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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FEDERAL GUIDELINES
PRETREATMENT OF POLLUTANTS
INTRODUCED INTO
PUBLICLY OWNED
TREATMENT WORKS
OCTOBER 1973
U.S. BtTlroaasntfcl ?r«tection
i 5.
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 important that the investment in publicly owned treatment
works be protected from damage and interference with proper operation.
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 publicly owned treat-
ment works. Such requirements are considered essential to ensure
compliance with permits issued under the National Pollutant Discharge
Elimination System.
The guidelines were the subject of numerous extensive reviews,
both within the Government and by affected segments of the public.
All of the many comments were carefully considered in arriving 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 Municipal
Waste Water Systems Division, Office of Air and Water Programs,
Environmental Protection Agency, Washington, D.C. 20460.
{/
Actin
cting Administrator
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TABLE OF CONTENTS
SECTION I
INTRODUCTION
Page No,
1
1. Purpose
2. Authority
3. Definitions
4. The Federal Water Pollution Control
Amendments of 1972
SECTION II EFFLUENT LIMITATIONS AND NPDES PERMITS
5. NPDES Municipal Permits
6. Effluent Limitations for Publicly
Owned Treatment Works
SECTION Mi JOINT TREATMENT AND PRETREATMENT
7. Joint Treatment
8. Pretreatment Policy
9. Federal Pretreatment Standards
SECTION IV STATE AND LOCAL PRETREATMENT
REQUIREMENTS
10. Objectives
11. Pretreatment Information
12. Pretreatment Ordinance
13. Example Calculations
14. Other Considerations
A Pretreatment Standards (40 CFR 128)
B Secondary Treatment Information
(40 CFR 133)
APPENDIX C Information on Materials Which Inhibit
Biological Treatment Systems
APPENDIX
APPENDIX
1
1
2
3
4
5
6
7
7
10
10
10
13
14
15
A-1
B-1
C-1
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TABLE OF CONTENTS
(cont inued)
APPENDIX D Information on Pretreatment Unit
Operat ions
Annex 1-Paper and Allied Products
Annex 2-Dairy Products
Annex 3-Textiles
Annex 4-Seafoods
Annex 5-Pharmaceutical s
Annex 6-Leather Tanning and
F i ni sh i ng
Annex 7-Sugar
Annex 8-Petroleum Refining
Annex 9-Meat Products
Annex 10-Grain Milling
Annex 11-Fruit and Vegetable
Annex 12-Beverages
Annex 13-Plastic and Synthetic
Materials
Annex 14-Blast Furnaces, Steel Works,
and Rolling and Finishing
Annex 15-Organic Chemicals
Annex 16-Metal Finishing
Annex 17-Other Industries
Inorganic Ferti1izer
Electric and Steam
Generat ion
Alumi num
Flat Glass, Cement,
Lime, Concrete
Products, Gypsum,
and Asbestos
Inorganic Chemicals
Industrial Gas Products
Page No.
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D-2-1
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D-8-1
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Federal Guidelines
Pretreatment of Pollutants Introduced
Into Publicly Owned Treatment Works
SECTION I
INTRODUCTION
1 . Purpose
These guidelines are established to assist municipalities,
States, and Federal agencies in developing requirements for
the pretreatment of wastewaters which are discharged to pub-
licly owned treatment works. The Guidelines also explain
the relationship between pretreatment and the effluent
limitations for a publicly owned treatment works.
The U.S. Environmental Protection Agency (EPA) has published
Pretreatment Standards in 40 CFR 128 (Appendix A). The stan-
dards will be enforceable by the EPA. These guidelines
provide technical information useful to States and municipal-
ities in establishing pretreatment requirements to supplement
the Federal pretreatment standards.
2. Author!ty
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 k02 of this Act, the Adminis-
trator shall publish . . . guidelines for pretreatment
of pollutants which he determines are not susceptible to
treatment by publicly owned treatment works. Guidelines
under this subsection shall be established 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. Defi n i t ions
Compatible Pollutant:
Biochemical oxygen demand, suspended solids, pH, and fecal
coliform bacteria, plus additional pollutants identified in
the NPDES permit if the publicly 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 publicly
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-
water.
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 k) has a significant impact,
either singly or in combination with other contributing
industries, on a publicly 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.
The Federal Water Pollution Control Act Amendments ofJ972
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 Elimination 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 available treatment technology. For publicly owned
treatment works, the initial objective is secondary treatment,
followed by best practicable treatment technology.
Monitoring for compliance with effluent limitations and pre-
treatment requirements will be in accordance with EPA guide-
lines established under Section J>Qk and implemented under
Section 308 of the Act.
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SECTION II
EFFLUENT LIMITATIONS NPDES PERMITS
5- NPDES Municipal Permits
Procedures developed under Section ^02 of the Act will provide
the details 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
gui de1ines.
Under the National Pollutant Discharge Elimination System
(NPDES), all point sources (including publicly owned treat-
ment works) must obtain a permit for the discharge of waste-
waters to the navigable waters of the United States. Permits
will not be required for industrial sources discharging into
publicly owned treatment works.
The pretreatment standards (Appendix A) will be directly en-
forceable by EPA on industry.
The effluent limitations 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 municipality. These effluent limitations will be in-
cluded in the discharge permit issued to the municipality for
the publicly owned treatment works.
Additionally the permit for a publicly owned treatment works
will 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 30o 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 will include information on the quantity and quality
of the wastewater introduced by the new source into the publicly
owned treatment works, and on any anticipated impact on the
effluent discharged from such works.
The permit programs developed under Section A02 of the Act
should be consulted for details regarding permit application.
6. Effluent Limitations for Publicly Owned Treatment Works
There are various sources of effluent limitations, including:
a. Effluent limitations for publicly owned treatment
works (Section 301(b) of the Act). Secondary treatment
information is contained in ^0 CFR Part 133 (Appendix B).
b. Toxic Effluent Standards or Prohibitions (Section 307
(a) of the Act) .
c. Water Quality Standards (Section 303 of the Act).
o
The most stringent limitation for each pollutant will govern.
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SECTION I I I
JOINT TREATMENT AND PRETREATMENT
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 municipality, 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 facilities.
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 flexibility.
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 will be
necessary to pretreat the wastewater.
8. Pretreatment Policy
The following 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
limitations 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 guidelines 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 publicly
owned treatment works are listed. This Section is applicable
to non-domestic users only.
Section 128.133 is designed to prevent the introduction of
incompatible pollutants to publicly 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
available as defined for industry categories in guidelines
issued pursuant to Section 30^(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 avail-
able. Provision is also made to permit a less stringent pre-
treatment standard for an incompatible pollutant if the munic-
ipality is committed in its NPDES permit to remove a specified
percentage of the incompatible pollutant. These requirements
are based on the premise that incompatible pollutants introduced
into a publicly owned treatment works generally should not
pass through such works in amounts greater than would be permitted
for direct discharge.
Biochemical oxygen demand, suspended solids, pH, and fecal
coliform 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
limitations are necessary to ensure compliance with water quality
standards or toxic effluent standards.
The terms compatible and incompatible pollutant should not be
misinterpreted. For incompatible pollutants, Jt will be
necessary for the municipality to assess the capabilities 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 will not cause harm to the treatment works or
interfere with its operation (including sludge handling and
disposal processes).
There will also be situations when the Federal pretreatment
standards (without credit for removal in the publicly owned
treatment works) will not be sufficient to protect the opea-
tion of the publicly owned treatment works. This might be
the case when the quantity of an incompatible pollutant intro-
duced by all 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 municipality would have to
supplement the Federal standards.
Pretreatment for removal of compatible pollutants is not re-
quired by the Federal pretreatment standards. This is based
on the premise that pretreatment facilities 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 equalization 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. Ob j ect i ves
The Act specifically provides for pretreatment requirements
established by State or local law not in conflict with the
Federal standards in Appendix A. The Federal standards were
established on the basis that each publicly owned treatment
works may require 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 municipalities
and others in arriving at effective pretreatment requirements
to supplement the Federal pretreatment standards for a specific
publicly owned treatment works. This subsection describes
the information available, how it was developed, and its applica-
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, trickling filter,
anaerobic digestion, and nitrification. This information was
derived from data reported in the technical literature. Docu-
mented information on this subject is limited, 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 publicly 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 waste-
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 already 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 realized 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 Information on Industrial 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 listed. It is emphasized that the
listed 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
Manual is available from the Superintendent of Documents,
Government Printing Office, Washington, D. C. 20k02. 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 Allied Products
Dairy Products
Texti1es
Seafoods
Pharmaceuticals
Leather Tanning and Finishing
Sugar
Petroleum Refining
Meat Products
Grain Mi 11 ing
Fruit and Vegetables
Beverages
Plastic and Synthetic Materials
Blast Furnaces, Steel Works, and Rolling and Finishing
Organic Chemicals
Metal Finishing
Inorganic Fertilizers
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
i nclude:
(1) Industrial effluent guidance documents developed by
EPA.
(2) EPA research reports.
(3) Information in the technical literature.
Most of the data were derived from EPA publications; other
sources were used to fill in data gaps. Ranges of different
waste constituents present in industrial wastewaters were
designated on the basis of a review of the data available.
The following classification system was used to describe the
characteristics of industrial wastewaters in relation to domestic
wastewaters:
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Low
200
: 300
200
15
: 6
Average
200-300
300-450
200-300
15-25
(acid) 6-9
Extremely
Hiqh Hiqh
300-1,000 > 1,000
450-1,500 > 1,500
300-1,000 > 1,000
> 25
> 9 (alkaline) -
Class i fi cat ion
Waste
Const i tuents
BOD , mg/L
COD; mg/L
SS, mg^L
Temp., C
PH
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 guideline 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 (trickling filter and modi-
fications, rotary disc).
3. Independent physical/chemical system (chemical addition,
sedimentation, pH adjustment, filtration, carbon
adsorption).
Before application of the pretreatment unit operations infor-
mation, full consideration must be given to Federal pretreat-
ment standards, permit effluent limitations, 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 publicly 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 controlling all discharges to the
publicly owned treatment works. A municipal ordinance or
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statute, embodying the pretreatment principles in these guide-
lines, 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.
Detailed 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 published 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. Examp1e Ca1cu1 at ions
When the Federal pretreatment standards (Appendix A) govern,
industrial users will be able to determine their pretreatment
requirements with other information which is publicly avail-
able. However, when effluent limitations (such as water quality
standards or toxic effluent standards) govern for a particular
pollutant, 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 municipality 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 municipalities, 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 allocate 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 100 tons/day
Wastewater flow 1 MGD
Wastewater contains incompatible pollutant I
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Industry Y
Production 200 tons/day
Wastewater flow 1 MGD
Wastewater contains incompatible pollutant I
The guidelines for best practicable control technology
currently available for pollutant I are:
Industry X 1.0 pounds/ton
Industry Y 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 ^00 pounds/day
However, the municipality 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 =
j£fi (280) = 70 pounds/day
Pollutant I Allocation to Industry Y =
^~ (280) = 210 pounds/day
Other Considerations
The sample calculations presented in the immediately preceding
Subsection show one method for determining waste load alloca-
tions. However, in addition to ensuring that the effluent limi-
tations are met, it is necessary to evaluate the industrial
wastewaters to ensure that there is no interference with the
publicly owned treatment works operation.
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Some of the factors to be evaluated are:
a. Conformance with Federal pretreatment standards
(Appendix 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) Severe corrosion damage.
(2) Significant deposits or abrasion which would
substantially reduce the design capacity of sewers
and wet wells or which would cause structural
col lapse.
(3) Pollutant concentration in sludges such that
sludge handling, stabilization, or disposal
is adversely affected.
c. Cost-effectiveness of treatment in the publicly
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. Applicability of more stringent State or local pretreat-
ment requirements which govern.
g. Need to conduct treatability studies or test programs
to verify findings.
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APPENDIX A
THURSDAY, NOVEMBER 8, 1973
WASHINGTON, D.C.
Volume 38 Number 215
PART III
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
Pretreatmcnt Standards
No, 216Pt, 1111
A-l
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30982
RULES AND REGULATIONS
Title 40Protection of the Environment
CHAPTER IENVIRONMENTAL
PROTECTION AGENCY
SUBCHAFTER DWATER PROGRAMS
PART 128PRETREATMENT STANDARDS
On July 19, 1973, notice was pub-
lished in the FEDERAL REGISTER that the
Environmental Protection Agency was
proposing standards for pretreatment of
pollutants introduced into publicly
owned treatment works pursuant to sec-
tion 307(b) of the Federal Water Pollu-
tion Control Act Amendments of 1972
(the Act). Written comments on the pro-
posed rulemaking were invited and re-
ceived from interested parties and the
public. In addition, a public hearing was
held in Washington, 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 written comments
and a transcript of the public hearing
are on file with the Agency. As indicated
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 standards are designed
to achieve two purposes: (1) To protect
the operation of publicly owned treat-
ment works, and (2/to prevent the dis-
charge of pollutants which pass through
such works inadequately treated.
Section 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 § 128.131 is deficient in that it fails
to impose specific numerical limitations
on the discharge of pollutants that in-
terfere with the operation of publicly
owned treatment works. However, the
Agency has been unable to formulate
such specific numerical limitations. In
the first place, the data that are
presently available are not considered
sufficient to support uniform national
standards prescribing permissible con-
centrations of particular pollutants in
publicly owned treatment works. More-
over, the degree that any pollutant in-
terferes with the operation of a publicly
owned treatment works depends on
the concentration of pollutant in
the treatment works itself, rather
than the concentration in each user's
effluent. But for a national pretreat-
ment standaard to be workable and
enforceable, it must prescribe the qual-
ity of the user's effluent; otherwise, the
user will not know what steps he must
take to comply with the standard. It is
impossible in a uniform national pre-
treatment standard to relate the quality
of the user's effluent to the concentration
of various pollutants in the publicly
owned treatment works, since this rela-
tionship will vary in each sewer system
depending on the quantity of the user's
effluent as compared with the quantity of
other effluents in the system.
Section 128.133 is based on the premise
that pollutants which pass through pub-
licly owned treatment works in amounts
greater than would be permitted as a
minimum treatment requirement for
similar industrial sources discharging di-
rectly to navigable waters should be con-
sidered adequately treated. The fact that
a discharger chooses to use a municipal
sewer system, rather than discharging
his wastes directly to the navigable
waters, should not as a matter of general
principle involve a penalty to the en-
vironment.
On the basis of this premise, § 128.133
requires users in industrial categories
subject to effluent guidelines issued under
section 304(b) of the Act, which are
discharging incompatible pollutants 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.
During the public comment period,
questions were raised as to 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-
ries should be considered in connection
with the promulgation of the individual
effluent guidelines, rather than in the na-
tional pretreatment standard. Accord-
ingly, when effluent limitations guidelines
are promulgated for individual industrial
categories, the Agency will also propose
a separate provision for their application
to users of publicly owned treatment
works. Additional language has been
added to § 128.133 to clarify this intent.
It was unclear whether § 128.133 as
proposed covered sources that would be
new sources if they were discharging di-
rectly into the navigable waters. Section
307(c) of the Act requires promulgation
of separate pretreatment standards for
such sources. Pursuant to section 307(c),
the Agency has proposed pretreatment
standards for such sources in connection
with its proposal of new source perform-
ance standards under Section 306 of the
Act. Accordingly, § 128.133 has been mod-
ified to make it clear that it covers only
sources that are not subject to section
307(c) of the Act.
Section 128.133 allows a credit for the
percentage removal of an incompatible
pollutant to which the publicly owned
treatment works is committed in its per-
mit. To insure the basis for allowing such
credit, a commitment with respect to a
percentage removal of an incompatible
pollutant will be included in the permit
at the request of a municipality where
a basis for such commitment can be
demonstrated.
Some commenters suggested that the
credit in § 128.133 for removal at the
joint treatment works, where there is a
commitment to such removal in the
NPDES permit, is unrealistic, since mu-
nicipalities will be unwilling to enter into
such commitments. However, in order to
achieve the goal of preventing the dis-
charge of incompatible pollutants
through municipal systems in amounts
greater than the minimum requirements
if the discharge were directly into the
navigable waters, it is necessary that the
required reduction be contained in an
enforceable commitment either on the
part of the industrial user or the joint
treatment works. The industrial user
should not be relieved of the commit-
ment to achieve the required degree of
reduction except to the extent 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 307(a)
of the Act, as well as the requirement of
best practicable control technology cur-
rently available under section 301 (b) and
304(b) of the Act. However, toxic effluent
standards will be designed to protect
aquatic life in the receiving body of
water from both acute and chronic ef-
fects. Acute effects will be covered by
concentration standards while chronic
effects will be covered by weight limita-
tions. Both types of standards will be
applicable to the discharge from the pub-
licly owned treatment works. Toxic efflu-
ent standards will not be designed to
protect sewer systems, and thus it would
not be appropriate to apply them to dis-
charges into the system. To the extent
that toxic materials in the users' dis-
charges interfere with the operation of
publicly owned treatment works, the
problem can be otherwise addressed
under these standards (§ 128.131) or
under local standards using the pretreat-
ment guidelines issued under section
304(f) of the Act. While toxic materials
in the users' discharge may appear in
the sludge generated by the publicly
owned treatment works, the Agency has
no basis for making a national deter-
mination that the resultant sludge dis-
posal problem is any worse than the
problem that would be created if the
individual users removed the toxics from
their effluent and disposed of the result-
ant materials individually. This is a
factor which must be determined by
State and local authorities, taking into
account the capabilities of their sludge
disposal system and the pollutants pres-
ent in the wastes from industrial users.
The presence of toxic pollutants in
toxic amounts is utilized in the regula-
tion in order to identify "major con-
tributing industries" for purposes of the
pretreatment requirements for incom-
patible pollutants. The purpose here is to
identify industrial users whose effluent
is significant enough to warrant the im-
position of controls based on best prac-
ticable control technology currently
available without undue administrative
burden, rather than to indicate that it
is appropriate to impose toxic effluent
standards on industrial users.
FEDERAL REGISTER, VOL. 38, NO. 215THURSDAY, NOVEMBER 8, 1973
A-2
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RULES AND REGULATIONS
30983
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 bactena).
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 available, since this
would lead to an uneconomical duplica-
tion of treatment facilities. While the
term "substantial removal" is not sub-
ject to precise definition, it generally con-
templates removals in the order of 80
percent or greater. Minor incidental re-
movals in the order of 10 to 30 percent
are not considered "substantial".
There was a diversity of comments on
the length of the time for compliance
and its relation to the promulgation of
the definition of best practicable 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
limitations guideline for a given in-
dustrial category.
Accordingly, § 128.140 provides that
the period of compliance with § 128.133
will 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
without 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 standards, Federally enforce-
able, and EPA pretreatment guidelines to
assist States and municipalities in
developing local pretreatment programs.
The Agency recognizes that in some cases,
these pretreatment standards may not be
sufficient to protect the operation of a
publicly owned 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
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 compli-
ance with the NPDES permit.
Pretreatment guidelines will be pub-
lished, pursuant to section 304 (f) of the
Act, to assist the States and municipali-
ties in establishing their own pretreat-
ment requirements.
Effective date. This regulation will be-
come effective December 10, 1973.
JOHN QTJARLES,
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-
ment.
Sec.
128.100
128 101
128 110
128 120
128 121
128 122
128.123
128.124
128.125
128.130
128.131
128.132
128 133
128 140
Purpose
Applicability.
State or local law.
Definitions.
Compatible pollutant.
Incompatible pollutant.
Joint treatment works.
Major contributing industry.
Pretreatment.
Pretreatment standards.
Prohibited wastes.
Pretreatment for compatible pol-
lutants.
Pretreatment for incompatible pol-
lutants
Time for compliance.
AUTHORITY: Sec. 307(b) Pub. L. 92-500; 86
Stat. 857 (33 U.S C 1317).
§ 128.100 Purpose.
The provisions of this part implement
section 307 (b) of the Federal Water Pol-
lution Control Act Amendments of 1972
(Public Law 92-500) hereinafter referred
to as "the Act".
§ 128.101 Applicability.
The standards set forth in § 128.131
apply to all non-domestic users of pub-
licly owned treatment works. The stand-
ard set forth in § 128.133 applies only to
major contributing industries.
§ 128.110 State 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 Definitions.
Definitions of terms used in this part
are as follows:
§ 128.121 Compatible pollutant
For purposes of establishing Federal
requirements for pretreatment, the term
"compatible pollutant" means biochem-
ical oxygen demand, suspended solids,
pH and fecal coliform bacteria, 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:
Chemical oxygen demand.
Total organic carbon.
Phosphorus and phosphorus compounds.
Nitrogen and nitrogen compounds.
Pats, oils, and greases of animal or vegeta-
ble origin except as prohibited under
i 128.131 (c).
§ 128.122 Incompatible pollutant.
The term "incompatible pollutant"
means any pollutant which is not a com-
patible pollutant as defined in § 128.121.
§128.123 Joint treatment works.
Publicly owned treatment works for
both non-industrial and industrial
wastewater.
§ 128.124 Major contributing industry.
A major contributing industry is an
industrial user of the publicly owned
treatment works that; (a) Has a flow
of 50,000 gallons or more per average
work day; (b) has a flow greater than
five percent of the flow carried by the
municipal system receiving the waste;
(c) has in its waste, a to'xic pollutant in
toxic amounts as defined in standards
issued under section 307(a) of the Act;
or (d) is found by the permit issuance
authority, in connection with the issu-
ance of an NPDES permit to the pub-
licly owned treatment works receiving
the waste, to have significant impact,
either singly or in combination with
other contributing industries, on that
treatment works or upon the quality of
effluent from that treatment works.
§ 128.125 Prelreatment.
Treatment of wastewaters from
sources before introduction into the joint
treatment works.
§ 128.130 Pretreatment standards.
The following sections set forth pre-
treatment standards for pollutants intro-
duced into publicly owned treatment
works.
§128.131 Prohibited wastes.
No waste introduced into a publicly
owned treatment works shall interfere
with the operation or performance of the
works. Specifically, the following wastes
shall not be introduced into the publicly
owned treatment works:
(a) Wastes which create a fire or ex-
plosion hazard in the publicly owned
treatment works.
(b) Wastes which will cause corrosive
structural damage to treatment works,
but in no case wastes with a pH lower
than 5.0, unless the works is designed to
accommodate such wastes.
(c) Solid or viscous wastes in amounts
which would cause obstruction to the
flow in sewers, or other interference with
the proper operation of the publicly
owned treatment works.
FEDERAL REGISTER, VOL. 38, NO. 215THURSDAY, NOVEMBER 8, 1973
A-3
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30984
RULES AND REGULATIONS
(d) Wastes at a flow rate and/or pol-
lutant discharge rate which is excessive
over relatively short time periods so that
there is a treatment process upset and
subsequent loss of treatment efficiency.
§ 128.132 Prctrcatmem Cor compatible
pollutant*.
Except as required by § 128.131, pre-
treatment for removal of compatible pol-
lutants is not required by these regula-
tions. However, States and municipalities
may require such pretreatment pursuant
to section 307 (b) <4) of the Act.
§ 128.133 Prctreatmenl for incompati-
ble pollutant*.
In addition to the prohibitions set
forth in § 128.131, the pretreatment
standard for incompatible pollutants in-
troduced into a publicly owned treat-
ment works by a major contributing in-
dustry not subject to section 307
-------
APPENDIX B
FRIDAY, AUGUST 17, 1973
WASHINGTON, D.C.
Volume 38 Number 159
PART II
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
Secondary Treatment
Information
No. 159Pt. II 1
B-l
-------
22298
RULES AND REGULATIONS
Title 40Protection of Environment
CHAPTER IENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER DWATER PROGRAMS
PART 133SECONDARY TREATMENT
INFORMATION
On April 30,1973, notice was published
in the FEDERAL REGISTER that the En-
vironmental Protection Agency was pro-
posing information on secondary treat-
ment pursuant to section 304(d)(l) 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 has care-
fully considered all comments received.
All written comments are on file with the
Agency.
The regulation has been reorganized
and rewritten to improve clarity.
Major changes that were made as a re-
sult of comments received are sum-
marized below:
(a) The terms "1-week" and "l-
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 (c)).
(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 § 133.102(g) of the proposed rule-
making) . The intent was that in no case
should the percentage removal of bio-
chemical oxygen demand and suspended
solids in a 30 day period be less than 85
percent. This has been clarified in the
regulation. In addition, it has been ex-
pressed as percent remaining rather than
percent removal calculated using the
arithmetic means of the values for in-
fluent and effluent samples collected in
a 30 day period (See § 133.102(a) and
(b)).
(c) 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
will allow waiver or adjustment of that
requirement on a case-by-case basis
(See§ 133.103(a)).
(d) The definition of a 24-hour com-
posite sample (See § 133.102(c) of the
proposed rulemaking) was deleted from
the regulation. The sampling require-
ments for publicly owned treatment
works will be established in guidelines
issued pursuant to sections 304(g) and
402 of the Act.
(e) In 1133.103 of the proposed rule-
making, it was recognized that secondary
treatment processes are subject to upsets
over which little or no control may be
exercised. This provision has been de-
leted. It is no longer considered necessary
In this regulation since procedures for
notice and review of upset incidents will
be included in discharge permits issued
pursuant to section 402 of the Act.
(f) Paragraph (f) of § 133.102 of the
proposed rulemaking, which relates to
treatment works 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 provision to only those cases in
which the flow or loading from an indus-
try category exceeds 10 percent of the
design flow or loading of the treatment
works. This intended to reduce or elimi-
nate the administrative burden which
would be involved in making insignifi-
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
duality 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-
menters 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
specified can be achieved with waste
stabiLzation ponds. A technical bulletin
will be published in the near future which
will provide guidance on the design and
operation of waste stabilization ponds.
(c) Disinfection must be employed in
order to achieve the fecal coliform bac-
teria levels specified. A few commenters
argued that disinfectant is not a second-
ary treatment process and therefore the
fecal coliform bacteria requirements
should be deleted. No changes were made
because disinfection is considered by the
Agency to be an important element of
secondary treatment which Is necessary
for protection of public health (See
§ 133,102(0).
Effective date. These regulations shall
become effective on August 17, 1973.
JOHN QTJARLES,
Acting Administrator
AUGUST 14, 1973.
Chapter I of title 40 of the Code of
Federal Regulations is amended by add-
In? a new Part 133 as follows:
Sec.
133.100 Purpose.
133.101 Authority.
133.102 Secondary treatment.
133.103 Special considerations.
133.104 Sampling and test procedures.
AOTHORITV: Sees. 304()(1), 301(b) (1) (B),
Federal Water Pollution Control Act Amend-
ments, 1972, PX. 92-500.
§ 133.100 Purpose.
This part provides information on the
level of effluent quality attainable
through the application of secondary
treatment.
§ 133.101 Authority.
The information contained in this
Part is provided pursuant to sections
304(d) (1) and 301(b) (1) (B) of the Fed-
eral Water Pollution Control Act
Amendments of 1972, PL 92-500 (the
Act).
§ 133.102 Secondary treatment.
The following paragraphs describe the
rninimum level of effluent quality attain-
able by secondary treatment in terms of
the parameters biochemical oxygen de-
mand, suspended solids, fecal coliform
bacteria and pH. All requirements for
each parameter shall be achieved except
as provided for in § 133.103.
(a) Biochemical oxygen demand (five-
day). (1) The arithmetic mean of the
values for effluent samples collected In a
period of 30 consecutive days shall not
exceed 30 milligrams per liter.
(2) The arithmetic mean of the val-
ues for effluent samples collected in a
period of seven consecutive days shall
not exceed 45 milligrams per liter.
(3) The arithmetic mean of the val-
ues for effluent samples collected in a
period of 30 consecutive days shall not
exceed 15 percent of the arithmetic mean
of the values for influent samples col-
lected at approximately the same times
during the same period (85 percent re-
moval).
(b) Suspended solids. (1) The arith-
metic mean of the values for effluent
samples collected in a period of 30 con-
secutive days shall not exceed 30 milli-
grams per liter.
(2) The arithmetic mean of the val-
ues for effluent samples collected in a
period of seven consecutive days shall
not exceed 45 milligrams per liter.
(3) The aritnmetic mean of the val-
ues for effluent samples collected In a
period of 30 consecutive days shall not
exceed 15 percent of the arithmetic mean
of the values for influent samples col-
lected at approximately the same times
during the same period (85 percent re-
moval) .
(c) Fecal coliform bacteria. (1) The
geometric mean of the value for effluent
samples collected In a period of 30 con-
secutive days shall not exceed 200 per
100 miUiUters.
FEDERAL REGISTER, VOL, 36, NO. 1 59-FRIDAY, AUGUST 17, 1973
B-2
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(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 effluent values for pH shall
remain within the limits of 6.0 to 9.0.
§133.103 Special considerations.
(a) Combined sewers. Secondary
treatment may not be capable of meet-
ing the percentage removal requirements
of paragraphs (a) (3) and (b)(3) of
§ 133.102 during wet weather in treat-
ment works which receive flows from
combined sewers (sewers which are de-
signed to transport both storm 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 percentage removal level
can be denned, and if so what that level
should be.
RULES AND REGULATIONS
(b) Industrial wastes. For certain in-
dustrial categories, the discharge to nav-
igable waters of biochemical oxygen de-
mand and suspended solids permitted
under sections 301(b) (1) (A) (i) or 306 of
the Act may be less stringent than the
values given in paragraphs (a)(l). and
(b) (1) of § 133.102. In cases when wastes
would be introduced from such an indus-
trial category into a publicly owned
treatment works, the values for biochemi-
cal oxygen demand and suspended solids
in paragraphs (a) (1) and (b)(l) of
§ 133.102 may be adjusted upwards pro-
vided that: (1) the permitted discharge
of such pollutants, attributable to the
industrial category, would not be greater
than that which would be permitted
under sections 301(b) (1) (a) (i) or 306
of the Act if such industrial category
were to discharge directly into the navi-
gable waters, and (2) the flow or loading
22299
of such pollutants introduced by the in-
dustrial category exceeds 10 percent of
the design flow or loading of the publicly
owned treatment works. When such an
adjustment is made, the values for bio-
chemical oxygen demand or suspended
solids in paragraphs (a) (2) and (b) (2)
of § 133.102 should be adjusted propor-
tionally.
§ 133.101 Sampling and test procedure-..
(a) Sampling and test procedures for
pollutants listed in § 133.102 shall be in
accordance with guidelines promulgated
by the Administrator pursuant to sec-
tions 304(g) and 402 of the Act.
(b) Chemical oxygen demand (COD)
or total organic carbon (TOO may be
substituted for biochemical oxygen de-
mand (BOD) when a long-term BOD:
COD or BOD:TOC correlation has been
demonstrated.
[FB Doc 73- X'7194 Filed 8-16-73;8.45 am]
FEDERAL REGISTER, VOL. 38, NO. 159FRIDAY, AUGUST 17, 1973
B-3
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Appendix C
Information on Materials which Inhibit
Biological Treatment Processes
The following 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 McDermott, et al (3) have shown, from pilot-
plant studies, that continuous addition 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
pilot-plant studies conducted with copper sulfate and copper-
cyanide complex additions.
When four-hour slug doses 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,^). 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.
With 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 raw sewage affected the digestion process (2).
However, 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 ZnSOj, or
in the form found in a typical alkaline cyanide plating bath)
added to raw sewage produced similar effects on biological
C-l
-------
systems. The maximum level of zinc that will not produce a
significant effect on treatment efficiency was indicated as
being between 2.5 and 10 mg/L when continuously added to the
biological system.
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 raw sewage reached 20 mg/L. This concentra-
tion is in agreement with 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 will inhibit or retard the aerobic biological
metabolism. This is in agreement with the values reported by
Kalabina from studies conducted using lead sulfate (5).
Kalabina also studied the effects of lead on nitrification
process and showed that 0.5 rng/L of lead in raw sewage
inhibited the nitrification process (5).
Cadmi urn
Mosey (10,11) 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 x 10~5 moles/L. The results
also 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 based on laboratory studies, and
the cadmium concentrations refer only to those present in
the digester.
Boron and Arsenic
Banerji, et al (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 adverse!
affected the performance of aerobic metabolism. However,
Rudolfs (1) indicated that boron in raw sewage affected the
-------
performance of activated sludge and trickling filters at
much lower levels (1.0 mg/L and less). He also indicated
that the addition of arsenic at concentrations of approximately
k mg/L to digesting sludge inhibited or retarded the performance
of digesters.
Chromi urn
Rudolfs (1) indicated that chromium was toxic to activated
sludge and trickling filter 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 pilot-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 trickling filter process, and
at the 1-50 mg/L level the anaerobic digestion process was
affected.
It 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.
Nickel
Pilot-plant studies conducted with continuous addition of
NiSO/j in raw sewage indicated that nickel 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 satisfactorily.
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
will be severely inhibited when the nickel concentration is
approximately 0.5 mg/L (9).
Cyan i des
Coburn (16) reported that 5 mg/L of cyanide in raw wastewater
(discharging continuously) interfered with activated sludge
treatment. In trickling filter studies, cyanide in raw sewage
at 30 mg/L produced poor effluent quality. However, when the
cyanide concentration was only 10 mg/L, 98 to 100 percent of
the cyanide was destroyed in the trickling filter (7). These
levels are higher than those reported by Rudolfs (1). According
to Rudolfs, 1 to 2.0 mg/L of cyanide (as HCN) in raw sewage
affected the performance of the activated sludge, trickling
filters, and anaerobic digestion processes (1,16). Generally,
however, secondary biological treatment processes can oxidize
the cyanide if acclimatized (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 literature
on anaerobic processes that when the sulfate concentration
exceeded 500 mg/L, the gas production was greatly reduced.
Similar 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.
Ammo n i a
Prague, 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.
-------
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 Nad 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 trickling filters.
Chloroform
Ghosh (11), in a review of the anaerobic digestion process
literature, 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 application was
as a slug dosage, the anaerobic process was adversely affected
at 1 mg/L concentration in the feed.
Free Oi1
Free oil of petroleum origin, at concentrations in the range
of 50-100 mg/L, has been reported as interfering with aerobic
biological treatment (2*1,25). The oil concentrations were
measured according to the API Manual using CCI^ 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 (2?) has presented data on the effects of several
cations on anaerobic digestion. The results indicated that:
Ca+H~ 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 C-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.
C-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 al, "Summary Report on the Effects of Heavy Metals
on the Biological Treatment Processes", Journal WPCF, 37, 1,
86-96 (1965).
3. "Interaction of Heavy Metals and Biological Sewage Treatment Processes",
Public Health Service Publication No. 999-WP-22, U.S. Dept. of Health,
Education and Welfare, Cincinnati, Ohio (May, 1965).
4. McDermott, G.N.,et al, "Copper and Anaerobic Sludge Digestion",
Journal WPCF, 35, 5, 655-662 (1963).
5. Kalabina, M. , et al . "Effect of Copper and Lead Bearing Wastes on
the Purification of Sewage", Water and Sewage Works, 93, 1, 30
(1946).
6. McDermott, G.N., et al, "Zinc in Relation to Activated Sludge and
Anaerobic Digestion", Proc. 17th Industrial Waste Conference,
Purdue University, Rafayette, Ind., 46J-475 (1962).
7. "The Effect of Industrial Wastes on Sewage Treatment", Publication
No. TR-13, Hew England Interstate Water Pollution Control Commission,
Boston, Mass. (1965).
8. Nemerow, N.L., "Theories and Practices of Industrial Waste Treatment",
Add!son-Wiley Publ i shing Company, Reading, Mass. (1963).
9. Air and Water News, 5, 40, 8-9 (October 11, 1970.
10. Mosey, F.E., "The Toxicity of Cadmium to Anaerobic Digestion: Its
Modification 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. Banerji, S.K., et al. "Effect of Boron on Aerobic Biological Waste
Treatment", Proc. 23rd Industrial Waste Conference, Purdue University,
Lafayette, Ind., 956-965 (1968).
13. Moore, W.A., et al, "Effects of Chromium on the Activated Sludge
Process", Journal WPCF, 33, 1, 54-72 (1961).
14. Whiteland, A.B., et al, "Pilot Plant Experiments on the Effects of
Some Constituents of Industrial Wastewaters on Sewage Treatment",
Water Pollution Control (G-B), 70, 626-643 (1971).
15. McDermott, G.N., et al, "Nickel in Relation to Activated Sludge
and Anaerobic Digestion Processes", Journal WPCF, 37, 2, 163-177
(1965).
C-7
-------
16. Coburn, S.E., "Limits for Toxic Wastes in Sewage Treatment",
Jour. Sew. Works. 2±, 3, 522-524 (1949).
17. "Controlling the Effects of Industrial Wastes on Sewaqe Treatment",
Publication No. TR-15, New England Interstate Water Pollution
Control Commission, Boston, Mass. (1971).
18. Pohland, F.G., and Kang, S.J., "Anaerobic Processes - Literature
Review." Jour. WPCF. 43. 6, 1129-1134 (1971).
19. Lawrence, A.W., et al, "The Effects of Sulfide on Anaerobic Treat-
ment ," ^rojEj^J^yLJlll^J^SifP-Hlfi* Purdue University, Lafayette,
Ind., 343-357 (1964).
20. Rudolfs, W., and Amberg, H.R., "White Water Treatment, II. Effect
of Sulfides on Digestion." Sew, and Ind. Wastes. 24, 10, 1278-1287
(1952).
21. Dague, R.R., et al, "Digestion Fundamentals Applied to Digester
Recovery - Two Case Studies." Jour. WPCF. 4_2, 9, 1666-1675 (1970).
22. Kincannon, D.F., "Studies on the Effects of Sodium Chloride on
Activated Sludge." 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." John Wiley & Sons, New York (1967).
25. "Manual on Disposal of Refinery Wastes," Volume on Liquid Wastes,
American Petroleum Institute, New York (1969).
26. "Manual on Disposal of Refinery Wastes," Vol. IV - "Sampling and
Analysis ot Wastewater," American Petroleum Institute, New York
(1957).
27. Malina, J.F., "Anaerobic Waste Treatment," Unpublished Report.
28. Kugelman, I.J., and McCarty, P.L., "Cation Toxicity and Stimulation
in Anaerobic Waste Treatment - II. Daily Feed Studies," Proc. 19th
Ind. Waste Conference, Purdue University, Lafayette, Ind., 667-686
(1964).
C-f
-------
29. Jackson, S., Phil, D., and Brown, V. M., "Effect of Toxic Wastes
on Treatment Processes and Watercourses." Proceedings 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., "Pilot
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." Jour. Appl. Chem., 4
(Aug. 195^).
C-9
-------
Table C-1
Information on Materials Which Inhibit Biological
Treatment Processes
Aerobic Processes
Pollutant
Copper 1.0
Zinc 5.0
Chromium (Hexavalent) 2.0
Chromium (Trivalent) 2.0
Total Chromium 5-0
Nickel 1.0
Lead 0.1
Boron 1.0
Cadmium *
Silver O.OJ
Vanadium 10
Sulf ides (S ") *
Sulfates ( SO, ") *
Ammonia *
Sodium (Na~) *
Potassium (K~) *
Calcium CCa") *
Magnes ium (Mg~ ") *
Aery lonitri te *
Benzene "
Carbon Tetrachloride *
Chloroform 18.0
Methylene Chloride *
Peintachloropheno1
1,1,1-Trichloroethane *
Tr ichlorof1uoromethane *
Trichlorotrif1uoroethane
Cyanide (HCN) *
Total oil (Petroleum origin) 50
0.5
0.5
Concentration , mg/L
Anaerobic Digestion N!tr!ficat ion
1.0
5.0
5.0
2000"
5.0
2.0
*
0.022
"t"
it
100^
500
1500"
3500
2500
2500
loog
5.PT
5°2
o.i2
1.0
o.k
1.0"
0.7
5.o2
1.0
50
*
*
*
*
*
*
*
*
*
References
(29)
(io)ri9)(2o)
(I0)(l7)fl8)(19)(20)
(I7)(l8)f30)
(27)(28)(30)
2.0
50
(29)
(l) (16) (17)
(2*0 (25) (26)
* Insufficient data
3
Concentrations refer to those present in raw wastewater unless otherwise indicated.
2
Concentrations apply to the digester influent only. Lower values may be required for protection of
other treatment process units.
Petroleum-based oil concentration measured according to the API Method 733-58 for determing
volatile and non-volatile oily materials. The inhibitory level does not apply to oil of
direct animal or vegetable origin.
C-10
-------
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 building 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 converted 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 fillers such as clays, calcium carbonate and sulfate,
talc, barium sulfate, aluminum compounds, and titanium
oxide. When fillers are used, retention aids (starches
or synthetic resins) are added to increase the retention
of the filler.
The principal operations involved in the manufacture of
pulp and paper are:
Wood Preparation
Pulping (mechanical, chemical, semi-chemical , and
dei nking)
Pulp Washing and Screening
Stock Preparation
Paper Making
The pretreatment sub-groups for this industry are as follows:
Integrated pulp and paper mills using mechanical pulping
processes (bleached and unbleached)
Integrated pulp and paper mills using chemical pulping
processes (unbleached)
D-1-1
-------
Integrated pulp and paper mills using chemical pulping
processes (bleached)
Integrated pulp and paper mills using deinked pulp
Paper and paperboard mills
Building products mills
2. Industrial Practices
The following industrial practices can significantly influence
pretreatment:
Pulping Process
The pulping process determines the pulp yield and quality,
and the probable organics loss in the wastewater from a pulp
mill. (Mechanical pulping results in minimum dissolution
of wood components, while chemical pulping solubilizes the
non-cellulose components of wood tannins, lignins, wood
sugars, and hemieellulose).
Recovery and Reuse of Spent Cooking Liquor
Most chemical pulping processes involve recovery and reuse
of spent cooking liquor and therefore do not generate
significant quantities of wastewater (1). The dissolved
organics present in the liquor usually are burned in the
chemical recovery furnace. The only pulping process where
the spent cooking liquor is not suitable for recovery is
the calcium-base acid sulfite process. The spent cooking
liquor from this process, with the dissolved organics, is
generally discharged with other process wastes.
Bleachi ng
When the desired quality 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 spills 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 D-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 mills (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 solids, dissolved solids,
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 solubilized organics
and the type of cooking liquor will determine the characteristics
of the wastewater.
D-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 facilities.
Information available on the joint treatment of paper and allied
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 established 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 trickling filter process (stone
and plastic media) for the treatment of paper mill
wastes have achieved only relatively low removals
(kO-60 percent BOD removal). This has been at-
tributed primarily to high organic loading and filter
clogging with fibers (k).
d. Paper mill wastewaters exhibit high chlorine demand
values (20-60 mg/L), even after secondary treatment.
Depending on the ratio of paper mill wastes to do-
mestic wastes, larger chlorination facilities may be
requi red.
e. When paper mill 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 treatability 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 solids, they are readily treatable in municipal
systems.
D-1-4
-------
Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment processes are shown in
Table D-1-2.
The neutralization requirements depend primarily 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
control 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. Spills 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 controlled.
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 facility.
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 limitations
are not exceeded where heavy metals are a significant
factor.
D-1-5
-------
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-------
REFERENCES
1. "Industrial Waste Survey of the Paper and Allied Products
Industries" Contracts #68-01-0022 and 68-01-0012, Environ-
mental Protection Agency, Washington, 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 Semichemical Pulp
Mill Waste," Technical Builetin #42, National Council 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,"
Water Pollution Control Research Series, Publication No. ORD 1
(July 1969).
D-1-8
-------
DAIRY PRODUCTS INDUSTRY
1. Industry Description
This industry includes Standard Industry Classifications (SIC)
2021, 2022, 2023, 202k, 2026, and 50A3. 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 utilized 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 facility. 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 Handling and Products.
2. Industrial Practices
Product recovery is the major method for reducing wastewater
loadings. The dairy 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 following industrial practices can have a major impact
on the wastewater characteristics:
Whey Handling
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 milk lost) (1).
Clean i ng
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 lines are sanitized.
3. Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table D-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
D-2-2
-------
(either acid or alkali) 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
spoiled or damaged products.
The wastewaters generated in the dairy industry can be char-
acterized generally as containing high concentrations of BOD,
COD, and IDS. Settleable solids 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 (k) . 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 normal ly would
not be a consideration because of dilution in the municipal
collection system.
Low-rate trickling filters are generally not effective in
treating dairy wastes, because these wastes produce large
quantities of biological solids which clog the filters.
This problem can be overcome by high hydraulic loading and
high rec i rculat ion rates (3)
** Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table D-2-2.
In general, dairy wastes are amenable to biological as well
as to chemical treatment if equalization and neutralization
are provided as pretreatment for the dairy wastes. As the
ratio of dairy waste to domestic waste increases » the need
D-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.
D-2-A
-------
Table D-2-1
Cha racteri st i cs
Industrial Operation
FLOW
BOD
TSS
IDS
COD
Grit
Cyanide
Chlorine Demand
PH
Color
Turbidi ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Sol ids
Volat i1e Organics
Pesticides
Phosphorus
Nitrogen
Temperature
Phenol
Sulfi des
Oi1 and Grease
Coli form
Wastewater Characteristics
Da i ry Products
Milk Handling
Milk Products
Year-round (BATCH)
INTERMITTENT
Average-HIGH
Low-Average
Average-HIGH
Average-HIGH
PRESENT
Absent
HIGH
ACID TO ALKALINE
HIGH
High
Absent
Absent
PRESENT
PRESENT
Absent
HIGH
Absent
Absent
Present
Adequate
Normal-High
Absent
Absent
Present
PRESENT
Natural and Cottage
Cheese Product
Year-round (BATCH)
INTERMITTENT
EXTREMELY HIGH
Average-EXT. HIGH
HIGH
EXTREMELY HIGH
PRESENT
Absent
HIGH
ACID TO ALKALI
NE
HIGH
High
Absent
Absent
PRESENT
PRESENT
Absent
HIGH
Absent
Absent
Present
DEFICIENT ,
Normal-High^
Absent
Absent
Present
PRESENT
There are possible bio-static effects in the joint treatment plant
attributable to large amounts of sanitizers and detergents in the
dairy products wastewater.
^Temperature equal to or higher than domestic wastewater. May
design but not harmful to joint treatment processes.
affect
NOTES: Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
UPPER CASE.
n
Wastewater characteristics shown reflect all
Practices described under Section D-2.
the Industrial
D-2-5
-------
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D-2-6
-------
REFERENCES
1. "Proceedings Second National Symposium on Food Processing
Wastes", Denver, Colorado, Environmental Protection Agency,
Water Pollution Control Research Series 12060 (March, 1971).
2. "The Cost of Clean Water, Vol. III. Industrial Profile
No. 9 - Dairies", Federal Water Pollution Control
Administration, Washington, D.C. (June, 1967).
3. "Study of Wastes and Effluent Requirements of the Dairy
Industry", Contract No. 68-01-UU23, Environmental Protection
Agency, Washington, D.C. (Unpublished).
k. "Industrial Wastewater Control". (Edited by) Gurnham, C.F.,
Academic Press, New York (1965,).
D-2-7
-------
TEXTILE 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, fulling, carbonizing, bleaching, and weaving.
Raw wool is scoured to remove grease and dirt. The process
employs a detergent and mild alkali at temperatures of 130°F.
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
olive oil) may be added before and during the fulling 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-
plished, 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, carboxymethy1 cellulose,
and polyacrylic acid.
After weaving, the fabric is desized using an acid enzyme re-
action. Desizing removes the chemicals added during sizing
by hydrolyzing them to a soluble form.
D-3-1
-------
During scouring cotton wax and other non-eel 1ulosic components
of cotton are removed by using hot alkaline solutions. Synthetic
materials require only light scouring because of the absence of
chemical impurities (3).
Both cotton and synthetic fabrics 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.
Alkaline Wool Scouring
Alkaline wool scouring may be used in place of neutral
scouring. In alkaline 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 or carboxy methyl-
cellulose for starch in the sizing of cotton reduces the
overall BOD in the wastewater.
Pressure Dyeing 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
concent rations.
D-3-2
-------
3. Wastewater Characteristics
The characteristics of the process wastewaters from each pre-
treatment sub-group are shown in Table D-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
orthophenyl 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 solids and grease
from the wool-scouring operation.
Textile wastewaters can vary from slightly acid to highly
alkaline depending on the individual processes carried out
within the plant. They generally are alkaline 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.
k. Pret reatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table D-3-2.
D-3-3
-------
Table D-3-1
Wastewater Characteristics
Textile Industry
Characteristics
Industrial Operation
Flow
BOO
TSS
TDS
COD
Grit
Cyan ide
Chlorine
pH
Color
Demand
Turbidity
Explos ives
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Solids
Volatile Organics
Pestici des
Phosphorus
Ni t rogen
Temperature
Phenol
Sulfides
0 i1 and G rease
Coli form (Fecal)
Wool
Year-round (batch)
INTERMITTENT
HIGH
HIGH
HIGH
HIGH
PRESENT
Absent
HIGH
BASIC
HIGH
High
Absent
Absent
PRESENT
Present
PRESENT
Present
Absent
Absent
PR SENT
DEFICIENT 2
Normal-High
Absent^
Absent
HIGH5
PRESENT
- Continuous
Cotton and Synthetics
Year-round (batch)
INTERMITTENT
Average-HIGH
Low-AVERAGE
HIGH
Average-HIGH
Absent
Absent
HIGH
BASIC
HIGH
High
Absent
Absent
PRESENT
Present
PRESENT
Present
Absent
Absent
PRESENT
- Continuous
DEFICIENT 2
Normal-High
Absent-5
Absent
Absent-Present
Absent
Wastewater flow characterized by an intermittent pattern over the day.
2
Temperature equal to or higher than domestic wastewater. May affect design but not
harmful to joint treatment processes.
Phenol may be present in dye carriers.
^
Oil present in wastewaters from synthetic textiles only.
Wool 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.
-------
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-------
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. "Industrial Waste Studies Program - Textile Mill Products",
Environmental Protection Agency (Unpublished)
3. "The Cost of Clean Water -Vol. Ill - Industrial Waste
Profile No. 4 Textile Mill Products", Federal Water Pollution
Control Administration (September, 1967).
D-3-6
-------
SEAFOODS INDUSTRY
1. Industry Description
This industry includes Standard Industry Classifications
(SIC) 2031 , 2036, and 209**
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 A billion pounds
(cleaned) with the catch being utilized as follows: 35%
rendered, 301 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 scallops); 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.
Solid 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 extract
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 liquor. The liquor 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 following industrial practices can significantly
influence the wastewater characteristics.
-------
Solid Waste Handling
The handling of the solid 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 D-A-1.
The seafood processing industry is seasonal, but wastewater
flows are relatively constant during operation. Wastewaters
include various auxiliary sources such as cooling water and
cooling waters from refrigeration systems.
The wastewaters generated from seafood processing contain as
major constituents BOD, COD, TSS, TDS, 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
coliform, and high concentrations of chlorides and other dis-
solved solids from sea water usage within the plant.
4. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table D-*»-2.
Very little treatability 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 so that dissolved solids 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 1 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
Character!sties
Industrial Operation
Flow
BOD
TSS
IDS
COD
Grit
Cyanide
Chlorine Demand
pH
Color
Turb id i ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Phosphorus
Ni trogen
Temperature
Phenol
Sulfides
Oi1 & Grease
Coliform (Fecal)
Coliform (Total)
Class i fication
SEASONAL
Conti nuous
Average-HIGH
Average-HIGH
Average-HIGH
Average-HIGH
Absent
Absent
Average-HIGH
Neutral
Average-HIGH
High
Absent
Absent
Present
Absent
Absent
Average-HIGH
Absent
Absent
Adequate
Adequate ,
Normal-Hi gh
Absent
Absent
Average-HIGH2
PRESENT
PRESENT
Temperature equal to or higher than domestic wastewater. May
affect design but not harmful to joint treatment processes.
^Depending 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 handling
and disposal of solid wastes in dry form as described
in Section 2.
D-k-3
-------
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-------
REFERENCES
1. "Current Practice in Seafoods Processing Waste Treatment",
Water Pollution Control Research Series, 12060 ECF,
Environmental Protection Agency, Washington, D.C. (April,
1970).
2. "Industrial Wastewater Control". (Edited by) Gurnham, C.F.,
Academic Press, New York (1965).
-------
PHARMACEUTICAL INDUSTRY
1 . Industry Description
This industry includes Standard Industry Classifications
(SIC) 2831, 2833, and 283*t. The industry produces medicinal
chemicals and pharmaceutical products, including some fine
chemicals which are marketed outside the pharmaceutical industry
as intermediates.
In 1970, there were 1,300 producers of pharmaceuticals in the
United States, and 150 of these firms produced over 95% of the
industry's products (1).
In general, the pharmaceutical industry may be divided into
two broad production categories; chemical synthesis products;
and antibiotics (penicillin and steroids).
The manufacturing operations for synthesis products may be
either dry or wet. Dry production involves dry mixing,
tableting or capsuling, and packaging. Process equipment is
generally vacuum cleaned to remove dry solids 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 pharmaceutical
product is often accomplished through solvents. The product
may then be washed, concentrated and filtered to the desired
purity, dried, capsulized, 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 presence of a particular
fungus or bacterium. The culture frequently is filtered
from the medium and marketed in cake or liquid form as an
animal feed supplement (2). The antibiotic is extracted
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.
D-5-1
-------
The pretreatment sub-groups for this industry are as follows:
Synthes is
Fermentat ion
2. Industrial Practices
The following 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.
2. 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 D-5-1.
The pharmaceutical plants operate continuously throughout
the year and are characterized by batch operations with
significant variations in pollutional 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 possibility
of nutrient deficiency.
D-5-2
-------
k. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table D-5-2.
The specific type and degree of pretreatment for heavy metals
and cyanide will be governed by the industrial effluent
guidelines for the pharmaceutical industry. Cyanide removal
or control is especially important.
Pharmaceutical industries generate wastewaters on an
intermittent basis and equalization may be needed as pre-
treatment. When solvents are used for extraction, solvent
removal can be accomplished by using gravity separation and
skimming. Neutralization may be required to neutralize
acidic or alkaline wastewaters generated from the production
of specific pharmaceutical products.
D-5-3
-------
Table D-5-1
Wastewater Characteristics
Pharmaceutical Industry
Characteristics
Synthes i s
Fermentat ion
Industrial Operation
Flow
BOD
TSS
TDS
COD
Grit
Cyan i de
Chlorine Demand
pH
Color
Turbidi ty
Explosi ves
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Solids
Volatile Organics
Pestici des
Phosophorus
Ni trogen
Temperature
Phenol
Sulfides
Oi 1 & Grease
Coliform (Total)
Year-Round (BATCH)
INTERMITTENT
AVERAGE-HIGH
HIGH
AVERAGE-HIGH
AVERAGE-HIGH
Absent
PRESENT
AVERAGE-HIGH
ACID-BASIC
Average-High
Average
Present
Absent
PRESENT
PRESENT
PRESENT
High
HIGH
Absent
DEFICIENT
DEFICIENT
Normal-High1
Absent
Absent
Absent-Present
Absent
Temperature equal to or higher than domestic wastewater.
harmful to joint treatment processes.
Year-Round (BATCH)
INTERMITTENT
EXTREMELY HIGH
EXTREMELY HIGH
HIGH
EXTREMELY HIGH
Absent
Absent
HIGH
ACID-BASIC
Average-High
High
Present
Absent
PRESENT
PRESENT
Absent
HIGH
HIGH
Absent
DEFICIENT-HIGH
DEFICIENT-HIGH
Normal-Hi gh
Absent
Absent
Absent-Present
Absent-Present
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-i*
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-------
REFERENCES
1. Lund, H.F., "Industrial Pollution Control Handbook.",
McGraw-Hill Book Co., New York (1971).
2. "Industrial Wastewater Control", (Edited by) Gurnham, C.F.,
Academic Press, New York (1965).
3. Rudolfs, W., "Industrial Wastes, Their Disposal and
Treatment", Reinhold Publishing Corp., New York (1953).
D-5-6
-------
LEATHER TANNING AND FINISHING INDUSTRY
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 metropolitan
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. Beam House
2. Tan House
3. Retan, color and fat liquor
4. Fi n i shing
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 oils 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 will
depend on whether the industry is practicing a "save hair" or
"pulp hair" operation. A low amount of sulfide (0.5 to 1.0
percent of hide weight) removes the hair with minimal damage,
while 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
chemical 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 will result in wastewater flow only
during weekdays. The seasonal variations in wastewater flow
are limited to the variations in hide characteristics. In
general, 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 solutions) are
derived from batch-type processes. These fractions are therefore
discharged intermittently (2, 3. ^> 5).
Liquid process wastes are generated in tanneries from soaking
and washing, fleshing, unhairing, bating, pickling, tanning,
coloring, and fat liquoring. Auxiliary wastewaters from tan-
neries result primarily from boiler blowdown and from cooling,
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, oil 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, oils, 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 total volume and approximately 70 percent of
the pollutional 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 clean-up operations.
The major wastewater sources from tanneries are the beam house
and the tan house operations. The beam house wastewater is
highly alkaline due to the large quantities of lime used in the
process. The wastewater generated from the tan house is
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 H~S 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 HLS gas
in the sewer lines and the effect of reducing characteristics
of the sulfides on biological treatment processes should be
taken into consideration in the design of joint treatment works.
Hydrogen sulfide is readily 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 H?S 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 H_S 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.
Q-6-k
-------
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 facilities may also be needed.
D-6-5
-------
Table D-6-1
Character? sti cs
Industry Operation
Flow
BOD
TSS
IDS
COD
Grit
Cyan!de
Chlorine Demand
PH
Color
Turbidi ty
Explosives
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Solids
Volatile Organ? cs
Pesticides
Phosphorus
N? trogen
Temperature
Phenol
Sulfides
0!1 & Grease
Coliform (Total)
Wastewater Characteristics
Leather Tanning and Finishing Industry
Chrome Tanning
Year-Round (Batch)
INTERMITTENT
EXTREMELY HIGH
EXTREMELY HIGH
HIGH
EXTREMELY rilGH
PRESENT
Absent
High
ACID - ALKALINE
Present
Present
Absent
Present
Present
Absent
PRESENT
Present
Present
Absent
DEFICIENT
Adequate
Normal^
Absent
Present
HI GH2
Low
Vegetable Tanning
Year-Round (Batch)
INTERMITTENT
EXTREMELY HIGH
EXTREMELY HIGH
HIGH
hXTREMELY HIGH
PRESENT
Absent
High
AUD - ALKALINE
Present
Present
Absent
Present
Present
Absent
Absent
Present
Present
Absent
DEFICIENT
Adequate
Normal^
Absent
Present
HIGH2
Low
Temperature equal to domestic wastewater.
Oil and grease (animal origin) are significant only in pigskin and sheepskin
processing wastewaters.
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
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REFERENCES
1. "The Cost of Clean Water, Vol. Ill, Industrial Waste Profiles
No. 7 - Leather Tanning and Fisnishing," U.S. Department of
the Interior, FWPCA (19&7).
2. "Activated Sludge Treatment of Chrome Tannery Wastes," Water
Pollution Control Research Series, ORD-5, U.S. Department
of the Interior, FWPCA, (19&9).
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, 0. J., Keshavan, K., and Hunter, R. W. , "Extreme
Removals of Suspended Solids 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 Activated Sludge Process," Proc. 18th
Industrial Waste Conference, Purdue University, 534-54-9
(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 4-5 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 filtration 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, while 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 film from the sugar
crystals, solution of the washed sugar, clarification of the
solution by phosphoric acid-lime precipitation, carbonation, and/or
pressure filtration, 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 crystalline
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 solids (waste filter 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 filter
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 from the sugar
industry, there are no separate pretreatment sub-groups for this
industry.
2. Industrial Practices
The following industrial practices can significantly affect the
wastewater characteristics.
The production of cane sugar involves by-products such as
residual sugar cane fibers and blackstrap molasses. The
residual 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 (A-,5)
The pulp press liquor and evaporator condensates can be re-
cycled for use in the flume-washing operation.
3. Wastewater Characteristics
The rh,-racter i st ics of the process wastewaterr from the industry
are shown in Table D-7-1. Sugar plants generally operate 2k
hours a day, but because of the nature of tne raw materials
(sugar cane and sugar beets), the domestic sugar industry oper-
ates seasonally 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-
D-7-2
-------
isties 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 spills 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 . Flume washing
2. Lime cake or slurry
3. Evaporator condensates
4. Spills, leaks, and floor washing
Process wastewaters originate from the following unit operations
in the refining of raw cane sugar:
1. Disposal of waste filter 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 will depend on the degree of recycle
practiced. The overall 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 constituents BOD, COD, suspended solids, and heat. The
wastewaters generated from sugar refineries are similar to
those from sugar production from sugar cane and contain as
major pollutants BOD 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 facilities.
D-7-3
-------
k. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities 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 available 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 collection systems. In addition, facilities for
supplemental nutrients (nitrogen and phosphorus) at the joint
treatment facility may be required.
-------
Table D-?-1
Wastewater Characteristics
Sugar Industry
Character 1st ics
Industrial Operation
Flow
BOD
TSS
IDS
SEASONAL1
Continuous-Variable
Low-EXT. HIGH
Low-EXT. HIGH
HIGH
COD
Grit
Cyan ide
Chlorine Demand
PH
Color
Turb id i ty
Exp1os ives
D issolved Gases
Detergents
Foam i ng
Heavy Metals
Col 1oidal Sol ids
Volat ile Organ ics
Pest ic i des
Phosphorus
N i t rogen
Temperature
Phenol
Su1f ides
Oil & Grease
Col i form (Feca1)
Coli form (Tota1)
Low-EXT. HIGH
PRESENT
Absent
HIGH
Neutral
LOW-HIGH
PRESENT
Absent
Absent
Absent
Absent
Absent
Low
Absent
Absent
DEFICIENT
DEFICIENT
HIGH
Absent
Absent
Absent
Absent
PRESENT
1 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.
Wastewater characteristics shown reflect all the In-
dustrial practices described under Section 2.
0-7-5
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D-7-b
-------
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 Find ley System," Proc. 17th Ind. Waste Conf.,
Purdue University, 116-135 (196I7T
3. Rogers, H.G., and Smith, L.H., "Beet Sugar Waste Lagooning,"
Proc. 8th Ind. Waste Conf., Purdue University, 136-1^7 (1953).
**. Biglane, K.E., "Some Current Waste Treatment Practices in
Louisiana Industry, "Proc. 13th Ind. Waste Conf., Purdue
University, 12-20
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 Standard Industrial Classification
(SiC) 2911. This classification includes those establishments
primarily engaged in producing gasoline, kerosine, fuel oils,
residual fuel oils, lubricants, and other products through
distillation of crude oil, cracking, or other processes.
Petroleum refining is a combination of several interdependent
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 oil.
The major operations within a refinery include: crude oil
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 oil stocks, sweetening of gasoline, extraction,
and stripping. Storage of crude oil to provide adequate
working supplies and to equalize process flow involves the
separation of water and suspended solids from crude oil
The first major operation in a refinery is the crude oil
desalting process for removing inorganic salts and suspended
solids from the crude oil prior to fractionation. Water
is used in the desalting process as a sequestering agent.
The crude oil after desalting is generally passsed through
atomspheric and/or vacuum distillation to separate light
overhead products (05 and lighter), side-stream distillates,
and residual crude oil. 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 oil fractionation
and distillation process can be cracked using either thermal,
catalytic, or hydrocracking processes to yield light oil
fractions such as domestic heating oil. 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 dilute 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 solid 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
oil fractions and aromatics from feedstocks containing
various types of hydrocarbons.
A more detailed description of the individual petroleum
refining processes is included in the "Industrial Waste
Profile" published by the Federal Water Pollution Control
Administration (now EPA) (1).
2. Industrial Practices
The petroleum refining industry uses very large quantities
of water for process and cooling purposes. Approximately
90 percent of the water used in refineries is for cooling
purposes. Lesser water uses include: steam generation
(boiler-feed.), direct processing, fire 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.
Oily process wastes and oil-free wastes are collected
separately in some refineries so that the oily wastes can
be treated for oil 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 sour water (condensates from various fractionation units)
containing sulfides and ammonia is generally steam or air-
stripped before being discharged to the sewer lines. A
survey of petroleum refining industries in 1967 indicates
that approximately 85 percent of the refineries strip the
sour water 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 neutralization
and oxidation, slop oil recovery, etc.) will determine
the final effluent characteristics and the level of pre-
treatment required for discharge to municipal 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 oil 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 following specific in-plant practices are frequently
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 burned in a furnace.
Hydrogen sulfides at concentrations in the range of
10 to 15 mg/L can cause upsets in biological treat-
ment plants (k) , and removal of sulfides from the
sour water by stripping would prevent such upsets.
b. Spent caustic neutralization is applied to both
phenolic and sulfidic waste streams, but oxidation
of spent caustics is limited to sulfide waste
streams, since phenols inhibit the oxidation of
sulfides in spent caustics.
c. Spent acids (generally sulfuric) can be recovered for
reuse or sold to acid manufacturers, thereby avoiding
their discharge to sewer systems. Spent catalysts
such as aluminum chloride and phosphoric acid can
either be regenerated for reuse or disposed of as
landfi11.
D-8-3
-------
Wastewater Characteristics
The characteristics of the process wastewaters from the
industry are shown in Table D-8-1. Practically all petroleum
refineries use gravity oil separators to recover free oil
from process effluents. The effluents from gravity oil
separators are therefore used to define the wastewater
characteristics in the table.
The petroleum refineries operate on a continuous basis
throughout the year except 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 'clean1 waters may
include pollution-free cooling waters, boiler blowdown,
and cooling tower blowdown.
The characteristics of wastewater drawn from storage tanks
will depend on the quality of the crude oil stored and may
contain dissolved inorganics, oil, 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
distillation, the condenser water will have very stable
oil in emulsion. However, if the barometric condensers
are replaced by surface condensers, the condenser water
will be essentially free of oil.
The major wastewater from the alkylation process is the
spent caustic from the neutralization of the hydrocarbon
stream from the reactor. Even though the spent acids are
recovered as salable by-product, leaks and spills of acid
catalysts could reach the sewer lines. The major pollutants
from the solvent refining processes include solvents such
as phenols, glycols, and amines. Other processes for the
manufacture of waxes and asphalt, and for finishing and
blending of gasoline, produce relatively low volumes of
dilute wastewater.
In general, the most significant process wastewaters from
petroleum refining are: crude oil desalting waste, storage
tank draw-off, steam condensates, spent caustics, spent
acids, product losses, and leaks and spills of solvents
used in extraction processes. The process wastev/aters,
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 oil (free and emulsified) in the wastewater
could vary between 30 and 200 mg/L in the effluent from API
gravity separators (3).
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 will depend on the phosphorus content of the cooling
tower blowdown and its inclusion in the process wastewater.
k. 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 following industrial practices:
a. Sour condensate stripping to reduce sulfides and/or
ammonia
b. Spent-caustic neutralizati
on
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
neutralization to the pretreatment operations listed in
Table D-8-2.
The oil concentration in the wastewater should be reduced
to approximately 50 mg/L in order to insure trouble-free
operation in secondary biological treatment facilities. 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).
k. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in Table
D-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 oil 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.
D-8-6
-------
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D-8-c:
-------
REFERENCES
1. "The Cost of Clean Waters, Volume III, Industrial Waste
Profile No. 5, Petroleum Refining," U.S. Department of the
Interior, FWPCA, (196?).
2. Nemerow, N.L., "Theories and Practices of Industrial Waste
Treatment," Addison-Wesley Publishing Company, Inc.,
Reading, Mass. (1963).
3. Beychok, M.R., Aqueous Wastes from Petroleum and Petrochemical
Plants", John Wiley and Sons, New York, (196?).
k. "Petroleum Refining Effluent Guidelines", Environmental
Protection Agency, Washington, D.C. (Unpublished)
D-8-9
-------
MEAT PRODUCTS INDUSTRY
1 . Industry Description
This industry includes Standard Industrial Classification
(SIC) Nos. 2011, 2013, 2014, and 209^.
These classifications include slaughterhouses, packing-
houses, processing plants (beef, poultry, hog, and sheep),
and rendering plants.
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 similarity of the wastewaters from meat
products industry, there are no separate pretreatment sub-
groups for this industry.
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
limits 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 desirable since
whole blood represents a BOD concentration of over
150,000 mg/L (1).
In addition, the dry handling of such wastes as manure
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 will affect the concentration
and quantity of waste constituents, but not the
quantity of wastewater.
D-9-1
-------
Render!nq
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 little wastewater is
produced. In wet rendering, the solids 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 will
generally be made up of wastewater from the operations,
sanitary wastes, and wastewaters from auxiliary sources
(e.g. cooling 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.
Wastewater Characteristics
The characteristics of wastewaters from the meat products
industry are shown in Table D-9-1. The meat products
industry is a year-round operation with daily operation
on an intermittent basis. Plants usually shut down daily
for an extensive clean-up period following the processing
period. 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 solids concentrations.
D-9-2
-------
The processes of skinning, defeathering or dehairing, and
eviscerating are sources of BOD, grease, and suspended
solids. 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 solids 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
coliform, 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.
Pretreatment
The pretreatment unit operations which may be necessary
for various types of joint treatment processes are shown
in Table D-9-2.
In addition to screening and free-floating grease removal,
various in-plant control practices, such as blood recovery,
and separate handling of paunch manure as solid waste
would greatly reduce the waste constituents in process
wa s t ewa t e r s (3) .
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.
D-9-3
-------
TABLE D-9-1
Wastewater Characteristics
Meat Products Industry
Character!sties
Industry Operation
Flow
BOD
TSS
TDS
COD
Grit
Cyanide
Chlorine Demand
pH
Color
Tu rb i d i ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Phosphorus
N i trogen
Temperature
Phenol
Sulfides
Oil and Grease
Coli form (Fecal)
Meat Products
Year-round
.1
INTERMITTENT
HIGH-EXT. HIGH
HIGH
HIGH
HIGH - EXT. HIGH
Absent
Absent
HIGH
Neutral
HIGH
High
Absent
Absent
Present
Absent
Absent
HIGH
Absent
Absent
Present
Present
Normal-Hi gh
PRESENT3
Absent
PRESENT
PRESENT
3
Wastewater flow is intermittent over the day or week.
>
"Temperature equal to higher than domestic Wastewater; may
affect design but not harmful to joint treatment processes.
Phenols 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.
-------
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D-9-5
-------
REFERENCES
1. "The Cost of Clean Water, Volume_lll, Industrial Profile
No. 8 - Meat Products1,1 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", (Edited by) Gurnham, C.F.,
Academic Press, New York (1965).
D-9-6
-------
GRA.j NI MjLL I NG I NDUSTRY
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 establishments process corn, wheat or
rice. Dry corn milling 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
inedible hull and the bran.
Because of the similarity of the wastewaters from the various
segments of the grain milling industry, there are no separate
pretreatment sub-groups for this industry.
2. Industrial Practices
The following industrial practices can significantly influence
pret reatment.
Dry Corn Mil 1 ing
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 milling, 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, auxiliary wastewaters
from water treatment, boiler blowdown, and cooling water will
be discharged from mills producing corn oil.
Wet Corn Mil 1i ng
The dry cleaned corn is steeped first in circulating water
containing S0? for 30 to 40 hours. The light steep water is
removed and concentrated by evaporation for use in preparing
animal feeds. The evaporator condensates and starch filtrates
D-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 Mi 11 ing
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 clean-
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 mills
vent the moisture to the atmosphere during the drying and
therefore do not produce any liquid wastes. In general,
most grain mills processing wheat do not generate any liquid
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
similar to those from corn starch preparation (1).
R ice Mi 11 ing
Rice milling generates wastewater only from the par-boiling
operation. The spent cooling water is the principal waste-
water generated from rice milling operations. Auxiliary
wastewaters in rice milling industry result from water soften-
ing and boiler blowdown operations. The process wastewater
(spent cooking liquor) is usually discharged to a municipal
collect ion system.
Wastewater Characteristics
The characteristics of the wastewaters from the grain milling
industry are shown in Table D-10-1. Most grain mills generate
wastewater with similar pollutants and treatability character-
istics.
Grain mills discharge wastewater varying in concentration and
flow. Most mills operate 5 to 7 days per week, and 2k 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 milling industry generates wastewater from wet clean-
ing, oil extraction,and starch and syrup manufacturing opera-
tions. Depending 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
primarily to the presence of starch, carbohydrates, and
protei ns (1,2).
k. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment facilities are shown in
Table 0-10-2. The level of pretreatment required will depend
on the ability of the joint treatment facility to absorb
shocks of varying wastewater volume and loading (3). Waste-
waters resulting from starch production are slightly acidic
(pH k to 5) and therefore may require neutralization prior
to discharging to municipal systems (k).
D-10-3
-------
TABLE D-10-1
Wastewater Characteristics
Gra in M i11 Industry
Character!st ic
Industry Operation
F 1 ow
BOD
TSS
IDS
COD
Grit
Cyan ide
Chlorine Demand
PH
Col or
Tu rb id i ty
Explos ives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Col 1oida1 Solids
Volat ile Organ ics
Pest ic ides
Phosphorus
N i t rogen
Temperatu re
Phenol
Su1f ides
Near-Round
CONTINUOUS
HIGH- EXT. HIGH
Low-EXT. HIGH
High
HIGH- EXT. HIGH
Present
Absent
High
ACIDIC-ALKALINE
Absent
Present
Absent
Absent
Absent
Absent
Absent
Present
Low
Absent
Low-Adequate
Low-Adequate
High
Absent
Absent
Oil and G rease
Coli form (Tota1)
Absent
Present
Higher temperature than domestic wastewaters. May effect
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.
Wastewater characteristics shown reflect all industrial
practices described in Section 2.
D-10-4
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D-10-5
-------
REFERENCES
1. "Industrial Waste Study Report - Grain MMlinq Industry",
Environmental Protection Agency, Washington, D.C.,
(unpubli shed).
2. Ling, J.T.,
Treatment",
Conference, Purdue University, 5'5-525 (196?).
"Pilot Investigation of Starch - Gluten Waste
Proceedings 16th Industrial Waste Conference,
3. Willenbrink, R.V., "Waste Control and Treatment by a Corn
and Soybean Processor", Proceedings 22nd Industrial Waste
Conference, Purdue University, 515-525 (1967).
k. Jeyfriend, C.F. ,
Proceedings 23rd
"Purification of
Industrial Waste
Starch Industry Wastewater",
Conference, Purdue
University, 1103-1119 (1968).
D-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 similarity 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 all 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 performed (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.
Peeling, when required, is accomplished by either
mechanical abrasion, by chemical (lye) treatment, or by
steam. An experimental method of dry caustic peeling
has been evaluated successfully for pears, peaches,
potatoes and beets (1). Mechanical abrasion utilizes
contoured knife peelers adjusted to maximize product yield
for the particular size of product being processed.
Steam and hot lye peeling depend on water sprays to remove
the softened skin. Hot lye solutions may be sewered as
frequently.as after each work shift (2).
The peeling process represents a substantial source of
pollutants, principally soluble, including: sugars,
starches, and carbohydrates leached from the fruits and
vegetables; and insoluble waste solids. 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-ll-1
-------
Stabilizing of the fruit or vegetable to preserve its
quality may be accomplished by blanching or pasteuriza-
tion. Blanching is accomplished 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 cans 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 Peeling Wastes
Trimmings and other large solids should be handled as
a dry solid 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 will generally preempt grit removal
as a pretreatment requirement.
Peel ing Process
The substitution of another peeling process for lye
treatment may nullify the need for neutralization
facilities for pH adjustment.
Washing Operation
Reduction of wastewater quantities is critical in
order to obtain a minimal capital investment for
pretreatment facilities. 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
establishments.
3. Wastewater Characteristics
The characteristics of the wastewaters from the processing
fruits and vegetables are shown in Table D-ll-1. The
D-ll-2
-------
Fruit and vegetable industry is a seasonal operation,
usually corresponding to the local growling 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 overall effect of prolonging the industry
operation. This industrial category can be classified
as a continuous operation, with the exception of fruits
and vegetables that are pickled or cooded. These latter
processes are batch types. In genera], the wastewaters
from this industry are high in BOD, COD, TSS, and grit
(3,4).
k. Pretreatment
The pretreatment unit operations which may be necessary
for various types of joint treatment processes are shown
in Table D-ll-2. Water re-use and process equipment with-
in each plant will dictate the pretreatment and subsequent
treatabi1ity. In general, fruit and vegetable wastewaters
are amenable 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 variability. 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.
D-ll-3
-------
TABLE D-l1-1
Wastewater Characteristics
Fruit and Vegetable Industry
Characterist?cs
Operation
Industrial
Flow
BOD
TSS
IDS
COD
Grit
Cyanide
Chlorine Demand
PH
Color
Turbidi ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Solids
Volatile Organ!cs
Pesticides
Phosphorus
Ni trogen
Temperature
Phenol
Sulfides
Oil &
Fecal
Grease
Coliform
SEASONAL
INTERMITTENT
Average-EXTt
HIGH
Average-EXT, HIGH
Average-HIGH
Average-EXT. HIGH
PRESENT
Absent
Average-HIGH ,
ACID-ALKALINE
Present (HIGH2)
High
Absent,
Absent
PRESENT
Absent
Absent
Average
Absent
Absent-Present
DEFICIENT
DEFICIENT ^
Normal-Hi gh
Absent
Absent
Absent
Absent
1. Fruit and tomato wastes are generally acidic; however, the
pH of the wastewater is affected by the peeling process,
e.g., 1 ye peeling.
2. Beet processing wastewaters are characterized by a red color.
3. Free SO may be dissolved in maraschino cherry brine.
4. Temperature equal to or 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.
Wastewater characteristics shown reflect all
industrial practices described in Section 2.
the
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REFERENCES
1. Industrial Waste Study - Canned and Frozen Fruits and
Vegetables, Contract No. 68-01-0021, Environmental
Protection Agency, Washington, D.C. (unpublished).
2. "Industrial Wastewater Control", (Edited by) Gurnham, C.F. ,_
Academic Press, New York (1965).
3. "Utilization of Cannery Fruit Waste by Continuous Fermenta-
tion", Bulletin No. 207, Washington State Institute of
Technology, Pullman, Washington (March 1950).
4. "Treatment of Citrus Processing Wastes", Water Pollution
Control Research Series 12060, Environmental Protection
Agency, Washington, D.C. (1970).
5. "The Cost of Clean Water, Volume III, Industrial Waste
Profile No. 6 - Canned and Frozen Fruits and Vegetables",
Federal Water Pollution Control Administration (June 1967).
D-ll-6
-------
BEVERAGES INDUSTRY
1 . Industry Description
This industry includes Standard Industrial Classification
(SIC) 2082, 2083, 2084, 2085, 2086, and 208?.
These industrial classifications include all establishments
engaged primarily in the manufacture of malt, malt beverages
(ale, beer, and malt liquors), wines (table wine, dessert
wine, and brandy), distilled spirits, bottled and canned
soft drinks, and flavoring extracts and syrups.
The products described above can be classified under two
major groups according to their basic manufacturing
processes as:
1. Fermentation Products (beer, wine, distilled spirits,
mal t)
2. Extraction Products (soft drinks, flavors, and extracts)
The fermentation products are made from grains or fruits,
while the extraction products are made from flavor sub-
stitutes of oils such as cocoa, vanilla, and orange oil.
The fermentation products derived from grains are manu-
factured by cooking the grains, fermenting the cooking
liquor 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 listed as follows:
1. Steam distillation and petroleum ether extraction
(essenti al oils).
2. Expression (hydraulic pressing) and petroleum
ether extraction (fruit syrup).
3. Expression and evaporation (jams).
k. Alcoholic extraction of vanilla and other tissue.
The soft drink bottling and canning plants use flavor extracts
and purchased syrups. The bottling and canning process
involves bottle washing and sterilizing, mixing of flavor
extracts and syrup, carbonation, and filling.
The pretreatment sub-groups for this industry are as follows:
D-12-1
-------
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 taste to the product. Water is used in the
process for cooking, cooling, container washing and other
miscellaneous uses. Both solid wastes and liquid wastes
are generated in the process. Spent grains, excess yeast,
and spent hops are the solid wastes, and are generally
hauled away or dried for livestock and poultry feed. The
only variation of this type of disposal is where certain
small distilleries manufacturing distilled wine or spirits,
the stillage is discharged with other liquid 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 auxiliary 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 liquid or
semi-liquid waste, which is either discharged directly
to the sewer or recovered in the case of large wineries.
In order to improve the quality of the wine, the fermented
liquid 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
solids 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 »^)
The manufacture of flavoring extracts and syrups also
generates both liquid and solid wastes. Solid wastes are
the residues after extraction of flavors and syrups. Waste-
waters from normal extraction operations are:
Fruit Expression:
1. Water used for washing fruits.
2. Hydraulic press clean-up.
D-12-2
-------
Evaporation:
1. Evaporator condensate.
2. Kettle wash water.
Steam Distillation:
1 . Boiler blowdown.
2. Bottoms from packed column.
The major wastewater sources in the bottling industry are
the bottle washing and clean-up operations. Auxiliary
wastewaters such as cooling, 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 Character!sties
The characteristics of process wastewaters from each
pretreatment sub-group are shown in Table D-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 scheduling 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 hydraulic
and organic loads. The follwing is a brief description
of the wastewater from each pretreatment group:
1. Malt Beverages and Distilled Spirits
The wastewaters generated from the malt and malt
beverages industries have as major constituents BOD,
SS, pH and temperature. The waste solids from the
malt house, and the excess yeast, spent grains, and
spent hops from the malt beverages industry are
disposed of either by hauling away or by on-site
drying to make cattle feeds. If the spent wet grain
is dried in the brewery, the spent grain liquid must
be disposed of; generally, it is discharged to
municipal sewers without pretreatment.
D-12-3
-------
The distilleries produce wastewaters from cooking and
fermentation of grains, the stillage or slops from
distilling operations, and from washing and bottling
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 solids, acidity, and heat.
2. Wine and Brandy
The wine and brandy industries produce wastewaters
from crusher-stemmer, pressing, fermentation,
clarification and filtration, distillation, and
bottling 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 liquid 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 little work, if any, has been done to delineate
the characteristics of the wastewater from this
segment of the industry. The bottling 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).
Pretreatment
Available information in the literature indicates that
pretreatment in the form of screening, grit removal, and
equalization 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 wastewaters from the beverage
industries are amenable to treatment by conventional
D-12-A
-------
processes, such as activated sludge and trickling filters.
The pretreatment unit operations recommended in Table D-12-2
are based on the assumption that the following in-plant
pollution control methods are practiced:
1. Hauling or drying of spent grains, hops, and stillage.
2. Separate solids-handling and disposal of crusher-
stemmer and pressing wastes.
Spent grains, hops, stillage, crusher-stemmer, and pressing
wastes can be characterized as solid 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 4-5 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
faci1i ties.
D-12-5
-------
TABLE D-12-1
Wastewater Characteristics
Beverages Industry
Character!sties
Industry Operation
Flow
BOO
TSS
TDS
COD
Grit
Cyanide
Chlorine Demand
pH
Color
Turbidi ty
Explos ives
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Phosphorus
Ni trogen
Temperature
Phenol
Sulfides
Oi1 and Grease
Col iform (Fecal)
Coli form (Total)
Malt Beverages and
P.isti1 led Spi r!ts
Year-round
INTERMITTENT-Continuous
HIGH
Low to H I GH
High
HIGH
PRESENT
Absent
No Data
ACID-NEUTRAL
Present
Present
Absent
Present,
Present
Present
Absent
Present
Present
Absent
DEFICIENT
DEFICIENT
Normal-High'
Absent
Absent
Absent
Absent
Present
Wine and Brandy
SEASONAL
INTERMITTENT
HIGH-EXT. HIGH
Low to EXT. HIGH
High
HIGH-EXT. HIGH
PRESENT
Absent
No Data
ACID-ALKALINE
Present
Present
Absent
Absent
Present'*
Present"
Absent
Present
Present
Absent
DEFICIENT
DEFICIENT
High'
Absent
Absent
Absent
Absent
Present
3
Soft Drinks Bottling
Year-round
INTERMITTENT
Average to HI GH
Low to HIGH
Low to High
Average to HIGH
PRESENT
Absent
No Data ,
ALKALINE5
Present
Present
Absent
Present
Present^*
Present
Absent
Present
Present
Absent
DEFICIENT
DEFICIENT
Normal
Absent
Absent
Absent
Absent
Present
Pollutants characteristics represent only Bottling Industry; no data available for flavors and syrups.
Malt beverages generate wastes on a continuous basis; distilled spirits waste flow will be cyclic.
3Alkaline pH due to caustic detergents used for bottle washing.
^Surface active agents are discharged primarily from bottle washing.
STemperature equal to or higher than domestic wastewater; may affect design but not harmful to
joint treatment processes.
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.
D-12-6
-------
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REFERENCES
1. 'Industrial Waste Survey on Malt Liquor Industry, prepared
for the Environmental Protection Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
2. "Industrial Waste Survey of the Malt Industry',1 prepared for
the Environmental Protection Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
3. "Industrial Waste Survey of the Wine Industry',' prepared
for the Environmental Protection Agency by Aware, Inc.,
Nashville, Tennessee (unpublished).
4. "Industrial Waste Survey of Distilled Spirits Industry',1
prepared for the Environmental Protection Agency by
Aware, Inc., Nashville, Tennessee (unpublished).
5. "A Report on Bottled and Canned Soft Drinks SIC 2086 and
Flavoring Extracts and Syrups SIC 2087',' prepared for the
Environmental Protection Agency by Aware, Inc., Nashville,
Tennessee (unpublished).
D-12-8
-------
PLASTIC AND SYNTHETIC MATERIALS INDUSTRY
Industry Description
This industry includes Standard Industrial Classifications
(SIC) No. 2821, 2823, and 282^. 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 million pounds per year was
selected as the criterion for inclusion of a polymer.
Based on the wastewater characteristics and treatability
information, the industry is divided into the following pre-
treatment sub-groups:
Pretreatment Sub-Group
1
Rayon
Nylon
Fi bers
Fi bers
High- and Low-Density
Polyethylene Resins
Urethane Resins
Polyolefin Fibers
Polyvinyl Acetate
Polyvinyl Alcohol
Polyester Fibers
Resins
Resi ns
Cel1ulosic Resi ns
Cellophane
Polypropylene Resins
Cellulose Acetate Fibers
Polyvinyl Chloride Resins
Polystyrene
ABS, SAN Resins
Phenolic Res i ns
Nylon Resins
Polyacetal Resins
Acrylic Fi bers
D-13-1
-------
2. Industrial Practices
The following 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 solubi1ization 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 milk-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 antisolvent (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 little or no process wastewater associated with
this process.
Wastewater Characteristics
The characteristics of the process wastewaters from the
manufacture of plastic and synthetic materials are shown in
Table D-13-1.
D-13-2
-------
The plastic and synthetic materials industry is typically a
continuous year-round operation. Because it is technically
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 (Zn, Cu) and synthetic fiber losses. Group ^
wastewater has low BOD and COD, may be either acidic or
alkaline, and has substantial amounts of oil and polymer
particles. Group 3 is characterized as either having no
process water or as having process wastewater containing
virtually no pollutants. Group k wastewater has variable
BOD and COD, may be either acidic or alkaline, and contains
synthetic fibers. Discharge of faulty batches from synthetic
fiber plants may introduce shock loads into the joint treat-
ment fac i1i ty.
Conditions significant in the design of joint treatment
facilities include high chlorine demand, the presence of
surface-active agents, high solids concentrations, and
nutrient deficiency. The process diversity and complexity,
as well 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.
k. Pretreatment
The pretreatment unit operations which may be necessary for
various types of joint treatment processes are shown in
Table D-13-2.
0-13-3
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D-13-5
-------
REFERENCES
1. "Industrial Waste Study of the Plastic Materials and
Synthetics Industry", Environmental Protection Agency
Contract No. 68-01-0030, Washington, D.C., (unpublished)
2. "The Cost of Clean Water - Vol. Ill, Industrial Waste
Profile No. 10 - Plastic Materials and Resins',' Federal
Water Quality Administration (October, 19&7).
D-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 rolling; 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 listed as follows:
a. Coke Works
b. Iron Works
c. Steel Works
d. Hot Forming
e. Cold Fi ni shi ng
Significant quantities of water are used, both for processing
and for cooling purposes. The steel industry generates
greater volumes of wastewater than any other industry (1).
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 distillation 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.
-------
In the by-product process, coal is heated in the
absence of air to a temperature at which the volatile
matter is driven off. At the end of coking cycle,
the hot residual coke (2,000° 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 cooling train, where tar and ammonia
liquor separate out. The tar contains a large
proportion of phenols removed from the furnace. The
ammonia is generally recovered from the liquor in a
still.
b. Iron Works
Iron is manufactured from iron ore (iron oxide)
in blast furnaces, with carbon monoxide (from coke)
as a reducing agent. The major impurity (silica)
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 1 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 similar wastes. Pure oxygen or air is
used to refine the hot iron into steel by oxidizing
and removing silicon, 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, skelp, and bars.
e. Cold Fin i shi ng
The cold finishing operations are used for the conversion
of hot-rolled products to give desired surface, shape,
or mechanical properties. These operations include
pickling, cold rolling, tinplating, coating, shaping,
and drawing to make various finished products.
-------
Integrated iron and steel mills 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 only two types of waste stream susceptible to
joint treatment are the coke oven wastewaters and
the pickling liquor. The other process wastes occur
in such large quantities 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 liquor, 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 neutralizing agent in waste treatment plants. Any
such use should be investigated before discharging the
spent pickle liquor as a waste stream. Recovery of
strong acid pickle liquor for reuse is practiced in a
limited 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 generated in steel industries vary widely
between operations and they are generally segregated for
treatment. Some older steel mills, however, still have
common collection systems for discharging the total plant
flow. The steel industry operates throughout the year and
generates wastewaters over a 2^-hour day. The volume and
characteristics of wastewater are subject to hourly
variations from batch dumping of acid baths and still
bottoms.
The major constituents present in the wastewater are
phenol, cyanides, ammonia, oil, suspended solids, heavy
metals (Cr, Ni, Zn, Sn), dissolved solids (chlorides,
sulfates), acidity, and heat. The process wastewaters
are generally treated on-site before disposal. Joint
treatment of these wastes with municipal wastes is limited
to small installations, which 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 mills (3). A significant
D-l^-3
-------
portion of the wastewater generated contains suspended
solids and dissolved solids 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 solids (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 utilizes the heat value
in the off-gases, only the quench water is discharged
as wastewater (l). 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 will depend
primarily 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 cooling purposes. The primary wastewaters are the
D-14-4
-------
scale-bearing waters and cooling waters containing
primarily scale and oil.
Steel pickling to remove oxides and scales is accomplished
through solutions of h^SO^, 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 electrolytical1y, and
is accomplished in either an alkaline or an acid electrolyte
solution. If acid electrolyte is used, the process system
will consist of alkaline washing, rinsing, pickling,
plating, quenching, chemical treating, rinsing, drying,
and oiling. The most commonly used metallic coatings are
tin, zinc, nickel, chromium, cadmium, copper, aluminum,
silver, gold, and lead. Wastewaters generated from
cold finishing operations include: rolling solutions,
cooling water, plating wastes, pickling rinse waters,
and concentrated waste-acid baths. Rolling solutions and
cooling 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
alkal i .
k. 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 limitation values for cyanide and heavy metals
must be considered in the design of pretreatment facilities.
D-14-5
-------
TABLE D-14-1
Wastewater Characteristics
Blast Furnaces, Steel Works, and Rolling and Finishing Industry
Character! sties
Operation
I ndustri al
Flow
BOD
TSS
IDS
COD
Gri t
Cyanide
Chlorine Demand
pH
Col or
Turbidi ty
Explosives
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Sol ids
Volati1e Organics
Pest ic ides
Coke Works
Year-round
INTERMITTENT
Low-Average
Low
Low
Low-Average
Present
PRESENT
High
Neutral
Absent
Present
Absent
Present
Absent
Absent
Absent
Present
Present
Absent
I ron Works
Year-round
Conti nuous
Low-Average
Low-Hi gh
Low
Low-Average
Present
Present
Low
Neutral
Absent
Present
Absent
Present
Absent
Absent
Present
Absent
Absent
Absent
Steel Works
Year-round
Conti nuous
Low
Average-Hi gh
Low
Low
Absent
Absent
Low
Neutral
Absent
Present
Absent
Present
Absent
Absent
Present
Absent
Absent
Absent
Hot Formi ng
Year-round
Conti nuous
Low
Low-Hi gh
Low
Low
Absent
Absent
Low
Neutral
Absent
Present
Absent
Absent
Absent
Absent
Present
Absent
Present
Absent
Cold Finishing
Year-round
INTERMITTENT
Low-Average
Low-High
High
Low-Average
Absent
PRESENT
Low
ACIDIC
Absent
Present
Absent
Absent
Present
Absent
PRESENT
Present
Present
Absent
Character! sties
Phosphorus
Ni trogen
Temperature
Phenol
Sulfides
Oi1 and Grease
Col i form (Total)
Coke Works
DEFICIENT
Adequate
HI GH
PRESENT
PRESENT
Present
Absent
I ron Works
DEFICIENT
Adequate
High
Present
Present
Absent
Absent
Steel Works
DEFICIENT
DEFICIENT
High
Absent
Absent
Absent
Absent
Hot Forming
DEFICIENT
DEFICIENT
High
Absent
Absent
Present
Absent
Cold Finishing
DEFICIENT
DEFICIENT
High'
Present
Absent
PRESENT
Absent
Temperature higher than domestic wastewater; may affect design but not harmful to joint treatment.
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 industrial practices described in Section 2.
D-14-6
-------
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REFERENCES
1. Nemerow, N.L., "Theories and Practices of Industrial
Waste Treatment", Addison-Wisiey Publishing Co. Inc.,
Reading, Mass. (1963).
2. "Industry Profile 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. Ill, Industrial Waste
Profile No. 1, Blast Furnaces and Steel Mills", U.S. Dept.
of the Interior, FWPCA (1967).
D-14-8
-------
ORGANIC CHEMICALS INDUSTRY
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
fertilizers to dyes, pigments, and petroleum compounds.
The total annual production of organic chemicals in the
United States has been estimated to be 120 billion pounds
for the year 19&9. 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 listing of the
products covered is shown below in the order of 1970
manufacturing volume (1):
I. Ethylene 15.
2. Benzene 16.
3. Propy1ene 17.
k. Ethylene Dichloride 18.
5. Toluene 19.
6. Methanol 20.
7. Ethylbenzene 21.
8. Styrene 22.
9. Formaldehyde 23.
10. Vinyl Chloride 2k.
11. Ethylene Oxide 25.
12. Xylene (Mixed) 26.
13. Butadiene 27.
14. Ethylene Glycol
Ethanol
Isopropanol
Acetic Acid
Cumene
Cyclohexane
Phenol
Aceta1dehyde
Acetic Anyhdride
Terephthalic Acid
Dimethyl Terephthalate
Acetone
Ad i p i c Ac i d
Aeryloni tri 1 e
The total annual U.S. production of these 27 organic
chemicals amounted to approximately 98 billion pounds
D-15-1
-------
for 1970. Depending upon the sequence of production 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 xylene).
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 follows:
Sub-Group 1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Benzene
Toluene
Xylene
Cyclohexane
Ad i p i c Ac i d
Ethyl benzene
Styrene
Phenol
Terephthalic Ac i d
13.
14.
15.
16.
17.
18.
19.
20.
(TPA)21.
Dimethyl Terephthal ate 22.
(DMT) 23.
Ethylene
Ethylene Dichloride
Vinyl Chloride (Monomer)
Ethanol
Acetaldehyde
Acetic Acid
Acetic Anyhdride
Propylene
Isopropanol
Acetone
Cumene
Ethylene Oxide
Ethylene Glycol
Sub-Group 2
1. Butadiene
2. Methanol
3. Formaldehyde
Sub-Group 3
Acryloni trile
2. Industrial Practices
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 cooling
purposes.
D-15-2
-------
3. Wastewater Character!sties
The characteristics of process wastewaters from the
manufacture of products under each pretreatment group
are shown in Table D-15-1.
The characteristics of wastewaters vary from plant to
plant, according to the products and processes used. The
Organic Chemicals plants generally operate 2k 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, crystalliza-
tion, solvent extraction, etc.). The wastewater collection
systems are generally segregated, to permit separate
collection of process wastewaters and relatively clean
cooling waters. The process wastewaters are usually
discharged to a common sewerage system for treatment and
di sposal.
The process wastewaters from the manufacture of chemicals
under Sub-Group 1 generally contain free or emulsified oil,
while under Sub-Group 2 generally do not contain oil.
Acrylonitri1e manufacture (Sub-Group 3) produces a wastewater
containing cyanides and substantial quantities of acids.
These wastewaters, in general, contain unreacted raw
materials and losses in products, by-products, coproducts,
and any auxiliary 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 products
under Sub-Group 1 may contain oil 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
primarily 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 small
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
-------
k to 11), and heavy metals (Cr, Cu, Zn, Hg). These
wastewaters are amenable to biological treatment, after
equalization and neutralization. The production of
butadiene may produce a wastewater containing free
or emulsified oil; an oil separation device may be
required as pretreatment when the oil content in the
wastewater exceeds 50 mg/|_ . Only unrecoverable heavy
metals (catalysts), generally in small concentrations,
appear in the wastewater.
The manufacture of aery 1onitrile produces a highly
toxic wastewater which is difficult to treat biologically.
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 k 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
collection systems. The pretreatment unit operations
developed in the following section do not include the
process wastewaters from the manufacture of acrylonitri1e
(Sub-Group 3).
k. 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 treatability
characteristics. However, the effluent limitations for
heavy metals and toxic pollutants may require additional
pretreatment (chemical precipitation) for removal of
these materia1s.
The pretreatment unit operations generally consist of
equalization, neutralization, and oil separation. In
addition, phenol recovery (to reduce the phenol concen-
tration) and spill protection for spent acids and spent
caustics may be required in some cases.
-------
Table D-15-1
Wastewater Characteristics
Organic Chemicals
Character!sties
Industrial Operation
Flow
BOO
TSS
IDS
COD
Grit
Cyani de
Chlorine Demand
pH
Color
Tu rb i d i ty
Explosives
Dissolved Gases
Detergents
Fo am i n g
Heavy Metals
Colloidal Solids
Volatile Organ ics
Pestic i des
Phosphorus
Ni trogen
Temperature
Phenol
Sulfides
Oi1 and Grease
Col i form (Total)
Sub-G.roup 1
Year-round
Continuous-Variable
Average-EXT. HIGH
Low-Hi gh
HI GH
Average-EXT. HIGH
Ab sent
Absent
High
ACIDIC-ALKALINE
Low-Average
Low
Absent
Present
Present
Present
Present
Absent
Present
Absent
DEFICIENT
DEFIC IENT
Normal-HI GH^
Low-H i gh
Present
low-HIGH
Low
Sub-Group 2
Year-round
Cont i nuous-Vari able
AVERAGE-HIGH
Low
Low-Hi gh
Average-HIGH
Absent
Absent
High
ACIDIC-ALKALINE
Low-Average
Low
Absent
Present
Present
Present
Present
Absent
Present
Absent
DEFICIENT
DEFIC IENT2
High^
Present
Present
LOW-HIGH
Low
Sub-Group 3
Year-round
Continuous-Variable
Low1 r
High
High
High
Absent
PRESENT
High
AC I 0 IC
Low
Low
Absent
Present
Present
Present
Present
Absent
Present
Absent
DEFICIENT
Adequate
No Data
Absent
Absent
Absent
Low
Low BOD is probably due to the toxicity characteristics of this waste;
Adequate when butadiene is manufactured.
3Temperature equal to or higher than domestic wastewater; may affect design but
not harmful to joint treatment.
NOTES: 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.
0-15-5
-------
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D-15-6
-------
REFERENCES
1. Chemical and Engineering News, (May 17, 1971).
2. "Reference Guidelines for Organic Chemical Industries",
Environmental Protection Agency, Washington, D.C.
(Unpubli shed)
3. "Projected Wastewater Treatment Costs in the Organic
Chemical Industry", Water Pollution Control Res. Series
12020 GND 07/71, Environmental Protection Agency, Research
and Monitoring (July, 1971).
D-15-7
-------
METAL FINISHING INDUSTRY
1 . Industry Descript!on
This industry includes Standard Industry Classification (SIC)
3^71.
The industries covered under this classification include those
primarily engaged in various types of plating, anodizing, color-
ing, forming, and finishing of metals. The metal-finishing
industry operations are related closely to those of many other
industries, including transportation (automobile parts and ac-
cessories), electrical, and jewelry.
The metal-finishing operation involves cleaning, conversion
coating, organic coating, plating, anodizing, coloring, and
case hardening. Acid pickling is the most common type of clean-
ing of metal being prepared for plating. Sulfuric acid is the
most commonly used pickling agent, but phosphoric, hydrochloric,
hydrofluoric, and other acids are used as well. Alkalies,
dichromates, and numerous proprietary compounds are also used
in various combinations for descaling, degreasing, desmudging,
stripping, brightening, or otherwise preparing different metals
(zinc, steel, brass, copper, etc.) for plating or anodizing.
The plating solutions for nickel, chromium copper, cadmium,
zinc, tin, and silver may be basically cyanide, acid, or alka-
line. Anodizing is done either in sulfuric acid or in chromate
solutions. Colorizing is accomplished with dyes, nickel acetate,
and chro.nates. Cyanides are used in case hardening.
2. Wastewater Character Isti cs
The characteristics of the process wastewaters from the industry
are shown in Table D-16-1.
The metal-finishing industry usually generates a continuous
stream of rinse waters containing dilute concentrations of
heavy metals and cyanides and intermittent batch dumpings of
spend acid and cleaning solutions. The nature of metal-finish-
ing operations and the consequent fluctuating (cyclic) charac-
teristics of the wastewater should oe taken into considsration
in the design of treatment facilities.
Water is used extensively in metal-finishing processes to clean,
strip, pickle, and rinse the metal products before and acter
plating operations. The rinse waters constitute the major
volume of wastewaters, while spant solutions discharged inter-
ittently add major poMutants to the total effluent. The
D-16-1
mi
-------
wastewaters contain, in general, spent acids, alkalis, oil and
grease, detergents, cyanides, and various heavy metals (Cr,
Ni, Cu, Ag, Fe, In, and Sn). The metal-finishing plants differ
from one another with respect to their processes, metals, and
chemicals, and the characteristics of wastewater may vary widely
from one to another. However, their wastewaters all contain
primarily inorganic pollutants, particularly heavy metals. In
addition, the wastewaters frequently are highly toxic due to
the presence of cyanides and heavy meials (1,2,3).
In general, the types of wastewaters from metal-finishing in-
dustries are:
1. Acid wastes
2. Alkali ne wastes
3. Heavy metals wastes
k. Cyanide-bearing wastes
5. Miscellaneous wastes (dyes, soluble and floating oils,
etc.)
Any of these wastewaters may occur as either dilute rinse waters
or concentrated baths. Except for the cyanide-bearing wastes,
the wastewaters are generally connected to a common sewerage
system for treatment and disposal. The cyanide wastes usually
are collected in a segregated sewer system in order to prevent
the release of toxic hydrogen cyanide gas under acidic condi-
tions. However, the cyanide wastes can be mixed A/ith other
waste streams provided that any acid streams are neutralized
prior to mixing with the cyanide waste stream (4,5,6).
The major constituents in the wastewaters generated from metal -
finishing operations are cyanides, metal ions, (Cr , Nf, Fe,
Cu, Ag, and Sn), oil and grease, organic solvents, acid;, and
alkalis. The wastewaters characteristically are so to
-------
3. Pretreatment
The pretreatment unit operations for various types of joint
treatment facilities are shown in Table D-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 lime to convert highly toxic cyanides to less toxic cyanates
or cyanide complexes, or can be oxidized to CC>2 and N2 with
chlorine under alkaline 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 D-16-2, the degree of reduction in heavy metals waste
loadings should consider the sludge handling 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 unless adequate
pretreatment is provided.
D-16-3
-------
Table D-16-I
Wastewater Characteristics
Metal Finishing Industry
Character!sties
Industrla1 Operation
Flow
BOD
T5S
IDS
COD
Grit
Cyan i de
Chlorine Demand
pH
Color
Turb i d i ty
Explos I ves
Dissolved Gases
Detergents
Foam'ng
Heavy Meta's
Collo idal Sol ids
Volat i1e Q rgan i cs
Pesti ci dei
Phosphorus
Ni t rogen
Ternperatu \~2
Phenol
Sulfides
0 i 1 and G rease
Col i f o'Ti (Total )
Year-round (BATCH)
Continuous-VARIABLE
Low
Average-Hi gh
HIGH
Low
Present
HI3H
HIGH
ACIDIC
Present
Present
Absent
Present
Present
Absent
HIGH
Absent
Present
Absent
t
Present
?res an
No ma I
Low
Absent
Present
Absent
Tempe.-a ture similar to domestic
NOTE: Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown in
UPPER CASE.
D-l 6-4
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D-16-5
-------
REFERENCES
1. Barnes, E.G., and Weinberger, L.W., "Complex Metal Finishing
Wastes Licked by Effective Chemical Treatment", Wastes
Engineering, 124-127 (1957).
2. Barnes, G.E., "Treatment Works for Plating Wastes Containing
Toxic Metals and Cyanides", Water and Sewage Works, £4, 8,
(19^7).
3. Nemerow, N.L., "Theories and Practices of Industrial Waste
Treatment", Add!son-Wesley Publishing Co., Inc., Reading,
Mass. (1963).
k. "An Investigation of Techniques for Removal of Cyanide
from Electroplating Wastes", Water Pollution Control
Research Series, 12010-EIE 11/71, EPA, Washington, D.C.
(1970.
5. "An Investigation of Techniques for Removal of Chromium
from Electroplating Wastes", Water Pollution Control Research
Series, 12010-EIE 3/71, EPA, Washington, D.C. (1970.
6. "Ultrathin Membranes for Treating Metal Finishing Effluents
for Reverse Osmosis", Water Pollution Control Research
Series, 12010-DRH 11/71, EPA - Research and Monitoring
(1970.
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 Fertilizer
(SIC 2071)
2. Electric and Steam Generation
(SIC 4911, 4961)
3. Aluminum
(SIC 333^, 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
-------
Characteristics
Industrial Operation
Flow
BOD
TSS
IDS
COD
Grit
Cyanide
Chlorine Demand
PH
Color
Turbidity
Explosive Chemicals
Dissolved Gases
Detergents
Foaming
Heavy Metals
Colloidal Solids
Volatile Organics
Pesticides
Phosphorus
Nitrogen
Temperature
Phenol
Sulfide
Oil & Grease
Coliform (Total)
Table D-17-1
Wastewater Characteristics
Inorganic Fertilizer
Phosphoric Acid
Normal Super Phosphate
Triple Super Phosphate
Mono-Ammonium Phosphate
Di-Ammonium Phosphate
N-P-K Fertilizers
Year-Round
Continuous
Low-Average
Average-High
HIGH
Low-Average
Absent
Absent
Low
ACID
No Data
No Data
Absent
PRESENT
Absent
No Data
Absent
Absent
Absent
Absent
Adequate
Adequate ,
Normal-High
No Data
No Data
Absent
Absent
Ammon i a
Year-Round
Continuous
Low
Low-Average
HIGH
Low
Absent
Absent
Low
ALKALINE
No Data
No Data
Absent
Absent
Absent
No Data
Absent
Absent
Absent
Absent
DEFICIENT
Adequate .
Normal-High
No Data
No Data
PRESENT2
Absent
Ammonium Nitrate
Urea
Ammonium Sulfate
Year-Round
Cont i nuous
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 ,
Normal-High
No Data
No Data
Absent
Absent
1
Temperature equal to higher than domestic wastewater; affect design but not
harmful to joint treatment.
Oil present in the wastewater is mineral in origin.
NOTE: Characteristics which may require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
D-17-2
-------
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D-17-3
-------
Table D-18-1
Wastewater Characteristics
Electric and Steam Generation
Character? st? c
Industry Operation
Flow
BOD
TSS
IDS
COD
Grit
Cyan? de
Chlorine Demand
pH
Color
Turbidity
Explosive Chemicals
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Colloidal Solids
Volat?le Organics
Pesticides
Phosphorus
Ni trogen
Temperature
Phenol
Sulfide
Oi1 and Grease
Coliform (Total)
Year-Round
INTERMITTENT
Low
Low
High
1
Low
Low
Present
Low
ACIDIC-ALKALINE
Low
Low
Absent
Absent
Present
Present
PRESENT
Absent
Present
Absent
DEFICIENT
DEFICIENT
HIGH -
Present
Absent
Present
Absent
^Cyanide may be present if cooling water is also dis-
charged to the sewers.
^Temperature higher than domestic wastewater; may
require cooling as pretreatment.
^Phenol may be used in cooling water treatment.
NOTE: Characteristics which may require pretreatment or are
significant to joint treatment plant design are shown
in UPPER CASE.
-------
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D-17-5
-------
Table D-19-1
Wastewater Characteristics
.onferrous Metals - Aluminum
Characterist ics
Industry Operat ion
F 1 ow
BOD
TSS
IDS
COD
Grit
Cyan ide
Chlorine Demand
pH
Col or
Turb i d i ty
Explosive Chemicals
Dissolved Gases
Detergents
Heavy Metals
Col 1oidal Sol ids
Volat ile Organics
Pest ic ides
Phosphorus
N i trogen
Temperature
Phenol
Sulfide
Oi1 and Grease
Coliform (Total)
Baux ite Ref in ing
Primary Smelting
Year-round
Cont i nuous
Low
HIGH
Low
Low .
PRESENT
Present
Low
'eutral
High
High
Absent ,
PRESENT^
Absent
Present
Absent
Absent
Absent
DEFICIENT
DEFICIENT
Normal-HIGH
Absent
Absent
Present
Absent
Direct Chill Ingot Coating
and Foundry Rolling,
Drawing and Extruding
'ear-round
Cont inuous
Low
HIGH
Low-Average
Low
Absent
Absent
Low
'EUTRAL-ACID
Average
Average
Absent ?
PRESENT
Absent
Absent
Absent
Absent
Absent ,
Def iclent-Adequate
DEFICIENT
Normal-HIGH
Absent
Absent ,-
Present
Absent
Present in bauxite refining wastewater.
Fluorine is generally present in scrubber water.
3
Chlorine is present in casting, foundry, and secondary smelting
scrubber waters.
4
Phosphate in high concentration ( 1,000 mg/L) is present only
when can stock is coated in preparation for painting by the can
manufacturer.
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-17-6
-------
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D-17-7
-------
Table D-20-1
Wastewater Characteristics
Glass, Cement, Lime, Concrete Products,
Asbestos and Gypsum Products
Character! st ic
Industry Operation
Flow
°OP
TSS
TDS
COD
Grit
Cyan ide
Chlorine Demand
PH
Color
Turb id i ty
Explosive Chemicals
Dissolved Gases
Detergents
Foami ng
Heavy Metals
Col 1 oidal Sol ids
Volat Me Organ ics
Pest ic ides
Phosphorus
N i t rogen
Temperature
Phenol
Sulf ide
0 i 1 and G rease
Col i form (Total )
Flat
Glass
Year-round
Cont inuous
Low
Low-H IGH
LOW-HIGH
Low
PRESENT
Absent
No Data
Neutral
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
PRESENT
DEFICIENT
Norma 1
Absent
Absent1
ABSENT
Absent
M i rrors
Year-round
Cunt i nuous
Low
HIGH
HIGH
Low
PRESENT
Absent
vo Data
ALKALINE
Absent
Present
Absent
Absent
PRESENT
Absent
Present
PRESENT
Absent
Absent
PRESENT
DEFICIENT
Normal
Absent
Absent
Absent
Absent
Cement
& L ime
Year-round
Cont inuous
Low
HIGH
HIGH
Low
Absent
Absent
No Data
ALKALINE
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFICIENT 2
Normal -H igh
Absent
Absent
Absent
Absent
Concrete
Products
Year-round
Cont i nuous
Low
LOW-HIGH
LOW-HIGH
Low
PRESENT "
Absent
Mo Data
ALKALINE
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFICIENT
-I o rma 1
Absent
Absent
Absent
Absent
Asbestos
& Gypsum
Year-round
Cont inuous
Low
LOW-HIGH
No data
Low
Absent
Absent
No Data
Neut ra1
Absent
Present
Absent
Absent
PRESENT
Absent
Absent
PRESENT
Absent
Absent
DEFICIENT
DEFICIENT ,
Norma1-H igh
Absent
Absent
Absent
Absent
Present 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 require pretreatment or are significant
to joint treatment plant design are shown in UPPER CASE.
D-17-8
-------
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Table D-21-1
Wastewater Characteristics
Sodium Chloride Hydrogen Peroxide Aluminum
Sodium Tripoly- Chlorine, Sodium Dichromate Chloride,
Character! st ic phosphate Etc. Sodium Sulf ate Etc.
Industry Operation Year-Round Year-Round Year-Round Year-Round
Flow Continuous Continuous Continuous Continuous
BOD Low Low Low Low
TSS No Data No Data No Data No Data
TDS AVERAGE HIGH HIGH HIGH
COD Low Low Low Low
Grit Absent Absent Absent Absent
Cyanide Absent Absent PRESENT Absent
Chlorine Demand Low Low Low Low
pH Nsutral ACID-BASIC ACID-BASIC ACID-BASIC
Color No Data No Data No Data No Data
Turbidity No Data No Data No Data No Data
Explosive Chemicals Absent Absent Absent Absent
Dissolved Gases Absent Absent Absent Absent
Detergents Absent Absent Absent Absent
Foaming No Data No Data No Data No Data
Heavy Matals Absent PRESENT3 PRESENT Absent
Colloi dal Soli ds
Volatile Organics Absent Absent Absent Absent
Pesticides Absent Absent Absent Absent
Phosphorus DEFICIENT DEFICIENT DEFICIENT DEFICIENT
Nitrogen DEFICIENT DEFICIENT DEFICIENT DEFICIENT
Temperature Normal-high Normal-high Normal-high Normal-high
Phenol No Data No Data No Data No Data
Sulfide No Data No Data No Data No Data
Oil and Grease Absent Absent Absent Absent
Coliform (Total) No Data No Data No Data No Data
Nad wastes have high salt concentrations.
2
Cyanide generated by electrolytic process for hydrogen peroxide.
Downs cell process for chlorine doesn't generate heavy metals.
Sodium Triphosphate Wastewater will have very high phosphate concentration ^2000 mg/1)
NOTE: Characteristics which may require pretreatment or are significant to joint treatment
plant design are shown in UPPER CASE.
D-17-10
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D-17-11
-------
Table D-22-1
Wastewater Characteristics
Industrial Gases
Character!st ic
Industry Operation
Flow
BOD
TSS
IDS
COD
Grit
Cyan!de
Chlorine Demand
pH
Color
Turbi dity
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Dissolved Gases
Detergents
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Colloi da 1 Sol ids
Volat ile Organics
Pest ic ides
Phosphorus
N i t rogen
Temperature
Phenol
Sulfide
Oi1 and Grease
Coliform (Total)
Hydrogen, Nitrogen, Oxygen,
and Carbon Dioxide
Year-Round
Cont i nuous
Low
Low-average
Low-average
Low
Absent
Absent
Low
ACID-BASIC
Low
Low
Absent
Absent
Absent
No Data
Absent
Absent
Absent
Absent
DEFICIENT
DEFICIENT
Average-hi gh
Absent
Absent
PRESENT
Absent
Wastewaters are constant over the daily operating period.
NOTE: Characteristics which may require pretreatment or are significant to joint
treatment plant design are shown in UPPER CASE.
D-17-12
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HU.S. GOVERNMENT PRINTING OFFICE-1973 546-313/J78 1-3
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