters, have a threshold value (for adverse effect on
biologic treatment processes) of 0.02 mg/L and occurs at a
carbonate ion concentration of 2 ~ 10-5 mo!es/L. The resul ts
a1so showed that the toxicity of cadmium to anaerobic digestion
was pH-dependent when the pH was greater than 7.0 and
independent of the pH when the pH was less than 7.0.
The foregoing results were
the cadmium concentratiuns
the digester.
based on laburatory studie's, and
refer only to those present in
Boron and Arsenic
Banerji, et aJ (12) studied the effects of boron added in
slug doses to activated sludge treatment. The results
indicated that a slug dosage of 10 mg/L in raw waste adversely
affected the performance of aerobic metabol ism. However,
Rudoifs (1) indicated that boron in raw sewage affected the
" ')
l, -~
-------
performance of activated sludge and trickl ing fi lters at
much lower levels (1.0 mg/L and less). He also indicated
that the addition of arsenic at concentrations of approximately
4 mg/L to digesting sludge inhibited or retarded the performance
of digesters.
Chromium
Rudolfs (1) indicated that chromium was toxic to activated
sludge and trickl ing fi Iter processes when the raw sewage
contained 3 mg/L total chromium. It was pointed out that
when the total chromium in raw sewage was in the range of
1-5 mg/L, the anaerobic digestion process was significantly
retarded.
However, the pilot-plant results of Barth, et al (2) indicate
that a continuous dosage of 10 mg/L of chromate chromium was
required before the aerobic process deteriorated. With respect
to slug dosage, the activated sludge pi lot-plant was able to
withstand up to 500 mg/L of chromate chromium when applied over
a four-hour period (13). Their studies also showed that the
anaerobic digestion process was affected when the hexavalent
chromium in raw sewage exceeded 50 mg/L. These values were
significantly higher than those reported by Rudolfs (1).
According to Rudolfs, hexavalent chromium concentrations at
1.0 mg/L in raw sewage affected trickl ing filter process, and
at the I-50 mg/L level the anaerobic digestion process was
affected.
I t is important to point out here that the toxicity of heavy
metals on biological systems is closely associated with sulfate
concentrations in raw wastewater and therefore should not be
compared directly with one another without considering the
concentration of the sulfate ion. Unfortunately, the studies
did not report the sulfate concentrations necessary for making
such a comparison.
With respect to the nitrification process, Whiteland, et al
(14) have reported that the nitrification process was severely
affected when the hexavalent chromium in raw sewage was in
the range of 2 to 5 mg/L.
Nicke I
Pilot-plant studies conducted with continuous addition of
NiS04 in raw sewage indicated that nicke1 concentrations at
2.5, 5, and 10 mg/L affected both biological treatment efficiency
and effluent clarity (15). The results indicated that nickel
doses of 1 mg/L on a continuous basis can be tolerated by aerobic
biological processes. However, it is important to point out
C -3
-------
that most of the nickel reaching the aeration process passed
through the effluent in soluble form (2,3). These results
also indicated that the anaerobic digestion process was very
resistant to nickel in the sludges. Primary sludges containing
up to 40 mg/L of nickel digested satisfactori ly.
However, other reports indicate (8) that nickel concentrations
of 2 mg/L in raw sewage would be inhibitory to the anaerobic
digestion process. In addition, the nitrification process
wi 1 1 be severely inhibited when the nickel concentration is
approximately 0.5 mg/L (9).
Cyanides
Coburn (16) reported that 5 mg/L of cyanide in raw wastewater
(discharging continuously) interfered with activated sludge
treatment. In trick1 ing fi Iter studies, cyanide in raw sewage
at 30 mg/L produced poor effluent qual ity. However, when the
cyanide concentration was only 10 mg/L, 98 to 100 percent of
the cyanide was destroyed in the trickl ing fi Iter (7). These
levels are higher than those reported by Rudolfs (1). According
to Rudolfs, I to 2.0 mg/L of cyanide (as HCN) in raw sewage
affected the performance of the activated sludge, trickl ing
fi 1 ters, and anaerobic digestion processes (1,16). Generally,
however, secondary biological treatment processes can oxidize
the cyanide if acc] imatized (17). Rudolfs (1) has also reported
that the nitrification process was inhibited when the cyanide
(HCN) concentration in raw sewage reached 2 mg/L.
Sulfides and Sulfates
Pohland and Kang (18) reported in their review of 1 iterature
on anaerobic processes that when the sulfate concentration
exceeded 500 mg/L, the gas production was greatly reduced.
Simi lar results were also reported indicating that sulfate
concentrations of 300 mg/L are toxic to anaerobic digestion.
The sulfate toxicity was related to the reduction to sulfides
during digestion (17).
Lawrence, et al (19) and Rudolfs (20) have reported that
sulfide concentrations in the range of 150-200 mg/L in the
digester feed would reduce gasification considerably.
Ammonia
Drague, et al (21) reported that ammonia concentrations in
the range of 1,500-3,000 mg/L inhibited the anaerobic digestion
process. When the ammonia concentration reached 3,000 mg/L,
the feed sludge became strongly toxic to the digestion process.
C-4
-------
This is in agreement with the values reported by Rudolfs (1).
The concentration of ammonia refers to that present in the
influent to the digesters of accumulated in the digesters.
Sodium Chloride
The presence of sodium chloride in raw sewage or in the
digester has been reported to produce deleterious effects
both in aerobic biological systems and in anaerobic digesters.
Rudolfs has indicated that the gas production in anaerobic
digestion will be greatly reduced when the NaCl concentration
reaches 50,000 mg/l in digesters (1). Studies conducted by
Kincannon (22) indicated that the laboratory-scale aerobic
biological system was greatly affected at NaCl concentrations
of 10,000 mg/l in raw wastewater. Similar results were reported
by Lawton and Eggert (23) in the case of trickl ing fi I ters.
Chloroform
Ghosh (11), in a review of the anaerobic digestion process
1 iterature, reported that chloroform addition to digesters
on a continuous basis produced noticeable effects at a concen-
tration of 10 to 11 mg/L. When chloroform appl ication was
as a slug dosage, the anaerobic process was adversely affected
at 1 mg/l concentration in the feed.
Free 0 i 1
Free oil of petroleum origin, at concentrations in the range
of 50-100 mg/l, has been reported as interfering with aerobic
biological treatment (24,25). The oil concentrations were
measured according to the API Manual using CCI4 extraction (26).
The measurement of free oil using the API procedure may also
include oily materials of animal and vegetable origin.
Other Cations (Na+, K+, Ca+, and Mg++)
Malina (27) has presented data on the effects of several
cations on anaerobic digestion. The results indicated that:
Ca++ strongly inhibited anaerobic digestion at a concen-
tration of 8,000 mg/L; Mg++ at a concentration of 2,000 mg/l;
K+ at 12,000 mg/l; and Na+ at 8,000 mg/L. These results were
in close agreement with those reported by Kugelman and
McCarty (28).
c -5
-------
Chlorinated Organic Compounds
The effect of several chlorinated organic compounds, at very
low concentrations, on anaerobic digestion of biological
sludges is marked, and constitutes a warning that a close
watch must be kept on the disposal of these compounds.
Jackson, et al (29) have summarized the results on toxicity
of various chlorinated organic compounds, as indicated in
Table (-1. These results indicate that chlorinated compounds
can be toxic to anaerobic digestion at levels varying between
0.1 to 20 mg/L. The degree of inhibition will depend on the
particular chemical itself. Further studies are required to
determine the long-term effects of chlorinated organic com-
pounds on municipal biological treatment processes when they
are present separately or in various combinations.
(-6
-------
REFERENCES
1.
Rudolfs, W., "Review of Literature on Toxic Materials Affecting
Sewage Treatment Processes, Streams, and BOD Determinations",
Sewage and Industrial Wastes, 22,9,1157-1191 (1950).
2.
Barth, E.B., et a1, "Summary Report on the Effects of Heavy Metals
on the Biological Treatment Processes", Journal \-IPCF, 37, ],
86-96 (1965). -
3.
"Interaction of Heavy Metals and Bioloqical Sewaqe Treatment Processes",
Publ ic Health Service Publication No. 999-WP-22, U.S. Dept. of Health,
Education and Welfare, Cincinnati, Ohio (May, 1965).
4.
McDermott, G.N.,et aI, "Copper and Anaerobic Sludge Digestion",
Journal WPCF, 35, 5, 655-662 (1963).
5.
Kalabina, M., et a1. "Effect of Copper and Lead Bearing Wastes on
the Purification of Sewage", Water and Sevvaqe Works, 93,1,30
( 1946) .
6.
McDermott, G.N., et a1, "Zinc in Relation to Activated Sludge and
Anaerobic Digestion", Proc. 17th Industrial Waste Conference,
Purdue University, Rafayette, Ind., 461-475 (1962).
7.
"The Effect of Industria] Wa"tes on Sewaqe Treatment", Publication
No. TR-13, N~w England Interstate Water Pollution Control Commission,
Boston, Mass. (1965).
8.
Nemerow, N.L., "Theories and Practices of Industrial Waste Treatment",
Addison-Wiley Publishing Company, Reading, Mass. (1963).
9.
Air and Water NeltJs, 5, 40,8-9 (October 11,197]).
10.
Mosey, F.E., "The Toxicity of Cadmium to Anaerobic Digestion: Its
Hodificatioll by Inorganic Ions", Water Pollution Control (G-B),
70, Part 5, 584-598 (1971).
11.
Ghosh, S., "Anaerobic Processes - Literature Review", Journal WPCF,
44, 6, 948-959 (1972).
12.
Banerj i, S.K., et al. "Effect of Boroll on Aerobic Biological Waste
Treatment", Proc. 23rd Industrial Waste Conference, Purdue University,
Lafayette, I nd., 956-965 ( 1968) .
13.
Moore, W.A., et aI, "Effects of Chromium on the Activated Sludge
Process", Journal WPCF, 33,1,54-72 (1961).
14.
Whiteland, A.B., et al, "Pi lot P1ant Experiments on the Effects of
Some Constituents of Industria1 Wastewaters on Sewage Treatment",
Water Pollution Control (G-B), 70, 626-643 (1971).
15.
McDermott, G.N., et aI, "Nickel in Relation to Activated Sludge
and Anaerobic Digestion Processes", Journal WPCF, 37, 2, 163-177
(1965).
C-7
-------
27.
28.
16.
Coburn, S.E., "Limits for Toxic Wastes in Sewage Treatment",
Jour. Sew. Works, ~, 3, 522-524 (1949).
17.
'IControlling the Effects of Industrial vJastes
Publ ication No. TR-15, New England Interstate
Control Commission, Boston, Mass. (1971).
on Sewaqe Treatment",
Water Pollution
18.
Pohland, F.G., and Kang, S.J., "Anaerobic Processes - Literature
Review," Jour. WPCF, 43, 6, 1129-1134 (1971).
19.
Lawrence, A.W., et aI, "The Effects of Sulfide on Anaerobic Treat-
ment," Proc. 19th Ind. Waste Conf., Purdue University, Lafayette,
Ind., 343-357 (1964).
20.
Rudolfs, W., and Amberg, H.R., "White Wat~r Treatment, II. Effect
of Sulfides on Digestion." Sew. and Ind. Wastes, 24, 10, 1278-1287
(1952).
21.
Dague, R.R , et aI, 'IDigestion Fundamentals Applied to Digester
Recovery - Two Case Studies.'1 Jour. WPCF, 42, 9, 1666-1675 (1970).
22.
Kincannon, D.F., "Studies on the Effects of Sodium Chloride on
Activated Sludge.'1 Ph.D. Thesis, Oklahoma State University, Still-
water, Okla. (1965).
23.
Lawton, G.W., and Eggert, C.V., "Effect of High Sodium Chloride
Concentration on Trickling Filter Slimes." Jour. WPCF~ 29,11,
1228-1242 (1957).
24.
Beychok, M.R., "Aqueous Wastes from Petroleum and Petrochemical
Plants.'1 John Wiley [, Sons, New York (1967).
25.
"Manual on Disposal of Refinery Was~ss,'1 Volume on Liquid Wastes,
American Petroleum Institute, New York (1969).
26.
'IManual on Disposal of Refinery Wastes," Vol. IV - "Sampling and
Analysis ot Wasrewater," American Petroleum Institute, New York
(1957) .
Mal ina, J.F., "Anaerobic Waste Treatment," Unpub1 ished Report.
Kugelman, I.J., and McCarty, P.L., "Cation Toxicity and Stimulation
in Anaerobic Waste Treatment - II. Dai ly Feed Studies," Proc. 19th
Ind. Waste Conference, Purdue University. Lafayette, Ind., 667-686
( 1 964) .
c-8
-------
29.
Jackson, S., Phi I, D., and Brown, V. M., "Effect of Toxic Wastes
on Treatment Processes and Watercourses .11 Proceed i nCjs of the
Annual Conference, The Institute of Water Pollution Control,
Douglas, Isle of Man, England (1969).
30.
McCarty, P. L., "Anaerobic Waste Treatment Fundamentals;
Part 3, Toxic Materials and Their Control." Jour. Public
Works (Nov. 1964).
31.
Wheatland, A. B., Bell, M. G. W., and Atkinson, A., 'IPilot
Plant Experiments on the Effects of Some Constituents of
Industrial Waste Waters on Sewage Treatment." Jour. Inst.
of Sew. Purif., No.6 (1971).
32.
Pettet, A. E. J., and Mills, E. V., "Biological Treatment of
Cyanide with and without Sewage.11 Jour. Appl. Chem., 4
(A ug. 1 954) .
C-9
-------
Po 11 utant
Coppe r
Zinc
Chromium (Hexavalent)
Chromium (Trivalent)
Total Chromium
N icke 1
Lead
Boron
Cadm i um
Silver
Va nad i um
Sulfides (S)
Sulfates' S04')
Ammonia
Sod i um (Na' )
Potassium (K'j
Ca Ie i um Ca" I
Mag ne s i um 'Mg' "
Acrylonitrite
Benzene
Carbon Tetrachloride
Chloroform
Methylene Chloride
Peintachlorophenol
l,l,l-Trichloroethane
Trichlorofluoromethane
Trlchlorotrifluoroethane
Cyanide (HCN)
Total oil (Petroleum origin)
* Insufficient data
Table C-1
Information on Materials Which Inhibit Biological
Treatment Processes
. 1
Concentrat I on .
mg/L
Aerobic Processes
Anaerobic Digestion
Nitrification
1.0
~.O
2.0
2.0
5.CJ
1.0
0.1
1.0
I.J
c,.O
5. ,J ')
2000
5.0
0.5
0.5
2.0
~'r
.,'r
2.0
0.5
0.5
,'r
.'.
.'.
"
J.
.'.
J.03
"
..,'(
1,'
--'r
"
.'.
.'.
1 (J(J
c':"J
.'.
.'.
-,'('
,,'(
1 c:; -)I~,
-z!~,X)
.'.
"
,;'(
?500
2:,1,)1)
1
,'r
.'.
.'.
-,'(
..,'r
"
'"
"
,;'r
IT
"
12.0
~
0.1-
1.0
0.40
1. O'
J.7
,'r
':r
..,'(
,'r
"
;<
-,'(
,'r
..
..
~
5.0-
I . '.1
SO
50
.,'(
.'.
? J
So
lConcentrations refer to those present in raw wastewater unless otherwise indicated.
2Concentrations apply to the digester influent only.
other treatment process units.
References
(l) ( 2) ( 3 \ ( ). ; I ~ ~ ( 16)
(?)(6)(7)(8)(9'
(1)(2)(13)( \
(1 )
(1 )
(1) (8)( 9)(15)
(1) ( 5) (
(1) (12)
( 1:)1
( ~c!,
(
(10)( 19)( 20)
( Ell ( 17) ( }Io) ( l C',) ( 2~' j
( ( i::-
( , "2.'"11
( ~7; ( - ,~,')' ~
I ~7j' ow, (.
( -~ '"7) ( ::;: \ I :: ~ ~
( ?~' ~
2;';
( ?(J;I
\ 2-;:1
(;: ?)
( 2:':'
( ?Cj:
-:':.\
(29)
(1) (16) (17)
(24) (25; (26)
Lower values may be required for protection of
3petroleum-based oil concentration measured according to the API Method 733-58 for determing
volati Ie and non-volati Ie oily materials.
direct animal or vegetable origin.
The inhibitory level does not apply to oil of
C -1 °
-------
PAPER AND ALLIED PRODUCTS
1.
Industry Description
This industry includes Standard Industrial Classifications
(SIC) 2610, 2620. 2630, 2640, 2650, and 2660. These clas-
sifications include the manufacture of pulp from wood. rag,
and other cellulose fibers and the manufacture of paper,
paperboard, and bui lding products, The manufacture of
converted paper and paperboard products from purchased paper
is not included since it involves a relatively dry process.
whose wastewater flows and loadings are not significant to
the design of municipal systems. Therefore, the plants
making convertep paper and paperboard products are excluded.
The manufacture of paper and allied products involves the
preparation of wood and other raw materials, separation and
recovery of cellulose fibers, and blending of the fibers
with proper additives to produce "furnish", which is formed
into paper, The additives include: sizing materials such
as alum and resins, sodium aluminate, and wax emulsions;
synthetics. such as acrylics, isocyanates, and fluocarbons;
and fi I lers such as clays, calcium carbonate and sulfate,
talc, barium sulfate, aluminum compounds, and titanium
oxide. When fi 1 lers are used, retention aids (starches
or synthetic resins) are added to increase the retention
of the fi ller.
The principal operations involved in the manufacture of
pulp and paper are:
Wood Preparation
Pulping (mechanical, chemical, semi-chemical, and
deinking)
Pulp Washing and Screening
Stock Preparation
Paper Making
The pretreatment sub-groups for this industry are as follows:
Integrated pulp and paper mi lIs using mechanical pulping
processes (bleached and unbleached)
Integrated pulp and paper mi lIs using chemical pulping
processes (unbleached)
D-1-1
-------
Integrated pulp and paper mi 1 15 using chemical pulping
processes (bleached)
Integrated pulp and paper mills using deinked pulp
Paper and paperboard mi 1 Is
Bui lding products mi I Is
2.
Industrial Practices
The fol lowing industrial practices can significantly influence
pretreatment:
~~~ng .!.~oc~ss
The pulping process determines the pulp yield and qual ity,
and the probable organics loss in the wastewater from a pulp
mill. (Mechanical pulping results in minimum dissolution
of wood components, whi Ie chemical pulping solubil izes the
non-cellulose components of wood tannins, 1 ignins, wood
sugars, and hemicellulose).
Recovery and Reuse of Spent Cooking Liquor
Most chemical pulping processes involve recovery and reuse
of spent cooking 1 iquor and therefore do not generate
significant quantities of wastewater (1). The dissolved
organics present in the 1 iquor usually are burned in the
chemical recovery furnace. The only pulping process where
the spent cooking 1 iquor is not suitable for recovery is
the calcium-base acid sulfite process. The spent cooking
1 iquor from this process, with the dissolved organics, is
generally discharged with other process wastes.
Bleaching
When the desired qual ity of the final product requires
bleaching of pulp recovered from wood, it is usually done
by the addition of oxidizing chemicals, such as chlorine,
chlorine compounds. peroxides, and hydrosulfites. The
oxidizing chemicals react with the non-cellulose portion
of the pulp, rendering it soluble in water or in alkaline
solutions. As a result, the bleaching step adds to the
wastewater volume and pollutant loading.
D-1-2
-------
In-Plant Pollution Control Methods
Control of spi lIs and leaks, and recovery and reuse of
chemicals constitute the major pollution control practices
within the paper and allied products industry. The extent
of pretreatment required is largely dependent on the extent
and effectiveness of the in-plant control processes adopted.
3.
Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-groups are shown in Table 0-1-1.
Integrated pulp and paper mills generally operate continuously
throughout the year except for the shutdowns for preventive
maintenance and equipment repair and replacement. Modern
practice is to employ continuous pulping processes,
however some mills are still using batch pulping processes which
result in intermittent discharges of wastewater. In addition, some
older mil Is (generally relatively small, less than 100 tons/day)
operate only 3 to 5 days per week.
The overall wastewater characteristics from wood pulping pro-
cesses may vary seasonally because of the changes in charac-
teristics of wood and variations in the temperature of the
water. The volume and characteristics of the process waste-
water depend upon the degree of water reuse, chemical recovery
systems, and the type and quality of paper involved.
The wastewaters generated from the paper and allied products in-
dustry contain BOD, COD, suspended sol ids, dissolved sol ids,
color, acidity or alkalinity, and heat. Chemical pulping
processes may produce wastewaters with heavy metals (Cr, Ni,
Hg, Pb, Zn). If pulp bleaching is part of the operation, the
wastewaters may contain additional heavy metals (Hg) and dis-
solved solids (chlorides). Mercury may be present in the
caustic used in pulping and bleaching operations. Zinc is
used in the bleaching of ground wood pulp. Chromium, nickel,
and iron may be introduced from the corrosion of process equip-
ment.
When spent cooking liquor recovery is not practiced, the waste-
waters may be acidic (pH 2 to 3) and have high concentrations
of dissolved organics and inorganics. The solubi lized organics
and the type of cooking 1 iquor wi II determine the characteristics
of the wastewater.
0-1-3
-------
Major considerations in the joint treatment of paper and allied
products industrial wastewaters with domestic wastewaters are
the high chlorine demand and nutrient deficiency (phosphorus
and nitrogen). These characteristics would significantly in-
fluence the kinetics and design of joint treatment faci lities.
Information avai lable on the joint treatment of paper and al lied
products wastewaters indicate the following effects:
a.
When neutral sulfite semichemical pulping wastewater
exceeded approximately 10 percent of the total flow
to a publicly owned treatment works, a retardation
in the rate of BOD exertion was observed (3). Under
such circumstances, the kinetic parameters and oxygen
requirements should be establ ished by specific in-
vestigation.
b.
The activated carbon adsorption process can not be
substituted for the biological processes to reduce
BOD.
c.
Attempts to use the trickl ing fi lter process (stone
and plastic media) for the treatment of paper mi 1 1
wastes have achieved only relatively low removals
(40-60 percent BOD removal). This has been at-
tributed primari ly to high organic loading and fi Iter
clogging with fibers (4).
d.
Paper mi 1 1 wastewaters exhibit high chlorine demand
values (20-60 mg/L), even after secondary treatment.
Depending on the ratio of paper mi 11 wastes to do-
mestic wastes, larger chlorination faci lities may be
required.
e.
When paper mi 1 1 waste sludge forms a significant portion
(approximately 60 percent) of total sludge, longer
digestion periods are required for anaerobic digestion (5).
The only exceptions to the wastewater and treatabi lity charac-
teristics noted in the preceding discussion are the wastewater
generated from the converted paper and paperboard manufacturing
segment of the industry, which segment uses relatively dry pro-
cesses. Since the process wastewaters from this type of plant
are very low in volume and contain as major constituents only
BOD and suspended sol ids, they are readi ly treatable in municipal
systems.
0-1-4
-------
4.
Pretreatment
The pretreatment
various types of
Table D-1-2.
unit operations which may be necessary for
joint treatment processes are shown in
The neutral ization requirements depend primari ly on the
pulping process and on the related recovery and reuse
practices. When spent cooking liquor is discharged to
municipal sewers. special care must be taken to insure
contro1 of pH, organic shock loads, and color (if present).
If bleaching is part of the operation, pH adjustment may
be necessary before mixing with other wastes. Spi 1 ls of
spent liquors and pulp washing water may introduce shock
loads of pH and organic material if their discharge into
the municipal sewer system is not carefully control led.
In the absence of effective in-plant control procedures,
adequate equalization and extensive pH and conductivity
control may be required to protect the operation of a
joint treatment faci 1 ity.
The heavy metal concentrations in the paper and allied
products industry wastewaters are very low and generally
do not require pretreatment. Nevertheless, their levels
should be determined to insure that effluent 1 imitations
are not exceeded where heavy metals are a significant
factor.
D-1-5
-------
fable D-l-l
Wastewater Characteristics
Paper and All ied Products
Mechanical Pulping Chemical Pulping Chemical Pulping Deinking Paper and Building
~h_a~a~~~ri~t i cs (B leached &.Unbleached) (Unbleached) (Bleached) Pulp Pa pe rboa rd P r"nduc t s
Industry Operat ion Yea r- round Yea r- round Yea r- round Yea r- round Yea r- round Yea r- round
Fl 0\./ Continuous Continuous Continuous Continuous Continuous Continuous
BOD EXTREMELY HIe; AVERAGE-::XT. HIGH AVERAGE-EXT.f.IGH HIGH AVERAGE-HIGH LXTREMELY HIGH
TSS HIGH LOW-HIGH LOW-HIGH HIGH AVERAGE-HIGH EXTREi.\ELY HIGH
TDS 1 HIGH HIGH HIGH Low-average Low
Mverage
COD HIGH HIGH HIGH HIGH HIGH HIGH
G r it PRESENT PRESENT PRESENT PRESENT PRES UJT PRESENT
Cyanide Absent Absent Absent Absent Absent Absent
Chlorine Demand HIGH 2 HIGH HIGH HIGH HIGH HIGH
pH "eutral ACID-ALKALINE ACIDIC ALKAL I NE neut ra 1 :,1, u t r a I
Color Low High High L0w Low Low
Turbidity High High High High High VERY HIGH
Explosives Absent Absent Absent Absent Absent Absent
Dissolved Gases Absent Present Present Absent Absent Absent
Detergents Absent Absent Absent Absent Absent Absent
Foam i ng PRESENT PRESENT PRESENT PRESENT PRESENT PRESENT
Heavy Meta Is ABSENT3 PRESENT PRESENT PRESENT Absent Absent
Co 11 0 i da 1 So lids Present Present present present present Pr'esent
<=> Volatile Organics Absent4 Present present absent absent Absent
I Absent4 absent4
I Pesticides Absent absent absent Absent
0',
Phosphorus DEFICIENT DEFICIENT DEFICIENT DEFICIENT DEFICIENT DEFICIENT
Nitrogen DEFICIENT DEFICIENT DEFICIENT DEFICIENT DEFICIENT DEFICIENT
Temperature HIGHS HIGHS HIGHS HIGHS HIGHS HIGHS
Phenol Absent Absent Absent Absent Absent Absent
Sulfides Absent Absent Absent Absent Absent Absent
0 i 1 & Grease Present Present Present Present Present Present
Co I i fo rm (Tota 1 ) Average Average Average Average Average Average
;High if bleaching of pulp is practiced.
3Acidic if bleaching of pulp is practiced.
4Present if bleaching of pulp is practiced.
Spresent only from log washing operations.
Higher temperature than domestic wastewater.
May affect design but nol harmful to joint treatment processes.
NOTE :
Characteristics which ma~ r~quire pretreatment or are significant to joint treatment plant design are shown in UPPER CASE.
The wastev/ater characteristics shown reflect the Indu~trial Practices described in Section 2.
-------
Pretreatment
Sub-G roup
Mechanical Pulping 1
(Unbleached)
Mechanical Pulping 1
(Bleached)
o
I
I
-...J
Chemical Pulping 1
(Unbleached)
Chemical Pulping 1
(Bleached)
Deinking Pulp 1
Paper & Paper Board
Bui lding Products
Table D-1-2
Pretreatment Unit Operations for the Paper and Al I ied Products Industry
Suspended Biological
System
Fixed Biological
System
Independent Physical - Chemical
System
Coarse Sol ids Separation
+ Grit Removal
Coarse 501 ids Separation
+ Grit Removal +
Neutral ization
Coarse Sol ids Separation
+ Grit Removal +
Neutral ization
Coarse Sol ids Separation
+ Grit Removal +
Neutralization
Coarse Sol ids Separation
+ Neutral ization
Coarse Sol ids Separation
Coarse Sol ids Separation
Where pulp and paper wastewaters
cvnstitute more than about 10 percent
of the total wastewater flow, fixed
biological systems or independent
physical chemical systems normally are
not used. Where the pulp and paper
wastewater constitute less than this
proportion, the pretreatment require-
ments wi 1 I be same as for suspended
biological systems.
1 E I. .
qua Izatlon may be required in addition to those shown when batch pulping processes are used.
-------
REFERENCES
1.
"Industrial Waste Survey of the Paper
Industries" Contracts #68-01-0022 and
mental Protection Agency. Washington,
and Allied Products
68-01-0012, Environ-
D.C. (Unpublished)
2.
"Paper Mills Industry Wastewater Profile," F.W.P.C.A. Contract
#14-12-10, F.W.P.C.A. (November 1967).
3.
"Combined Treatment of Sanitary Sewage and Semi chemical Pulp
Mi 11 Waste," Technical Bulletin #42, National Counci I for
Steam Improvement (1951).
4.
"Industrial Wastewater Control," (Edited by) Gurnham, F.C.,
Academic Press, New York (1965).
5.
"Joint Municipal and Semichemical Pulping Waste Treatment,11
Water Pollution Control Research Series, Publ ication No. ORO 1
(J u 1 y 1969).
0-1-8
-------
DAIRY PRODUCTS INDUSTRY
1.
Industry Description
This industry includes Standard Industry Classifications (SIC)
2021, 2022, 2023, 2024, 2026, and 5043. These classifications
include bulk handling, packaging, and processing (pasteurizing,
homogenizing, and vitaminizing) of milk, and the manufacture
of dairy products including butter, cheese, ice cream, con-
densed evaporated milk, and dry milk and whey.
The manufacture of dairy products involves receiving and stor-
ing raw milk, separation of excess cream, pasteurization and
homogenization, fluid milk packaging, and making butter, ice
cream, and cheese. In the separation step, excess cream may
be skimmed off in order to standardize the butter fat content,
or the raw milk may be separated by centrifuge into cream
and skim milk. Separated cream is then used in butter or ice
cream making, while the skim milk may be used in the production
of cottage cheese and non-fat dry milk solids. Natural
cheese (i.e., not cottage cheese) is made with whole milk.
Some of these processes generate by-products which may be re-
covered and util ized in other food manufacturing operations.
Buttermilk, skim milk, and whey are produced from butter and
cheese making. The regional market potential for these by-
products often determines the amount of in-plant recovery.
The dairy industry is a year-round operation. Raw-milk re-
ceiving stations handle milk from the local farms for subse-
quent transfer to tank trucks. These stations are operated
on an intermittent daily basis. The rest of the industry
will operate either continuously or on an intermittent basis
depending on the economics of the individual facil ity. In
general, larger processing plants tend to be integrated plants
producing more than one product.
The pretreatment sub-groups for this industry are as follows:
Cottage and Natural Cheese Products
Milk Handl ing and Products.
2.
Industrial Practices
Product recovery is the major method for reducing wastewater
loadings. The dai ry industry, however, must maintain sani-
tary conditions and this tends to limit the amount of waste-
water recycle which is practicable.
D-2-1
-------
The fol lowing industrial practices can have a major impact
on the wastewater characteristics:
Whey Hand ling
Whey can be condensed and dried, and used as a food and
feed supplement. However, there are inherent diffi-
culties in drying the acid whey derived from cottage
cheese because of its lactic acid content.
Operating Procedures
Spillage, overflow, and leakage caused by improperly
maintained equipment and poor operating procedures can
result in major pollutional loads due to the concen-
trated nature of the dairy products, e.g., whole milk
has a BOD over 100,000 mg/L (0.8 pounds of BOD for every
gallon of mi lk lost) (1).
Cleaning
High efficiency in sanitizing operations is important
to minimize the usage of sanitizers and detergents. In
addition, rinses can be collected and used as make-up
water for sanitizers (2). Milk processing lines should
be sloped to central collection points so that the milk
product may be collected before the I ines are sanitized.
3.
Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table 0-2-1.
Daily wastewater flows are characterized as intermittent be-
cause some major unit processes, e.g., cheese and butter
making, are batch, and because milk processing equipment must
be shut down daily for sanitizing to maintain rigid health
standards. Relatively clean water may be a substantial
portion of the total wastewater from a dairy plant. These
waters are from condensers, refrigeration compressors, milk
coolers, and air conditioning systems.
The major types of wastewaters from the dairy industry are:
1.
Wash and rinse water from cans, tank trucks, equip-
ment, and floors. In general, the pH of the waste-
water will be affected by the cleaning compound
0-2-2
-------
(either acid or alkal i) and the proportion of the
wash water in the total plant wastewater flow.
2.
By-products (such as buttermilk, skim milk, or whey)
they are sewered rather than recovered. Buttermilk
and skim milk have BOD values as high as 70,000 mg/L,
while the BOD of whey is 50,000 mg/L (3).
3.
Entrainment from evaporators and the sewering of
spoi led or damaged products.
The wastewaters generated in the dai ry industry can be char-
acterized generally as containing high concentrations of BOD,
COD, and TOS. Settleable sol ids are not an important con-
sideration in most dairy wastewaters, since all the organic
material is in a colloidal or dissolved state. However, sand
or other gritty material may be present from tank truck wash-
ings (4). Cheese wastewaters, on the other hand, have higher
concentrations of settleable solids due to the presence of
curd sol ids.
Design considerations in the joint treatment of dairy and
domestic wastewaters are the high chlorine demand and the
presence of surface-active agents, coliforms, and high-
septicity potential. In addition, cheese production waste-
waters are usually nitrogen-deficient. Septicity should be
a consideration in the design of any equalization or clari-
fication facilities. Wastewater temperature normally would
not be a consideration because of dilution in the municipal
collection system.
Low-rate trickl ing filters are generally not effective in
treating dairy wastes, because these wastes produce large
quantities of biological solids which c log the fi lters.
This problem can be overcome by high hydraul ic loading and
high recirculation rates (3).
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table 0-2-2.
In general, dairy wastes are amenable to biological as well
as to chemical treatment if equal ization and neutral ization
are provided as pretreatment for the dai ry wastes. As the
ratio of dairy waste to domestic waste increases, the need
0-2-3
-------
for the suggested pretreatment also increases markedly.
Where whey is present, it may be necessary to control the
rate of discharge and to provide nutrient supplements at the
joint treatment plant.
0-2-4
-------
Table D-2-1
Wastewater Characteristics
Da i ry Products
Characteristics
Mi lk Hand1 ing
Mil k Pro d u c t s
Natural and Cottage
Cheese Product
Industrial
FLOW
BOD
TSS
TDS
Operation
Year-round (BATCH)
INTERMITTENT
Average-HIGH
Low-Average
Average-HIGH
Year-round (BATCH)
INTERMITTENT
EXTREMELY HIGH
Average-EXT. HIGH
HIGH
COD
G r it
Cyanide
Chlorine
pH
Demand
Average-H IGH
PRESENT
Absent
HIGH
ACID TO ALKALINE
EXTREMELY HIGH
PRESENT
Absent
HIGH
ACID TO ALKALINE
Co lor
Turbidity
Explosives
Dissolved Gases
Detergents 1
HIGH
High
Absent
Absent
PRESENT
HIGH
High
Absent
Absent
PRESENT
Foaming
Heavy Metals
Colloidal Sol ids
Volatile Organics
Pesticides
PRESENT
Absent
HIGH
Absent
Absent
PRESENT
Absent
HIGH
Absent
Absent
Phospho rus
Nitrogen
Temperature
Phenol
Sulfides
Present
Adequate 2
Normal-High
Absent
Absent
Present
DEFICIENT
Normal-High2
Absent
Absent
Oil and G rea s e
Co 1 i fo rm
Present
PRESENT
Present
PRESENT
IThere are possible bio-static
attributable to large amounts
dairy products wastewater.
effects in the joint treatment plant
of sanitizers and detergents in the
2Temperature equal to or higher than domestic wastewater.
design but not harmful to joint treatment processes.
May affect
NOTES:
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown in
UPPER CASE.
Wastewater characteristics shown reflect all the Industrial
Practices described under Section D-2.
D-2-5
-------
o
I
N
I
(j\
Pretreatment
Sub-G roup
Milk Handling
Mi lk Products
Natura I and
Cottage Cheese
Products
Table [1-2-2
Pretreatment Unit Operations for the Dairy Products Industry
Suspended Biological
System
Equalization +
Neutra Ii zat i on
Equal i zat ion +
Neutralization
Fixed Biological
System
Independent Physical
Chemical System
Eq ua 1 i za t ion +
Neutralization
Equal ization +
Ne u t r a I i za t i on
Eq ua I i za t i on +
Neutral ization
Equalization +
Neutra Ii zat ion
-------
REFERENCES
----
1.
"Proceedings Second NAtional Symposium on Food Processinq
Wastes", Denver, Colorado, Environmental Protection Agency,
Water Pollution Control Research Series 12060 (March, 1971).
2.
liThe Cost of Clean Water, Vol III. Industrial Profi le
No. g - Dairies", Federal Water Pollution Control
Administration, Washington, D.C. (June, 1967).
3.
"Studv of Wastes and Effluent Requirements of the
Industry", Contract No. b8-01-Uu23, environmental
Agency, Washington, D.C. (Unpublished).
Da i ry
Protection
4.
(Edited by) Gurnham, C.F.,
"Inrlustrial Wi'1stewater Control".
Academic Press, New York (1965).
D-2-7
-------
TEXT I LE INDUSTRY
1.
Industry Description
This industry includes Standard Industry Classifications (SIC)
2231, 2250, 2260, 2270, 2284, and 2297.
The textile industry involves the manufacture of fabrics from
wool, cotton, and synthetic fibers; the synthesis or spinning
of synthetic fibers is not included in this group, but rather is
included under synthetic organic chemicals. Of the three major
textiles, wool represents the smallest market and synthetic
textiles the largest.
The major unit processes of the woolen textile industry include
scouring, dyeing, full ing, carbonizing, bleaching, and weaving.
Raw woo 1 is scou red to remove grease and dirt. The process
employs a detergent and mild alkal i at temperatures of 130oF.
This operation is responsible for 55-75 percent of the total
BOD load from wool finishing (1).
The dyeing process uses dyes, dyeing assistants, (e.g. acetic
acid, ammonium sulfate), and dye carriers containing heavy
metals. The dye carriers will be present only if the wool
is being combined with a synthetic fabric, which requires a
dye carrier to facilitate dye penetration (2).
Various chemicals (e.g. sulfuric acid, hydrogen peroxide, and
01 ive oil) may be added before and during the full ing operation.
These chemicals then enter the wastewater during a subsequent
washing step.
Carbonizing impregnates the wool with sulfuric acid to remove
any traces of vegetable matter. Bleaching may then be accom-
pI ished, with either sulfur dioxide, hydrogen peroxide, or
optical brighteners.
The major unit processes employed in the cotton and synthetic
textile industry include sizing, weaving, desizing, scouring,
dyeing, and finishing. Chemicals used in the sizing process
include starch, polyvinyl alcohol, carboxymethyl cellulose,
and polyacryl ic acid.
After weaving, the fabric is desized using an
action. Desizing removes the chemicals added
by hydrolyzing them to a soluble form.
acid enzyme re-
during sizing
0-3-1
-------
During scouring cotton wax and other non-cellulosic components
of cotton are removed by using hot alkaline solutions. Synthetic
materials require only I ight scouring because of the absence of
chem i ca I i mpu r i ties (3).
Both cotton and synthetic fanrics are treated with special
finishes. using formaldehyde and urea, and with fire retard-
ants, such as triaziridyl phosphine oxide.
The pretreatment sub-groups for this industry are:
Wool
Cotton and Synthetic Fabrics
2.
Industrial Practices
The following industrial practices can significantly affect the
wastewater characteristics:
Segregation of Waste Streams
The segregation of waste streams permits recovery of
heavy metals, caustic recovery and reuse, and control
of toxic spills (such as dieldrin used for moth-
proofing). Many of the older textile mills have a
common collection system with chemical reuse, but the
modern mills have a segregated collection system to
permit chemical recovery and reuse.
Alkal ine Wool Scouring
Alkal ine wool scouring may be used in place of neutral
scouring. In alkal ine scouring, soda ash is added to
the wash water and subsequently combines with a portion
of the wool grease to from natural soap. This pro-
cedure reduces the amount of detergent required and
reduces the BOD and the concentration of residual
surface-active agents.
Chemical Sizing
The substitution of polyvinyl alcohol
cellulose for starch in the sizing of
overall BOD in the wastewater.
or carboxy methyl-
cotton reduces the
Pressure Dyeinq Becks
The use of pressure dyeing becks in the place of atmospheric
units permits reduction in the amount of dye carriers
required thereby reducing the BOD and heavy metal
concentrations.
D-3-2
-------
3.
Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table 0-3-1.
The textile industry generally operates continuously through-
out the year except for scheduled shutdowns. However, many
of the individual unit operations within the industry are
batch oriented. Daily wastewater flows are continuous with
peak flows occurring if certain batch-type operations are
used. The textile industry is usually in a state of flux,
with the manufacturing process continually being modified
to reflect changes in consumer trends.
Wastewaters generated in the textile industry are high in
BOD, COD, TDS, and color. For synthetics, dyeing results
in the largest BOD contribution, attributed to the use of
dye carriers such as methyl naphthalene, biphenyl, and
orthopheny1 phenol, all of which have a high BOD. For cotton
finishing, desizing contributes about 45 percent of the total
BOD, scouring about 30 percent, and dyeing about 17 percent (1).
The most significant difference between wool process wastewaters
and those from the rest of the industry is the release of waste-
waters with high concentrations of suspended sol ids and grease
from the wool-scouring operation.
Textile wastewaters can vary from sl ight1y acid to highly
a1ka1 ine depending on the individual processes carried out
within the plant. They generally are a1kal ine when caustic
scouring or mercerizing is involved. Heavy metals such as
copper, chromium and zinc result from the use of certain
dye carriers in the dyeing operation of synthetic fabrics
and of blended fabrics, e.g. cotton and rayon.
4.
Pretreatment
The pretreatment
various types of
Table 0-3-2.
unit operations which may be necessary for
joint treatment facilities are shown in
0-3-3
-------
Table 0-3-1
Wastewater Characteristics
Textile Industry
Characteristics
Wool
Cotton and Synthetics
Industrial Operation
Yea r- round (batch)
I NTERM I TTENT 1
HIGH
HIGH
HIGH
HIGH
- Continuous
Year-round (batch)
I NTERM I TTENT I
Average-HIGH
Low-AVERAGE
HIGH
Average-HIGH
- Continuous
Flow
BOD
TSS
TDS
COD
G r it
Cyanide
Chlorine
pH
Color
Demand
PRESENT
Absent
HIGH
BASIC
HIGH
Absent
Absent
HIGH
BASIC
HIGH
Turbidity
Explosives
Dissolved Gases
Detergents
Foaming
High
Absent
Absent
PRESENT
Present
High
Absent
Absent
PRESENT
Present
Heavy Meta 1 s
Colloidal Sol ids
Volatile Organics
Pesticides
Phosphorus
PRESENT
Present
Absent
Absent
PR SENT
PRESENT
Present
Absent
Absent
PRESENT
Nitrogen
Temperature
Phenol
Sulfides
Oil and G rea s e
Co 1 i form (Feca 1)
DEFICIENT 2
Normal-High
Absent3
Absent
HIGH5
PRESENT
DEFICIENT 2
Normal3High
Absent
Absent
Absent-Present4
Absent
1
Wastewater flow characterized by an intermittent pattern over the day.
2Temperature equal to or higher than domestic wastewater.
harmful to joint treatment processes.
May affect design but not
3
Phenol may be present in dye carriers.
40il present in wastewaters from synthetic textiles only.
5Wool processing wastewaters contain high concentration of animal grease.
NOTES:
Characteristics which may require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
Wastewater characteristics shown do not reflect the industrial practices
described in Section 2.
D-3-4
-------
Pretreatment
Sub-Group
Wool
Cotton & Synthetics
<::>
I
W
I
\J1
Table D-3-2
Pretreatment Unit Operations for the Tpxti le Industry
~uspended Biological
System
Coarse Solids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals) + Equal ization +
Neutralization
Coarse 501 ids Separation +
Chemical Precipitation
(color,heavy metals) +
Equal ization + Neutral ization
Fixed Biological
System
Coarse Sol ids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals) + Equal ization +
Neutral ization
Coarse Sol ids Separation +
Chemical Precipitation
(color,heavy metals) +
Fqual ization + Neutralization
Independent Physical - Chemical
System
Coarse 501 ids Separation +
Grease Removal + Chemical
Precipitation (color, heavy
metals) + Equal ization +
Neutralization
Coarse 501 ids Separation +
Chemical Precipitation
(color,heavy metals) +
Equalization + Neutralization
-------
REFERENCES
1.
"State of the Art of Textile Waste Treatment'!. Water
Pollution Control Research Series, 12090 ECS; Environmental
Protection Agency, Washington, D.C. (1971).
2.
"Industria1 Waste Studies Program - Textile Mill
Environmental Protection Agency (Unpub1 ished)
P ro d u c t S ! I ,
3.
"The Cost of Clean Water - Vol. 1'1 - Industrial Waste
Profile No.4 Textile Mill Products", Federal Water Pollution
Control Administration (September, 1967).
0-3-6
-------
SEAFOODS INDUSTRY
1.
Industry Description
This industry includes Standard Industry Classifications
(S I C) 2031, 2036, and 2094
The seafood industry is made up of many processing centers,
located along the United States coastlines, with a number
of the larger plants remotely located with respect to
neighboring industry and population centers. The annual
U.S. catch in 1968 was approximately 4 billion pounds
(cleaned) with the catch being uti 1 ized as follows: 35%
rendered, 30% marketed fresh, 20% canned, 10% frozen, and
5% to miscellaneous processing (1).
The seafood industry involves the processing of numerous
species of seafood including: mollusks (oysters, clams,
and scal lops); crustaceans (crabs and lobsters); and
various species of both salt- and fresh-water fish.
This industry uses the following major unit processes (1, 2):
washing, eviscerating, dressing, processing, and rendering.
Sol id waste from these processes is significant. Average
wastage for all fish and shellfish is about 30% of body
weight, with values ranging from zero for whole rendered
fish to 85% for some crabs (1). Some boats eviscerate
and clean fish at sea, thereby decreasing waste quantities
at the shore-side processing plant. Many plants use sub-
stantial amounts of sea water for cleaning operations.
Rendering of whole fish and fish by-products produces fish
meal, oil, and solubles. Currently, four c.lasses of
rendering processes are used: dry, wet, solvent extrac-,
tion, and digestion. Wet rendering is the most prominent
process. In this process, the by-products are cooked with
steam, and the material is pressed to yield a solid cake
and press 1 iquor. The 1 iquor is centrifuged to obtain fish
oil and stick water. The stick water is evaporated to
give condensed fish solubles.
Because of the similarity of the pollutants significant to
pretreatment of wastewaters from the seafood industry,
there are no separate pretreatment sub-groups for this
industry.
2.
Industrial Practices
The fol lowing industrial practices can significantly
influence the wastewater characteristics.
D-4-1
-------
501 id Waste Handl ing
The handl ing of the sol id process wastes in a dry form
substantially decreases waste loadings in the wastewater.
Process Water Conservation
New techniques may be introduced to reduce the amount of
process water usage, e.g., using counter-current washing.
3.
Wastewater Characteristics
The characteristics of the process wastewaters from the industry
are shown in Table 0-4-1.
The seafood processing industry is seasonal, but wastewater
flows are relatively constant during operation. Wastewaters
include various auxil iary sources such as cooling water and
cool ing waters from refrigeration systems.
The wastewaters generated from seafood processing contain as
major constituents BOD, COD, T55, TD5, and oil. The occurrence
of the oil component depends on whether oily or non-oily
seafood is being processed and the processing operations
employed. Considerations of significance to the joint treat-
ment of seafood wastewaters and domestic waste include high
chlorine demand, the presence of surface-active agent, fecal
col iform, and high concentrations of chlorides and other dis-
solved sol ids from sea water usage within the plant.
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facil ities are shown in
Table D-4-2.
Very little treatabil ity information is available for seafood-
processing wastewaters. If seawater is used as process water,
a sufficient dilution of the process water by domestic waste-
water is required 50 that dissolved sol ids and chlorides will
not cause problems in a joint biological treatment plant. When
seawater is used exclusively, the dilution ratio should be
about 3 parts domestic wastewater to I part seawater. Oil
separation may be a pretreatment consideration if oily fish,
such as tuna, sardines, herring, cod, haddock, halibut, etc.,
are processed in a manner which results in significant quanti-
ties of oil in the wastewater.
D-4-2
-------
Table D-4-1
Wastewater Characteristics
Seafood Industry
Characteristics
Classification
Industrial
Flow
BOD
TSS
TDS
Operation
SEASONAL
Continuous
Average-HIGH
Average-HIGH
Average-HIGH
COD
G r it
Cyanide
Chlorine
pH
Demand
Average-HIGH
Absent
Absent
Average-HIGH
Neutral
Color
Turbidity
Explosives
Dissolved Gases
Detergents
Average-HIGH
High
Absent
Ab sen t
Pre sen t
Foaming
Heavy Metals
Co I J 0 i d a 1 So lid s
Volatile Organics
Pesticides
Absent
Absent
Average-HIGH
Absent
Absent
Phosphorus
Nitrogen
Temperatu re
Phenol
Sulfides
Adequate
Adequate I
Normal-High
Absent
Absent
Oil & Grease
Co 1 i form (Feca 1)
Coliform (Total)
2
Average-HIGH
PRESENT
PRESENT
I Temperature equal to or higher than domestic wastewater. May
affect design but not harmful to joint treatment processes.
2Depending upon whether oily or non-oily seafood is being
processed.
NOTE:
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
in UPPER CASE.
Wastewater characteristics shown reflect the handl ing
and disposal of solid wastes in dry form as described
in Section 2.
D-4-3
-------
Table 0-4-2
Pretreatment Unit Operations for the Seafood Industry
Suspended Biological
System
Fixed Biological
System
Independent Physical
Chemical System
Coarse Sol ids
g r i t remova 11
separation2
Separation +
+ oi 1
Coarse Sol idr
grit removal
sepa rat i on2
Sepa rat ion +
+ oi 1
Coarse Sol idr
g r it remova 1
separation2
Separation +
+ oi 1
o
I
+-
I
+-
lFor shellfish processing.
20il separation may be required
seafood processed.
to reduce free floating oir and grease depending on
-------
REFERENCES
---
1.
"Current Practice in Seafoods Processing Waste Treatment",
Water Pollution Control Research Series, 12060 ECF,
Environmental Protection Agency, Washington, D.C. (Apri1,
1970) .
2.
(Edited by) Gurnham, C.F.,
"Industrial Wastewater Controll'.
Academic Press, New York (1965).
D-4-5
-------
PYARMACEUTICAL INDUSTRY
1.
Industry Description
This industry includes Standard Industry Classifications
(SIC) 2831, 2833, and 2834. The industry produces medicina1
chemicals and pharmaceutical products, including some fine
chemicals which are marketed outside the pharmaceutical industry
as intermediates.
In 1970, there were 1,300
United States, and 150 of
industry's products (1).
producers of pharmaceuticals in the
these firms produced over 95Y of the
In general, the pharmaceutical industry may be divided into
two broad production categories; chemical synthesis products;
and antibiotics (penicillin and steruids).
The manufacturing operations for synthesis products may be
either dry or wet. Dry production involves dry mixing,
tableting or capsul ing, and packaging. Process equipment is
generally vacuum cleaned to remove dry sol ids and then washed
down.
The production of wet synthesis products and antibiotics is
very similar to fine chemicals production, and uses the
following major unit processes: reaction, extraction and
concentration, separation, solvent recovery, and drying.
Wet synthesis reactions generally are batch types followed by
extraction of the product. Extraction of the pharmaceut;cal
product is often accompl ished through solvents. The product
may then be washed, concentrated and filtered to the desired
purity, dried, capsul ized, and packaged.
The production of antibiotics is restricted to a few of the
larger pharmaceutical firms. Some antibiotics are produced
in batch fermentatIon tanks in the ~resence of a particular
fungus or bacterium. The culture frequently is filtered
from the medium and nlarketed in cake or 1 iquid form as an
animal feed supplement (2). The antibiotic is extract2d
from the culture medium through the use of solvents, activated
carbon, etc. The antibiotic is then washed to remove res-
idual impurities, concentrated, filtered, and packaged.
0-5-1
-------
The pretreatment sub-groups for this industry are as follows:
Synthesis
Fermentat ion
2.
Industrial Practices
The fol lowing industrial practices can significantly influence
the wastewater characteristics:
1.
Solvent recovery is practiced in both the synthesis
and the fermentation products segment of the
industry. Certain products may require a high-purity
solvent in order to achieve the required extraction
efficiency required (3). This increases the incentive
for making the recovery process highly efficient.
'I
L.
Some solvent streams which cannot be recovered
economically, are incinerated. Incineration is
also used to dispose of "still bottoms" from
solvent recovery units.
3.
Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table 0-5-1.
The pharmaceutical plants operate continuously throughout
the year and are characterized by batch operations with
significant variations in pol1utional characteristics over
any typical operating period.
The major sources of wastewaters are product washings,
concentration and drying procedures, and equipment washdown.
Wastewaters generated from the pharmaceutical industry can be
characterized as containing high concentrations of BOD, COD,
TSS, and volatile organics. Wastewaters from some wet chemical
syntheses may contain heavy metals (Fe, Cu, Ni, V, Ag) or
cyanide, and generally have anti-bacterial constituents,
which may exert a toxic effect on biological waste treatment
processes.
Considerations significant to the design of joint treatment
works are the highly variable BOD loadings, high chlorine
demand, presence of surface-active agents, and the possibil ity
of nutrient deficiency.
0-5-2
-------
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment faci1 ities are shown in
Table D-5-2.
The specific type and degree of pretreatment for heavy metals
and cyanide will be governed by the industria] effluent
guidel ines for the pharmaceutical industry. Cyanide removal
or control is especially important.
Pharmaceutical industries generate wastewaters on an
intermittent basis and equal ization may be needed as pre-
treatment. When solvents are used for extraction, solvent
removal can be accomplished by using gravity separation and
skimming. Neutral ization may be required to neutral ize
acidic or alkal ine wastewaters generated from the production
of specific pharmaceutical products.
D-5-3
-------
Table D-5-1
Wastewater Characteristics
Pharmaceutical Industry
Characteristics Synthesis Fermentation
Industrial Operation Year-Round (BATCH) Year-Round (BATCH)
Flow INTERMITTENT INTERMITTENT
BOD AVERAGE-HIGH EXTREMELY HIGH
TSS HIGH EXTREMELY HIGH
TDS AVERAGE-HIGH HIGH
COD AVERAGE-HIGH EXTREMELY HIGH
Grit Absent Absent
Cyanide PRESENT Absent
Chlorine Demand AVERAGE-HIGH HIGH
pH ACID-BASIC ACID-BASIC
Color Average-High Average-High
Turbidi ty Average High
Explosives Present Present
Dissolved Gases Absent Absent
Detergents PRESENT PRESENT
Foaming PRESENT PRESENT
Heavy Metals PRESENT Absent
Colloidal Sol ids High HIGH
Volatile Organics HIGH HIGH
Pesticides Absent Absent
Phosophorus DEFICIENT DEFICIENT-HIGH
Nitrogen DEFICIENT DEFICIENT-HIGH
Temperature Normal-Highl Normal-High
Phenol Absent Absent
Sulfides Absent Absent
Oi 1 & Grease Absent-Present Absent-Present
Coliform (Total) Absent Absent-Present
lTemperature equal to or higher than domestic wastewater.
harmful to joint treatment processes.
May affect design but not
NOTES:
Characteristics which may require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
Wastewater characteristics shown reflect all the Industrial Practices described
in Section 2.
D-5-4
-------
Table D-5-2
Pretreatment Unit Operations for the Pharmaceutical
Pretr~atment
Sub-G roup
Suspended Biological System
Synthesis
Chemica1 Precipitation
(Heavy Metals) + Solvent
Separation t Neutral iz~tion
+ Cyanide Oxidation
o
I
V1
I
V1
F2rmentation
Solvent Separation + Equal i-
zation + Neutral ization
Industry
Fixed Biological System
Chemical Precipitation
(Heavy Metals) + Solvent
Separation + ELjuali-
zation + Neutralization +
Cyanide Oxidation
Solvent Separation + Equdli-
zat ion + Neutra Ii zat ion
Independent Physical
Chemical System
Chemical Precipitation
(Heavy Metals) + Solvent
Separation + Equali-
zation + Neutralization
+ Cyanide Oxidation
Solvent Separation +
Equalization + Neutral-
ization
-------
REFERENCES
1.
Lund, H.F., "Industrial Pollution Control Handbook'l,
McGraw-Hi 1 1 Book Co., New York (1971).
2.
"Industrial Wastewater Control",
Academic Press, New York (1965).
(Edited by) Gurnham, C.F.,
3.
Rudolfs, W., "Industrial Wastes, Their Disposal and
Treatment", Reinhold Publ ishing Corp., New York (1953)-
0-5-6
-------
LEATHER TANNING AND FINISHING INDUSTRY
1 .
Industry Description
This industry includes Standard Industrial Classification (SIC)
3111. This classification includes tanning, curing, and fin-
ishing hides and skins into leather. The trend in the tannery
industry is toward greater centralization near large metropol itan
areas. This results in an increased number of municipal treat-
ment plants treating tannery wastes. Approximately 80 percent
of the output from tanneries is from cattle-hide processing,
with the remainder being pigskin, calfskin, goatskin, and sheep-
skin processing (1)-
The tanning process involves conversion of animal hide and
skins into leather. The grain layer and the corium portion of
the skins constitute the leather-making material and consist
mainly of the protein collagen. During the tanning process,
the collagen fibers are reacted with tannin, chromium, alum,
or other tanning agents to form the leather. Four basic oper-
ations are involved in tanneries:
1 .
2.
3.
4.
Beam House
Tan House
Retan, color
Finishing
and fat liquor
The beam house operation involves: storage and trimming of
hides; washing and soaking to remove dirt, salt, blood, manure
and non-fibrous proteins; green fleshing for the removal of
adipose fatty tissues and meat; unhairing to remove epidermis
and hair; bating to remove non-collagenous proteins; and pickling
in some current operations to stabilize and preserve the unhaired
stock for subsequent operations. The beam house operation is
typical of hide and skin processing with cattlehide processing
being the most important in the U.S.
The tan house operation consists of preparing the stock for
tanning. Pickling is done to make the skin acid enough to pre-
vent precipitation of chromium during tanning. Two types of
tanning are common in the United States: vegetable tanning;
and chrome tanning. Vegetable tanning, the older process, is
carried out in a solution containing plant extracts (such as
vegetable tannin) to produce heavy leathers such as sole leathers
and saddle leathers. Light leathers, such as shoe upper leathers,
D-6-1
-------
are usually chrome-tanned by immersion in a bath containing
proprietary mixtures of basic chromium sulfate.
Hides which have not been fully tanned in the chrome-tanning
process may be retanned with either chrome, vegetable, or syn-
thetic tanning agents. The fat liquor process involves the
addition of many types of oi Is and greases to the tanned hides
to prevent cracking and to make the leather soft, pliable,
strong, and resistant to tearing. Coloring or dyeing of tanned
leather may be done either before or after fat liquoring and
uses either natural or synthetic dyestuffs. Finishing oper-
ations such as drying, coating, staking, and plating follow
the foregoing wet processes.
The pretreatment sub-groups for this industry are:
Chrome Tanning
Vegetable Tanning
2.
Industrial Practices
In-plant pollution control techniques and chemical recovery
practices in tanneries vary depending on the tanning process
and the economics of chemical recovery systems. In vegetable
tanning, it is common practice to recycle the tanning solution.
(In chrome tanning, a number of tanneries are practicing re-
cycling of tanning solution.) Recovery of grease is normally
practiced in pigskin and sheepskin tanneries.
The wastewater characteristics from the unhairing process wi 1 1
depend on whether the industry is practicing a "save hairl' or
"pulp hair" operation. A low amount of sulfide (0.5 to 1.0
percent of hide weight) removes the hair with minimal damage,
whi Ie a high amount (2 to 3 percent) pulps and partially dis-
solves the hair. The "save hair" operation involves mechanical
pulling and recovery of hair. Dissolution of hair through
chemica1 reactions is referred to as "pulping" or "burning".
3.
Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table D-6-1.
Most sub-processes within the tanneries are batch operated,
and, therefore, the wastewater flow and characteristics
fluctuate during the industry operation. In addition, week-end
D-6-2
-------
shutdowns in some tanneries wi I I result in wastewater f10w only
during weekdays. The seasonal variations in wastewater flow
are I imited to the variations in hide characteristics. In
genera1, the waste characteristics and volume vary widely through-
out the day and throughout the week in tanneries. The concen-
trated waste fractions (lime liquors and spent tan s01utions) are
derived from batch-type processes. These fractions are thelefore
discharged intermittently (2,3,4,5).
Liquid process wastes are generated in tanneries from soaking
and washing, fleshing, unhairing, bating, pick1 ing, tanning,
coloring, and fat liquoring. Auxiliary wastewaters from tan-
neries result primari Iy from boi 1er blowdown and frorn cool ing,
and represent only a minor fraction of the total waste load from
tanneries. Therefore, only process waste streams are considered
for establishing wastewater characteristics and recommending
pretreatment.
The characteristics of wastewaters from tanneries vary according
to the type of hide processed and the tanning process (vegetable
or chrome tanning) used. The tanning process is more of an art
than science, and as a result the wastewater characteristics
can vary widely for the same type of hide and tanning process.
The process wastewaters from tanneries contain as major con-
stituents: BOD, COD. chromium, oi I and grease, sulfide, sus-
pended and dissolved solids, alkalinity, hardness, color, and
sodium chloride. Significant pollutants that may be present in
tannery wastes include: hair, hide, scraps, bits of flesh,
blood, manure, dirt, salts, suspended lime, soluble proteins,
sulfites, sulfides, amines, chromium salts, vegetable tannin,
soda ash, sugar and starches, oi 1s, fats and grease, surface
active agents, mineral acids, and dyes (6) which contribute to
the BOD and COD.
In general, washing, fleshing, and unhairing operations produce
50 percent of the tota1 volume and approximately 70 percent of
the pollutiona] load from tanneries. The tanning process
generates from 5 to 20 percent of wastewater volume and loading
(1). The dry finishing operations produce only minor quantities
of wastewater from c1ean-up operations.
The major wastewater sources from tanneries are the beam
and the tan house operations. The beam house wastewater
highly alkaline due to the large quantities of lime used
process. The wastewater generated from the tan house is
house
is
in the
D-6-3
-------
generally acidic due to the discharge of spent tanning solution.
Normally, these wastewaters are discharged to a common collecting
sewer before treatment or discharge to a municipal system. The
unregulated batch dumping from bean house and tan house result
in a total waste stream with varying pH values.
Mixing alkaline waste streams (from the beam house) with the
acidic chrome tanning wastes would result in partial precipi-
tation of chromium, which can be removed by clarification.
There is also the hazard of the evolution of H2S gas. Average
chromium concentrations in the total tannery waste can be as
high as 300 mg/L in the chrome tanning process.
The other major pollutant in tannery waste is the effluent from
the lime-sulfide unhairing operation. The concentration of
sulfides in tannery wastes may vary between 30 and 100 mg/L in
the total effluent (2). The consequences of release of H2S gas
in the sewer lines and the effect of reducing characterisfics
of the sulfides on biological treatment processes should be
taken into consideration in the design of joint treatment works.
Hydrogen sulfide is readi]y released from solution as a corrosive
and extremely toxic gas with an obnoxious odor. By controlling
the pH of the solution above 10.0, the H2S release can be mini-
mized. If the pH of the wastewater is expected to be lower,
the sulfide concentration should be reduced below 1.0 mg/L to
prevent H2S odor problems.
In general, tannery wastewaters are amenable to joint treatment
by conventional methods, if the industrial wastewater is ade-
quately pretreated. Most available information on the combined
treatment of tannery and municipal wastewaters is from bench-
scale or pilot plant operations, rather than from full-scale
plant operation. This information indicates that when the
tannery waste does not exceed about 10 percent of the total flow
and when the tannery discharge is regular and well equalized,
no difficulty with conventional sewage treatment is likely to
occur (7). The tannery waste solids from the vegetable tanning
process can amount to approximately 30 percent before seriously
impairing gas production in anaerobic digestion. However,
digestion of solids developed from chrome tannery wastes may
result in gradual build-up of chromium in the digester and
eventual failure of the process.
D-6-4
-------
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment processes are shown in Table
D-6-2. Screening to remove debris, equalization to provide
uniformity of effluent, and neutralization with precautions
for possible generation of hydrogen sulfide gas, to prevent
excessively high pH values are generally necessary prior to
discharge to a municipal collection system. Chemical precipi-
tation may be needed to reduce the amount of chromium in the
effluent.
The considerations in Table D-6-2 are based on the assumption
of fat and grease recovery as a by-product. Where this is not
practiced, grease removal faci lities may also be needed.
D-6-5
-------
Table D-6-1
Wastewater Characteristics
Leather Tanning and Finishing Industry
Characteristics
Chrome Tanninq
Veqetable Tanninq
Industry
Flow
BOD
TSS
TDS
Ope rat i on
Year-Round (Batch)
I NTE RM I TTENT
EXTREMEL',' HIGH
EXTREMEL\' HIGH
HIGH
Year-Round (Batch)
INTERMITTENT
EXTREMELY HIGH
EXTREMELY HIGH
HIGH
COD
Grit
Cyanide
Chlorine
pH
Demand
EXTREMELY dllJH
PRESENT
Absent
High
AC I D - ALKALI NE
t:: ;~ TR EM E L Y H I G H
PRESENT
Absent
High
AC I D - ALKALI NE
CoJor
Turbidity
Explosives
Dissolved Gases
Detergents
Present
Present
Absent
Present
Present
Present
Present
Absent
Present
Present
Foaming
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Absent
PRESENT
Present
Present
Absent
Absent
Absent
Present
Present
Absent
Phosphorus
Nitrogen
Temperature
Pheno I
Sulfides
DEFICIENT
Adequate
Normal'
Absent
Present
DEFICIENT
Adequate
Normal'
Absent
Present
01 I & Grease
Coliform (Total)
HIGH2
Low
HIGH2
Low
lTemperature equal to domestic wastewater.
20i 1 and grease (animal origin) are significant
processing wastewaters.
only in pigskin and sheepskin
NOTES:
Characteristics which may require pretreatment or are significant to
joint treatment plant design are shown in UPPER CASE,
Wastewater characteristics shown reflect all the Industrial Practices
described in Section 2.
D-6-6
-------
TAble D-6-2
Pretreatment Unit Operations for the Leather Tanning and Finishing Industry
Pretreatment
Group
Suspended Biological
System
Chrome Tanning
Coarse Solids Separation +
Grit Removal + Equal ization
+ Chemical Precipitation
(Heavy Metals) + Solids
Separation + Neutralization
Vegetable Tanning
Coarse Sol ids Separation +
Grit Removal + Equalization
+ Neutralization
o
I
~
I
~
I.
Fixed Biological
System
Independent Physical
Chemical System
Coarse Sol ids Separation +
Grit Removal + Equalization
+ Chemical Precipitation
(Heavy Metals) + Sol ids
Separation + Neutralization
Coarse Sol ids Separation +
Grit Removal + Equal ization
Coarse Sol ids Separaration +
Grit Removal + Equal ization
+ Neutral ization
Coarse Solids Separation +
Grit Removal + Equal ization
Pretreatment requirements assume fat and grease recovery as saleable by-product.
-------
REFERENCES
1.
"The Cost of Clean Water, Vol. III, I ndustrial Waste Profi les
No.7 - Leather Tanning and Fisnishing,!1 U.S. Department of
the Interior, FWPCA (1967).
2.
"Activated Sludge Treatment of Chrome Tannery Wastes," Water
Pollution Control Research Series, ORD-5, U.S. Department
of the Interior, FWPCA, (1969).
3.
Eye, D. J., Adldons, J. G., "Anaerobic - Aerobic Treatment
of Spent Vegetable Tan Liquors from a Sole Leather Tannery,"
Proc. 23rd Industrial Waste Conference, Purdue University,
126-139 (1968).
4.
Sproul, O. J., Keshavan, K., and Hunter, R. W., "Extreme
Removals of Suspended Sol ids and BOD in Tannery Wastes by
Coagulation with Chrome Tan Dump Liquors," Proc. 21st
Industrial Waste Conference, Purdue University, 600-612
(1966).
5.
Nemerow, N. L., and Armstrong, A., "Combined Tannery and
Municipal Waste Treatment," Proc. 21st Industrial Waste
Conference, Purdue University, 447-467 (1966).
6.
"Effluent Requirements for the Leather Tanning and Finishing
Industry," by Stanley Consultants, Inc., Muscatine, Iowa,
for the Water Quality Office, Environmental Protection
Agency, Contract No. 68-01-0024 (Unpublished).
7.
Wims, F. J., "Treatment of Chrome Tanning Wastes for
Acceptance by an Act i vated Sludge Process, r I Proc. 18th
Industrial Waste Conference, Purdue University, 534-549
(1963).
D-6-8
-------
SUGAR INDUSTRY
1.
Industry Description
This industry includes Standard Industrial Classifications
(SIC) 2061,2062, and 2063. These classifications include
establishments engaged in the manufacture of raw sugar, syrup,
or finished (granulated or clarified) sugar from sugar cane,
and the manufacture of sugar from sugar beets.
Domestic cane sugars and beet sugars provide only about 55
percent of the total sugar consumed in the United States. The
remaining 45 percent of the sugar requirement is imported as
raw cane sugar from foreign countries. The raw cane sugar
(approximately 96 percent purity) is further purified in local
sugar refineries in the United States (SIC 2062).
The production of raw sugar from sugar cane or refined sugar
from sugar beets essentially involves the washing or cleaning
of sugar cane or beets, extraction of sugar juice, precipitation
and fi ltration of impurities (using lime and carbon dioxide),
evaporation, crystallization, and drying of sugar crystals.
Water is used in the process to wash the sugar cane or beets,
to dissolve or extract sugar, and for cooling purposes.
The manufacture of sugar from sugar beets produces beet pulp
and molasses as by-products. The beet pulp is pressed and
dried for use as animal feed. The molasses, containing soluble
non-sugars and some sugar, either is sold or is used in the
Steffen Process to recover additional sugar. The Steffen
Process involves the treatment of molasses with lime to recover
additional sugar for recycle to the process. Wastewaters are
typically added to the beet pulp and then dried, and sold as
animal feed. A recent survey of 14 plants using the Steffen
Process indicates that 5 plants use the Steffen Process waste
to produce monosodium glutamate, whi le the others concentrate
and dry the waste with beet pulp for use as animal feed (1).
A modification of the Steffen Process, with barium hydroxide
in place of the lime, is also used by some beet sugar plants
(2,3) .
The production of refined sugar from raw cane sugar involves
washing the raw sugar to remove the molasses fi 1m from the sugar
crystals, solution of the washed sugar, clarification of the
solution by phosphoric acid-l ime precipitation, carbonation, and/or
pressure fi ltration, decolorization of the solution using
D-7-1
-------
powdered or granular carbon, bone char or resins, and evaporation
of the clarified and decolorized solution to yield crystal line
sugar.
The primary uses of water are to wash the decolorizing adsorbent
and to serve as a cooling and condensing medium in the evapor-
ating processes. The first use produces an effluent containing
BOD and frequently suspended sol ids (waste fi Iter aid)- The
second use leaves the water essentially unchanged except for an
increase in temperature.
The principal by-product of the process is refinery molasses
which is now sold for animal feeding purposes. Spent fi Iter
aid is generally sent to authorized dump sites. Waste bone
char is sold to dealers for a variety of uses such as poultry
feeding.
Because of the similarity of the wastewaters
industry, there are no separate pretreatment
industry.
from the sugar
sub-groups for this
2.
IndustridJ Practices
The following industrial practices can significantly affect the
wastewater characteristics.
The production of cane sugar involves by-products such as
residua] sugar cane fibers and blackstrap molasses. The
residua1 fibers are generally used as fuel or in the production
of fiberboard and paper products; the blackstrap molasses is
recovered and sold as such. No additional waste loads result
from the recovery or reuse of by-products (4,5).
The pulp press liquor and evaporator condensates can be re-
cycled for use in the flume-washing operation.
3.
Wastewater Characteristics
The rh~racteristics of the process wastewater' from the industry
are shown in Table 0-7-1. Sugar plants generally operate 24
hours a day, but because of the naLUI"c of tne raw materials
(sugar cone and sugar beets), the domestic sugar industry oper-
ates seasc,lldlly from 60 to 100 days a year. The sugar refin-
eries processing domestic and imported raw sugar can operate
year-round. The sugar plants generate wastewater on a contin-
uous basis during operational periods. However, the character-
0-7-2
-------
istics of the wastewater may fluctuate widely, becuase of
variations in sugar content of the raw materials at different
periods of the season. The variations in sugar content of raw
materials are caused either by changes in weather conditions
or in the storage of raw material (sugar cane or beets). In
addition, hourly variations in wastewater characteristics may
result from spi lIs and leaks of sugar juice and from equipment
cleanups.
The process wastewaters originate from the following operations
in the production of raw cane sugar and refined beet sugar:
1 .
2.
3.
4.
Flume washing
Lime cake or slurry
Evaporator condensates
Spills, leaks, and floor
washing
Process wastewaters originate from the following unit operations
in the refining of raw cane sugar:
1 .
Disposal of waste fi Iter aid, carbonate cake,
phosphoric acid precipitation scums, etc.
2.
Washing of bone char and/or regeneration and re-
using of resins.
3.
Evaporator condensates.
The volume and characteristics of wastewater generated from
the foregoing operations wi 1 1 depend on the degree of recycle
practiced. The overal I process wastewaters generally contain
high concentrations of dissolved organics and suspended im-
purities, and are deficient in nutrients. The process waste-
waters generated from each of the operations contain as major
waste const i tuents BOD, COD, suspended so lids, and heat. Th:~
wastewaters generated from sugar refineries are simi lar to
those from sugar production from sugar cane and contain as
major pollutants BOD5 and suspended solids.
In general, the sugar industry wastewaters are amenable to
treatment by joint treatment processes. The seasonal operation
of some of the sugar plants and the widely-varying character-
istics of the wastewaters should be taken into consideration
in the design of joint treatment faci lities.
0-7-3
-------
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment faci lities are shown in Table
D-7-2.
Many sugar plants treat their wastewaters in holding lagoons,
with controlled discharge of the lagoon effluent to municipal
collection systems. The lagoons are effective for the removal
of suspended solids and grit present in the wastewater. Typi-
cally, however, they are designed to remove only a small per-
centage of the BOD present in the raw wastewater (6).
The limited information avai lable on the treatment of sugar
industry wastes indicates that equalization (to reduce the
fluctuations in organic loading), screening (to remove fibers),
and clarification (to separate lime slurry and grit) would be
needed as pretreatment before discharging these wastewaters to
municipal co1 lection systems. In addition, faci lities for
supplemental nutrients (nitrogen and phosphorus) at the joint
treatment faci 1 ity may be required.
D-7-4
-------
Table 0-7-1
Wastewater Characteristics
Sugar Industry
Characteristics
Industrial
Flow
BOD
TSS
TDS
Operation
SEA S 0 NA L 1
Cant inuolls-Vari ab le
Low-EXT. HIGH
Low-~XT. HIGH
HIGH
COD
G r it
Cyanide
C h lor i ne
pH
Demand
Low-:::XT.
PRESENT
Absent
HIGH
Neutral
HIGH
Color
Turbidity
Explosives
Dissolved Gases
Dete rgents
Low-HIGH
PRESENT
Absent
Absent
Absent
Foaming
Heavy Metals
Colloidal S01 ids
Volatile Organics
Pesticides
Absent
Absent
Low
Absent
Absent
Phosphorus
Nitrogen
Temperature
Phenol
Sulfides
DEFICIENT
DEFISIENT
HIGH
Absent
Absent
Oil & G rea se
Co 1 i form (F ec a 1 )
Co 1 i form (T a tal )
Absent
Absent
PRESENT
Industries which only process imported raw cane sugar
operate year-round.
2. Temperature higher than domestic wastewater May affect
design but not harmful to joint treatment processes.
NOTES: Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
in UPPER CASE.
\~astewater characteristics shown reflect all the in-
dustria] practices described under Section 2.
f)-7-5
-------
o
I
'-..J
I
0-
Pretreatment Unit Operations for the Sugar Industry
Suspended Biological System
coarse sol ids separation +
equ11 ization + grit removal +
sol ids ,eparation (1 ime
slurry)2
rixed Biological System
coarse sol ids separation
equal ization + grit rem0val
+ grit removal + sol ids 2
separation (1 ime slurry)
Independent
Physical-Chemical System
coarse sol ids separation
+ grit removal + sol ids 2
separation (1 ime slurry)
Equal ization may not be necessary, depending on specific physical-chemical processes used.
2
Grit removal and sol ids separation for 1 ime slurry may be combined.
-------
REFERENCES
1.
"State-of-Art, Sugarbeet Processing Waste Treatment," Water Pol-
lution Control Research Series, 12060 DSI 7/71, Environmental
Protection Agency, Washington, D.C. (1971).
2.
Force, S.L., "Beet Sugar Factory Wastes and Their Treatment-
Primarily the Findley System," Proc. 17th Ind. Waste Conf.,
Purdue University, 116-135 (196~
3.
Rogers, H.G., and Smith, L.H., "Beet Sugar Waste Lagooning,"
Proc. 8th Ind. Waste Conf., Purdue University, 136-147 (1953).
4.
Biglane, K.E., "Some Current Waste Treatment Practices in
Louisiana Industry, "Proc. 13th Ind. Waste Conf., Purdue
Un i ve r sit y, 1 2 - 2 0 (1 95 8) .
5.
"Industrial Wastewater Control ," (Ed.) Gurnham, C.F., Academic
Press, New York (1965).
6.
Kalda, D.C., "Treatment of Sugar Beet Wastes by Lagooning,"
Proc. 13th Ind. Waste Conf., Purdue University, 126-139 (1958).
D-7-7
-------
PETROLEUM REFINING INDUSTRY
1.
Industry Description
This industry includes Stand~rd Industrial Classification
(SIC) 2911. This classification includes those establishments
primari ly engaged in producing gasol ine, kerosine, fuel oi ls,
residual fuel oils, lubricants, and other products through
di sti llation of crude oi 1, cracking, or other processes.
Petroleum refining is a combination of several interdep~ndent
processes and operations, many of which are highly complex.
There are at least twenty separate processes fundamental
to the operation of a refinery producing the full spectrum
of products from crude oi 1 .
The major operations within a refinery include: crude oi 1
storage; desalting; fractionation by pressure, atmospheric
and vacuum distillation; thermal and catalytic cracking;
reforming; polymerization; and alkylation. Other incidental
operations, generally involving separation and finishing of
the products to specifications, include acid treatment of
lubricating oi 1 stocks, sweetening of gasol ine, extraction,
and stripping. Storage of crude oi 1 to provide ad~quate
working supplies and to equalize process flow involves the
separation of water and suspended solids from crude oi 1
The first major operation in a refinery is the crude oi 1
desalting process for removing inorganic salts and suspended
solids from the crude oi 1 prior to fractionation. Water
is used in the desalting process as a sequestering agent.
The crude oi 1 after desalting is generally passsed through
atomspheric and/or vacuum distillation to separate light
overhead products (C5 and lighter), side-stream disti llates,
and residual crude oi 1. Steam is used in this process,
and the steam condensate from the overhead accumulation is
discharged as wastewater.
The heavy fractions removed during the crude oi 1 fractionation
and disti 1 lation process can be cracked using either thermal,
catalytic, or hydrocracking processes to yield 1 ight oil
fractions such as domestic heating oi I. The low-octane
fractions obtained from the foregoing processes can be
converted to yield high-octane gasoline blending stock by
reforming, polymerization, and/or alkylation processes.
The reforming converts naphthas to finished high-octane
D-8-1
-------
gasoline. Reforming is a relatively clean process producing
a low volume of di lute wastewater. The polymerization
process produces wastewaters containing sulfide, mercaptans,
high pH materials, and nitrogen compounds. Phosphoric
acid or sulfuric acid is used in the polymerization process
and generates sol id wastes. The alkylation process uses a
sulfuric acid or hydrofluoric acid catalyst to convert
isoparaffins and olefins into high-octane motor fuel.
Solvent refining is used in a refinery to extract lubricating
oi 1 fractions and aromatics from feedstocks containing
various types of hydrocarbons.
A more detai led description of the individual petroleum
refining processes is included in the "Industrial Waste
Profi le" publ ished by the Federal Water Po] lution Control
Administration (now EPA) (1).
2.
Industrial Practices
The petroleum refining industry uses very large quantities
of water for process and cool ing purposes. Approximately
90 percent of the water used in refineries is for cool ing
purposes. Lesser water uses include: steam generation
(boi ler-feed.), di rect processi ng, fi re protection, and
sanitary uses. Steam is used in stripping and distillation
processes, where it comes in contact with petroleum
products, thereby contributing to the total wastewater
flow from refineries.
Oi ly process wastes and oi l-free wastes are collected
separately in some refineries so that the oi 1y wastes can
be treated for oi 1 removal before mixing with other waste
streams.
The spent caustics and spent acids are generally collected
and sold or disposed by other means. Few refineries
neutralize these wastes for discharge, to the wastewater
collection system.
The '0,-,,1- "/,'1ter (condensates from various fractionation units)
cont:'!; '1llHides and ammonia is generally steam or air-
strip,' , 'lore- being discharged to the sewer lines. A
"urvel (j' fJdi-oleum refining industries in 1967 indicates
n,]1: approximijtely 85 percent of the refineries strip the
sour walcr before discharging to sewer lines. Depending
on the pH of the sour water, the stripping can reduce the
sulfide and ammonia concentrations in the final effluent.
D-8-2
-------
In general, the in-plant control methods employed by the
industry (sour-water stripping, spent-caustic neutral ization
and oxidation, slop oil recovery, etc.) will determine
the final effluent chardcteristics and the level of pre-
treatment required for discharge to munici~al collection
system.
The technological advances in the refining process have
resulted in increasing amounts of by-product recovery and a
reduction in wastewater loading. Other advances in water
usage and cooling water recirculation have also resulted in
the reductions in volume of wastewater discharged per unit
volume of crude oi 1 processed. It has been reported that
the total effluent from older, typical, and newer refineries
are approximately 250,100 and 50 gal ./bbl of crude oil
respectively.
The f 0 1 I ow i n g s pee i fie i n - pIa n t p r act ice s are f r e que n t 1 y
employed:
a.
Sour-condensate stripping is used to remove sulfides
(as hydrogen sulfide, ammonium sulfide, and
polysulfides) before the wastewater enters the
sewer. The sour water is usually treated by strip-
ping with air, stream, or flue gas. Hydrogen sulfide
released from the wastewater can be recovered as
sulfuric acid or can be bu~ned in a furnace.
Hydrogen sulfides at concentrations in the range of
10 to 15 mg/L can cause upsets in biological treat-
ment plants (4), and removal of sulfides from the
sour water by stripping would prevent such upsets.
b.
Spent caustic neutralization is applied to both
phenol ic and sulfidic waste streams, but oxidation
of spent caustics is 1 imited to sulfide waste
streams, since phenols inhibit the oxidation of
sulfides in spent caus~ics.
c.
Spent acids (generally sulfuric) can be recovered for
reuse or sold to acid manufacturers, thereby avoiding
their discharge to s~wer systems. Spent catalysts
such as aluminum chloride and phosphoric acid can
either be regenerated for reuse or disposed of as
1 andfi 11 .
0-8-3
-------
3.
Wastewater Characteristics
The :haracteristics of the process wastewaters from the
industry are shown in Table 0-8-1. Practically all petroleum
refineries use gravity oi 1 separators to recover free oi 1
from process effluents. fhe effluents from gravity oi 1
separators are therefore used to define the wastewater
characteristics in the table.
The petroleum refineries operate on a continuous basis
throughout thc year exceDt for separate process shutdowns
for preventive maintenance and equipment repair and
rep cement. Many refineries have a segregated wastewater
collection system, with separate subsystems for clean
and polluted waste streams. The 'clean' waters may
include pollution-free cooling waters, boi ler blowdown,
and cooling tower blowdown.
The characteristics of wastewater drawn from storage tanks
wi 1 1 depend on the quality of the crude oi 1 stored and may
contain dissolved inorganics, oi 1, and suspended solids.
The steam condensate from the overhead accumulator can be
characterized as having oil, sulfides, mercaptans, and
phenol. If barometric condensers are used in vacuum
disti 1 lation, the condenser water wi 11 have very stable
oil in emuls:on. However, if the barometric condensers
are replaced ~y surface condensers, the condenser water
vvi 11 be essentially free of oi 1.
The major vlastewater from the al~ylation process is the
spent caustic from the neutral ization of the hydrocarbon
stream from the reactor. Even though the spent acids are
recovereo as salable by-product, leaks and spi 1 Is of acid
catalysts could reach the sewer lines. The major pollutants
from the solvent refining orocesses inslude solvents such
as phenols, glycols, and amines. Other processes for the
manufacture of waxes and as~halt, and for finishing and
blending of gaso1 ine, produce relatively low volu~es of
di lute wastewater.
In general, the most ::;qni ficant :>I-ocess waste~vaters from
petroleum refi~ing are: crude oi; desalting waste, storage
tank draw-off, steam conde~sate5, spent caustics, speGt
acids, product losses, and leaks and spi lIs of solventc,
used in extractiJn processes. The process wastewaters,
D-8-4
-------
which come in direct contact with petroleum hydrocarbons,
contain free and emulsified oil, sulfides, phenols, ammonia,
BOD. COD, heavy metals, and alkalinity as major waste
constituents.
The presence of oi 1 (free and
could vary between 30 and 200
gravity separators (3).
emulsified) in the wastewater
mg/L in the effluent from API
Refinery wastewaters generally are susceptible to conventional
biological treatment methods after adequate pretreatment.
In addition, phosphorus supplementation may be required in
some cases to provide a nutrient-balanced system for
biological treatment. This supplemental nutrient require-
ment wi 1 1 depend on the phosphorus content of the cooling
tower blowdown and its inclusion in the process wastewater.
4.
Pretreatment
The pretreatment unit operations for various types of joint
treatment facilities are shown in Table D-8-2.
These pretreatment operations were developed primarily
from information on separate treatment of these wastewaters
and assume the fol lowing industrial practices:
a.
Sour condensate stripping to reduce sulfides and/or
ammonia
b.
Spent-caustic neutralization
c.
Spent-acid neutralization and recovery or disposal by
other means
d.
Separate collection and disposal of acid sludges,
clay. and spent catalysts
e.
Gravity separation of free oil from process effluents
Depending upon the in-plant control methods used within a
refinery it may be necessary to add sulfide removal and
neutral ization to the pretreatment operations 1 isted in
Table D-8-2.
The oi 1 concentration in the wastewater should be reduced
to approximately 50 mg/L in order to insure trouble-free
operation in secondary biological treatment faci] ities.
In
D-8-5
-------
addition, the presence of oil in a municipal sewer would con-
stitute a fire and explosive hazard. For this reason, sewer
ordinances generally have prohibited the discharge of refinery
wastewaters to municipal facilities. A 1967 survey indicates
that only 1 to 2 percent of the refineries discharge their
effluent to municipal treatment systems.
Even though the current practice is to treat refinery effluent
on-site, it appears that joint treatment with domestic wastes
has a potential for adoption. The heavy metals present in
refinery effluents (As, Cd, Cr, Co, Cu, Fe, Pb, Ni, and Zn) are
generally in such low concentrations that they would not be a
problem for joint treatment. If heavy metals reduction should
be required by effluent guidelines, provisions should be made
for their removal before discharging to municipal systems. The
biological sludge developed from refinery wastewaters can be
thickened and dewatered by conventional methods (vacuum filters
and centrifugation).
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities"are shown in Table
0-8-2.
The technological advancements in the refining process have
resulted in increasing amounts of by-product recovery and a
concomitant reduction in wastewater loading. Other advances
in water usage and cooling water recirculation have also re-
sulted in the reductions in volume of wastewater discharged
per unit volume of crude oil processed.
The most prevalent in-plant treatment methods are sour-water
stripping, neutralization and oxidation of spent caustics,
ballast water treatment, and slop-oil recovery. These measures
substantially reduce the waste loadings and to a significant
degree are required to protect subsequent treatment. In addi-
tion to these in-plant control methods, practically all of
today's refineries use gravity oi 1 separators to recover free
oil from process effluents. For these reasons and because
the data available on raw wastewater characteristics are
limited, the effluents from gravity oil separators are used
to define the wastewater characteristics from petroleum refin-
eries.
0-8-6
-------
\,/astewater Characteri st ics'
Table 0-8-1
Petroleum Refining Industry
Characteri st ics
Industry Operation
Flow
BOD
TSS
TDS
COD
Grit
Cyanide
Chlorine
pH
Color
Demand
C>
I
(X)
I
---J
Turbidity
Explosives
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal S01 ids
Volatile Organics
Pesticides
Phosphorus
Nitrogen
Tempe ra t u re
Phenol
Sulfides
Oil & Grease
Coliform (Total)
"After gravi ty oi' separation (API Separators).
IThe refinery wastewaters have high COD/BOD ratios
21f cooling tower bJowdown is also discharged with
3Temperature higher than domestic wastewater. May
Year-Round
Continuous
Averagel
Low
HIGH
HIGH
PRESENT
Present
High
AC I 0 -ALKALI NE
Low
Low
PRESENT
Present
Low
Absent
PRESENT
Low
Present
Absent
DEFICIENT2
Adequate
HIGH3
HIGH
HIGH
HIGH
Low
indicating the presence of biologically resistant organic chemicals.
the process wastewater, phosphates may be present depending on water
affect design but not harmful to joint treatment processes.
treatment.
NOTES:
C~aracteristics which may require pretreatment or are significant to joint treatment plant design are shown
in UPPER CASE. Wastewater characteristics reflect all the Industrial Practices described in Section 2.
-------
Table D-8-2
1
Pretreatment Unit Operations for the Petroleum Refining Industry
Suspended Biological
System
Fixed Biological
System
Equal ization + Coagulation -
Solids Separation2 +
Neutralization
Equal ization + Coagulation -
S01 ids Separation2 +
Neutral ization
c::>
I
co
I
co
lpretreatment Unit Operations Apply to API Separator Effluent
2Combined with Oil Removal to insure oi 1 concentration below 50 mg/L
Independent Physical Chemical
System
Equalization + Coagulation -
Solids Separation2 +
Neutral ization
-------
REFERENCES
1.
liThe Cost of Clean Waters, Volume III, Industrial Waste
Profi le No.5, Petroleum Refining," U.S. Department of the
Interior, FWPCA, (1967).
2.
Nemerow, N.L., "Theories and Practices of Industrial
Treatment," Addison-Wesley Publishing Company, Inc.,
Reading, Mass. (1963).
Wa s t e
3.
Beychok, M.R., Aqueous Wastes from Petroleum and Petrochemical
Plants", John Wiley and Sons, New York, (1967).
4.
"Petroleum Refining Effluent Guidelines", Environmental
Protection Agency, Washington, D.C. (U~oublished)
0-<3-9
-------
MEAT PRODUCTS INDUSTRY
I.
Industry Description
This industry includes Standard Industrial Classification
(SIC) Nos. 2011, 2013, 2014, and 2094.
These classifications include slaughterhouses,
houses, processing plants (beef, poultry, hog,
and rendering plants.
packing-
and sheep),
Live animals are usually held in holding pens for less
than one day prior to slaughter. In the killing area,
the animals are slaughtered and the carcasses drained of
blood. The processes of skinning, defeathering or dehairing,
and eviscerating follow the slaughtering of the animals.
Depending on the desired product, carcasses may be cut
into smaller pieces, e.g. hogs are cut into parts such as
hams, sides, loins, and shoulders. These parts may be
further processed (e.g. smoked or pickled), or they may
be shipped directly to wholesalers without further processing.
Because of the simi 1arity of
products industry, there are
groups for this industry.
the wastewaters from meat
no separate pretreatment sub-
2.
Industrial Practices
The following industrial practices can significantly
influence the wastewater characteristics:
Sanitation Requirements
Unlike most other industries, the food industry is
required to maintain strict sanitary conditions, which
I imits the amount of process wastewaters that can be
recycled. The industry practices in-plant recovery
(e.g. blood or grease) to reduce wastewater strength.
In most plants, blood is collected and subsequently
processed. The recovery of blood represents an
in-plant practice which is extremely desi rab1e since
whole blood represents a BOD concentration of over
150,000mg/L (1).
I n add it i on, the dry hand 1 i ng of such \-vas tes as manu re
and bedding materials from holding pens, paunch
manure from eviscerating, and meat cuttings and
trimmings will significantly reduce the quantity of
waste materials discharged to the sewers. Implementa-
tion of these practices wi I 1 affect the concentration
and quantity of waste constituents, but not the
quantity of wastewater.
D-9-1
-------
Rendering
Rendering is a major unit process where in-plant
modifications can significantly influence the pre-
treatment considerations. Wet and dry rendering are
two subprocesses presently used within the industry.
In the wet process, the meat by-products in a batch
tank are cooked by direct injection of steam. Dry
rendering uses only heat, and 1 ittle wastewater is
produced. In wet rendering, the sol ids in the water
phase are screened out, and the remaining tank water
may be evaporated or sewered. The tank water is a
major source of organic pollution, when sewered, and
has a BOD value of approximately 45,000 mg/L (2).
Evaporation of wet-rendering tank water and the
installation of entrainment separators on barometric
condensers may reduce the need for pretreatment of
wet-rendering process wastewaters.
Wastewater Segregation
Wastewater originating within a meat products plant wi 1 1
generally be made up of wastewater from the operations,
sanitary wastes, and wastewaters from auxiliary sources
(e.g. cool ing water from ammonia condensers in the
refrigeration systems). Many large plants providing their
own complete or partial treatment have found it economical
to segregate wastewaters into blood, clean water, manure-
free water, and manure waters.
3.
Wastewater Characteristics
The ch~racteristics of wastewaters from the meat products
industry are shown in Table D-9-1. The meat products
industr/ ;, :1 year-round oper.ation with daily operation
on an in':rrnittent basis. Plants usually shut down daily
for an e~tensive clean-up period fol lowing the processing
pel-i0'J. This practice results in the generation of
intermittent wastewater flows.
Each plant may have a number of operations, depending on
the products and degree of processing. However, the
wastewaters generated from any meat products plant can
be characterized as containing high concentrations of
BOD, COD, TSS, TDS, and grease. Washdown of holding pens,
mainly to remove manure and urine, will add to the BOD
and suspended sol ids concentrations.
D-9-2
-------
The processes of skinning, defeathering or dehairing, and
eviscerating are sources of BOD, grease, and suspended
sol ids. The disposal of paunch manure and the washing
of carcasses during eviscerating are particular operations
which generate substantial pollutants. The processing
of hogs and fowl produce a floating s01 ids problem
caused by hair and feathers.
Dressing and processing operations are minor wastewater
sources compared to the slaughterhouse operations.
Wastewaters from these operations contain grease and
solids originating from equipment washdown and product
losses. Druing these operations, various trimmings, fat.
and fleshings are produced
Considerations in the joint treatment of meat product
wastewaters with domestic wastes are the high chlorine
demand, the presence of surface-active agents, fecal
coli rorm, intermittent flows, and the high septicity
potential due to the high organic content of meat product
wastewaters. In general, meat product wastewaters are
amenable to either biological or chemical treatment.
4.
Pretreatment
The pretreatment unit operations which may be necessary
for various types of joint treatment processes are shown
in Table 0-9-2.
In addition to screening
various in-plant control
and separate handl ing of
would greatly reduce the
wa s t ewa t e r s (3).
and free-floating grease removal,
practices, such as blood recovery,
paunch manure as sol id waste
waste constituents in process
When the ratio of meat product wastewater to domestic
wastewater is over 50 percent, pretreatment should
include equalization to reduce organic and hydraulic
fluctuations. The equalization basin should be aerated
to prevent septic conditions.
0-9-3
-------
TABLE 0-9-1
Wastewater Characteristics
Meat Products Industry
Characteristics
Meat Products
Industry
Flow
BOD
TSS
TDS
Operation
Year-round
I NTERM I TTENT 1
H I G H - E XT. H I G H
HIGH
HIGH
Demand
HIGH -
Absent
Absent
HIGH
Neutral
COD
Grit
Cyanide
Chlorine
pH
E XT. H I G H
Color
Tu rb i d i ty
Explosives
Dissolved Gases
Detergents
HIGH
High
Absent
Absent
Present
Foam i ng
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Absent
Absent
HIGH
Absent
Absent
Phospho ru s
Nitrogen
Temperature
Phenol
Sulfides
Present
Present 2
Normal-High
PRESENT3
Absent
Oil and Grease
Coliform (Fecal)
PRESENT
PRESENT
lWastewater flow is intermittent over the day or week.
2
Temperature equal to higher than domestic wastewater; may
affect design but not harmful to joint treatment processes.
3Phenols may be present in sanitizers used for clean-up.
NOTES:
Characteristics which may require pretreatment or are
significant to joint treatment plant design in UPPER CASE.
Wastewater characteristics shown reflect all industry
practices described in Section 2.
0-9-4
-------
TABLE 0-9-2
Pretreatment Unit Operations for the
Meat Products Industry
Suspended Biological System
Fixed Biological System
Independent PhysicaJ-
Chemical System
Coarse Sol ids Separation +
Grease Remova 12
Coarse Sol ids Separation +
Grease Remova12
Coarse 501 ids Se~aration
+ Grease Removal
o
I
\.D
I
VI
lAssumes in-plant recovery and separate handl ing of blood, manure, and paunch manure.
2
Only free-floating oi 1 and grease.
-------
REFERENCES
1. "The Cost of Clean Water, Volume_III, Industrial Profile
No.8 - Meat Products~ Federal Water Pollution Control
Administration, Washington, D.C., (September 1967).
2.
"Industrial Waste Study of the Meat Products Industry",
Contract No. 68-01-0031, Environmental Protection Agency,
Washington, D.C., (unpublished).
3.
"Industrial Wastewater Control",
Academic Press, New York (1965).
(Edited by) Gurnham, C.F.,
0-9-6
-------
GRAIN MILLING INDUSTRY
I.
Industry Description
This industry includes Standard Industrial Classification (SIC)
2041, 2044, and 2046. These classifications include milling
flour or meal from grains, by either dry or wet processes.
The major grain milling establ ishments process corn, wheat or
rice. Dry corn mill ing involves grinding and processing corn
for the production of corn meal, flour, grits, and related
products. Wet corn milling involves the separation of corn
into several components such as starch, syrup, animal feeds,
and various other products. Wheat milling generally uses a
dry cleaning process. Par-boiling of rice is a wet process
for boiling rough rice to force nutrients in the bran into
the grain. The par-boiled rice is then milled to remove the
i ned i b 1 e hu 11 and the bran.
Because of the similarity of the wastewaters from
segments of the grain mill ing industry, there are
pretreatment sub-groups for this industry.
the various
no sepa rate
2.
Industrial Practices
----------
The following industrial practices can significantly influence
pretreatment.
Dry Co rn Mill i nq
The smaller plants use dry cleaning processes and produce only
ground whole corn meal. The large plants, however, wash the
corn prior to tempering and mill ing, to produce a variety of
products. Water used to wash the corn is separated in centri-
fuges. The spent wash water, which constitutes the major
wastewater source in a dry grain milling operation, is gen-
erally screened before being discharged to the sewers, and
the screenings are recovered to prepare animal feeds. If
corn oil is also produced (only in larger mills), steam and
cooling water will be required to separate the oil from the
solvent by evaporation. As a result, auxil iary wastewaters
from water treatment, boiler blowdown, and cooling water will
be discharged from mills producing corn oil.
Wet Corn Mil~
The dry cleaned corn is steeped first in circulating water
containing S02 for 30 to 40 hours. The 1 ight steep water is
removed and concentrated by evaporation for use in preparing
animal feeds. The evaporator condensates and starch filtrates
0-10-1
-------
constitute major wastewater sources from this industry. Small
quantities of wastewater are added to the above source from equip-
ment cleaning and washing operations. The starch slurry remaining
after the separation of hulls, fiber, and germs is either used as
starch or converted to syrup. The conversion of starch to acids.
Even though the conversion of starch slurry to syrup and sugars
(dextrose, lactic acid, etc.) generates large quantities of
wastewater, these are generally reused for steeping corn and
therefore cause only small quantities of wastewater to be discharged.
Wheat Mill inq
The dry process for milling and cleaning wheat produces no
significant quantities of process wastewater. Only 5 percent
of the wheat mills in the United States use water for c1ean-
ing wheat, and these wastes are discharged to municipal sewers.
The manufacture of bulgur may produce a wastewater stream if
the water is drained from bulgur wheat. However, most mil Is
vent the moisture to the atmosphere during the drying and
therefore do not produce any 1 iquid wastes. In general,
most grain mills processing wheat do not generate any 1 iquid
wastes,and those that employ wet cleaning of wheat discharge
the wastewaters to municipal collection systems. Only five
mills (estimated) in the United States make wheat starch from
wheat flour. The wastewater from wheat starch production is
~imilar to those from corn starch preparation (1).
Rice Mill i nq
Rice milling generates wastewater only from the par-boil ing
operation. The spent cooling water is the principal waste-
water generated from rice milling operations. Auxiliary
wastewaters in rice mi 11 ing industry result from water soften-
ing and boiler blowdown operations. The process wastewater
(spent cooking 1 iquor) is usually discharged to a municipal
collection system.
3.
Wastewater Characteristics
The characteristics of the wastewaters from the grain milling
industry are shown in Table D-IO-l. Most grain mills generate
wastewater with similar pollutants and treatability character-
is tics.
Grain mills discharge wastewater varying in concentration and
flow. Most mills operate 5 to 7 days per week, and 24 hours/day,
and the operations are continuous batch-type. As a result, the
wastewater quantity and characteristics are subject to hourly
and daily variations. In addition, the starch-syrup plants may
D-10-2
-------
use different grains and product mixes at various times, thus
contributing to the variations in wastewater volume and loading.
the wastewater is generally rich in carbohydrates. However,
nutrient addition may be required for specific cases.
The grain mil ling industry generates wastewater from wet clean-
ing, oil extraction,and starch and syrup manufacturing opera-
tions. repending on the product mix and the type of grain used
(corn, wheat, or rice), the wastewater characteristics vary
widely within the industry. In general, the wastewaters
constituents include: COD, BOD, suspended solids, heat, and
acidity. The BOD and COD of the wastewater are attributed
primari 1y to the presence of starch, carbohydrates, and
pro te ins (1,2).
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment faci1 ities are shown in
Table rl-10-2. The level of pretreatment requi red wi 11 depend
on the abil ity of the joint treatment faci 1 ity to absorb
shocks of varying wastewater volume and loading (3). Waste-
waters resul ting from starch production are s1 ightly acidic
(pH 4 to 5) and therefore may require neutral ization prior
to discharging to municipal systems (4)-
D-10-3
-------
TABLE 0-10-1
Wastewater Characteristics
Grain Mill Industry
Characterist ic
Industry
Flow
BOD
TSS
TDS
Operation
\ ea r-Round
CONT I NUOUS
HIGH- EXT, HIGH
Low- EXT. HIGH
High
COD
G r i t
Cyanide
Chlorine
pH
Demand
HIGH- EXT, HIGH
Present
Absent
High
PIC 10 I C-ALKAL I NE
Color
Turbidity
Explosives
Dissolved Gases
Detergents
Absent
Present
Absent
Absent
/\bsent
Foaming
Heavy l1etals
Colloidal Sol ids
Volatile Organics
Pesticides
Absent
Absent
Present
Low
Absent
Phosphorus
Nitrogen
Temperature
Phenol
Sulfides
Low-Adequate
Low-Adequate
High
Absent
Absent
Oi 1 and Grease
C01 iform (Total)
Absent
Present
Higher temperature than domestic wastewaters. May effect
design but not harmful to joint treatment processes.
NOT ES :
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown in
UPPER CASE.
Wastewater characteristics shown reflect all industrial
practices described in Section 2.
0- 1 0 -4
-------
Table D-10-2
Pretreatment Unit Operations for the Grain 1'lill Industry
Suspended Biological System
Coarse Sol ids Separation +
Equal ization +
Neutral ization
CJ
I
o
I
\J1
Fixed Biological System
Coarse Sol ids Separation +
Equalization +
Neutral ization
Independent
Physical/Chemical System
Coarse Sol ids Separation +
Equalization +
Neutral ization
-------
REFERENCES
1.
"lndustria1 Waste Study Report - Grain Mill inq Industry",
Environmental Protection Agency, Washington, D.C.,
(unpub 1 i shed).
2.
Ling, J. T., "Pi 10t Investigation of Starch - Gluten Waste
Treatment", Proceedinqs 16th Industrial Waste Conference,
Conference, Purdue University, 515-525 (1967).
3.
Wi11enbrink, R.V., "Waste Control and Treatment by a Corn
and Soybean Processor", Proceedings 22nd Industrial Waste
Conference, Purdue University, 515-525 (1967).
4.
Jeyfriend, C.F., "Purification of Starch Industry Wastewater",
Proceedings 23rd Industrial Waste Conference, Purdue
University, 1103-1119 (1968).
0-10-6
-------
FRUIT VEGETABLE INDUSTRY
1.
Industry Description
This industry includes Standard Industrial Classifications
(SIC) 2033, 2034, 2035, and 2037. These industrial
classifications include the processing of fruits and veget-
ables, including cleaning, sorting, sizing, peeling, stabiliz-
ing, and final processing.
Because of the simi larity of the pollutants significant to
pretreatment of wastewaters from the various segments of the
fruit and vegetable industry, there are no separate pretreat-
ment sub-groups for this industry.
Washing is a unit process integral to al I fruit and vegetable
processing. Wash water is used to remove dirt, insects,
and residual pesticides. Root crops, such as potatoes and
carrots, have greater amounts of dirt than fruits and
vegetables grown above ground.
Sorting is ~erformed (usually manually) to remove inferior
fruits and vegetables, which are then directed into end
products which are not sensitive to appearance. Conveyance
between unit processes is often done in flumes to prevent
damage to the product and to minimize the deteriorating
effect that air has on many products, e.g., apples turn
brown in the presence of air.
Separation of fruits and vegetables into desired size
ranges is generally performed by using mechanical equipment.
Peel ing, when required, is accomplished by either
mechanical abrasion, by chemical (lye) treatment, or by
steam. An experimental method of dry caustic peel ing
has been evaluated successfully for pears, peaches,
potatoes and beets (I). Mechanical abrasion uti I izes
contoured knife peelers adjusted to maximize product yield
for the particular size of product being processed.
Steam and hot lye peel ing depend on water sprays to remove
the softened skin. Hot lye solutions may be sewered as
frequently.as after each work shift (2).
The peel ing process represents a substantial source of
pollutants, principally soluble, including: sugars,
starches, and carbohydrates leached from the fruits and
vegetables; and insoluble waste sol ids. The form of the
final product is also a factor in the relative quantity
of pollutants generated. For example, fruits are generally
marketed in a whole, halved, quartered, or diced form.
The greater the exposed area (diced vs. halved), the
greater the extent of leaching of pollutants from the product.
D-11- 1
-------
Stabi I izing of the fruit or vegetable to preserve its
quality may be accompl ished by blanching or pasteuriza-
tion. Blanching is accompl ished with steam, to expel air
and inactivate enzymes which would cause color
change and wilting. Generally, only juices and some
commodities are pasteurized to prevent deterioration.
Fruit and vegetable processing can also include canning,
frying, freezing, or dehydration. Canning can also in-
volve cooking, which is done in a pressurized steam
cooker; thereafter. the Cqns are cooled with water before
being labeled and packed in cartons.
2.
Industrial Practices
The following industrial practices can significantly infl
influence pretreatment:
Trimming and Peel ing Wastes
Trimmings and other large sol ids should be handled as
a dry sol id waste and not sewered. This practice
would affect the pretreatment screening requirements.
Wash Water Recycle
A closed wash water recycle system with separate
grit disposal wi1 1 generally preempt grit removal
as a pretreatment requirement.
Peeling Process
The substitution of another peeling process for lye
treatment may null ify the need for neutralization
faci I ities for pH adjustment.
Washing Operation
Reduction of wastewater quantities is critical in
order to obtain a minimal capital investment for
pretreatment facil ities. Counter-current flow
during the washing operation has been credited with
substantially reducing the overall volume of wash
water. In addition, low-volume, high-pressure
sprays have been successfully employed in various
establ ishments.
3.
Wastewater Characteristics
The characteristics of the wastewaters from the processing
fruits and vegetables are shown in Table 0-11-1. The
0- I 1-2
-------
Fruit and vegetable industry is a seasonal operation,
usually corresponding to the local growl ing season.
Within this industry one particular cannery may process
more than one fruit or vegetable, e.g. corn in summer
and apples in the fall. In addition, apples and potatoes
are stored under controlled temperature and humidity,
with the overal I effect of prolonging the industry
operation. This industria1 category can be classified
as a continuous operation, with the exception of fruits
and vegetables that are pick1ed or cooded. These latter
processes are batch types. In general, the wastewaters
from this industry are high in BOD, COD, TSS, and grit
(3,4) .
4.
Pretreatment
The pretreatment unit operations which may be necessary
for various types of joint treatment processes are shown
in Table 0-11-2. Water re-use and process equipment with-
in each plant will dictate the pretreatment and subsequent
treatabi I ity. In general, fruit and vegetable wastewaters
are amen3ble to either biological or chemical treatment (5).
Design consideration in the joint treatment of vegetable and
fruit wastewater with domestic wastes should include the
high chlorine demand, presence of surface-active agents,
nutrient deficiency, and pH variabil ity. Pesticides may
have ever been sprayed with a long-life pesticide. There
is no substantial information at present on the measurable
quantities of pesticides in the wastewaters.
0-11-3
-------
TABLE D-11-1
Wastewater Characteristics
Fruit and Vegetable Industry
Characteri sti cs
Industrial
Flow
BOD
TSS
TDS
Operation
SEASONAL
INTERMITTENT
Average-EXT. HIGH
Average-EXT. HIGH
Average-HIGH
COD
G ri t
Cyanide
Chlorine
pH
Demand
Average-EXT. HIGH
PRESENT
Absent
Average-HIGH I
ACID-ALKALINE
Color
Turbidity
Explosives
Dissolved Gases
Detergents
(HIGH2)
Present
High
Absent3
Absent
PRESENT
Foami ng
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Absent
Absent
Average
Absent
Absent-Present
Phosphorus
Nitrogen
Temperature
Phenol
Sulfides
DEFICIENT
DEFICIENT 4
Norm a 1 - H i g h
Absent
Absent
Oi 1 & Grease
Fecal Coliform
Absent
Absent
I.
Fruit and tomato wastes are generally acidic; however, the
pH of the wastewater is affected by the peeling process,
e.g., lye peel ing.
Beet processing wastewaters are characterized by a red color.
Free SO may be dissolved in maraschino cherry brine.
Temperature equal to or higher than domestic wastewater. May
affect design but not harmful to joint treatment processes.
2.
3.
4.
NOTES:
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
in UPPER CASE.
Wastewater characteristics shown reflect all the
industrial practices described in Section 2.
D-11-4
-------
TABLE D-II-2
Pretreatment Unit Operations for the Fruit and Veqetable Industrv
Suspended Bioloqical System
o
I
Coarse Sol ids Separation + 1
Grit Removal + Neutral ization
I
~
1.
Fixed Bioloqical System
Coarse Sol ids Separation +
GritlRemoval + Neutral iza-
tion
Neutralization is dependent on commodi ty and peeling process employed.
Independent Physical
Chemical System
Coarse Sol ids Separation
+ Grit Rrmoval + Neutra-
l ization
-------
REFERENCES
1.
Industrial Waste Study - Canned and Frozen Fruits and
Vegetahles, Contract No. 68-01-0021, Environmental
Protection Agency, Washington, D.C. (unpublished).
2.
"Industrial Wastewater Control",
Academic Press, New York (1965).
(Edited by) Gurnham, C.F.,.,
3.
"Uti 1 ization of Cannery Frui t Waste by Continuous Fermenta-
tion", Bulletin No. 207, Washington State Institute of
Technology, Pullman, Washington (March 1950).
4.
"Treatment of Citrus Processinq Wastes", Water Pollution
Control Research Series 12060, Environmental Protection
Agency, Washington, D.C. (1970).
5.
"The Cost of CJean Water, Volume III, Industrial Waste
Profile No.6 - CAnned and Frozen Fruits and Veqetables",
Federal Water Pollution Control Administration ~June 1967).
0-11-6
-------
BEVERAGES INDUSTRY
I.
Industry Description
This industry includes Standard Industrial Classification
(SIC) 2082, 2083, 2084, 2085, 2086, and 2087.
These industrial classifications include all establishments
engaged primari ly in the manufacture of malt, malt beverages
(ale. beer, and malt liquors), wines (table wine, dessert
wine, and brandy), disti I led spi rits, bottled and canned
soft drinks, and flavoring extracts and syrups.
The products described
major groups according
p roces ses as:
above can be classified under two
to their basic manufacturing
1.
Fermentation Products (beer, wine, distil led spirits,
malt)
Extraction Products (soft drinks, flavors, and extracts)
2.
The fermentation products are made from grains or fruits,
whi le the extraction products are made from flavor sub-
stitutes of oi ls such as cocoa, vani I la, and orange oil.
The fermentation products derived from grains are manu-
factured by cooking the grains, fermenting the cooking
1 iquor with a yeast culture, and separating the fermented
alcohol by clarification and filtration.
The manufacturing processes used for the production of
flavoring extracts and syrups are proprietary in nature.
The basic processes for the recovery of natural flavoring
can be 1 isted as fol lows:
1.
Steam distillation and petroleum ether extraction
(essential oils).
2.
Expression (hydraul ic pressing) and petroleum
ether extraction (fruit syrup).
3.
Expression and evaporation (jams).
4.
Alcoholic extraction of vanilla and other tissue.
The soft drink bottl ing and canning plants use flavor extracts
and purchased syrups. The bottl ing and canning process
involves bottle washing and steri I izing, mixing of flavor
extracts and syrup, carbonation, and fi I 1 ing.
The pretreatment sub-groups for this industry are as follows:
[-12- I
-------
Malt, malt beverage, and distilled spirits (except
industrial alcohol).
Wine and brandy.
Bottled and canned soft drinks, and flavors and syrups.
2.
Industrial Practices
During the brewing and fermentation process, malt and
hops are added to convert starch to sugar and to incor-
porate a bitter tas te to the product. Water is used in the
process for cooking, cool ing, container washing and other
miscellaneous uses. Both sol id wastes and 1 iquid wastes
are generated in the process. Spent grains, excess yeast,
and spent hops are the sol id wastes, and are generally
hauled away or dried for 1 ivestock and poultry feed. The
only variation of this type of disposal is where certain
small distilleries manufacturing distil led wine or spirits,
the stillage is discharged with other 1 iquid wastes. Liquid
process wastes result from fermentation, aging, filtration
and evaporation, and washing and clean-up operations (1,2).
Liquid wastes are also discharged from auxil iary operations
such as cooling, boiler blowdown, and water softening.
The fermentation process results in the generation of
"lees", which is a mixture of wine, yeast ceels, and
other sediment. The lees is considered a 1 iquid or
semi-l iquid waste, which is either discharged directly
to the sewer or recovered in the case of large wineries.
In order to improve the qual ity of the wine, the fermented
1 iquid is often processed by a sequence of racking,
filtration, and fining operations. The wastes from racking
(clarification) and filtration often produce a sludge
containing significant quantities of wine. When these
wastes are sewered, they add significantly to the BOD and
sol ids concentration of the wastewater. Brandy is produced
by distillation of wine and condensation of the overhead
in order to obtain a beverage with high alcohol content.
The stillage from such distillation is a very significant
1 iqu id waste (3,4).
The manufacture of flavoring extracts and syrups also
generates both 1 iquid and sol id wastes. Sol id wastes
the residues after extraction of flavors and syrups.
waters from normal extraction operations are:
are
Waste-
Fruit Expression:
1.
2.
Water used for washing fruits.
Hydraul ic press clean-up.
0-12-2
-------
Evaporation:
I .
2.
Evaporator condensate.
Kettle wash water.
Steam ~istillation:
1 .
2.
Boiler blowdown.
Bottoms from packed column.
The major wastewater sources in the bott1 ing industry are
the bottle washing and clean-up operations. Auxil iary
wastewaters such as cool ing, air conditioning, and boiler
blowdown are also generated (5).
The predominant method of disposing of liquid wastes from
beverage plants is by discharging to municipal sewerage
systems. A typical plant collects all its wastewaters
in a common sewer and discharges them to municipal sewers.
3.
Wastewater Characteristics
The characteristics of process wastewaters from each
pretreatment sub-group are shown in Table 0-12-1.
The beverage industries generally operate throughout the
year. However, the volume of waste production and the
loading will vary with the season depending upon product
demand. A recent survey of the malt beverage industry
indicates that wastewater volume and load both peak during
the summer months, and are lowest during the winter months.
This is probably due to the schedul ing of production in
response to demand and usage.
Major considerations in the joint treatment of beverage
wastewaters are the presence of large particulate
matter in suspension and the fluctuations in hydraul ic
and organic loads. The follwing is a brief description
of the wastewater from each pretreatment group:
1 .
Malt Oeverages and Oisti I led Spirits
The wastewaters generated from the mal t and malt
beverages industries have as major constituents BOD,
55, pH and temperature. The waste sol ids from the
malt house, and the excess yeast, spent grains, and
spent hops from the malt beverages industry are
disposed of either by haul ing away or by on-site
drying to make cattle feeds. If the spent wet grain
is dried in the brewery, the spent grain 1 iquid must
be disposed of; generally, it is discharged to
municipal sewers without pretreatment.
0-12-3
-------
The distilleries produce wastewaters from cooking and
fermentation of grains, the stillage or slops from.
distill ing operations, and from washing and bottl ing
operations. The stillage from the distilleries
contain yeast, proteins, and vitamins. Depending
upon the size of the plant, complete or partial
recovery of stillage is practiced. The major
constituents in distillery wastewaters include BOD,
suspended sol ids, acidity, and heat.
"
t. .
Wi ne and Brandy
The wine and brandy industries produce wastewaters
from crusher-stemmer, pressing, fermentation,
clarification and filtration, distillation, and
bottl ing operations. Brandy is manufactured by
distillation of wine and, therefore, results in the
generation of stillage or "still slop". The stillage
is a very significant I iquid waste in the manufacture
of brandy. The wastewaters are high in organics and
have the potential of introducing shock loads in joint
treatment works (3).
3.
Soft Drinks, Flavors. and Syrups
The wastewaters generated from the manufacture of
flavor extracts and syrups are generally discharged
to municipal sewerage systems without treatment.
Very I ittle work, if any, has been done to del ineate
the characteristics of the wastewater from this
segment of the industry. The bott! ing and canning
of soft drinks generate wastewaters primarily from
bottle-washing operations. These wastes contain
BOD, suspended solids, and alkalinity. Some bottling
industries practice recirculation of final rinse
water for pre-rinsing, thereby reducing the volume
of wastewater discharged to the sewers (5).
4.
Pretreatment
Available information in the I iterature indicates that
pretreatment in the form of screening, grit removal, and
equal ization are practiced by some industries.
The pretreatment unit operations shown in Table D-12-2 are
based upon total process wastewater discharge from all unit
operations within the industry. The addition of auxiliary
wastes (cooling, boiler blowdown, and water softening)
will lower the strength of total effluent from the
industry. In general, the wastewarers from the beverage
industries are amenable to treatment by conventional
D-12-4
-------
processes, such as activated sludge and trickling filters.
The pretreatment unit operations reconllT:ended in Table 0-12-2
are based on the assumption that the fol lowing in-plant
pollution control methods are practiced:
I.
Haul ing or drying of spent grains, hops, and stillage.
2.
Separate sol ids-handling and disposal of crusher-
stemmer and pressing wastes.
Spent grains, hops, stillage, crushe(-sternr'IEr, and pressing
wastes can be characterized as sol id wastes rather than
liquid wastes. Therefore, it is desirable to collect
them separately for disposal.
Wastes from the malt industry have been successfully
treated even when they constitute 45 percent of the
total flow and 76 percent of the total BOD loadings in
joint treatment works (2). Similar results have been
reported for the joint treatment of malt beverage waste-
waters when they form 4.2 percent of the total flow and
25 percent of the total organic loading (2). These results
suggest that in a well designed and well operated joint
treatment works, the beverages industrial wastes are
similar to domestic wastes, and that the ratio of industrial
wastes to domestic wastes does not significantly influence
the treatability characteristics of the combined waste.
However, it may be necessary to provide supplemental
nutrients (nitrogen and phosphorus) in joint treatment
f ac i 1 i tie s .
0-12-5
-------
TABLE 0-12-1
Wastewater Characteristics
Beverages Industry
Characteristics
Malt Beverages and
Di sti 1 led Spi ri ts
Wine and Brandy
I. I
Soft Drinks Bott Ing
Operation
Year-round 2
INTERMITTENT-Continuous
HIGH
LO~I to HIGH
High
SEASONAL
I NTERMI TTENT
HIGH-EXT. HIGH
Low to oXT. HIGH
High
Year-round
INTERMITTENT
Average to HIGH
Low to HIGH
Low to Hi gh
Industry
Flow
BOD
TSS
TDS
COD
Grit
Cyanide
Chlorine
pH
Demand
HIGH
PRESEN T
Absent
No Data
ACID-NEUTRAL
HIGH-~XT. HIGH
PRESENT
Absent
No Data
ACID-ALKALINE3
Average to HIGH
PRESENT
Absent
No Data
ALKALI NE3
Color
Turbidity
Explosives
Dissolved Gases
Detergents
Present
Present
Absent
Present4
Present
Present
Present
Absent
Absent
present4
Present
Present
Absent
Present
Present4
Foaming
Heavy Metals
Colloidal Solids
Volati Ie Organics
Pesticides
Present
Absent
Present
Present
Absent
Present'
Absent
Present
Present
Absent
Present
Absent
Present
Present
Absent
Phosphorus
Nit rogen
Temperature
Phenol
Sui fides
DEFICIENT
DEFIC lENT 5
Normal-High
Absent
Ab s en t
DEFICIENT
DEFI~IENT
High
Absent
Absent
DEFICIENT
DEFICIENT
Normal
Ab sen t
Absent
Oi I and Grease
Coliform (Fecal)
Col iform (Total)
Absent
Absent
Present
Absent
Ab sen t
Present
Absent
Absent
Present
Ipol lutants characteristics represent only Botti ing Industry; no data avai lable for flavors and syrups.
2Malt Lav~rages generate wastes on a continuous basis; distil led spirits waste flow wi 1 I be cycl ic.
3Alkal ine I'H due to caustic detergents used for bottle washing.
4Surface active agents are discharged primari Iy from bottle washing.
5Temperature equal to or hiqher than domestic wastewater; may affect design but not harmful to
joint treatment processes.
NOTE:
Characteristics which may requi re pretreatment or are significant to joint treatment
plant design are shown in UPPER CASE.
Wastewater characteristics shown reflect the industrial practices described in
Section 2.
D-12-6
-------
Pretredtment 5uh-Group
Malt Beverages
Wine and Brandy
CJ
I
N
I
'-.i
Soft Drinks Bottling
TABLE D-12-2
Pr-etr,-,atment IJnit Operations for the Bevaerages Industry
Susrended
Biolugical System
Coarse Solids SepC1ration
+ Grit ~emovC11 + Equal-
ization + Neutral ization
Coar-se So 1 ids Separat ion
+ Grit Removal + Equal-
ization + Neutralization
Grit Removal +
Neutral ization
rixed
Biological System
Coarse Solids Separation
+ Grit Removal + E~ual-
ization + Neutral ization
Coarse So 1 ids Separat i on
+ Grit Removal + Equal-
ization + Neutralization
Grit Removal +
Neutral ization
Independent Physical-
Chemical System
Coarse 501 ids Separation
+ Grit Removal + Equal-
ization + Neutral ization
Coarse Sol ids Separation
+ Grit Remo,-al+ Equal-
ization + Neutral ization
Gri t Removal +
Neutra 1 i zat ion
-------
RE FERENCES
I.
'~ndustrial Waste Survey on Malt Liquor Industry~ prepared
for the Environmental Protection Agency by Aware, Inc.,
Nashv ill e, Tennes see (unpub 1 i shed) .
2. "Industrial \./aste Survey of the Malt
the Environmental Protection Agency
Nashville, Tennessee (unpublished).
Industry~ prepared for
by Aware, Inc.,
j. "Industrial Waste Survey of the Wine Industry',' prepared
for the Environment",] Protecti('Jn Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
4. "Industrial Waste Survey of Distilled Spirits Industry','
prepared for the Envi ronmenta] Protection Agency by
P,ware, Inc., Nashvi I Ie, Tennessee (unpub1 ished).
5. "A Report on Bottled and Canned Soft Drinks SIC 2086 and
Flavoring Extracts and Syrups SIC 2087',1 prepared for the
Envi ronmental Protection Agency by Aware, Inc., Nashvi 11e,
Tennessee (unpubl i shed).
[)-12-8
-------
PLASTIC AND SYNTHETIC MATERIALS INDUSTRY
Industry Description
This industry includes Standard Industrial Classifications
(SIC) No. 2821, 2823, and 2824. These classifications include
the manufacture of plastic and synthetic materials, but not
the manufacture of monomers, formed plastic products (other
than fibers), and paint formulations. The manufacture of
resins used in paints is also included.
Plastics and resins are chain-like structures known chemically
as polymers. All polymers are synthesized by one or more of
the following processes: bulk, solution, emulsion, and
suspension. After polymerization, the products undergo
separation, recovery, and finishing before being marketed.
There are numerous plastics and synthetics manufactured in
this industry. For these guidelines, a national production
volume of greater than 50 mi l1ion pounds per year was
selected as the criterion for inclusion of a polymer.
Based on the wastewater characteristics and treatabil ity
information, the industry is divided into the fol lowing pre-
treatment sub-groups:
Pretreatment Sub-Group
Rayon Fibers
Nylon Fibers
2
High- and Low-Density
Polyethylene Resins
3
Urethane Resins
Polyolefin Fibers
Polyvinyl Acetate
Polyvinyl Alcohol
Polyester Fibers
Resins
Resins
4
Cellulosic Resins
Cellophane
Polypropylene Resins
Cellulose Acetate Fibers
Polyvinyl Chloride Resins
Polystyrene
ABS, SAN Resins
Phenol ic Resins
Nylon Resins
Po1yacetal Resins
Acrylic Fibers
0-13-1
-------
2.
Industria1 Practices
The fol lowing industrial practices can significantly influence
the wastewater characteristics.
Suspension Polymerization
In suspension polymerization, a monomer (e.g. vinyl acetate)
is dispersed in a suspending medium consiting of a mixture of
water and suspending agents such as polyvinyl alcohol, gelatin,
etc. The suspension is heated, and polymerization occurs.
The polymer is then separated in a centrifuge, washed, and
dried in rotary driers. The centrate from the separation
process may contain suspending agents, surface-active agents,
catalysts, (e.g. benzoyl, lauroyl) and small amounts of unreacted
monomer (1).
Emulsion Polymerization
Emulsion polymerization consists of solubil ization and dispersion
of the monomer in a solvent (e.g., water, cyclohexane, or
tetrahydrofuran) with the appropriate emulsifiers (e.g., soaps
or surfactants). Before polymerization occurs, initiators
such as persulfates, hydrogen peroxides, etc. are added. When
polymerization is complete, the product is a mi lk-like latex
of permanently dispersed polymer, from which the polymer
particles are recovered, generally by spray drying or by
coagulation and centrifugation.
Solution Polymerization
Solution polymerization relies on a solvent to dissolve the
monomer and catalyst. After reaction, the polymer is pre-
cipitated using an anti solvent (e.g. n-hexane, methanol).
The polymer is then filtered and dried.
Bulk or Mass Polymerization
Bulk or mass polymerization is different from the foregoing
processes in that no carrier liquid is used. Therefore, there
is generally 1 ittle or no process wastewater associated with
this process.
3.
Wastewater Characteristics
The characteristics of
manufacture of plastic
Table 0-13-1.
the process wastewaters from the
and synthetic materials are shown in
0-13-2
-------
The plastic and synthetic materials industry is typically a
continuous year-round operation. Because it is technical ly
and economically advantageous, many firms manufacture several
different, but related chemical products at one location. For
example, a typical complex makes ethylene, polyethylene,
sulfuric acid, ethyl chloride, ammonia, nitric-acid and
phosphoric acid (2).
In group 1, the wastewater has relatively high BOD, COD, and
TSS; heavy metals (In, Cu) and synthetic fiber losses. Group 2
wastewater has low BOD and COD, may be either acidic or
alkal ine, and has substantial amounts of oi I and polymer
particles. Group 3 is characterized as either having no
process water or as having process wastewater containing
virtually no pollutants. Group 4 wastewater has variable
BOD and COD, may be either acidic or alk?l ine, and contains
synthetic fibers. Discharge of faulty batches from synthetic
fiber plants may introduce shock loads into the joint treat-
me n t f ac i lit y .
Conditions significant in the design of joint treatment
facil ities include high chlorine demand, the presence of
surface-active agents, high sol ids concentrati0ns, and
nutrient deficiency. The process diversity and complexity,
as we!l as the proprieta'ry nature of many of the process
chemicals, require that the pretreatment be established on
a case-by-case basis after thorough investigation.
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment processes are shown in
Table 0-13-2.
0-13-3
-------
TABLE D-13-l
\.Jastewater Characteristics
P13stic and Synthetics Industry
Characteristics
Sub -G roup 3
Sub-Group 3
Sub-Group I
Sub-Group 2
Industry
Flow
BOD
TSS
TDS
COD
Operation
Year-Round
Continuous-Variable
HIGH
HIGH
HIGH
HIGH
Year-Round
Continous
Low
Low
Low
Low
__3
Year-Round
Continuous
Average-HIGH
Low-HIGH
Low-HIGH
Average-HIGH
Low
Low
Low
Low
Gr it
Cyanide
Chlorine
pH
Color
Absent
Absent
AVERAGE-HIGH
ACID-BASIC
Low-Average
Absent
Absent
HIGH
ACID-BASIC
Low-Average
Absent
Absent
Low
ACID-BASIC
Low-Average
Absent
Absent
Low
Neutral
Low
Demand
o
I
Turbidity
Explosives
Dissolved Gases
Detergents
Foaming
Lmv-H i gh
Absent
Absent
PRESENT
Absent
High
Absent
Absent
Absent
Absent
Low
Absent
Absent
Absent
Absent
Low
Absent
Absent
Absent
Absent
VJ
I
.j:"-
Heavy Metals
Colloidal Sol ids
Volati Ie Organics
Pesticides
Absent
Average
Present
Absent
PRESENT
HIGH
Absent
Absent
Absent
Low
Present
Absent
Absent
Low
Absent
Absent
Phosphorus
Nitrogen
Temperature
Phenol
Sulfides
DEFICIENT
DEFICIENT
Normal-High
Absent
Absent
DEFICIENT
DEFICIENT
Normal-High
Present
Absent
DEFICIENT
DEFICIENT
Normal-High
Absent
Absent
DEFICIENT
DEFICIENT
Normal-High
Absent
Absent
Oi I and Grease
Coliform (Fecal)
Absent
Absent
PRESENT
Absent
Absent
Absent
Absent
Absent
lproducts general 1y associated with 1 ittle or
2Temperature equal to or higher than domestic
3 treatment processes.
See text page D-13-3
no process wastewater
wastewater. May affect the des i gn but not ha rmful to j oi nt
NOTE: Characteristics which may require pretreatment or are significant to joint treatment plant design
are shown in UPPER CASE.
Wastewater characteristics shown reflect the industrial practices described in Section 2.
-------
Pretreatment
Sub-Group
2
3
CJ
I 4
'--'>
I
V1
TABLE D-13-2
Pretreatment Unit Operations for the Plastic and Synthetic Materials Industry
Suspended Biological
System
Fixed Biological
System
Coarse Sol ids Separation +
Neutr~l ization + Chemical
Precipitation (heavy
metals)
Coarse Solids Separation
+ Neutral ization + Chemical
Precipitation (heavy
metals)
Oil Separationl +
Neutral ization
0'1 . 1
I Separat J on
Neutral ization
+
Pretreatment Not Required
Pretreatment Not Required
Coarse Sol ids Separation +
Neutral ization
Coarse Sol ids ~eparation ~
Neutral ization
1 O. 1 .
I. separation required to reduce mineral oil
50 mg/L.
Independent ~hysical-Chemical
System
Coarse Sol ids Separation +
Neutral ization + Chemical
Precipitation (heavy
metc,ls)
Oil Separation]
Neutral ization
+
Pretreatment Not Required
Coarse S01 ids Separatio~ +
NeuUal ization
(petroleum sources) concentration below
NOTE:
Publ :cly owned treatment works must be protected from batch dumpings of
faul ty pronuct materials.
-------
RE FERENCES
1.
"Industrial Waste Study of the Plastic Materials and
Synthecics Industry", Environmental Protection Agency
Contract No. 68-01-0030, Washington, D.C., (unpublished).
2. "The Cost of Clean Water -Vol. III, Industrial
Profile No. 10 - Plastic Materials and Resins','
Water Qual ity Administration (October, 1967).
Waste
Federal
0-13-6
-------
BLAST FURNACES, STEEL WORKS, AND ROLLING AND FINISHING
1.
Industry Description
This industry includes Standard Industrial Classification
(SIC) 3312.
This classification includes: pig iron manufacture;
manufacture of ferroalloys from iron ore and from iron
and steel scrap; converting pig iron, scrap iron, and
scrap steel into steel; hot roll ing; and cold finishing.
Blast furnaces and by-product (or beehive) coke ovens
are also included under this category. The complex
and interdependent operations involved in a steel industry
can be I isted as follows:
a. Coke Works
b. I ron Works
<:. Steel Works
d. Hot Formi ng
e. Cold Finishing
Significant quantities of water are used, both for processing
and for cool ing purposes. The steel industry generates
greater volumes of wastewater than any other industry (I).
a. Coke Works
Coke is used in large quantities for the production
of pig iron. Therefore, most large iron and steel
manufacturing operations include the production of
coke from coal. There are two methods generally
used for the production of coke: 1) the beehive
process; and 2) the by-product or chemical recovery
process. The beehive process uses air in the coking
oven to oxidize the volatile organics released from
coal and to recover the heat for further distillation.
The by-product or chemical recovery process is
operated in the absence of oxygen, and the heat
required for disti llation is provided from external
fuel sources. Today, the by-product process accounts
for 99.9 percent of all metallurgical coke. Therefore,
only the by-product or the chemical recovery process
is described in detail.
D-14-1
-------
In the by-product process, coal is heated in the
absence of air to a temperature at which the volati Ie
matter is driven off. At the end of coking cycle,
the hot residual coke (2,0000 F) is conveyed to a
quenching station, where it is cooled with a spray
of water. The off-gases from the coke oven are
cooled in a cool ing train, where tar and ammonia
1 iquor separate out. The tar contains a large
proportion of phenols removed from the furnace. The
ammonia is generally recovered from the 1 iquor in a
s till.
b.
I ron Works
Iron is manufactured from iron ore (iron oxide)
in blast furnaces, with carbon monoxide (from coke)
a s are due i n gag e n t . Th e m a j 0 r i mp u r i t y (s i 1 i c a )
in the iron ore is removed from the blast furnace
as molten slag, through the use of limestone.
c.
Steel Works
Steel is manufactured from pig iron by adjusting the
carbon content of the alloy to approximately I percent.
The three principal steel-making units are the electric
arc furnace, the open-hearth furnace, and the basic
oxygen furnace. The basic oxygen furnace produces
approximately 50 percent of the total steel produced
in the United States (2).
All three methods use the same raw materials and
produce simi lar wastes. Pure oxygen or ai r is
used to refine the hot iron into steel by oxidizing
and removing si1 icon, phosphorus, manganese, and
carbon from the iron.
d.
Hot Forming
The steel ingot obtained from the furnace is reheated
to provide uniform temperature for further processing
or hot forming. The ingot steel is generally processed
in a blooming mill or slab mill to form plates, sheets,
strip, ske1p, and bars.
e.
Cold Finishing
The cold finishing operations are used for the conversion
of hot-ro1 led products to give desired surface, shape,
or mechanical properties. These operations include
pick] ing, cold roll ing, tinplating, coating, shaping,
and drawing to make various finished products.
0-14-2
-------
Integrated iron and steel mi I Is may operate many
different subprocesses generating wastewaters of
varying characteristics. There are, however, mills
which are not integrated and which have only a few
of the foregoing manufacturing operations.
The on1y two types of waste stream susceptible to
joint treatment are the coke oven wastewaters and
the pick ling I i quo r. The othe r process was tes occu r
in such large quanti ties and contain only suspended
impurities that it is more logical to treat them on-
site and discharge directly to surface waters.
Consequently, the pretreatment sub-groups for this
industry are:
Coke Works
Cold Finishing
2.
Industrial Practices
The strong acid pickle I iquor, containing iron salts of
mineral acids, is usually collected separately for other
means of disposal or for use in waste treatment plants.
The acid salts of iron are useful either as a flocculent
aid, as a precipitating agent for phosphorus removal, or
as a neutral izing agent in waste treatment plants. Any
such use should be investigated before discharging the
spent pickle 1 iquor as a waste stream. Recovery of
strong acid pickle 1 iquor for reuse is practiced in a
1 imited number of cases for hydrochloric acid systems.
3.
Wastewater Characteristics
The characteristics of the process wastewaters from various
operations within the steel industry are shown in Table D-14-1.
The wastewaters gellerated in steel industries vary widely
between operations and they are generally segregated for
treatment. Some older steel mills, however, stil I have
common collection systems for discharging the total plant
flow. The stee! industry operates throughout the year and
generates wastewaters over a 24-hour day. The volume and
characteristics of wastewater are subject to hourly
variations from batch dumping of acid baths and sti 11
bottoms.
The major constituents present in the wastewater are
phenol, cyanides, ammoni a, oi I, suspended s01 ids, heavy
metals (Cr, Ni, Zn, Sn), dissolved solids (chlorides,
sulfates), acidity, and heat. The process \iJastewaters
are generally treated on-site before disposal. Joint
treatment of these wastes with municipal wastes is 1 imited
to small instal lations, \tJhich handle only approximately
5 percent of the overall steel industry. This is probably
due to the excessive volumes of wastewater (12,000-25,000 gpm)
generated by large integrated steel mi lls (3), A significant
D-14-3
-------
portion of the wastewater generated contains suspended
sol ids and dissolved sol ids that are inorganic in nature.
Most municipal treatment plants are not equipped to
handle or treat this type of wastewater.
The only two waste streams generally susceptible to
joint treatment are the coke oven wastewaters (ammonia
liquor, still bottoms, and light oil recovery wastewaters)
and the pickling liquor. The other process wastewaters
are high in sol ids (sub-micron iron oxide dust) and heavy
metals. Pretreatment to reduce these waste constituents
generally results in an effluent which can be discharged
directly to surface waters, for which further joint treatment
is not cost effective.
The coke oven process wastewaters are amenable to biological
treatment when they constitute only a minor fraction
(approximately 25 percent) of the total wastewater flow
to the joint treatment facility (2). The cyanide
concentration (with its resulting aquatic toxicity
characteristics) is the primary consideration in the
joint treatment of coke oven process wastes.
The following are characteristics of the process wastewaters:
The still bottoms, containing phenol, constitute the
major wastewater source from the coke oven process.
Since the beehive oven process uti 1 izes the heat value
in the off-gases, only the quench water is discharged
as wastewater (1). The gases (C02' CO, N, and HCN)
leaving the furnace are hot and contain dust particles.
The gases also contain water vapor and traces of hydrogen
sulfide. In order to clean the exit gas from the blast
furnace operations, the gas is generally passed through
dust collectors, scrubbers, and coolers. The water used
in the scrubbers and coolers is the primary wastewater
source in iron manufacture. The waste products from this
process are slag and the oxides of iron released as sub-
micron dust particles. Precipitators or venturi scrubbers
are used to clean the exit gas, and the characteristics of
the wastewater discharged from the process wi II depend
primari ly on the gas cleaning system. If scrubbers are used,
the wastewater generated will be acidic in nature due to
the presence of sulfur oxides in the exit gas.
Water is used under high pressure to remove scale and
for cool ing purposes. The primary wastewaters are the
D-14-4
-------
scale-bearing waters and cooling waters containing
primarily scale and oil.
Steel pickl ing to remove oxides and scales is accompl ished
through solutions of H2S04, HCI, or hydrofluoric acid. The
pickled steel is then rinsed with water and coated with oil
before proceeding to the next step.
The cold rolling process involves passing unheated metal
through rolls for reducing size or thickness, and improving
the surface finish.
Plating of steel products is done electrolytically, and
is accompl ished in either an alkaline or an acid electrolyte
solution. If acid electrolyte is used, the process system
will consist of alkal ine washing, rinsing, pickling,
plating, quenching, chemical treating, rinsing, drying,
and oiling. The most commonly used metall ic coatings are
tin, zinc, nickel, chromium, cadmium, copper, aluminum,
silver, gold, and lead. Wastewaters generated from
cold finishing operations include: rolling solutions,
cool ing water, plating wastes, pickling rinse waters,
and concentrated waste-acid baths. Roll ing solutions and
cool ing water generally contain oil and suspended solids
as pollutants. Plating wastes, pickling rinse, and
concentrated acid baths may contain various heavy metals
(Cr, Cd, Ni, Zn, Sn) as well as cyanides, acids, and
al kal i.
4.
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment processes are shown in Table
D-14-2. Even though the wastewaters from the coke oven and
cold finishing operations are susceptible to joint treatment,
the effluent 1 imitation values for cyanide and heavy metals
must be considered in the design of pretreatment facil ities.
D-14-5
-------
Characteristics
Industrial
Flow
BOD
TSS
TDS
Operation
COD
Grit
Cyanfde
Chlorine
pH
Demand
Color
Turbidity
Explosives
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
C h a r ac te r i s tic s
Phosphorus
Nitrogen
Temperature
Phenol
Sulfides
Oi I and Grease
Coliform (Total)
TABLE D-14-1
Wastewater Characteristics
Blast Furnaces, Steel Works, and Rolling and Finishing Industry
Coke Works
Year-round
I N TE RM I HE N T
Low-Average
Low
Low
Low-Average
Present
PRESENT
High
Neutral
Absent
Present
Absent
Present
Absent
Absent
Absent
Present
Present
Absent
Coke Works
DEFICIENT
Adequate
HIGH
PRESENT
PRESENT
P res en t
Absent
I ron Works
Year-round
Continuous
Low-Average
Low-H i gh
Low
Low-Average
Present
Present
Low
Neutral
Ab sen t
Present
Absent
Present
Absent
Absent
Present
Absent
Absent
Absent
Iron Wo rks
DEFICIENT
Adequate
High
Present
Present
Absent
Absent
Steel Works
Year-round
Continuous
Low
Average-High
Low
Low
Absent
Absent
Low
Neutral
Absent
Present
Ab sen t
Present
Absent
Absent
Present
Absent
Absent
Absent
Steel Works
DEFICIENT
DEFICIENT
High
Absent
Absent
Absent
Ab sen t
Hot Forminq
Year-round
Continuous
Low
Low-High
Low
Low
Absent
Absent
Low
Neutral
Ab sen t
Present
Ab s en t
Absent
Absent
Absent
Present
Absent
Present
Absent
Hot Formi nq
DEFICIENT
DEFICIENT
High
Ab sen t
Absent
Present
Absent
Cold Finishing
Year-round
I N TE RM I TTE N T
Low-Average
Low-High
High
Low-Average
Absent
PRESENT
Low
ACIDIC
Absent
Present
Absent
Absent
Present
Absent
PRESENT
Present
Present
Absent
Cold Finishinq
DEFICIENT
DEFICIENT
Highl
Present
Absent
PRESENT
Absent
1
Temperature higher than domestic wastewater; may affect design but not harmful to joint treatment.
NOT ES :
Characteristics which may require pretreatment or are significant to joint treatment plant
design are shown in UPPER CASE.
Wastewater characteristics shown do not reflect industrial practices described in Section 2.
D-14-6
-------
+-
I
'-J
Pretreatment Sub-Group
Coke P roduc t i on
Cold Finishing
o
I
TABLE lJ-14-2
Pretreatment Unit Operations for the
Blast Furnaces, Steel Works, and R01 I ing and Finishing Industry
Suspended
Bioloqical System
EquaJ ization +
Sol ids Separation
Equalization + Oil
Separation or Skimming
+ Chemica! Precipita-
tion (heavy metals) +
Neutral ization
Fixed
Biological System
Equalization +
S01 ids Separation
Equal ization + Oi I
Separation or Skimming
+ Chemical Precipita-
tion (heavy metals) +
Neutral ization
Independent Physical-
Chemical System
Equal ization +
Solids Separation
Equal ization + Oi I
Separation or Skimming
+ Neutral ization
-------
REFERENCES
I.
Neme, rOI.J ~!.L., "Theories and Practices of Industrial
Waste Treatment", Addison-Wisley Publishing Co. Inc.,
Reading, Mass. (1963).
2.
"Industrv Profi Ie Study on Blast Furnace and Basic Steel
Products", Water Quality Office, Contract No. 68-01-0006,
Environmental Protection Agency, Washington, D.C. (unpublished).
3.
"The Cost of Clean Water, Vol. III, Industri al Waste
Profile No.1, Rlast Furnaces and Steel Mills", U.S. Dept.
of the Interior, FWPCA (1967J.
D-14-8
-------
ORGANIC CHEMICALS INDUSTRY
1.
Industry Description
This industry includes Standard Industrial Classifications
(SIC) 2811, 2813, 2814, 2815, and 2818.
These classifications include the manufacture of a wide
variety of products ranging from industrial gases and
ferti I izers to dyes, pigments, and petroleum compounds.
The total annual production of organic chemicals in the
Uni ted States has been estimated to be 120 bi 1 lion pounds
for the year 1969. A major portion of these chemicals
falls under Standard Industrial Classifications 2815 and
2818. The important products of the industry are those
derived from petroleum fractions.
The Organic Chemicals industry consists of such a complex
combination of processes and products that a "typical or
average" plant exists only in a statistical sense. The
product mix and output of an industry depend primarily
on the total economic activity and the demand for products.
The Organic Chemicals industry is very dynamic in develop-
ment of new products and processes.
Considering the number of products involved within the
industry (several hundred), this study has been limited
to the high-volume products, and only 27 major chemicals
are included. These products in combination represent
approximately 81 percent of the total organic chemicals
manufactured in the United States. A 1 isting of the
products covered is shown below in the order of 1970
manufacturing volume (1):
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
II.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
Ethanol
Isopropanol
Ace tic Ac i d
Cumene
Cyclohexane
Phenol
Acetaldehyde
Acetic Anyhdride
Terephthalic Acid
Dimethyl Terephthalate
Acetone
Adipic Acid
Acryloni tri Ie
Ethylene
Benzene
Propylene
Ethylene Dichloride
To 1 uene
Methanol
Ethylbenzene
Styrene
Fo rma I dehyde
Vinyl Chloride
Ethylene Oxide
Xylene (Mixed)
Butadiene
Ethylene Glycol
The total annual U.S. production of these 27 organic
chemicals amounted to approximately 98 bill ion pounds
D-15-1
-------
fo r ] 970. Depend i ng upon the sequence 0 f P roduc t i on from
petroleum sources, chemicals are referred to as either
feedstocks or intermediate petrochemicals. Of the 27
chemicals there are 22 intermediate chemicals and five
feedstocks (i .e., ethylene, propylene, benzene, toluene,
and xy 1 ene) .
A review of wastewater characteristics indicated that
certain products can be grouped together on the basis
of pollutants present in the wastewater. Accordingly,
the 27 product chemicals covered under this category are
divided into three Sub-groups as fol lows:
Sub-Group 1
2.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Benzene 13.
Toluene 14.
Xylene 15.
Cyclohexane 16.
Adipic Acid 17.
Ethylbenzene 18.
Styrene 19.
Pheno 1 20.
Terephthal ic Acid (TPA)21.
Dimethyl Terephthal ate 22.
(DMT) 23.
Ethylene
Ethylene Dichloride
Vinyl Chloride (Monomer)
Ethano 1
Acetaldehyde
Ace tic Ac i d
Acetic Anyhdride
Propylene
Isopropanol
Acetone
Cumene
Ethylene Oxide
Ethylene Glycol
The chemical reactions involved in the production of the
foregoing chemicals include petroleum reforming, thermal
or catalytic cracking, oxidation, alkylation, dehydrogena-
tion, hydration, and chlorination. Most processes use
proprietary catalysts to increase product yield and to
reduce severe operating conditions and pollution. Water
is used extensively both in the process and for cool ing
pu rpo ses.
11.
12.
Sub-Group 2
1.
2.
3.
Butadiene
Methanol
Fo rma 1 dehyde
Sub-Group 3
Ac ry 1 on i t r i 1 e
Industrial Practices
D-15-2
-------
3.
Wastewater Characteristics
The characteristics of process wastewaters from
manufacture of products under each pretreatment
are shown in Table D-15-1.
the
g ro u p
The characteristics of wastewaters vary from plant to
plant, according to the products and processes used.
Organic Chemicals plants generally operate 24 hours a
day throughout the year. Depending upon the product
mix and the manufacturing process, hourly variations in
wastewater volume and loading may occur as a result of
certain batch operations (filter washing, crystall iza-
tion, solvent extraction, etc.). The wastewater collection
systems are generally segregated, to permit separate
collection of process wastewaters and relatively clean
cool ing waters. The process wastewaters are usually
discharged to a common sewerage system for treatment and
disposal.
The
The process wastewaters from the manufacture of chemicals
under Sub-Group 1 genera11y contain free or emulsified oi 1,
whi le under Sub-Group 2 generally do not contain oi I.
Acrylonitri le manufacture ~ub-Group 3) produces a wastewater
containing cyanides and substantia] quantities of acids.
These wastewaters, in general, contain unreacted raw
materials and losses in products, by-products, coproducts,
and any auxi I iary chemicals used in the process. Detailed
analyses for every specific chemical present in the waste-
water is difficult and are not generally used to describe
the characteristics of wastes. However, the available
information indicates that the wastewaters contain: BOD,
COD, oil, suspended solids, acidity, alkalinity. heavy
metals, and heat.
The wastewaters discharged from the manufacture of pro~ucts
under Sub-Group I may contain oi] and grease and a series
of heavy metals (Fe, Cd, Cu, Co, V, Pd) (2,3). The types
and amounts of heavy metals in the wastewater depend
primari ly on the manufacturing process and the amount and
type of catalysts lost from the process. Most catalysts
are expensive and, therefore, recovered for reuse.. Only
unrecoverable catalysts (heavy metals), generally In smal I
concentrations, appear in the wastewater.
The wastewaters generated from the manufacture of products
under Sub-Group 2 contain: BOD, acidity or alkalinity (pH
D-15-3
-------
4 to 11), and heavy metals (Cr, Cu, Zn, I-Ig). These
wastewaters are amenable to biological treatment after
equalization and neutral ization. The production of
butadiene may produce a wastewater containing free
or emulsified oi I; an oi 1 separation device may be
requi red as pretreatment when the oi 1 content in the
,Jastewater exceeds 50 mg/L. Only unrecoverable heavy
metals (catalysts), generally in small concentrations,
appear in the wastewater.
The manufacture of acrylonitri le produces a highly
toxic wastewater which is difficult to treat biological1y.
The toxicity characteristics have been attributed to
the presence of hydrogen cyanide in excessive quantities
(500 to 1,800 mg/L). In addition, the wastewater is
generally acidic (pH 4 to 6) and contains high concen-
trations of organic carbon. These wastewaters are
generally segregated from other process wastes and
disposed of by other means (e.g. incineration). These
wastewaters are not generally discharged to municipal
col lection systems. The pretreatment unit operations
developed in the fol lowing section do not include the
process wastewaters from the manufacture of acrylonitri Ie
(Sub-Group 3).
4.
Pretreatment
Table D-15-2 shows the pretreatment unit operations
which may be necessary for joint treatment processes.
The heavy metals present in organic chemical wastes are
in many cases so low in concentration that heavy metals
removal is not required from the standpoint of treatabi 1 ity
characteristics. However, the effluent I imitations for
heavy metals and toxic pollutants may require additional
pretreatment (chemical precipitation) for removal of
the s e ma t e ri a 1 s .
The pretreatment unit operations generally consist of
equalization, neutralization, and oil separation. In
addition, phenol recovery (to reduce the phenol concen-
tration) and spi 11 protection for spent acids and spent
caustics may be requi red in some cases.
D-15-4
-------
Table 0-15-1
\Jastei,ater Char"cteri stics
Organic Chemicals
Characteri stics
SlIh-Grolll' 1
Sub-GronD ?
Sub-GrQ'd.1L3.
Industrial
F I 01-,
20ll
TSS
TCIS
Operation
Year-round
Continuous-V~ri~b1e
Aver ,ne-c':T. H II~H
Lo\',-High
HIGH
Year-round
Continuous.Variabie
/~\)E RkSE -f-III~~
Lovi
LO\!-H i gh
Year-round
Con~inuou5-Variable
LO'.'I
H i '~r
High
Oerland
Averaqe-'XT. HIGH
Ab 5 e 11 t
Ah ~,erl t
Hiqh
I~CIOIC-ALKALINE
Averaqe-HIGH
Ahsent
High
Absent
PRESENT
High
ACIGIC
COD
G r i t
Cyanide
Ch lori ne
pH
hij sen t
High
ACIDIC-ALKALINE
Co lor
Turbidity
Explosives
Cissolved Gases
Oeterqents
L,~,.,-r\v2rage
Lo'"
Absent
Present
Present
La..r-Ave rage
LOVI
,'.\bsent
Fre'en t
Pre::,ent
LCi,
Lo\!
Absent
Present
Present
Foaming
Heavy Metals
Colloidal Solids
Volati Ie Organics
Pesticijes
Pre'ent
P resen t
Aosent
Present
Ab 5 e n t
Present
Present
Absent
Present
~tJsent
Present
-Present
Absent
Present
Absent
Phospho rue
f. i t rogen
Temperature
Phenol
Sulfides
OEFICIEIH
JEFICIENT
Normal-HI GH3
LO';I-High
Present
DEFIC I ElF
DEFICIEI1T2
II i gh 3
Present
Present
DEFICIEIIT
"de, ca te
110 Data
Ab sen t
Absent
Oi I and Grease
Coliform (Total)
I o\V-H I GH
Lo\!
L0"I-~1 GH
LOI,
Absent
Lo\!
I Lo'" BOu is probably cue to the toxicity characteristics of this ',Iaste.
2AdeQUate ',Ihen butadiene is manufactured.
3Temperature equal to or higher than domestic \!astev1ater; Clay affect design hut
not har~ful to joint treatment.
NOTE S ;
Characteristics Clhich may requi re pretreatment or are significant to joint treatment plant design
rl'P S'':!'.!Il in UPPER CASE.
~Iastevlater characteristics shovin reflect all
industrial practices described in Section 2.
D - I 5- 5
-------
Table 0-15-2
Pretreatment Unit Operations for the
Organic Chemicals Industry
Pretreatment Sub-Group
Suspended
Biological System
Oil Separation +
Equal ization +
Neutral ization +
Spi 11 Protection +
Chemical Precipita-
tionl
<::1
I
I..Il
I
(j\
2
Oil Separation2 +
Equal ization +
Neutral ization
Fixed
Biological System
Oil Separation +
Equal ization +
Neutral ization +
Spil I Protection +
Chemical Precipita-
t ion I
Oi J Separation2 +
Equal ization +
Neutral ization
lNeed for chemical precipitation depends on extent of catalyst recovery.
20' 1 .
I separation required for butadiene manufacture only.
Independent Physical-
Chemical System
Equal ization +
Neutralization +
Chemical Precipitationl
Equal ization +
Neutral ization
-------
REFERENCES
1.
Chemical and EnCJineerinCJ News, (May 17, 1971).
2.
"Reference Guidel ines for Organic Chemical Industries",
Environmental Protection Agency, Washington, D.C.
(Unpubl ished)
3.
"Projected Wastewater Treatment Costs in the Organic
Chemical Industry", Water Pollution Control Res. Series
12020 GND 07171, Envi ronmental Protection Agency, Research
and Monitoring (July, 1971).
D-15-7
-------
METAL FINISHING INDUSTRY
I.
Industry Description
This industry includes Standard Industry Classification (SIC)
3471.
The industries cO/ered Jnder this classification include those
primarily enga']ed in various types of plating, anodizing, color-
ing, fonning, and finishing of metals. The metal-finishing
industry operations are ~elated closely to those of many other
industries, including transportation (auto~o~ile parts and ac-
cessories), electrical, and jewelry.
The metal-finishing operation involve> cleaning, co~version
coating, organic coating, plating, an~dizing, coloring, and
case hardening. Acid ,Jickl ing is the most CO'11111011 type of clean-
ing of met~l being prepared for pla~ing. Su1fu-ic acid is the
most commonly used pick! ing agent. but pho~p~oric, hydrochloric,
hydrofluo~ic, ald other acids are used as well. Alkal ie3,
dichro,nates, and lum'2rous proprietary compound; are als'J .Jsed
in vario.Js combinations for descal ing, degreasing, desmudging,
stripping, brig~te'ling, 0- otherw;se preparing different metals
(zinc, steel, brass, co;:>per, etc,) for plating or a'lodizing.
The plating solutions for nickel, chrom:ul11 copper, cad,niull,
zinc, tin, and silver may be bac,ically cyanide, acid, or alka-
line. Anodizing is done either in sulfuric acid or in chromate
solutions. Colorizing is accomplished with dye" nickel acetate,
and chro~ates. Cyanides are used in case harde~in3.
2.
Wastewater Characteristics
The characteristics of the process wastewaters fro~ the in~ustry
are shown in Table D-16-1.
The metal-finishing industry usually generates a :o,ltinuu.Js
$trea'1l ,:,f rinse Wijters containing dilut(:; ,;;ollr;elltrations Qf
heavy metals and c;yanid=s3ild intermittent batch dumpings of
spend acid a1d cleaning solutions. The nature of metal~finish~
ing o~erations 31d the consequent fluctuating (cyel ic) charac-
teristics of the wastewater should Je taken into co~sid8ration
in the design of treatment facil ities.
Water is :Js'2d I~,.;te"sively in tllctal-finishil19 processes to clean,
strip, pickle, and rinse the metal products before and aCter
pla~ing operations. The rinse waters cOl1stitu~e the major
volUine of w3stei'Jaters, whi Ie spent solutions discharged inter-
mittently add major polluta!lts to the total effluent. The
0-16-1
-------
wastewaters contain, in general, spent acids, a1k<31is, oil and
grease, detergents, cyanides, 3~dJ3rious heavy metals (Cr,
N i, C u, A g, Fe, Z n, and S n) . The IIl~:: a 1 - fin ish i n g p 1 ant s d iff e r
from one another with respect to t~ei r prJcesses, ~eta1s, and
chemicals, and the characteristics OC ~a~tew~~er mal va~y widely
from one to another. However, their wastewaters all contain
p~i~arily inorganic pollutants, particu1ar1y heavy metals. In
addition, the wastewaters frequ,~nt1y are highly toxic du,= to
the presence of cyanides and heavy :n~[als (1,2,3).
In general, the types of wastewaters from ,Ie tal-finishing i.l-
d'Jstries are:
1.
Acid wastes
2.
A 1 ka 1 i ne \,J:'J" t es
3.
Hea'/'l metals wastes
4.
Cyalide-bearing wastes
5.
Misse1laneous wastes (dies, soluble and floating o:ls,
etc. )
An,! of these waste'iV.Hers may occur as either dilute r-inse ,v.::Jters
or concentrated baths. Except for the cyanide-bearing wastes,
the wastevoJaters are generally cOlnected to a::ornmon sew'erage
system for treatment a,d disposal. The cyanid2 w~stes usually
are collected in a segregated sew~r system in order to ~revent
the release of to
-------
3.
Pretreatment
The pretreatment unit operations for various types of joint
treatment faci I ities are shown in Table 0-16-2.
The pretreatment processes generally involve separate treat-
ment of cyanide wastes and other acid wastes containing metal
ions. The cyanide wastes can be treated with ferrous sulfate
and 1 ime to convert highly toxic cyanides to less toxic cyanates
or cyanide complexes, or can be oxidized to C02 and N2 with
chlorine under alkal ine conditions. The acid waste streams are
treated first to reduce hexavalent chromium to trivalent
chromium, using ferrous sulfate, scrap iron, or sulfur dioxide,
and then precipitating the metal ions (Cr3+) as metal hydroxides.
In addition to the effluent limitations and the processes shown
in Table 0-16-2, the degree of reduction in heavy metals waste
loadings should consider the sludge handl ing and disposal methods
used for the combined domestic and metal finishing wastewaters.
Some processes (e.g. anaerobic digestion) concentrate these
metals, and this can lead to process failure un1ess adequate
pretreatment is provided.
D-16-3
-------
Table 0-16-1
Wastewater Charocteristics
Metal Fi1ishing Industry
Characteristics
Indlls~r;03'
)pe i-3 ~ i ::)1)
Year-round (BATCH)
Flow
t3JD
,55
TOS
COD
Continuous-VARIABLE
~O~J
Av~ ra9'~-':~ i.:Jh
HIGH
Low
G r it
Cyall i d,~
C h 1 <) ," i n e
pH
Color
Demal1d
Present
HI~H
HIGH
ACIDIC
Present
Turbidity
Exp 1 'Js; VC~-'
D i 550' ved Ga',es
Detergents
F o:J,n; 19
? re"en:
Ahsent
Present
P re~-'ent
,1\,bsent
He.:Jvy '1e::315
Colloidal 501 ids
V 0 1 a : i 1 e 0 r 9 " n i c s
Pesticide:;
~IGH
Absent
;:>re~-'.=nt
,Cib5en t
Phosphorus
Nit rJ':Je11
T ernp era': U I- ~
::>' 1
, ne,)c>
S 'J 1 f i d ':0 S
Present
') rQ;: -::10"1 "'-
, ~-> '-' T
;~onkJ1
LOVJ
Absent
Oi 1 and Grea,e
Co1ifo'n (Total)
?re~-',=nt
A':J s e ') t
lr
e:npe;-a t u re
similar to domestic W~jtew~ter
NOTE:
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown in
UPPER CASE,
0-16-4
-------
TABLE 0-16-2
Pretreatment Unit Operations for the Metal Finishing Industry
Suspended Biological
----. .::y"s_t_~fT2 ------
EqlJ;J1 iZ_3~ioil + Nr;u..
tr~l ization + Cyanide
Remova I + Ch r'JI,li Jrl
Reducti8'1 + Chemical
Preci~itatio~ (Heavy
Metals)+ S01 ids Separation
o
I
(j\
I
\J1
Fixed 0 i 'J 1 ':>9 i CrJ I
--- - __~2.tem_-
I r) d ;~ P '2 IFI e n t P ~l >,', i ::3 1
C hem; ~~ _~'LS- t_~,;~- -
Equal ization +
Neutral ization +
Cyanide Removal
+ C h rom i um Re-
duction + Chemical
P rec i pita t i on
(Heavy Metals) +
501 ids Separation
Equal ization +
Cyanide Removal +
Chemical Precipita-
tion + Neutral ization
lChemical precipitation may not be needed, depending on the processes used in the independent physical
chemical joint treatment plant.
-------
REFERENCES
1.
"Complex Metal Finishing
Treatmen t", Was tes
Barnes, E.G., and Weinberger, L.W.,
Wastes Licked by Effective Chemical
EnqineerinCj, 124-127 (1957).
2.
Barnes, G.E., "Treatment Works for Plating Wastes Containing
Toxic Metals and Cyanides", Water and SewaCje Works, 94, 8,
(1947) .
3.
Nemerow, N.L., "Theories and Practices of Industrial Waste
Treatment", Addison-Wesley Pub1ishing Co., Inc., Reading,
Mass. (1963).
4.
"An Investigation of Techniques for Removal of Cyanide
from Electroplating Wastes", Water Pol1ution Control
Research Series, 12010-EIE 11171, EPA, Washington, D.C.
(1971 ) .
5.
"An Investiqation of Techniques for Removal of Chromium
from Electroplating Wastes", Water Pollution Control Research
Series, l2010-EIE 3171, EPA, Washington, D.C. (1971).
6.
"Ultrathin Membranes for Treatinq Metal Finishing Effluents
for Reverse Osmosis", Water Pollution Control Research
Series, 12010-DRH 11171, EPA - Research and Monitoring
( 1971 ) .
D-16-6
-------
Annex 17
Other Industries
Six industries have been included in this group, on the
basis of the following considerations:
1 .
Wastewaters from the industry contain only
inorganic waste constituents.
2.
Wastewaters from the industry are not usually
discharged to joint treatment plants.
The following industries are included in this group:
1 .
Inorganic Fertil izer
(SIC 2071)
2.
Electric and Steam Generation
(SIC 4911,4961)
3.
Aluminum
(SIC 3334,3341,3361)
4.
Flat Glass, Cement, Lime, Concrete Products,
Gypsum, and Asbestos
(SIC 3211,3241,3274,3275,3292)
5.
Inorganic Chemicals
(SIC 2812,2819)
6.
Industrial Gas Products
(SIC 2813)
Two tables are provided for each of these six industries;
the first shows the wastewater characteristics, and the
other shows pretreatment unit operations for various joint
treatment processes.
D-17-1
-------
Table
D-17-1
Wastewater Characteristics
Inorganic Fertilizer
Characteristics
Phosphoric Acid
Normal Super Phosphate
Triple Super Phosphate
Mono-Ammonium Phosphate
Di-Ammonium Phosphate
N-P-K Fertil izers
Ammonia
Industrial
Flow
BOD
TSS
TDS
Year-Round Year-Round
Continuous Continuous
Low-Average Low
Average-High Low-Average
HIGH HIGH
Low-Average Low
Absent Absent
Absent Absent
Low Low
ACID ALKAL I NE
No Data No Data
No Data No Data
Absent Absent
PRESENT Absent
Absent Absent
No Data No Data
Absent Absent
Absent Absent
Absent Absent
Absent Absent
Adequate D EF I C I E NT
Adequate 1 Adequate 1
Normal-High Norma l-H i gh
No Data No Dat~
No Data No Data
Absent PRESENT2
Absent Absent
Operation
COD
Gr i t
Cyanide
Chlorine
pH
Demand
Color
Turbidity
Explosive Chemicals
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Sol ids
Volatile Organics
Pesticides
Phosphorus
Nitrogen
Temperature
:leno 1
~.~Ifide
Oi I & Grease
Col iform (Total)
Ammonium Nitrate
Urea
Ammonium Sulfate
Year-Round
Continuous
Low-Average
Low-Average
HIGH
Low-Average
Absent
Absent
Low
ALKALINE
No Data
No Data
Absent
Absent
Absent
No Data
Absent
Absent
Absent
Absent
Adequate
Adequate 1
Normal-High
No Data
No Data
Absent
Absent
1 Temperature equal to higher than domestic wastewater; affect design but not
harmful to joint treatment.
2 Oil present in the wastewater is mineral in origin.
NOTE:
Characteristics which llIay require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
D-17-2
-------
Table D-17-2
Pretreatment Unit Operations for the Inorganic Fertil izers Industry
Pretreatment Group
Phosphoric Acid
Normal Super Phosphate
Triple Super Phosphate
Mono-Ammonium Phosphate
Di-Ammonium Phosphate
N-P-K Fertil izers
Ammonia
o
I
'-J
I
V-J
Ammonium Nitrate
Urea
Ammonium Sulfate
Suspended Biological
System
s01 ids separation +
neutral ization
neutral ization +
oil separation
neutral ization
Fixed Biological
System
Independent Physical-Chemical
System
sol ids separation
+ neutral ization
sol ids separation +
neutral ization
neutral ization +
oil separation
neutralization +
oil separation
neutral ization
neutral ization
-------
Table 0-18-1
Wastewater Characteristics
Electric and Steam Generation
Characteristic
Industry
Flow
")00
rss
T[)S
Ope rat i on
Year-Round
INTERMITTENT
Low
Low
High
COD
G r i t
Cyanide
Chlodne
pH
Demand
Low
Low I
Present
Low
ACIDIC-ALKALINE
Co 101.
Tu rb i d it),
Explosive Chemicals
Dissolved Gases
De te rgent s
Low
Low
Absent
Absent
Present
FoaminS]
He'3v,/ ,'Ie tal s
Colloidal Solids
'Jalati Ie Ol'ganics
Pesticides
Present
PRESENT
Absent
Present
Absent
Phosphorus
~J: t rogen
Temperature
Phenol
Sulfide
DEFICIENT
DErl11ENT
HIGH 3
Present
i~bsen t
Oi I <3nd G ,'ease
Co1 i form (Tot <3 1 )
?resent
Absent
lCyanid8 may be pl'esent if coo1ing water is also dis-
charged to the sewers.
2Temperc.t:.Ire higher than domestic wastewater; may
reoui re cO'Jling as pretreatment.
3Phenol may be used in cooling water treatment.
~\JOT [ ~
Characteristics ItJl,ich may require pretreatment or are
sign;ficant to Joint treatment plant design are shown
in UPPER C;'SE.
0-17-4
-------
Table D-18-2
Pretreatment Unit Operations for the Electric and Steam Generation Industry
Suspended Biolo~ical System
o
I
Equalization (cooling) +
Neutralization + Chemical
Precipitation (heavy
metals) + Cyanide
Oxidation
-....J
I
Vl
Fixed Bio1o~ical System
Equa1ization (cooling)
+ Neutralization +
Chemical Precipitation
(heavy metals) +
Cyanide Oxidation
Independent Physical-
Chemical System
Equaliation (cooling)
+ Neutralization +
Chemical Precipitation
(heavy metals) +
Cyanide Oxidation
-------
Table D-19-1
Wastewater Characteristics
onferrous Metals - Aluminum
Characterist ics
Industry
F I 01"
BOD
TSS
T DS
Ope rat ion
COD
G r i t
Cyanide
Chlorine
pH
Demand
Color
Turbidity
Explosive Chemicals
Dissclved Gases
Detergents
He a v \ '1 eta I s
Colloida I Sol ids
Volati Ie Organics
Pesticides
Phosphorus
r! i t rogen
Tempe ratu re
Phenol
Sulfide
Oi I and Grease
Col iform (Total)
Bauxite Refining
Primary Smelting
Year-round
Cont i nuous
Low
HIGH
Low
Direct Chill Ingot Coating
and Foundry Roll ing,
Drawing and Extruding
'ear-round
Continuous
Low
HIGH
Low-A'le rage
Low
PRESENT'
Present
Low
'eutral
Low
i'lbsent
/'Ibsent
Low
EUTRAL-AC I D
High
High
!Ibsent
PRESENT2
Absent
Ave rage
Ave rage
Absent
PRE S E;H 2
Absent
Present
Absent
Absent
Absent
DEFICIENT
DEFICIENT
Normal-HIGH
Absent
Absent
Present
Absent
Absent
Absent
Absent 4
Deficient-Adeouate
DEFICIENT
Normal-HIGH
Absent
Absent 5
Present
Absent
Absent
1 P .
resent In bauyite refining wastewater.
2 Fluorine is generally present in scrubber water.
3
Chlorine is present in casting, foundry, and secolldary smelting
scrubber Haters.
4 Phos pha te In high
vlhen can s tod is
manufacturer
concentration ( 1,000 :ng/L) is present on1\
coated in preparation for painting by the car
5
Oil and Grease may be present in emulsified form: not animal or
vegetable origin.
NOTE :
Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
in UPPER CASE.
D- 1 7-6
-------
Table 0-19-2
Pretreatment Unit Operations for the Aluminum Industry
Pretreatment
Group
Suspended Biological
System
Bauxite Refining
P rima ry Sme) t i ng
solids separation
Direct Chil) Ingot
Cas t ; n g and F ou n d ry
Roll ing, Drawing,
Foundry Extruding
Secondary Smelting
oi I separation +
neutral ization +
chemical precipita-
tion (phosphate re-
mova 1 )
CJ
I
-....;
I
-....;
Fixed Biological
System
Independent Physical-
Chemica] System
sol ids separation
sol ids separation
oil separation +
neutral ization +
chemical precipi-
tation (phosphate
remova 1 )
0;) separation +
neutral ization +
chemical precipi-
tation (phosphate
remova I)
-------
Characteristic
Industry Operation
F 1 0"1
DI)I""I
TSS
TDS
COD
G r i t
Cyanide
C h lor i ne
pH
Demand
Color
T u rb i d i t Y
Explosive Chemicals
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Sol ids
Volatile Organics
Pesticides
Phosphorus
Nitrogen
Temperature
Phenol
Sulfide
Oil and Grease
Coliform (Total)
Table D-20-1
Wastewater Characteristics
Glass, Cement, Lime, Concrete Products,
Asbestos and Gypsum Products
Flat
Glass
Year-round
Continuous
Low
Low-HIGH
Low-HIGH
Low
PRESENT
Absent
No Data
Neutral
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
PRESENT
DEFICI~NT
Normal
Absent
Absent 1
ABSENT
Absent
Mirrors
Year-round
Cuntinuous
Low
HIGH
HIGH
Low
PRESENT
Absent
.'0 Data
ALKALINE
Absent
Present
Absent
Absent
PRESENT
Absent
Present
PRESENT
Absent
Absent
PRESENT
DEFICI~NT
!Iorma 1
Absent
Absent
Absent
Absent
Cement
& Lime
Year-round
Continuous
Low
HIGH
HIGH
Low
Absent
Absent
~!o Da ta
ALKALI NE
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFICIENT 2
IJormal-High
Ab'5ent
Absent
Absent
Absent
Conc rete
Products
Year-round
Continuous
Low
Low-HIGH
LOW-HIGH
Low
PRESENT'
Absent
~Io Data
ALKALINE
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFI C I ~NT
.Iorma I
Absent
Absent
Absent
Absent
1 P .
resent In automotive glass and glass bottles manufacturing wastewaters.
2
Temperature equal to or greater than domestic wastewater; may affect de-
sign but not harmful to joint treatment.
NOTE:
Characteristics which may requi re pretreatment or are significant
to joint treatment plant design are shown in UPPER CASE.
D-17-8
Asbestos
CT Gypsum
Year-round
Continuous
Low
Low-HIGH
No data
Low
Absent
Absent
t-.Jo Data
Neut ra I
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFICIENT 2
;'Jorma l-H i gh
Absent
Absent
Absent
Absent
-------
LJb 1 e D-20-2
Pretreatment Unit Operations for the
Glass, Cement, Lime, Concrete Products, Asbestos, and Gypsum Products Industry
Pretreatment Group
Flat Glass
Mirrors
Cement & Lime
0 Products
I Conc rete
-.....j
I
1..0
Asbestos & Gypsum Products
Suspended Biological System
Fixed Biological System
grit removal +
sol ids separation
grit removal +
s01 ids separation
g r it remova 1 +
neutral ization
+ chemical precipitation
(heavy metals)
grit removal +
neutral ization
+ chemical precipitation
(heavy metals)
neutral ization
neutralization
g r i t removal +
neu t ra 1 i za t ion
grit removal +
neu t r a 1 i za t ion
sol ids separat ion
sol ids separation
Independent Physical
Chemical System
grit removal +
sol ids separation
g r it remova 1 +
neutral ization
+ chemical precipitation
(heavy metals)
neutral izat io'i
9 r it remova 1 +
neutral ization
s01 ids separat ion
-------
Characteristic
Industry Operation
Flow
BOD
TSS
TDS
COD
G r i t
Cyanide
Chlorine Demand
pH
Color
Turbidity
~xplosive Chemicals
Dissolved Gases
D~tergents
Foaming
Ho.avy M~tals
Co 1 10 i da 1 So 1 ids
Volatile Orgallir:s
P~sticides
Phosphorus
Ni trogen
TJmper.'1ture
Phenol
Sulfide
Oil and Gre"Jse
Co 1 i for'n (Tota I)
Table D-21-1
Wastewater Ch~racteristics
Inorganic Chemicals
Calcium Carbid~
:3odium Chloride
Sodium Tripoly-
phosphate
Chlorine,
Etc.
Hydrogen Peroxide
Sodium Dichromate
Sodium Sulfate
Y~~r-Round
Year-Round
Ye~r-Round
Continuous
Continuous
Continuous
Low
Lov"
Low
No Dat~
E ,..1
A V :\AG c
No Data
No Data
HIGH
HIGH
Low
Low
Low
Absent
Absent
Absent
Absent
Absent
2
PRESENT
Low
Low
Low
N~utral
No Da ta
ACID-BASIC
ACID-BASIC
No Data
No Data
No Data
No Data
No Data
Absent
Absent
Absent
Absent
Absent
Absent
Abs.nt
Absent
Absent
No Dati'!
r~o D~ta
Absent
No Data
PRESENT3
PRESf':NT
Absent
Absent
Absent
Absent
Absent
Absent
4
DEFICIENT
DEFICIENT
DEFICIENT
DEFICIEfH
DEFICIENT
DEFICIENT
Normal-high
No Data
Normal-high
No Data
Normal-high
No D3tC1
No Data
Absent
No Da t a
No Data
Absent
Absent
No Data
No Data
No Da ta
I
NaCl wastes have high salt concentrations.
)
Cyanide generated by electrolytic process for hydrogen peroxide.
3Downs cel I process for chlorine doesn't generate h~avy metals.
"
Sodium Triphosphate Wast~water will have very high phosphate concentri'ltion
NOTE: Characteristics which may requi re pretreatment or are significant to
plant design are shown in UPPER CASE.
D- 17-1 0
Aluminum
Chloride,
Etc.
Year-Round
Continuous
Low
No Data
HIGH
Low
Absent
Absent
Low
ACID-BASIC
No Data
No Data
Absent
Absent
Absent
No Data
Absent
Absent
Absent
DEFICIENT
DEFICIENT
Normal-high
No Data
No Da t a
Absent
No Data
'~2000 mg/l)
joint treatment
-------
Pretreatment
Group
Calcium Carbide
Sodium Chloride
Sodium Tripolyphosphate
Chlorine
Sodium Hydroxirie
Potassium Hydroxide
Sodium Metal
Hydrochloric Acid
Hydrogen Peroxide
Sodium Dichromate
? Sodium Sulfate
~Aluminum Chloride
- Aluminum Sulfate
Hydrofluoric Acid
Nitric Acid
Sodium Bicarbonate
Sodium Si I icate
Sodium Sulfite
Sulfuric Acid
Sodium Carbonate
Table 0-21-2
Pretreatment Unit Operations for the Inorganic Chemicals Industry
Suspended Biological
System
pretreatment not
requ ired
rtutral ization +
chemical precipitation
(heavy metals)
+ equal ization
n~utalization +
chemical precipitation
(heavy metals)
neutral ization
Fixed Biological
System
Independent Physicai-
Chemical System
pretreatment not
required
pretreatment not
required
neutralization +
chemical precipitation
(heavy metals)
+ equalization
neutralization +
chemical precipitation
(heavy metals)
neutral ization +
chemical precipitation
(heavy metals)
neutral ization +
chemical precipitation
(heavy metals)
neutral ization
neutral ization
-------
Table D-22-1
Wastewater Characteristics
Industrial Gases
Characteristic
Hydrogen, Nitrogen, Oxygen,
and Carbon Dioxide
Industry Operation
Flow
Yea r-Round
Continuous
BOD
TSS
Low
TDS
Low-average
Low-average
COI)
Grit
Low
Absent
Cyanide
Chlorine Demand
Absent
Low
pH
Color
ACID-BASIC
Low
Turbidity
Explosive Chemicals
Low
Dissolved
Ga s e s
A b se n t
Absent
Detergents
Foaming
Absent
No Data
Heavy Metals
Co 11 0 i da I 50 lid '"
Absent
Volati Ie Orrl(l";CS
Pesticides
Absent
Absent
Absent
Phosphorus
Nitrogen
DEFICIENT
DEFICIENT
Temperature
Phenol
Average-high
Absent
Sulfide
Absent
Oil and Grease
PRESENT
Co 1 i form (Tota 1 )
Absent
lWastewaters are constant over the dai 1y operating period.
NOTE :
Char
-------
Pretreatment Unit Operations for the Industrial Gases Industry
Table 0-22-2
Industry
Suspended Biological
System
Hydrogen
Nitrogen
Carbon Dioxide
Oxygen
oil separation
+ neutral ization
Fixed Biological
System
Independ2nt Physical-
Chemical System
oil separation
+ neutral ization
oil separation
+ neutral ization
10il Separation required to reduce mineral oil concentration below 50 mg/L.
o
I
--..J
I
VJ
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